Thesis Moham

Copyright
by
Hourshad Mohammadi
2008
The Dissertation Committee for Hourshad Mohammadi Certifies that this is the
approved version of the following dissertation:
Mechanistic Modeling, Design, and Optimization of

Alkaline/Surfactant/Polymer Flooding
Committee:
Gary A. Pope, Supervisor
Mojdeh Delshad, Supervisor
Larry W. Lake
George Hirasaki
Kamy Sepehrnoori

by
Hourshad Mohammadi, B.S.; M.S.
Dissertation
Presented to the Faculty of the Graduate School of
The University of Texas at Austin
in Partial Fulfillment
of the Requirements
for the Degree of
Doctor of Philosophy
The University of Texas at Austin

December 2008
Dedicated to my parents and my husband

without whose love and support this could not have happened
Acknowledgements
I would like to express my deepest gratitude to my supervising professors, Dr.

Gary A. Pope and Dr. Mojdeh Delshad for their support, advice, guidance, and
patience. I appreciate the way they have taught me to approach, analyze and solve the
problems; these invaluable gifts I will carry in my career and life.
I would like to express my appreciation to Dr. Kamy Sepehrnoori for his
advice, direction and support during my graduate studies. I also would like to extend
my gratitude to the members of my committee Dr. Larry W. Lake and Dr. George
Hirasaki for their time and effort.
I would like to acknowledge the financial support of DOE and companies who
participate in the Chemical EOR Industrial Associates Project in the Center for
Petroleum and Geosystems Engineering (CPGE) at The University of Texas at
Austin.
I am thankful of my friends for their company and suggestions- Abraham
John, Ali Farhadinia, Xingru Wu, Yousef Ghomian, Glen Anderson and Oluwaseun
Magbagbeola to name a few. Also I would like to thank Do Hoon Kim and Chris
Britton for providing me with the experimental data. Chrissi King's assistance in
revising my dissertation is greatly appreciated.
I am grateful of Dr. Bob Gochnour and Dr. Gary Jerauld for their mentorship
and support during my summer internship in BP and also Dr. Dwarakanath
Varadarajan for his guidance during my research.
v
Last but definitely not least; I would like to thank my dearest husband, Renzo
Angeles, for being such a unique friend. His cheerful character has always been my
driving force to pursue my goal. He joins me in expressing his appreciation to all who
made this possible.
vi

Publication No._____________
Hourshad Mohammadi, Ph.D.

The University of Texas at Austin, 2008
Supervisors: Gary A. Pope

Mojdeh Delshad
Alkaline/surfactant/polymer (ASP) flooding is of increasing interest and

importance because of high oil prices and the need to increase oil production. The
benefits of combining alkali with surfactant are well established. The alkali has very
important benefits such as lowering interfacial tension and reducing adsorption of
anionic surfactants that decrease costs and make ASP a very attractive enhanced oil
recovery method provided the consumption is not too large and the alkali can be
propagated at the same rate as a synthetic surfactant and polymer. However, the
process is complex so it is important that new candidates for ASP be selected taking
into account the numerous chemical reactions that occur in the reservoir. The reaction
vii
of acid and alkali to generate soap and its subsequent effect on phase behavior is the
most crucial for crude oils containing naphthenic acids.
Using numerical models, the process can be designed and optimized to ensure
the proper propagation of alkali and effective soap and surfactant concentrations to
promote low interfacial tension and a favorable salinity gradient. The first step in this
investigation was to determine what geochemical reactions have the most impact on
ASP flooding under different reservoir conditions and to quantify the consumption of
alkali by different mechanisms.
We describe the ASP module of UTCHEM simulator with particular attention
to phase behavior and the effect of soap on optimum salinity and solubilization ratio.
Several phase behavior measurements for a variety of surfactant formulations and
crude oils were successfully modeled. The phase behavior results for sodium
carbonate, blends of surfactants with an acidic crude oil followed the conventional
Winsor phase transition with significant three-phase regions even at low surfactant
concentrations. The solubilization data at different oil concentrations were
successfully modeled using Hand's rule. Optimum salinity and solubilization ratio
were correlated with soap mole fractions using mixing rules.
New ASP corefloods were successfully modeled taking into account the
aqueous reactions, alkali/rock interactions, and the phase behavior of soap and
surfactant.
These corefloods were performed in different sandstone cores with
several chemical formulations, crude oils with a wide range of acid numbers, brine
with a wide range of salinities, and a wide range of temperatures.
viii
2D and 3D sector model ASP simulations were performed based on field data
and design parameters obtained from coreflood history matches. The phenomena
modeled included aqueous phase chemical reactions of the alkaline agent and
consequent consumption of alkali, the in-situ generation of surfactant by reaction with
the acid in the crude, surfactant/soap phase behavior, reduction of surfactant
adsorption at high pH, cation exchange with clay, and the effect of co-solvent on
phase behavior. Sensitivity simulations on chemical design parameters such as mass
of surfactant and uncertain reservoir parameters such as kv/kh ratio were performed
to provide insight as the importance of each of these variables in chemical oil
recovery. Simulations with different permeability realizations provided the range for
chemical oil recoveries.
This study showed that it is very important to model both surface active
components and their effect on phase behavior when doing mechanistic ASP
simulations. The reactions between the alkali and the minerals in the formation
depend very much on which alkali is used, the minerals in the formation, and the
temperature. This research helped us increase our understanding on the process of
ASP flooding. In general, these mechanistic simulations gave insights into the
propagation of alkali, soap, and surfactant in the core and aid in future coreflood and
field scale ASP designs.
ix
Table of Contents
List of Tables.....
xvii
List of Figures....
xxi
CHAPTER 1
Introduction
1.1 Alkaline/Surfactant/Polymer Flooding.....................................
1.2 Effect of Sodium Carbonate
1.3 Alkalinity Loss Mechanisms...
1.4 Modeling of Alkaline Flooding..
11
1.4.1 Oil-Alkali Chemistry
12
1.4.2 Homogeneous Aqueous Reactions..
13
1.4.3 Dissolution/Precipitation Reactions.
14
1.4.4 Ion Exchange Reactions with Rock Minerals and

Micelles.....................................................................
15
1.5 Basic Assumptions for Modeling Geochemical Reactions.
16
1.6 Objective of this research
16
1.7 Review of Chapters.
17
CHAPTER 2
20
A Review of UTCHEM Simulator
20
2.1 General Description of the Simulator.
20
2.2 Mass Conservation Equations.
22
2.3 Pressure Equation
24
2.4 Calculation of Phase Density...
25
2.5 Modeling of Polymer Properties..
25
2.5.1 Polymer Solution Viscosity at Zero Shear Rate...
26
2.5.2 Calculation of Shear Rate.
27
2.5.3 Polymer Permeability Reduction and Resistance Factor
28
2.5.4 Polymer Inaccessible Pore Volume..
29
2.5.5 Polymer Adsorption..
30
2.6 Surfactant Adsorption..
31
2.7 Microemulsion Viscosity
33
2.8 Capillary Pressure
33
2.9 Relative Permeability Model...
34
2.10 Capillary Desaturation...
36
2.11 Interfacial Tension Model..
38
2.11.1 Healy and Reed's Model.
38
2.11.2 Chun-Huh's Model......
39
2.12 Phase Behavior..
40
2.12.1 Effective Salinity
40
2.12.2 Flash Calculations..
41
2.13 Cation Exchange Model
43
2.14 Effect of Alcohol on Phase Behavior
45
2.14.1 Alcohol Partitioning
46
48
2.14.3 Effect of Alcohol on Solubilization Parameters.....
49
2.15 Mathematical Formulation of Reaction Equilibrium.
50
2.15.1 Basic Assumptions..
51
2.15.2 Mathematical Statement of the Reaction Equilibrium
52
2.15.2.1 Mass Balance Equations......
52
2.15.2.2 Aqueous Reaction Equilibria Relations...
52
2.15.2.3 Solubility Product Constraints.
53
2.15.2.4 Ion Exchange Equilibrium on Matrix

Substrate..
53
2.15.2.5 Ion Exchange Equilibrium on Micelles.......
54
xi
2.15.2.6 Partitioning Equilibrium of Acid Component

between Crude Oil and Water.........................
55
CHAPTER 3
57
Alkaline Consumption Studies..........................................................................
57
3.1 Reactions that Consume Alkaline....................................................
58
3.2 Alkali Consumption in a Sandstone Rock......................................
63
3.2.1 Simulation Input Description........................................ ...
64
3.2.2 Reactions Modeled...........................................................
65
3.2.2.1 Simulation with no Alkali Consumption

(Case 3.1)...........................................................
66
3.2.2.2 Simulation with Cation Exchange

(Case 3.2)............................................................
67
3.2.2.3 Simulation with Quartz Dissolution

(Case 3.3)...........................................................
67
3.2.2.4 Simulation with Congruent Kaolinite

Dissolution (Case 3.4) .......................................
68
3.2.2.5 Simulation with Incongruent

Kaolinite Dissolution (Case 3.5)........................
69
3.2.2.6 Simulation with Congruent Silica

and Incongruent Kaolinite Dissolution
(Case 3.6)............................................................
69
3.2.2.7 Simulation with Soap Generation (Case 3.7).....
69
3.2.2.8 Simulation using Sodium Hydroxide

(Case 3.8)............................................................
70
3.3 Alkali Consumption in a Carbonate Rock using

Sodium Carbonate and Sodium Metaborate.....................................
71
3.3.1 Simulation Input Description............................................
72
3.3.2 Reactions Modeled............................................................
73
xii
3.3.2.1 Simulation in Limestone Rock (Case 3.9)..........
74
3.3.2.2 Simulation in Dolomite Rock (Case 3.10).........
75
3.4 Summary...........................................................................................
76
CHAPTER 4
95
Soap/Surfactant Phase behavior........................................................................
95
4.1 Soap/Surfactant Background...........................................................
96
4.2 Laboratory Phase Behavior Results.................................................
99
4.2.1 Phase Behavior-Case A....................................................
99
4.2.2 Phase Behavior-Case B....................................................
101
4.3 Modeling the Phase Behavior of the Soap and Surfactant Mixture
101
4.4 Summary..........................................................................................
104
CHAPTER 5
117
ASP Coreflood Simulations...............................................................................
117
5.1 Description of Laboratory Core Floods- Cases AI and AII.............
118
5.1.1 Phase Behavior.................................................................
119
5.1.2 Polymer Properties............................................................
120
5.1.3 1D Coreflood Simulation Procedure (Case AI and AII)..
120
5.1.4 Fractional Flow Curve......................................................
121
5.1.5 Reactions...........................................................................
121
5.1.6 Simulations of Corefloods AI and AII..............................
123
5.1.7 Type III sensitivity simulation..........................................
124
5.2 Description of Laboratory Core Floods- Cases BI and BII.............
125
5.2.1 Polymer Properties............................................................
126
5.2.2 1-D Coreflood Simulation Procedure (Case BI and BII)..
127
5.2.3 Fractional Flow for ASP flooding....................................
127
5.2.4 Simulations of Corefloods BI and BII..............................
128
5.2.5 Sensitivity to Alkali Concentration...................................
130
xiii
5.3 Alkaline/Polymer (AP) Simulations................................................
130
5.4 Summary..........................................................................................
132
CHAPTER 6
156
Field-Scale Chemical Flooding Simulations for a Viscous Crude Oil in a

Saline Reservoir.................................................................................................
156
6.1 Phase Behavior.................................................................................
157
6.2 Reactions..........................................................................................
157
6.3 ASP Fractional Flow Analysis.........................................................
159
6.4 ASP Coreflood Design and Simulation...........................................
159
6.5 Field-scale Simulations..................................................................
161
6.5.1 Water Flood......................................................................
162
6.5.2 Polymer Flood.................................................................
162
6.5.3 ASP Flood.......................................................................
163
6.5.4 AP Flood...........................................................................
166
6.6 Chemical Cost Calculation...............................................................
167
6.7 Summary..........................................................................................
168
CHAPTER 7
191
Design and Optimization of High pH Surfactant/Polymer Flooding in a High

Temperature Sandstone Reservoir...................................................................... 191
7.1 Sodium Carbonate as Alkali.............................................................
193
7.2 Modeling Coreflood M1................................................................... 194

7.2.1 Surfactant Phase Behavior and Polymer Modeling
Parameters.........................................................................
195
7.2.2 Fractional Flow Diagram..................................................
197
7.2.3 Reactions Considered for Simulation...............................
197
7.2.4 Coreflood M1 Simulation Results....................................
198
7.3 Aqueous Stability.............................................................................
200
xiv
7.3.1 Modeling the Effects of Co-solvent on Phase Behavior...
200
7.4 Simulation Results for Corefloods BM-07 and M5.........................
203
7.5 1D simulations to Optimize the Design...........................................
206
7.5.1 Simulation of Coreflood BM-08 with Cost Effective

Design................................................................................ 206
7.6 Series I: Sector Model Simulations With Surfactant Formulation
Used in Coreflood M1....................................................................
207
7.6.1 Regular 7-Spot Pattern vs. Inverted 7-Spot Pattern..........
208
7.6.2 Sensitivity Simulations.....................................................
209
7.6.2.1 Polymer Flood...................................................
209
7.6.2.2 Base Case ASP simulation.................................
210
7.6.2.3 ASP Design Variable Sensitivity.......................
211
7.6.2.4 ASP Uncertain Variable Sensitivity..................
212
7.6.2.5 Summary and Conclusions for

Series I Simulations..........................................
213
7.7 Series II: Sector Model Simulations with Chemical Formulation

Used in Corefloods BM-07 and M5............................................
215
7.7.1 Waterflood........................................................................
217
7.7.2 Tracer test.........................................................................
217
7.7.3 Sensitivity Simulations for Chemical Flooding................
219
7.7.3.1 Chemical Slug Injection Design....................
219
7.7.3.2 Base Case.......................................................
221
7.7.3.3 Sensitivity on Design Parameters..................
222
7.7.3.4 Summary and Conclusions for

Series II Simulations......................................
224
CHAPTER 8
269
Summary, Conclusions, and Recommendations...............................................
269
8.1 Summary......................................................................................
xv
269
8.2 Conclusions......................................................................................
271
8.3 Recommendations............................................................................
274
APPENDIX A
275
EQBATCH Reaction Tables..............................................................................
275
APPENDIX B
291
EQBATCH Setup.............................................................................................
291
APPENDIX C
303
BATCH INPUT Example of Soap/Surfactant Phase Behavior.........................
303
APPENDIX D
312
EQBATCH and UTCHEM INPUT Examples...................................................
312
APPENDIX E
388
Alkaline Consumption for a Reservoir Rock.....................................................
388
APPENDIX F
397
Modeling the Effect of Co-solvent on the Phase Behavior...............................
397
Nomenclature....................................................................................................
410
References......................................................................................................
416
VITA................................................................................................................... 428
xvi
List of Tables
Table 3.1:
Example cases studied in this chapter........................................
78
Table 3.2:
Input for 1-D coreflood simulation............................................
79
Table 3.3:
Brine composition for sandstone rock simulations....................
79
Table 3.4:
Injection scheme for sandstone rock..........................................
79
Table 3.5:
Elements and species for simulation in sandstone rock.............
80
Table 3.6:
Equilibrium constants for aqueous species- The

equilibrium constants are from Geochemist's Workbench........
80
Table 3.7:
Solubility products for minerals.................................................
81
Table 3.8:
Brine composition for carbonate rock simulations....................
81
Table 3.9:
Injection scheme for carbonate rock..........................................
81
Table 3.10:
Elements and species for carbonate rock simulations................
82
Table 4.1:
Crude oil properties and temperature of the cases studied.........
106
Table 4.2:
Composition of synthetic brine Case B.................................
106
Table 5.1:
Case A- Core properties.............................................................
133
Table 5.2:
Composition of brine-Case A....................................................
133
Table 5.3:
Case A- Core injection design...................................................
134
Table 5.4:
Composition of brine-Case B.....................................................
134
Table 5.5:
Core properties for Cases BI and BII.........................................
135
Table 5.6:
ASP corefloods BI and BII injection design.............................
135
Table 5.7:
Alkaline/polymer injection design for 1D simulation................
136
Table 6.1:
Formation brine composition.....................................................
170
Table 6.2:
Reservoir minerals.....................................................................
170
Table 6.3:
Comparison of the elemental compositions of experimental

and simulated connate brine......................................................
171
Table 6.4:
Type III salinity windows for soap and surfactant.....................
171
Table 6.5:
ASP core flood design...............................................................
172
xvii
Table 6.6:
Summary of core flood input parameters...................................
Table 6.7:
Reservoir size and dimensions for 2-D field-scale
172
simulations.................................................................................
174
Table 6.8:
Chemical designs for field-scale simulations.............................
174
Table 6.9:
Total amount of chemical injected in

different chemicalflood designs.................................................
175
Table 6.10:
Cost analysis for polymer and AP floods...................................
175
Table 6.11:
Cost analysis for polymer and ASP floods................................
175
Table 7.1:
Rock and fluid properties for coreflood M1..............................
226
Table 7.2:
Core M1 flood design................................................................
226
Table 7.3:
Summary of UTCHEM phase behavior input parameters.........
227
Table 7.4:
Corefloods BM-07 and M5 properties.......................................
227
Table 7.5:
Synthetic Brine Composition.....................................................
227
Table 7.6:
Core flood BM-07 and M5 designs............................................
228
Table 7.7:
Coreflood simulations for optimization.....................................
229
Table 7.8:
Sensitivity simulations for series I............................................
230
Table 7.9:
Sector model specifications for series II...................................
231
Table 7.10:
Corey relative permeability data for water.................................
231
Table 7.11:
Corey relative permeability data for oil.....................................
231
Table 7.12:
Fluid properties for simulations series II..................................
232
Table 7.13:
Oil saturation calculated for each pair of tracers for

series II simulations (base case)...............................................
232
Table 7.14:
Dilution sensitivity study for series II.....................................
232
Table 7.15:
Base case design for series II...................................................
233
Table 7.16:
Sensitivity simulations for series II.........................................
234
Table A.1:
Example list of elements and reactive species...........................
283
Table A.2:
Stoichiometric coefficient of Ith element in Jth fluid

species (for the AR array)..........................................................
Table A.3:
Stoichiometric coefficient of Ith element in Jth solid

xviii
283
species (for the BR array)........................................................

Table A.4:
Stoichiometric coefficient of Ith element in Jth sorbed

species (for the DR array)........................................................
Table A.5:
284
Exponent of Jth independent fluid species (for BB

array).........................................................................................
Table A.6:
283
284
Exponent of Jth independent species in the Ith solid (for

EXSLD array)...........................................................................
284
Table A.7:
Charge of Ith fluid species (for CHARGE array).....................
285
Table A.8:
Equilibrium constants for Ith fluid species (for EQK

array) ........................................................................................
285
Table A.9:
Charge of Jth sorbed species (for SCHARG array)..................
286
Table A.10:
Exponent of Kth independent species in Jth equilibrium

relation (for EXEX array).........................................................
286
Table A.11:
Example list of elements and reactive species..........................
286
Table A.12:
Stoichiometric coefficient of Ith element in Jth fluid

species (for the AR array)........................................................
Table A.13:
Stoichiometric coefficient of Ith element in Jth solid

species (for the BR array).........................................................
Table A.14:
287
Exponent of Jth independent fluid species (for BB

array) ........................................................................................
Table A.15:
287
288
Exponent of Jth independent species in the Ith solid (for

EXSLD array)...........................................................................
288
Table A.16:
Charge of Ith fluid species (for CHARGE array).....................
289
Table A.17:
Equilibrium constants for Ith fluid species (for EQK

array).........................................................................................
290
Table B.1:
Formation brine composition....................................................
299
Table B.2:
Reservoir minerals....................................................................
299
Table B.3:
Table of AR array for EQBATCH input file............................
300
Table B.4:
Table of BB array for EQBATCH input file............................
300
xix
Table B.5:
EQBATCH input parameters.................................................
Table B.6:
Comparison of the elemental compositions of experimental

and simulated connate brine.....................................................
Table E.1:
302
Rock and fluid properties for example coreflood

similar to coreflood M1.............................................................
Table E.2:
301
393
Chemical flood design of example coreflood similar to

coreflood M1.............................................................................
393
Table E.3:
Elements and species simulated for case study.........................
394
Table E.4:
Contribution of each reaction on alkaline consumption...........
394
xx
List of Figures
Figure 1.1:
Solubilization ratio of 0.75 wt% 7POS C16-17, 0.25 wt%

IOS C15-18 and 2wt% SBA on West Texas crude oil at WOR
1:1
and
38oC
with
and
without
Na2CO3
(Jackson,
2006)..........................................................................................
Figure 1.2:
18
Effect of sodium carbonate on West Texas crude oil at a

WOR 1:1 and 38oC with 0.75 wt% 7POS C16-17, 0.25 wt%
IOS C15-18 and 2 wt% SBA (Jackson, 2006)..........................
Figure 1.3:
18
Effect of sodium carbonate on phase behavior using 2 wt%

AOS C20-24, 4 wt% SBA with Elk Hills crude oil at
100oC (Jackson, 2006)...............................................................
Figure 1.4:
19
Equilibration of Elk Hills crude oil with and without sodium

carbonate in a mixture of 2 wt% AOS C20-24, 4 wt%
SBA at 100oC (Jackson, 2006)..................................................
Figure 3.1:
Comparison of alkali and tracer concentrations for Case 3.1

with no alkali consumption.......................................................
Figure 3.2:
83
pH front at 0.2 and 0.4 PV with no alkali consumption for

Case 3.1......................................................................................
Figure 3.3:
19
83
pH front at 0.2 PV with different cation exchange capacities

for Case 3.1 and 3.2a-b-c...........................................................
84
Figure 3.4:
Adsorbed cation concentrations at 0.2 PV for Case 3.2b...........
84
Figure 3.5:
pH front @0.2 PV with quartz dissolution reaction (Case 3.3).
85
Figure 3.6:
H3SiO4- concentration at 0.2 PV (Case 3.3. quartz dissolution

reaction) at different temperatures............................................
Figure 3.7:
85
pH front at 0.2 PV including congruent kaolinite dissolution

reaction (Case 3.4) at different temperatures (no zeolite is
formed).......................................................................................
xxi
86
Figure 3.8:
H3SiO4- and Al(OH)4- concentrations at 0.2 PV at 85oC due to

congruent kaolinite concentration (Case 3.4).............................
Figure 3.9:
pH front at 0.2 PV with incongruent kaolinite dissolution

reaction (Case 3.5) at different temperatures.............................
Figure 3.10:
87
H3SiO4- and Al(OH)4- concentrations at 0.2 PV at 85oC due to

incongruent kaolinite concentration (Case 3.5).........................
Figure 3.11:
86
87
pH front at 0.2 PV including silica dissolution and

incongruent kaolinite dissolution reaction (Case 3.6) at
different temperatures................................................................
Figure 3.12:
Solid concentrations at 0.2 PV including silica dissolution

and incongruent kaolinite dissolution reaction (Case 3.6)......
Figure 3.13:
88
88
Comparison of pH front at 0.2 PV including soap generation

reactions for Case 3.7 (Oil with acid no. of 1 and non
reactive oil curves overlap)........................................................
Figure 3.14:
Molar concentration of soap at 0.2 PV for various acid

numbers (Case 3.7)....................................................................
Figure 3.15:
90
Comparison of pH profile for NaOH and Na2CO3 at 0.2 PV

at 85oC (Case 3.8)...................................................................
Figure 3.17:
89
Comparison of pH profile for NaOH and Na2CO3 at 0.2 PV

at 25oC (Case 3.8)...................................................................
Figure 3.16:
89
90
Comparison of pH profile for Na2CO3 (Case 3.9a) and

sodium metaborate (Case 3.9b) at 0.5 PV (in a Limestone
rock)...........................................................................................
Figure 3.18:
Solid concentration for limestone rock with injection of

Na2CO3 at 0.5 PV (Case 3.9a)....................................................
Figure 3.19:
91
Solid concentration for limestone rock with injection of

sodium metaborate at 0.5 PV (Case 3.9b)..................................
Figure 3.20:
91
92
Solution species concentration for limestone rock with

injection of sodium metaborate at 0.5 PV (Case 3.9b)..............
xxii
92
Figure 3.21:
Comparison of pH profile for Na2CO3 (Case 3.10a) and

sodium metaborate (Case 3.10b) at 0.5 PV (Dolomite rock).....
Figure 3.22:
Solid concentrations for dolomite rock with injection of

Na2CO3 (Case 3.10a) at 0.5 PV..................................................
Figure 3.23:
94
Solution species concentration for dolomite rock with

injection of sodium metaborate (Case 3.10b) at 0.5 PV............
Figure 4.1:
93
Solid concentrations for dolomite rock with injection of

sodium metaborate (Case 3.10b) at 0.5 PV................................
Figure 3.24:
93
94
Activity map for Case A, lines are the limits of Winsor's

Type III calculated from UTCHEM........................................... 107
Figure 4.2:
Solubilization ratio vs. salinity for 50% oil concentration

(Case A) Curves: UTCHEM and points: Experimental data.....
Figure 4.3:
Solubilization ratio vs. salinity for 30% oil concentration

(Case A) Curves: UTCHEM and points: Experimental data
Figure 4.4:
107
108
Activity map for Case B (0.3% surfactant) Lines are the

calculated Winsor's type III region from UTCHEM.................. 108
Figure 4.5:

calculated Winsor's type III region from UTCHEM................
Figure 4.6:

calculated Winsor's type III region from UTCHEM.................
Figure 4.7:
109
109
Solubilization ratio vs salinity for Case B with 50% oil and

0.3% surfactant, Curves: UTCHEM and points:
Experimental data......................................................................
Figure 4.8:
110

Figure 4.9:
110

xxiii
111
Figure 4.10:

Figure 4.11:
111
Solubilization ratio vs salinity for 50% oil and 1.0%

surfactant, Curves: UTCHEM and points: Experimental
data.............................................................................................
Figure 4.12:
112
Type III salinity window calculated as a function of soap

mole fraction (Case A). The limits of the Winsor's Type
III are calculated from Equation 4-1..........................................
Figure 4.13:
Type III salinity window for Case B- Lines are obtained

from UTCHEM..........................................................................
Figure 4.14:
113
Optimum salinity as a function of soap mole fraction

(Case A) Line: UTCHEM and points: Experimental data........
Figure 4.15:
112
113
Normalized solubilization ratio as a function of soap

mole fraction in a linear scale (Case A) Curves:
UTCHEM - Black line is hand drawn showing the trend
of the solubilization ratio...........................................................
Figure 4.16:
114
Solubilization ratio as a function of soap mole fraction

in a logarithmic scale (Case A) Curves: UTCHEM - Black
line is hand drawn showing the trend of the solubilization
ratio............................................................................................
Figure 4.17:
114
Solubilization ratio at optimum salinity for Case B Curves:

UTCHEM- Black line is hand drawn showing the trend
of the solubilization ratio...........................................................
Figure 4.18:
Case A optimum solubilization ratio as a function of soap

mole fraction (linear scale)........................................................
Figure 4.19:
115
Case A optimum solubilization ratio as a function of soap

mole fraction (logarithmic scale)...............................................
Figure 5.1:
115
Floppam 3630S polymer viscosity vs. polymer

xxiv
116
concentration at different salinities (62 oC)...............................

Figure 5.2:
137
Flopaam 3630S polymer viscosity vs. salinity (Line was

curve fit to the laboratory data points to find the slope)............
137
Figure 5.3:
Floppam 3630S polymer bulk viscosity vs. shear rate............... 138
Figure 5.4:
Oil/water relatively permeability curves in Berea sandstone

core AII......................................................................................
Figure 5.5:
138
Fractional flow curves for water, polymer, and SP floods

for Core AII................................................................................ 139
Figure 5.6:
Comparison of simulation and measured oil recovery and

oil cut for coreflood AI.............................................................
Figure 5.7:
Comparison of the effluent surfactant concentration

between UTCHEM and measured data (Case AI).....................
Figure 5.8:
141
Comparison of the oil recovery between UTCHEM

and measured data (Case AII)....................................................
Figure 5.12:
141
Simulated surfactant and soap concentrations of coreflood

AI at 0.5 PV...............................................................................
Figure 5.11:
140
Comparison of the Pressure drop between UTCHEM

and measured data (Case AI).....................................................
Figure 5.10:
140
Comparison of the effluent pH between UTCHEM and

measured data (Case AI)............................................................
Figure 5.9:
139
142
Comparison of the pressure drop between UTCHEM

and measured data (Case AII)....................................................
142
Figure 5.13:
Simulated salinity and IFT for coreflood AII at 0.5 PV............
143
Figure 5.14:
Simulated surfactant and soap concentrations for coreflood

AII at 0.5 PV..............................................................................
143
Figure 5.15:
Simulated pH and oil concentration for coreflood AII..............
144
Figure 5.16:
Comparison of the oil recovery and oil concentration

between the Case AII and sensitivity case in which no
Type III was modeled............................................................
xxv
144
Figure 5.17:
Simulated IFT and optimum salinity at 0.5 PV- sensitivity

for case AII (no Type III)..........................................................
Figure 5.18:
145
Simulated soap and surfactant concentrations - sensitivity

for Case AII (no Type III).........................................................
145
Figure 5.19:
Flopaam 3630S polymer viscosity vs. salinity- Case B............
146
Figure 5.20:
Flopaam 3630S polymer viscosity vs. polymer

concentration, Case B................................................................
146
Figure 5.21:
Flopaam 3630S polymer viscosity vs. shear rate- Case B.........
147
Figure 5.22:
Oil/water relative permeability curves -Case B.........................
147
Figure 5.23:
Fractional flow curves, coreflood B..........................................
148
Figure 5.24:
Coreflood on case BIII with lower polymer concentration.......
148
Figure 5.25:
Comparison of simulation and measured oil recovery and

oil cut for coreflood BI..............................................................
Figure 5.26:
Comparison of simulation and measured pH for

coreflood BI...............................................................................
Figure 5.27:
149
149
Comparison of simulation and measured pressure drop

for coreflood BI.......................................................................... 150
Figure 5.28:
Comparison of simulation and measured effluent

surfactant concentration for coreflood BI..................................
Figure 5.29:
150
Simulated soap and surfactant concentrations for coreflood

BI................................................................................................ 151
Figure 5.30:
IFT and salinity at 0.5 PV for coreflood BI...............................
Figure 5.31:
Comparison of measure and simulated oil recovery and oil

cut for coreflood BII..................................................................
Figure 5.32:
152
Oil recovery comparison for Case BII and sensitivity case

with reduced alkali concentration (1wt% Na2CO3)...................
Figure 5.34:
152
Comparison of measured and simulated pressure drop

for coreflood B-II.......................................................................
Figure 5.33:
151
Soap and surfactant concentrations and Type III

xxvi
153
salinity windows at 0.5 PV for sensitivity case on

coreflood BII with reduced sodium carbonate concentration
Figure 5.35:
153
IFT and effective salinity at 0.5 PV for sensitivity case

with reduced sodium carbonate concentration........................ 154
Figure 5.36:
Oil recovery plot for alkaline polymer case (AP-1)................ 154
Figure 5.37:
Sensitivity of the oil recovery on acid number

for alkaline/polymer floods.....................................................
155
Figure 5.38:
Profile of the alkaline/polymer flood at 0.5 PV- AP-4...........
155
Figure 6.1:
Phase behavior for the simulation of reservoir B with 0.3

wt% surfactant, 50% crude oil at 38oC...................................
Figure 6.2:
176
Fractional flow curve for waterflood, polymerflood, and

ASP flood using the reservoir petrophysical properties.........
176
Figure 6.3:
Immiscible and miscible relative permeability curves...........
177
Figure 6.4:
Cumulative oil recovery and oil cut for 1D ASP simulation..
177
Figure 6.5:
Soap and surfactant concentration, IFT, and effective

salinity profiles at 0.8 PV for 1D ASP simulation..................
Figure 6.6:
178
Well location for sector model (Dark blue color

indicating the aquifer, light blue is the capillary transition
and red is the top layers containing 93% oil concentration)...
Figure 6.7:
Oil saturation at the end of waterflood for 2D and 3D

sector model............................................................................
Figure 6.8:
178
179
Oil saturation at the end of polymerflood for 2D

and 3D sector model...............................................................
179
Figure 6.9:
Polymer concentration profile for polymer flooding (wt%)...
180
Figure 6.10:
Oil saturation profile during polymer flooding

(volume fraction)..................................................................... 180
Figure 6.11:
Figure 6.12:
Comparison of oil recoveries (2D and 3D) for waterflood

and polymer flood...................................................................
181
Oil rate comparison between the polymer and ASP...............
181
xxvii
Figure 6.13:
Cumulative oil recovery for water, polymer, and ASP

floods........................................................................................
Figure 6.14:
Comparison of cumulative oil recovery for 2D and

3D simulations of water flood and ASP flood..........................
Figure 6.15:
182
182
History plot of soap, surfactant, polymer and oil for

producer 1 (3D).........................................................................
183
Figure 6.16:
pH profile for ASP flood (2D)..................................................
183
Figure 6.17:
Soap concentration profile for ASP (volume fraction) (2D)..... 184
Figure 6.18:
Surfactant concentration profile for ASP (volume fraction)

(2D)...........................................................................................
184
Figure 6.19:
Polymer concentration profile for ASP (wt%) (2D).................
185
Figure 6.20:
Oil saturation profile for 2D ASP.............................................
185
Figure 6.21:
Effective salinity (meq/ml) profiles for 2D ASP......................
186
Figure 6.22:
CSEL (meq/ml) profile for 2D ASP.........................................
186
Figure 6.23:
CSEU (meq/ml) profile for 2D ASP.........................................
187
Figure 6.24:
Comparison of cumulative oil production for 2D

chemical flood cases.................................................................
187
Figure 6.25:
pH profiles for 2D AP flood.....................................................
188
Figure 6.26:
Soap concentration (volume fraction) profiles for AP.............. 188
Figure 6.27:
Oil saturation profiles for 2D AP.............................................. 189
Figure 6.28:
Effective salinity (meq/ml) profiles for 2D AP........................
Figure 6.29:
Comparison of oil saturation profiles for different

processes at the end of 3000 days.............................................
Figure 7.1:
190
Phase behavior data and UTCHEM match for Coreflood

M1.............................................................................................
Figure 7.2:
189
235
AN 125 Polymer viscosity vs. salinity (2500 ppm AN-125,

Temp @ 85oC, Shear rate = 11 sec-1)......................................... 235
Figure 7.3:
AN 125 Polymer viscosity vs. concentration (85oC, 2 wt%

NaCl and 11 sec-1)...................................................................... 236
xxviii
Figure 7.4:
AN 125 Polymer viscosity vs. shear rate (2500 ppm

AN-125, Temp @ 80 oC with 2% NaCl and 1% Na2CO3)......... 236
Figure 7.5:
Calculated microemulsion viscosity (Coreflood M1) ................ 237
Figure 7.6:
Calculated surfactant adsorption isotherm.................................
Figure 7.7:
Calculated surfactant adsorption as a function of pH ................ 238
Figure 7.8:
Oil capillary desaturation curve.................................................
Figure 7.9:
Relative permeability for the Berea core flood (M1)................. 239
Figure 7.10:
Fractional flow curve for the Berea coreflood M1..................... 239
Figure 7.11:
Measured and modeled oil recovery and oil cut for
237
238
Coreflood M1.............................................................................
240
Figure 7.12:
Pressure drop history match for Coreflood M1.........................
240
Figure 7.13:
Salinity and surfactant concentration profile at 0.5 PV

for coreflood M1........................................................................
Figure 7.14:
pH and surfactant concentration at 0.5 PV for Coreflood

M1.........................................................................................
Figure 7.15:
242
Adsorbed sodium and hydrogen on the clay at 0.5 PV

(Coreflood M1).........................................................................
Figure 7.17:
241
Surfactant adsorption profile modeled with and without the

effect of pH at 0.5 PV for Coreflood M1...................................
Figure 7.16:
241
242
Partition coefficient of the co-solvent with formation water

and oil (The line is drawn through the data)
(Dwarakanath, 2008).................................................................. 243
Figure 7.18:
The effect of cosolvent on the effective salinity and

phase behavior (Dwarakanath et al., 2008).............................
Figure 7.19:
243
Comparison of measured and UTCHEM

solubilization parameters for the formulation containing
EGBE.......................................................................................
Figure 7.20:
244
The effect of cosolvent concentration on optimal

salinity (formulation containing the EGBE)..............................
xxix
244
Figure 7.21:
The effect of cosolvent concentration on optimum

solubilization ratio (formulation containing the EGBE)............ 245
Figure 7.22:
Surfactant adsorption isotherm for formulation

containing the EGBE (Corefloods BM-07 and M5)..................
Figure 7.23:
245
Surfactant adsorption as a function of pH

(formulation containing the EGBE (Corefloods BM-07
and M5))...................................................................................
Figure 7.24:
246
Simulated and measured tracer concentrations for

Coreflood BM-07)...................................................................... 246
Figure 7.25:
UTCHEM and measured oil cut and oil recovery for

coreflood BM-07........................................................................ 247
Figure 7.26:
Pressure drop (along the core) match for Coreflood BM-07.....
247
Figure 7.27:
Surfactant concentration match for coreflood BM-07...............
248
Figure 7.28:
Cosolvent concentration match for coreflood BM-07...............
248
Figure 7.29:
pH match for the coreflood BM-07............................................ 249
Figure 7.30:
Measured and UTCHEM carbonate and bicarbonate

concentrations for Coreflood BM-07 (points: experimental
and curves: UTCHEM simulation)............................................
Figure 7.31:
Surfactant, oil, cosolvent, polymer concentrations and

effective salinity profiles at 0.5 PV for Coreflood BM-07.......
Figure 7.32:
250
Comparison of UTCHEM and measured oil cut and

oil recovery for coreflood M5....................................................
Figure 7.33:
249
250
Comparison of UTCHEM and measured oil recovery and

oil cut for BM-08 Coreflood.....................................................
251
Figure 7.34:
Top view of the regular 7-spot pattern for the sector model....
251
Figure 7.35:
Grid top of the regular 7-spot pattern for the sector

model, ft.....................................................................................
Figure 7.36:
252
Pressure of the regular 7-spot pattern for the sector

model, psi...................................................................................
xxx
252
Figure 7.37:
Porosity of the regular 7-spot pattern for the sector model........ 253
Figure 7.38:
Permeability of the regular 7-spot pattern for the sector

model, md................................................................................... 253
Figure 7.39:
Comparison of the water flood oil recovery for the regular

and inverted 7-spot patterns, cumulative oil recovery is
reported in fraction..................................................................... 254
Figure 7.40:
Comparison of the chemical flood oil recovery for the

regular and inverted 7-spot patterns, cumulative oil
recovery is reported in fraction.................................................
Figure 7.41:
254
Oil recovery vs. time for different sensitivity analysis

(Series I)....................................................................................
255
Figure 7.42:
Injection and production well flow rate (Case 3)....................... 255
Figure 7.43:
Effective salinity and surfactant concentration in the

second layer between one injector and producer (Base case)....
Figure 7.44:
256
Effective salinity and surfactant concentration in the

second layer between one injector and producer (Case 3)......... 256
Figure 7.45:
Top view of the fine mesh model............................................... 257
Figure 7.46:
Horizontal permeability of the realization 1 (md)...................... 257
Figure 7.47:
Vertical permeability of the realization 1 (md).......................... 258
Figure 7.48:
Porosity of the realization 1.......................................................
Figure 7.49:
Cross-section of the horizontal permeability of the
258
realization 1, md......................................................................... 259

Figure 7.50:
Cross section of the porosity of the realization 1....................... 259
Figure 7.51:
Initial water saturation for realization 1.....................................
Figure 7.52:
Cross-section showing the residual water saturation

for realization 1..........................................................................
Figure 7.53:
260
260
Cross-section showing the residual oil saturation for

realization 1................................................................................ 261
Figure 7.54:
Waterflood oil recovery for different realizations, Y axis

xxxi
is the cumulative oil recovery for different realizations and

x axis is the pore volumes..........................................................
Figure 7.55:
Oil saturation profile at the end of the water flood

for the realization 1....................................................................
Figure 7.56:
261
262
Tracer concentrations after the waterflood for the

realization 1................................................................................ 262
Figure 7.57:
Sweep efficiency calculated from the tracer test........................ 263
Figure 7.58:
Swept pore volume calculated from the tracer test....................
Figure 7.59:
Cumulative oil recovery for the effect of dilution
263
sensitivity cases.......................................................................... 264

Figure 7.60:
Effect of the surfactant slug size on the cumulative oil

recovery with fixed mass of surfactant......................................
264
Figure 7.61:
Comparison of the oil recovery for 10 and 30% slug................
265
Figure 7.62:
Effective salinity and surfactant concentration between

one injector and one producer in layer 10 (1 wt% surfactant
and 30% PV)..............................................................................
Figure 7.63:
265
Effective salinity and surfactant concentration between

one injector and one producer in Layer 10 (3 wt% surfactant
and 10% PV)..............................................................................
Figure 7.64:
Oil saturation at the end of base case chemical flood

simulation..................................................................................
Figure 7.65:
267
Surfactant concentration and salinity profile between one

injector and one producer in layer 10 for Case 5- Series II.......
Figure 7.67:
266
Surfactant concentration and salinity profile between one

injector and one producer in layer 10 for Case 3- Series II.......
Figure 7.66:
266
267
Effluent concentration of polymer, EGBE, surfactant and

salinity from the middle producer (Case 5-Series II)................. 268
Figure 7.68:
Chemical oil recovery for different realizations, y axis

is the fraction of remaining oil recovered due to chemical
xxxii
flood and x axis is the pore volumes.......................................... 268

Figure E.1:
pH and surfactant concentration at the end of 1.0 PV................ 395
Figure E.2:
Adsorbed cation concentration (1.0 PV).................................... 395
Figure E.3:
Effect of silica dissolution on the pH front................................
396
Figure E.4:
Solution species concentration (1.0 PV)....................................
396
Figure F.1:
The effect of cosolvent concentration on optimal

salinity (formulation containing the EGBE)..............................
Figure F.2:
401
The effect of cosolvent concentration on optimum

solubilization ratio (formulation containing the EGBE)............ 401
xxxiii
CHAPTER 1
Introduction
Chemical flooding, in particular alkaline/surfactant/polymer (ASP) flooding,

is of increasing interest because of current high oil prices and the need to increase oil
production. Recent laboratory research has shown significant benefits to using
surfactants at high pH even if the oil has a low acid number and thus little if any
surfactant is generated in-situ, so high pH surfactant-polymer flooding is also of great
current interest.
This study focused on modeling processes to improve oil recovery through the
use of a displacing fluid that has a low interfacial tension (IFT) against the displaced
crude oil. The IFT between brine and oil must be reduced from 10-30 dynes/cm to
about 10-3 dynes/cm to reduce the residual oil saturation to nearly zero under typical
reservoir flooding conditions (Green and Willhite, 1998). The effect of IFT on oil
recovery is modeled by the capillary desaturation curve where residual oil saturation
is correlated as a function of capillary number.
To be able to obtain low IFT and achieve good oil recovery, surfactant and
polymer are added to the injection water. Surfactant is responsible for reducing the
IFT and consequently the residual oil saturation. However, polymer is also necessary
for mobility control (Sorbie, 1991). In a typical surfactant/polymer flood, a small slug
1
of about 30% PV containing a relatively low concentration of surfactant and polymer

is injected. The injection of the surfactant slug is followed by a polymer drive to
maintain mobility control (Green and Willhite, 1998).
In alkaline/polymer flooding, only polymer and alkali are injected and the
process relies solely on the generation of surfactant in-situ. Jennings et al. (1974)
described recovery by emulsification and entrapment. In this mechanism, an emulsion
formed by decreasing the IFT is subsequently trapped by the pore throats. This causes
a reduction of flow in high permeability zones and results in an improvement of the
effective mobility ratio. The effectiveness of alkaline flooding is attributed to a
number of mechanisms. Johnson (1976) categorized the four most important
mechanisms as: emulsification and entrainment, wettability reversal--oil-wet to
water-wet, wettability reversal--water-wet to oil-wet, and emulsification and
entrapment. The first mechanism, emulsification and entrainment, results from
reduction of the IFT and the formation of an emulsion in which oil is entrained. If the
emulsion is mobile, the oil saturation will decrease and oil will move through the
reservoir. Injection of alkaline chemicals can also cause a reversal of wettability from
either oil-wet to water-wet or vice versa. The change in wettability and subsequent
readjustment of fluids within the pores favorably affects the relative permeability to
the oil phase. Discontinuous residual oil can be reconnected and caused to flow.
When this wettability reversal is coupled with IFT reduction, the waterflood residual
oil saturation can significantly decrease.
The chemical enhanced oil recovery process of most interest currently is

alkaline/surfactant/polymer (ASP) flooding. ASP flooding was first introduced by
Nelson (1984) as cosurfactant-enhanced alkaline flooding. ASP flooding has
advantages over both surfactant-polymer flooding and alkaline-polymer flooding as
discussed below in section 1.1.
The challenges of all these chemical flooding processes were addressed in this
research. This research was performed primarily to understand ASP flooding in
detail. The emphasis was on reactions and phase behavior studies. This study used
mechanistic simulations of chemical flooding, especially ASP flooding, to evaluate
the benefits of using alkali under different reservoir conditions.
Mechanistic simulation of ASP flooding considers the chemical reactions
between the alkali and the oil to form soap and between the alkali and both the
minerals and brine. In this introduction, highlights of the alkaline/surfactant/polymer
process are discussed. These issues are expanded in the following chapters in detail.
Such simulations can be done with the UTCHEM simulator (Delshad et al.,
1999) both to interpret laboratory experiments and to scale up to the field, since it is
now computationally feasible to perform such mechanistic simulations in threedimensions for sector models. We illustrate the use of such simulations to design ASP
floods that are more robust and efficient for appropriate reservoir targets.
Alkali and surfactants can also be used to improve oil recovery from fractured
reservoirs. Depending on the rock and crude properties, wettability alteration can play
a major role in oil recovery from mixed-wet naturally fractured carbonates (Liu et al.,
3
2008; Fathi et al., 2008; Zhang et al., 2008). This study did not include such
processes.
1.1 ALKALINE/SURFACTANT/POLYMER FLOODING
If the reservoir crude oil has sufficient "saponifiable components," a reaction
will occur with alkali in which surfactants are formed in-situ. These saponifiable
components are described as petroleum acids, even though their structure is often not
known. The most important mechanism for alkaline flooding is the reduction of IFT.
The relatively low cost of alkaline agents stimulated other variations of the
chemical flooding process. Cosurfactant-enhanced alkaline flooding is a modification
of the basic process in which a surfactant (called a cosurfactant) is added to the
chemical formulation. The complementary effect of the cosurfactant improves the
performance of alkaline flooding.
Nelson (1984) proposed the use of cosurfactant-enhanced alkaline flooding.
Numerous studies had shown that the lowest interfacial tension between a crude oil
and alkali typcially occurs at low alkali concentration. For this and other reasons,
obtaining a low IFT between oil and alkali in the reservoir has limitations. Firstly, a
large concentration of alkali is needed to compensate for the consumption of alkali
because of several geochemical reactions. Secondly, increasing the alkali
concentration shifts the phase behavior to an over optimum condition, which does not
have the lowest interfacial tension. Nelson resolved this dilemma by introducing
cosurfactant that was more hydrophilic than the soap to increase the optimum salinity.
4
Although Bhuyan (1989) developed the geochemical model in UTCHEM and

validated it for several cases, he did not simulate ASP flooding, which was a new
process at the time and not widely used until recently. Wu (1996) and Delshad et al.
(1999) modeled the geochemical reactions that occur during the injection of alkali,
but the effect of soap on the phase behavior was not modeled in their simulations.
New and more accurate laboratory phase behavior and core flood data, improved ASP
models and much faster computing have enabled a much more complete and
systematic investigation than previously possible.
Zhang (2006) and Liu (2008) made an interesting observation based on a
laboratory phase behavior study: The optimum salinity for a mixture of surfactant,
sodium carbonate, and crude oil containing naphthenic acids depends on the soap-tosurfactant molar ratio. They developed a one-dimensional simulator to history match
their oil recovery experiments in sandpacks. Both soap and surfactant components
were tracked, but no chemical reactions were modeled. Instead, soap concentrations
were calculated assuming alkali is present and that the naphthenic acid in the oil is
completely converted to soap based on the mass of oil present. The phase behavior
was modeled using a partition coefficient between oil and water for the
soap/surfactant mixture that depends on the ratio of optimum salinity to salinity.
The success of cosurfactant-enhanced alkaline flood depends on the
simultaneous propagation of injected and in situ generated surfactants in the reservoir.
If the in-situ generated surfactant (soap) moves faster than the injected surfactant, the
phase behavior becomes over optimum and soap partitions into the trapped oil. The
5
soap will be there until the injected surfactant catches up and shifts the phase
behavior towards the optimum. If the cosurfactant moves ahead of the soap, its
adsorption will be high since the pH is low. The adsorbed surfactant later gets
partially desorbed when the high pH front propagates.
1.2 EFFECT OF SODIUM CARBONATE
NaOH, Na2CO3, NaBO2 are all alkali agents that have been tested in phase
behavior experiments. NaOH can raise the pH to very high values. A pH above 12
has been shown to be detrimental since it can speed up the alkali consumption. Based
on Sydansk's (1982) laboratory experiments, it was concluded that the NaOH
solutions at elevated temperature (185oF) strongly interact with sandstone, resulting
in sandstone weight loss and increased porosity. The effect of temperature on reaction
rates depends on the rock minerals, contact time, caustic concentration, and
temperature. He also concluded that the caustic consumption resulting from NaOH
dissolution of silicate minerals can be a significant and detrimental factor during field
applications.
Calcium and other divalent cations can cause precipitation of an alkali, such
as Na2CO3, unless soft brine is used. This is a limitation of sodium carbonate. Some
recent studies have emphasized the use of sodium metaborate as a replacement for
sodium carbonate (Flaaten et al. 2008 and Zhang et al. 2008).. These alkalis gave pH
values of about 11 at 1 wt% alkali concentration and generated soap for acidic crude
oils. A major advantage of sodium metaborate species are their tolerance to divalent
6
cations. This significant finding expands the application of ASP flooding to reservoirs
with high salinity and hardness and formations with anhydrite minerals (Zhang et al.,
2008).
The addition of alkali can be beneficial in reducing the surfactant adsorption.
The smaller the surfactant adsorption, the smaller the amount of required surfactant
for injection, and the lower the costs. Hirasaki et al. (2004) gave another strong
reason why sodium hydroxide should not be used as an alkali agent. They observed
that anionic surfactants show much smaller adsorption in the presence of sodium
carbonate compared to sodium hydroxide. They concluded that the hydroxide is not a
potential determining ion for carbonate surfaces. The importance of the zeta potential
(of the crude-oil/brine interface and of the mineral/brine interface) in wettability
determination was emphasized. The zeta potential of most crude oils is negative for a
pH greater than 3 because dissociation of naphthenic acids in the crude oil and that of
the surface of calcite is positive for a pH less than 9. The opposite charge between the
oil/brine and mineral/brine surfaces results in an electrostatic attraction between the
two interfaces, which tends to collapse the brine film and bring the oil in direct
contact with the mineral surface. In the presence of potential determining ions such as
Ca2+, CO32- and HCO3-, both the crude oil/brine and calcite/brine interfaces are
negatively charged, which results in an electrical repulsion between the two surfaces
and a brine film between the two surfaces.
Jackson (2006) tested the effect of sodium carbonate on the phase behavior of
surfactants using a crude oil with little or no acid. Figure 1.1 shows the phase
7
behavior results for 0.02 and 1.0 wt% sodium carbonate. The optimum solubilization
ratio is about 12 for both cases. He observed that the equilibration time is more rapid
for the sample containing the higher sodium carbonate concentration (Figure 1.2). E
He also screened the surfactant mixtures with crude oil from the Elk Hills reservoir in
California. The optimum solubilization ratio increased from 7 to 12 by adding 1 wt%
Na2CO3 (Figure 1.3). Sodium carbonate also shortened the time required for the
mixture to coalesce to a microemulsion (Figure 1.4). These are extremely valuable
observations showing the benefits of using an alkali such as sodium carbonate. It
demonstrates the benefits of adding sodium carbonate to surfactant formulations
going beyond the traditional ASP processes.
1.3 ALKALINITY LOSS MECHANISMS
One major concern in any chemical flood is the consumption of injected
chemicals in the reservoir. This is particularly important in the case of high-pH
chemical flooding because of the high reactivity of the alkaline solutions. The
interactions of alkaline agents with the reservoir rock, oil, and brine can consume
large amounts of alkali.
Large consumption of chemicals could mean that the chemical requirements
are prohibitively high for achieving a satisfactory rate of propagation. Therefore, the
loss of alkali due to the interactions with rock minerals can not be neglected in the
design of any high-pH chemical flood.
It is very important that new candidates for ASP be selected taking into
account the numerous chemical reactions that occur during the process and, in
particular, the consumption of alkali for reservoirs with different minerals, especially
at high temperatures. Once an appropriate reservoir candidate is selected, it is equally
important to do careful quantitative studies of the reactions that consume alkali during
the ASP flood.
There was a considerable amount of work during the 1980s to find the
important reactions responsible for consuming alkali. According to these studies, the
hydroxide consumption falls into three broad categories:
1. Reversible cation exchange
2. Mineral dissolution
3. Precipitation of insoluble hydroxides
Reversible hydroxide ion exchange was overlooked in alkali/rock interaction
studies for many years. deZabala et al. (1982) pointed out for the first time that the
equilibrium hydroxide ion exchange causes a chromatographic lag of the alkali and
thus the soap generation, which in turn slows oil production. It was shown that even if
alkali consumption could be eliminated, ion-exchange delay can limit the success of
alkaline EOR. Bunge and Radke (1985) provided a theoretical explanation that both
CEC (cation exchange capacity) and HEC (hydrogen exchange capacity) are
equivalent in principle and equal to the total surface exchange sites. They used mass
action to model reversible hydroxide ion uptake by sodium/hydrogen ion exchange
with minerals.
9
Novosad (1984) carried out experiments to measure the alkalinity loss

resulting from CEC. Their method was tested in Berea cores and they found out the
CEC is between 0.1 and 0.4 meq/100 g rock. They noted that the cation exchange
capacity was about half of the total exchange capacity.
Generally cation exchange reactions are very significant for large-surface-area
clays. The ion-exchange equilibrium depends on the concentration of cations because
of competition for surface sites. Therefore, Na+/H+ exchange and resultant OH- loss
will be less in a reservoir of high Na+ concentration. Hydrogen-ion-exchange capacity
(HEC) is the plateau value of hydroxide uptake as pH is increased. However, the
Ca2+/Na+ exchange capacity at a pH of 7 is normally all that is measured.
Another cause of alkali consumption lies in the reaction of alkali agents with
rock minerals. A vast majority of the research on alkali consumption has been
dedicated to the study of mineral dissolution reactions. Many researchers have been
trying to identify the kinetics of alkali consuming dissolution reactions. Most of their
experiments have been performed under different conditions, which make them
difficult to compare. However, they have concluded that the increase of pH,
temperature, and contact time with minerals increases the alkali consumption.
Mohnot et al. (1987) presented alkali consumption data for minerals normally
found in oil reservoir rocks. Among the different clays, kaolinite consumed a
significantly higher amount of alkali than montmorillonite and illite. Among non-clay
minerals, alkalinity loss was the largest for gypsum, followed by dolomite, feldspar
and fine quartz, in decreasing order of consumption. They discovered the
10
consumption by calcite and quartz was the lowest under the reaction conditions of 5%
NaOH, 180oF and 11 days.
Sydansk (1982) showed that a sodium hydroxide solution reacted strongly
with sandstone formations at an elevated temperature (85oC). Cheng (1986)
conducted similar studies comparing sodium hydroxide, sodium carbonate and
sodium orthosilicate solutions. He also observed lower alkali loss for the sodium
carbonate compared to other two alkalis.
1.4 MODELING OF ALKALINE FLOODING
The mathematical model used in this study was a three-dimensional
multiphase, multicomponent chemical flooding simulator, UTCHEM, developed in
the Center for Petroleum and Geosystems Engineering at The University of Texas at
Austin. The geochemical part of UTCHEM was initially developed by Bhuyan in
1989 and was later generalized to take into account any number of elements and
reactions by Wang in 1994 (UTCHEM Technical Documentation, 2000). This model
has been recognized as the most comprehensive model existing for modeling alkaline
flooding to date. A combination of different modules of UTCHEM makes it a unique
multipurpose chemical flooding simulator. Modeling the physical properties is
explained in Chapter 2.
As previously mentioned, the complexity of high-pH chemical flooding
processes is due to the large number of reactions that may occur by injection of an
11
alkaline solution. All the important reactions in alkaline flooding are modeled in
UTCHEM. A brief review of these reactions is described below.
1.4.1 Oil-Alkali Chemistry
Soap produced from the reaction between the acidic components of a crude oil
and the injected alkali is the principal mechanism of oil recovery in alkaline flooding.
Mayer (1983) discussed how the oil components responsible for surface active
materials have been identified as carboxylic acids and to a lesser extent as
caboxyphenols, porphyrins, or asphaltene fractions. The acidic components of oil are
measured and referred to as acid number. The acid number is defined as the
milligrams of potassium hydroxide required to neutralize one gram of crude oil.
However, the acid number may not be a good indicator of the acid components
present in crude oil that generate soap. Recently, Fan and Buckley (2006) and
Hirasaki (2007) discuss new protocols for acid number measurements that better
reflect the generation of soap.
In UTCHEM, the generation of soap is modeled by the partitioning of acid in
the crude oil (HAo) to water according to the solubility as
K
HA o
HA w
KD =
[ HA w ]
[ HAo ]
where HAw is the concentration of acid in water and KD is the partition coefficient.
12
The acid in water will then dissociate in the aqueous phase to produce soluble
anionic surfactant (A-) referred to as soap according to the expression
K
a +
HA w
H +A
where Ka is the reaction constant following the equilibrium relationship

H+ A

Ka =
[ HA w ]
This reaction is one of the sources of alkali consumption since the alkali uses
OH- to generate soap by the following reaction
K
HA w + OH
H2 O + A
1.4.2 Homogeneous Aqueous Reactions

Homogeneous aqueous reactions are one of the most important classes of
reactions in high-pH chemical flooding. Association and dissociation of one or more
chemical species result in the formation of one or more different species in the
aqueous solution. It should be noted that the redox reactions are not modeled in
UTCHEM.
The other class of aqueous reactions involves weak acids and their solids, the
so-called buffered solutions. The buffering action can have a significant effect on the
amount of alkaline chemical required to achieve a certain pH level in an aqueous
solution. Carbonate-bicarbonate, silicate and aluminate buffered solutions are a few
examples of these type of reactions.
13
H 2 O H + + OH
H + + CO32 HCO3
2H + + CO32 H 2 CO3
1.4.3 Dissolution/Precipitation Reactions

Dissolution/precipitation of solid minerals can contribute to high alkali
consumption. Many of these reactions are kinetically controlled. Under equilibrium
conditions, however, the extent of these reactions is controlled by the solubility
product constraints of all the possible solids. These reactions also determine
multivalent cation concentrations in the aqueous solutions which generally have a
significant effect on phase behavior. An example is insoluble salt formation by
reaction with divalent ions such as calcium and magnesium as a result of ion
exchange from the rock surfaces. These reactions can result in significant loss of
alkalinity over an extended period of time. Below is an example of these types of
reactions.
Ca 2 + + CO32 CaCO3
Dissolution and precipitation of clays can also be modeled. For example,
kaolinite, Al2Si2O5(OH)4, is found in most sandstone formations. The dissolution of
kaolinite at high pH can result in generation of aqueous species such as
Kaolinite + 4OH +3H 2 O 2 Al(OH) 4 + 2 H3SiO 4
or dissolution of kaolinite can lead to precipitation of analcime:

14
Al2Si 2 O5 (OH)4 + 2Na + + 2OH + 2H 4SiO 4 2 Na AlSi 2 O6 H 2 O(Analcime) + 5 H 2 O
There are other reactions that might be important, such as the alkaline
transformation of clay mineral to zeolites and kaolinite to sodalite (deZabala, 2007;
Zhao, et al., 2004).
1.4.4 Ion Exchange Reactions with Rock Minerals and Micelles

Ion exchange reactions can have a significant effect on the performance of
alkaline flooding. Cation exchange reactions are of particular interest. These reactions
are fast and reversible. The hydrogen exchange reaction alone can be a limiting factor
in the application of alkaline flooding due to large alkali consumption. Exchange
reactions between the monovalent and multivalent cations can release multivalent
cations which could affect the phase behavior and cause precipitation of solids.
Ion exchange reactions occurring at the micellar surface are of particular
importance in alkaline and surfactant/polymer flooding. Some key ion exchange
reactions are the hydrogen/sodium and sodium/calcium. The hydrogen/sodium ion
exchange can have a great impact on alkali consumption in proportion to the cation
exchange capacity.
+
H + Na + + OH Na + H 2 O
+
Where H and Na are the adsorbed ions on the rock.
15
1.5 BASIC ASSUMPTIONS FOR MODELING GEOCHEMICAL REACTIONS

The following assumptions have been made in developing the reaction
equilibrium model in UTCHEM.
1. All reactions attain thermodynamic equilibrium.
2. The molar activity coefficients of all reactive species are unity so that molar
concentrations replace activities in reaction equilibrium calculations.
3. No redox reactions are present.
4. The reservoir is isothermal. Temperature changes resulting from chemical
reactions are negligibly small.
5. Pressure and volume changes resulting from chemical reactions are negligibly
small.
6. The water present in any phase has the same chemical composition and is in
equilibrium with matrix minerals.
7. The active acid species in the crude oil can be represented collectively by a
single pseudo acid component, HA. HA is highly soluble in oil and partitions
between oil and water with a constant partition coefficient.
8. Supersaturation of aqueous species is not allowed.
1.6 OBJECTIVE OF THIS RESEARCH
This research focuses on chemical enhanced oil recovery to better understand
the processes in chemical flooding with an emphasis on modeling aspects. The aim
was to mechanistically simulate and optimize chemical flooding processes using
16
UTCHEM. Use of an accurate reservoir simulator with appropriate chemical and

physical property models is needed to design and optimize chemical flooding. The
main objective of this research was to apply this simulator in a variety of applications
and test the validity of the model by simulating several ASP corefloods and
comparing the numerical results with the laboratory results.
1.7 REVIEW OF CHAPTERS
Chapter 2 explains the mathematical formulation and physical property
models in UTCHEM. Chapter 3 discusses results of the alkali consumption studies.
This is done to see what reactions have the most impact on the propagation of the
alkali front. Chapter 4 illustrates the phase behavior of the soap and surfactant
mixtures. The effect of soap on the optimum salinity and solubilization ratio is
discussed and mixing rules are used to show the effect of soap on the phase behavior.
Chapter 5 demonstrates the simulation of ASP corefloods. Mechanistic simulations
are presented in this chapter for several corefloods. Chapter 6 shows a sector model
simulation for an ASP flood and a comparison of different scenarios of chemical
floods. This was done to check the feasibility of the chemical flood in for a high
viscosity reservoir oil. Chapter 7 illustrates the design and simulation of a high pH
surfactant/polymer flood first for a core flood and then for a 3D sector model. In
chapter 8, observations and findings of this research are presented, along with ideas
for future work.
17
Figure 1.1: Solubilization ratio of 0.75 wt% 7POS C16-17, 0.25 wt% IOS C15-18
and 2wt% SBA on West Texas crude oil at WOR 1:1 and 38oC with and without
Na2CO3 (Jackson, 2006)
Figure 1.2: Effect of sodium carbonate on a West Texas crude oil at WOR 1:1 and
38oC with 0.75 wt% 7POS C16-17, 0.25 wt% IOS C15-18 and 2 wt% SBA (Jackson,
2006)
18
Figure 1.3: Effect of sodium carbonate on phase behavior using 2 wt% AOS C20-24,
4 wt% SBA with Elk Hills Crude Oil at 100oC (Jackson, 2006)
Figure 1.4: Equilibration of Elk Hills crude oil with and without sodium carbonate in
a mixture of 2 wt% AOS C20-24, 4 wt% SBA at 100oC (Jackson, 2006)
19
CHAPTER 2
A Review of UTCHEM Simulator
This chapter describes the governing equations used in UTCHEM, a threedimensional, multiphase, multicomponent chemical flooding simulator developed by
The University of Texas at Austin.
2.1. GENERAL DESCRIPTION OF THE SIMULATOR
UTCHEM is a three-dimensional chemical flooding compositional simulator.
The simulator takes into account aqueous species such as water, electrolytes (anions
and cations), chemical species such as surfactant, polymer, tracers, and oleic species
such as crude oil. These components may form up to three liquid phases -aqueous,
oleic, and microemulsion- depending on the amount and effective salinity of the
phase environment.
Surfactant phase behavior (Pope and Nelson, 1978; Satoh, 1984; Prouvost et
al., 1985; Camilleri et al., 1987), three phase relative permeability (Delshad et al.,
1987; 1989), oil desaturation (Delshad et al., 1986; Delshad, 1990), well models
(Saad, 1989), shear-thinning polymer viscosity (Wreath et al., 1990), cation exchange
with clays and micelles (Hirasaki, 1982; Bhuyan et al., 1990), tracer partitioning (Jin
et al. 1995), geochemical reactions (Bhuyan et al., 1990; 1991, Wu, 1990) are
included in UTCHEM.
20
The solution scheme used is analogous to IMPES. First, the pressure equation
is solved implicitly for an aqueous phase pressure using explicit dating of saturation
dependent terms. Second, the conservation equations are solved explicitly for total
concentrations. Liu et al. (1994) implemented a third order total variation diminishing
(TVD) numerical scheme to reduce the numerical dispersion.
Following are the basic assumptions made in the development of the
mathematical models of the simulator:
1. Fluids and rock are slightly compressible.
2. The solid phase is immobile.
3. Darcy's law applies (for non-Newtonian flow, apparent viscosity is used in
Darcy's equation).
4. Dispersion follows a generalization of Fick's law to multiphase flow in porous
media.
5. Ideal mixing holds (i.e. volume changes of mixing are zero).
6. Surfactant and polymer are treated as monospecies with no molecular weight
distribution.
7. Polymer, electrolytes, and tracers do not occupy any pore space.
8. The fluid phase behavior is independent of reservoir pressure.
21
2.2 MASS CONSERVATION EQUATIONS

A set of partial differential mass conservation equations and one overall mass
conservation equation describe the isothermal, multiphase flow of N components.
These mass balance equations are:
i
np
C A
C A
C A
C
+
C
u
S
(K
+
K
+
K
)
x
xx
xy
xz
A
A
A
A
A
A
t
x A =1
x
y
z
n
C A
C A
C A
+ A =p 1 C A u yA SA (K yyA
+ K yzA
+ K yxA
)
y
y
z
x
np
C A
C A
C A
C
u
S
(K
+
K
+
K
)
z
zz
zx
zy
A
A
A
A
A
A
z A =1
z
x
y
= R
for
= 1,..., n c
(2 1)
i in Equation 2-1 are defined on a unit pore

The overall concentrations C
volume basis and include both fluid and adsorbed species concentrations.
Physical dispersion is modeled in these equations using a full dispersion
tensor given by
K xxA
JG
JG
K A = K yxA
K zxA
K xyA
K yyA
K zyA
K xzA
K yzA
K zzA
The elements of the dispersion tensor for multiphase and multicomponent

flow in permeable media including molecular diffusion are given by
22
u 2 u yA
u 2
D
+ TA . zA
K xxA = A + LA . xA + TA .
SA u A
SA u A
SA u A
(2 2a)
TA u xA 2 TA u zA 2
D A LA u yA
+
+
+
K yyA =
.
.
.
SA u A
SA u A
SA u A
(2 2b)
u 2 u yA
u 2
D
+ T A . xA
K zzA = A + LA . zA + TA .
SA u A
SA u A
SA u A
(2 2c)
K xyA = K yxA =
( LA TA ) u xA u yA
.
uA
SA
(2 2d)
K xzA = K zxA =
( LA TA ) u xA u zA
.
SA
uA
(2 2e)
K zyA = K yzA =
( LA TA ) u zA u yA
.
SA
uA
(2 2f )
where
u A = u xA 2 + u yA 2 + u zA 2
(2 2g)
The fluxes u xA , u yA , and u zA are calculated using Darcy's equation for

multiphase flow through a permeable medium:
GG k JG
JJG
JG
u A = k . rA (PA A D)
A
(2 3)
GG
where k is assumed to be a diagonal tensor.
JJG
The pressure field required to determine u A is obtained by solving the
pressure equation presented in the next section.
23
2.3 PRESSURE EQUATION
The pressure equation is developed by summing the mass balance equations

over all volume-occupying components (ncv), substituting Darcy's law for the phase
flux terms, using the definition of capillary pressure and noting that
n
=cv1 CA
=1
(2 4)
The pressure equation in terms of the reference phase pressure (phase 1) is

Ct
JG
JG
GG
JG
n
P1 JG GG
+ k rTc P 1 = A =P1 k rA h +
t
JG
JG
n GG
n
A=P1 k rAc P cA1 + k cv
Q
=1
(2 5)
where
k
rAc = rA
A
=cv1 A
(2 6)
C A
and total relative mobility with the correction for fluid compressibility is
n
rTc = A =P1 rAc
(2 7)
The total compressibility, Ct, is the volume-weighted sum of the rock (Cr) and
component compressibilities C o A :
C t = Cr +
=cv1 Co Ci
(2 8)
where
= R [1 + C r (PR PRO ) ]
(2 9)
24
2.4 CALCULATION OF PHASE DENSITY
Phase densities are modeled as a function of both pressure and composition

for a slightly compressible fluid assumption. However, since only specific weights
(g) are required in the simulator, instead of phase densities, phase specific weights
are calculated according to:
A = C1A 1A + C2A 2A + C3A 3A + 0.00433 C4A + 0.02533 C5A
0.001299 C6A + C7A 7 + C8A 8
where
A
A = 1, n p
g
g
=
R 1 + C o (PA PR )
gc gc
R =
(2 10)
(2 11)
g
R , are the specific weights at the reference pressure PR are input values.
gc
The constants in Equation 2-10 account for the weight of the dissolved ions and
polymer. The constant 0.00433 has units of psi/ft per wt% of polymer; the constant
0.02533 has units of psi/ft per meq/ml of chloride, and the constant 0.001299 has
units of psi/ft per meq/ml of calcium. Additional terms are included for dissolved ions
considered in the geochemical options (Bhuyan et al., 1990).
2.5 MODELING OF POLYMER PROPERTIES
In this section, the polymer property models used in the simulator are
presented.
25
2.5.1 Polymer Solution Viscosity at Zero Shear Rate
The polymer solution viscosity at zero shear rate is calculated as a function of

polymer and electrolyte concentrations:
p = w 1 + A p1 C4A + A p2 C4A 2 + A p3 C4A3 CSp

SEP
(2 12)
A p1 , A p2 , and A p3 are empirical constants for a given polymer and are determined
from experimental data. CSEP is the effective salinity, defined for use in polymer
property calculations:
CSEP =
C5 + (p 1) C6
(2 13)
C1
It is widely recognized that the presence of multivalent cations has a more

drastic effect on polymer properties than does the presence of sodium ions (Levitt,
2008). This effect is more pronounced for partially hydrolyzed polyacrylamide
polymers than for polysaccharides such as xanthan gum. p is a parameter used to
determine the effects of divalent cations on the effective salinity for polymer. When
p is equal to one, the monovalent and divalent cations have the same effect on
polymer properties; when p is greater than one, divalent cations have a stronger
effect on the polymer properties. Note that the quantity ( C5 C6 ) equals to the
concentration of monovalent cations. In Equation 2-12, phase index A refers to the
phase with the maximum polymer concentration, which is either aqueous phase or
26
microemulsion phase. Sp is an input parameter to determine polymer viscosity as a

function of salinity. Plotting
o w
w
vs. CSEP , which is assumed to be a straight
line on a log-log plot, gives Sp. At very low salinity CSE1 (on the order of 0.01 wt%),
the salinity dependence in Equation 2-12 is not applicable and the salinity is fixed at
the cut of value of CSE1.
2.5.2 Calculation of Shear Rate
The effect of shear rate on polymer viscosity is modeled by Meter's equation

(1964)
p = w +
po w

1+

1/ 2
(2 14)
P 1
where 1/ 2 is the shear rate at which viscosity is the average of po and w and P
is an empirical coefficient. When the above equation is applied to flow in permeable
media, p is usually called the apparent viscosity and the shear rate is an equivalent
shear rate eq . The equivalent shear rate for phase A in permeable media is calculated
by
n'
1 + 3n ' n '1
eq =
4n '
G
4C u A
8kk rA S
G
c u A
(2 15)
kk rA S
27
G
where u A is in ft. day, k in Darcy, and c in sec-1. n' in the above equation is the
power law exponent which indicates the degree of deviation from Newtonian
behavior. n' can change between zero and one, so the first term in Equation 2.15 is
bounded between 0.779 and 1. c is equal to 3.97C sec-1 where C is the shear rate
coefficient used to account for non-ideal effects such as slip at the pore walls (Wreath
et al., 1990; Sorbie, 1991). The appropriate average permeability k is given by
1
k=
kx
u xA
uA
1
+
ky
u yA
uA
1
+
kz
u zA
uA
(2 16)
2.5.3 Polymer Permeability Reduction and Resistance Factor
Polymers not only reduce the mobility due to increase of polymer viscosity,
but also they reduce the effective permeability of the permeable medium due to
trapping of polymer molecules in pores. This trapping can also reduce the mobility.
The permeability reduction is measured by a permeability reduction factor, Rk,
defined as
Rk =
effective permeability of water

effective permeability of polymer
(2 17)
The change in mobility due to the combined effect of increased viscosity and
reduced permeability is called resistance factor, RF, calculated by
28
(2 18)
w
The effect of permeability reduction lasts even after the polymer has been
R F =R k
flushed with water and is called the residual resistance factor, RRF, defined as
R RF =
mobility before polymer solution

mobility after polymer solution
(2 19)
The permeability reduction factor is modeled as

R k =1+
(R kmax -1) b rk C4A

1+ brk C4A
(2 20)
where
R kmax
1/
3
Sp
crk A p1 CSEP
=max 1,10
1/ 2
kx ky
(2 21)
where A refers to the phase with the highest polymer concentration and brk and crk are
the input parameters. The effect of permeability reduction is assumed to be
irreversible, i.e. it does not decrease as polymer concentration decreases.
2.5.4 Polymer Inaccessible Pore Volume
Laboratory experiments have shown that polymer sometimes travels faster in

the permeable medium than the average velocity of water measured by an ideal tracer
even though the polymer adsorption would be expected to make its velocity less than
the ideal tracer velocity. This effect is called inaccessible pore volume. However, this
29
term is misleading since the polymer molecules actually are small enough to enter
almost all pores in at typical laboratory experiment. The increased velocity is mostly
because the polymer molecules are excluded from the pore walls due to their large
size rather than not actually entering the pores.
2.5.5 Polymer Adsorption
The retention of polymer molecules in permeable media is due to both

adsorption onto solid surfaces and trapping in pore throats. The polymer retention
slows down the polymer velocity and depletes the polymer slug. Polymer adsorption
is modeled by a Langmuir-type isotherm, and is a function of salinity, polymer
concentration and permeability. Polymer adsorption is modeled as irreversible with
respect to both concentration and salinity. The adsorbed concentration of polymer is
given by
a (c c )
c = min c ,
c )
+
1
b
(c

=4
(2 22)
The minimum is taken to guarantee that the adsorption is no greater than the total
polymer concentration. The parameter a is defined as
0.5
k
a = (a 1 + a 2 C SEP )( ref )
k
(2 23)
30
The reference permeability (kref) is the permeability at which the input adsorption
parameters are specified. a 1 and a 2 are the input parameters. CSEP, effective
salinity for polymer, is calculated using Equation 2-13. bk determines the curvature of
the isotherm and ak/bk is the plateau value of the adsorption isotherm.
2.6 SURFACTANT ADSORPTION
Surfactant adsorption is important mechanism since it causes retardation and

consumption of surfactant. Researchers have found that for many conditions of
interest the general tendency is for the surfactant isotherm to reach a plateau at
sufficiently large surfactant concentration. For pure surfactants, this concentration is
in fact the critical micelle concentration (CMC), which is often 100 times or more
below the injected surfactant concentration. Thus, the complex detailed shape of the
isotherm below the CMC has little practical impact on the transport and effectiveness
of the surfactant. For this reason it has been found that a Langmuir-type isotherm can
be used to capture the essential features of the adsorption isotherm for this purpose.
Camilleri et al. (1987) illustrate this by simulating an oil recovery experiment and
Saad et al. (1989) by successfully simulating a surfactant field project using this
approach. A Langmuir-type isotherm is used to describe the adsorption level of
surfactant which takes into account the salinity, surfactant concentration, and
permeability. The adsorption is irreversible with concentration and reversible with
salinity. The adsorbed concentration of surfactant is given by
31

a (c c )
c = min c ,
c )
1
b
(c
+

=3
(2 24)
The minimum is taken to guarantee that the adsorption is no greater than the
total surfactant concentration. Adsorption increases linearly with effective salinity
and decreases as the permeability increases as follows:
0.5
k
a 3 = (a 31 + a 32 C SE )( ref )
k
(2 25)
where CSE is the effective salinity described later. The value of a3/b3 represents the
maximum level of adsorbed surfactant and b3 controls the curvature of the isotherm.
The adsorption model parameters a31, a32, and b3 are found by matching laboratory
surfactant adsorption data. The reference permeability (kref) is the permeability at
which the input adsorption parameters are specified.
The following model is used to take into account the effect of pH on the
surfactant adsorption.
a 3 = (a 31 + a 32 C SE )
for
pH < (pH)c
(2 25a)
and
a 3 = {a 31 + a 32 C SE }(1
and
a 3 = a 33
for
pH (pH)c
)
(pH) t (pH)c
for
pH > (pH) t1
(pH)c < pH (pH) t1
(2 25b)
(2 25c)
32
This model accounts for the experimental observation that plateau adsorbed
concentrations of surfactant remain almost constant in the slightly acidic and neutral
pH range up to a pH equal to (pH)c and then decrease linearly with increasing pH and
become a small constant fraction at
pH (pH)t1 (Harwell et al., 1985). The
parameters a33, pHc, pHt1, and pHt must be determined experimentally along with a31,
a32, and b3. This model also takes into account the effect of salinity on the adsorption
of surfactant through the input parameter a32.
2.7 MICROEMULSION VISCOSITY
Microemulsion viscosity is modeled in terms of pure component viscosities

and the phase concentrations of the oil, water and surfactant:
A =C1A 1 exp 1 ( C2A + C3A ) +C2A 2 exp 2 ( C1A + C3A ) +
C3A 3 exp [ 4 C1A + 5 C2A ]
A = 1,3
(2 26)
where the parameters are determined by matching laboratory microemulsion

viscosities at several compositions. In the absence of surfactant and polymer, water
and oil phase viscosities reduce to pure water and oil viscosities (w, o). When
polymer is present, w is replaced by p, which takes into account the effect of
polymer on the water viscosity.
2.8 CAPILLARY PRESSURE
Capillary pressure for two phases is modeled as a function of interfacial

tension, permeability, porosity, and saturation:
33
n pc
AA '
(1 SnA )
k a wo
PcAA ' =cpc
(2 27)
where
SnA =
SA SrA
(2 28)
np
1 SrA
A =1
and k a = k x k y . The input parameters cpc and npc are determined by curve fitting
capillary pressure vs. normalized water saturation.
For three liquid phases, there is no data available for capillary pressure.
Similar assumptions for three phase gas/oil/water were made for three phase water,
oil, and microemulsion flow. Similar equations as the above equations are derived
Pc13 =cpc
n pc
13
(1 Sn1 )
k a wo
(2 29)
n pc
Sn2
32
(
)
k a wo Sn3 + Sn2
(2 30)
and
Pc32 =cpc
The capillary pressure is scaled with permeability, porosity, and interfacial

tension. In general the capillary pressure becomes insignificant as the interfacial
tension is reduced during the surfactant or alkaline flooding.
2.9 RELATIVE PERMEABILITY MODEL
Multiphase relative permeabilities are modeled based on either modified

Corey functions (Brooks and Corey, 1966; Delshad and Pope, 1989) or the Parker et
al. (1987) extension of van Genuchten two-phase flow equation to three-phase flow.
34
The exponential relative permeability model is:

k rA = k orA SnnAA
A = 1, 2,3
(2 31)
where
SnA =
SA SrA
(2 32)
np
1 SrA
A =1
The relative permeabilities reduce to water/oil, water/microemulsion, or

oil/microemulsion two phase flow functions. The residual saturations, relative
permeability endpoints, and exponents are either constants and input parameters or
functions of trapping number as discussed in the next section.
The endpoints and exponents of both the relative permeability curves change
as the residual saturations change at high trapping numbers because of detrapping
(Morrow and Chatzis, 1981; Morrow et al., 1985; Delshad et al., 1986). The
endpoints and exponents in relative permeability functions are computed as a linear
interpolation (Delshad et al., 1986) between the given input values at low and high
trapping numbers.
k orA
low
k orA
nA = nA
low
SAlow
' r SA ' r k o high k o low
+
rA
rA
Slow Shigh
A'r
A'r
SAlow
' r SA ' r n high
high A
Slow
S
A'r
A'r
nA
low
for A = 1,..., n p
for A = 1,..., n p
(2 33)
(2 34)
The above correlations have been validated by comparison with experimental

data (Delshad et al., 1986).
35
2.10 CAPILLARY DESATURATION
The capillary number (Brownell and Katz, 1949) has traditionally been used
to correlate the mobilization of residual oil due to the reduction of interfacial tension.
Buoyancy forces can also affect the mobilization of a trapped oil phase and can be
expressed by the Bond number (Morrow and Songkran, 1982). The Bond and
capillary numbers are usually treated as two separate dimensionless groups, one to
represent gravity/capillary forces (Bond number) and the other to represent
viscous/capillary forces (capillary number). One of several classical definitions of
capillary number (Stegemeier, 1977) is as follows:
N cA =
JJ
JJGG JG
k . A '
for A = 1,..., n p
AA '
(2 35)
where A and A ' are the displaced and displacing fluids respectively and the gradient
JG
JG
JG
of the flow potential is given by A ' = PA ' gA ' h
Bond number can be defined as

JJGG
JJ
JG
k g(A ' A )h
N BA =
AA '
for A = 1,..., n p
(2 36)
where k is the permeability and g is the gravitational force constant.

A dimensionless number called the trapping number was developed by Pope
and Jin (1995) that includes both gravity and viscous forces. The dependence of
residual saturations on interfacial tension is modeled in UTCHEM as a function of the
trapping number. This formulation was found necessary to adequately model the
combined effect of viscous and buoyancy forces in three dimensions. The trapping
36
number is derived by applying a force balance on the trapped oil globule. The forces
controlling the movement of the blob is the viscous force due to the hydraulic
gradient, the trapping force due to capillary pressure and the gravity force, which can
act as either a driving or trapping force depending on the direction of the flow. The
condition for mobilizing a trapped blob of length L is as follows
Hydraulic force + Buoyancy force Capillary force
Therefore, the trapping number is defined by
N cA =
JJGG JG
JJ
JJ
JJGG
JG
k . A ' k g(A ' A )h
(2 37)
AA '
Residual saturations are then computed as a function of trapping number as

low
high
high SAr SAr
SAr = min SA ,SAr +
1 + TA NTA
for A = 1,....., n p
(2 38)
where TA is a positive input parameter based on the experimental observation of the

relation between residual saturations and trapping number. Slow and Shigh are the
Ar
Ar
input residual saturations for phase A at low and high trapping numbers. This
correlation was derived based on the experimental data for n-decane/surfactant/brine
mixtures (Delshad, 1986).
37
2.11 INTERFACIAL TENSION MODELS
The
two
models
for
calculating
microemulsion/oil
(23)
and
microemulsion/water (13) interfacial tension (IFT) are based on Healy and Reed
(1974) and Huh (1979). The IFT for water and oil (ow) is assumed to be a known
constant.
2.11.1 Healy and Reed's Model
The first IFT model is based on Hirasaki's modification (1981) of the model of
Healy and Reed (1974). Once the phase compositions have been determined, the
interfacial tensions between microemulsion and the excess phases (13, 23) are
calculated as functions of solubilization parameters:
G A1
for R A3 1
log10 A3 = log10 FA + G A2 +
1 + G A3 R A3
G A1
log10 A3 = log10 FA + (1 R A3 ) log10 ow + R A3 (G A2 + 1 + G )

A3
for A = 1, 2
for R A3 < 1
(2-39)
where G A1 , G A 2 and G A3 are input parameters. R A3 is the solubilization ratio (
C A3
C 33
).
The correction factor introduced by Hirasaki, FA , ensures that the IFT at the
plait point is zero and is
38
FA =
1 e
con A
1 e
for A = 1, 2
(2 40)
where
con A =
(CA C3 )2
(2 41)
=1
and in the absence of surfactant or the surfactant concentration below CMC, the IFT
is equal to ow.
2.11.2 Chun-Huh Model
The interfacial tension is related to solubilization ratio in the Chun-Huh

equation as
A3 =
for A = 1or 2
R A23
(2 42)
where c is typically equal to about 0.3. Hirasaki's correction factor FA was introduced
to Huh's equation. Hirasaki's correction factor ensures that the IFT at the plait point is
zero. Additional terms were introduced to Huh's equation so that it reduces to the
water-oil IFT (ow) as the surfactant concentration approaches zero.
A3 = ow e
a R A3
cFA
2
(1 e
3
aR A 3
for A = 1or 2
R A3
where a is a constant input parameter with a default value of 10.
39
(2 43)
2.12 PHASE BEHAVIOR
The surfactant/oil/water phase behavior is based on Winsor (1954), Reed and

Healy (1977), Nelson and Pope (1978), Prouvost et al. (1985). Surfactant phase
behavior considers up to five volumetric components (oil, water, surfactant, and up to
two alcohols) which form three pseudocomponents in a solution. In the absence of
alcohols, only three components are modeled. The volumetric concentrations of these
three components are used as the coordinates on a ternary diagram.
Salinity and divalent cation concentrations have a strong influence on phase
behavior. Other variables besides electrolyte concentrations, e.g. alcohol type and
concentration, the equivalent alkane carbon number of the oil or solvent and changes
in temperature or pressure also cause a phase environment shift from one type of
phase behavior to another type. The surfactant/oil/water phase behavior can be
represented as a function of effective salinity once the binodal curve and tie lines are
described. The phase behavior model uses Hand's rule (1939) and is based on the
work by Pope and Nelson (1978), Prouvost et al. (1984, 1985, 1986), Satoh (1984),
and Camilleri et al. (1987).
The effective salinity increases with the divalent cations (Hirasaki, 1982;
Camilleri et al., 1987) and decreases as the temperature increases for anionic
surfactants and increases as the temperature increases for nonionic surfactants
40
(Bourrel and Schechter, 1988). The effect of co-solvent on the phase behavior is
discussed later.
CSE =
C51
s
(1 6 f6 )(1 + T (T Tref ))
(2 44)
where C51 is the aqueous phase anion concentration; 6 is a positive constant; f6s is the
fraction of the total divalent cations bound to surfactant micelles as
f 6s =
Cs6
(2 45)
C3m
and is a positive temperature coefficient.

The effective salinities at which the three equilibrium phases form or
disappear are called lower and upper limits of effective salinity (CSEL and CSEU). A
nonlinear mixing rule is used to model the changes in the lower and upper effective
salinity limits (optimum salinity is the mean of these two limits) as a function of soap
and surfactant concentrations (Salager et al., 1979; Bhuyan et al., 1990). This model
will be discussed in Chapter 4.
2.12.2 Flash Calculations
The formulation of the binodal curve using Hand's rule (Hand, 1939) is
assumed to be the same in all phase environments. Hand's rule is based on the
empirical observation that equilibrium phase concentration ratios are straight lines on
a log-log scale. The binodal curve is computed from
41
C3A
C B
= A( 3A )
C 2A
C1A
A = 1, 2, or 3
(2 46)
where A and B are empirical parameters. For a symmetric binodal curve where B =
1, which is the current formulation used in UTCHEM, all phase concentrations are
3
calculated explicitly in terms of oil concentration C2A (recalling C A = 1).

=1
C3A =
1
AC2A +
2
( AC2A ) 2 + 4AC2A (1 C2A )
A = 1, 2, or 3
(2 47)
Parameter A is related to the height of the binodal curve as follows
2C3 max,m
Am =
1 C3 max,m
m = 0,1, and 2
(2 48)
where m=0, 1, and 2 are corresponding to low, optimal, and high salinities. Am is
linearly interpolated as
C
A = (A o A1 ) 1 SE + A1
CSEOP
C
A = (A 2 A1 ) SE 1 + A1
CSEOP
for CSE CSEOP
(2 49)
for CSE > CSEOP
(2 50)
where CSEOP is the optimum effective salinity and the arithmetic average of CSEL and
CSEU. The heights of the binodal curve at three reference salinities are input to the
simulator and are estimated based on the phase behavior experiments.
42
For both Type II() and Type II(+) phase behavior, there are only two phases
below the binodal curve. The following equation defines the distribution curves
(tielines) when two phases exist.
C
C3A
= E 3A '
C 2A
C1A '
(2 51)
where A and A ' are the two phases. In the absence of available data for tie lines, F is
calculated from F = 1/B. For a symmetric binodal curve (B=1), F is equal to 1.
Because the component concentrations are in volume fractions, they must add up to
one; therefore, imposing the constraint equations gives:
C1A + C2A + C3A = 1
C1A ' + C2A ' + C3A ' = 1
(2 52)
(2 53)
There are 5 equations and 6 unknowns. Unknowns could be found by

choosing any phase concentration between 0 and 1 to sweep the phase diagram. C 2A
is chosen to be varied. Oil concentrations at the plait point for Type II(-) and Type
II(+) are entered as input parameters to solve the phase behavior equations for any
region.
2.13 CATION EXCHANGE MODEL
There are two cation exchange models in UTCHEM. One is based on

Hirasaki's model in which hydrogen cation exchange is not considered (at neutral
pH). The other model includes cation exchange reactions in the presence of other
43
reactions presented by Bhuyan (1989). The geochemical module uses the latter model
and takes into account hydrogen concentrations (or pH). In this section, the first
model is explained. The ion exchange model in the geochemical module is described
later (Equations 2-78 to 2-82).
Cations exist in three forms: as free ions, adsorbed on a clay surface and in
association with surfactant, as either surfactant micelles or adsorbed micelles. The
mass action equations for the exchange of calcium (=6) and sodium (=12) on clay
and surfactant describe the cation exchange model as
C s 2
C f 2
( 12 ) = s C3m ( 12 )
C 6s
C 6f
(
C12c
C6 c
) = Qv (
C12f
C6f
(2 54)
(2 55)
where the superscripts f, c, and s denote free cation, adsorbed cation on clay, and
adsorbed cation on micelles, respectively. The simulator input parameters are Qv, the
cation exchange capacity of the mineral, c and s, the ion exchange constants for
clay and surfactant, and C3m, the concentration of surfactant in meq/ml. The electrical
neutrality and mass balances needed to close the system of ion exchange equations
are
44
C5 = C12f + C6f
(2 56)
C6 = C6f + C6s + C6c
(2 57)
C3 = C6s + C12s
(2 58)
Q v = C6c + C12c
(2 59)
The cation exchange equations are solved for the six unknowns
C6c , C12c , C6f , C12f , C6s , and C12s using the Newton-Raphson method.
2.14 EFFECT OF ALCOHOL ON PHASE BEHAVIOR
The presence of alcohol affects the effective salinities and causes a shift in the
phase boundaries. The effect of alcohol on the solubility is accounted for by shifting
the maximum height of binodal curve. The amount of alcohol that partitions in the
excess phase(s) is modeled either by constant partitioning coefficients as in Hirasaki's
model (1982) or as a function of total composition with the concept of
pseudocomponent and pseudophase as in Provoust's model (Prouvost et al., 1984 and
1985).
The phase behavior is modeled as a tetrahedron at a fixed salinity. Four
pseudocomponents are surfactant, alcohol, oil, and water represented in a tetrahedron.
The tielines and binodal curves are located on the ternaries sliced through
tetrahedrons. The pseudophases are (1) the aqueous phase consisting of water and
alcohol(s), (2) the oleic phase consisting of oil and alcohol(s), and (3) the
microemulsion phase consisting of surfactant and alcohol(s). Similar to the no alcohol
mixture, the phase behavior parameters such as binodal curve, plait point and
45
invariant point are calculated as a function of effective salinity using Hand's rule
(1939).
2.14.1 Alcohol Partitioning
The two options available in UTCHEM to calculate the alcohol partitioning

are based on the models of Hirasaki and Prouvost. Hirasaki's model assumes a
constant partition coefficient whereas experimental results show that alcohol partition
coefficients vary with total composition. Prouvost extended the pseudophase model to
calculate variable alcohol partition coefficients and to be applicable to two alcohols.
The following intensive composition parameters are defined in the model.
C17
1 =
C1
C18
2 =
C1
(2 60)
C72
1 =
C2
C82
2 =
C2
(2 61)
C37
1 =
C3
C83
2 =
(2 62)
C3
where C1, C2, and C3 are overall water, oil and surfactant volumes respectively.
Superscripts 1, 2 and 3 represent the association of alcohol with aqueous, oleic, and
pseudophases. Therefore, C17 is the volume of first alcohol (species no. 7) in the
aqueous phase and C18 is the volume of second alcohol (species no. 8) in the aqueous
phase. The partition coefficients used in Hirasaki's model can be defined using the
above parameters:
46

K 72 = 1
1
K82 = 2
2
(2 63)
K 37 = 1
1
K83 = 2
2
(2 64)
In Provoust's model, monomeric alcohol reactions are considered. The

following thermodynamic constants are used in the model.
kw1: partition coefficient of monomeric alcohol 7 between aqueous and oleic
pseudophases
km1: partition coefficient of monomeric alcohol 7 between interfacial and oleic
pseudophases
k1: self-association constant of monomeric alcohol 7 in oleic pseudophase
a: ratio of molar volume of monomeric alcohol 7 to equivalent molar volume
of surfactant
kw2, km2, k2, and b are similar constants for alcohol 8.
The above parameters are input to the simulator. Knowing C7 and C8, which
are the overall volume fractions of alcohol 7 and alcohol 8 in the gridblock, and using
material balance, permits the calculation of 1 and 2 . The other four intensive
parameters 1 , 2 , 1 , and 2 are calculated subsequently. Once these parameters are
known, alcohol partition coefficients are calculated based on Equations 2-61 and 262. These intensive parameters are used for calculating the pseudocomponenets.
47
Camilleri extended Hirasaki's model to account for the change in optimal

salinity with change in co-solvent concentration.
CSE =
C51
(1 6 f 6s )(1 + a f a s )(1 + T (T Tref ))
(2 65)
f 6s and fas are the slope parameters for calcium and alcohol effects, respectively.
fas =
total volume of alcohol associated with surfactant

total volume of surfactant pseudocomponent
(2 66)
For the two alcohols (components 7 and 8), the effective salinity is defined by
CSE =
C51
(2 67)
(1 6 f 6s )(1 + 7 f 7s + 8 f8s )
The effective salinity limits are not constants when there are two alcohols in
the system since each alcohol gives a different Type III phase behavior salinity
window:
CSEL =
CSEU =
CSEL7 7 f 7s + CSEL8 8 f8s
(2 68)
7 f 7s + 8 f8s
CSEU7 7 f 7s + CSEU8 8 f8s
(2 69)
7 f 7s + 8 f8s
48
2.14.3 Effect of Alcohol on Solubilization Parameters
Satoh (1984) considered the effects of alcohol on the height of the binodal
curve which can increase as the total chemical increases. The following linear
relationship between the height of the binodal curve (C3max) and fas is used for the one
alcohol case:
C3 max,A = maA f s + CaA
a
A = 0, 1, 2
(2 70)
where the subscript A assumes values of 0, 1, or 2 denoting the salinity: 0 means at

zero salinity, 1 means at optimal salinity, and 2 means at two times the optimal
salinity. maA is the slope for maximum height of binodal curve vs. fraction of alcohol
associated with the surfactant pseudocomponent at salinity A . CaA is the intercept of
maximum height of the binodal curve at zero fraction of alcohol associated with the
surfactant pseudocomponent at salinity A . Parameters maA and CaA are input
parameters which are obtained by matching the phase behavior data. This matching is
done using single alcohol experiments independently for alcohol 7 and alcohol 8. The
following equations are used for calculating the height of the binodal curve for the
two alcohol case:
49
C3 max,7A = m7A (f7s + f8s ) + C7A
(2 71)
C3 max,8A = m8A (f7s + f8s ) + C8A
(2 72)
f7s
C3 max,A = C3 max,8A + (C3 max,7A C3 max,8A )
f 7s + f8s
C7 A
C8A
= (m7A +
) f 7s + (m8A +
) fs
s
s
s
s 8
f 7 + f8
f 7 + f8
(2 73)
2.15 MATHEMATICAL FORMULATION OF REACTION EQUILIBRIUM
This section describes the geochemistry model and is based on work by

Bhuyan (1989) and Bhuyan et al. (1990). The geochemical model is based on a local
thermodynamic equilibrium assumption to compute the detailed composition of the
reservoir rock and fluids in the presence of reactions among the injected species and
reservoir rock and fluids. The reactions include aqueous electrolytes chemistry,
precipitation/dissolution of minerals, ion-exchange reactions with the matrix, and the
reaction of acidic components of the oil with bases in the aqueous solution.
A program called EQBATCH was developed by Bhuyan (1989) to perform
batch reaction equilibrium calculations. EQBATCH can be used as a preprocessor for
UTCHEM to calculate the initial equilibrium state of the reservoir. EQBATCH writes
the output data in a format similar to the geochemical input data of UTCHEM, so it
can be directly pasted into an input file for UTCHEM. Other uses of EQBATCH
include: determination of compatibility between injection water and formation water,
equilibrium composition and compatibility of mixing injection water from different
50
sources, and equilibrium composition and the resulting pH of the injection water after
addition of various electrolytes. Appendices A and B describe how to set up the
EQBATCH input file.
2.15.1 Basic Assumptions
The following assumptions have been made in developing the reaction

equilibrium model:
1. All reactions attain thermodynamic equilibrium.
2. Activity coefficients of all reactive species are unity so that molar
concentrations replace activities in reaction equilibria calculations.
3. No redox reactions are present.
4. The reservoir is isothermal. Temperature changes resulting from chemical
reactions are negligibly small.
5. Pressure and volume changes resulting from chemical reactions are negligibly
small.
6. The water present in any phase has the same chemical composition and is in
equilibrium with matrix minerals.
7. The active acid species in the crude oil can be represented collectively by a
single pseudo acid component, HA. HA is highly soluble in oil and partitions
into the water with a constant partition coefficient.
8. Supersaturation of aqueous species is not allowed.
9. The activity of water is equal to unity.
51
2.15.2 Mathematical Statement of the Reaction Equilibrium
Let the reactive system be comprised of J fluid species, K solid species, I

matrix-adsorbed cations and M micelle-associated cations all made up of N elements.
There are then (J+K+I+M) unknown equilibrium concentrations. To determine the
equilibrium state of the system, therefore, one needs (J+K+I+M) number of
independent equations. These equations are given below.
2.15.2.1 Mass Balance Equations
Elemental mass balances provide N equations of the form

CTn
j=1
k =1
lk +
= h njC j + g nk C
i =1
m =1
f ni Ci + enm Cm
for n = 1,..., N
(2 74)
Electrical neutrality in the bulk fluid phase gives one more equation
J
z jC j +
j=1
z m Cm = 0
(2 75)
m =1
However, Equation 2-75 is actually a linear combination of the set of mass

balance equations given by Equation 2-74. This equation is, therefore, not an
independent equation, but can be used in place of any one of the elemental material
balance equations.
2.15.2.2 Aqueous Reaction Equilibria Relations
Out of the J fluid chemical species, we can arbitrarily select N independent

species such that the concentrations of the remaining (J-N) fluid species can be
52
expressed in terms of the concentrations of these N independent species through

equilibrium relationships of the form
N
w rj
Cr = K eq
r Cj
for r = (N + 1),....., J
(2 76)
j=1
2.15.2.3 Solubility Product Constraints
For each solid there is a solubility product constraint given

N
w rj
eq
K sp
k Kr C j
for k = 1,....., K
(2 77)
j=1
where the solubility product constants K sp

k are defined in terms of the concentrations
of the independent chemical species only. If a solid is not present, the corresponding
solubility product constraint is the inequality; if the solid is present, the constraint is
equality.
2.15.2.4 Ion Exchange Equilibrium on Matrix Substrate
For each substrate allowing exchange among I cations, there is one

electroneutrality condition given by
I
Q v = zi Ci
(2 78)
i=1
Additionally, for these I adsorbed cations there will be (I-1) independent exchange
equilibria relations of the form
53
pj
pi
K ex
p = Cj Cj
j=1
for p = 1,....., (I 1)
(2 79)
i =1
2.15.2.5 Ion Exchange Equilibrium on Micelles
For M cations associated with surfactant micelles there will be (M-1) cation
exchange (on micelle) equilibria relations of the form
N
K exm
= C j qj
q
j=1
x qm
Cm
for q = 1,....., (M 1)
(2 80)
m =1
It has been shown that an electrostatic association model where the mass
action equilibria constants are not really constants, but are functions of total anionic
surfactant concentration, adequately describes these ion exchange equilibria relations
(Hirasaki, 1982). Thus, these equilibria constants are given by
K exm
= qexm (C
q
+C
(2 81)
Additionally, the electroneutrality conditions for the micelles as a whole

provide one more equation as
C
+C
zm Cm
(2 82)
m =1
54
2.15.2.6 Partitioning Equilibrium of Acid Component between Crude Oil and

Water
For cases where partitioning of an acidic component between oil and water is
considered, the acid component remaining with the oil (HAo), but available for
partitioning into the water, is selected as one of the independent chemical species as
described in Sec. 2.15.2.2. Since all aqueous reaction equilibria calculations are done
on a unit water volume basis, the concentration of HAo also needs to be expressed on
the same basis. Let a unit volume of pore space at a given time and position have v1
fraction filled by water and v2 fraction filled by oil. Now defining the concentration of
HAo as
C HAo =
moles of H Ao
liter of water
gives the concentration of the dependent variables HAw as

C HAw =
moles of H Aw
liter water
= KD
moles of H Ao
liter oil
liter water
= KD
C HAo
liter oil
v
= K D 1 C HAo
v2
and that of A as
55
moles of A
liter water
CHA w
= Ka
C +
H
= KD Ka
liter water CHAo

liter oil C +
H
= KD Ka
v1 CHAo
v2 C +
H
Thus, it is seen that for these two dependent chemical species, the reaction
equilibria constants, as defined in Sec. 2.15.2.2, are actually functions of the relative
amounts of water and oil available. For a given water-oil ratio, these two equilibrium
constants can be calculated from the partition coefficient (KD=10-4) and acid
dissociation constant (Ka=10-10). Once calculated, these constants can be treated the
same as other reaction equilibria constants in the computation procedure for that
position and time.
56
CHAPTER 3
Alkali Consumption Studies
It is very important that new candidates for ASP be selected taking into
account the numerous chemical reactions that occur during the process and, in
particular, the consumption of alkali for reservoirs with different minerals and
temperatures. Once an appropriate reservoir candidate is selected, it is equally
important to do careful quantitative studies of the reactions consuming alkali during
the ASP flood. If there is a large consumption of alkali, it cannot be propagated at the
same rate as the synthetic surfactant, thereby reducing its effectiveness compared to
other techniques, such as surfactant/polymer (SP) floods. Large consumption of alkali
also causes the change in the phase behavior and inadequate salinity if most of the
alkali is consumed.
This chapter introduces mechanistic simulations of alkaline flooding and the
benefits of using alkali under different reservoir conditions. It is demonstrated that the
use of such simulations to design ASP floods leads to more robust and efficient
operations in appropriate reservoir targets. Alkali consumption is studied for different
alkalis (Na2CO3, NaOH, NaB(OH)4) and their interactions with different rocks. Table
3.1 lists all the example cases studied in this chapter. It is shown that fast reactions,
such as the cation exchange reaction, could retard the pH front. Likewise, kineticallycontrolled reactions, such as dissolution of silica and kaolinite, could cause
57
significant pH loss. The mechanistic procedure presented here can also be used as
screening criteria to recognize potential candidates for ASP flooding.
The objective of this study is to:
Investigate reactions which are responsible for alkali consumption.
Model these reactions in UTCHEM and study their effects on the propagation
of the alkali front.
3.1 REACTIONS THAT CONSUME ALKALINE
The interactions of alkaline agents with the reservoir rock, oil, and connate
water can consume large amounts of alkali. The loss mechanisms of hydroxide may
be categorized by the following reactions:
1. Alkaline chemicals such as sodium carbonate are injected to react with
crude oil to generate soap and increase pH. In UTCHEM, generation of soap is
modeled by two reactions.
Partitioning of acid component between oil and aqueous phase

K
HA o
HA w
KD =
[ HA w ]
[ HAo ]
(3-1)
HAo: Concentration of acid in oil

HAw: Concentration of acid in water
KD: Partition coefficient of HAo
58
Dissociation of acid component in the presence of alkali to produce soluble

anionic surfactant (A-). This reaction consumes alkali to generate soap.
K
a +
HA w
H +A
H+ A
Ka =
[ HA w ]
(3-2)
2. Another class of reactions that consume alkali is the ion exchange on the
rock surface. The importance of these reactions was overlooked for years until the
1980s. In modeling the alkaline oil recovery process, de Zabala et al. (1982) pointed
out that equilibrium hydroxide ion uptake causes a lag in alkali front propagation and
in the accompanying in-situ generated surfactants, which in turn delays the oil
production. Ion exchange is a fast reaction; therefore, the assumption of local
equilibrium is valid for modeling these types of reactions. This reaction alone can
limit the feasibility of alkaline EOR.
Bunge and Radke (1985) also shed more light on the importance of this
reaction in consumption of alkali. They provided a theoretical explanation that both
CEC and HEC are equivalent in principle and equal to the total surface exchange
sites.
3. Insoluble salt formation by reaction with hardness ions in the aqueous
phase and exchanged from the rock surfaces
Ca 2 + + CO32 CaCO3
(3-3)
59
Baviere (1991) showed the advantage of using Na2CO3 compared to sodium

silicate and sodium hydroxide. Scales can originate from the reactions of alkalis with
the carbonate minerals in the rock.
FeCO3 (s) + SiO32 FeSiO3 + CO32
MgCO3 (s) + 2OH
Mg(OH)2 +CO32
(3-4)
CaCO3 (s) + SiO32 CaSiO3 + CO32
Although solubilities of carbonate minerals could be lower than those of

corresponding silicates or hydroxides, the continuous supply of fresh alkaline solution
under the dynamic field conditions may be expected to result in a continuous release
of carbonate ions from rock minerals into the solution.
Silicate precipitates are generally hydrated, flocculent and highly plugging
even at low concentrations. Carbonate precipitates are relatively granular and less
adhering on solid surfaces (Cheng, 1986). Thus, under similar experimental
conditions of porosity and flow rate, Na2CO3 shows the least degree of permeability
damage in the presence of hard water. Calcium carbonate scales can easily be
removed at production wells by acidizing or by using inhibitors, whereas there is no
long-term treatment currently existing for the control of silicate-containing
precipitates.
4. Congruent and incongruent dissolution reactions are also responsible for
alkali consumption. Congruent dissolution refers to a mineral reaction that generates
soluble aqueous species. The simplest example is the dissolution of a mineral such as
quartz. At pH values below about 9 this can be represented by the equation
60
SiO2 (quartz) + 2H 2 O H 4SiO4 (aq)

K eq = [H 4SiO 4 ] = 1 104 @ 25o C
(3-5)
A solution with H4SiO4 concentration of 1x10-4 mole/L (at 25oC) is in

equilibrium with the quartz. Solutions with higher H4SiO4 concentrations would be
supersaturated, and those with lower values would be undersaturated. Similar
relationships hold for amorphous silica, which has a solubility of 2x10-3 at 25oC.
At high pH, the equilibrium solubility is slightly more complicated. H4SiO4 is
an acid similar to H2CO3, and at high pH it dissociates into H3SiO4- and H2SiO42-. The
equilibrium constants are
H 4SiO4 H3SiO4 + H +
K1 =
[H3SiO 4 ] [H + ]
= 1 109.9 @ 25o C
[H 4SiO4 ]
H3SiO4 H 2SiO42 + H +
K2 =
[H 2SiO42 ] [H + ]
[H3SiO4 ]
(3-6)
= 1 1011.7 @ 25o C
H2SiO42- is the primary monomeric silicon species above pH of 13, while

H3SiO4- dominates at pH of 11.
Incongruent dissolution refers to dissolving a mineral and the formation of a
different mineral. Kaolinite is one of the important clays found in most sandstones.
The chemical formula of kaolinite is Al2Si2O5(OH)4; i.e., Si and Al atoms are
stoichiometrically equal in the clay structure. From the concentration of dissolved Si
and Al, one can determine whether the dissolution of kaolinite is congruent, resulting
61
in equal molar concentrations of Si and Al to form buffer species, or whether the

dissolution is incongruent to form another mineral.
Congruent dissolution of kaolinite at alkaline pH can be written as
Kaolinite + 4OH +3H2 O 2 Al(OH)4 + 2 H3SiO4
(3-7)
and incongruent dissolution of kaolinite can precipitate analcime:

Al2Si2O5 (OH)4 (Kaolinite) + 2Na+ + 2OH + 2H4SiO4 2NaAlSi2O6 .H2O(Analcime) + 5H2O
(3 8)
The temperature and pH-dependencies of the dissolution behavior of

aluminosilicates are not well understood. Bunge and Radke (1983) reported that the
kaolinite dissolution at 158oF (70oC) is congruent. Mohont et al. (1987) measured the
Si and Al concentrations at 180oF (85oC) and found out that the long-term
concentrations of Si and Al are unequal, meaning that the dissolution is incongruent.
At lower temperatures, they observed that the long-term concentrations of Si and Al
are almost equal; apparently implying congruent dissolution of kaolinite. Drever
(1982) showed the stability relationships among some minerals in the system of
Na2O/Al2O3/SiO2/H2O at 77oF (25oC). Diallo et al. (1987) observed congruent
dissolution of kaolinite occurs when the samples are not shaken and even small
amounts of mixing seem to cause incongruent dissolution.
Carroll and Walther later (1990) studied the dissolution of kaolinite at 25o,
60o, and 80oC. They concluded that at all three temperatures, the pH-dependencies of
kaolinite dissolution behavior are similar. Based on their findings, they showed
62
kaolinite dissolution is controlled by the detachment of Al and Si reaction sites.

Initially they observed that the detachment of Al and Si is somewhat independent,
meaning that the dissolution is incongruent. However, with increasing time, the
dissolution of kaolinite approached congruency, requiring the detachment of Al and
Si to become interdependent.
Another well-documented example of an incongruent reaction is that of
gypsum or anhydrite with alkali to produce much less soluble calcite.
CaSO4 + Na 2 CO3 CaCO3 + Na 2SO 4
(3-9)
Radke (1979) and deZabala (1982) showed that kinetically controlled mineral
dissolution reactions may reduce the produced alkalinity to a lower concentration
than the injected concentration, whereas ion-exchange processes may cause delay in
the produced alkalinity and pH front, which in turn delays tertiary oil production.
In the following section, we use UTCHEM in modeling all these reactions. It
is shown how each of these reactions can affect the alkali front. This can be
considered as a screening step for candidate reservoirs before ASP flooding. In this
chapter, we study the interaction of sandstone and carbonate reservoirs with different
alkalis such as sodium carbonate, sodium hydroxide, and sodium metaborate.
3.2 ALKALI CONSUMPTION IN A SANDSTONE ROCK
A sandstone rock containing 98 wt% silica and 2 wt% kaolinite is chosen to

investigate the effect of cation exchange and silica and kaolinite dissolutions on alkali
consumption. Hydrogen exchange capacity (HEC) varies from 0.1 to 1.0 meq/100 g
63
rock. We study the consumption due to the above mentioned reactions at different
temperatures. The reaction with the crude oil is also studied.
3.2.1 Simulation Input Description
In the following sections, the results of several example 1D alkaline

coreflood simulations are given to study the key alkali consuming reactions. The grid
size, dimensions of the core, injection rate and some primary core properties are listed
in Table 3.2. A one foot long, rectangular, vertical core is simulated with 100
gridblocks of equal lengths. To reduce the numerical dispersion, the improved total
variation diminishing third order method is used.
For this study, initial brine salinity is low with a pH of about 8 (Table 3.3).
The initial equilibrium species concentrations are calculated from EQBATCH.
EQBATCH has been developed separately from the geochemical model used in
UTCHEM to do batch reaction equilibrium calculations. It can calculate the initial
equilibrium state of the reservoir. The equilibrium concentrations for all the flow and
solid species based on the chemical reactions considered in UTCHEM simulations are
calculated. The output of EQBATCH can be used as the input data of UTCHEM:
EQBATCH writes the output data in a format similar to the geochemical input data of
UTCHEM so it can be directly copied and pasted into an input file for UTCHEM.
Different example cases were studied by implementing various reactions for
geochemical part of the UTCHEM. The injection scheme is given in Table 3.4.
64
Simulations are performed injecting 1 PV of either 1 wt% Na2CO3 or 1 wt% NaOH.

Then the core was waterflooded with brine similar to the in-situ brine.
3.2.2 Reactions Modeled
Table 3.5 lists the reactive elements and chemical species considered in these
simulations. Tables 3.6 and 3.7 give the thermodynamic reaction equilibrium data for
aqueous and solid species obtained from the Geochemists Workbench Release 6.0
database. The effect of temperature on the cation exchange reaction and oil-alkali
reactions was not modeled. The list of the reactions considered is as follows:
a) Aqueous species reactions
H 2 O H + + OH
Ca 2 + + H 2 O Ca(OH)+ + H +
H + + CO32 HCO3
Ca 2 + + H + + CO32 Ca(HCO3 )+
2H + + CO32 H 2 CO3
Al3 + + 4H 2 O Al(OH)4 + 4H +
H 4SiO4 H + + H3SiO 4
b) Oil-alkali reactions
KD
HA o HA w
Ka
HA w H + + A
c) Cation exchange reaction
+
H + Na + + OH Na + H 2 O
65
d) Solid reactions
Quartz dissolution
H 4SiO4 H3SiO 4 + H +
Congruent kaolinite dissolution
Kaolinite + 4OH +3H 2 O 2 Al(OH)4 + 2 H3SiO4
Incongruent kaolinite dissolution
Al2Si 2 O5 (OH)4 (Kaolinite) + 2Na + + 2OH + 2H 4SiO 4
2NaAlSi 2 O6 .H 2 O(Analcime) + 5H 2 O
3.2.2.1 Simulation with no alkali consumption (Case 3.1)
This case was done as a reference with no reactions to consume alkali

included. Therefore, the propagation of alkali front is not retarded by reactions. All
the elements, aqueous species and reactions are given in Tables 3.5 and 3.6. Na2CO3
is used as the alkali here.
When there is no consumption, the alkali front propagates with the same
speed as a tracer. Figure 3.1 shows the alkali and tracer concentrations as a function
of time. In this case alkali and tracer propagate together and breakthrough at the same
time.
Figure 3.2 shows the pH propagation at 0.2 and 0.4 PV. As shown in this plot,
the pH front has propagated beyond XD=0.2 at 0.2 PV and XD=0.4 at 0.4 PV because
the core is at residual oil saturation Sor=0.35.
corresponds to 0.61 aqueous phase pore volumes.
66
Thus, 0.4 total pore volumes
3.2.2.2 Simulation with cation exchange (Case 3.2)
In this case, the cation exchange reaction was added to the Case 3.1
simulation. Novosad et al. (1984) developed a technique for the determination of
alkalinity losses resulting from hydrogen ion exchange in reservoir rocks. They
measured the alkalinity loss resulting from hydrogen exchange to be between 0.1 and
0.4 meq/100 g rock in Berea sandstone cores. Various hydrogen exchange capacities
(HEC) were considered to study how they affect the alkali propagation.
To evaluate alkali consumption, the cation exchange reaction between sodium
and hydrogen was studied without taking into account the effect of temperature on the
cation exchange reaction.
Figure 3.3 demonstrates the effect of HEC on pH
propagation at 0.2 PV. Four different cases are compared; Case 3.1: no consumption,
HEC=0.1 (Case 3.2a), 0.4 (Case 3.2b), and 1.0 (Case 3.2c) meq/100 g rock. The
higher the cation exchange the higher the consumption, which translates to slower
propagation of the alkali and pH front.
Figure 3.4 also shows the adsorbed cation concentrations at 0.2 PV for the
case with HEC=0.4 meq/100 g rock. As expected, adsorbed hydrogen gets detached
and sodium instead adsorbed on the surface of the clay.
3.2.2.3 Simulation with quartz dissolution (Case 3.3)
Quartz is the main mineral for many sandstone reservoirs. As mentioned

before, dissolution of quartz with the injection of alkali has been studied by several
researchers. It is important to investigate how this reaction consumes alkali.
67
In this section, a quartz dissolution reaction was added to Case 3.2. A

hydrogen exchange capacity of 0.1 meq/100 g rock is used. The dissolution of quartz
is a strong function of temperature since the solubility product varies significantly
with temperature. We studied the effect of alkali consumption at three different
temperatures of 25, 55, and 85oC. Figure 3.5 and compared the pH profile for these
three temperatures as a result of quartz dissolution. Figure 3.5 shows that as the
temperature increases from 25 to 85oC, there is a drop in the hydrogen ion
concentration and a decrease in pH is observed, but there is little effect on the
position of the pH front.
Dissolution of quartz causes the concentration of aqueous species such as
H3SiO4- to increase. Figure 3.6 shows the H3SiO4- concentration profile at 0.2 PV.
The maximum amount of H3SiO4- is observed at the highest temperature of 85oC.
3.2.2.4 Simulation with congruent kaolinite dissolution (Case 3.4)
Kaolinite consumes the largest amount of alkali among the clay minerals. In
this case, the dissolution of kaolinite where minerals such as analcime are precipitated
(Reaction 3.7) was modeled.
In Figure 3.7, a similar pH decrease is observed with the kaolinite dissolution
compared to the silica dissolution shown in Figure 3.5. Similar results were also
observed at higher temperature with a larger dissolution. Similar concentrations of
H3SiO4- and Al(OH)4- are dissolved as the result of the congruent kaolinite dissolution
68
as demonstrated in Figure 3.8 at 0.2 PV and 85oC. EQBATCH and UTCHEM input
files for this case are given in Appendix D.
3.2.2.5 Simulation with incongruent kaolinite dissolution (Case 3.5)
Next the incongruent dissolution of kaolinite was modeled. The incongruent

dissolution of kaolinite consumed a lot more alkali compared to Case 3.4.
Consumption of alkali with incongruent dissolution of kaolinite both lowers the pH
(Figure 3.9) and retards the pH front. The kaolinite dissolution results in
concentrations of dissolved species such as H3SiO4- and Al(OH)4-, as shown at 0.2 PV
in Figure 3.10.
3.2.2.6 Simulation with Congruent silica and incongruent kaolinite dissolution
(Case 3.6)
Incongruent kaolinite dissolution in a sandstone rock dissolves kaolinite and

precipitates analcime. For this case, the pH front is retarded at higher temperatures of
55 and 85oC (Figure 3.11). Figure 3.12 shows the concentration of solids along the
core at 0.2 PV. Each mole of kaolinite dissolves and is precipitated as two moles of
analcime during alkali consumption.
3.2.2.7 Simulation with Soap generation (Case 3.7)
Generation of soap from acidic components of oil consumes alkali so it is

important to understand how this reaction can impact the alkali propagation. No solid
reaction was included here to study the effect of the crude oil reaction alone. Cation
69
exchange with a CEC of 0.1 meq/100 g rock is included. Three different cases were
simulated to study the importance of this reaction on the alkali front. The first case
has an acid number of zero; therefore, no soap is generated (Case 3.2a). The second
case has an acid number of 1 (Case 3.7a) and the third case has an acid number of 4
(Case 3.7b).
Figure 3.13 shows the profile of pH for the three acid number cases at 0.2 PV.
An acid number of 1 does not have a significant effect on the pH or alkali front.
However, higher acid numbers can retard the pH front to some extent. The
combination of large amount of acidic components capable of transferring to soap and
large cation exchange can be detrimental to propagation of pH or alkali front and
could retard it significantly.
Figure 3.14 shows the amount of soap generated for crude oil with acid
numbers of 1 and 4, respectively. The higher the acid number, the higher the
generated soap. It should be noted once again that acid number by itself may not be a
quantitative measure of oil reactivity and ability to generate soap to lower the
interfacial tension.
3.2.2.8. Simulation using sodium hydroxide (Case 3.8)
Simulations were performed to study the consumption of sodium hydroxide.

The reactions modeled that consume alkali were cation exchange and quartz
dissolution. 1 wt% of sodium hydroxide is injected for 1.0 PV. Figure 3.15 shows the
comparison of pH profile at 0.2 PV at 25oC. 1 wt% of sodium hydroxide increases the
70
pH to 13 compared to a pH of 11 for 1 wt% Na2CO3. It is also shown that NaOH can

advance faster than Na2CO3.
The same comparison was done for these two alkalis at 85 oC (Figure 3.16). It
is clear that alkali consumption is higher for NaOH compared to Na2CO3 at higher
temperatures. For NaOH, pH drops from 13 to 11.5 when temperature increases from
25 to 85 oC whereas pH drops from 11 to 10.5 when Na2CO3 is used.
3.3 ALKALI CONSUMPTION IN A CARBONATE ROCK USING SODIUM CARBONATE
AND SODIUM METABORATE
Conventional alkaline-surfactant-polymer (ASP) flooding uses an alkali such

as sodium carbonate to reduce the adsorption of the surfactant and generate soap insitu, and thus reduce the cost compared to surfactant-polymer flooding. One major
limitation for ASP is the requirement for relatively soft water (i.e. small
concentrations of divalent cations such as Mg++ and Ca++). However, soft water is not
always available, and softening hard brines may be very costly or infeasible in many
cases depending on the location and other factors (Ayirala, 2008). A form of borax
known as metaborate has been found which might tolerate divalent cations such as
Ca2+ under specific conditions. It can also be combined with a surfactant to increase
the pH and reduce the surfactant adsorption.
Sodium metaborate (NaB(OH)4) was tested as an alternative, novel alkali.
Flaaten (2008) and Zhang (2008) performed phase behavior tests with several
surfactants using metaborate to identify suitable formulations for high optimum
71
salinities and hardness. They also found that sodium metaborate could tolerate as high
a divalent concentration as 6000 ppm Ca2+ and Mg2+. Like other alkalis, metal
borates, monomoric borate ion (B(OH)4-) is strongly hydrolyzed to form polymeric
borate ions when its concentration and solution pH change (Ingri, 1963). It is a
classical alkaline buffer in detergent formulations, with the pH determined principally
by the acid-to-base ratio as shown by the following equation:
H+ = Ka
B(OH)3
(3-10)
B(OH) 4
Using an alkali that can be used with hard brine vastly increases the number of
oil reservoirs that can be considered as candidates for ASP flooding and reduces the
chemical costs. It is important to compare sodium carbonate and sodium metaborate
and study the key reactions. In this section, we model the chemistry of carbonate
reservoirs with high divalent cation concentrations.
3.3.1. Simulation Input Description
The same 1D input file as was used for the sandstone cases is used for these
simulations (Table 3.2). The core is initially at residual oil saturation with a brine
composition as shown in Table 3.8. Species concentrations are first obtained using
EQBATCH program to serve as initial conditions for the UTCHEM geochemical
module. Initial water has a salinity equivalent to 4 wt% NaCl in meq/ml. The
injection scheme is given in Table 3.9. We performed simulations comparing the
injection of 1 wt% Na2CO3 and 1 wt% NaB(OH)4 added to 4 wt% NaCl for 1.0 PV.
72
The injected water was considered to be soft water. The core was then waterflooded
with 4% NaCl with no hardness for another 1.0 PV.
3.3.2 Reactions Modeled
To investigate the alkali/rock interactions between the alkalis and carbonate

rocks, two scenarios were studied. The first case was a reservoir rock with gypsum
and calcite to represent a limestone formation and second case was a rock with
dolomite, gypsum, and calcite to represent a dolomite formation. Sodium metaborate
and sodium carbonate are considered in each case to compare the resulting reactions.
Table 3.10 lists the elements and solids to set up the reactions. PHREEQC
was used to help in identifying fluid and solid species which form or precipitate by
the injection of these alkalis. The equilibrium constants are from the Geochemist's
Workbench database. Table 3.10 presents the fluid and solid species included in the
simulations. Ca(OH)2, Mg(OH)2, and borax were added to the solid minerals present
in the rock to study the precipitation reactions due to alkaline injection. No cation
exchange was modeled. The list of the aqueous reactions is as follows:
H 2 O H + + OH
H + + CO32 HCO3
B(OH)4 + H + B(OH)3 + H 2 O
Ca 2 + + B(OH)3 + H 2 O CaB(OH)4+ + H +
Mg 2 + + B(OH)3 + H 2 O MgB(OH) 4+ + H +
2H + + CO32 H 2 CO3
The solids modeled are as follows;
73
Ca 2 + + CO32 CaCO3
Ca 2 + + Mg 2 + + CO32 CaMg(CO3 )2
Ca 2 + + 2OH Ca(OH) 2
Mg 2 + + 2OH Mg(OH) 2
Na 2 B4 O7 10H 2 O(Borax) 4B(OH) 4 + 2H + + 2Na + + H 2 O
Ca 2 + + SO 24 CaSO 4
3.3.2.1 Simulation in Limestone rock (Case 3.9)
The same 1D input as the previous cases was set up by using the reactions
previously listed for the limestone rock. EQBATCH and UTCHEM input file of this
case is given in Appendix D. Here is the composition of minerals modeled in the
simulations.
10 g-mol/kg water calcite
1 g-mol/kg water gypsum
The injection water contains no hardness. The only hardness present is from
the brine initially in the core (Table 3.8). 1 wt% sodium carbonate or sodium
metaborate is injected for 1.0 PV. Figure 3.17 compares the pH propagation between
sodium carbonate and sodium metaborate at 0.5 PV. pH moves faster in the case of
sodium metaborate. However, the pH rises to 11 during the injection of 1 wt%
sodium carbonate compared to only 10 for sodium metaborate. Delay in the pH
profile for sodium carbonate injection is due to consumption of alkali.
Figure 3.18 shows that gypsum is dissolved and calcite is precipitated by the
injection of sodium carbonate. Figure 3.19 shows the gypsum dissolution during
74
sodium metaborate injection. No calcite, Ca(OH)2, Mg(OH)2 or brucite is precipitated

by injection of sodium metaborate.
Concentrations of aqueous species are shown in Figure 3.20 where
CaB(OH)4+ is formed during sodium metaborate injection indicating the sequestration
of calcium. Calcium sequestration can affect the surfactant phase behavior as
explained in Equation 2-42.
3.3.2.2 Simulation in Dolomite rock (Case 3.10)
The main difference between this case and Case 3.9 is in the solid
concentration. Here is the composition of minerals modeled in the simulations.
1 g-mol/kg water calcite
1 g-mol/kg water gypsum
10 g-mol/kg water dolomite
Figure 3.21 compares the pH in the dolomite rock during the injection of
sodium carbonate and sodium metaborate. The pH during the injection of sodium
carbonate in dolomite rock is similar to pH in the limestone rock (Figure 3.17),
whereas the pH drops from 10 to about 9.5 during the injection of sodium metaborate.
In the case of sodium carbonate, the same precipitation and dissolution reactions
occur (gypsum dissolves and calcite precipitates) and cause the delay of pH front
(Figure 3.22). Figure 3.23 shows the dissolution and precipitation reactions which
occur during the sodium metaborate injection in the dolomite rock. As shown in this
figure, gypsum and dolomite dissolve and calcite, small amount of borax and
75
Mg(OH)2 precipitate. Solution species concentrations at 0.5 PV is also shown in

Figure 3.24 during the injection of sodium metaborate in the dolomite rock.
3.4 SUMMARY
Some of the findings of this chapter are as follows:

1. Cation exchange can retard the alkali front significantly. The cation exchange
reaction is a fast reaction.
2. Kinetically controlled reactions such as dissolution of silica reduce the pH
plateau to smaller values. It was shown that for the case studied with 1 wt%
Na2CO3, pH drops from 11 (at 25oC) to 10.5 (at 85oC).
3. UTCHEM can model kaolinite dissolution and its impact on pH, including the
congruent and incongruent dissolution of kaolinite. Congruent dissolution of
kaolinite is a kinetically controlled reaction which affects the pH plateau in a
manner similar to silica dissolution. For the case studied, pH decreases from
11 to 10.5 (at 85oC).
4. Incongruent dissolution of kaolinite also consumes a major amount of alkali.
Kaolinite dissolution was studied in two cases: once it was modeled as a clay
and once as a clay present in sandstone. It was shown that incongruent
dissolution of kaolinite could retard the pH front as well as reducing the pH
plateau. Consumption is smaller if kaolinite is present in sandstone as a small
percentage. Consumption can be significant in pure kaolinite.
76
5. Injection of alkali for both low and high acid number crude oils was
simulated. An acid number of 4 caused a significant retardation of the pH
front. An acid number of about 1 had a small effect on the pH propagation.
6. A sandstone reservoir at high temperature with a high acid number oil and a
high clay content can have a high consumption of alkali and thus the use of
alkali needs in such cases needs to be carefully considered and quantified with
a combination of appropriate experimental data and simulations.
7. Sodium metaborate seems to be a promising alkali for reservoirs with
formation brine containing considerable amount of divalent cations such a
calcium and magnesium. However, more laboratory experiments are needed
to understand its interactions with different rock minerals and at different
temperatures.
77
Table 3.1: Example cases studied in this chapter

Case
Alkali
Rock type
Description
3.1
Na2CO3
Sandstone
No consumption
3.2(a, b, and
Na2CO3
Sandstone
Different cation
Number
c)
3.3
3.4
3.5
exchange
Na2CO3
Sandstone
Quartz dissolution
Na2CO3
Sandstone
Congruent kaolinite
dissolution
Na2CO3
Sandstone
Incongruent kaolinite
dissolution
Na2CO3
Sandstone
3.6
Quartz dissolution
and incongruent
kaolinite dissolution
3.7
Na2CO3
Sandstone
Soap generation
3.8
NaOH
Sandstone
Quartz dissolution
Na2CO3
Carbonate (Limestone)
Mineral dissolution
3.9
3.10
and precipitation
NaB(OH)4
Na2CO3
Carbonate (Dolomite)
Mineral dissolution
and precipitation
NaB(OH)4
78
Table 3.2: Input for 1D coreflood simulation

No. of grids in X direction
Components
100
Porosity
Permeability, md
Residual water saturation
Residual oil saturation
Oil relative permeability end
point
Water relative permeability
end point
0.165
1500
0.38
0.35
0.4
WATER, OIL, ANION, CALCIUM,

CARBON (As Carbonate), ALUMINIUM,
SILICON, SODIUM, HYDROGEN
0.05
Table 3.3: Brine composition for sandstone rock simulations

Ion
mg/L
900
++
Mg
Ca++
20
HCO3-
1100
Cl-
800
SO4-2
18
Na
Table 3.4: Injection scheme for sandstone rock

Step 1: Alkaline slug
1.0 PV of
1.0 wt% Na2CO3 or 1.0 wt% NaOH added to the brine
frontal velocity: 1 ft/day
Step 2: Water flood
1.0 PV brine
frontal velocity:1 ft/day
79
Table 3.5: Elements and species for simulation in sandstone rock

Hydrogen (reactive), Sodium,
Calcium, Aluminum, Silicon, Oxygen,
Carbonate, Chlorine
Elements or
pseudo-elements
Independent aqueous species
H+, Na+, Ca2+, Al3+, CO32-, Cl-, , H2O,

H4SiO4
Dependent aqueous species
Ca(OH)+, HCO3-, Ca(HCO3)+, H2CO3,

Al(OH)4-, H3SiO4-,
Adsorbed cations
H+, Na+
Solid
SiO2 (Silica), Al2Si2O5(OH)4 (Kaolinite)
Table 3.6: Equilibrium constants for aqueous species- The equilibrium constants are
from Geochemist's Workbench
Fluid species
H+
Na+
Ca2+
Al3+
CO32H4SiO4
H2O
Ca(OH)+
Ca(HCO3)+
OHHCO3H3SiO4Al(OH)4H2CO3
Equilibrium Constants
55 oC
1
1
1
1
1
1
1
2.18E-12
3.58E+11
7.3E-14
1.67E+10
3.24E-10
3.26E-20
3.48E+16
25 C
1
1
1
1
1
1
1
2.0479E-13
3.6804E+11
1.0309E-14
2.2075E+10
1.5531E-10
6.9711E-23
5.1274E+16
80
85 oC
1
1
1
1
1
1
1
1.56E-11
5.08E+11
3.21E-13
1.66E+10
5.31E-10
1.51E-18
3.9E+16
Table 3.7: Solubility products for minerals

Solids
55 oC
1.16x10-9
0.000273716
130226.6894
771969.2476
25 C
2. 34x10-9
0.0001
26865814
19054607
CaCO3
SiO2
Al2Si2O5(OH)4
NaAlSi2O6.H2O
85 oC
4.5698x10-10
0.000594429
1627.796086
53789.80873
Table 3.8: Brine composition for carbonate rock simulations

pH
6.8
Temperature Na+
ppm
38oC
15700
Ca2+
ppm
850
Mg2+
ppm
60
Clppm
24300
Table 3.9: Injection scheme for carbonate rock

Step 1: Alkaline slug
1.0 PV
1.0 wt% Na2CO3 or 1.0 wt% NaB(OH)4 added to 4 wt% NaCl
front velocity:1 ft/day
Step 2: Water flood
1.0 PV of 4 wt% NaCl
front velocity:1 ft/day
81
CO32ppm
500
SO42ppm
2000
Table 3.10: Elements and species for carbonate rock simulations

Elements or
pseudo-elements

Calcium, Magnesium , Sulfate, Carbonate, Chlorine,
B(OH)4-
Independent aqueous
H + , Na + , Ca 2 + , Mg 2 + ,SO 24 , CO32 ,
species
Dependent aqueous
species
Solid species
B(OH)4 , H 2 O
OH , HCO3 , H 2 CO3 , B(OH)3 ,
CaB(OH) 4+ , MgB(OH)4+
CaCO3 (Calcite), CaSO4.2H2O (Gypsum) and Dolomite
82
1.2
0.1
Alkali
0.09
0.07
0.8
0.06
0.05
0.6
0.04
0.4
0.03
0.02
Tracer concentration
Carbonate concentration, mole/L
Tracer
0.08
0.2
0.01
0
0
0
0.5
1.5
2.5
Pore volume injected
Figure 3.1: Comparison of alkali and tracer concentrations for Case 3.1 with no alkali
consumption
12
11
10
0.2 PV
0.4 PV
pH
5
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Dimensionless Distance, XD
Figure 3.2: pH front at 0.2 and 0.4 PV with no alkali consumption for Case 3.1
83
12
3.2b -CEC=0.4 meq/100 g
k
3.2a -CEC=0.1 meq/100 g
11
10
3.1- No cation exchange
pH
9
8
7
3.2c -CEC=1.0 meq/100
k
6
5
0
0.2
0.4
0.6
0.8
Dimensionless Distance
Figure 3.3: pH front at 0.2 PV with different cation exchange capacities for Case 3.1
and 3.2a-b-c
Adsorbed cation concentration, meq/ml PV
0.030
0.025
0.020
Sodium
0.015
0.010
Hydrogen
0.005
0.000
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Dimensionless distance, XD
Figure 3.4: Adsorbed cation concentrations at 0.2 PV for Case 3.2a

84
0.8
0.9
12
11
10
85C
55C
25C
pH
5
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 3.5: pH front @0.2 PV with quartz dissolution reaction (Case 3.3)
0.010
0.009
0.007
85C
55C
25C
0.006
0.005
0.004
H3SiO4 Concentration, mole/L
0.008
0.003
0.002
0.001
0.000
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 3.6: H3SiO4- concentration at 0.2 PV (Case 3.3 with quartz dissolution
reaction) at different temperatures
85
12
11
10
25C
55C
85C
pH
5
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 3.7: pH front at 0.2 PV including congruent kaolinite dissolution reaction

(Case 3.4) at different temperatures (no zeolite is formed)
0.007
Concentration, mole/L
0.006
0.005
H3SiO4Al(OH)4-
0.004
0.003
0.002
0.001
0.000
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 3.8: H3SiO4- and Al(OH)4- concentrations at 0.2 PV at 85oC due to congruent
kaolinite concentration (Case 3.4)
86
12
25C
55C
85C
10
pH
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 3.9: pH front at 0.2 PV with incongruent kaolinite dissolution reaction (Case
3.5) at different temperatures
3.0E-06
0.018
0.016
0.012
2.0E-06
Al(OH)4H3SiO4-
0.010
1.5E-06
0.008
1.0E-06
0.006
0.004
5.0E-07
0.002
0.000
0.0E+00
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 3.10: H3SiO4- and Al(OH)4- concentrations at 0.2 PV at 85oC due to

incongruent kaolinite concentration (Case 3.5)
87
H3SiO4-, mole/L
Al(OH)4- concentration, mole/L
2.5E-06
0.014
12
11
10
25C
55C
85C
pH
5
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 3.11: pH front at 0.2 PV including silica dissolution and incongruent kaolinite
dissolution reaction (Case 3.6) at different temperatures
0.07
Solid concentration, mole/L PV
0.06
0.05
Kaolinite
0.04
Analcime
0.03
0.02
0.01
0.00
0
0.2
0.4
0.6
0.8
Figure 3.12: Solid concentrations at 0.2 PV including silica dissolution and

incongruent kaolinite dissolution reaction (Case 3.6)
88
12
11
10
Oil not reactive
Acid no.=1
Acid no.=4
pH
5
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 3.13: Comparison of pH front at 0.2 PV including soap generation reactions

for Case 3.7 (oil with acid number of 1 and non reactive oil curves overlap)
0.008
0.007
A- concentration, mole/L
0.006
0.005
Acid no.=1
Acid no.=4
0.004
0.003
0.002
0.001
0.000
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 3.14: Molar concentration of soap at 0.2 PV for various acid numbers (Case
3.7)
89
14
NaOH
13
12
Na2CO3
11
pH
10
9
8
7
6
5
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 3.15: Comparison of pH profile for NaOH and Na2CO3 at 0.2 PV at 25oC
(Case 3.8)
14
13
12
NaOH
11
Na2CO3
pH
10
9
8
7
6
5
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 3.16: Comparison of pH profile for NaOH and Na2CO3 at 0.2 PV at 85oC
(Case 3.8)
90
12
Sodium Carbonate
Sodium Metaborate
10
pH
8
6
4
2
0
0
0.2
0.4
0.6
0.8
Figure 3.17: Comparison of pH profile for Na2CO3 (Case 3.9a) and sodium
metaborate (Case 3.9b) at 0.5 PV (in a limestone rock)
Calcite concentration, mole/L PV
10.10
Calcite
10.08
0.10
Gypsum
0.08
10.06
0.06
10.04
0.04
10.02
10.00
0.02
9.98
0.00
0
0.2
0.4
0.6
0.8
Gypsum concentration, mole/L PV
0.12
10.12
Figure 3.18: Solid concentration for limestone rock with injection of Na2CO3 at 0.5
PV (Case 3.9a)
91
0.12
Gypsum
0.10
0.08
0.06
0.04
0.02
0.00
0
0.2
0.4
0.6
0.8
Figure 3.19: Solid concentration for limestone rock with injection of sodium
metaborate at 0.5 PV (Case 3.9b)
Solution species concentration, mole/L
0.09
0.08
0.07
0.06
CaB(OH)4+
0.05
0.04
0.03
B(OH)4-
0.02
0.01
Ca2+
0.00
0
0.2
0.4
0.6
0.8
Figure 3.20: Solution species concentration for limestone rock with injection of
sodium metaborate at 0.5 PV (Case 3.9b)
92
12
Sodium Carbonate
10
Sodium Metaborate
pH
8
6
4
2
0
0
0.2
0.4
0.6
0.8
Figure 3.21: Comparison of pH profile for Na2CO3 (Case 3.10a) and sodium
metaborate (Case 3.10b) at 0.5 PV (dolomite rock)
0.12
Gypsum
1.10
0.10
Calcite
1.08
0.08
1.06
0.06
1.04
0.04
1.02
0.02
1.00
0.00
0
0.2
0.4
0.6
0.8
Calcite concentration, mole/L PV
1.12
Figure 3.22: Solid concentrations for dolomite rock with injection of Na2CO3 (Case
3.10a) at 0.5 PV
93
10.04
Calcite
10.02
1.0
10.00
0.8
9.98
0.6
9.96
0.4
Dolomite
0.2
9.94
Borax Mg(OH)2
9.92
Gypsum
0.0
Dolomite concentration, mole/L

PV
Solid concentration, mole/L PV
1.2
9.90
0
0.2
0.4
0.6
0.8
Solution species concentration, mole/L
Figure 3.23: Solid concentrations for dolomite rock with injection of sodium
metaborate (Case 3.10b) at 0.5 PV
0.10
0.09
0.08
0.07
0.06
0.05
0.04
0.03
B(OH)4-
0.02
0.01
CaB(OH)4+
0.00
0
0.2
0.4
0.6
0.8
Figure 3.24: Solution species concentration for dolomite rock with injection of
sodium metaborate (Case 3.10b) at 0.5 PV
94
CHAPTER 4
Soap/Surfactant Phase behavior
In Chapter 3, it was shown that alkali consumption can be detrimental to the

propagation of alkali in the reservoir. Numerous benefits in the use of alkali make it
attractive even with the complexity and uncertainties of the ASP process. In addition
to the complexity of modeling the chemical reactions, the effect of the soap on the
phase behavior must be taken into account. Mechanistic simulation of the ASP flood
considering the chemical reactions, alkali consumption, and soap generation and the
effect on the phase behavior is the key to successful field operations. Using numerical
simulation models, the process can be designed and optimized to ensure the proper
propagation of alkali and effective soap and surfactant concentrations to promote low
interfacial tension and a favorable salinity gradient.
In this chapter, we describe the ASP module of the UTCHEM simulator, with
particular emphasis on the phase behavior and the effect of soap on optimum salinity
and solubilization ratio. Phase behavior data are presented for sodium carbonate and a
blend of surfactants with an acidic crude oil that followed the conventional Winsor
phase transition with significant three-phase regions even at low surfactant
concentrations. The solubilization data at different oil concentrations were
successfully modeled using Hand's rule. Optimum salinity and solubilization ratios
were correlated with soap mole fractions using mixing rules. Mechanistic simulations
95
give insights into the propagation of alkali, soap, and surfactant and aid in future
coreflood and field scale ASP designs.
4.1 SOAP/SURFACTANT BACKGROUND
A rich literature on alkaline flooding exists. A majority of the papers discuss

the importance of maintaining an effective level of alkalinity during the flood and
alkali consumption due to chemical reactions or ion exchange (Bunge and Radke,
1983; 1985; Novosad and Novosad, 1984).
In 1956, the concept of combining surface active agents and alkaline
chemicals for enhanced oil recovery (EOR) was first proposed by Reisberg and
Doscher. Low concentrations (~0.5 wt%) of a nonionic surfactant mixed with 1 to 2
wt% sodium hydroxide produced additional oil from laboratory sandpacks and
consolidated cores. They reported surfactant concentrations as low as 0.02 wt% in 0.5
wt% NaOH were effective in displacement of a California crude oil. However, Taber
(1958) observed that because of high surfactant adsorption, low concentrations of
surfactants are not easily propagated in a reservoir and that higher concentrations are
needed if the surfactant is to advance at a satisfactory rate compared to that of water.
The paper by Nelson et al. (1984) is the first that describes the benefits of combining
alkali with surfactants and demonstrates the effect of in-situ generated surfactant
referred to as soap on phase behavior. Nelson et al. pointed out that the generated
soap is a distribution of relatively high molecular weight carboxylic structures which
96
result in a very low optimal salinity. By adding a more water soluble surfactant, the
region of optimum salinity could be raised to the desired level.
Martin et al. (1985) studied the effect of different alkalis on the mixtures of
surfactants, brine, and oil. The results showed that the presence of any alkali lowered
the optimum salinity of the surfactant. At a 1 wt% sodium alkali concentration,
sodium silicate had the least effect, sodium carbonate was intermediate, and sodium
hydroxide had the most effect. They found a linear relationship between the optimal
salinity and milliequivalents of sodium present. Their conclusion was that the alkaline
chemicals affect phase behavior because they provide an additional source of
electrolytes. The cations were effective in the order of potassium > sodium
>ammonium. The alkali anion had very little effect on the phase behavior. In their
study, they used light crude oil which did not contain many of the organic acids that
produce natural surfactants in-situ.
More recently, Zhang (2006) and Liu et al. (2008) made an interesting
observation based on the laboratory phase behavior study in which the optimum
salinity for a mixture of surfactant, sodium carbonate, and crude oil containing
naphthenic acids depends only on the soap-to-surfactant molar ratio. A onedimensional simulator was developed to history match their oil recovery experiments
in sandpacks. Both soap and surfactant components were tracked, but no chemical
reactions were modeled. Soap concentrations were calculated assuming alkali is
present and that the naphthenic acid in oil is completely converted to soap based on
the mass of oil present. The phase behavior was modeled using a two-phase
97
simulation model with a partition coefficient between oil and water for the
soap/surfactant mixture.
The challenge and success of an ASP flood depends on the simultaneous
propagation of surfactant and soap in the reservoir and proper mobility control. If
soap moves ahead of the injected surfactant, the phase behavior becomes over
optimum and soap partitions into the trapped oil. It remains trapped until the injected
surfactant reaches that point and moves the phase behavior back towards the optimum
salinity. On the other hand, if the injected surfactant moves ahead of soap, it will
adsorb on the rock. The adsorbed surfactant later gets partially desorbed when the
high pH alkali front reaches it.
Alkali coupled with surfactant and polymers is also beneficial even if the
crude oils have a low acid number when the major effects of alkalis are lowering
interfacial tension and decreasing surfactant retention by increasing pH (Martin et al.,
1985) or potential determining ion, i.e. CO32- (Hirasaki, 2004).
In this chapter, the effect of soap on phase behavior is emphasized. Laboratory
phase behavior data are presented for two mixtures of surfactant/alkali/crude oil and
successfully modeled. It is shown how optimum salinity and solubilization ratio are
modeled in the presence of soap and surfactant. The experimental data obtained in the
laboratory helps in understanding the effect of soap on the solubilization ratio which
has not been discussed elsewhere.
Numerous laboratory measurements are needed before a test can be designed
and implemented in the field and have a high chance of success. Some laboratory
98
evaluations that are needed include phase behavior measurements as a function of oil,
surfactant, co-surfactant, co-solvent, salinity and alkali concentrations. Fluid
compatibilities,
rock-alkali
interactions
to
measure
alkali
and
surfactant
consumptions, mobility control, and oil recovery need to be evaluated based on

corefloods performed at the reservoir temperature.
Mechanistic modeling of the mixture of soap and synthetic surfactant is also
the key to successful implementation of these processes. Mechanistic modeling of
soap and surfactant mixtures not only gives insight into the complexity of the process,
but also shows the need for reservoir simulation taking into account the dominant
mechanisms for design, optimization, and scale up.
4.2 LABORATORY PHASE BEHAVIOR RESULTS
In this section, the phase behavior results of two different surfactant/soap

mixtures are studied. These cases are different in terms of oil viscosity, acid number,
temperature, and formation brine salinity. Table 4.1 lists the crude oil properties of
these two cases.
4.2.1 Phase Behavior-Case A
The phase behavior measurements presented here are for a blend of two
surfactants, co-solvent (1% Diethylene Glycol Butyl Ether (DGBE)), and sodium
carbonate mixed in 0.6 wt% NaCl brine. Surfactants were 0.1 wt% C20-24 IOS and 0.1
wt% C16 bABS (Zhao et al., 2008). The phase behavior screening was performed for
the sodium carbonate in the range of 0 to 50,000 ppm. The oil concentration varied
99
from 10 to 50 vol%. The sodium carbonate scans showed a large middle phase
microemulsion at and near optimum salinity. The activity map shown in Figure 4.1
indicates a significant three-phase (Type III) region for a surfactant concentration of
0.2 wt% and for the entire range of oil concentrations studied. Figure 4.2 is an
example of oil solubilization ratios as a function of Na2CO3 for 50% oil
concentration, which indicates a solubilization ratio of 50 at the optimum salinity of
about 20,000 ppm sodium carbonate. The solubilization ratios are calculated based on
the synthetic surfactant concentration added to the test tubes and do not include the
concentration of soap generated in each test tube. The high solubilization ratio of 50
corresponds to a very low interfacial tension. Solubilization ratios for 30 vol% oil
concentration are illustrated in Figure 4.3 where the optimum salinity is about 29,000
ppm and the optimum solubilization ratio is about 30 cc/cc. The optimum salinity
increases as the oil concentration decreases. The change in optimum salinity is the
result of the relative concentrations of soap and surfactant. At low oil concentration,
the optimum salinity is high and approaches that of the synthetic surfactant, whereas
at high oil concentrations or high soap concentrations, the optimum salinity is low
and approaches that of the soap.
A careful look at Figures 4.2 and 4.3 also shows not only that the optimum
salinity shifts as oil concentration changes but also that the solubilization ratio varies
with the oil concentration. It should be noted that the data shown in these figures is
based on the surfactant concentration alone and not taking into account the
100
concentration of generated soap. Both surfactant and soap are taken into account in
Section 4.3
4.2.2 Phase Behavior-Case B
The phase behavior measurements presented in this case are for a blend of two
surfactants, cosolvent (1 wt% DGBE), and sodium carbonate mixed in synthetic
brine. Surfactants were TDA-7PO-SO4 and IOS C2024 (Zhao, 2008). The phase
behavior screening was performed for the sodium carbonate in the range of 0 to
70,000 ppm. The oil concentration varied from 10 to 50 vol%. The activity maps for
different synthetic surfactant concentrations are shown in Figures 4.4, 4.5, and 4.6.
The results indicate a very large three-phase (Type III) region for the entire range of
oil concentrations studied at different surfactant concentrations. Figures 4.7-4.11 are
examples of solubilization ratio curves as a function of Na2CO3 concentration at
different oil and surfactant concentrations. The same observations as for Case A are
valid here, as well: the optimum salinity increases and solubilization ratio decreases
as the oil concentration decreases. Table 4.2 gives the composition of the brine for
this case.
4.3 MODELING THE PHASE BEHAVIOR OF THE SOAP AND SURFACTANT
MIXTURE
A nonlinear mixing rule was used to model the changes in the lower and upper
effective salinity limits (optimum salinity is the mean of these two limits) as a
101
function of soap and surfactant concentrations (Salager et al., 1979; Bhuyan et al.,
1990).
ln SM = Xsoap ln Ssoap + Xsurfactant ln Ssurfactant

CSEL
CSEL
ln SCSEL
= Xsoap ln Ssoap
+ Xsurfactant ln Ssurfactant
M
(4-1)
CSEU
CSEU
ln SCSEU
= Xsoap ln Ssoap
+ Xsurfactant ln Ssurfactant
M
where SM , Ssoap , and Ssurfactant are the optimum salinities of the mixture, soap, and
surfactant, respectively. CSEL and CSEU superscripts indicate the lower and upper
salinity limits of the Type III region. Soap and surfactant mole fractions are Xsoap and
Xsurfactant. The molecular weight of the surfactant mixture is about 420 for Case A and
450 for Case B and the soap molecular weight is assumed to be 500. As the the oil
concentration decreases the mole fraction of the soap decreases and the optimum
salinity increases and approaches that of the injected surfactant. This acts as a
favorable salinity gradient and is one of the reasons for the effectiveness of the ASP
process when the added surfactant is properly selected to be more hydrophilic than
the soap. The Winsor Type III region boundaries calculated from Equation 4-1 are
shown in the activity map of Figures. 4.1, 4.4, 4.5, and 4.6.
UTCHEM batch calculations provided the soap concentrations for each test
tube with different concentrations of oil and sodium carbonate with all other variables
fixed. An example of the batch input file for Case A is given in Appendix C for 50
vol% oil and 19000 ppm Na2CO3 added to 0.6 wt% NaCl. In these batch calculations,
102
the reactions for soap generation are added without any rock/alkali reactions such as
cation exchange reactions and dissolution/precipitation reactions.
First the acid number is converted from mg KOH/g oil to mole/L water.
mg KOH
1g
1000 cc
g oil
CHAo mole L water = acid no.
x
x
x
x o
cc
oil
1000 mg
1L
g oil
S2 ( L oil )
1
x
(4-2)
S1 ( L Water ) 56.098 g
mole
CHAo will be an input to UTCHEM batch calculation as well as synthetic
surfactant and alkali concentrations to find the amount of generated soap. Phase
behavior parameters such as salinity limits of the Winsor's Type III for synthetic
surfactant and soap and solubilization ratios (input as HBNC, height of binodal curve)
are adjusted to match the phase behavior parameters. This calculation is performed
over the entire range of the oil concentrations studied and alkali concentrations to
come up with a set of phase behavior parameters representative for all the data points.
The phase behavior parameters matching the experimental data points are later used
in the core flood simulations. We obtain the amount of soap generated in each test
tube in the unit of volume fraction from UTCHEM batch calculations. By knowing
the soap and surfactant molecular weights, we can calculate their respective mole
fractions in the mixture of the two. CHAo is calculated to be 0.00832 mol/L for an acid
number of 0.5 mg KOH/g oil from Equation 4-2 above. From the UTCHEM batch
simulation, the amount of A- (soap) generated in the test tube is 0.002 mol/L.
Therefore, one-fourth of HAo is converted to A-.
103
Figures 4.12 and 4.13 demonstrate the salinity limits of Winsor's Type III as a
function of soap concentration. Optimum salinity is plotted on a semi-log scale in
Figure 4.14 as a function of soap mole fraction. Figure 4.14 shows a close agreement
between the correlation (Equation 4-1) and the experimental data.
Figures 4.2 and 4.3 compare the calculated solubilization curves for both oil
and water at 50 and 30% oil. Figures 4.15-4.17 are the plots of solubilization ratios on
a linear and semi-log scale for several oil concentrations. These plots indicate that the
solubilization ratio increases as oil concentration or equivalently the soap mole
fraction (Xsoap) increases. The solubilization ratios in these plots are based on total
surfactant and soap concentrations. Solubilization ratios at optimum salinity as a
function of soap mole fraction are plotted in Figure 4.18 on a linear and in Figure
4.19 on a semi-log scale. The data suggests that the optimum oil solubilization ratio
can follow either a linear or logarithmic mixing rule. However, we decided to use the
linear relationship as
M = Xsoap soap + Xsurfactant surfactant
(4-3)
where M , soap , and surfactant are the optimum oil solubilization ratio of the
mixture, soap, and surfactant, respectively.
4.4 SUMMARY
1.
The phase behavior data for a mixture of sodium carbonate and a blend of
surfactants with an acidic crude oil followed the conventional Winsor phase
104
transition with significant three-phase regions even at a low surfactant

concentration of 0.2 wt%.
2.
Solubilization ratios as high as 50 were observed for a mixture of surfactant,

sodium carbonate, and an acidic crude oil. However, these large solubilization
ratios should be normalized based on the total amount of synthetic surfactant
and soap.
3.
Optimum salinity followed a log mixing rule based on the optimum salinities
of synthetic surfactant and in situ generated soap.
4.
Optimum solubilization ratios were shown to follow a linear or logarithmic

mixing rule.
5.
Optimum salinity and solubilization ratio were successfully correlated with

soap mole fractions using mixing rules.
6.
The solubilization data for different oil concentrations are in good agreement
with UTCHEM model calculations.
105
Table 4.1: Crude oil properties and temperature of the cases studied
Case A
Case B
Oil Viscosity, cp
19
80
Acid number, mg KOH/g oil
0.5
1.5
Temperature, oC
62
46
Table 4.2: Composition of synthetic brine Case B

Concentration, ppm
3100
NaCl
NaHCO3
1310
Na2SO4-10H2O
537
KCl
54
TDS
5001
106
100000
Type II
Na2CO3 ,ppm
Type III
10000
Type I
1000
0
10
20
30
40
Concentration of oil , %
50
60
Figure 4.1: Activity map for Case A, lines are the limits of Winsor's Type III
calculated from UTCHEM
70
Points: Experiments
Curves: UTCHEM
Solubilization Ratio (cc/cc)
60
50
40
30
20
Oil
Water
10
0
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
Na2CO3 Concentration (ppm)
Figure 4.2: Solubilization ratio vs. salinity for 50% oil concentration (Case A)
Curves: UTCHEM and points: Experimental data
107
70
Points: Experiment
Curves: UTCHEM
60
50
40
30
20
Oil
10
Water
0
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
Na2CO3 Concentration (ppm)
Figure 4.3: Solubilization ratio vs. salinity for 30 vol% oil concentration (Case A)
Curves: UTCHEM and points: experimental data
Na2CO3,ppm
100000
10000
0
10
20
30
Coil
40
50
60
Figure 4.4: Activity map for Case B (0.3 wt% surfactant). Lines are the calculated
Winsor's Type III region from UTCHEM
108
Na2CO3, ppm
100000
10000
0
10
20
30
40
50
60
Coil
Figure 4.5: Activity map for Case B (0.6 wt% surfactant), lines are the calculated
Na2CO3, ppm
100000
10000
0
10
20
30
40
50
60
Coil
Figure 4.6: Activity map for Case B (1.0 wt% surfactant), lines are the calculated
109
70
0.3 % Surfactant
Temp = 46 C
After 58 days
Sodium Carbonate scan
50% Oil
60
50
40
30
20
10
0
0
10000
20000
30000
40000
50000
60000
Electrolyte Concentration (ppm Na2CO3)
Figure 4.7: Solubilization ratio vs. salinity for Case B with 50 vol% oil and 0.3 wt.%
surfactant, curves: UTCHEM and points: experimental data
70
0.3% Surfactant
Temp = 46 C
After 58 days
30% Oil
60
50
40
30
20
10
0
0
10000
20000
30000
40000
50000
60000
Figure 4.8: Solubilization ratio vs. salinity for Case B with 30 vol% oil and 0.3 wt%
110
90
80
0.6% Surfactant
Temp = 46 C
After 14 days
40% Oil
70
60
50
40
30
20
10
0
0
10000
20000
30000
40000
50000
60000
70
0.6% Surfactant
Temp = 46 C
After 14 days
30% Oil
60
50
40
30
20
10
0
0
10000
20000
30000
40000
50000
60000
111
70
60
1.0% Surfactant
Temp = 46 C
After 35 days
50% Oil
50
40
30
20
10
0
0
10000
20000
30000
40000
50000
60000
Figure 4.11: Solubilization ratio vs. salinity for 50 vol% oil and 1.0 wt% surfactant,
curves: UTCHEM and points: experimental data
Effective salinity, meq/ml
10.00
Type II
1.00
Type III
Type I
0.10
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
Soap Mole Fraction, Xsoap
Figure 4.12: Type III salinity window calculated as a function of soap mole fraction
(Case A) The limits of the Winsor's Type III are calculated from Equation 4-1
112
100000
Na2CO3, ppm
Blue (0.3% surfactant)

Red (0.6% surfactant)
Green (1.0% surfactant)
10000
0
0.1
0.2
0.3
0.4
Soap mole fraction

Figure 4.13: Type III salinity window for Case B, lines are obtained from UTCHEM
Optimum Salinity, meq/ml
10
0.1
0
0.1
0.2
0.3
Soap mole fraction, Xsoap
Figure 4.14: Optimum salinity as a function of soap mole fraction (Case A), line:
UTCHEM and points: experimental data
113
0.4
40
50% Oil
40% Oil
Solubilization ratio
35
30
20% Oil
25
30% Oil
10% Oil
20
15
10
5
0
0
0.1
0.2
0.3
0.4
Figure 4.15: Solubilization ratio as a function of soap mole fraction in a linear scale
(Case A) curves: UTCHEM, black line is hand-drawn showing the trend of the
solubilization ratio at optimum salinity
100
10% Oil
20% Oil
50% Oil
40% Oil
30% Oil
10
1
0
0.1
0.2
0.3
0.4
Figure 4.16: Solubilization ratio as a function of soap mole fraction in a logarithmic

scale (Case A) Curves: UTCHEM, black line is hand-drawn showing the trend of the
solubilization ratio at optimum salinity
114
100
Solubilization ratio of mixture
0.3%surf, 50% oil

1.0 %surf, 50% oil
0.6 %surf, 40% oil

0.3%surf, 30% oil
0.6 %surf, 30% oil
10
1
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
Soap mole fraction
Solubilization Ratio at Optimum Salinity
Figure 4.17: Solubilization ratio at optimum salinity for Case B, curves: UTCHEM,
black line is hand-drawn showing the trend of the solubilization ratio at optimum
salinity
50
45
40
35
30
25
20
Points: Experimental data
Curve: Correlation
15
10
0
0.1
0.2
0.3
0.4
Figure 4.18: Case A optimum solubilization ratio as a function of soap mole fraction
(linear scale)
115
Solubilization Ratio at Optimum Salinity
1000
Experimental
Correlation
Logarithmic Scale
100
10
0
0.1
0.2
0.3
0.4
Figure 4.19: Case A optimum solubilization ratio as a function of soap mole fraction
(logarithmic scale)
116
CHAPTER 5
ASP Coreflood Simulations
In Chapter 4, the phase behavior modeling of the soap and surfactant mixtures
was discussed. This chapter presents ASP coreflood simulation. These mechanistic
simulations include aqueous reactions, alkali/rock interactions, pH tracking, soap
generation, aqueous, oleic, and microemulsion phase behavior, and shifts in optimum
salinity due to varying proportions of soap and surfactant. Mechanistic simulations
give insights into the propagation of alkali, soap, and surfactant in the core and aid in
future corefloods and field scale ASP designs. Using numerical models, the ASP
process can be designed and optimized to ensure the proper propagation of alkali and
effective soap and surfactant concentrations to promote low interfacial tension and a
favorable salinity gradient, while minimizing the amount and costs of chemicals
required.
The cases presented here are the same as those mentioned in the previous
chapter (Cases A and B). Numerous laboratory measurements are needed before a test
can be designed and implemented in the field to ensure a high chance of success.
Laboratory evaluations that are needed include phase behavior as a function of oil,
surfactant, and alkali concentrations for candidate surfactants, and fluid compatibility
studies. Next, reservoir temperature corefloods should be conducted to evaluate
alkali and surfactant consumption due to rock-alkali interactions, mobility control,
117
and oil recovery for the most attractive candidate surfactant formulations. The next
step is simulation of the corefloods, the focus of this chapter. Only after these steps
are completed can reasonably accurate pilot scale or field scale simulation models be
developed to evaluate and design ASP processes.
5.1 DESCRIPTION OF LABORATORY CORE FLOODS- CASES AI AND AII
Two laboratory corefloods (AI and AII) were performed to evaluate the
performance of the selected surfactant formulation (Zhao, et al. 2008). The rock/fluid
properties are given in Table 5.1. The acid number of this crude is 0.5 mg KOH/g oil.
This crude oil is a viscous oil of about 19 cp. The brine composition is given in Table
5.2. The injected brine contains 27,500 ppm Na2CO3 in 0.6 wt% NaCl.
The coreflood configuration is vertical and the ASP slug and polymer drive
are injected from the bottom of the core. The water-saturated core was first flooded
with crude oil to residual water saturation (0.25) and subsequently waterflooded to
residual oil saturation (0.43). The endpoint saturations and relative permeabilities
obtained are listed in Table 5.1. The first Berea sandstone core (Core AI) was flooded
with about 0.5 PV of 0.2 wt% surfactant in the ASP slug and followed with a polymer
drive with an average flow rate of ~0.11 ml/min (frontal advance rate of ~1.3 ft/day).
Oil breakthrough occurred at ~0.25 PV with an oil cut of ~ 55% in the oil bank. The
oil recovery was about 95% OOIP and the final oil saturation was Sorc=0.02. The
surfactant adsorption/retention was very low at about 0.06 mg/g rock. The polymer
adsorption and alkali consumption were not measured for this coreflood experiment.
118
The surfactants selected for this first coreflood are a 1:1 mixture of two Stepan
sulfonates (0.1 wt% C20-24 IOS and 0.1 wt% C16 bABS). 1 wt% co-solvent DGBE
(Diethylene Glycol Butyl Ether) was used to increase the aqueous solubility of these
high molecular weight surfactants needed to solubilize the waxy crude oil. Adding the
cosolvent to the surfactant mixture greatly improves the quality of the microemulsion,
i.e. lowers the microemulsion viscosity and causes a faster separation and
equilibration of the phases. The ASP slug composition and the polymer drive
composition were given in Table 5.3. In the second coreflood (Core AII), the ASP
slug was injected for 0.3 PV instead of 0.5 PV. This coreflood was performed to
evaluate the effectiveness of a smaller ASP slug size to reduce the chemical
requirement for a more cost effective field design.
5.1.1 Phase Behavior
The first important step to obtain high oil recovery of greater than 90% OOIP
in the core is to develop an effective soap/surfactant phase behavior as a function of
soap, oil, surfactant, and alkali concentration. The phase behavior experiments of
soap-surfactant formulation need to be performed at different oil and surfactant
concentrations since both solubilization ratio and optimum salinity change with the
soap to surfactant molar ratio. The phase behavior model was described in the
previous chapter (4.2.1 and 4.2.2), and illustrated in Figures 4.1-4.3.
119
5.1.2 Polymer Properties
Polymer viscosity is modeled as a function of salinity, shear rate, and polymer

concentration (Figures 5.1-5.3). High molecular weight Flopaam 3630S was chosen
for both corefloods. The viscosities of the ASP slug and polymer drive were 28 cp
and 33 cp at 10 s-1 and 62oC. Polymer viscosity was measured at various polymer
concentrations (1500, 2000, and 2500 ppm) and shear rates at 62oC. Different
Na2CO3 concentrations (from 0 to 3 wt%) were added to the polymer and 0.6 wt%
NaCl to find the salinity dependency of the polymer viscosity. The filtration ratios
were less than 1.2, which indicates a very good polymer solution acceptable for the
use in a coreflood.
5.1.3 1D Coreflood Simulation Procedure (Case AI and AII)
The 1D simulation was set up vertically for a foot long core with a diameter of
about 5.08 cm. The input file was created based on the core properties and chemical
design injection given in Tables 5.1 and 5.3. Phase behavior input parameters are
based on Case A phase behavior discussed in Chapter 4 (4.2.1).
Other measured
parameters such as the relative permeability residual saturations and Corey's

endpoints, and surfactant adsorption are updated in the input. The EQBATCH input
was
updated
by
adding
other
reactions such
dissolution/precipitation reactions, as needed.
120
as
cation
exchange
and
5.1.4 Fractional Flow Curve
Figure 5.4 shows the relative permeability curves based on an exponential

Corey type function. The endpoints and residual saturations were measured, see Table
5.1. The exponents were chosen based on typical values for Berea sandstone (~2).
They were slightly modified if needed to improve the match for waterflood and oil
flood pressure drop measurements.
Based on the fractional flow calculations (Figure 5.5), the minimum polymer
viscosity required for the ASP flood to have a stable front with Mo=0.9 is about 19
cp. It should be noted that polymer flooding alone requires a lower polymer viscosity
to make a stable front. The reason why the ASP requires a higher viscosity or higher
polymer concentrations is due to the increase in relative permeabilities at higher
capillary numbers (lower IFTs). According to the fractional flow curve, the oil
breakthrough should occur at about 0.27 PV and oil saturation at breakthrough is
about 53%.
5.1.5 Reactions
The thermodynamic reaction equilibrium data at 62oC for solution and solid
species are found from the Geochemists Workbench Release 6.0 database. The
EQBATCH program, which is UTCHEM's preprocessor, is used to set up the initial
state of the formation brine such as pH and species concentrations. Precipitation
reactions of divalent cations are ignored because of the relatively small
concentrations. Dissolution of quartz and clays were not considered due to time scale
121
of the injection. However, there are other reactions which are essential and cannot be
neglected for the purpose of ASP flooding. Three sets of reactions were included in
the geochemistry model:
1. In-situ generation of soap by the reaction between alkali and the acidic
component of crude oil. In situ generation of soap was included because
the acid number of the oil is ~0.5.
2. Aqueous reactions involving alkali.
3. The sodium-hydrogen exchange reaction on clay. This is modeled since it
is one of the main alkali consuming reactions. The core is a clean Berea
sandstone rock with a cation exchange capacity of 0.1 meq/100 g rock.
These sets of reactions seem adequate to investigate and study the behavior
and performance of ASP flooding in this coreflood. The three sets of reactions
modeled are listed below. EQBATCH and UTCHEM input files of case A are given
in Appendix D.
HA o HA w
1.
HA H + + A
w
H O H + + OH
2
+

2. H + CO3 HCO3
2H + + CO32 H 2 CO3
+
+
3. H + Na + + OH Na + H 2 O
122
5.1.6 Simulation Results for Corefloods AI and AII
Oil recovery, oil cut, pressure drop, and pH of the effluent were measured for
these two corefloods. Surfactant concentrations were also measured for coreflood AII.
Figures 5.6 to 5.9 show the match between the simulation and measured data for
Coreflood AI. As shown in Figure 5.6, oil breakthrough occurred at about 0.2 PV
with an oil cut of about 60%, which is in close agreement with those calculated from
the fractional flow curve analysis (Figure 5.5). We also successfully matched the
cumulative oil recovery and oil cut as shown in Figure 5.6. Figure 5.7 shows close
agreement between the measured and simulated concentration breakthrough, peak,
and trend of the effluent curve. Figures 5.8 and 5.9 show an excellent match between
the simulation and measured data for pressure drop along the core and effluent pH.
Figure 5.10 is a plot of Winsor's Type III region salinity and soap and
surfactant concentration profiles at 0.5 PV. This is a good illustration of how these
chemicals move along the core and affect the Type III region. As shown in this plot,
where there is more soap present the Type III window is shifting towards the soap
salinity window. The optimum salinity changes to that of the injected surfactant
where the surfactant concentration is higher than the soap concentration.
The size of the ASP slug was reduced to 0.3 PV in the coreflood AII. Table
5.1 lists some of the differences between Cores AI and AII. During the ASP slug,
27,500 ppm Na2CO3 was added to the formation brine (Table 5.3). Figures 5.11 and
5.12 show the results of the match for coreflood AII. Oil recovery is about 98% OOIP
for coreflood AII confirming that the reduction in the slug size does not reduce the oil
123
recovery significantly. It should also be noted that the coreflood AII is very efficient
in a sense that it uses a very small amount of synthetic surfactant (0.2 wt% surfactant
injected for 0.3 PV). Another very important observation is that this small surfactant
concentration and slug is effective because the surfactant adsorption is very low (0.06
mg/g rock).
The profiles of this coreflood at 0.5 PV are plotted in Figures 5.13-5.15.
Na2CO3 or in other words, effective salinity passes through the Type II, then Type III,
and lastly Type I. This gives a salinity gradient to the system and makes it more
robust. A low IFT of less than 0.001 dynes/cm is achieved where the salinity passes
through the Type III region (Figure 5.13).
Figure 5.14 demonstrates the salinity and concentration profiles at 0.5 PV for
this coreflood. pH and oil concentration are shown in Figure 5.15. The pH has
advanced to a dimensionless distance along the core from the injector to XD=0.7 at
0.5 PV injection, indicating an insignificant alkali consumption due to the cation
exchange reaction.
5.1.7 Type III sensitivity simulation
As mentioned in the phase behavior section (4.2.1) for Case A in Chapter 4

(Figures 4.1 to 4.3), a large middle phase was observed in the test tubes. To
emphasize the importance of Type III and the ability to accurately model this phase
region, a simulation (Case III) was performed neglecting the three-phase region and
modeling the Type I and Type II only. This was achieved by using the same input
124
file was used as for the coreflood AII, except setting equal values for lower and upper
salinity windows (CSEL = CSEU) for both surfactant and soap. The results of this
sensitivity case show a reduction in oil recovery from 98% to 84% OOIP when the
Type III region is collapsed in the model (Figure 5.16).
Figure 5.17 shows the effective salinity, optimum salinity, and IFT at 0.5 PV.
It is observed that the low IFT values are obtained for a much shorter duration
compared to the coreflood AII simulation where Type III was modeled (Figure 5.13).
This shows the importance of including Type III when modeling ASP floods. The
plot of soap and surfactant concentrations at 0.5 PV is also shown in Figure 5.18.
5.2 DESCRIPTION OF LABORATORY CORE FLOODS- CASES BI AND BII
This coreflood is based on the phase behavior results discussed in Chapter 4

(Section 4.2.2, Case B, Tables 4.1 to 4.2 and Figures 4.4 to 4.11). The coreflood
configuration is vertical and the ASP slug and polymer drive are injected from the
bottom of the core. The core was flooded with brine, oil and then water flooded to
determine the relative permeability parameters. Table 5.4 lists the composition of the
brine in this coreflood. Core BI was a Bentheimer sandstone core. The core was
waterflooded with the brine composition listed in Table 5.4 to the remaining oil
saturation of 0.48. Then it was flooded with the 0.3 PV of ASP slug and followed
with a polymer drive with an average flow rate of ~0.09 ml/min (for a frontal advance
rate of ~1.0 ft/day).
125
The coreflood was flooded with 0.6 wt% surfactant and 25,000 ppm Na2CO3.
The Flopaam 3630S polymer concentration was kept at 3500 ppm during the ASP
slug and 2700 ppm during the polymer drive. The pressure drop along the core for
the ASP flood was as high as 4.5 psi at oil breakthrough (Figure 5.27). The surfactant
adsorption/retention was estimated at about 0.02 mg/g rock. As shown in Figure 5.25,
oil breakthrough occurred at ~0.35 PV with an oil cut of ~ 85% which is in good
agreement with the fractional flow curve (Figure 5.23). Oil recovery is about 98%
OOIP for this coreflood.
In the second coreflood (BII), surfactant concentration was reduced from 0.6
to 0.3 wt% and Na2CO3 concentration was reduced from 25,000 to 20,000 ppm. The
differences in the properties between Cores BI and BII are shown in Table 5.5. 100%
oil recovery was achieved for this coreflood. These results confirm that even these
small concentrations of surfactant are sufficient for high oil recoveries, if the entire
chemical formulation is carefully designed.
5.2.1 Polymer Properties
Flopaam 3630S was chosen for corefloods BI and BII. Different Na2CO3
concentrations were added to 2750 ppm Flopaam 3630S @ filtered brine to find the
salinity dependency of the polymer viscosity (Figure 5.19). Polymer viscosity was
also measured at various polymer concentrations and shear rates (Figures 5.20 and
5.21) at 46oC.
126
5.2.2 1-D Coreflood Simulation Procedure (Case BI and BII)
The coreflood simulation was set up for a core with a length of 30 cm and a
diameter of 5.08 cm. The input file was prepared based on the core properties and
chemical injection given in Tables 5.4 to 5.6. Phase behavior input parameters were
based on Case B in Chapter 4. The oil viscosity is 100 cp and the acid number is 1.5
mg KOH/g oil.
5.2.3 Fractional Flow for ASP flooding
Figure 5.22 shows the relative permeability curves. The endpoint relative
permeabilities and residual saturations were based on the laboratory results. Both oil
and water relative permeability exponents were assumed to be 2.
Based on fractional flow theory (Figure 5.23), the minimum polymer viscosity
required for a stable ASP flood with Mo=0.9 is about 85 cp. According to this
fractional flow curve, the oil breakthrough should occur at about 0.4 PV and the oil
cut at breakthrough is about 80%. It is important to note that oil cut is high due to the
high viscosity of oil.
Another coreflood (BIII) was performed with this 100 cp crude oil at 46 oC,
which was not as successful as the other two corefloods due to the lower polymer
concentration used and inadequate mobility ratio. The polymer concentration was
2750 and 1875 ppm Flopaam 3630S in the ASP slug and polymer drive
corresponding to a viscosity of about 40 cp in both the slug and the drive. As shown
in Figure 5.24, the oil recovery was reduced to only 70% OOIP. This coreflood
127
highlights the importance of injecting polymer at high enough concentrations to

achieve a favorable mobility in both the ASP slug and polymer drive.
5.2.4 SIMULATION RESULTS OF COREFLOODS BI AND BII
Oil recovery, oil cut, pressure drop, and pH of the effluent were measured for
the two corefloods (BI and BII). Surfactant concentration was also measured for the
core flood BI. The same reaction model as in Case A was used to describe the
reactions occurring during the alkali injection for Case B.
Figures 5.25 to 5.28 show the comparison between the simulation and
measured data. The simulated cumulative oil recovery and oil cut matches the
coreflood measured data very well, as shown in Figure 5.25. Pressure drop, pH, and
surfactant concentration are matched reasonably well. Figure 5.25 indicates an oil
breakthrough of about 0.4 PV with an oil cut of about 80% which is in close
agreement with those obtained from fractional flow curves (Figure 5.23). Figures
5.26 and 5.27 show an excellent match between the simulation and measured data for
effluent pH and pressure drop across the core. The measured and the simulated final
pH value is about 11. The higher pH value in the simulation can be due to lack of
modeling mineral dissolution/ precipitation reactions. The pressure drop increases to
near 5 psi as the oil bank is produced and then drops to about 4 psi. Figure 5.28 shows
the surfactant concentration match. The simulated surfactant concentration is less
dispersed compared to the measured data. Increasing the physical dispersivity may
128
give a better match between the two. 100 gridblocks is used to simulate a one foot
coreflood. The physical dispersivity is considered to be as large as one gridblock.
Figure 5.29 shows the Type III effective salinity window (CSEL and CSEU), and
soap and surfactant concentration profiles along the core at 0.5 PV. This is a good
illustration of how these chemicals move along the core and affect the phase behavior
and the optimum salinity. As shown in this plot, where there is more soap than
surfactant, the Type III window is shifting towards the soap effective salinity
window. The optimal salinity approaches the optimum salinity of the injected
surfactant when there is a higher concentration of surfactant compared to soap.
The core is initially filled with formation brine of 5101 ppm TDS (Table 5.4).
About 25,000 ppm Na2CO3 was added to the formation brine during the ASP slug
which helps the effective salinity pass through the Type II, then Type III, and lastly
Type I. This creates a more robust design with a favorable salinity gradient. A low
IFT of less than 0.001 dynes/cm is achieved where the Type III region is observed
(Figure 5.30).
Coreflood properties and the chemical design of BII is given in Tables 5.5 and
5.6. There are no major differences in properties between cores BI and BII. In
coreflood BII, 0.3 wt% surfactant and 20000 ppm Na2CO3 is added to the slug
compared to 0.6 wt% surfactant and 25000 ppm Na2CO3 in coreflood BI. Figures
5.31 and 5.32 demonstrate the match of oil cut, oil recovery and pressure drop for
coreflood BII.
129
5.2.5 Sensitivity to alkali concentration
To study the effect of alkali concentration on the oil recovery, a simulation

was performed (Case CI) with 10,000 ppm Na2CO3 in the slug compared to 25,000
ppm, keeping all other data the same as Coreflood BII. The oil recovery dropped
from 98% OOIP of core BII to 80% OOIP (Figure 5.33), in Case CI by reducing the
injected alkali concentration. Plots of effective salinities and soap and surfactant
concentrations are shown in Figures 5.34 and 5.35. Figure 5.34 shows that the
addition of only 1 wt% Na2CO3 (10,000 ppm) to the brine does not generate enough
soap. As discussed in the previous chapter, the phase behavior of soap/surfactant
mixtures dictates that the salinity gradient is vital for the oil recovery. The low
concentration of Na2CO3 added to the low salinity brine does not create the salinity
gradient needed for high oil recoveries. Figure 5.35 shows that the effective salinity
does not cross the Type III salinity region. Therefore, the IFT is not low enough to
mobilize the residual oil saturation.
This is an important issue which needs considerable attention for scaling up
the process to field applications. This is because of dilution and mixing which occur
during the injection of the alkali and surfactant in the reservoir.
5.3 ALKALINE/POLYMER (AP) SIMULATIONS
Any crude oil containing acidic components should be considered for its
potential for an alkaline/polymer flood with no added surfactant. This is especially
worthy of evaluation when the reservoir brine is low salinity. The soap Type III
130
effective salinity window is usually low and narrow and a reservoir brine with low
TDS is desirable for AP processes. Adding the alkali to a high salinity brine causes
the phase behavior to shift to Type II+ and this results in a design challenge to lower
the effective salinity to below optimum values for high salinity brine reservoirs.
Some cosolvents such as DGBE or EGBE might be needed to add to the
formulation of AP flood for aqueous stability even when no surfactant is present. 1D
coreflood simulations are performed to evaluate its potential. However, this needs to
be tested in the laboratory to assure its feasibility. The first and most important
uncertainty here is the phase behavior of the soap by itself. For these example runs,
we assume the optimum solubilization ratio is about 12 for soap.
To illustrate the AP floods, several different scenarios are devised. Table 5.7
lists the simulation cases. The first 1D AP simulation (AP-1) was run based on the
ASP core flood (Case BII). 2 wt% Na2CO3 was added to the formation brine. As
shown in Figure 5.36, AP flood oil recovery is about 55% OOIP much lower than the
ASP coreflood cases presented previously. To improve the oil recovery, in the second
AP run (AP-2), the alkaline slug is increased from 0.3 to 0.6 PV, which might be
sufficient to generate soap and reduce the IFT. As mentioned before, due to adding
sodium carbonate we might need to also add cosolvent for aqueous stability. The oil
recovery did not improve much for the larger slug size. No significant improvement
can be achieved by increasing the slug size. In this case, addition of more alkali
causes the system to shift to Type II+ for a longer time period.
131
Next, we studied cases with higher acid numbers for the crude oil. Two more
cases (AP-3 & AP-4) were run to investigate the effect of acid number on AP oil
recoveries. The acid number was increased to 2 and 4. Consequently, oil recovery
increased to 75% OOIP for AP-3 and 95% OOIP for AP-4 cases, respectively (Figure
5.37). The higher the acid number, the more soap is generated, as shown in Figure
5.38. Therefore, a more reactive crude oil (higher acid number) has a higher potential
for AP floods.
Based on these scoping studies of AP corefloods, it appears that the addition
of surfactant to the alkaline solution makes the chemical flood more efficient and
robust. For possible AP candidates (high acid number oil, low salinity reservoirs),
laboratory experiments are essential to determine the soap phase behavior and AP
core floods experiments are essential to test the suitability of AP floods for a
particular crude oil and reservoir brine system.
5.4 SUMMARY
In this chapter, several ASP laboratory corefloods were successfully modeled

with UTCHEM taking into account the aqueous reactions, alkali/rock interactions,
and phase behavior of soap and surfactant. Sensitivity simulation studies were
performed based on the corefloods. The ASP laboratory coreflood gave a high oil
recovery of 98% OOIP for a small chemical slug of 0.3 PV with 0.2 wt% surfactant.
Mechanistic simulations give insight into the propagation of alkali, soap, and
surfactant in the core and aid in future coreflood and field-scale ASP designs.
132
Table 5.1: Case A- Core Properties

Core
Permeability, md
Porosity, fraction
Water endpoint relative
permeability
Oil endpoint relative
permeability
Water viscosity, cp
Oil Viscosity, cp
Temperature, oC
A-I
0.43
0.25
673
0.2
0.05
A-II
0.43
0.32
683
0.17
0.05
0.52
0.6
0.5
19
62
0.5
19
62
Table 5.2: Composition of brine for Case A

Concentration (ppm)
NaCl
NaHCO3
Na2SO4
TDS
4416
348
661
5425
133
Table 5.3: Case A-Core Injection Design

Core
AI
AII
ASP slug 0.5 PV

0.2 wt% Surfactant
1 wt% DGBE
3000 ppm Flopaam 3630S
27,500 ppm Na2CO3 in 0.6 wt% NaCl
Frontal Velocity: 1.3 ft/day (0.11
ml/min)
Viscosity: 28 cp @ 10 s-1, 62 oC
Polymer
drive
~1.5 PVs
in 0.6 wt% NaCl
ml/min)
Viscosity: 33 cP @ 10 s-1, 62 oC
0.3 PV
0.2 wt% Surfactant
1 wt% DGBE
27,500 ppm Na2CO3
in 0.6 wt% NaCl
ml/min)
Viscosity: 28 cp @ 10 s-1, 62 oC
~1.5 PVs
in 0.6 wt% NaCl
ml/min)
Viscosity: 33 cP @ 10 s-1, 62 oC
Table 5.4: Composition of brine Case B

Concentration, ppm
3100
1310
537
54
100
5101
NaCl
NaHCO3
Na2SO4-10H2O
KCl
Dithionite
TDS
134
Table 5.5: Core Properties for Cases BI and BII

Core
BI
BII
Porosity
Temperature, oF
Permeability, md
Length, cm
0.21
115
1476
30
0.21
115
1923
30
Diameter, cm
5.08
0.14
5.08
0.12
0.4
0.4
Oil endpoint relative

permeability
Water endpoint relative
permeability
Oil viscosity , cp
1.0
0.04
100
100
Water viscosity, cp
0.67
0.67
1.0
0.06
Table 5.6: ASP Corefloods BI and BII Injection Design

Core
BI
BII
ASP
slug
0.3 PV
0.6 wt % Surfactant
(0.3 wt% TDA-7PO-SO4 and
0.3 wt% IOS 2024)
1.0 wt% EGBE,
25,000 ppm Na2CO3 added to
formation brine
1.0 ft/day (0.09 ml/min)
Polymer ~1.5 PV
drive
2700ppm AN125 in formation brine
135
0.3 PV
0.3 wt% Surfactant
(0.15 wt% TDA-7PO-SO4 and
0.15 wt% IOS 2024)
1.0 wt% EGBE,
20,000 ppm Na2CO3 added to formation
brine
1.0 ft/day (0.09 ml/min)
~1.5 PV
2700ppm AN125 in formation brine
Table 5.7: Alkaline/polymer Injection Design for 1D Simulations

Core
AP-2
AP-3
AP-4
AP slug 0.3 PV
3500 ppm
Flopaam 3630S
0.6 PV
3500 ppm
Flopaam 3630S
0.3 PV
3500 ppm
Flopaam 3630S
0.3 PV
3500 ppm
Flopaam 3630S
20000 ppm Na2CO3

1.0 ft/day
Polymer ~1.5 PV
drive
2700ppm AN125 in
SSMB
20000 ppm Na2CO3

1.0 ft/day
~1.5 PV
2700ppm AN125 in
SSMB
20000 ppm Na2CO3

1.0 ft/day
~1.5 PV
2700ppm AN125 in
SSMB
20000 ppm Na2CO3

1.0 ft/day
~1.5 PV
2700ppm AN125 in
SSMB
1.0
2.0
4.0
Acid
number
AP-1
1.0
136
50
45
40
Correlation
35
viscosity, cp
0% Na2CO3
Lab data
1% Na2CO3
30
2% Na2CO3
25
20
3% Na2CO3
15
10
5
0
0
0.05
0.1
0.15
0.2
0.25
0.3
Polymer concentration(wt%)
(poly viscosity-water viscosity)/ water viscosity
Figure 5.1: Flopaam 3630S polymer viscosity vs. polymer concentration at different
salinities (62 oC)
1000
100
10
-0.3792
y = 38.114x
1
0.01
0.1
Csep,meq/ml
Figure 5.2: Flopaam 3630S polymer viscosity vs. salinity, (Line was curve fit to the
laboratory data to find the exponent) (2500 ppm polymer)
137
60
viscosity, cp
50
Lab
UTCHEM
40
30
20
10
0
0.01
0.1
10
shear rate, sec
100
1000
-1
Figure 5.3: Flopaam 3630S polymer bulk viscosity vs. shear rate (62 oC, 3 wt%
Na2CO3 added to 0.6 wt% NaCl, 2500 ppm polymer)
1.0
Relative Permeability, krj
0.9
0.8
0.7
kro
krw
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0.0
0.2
0.4
0.6
0.8
Water Saturation, Sw
Figure 5.4: Oil/water relatively permeability curves in Berea sandstone core AII
138
1.0
1.0
(S1I, f1I)
(S1*, f1*)
Fractional Flow of Water, f w
0.9
0.8
0.7
0.6
(S1B, f1B)
0.5
0.4
0.3
water-oil
polymer-surfactant-oil
0.2
0.1
0.0
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Figure 5.5: Fractional flow plot for water, and ASP floods for Core AII with
negligible adsorption
100%
Cumulative Oil Recovered and Oil

Concentration(%)
90%
80%
70%
60%
Emulsion
breakthrough
50%
Cum Oil
Oil Cut
40%
Cum Oil-UTCHEM
30%
Oil Cut-UTCHEM
20%
10%
0%
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Pore Volumes
1.4
1.6
1.8
Figure 5.6: Comparison of simulation and measured oil recovery and oil cut for
coreflood AI
139
2.0
Surfactant Recovered,ppm
4000
3500
Surfactant Concentration
3000
UTCHEM
2500
2000
1500
1000
500
0
0.0
0.5
1.0
1.5
2.0
Pore Volumes
Figure 5.7: Comparison of the effluent surfactant concentration between UTCHEM

and measured data (Case AI)
14
12
10
pH
8
6
4
pH
UTCHEM
2
0
0.0
0.2
0.4
0.6
0.8
1.0 1.2 1.4 1.6

Pore Volumes
1.8
2.0
2.2
2.4
Figure 5.8: Comparison of the effluent pH between UTCHEM and measured data
(Case AI)
140
10
9
Whole
pressure drop-UTCHEM
Pressure Drop, psi
7
6
5
Emulsion
breakthrough
4
3
2
1
0
0.0
0.5
1.0
1.5
2.0
2.5
Pore Volumes
Figure 5.9: Comparison of the pressure drop between UTCHEM and measured data
(Case AI)
1.E-02
Surfactant
1.0
1.E-03
0.8
Soap
0.6
1.E-04
0.4
1.E-05
CSEU
0.2
CSEL
0.0
0
0.2
0.4
0.6
0.8
Total Soap& Surfactant

Concentration(v/v)
Optimal Salinity, meq/ml
1.2
1.E-06
1
Figure 5.10: Simulated surfactant and soap concentrations and type III salinity
window of coreflood AI at 0.5 PV
141
100%
Cum Oil Recovered (%) and Oil

Concentration
90%
Cumulative Oil
Oil Cut
Cumulative Oil-UTCHEM
Oil Cut-UTCHEM
80%
70%
60%
Emulsion
breakthrough
50%
40%
30%
20%
10%
0%
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Pore Volumes
1.4
1.6
1.8
2.0
Figure 5.11: Comparison of the oil recovery between UTCHEM and measured data
(Case AII)
10.0
Pressure Drop, psi
9.0
8.0
Experimental data
7.0
UTCHEM simulation
6.0
5.0
4.0
3.0
2.0
1.0
0.0
0.0
0.5
1.0
1.5
Pore Volumes
Figure 5.12: Comparison of the pressure drop between UTCHEM and measured data
(Case AII)
142
2.0
1.2
100
IFT
1.0
10
0.8
1
Effective Salinity
0.6
0.1
CSEL
IFT (dyne/cm)
Effective Salinity (meq/ml)
CSEU
0.4
0.01
0.2
0.001
0.0
0.0001
0
0.2
0.4
0.6
Dimensionless Distance
0.8
Figure 5.13: Simulated salinity and IFT for coreflood AII at 0.5 PV
1.E-02
CSEU
1.0
Surfactant
1.E-03
0.8
0.6
1.E-04
Soap
CSEL
0.4
1.E-05
0.2
0.0

Concentration(v/v)
1.2
1.E-06
0
0.2
0.4
0.6
0.8
Figure 5.14: Simulated surfactant and soap concentrations for coreflood AII at 0.5 PV
143
14
1.2
pH
12
10
0.8
8
pH
Oil conc. (v/v)
1.0
0.6
6
Oil
0.4
0.2
0.0
0
0
0.2
0.4
0.6
0.8
Figure 5.15: Simulated pH and oil concentration for coreflood AII
Cum Oil Recovered (%) and Oil

Concentration
100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
0.0
0.2
0.4
0.6
0.8 1.0 1.2

Pore Volumes
1.4
1.6
1.8
Figure 5.16: Comparison of the oil recovery and oil concentration between the Case
AII and sensitivity case in which no Type III was modeled
144
2.0
1.2
1.E+02
1.E+00
CSEL, CSEU
0.8
1.E-01
0.6
1.E-02
1.E-03
Salinity
0.4
IFT (dyne/cm)
Salinity, meq/ml
1.E+01
IFT
1.0
1.E-04
0.2
1.E-05
0.0
1.E-06
0
0.2
0.4
0.6
0.8
Figure 5.17: Simulated IFT and optimum salinity at 0.5 PV for sensitivity case AII
(no Type III)
1.E-02
1.0
Surfactant
1.E-03
0.8
0.6
1.E-04
Soap
0.4
1.E-05
0.2
CSEL, CSEU
0.0

Concentration(v/v)
1.2
1.E-06
0
0.2
0.4
0.6
0.8
Figure 5.18: Simulated soap and surfactant concentrations for sensitivity Case AII (no
Type III)
145
(polymer viscosity-water viscosity)

water viscosity
1000
100
y = 58.761x
10
0.01
-0.3236
0.1
10
Csep,meq/ml
Figure 5.19: Flopaam 3630S polymer viscosity vs. salinity, Case B (2750 ppm
polymer, 46 oC at 10 s-1)
120
100
Viscosity, cp
80
60
Experimental data
Model
40
20
0
0
0.05
0.1
0.15
0.2
0.25
0.3
Polymer Concentration(wt%)
Figure 5.20: Flopaam 3630S polymer viscosity vs. polymer concentration, Case B (46
o
C at 10 s-1 with formation brine)
146
160
140
Viscosity, cp
120
100
80
Experimental Data
Correlation
60
40
20
0
0.01
0.1
10
100
1000
Shear Rate, sec^-1
Figure 5.21: Flopaam 3630S polymer viscosity vs. shear rate, Case B (2 wt%Na2CO3
added to formation brine, 46 oC)
1.0
0.9
0.8
0.7
kro
krw
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0.0
0.2
0.4
0.6
0.8
Figure 5.22: Oil/water relative permeability curves, Coreflood BI and BII

147
1.0
1.0
(S1I, f1I)
(S1*, f1*)
Fractional Flow of Water, fw
0.9
0.8
0.7
0.6
0.5
0.4
0.3
(S1B, f1B)
0.2
water-oil
polymer
0.1
0.0
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Figure 5.23: Fractional flow curves, coreflood BI and BII

100%
Cumulative Oil Recovered (%)- Oil Cut
90%
80%
70%
60%
50%
Cum Oil
40%
Oil Cut
30%
20%
10%
0%
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Pore Volumes
Figure 5.24: Case BIII Coreflood, with lower polymer concentration

148
1.6
1.8
2.0
Cumulative Oil Recovered (%)- Oil Cut
100%
90%
80%
70%
60%
50%
Cum Oil
40%
Oil Cut
30%
Cum Oil-UTCHEM
20%
Oil Cut-UTCHEM
10%
0%
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
Pore Volumes
Figure 5.25: Comparison of simulation and measured oil recovery and oil cut for
coreflood BI
14
UTCHEM
12
Experimental Data
10
pH
8
6
4
2
0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
Pore Volumes
Figure 5.26: Comparison of simulation and measured pH for coreflood BI

149
1.8
2.0
10.0
9.0
Pressure Drop, psi
8.0
7.0
6.0
UTCHEM
5.0
Experimental Data
4.0
3.0
2.0
1.0
0.0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
Pore Volumes
Figure 5.27: Comparison of simulation and measured pressure drop for coreflood BI
Surfactant Concentration,wt%
1
0.9
0.8
0.7
UTCHEM
0.6
0.5
0.4
0.3
Experimental data
0.2
0.1
0
0.0
0.5
1.0
1.5
PVs
Figure 5.28: Comparison of simulation and measured effluent surfactant

concentration for coreflood BI
150
2.0
CSEU
Salinity, meq/ml
1.2
1.0
1.E-01
Surfactant
0.8
1.E-02
CSEL
1.E-03
Soap
0.6
1.E-04
0.4
0.2
1.E-05
0.0
1.E-06
0
0.2
0.4
0.6
0.8
Total Soap& Surfactant (v/v)
1.E+00
1.4
Figure 5.29: Simulated soap and surfactant concentrations for coreflood BI

1.4
1.E+02
1.E+00
1.0
1.E-01
0.8
CSEL
1.E-02
0.6
1.E-03
Salinity
0.4
1.E-04
0.2
1.E-05
0.0
1.E-06
0
0.2
0.4
0.6
Figure 5.30: IFT and salinity at 0.5 PV for coreflood BI

151
0.8
IFT (dyne/cm)
Salinity, meq/ml
1.E+01
IFT
CSEU
1.2
Cum Oil Recovered (%)- Oil Cut
100%
90%
80%
70%
60%
Emulsion
50%
Cum Oil
40%
Oil Cut
30%
Cum Oil-UTCHEM
20%
Oil Cut-UTCHEM
10%
0%
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Pore Volumes
1.4
1.6
1.8
2.0
Figure 5.31: Comparison of measured and simulated oil recovery and oil cut for
coreflood BII
6.0
Emulsion breakthrough
Pressure Drop, psi
5.0
4.0
3.0
2.0
Whole(0-10)
Pressure drop- UTCHEM
1.0
0.0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
Pore Volumes
Figure 5.32: Comparison of measured and simulated pressure drop for coreflood BII
152
100%
Case BII
Cum Oil Recovered (%)
90%
80%
1wt % Na2CO3
70%
60%
50%
40%
30%
20%
10%
0%
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Pore Volumes
1.4
1.6
1.8
2.0
Figure 5.33: Oil recovery comparison for Case BII and sensitivity Case CI with
reduced alkali concentration (1wt% Na2CO3)
1.4
Salinity(meq/ml)
1.2
1.E+01
CSEU
1.E+00
1.0
CSEL
0.8
1.E-01
1.E-02
0.6
1.E-03
Surfactant
0.4
Soap
1.E-04
0.2
1.E-05
0.0
1.E-06
0
0.2
0.4
0.6
0.8
Figure 5.34: Soap and surfactant concentrations and Type III salinity windows at 0.5
PV for sensitivity Case CI with reduced sodium carbonate concentration
153
Total Soap& Surfactant (v/v)
1.E+02
1.4
1.E+02
IFT
1.E+01
1.E+00
1.0
0.8
CSEL
1.E-01
1.E-02
0.6
1.E-03
0.4
1.E-04
Salinity
0.2
1.E-05
0.0
1.E-06
0
0.2
IFT (dyne/cm)
Salinity(meq/ml)
1.2 CSEU
0.4
0.6
0.8
Figure 5.35: IFT and effective salinity at 0.5 PV for sensitivity Case CI with reduced
sodium carbonate concentration
1
Cumulative oil recovery,

vol fraction
0.9
0.8
0.7
AP-1,Acid no. =1.0
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.5
1.5
PV
Figure 5.36: Oil recovery for alkaline/polymer case (AP-1)

154
2.5
Acid no. =4.0
Cumulative oil recovery,

vol fraction
0.9
0.8
Acid no. =2.0
0.7
0.6
Acid no. =1.0
0.5
0.4
0.3
0.2
0.1
0
0
0.5
1.5
2.5
PV
Figure 5.37: Sensitivity of the oil recovery to acid number for alkaline/polymer floods
1.E+02
1.4
IFT
1.E+01
1.E+00
1.0
1.E-01
0.8
Soap
0.6
1.E-02
1.E-03
0.4
1.E-04
Salinity
0.2
CSEL, CSEU
1.E-05
0.0
1.E-06
0
0.2
0.4
0.6
0.8
Figure 5.38: Profile of the alkaline/polymer flood at 0.5 PV- Case AP-4 (acid number
of 4)
155
Total Soap (v/v), IFT

(dyne/cm)
Salinity(meq/ml)
1.2
CHAPTER 6
Field-Scale Chemical Flooding Simulations for a Viscous Crude Oil

in a Saline Reservoir
In this chapter, we extend the modeling and simulation of ASP flooding to the
field-scale. We investigate the feasibility of the ASP process for an offshore
sandstone reservoir with a high acid number viscous crude oil with a bottom water
drive, using horizontal injectors and producers. The sandstone formation has a high
porosity of 0.31 and high permeability of about 7 D. The crude oil acid number is
about 2.4 mg KOH/g oil. Because of the high viscosity of the crude oil (about 82 cp),
the waterflood oil recovery is poor, leaving the majority of the oil behind. The initial
salinity is about 2 wt% NaCl and the reservoir temperature is 87oF.
Prior to field-scale simulations, we first developed the aqueous, precipitation,
dissolution, and ion exchange reactions based on the composition of formation water,
reservoir rock mineralogy, injection water composition, and the injected sodium
carbonate. A series of 1D coreflood simulations were first performed using the
reservoir conditions of permeability, formation and injection water, crude oil, and
temperature for a conceptual design of the chemical flood injection strategy needed to
obtain high oil recoveries. Surfactant/alkali/crude oil phase behavior data were based
on the laboratory measurements for a similar crude oil. Polymer viscosity was
156
measured as a function of the shear rate, salinity, and polymer concentration at the
reservoir temperature.
6.1 PHASE BEHAVIOR
The surfactant and polymer formulation are chosen similar to the Case B
discussed in Chapters 4 and 5 (Sections 4.2.2 and 5.2, Figures 4.4 to 4.11 and Figures
5.19 to 5.21). The crude oil has an acid number of about 2.4 mg KOH/g oil. Table
6.1 gives the composition of the formation brine, with a salinity of about 2 wt%.
Figure 6.1 shows the calculated solubilization ratios with 0.3 wt% surfactant and 50
vol% crude oil as a function of added sodium carbonate concentration. Due to the
lack of phase behavior screening data for this specific reservoir crude, we used the
phase behavior results from a very similar crude oil at similar temperature.
6.2 REACTIONS
The formation water analysis and the rock mineralogy are listed in Tables 6.1
and 6.2, respectively. The initial equilibrium concentrations of aqueous, solid, and
adsorbed species were calculated using the EQBATCH program. Precipitation
reactions of divalent cations were ignored because of their negligible concentrations
in the formation and injected water. Table 6.3 compares the EQBATCH calculated
composition of brine with the measured values assuming no divalent cations.
Appendix D gives the details of the EQBATCH input file for this case.
Dissolution of quartz and clays were not considered due to the low reservoir
temperature of about 87oF. The reactions included:
157
1. In situ generation of soap was included because the acid number of oil is
high (~2. 4 mg KOH/g oil). Generation of soap consist of two reactions:
a. Partitioning of acid component between oil and aqueous phase
K
HA w
H A o
[H A w ]
KD =
[H A o ]
HAo : Concentration of acid in oil

HAw : Concentration of acid in water
KD : Partition coefficient of HAo
b. Dissociation of acid component in the presence of alkali to produce
soluble anionic surfactant (A-)
K
a +
HA w
H + A
H+ A
Ka =
[HA w ]
2. Aqueous reactions: The following few reactions are crucial to accurately

model the hydrogen ion concentration (pH).
H 2 O H + + OH
H + + CO 32 HCO 3
2H + + CO 32 H 2 CO 3
158
3. Exchange reactions on clay: The exchange reaction between sodium and

hydrogen on the clay surface is modeled since it can greatly impact the
alkali concentration and its propagation due to the consumption.
+
H + Na + + OH Na + H 2 O
The cation exchange capacity is 0.4 meq/100 g rock, which is equivalent to
0.033meq/ml PV for the UTCHEM cation exchange capacity input parameter,
assuming a porosity of 0.31.
6.3 ASP FRACTIONAL FLOW ANALYSIS
We constructed the fractional flow curve for ASP assuming the surfactant
adsorption is negligible at high pH. The minimum polymer viscosity in the ASP slug
needed to have a stable front (Mo=0.9) is about 70 cp (Figure 6.2). It should be noted
that polymer flooding requires a polymer solution with only 20 cp viscosity compared
to the higher viscosity required for ASP flooding because of an increase in relative
permeabilities at high capillary numbers or low interfacial tension (Figure 6.3).
This is an interesting observation especially important for viscous oils.
According to the fractional flow curve, the oil cut at breakthrough is about 75%.
6.4 ASP COREFLOOD DESIGN AND SIMULATION
A 1D ASP simulation was first performed to explore different chemical

injection strategies. The phase behavior data are based on an actual phase behavior
screening study for a similar crude oil with similar reservoir conditions (Figures 4.4
159
to 4.11). The optimum salinity ranges from 1.5 wt% for soap to 5.3 wt% for
surfactant. Table 6.4 lists the Type III salinity window for soap and surfactant used in
these simulations. The surfactant Type III salinity window is about twice as large as
that for soap.
The coreflood simulation model was set up with a length of 30 cm and a
diameter of 5.08 cm. Table 6.6 shows the core properties and simulation input
parameters. The permeability, porosity, and water/oil relative permeabilities are the
same as the field data. The initial core conditions at the time of ASP injection is at a
brine salinity of about 2 wt% NaCl. The ASP slug was injected at a frontal velocity
of 1.0 ft/day for a period of 0.3 PV followed by the polymer drive. Table 6.5
summarizes the ASP design. UTCHEM input file of this case is given in Appendix D.
Figure 6.4 shows the oil concentration and cumulative oil recovery, consistent
with the fractional flow analysis of an oil bank cut of 75%.
The oil bank
breakthrough time is very early because of the high initial oil saturation of 0.72. A
very high oil recovery of 97% OOIP is obtained and the results are consistent with a
coreflood experiment performed with a very similar crude oil (coreflood Cases BI and
BII in Chapter 4). The oil bank cut is high because of the high oil viscosity of about
81 cp.
Figure 6.5 demonstrates oil, surfactant, soap, and polymer concentrations,
effective salinity and IFT profiles at 0.8 PV where XD=0 indicates the location of the
injector and XD=1 is that of the producer. Surfactant adsorption is calculated to be
about 0.05 mg/g rock at high pH. It is observed that the soap has advanced slightly
160
ahead of the surfactant at the time of the profile, 0.8 PV. This is because alkali
consumption (~0.05 meq/100 g rock) is small relative to surfactant adsorption. Figure
6.5 shows that, as the surfactant concentration increases, the Type III region shifts
from the soap to the surfactant three-phase salinity window. When salinity passes
through the Type III region, the IFT reduces significantly, to about 10-6 dynes/cm.
6.5 FIELD-SCALE SIMULATIONS
In this section, we extend our work to field scale simulations to study different
chemical flood options that might be applied in this reservoir. The sector model has
48 gridblocks in the x direction, 20 gridblocks in y direction, and 16 gridblocks in the
z direction. The four bottom layers are the aquifer. The middle four layers are the
capillary transition zone as shown in Figure 6.6. The initial oil saturation is about
93% in the first 9 top layers. The vertical permeability in the field scale simulation is
0.7 times the horizontal permeability. All the rock and fluid, phase behavior and
polymer model parameters are identical to those in 1D simulation (Table 6.6). There
are 3 producers in layer 1 and one injector in layer 12. Injection and production wells
are rate constrained. The injection well rate is 18000 bpd and 6000 bpd is produced
from each of the three production wells, for balanced injection and production.
All properties in the model are homogeneous except for porosity, which
averages 0.31 and varies only slightly from this mean for each grid block. Since this
is an essentially homogeneous model and the gridblocks in the y direction are
identical in size, one slab out of 20 in y direction can be simulated (converting the 3D
161
model to 2D) to speed up the simulation run time for ASP and AP simulations. Table
6.7 lists the dimensions of the simplified reservoir model, which is very
representative for the purpose of this study. The UTCHEM input file for 2D
simulation is given in Appendix D.Injection and total production rates were reduced
to 900 bpd (18000 bpd/20 slabs), for the 2D model to mimic the 3D model.
Comparisons of the waterflood and polymerflood 2D and 3D simulations are
discussed in the following sections. To confirm the consistency of the simulation
results for 2D and 3D ASP models, we conducted a benchmark 3D ASP simulation to
compare with the 2D results.
6.5.1 Water Flood
The reservoir was first water flooded for about 12.25 years (water cut of about
98%). Figure 6.7 demonstrates the oil saturation at the end of the waterflood for the
2D and 3D cases. Water cones toward the production wells and large pockets of
unswept oil still exist after the waterflood. The 2D oil saturation distribution is
virtually identical to the 3D results.
6.5.2. Polymer Flood
A polymer solution of 1500 ppm with a viscosity of about 20 cp is injected

after the 12.25 years of waterflood for another 3000 days. Oil saturation reaches its
residual value of 0.25 for polymer flooding in much of the swept zone between wells,
as shown in Figure 6.8. Figure 6.9 shows the polymer concentration at different
times during the polymerflood. A large amount of polymer is lost to the aquifer (the
162
four bottom layers). The simulation results indicate the role of polymer in creating a
favorable mobility ratio and enhancing sweep efficiency, where the oil from the
unswept zones after waterflood is pushed towards the producers. Oil saturation is
shown in Figure 6.10 at different times during the polymerflood, demonstrating how
the oil is recovered due to polymer injection. Figure 6.11 compares the cumulative oil
recovery of waterflood and polymerflood for both 2D and 3D simulations. The results
are very similar for 2D and 3D simulations for both water and polymer flooding due
to the near homogeneous properties of the reservoir.
Cumulative oil recovery
increases from 6x106 bbls for waterflood to 1.4x107 bbls for polymerflood. If we
continue the waterflood for another 3000 days the cumulative oil recovery would only
increase to 8x106 bbls (Figure 6.13), as oilcuts are very low, less than 2% at this stage
of the waterflood. The cumulative oil production increases from 20% OOIP for
waterflood to 50% OOIP for polymerflood.
6.5.3. ASP Flood
Additional input parameters for ASP simulation such as phase behavior and
geochemical model parameters are the same as those used in the 1D simulation
(Table 6.6). Surfactant adsorption is assumed to be 0.05 mg/g rock at high pH. Alkali
consumption is small (~0.05 meq/ 100 g rock) because this reservoir is a low
temperature, clean 7 D sandstone rock. To mimic the same injection strategy as for
the 1D simulation, an ASP slug was injected for 750 days or 0.3 PV after the 12.25
days of waterflood followed by 2250 days of polymer drive (1.5 PV). Table 6.8 lists
163
the design strategy for polymer, alkaline/polymer and alkaline/surfactant/polymer

flooding simulations. A polymer concentration of 3000 ppm polymer was used in the
ASP slug and the polymer drive for a favorable mobility control. As mentioned
previously, the viscosity requirement for a favorable mobility ratio is higher for an
ASP flood compared to a polymer flood. This is the reason for using a polymer
concentration of 3000 ppm, twice than what was used in the polymer flood simulation
(1500 ppm).
Figures 6.12 compares the oil rate for ASP and polymer floods. The three
peaks observed in this graph represent the oil bank reaching each of the three
horizontal producers. The oil production rate peak is about the same for ASP and
polymer simulations at 6500 b/d for the producer closest to the injection well. The oil
rate peaks are substantially higher in ASP compared to polymer flood for the two
wells farther from the injection well. The maximum oil rate reaches as high as 8000
b/d for ASP. Cumulative oil production at the end of the simulation (Figure 6.13)
increases from 1.4x107 bbls for polymerflood to 1.8x107 bbls for the ASP flood. The
cumulative recovery for waterflood is only about 7.8x106 bbls. Figure 6.14 compares
the result of 2D and 3D simulations for ASP flood. This comparison shows close
simulation results between the 2D and 3D cases. Effluent chemical concentrations
during the ASP flood for producer 1 (the horizontal producer nearest the injector) is
shown in Figure 6.15. This plot shows the soap, surfactant, polymer and oil
concentrations. Soap and surfactant are produced together which confirms these two
chemicals are moving together within the reservoir. Total injection and production
164
rates are 18000 bpd. In these simulations, each producer produces a total of 6000 bpd.
The peak oil concentration of 90% is consistent with the observation of high oil
concentration at the oil bank from the fractional flow curve.
Figure 6.16 shows the pH profiles at the end of the ASP slug (750 days), in
the middle of the polymer drive (1500 days), and at the end of the flood (3000 days).
We observe that 1 wt% of Na2CO3 injected for about 750 days can increase the pH to
about 11.5, high enough to generate soap. It is also important to evaluate the
simulation to ensure that pH, soap, and surfactant are moving together. If pH and
surfactant have the same pace the process will benefit from lower surfactant
adsorption at high pH. Figures 6.17 and 6.18 show soap and surfactant concentration
profiles at three different times. The pH, soap, and surfactant are moving together.
Both soap and surfactant move from the oil band to the aquifer, but later are pushed
upwards towards the production wells by polymer injection. An insignificant amount
of soap and surfactant is lost in the neighboring grids, outside the injection/producer
pattern area.
Figures 6.19 and 6.20 show polymer and oil concentrations at different times.
Some amount of polymer is lost to the aquifer. Oil saturation is reduced to very low
values in the range of 0 to 0.1 indicating the effectiveness of the ASP flood in
recovering the unswept oil left from the waterflood and the trapped oil saturation.
Figures 6.21 to 6.23 show the effective salinity, lower and upper Type III effective
salinities (CSEL and CSEU) at different times for the ASP flood. The red color in
Figure 6.21 shows the 1 wt% sodium carbonate which has been added to the
165
formation brine salinity (blue color). As previously mentioned, the lower and upper
Type III salinity limits are calculated based on the soap and surfactant concentrations.
It is clearly seen that where there is more surfactant present, the upper and lower
effective salinities (CSEL and CSEU) of the soap/surfactant mixture shift towards
those of the surfactant. On the other hand, the mixture salinity window approaches
that of the soap when there is a greater ratio of soap compared to surfactant.
6.5.4 AP Flood
The next case is the alkaline/polymer (AP) flood. The input for this simulation
is the same as for the ASP simulations with the exception that no surfactant is added
to the slug and the phase behavior parameters are altered to reflect an optimum
solubilization ratio of about 12. The solubilization value used is just an estimate
since there is no phase behavior measurements for alkali and this crude oil. Figure
6.24 compares the oil recovery for the different chemical floods that are considered in
this reservoir. AP flood oil recovery is somewhere between the polymer and ASP
flood with a cumulative oil recovery of 1.7x107 bbls. In Figure 6.25, pH increases to
almost 12 as sodium carbonate is injected and consequently soap is generated with
concentrations as high as 0.003 vol. fraction where pH is high. Some soap is diluted
in the aquifer which is pushed away to the farther producers as polymer is injected
(Figure 6.26).
Oil saturation is reduced to values below the residual saturation in the AP
simulation, in a range of 0.0 to 0.1 (Figure 6.27). However, this AP process seems to
166
be not as efficient as ASP. Figure 6.28 shows the effective salinity profiles where the
red color shows the 1 wt% sodium carbonate added to the formation brine in blue
color. The Type III salinity window for the soap is narrow (CSEL = 0.25, CSEU =
0.35 meq/ml) and this consequently results in a lower oil recovery compared to that
for an ASP flood.
Figure 6.29 compares the oil saturation distributions at the end of 3000 days
for different chemical floods and waterflood. Polymer flooding has produced the oil
which could not be swept by water because of the highly unfavorable mobility ratio.
Polymer pushes the oil to the producers much more efficiently than water, resulting in
a more "piston-like" displacement compared to the coning seen for the waterflood
case. In contrast to the polymer flood, the AP flood could produce oil below the
residual oil (0.25), but it is not as efficient as ASP due to the typically more narrow
Type III region assumed in the simulations. The ASP flood has recovered the most oil
from the pattern area.
6.6 CHEMICAL COST CALCULATION
Table 6.9 lists the amount of each chemical used in polymer, AP and ASP
simulations. The amount of chemical is obtained from the chemical flood design
shown in Table 6.8. The amount of polymer injected is about 2.84x107 lbs (the
overall quantities for each injected chemical are reported in the UTCHEM OVERAL
output file). The polymerflood incremental oil recovery is 6.6x106 bbls compared to
the waterflood. For this analysis, the cost of polymer, surfactant, and Na2CO3 was
167
estimated to be $1.0, $1.5 and $0.1 per lb, respectively. Therefore, the polymer cost is
$4.3 per bbl of incremental oil produced for the polymer flood. A similar calculation
is done for the AP and ASP cases. Tables 6.10 and 6.11 compare the chemical cost
per bbl of incremental oil produced for polymer, AP, and ASP chemical EOR
projects. These calculation are based on the 3D simulation results. These simplified
economics suggest that all three of these chemical EOR processes are likely to be
attractive, especially in a high oil price environment, with the ASP process producing
the most incremental oil and the polymer case having the lowest chemical cost per bbl
inc. oil. Which chemical EOR process is the most attractive would require a more
careful analysis of the economics and also of the relative risks and benefits of these
three possible design scenarios.
6.7 SUMMARY
We investigated the feasibility of different chemical flooding processes such

as polymer, AP, and ASP for an offshore sandstone reservoir with a viscous crude oil
with a high acid number and a bottom water drive utilizing horizontal injectors and
producers. The sandstone formation has a high porosity of 0.31 and a high
permeability of about 7 D. The crude oil acid number is about 2.4 mg KOH/g oil.
Because of the high viscosity of the crude oil, the waterflood oil recovery is poor,
leaving the majority of the oil behind. A summary of the results are listed below.
The oil production rate increase of about 1000 b/d occurs as early as 2 yrs
after injection of the ASP slug.
168
The incremental oil recovery of ASP can be as high as 25% OOIP over
polymerflood recovery for this homogeneous reservoir model.
The AP flood has the potential to recover additional oil with minimal
additional cost of alkali over polymer. However, there are uncertainties in the
phase behavior of the soap that should be evaluated in the laboratory
corefloods.
Cumulative oil production at the end of the simulation is 7.8x106 bbls for the
waterflood, 1.4x107 bbls for the polymerflood, 1.7x107 bbls for the AP flood,
and 1.8 x107 bbls for the ASP flood. The ASP flood increased oil production
rates greatly compared to the polymerflood.
Despite the uncertainties in the missing data, this was still a very useful study,
since
a. It helped to obtain preliminary idea of the qualitative responses to
different chemical flood processes
b. It helped to explore alternative designs for better economics
169
Table 6.1: Formation brine composition

anion
Conc., mg/l
Cl
11567
SO4
0
HCO3
500
CO3
0
Br
0
I
0
total anion concentration
divalent cation
Mg
260
2+
Ca
640
SR
160
Ba
80
total divalent concentration
MW
35.5
98
61
60
79.9
126.9
charge
1
2
1
2
1
1
Conc., meq/ml
0.32583
0
0.0082
0
0
0
0.334
24.3
40
87.62
137.3
2
2
2
2
0.0214
0.032
0.0037
0.0012
0.0582
Table 6.2: Reservoir Minerals

Mineral
Wt%
Quartz
88.4
K-spar
Plagioclase
2.4
1.0
Clays
Kaolinite
[Al2Si2O5(OH)4]
2:1 Al-rich clay
2:1 Fe-rich clay
Calcite (CaCO3)
0.7
Berthierine
0.1
High Mg Calcite
Dolomite [CaMg(CO3)2]
0.5
0.7
Ankerite
0.7
Siderite (FeCO3)
0.8
total Clay
4.8
SUM (Total)
Wt%
1.4
0.1
3.2
100
170
Table 6.3: Comparison of the elemental compositions of experimental and simulated

connate brine
Element
Synthetic Brine (meq/ml)
Simulated Brine (meq/ml)
Na+
ClDivalent cations
0.27
0.325
0.326
0.325
0.0528
0.0
pH
6.5
Table 6.4: Type III salinity windows for soap and surfactant
Soap
Surfactant
meq/ml
wt%
meq/ml
wt%
CSEL
0.25
1.325
0.8
4.24
CSEopt
0.3
1.5
1.0
5.30
CSEU
0.35
1.855
1.2
6.36
1 wt% of Na2CO3 is 0.1887 meq/ml.
171
Table 6.5: ASP core flood design

ASP Slug
Polymer Drive
0.3 PV
0.3 wt% surfactant
1 wt% Na2CO3 in simulated
formation water in Table 6.3
1.5 PV
3000 ppm Flopaam 3630S in simulated
formation water in Table 6.3
Table 6.6: Summary of core flood input parameters

Length, ft
1.0
number of grids in x, y, z directions
1, 1, 100
gridblock sizes in x, y, z directions, ft
0.1445, 0.1445, 0.01
Components simulated
water, oil, surfactant polymer,

anion, carbonate, sodium,
hydrogen, petroleum acid
Average porosity
0.31
Permeability, md
7000
Initial water saturation, fraction
0.28
Capillary desaturation parameter for water, oil, ME
1865 59074 364.2
Residual water saturation, fraction
0.075
Residual oil saturation, fraction
0.25
Endpoint relative permeability of water
0.3
Endpoint relative permeability of oil
1.0
Relative permeability exponent of water
3.8
Relative permeability exponent of oil
1.9
Water viscosity, cp
0.8 at 87 oF
172
Oil viscosity, cp
81.39 at 87 oF
Intercept of binodal curve at zero, OPT., and 2xOPT salinity
0.05
Critcal micelle conc., volume fraction
0.001
Interfacial Tension Parameters for Huhs model, CHUH,AHUH
0.3 , 10
Log10 of oil/water interfacial tension , XIFTW
1.3
CMC, volume fraction
0.001
Compositional phase viscosity parameters for microemulsion
0.5,
(ALPHAV1- ALPHAV5)
0.0
Parameters to calculate polymer viscosity at zero shear rate
55 , 550 , 300
1.9,
0.02
0.0,
(AP1, AP2 , AP3), wt%-1

Parameter for salinity dependence of polymer viscosity
-0.33
(SSLOPE), dimensionless
Parameter for shear rate dependence of polymer viscosity
2.0
(POWN)
Permeability reduction factors, (BRK , CRK)
Surfactant
adsorption
parameters,
(AD31,
100. , 0.04
dimensionless)
1.9,
(AD32, ml/meq) (B3D,volume of water/volume of surfactant)

Longitudinal dispersivity (ft)
0.005
173
0.1, 1000.
, 0.05
0.0,
Table 6.7: Reservoir size and dimensions for field-scale simulations

Length, L ft
4593.2
Width, W ft
65.6 (2D)- 1312 (3D)
Height, H ft
131.2
Number of grids in x,y, z
48 x 1 x 16 (2D) - 48 x 20 x 16 (3D)
Cell dimensions in x direction, ft
328. 164.
Cell dimension in y direction, ft
65.6 (the same for 2D and 3D)
Cell dimension in z direction, ft
8.2
44x82. 164. 328.
Table 6.8: Chemical designs for field-scale simulations

Chemical EOR Method
Slug
Polymer drive
3000 days
1500 ppm Flopaam 3630S in
simulated formation water in
Table 6.3
Polymer
AP
ASP
750 days (~0.3 PV)

1 wt% Na2CO3 added to
Table 6.3
2250 days (~1.5 PV)

Table 6.3
750 days (~0.3 PV)

0.3 wt% surfactant
1 wt% Na2CO3 added to
Table 6.3
2250 days (~1.5 PV)

Table 6.3
174
Table 6.9: Total amount of chemical injected in different 3D chemical floods

Process
Polymer, lb
Polymer
2.84 10
AP
5.68 107
ASP
5.68 107
Surfactant, lb
Alkali (Na2CO3), lb
------
------
------
4.73 107
1.42 107
4.73 107
Table 6.10: Cost analysis for 3D polymer and AP floods*

Process
Water
Cum oil
recovered
%OOIP
Incremental oil over

waterflood
106 bbls
$/bbl
over water
flood
$/bbl
over polymer flood
26.74
--
--
--
50.15
6.595
4.34
--
AP
70.78
9.623
6.45
11.04
* For this analysis the cost of polymer, surfactant and Na2CO3 as alkali was estimated
$1.0, $1.5 and $0.1 per lb.
Table 6.11: Cost analysis for 3D polymer and ASP floods *
Cum oil
%OOIP
Incremental oil over

waterflood
106 bbls
$/bbl
over water
$/bbl
over polymer
Water
(3000 d)
P
26.74
50.15
-6.595
-4.34
---
ASP
75.81
10.836
7.7
12.92
Process
* For this analysis the cost of polymer, surfactant and Na2CO3 as alkali was estimated
$1.0, $1.5 and $0.1 per lb.
175
35
30
Oil
Water
25
20
15
10
5
0
0
0.5
1.5
wt% Na2CO3
Figure 6.1: Phase behavior for the simulation of reservoir B with 0.3 wt% surfactant,
50% crude oil at 87oF
1.0
(S1*, f1*)
water-oil
0.9
Fractional Flow of Water
0.8
polymer
0.7
0.6
0.5
0.4
0.3
(S1B,
0.2
(S1I, f1I)
0.1
0.0
-0.2 -0.1 0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8 0.9
1.0
Water Saturation
Figure 6.2: Fractional flow curve for waterflood, polymer flood, and ASP flood using
reservoir fluid properties
176
1.0
0.9
Miscible Relative Permeability
Relative Permeability
0.8
0.7
0.6
0.5
0.4
0.3
0.2
Oil
0.1
Water
0.0
0.0
0.2
0.4
0.6
0.8
Water Saturation
Figure 6.3: Low and high capillary number relative permeability curves
Cumulative Oil
Oil Conc.
Figure 6.4: Cumulative oil recovery and oil concentration for 1D ASP simulation
177
1.0
Figure 6.5: Soap and surfactant concentration, IFT, and effective salinity profiles at
0.8 PV for 1D ASP simulation
Figure 6.6: Well location for sector model (Dark blue color indicates the aquifer, light
blue is the capillary transition zone and red is the top layers containing 93% oil
saturation)
178
3-D at 4475 d (12.25 yrs)
2-D at 4475 d (12.25 yrs)
Figure 6.7: Oil saturation at the end of waterflood for 2D and 3D sector model
v/v
2D
3D
Figure 6.8: Oil saturation at the end of 2D and 3D polymer floods
179
750 days
1500 days
3000 days
Figure 6.9: Polymer concentration (wt%) profiles for 2D polymer flooding
0 days
750 days
1500 days
3000 days
Figure 6.10: Oil saturation profiles during 2D polymer flooding
180
Cumulative oil production, bbls
16000000
Polymerflood
14000000
2D
3D
12000000
10000000
8000000
6000000
Waterflood
4000000
2000000
0
0
2000
4000
6000
8000
Time, days
Figure 6.11: Comparison of oil recoveries (2D and 3D) for waterflood and polymer
flood
10000
9000
8000
Oil rate,B/D
7000
polymerflood
ASPflood
6000
5000
4000
3000
2000
1000
0
0
0.2
0.4
0.6
0.8
1.2
PVs
Figure 6.12: Oil rate comparison between 2D polymer and ASP floods
181
1.4
20000000
Cumulative oil production,bbls
18000000
16000000
waterflood
polymerflood
ASPflood
14000000
12000000
10000000
8000000
6000000
4000000
2000000
0
0
10
15
20
Time, years
Figure 6.13: Cumulative oil recovery for 2D water, polymer, and ASP floods
2.0E+07
1.8E+07
1.6E+07
1.4E+07
2D ASP simulation
1.2E+07
3D ASP simulation
1.0E+07
8.0E+06
6.0E+06
4.0E+06
2.0E+06
0.0E+00
0
10
15
20
Time, years
Figure 6.14: Comparison of cumulative oil recovery for 2D and 3D simulations of

waterflood and ASP flood
182
0.003
Oil
0.9
Surfactant
0.8
0.0025
0.7
0.002
0.6
0.5
0.0015
0.4
Soap
0.3
0.001
Polymer
0.2
0.0005
0.1
0
0
500
1000
1500
2000
2500
Surfactant and soap concentration,

volume fraction
Oil conc, volume fraction-Polymer,

wt%
0
3000
Time, days
Figure 6.15: History plot of soap, surfactant, polymer and oil concentrations for
producer 1 (3D ASP simulation))
750 days
1500 days
3000 days
Figure 6.16: pH profiles for ASP flood (2D)
183
750 days
1500 days
3000 days
Figure 6.17: Soap concentration profiles for ASP (volume fraction) (2D)
750 days
1500 days
3000 days
Figure 6.18: Surfactant concentration profiles for ASP (volume fraction) (2D)
184
750 days
1500 days
3000 days
Figure 6.19: Polymer concentration (wt%) profile for ASP -(2D)
0 days
750 days
1500 days
3000 days
Figure 6.20: Oil saturation profiles for 2D ASP
185
750 days
1500 days
3000 days
Figure 6.21: Effective salinity (meq/ml) profiles for 2D ASP
750 days
1500 days
3000 days
Figure 6.22: CSEL (meq/ml) profiles for 2D ASP
186
750 days
1500 days
3000 days
Figure 6.23: CSEU (meq/ml) profiles for 2D ASP
20000000
18000000
16000000
waterflood
polymerflood
ASPflood
APflood
14000000
12000000
10000000
8000000
6000000
4000000
2000000
0
0
10
15
20
Time, years
Figure 6.24: Comparison of cumulative oil production for 2D chemical flood cases
187
Figure 6.25: pH profiles for 2D AP flood
Figure 6.26: Soap concentration (volume fraction) profiles for 2D AP
188
v/v
750 days
1500 days
3000 days
Figure 6.27: Oil saturation profiles for 2D AP
750 days
1500 days
3000 days
Figure 6.28: Effective salinity (meq/ml) profiles for 2D AP
189
Water
Polymer
AP
ASP
Figure 6.29: Comparison of oil saturation profiles for different processes at the end of
3000 days for 2D simulations
190
CHAPTER 7
Design and Optimization of High pH Surfactant/Polymer Flooding in
a High Temperature Sandstone Reservoir
Recent laboratory research has shown significant benefits in using surfactants

at high pH. Surfactant adsorption reduction can be achieved at high pH even if the oil
has a low acid number and little, if any surfactant is generated in-situ. High pH
surfactant/polymer flooding is a very attractive enhanced oil recovery method
provided the consumption is not too large and the alkali can be propagated at the
same rate as the synthetic surfactant and polymer. Otherwise, polymer or SP may be
preferred methods in some cases.
Implementing chemical flooding in reservoirs with high temperature is
challenging. Extensive laboratory phase behavior was performed to select an efficient
surfactant formulation at a high reservoir temperature of 85oC. Several corefloods
were conducted to assess the performance and propagation of the selected chemicals
(Jackson, 2006; Levitt et al., 2006; Zhao et al., 2008; Dwarakanath et al., 2008). 1D
coreflood simulations were run to help with the design of the corefloods and to
identify key parameters such as surfactant adsorption.
This chapter presents mechanistic simulations of high pH chemical flooding at
high temperature. These simulations take into account a large number of reactions,
e.g. cation exchange and precipitation/dissolution reactions and their effects on the
191
propagation of an alkali front. Chemical properties such as phase behavior are based
on extensive laboratory data. 1D simulations are performed to model several
corefloods with different chemical designs. An optimum design case is selected based
on simulation studies. The optimization leads to additional corefloods to ensure the
high oil recovery and low surfactant adsorption.
Such simulations are performed to both interpret laboratory experiments and
to scale up to the field since it is now computationally feasible to perform such
mechanistic simulations in three-dimensions for sector models. We demonstrate the
use of such simulations to design chemical floods that are more robust and efficient
for appropriate reservoir targets.
Many pilot tests and several commercial field projects have been performed
over the past few decades and have shown that surfactant/polymer and
alkaline/surfactant/polymer floods can recover high percentages of residual oil
saturation. However, these chemical processes are sensitive to parameters such as
chemical slug size and concentrations, salinity, reservoir heterogeneity and surfactant
adsorption, and other key parameters. In this chapter, a design and sensitivity analysis
of these key parameters was performed to optimize a chemical flood design for this
sandstone reservoir. The base case design was developed using a geological model
provided by the operator. Injection and production rates are based on field operating
conditions. Reservoir fluid properties are for the field conditions and chemical
properties are measured in the laboratories of the operator and the Center for
192
Petroleum and Geosystems Engineering at the University of Texas (Jackson, 2006;

Levitt, 2006; Zhao, 2008; Dwarakanath, 2008).
The success of an SP or ASP flood depends on the ability to propagate the
alkali, surfactant, and polymer at the same rate, overcome chemical consumption and
adsorption, and improve the sweep efficiency. In this chapter, an optimization study
was performed to meet these goals.
7.1 SODIUM CARBONATE AS ALKALI
NaOH, Na2CO3, and NaBO2 are all alkali agents which have been tested in the
phase behavior experiments. NaOH can raise the pH to very high values and as
previously discussed in Chapter 3, a pH above 12 is to some extent detrimental since
it can speed up the consumption of alkali. NaBO2 is usually applied in carbonate
reservoirs. In this chapter, we focus on Na2CO3 for this sandstone reservoir.
Crude oils which have acidic components may saponify upon the addition of
alkali. This is the basis for ASP processes. The interaction of oil and alkali should be
tested and the changes in phase behavior need to be carefully evaluated. Most of the
light oils have low acid number which means less soap is generated in-situ. However,
other beneficial effects of adding alkali make it very desirable.
The addition of alkali can be beneficial in reducing the surfactant adsorption.
The smaller the surfactant adsorption, the smaller the amount of required surfactant
for injection and the lower the chemical costs. The addition of alkali could also help
with a better coalescence resulting in faster emulsifications and equilibration of
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surfactant solution. The addition of alkali can also improve the polymer hydration
(Jackson, 2006).
As mentioned in Chapter 1, Jackson (2006) tested the effect of sodium
carbonate on a formulation of 0.75 wt% 7POS C16-17, 0.25 wt% IOS C15-18 and 2
wt% SBA with a West Texas crude oil. He demonstrated that the equilibration time is
more rapid for the samples containing the sodium carbonate. It is shown that even if
the alkali has no other benefits on the phase behavior, such as soap generation and
significantly lowering the interfacial tension; it can still be used to lower the
surfactant adsorption and speed up the equilibration time.
He also screened several surfactant mixtures with crude oil from the Elk Hills
reservoir in California. These formulations are tested at the reservoir temperature of
100oC. Sulfonate surfactants were selected and tested for this crude due to the high
temperature. With a chemical formulation of 2 wt% AOS C20-24 and 4 wt% SBA,
the solubilization ratio increased from 9 to 12 when 1 wt% Na2CO3 was added instead
of NaCl. Sodium carbonate also shortened the time required for the mixture to
coalesce to a microemulsion and reduced the time for samples to equilibrate. The
following section presents the results of two corefloods and the approach for
modeling them with UTCHEM.
7.2 MODELING COREFLOOD M1
The purpose of this coreflood was to conduct an oil recovery experiment with
Crude M and test the performance of the IOS C20-24 surfactant. The surfactant
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formulation contains 3 wt% IOS C2024, 1 wt% iso-pentanol, 1 wt% SBA, 1 wt%
Na2CO3 (85 oC). Additionally, the AMPS polymer was tested for providing favorable
mobility with a reasonable pressure gradient across the core (Jackson, 2006; Levitt,
2006; Zhao, 2008). A relatively small slug of 0.1 PV with 3 wt% surfactant
concentration was injected and 1 wt% sodium carbonate was included in the design to
improve the phase behavior, to reduce surfactant adsorption, and to raise the pH of
the injected fluids. The sodium carbonate was included in the surfactant slug and also
in the polymer drive.
The core was a Berea sandstone rock. The rock properties and fluid data are
presented in Table 7.1. The core was initially saturated with a 3 wt% NaCl solution.
The core was then oil flooded with the filtered Crude M and then water flooded with
the 3 wt% NaCl to a residual oil saturation of 0.35. The core was then flooded with an
ASP slug and followed with a polymer drive solution. Table 7.2 summarizes the
chemical injection data.
7.2.1 Surfactant Phase Behavior and Polymer Modeling Parameters
The phase behavior data were matched with UTCHEM and a batch input file.
The results are shown in Figure 7.1. Table 7.3 lists the phase behavior parameters that
were adjusted to match the measured oil and water solubilization ratios.
The polymer chosen was the AMPS polymer, AN-125 due to compatibility
with surfactant (Levitt et al., 2006; Jackson et al., 2006; Flaaten, et al. 2007).
Polymer viscosity was measured as a function of polymer concentration, salinity, and
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shear rate at 85oC. Polymer viscosity parameters were found by matching the
viscosity data to UTCHEM polymer property correlations. Polymer viscosity vs.
salinity was measured at 2500 ppm AN-125, 85oC and 11 sec-1. Polymer viscosity vs.
polymer concentration was measured at 85oC, 2 wt% NaCl, and at the shear rate of
11sec-1. Polymer viscosity vs. shear rate was measured at 2500 ppm polymer
concentration with 2wt% NaCl and 1% Na2CO3 (85 oC). Figures 7.2 to 7.4 show a
comparison of polymer experimental data and UTCHEM model. The microemulsion
viscosity was not measured. However, the calculated microemulsion viscosity is
shown in Figure 7.5. The microemulsion viscosity input parameters are adjusted if
needed until a good match of measured coreflood pressure drop and oil recovery is
obtained.
The permeability reduction factor measured in the lab was found to be about
1.3. Therefore, the permeability reduction model parameters of crk and brk were set to
0.034 and 100 respectively to give a similar permeability reduction factor to that
measured in the coreflood. There was no measurement in this experiment of
surfactant adsorption or effluent surfactant concentration. Therefore, surfactant
adsorption was used as a history match parameter by adjusting a31 and a32. This value
was found to be around 0.3 mg/g rock at neutral pH and 0.15 mg/g rock at high pH of
about 10 (Figures 7.6 and 7.7).
The trapping number parameters for aqueous, oil, and ME was chosen to be
1865, 59000, and 364, respectively. These values are representative of the capillary
desaturation curve measured in a Berea sandstone core (Delshad et al., 1986; 1987).
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Figure 7.8 shows the oil phase capillary desaturation curve used for this simulation. A
complete listing of the UTCHEM input file is given in the Appendix D.
7.2.2 Fractional Flow Diagram
Table 7.1 lists the relative permeability data measured in the laboratory. The
relative permeability exponents are chosen to be 2 for the Berea sandstone rock
(Figure 7.9). Reservoir temperature is about 85oC. Water and oil viscosities are 0.37
and 8.0 cp, respectively. Water mobility ratio for this system is 1.3. Polymer viscosity
is 8.5 cp at a shear rate of 11 sec-1. Therefore, the ASP mobility ratio is very favorable
at 0.7. The fractional flow diagram is shown in Figure 7.10. The oil bank saturation
is about 50% with the breakthrough at about 0.3 PV.
7.2.3 Reactions Considered for Simulation
Sodium carbonate was used in this formulation mainly to reduce the surfactant
adsorption and help with the phase behavior. The crude oil in this reservoir is not
reactive to generate soap. A simplified set of reactions representative of this case are
chosen. These reactions include aqueous reactions responsible for change of pH due
to injection of sodium carbonate and also the cation exchange reaction. Cation
exchange reaction is the alkali consumer. A silica dissolution reaction is also
modeled. There is a need to model the silica dissolution due to high reservoir
temperature (85oC). A quantitative calculation of alkaline consumption for this
reservoir is given in Appendix E. A List of aqueous reaction is as follows:
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H 2 O H + + OH
Ca 2 + + H 2 O Ca(OH)+ + H +
H + + CO32 HCO3
Ca 2 + + H + + CO32 Ca(HCO3 )+
2H + + CO32 H 2 CO3
Al3 + + 4H 2 O Al(OH)4 + 4H +
Cation exchange capacity for the Berea sandstone rock is about 0.3 meq/100g
rock. We have included the sodium-hydrogen exchange reaction.
+
H + Na + + OH Na + H 2 O
7.2.4 Coreflood M1 Simulation Results
A history match of coreflood M1 was performed to obtain and adjust input

parameters for field applications. The following data was provided from the
laboratory work for matching the corefloods:
Oil recovery/oil cut
Pressure drop
As previously discussed, based on the fractional flow curve, the oil
breakthrough occurs at about 0.3 pv and the oil cut of the oil bank is about 50%.
UTCHEM history match simulation results are in close agreement with the fractional
flow calculations. An excellent agreement was obtained for oil cut, oil recovery, and
pressure drop across the core (Figures 7.11 and 7.12). In addition, the UTCHEM
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history match was satisfactory in estimating unknown parameters such as surfactant

adsorption.
Figure 7.13 demonstrates the surfactant concentration and salinity profile for
the coreflood at 0.5 PV. The area between CSEL and CSEU is the low IFT region (or
Winsor Type III). We would like to operate within this region where surfactant is
present. This profile is very educational and helps us design our process more
efficiently. As shown in this plot, the surfactant concentration peak exists in the low
IFT region.
The challenge of high pH flooding is to propagate the alkali and surfactant
simultaneously to benefit from the effect of high pH as discussed before. Effluent pH
was not measured during the coreflood. However, Figure 7.14 shows the simulated
pH and surfactant concentration profiles at 0.5 PV. Cation exchange is the major
consumer of alkali in this case. Cation exchange is chosen to be around 0.3 meq/ 100
g rock. This value is reasonable for Berea sandstone and provides an estimate for the
alkali consumption. Surfactant and pH move together as shown in Figure 7.14. This
means we could take advantage of alkali and high pH for surfactant adsorption
reduction.
Figure 7.15 demonstrates the surfactant adsorption profile with and without
the pH effect dependence modeled. As modeled, surfactant adsorption is about 0.3 at
neutral pH and 0.15 mg/g rock at about a pH of 10. Figure 7.16 shows the adsorbed
cation concentration at 0.5 PV. Based on the cation exchange reaction, at high pH
sodium is adsorbed on the rock surface and hydrogen is desorbed.
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7.3 AQUEOUS STABILITY
The aqueous stability of the surfactant slug in the first formulation (M1) was
tested and observed to separate into two phases after several hours at 85oC. More
laboratory work was performed to resolve the aqueous stability dilemma which led to
the selection of alternative surfactant formulations that are more stable (Jackson,
2006; Levitt, 2006; Zhao, 2008 and Dwarakanath et al., 2008).
To resolve the aqueous stability problem, the effect of co-solvent on phase
behavior was evaluated. Optimal surfactant/co-solvent formulation was selected
based upon a combination of simulations and laboratory experiments (Jackson, 2006;
Levitt, 2006; Zhao, 2008 and Dwarakanath et al., 2008). The new formulation
includes a 2 wt% mixture of anionic surfactant, 3 wt% ethylene glycol butyl ether
(EGBE) as the co-solvent and 0.85 wt% sodium carbonate in the formation brine.
7.3.1 Modeling the Effects of Co-solvent on Phase Behavior
Co-solvents used for oil recovery are amphiphiles. They have the ability to
partition into aqueous, oleic, and microemulsion phases. This property allows cosolvents to significantly alter the phase behavior. When a hydrophilic co-solvent is
mixed with an anionic surfactant, an increase in optimal salinity is observed.
Conversely, a lipophilic co-solvent will induce a reduction in optimal salinity. While
co-solvents have been used widely in surfactant trials, their effect on phase behavior
is often neglected due to the complexity of experimental measurements and
incorporation into numerical simulation. An adverse consequence of ignoring co200
solvent behavior could be chromatographic separation from the surfactant due to

preferential partitioning. Such separation would induce changes in overall
surfactant/co-solvent compositions along a dilution path and undesirable phase
behavior (Dwarakanath et al., 2008).
Ethylene glycol butyl ether (EGBE) was added as the co-solvent to improve
the coalescence and equilibration times. EGBE could increase the optimum salinity
and also reduce the solubilization ratio. The partitioning of EGBE and the effects on
the phase behavior were measured and provided additional information needed for
modeling the new corefloods with UTCHEM taking into account the effects of cosolvent on the phase behavior. The partition coefficient of the co-solvent (0.31) was
measured with crude oil and reservoir brine (Dwarakanath et al., 2008). Appendix F
explains how we model the effect of cosolvent on the phase behavior.
The Provoust alcohol partitioning model was used to model the effect of
alcohol on phase behavior (Prouvost et al., 1984a, and b, 1985 and 1986). This model
was described in Chapter 2. Provoust et al. introduced a pseudophase theory and
modeled alcohol partition coefficients. The alcohol fractions in the pseudosurfactant
component faS are defined by
faS =
total alcohol associated with surfactant

total pseudosurfactant
The effect of cosolvent on the effective salinity is modeled using the slope
factor a
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CSE =
C51
(1 + a f a S )
where CSE is the effective salinity and C51 is the brine salinity. Other variables such as
calcium and temperature cause a shift in effective salinity and are also modeled in
UTCHEM as discussed in Chapter 2.
Phase behavior model parameters for the effect of alcohol on phase behavior
were obtained by running UTCHEM batch simulations. The effect of alcohol on the
optimum salinity is modeled using a.
Dwarakanath et al. (2008) discussed how co-solvent/electrolyte combinations
can be used to design effective gradients for chemical floods. Concerns about cosolvent partitioning can be assuaged by estimating the static and dynamic partition
coefficients from co-solvent partitioning experiments as well as history matching a
large number of phase behavior experiments (Figure 7.17). They concluded that the
resulting formulations containing co-solvent maintained Winsor Type III behavior for
a longer time than the surfactant injection period, effectively making the surfactant
slug seem larger. As shown in Figure 7.18, the profile for the simulation with
electrolyte plus co-solvent results in a much larger Winsor's Type III region compard
to the simulation injecting electrolyte without co-solvent. The design of such optimal
co-solvent gradients requires a mechanistic simulator capable of modeling the effect
of co-solvent on surfactant phase behavior.
They also showed how UTCHEM can capture the effect of co-solvent on
surfactant phase behavior and how it can be used to design and interpret corefloods.
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The chemical input parameters obtained through these means are then calibrated to
corefloods. They can then be scaled up with a high level of confidence.
Figure 7.19 shows the phase behavior measured data and UTCHEM match for
the above formulation and 3 wt% EGBE. To honor the phase behavior data, there is a
need to expand the low IFT region (Winsor Type III). Figures 7.20 and 7.21
demonstrate the data measured and UTCHEM match for the effect of EGBE on
optimal salinity and solubilization ratio. Refer to Appendix F for more explanation on
how to find the UTCHEM phase behavior parameters when cosolvent is present.
7.4 SIMULATION RESULTS FOR COREFLOODS BM-07 AND M5
Several corefloods were performed in Briar Hill sandstone rock to test the
surfactant formulation containing EGBE. Table 7.4 lists the core properties for three
corefloods; BM-08 is discussed in Section 7.5.1. Corefloods BM-07 and M5 are very
similar with the exception that one is 4 ft and the other is 1 ft. There are slight
differences in the permeability of these two cores (1500 md for coreflood BM-07 vs.
1300 md for coreflood M5). These corefloods are both mounted vertically with
injection from the bottom of the core and production from the top.
Synthetic brine is used during the ASP flood and polymer drive in these
corefloods. The synthetic brine contains very low salinity with the composition listed
in Table 7.5. The cores are initially saturated with brine similar to the synthetic
reservoir brine but without bicarbonate.
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The procedure used in the ASP flood of these two cores is given in Table 7.6.
The main difference between the two corefloods is the ASP slug size. For coreflood
BM-07, 15% PV of ASP was injected and that for M5 coreflood was 20% PV. The
slug contained 2 wt% surfactant, 3 wt% EGBE, 0.85 wt% sodium carbonate, and
2500 ppm AN125 polymer. The slug was followed by 0.2 PV of polymer drive with
polymer concentration of 2200 ppm and 1.5 wt% EGBE and 0.65 wt% sodium
carbonate. A second polymer drive was followed with 1.5 PV of 1800 ppm polymer.
The interstitial velocity was kept at 1ft/day (0.45 ml/min).
The polymer model inputs are the same as those used in coreflood M1. The
effluent surfactant concentration was measured for coreflood M5. Surfactant
adsorption was estimated by matching the effluent surfactant concentrations. This
value was about 0.22 mg/g rock at neutral pH and 0.1 mg/g rock at high pH (~10),
(Figures 7.22 and 7.23).
A tracer test was conducted in coreflood BM-07 after the brine flood to
calculate the pore volume. The tracer was injected at a flow rate of 9 ml/min. Samples
were collected every minute. Figure 7.24 shows the effluent tracer concentrations for
coreflood BM-07. The tracer response shows a long tail. The tracer breakthrough and
the peak concentration arrival were much earlier than expected. Further analysis of
the tracer response curve confirmed a non-equilibrium condition during this coreflood
as a result of a relatively high injection rate (9 ml/min). The tracer capacitance model
in UTCHEM was used to match the tracer response curve.
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Oil recovery and oil cut were successfully modeled with UTCHEM (Figure
7.25). A large value for polymer inaccessible pore volume (~0.2) was used to account
for the early oil breakthrough because of high flow rate and non-equilibrium
conditions observed in this experiment. The simulated pressure drop is very similar to
the measured values across the core as shown in Figure 7.26. Adjusting the five alpha
microemulsion viscosity parameters resulted in a good match for pressure drop.
Effluent surfactant and EGBE concentrations, pH, and carbonate and
bicarbonate concentrations were measured and compared favorably with UTCHEM
simulation results (Figure 7.27 to 7.30). The peak and trend for carbonate and
bicarbonate were matched very closely with the simulation, given the considerable
uncertainty in laboratory measurement for these solution species. The simulated pH
was higher than those measured due to difficulties in pH measurements (Figure 7.29).
Figure 7.31 shows the profiles of salinity and concentrations at 0.5 PV. The
concentration profiles include oil, polymer, surfactant, and EGBE (the value of 0 on
the axis corresponds to the bottom of the core where the fluids are injected). The
results indicate that surfactant and EGBE are moving together in the core. Slight
changes were made to the input file of coreflood BM-07 to simulate coreflood M5.
As mentioned before, this coreflood is very similar to the first coreflood except that it
is one foot long and a slightly larger ASP slug of 20% PV is injected compared to
15% PV in BM-07. Figure 7.32 compares simulation results and experimental data
for oil recovery and oil cut. The history match confirms the surfactant adsorption is as
low as 0.1 mg/g rock.
205
Several 1D simulations were performed and are discussed in the next section
for a design with better chemical efficiency. The design can be more cost effective by
reducing the amount of EGBE required in the slug and drive.
7.5 1D SIMULATIONS TO OPTIMIZE THE DESIGN
Several 1D coreflood simulations were performed based on Coreflood M5.

The polymer drive I was eliminated to reduce the cost of chemicals. Three different
scenarios were tested as shown in Table 7.7. Different slug sizes of 20%, 15%, and
10% PV were simulated with 1.5 PV of polymer drive with no added EGBE. The
ASP slug contains the same chemical concentrations as coreflood M5.
The oil
recoveries were 92%, 90%, and 87% for Cases #1, 2, and 3, consecutively (Table
7.7). The surfactant adsorption of 0.1 mg/g rock was assumed in these simulations.
7.5.1 Simulation of Coreflood BM-08 with Cost Effective Design
Another coreflood (BM-08) was performed to test the same chemical

formulation as used in corefloods BM-07 and M5, but with a more cost-effective
design, see Table 7.4. The design of this coreflood (Table 7.6) was similar to the
sensitivity simulation Case #3 (Table 7.7). In this coreflood, the slug size was reduced
to 0.1 PV decreasing the cost of surfactant and EGBE. Then the first polymer drive
containing EGBE was also eliminated. The oil recovery was about 93% suggesting a
smaller surfactant adsorption value than 0.1 mg/g rock as used in the simulation.
UTCHEM simulation was run to estimate the surfactant adsorption for
coreflood BM-08. The surfactant adsorption was reduced to about 0.05 mg/g rock in
206
order to successfully match the measured oil recovery. Figure 7.33 shows the
comparison of simulated and measured oil recovery and oil cut for the BM-08
coreflood.
7.6 SERIES I: SECTOR MODEL SIMULATIONS WITH SURFACTANT FORMULATION
USED IN COREFLOOD M1
ASP coreflood results were successfully matched to verify the chemical model
parameters and obtain the missing process parameters, such as surfactant and polymer
adsorption, capillary desaturation curves, and interfacial tension.
The coreflood
history matches provided the necessary process data for simulating the sector model.
The high pH surfactant/polymer coreflood simulations confirmed that the major effect
of sodium carbonate with respect to modeling is to increase the pH and redcue the
surfactant adsorption. For the purpose of simplicity and faster simulations, subsequent
3D sector model simulations were performed without the reactions discussed in
coreflood simulations but adjusting the surfactant adsorption.
The simulation model is an 18-acre regular seven-spot pattern. A top view of
the reservoir is shown in Figure 7.34. The number of gridblocks in the x, y and z
directions is 22, 25 and 17, respectively. The gridblock sizes are 75.4 ft in the x and y
directions and vary from 1.1 to 5.5 ft in the z direction. The depth to the top of the
formation, initial reservoir pressure, porosity, and permeability model are shown in
Figures 7.35 to 7.38. Injection wells were constrained to an injection pressure of 1300
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psi and production wells were operating at a constant BHP of 300 psi. Water flood
was performed to achieve a 98% water cut.
For chemical flood simulations, 30% PV of an SP slug containing 2 wt%
surfactant was injected and followed by 1.0 PV of polymer drive. The physical
properties were based on the coreflood results (M1). The surfactant adsorption of 0.15
mg/g rock corresponding to high pH value of 10 was used to take into account the
effect of high pH on surfactant adsorption.
7.6.1 Regular 7-spot pattern vs. inverted 7-spot pattern
This section investigates the effect of well pattern on the chemical oil
recovery and the project life. As shown in Figure 7.34, the ratio of injection wells to
production wells is 2 for a regular 7-spot pattern. This model includes 10 injection
wells constituting of 6 full wells and 4 half wells, which is equal to 8 full wells plus a
total of 7 production wells constituting of 1 full well and 6 half wells which is equal
to 4 full wells. The ratio of injection wells to production wells is half for an inverted
7-spot pattern, for a total of 7 injection wells (1 full well and 6 half wells = 4 full
wells) and a total of 10 production wells (6 full wells and 4 half wells = 8 full wells).
Injection wells were constrained to an injection pressure of 1300 psi and
production wells were operated at a constant BHP of 300 psi. Water was injected
until a water cut of 98.5 to 99% was achieved. Figure 7.39 shows very similar
waterflood oil recoveries of about 60% OOIP for either pattern.
208
For the chemical flood simulations, 30% PV of SP slug containing 2 wt%

surfactant was injected and followed by 1.0 PV of polymer drive. This design was
implemented to compare the regular and inverted well patterns. The physical
properties were based on the coreflood results (M1). Figure 7.40 compares the
cumulative oil recovery where the regular 7-spot gives a faster oil recovery. Major
concerns in chemical flooding are the project life and how quickly oil is produced.
The comparison indicates that the regular 7-spot pattern recovers the oil faster than
the inverted pattern. Therefore, the regular 7 spot well pattern was used in the
subsequent simulations.
The faster oil recovery is due to a two-to-one ratio of injection to production
wells. A series of sector model simulations was performed to design and optimize the
chemical flood in this reservoir.
7.6.2 Sensitivity simulations
In this section, we analyze the effect of chemical flood design variables on the
oil recovery. These design variables include the slug size, surfactant concentration,
polymer concentration, and salinity. We varied these variables within acceptable
ranges to optimize the design for the highest oil recovery. These results need to be
coupled with the economic analysis to find the best design in terms of profit and
economic feasibility. Table 7.8 lists the sensitivity runs performed and compares the
oil recoveries to optimize the chemical flood design for this field case study. Oil
recovery (%ROIP) for some of the sensitivity analysis performed on Series I
209
simulations is shown in Figure 7.41. Injection and production well flow rates are also
shown in Figure 7.42. The production well rate is about twice the injection well rate.
7.6.2.1 Polymer flood
For comparison of SP and ASP and to obtain the incremental oil recovery for
each process, we first performed a polymer flood simulation. A polymer solution
(AN125) with the concentration of 1500 ppm was added to the formation brine and
injected for 1.0 PV. The oil recovery was 10.6% OOIP. The properties of polymer
are listed in Figures 7.2 to 7.4.
7.6.2.2 Base Case ASP simulation
The base case simulation was designed with a surfactant/alkali slug followed
by a polymer drive. A 0.15 PV chemical slug with 2 wt% surfactant and 1 wt%
Na2CO3 and no other electrolyte was injected. The surfactant solution contains 2.0
wt% IOS C20-24 with 1.0 wt% n-Pentanol and 1.0 wt% SBA. The slug was driven by
a 1.0 PV polymer drive. Two polymer drives were injected, a 0.2 PV drive at the
optimum salinity (1 wt% Na2CO3 added to the formation brine) and polymer
concentration of 2000 ppm and a 0.80 PV drive of 1700 ppm polymer with the
salinity below the optimum (0.26 wt% Na2CO3 added to the formation brine). The
chemical flood was followed by a post-waterflood. The cumulative oil recovery was
about 21.5% OOIP. Figure 7.43 shows the profiles of effective salinity and surfactant
concentration between one injector and one producer in the second layer at 0.5 PV.
The effective salinity exhibits a dispersed profile and does not reach the injected
210
optimum salinity. This is not a desirable design since the IFT tension is obtained at
salinity at or near optimum. The results suggest that we need to inject at optimum
salinity for a longer time than considered in the base case simulation.
7.6.2.3 ASP design variable sensitivity
In Case 3, we injected at optimum salinity for a longer time period. Therefore,

the polymer drive salinity was kept at optimum salinity for 0.40 PV compared to 0.2
PV in the base case. The oil recovery was increased 4% OOIP compared to the base
case.
Figure 7.44 demonstrates the effective salinity and surfactant concentration
profiles between one injector and one producer in the second layer for Case 3. The
effective salinity reached the optimum and as a result the oil recovery was increased
by about 4%OOIP.
To investigate the sensitivity of surfactant slug size upon recovery, we
increased the slug size from 0.15 PV to 0.2 PV in Case 4 and 0.25 PV in Case 5. All
other parameters were kept as Case 3. The oil recovery was increased to 28.3% OOIP
for Case 4 and 30% OOIP in Case 5. Oil recovery increased due to the higher mass of
surfactant injected. Economic analysis would be needed to determine which case
gives the highest cash flow and NPV.
Due to dilution and dispersion, salt and surfactant concentrations are diluted
and dispersed. The slug salinity was increased to a slightly higher value (from 0.225
to 0.3 meq/ml) in Case 6. All other variables are the same as Case 3. The oil recovery
211
was 25.8% OOIP indicating an increase of about 0.5% OOIP compared to that in
Case 3.
A water preflush period was added in Case 7. This case is the same as Case 3
but with 0.2 PV of water injection (at optimum salinity) prior to chemical flooding.
This change increased the oil recovery to 26.5% OOIP compared to 25.3% OOIP in
Case 3. This change helps us increase the salinity to optimum salinity during the
surfactant injection.
7.6.2.4 ASP uncertain variable sensitivity
Some sensitivity should be performed on uncertain parameters such as

surfactant adsorption or vertical to horizontal permeability ratio. There is always
uncertainty in the vertical to horizontal permeability ratio. This value is assumed to be
0.5 for all the above mentioned simulations. We studied the effect of this parameter
on the oil recovery. Vertical to horizontal permeability ratio was reduced from 0.5 in
Case 3 to 0.1 in Case 8. The oil recovery was significantly reduced, from 25.3 to 18.2
% OOIP. As shown in Figure 7.38, there are some low and high permeability layers
in this reservoir. High vertical to horizontal permeability helps the mixing and
crossflow in the reservoir and consequently increases oil production.
The base case or Case 3 surfactant adsorption was 0.3 mg/g rock. There is
laboratory evidence that the surfactant adsorption is reduced at higher pH. Since we
added Na2CO3 to the surfactant slug, there will be an increase in pH and a significant
reduction in surfactant adsorption is expected. Case 9 was performed where the
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surfactant adsorption was reduced from 0.3 mg/g rock in the base case to 0.15 mg/g
rock to study the effect of adsorption. The oil recovery was 27.2 % OOIP which is
about 2% OOIP higher than in Case 3.
As shown in Figure 7.41, polymer flooding (Case 1) is not as efficient in
recovering oil as an alkaline/surfactant/polymer flood. Increasing the polymer drive
salinity increases the oil recovery (Case 3). The kv/kh sensitivity (Case 8) shows that
this parameter can have a significant impact on the oil recovery. The chemical flood
simulations suggest that the project time for this reservoir is less than one year
indicating a high potential in terms of profitability.
7.6.2.5 Summary and Conclusions for Series I Simulations
This section presents mechanistic simulations of high pH chemical flooding at

high temperature of 85 C. Chemical properties such as phase behavior are based on
extensive laboratory data. ASP coreflood results are successfully matched to verify
the chemical model parameters and obtain the missing process parameters, such as
surfactant and polymer adsorption, capillary desaturation curves, and interfacial
tension.
The coreflood history matches provide the necessary process data for
simulating the sector model.

1D simulations are performed to further refine and optimize the chemical
injection design.The optimization study leads to additional corefloods to ensure the
high oil recovery and low surfactant adsorption.
213
3D sector model simulations are performed with regular and inverted 7 spot
patterns. Sensitivities to surfactant adsorption, polymer drive salinity, kv/kh ratio,
and slug size are studied. Some key results are summarized as follows.
Several corefloods are successfully matched modeling the reactions and the
effect of co-solvent on phase behavior.
Additional 1D simulations are performed to model several corefloods with

different chemical designs. An optimum design case is selected based on
simulation studies. The simulation optimization study leads to additional
corefloods to ensure the high oil recovery and low surfactant adsorption. The
results are consistent with the design simulation results
3D water and chemical flooding simulations are performed on an 18 acre well

spacing to compare the regular and inverted seven spot well patterns.
Waterflood oil recoveries are similar for both patterns at 60% OOIP. The
chemical flooding oil recovery is higher with about 4% ROIP for the regular 7
spot compared to the inverted 7 spot.
The regualr 7 spot is chosen for further simulation study because of the
shorter project life as the result of 2 to 1 injection to production ratio.
Although UTCHEM formulation uses a high order scheme to reduce the

numerical dispersion, there is still some degrees of smearing evident in the
concentration profiles (Figures 7.43 and 7.44) due to relatively large
gridblocks and resulting numerical dispersion. In order the further reduce the
214
numerical dispersion, the gridblock sizes need to be reduced. This will be

addressed in the Series II sector model simulations discussed next.
The kv/kh ratio affects the oil recovery significantly. The oil recovery is
reduced by almost 10% ROIP when the kv/kh ratio is reduced from 0.5 to 0.2.
An increase in the surfactant slug size from 15% PV to 25% PV increases the
oil recovery. The optimum slug size needs to be obtained based on economics
calculations.
7.7 SERIES II: SECTOR MODEL SIMULATIONS WITH THE CHEMICAL

FORMULATION USED IN COREFLOODS BM-07 AND M5
In this section, we use the same surfactant formulation as used in corefloods

BM-07 and M5 for the sector model simulations. There are some other differences
which are discussed later.
The sandstone reservoir investigated in this study is considered high
temperature reservoir (~85oC). This reservoir has been water flooded and produced
about 98% water cut, which is close to its economic limit.
The simulation model is an 18-acre regular 7-spot model. A top view of the
reservoir is shown in Figure 7.45. This model has a larger number of gridblocks with
finer gridblock sizes compared to the previous case. Grids in the middle section of
reservoir in X, and Y directions are about half of the corner grids. This has been done
to reduce the numerical dispersion and obtain more accurate results in the center 7-
215
spot pattern. The number of gridblocks is 74,777 cells. Table 7.9 lists the dimensions
and grid sizes of the new model.
Ten realizations were available from geological models for this study. Each of
these models is different in permeability and porosity distribution. Figures 7.46 to
7.48 show the horizontal and vertical permeability, and porosity for realization 1.
Sections of permeability and porosity are shown in Figures 7.49 and 7.50. There are
two major lithofacies classifications in the reservoir interval based on grain size. The
vertical to horizontal permeability ratio is likely quite different between these two
intervals. Therefore, the gridblocks with permeability below 200 md were assumed
to be representative of the lower quality reservoir and were assigned a kv/kh ratio of
0.001. The rest of the gridblocks had a kv/kh ratio of 0.1. A cross-section view of the
permeability shows that the lower permeability layer is at the top of the reservoir and
higher permeability layers are at the center and bottom of the reservoir. The average
porosity is about 0.2.
The initial water saturation was correlated with the permeability using the
following correlation.
Swi (u)* = 80.187 * k x (u) 0.1682

where Swi is the initial water saturation, kx is the horizontal permeability in md, and u
indicates the cell location.
Figure 7.51 is the profile of initial water saturation generated for realization 1
based on the above correlation. Residual water and oil saturations were also
correlated with permeability based as shown in Figures 7.52 and 7.53. Corey type
216
relative permeabilities for oil and water were also correlated with horizontal
permeability as described in Tables 7.10 and 7.11.
7.7.1 Waterflood
Figure 7.45 shows the location of wells for the regular 7-spot pattern. In this
sector model, there are 10 injection wells and 7 production wells. All ten realizations
were waterflooded to reach to a water cut of about 98% corresponding to the current
conditions in the field producers. Some of the fluid properties are reported in Table
7.12. All the injectors and producers were operated at constant bottomhole pressures
with injectors at 1300 psi and producers at 300 psi. The waterflood was performed for
about 5 PVs. The oil recovery at the end of the waterflood for 10 realizations varied
from 54.8 to 58.3 %OOIP (Figure 7.54). Figure 7.55 shows the cross-sectional profile
of the oil saturation at the end of the waterflood for realization 1.
7.7.2 Tracer test
Tracer test simulation was performed to estimate the average oil saturation
within the swept pore volume at the end of the waterflood. The key equations needed
to calculate swept pore volume and oil saturation are given below (Asakawa, 2005).
Asakawa (2005) has extended the derivation of the method of moments to include
three-dimensional, heterogeneous reservoirs.
The swept pore volume is defined as the pore volume of the reservoir
contacted by the injected fluid. The swept pore volume (Vs) can be calculated from
the produced tracer concentrations as follows:
217
V (K 1) V1 (K 2 1)
Vs = 2 1
K1 K 2
(7 1)
The definition of Vi (the mean residence volume of tracer i) depends on the

injection scheme for the tracers for example as a finite slug or continuous injection.
Ki is the partitioning coefficient of the tracer i (1 and 2).
The average oil saturation in the swept pore volume can be calculated as
follows:
S o =
V1 V2
(7 2)
V2 (K1 1) V1 (K 2 1)
The partition coefficient of tracer i is defined as follows:

Ki =
Cio
Ciw
(7 3)
Cij is the concentration of tracer i in phase j. The subscripts o and w stand for oil and
water. For a tracer slug during two-phase flow of oil and water, Vi is defined as
follows:
qCit t dt
Vi = 0
Cit dt
Vslug
(7 4)
Cit is the total concentration of tracer i; q is the liquid flow rate; Vslug is the volume of
tracer slug; and t is time.
The total effluent tracer concentration is defined as follows:
218
Cit = f w Ciw + f o Cio
(7 5)
fw and fo are the fractional flow of the oil and water.

One conservative and two partitioning tracers with partition coefficients of
K i = 0,1, and 2 were injected after the waterflood for 0.3 PV and were followed by
3.0 PVs of water injection with no tracers added. Figure 7.56 shows the tracer
concentration in the middle producer. Sweep efficiency and swept pore volume were
calculated from the method of moments (Figures 7.57 and 7.58).
Table 7.13 shows the oil saturation calculated for each pair of tracers. The
average oil saturation within the swept pore volume at the end of waterflood is
calculated to be about 0.18. This average oil saturation for chemical flooding is not
very large; therefore, the relatively low oil recovery (about 20% OOIP) presented in
the following sections can be explained by the low starting average oil saturation.
7.7.3 Sensitivity Simulations for Chemical Flooding
7.7.3.1 Chemical Slug Injection Design
In this section, we investigate the effect of chemical slug injection design. The
question is; "For a fixed mass of surfactant, is a large dilute slug or a small
concentrated slug preferred?". To study the effect of slug size on oil recovery for a
fixed mass of surfactant, the following assumptions were made.
Co- solvent was excluded.
219
The product of slug size (%PV) and surfactant concentration (vol. %) was
30%.
During the injection of surfactant slug, salinity was kept at optimum (0.85
wt% Na2CO3).
The effect of salinity on polymer viscosity was not modeled. A constant

polymer concentration of 2200 ppm polymer was injected for 1.15 PVs which
includes the slug and the drive.
Five different cases were investigated so that the product of surfactant

concentration and slug size remains the same. Surfactant concentration was
varied from 3.0, 2.0, 1.0, 0.5 to 0.3% and surfactant slug size changed from
10, 15, 30, 60, 100% PV, respectively. Table 7.14 gives the details for each
case.
Figure 7.59 shows the oil recovery plot for all these cases. The range of oil
recovery is from 12 to 15%OOIP. The lowest oil recovery is for the largest slug size
of 1 PV with the 0.3 wt% surfactant concentration and the highest recovery is for the
case with 1 wt% surfactant and 0.3 PV slug size. Figure 7.60 shows the effect of slug
size for a fixed mass of surfactant at the end of the chemical flood. It appears that the
oil recovery passes through a maximum. Figure 7.61 compares the oil recovery for
10% and 30% PV slug size. 1 wt% surfactant injected for 30% PV recovers more oil
than the 3 wt% surfactant injected for 10% PV. Profiles of the effective salinity and
surfactant concentration are plotted in layer 10 between one injector and one producer
at 0.5 PV (Figures 7.62 and 7.63). Comparing the results in Figures 7.62 and 7.63
220
shows that salinity for 1 wt% surfactant and 30% slug size can reach the optimum
whereas for the smaller slug size salinity can not reach the optimum. This is the
reason for the higher oil recovery for larger slug size. A more careful study needs to
be done to take into account the effect of co-solvent and the impact on the optimum
salinity to draw a more concrete conclusion.
7.7.3.2 Base Case
The waterflood oil recovery was very similar for the ten permeability
realizations. The injection and pressure constraints were the same as before with 1300
psi injection pressure and 300 psi producing BHP. The laboratory coreflood designs
were utilized to develop the base case injection scheme for the chemical flood. Base
case design is summarized in Table 7.15. The chemical formulation, injection
scheme, and the physical properties are also based on coreflood BM-07 (Table 7.6).
0.15 PV ASP slug contains 2 wt% surfactant, 3 wt% EGBE, 0.85 wt% Na2CO3, 2500
ppm AN125. The main difference for the field scale simulation compared to the
coreflood was that we did not model the reactions in the field scale simulation. This
simplification was justified since the crude oil did not contain acidic components to
generate soap. Also, it was shown that consumption was not significant for a clean
sandstone rock. Surfactant adsorption was adjusted to represent the lower adsorption
value due to injection of alkali. However, sensitivity analysis on the surfactant
adsorption was performed as an uncertainty parameter. Other than the geochemical
option, all the other chemicals such as surfactant, DGBE, and polymer were modeled
221
and the concentration of injected sodium carbonate was modeled as the total anion
concentration.
Table 7.15 shows the design of the base case. A 0.15 PV slug was injected
containing 2 wt% surfactant, 3 wt% EGBE, and 0.85 wt% Na2CO3 to reach the
optimum salinity of about 1 wt% Na2CO3. 2500 ppm AN125 polymer was added to
the slug. The polymer drive was injected for 1.0 PV. An initial 0.2 PV polymer drive
contained 0.65 wt% Na2CO3, 1.5 wt% EGBE, and 2200 ppm of the polymer. The
second polymer drive injected 0.8 PV with 1800 ppm polymer in formation brine.
The polymer concentration reduced in each stage to compensate the change in
salinity. The oil recovery for the base case is 17% OOIP. Figure 7.64 shows oil
concentration at the end of chemical flood for the base case design.
7.7.3.3 Sensitivity on Design Parameters
The base case design was adopted in the coreflood to make sure that 100% oil
recovery is obtained. Since EGBE is very costly, any efforts to reduce or remove this
chemical makes the project more economically feasible.
Table 7.16 lists all the cases studied to optimize the design for this reservoir
with the formulation including EGBE. The concentration of EGBE remains 3 wt%.
The first sensitivity (Case 2) was to eliminate the first polymer drive which contains
the EGBE and sodium carbonate. This case gives the same oil recovery (~17%) as the
base case and it is more cost effective due to elimination of EGBE in the polymer
drive. All the other cases are run without EGBE in the polymer drive.
222
Case 3 is similar to Case 2, but Case 3 has a higher polymer concentration in

the slug and the drive. Polymer concentration increases from 2500 to 3000 ppm in
slug and from 1800 to 2200 ppm in the drive. The oil recovery increased by about
2%. All the later cases are run with 3000 and 2200 ppm polymer concentration in the
slug and drive, respectively. The increase in polymer concentration decreases the
mobility and consequently enhances the sweep efficiency resulting in a better oil
recovery. The importance of achieving optimum salinity at the same time as the
surfactant slug propagates has already been emphasized. Figure 7.65 illustrates the
effective salinity and surfactant concentration between one injector and producer in
layer 10 for Case 3. It is observed that the effective salinity does not reach the
optimum. Therefore, the next simulations conducted were Cases 4 and 5 where the
salinity of the slug was increased from 0.85 wt% Na2CO3 to 1.0 and 1.5 wt%
Na2CO3. Figure 7.66 shows how the effective salinity increased to about optimum
salinity (Case 5). The oil recovery in Cases 4 and 5 is about 20 and 21.5% OOIP,
respectively, compared to 19% OOIP for Case 3. In Case 5, the Na2CO3 concentration
was almost doubled to 1.5 wt% Na2CO3 resulting in an oil recovery of 21.5% OOIP,
or 2.5% increase compared to the base case. However, this needs to be tested in the
laboratory in terms of aqueous stability to make sure that the increase in Na2CO3
concentration does not cause any problems. Figure 7.67 shows the effluent
concentration of polymer, EGBE, surfactant and salinity from the middle producer for
Case 5. It is observed the peak of salinity, surfactant and cosolvent all coincide and
the salinity has reached the optimum value.
223
In the next two Cases 6 & 7, a smaller slug size was tested. These cases were
performed because small slug size translates to a lower chemical cost. A 0.1 PV slug
was injected in Case 6 instead of 0.15 PV in the base case. The slug salinity was 1.0
and 1.5 wt% Na2CO3 for Cases 6 and 7, respectively, and the oil recovery was 19.3
and 20.4% OOIP for Cases 6 and 7, respectively. The oil recovery decrease in these
cases compared to Cases 4 and 5 can be explained by the fact that the salinity of the
slug is not sufficient to reach the optimum salinity, due to the small slug size.
The Case 5 chemical design was tested on realizations 1, 2, 3, 5 and 7. Figure
7.68 shows the oil recovery for all these cases. The chemical oil recovery ranges from
45 to 55% ROIP (20 to 25% OOIP). This variation shows the uncertainty of the oil
recovery due to heterogeneity.
7.7.3.4 Summary and Conclusions for Series II Simulations
This section presents 3D simulations of high pH chemical flooding in a sandstone

reservoir with a temperature of about 85 oC taking into account the uncertainty in
reservoir properties such as permeability, porosity, and initial water saturation. The
surfactant formulation is the same as that used in Corefloods BM-07 and M5. The
simulation model is an 18-acre regular 7-spot well pattern. A finer grid cells are used
to reduce the numerical dispersion observed in the earlier simulations (Series I). Ten
different permeability realizations are simulated and oil recoveries are compared.
The effect of slug size is also investigated. Additional simulations are performed to
224
optimize the design by reducing the chemical requirements. A summary of the key
results are listed below.
The oil recovery at the end of the waterflood for 10 realizations varies from
54.8 to 58.3 %OOIP.
Tracer simulations are performed at the end of the waterflood to obtain the
swept poer volume and the average oil saturation within the swept volume.
The average oil saturation is calculated to be about 0.18. This low remaining
oil saturation resulted a relatively low chemical oil recovery of about 20 to
25%OOIP.
The chemical oil recovery ranges from 45 to 55% ROIP ( 20 to 25 % OOIP)

for Realizations 1, 2, 3, 5, and 7.
The effect of slug size keeping the same mass of surfactant is studied with
different combinations of slug size and surfactant concentration. The results
indicate that the oil recovery is higher with a larger slug size (30% vs. 10%
PV). However, a more careful study needs to be done to take into account the
effect of co-solvent and the impact on the optimum salinity to draw a more
concrete conclusion.
Optimization simulations show that, by eliminating the cosolvent in the first

polymer drive, the chemical costs can be reduced significantly.
225
Table 7.1: Rock and fluid properties for Coreflood M1

Porosity
0.14
Permeability, md
448
0.32
Waterflood residual oil saturation
0.35
Endpoint oil relative perm.
0.35
Endpoint water relative perm.
0.08
Water viscosity (85oC), cp
0.37
Oil viscosity (85oC), cp
8.0
Table 7.2: Core M1 flood design

Alkaline/Surfactant/Polymer Slug
0.1 PV
3.0 wt% IOS C20-24 (batch#26519844-2) with 1.0 wt% n-Pentanol and 1.0 wt% SBA
1.0 wt% Na2CO3
2500 ppm AN125 (lot#UB 4558)
19,000 ppm NaCl
flow rate: 0.5 ml/min
Polymer Drive
1.6 PV
2500 ppm AN125 (lot#UB 4558)
10,000 ppm NaCl
1.0 wt% Na2CO3
flow rate; 0.5 ml/min
226
Table 7.3: Summary of UTCHEM phase behavior input parameters

HBNC70
HBNC71
HBNC72
0.05
0.045
0.06
CSEL
CSEU
0.4 meq/ml (12,362.3 ppm NaCl)
0.667311 meq/ml (28,000 ppm NaCl)
Table 7.4: Corefloods BM-07 and M5 properties

Core BM-07
Core M5
Core BM-08
Permeability, md
1300
1500
1540
Porosity, fraction
0.165
0.165
0.174
Oil viscosity, cp
3.4
3.4
3.4
Temperature, C
85
85
85
Length, ft
Table 7.5: Synthetic brine composition

Na
900 ppm
Ca
20 ppm
Mg
5 ppm
15 ppm
Cl
800 ppm
SO4
18 ppm
HCO3
1100 ppm
Total Dissolved Solids: 2,858 ppm
227
Table 7.6: Core flood BM-07 and M5 designs

Coreflood BM-07
Coreflood M5
Coreflood BM-08
0.15 PV ASP
0.2 PV ASP
0.1 PV ASP
2 wt% Surfactant
2 wt% Surfactant,
2 wt% Surfactant
3 wt% EGBE,
3 wt% EGBE,
3 wt% EGBE,
0.85 wt% Na2CO3
0.85 wt% Na2CO3
0.85 wt% Na2CO3
added to formation
added to formation brine
added to formation brine
brine (Table 7.5)
(Table 7.5)
(Table 7.5)
2500 ppm AN125
2500 ppm AN125
2500 ppm AN125
0.2 PV
0.2 PV
1.5 wt% EGBE,
1.5 wt% EGBE,
0.65wt % Na2CO3,
0.65wt % Na2CO3,
2200 ppm AN125
2200ppm AN125
Polymer
~1.5 PV
~1.5 PV
~1.5 PV
drive II
1800 ppm AN125
1800 ppm AN125
1800 ppm AN125
Surfactant
slug
Polymer
drive I
228
Table 7.7: Coreflood simulations for optimization

Simulation
Coreflood M5
Surfactant slug containing 0.2 PV ASP
Optimization simulations
#1
#2
#3
0.2 PV
0.15 PV
0.1 PV
_______
_______
_______
~1.5 PV
~1.5 PV
~1.5 PV
0.85 wt% Na2CO3 added 2 wt% Surfactant

to the formation brine 3 wt% EGBE
(Table 7.5)
2500ppm AN 125
Polymer drive I containing 0.2 PV

0.65 wt% Na2CO3 added to 1.5 wt% EGBE
the formation brine
2200 ppm AN 125
(Table 7.5)
Polymer drive II
~1.5 PV
formation brine
1800 ppm AN 125
(Table 7.5)
Adsorption (mg/g rock)
0.1
0.1
0.1
0.1
Oil Recovery, %OOIP
98
92
90
87
229
Table 7.8: Sensitivity simulations for Series I

polymer drive (1)
polymer drive (2)
slug slug
polymer
polymer %
Comments
Case Sensitivity size, salinity, polymer polymer drive polymer polymer drive
ROIP
conc.
drive conc.
PV meq/ml drive
salinity,
salinity,
size, PV ppm
size, PV ppm
meq/ml
meq/ml
1500ppm
polymer at
polymer
1
___
___ 100%
1500
0.0513 ___
___
___
26
flood
formation
salinity
Keeping the
20% of
2 base case 15% 0.225 20%
2000
0.225
80%
1700
0.1
51 polymer drive
at optimum
salinity
Keeping the
salinity of
40% of
3 polymer 15% 0.225 40%
2000
0.225
60%
1700
0.1
61 polymer drive
drive
at optimum
salinity
Same as 3surf. slug
4
20% 0.225 40%
2000
0.225
60%
1700
0.1
68 surfactant slug
size
size=20% PV
Same as 3surf. slug
5
25% 0.225 40%
2000
0.225
60%
1700
0.1
72 surfactant slug
size
size=25% PV
Same as 3Keeping the
slug
6
15% 0.3
40%
2000
0.225
60%
1700
0.1
61
slug salinity
salinity
higher than
optimum
Same as 3Preflush at
7 preflush 15% 0.225 40%
2000
0.225
60%
1700
0.1
64
optimum
salinity for
20% PV
Same as 38
kv/kh
15% 0.225 40%
2000
0.225
60%
1700
0.1
44
kv/kh=0.1
Same as 3- half
9 Surf. ads. 15% 0.225 40%
2000
0.225
60%
1700
0.1
63
adsorption
230
Table 7.9: Sector model specifications for series II

No. of grids
74,777
NX
43
NY
47
NZ
37
Reservoir length, ft
2115
Reservoir width, ft
2057
Reservoir thickness, ft
40
Depth to pay, ft
2025.15
Initial pressure, psi
550
Table 7.10: Modified Corey water relative permeability data

kx <700 md
700 md< kx <1400 md
kx >1400 md
Water endpoint
0.405
0.385
0.365
Water exponent
1.25
1.35
1.5
Table 7.11: Modifed Corey oil relative permeability data

kx <700 md
700 md< kx <1400 md
kx >1400 md
Oil endpoint
1.0
1.0
1.0
Oil exponent
3.75
2.75
1.75
231
Table 7.12: Fluid properties for simulations Series II

Water density
62.43 lb/ft3
Oil density
54.33 lb/ft3
Water viscosity
0.3 cp
Oil viscosity
2.7 cp
Water/oil IFT
30 dynes/cm
Water compressibility
3x10-6 psi-1
Oil compressibility
1x10-5 psi-1
Table 7.13: Oil saturation calculated for each pair of tracers for Series II simulations
(base case)
Oil saturation
K = 0.0 and 1.0
K = 1.0 and 2.0
K = 0.0 and 2.0
0.188
0.176
0.183
Table 7.14: Dilution Sensitivity Study for Series II
Surfactant slug
containing
0.85 wt% Na2CO3
Case #1
Case #2
Case #3
Case #4
Case #5
1.0 PV ASP
0.6 PV ASP
0.3 PV ASP
0.15 PV ASP
0.1 PV ASP
0.3 wt%
0.5 wt%
1.0 wt%
2.0 wt%
3.0 wt%
Surfactant
Surfactant
Surfactant
Surfactant
Surfactant
0.15 PV
0.55 PV
0.85 PV
1.0 PV
1.05 PV
12.5%
14.5%
15.2%
14.5%
13.5%
2200 ppm AN125

in formation brine
Polymer drive
containing
2200 ppm AN125
Oil
recovery,
%OOIP
232
Table 7.15: Base case design for Series II

Case #1_ Base case
Based on BM-07 coreflood
Surfactant slug
0.15 PV ASP
1.5 wt% CS2000A Batch 2,0.5 wt% XC6251C,
3 wt% EGBE, 0.85 wt% Na2CO3
, 2500 ppm AN125 in formation brine
Polymer drive I
0.2 PV of 1.5 wt% EGBE, 0.65 wt% Na2CO3

, 2200 ppm AN125 in formation brine
Polymer drive II
0.8 PV
1800 ppm AN125 in formation brine
Oil recovery , %OOIP
17%
233
Table 7.16: Sensitivity Simulations for Series II

Case #1
Case #3
Case #4
Case #5
Case #6
Case #7
Surfactant 0.15 PV
0.15 PV 0.15 PV
0.15 PV
0.15 PV
0.1 PV
0.1 PV
slug
2.0wt%
2.0 wt% 2.0 wt%
2.0 wt%
2.0 wt%
3.0 wt%
3.0 wt%
3 wt%
Surfactant
Surfactant Surfactant, Surfactant
EGBE
0.85 wt %
0.85 wt% 0.85%
1.0%
1.5%
1.0%
1.5%
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
2500 ppm
2500 ppm 3000 ppm 3000 ppm
3000 ppm
3000 ppm 3000 ppm
AN125
AN125
AN125
AN125
AN125
AN125
AN125
1.0 PV
1.0 PV
1.0 PV
1.05 PV
1.05 PV
Polymer
0.2 PV
drive I
1.5 wt%EGBE,
Case #2
Na2CO3
Surfactant, Surfactant Surfactant
0.65 wt%
Na2CO3
2200 ppm
AN125
Polymer
0.8 PV
1.0 PV
drive II
1800 ppm
1800 ppm 2200 ppm 2200 ppm
2200 ppm
2200 ppm 2200 ppm
21.5%
19.3%
Increased
Reduced Increased
polymer
%OOIP
17%
17%
19%
20%
Comment
Same as
Polymer Increased Increased
20.4%
coreflood BM- drive I
polymer
alkali conc. alkali conc. the slug
07
conc. in
from 0.85% from 1.0 % (Keeping conc. from
was
excluded slug and

drive
234
to 1%
the alkali
to 1.5%
the
1.0 % to
(case4)
product
1.5%
30%)
(case6)
16
Lab- Oil Sol. Ratio
Lab-Water Sol. Ratio
Model-Oil Sol. Ratio
Model-Water Sol. Ratio
14
12
10
Temp = 85 C
After 22 days
8
6
4
2
0
0
5000
10000
15000
20000
25000
30000
35000
Electrolyte Concentration (ppm NaCl)
Figure 7.1: Phase behavior data and UTCHEM match (used in Coreflood M1
(poly vis-water vis)/ water vis
100
y = 16.816x-0.3849
10
1
0.01
1
Csep,meq/ml
Figure 7.2: AN 125 Polymer viscosity vs. effective salinity (2500 ppm AN-125,
Temp @ 85oC, Shear rate = 11 sec-1)
235
12
10
viscosity(cp)
0
0
0.05
0.1
0.15
0.2
0.25
0.3
Polymer concentration (wt%)
Figure 7.3: AN 125 Polymer viscosity vs. concentration (85oC, 2 wt% NaCl and 11
sec-1)
Viscosity (cp)
100
Lab
Correlation
10
1
0.1
10
100
1000
shear rate (1/sec)
Figure 7.4: AN 125 Polymer viscosity vs. shear rate (2500 ppm AN-125, Temp @ 80
C with 2wt% NaCl and 1wt% Na2CO3)
236
16.0
Microemulsion Viscosity, cp
14.0
12.0
10.0
8.0
6.0
4.0
2.0
0.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Oil Concentration in Microemulsion, C23
Figure 7.5: Calculated microemulsion viscosity (Coreflood M1)

0.35
Ads. Surf. Conc., mg/g
0.3
0.25
0.2
0.15
0.1
0.05
0
0
0.01
0.02
0.03
0.04
0.05
Surfactant Concentration in Microemulsion, vol. fraction
Figure 7.6: Calculated surfactant adsorption isotherm

237
0.06
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
1
11
13
pH
Figure 7.7: Calculated surfactant adsorption concentration as a function of pH

0.4
Residual Oil Saturation, Sor
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
1.E-08
1.E-07
1.E-06
1.E-05
1.E-04
Capillary number, Nc
Figure 7.8: Oil capillary desaturation curve

238
1.E-03
1.E-02
1.E-01
1.0
0.9
0.8
0.7
kro
krw
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0.0
0.2
0.4
0.6
0.8
1.0
Figure 7.9: Relative permeability for the Berea Coreflood (M1)

1
(S1*, f1*)
(S1I, f1I)
0.9
Fractional Flow of Water, fw
0.8
0.7
0.6
(S1B, f1B)
0.5
0.4
Water-Oil
Surfactant-Polymer-Oil
0.3
0.2
0.1
0
-0.2
0.0
0.2
0.4
0.6
Figure 7.10: Fractional flow curve for the Berea Coreflood M1

239
0.8
1.0
100%
80%
70%
Measured- Oil Recovery

Measured -Oil Cut
UTCHEM- Oil Recovery
UTCHEM- Oil Cut
60%
50%
40%
30%
20%
10%
0%
0.00
0.25
0.50
0.75
1.00
1.25
Pore Volumes
1.50
1.75
2.00
Figure 7.11: Measured and modeled oil recovery (% OOIP) and oil cut for Coreflood
M1
12
10
Pressure Drop [psi]
% Total Oil Recovered and Oil Cut
90%
Measured
UTCHEM
6
0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
Pore Volumes
Figure 7.12: Pressure drop history match (across the core) for Coreflood M1
240
2.0
0.9
0.025
0.7
0.020
CSEU
Salinity, meq/ml
0.6
Salinity
0.015
0.5
CSEL
0.4
0.010
0.3
0.2
0.005
0.1
0.0
Surfactant concentration, volume fraction
Surfactant
0.8
0.000
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 7.13: Effective salinity and surfactant concentration profiles at 0.5 PV for
Coreflood M1
11
pH
Surfactant
10
0.020
pH
0.015
8
0.010
7
0.005
0.000
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 7.14: pH and surfactant concentrations at 0.5 PV for Coreflood M1

241
Surfactant concentration, volume fraction
0.025
0.35
Surfactant adsorption, mg/g rock
0.3
0.25
Not pH dependence
pH dependence
0.2
0.15
0.1
0.05
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 7.15: Surfactant adsorption profile modeled with and without the effect of pH
at 0.5 PV for Coreflood M1
Adsorbed cation concentration, meq/ml PV
0.030
0.025
Hydrogen
Sosdium
0.020
0.015
0.010
0.005
0.000
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 7.16: Adsorbed sodium and hydrogen concentrations on the clay at 0.5 PV
(Coreflood M1)
242
Figure 7.17: Partition coefficient of the co-solvent with formation water and oil (The
slope of the line indicates the partitioning coefficient) (Dwarakanath et al., 2008)
Figure 7.18: The effect of cosolvent on the effective salinity and phase behavior
(Dwarakanath et al., 2008)
243
16
Oil
Water
Oil-UTCHEM
Water-UTCHEM
12
0
0
2000
4000
6000
8000
10000
12000
14000
Figure 7.19: Comparison of measured and UTCHEM solubilization parameters for

the formulation containing EGBE
1.2
Optimal Salinity, S* (wt% Na2CO3)
1.1
1.0
0.9
0.8
0.7
0.6
S*
0.5
UTCHEM
0.4
0.3
0.2
0.1
0.0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
% EGBE
Figure 7.20: The effect of cosolvent concentration on optimal salinity where points
are the lab data and line is the model (formulation containing the EGBE)
244
20
SP
18
Not Equilibrated
Optimal Solubilization, SP
16
Linear (UTCHEM)
14
12
10
8
6
4
2
0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
% EGBE
Figure 7.21: The effect of cosolvent concentration on optimum solubilization ratio

where points are lab data and line is the model (formulation containing the EGBE)
0.25
0.2
0.15
0.1
0.05
0
0
0.01
0.02
0.03
0.04
0.05
0.06
Surfactant Concentration in Microemulsion, vol. fraction
Figure 7.22: Surfactant adsorption isotherm for formulation containing the EGBE
(Corefloods BM-07 and M5)
245
Surfactant adsorption, mg/g rock
0.25
0.2
0.15
0.1
0.05
0
1
11
13
pH
Figure 7.23: Surfactant adsorption as a function of pH (formulation containing the

EGBE, corefloods BM-07 and M5)
Normalized tracer concentration
0.1
0.01
0.001
Simulated tracer- Capacitance model
experimental data
Simulated tracer
0.0001
0
0.5
1.5
PVs
Figure 7.24: Simulated and measured tracer concentrations for coreflood BM-07
246
2.5
100%
Cum Oil Recovered (%) and Oil Cut
90%
80%
Cum Oil
70%
Oil Cut
UTCHEM-Cum Oil
60%
UTCHEM-Oil Cut
50%
40%
30%
20%
10%
0%
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
Pore Volumes
Figure 7.25: UTCHEM and measured oil cut and oil recovery (% OOIP) for
Coreflood BM-07
6
Pressure Drop, psi/ft
BM-07- pressure data measured
UTCHEM
0
0.0
0.2
0.4
0.6
0.8
1.0
PVs
1.2
1.4
1.6
Figure 7.26: Pressure drop (along the core) match for Coreflood BM-07
247
1.8
2.0
0.8
0.7
Surf %
0.6
Surf Conc (%)
Surf %-UTCHEM
0.5
0.4
0.3
0.2
0.1
0.0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
Pore Volumes
Figure 7.27: Surfactant concentration match for Coreflood BM-07

12000
BM-07, EGBE
EGBE Concentration (ppm)
UTCHEM- EGBE
9000
6000
3000
0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
Pore Volumes
Figure 7.28: Cosolvent (EGBE) concentration match for Coreflood BM-07
248
1.8
2.0
12
11
10
pH
9
pH-UTCHEM
pH
7
6
5
4
3
2
1
0
0.0
0.3
0.5
0.8
1.0
1.3
1.5
1.8
2.0
Pore Volumes
Figure 7.29: pH match for the coreflood BM-07

0.08
species concentration, eq/L
0.07
0.06
CO3--
0.05
0.04
0.03
0.02
HCO3-
0.01
0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
PVs
Figure 7.30: Measured and UTCHEM carbonate and bicarbonate concentrations for
Coreflood BM-07 (points: experimental and curves: UTCHEM simulation)
249
2.0
0.030
Oil
0.50
0.025
EGBE
0.40
0.020
Surfactant
0.30
0.015
CSEU
0.20
0.010
Salinity
Polymer
CSEL
0.10
0.005
0.00
0.000
0
0.2
0.4
0.6
0.8
Figure 7.31: Surfactant, oil, cosolvent, polymer concentrations and effective salinity
profiles at 0.5 PV for Coreflood BM-07
100%
90%
Cum Oil Recovered (%)

Oil Concentration
80%
70%
60%
Cum Oil
50%
Oil Cut
UTCHEM-Cum Oil
40%
UTCHEM- Oil Cut

30%
20%
10%
0%
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
Pore Volumes
Figure 7.32: Comparison of UTCHEM and measured oil concentration and oil
recovery (%OOIP) for coreflood M5
250
Surfactant and EGBE concentration, v/v
Salinity, meq/ml- Polymer, wt%- Oil, v/v
0.60
100%
90%
Oil Recovered, Oil Cut
80%
Cum Oil
Oil Cut
Cum Oil-UTCHEM
Oil Cut-UTCHEM
70%
60%
Slug (0.1PV)
1.5% CS2000
0.5% IOS (6300M)
3% EGBE
0.85% Na2CO3
2500ppm AN-125
50%
40%
30%
Chase (1.3PV)
0.25% EGBE
1800ppm AN-125
20%
10%
0%
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Pore Volumes
Figure 7.33: Comparison of UTCHEM and measured oil recovery (% OOIP) and oil
cut for Coreflood BM-08
Figure 7.34: Top view of the regular 7-spot pattern for the sector model
251
Figure 7.35: Grid top of the regular 7-spot pattern for the sector model, ft
Figure 7.36: Pressure of the regular 7-spot pattern for the sector model, psi
252
Figure 7.37: Porosity of the regular 7-spot pattern for the sector model
Figure 7.38: Permeability of the regular 7-spot pattern for the sector model, md
253
Figure 7.39: Comparison of the water flood oil recovery for the regular and inverted
7-spot patterns, cumulative oil recovery is reported in fraction of OOIP
Figure 7.40: Comparison of the chemical flood oil recovery for the regular and
inverted 7-spot patterns, cumulative oil recovery is reported in fraction of ROIP
254
80
Oil Recovery of different sensitivities,
%ROIP
Run 1-Polymerflood
Run 2-Base Case
Run 3-Increase of polymer drive salinity
Run 4-Increase of Surfactant Slug to 20%PV
Run 5-Increase of Surfactant Slug to 25%PV
Run 8-kv/kh=0.1
70
60
50
40
30
20
10
0
0
50
100
150
Time, days
200
250
300
Figure 7.41: Oil recovery vs. time for different sensitivity analysis (Series I)
Injectors and producers rates, b/d
25000
20000
15000
10000
Producer
5000
Injectors
0
0
50
100
Time, days
Figure 7.42: Injection and production well flow rates (Case 3)

255
150
200
0.35
2.0
1.6
salinity, meq/ml
0.25
Slug salinity or optimum salinity

1.2
0.20
0.15
0.8
CSEL
surfactant
0.10
0.4
0.05
surfactant concentration, wt%
CSEU
0.30
Initial salinity
0.00
0.0
0
0.2
0.4
0.6
0.8
Dimensionless distance
Figure 7.43: Effective salinity and surfactant concentration in the second layer
between one full injector (#6) and the middle producer (Base case)- 0.5 PV
0.35
0.020
0.014
Slug Salinity
0.012
0.20
0.010
0.15
CSEL
0.008
0.006
0.10
0.004
0.05
surfactant concentration, wt%
0.016
0.25
salinity, meq/ml
0.018
CSEU
0.30
0.002
0.00
0.000
0
0.2
0.4
0.6
0.8
Figure 7.44: Effective salinity and surfactant concentration in the second layer
between one full injector (#6) and the middle producer (Case 3) - 0.5 PV
256
Figure 7.45: Top view of the fine mesh model
Figure 7.46: Horizontal permeability (md) of the realization 1
257
Figure 7.47: Vertical permeability (md) of the realization 1
Figure 7.48: Porosity of the realization 1
258
Figure 7.49: Cross-section of the horizontal permeability (md) of the realization 1
Figure 7.50: Cross-section of the porosity of the realization 1
259
Figure 7.51: Initial water saturation for realization 1
Figure 7.52: Cross-section showing the residual water saturation for realization 1
260
Figure 7.53: Cross-section showing the residual oil saturation for realization 1
60
50
%OOIP
40
30
Rea lization0 1
Rea lization0 2
Rea lization0 3
Rea lization0 4
Rea lization0 5
Rea lization0 6
Rea lization0 7
Rea lization0 8
Rea lization0 9
Rea lization1 0
20
10
0
0
P Vs
Figure 7.54: Waterflood oil recovery for different realizations, Y axis is the
cumulative oil recovery and x axis is the pore volumes
261
Figure 7.55: Oil saturation profile at the end of the waterflood for the realization 1
Normalized concentration
0.1
0.01
Ki=2.0
Ki=1.0
Ki=0.0
0.001
0.0001
0
50
100
150
200
Time, days
Figure 7.56: Tracer concentrations following the waterflood for realization 1

262
250
1
0.9
0.8
Ki=2.0
Sweep Efficiency
0.7
Ki=1.0
0.6
Ki=0.0
0.5
0.4
0.3
0.2
0.1
0
0
50
100
150
200
250
Time, days
Figure 7.57: Sweep efficiency calculated from the tracer test simulation
2.5E+07
Ki=2.0
2.0E+07
Swept pore volume, ft
Ki=1.0
Ki=0.0
1.5E+07
1.0E+07
5.0E+06
0.0E+00
0
50
100
150
200
Time, days
Figure 7.58: Swept pore volume calculated from the tracer test simulation
263
250
20
18
16
14
%OOIP
12
10
8
2.0%surfactant x 15%PV
4
0
0
0.2
0.4
0.6
0.8
PVs
1.2
1.4
1.6
Figure 7.59: Cumulative oil recovery for the effect of dilution sensitivity cases
20
18
16
14
%OOIP
12
10
8
6
4
2
0
0
20
40
60
80
100
120
Surfactant Slug, %PV
Figure 7.60: Effect of the surfactant slug size on the cumulative oil recovery with
fixed mass of surfactant.
264
20
18
16
14
%OOIP
12
10
8
6
2
0
0
0.2
0.4
0.6
0.8
PVs
1.2
1.4
1.6
Figure 7.61: Comparison of the oil recovery for 10% and 30% PV slug size
0.30
0.016
0.012
Salinity, meq/ml
0.20
0.010
Salinity
0.15
0.008
0.006
0.10
CSEL
0.004
0.05
0.002
Surfactant
0.00
0.000
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 7.62: Effective salinity and surfactant concentration between one full injector
(#6) and the middle producer in layer 10 (1 wt% surfactant and 30% PV) @ 0.5 PV
265
Surfactant concentration, vol fraction
0.014
CSEU
0.25
0.016
Surfactant
0.014
CSEU
0.25
0.012
Salinity, meq/ml
0.20
0.010
0.15
0.008
Salinity
0.006
0.10
CSEL
0.004
0.05
0.002
0.00
0.000
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 7.63: Effective salinity and surfactant concentration between one full injector
(#6) and the middle producer in Layer 10 (3 wt% surfactant and 10% PV) @ 0.5 PV
Figure 7.64: Final oil saturation for the base case simulation
266
Surfactant concentration, vol fraction
0.30
0.20
0.020
0.16
Salinity, meq/ml
CSEU
Surfactant
0.14
0.018
0.016
0.014
Salinity
0.12
0.012
CSEL
0.10
0.010
0.08
0.008
0.06
0.006
0.04
0.004
0.02
0.002
0.00
0.000
0
0.2
0.4
0.6
0.8
Surfactant concentration, vol

fraction
0.18
Figure 7.65: Surfactant concentration and effective salinity profile between one full
injector (#6) and the middle producer in layer 10 for Case 3- Series II
0.20
0.020
0.018
Salinity
0.16
Salinity, meq/ml
CSEU
Surfactant
0.016
0.14
0.014
0.12
0.012
CSEL
0.10
0.010
0.08
0.008
0.06
0.006
0.04
0.004
0.02
0.002
0.00
0.000
0
0.2
0.4
0.6
0.8
Surfactant concentration, vol

fraction
0.18
Figure 7.66: Surfactant concentration and effective salinity profile between one full
injector (#6) and the middle producer in layer 10 for Case 5- Series II
267
0.012
EGBE
Salinity, meq/ml
Polymer concentration, wt%
polymer
0.01
0.2
0.008
Salinity
0.15
0.006
0.1
0.004
0.05
Surfactant
0.002
0
0
20
40
60
80
100
120
Surfactant and EGBE, vol fraction
0.25
0
140
Time, days
Figure 7.67: Effluent concentration of polymer, EGBE, surfactant and salinity from
the middle producer (Case 5-Series II)
0.6
Chemical Oil Recovery
0.5
0.4
0.3
Realization 1
Realization 2
Realization 3
Realization 5
Realization 7
0.2
0.1
0
0
0.5
1
PVs
1.5
Figure 7.68: Chemical oil recovery for different realizations, y axis is the fraction of
remaining oil recovered due to chemical flood and x axis is the pore volumes injected
268
CHAPTER 8
Summary, Conclusions, and Recommendations
8.1 SUMMARY
This study focused on the mechanistic simulation of the alkaline-surfactantpolymer (ASP) chemical flooding process for enhanced oil recovery using the
UTCHEM simulator developed at the University of Texas. ASP flooding is a very
complex process due to the chemical reactions that occur at high pH between the
alkali and both the formation and the crude oil. The geochemical model in UTCHEM
was used to account for these reactions and the effect they have on alkali
consumption, the generation of soap and other effects of high pH such as reducing the
surfactant adsorption. Although Bhuyan (1989) developed the geochemical model in
UTCHEM and validated it for several cases, he did not simulate ASP flooding, which
was a new process at the time and not widely used until recently. Wu (1996) and
Delshad et al. (1999) did simulate ASP flooding, but new and more accurate
laboratory data, improved ASP models and much faster computing have enabled a
much more complete and systematic investigation than previously possible. More
recently, Liu et al. (2008) developed an ASP simulator and used it to match oil
recovery from a sandpack experiment, but their model does not include many of the
key features found in UTCHEM and is only one-dimensional as well.
269
The first step in this investigation was to determine what geochemical

reactions have the most impact on ASP flooding under different reservoir conditions
and to quantify the consumption of alkali by different mechanisms. After the most
important reactions were identified, ASP simulations with these reactions were
performed to better understand other important phenomena such as the effect of the
soap on the microemulsion phase behavior. Microemulsion phase behavior is the key
phenomena in both surfactant-polymer (SP) flooding and ASP flooding, so it was
both the first and most important part of the process to model. The phase behavior
model in UTCHEM was used to model the phase behavior data measured in the
laboratories of the Center for Petroleum and Geosystems Engineering at the
University of Texas (UT). Data for sodium carbonate and a blend of surfactants with
an acidic crude oil followed the conventional Winsor phase transition with significant
three phase regions even at a low surfactant concentration of 0.2 wt%. The effect of
soap on the phase behavior of the soap/surfactant mixtures was investigated and its
effect on both the optimum salinity and solubilization ratios modeled for the first
time.
The next logical step in the investigation was to simulate ASP core floods.
New ASP corefloods from the UT laboratories were successfully modeled taking into
account the aqueous reactions, alkali/rock interactions, and phase behavior of soap
and surfactant mixtures. These mechanistic coreflood simulations provided important
new insights into the validity of the ASP models and a better understanding of the
ASP process.
270
The final step was to do three-dimensional field simulations to better

understand high pH SP and ASP processes on the field scale and how to better design
these complex processes for pilot applications. Both field studies included the use of
alkali. One case involved a highly acidic crude oil with a significant impact of the
soap on the phase behavior. The other crude did not react with the alkali to form
soap, but geochemical reactions still had to be considered. Sensitivity simulations of
both the process design parameters and the key reservoir parameters were performed
to provide insight into the importance of each of these variables in chemical oil
recovery.
8.2 CONCLUSIONS
Several conclusions are highlighted based on the results discussed in the
previous chapters.
1.
Laboratory microemulsion phase behavior data were matched taking into

account the effect of soap concentration on the solubilization ratios and
optimum salinity. The UTCHEM phase behavior model and mixing rules for
surfactant and soap were validated using two sets of high quality data that
exhibit classical three-phase microemulsion behavior. The increase in the
solubilization ratio as the mole fraction of the soap increased in these cases
was very significant. This shows that it is very important to model both
surface active components and their effect on phase behavior when doing
mechanistic ASP simulations.
271
2.
The phase behavior model was found to be less accurate in the Type I and
Type II regions than in the Type III region. The data are also less accurate in
these regions because the solubilization ratios are lower and thus the values
are more difficult to measure, but fortunately the values matter less as well
since the ultra-low IFT occurs in the Type III region. Adjustment of the lower
and upper salinity limits (CSEL and CSEU) was used to better match the data.
Nevertheless, some refinement of the model to better match the Type I and II
data would be desirable.
3.
The reactions between the alkali and the minerals in the formation depend
very much on which alkali is used, the minerals in the formation, and the
temperature. The three alkalis studied in this research were sodium carbonate,
sodium metaborate and sodium hydroxide. Sodium carbonate is currently the
most commonly used alkali in ASP flooding and was also the alkali used in
the ASP data that were matched. Zhang et al. (2008) and Flaaten et al. (2008)
have recently reported new data showing that sodium metaborate can be used
in hard brine under some circumstances whereas sodium carbonate requires
soft water, so this was the motive for including some preliminary modeling
work on it in this study. Both these alkalis increase the pH to about 11
whereas sodium hydroxide increases it to about 13. Geochemical calculations
show that at a pH of 13 the reactions with kaolinite are significant and
consume large amount of alkali. With sodium carbonate at a pH of about 11,
the main source of consumption was found to be the exchange reaction
272
between H+ and Na+ on the clays. However, this reaction does not consume
large amounts of alkali or cause a significant retardation of the pH front unless
the exchange capacity is very large.
4.
Several ASP coreflood experiments were simulated with UTCHEM taking

into account the geochemistry, the reaction with the acid from the crude oil to
form soap, and the effect of these reactions on the phase behavior and physical
properties. A good agreement was obtained between the experimental data
and the simulations. As previously discussed, first the phase behavior is
matched. It is also important to model the polymer viscosity data and this is
simple to do using a spreadsheet with the UTCHEM models. Then matching
the oil recovery and other core flood data did not require extensive adjustment
of other input parameters. Although there are many input parameters, most of
them are either measured or reasonable estimates can be obtained from the
literature for commonly used cores such as Berea sandstone.
5.
The use of fractional flow curves is an extremely useful way to both

understand the performance of ASP floods and as a guide to how to match
core floods using a numerical simulator such as UTCHEM. A simplified
version of fractional flow theory (Pope, 1980) was used in this study, but it
still captured important aspects of the process such as the oil cut in the oil
bank, oil breakthrough time, and the effect of viscosity remarkably well. For
example, it is easy to show that the oil cut increases as the oil viscosity
increases (assuming sufficient polymer is used in the slug and drive to make
273
the displacement stable), which is not intuitively obvious. Additional insights

could still come from more use of fractional flow theory.
8.3 RECOMMENDATIONS
Several recommendations are made for the use and further development of the
UTCHEM simulator:
1. Some preliminary alkaline-polymer (AP) simulations were done to evaluate
the potential for AP flooding. Additional simulations to explore this potential
under different circumstances would be justified if specific data were
available for particular favorable reservoir conditions.
2. A spreadsheet should be developed to aid the user in matching the phase
behavior data to set up the input for ASP simulations.
3. A systematic method needs to be developed to scale up chemical flooding
processes from the laboratory to the field.
4. It is desirable to quickly set up the input and perform fast ASP simulations for
full field models. Therefore, a simplified but still mechanistic ASP model
should be developed and tested to determine the accuracy and computational
efficiency obtained from such simplifications.
274
APPENDIX A
EQBATCH Reaction Tables
This appendix describes chemical reactions for two typical cases introduced in
Chapter 3, and the consequent EQBATCH input needed for these reactions. Refer to
"UTCHEM_Users_Guide" and "UTCHEM_Tech_Doc" for more information on
EQBATCH Description. The next section, Appendix B, discusses in more detail the
step-by-step process for developing all the EQBATCH input and matching measured
data, using the Chapter 6 case study.
EQBATCH has been developed as a stand-alone software program to perform
batch reaction equilibrium calculations and to serve as a preprocessor for developing
UTCHEM geochemical input data. Once the key reactions are identified, the initial
reservoir equilibrium concentrations for the aqueous and solid species can be
determined by EQBATCH. It is assumed that all fluid species dissolve in the water
phase. The initial pH of the formation or makeup water can be matched by adjusting
EQBATCH input parameters as described in Appendix B. The output from
EQBATCH is directly used in the UTCHEM input file, as the geochemical input data.
The UTCHEM Technical Documentation (2000), especially Section 8,
"Mathematical Formulation of Reaction Equilibria," and Appendix C, "EQBATCH
Program Description," are essential references for using EQBATCH.
275
To determine the reactions that should be included in the UTCHEM

simulation, elements and chemical species need to be identified. Based on
information from the formation and makeup water analyses and from the rock
mineralogy data, the key elements and chemical species are selected. Any
combination of elements based on the brine species, oil, and rock can be considered
for modeling. However, elements such as hydrogen, sodium, calcium, magnesium,
carbonate, and chlorine are usually considered since these chemicals are the primary
ions contained in the formation and makeup water. A pseudo-element, oleic acid,
"A", is included when in-situ surfactant is generated in the presence of alkali. From
these elements, the expected chemical species involved in fluid reactions, clay
adsorption, cation exchange, and solid dissolution/precipitation reactions can be
specified.
This Appendix presents the use of EQBATCH to develop the UTCHEM
geochemical input for two examples; one a sandstone rock (Case 3.4 in Chapter 3,
Section 3.2.2.4) and one a carbonate rock (Case 3.9 in Chapter 3, Section 3.3.2.1).
The thermodynamic reaction equilibrium data at any temperature are found from the
Geochemists Workbench Release 6.0 database. The EQBATCH program has been
devised so that all the stoichiometric coefficients of the reactions, exponents of
different species in equilibrium relations, charges and equilibrium constants are
entered in tables as described below.
276
The first case is based on Example 3.4 (Section 3.2.2.4), modeling a sandstone
rock with cation exchange reactions.
The aqueous, dissolution/precipitation and
cation exchange reactions are as follows:

Aqueous Reactions:
H 2 O H + + OH
Ca 2 + + H 2 O Ca(OH)+ + H +
H + + CO32 HCO3
Ca 2 + + H + + CO32 Ca(HCO3 )+
2H + + CO32 H 2 CO3
Al3 + + 4H 2 O Al(OH)4 + 4H +
Cation Exchange Reactions:

+
H + Na + + OH Na + H 2 O
+
2Na + Ca 2 + 2Na + + Ca
2+
277
Dissolution/Precipitation Reactions:
Calcite precipitation
Ca 2+ + CO32 CaCO3
Quartz dissolution
H4SiO4 H3SiO4 + H+
Congruent kaolinite dissolution
Kaolinite + 4OH +3H2 O 2 Al(OH)4 + 2 H3SiO4
Incongruent kaolinite dissolution
Al2Si 2 O5 (OH)4 (Kaolinite) + 2Na + + 2OH + 2H4SiO4
2NaAlSi 2 O6 .H2 O(Analcime) + 5H2 O
Tables A.1 to A.10 detail all the reaction information needed, to set up the
EQBATCH input arrays for this example. Other data needed include acid number,
water saturation, species concentrations; development of these data is discussed in
Appendix B, for another case study. MS Excel spreadsheets have been developed to
facilitate preparation of these arrays and other EQBATCH inputs and may be
obtained upon request from the author or from Professor Mojdeh Delshad.
Table A1 is simply the list of elements and species in the reactions above.
Table A.2, the "AR" array in the EQBATCH and UTCHEM input data, is a listing of
the stoichiometric coefficients for each element in each fluid species (the subscripts in
the reactions above). Table A.3, the "BR" array in the EQBATCH and UTCHEM
input data, is the same as Table A.2, except it is for the solid species. Table A.4, the
278
"DR" array in the EQBATCH and UTCHEM input data, is the same as Tables A.2
and A.3, except it is for the adsorbed species.
Table A.5, the "BB" array in the EQBATCH and UTCHEM input data, is
determined from the exponents of the fluid species in the reactions, and may be
negative or positive, depending upon the species charge. Table A.6, the "EXSLD"
array, is the same as Table A.5, except for the solid species.
Table A.7, the "CHARGE" array, is the charge for each of the fluid species.
Table A.8, the "EQK" array in the EQBATCH and UTCHEM input data,
contains the equilibrium constants for the independent and dependent aqueous
species. The equilibrium constants for the independent species are, by definition, all
equal to "1". The equilibrium constants for the dependent species are obtained from
the Geochemist's Workbench Release 6.0 Database software (2008). Table A.8 lists
these constants at three different temperatures, even though UTCHEM requires these
data at only one temperature, the reservoir temperature, as isothermal conditions are
assumed. However listing the constants at three different temperatures in this table
indicates the large variation as a function of temperature for some species but not for
others. Furthermore, it highlights the importance of actually determining these values
for each study, rather than simply cutting and pasting from previous study
EQBATCH inputs, where the reservoir may have a different temperature.
Table A.9, the "EQK" array in the EQBATCH and UTCHEM input data, is
similar to Table A.7, except that it is for the sorbed species.
279
Table A.10, the "EXEX" array, is required for the two cation exchange
reactions; the values are positive for species on the right side of the reaction equations
and negative for species on the left side of the reaction equations (consistent with the
exponents in the exchange equilibrium constant equation).
The second case is based on Example 3.9 (Chapter 3) modeling a carbonate
rock with the purpose of injecting sodium carbonate or sodium metaborate as alkali.
Tables A.11 to A.17 list all the information needed to set up the EQBATCH input for
this example. These tables are similar to Tables A.1 to A.10, except that they refer to
the second case. The aqueous, and dissolution/precipitation reactions are as follows:
280
Aqueous Reactions:
H 2 O H + + OH
Na + + H 2 O Na(OH) + H +
Ca 2 + + H 2 O Ca(OH) + + H +
Mg 2 + + H 2 O Mg(OH) + + H +
H + + CO32 HCO3
Na + + H + + CO32 Na(HCO3 )
Ca 2 + + H + + CO32 Ca(HCO3 )+
Mg 2 + + H + + CO32 Mg(HCO3 ) +
B(OH)4 + H + B(OH)3 + H 2 O
Na + + B(OH)3 + H 2 O NaB(OH)4 + H +
Ca 2 + + B(OH)3 + H 2 O CaB(OH) 4+ + H +
Mg 2 + + B(OH)3 + H 2 O MgB(OH) 4+ + H +
Na + + CO32 NaCO3
Ca 2 + + CO32 CaCO3
Mg 2 + + CO32 MgCO3
2H + + CO32 H 2 CO3
Na + + SO 24 NaSO 4
Ca 2 + + SO42 CaSO4
Mg 2 + + SO42 MgSO 4
281
Solid reactions are:
Ca 2 + + CO32 CaCO3
Ca 2 + + Mg 2 + + CO32 CaMg(CO3 )2
Ca 2 + + 2OH Ca(OH)2
Mg 2 + + 2OH Mg(OH)2
Na 2 B4 O7 .10H 2 O(Borax) 4B(OH) 4 + 2H + + 2Na + + H 2 O
Ca 2 + + SO 42 CaSO 4
The reactions presented here for these two cases highlight differences that
may be encountered for the two lithologies.
282
Table A.1: List of Elements and Reactive Species

Calcium, Aluminum, Silicon, Oxygen,
Carbonate, Chlorine
Elements or
pseudo-elements
Independent aqueous species
H+, Na+, Ca2+, Al3+, CO32-, Cl-, H2O,

H4SiO4
Dependent aqueous species

Al(OH)4-, H3SiO4-
Adsorbed cations
H+, Na+
Solid
SiO2 (Silica), Al2Si2O5(OH)4 (Kaolinite),

Analcime
Table A.2: Stoichiometric Coefficient of Ith Element in Jth Fluid Species
(for the AR Array)
Ca
CO3
Al
Si
O
Na
H
1
H+
0
0
0
0
0
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Na+ Ca2+ Al3+ CO32- H4SiO4 H2O Ca(OH)+ Ca(HCO3)+ OH- HCO3- H3SiO4- Al(OH)4- H2CO3
0
1
0
0
0
0
1
1
0
0
0
0
0
0
0
0
1
0
0
0
1
0
1
0
0
1
0
0
1
0
0
0
0
0
0
0
0
1
0
0
0
0
0
1
0
0
0
0
0
1
0
0
0
0
0
0
4
1
1
0
1
0
4
4
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
4
2
1
1
1
1
3
4
2
Table A.3: Stoichiometric Coefficient of Ith Element in Jth Solid Species

(for the BR Array)
NaAlSi2O6.H2O
BR CaCO3 SiO2 Al2Si2O5(OH)4
Ca
CO3
Al
Si
O
Na
H
1
1
0
0
0
0
0
0
0
0
1
2
0
0
0
0
2
2
9
0
4
283
0
0
1
2
7
1
2
Table A.4: Stoichiometric Coefficient of Ith Element in Jth Sorbed Species

(for the DR Array)
DR
H+
Ca
CO3
Al
Si
O
Na
H
0
0
0
0
0
0
1
Na+ Ca2+
0
0
0
0
0
1
0
1
0
0
0
0
0
0
Table A.5: Exponent of Jth Independent Fluid Species (for BB Array)

BB
H+
Na+
Ca2+
Al3+
CO32H4SiO4
H2O
Ca(OH)+
Ca(HCO3)+
H+s
Na+s
Ca2+s
H+ Na+
1
0
0
1
0
0
0
0
0
0
0
0
0
0
-1
0
1
0
-1
0
1
0
-1
0
-4
0
2
0
0
0
0
0
0
0
Ca2+
0
0
1
0
0
0
0
1
1
0
0
0
0
0
0
0
0
Al3+
0
0
0
1
0
0
0
0
0
0
0
0
1
0
0
0
0
CO320
0
0
0
1
0
0
0
1
0
1
0
0
1
0
0
0
H4SiO4
0
0
0
0
0
1
0
0
0
0
0
1
0
0
0
0
0
H2O H+ Na+
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
1
0
0
0
Table A.6: Exponent of Jth Independent Species in the Ith Solid (for EXSLD Array)
EXSLD
CaCO3
SiO2
Al2Si2O5(OH)4
NaAlSi2O6.H2O
H+ Na+ Ca2+ Al3+ CO32- H4SiO4 H2O

0 0
1
0
1
0
0
0 0
0
0
0
1
0
-6 0
0
2
0
2
0
-4 1
0
1
0
2
0
284
Ca2+
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
Table A.7: Charge of Ith Fluid Species (for CHARGE Array)

CHARGE
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Fluid
species
H+
Na+
Ca2+
Al3+
CO32H4SiO4
H2O
Ca(OH)+
Ca(HCO3)+
Charge
1
1
2
3
-2
0
0
1
1
-1
-1
-1
-1
0
Table A.8: Equilibrium Constants for Ith Fluid Species (for EQK Array)
EQK
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Fluid
species
+
Equilibrium Constants at different Temperature

25C
1
1
1
1
1
1
1
2.0479E-13
H
Na+
Ca2+
Al3+
CO32H4SiO4
H2O
Ca(OH)+
Ca(HCO3)+ 3.6804E+11
-
OH
HCO3H3SiO4Al(OH)4H2CO3
1.0309E-14
2.2075E+10
1.5531E-10
6.9711E-23
5.1274E+16
55C
1
1
1
1
1
1
1
2.18E-12
85C
1
1
1
1
1
1
1
1.56E-11
3.58E+11
5.08E+11
7.3E-14
1.67E+10
3.24E-10
3.26E-20
3.48E+16
3.21E-13
1.66E+10
5.31E-10
1.51E-18
3.9E+16
285
Table A.9: Charge of Jth Sorbed Species (for SCHARG Array)

Adsorbed species
Charge
H+ (sorbed)
Na+ (sorbed)
Ca2+ (sorbed)
1
1
2
Table A.10: Exponent of Kth Independent Species in Jth Equilibrium Relation

(for EXEX Array)
CO32- H4SiO4 H2O H+ (s) Na+ Ca2+
H+ Na+ Ca2+ Al3+
(s)
(s)
-1
-2
-1
-1
Table A.11: Example List of Elements and Reactive Species

Elements or
pseudo-elements

Calcium, Magnesium , Sulfate, Carbonate, Chlorine,
B(OH)4-
Independent aqueous
H + , Na + , Ca 2 + , Mg 2 + ,SO 42 , CO32 ,
or oleic species
Dependent aqueous
or oleic species
B(OH)4 , H 2 O
NaOH, Ca(OH)+ , Mg(OH) + , NaHCO3 , Ca(HCO3 ) + ,

Mg(HCO3 )+ , OH , HCO3 , H 2 CO3 , B(OH)3 , NaB(OH)3 ,
CaB(OH)4+ , MgB(OH) 4+ , NaCO3 ,
CaCO3 , MgCO3 , NaSO 4 , CaSO 4 , MgSO4
Solid species
CaCO3 (Calcite), CaSO4.2H2O (Gypsum) and Dolomite
286
Table A.12: Stoichiometric Coefficient of Ith Element in Jth Fluid Species

(for the AR Array)
Ca(HCO3)+
Mg(HCO3)+
OH-
B(OH)3
CaB(OH)4+
MgB(OH)4+
HCO3-
0
1
0
0
1
0
0
0
0
1
1
1
0
0
1
0
1
0
1
0
0
0
1
1
0
1
0
0
0
0
0
0
1
0
1
1
0
0
0
1
0
1
0
1
0
0
1
0
1
0
1
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
2
0
0
0
0
0
1
1
0
0
0
0
0
0
1
0
0
0
0
1
0
1
0
0
0
0
1
1
0
0
0
1
0
1
0
0
0
0
0
1
1
0
0
0
0
0
0
0
1
0
1
0
1
0
0
0
0
1
0
Table A.13: Stoichiometric Coefficient of Ith Element in Jth Solid Species

(for the BR Array)
BR
CaCO3 CaMg(CO3)2 Ca(OH)2 Mg(OH)2 CaSO4 Boric acid Borax
Ca
1
1
1
0
1
0
0
Mg
0
1
0
1
0
0
0
CO3
1
2
0
0
0
0
0
Na
0
0
0
0
0
0
2
H
0
0
2
2
0
1
2
SO4
0
0
0
0
1
0
0
B(OH)40
0
0
0
0
1
4
287
MgSO4
H2CO3
Na(HCO3)
1
0
0
0
1
0
0
1
0
0
0
0
0
0
NaSO4CaSO4
Mg(OH)+
0
0
0
0
0
0
1
0
0
0
1
0
0
0
MgCO3
Ca(OH)+
0
0
0
0
1
0
0
NaCO3CaCO3
B(OH)4H2O
NaOH
Ca
Mg
CO3
Na
H
SO4
B(OH)4-
7 8 9 10 11 12 13 14 15 16 18 19 20 21 22 23 24 25 26 27
H+
Na+
Ca2+
Mg2+
CO32SO42-
1 2 3 4 5 6
0
1
0
0
0
1
0
0
0
1
0
2
0
0
Table A.14: Exponent of Jth Independent Fluid Species (for BB Array)

BB
H+
Na+
Ca2+
Mg2+
CO32SO42B(OH)4H2O
NaOH
Ca(OH)+
Mg(OH)+
Na(HCO3)
Ca(HCO3)+
Mg(HCO3)+
OHB(OH)3
CaB(OH)4+
MgB(OH)4+
HCO3NaCO3CaCO3
MgCO3
NaSO4CaSO4
MgSO4
H2CO3
H+ Na+ Ca2+ Mg2+

1
0
0
0
0
1
0
0
0
0
1
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
-1 1
0
0
-1 0
1
0
-1 0
0
1
1
1
0
0
1
0
1
0
1
0
0
1
-1 0
0
0
1
0
0
0
-1 0
1
0
-1 0
0
1
1
0
0
0
0
1
0
0
0
0
1
0
0
0
0
1
0
1
0
0
0
0
1
0
0
0
0
1
2
0
0
0
CO320
0
0
0
1
0
0
0
0
0
0
1
1
1
0
0
0
0
1
1
1
1
0
0
0
1
SO420
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
0
B(OH)40
0
0
0
0
0
1
0
0
0
0
0
0
0
0
1
1
1
0
0
0
0
0
0
0
0
H2O
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Table A.15: Exponent of Jth Independent Species in the Ith Solid (for EXSLD Array)
EXSLD
CaCO3
CaMg(CO3)2
Ca(OH)2
Mg(OH)2
CaSO4
Boric acid
Borax
H+ Na+ Ca2+ Mg2+ CO32- SO42- B(OH)4- H2O

0 0
1
0
1
0
0
0
0 0
1
1
2
0
0
0
-2 0
1
0
0
0
0
0
-2 0
0
1
0
0
0
0
0 0
1
0
0
1
0
0
1 0
0
0
0
0
1
0
2 2
0
0
0
0
4
0
288
Table A.16: Charge of Ith Fluid Species (for CHARGE Array)

CHARGE
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
Fluid species
H
Na+
Ca2+
Mg2+
CO32SO42B(OH)4H2O
NaOH
Ca(OH)+
Mg(OH)+
Na(HCO3)
Ca(HCO3)+
Mg(HCO3)+
OHB(OH)3
CaB(OH)4+
MgB(OH)4+
HCO3NaCO3CaCO3
MgCO3
NaSO4CaSO4
MgSO4
H2CO3
289
Charge
1
1
2
2
-2
-2
-1
0
0
1
1
0
1
1
-1
0
1
1
-1
-1
0
0
-1
0
0
0
Table A.17: Equilibrium Constants for Ith Fluid Species (for EQK Array)
EQK
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
Fluid species
H+
Na+
Ca2+
Mg2+
CO32SO42B(OH)4H2O
NaOH
Ca(OH)+
Mg(OH)+
Na(HCO3)
Ca(HCO3)+
Mg(HCO3)+
OHB(OH)3
CaB(OH)4+
MgB(OH)4+
HCO3NaCO3CaCO3
MgCO3
NaSO4CaSO4
MgSO4
H2CO3
1
1
1
1
1
1
1
1
1.60E-14
6.01E-13
4.92E-12
2.05E+10
3.42E+11
2.12E+11
2.55E-14
1.68E+09
3.58E-08
3.25E-08
1.91E+10
2.33E+00
2.03E+03
1.01E+03
5.32E+00
2.43E+02
1.91E+02
4.18E+16
290
APPENDIX B
EQBATCH SETUP
In appendix A, we described two example sets of reactions for EQBATCH,
'UTCHEM's geochemistry preprocessor'. This program can perform batch reaction
equilibrium calculations and calculate the initial equilibrium state of the reservoir.
Here in this appendix, we emphasize how the initial pH of the formation or
makeup water and their concentration can be matched by using EQBATCH with
suitable input data. It is important for the user to have data such as formation brine
composition and elemental concentration, pH, acid number of the crude oil, cation
exchange capacity and some knowledge about the rock and its minerals. Reservoir
temperature is also important since we need to find all the equilibrium constants and
solubility products at one specific temperature.
It should be noted that EQBATCH is not linked to a geochemistry database
and therefore, the user needs to decide on the species or reactions that are important.
Therefore, other geochemistry software packages such as PHREEQC (2008) or
Geochemist's Workbench (2008) are used to determine the important species to be
input for EQBATCH. The acronym PHREEQC stands for PH (pH), RE (redox), EQ
(equilibrium), C (program written in C). One needs to input the formation brine and
injected brine species and elements and their concentration at a specific temperature
in equilibrium with minerals in the rock, excluding insignificant or low concentration
species. These softwares according to their database can determine what solution
291
species and rock minerals can exist under the new reservoir condition. The species
with high concentrations are selected to be modeled in EQBATCH. The equilibrium
constants and solubility products of all possible reactions for these conditions are
found from the database.
In some cases, the user's experience and knowledge can also help identify the
key reactions needed to match the initial state of the reservoir and further to simulate
the alkaline flooding in the reservoir. In addition, case studies, such as those
presented here or in Bhuyan (1989) and Wu (1990) or other sources may also provide
guidance.
The main procedure on how to set up the eqbatch input and match the species
concentration data is given here for the reservoir information from Chapter 6. Tables
B.1 and B.2 (The same as Tables 6.1 and 6.2) give the formation brine composition
and rock mineralogy. The crude oil acid number is about 2.4 mg KOH/g oil. The
reservoir initial salinity is about 2 wt% NaCl and reservoir temperature is 38oC. The
cation exchange capacity of the rock was assumed to be 0.4 meq/100 g rock.
1. Finding out the important species for modeling

Table B.1 lists the formation brine composition analysis. Calcium and
magnesium are the main divalent cations, the major monovalent cation is sodium. The
major anion is Cl- and HCO3- is a minor anion species present in this brine.
The small amount of carbonate in the solution for formation brine
composition match could be ignored in some cases. However, it should be noted since
292
in most cases the output of EQBATCH becomes the input for UTCHEM simulation;
therefore, all the possible species later used in the simulation should be considered in
the EQBATCH input. For example, if the alkali injected is Na2CO3 or sodium
metaborate, carbonate or borate need to be added to the species for further application
in UTCHEM. The same is true about minerals. To initialize the EQBATCH input file,
all the possible minerals which dissolve or precipitate due to injection of alkali need
to be considered. Here in this case, if there is no or insignificant calcite initially
among the minerals but it can not be ignored because sodium carbonate injected in
the presence of divalent cations can cause calcite precipitation. Software packages
such as Geochemist's workbench or PHREEQC are helpful in identifying these
species.
In this example, the important elements are Na+, Ca++, Mg++, CO32-, Cl-. Since
the Mg++ concentration is not too large it can be coupled with Ca++ for simplicity.
Therefore, the minimum number of elements for this case is Na+, Ca++, CO32-, Cl- and
HAo which is the concentration of acid in oil. HAo needs to be added to the elements
because the crude oil contains the acidic components.
In EQBATCH the elements are introduced as dependent or independent
solution species, as rock minerals and or as adsorbed cations on clay or micelles.
Independent fluid species are those species which stand alone and are not a
combination of two or more of the species. For example Ca++, H+ or CO32- are all
defined as independent solution species but CaHCO3+ is a dependent species since it
is the result of the reaction from the independent species. In this example, the
293
dependent solution species are hydrogen ion, sodium ion, calcium ion, carbonate ion,
HAo and water. Cl- is not defined as a dependent species because it does not
participate in the reactions. The dependent species are defined as Ca(OH)+,
Ca(HCO3)+, A-, OH-, HCO3-, H2CO3, CaCO3, HAw. A- (soap) and HAw
(Concentration of acid in water) are dependent species (dependent on the
concentration of acid in oil 'HAo'). Ca(OH)+, Ca(HCO3)+, OH-, HCO3-, H2CO3,
CaCO3 are the dependent species for the system of defined elements. These
dependent species can be found from the geochemistry software packages as
explained earlier.
As shown in Table B.2, the rock is a sandstone rock which mainly contains
silica and kaolinite. The reservoir temperature is 87oF. This temperature is not high
enough to promote substantial quartz or clay dissolution. Therefore, we do not model
these solids for the simplification of the problem. Calcium carbonate (CaCO3) and
calcium hydroxide (Ca(OH)2) here are chosen as the solid species. These minerals are
added in case they precipitate after injection of alkali. Then we choose sorbed
hydrogen, sodium and calcium ions as sorbed cation species.
2. Preparing the required tables

As discussed in the appendix A, EQBATCH has been developed in such a
way that it requires all the reaction specifications such as the reaction stoichiometric
coefficient, exponents and equilibrium constants to be input in table format. Tables
294
A.2 to A.10 and A.12 to A.17 are examples of these tables. Some examples on how to
fill out these tables are given below.
In Table B.3 defining the stoichiometric coefficient of Ith Element in Jth Fluid
Species (for the AR Array), the row is defined as all the solution species and the
columns are the elements (No chlorine is added because it is not included in the
reactions). The solution species and elements have to have the same order in all the
tables as defined in the EQBATCH input file. As shown in this table, the cells are
filled with zeros, ones and twos. If the solution species has that element in it the cell
is filled with a number rather than zero. For example H2CO3 has 2 hydrogens and one
CO32-, therefore, the cell that crosses the solution species and element is filled with
the number of that specific element in the solution species.
Another example is how to set up the BB Array which defines the exponent of
Jth independent fluid species (Table B.4). The row is defined as the independent fluid
species plus the sorbed cations on clay and micelles. The column is defined as all the
solution species plus the sorbed cations on clay and micelles. The cells are filled
based on the exponents of the reactions. For example, Ca(OH)+ reaction as dependent
solution species is expressed as:
Ca 2 + + H 2 O Ca(OH)+ + H +
or it can be written as :
Ca(OH)+ = K
Ca 2 +
H+
= K Ca 2 + H +
295
Therefore, the cells related to Ca(OH)+ are filled with -1 for hydrogen ion and
1 for calcium.
3. Determining the equilibrium constants and solubility products

All the equilibrium constants and solubility products need to be found from a
database or based on laboratory measurements at a specific temperature.
Geochemist's workbench database has a very comprehensive number of solution
species and rock minerals with all the equilibrium constants.
4. Converting the solution species, mineral concentration, and CEC to

meq/ml
All the species have to be input as meq/ml water in EQBATCH and
UTCHEM. In this example, the Cl- concentration is 11567 mg/l and is converted from
mg/l to meq/ml as follows.
11567 mg / L Cl
1mole
1eq
1g
= 0.325 meq / ml
35.5g 1000mg 1mole
or Ca2+ concentration in meq/ml is

640 mg / L Ca 2 +
1mole
2 eq
1g
= 0.032 meq / ml
40g 1000mg 1mole
All the other species concentrations are converted the same way.
296
5. Converting the acid number to Mole/l water of acid concentration in oil
Acid number is converted based on the following equation from mg KOH/g

oil to mole/L water (or meq/ml). In this example, acid number is 2.4 mg KOH/g oil.
mg KOH
1g
1000 cc
g oil
CHAo mole L water = acid no.
x
x
x
x o
cc
oil
1000 mg
1L
g oil
S2 ( L oil )
1
x
(4.2)
g KOH
S1 ( L Water )
56.098 (
)
mole
CHAo is calculated 0.04 mole/ L water for water saturation of 0.5 and oil density of
0.934 g/cc.
6. Finding the species concentration match in EQBATCH
All the species, the corresponding tables, charges, equilibrium constants and
so on are prepared as we explained. They then are added to EQBATCH input file
based on the step by step procedure described in the UTCHEM technical
documentation. The next step is to run Eqbatch and find the match with the initial
state of the reservoir such as formation brine concentration, and pH.
EQBATCH input parameters such as C5I, CELAQI(J), for J = 1, NELET-1,
CSLDI(I), for I = 1, NSLD, CSORBI(I), for I = 1, NSORB are adjusted to get the
match with the initial state of the reservoir (Table B.5). This will typically require
several trials before a satisfactory match is obtained. Usually a first good guess can be
the solution species concentration in the formation brine.
297
The output of the EQBATCH needs to be checked in each try to see the match
of the EQBATCH results to the initial state of the reservoir for the following
parameters: C5I (Initial concentration of nonreacting anions), C6I (Initial
concentration of calcium in aqueous phase), CELAQI(J), for J=1, NGC (Initial
concentrations of Jth geochemistry component), CAC2I - Initial concentration of acid
in oil and CAQI(J) - Initial guesses for Jth independent species concentration are
compared with the solution species concentrations. (Lines 3.5.34 to 3.5.37 of
UTCHEM user's manual for a description of these parameters.)
One good matching indicator can be the pH of the formation brine. For
example, usually hydrogen is defined as the first dependent solution species
corresponding to CAQI(J) for J=1 in the EQBATCH output. CAQI(J) for J=1 is the
concentration of hydrogen and the negative logarithm of this number gives the pH.
This can be used as a matching parameter with the formation brine pH. Table B.6
shows the comparison of the elemental compositions of experimental and simulated
connate brine.
The EQBATCH manual and input and output were developed assuming a user
is very experienced with ASP and UTCHEM simuilation. For this reason, it is not
extensively documentated or annotated with output and warning and diagnostic
messages; therefore, caution and diligence are required to use this program
successfully.
298
Table B.1: Formation brine composition

anion
Conc., mg/l
Cl11567
HCO3
500
total anion concentration
divalent cation
Mg++
260
++
Ca
640
SR++
160
++
Ba
80
total divalent concentration
MW
35.5
61
charge
1
1
Conc., meq/ml
0.32583
0.0082
0.334
24.3
40
87.62
137.3
2
2
2
2
0.0214
0.032
0.0037
0.0012
0.0582
Table B.2: Reservoir Minerals

Mineral
Wt%
Wt%
88.4
Clays
Kaolinite
[Al2Si2O5(OH)4]
Quartz
K-spar
2.4
2:1 Al-rich clay
0.1
Plagioclase
1.0
2:1 Fe-rich clay
3.2
Calcite (CaCO3)
0.7
Berthierine
0.1
High Mg Calcite
0.5
Dolomite [CaMg(CO3)2]
0.7
Ankerite
0.7
Siderite (FeCO3)
0.8
total Clay
4.8
SUM (Total)
1.4
100
299
Table B.3: Table of AR array for EQBATCH input file

1 2
3
4
5
6
7
8
+
+
2+
2+
H Na Ca CO3 HAo H2O Ca(OH) Ca(HCO3)+
Ca 0 0
1
0
0
0
1
1
CO3 0 0
0
1
0
0
0
1
Na 0 1
0
0
0
0
0
0
H 1 0
0
0
1
2
1
1
A 0 0
0
0
1
0
0
0
Table B.4:
1
2
3
4
5
6
7
8
9
10
11
12
13
14
1
2
3
9 10
11
12
13
14
A OH HCO3 H2CO3 CaCO3 HAw
0 0
0
0
1
0
0 0
1
1
1
0
0 0
0
0
0
0
0 1
1
2
0
1
1 0
0
0
0
1
Table of BB array for EQBATCH input file
H+ Na+ Ca2+ CO32- HAo H2O H+ Na+ Ca2+

H+
1 0
0
0
0
0
0
0
0
Na+
0 1
0
0
0
0
0
0
0
Ca 2+
0 0
1
0
0
0
0
0
0
CO3 20 0
0
1
0
0
0
0
0
HAo
0 0
0
0
1
0
0
0
0
H2O
0 0
0
0
0
1
0
0
0
Ca(OH)+
-1 0
1
0
0
0
0
0
0
Ca(HCO3)+ 1 0
1
1
0
0
0
0
0
A-1 0
0
0
1
0
0
0
0
OH-1 0
0
0
0
0
0
0
0
HCO31 0
0
1
0
0
0
0
0
H2CO3
2 0
0
1
0
0
0
0
0
CaCO3
0 0
1
1
0
0
0
0
0
HAw
0 0
0
0
1
0
0
0
0
H+s
0 0
0
0
0
0
1
0
0
Na+s
0 0
0
0
0
0
0
1
0
Ca2+s
0 0
0
0
0
0
0
0
1
Fluid Species
Sorbed Species
300
Table B.5: EQBATCH input parameters

Initial
chloride in
water
C51, meq/ml
Initial surf.
conc.
Surf., vol.
fraction
0.325
0.0
Total elemental conc. in aqueous phase (formation water analysis), only fluid conc.
(CELAQ, mole/L)
Ca2+
Mg2+
Na+
H+
A0.030
0.001
0.27
111.00
0.04
Initial solid conc.
(CSLD, mole/L PV)
CaCO3
Ca(OH)2
1.5
0.0
Initial adsorbed conc.
(CSORB, mole/L PV)
H+
Na+
Ca2+
0.024
0.015
0.0001
Independent Species.
(CAQI, mole/L)
H+
Na+
Ca2+
CO32HAo
Water
0.1e-07
0.01
0.1e-04 0.3e-03
1.1e-3
55.5
Adsorbed species
(CAQI, mole/L)
H+, s
Na+, s
Ca2+, s
1.0e-06
1.0e-04
1.0e-04
S, initial water sat (L/L
EQW, equivalent weight of generated Surfactant
PV)
(MW/valence)
0.5
500
301
Table B.6: Comparison of the elemental compositions of experimental and simulated

connate brine
Element
Synthetic Brine (meq/ml) Simulated Brine (meq/ml)
Na+
0.27
0.267
Cl-
0.326
0.325
Divalent cations
(Ca2+, Mg2+)
0.0528
0.057
pH
6.5
* The pH of the synthetic brine is reported to be about neutral.
302
APPENDIX C
BATCH INPUT Example of Soap/Surfactant Phase Behavior
This appendix is one batch input example for matching the phase behavior for
a soap/surfactant mixture. The reactions needed to generate soap in a test tube are
included in this input (Refer to Chapter 4 for more disscusion on the soap/surfactant
phase behavior modeling).
CC*******************************************************************
CC
*
CC BRIEF DESCRIPTION OF DATA SET : UTCHEM (VERSION 9.82 )
*
CC
*
CC*******************************************************************
CC
*
CC batch calculation to obtain UTCHEM phase behavior
*
CC
*
CC LENGTH (FT) :
PROCESS : SURFACTANT
*
CC THICKNESS (FT) :
INJ. RATE (FT3/DAY) :
*
CC WIDTH (FT) :
COORDINATES : CARTESIAN
*
CC POROSITY :
*
CC GRID BLOCKS : 5x 1x1
*
CC DATE :
*
CC
*
CC*******************************************************************
CC
CC*******************************************************************
CC
*
CC RESERVOIR DESCRIPTION
*
CC
*
CC*******************************************************************
CC
CC Run number
*---- RUNNO
UTBATC
CC
CC Title and run description
*---- title(i)
get the hand's parameter from batch samples
soap/surfactant phase behavior- Case A- Chapter 4
NO Correct fluid properties, only match of phase behavior parameters
CC
303
CC SIMULATION FLAGS
*---- IMODE IMES IDISPC ICWM ICAP IREACT IBIO ICOORD ITREAC ITC IGAS IENG
1 4 0 0 0 3 0 1 0 0 0 0
CC
CC no. of gridblocks,flag specifies constant or variable grid size,unit
*---- NX NY NZ IDXYZ IUNIT
5 1 1 0 0
CC
CC constant grid block size in x,y,and z
*---- dx1
dy1
dz1
1
1
1
CC
CC TOTAL NO. OF COMPONENTS, NO. OF TRACERS, NO. OF GEL COMPONENTS
*----N no NTw nta ngc ng noth
12 0 0 0 4 0 0
CC
CC
*---- SPNAME(I),I=1,N
WATER
OIL
SURFACTANT
POLYMER
ANION
CALCIUM
alc1
alc2
CARBONATE
SODIUM
HYDROGEN
pet acid
CC
CC FLAG INDICATING IF THE COMPONENT IS INCLUDED IN CALCULATIONS OR NOT
*----ICF(KC) FOR KC=1,N
1 1 1 1 1 1 0 0 1 1 11
CC
CC*******************************************************************
CC
*
CC OUTPUT OPTIONS
*
CC
*
CC*******************************************************************
CC
CC
CC FLAG TO WRITE TO UNIT 3,FLAG FOR PV OR DAYS TO PRINT OR TO STOP THE RUN
*---- ICUMTM ISTOP IOUTGMS
0
0
0
CC
CC FLAG INDICATING IF THE PROFILE OF KCTH COMPONENT SHOULD BE WRITTEN
*---- IPRFLG(KC),KC=1,N
1 1 1 1 1 1 0 0 1 1 11
CC
CC FLAG FOR PRES.,SAT.,TOTAL CONC.,TRACER CONC.,CAP.,GEL, ALKALINE PROFILES
*---- IPPRES IPSAT IPCTOT IPBIO IPCAP IPGEL IPALK IPTEMP IPOBS
304
1 1 0 0 0 0 1 0 0
CC
CC FLAG FOR WRITING SEVERAL PROPERTIES TO UNIT 4 (Prof)
*---- ICKL IVIS IPER ICNM ICSE IHYSTP IFOAMP INONEQ
0 0 0 0 0 0 0 0
CC
CC FLAG for variables to PROF output file
*---- IADS IVEL IRKF IPHSE
0 0 0 0
CC
CC*******************************************************************
CC
*
CC RESERVOIR PROPERTIES
*
CC
*
CC*******************************************************************
CC
CC
CC MAX. SIMULATION TIME ( DAYS)
*---- TMAX
250
CC
CC ROCK COMPRESSIBILITY (1/PSI), STAND. PRESSURE(PSIA)
*---- COMPR
PSTAND
0
0
CC
CC FLAGS INDICATING CONSTANT OR VARIABLE POROSITY, X,Y,AND Z
PERMEABILITY
*---- IPOR1 IPERMX IPERMY IPERMZ IMOD
0 1 1 0 0
CC
CC CONSTANT POROSITY FOR WHOLE RESERVOIR
*---- PORC1
1
CC
CC CONSTANT X-PERMEABILITY (MILIDARCY) FOR LAYER K = 1,NZ
*---- PERMX(K),K=1,NZ
1000000
CC
CC CONSTANT Y-PERMEABILITY (MILIDARCY) FOR LAYER K = 1,NZ
*---- PERMY(K),K=1,NZ
1000000
CC
CC CONSTANT Z-PERMEABILITY FOR WHOLE RESERVOIR
*---- PERMZC
1000000
CC
CC FLAG FOR CONSTANT OR VARIABLE DEPTH, PRESSURE, WATER
SATURATION,INITIAL AQUEOUS PHASE cOMPOSITIONS
*----IDEPTH IPRESS ISWI ICWI
0
0 0 -1
CC
CC CONSTANT DEPTH (FT)
305
*---- D111
0
CC
CC CONSTANT PRESSURE (PSIA)
*---- PRESS1
1
CC
CC CONSTANT INITIAL WATER SATURATION
*---- SWI
0.5
CC
CC BRINE SALINITY AND DIVALENT CATION CONCENTRATION (MEQ/ML)
*---- C50
C60
0.16 0.0
CC
CC*******************************************************************
CC
*
CC PHYSICAL PROPERTY DATA
*
CC
*
CC*******************************************************************
CC
CC
CC OIL CONC. AT PLAIT POINT FOR TYPE II(+)AND TYPE II(-), CMC
*---- c2plc c2prc epsme ihand
0 1 0.001 0
CC
CC flag indicating type of phase behavior parameters
*---- ifghbn
0
CC SLOPE AND INTERCEPT OF BINODAL CURVE AT ZERO, OPT., AND 2XOPT SALINITY
CC FOR ALCOHOL 1
*----HBNS70 HBNC70 HBNS71 HBNC71 HBNS72 HBNC72
0. .03 0. .015 0.0 .03
CC FOR ALCOHOL 2
0. 0. 0. 0. 0. 0.
CC
CC LOWER AND UPPER EFFECTIVE SALINITY FOR ALCOHOL 1 AND ALCOHOL 2
*---- csel7 cseu7 csel8 cseu8
0.55 1.1 0
0
CC
CC THE CSE SLOPE PARAMETER FOR CALCIUM AND ALCOHOL 1 AND ALCOHOL 2
*---- beta6 beta7 beta8
0
0
0
CC
CC FLAG FOR ALCOHOL PART. MODEL AND PARTITION COEFFICIENTS
*---- ialc opsk7o opsk7s opsk8o opsk8s
0 0.0 0.0
0
0
CC
CC NO. OF ITERATIONS, AND TOLERANCE
*---- nalmax epsalc
306
20
0.0001
CC
CC ALCOHOL 1 PARTITIONING PARAMETERS IF IALC=1
*---- akwc7 akws7 akm7 ak7 pt7
0
0
0 0
0
CC
0
0
0 0
0
CC
CC ift model flag
*---- ift
1
CC
CC INTERFACIAL TENSION PARAMETERS
*---- chuh ahuh
0.3
10
CC
CC LOG10 OF OIL/WATER INTERFACIAL TENSION
*---- xiftw
1.5
CC
CC ORGANIC MASS TRANSFER FLAG
*---- imass icor
0
0
CC
CC CAPILLARY DESATURATION PARAMETERS FOR PHASE 1, 2, AND 3
*---- itrap t11
t22
t33
0
1865 59074 364.2
CC
CC FLAG FOR RELATIVE PERMEABILITY AND CAPILLARY PRESSURE MODEL
*---- iperm
0
CC
CC FLAG FOR CONSTANT OR VARIABLE REL. PERM. PARAMETERS
*---- isrw iprw iew
0 0
0
CC
CC CONSTANT RES. SATURATION OF PHASES 1,2,AND 3 AT LOW CAPILLARY NO.
*---- s1rwc s2rwc s3rwc
0 0 0
CC
CC CONSTANT ENDPOINT REL. PERM. OF PHASES 1,2,AND 3 AT LOW CAPILLARY NO.
*---- p1rwc p2rwc p3rwc
1
1 1
CC
CC CONSTANT REL. PERM. EXPONENT OF PHASES 1,2,AND 3 AT LOW CAPILLARY NO.
*---- e1wc e2wc e3wc
1
1
1
CC
CC WATER AND OIL VISCOSITY , RESERVOIR TEMPERATURE
*---- VIS1 VIS2 TSTAND
307
1 1 0
CC
CC COMPOSITIONAL PHASE VISCOSITY PARAMETERS
*---- ALPHAV1 ALPHAV2 ALPHAV3 ALPHAV4 ALPHAV5
0
0
0
0
0
CC
CC PARAMETERS TO CALCULATE POLYMER VISCOSITY AT ZERO SHEAR RATE
*---- AP1 AP2 AP3
81 2700 2500
CC
CC PARAMETER TO COMPUTE CSEP,MIN. CSEP, AND SLOPE OF LOG VIS. VS. LOG CSEP
*---- BETAP CSE1 SSLOPE
10 0.01 0.17
CC
CC PARAMETER FOR SHEAR RATE DEPENDENCE OF POLYMER VISCOSITY
*---- GAMMAC GAMHF POWN
20
10 1.8
CC
CC CC FLAG FOR POLYMER PARTITIONING, PERM. REDUCTION PARAMETERS
*---- IPOLYM EPHI3 EPHI4 BRK CRK
1
1
1.0 1000 0.0186
CC
CC SPECIFIC WEIGHT FOR COMPONENTS 1,2,3,7,8 ,Coeffient of oil and GRAVITY FLAG
*---- DEN1 DEN2 DEN23 DEN3 DEN7 DEN8 IDEN
0.433 0.433 0.433 0.433 0.433 0
2
CC
CC FLAG FOR CHOICE OF UNITS ( 0:BOTTOMHOLE CONDITION , 1: STOCK TANK)
*----- ISTB
0
CC
CC COMPRESSIBILITY FOR VOL. OCCUPYING COMPONENTS 1,2,3,7,AND 8
*---- COMPC(1) COMPC(2) COMPC(3) COMPC(7) COMPC(8)
0
0
0
0
0
CC
CC CONSTANT OR VARIABLE PC PARAM., WATER-WET OR OIL-WET PC CURVE FLAG
*---- ICPC IEPC IOW
0
0 0
CC
CC CAPILLARY PRESSURE PARAMETER, CPC0
*---- CPC0
0
CC
CC CAPILLARY PRESSURE PARAMETER, EPC0
*---- EPC0
2
CC
CC MOLECULAR DIFFUSION COEF. KCTH COMPONENT IN PHASE 1
*---- D(KC,1),KC=1,N
0
0
0
0
0
0
0
0
0
0
0
0
0
CC
*---- D(KC,2),KC=1,N
308
0
0
0
0
0
0
0
0
0
0
0
0
0
CC
*---- D(KC,3),KC=1,N
0
0
0
0
0
0
0
0
0
0
0
0
0
CC
CC LONGITUDINAL AND TRANSVERSE DISPERSIVITY OF PHASE 1
*---- ALPHAL(1) ALPHAT(1)
0
0
CC
0
0
CC
0
0
CC
CC flag to specify organic adsorption calculation
*---- iadso
0
CC
CC SURFACTANT AND POLYMER ADSORPTION PARAMETERS
*---- AD31 AD32 B3D AD41 AD42 B4D IADK IADS1 FADS REFK
0 0 1000 0.7 0 100 0 0 0 0
CC
CC PARAMETERS FOR CATION EXCHANGE OF CLAY AND SURFACTANT
*---- QV XKC XKS EQW
0 0 0 419
2 0
0.1 0.2
6 11 0 0 0 1
6 0 0 7
4 3 1 0 2
0 0 0
5
CALCIUM
2.00
CARBON (AS CARBOBATES)
-2.00
SODIUM
1.00
HYDROGEN (REACTIVE)
1.00
oleic acid
-1.00
CHLORINE (* ELEMNT *)
-1.00
H+
Na+
Ca2+
CO32Hao
H2O
AOHHCO3H2CO3
309
Haw (* FLDSPS *)
0. 0. 1. 0. 0. 0. 0. 0. 0. 0. 0.
0. 0. 0. 1. 0. 0. 0. 0. 1. 1. 0.
0. 1. 0. 0. 0. 0. 0. 0. 0. 0. 0.
1. 0. 0. 0. 1. 2. 0. 1. 1. 2. 1.
0. 0. 0. 0. 1. 0. 1. 0. 0. 0. 1.
1.0 0.0 0.0 0.0 0.0 0.0
0.0 1.0 0.0 0.0 0.0 0.0
0.0 0.0 1.0 0.0 0.0 0.0
0.0 0.0 0.0 1.0 0.0 0.0
0.0 0.0 0.0 0.0 1.0 0.0
0.0 0.0 0.0 0.0 0.0 1.0
-1.0 0.0 0.0 0.0 1.0 0.0
-1.0 0.0 0.0 0.0 0.0 0.0
1.0 0.0 0.0 1.0 0.0 0.0
2.0 0.0 0.0 1.0 0.0 0.0
0.0 0.0 0.0 0.0 1.0 0.0
1.0 1.0 2.0 -2.0 0.0 0.0 -1.0 -1.0 -1.0 0.0 0.0
0.1000000000000E+01 0.1000000000000E+01 0.1000000000000E+01
0.1000000000000E+01 0.1000000000000E+01 0.1000000000000E+01
0.9589952058430E-12 0.2550000000000E-13 0.1910000000000E+11
0.4180000000000E+17 0.9589952058430E-04
0.5200000000000E-01 0.2000000000000E-04
0.1461198989995E-05
0.1000000000000E+00
0.1109999991769E+03
0.1758115235883E-08
0.1000004999146E-04
0.1200077231590E-07 0.1000000000000E+00 0.1000000000000E-04
0.3092684582095E-08 0.1000000000000E-04 0.5549999314650E+02
0.9999999991209E+00 0.9999950000000E+00
0.1000000000000E-07 0.5000000000000E+03
CC
CC*******************************************************************
CC
*
CC WELL DATA
*
CC
*
CC*******************************************************************
CC
CC
CC FLAG FOR SPECIFIED BOUNDARY AND ZONE IS MODELED
*---- IBOUND IZONE
0 0
CC
CC TOTAL NUMBER OF WELLS, WELL RADIUS FLAG, FLAG FOR TIME OR COURANT NO.
*---- NWELL IRO ITIME NWREL
2 2
1
2
CC
CC WELL ID,LOCATIONS,AND FLAG FOR SPECIFYING WELL TYPE, WELL RADIUS, SKIN
*---- IDW IW JW IFLAG RW SWELL IDIR IFIRST ILAST IPRF
1 1 1
1 0.5
0
3 1 1 0
CC
310
CC WELL NAME
*---- WELNAM
INJECTOR
CC
CC ICHEK , MAX. AND MIN. ALLOWABLE BOTTOMHOLE PRESSURE AND RATE
*---- ICHEK PWFMIN PWFMAX QTMIN QTMAX
0
0
5000 0
1000
CC
2 5 1
2 0.5
0
3 1 1 0
CC
CC WELL NAME
*---- WELNAM
PRODUCER
CC
0
0
5000 0
50000
CC
CC ID,INJ. RATE AND INJ. COMP. FOR RATE CONS. WELLS FOR EACH PHASE (L=1,3)
*---- ID QI(M,L) C(M,KC,L)
1 0.05 0.998 0. 0.002 0.0 0.1025 0.001 0. 0. 0.358 0.461 111 0.0
1 0.05 0. 1. 0. 0.
0.
0. 0. 0.
0. 0. 0. 0.008324717
1 0. 0. 0. 0. 0.
0.
0. 0. 0.
0. 0. 0. 0.
CC
CC ID, BOTTOM HOLE PRESSURE FOR PRESSURE CONSTRAINT WELL (IFLAG=2 OR 3)
*---- ID PWF
2 1
CC
CC CUM. INJ. TIME , AND INTERVALS (PV OR DAY) FOR WRITING TO OUTPUT FILES
*---- TINJ CUMPR1 CUMHI1 WRHPV WRPRF RSTC
500 5
5
0.5 5
50
CC
CC FOR IMES=2 ,THE INI. TIME STEP,CONC. TOLERANCE,MAX.,MIN. courant numbers
*---- DT DCLIM CNMAX CNMIN
0.001 12*0.05 0.2
0.02
311
APPENDIX D
EQBATCH and UTCHEM INPUT Examples
The following examples are given in this appendix:
1. EQBATCH Input File for Case 3.4 in Chapter 3
3. EQBATCH Input File for Case A in Chapter 5
4. EQBATCH Input File for ASP Coreflood in Chapter 6
5. EQBATCH Input File for Coreflood BM-07 in Chapter 7
6. UTCHEM Input File for Case 3.4 in Chapter 3
8. UTCHEM Input File for Case AII in Chapter 5
9. UTCHEM Input File for ASP (1D Case) Coreflood in Chapter 6
10. UTCHEM Input File for ASP Field Scale (2D) in Chapter 6
11. UTCHEM Input File for Coreflood BM-07 in Chapter 7

Case 3.4 (* Describing a sandstone rock -Quartz dissolution and cation exchange reactions are
included*)
2 0 0 (* IREACT ICHARGE IMG *)
7 14 4 3 0 (* NNELET NFLD NSLD NSORB NACAT *)
7 1 7 0 (* NIAQ NEX NSLWL NSURF1 *)
7 6 1 0 2 (* NH NNA NCA NMG NCARB *)
3 4 5 (* NALU NSILI NOXYG *)
CALCIUM
ALUMINIUM
SILICON
OXYGEN
SODIUM
HYDROGEN (REACTIVE) (* ELEMNT *)
2 -2 3 4 -2 1 1 (* ELCRG *)
312
HYDROGEN ION
SODIUM ION
CALCIUM ION
ALUMINIUM ION
CARBONATE ION
H4SiO4
WATER
CALCIUM MONOHYDROXIDE ION
CA (HC03) +
HYDROXIDE ION
BICARBONATE ION
H3SiO4- ION
Al(OH)4- ION
DISSOLVED CARBON MONOHYDROXIDE (* FLDSPS *)
Calcite (SOLID)
SILICA (SOLID)
KAOLINITE (SOLID)
ANALCITE (SOLID) (* SLDSPS *)
SORBED HYDROGEN ION
SORBED SODIUM ION
SORBED CALCIUM ION (* SORBSPS *)
3 (* NSORBX *)
0
0
1
0
0
0
0
1
0
0
0
0
0
0
1
0
0
0
0
1
0
0
0
1
0
0
0
0
1
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
4
1
1
4
0
0
1
0
0
0
0
0
0
0
0
1
0
0
0
0
4
2
1
4
2 (* AR *)
1
0
0
0
1
0
0
0
0
0
2
1
0
1
2
2
0
2
9
7
0
0
0
1
0
0
4
2 (* BR *)
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
1
0
0 (* DR *)
1
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
313
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
-1
0
1
1
0
1
-1
0
0
1
0
0
-1
0
0
-4
0
0
2
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
-6
0
0
-4
1
0
1
1
2
3
-2
0
0
1
1
-1
-1
-1
-1
0 (* CHARGE *)
1
1
1
1
1
1
1
1.56171E-11
5.08042E+11
3.2107E-13
16607337055
5.31007E-10
1.51008E-18
3.90122E+16 (* KEQ *)
1. 1. 2. (* SCHARGE *)
7.93 2.7e+06 (* KEX *)
0
2
-1
-1
1
0
-1. 0. (* REDUC *)
0
1
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
2
1
0
0
1
0
0
0
1
0
1
0
0
1
0
0
0
1
0
0
0
0
0
0
1
0
0
0
0
0
1
0
0
0
0
0
0
1
2
2
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0 (* EXSLD *)
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1 (* BB *)
0
0
0
0
0
0
0
0
-2
-1
1
0 (* EXEX *)
314
0
1
0.026 (* EXCAI *)
4.56983E-10 0.000594429 1627.796086 53789.80873 (* KSP *)
0.024 0.0 (*C50, Csurf*)
0.001 0.02 0.001 0.001 55.5004 0.0425 111.0117 (*CELFLT 1,NELEMENT-1*)
1.63 100.0 0.0 0.0 (*CSLD(I), I=1,NSLD*)
0.011 0.013 0.001 (* CSORBI *)
1.9e-06 0.5 1.5e-03 1.e-14
3.e-06 1.e-04
55.5 1.0e-06 1.0e-02 1.0e-03 (*CIND*)
1.0 (*S1*)

Case 3.9 (*Describing a limestone (Calcite) rock with the purpose of injecting Na2CO3 or sodium
metaborate *)
CALCIUM
MAGNESIUM
SODIUM
HYDROGEN (REACTIVE)
Sulfur (AS SULFATE)
B(OH)4CHLORINE (* ELEMNT *)
2 2 -2 1 1 -2 -1 -1 (* ELCRG *)
HYDROGEN ION
SODIUM ION
CALCIUM ION
MAGENSIUM ION
CARBONATE ION
SULFATE ION
B(OH)4WATER
SODIUM MONOHYDROXIDE
MAGNESIUM MONOHYROXIDE ION
Na(HCO3)
CA (HC03) +
MG (HCO3) +
HYDROXIDE ION
B(OH)3
CaB(OH)4+
MgB(OH)4+
BICARBONATE ION
AQUEOUS SODIUM CARBONATE
AQUEOUS CALCIUM CARBONATE
315
AQUEOUS MAGNESIUM CARBONATE

AQUEOUS SODIUM SULFATE
AQUEOUS CALCIUM SULFATE
AQUEOUS MAGNESIUM SULFATE
H2CO3 (* FLDSPS *)
CALCIUM CARBONATE(SOLID)
DOLOMITE (SOLID)
CALCIUM HYDROXIDE (SOLID)
MAGNESIUM HYDROXIDE(SOLID)
GYPSUM(SOLID)
Boric acid
Borax (* SLDSPS *)
0
0
1
0
0
1
0
0
0
1
0
0
0
0
0
1
0
0
1
0
0
0
1
0
0
0
0
0
1
1
1
0
0
0
0
1
0
1
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
1
1
1
1
0
0
2
0
0
0
0
0
0
0
0
0
1
1
0
0
0
0
0
0
0
0
0
1
0
0
0
1
1
1
0
1
0
1
0
1
0
1
2
0
0
0
0
0
0
0
0
0
0
2
2
0
0
0
0
0
1
0
0
0
0
0
1
0
0
0
0
0
1
0
0
0
0
0
1
0
0
0
0
0
1
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
-1
1
0
0
0
-1
0
1
0
0
-1
0
0
1
0
1
1
0
0
1
0
1
0
0
0
0
0
0
1
1
0
0
0
0
0
0
0
1
0
0
0
0
0
0
1
1
0
0
0
0
0
0
0
1
0
1
0
1
0
1
1
0
0
0
0
0
0
0
1
1
0
0
0
0
1
1
0
1
0
1
2
1
1
0
1
0
1
0
1
0
1
0
0
0
0
0
0
0
0
0
0
0
0
1
0
1
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
1
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
2
2
0
4 (* BR *)
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
1
0
0
0
0
0
0
0
0
316
1
0
1
1
0
0
-1
0
0
1
0
0
-1
0
1
-1
0
0
1
0
0
0
1
0
0
0
1
0
0
0
0
1
0
0
0
1
0
0
0
2
0
0
0
0
1
0
0
1
-2
0
1
-2
0
0
0
0
1
1
0
0
2
2
0
1
1
2
2
-2
-2
-1
0
0
1
1
0
1
1
-1
0
1
1
-1
-1
0
0
-1
0
0
0 (* CHAEGE *)
1
1
1
1
1
0
1
0
0
0
1
0
0
0
1
0
0
1
0
0
1
0
1
0
0
0
1
1
0
0
0
0
1
1
1
1
0
0
0
1
1
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
0
0
0
0
0
1
0
0
0
0
0
1
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
1
4
317
0
0
0
0
0
0
0
0
0
0
0
0
0
0
(* BB *)
0
0
0
0
0
0
0 (* EXSLD *)
1
1
1
1.60E-14
6.01E-13
4.92E-12
2.05E+10
3.42E+11
2.12E+11
2.55E-14
1.68E+09
3.58E-08
3.25E-08
1.91E+10
2.33E+00
2.03E+03
1.01E+03
5.32E+00
2.43E+02
1.91E+02
4.18E+16 (* KEQ *)
1.65768E-09
3.245E-19
4.39744E+21
4.25E+15
3.36047E-05 3.52939E-10
2.49977E-26 (* KSP *)
0.68 0.0 (*C50, Csurf*)
0.002 0.002 0.002 0.679 111.00 0.002 0.002 (*CELFLT 1,NELEMENT-1*)
10.0 0.0 0.0 0.0 0.12 0.0 0.0 (*CSLD(I), I=1,NSLD*)
0.1200077231590e-07 0.1 0.1e-04
0.4616423363603e-05 0.3092684582095e-08 0.1e-08 0.1e-08
55.49999314650 (*CIND*)
1.0 (*S1*)
3. EQBATCH Input File for Case A in Chapter 4

Case A (* Setting up the important reactions for soap generation including aqueous and cation
exchange reactions *)
4 (* NACD *)
SODIUM
HYDROGEN (REACTIVE)
Oleic acid
chlorine (* ELEMNT *)
-2 1 1 -1 -1 (* ELCRG *)
HYDROGEN ION
SODIUM ION
CARBONATE ION
318
HAo
WATER
AOHHCO3H2CO3
HAw (* FLDSPS *)
SORBED HYDROGEN ION
SORBED SODIUM ION (* SORBSPS *)
2 (* NSORBX *)
0
0
1
0
0
0
1
0
0
0
1
0
0
1
2
0
0
0
1
0
0
0
0
1
1
0
0
0 (* DR *)
1
0
0
0
0
0
1
0
0
0
0
0
1
0
0
0
0
0
1
0
0
0
0
0
1
-1
0
0
1
0
-1
0
0
0
0
1
0
1
0
0
2
0
1
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
1
1
-2
0
0
-1
-1
-1
0
0 (* CHAEGE *)
1
1
1
1
1
9.59E-13
1.46E-14
2.11E+10
4.89E+16
9.59E-05 (* KEQ *)
1. 1. (* SCHARGE *)
2.7e+06 (* KEX *)
0
0
0
1
0
0
1
0
1
0
1
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
1
(* BB *)
319
1
0
2
0
0
0
1
1 (* AR *)
-1
1
0
0
0
1
-1
0. (* REDUC *)
0.018 (* EXCAI *)
0.085 0.0 (*C50, Csurf*)
0.004 0.088 111.00 0.0055 (*CELFLT 1,NELEMENT-1*)
0.005 0.01 (* CSORBI *)
0.1200077231590e-07 0.01
0.3092684582095e-03 1.13e-3
55.49999314650 1.0e-06 1.0e-04 (*CIND*)
0.6 (*S1*)
500
(* EXEX *)
4. EQBATCH Input File for ASP Coreflood in Chapter 6

CoreASP (* Setting up the important reactions for soap generation including aqueous and cation
exchange reactions *)
4 (* NACD *)
SODIUM
HYDROGEN (REACTIVE)
Oleic acid
-2 1 1 -1 -1 (* ELCRG *)
HYDROGEN ION
SODIUM ION
CARBONATE ION
HAo
WATER
AOHHCO3H2CO3
HAw (* FLDSPS *)
SORBED HYDROGEN ION
2 (* NSORBX *)
0
0
1
0
0
0
0
1
1
0
0
1
0
0
0
0
0
0
0
0
1
0
0
1
2
0
1
1
2
1
0
0
0
1
0
1
0
0
0
1 (* AR *)
0
0
0
1
1
0
0
0 (* DR *)
1
0
0
0
0
0
0
0
1
0
0
0
0
0
320
0
0
1
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
1
0
0
-1
0
0
1
0
0
0
-1
0
0
0
0
0
0
1
0
1
0
0
0
0
2
0
1
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
1
1
1
-2
0
0
-1
-1
-1
0
0 (* CHAEGE *)
1
1
1
1
1
9.59E-13
1.46E-14
2.11E+10
4.89E+16
9.59E-05 (* KEQ *)
1. 1. (* SCHARGE *)
2.7e+06 (* KEX *)
-1
1
0
0
0
1
-1
0. (* REDUC *)
0.118 (* EXCAI *)
0.325 0.0 (*C50, Csurf*)
0.001 0.325 111.00 0.235 (*CELFLT 1,NELEMENT-1*)
0.024 0.015 (* CSORBI *)
0.1200077231590e-07 0.01
0.3092684582095e-03 1.13e-3
55.49999314650 1.0e-06 1.0e-04 (*CIND*)
0.28 (*S1*)
500
(* BB *)
(* EXEX *)
5. EQBATCH Input File for Coreflood BM-07 in Chapter 7

MB07 (* Setting up the important reactions for high pH flood- no solid reaction included*)
321

CALCIUM
SODIUM
HYDROGEN (REACTIVE)
2 -2 1 1 -1 (* ELCRG *)
HYDROGEN ION
SODIUM ION
CALCIUM ION
CARBONATE ION
WATER
CA (HC03) +
HYDROXIDE ION
BICARBONATE ION
DISSOLVED CARBON MONOHYDROXIDE
AQUEOUS CALCIUM CARBONATE (* FLDSPS *)
SORBED HYDROGEN ION
SORBED SODIUM ION
3 (* NSORBX *)
0
0
1
0
0
1
1
0
0
0
1
0
0
1
0
1
0
0
0
0
0
1
0
0
0
2
1
1
0
0
1
0
0
0
0
1
0
1
0
0 (* DR *)
1
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
1
0
0
-1
0
1
0
0
0
0
1
0
1
1
0
0
0
-1
0
0
0
0
0
0
1
0
0
1
0
0
0
2
0
0
1
0
0
0
0
0
1
1
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
1
1
2
-2
0
1
1
322
0
0
0
1
0
1
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
1 (* BB *)
0
1
0
2
1
1
0
0 (* AR *)
-1
-1
0
0 (* CHAEGE *)
1
1
1
1
1
1.56E-11
5.08E+11
3.21E-13
1.66E+10
3.90E+16
1.58E+03 (* KEQ *)
1. 1. 2. (* SCHARGE *)
100 0.1e+05 (* KEX *)
0
2
-1
0
0
0
-2
1
-1
1
0
0
0
1
-1
0 (* EXEX *)
-1. 0. (* REDUC *)
0.026 (* EXCAI *)
0.042 0.0 (*C50, Csurf*)
0.001 0.00001 0.039 111.00 (*CELFLT 1,NELEMENT-1*)
0.005 0.020 0.001 (* CSORBI *)
0.1200077231590e-07 0.01 0.1e-04
0.3092684582095e-03
55.49999314650 1.0e-06 1.0e-04 1.0e-04 (*CIND*)
0.65 (*S1*)

CC*******************************************************************
CC
*
CC BRIEF DESCRIPTION OF DATA SET : UTCHEM (VERSION 9.3)
*
CC
*
CC*******************************************************************
CC
*
CC Alkaline FLOODING
*
CC
*
CC LENGTH (FT) :
PROCESS :
*
CC THICKNESS (FT) :
INJ. PRESSURE (PSI) :
*
CC WIDTH (FT) :
*
CC POROSITY :
*
CC GRID BLOCKS :
*
CC DATE :
*
CC
*
CC*******************************************************************
CC
CC*******************************************************************
323
CC
*
*
CC
*
CC*******************************************************************
CC
CC
*----RUNNO
Case3-4
CC
CC
*----HEADER
Simulation with congruent kaolinite dissolution (Case3.4) @85C
using Berea core (Reactions included are cation exchange and kaolinite dissolution)
Sodium Carbonate as alkali injected
CC
CC SIMULATION FLAGS
1 4 3 0 0 2 0 1 0 0 0 0
CC
CC NUMBER OF GRID BLOCKS AND FLAG SPECIFIES CONSTANT OR VARIABLE GRID
SIZE
*----NX NY NZ IDXYZ IUNIT
1 1 100 0
0
CC
CC CONSTANT GRID BLOCK SIZE IN X, Y, AND Z
*----DX
DY
DZ
0.1665 0.1665 0.01
CC
13 0 0 0 5 0 0
CC
CC
WATER
OIL
SURFACTANT
POLYMER
ANION
CALCIUM
alc1
alc2
CARBON(As Carbonate)
ALUMINIUM
SILICON
SODIUM
HYDROGEN
CC
1 1 1 1 1 1 0 0 1 1 1 1 1
CC
324
CC*******************************************************************
CC
*
CC OUTPUT OPTIONS
*
CC
*
CC*******************************************************************
CC
CC
CC FLAG FOR PV OR DAYS FOR OUTPUT AND STOP THE RUN
*----ICUMTM ISTOP IOUTGMS
1
1 0
CC
*----IPRFLG(KC),KC=1,N
1 1 1 1 1 1 0 0 1 1 1 1 1
CC
CC FLAG FOR PRES,SAT.,TOTAL CONC.,TRACER CONC.,CAP.,GEL, ALKALINE PROFILES
*----IPPRES IPSAT IPCTOT IPBIO IPCAP IPGEL IPALK ITEMP IPOBS
1 1 1 0 0 0 1 0
0
CC
CC FLAG FOR WRITING SEVERAL PROPERTIES
*----ICKL IVIS IPER ICNM ICSE IFOAM IHYST INONEQ
1 1 0 0 1 0 0
0
CC
CC FLAG FOR WRITING SEVERAL PROPERTIES TO PROF
*----IADS IVEL IRKF IPHSE
1 0 1 1
CC
CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
CC
CC MAX. SIMULATION TIME ( PV)
*---- TMAX
2.0
CC
*----COMPR PSTAND
0. 0.
CC
PERMEABILITY
*----IPOR1 IPERMX IPERMY IPERMZ IMOD ITRANZ
0 0 3 3 0
0
CC
CC CONSTANT POROSITY
*----PORC1
.165
CC
325
*----PERMX
1500
CC
CC Y DIRECTION PERMEABILITY IS DEPENDENT ON X DIRECTION PERMEABILITY
*---- CONSTANT PERMEABILITY MULTIPLIER FOR Y DIRECTION PERMEABILITY
1
CC
CC Z DIRECTION PERMEABILITY IS DEPENDENT ON X DIRECTION PERMEABILITY
*---- CONSTANT PERMEABILITY MULTIPLIER FOR Z DIRECTION PERMEABILITY
1
CC
CC FLAG FOR CONSTANT OR VARIABLE DEPTH, PRESSURE, WATER SATURATION
0
0
0 -1
CC
*----D111
0.
CC
CC INITIAL PRESSURE (PSIA)
*----PINIT DEPTH
14.7 0.0
CC
CC CONSTANT INITIAL WATER SATURATION (residual oil)
*----SWI
1.0
CC
CC CONSTANT CHLORIDE AND CALCIUM CONCENTRATIONS (MEQ/ML)
*----C50
C60
0.0396 0.0
CC
CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
CC
*---- C2PLC C2PRC EPSME IHAND
0. 1. .001 0
CC
CC FLAG INDICATING TYPE OF PHASE BEHAVIOR PARAMETERS
*---- IFGHBN
0
CC FOR ALCOHOL 1
*---- hbns70 hbnc70 hbns71 hbnc71 hbns72 hbnc72
0.0
0.04 0.14 0.024 0.0 0.04
CC FOR ALCOHOL 2
326
0
0
0
0
0
0
CC
0.10
0.2 0
0
CC
0 2.89
0
CC
1 0.0
0.0
0
0
CC
*---- nalmax epsalc
20
0.0001
CC
3.
1.76
90 35.31 0.172
CC
0
0
0 0
0
cc
cc
*--- ift
1
CC
*----CHUH
AHUH
0.3 10
CC
*----XIFTW
1.48
CC
CC FLAG TO ALLOW SOLUBILITY OF OIL IN WATER
*---- IMASS ICOR
0 0
CC
*----ITRAP T11
T22
T33
2
1865. 59000 364.2
CC
CC REL. PERM. AND PC CURVES
*---- IPERM
0
CC
*----ISRW IPRW IEW
327
0 0 0
CC
*----S1RWC S2RWC S3RWC
.38 .35 .38
CC
*----P1RW P2RW P3RW
.05 .4 .05
CC
*----E1W E2W E3W
2.0 2.0 2.0
CC
CC RES. SATURATION OF PHASES 1,2,AND 3 AT HIGH CAPILLARY NO.
*----S1RC S2RC S3RC
.0 .0 .0
CC
CC ENDPOINT REL. PERM. OF PHASES 1,2,AND 3 AT HIGH CAPILLARY NO.
*----P1RC P2RC P3RC
1.0 1.0 1.0
CC
CC REL. PERM. EXPONENT OF PHASES 1,2,AND 3 AT HIGH CAPILLARY NO.
*----E13CW E23C E31C
1. 1. 1.0
CC
*----VIS1 VIS2 TEMPV
0.370 3.4 0.0
CC
CC VISCOSITY PARAMETERS
*----ALPHA1 ALPHA2 ALPHA3 ALPHA4 ALPHA5
0.2 2.9 0.0 0.0 0.0
CC
*----AP1 AP2 AP3
20 50. 400.
CC
*----BETAP CSE1 SSLOPE
1. .01 -0.4112
CC
*----GAMMAC GAMHF POWN IPMOD
4.0 350. 1.7 0
CC
CC FLAG FOR POLYMER PARTITIONING, PERM. REDUCTION PARAMETERS
*----IPOLYM EPHI3 EPHI4 BRK CRK rkcut
1
1.0 0.70 100. 0.04 10
CC
CC SPECIFIC WEIGHT FOR COMPONENTS 1,2,3,7,AND 8 , AND GRAVITY FLAG
*----DEN1 DEN2 den23 DEN3 DEN7 DEN8 IDEN
328
.433 .390 0.397 .42 .346 0. 2

CC
*-----ISTB
1
CC
CC FVF FOR PHASE 1,2,3
*-----(FVF(L),L=1,NPHAS)
1 1 1
CC
*----COMPC(1) COMPC(2) COMPC(3) COMPC(7) COMPC(8)
0.
0.
0.
0.
0.
CC
*----ICPC IEPC IOW
0
0 0
CC
CC CAPILLARY PRESSURE PARAMETERS, CPC
*----CPC
0.
CC
CC CAPILLARY PRESSURE PARAMETERS, EPC
*---- EPC
2.
CC
CC MOLECULAR DIFFUSIVITY OF KCTH COMPONENT IN PHASE 1 (D(KC),KC=1,N)
*----D(1) D(2) D(3) D(4) D(5) D(6)
0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0.
CC
*----D(1) D(2) D(3) D(4) D(5) D(6)
0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0.
CC
*----D(1) D(2) D(3) D(4) D(5) D(6)
0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0.
CC
*----ALPHAL(1) ALPHAT(1)
0.005
0.0011
CC
0.005
0.0011
CC
0.005
0.0011
CC
CC FLAG TO SPECIFY ORGANIC ADSORPTION CALCULATION
*----IADSO
329
0
CC
*----AD31 AD32 B3D AD41 AD42 B4D IADK, IADS1, FADS refk
2.0 0.1 1000. 1.0 0. 100. 0 0 0 0
CC
*----QV
XKC XKS EQW
0.16 0.25 0.4 429.
21
7 13 13 0.1
7 14 4 3 0 0
7 1 7 0
7 6 1 0 2
3 4 5
CALCIUM
2.00
-2.00
ALUMINIUM
3.00
SILICON
4.00
OXYGEN
-2.00
SODIUM
1.00
HYDROGEN (REACTIVE) (* ELEMNT 1.00
HYDROGEN ION
SODIUM ION
CALCIUM ION
ALUMINIUM ION
CARBONATE ION
H4SiO4
WATER
CA (HC03) +
HYDROXIDE ION
BICARBONATE ION
H3SiO4- ION
Al(OH)4- ION
DISSOLVED CARBON MONOHYDROXIDE (
Calcite (SOLID)
SILICA (SOLID)
KAOLINITE (SOLID)
ANALCITE (SOLID) (* SLDSPS *)
SORBED HYDROGEN ION
SORBED SODIUM ION
3
0. 0. 1. 0. 0. 0. 0. 1. 1. 0. 0. 0. 0. 0.
0. 0. 0. 0. 1. 0. 0. 0. 1. 0. 1. 0. 0. 1.
0. 0. 0. 1. 0. 0. 0. 0. 0. 0. 0. 0. 1. 0.
0. 0. 0. 0. 0. 1. 0. 0. 0. 0. 0. 1. 0. 0.
0. 0. 0. 0. 0. 4. 1. 1. 0. 1. 0. 4. 4. 0.
0. 1. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0.
1. 0. 0. 0. 0. 4. 2. 1. 1. 1. 1. 3. 4. 2.
1. 0. 0. 0.
330
1. 0. 0. 0.
0. 0. 2. 1.
0. 1. 2. 2.
0. 2. 9. 7.
0. 0. 0. 1.
0. 0. 4. 2.
0. 0. 1.
0. 0. 0.
0. 0. 0.
0. 0. 0.
0. 0. 0.
0. 1. 0.
1. 0. 0.
1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0
-1.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
1.0 0.0 1.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0
-1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
1.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0
-1.0 0.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0
-4.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0 0.0
2.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.0
0.0 0.0 1.0 0.0 1.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 1.0 0.0
-6.0 0.0 0.0 2.0 0.0 2.0 0.0
-4.0 1.0 0.0 1.0 0.0 2.0 0.0
1.0 1.0 2.0 3.0 -2.0 0.0 0.0 1.0 1.0 -1.0 -1.0 -1.0
-1.0 0.0
1.0 1.0 2.0
0.1000000000000E+01 0.1000000000000E+01 0.1000000000000E+01
0.1000000000000E+01 0.1000000000000E+01 0.1000000000000E+01
0.1000000000000E+01 0.1561710000000E-10 0.5080420000000E+12
0.3210700000000E-12 0.1660733705500E+11 0.5310070000000E-09
0.1510080000000E-17 0.3901220000000E+17
0.7930000000000E+01 0.2700000000000E+07
0.0 2.0 -1.0 0.0 0.0 0.0 0.0 0.0 -2.0 1.0
-1.0 1.0 0.0 0.0 0.0 0.0 0.0 1.0 -1.0 0.0
-1.0 0.0
0.2600000000000E-01
0.4569830000000E-09 0.5944290000000E-03 0.1627796086000E+04
0.5378980873000E+05
0.2240000000001E-01 0.1583932603572E-04
0.3602648213039E-01
0.1721522104167E-04
331
0.2484210600676E-02
0.4005978639175E-01
0.1110091680716E+03
0.1185584839040E-07 0.4005978639175E-01 0.5160334070395E-05
0.7507959842790E-19 0.8855686352203E-04 0.5944290000000E-03
0.5549412506835E+02
0.1631986758935E+01 0.9999839042416E+02 0.0000000000000E+00
0.9942615929861E-03
0.1154340518038E-01 0.1444595201527E-01 0.5321402174493E-05
CC
CC*******************************************************************
CC
*
CC WELL DATA
*
CC
*
CC*******************************************************************
CC
CC
CC FLAG FOR PRESSURE CONST. BOUNDARIES
*---- IBOUND IZONE
0 0
CC
*----NWELL IRO ITIME NWREL
2 2 1 2
CC
*----IDW IW JW IFLAG RW SWELL IDIR IFIRST ILAST IPRF
1 1 1 1 .003
0. 3 100 100 0
CC
CC WELL NAME
*---- WELNAM
INJECTOR
CC
CC ICHEK MAX. AND MIN. ALLOWABLE BOTTOMHOLE PRESSURE AND RATE
*----ICHEK PWFMIN PWFMAX QTMIN QTMAX
0 0.0 5000. 0.0 50000.
CC
CC WELL ID, LOCATION, AND FLAG FOR SPECIFYING WELL TYPE, WELL RADIUS, SKIN
2 1 1 2
.003 0. 3 1
1
0
CC
CC WELL NAME
*---- WELNAM
PRODUCER
CC
CC MAX. AND MIN. ALLOWABLE BOTTOMHOLE PRESSURE AND RATE
0 0.0 5000. 0.0 50000.
CC
*----ID QI(M,L) C(M,KC,L)
1 0.0046 1.0 0. 0.0 .0 0.022 0.0001 0.0 0. 0.22468 0.0001 0.0001 0.22768 111
332
1 0.
0. 0. 0. 0. 0.
0. 0. 0. 0. 0. 0. 0. 0.
1 0.
0. 0. 0. 0. 0.
0. 0. 0. 0. 0. 0. 0. 0.
CC
CC ID,
*----ID PWF
2 14.7
CC
*----TINJ CUMPR1 CUMHI1 WRHPV WRPRF RSTC
1.0 0.05 0.05
0.05 0.05
0.1
CC
CC FOR IMES=2 ,THE INI. TIME STEP,CONC. TOLERANCE,MAX.,MIN. COURANT NO.
*----DT DCLIM CNMAX CNMIN
0.0001 13*0.01 0.1 0.01
CC
CC
*--- IBMOD
0
CC34567890---------2---------3---------4---------5---------6---------7---------8
CC IRO, ITIME, NEW FLAGS FOR ALL THE WELLS (POLYMER DRIVE)
*---- IRO ITIME IFLAG
2 1 1 2
CC
CC NUMBER OF WELLS changes IN LOCATION OR SKIN OR PWF
*----NWEL1
0
CC
CC NUMBER OF WELLS WITH RATE changes, id
*----NWEL1 Id
1
1
CC
CC id,INJ. RATE AND INJ. COMP. FOR RATE CONS. WELLS FOR EACH PHASE (L=1,3)
*----id QI(M,L) C(M,KC,L)
1 0.0046 1.0
0.0 0. .0 0.022
0.0001 0. 0. 0.036 0.0001 0.0001 0.039 111.
1 0.
0. 0. 0. 0. 0.
0. 0. 0. 0. 0. 0. 0. 0.
1 0.
0. 0. 0. 0. 0.
0. 0. 0. 0. 0. 0. 0. 0.
CC
CC CUM. INJ. TIME , AND INTERVALS (PV) FOR WRITING TO OUTPUT FILES
*----TINJ CUMPR1 CUMHI2(SUMARY) WRHPV(HIST) WRPRF(PLOT) RSTC
2.0 0.02 0.02
0.02 0.02
0.2
CC
CC FOR IMES=2 ,THE INI. TIME STEP,CONC. TOLERANCE,MAX.,MIN. time steps
0.0001 13*0.01 0.1 0.01
333

CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
*
CC Alkaline FLOODING
*
CC
*
CC LENGTH (FT) :
PROCESS :
*
CC THICKNESS (FT) :
*
CC WIDTH (FT) :
*
CC POROSITY :
*
CC GRID BLOCKS :
*
CC DATE :
*
CC
*
CC*******************************************************************
CC
CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
CC
*----RUNNO
Case3-9
CC
CC
*----HEADER
Simulation with limestone rock containing calcite and gypsum (Case3.9)
Sodium metaborate as alkali injected
*****************************************************
CC
CC SIMULATION FLAGS
1 3 3 0 0 2 0 1 0 0 0 0
CC
SIZE
100 1 1 0
0
CC
*----DX
DY
DZ
0.0091185 0.124 0.124
CC
14 0 0 0 6 0 0
334
CC
CC
WATER
OIL
SURFACTANT
POLYMER
ANION
CALCIUM
alcohol1
alcohol2
Magnesium
CARBON(As Carbonate)
SODIUM
HYDROGEN
Sulfur (AS SULFATE)
B(OH)3
CC
1 1 1 1 1 1 0 0 1 1 1 1 1 1
CC
CC*******************************************************************
CC
*
CC OUTPUT OPTIONS
*
CC
*
CC*******************************************************************
CC
CC
1
1 0
CC
1 1 1 1 1 1 0 0 1 1 1 1 1 1
CC
1 1 1 0 0 0 1 0
0
CC
1 1 1 1 1 0 0
0
CC
1 0 1 1
CC
CC*******************************************************************
CC
*
*
335
CC
*
CC*******************************************************************
CC
CC
*---- TMAX
2
CC
*----COMPR PSTAND
0. 0.
CC
PERMEABILITY
*----IPOR1 IPERMX IPERMY IPERMZ IMOD
0 0 3 3 0
CC
*----PORC1
.19
CC
*----PERMX
448
CC
1
CC
1
CC
0
0
0 -1
CC
*----D111
0.
CC
*----PINIT DEPTH
14.7 0.0
CC
*----SWI
1.0
CC
*----C50
C60
0.51282 0.0
336
CC
CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
CC
0. 1. .0001 0
CC
*---- IFGHBN
0
CC FOR ALCOHOL 1
0. .05 0. .045 0.0 .06
CC FOR ALCOHOL 2
0. 0. 0. 0. 0. 0.
CC
0.5 1.0 0
0
CC
*----BETA6 BETA7 BETA8
0.8 0. 0.
CC
*----IALC OPSK7O OPSK7S OPSK8O OPSK8S
0 0. 0. 0. 0.
CC
*----NALMAX EPSALC
20
.0001
CC
*----AKWC7 AKWS7 AKM7 AK7 PT7
4.671 1.79 48. 35.31 .222
CC
*----AKWC8 AKWS8 AKM8 AK8 PT8
0. 0. 0. 0. 0.
cc
cc
*--- ift
1
CC
337

*----CHUH
AHUH
0.3 10
CC
*----XIFTW
1.5
CC
*---- IMASS ICOR
0 0
CC
*----ITRAP T11
T22
T33
1
1865. 70000 364.2
CC
*---- IPERM
0
CC
*----ISRW IPRW IEW
0 0 0
CC
.35 .35 .35
CC
*----P1RW P2RW P3RW
.08 0.4 .08
CC
*----E1W E2W E3W
2.0 2.0 2.0
CC
*----S1RC S2RC S3RC
.0 .0 .0
CC
*----P1RC P2RC P3RC
1.0 1.0 1.0
CC
*----E13CW E23C E31C
1. 1. 1.0
CC
0.37 3.0 0.0
CC
338
1.
1.5 .2 .5 .5
CC
*----AP1 AP2 AP3
20 40. 500.
CC
1. .01 -0.38
CC
*----GAMMAC GAMHF POWN
24. 200. 1.63
CC
*----IPOLYM EPHI3 EPHI4 BRK CRK
1 1. 1 100. 0.034
CC
.433 .390 0.39 .42 .346 0. 1
CC
*-----ISTB
1
CC
1 1 1
CC
0.
0.
0.
0.
0.
CC
*----ICPC IEPC IOW
0
0 0
CC
*----CPC
0.
CC
*---- EPC
2.
CC
*----D(1) D(2) D(3) D(4) D(5) D(6)
0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0
CC
339

*----D(1) D(2) D(3) D(4) D(5) D(6)
0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0
CC
*----D(1) D(2) D(3) D(4) D(5) D(6)
0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0
CC
0.000
0.000
CC
0.000
0.000
CC
0.000
0.000
CC
*----IADSO
0
CC
0.0 0 1000. 0 0.0 100. 0 0 0 0
CC
*----QV
XKC XKS EQW
0.044 .25 .2 419.
2 0
8 26 7 0 0 1
8 0 5 0
5 4 1 2 3
0 0 0
CALCIUM
2.00
MAGNESIUM
2.00
-2.00
SODIUM
1.00
HYDROGEN (REACTIVE)
1.00
Sulfur (AS SULFATE)
-2.00
B(OH)4-1.00
-1.00
HYDROGEN ION
SODIUM ION
CALCIUM ION
MAGENSIUM ION
CARBONATE ION
SULFATE ION
B(OH)4WATER
340
SODIUM MONOHYDROXIDE
MAGNESIUM MONOHYROXIDE ION
Na(HCO3)
CA (HC03) +
MG (HCO3) +
HYDROXIDE ION
B(OH)3
CaB(OH)4+
MgB(OH)4+
BICARBONATE ION
AQUEOUS SODIUM CARBONATE
AQUEOUS CALCIUM CARBONATE
AQUEOUS MAGNESIUM CARBONATE
AQUEOUS SODIUM SULFATE
AQUEOUS CALCIUM SULFATE
AQUEOUS MAGNESIUM SULFATE
H2CO3 (* FLDSPS *)
CALCIUM CARBONATE(SOLID)
DOLOMITE (SOLID)
CALCIUM HYDROXIDE (SOLID)
MAGNESIUM HYDROXIDE(SOLID)
GYPSUM(SOLID)
Boric acid
Borax (* SLDSPS *)
0. 0. 1. 0. 0. 0. 0. 0. 0. 1. 0. 0. 1. 0. 0.
0. 1. 0. 0. 0. 1. 0. 0. 1. 0. 0.
0. 0. 0. 1. 0. 0. 0. 0. 0. 0. 1. 0. 0. 1. 0.
0. 0. 1. 0. 0. 0. 1. 0. 0. 1. 0.
0. 0. 0. 0. 1. 0. 0. 0. 0. 0. 0. 1. 1. 1. 0.
0. 0. 0. 1. 1. 1. 1. 0. 0. 0. 1.
0. 1. 0. 0. 0. 0. 0. 0. 1. 0. 0. 1. 0. 0. 0.
0. 0. 0. 0. 1. 0. 0. 1. 0. 0. 0.
1. 0. 0. 0. 0. 0. 0. 2. 1. 1. 1. 1. 1. 1. 1.
1. 1. 1. 1. 0. 0. 0. 0. 0. 0. 2.
0. 0. 0. 0. 0. 1. 0. 0. 0. 0. 0. 0. 0. 0. 0.
0. 0. 0. 0. 0. 0. 0. 1. 1. 1. 0.
0. 0. 0. 0. 0. 0. 1. 0. 0. 0. 0. 0. 0. 0. 0.
1. 1. 1. 0. 0. 0. 0. 0. 0. 0. 0.
1. 1. 1. 0. 1. 0. 0.
0. 1. 0. 1. 0. 0. 0.
1. 2. 0. 0. 0. 0. 0.
0. 0. 0. 0. 0. 0. 2.
0. 0. 2. 2. 0. 1. 2.
0. 0. 0. 0. 1. 0. 0.
0. 0. 0. 0. 0. 1. 4.
1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 1.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 1.0 0.0 0.0
341
0.0 0.0 0.0 0.0 0.0 0.0 1.0 0.0

0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.0
-1.0 1.0 0.0 0.0 0.0 0.0 0.0 0.0
-1.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0
-1.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0
1.0 1.0 0.0 0.0 1.0 0.0 0.0 0.0
1.0 0.0 1.0 0.0 1.0 0.0 0.0 0.0
1.0 0.0 0.0 1.0 1.0 0.0 0.0 0.0
-1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
1.0 0.0 0.0 0.0 0.0 0.0 1.0 0.0
-1.0 0.0 1.0 0.0 0.0 0.0 1.0 0.0
-1.0 0.0 0.0 1.0 0.0 0.0 1.0 0.0
1.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0
0.0 1.0 0.0 0.0 1.0 0.0 0.0 0.0
0.0 0.0 1.0 0.0 1.0 0.0 0.0 0.0
0.0 0.0 0.0 1.0 1.0 0.0 0.0 0.0
0.0 1.0 0.0 0.0 0.0 1.0 0.0 0.0
0.0 0.0 1.0 0.0 0.0 1.0 0.0 0.0
0.0 0.0 0.0 1.0 0.0 1.0 0.0 0.0
2.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0
0.0 0.0 1.0 0.0 1.0 0.0 0.0 0.0
0.0 0.0 1.0 1.0 2.0 0.0 0.0 0.0
-2.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0
-2.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0
0.0 0.0 1.0 0.0 0.0 1.0 0.0 0.0
1.0 0.0 0.0 0.0 0.0 0.0 1.0 0.0
2.0 2.0 0.0 0.0 0.0 0.0 4.0 0.0
1.0 1.0 2.0 2.0 -2.0 -2.0 -1.0 0.0 0.0 1.0 1.0 0.0
1.0 1.0 -1.0 0.0 1.0 1.0 -1.0 -1.0 0.0 0.0 -1.0 0.0
0.0 0.0
0.1000000000000E+01 0.1000000000000E+01 0.1000000000000E+01
0.1000000000000E+01 0.1000000000000E+01 0.1000000000000E+01
0.1000000000000E+01 0.1000000000000E+01 0.1600000000000E-13
0.6010000000000E-12 0.4920000000000E-11 0.2050000000000E+11
0.3420000000000E+12 0.2120000000000E+12 0.2550000000000E-13
0.1680000000000E+10 0.3580000000000E-07 0.3250000000000E-07
0.1910000000000E+11 0.2330000000000E+01 0.2030000000000E+04
0.1010000000000E+04 0.5320000000000E+01 0.2430000000000E+03
0.1910000000000E+03 0.4180000000000E+17
0.1657680000000E-08 0.3245000000000E-18 0.4397440000000E+22
0.4250000000000E+16 0.3360470000000E-04 0.3529390000000E-09
0.2499770000000E-25
0.6800000000000E+00 0.4075440274555E-01
0.4000000000000E-02
0.1772072204895E-02
0.6790000000000E+00
0.1110000000000E+03
0.4298233054065E-01
0.2000000000000E-02
0.1485112902279E-06 0.6688581917580E+00 0.1212362679201E-01
0.1303867260699E-02 0.1367313616989E-06 0.2771835571692E-02
0.7983962600592E-05 0.5549849965117E+02
342
0.1000111396390E+02 0.0000000000000E+00 0.0000000000000E+00

0.0000000000000E+00 0.1005088347297E+00 0.0000000000000E+00
0.0000000000000E+00
CC
CC*******************************************************************
CC
*
CC WELL DATA
*
CC
*
CC*******************************************************************
CC
CC
*---- IBOUND IZONE
0 0
CC
2 2 1 2
CC
1 1 1 1 .003 0 3 1
1 0
CC
CC WELL NAME
*---- WELNAM
INJECTOR
CC
0 0.0 5000. 0.0 50000.
CC
2 100 1 2
.003 0. 3 1
1
0
CC
CC WELL NAME
*---- WELNAM
PRODUCER
CC
0 0.0 5000. 0.0 50000.
CC
1 0.025 1.0 0. 0.0 .0 0.68 0.001 0. 0. 0.001 0.001 0.77 111 0.001 0.1
1 0. 0.
0. 0.
0. 0. 0. 0. 0. 0.
0.
0. 0.
0. 0
1 0. 0.
0. 0.
0. 0. 0. 0. 0. 0.
0.
0. 0.
0. 0
CC
CC ID,
*----ID PWF
2 14.7
343
CC
1.0 0.05 0.05
0.05 0.05
1.
CC
0.00001 0.1 0.1 0.001 .01 0.01 0.0001 0. 0.
0.0001 0.0001 0.01 11.1 0.0001
0.01 0.1 0.01
CC
CC
*--- IBMOD
0
CC34567890---------2---------3---------4---------5---------6---------7---------8
2 1 1 2
CC
*----NWEL1
0
CC
*----NWEL1 Id
1
1
CC
1 0.025 1.0
0. 0.0 .0 0.68 0.001 0. 0. 0.001 0.001 0.67 111 0.001 0.001
1 0. 0.
0. 0.
0. 0. 0. 0. 0. 0.
0.
0. 0.
0. 0
1 0. 0.
0. 0.
0. 0. 0. 0. 0. 0.
0.
0. 0.
0. 0
CC
2.0 0.1 0.1
0.02
0.1
2.2
CC
0.00001 0.1 0.1 0.001 .01 0.01 0.0001 0. 0.
0.0001 0.0001 0.01 11.1 0.0001
0.01 0.1 0.01
8. UTCHEM Input File for Case AII in Chapter 5

CC*******************************************************************
CC
*
*
344
CC
*
CC*******************************************************************
CC
*
CC History match of ASP core flood
*
CC
*
CC LENGTH (FT) :
PROCESS : A/S/P FLOODING
*
CC THICKNESS (FT) :
*
CC WIDTH (FT) :
*
CC POROSITY :
*
CC GRID BLOCKS : 1X1X100
*
CC DATE :
*
CC
*
CC*******************************************************************
CC
CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
CC
*----RUNNO
#C1
CC
CC
*----HEADER
ASP coreflood
Experiment
***********************************************************
CC
CC SIMULATION FLAGS
1 4 3 0 0 3 0 1 0 0 0 0
CC
SIZE
1 1 100 0
0
CC
*----DX
DY
DZ
0.1475 0.1475 0.01
CC
12 0 0 0 4 0 0
CC
CC
WATER
OIL
SURFACTANT
345
POLYMER
ANION
CALCIUM
alc1
alc2
CARBONATE
SODIUM
HYDROGEN
pet acid
CC
1 1 1 1 1 1 0 0 1 1 11
CC
CC*******************************************************************
CC
*
CC OUTPUT OPTIONS
*
CC
*
CC*******************************************************************
CC
CC
1
1 0
CC
1 1 1 1 1 1 0 0 1 1 1 1 1
CC
1 1 1 0 0 0 1 0
0
CC
1 1 1 1 1 0 0
0
CC
1 0 1 1
CC
CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
CC
*---- TMAX
2.5
CC
346

*----COMPR PSTAND
0. 0.
CC
CC FLAGS INDICATING CONSTANT OR VARIABLE POROSITY, X,Y,AND
PERMEABILITY
*----IPOR1 IPERMX IPERMY IPERMZ IMOD ITRANZ INTG
0 0 3 3 0
0
0
CC
*----PORC1
.17
CC
*----PERMX
683
CC
1
CC
1
CC
0
0
0 -1
CC
*----D111
0.
CC
*----PINIT DEPTH
14.7 0.0
CC
*----SWI
0.6
CC
*----C50
C60
0.0396 0.0
CC
CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
CC 3.4.1 OIL CONC. AT PLAIT POINT FOR TYPE II(+)AND TYPE II(-), CMC
347
CC
CMC
0 1 0.001 0
CC
CC 3.4.2 flag indicating type of phase behavior parameters
*---- ifghbn=0 for input height of binodal curve; =1 for input sol. ratio
0
CC 3.4.3 SLOPE AND INTERCEPT OF BINODAL CURVE AT ZERO, OPT., AND 2XOPT
SALINITY
CC FOR ALCOHOL 1
0 0.035
0 0.0175 0 0.035
SALINITY
CC FOR ALCOHOL 2
0
0.0
0
0.0
0
0.0
CC
CC 3.4.6 LOWER AND UPPER EFFECTIVE SALINITY FOR ALCOHOL 1 AND ALCOHOL 2
0.55 1.1 0
0
CC 3.4.7 THE CSE SLOPE PARAMETER FOR CALCIUM AND ALCOHOL 1 AND ALCOHOL 2
CC Ca Alcohol#1 Alcohol#2
0
0
0
CC
CC 3.4.8 FLAG FOR ALCOHOL PART. MODEL AND PARTITION COEFFICIENTS
0 0
0
0
0
CC these are used only for alcohol partitioning in a two alcohol system:
CC 3.4.9 NO. OF ITERATIONS, AND TOLERANCE
*---- nalmax epsalc
20
0.0001
CC 3.4.10 ALCOHOL 1 PARTITIONING PARAMETERS IF IALC=1
CC aq-oleic aq-oleic surf-oleic
*---- akwc7 akws7 akm7
ak7 pt7
4.671 1.79
48
35.31 0.222
CC
0
0
0 0
0
CC
CC 3.4.22 ift model flag
*---- ift=0 for Healy&Reed; =1 for Chun Huh correl.
1
CC 3.4.24 INTERFACIAL TENSION PARAMETERS
CC typ=.1-.35 typ=5-20
*---- chuh
ahuh
0.3
10
CC 3.4.25 LOG10 OF OIL/WATER INTERFACIAL TENSION
CC units of log 10 dynes/cm = mN/m
*---- xiftw
348
1.3
CC 3.4.26 ORGANIC MASS TRANSFER FLAG
CC imass=0 for no oil sol. in water. icorr=0 for constant MTC
*---- imass icor
0
0
CC 3.4.31 CAPILLARY DESATURATION PARAMETERS FOR PHASE 1, 2, AND 3
CC
AQ OLEIC ME
*---- itrap t11
t22
t33
2
1865 59074 364.2
CC
CC 3.4.32 FLAG FOR RELATIVE PERMEABILITY AND CAPILLARY PRESSURE MODEL
*---- iperm=0 IRTYPE
0
0
CC
CC 3.4.35 FLAG FOR CONSTANT OR VARIABLE REL. PERM. PARAMETERS
*---- isrw iprw iew
0 0
0
CC
.32 .35 .32
CC
*----P1RW P2RW P3RW
.05 0.6 .05
CC
*----E1W E2W E3W
3.5 2.0 3.5
CC
*----S1RC S2RC S3RC
.0 .0 .0
CC
*----P1RC P2RC P3RC
1.0 1.0 1.0
CC
*----E13CW E23C E31C
1.0 1.0 1.0
CC 3.4.61 WATER AND OIL VISCOSITY , RESERVOIR TEMPERATURE
CC water oil
=0 for isothermal modeling
0.5 19 0
CC
CC 3.4.80 COMPOSITIONAL PHASE VISCOSITY PARAMETERS for microemulsion
1.0
2.0
0.5
0.5 0.5
CC
CC 3.4.81 PARAMETERS TO CALCULATE POLYMER VISCOSITY AT ZERO SHEAR RATE
*---- AP1 AP2 AP3
349
45
200 850
CC
CC 3.4.82 PARAMETER TO COMPUTE CSEP,MIN. CSEP, AND SLOPE OF LOG VIS. VS. LOG
CSEP
1 0.01 -0.38
CC
CC 3.4.83 PARAMETER FOR SHEAR RATE DEPENDENCE OF POLYMER VISCOSITY
*---- GAMMAC GAMHF POWN IPMOD
4.0 10.0 1.9 0
CC
CC 3.4.84 FLAG FOR POLYMER PARTITIONING, PERM. REDUCTION PARAMETERS
RKCUT
1
1.0 0.80 100 0.05
10
CC 3.4.85 SPECIFIC WEIGHT FOR COMPONENTS 1,2,3,7,8 ,Coeffient of oil and GRAVITY
FLAG
CC if IDEN=1 ignore gravity effect; =2 then include gravity effect
0.44 0.4065 0.4065 0.42 0.346 0
2
CC ISTB=0:BOTTOMHOLE CONDITION , 1: STOCK TANK
CC 3.4.93 FLAG FOR CHOICE OF UNITS when printing
*----- ISTB
1
CC 3.4.94 FORMATION VOLUME FACTOR - may set all these to 1.0 and just factor in post-proc
CC
water oil
me
*----- FVF(I), I=1 TO MXP (IGAS=0 MXP=3,IGAS=1 MXP=4)
1.00265
1.057
1
CC
CC 3.4.95 COMPRESSIBILITY FOR VOL. OCCUPYING COMPONENTS 1,2,3,7,AND 8
*---- COMPC(1)
COMPC(2) COMPC(3) COMPC(7) COMPC(8)
0.0000033
0.0000234
0
0
0
CC IOW=0 water wet, =1 oil wet, =2 mixed wet
CC 3.4.99 CONSTANT OR VARIABLE PC PARAM., WATER-WET OR OIL-WET PC CURVE
FLAG
*---- ICPC IEPC IOW
0
0 0
CC
CC 3.4.100 CAPILLARY PRESSURE PARAMETER, CPC0
*---- CPC0
0
CC
CC 3.4.103 CAPILLARY PRESSURE PARAMETER, EPC0
*---- EPC0
0.0
CC
CC 3.4.117 MOLECULAR DIFFUSION COEF. KCTH COMPONENT IN PHASE 1
*---- D(KC,1),KC=1,N
0
0
0
0
0
0
0
0
0
0
0
0
CC
*---- D(KC,2),KC=1,N
0
0
0
0
0
0
0
0
0
0
0
0
350
CC
*---- D(KC,3),KC=1,N
0
0
0
0
0
0
0
0
0
0
0
0
CC
CC 3.4.121 LONGITUDINAL AND TRANSVERSE DISPERSIVITY OF PHASE 1
0.02
0.002
CC
0.02
0.002
CC
0.02
0.002
CC
CC 3.4.125 flag to specify organic adsorption calculation
*---- iadso=0 if organic adsorption is not considered
0
CC
CC 3.4.130 SURFACTANT AND POLYMER ADSORPTION PARAMETERS
3.0 0.1 1000 2.0 0.1 100 0 0 0 50
CC
CC 3.4.131 PARAMETERS FOR CATION EXCHANGE OF CLAY AND SURFACTANT
0
0 0
400
2 1
7 13 13 0.1
0.1 0.2
5 10 0 2 0 1
5 1 4 6
3 2 0 0 1
0 0 0
4
-2.00
SODIUM
1.00
HYDROGEN (REACTIVE)
1.00
Oleic acid
-1.00
-1.00
HYDROGEN ION
SODIUM ION
CARBONATE ION
HAo
WATER
AOHHCO3H2CO3
HAw (* FLDSPS *)
SORBED HYDROGEN ION
351

2
0. 0. 1. 0. 0. 0. 0. 1. 1. 0.
0. 1. 0. 0. 0. 0. 0. 0. 0. 0.
1. 0. 0. 1. 2. 0. 1. 1. 2. 1.
0. 0. 0. 1. 0. 1. 0. 0. 0. 1.
0. 0.
0. 1.
1. 0.
0. 0.
1.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 1.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 1.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 1.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 1.0 0.0 0.0
-1.0 0.0 0.0 1.0 0.0 0.0 0.0
-1.0 0.0 0.0 0.0 0.0 0.0 0.0
1.0 0.0 1.0 0.0 0.0 0.0 0.0
2.0 0.0 1.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 1.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 1.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 1.0
1.0 1.0 -2.0 0.0 0.0 -1.0 -1.0 -1.0 0.0 0.0
1.0 1.0
0.1000000000000E+01 0.1000000000000E+01 0.1000000000000E+01
0.1000000000000E+01 0.1000000000000E+01 0.7208194655797E-12
0.1460000000000E-13 0.2110000000000E+11 0.4890000000000E+17
0.7208194655797E-04
0.2700000000000E+07
-1.0 1.0 0.0 0.0 0.0 1.0 -1.0
0.0
0.1025999649213E-01
0.8500000000000E-01 0.0000000000000E+00
0.8000000000000E-02
0.8871622831864E-01
0.1109938837717E+03
0.6837964666253E-06
0.7316456465209E-02
0.3371763547059E-07 0.8871622831864E-01 0.5208092671440E-05
0.5499316203533E-02 0.5549204956699E+02
0.5196248365037E-02 0.5063748127088E-02
0.9999996581019E+00 0.9963551056229E+00
0.1000000000000E-07 0.5000000000000E+03
CC
CC*******************************************************************
CC
*
CC WELL DATA
*
CC
*
CC*******************************************************************
CC
CC
352
*---- IBOUND IZONE

0 0
CC
2 2 1 2
CC
1 1 1 1 .003
0. 3 100 100 0
CC
CC WELL NAME
*---- WELNAM
INJECTOR
CC
0 0.0 5000. 0.0 50000.
CC
2 1 1 2
.003 0. 3 1
1
0
CC
CC WELL NAME
*---- WELNAM
PRODUCER
CC
0 0.0 5000. 0.0 50000.
CC
1 0.004712 0.998 0. 0.002 0.3 0.102564 0.001 0. 0. 0.512 0.6214 111 0.0
1
0. 0. 0. 0. 0.
0. 0. 0. 0.
0. 0. 0. 0.
1
0. 0. 0. 0. 0.
0. 0. 0. 0.
0. 0. 0. 0.
CC
CC ID,
*----ID PWF
2 14.7
CC
0.3
0.03 0.03
0.03 0.03 0.3
CC
0.0001 12*0.01 0.1 0.01
CC****** INJECT no surfactant *********************
CC FLAG FOR INDICATING BOUNDARY CHANGE
*---- IBMOD
0
353
CC
CC IRO, ITIME, NEW FLAGS FOR ALL THE WELLS
2
1
1 2
CC
CC NUMBER OF WELLS CHANGES IN LOCATION OR SKIN OR PWF
*---- NWEL1
0
CC
CC NUMBER OF WELLS WITH RATE CHANGES, ID
*---- NWEL2 ID
1
1
CC
*---- ID QI(M,L) water oil surf polymer Chlor divalent
1 0.004712 1.0 0. 0.0 0.20
0.102564 0.001 0. 0. 0.001 0.102564 111 0.00000001
1
0. 0. 0. 0. 0.
0. 0. 0. 0.
0. 0. 0. 0.
1
0. 0. 0. 0. 0.
0. 0. 0. 0.
0. 0. 0. 0.
CC
*---- TINJ
CUMPR1
CUMHI1 WRHPV WRPRF RSTC
2.5
0.03 0.03
0.03 0.03
2.5
CC
CC FOR IMES=4 ,THE INI. TIME STEP,CONC. TOLERANCE,MAX.,MIN. TIME STEPS
*---- DT
DCLIM
CNMAX CNMIN
0.0001
12*0.01 0.1
0.01
9. UTCHEM Input File for ASP (1D Case) Coreflood in Chapter 6

CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
*
CC ALKALINE SURFACTANT POLYMER FLOODING
*
CC
*
CC LENGTH (FT) :
PROCESS : A/S/P FLOODING
*
CC THICKNESS (FT) :
*
CC WIDTH (FT) :
*
CC POROSITY :
*
*
CC DATE :
*
CC
*
CC*******************************************************************
CC
CC*******************************************************************
354
CC
*
*
CC
*
CC*******************************************************************
CC
CC
*----RUNNO
ASP-03
CC
CC
*----HEADER
ASP coreflood
Experiment -- based on reservoir properties
1% Na2CO3 is injected
CC
CC SIMULATION FLAGS
1 4 3 0 0 3 0 1 0 0 0 0
CC
SIZE
1 1 100 0
0
CC
*----DX
DY
DZ
0.1445 0.1445 0.01
CC
12 0 0 0 4 0 0
CC
CC
WATER
OIL
SURFACTANT
POLYMER
ANION
CALCIUM
alc1
alc2
CARBONATE
SODIUM
HYDROGEN
pet acid
CC
1 1 1 1 1 1 0 0 1 1 11
CC
CC*******************************************************************
355
CC
*
CC OUTPUT OPTIONS
*
CC
*
CC*******************************************************************
CC
CC
1
1 0
CC
1 1 1 1 1 1 0 0 1 1 1 1 1
CC
1 1 1 0 0 0 1 0
0
CC
1 1 0 1 1 0 0
0
CC
1 0 1 1
CC
CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
CC
*---- TMAX
2
CC
*----COMPR PSTAND
0. 0.
CC
PERMEABILITY
0 0 3 3 0
0
CC
*----PORC1
.31
CC
*----PERMX
356
7000
CC
1
CC
1
CC
0
0
0 -1
CC
*----D111
0.
CC
*----PINIT DEPTH
14.7 0.0
CC 72% oil sat. initially
*----SWI
0.28
CC
*----C50
C60
0.33 0.0
CC
CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
CC
CMC
0 1 0.001 0
CC
0
SALINITY
CC FOR ALCOHOL 1
0 0.05
0 0.02 0 0.05
SALINITY
CC FOR ALCOHOL 2
357

0
0
0
0
0
0
CC
0.8 1.2 0
0
0
0
0
CC
0 0
0
0
0
*---- nalmax epsalc
20
0.0001
ak7 pt7
4.671 1.79
48
35.31 0.222
CC
0
0
0 0
0
CC
1
CC typ=.1-.35 typ=5-20
*---- chuh
ahuh
0.3
10
*---- xiftw
1.3
*---- imass icor
0
0
CC
AQ OLEIC ME
*---- itrap t11
t22
t33
2
1865 59074 364.2
CC
*---- iperm=0 for constant; =1 varies by layer; =2 varies by gridblock
0
CC
358
*---- isrw iprw iew

0 0
0
CC
.075 .25 .075
CC
*----P1RW P2RW P3RW
.3 1.0 0.3
CC
*----E1W E2W E3W
3.8 1.9 3.8
CC
*----S1RC S2RC S3RC
.0 .0 .0
CC
*----P1RC P2RC P3RC
1.0 1.0 1.0
CC
*----E13CW E23C E31C
1. 1. 1.0
CC water oil
0.80 81.39 0
CC
0.5
1.9
0.0
0.0
0.0
CC
*---- AP1 AP2 AP3
55
550
300
CC
CC 3.4.82 PARAMETER TO COMPUTE CSEP,MIN. CSEP, AND SLOPE OF LOG VIS. VS.
LOGCSEP
1 0.01 -0.33
CC
3.97 10 2.0
CC
1
1
1 100 0.04
359
CC 3.4.85 SPECIFIC WEIGHT FOR COMPONENTS 1,2,3,7,8 ,Coeffient of oil and GRAVITY
FLAG
0.44 0.4065 0.4065 0.42 0.346 0
2
*----- ISTB
0
CC
*---- COMPC(1)
0.00000
0.0000
0
0
0
FLAG
*---- ICPC IEPC IOW
0
0 0
CC
*---- CPC0
0
CC
*---- EPC0
0.0
CC
*---- D(KC,1),KC=1,N
0
0
0
0
0
0
0
0
0
0
0
0
CC
*---- D(KC,2),KC=1,N
0
0
0
0
0
0
0
0
0
0
0
0
CC
*---- D(KC,3),KC=1,N
0
0
0
0
0
0
0
0
0
0
0
0
CC
0.005
0.001
CC
0.005
0.001
CC
0.005
0.001
CC
360

0
CC
1.9 0.1 1000 0.0 0.0 100 0 0 0 50
CC
0
0 0
500
2 1
7 13 13 0.1
0.25 0.35
5 10 0 2 0 1
5 1 4 6
3 2 0 0 1
0 0 0
4
-2.00
SODIUM
1.00
HYDROGEN (REACTIVE)
1.00
Oleic acid
-1.00
-1.00
HYDROGEN ION
SODIUM ION
CARBONATE ION
HAo
WATER
AOHHCO3H2CO3
HAw (* FLDSPS *)
SORBED HYDROGEN ION
2
0. 0. 1. 0. 0. 0. 0. 1. 1. 0.
0. 1. 0. 0. 0. 0. 0. 0. 0. 0.
1. 0. 0. 1. 2. 0. 1. 1. 2. 1.
0. 0. 0. 1. 0. 1. 0. 0. 0. 1.
0. 0.
0. 1.
1. 0.
0. 0.
1.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 1.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 1.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 1.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 1.0 0.0 0.0
-1.0 0.0 0.0 1.0 0.0 0.0 0.0
-1.0 0.0 0.0 0.0 0.0 0.0 0.0
1.0 0.0 1.0 0.0 0.0 0.0 0.0
361
2.0 0.0 1.0 0.0 0.0 0.0 0.0

0.0 0.0 0.0 1.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 1.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 1.0
1.0 1.0 -2.0 0.0 0.0 -1.0 -1.0 -1.0 0.0 0.0
1.0 1.0
0.1000000000000E+01 0.1000000000000E+01 0.1000000000000E+01
0.1000000000000E+01 0.1000000000000E+01 0.2353356544469E-11
0.1460000000000E-13 0.2110000000000E+11 0.4890000000000E+17
0.2353356544469E-03
0.2700000000000E+07
-1.0 1.0 0.0 0.0 0.0 1.0 -1.0
0.0
0.3303962335341E-01
0.3250000000000E+00 0.0000000000000E+00
0.2000000000000E-02
0.3253364006949E+00
0.1109206635993E+03
0.2279969015076E-04
0.9575392884122E-01
0.8491445750778E-06 0.3253364006949E+00 0.1880507836691E-07
0.2349772003098E+00 0.5534199998281E+02
0.2893386235302E-01 0.4105761000392E-02
0.9999886002849E+00 0.9543105096818E+00
0.1000000000000E-07 0.5000000000000E+03
CC
CC*******************************************************************
CC
*
CC WELL DATA
*
CC
*
CC*******************************************************************
CC
CC
*---- IBOUND IZONE
0 0
CC
2 2 1 2
CC
1 1 1 1 .003
0. 3 100 100 0
CC
CC WELL NAME
*---- WELNAM
INJECTOR
CC
0 0.0 5000. 0.0 50000.
362
CC
2 1 1 2
.003 0. 3 1
1
0
CC
CC WELL NAME
*---- WELNAM
PRODUCER
CC
0 0.0 5000. 0.0 50000.
CC
*----ID QI(M,L) C(M,KC,L) 1% Na2CO3 in Captain water with no divalent
1 0.0064729 0.999 0. 0.001 0.30 0.325 0.001 0. 0. 0.188 0.514 111 0.0
1
0.
0. 0. 0. 0.
0. 0. 0. 0.
0. 0. 0. 0.
1
0.
0. 0. 0. 0.
0. 0. 0. 0.
0. 0. 0. 0.
CC
CC ID,
*----ID PWF
2 14.7
CC
0.3 0.01 0.01
0.01 0.01
2.0
CC
0.000001 12*0.01 0.1 0.01
CC****** INJECT no surfactant *********************
CC FLAG FOR INDICATING BOUNDARY CHANGE
*---- IBMOD
0
CC
CC IRO, ITIME, NEW FLAGS FOR ALL THE WELLS
2
1
1 2
CC
CC NUMBER OF WELLS CHANGES IN LOCATION OR SKIN OR PWF
*---- NWEL1
0
CC
CC NUMBER OF WELLS WITH RATE CHANGES, ID
*---- NWEL2 ID
1
1
CC
*---- ID QI(M,L) water oil surf polymer Chloride divalent
1 0.0064729 1.0 0. 0.0 0.30 0.325 0.001 0. 0. 0.001 0.325 111 0.00000001
1
0. 0. 0. 0. 0.
0. 0. 0. 0.
0. 0. 0. 0.
1
0. 0. 0. 0. 0.
0. 0. 0. 0.
0. 0. 0. 0.
363
CC
*---- TINJ
CUMPR1
CUMHI1 WRHPV WRPRF RSTC
2
0.01 0.01
0.01 0.01
2.0
CC
CC FOR IMES=4 ,THE INI. TIME STEP,CONC. TOLERANCE,MAX.,MIN. TIME STEPS
*---- DT
DCLIM
CNMAX CNMIN
0.00001
12*0.01 0.1
0.01
10. UTCHEM Input File for ASP Field Scale (2D) in Chapter 6
*************************************************************************
CC
*
*
CC
*
CC***********************************************************************
CC
*
CC Field ASP Flood Evaluation
*
CC
*
CC LENGTH (FT) :
PROCESS : ASP
*
CC THICKNESS (FT) :
Rate (p & i) CONSTRAINTS
*
CC WIDTH (FT) :
*
CC POROSITY :
DAY SPECIFICATION
*
CC GRID BLOCKS :
COURANT NUMBER SPECIFICATION
*
CC NON UNIFORM GRIDBLOCK SIZES
WELL SKIN = 0
*
CC
*
CC***********************************************************************
CC
*
CC***********************************************************************
CC
*
*
CC
*
CC***********************************************************************
CC
CC Run number
*---- RUNNO
ASP-2D
CC
*---- title(i)
ASP flood: 18000 bpd inj and 6000 bpd prod each well
after 12.25 yr of waterflood (injection and production well rater constraint)
****************************************************
CC
CC SIMULATION FLAGS: IMODE = 1 for new case, IMODE=2 for restart
1 4 3 0 0 3 0 1 0 0 0 0
364
CC
CC no. of gridblocks,flag specifies constant or variable grid size, unit
48 1 16 1 0
CC
CC VARIABLE GRID SIZE ON A REGIONAL BASIS IN X DIRECTION
*---- II1, II2, DX1
1
1
328.084
2
2
164.042
3
46
82.021
47
47
164.042
48
48
328.084
CC
CC VARIABLE GRID SIZE ON A REGIONAL BASIS IN Y DIRECTION
*---- JJ1, JJ2, DY1
1
1
65.61675
CC
CC VARIABLE GRID SIZE ON A REGIONAL BASIS IN Z DIRECTION
*---- KK1, KK2, DZ1
1
16
8.2021
CC
CC total no. of components, no. of tracers, no. of gel components
*----n no ntw nta ngc ng noth
12 0 0 0 4 0 0
CC
CC Name of the components
*----spname(i) for i=1 to n
WATER
OIL
SURFACTANT
POLYMER
ANION
CALCIUM
alc1
alc2
CARBONATE
SODIUM
HYDROGEN
pet acid
CC
CC flag indicating if the component is included in calculations or not
*----icf(kc) for kc=1,n
1 1 1 1 1 0 0 0 1 1 11
CC
CC*******************************************************************
CC
*
CC 3.2 OUTPUT OPTIONS
*
CC
*
CC*******************************************************************
CC ICUM=0 for output in days, =1 for PV
CC ISTOP=0 for TMAX & TINJ in days, =1 for PV
365
CC 3.2.1 FLAG TO WRITE TO UNIT 3,FLAG FOR PV OR DAYS TO PRINT OR TO STOP THE
RUN
0
0
0
CC
CC 3.2.2 FLAG INDICATING IF THE PROFILE OF KCTH COMPONENT SHOULD BE
WRITTEN
1 1 1 1 1 0 0 0 0 1 11
CC
CC 3.2.3 FLAG FOR PRES.,SAT.,TOTAL CONC.,TRACER CONC.,CAP.,GEL,
ALKALINEPROFILES
1 1 1 0 0 0 1 0 0
CC
CC 3.2.4 FLAG FOR WRITING SEVERAL PROPERTIES TO UNIT 4 (Prof)
1 1 0 1 1 0 0 0
CC
CC 3.2.5 FLAG for variables to PROF output file
1 0 1 0
CC
CC*******************************************************************
CC
*
CC 3.3 RESERVOIR PROPERTIES
*
CC
*
CC*******************************************************************
CC
CC
CC 3.3.1 MAX. SIMULATION TIME ( DAYS)
*---- TMAX
3000.0
CC
CC 3.3.2 ROCK COMPRESSIBILITY (1/PSI), STAND. PRESSURE(PSIA)
*---- COMPR
PSTAND
0
1270.
CC
CC 3.3.3 FLAGS INDICATING CONSTANT OR VARIABLE POROSITY, X,Y,AND Z
PERMEABILITY
0 0 3 3 0
CC
CC 3.3.6 utchem and eclipse same index order: x fastest, then y, then z
*---- POR, pore volume / bulk volume: 1,1,1 2,1,1 3,1,1 1,2,1 2,2,1
0.31
CC
CC 3.3.7 Constant PERMEABILITY OVER RESERVOIR
*---- PERMX, in md
7000.
CC
366
CC 3.3.13 Y DIRECTION PERMEABILITY IS DEPENDENT ON X DIRECTION

PERMEABILITY
*---- FACTY, CONSTANT PERMEABILITY MULTIPLIER FOR Y DIRECTION
PERMEABILITY
1
CC
CC 3.3.17 Z DIRECTION PERMEABILITY IS DEPENDENT ON X DIRECTION PERMEABILITY
*---- FACTZ, CONSTANT PERMEABILITY MULTIPLIER FOR Z DIRECTION PERMEABILITY
0.7
CC =0 for constant for reservoir, =1 by layer, =2 by gridblock, =-1 for backward compatibility
CC 3.3.18 FLAG FOR CONSTANT OR VARIABLE DEPTH, PRESSURE, WATER
0
1 2 -1
CC
CC 3.3.19 CONSTANT DEPTH (FT)
*---- D111
2800
CC
CC 3.3.23 INITIAL PRESSURE FOR A POINT AT A SPECIFIED DEPTH IS SPECIFIED
*---- PINIT HINIT
1270. 2810.
CC
CC 3.3.26 INITIAL WATER SATURATION
*---- SWI(K,1)
0.7527E-001 0.7527E-001 0.7527E-001 0.7527E-001 0.7527E-001 0.7528E-001 0.7528E001 0.7528E-001 0.7528E-001 0.7528E-001
0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001
0.4318E+000 0.2471E+000 0.1836E+000
0.7530E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001
0.7528E-001 0.8387E-001 0.4422E+000
0.1953E+000 0.7856E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E001 0.7528E-001 0.7528E-001 0.7528E-001
0.1223E+000 0.4442E+000 0.1575E+000 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E001 0.7528E-001
0.7527E-001 0.7527E-001 0.7527E-001 0.7527E-001 0.7527E-001 0.1114E+000 0.9491E001 0.7528E-001 0.7528E-001 0.7528E-001
0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001
0.1086E+000 0.5025E+000 0.3045E+000 0.2143E+000
0.1047E+000 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E001 0.7528E-001 0.1405E+000 0.5272E+000
0.2292E+000 0.1519E+000 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E001 0.7528E-001 0.7528E-001 0.7528E-001
0.1590E+000 0.5321E+000 0.1866E+000 0.7529E-001 0.7528E-001 0.7528E-001 0.7528E001 0.7528E-001
0.7527E-001 0.7527E-001 0.7527E-001 0.7527E-001 0.7688E-001 0.1667E+000
0.1608E+000 0.1227E+000 0.7528E-001 0.7528E-001
0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001
0.1433E+000 0.5302E+000 0.4162E+000 0.2496E+000
0.1725E+000 0.8999E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E001 0.7528E-001 0.1705E+000 0.5594E+000
0.2731E+000 0.1887E+000 0.9208E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E001 0.7528E-001 0.7528E-001 0.7528E-001
367
0.1895E+000 0.5651E+000 0.2194E+000 0.1395E+000 0.7528E-001 0.7528E-001 0.7528E001 0.7528E-001

0.7527E-001 0.7527E-001 0.7527E-001 0.7527E-001 0.1237E+000 0.2038E+000
0.1971E+000 0.1754E+000 0.1319E+000 0.7528E-001
0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001
0.1702E+000 0.5651E+000 0.6604E+000 0.2998E+000
0.2115E+000 0.1674E+000 0.9262E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E001 0.8150E-001 0.2012E+000 0.5999E+000
0.3425E+000 0.2226E+000 0.1644E+000 0.7639E-001 0.7528E-001 0.7528E-001 0.7528E001 0.7528E-001 0.7528E-001 0.1356E+000
0.2239E+000 0.6112E+000 0.2597E+000 0.1783E+000 0.7779E-001 0.7528E-001 0.7528E001 0.7528E-001
0.7527E-001 0.7527E-001 0.7527E-001 0.7632E-001 0.1693E+000 0.2462E+000
0.2332E+000 0.2117E+000 0.1840E+000 0.1430E+000
0.7921E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.7528E-001 0.8478E-001
0.2011E+000 0.5950E+000 0.7087E+000 0.3643E+000
0.2507E+000 0.2074E+000 0.1687E+000 0.1084E+000 0.7542E-001 0.7528E-001 0.7876E001 0.1511E+000 0.2387E+000 0.6335E+000
0.4999E+000 0.2625E+000 0.2026E+000 0.1528E+000 0.8191E-001 0.7528E-001 0.7528E001 0.7528E-001 0.9614E-001 0.1746E+000
0.2669E+000 0.6557E+000 0.3170E+000 0.2123E+000 0.1509E+000 0.7528E-001 0.7528E001 0.7528E-001
0.7527E-001 0.7527E-001 0.8110E-001 0.1512E+000 0.2043E+000 0.3099E+000
0.2806E+000 0.2496E+000 0.2225E+000 0.1924E+000
0.1629E+000 0.1113E+000 0.8293E-001 0.8000E-001 0.9228E-001 0.1505E+000
0.2399E+000 0.6291E+000 0.7137E+000 0.4929E+000
0.3025E+000 0.2465E+000 0.2089E+000 0.1755E+000 0.1513E+000 0.1379E+000
0.1542E+000 0.1875E+000 0.2864E+000 0.6709E+000
0.6983E+000 0.3206E+000 0.2400E+000 0.1933E+000 0.1596E+000 0.1201E+000
0.1070E+000 0.1230E+000 0.1609E+000 0.2094E+000
0.3294E+000 0.6937E+000 0.4232E+000 0.2500E+000 0.1886E+000 0.1364E+000 0.7528E001 0.7528E-001
0.7773E-001 0.1010E+000 0.1550E+000 0.1912E+000 0.2428E+000 0.4337E+000
0.3560E+000 0.3002E+000 0.2640E+000 0.2331E+000
0.2052E+000 0.1796E+000 0.1633E+000 0.1572E+000 0.1613E+000 0.1869E+000
0.2910E+000 0.6690E+000 0.7183E+000 0.6959E+000
0.3899E+000 0.2958E+000 0.2492E+000 0.2167E+000 0.1946E+000 0.1856E+000
0.1936E+000 0.2252E+000 0.3608E+000 0.7021E+000
0.7189E+000 0.4157E+000 0.2866E+000 0.2324E+000 0.1994E+000 0.1773E+000
0.1703E+000 0.1757E+000 0.1990E+000 0.2495E+000
0.4493E+000 0.7180E+000 0.6673E+000 0.2993E+000 0.2258E+000 0.1801E+000
0.1299E+000 0.7897E-001
0.1412E+000 0.1609E+000 0.1942E+000 0.2319E+000 0.2956E+000 0.6837E+000
0.5632E+000 0.3866E+000 0.3213E+000 0.2795E+000
0.2475E+000 0.2233E+000 0.2059E+000 0.1982E+000 0.2018E+000 0.2267E+000
0.3744E+000 0.7045E+000 0.7247E+000 0.7218E+000
0.5956E+000 0.3753E+000 0.3005E+000 0.2609E+000 0.2366E+000 0.2277E+000
0.2350E+000 0.2732E+000 0.5229E+000 0.7251E+000
0.7233E+000 0.6664E+000 0.3606E+000 0.2801E+000 0.2407E+000 0.2194E+000
0.2117E+000 0.2168E+000 0.2406E+000 0.3055E+000
0.6694E+000 0.7281E+000 0.7166E+000 0.3779E+000 0.2716E+000 0.2198E+000
0.1746E+000 0.1446E+000
368
0.1766E+000 0.2009E+000 0.2373E+000 0.2833E+000 0.3792E+000 0.7258E+000

0.7192E+000 0.6307E+000 0.4310E+000 0.3463E+000
0.3002E+000 0.2721E+000 0.2516E+000 0.2428E+000 0.2476E+000 0.2785E+000
0.5509E+000 0.7313E+000 0.7294E+000 0.7272E+000
0.7163E+000 0.5862E+000 0.3830E+000 0.3203E+000 0.2878E+000 0.2784E+000
0.2882E+000 0.3451E+000 0.6839E+000 0.7328E+000
0.7278E+000 0.7259E+000 0.5439E+000 0.3512E+000 0.2935E+000 0.2683E+000
0.2593E+000 0.2659E+000 0.2967E+000 0.4027E+000
0.7160E+000 0.7312E+000 0.7294E+000 0.6074E+000 0.3385E+000 0.2686E+000
0.2156E+000 0.1811E+000
0.2176E+000 0.2485E+000 0.2948E+000 0.3607E+000 0.6213E+000 0.7363E+000
0.7304E+000 0.7223E+000 0.6750E+000 0.5030E+000
0.3824E+000 0.3395E+000 0.3110E+000 0.3012E+000 0.3102E+000 0.3578E+000
0.6820E+000 0.7377E+000 0.7338E+000 0.7315E+000
0.7293E+000 0.7191E+000 0.6080E+000 0.4257E+000 0.3635E+000 0.3516E+000
0.3694E+000 0.5073E+000 0.7227E+000 0.7358E+000
0.7339E+000 0.7326E+000 0.7196E+000 0.5199E+000 0.3751E+000 0.3374E+000
0.3258E+000 0.3364E+000 0.3882E+000 0.6674E+000
0.7341E+000 0.7363E+000 0.7334E+000 0.7272E+000 0.4775E+000 0.3400E+000
0.2670E+000 0.2235E+000
0.2727E+000 0.3163E+000 0.3880E+000 0.5615E+000 0.7274E+000 0.7400E+000
0.7350E+000 0.7319E+000 0.7259E+000 0.7047E+000
0.6172E+000 0.4808E+000 0.4088E+000 0.3953E+000 0.4192E+000 0.5598E+000
0.7262E+000 0.7403E+000 0.7385E+000 0.7368E+000
0.7350E+000 0.7325E+000 0.7223E+000 0.6775E+000 0.5669E+000 0.5258E+000
0.5928E+000 0.7188E+000 0.7385E+000 0.7402E+000
0.7383E+000 0.7368E+000 0.7341E+000 0.7176E+000 0.6118E+000 0.4786E+000
0.4494E+000 0.4839E+000 0.6526E+000 0.7341E+000
0.7383E+000 0.7396E+000 0.7378E+000 0.7369E+000 0.7178E+000 0.4979E+000
0.3434E+000 0.2813E+000
0.3596E+000 0.4481E+000 0.6375E+000 0.7188E+000 0.7349E+000 0.7426E+000
0.7386E+000 0.7363E+000 0.7329E+000 0.7269E+000
0.7148E+000 0.6886E+000 0.6452E+000 0.6353E+000 0.6656E+000 0.7221E+000
0.7417E+000 0.7429E+000 0.7412E+000 0.7401E+000
0.7386E+000 0.7370E+000 0.7326E+000 0.7251E+000 0.7132E+000 0.7119E+000
0.7232E+000 0.7375E+000 0.7413E+000 0.7424E+000
0.7410E+000 0.7401E+000 0.7382E+000 0.7327E+000 0.7211E+000 0.6998E+000
0.6905E+000 0.7072E+000 0.7309E+000 0.7397E+000
0.7411E+000 0.7422E+000 0.7410E+000 0.7401E+000 0.7356E+000 0.7156E+000
0.5285E+000 0.3755E+000
0.8420E+000 0.9104E+000 0.9687E+000 0.9981E+000 0.999 0.9066E+000 0.9891E+000
0.9992E+000 0.9717E+000 0.9431E+000
0.9266E+000 0.9428E+000 0.9910E+000 0.999 0.999 0.999 0.999 0.999 0.999 0.999
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
0.999 0.999 0.999 0.999 0.999 0.999 0.9880E+000 0.8696E+000
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
369
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
0.999 0.999 0.999 0.999 0.999 0.999 0.999 0.999
CC C50=anion C60=divalent cation
CC 3.3.52 BRINE SALINITY AND DIVALENT CATION CONCENTRATION (MEQ/ML)
*---- C50
C60
0.33
0
CC
CC*******************************************************************
CC
*
CC 3.4 PHYSICAL PROPERTY DATA
*
CC
*
CC*******************************************************************
CC
CC
CMC
0 1 0.001 0
CC
0
SALINITY
CC FOR ALCOHOL 1
0 0.05
0 0.02 0 0.05
SALINITY
CC FOR ALCOHOL 2
0
0
0
0
0
0
CC
0.8 1.2 0
0
0
0
0
CC
0 0
0
0
0
370
*---- nalmax epsalc

20
0.0001
ak7 pt7
4.671 1.79
48
35.31 0.222
CC
0
0
0 0
0
CC
1
CC typ=.1-.35 typ=5-20
*---- chuh
ahuh
0.3
10
*---- xiftw
1.3
*---- imass icor
0
0
CC
AQ OLEIC ME
*---- itrap t11
t22
t33
2
1865 59074 364.2
CC
*---- iperm=0 for constant; =1 varies by layer; =2 varies by gridblock
0
CC
*---- isrw iprw iew
0 0
0
CC
CC 3.4.37 CONSTANT RES. SATURATION OF PHASES 1,2,AND 3 AT LOW CAPILLARY NO.
0.075 0.25 0.075
CC
CC 3.4.44 CONSTANT ENDPOINT REL. PERM. OF PHASES 1,2,AND 3 AT LOW CAPILLARY
NO.
0.3
1.0 0.3
CC
CC 3.4.51 CONSTANT REL. PERM. EXPONENT OF PHASES 1,2,AND 3 AT LOW
CAPILLARY NO.
*---- e1wc e2wc
e3wc
3.8
1.9
3.8
371
CC
CC 3.4.58 RES. SATURATION OF PHASES 1,2,AND 3 AT HIGH CAPILLARY NO.
*---- s1rc s2rc s3rc
0 0 0
CC
CC 3.4.59 ENDPOINT REL. PERM. OF PHASES 1,2,AND 3 AT HIGH CAPILLARY NO.
*---- p1rc p2rc p3rc
1 1 1
CC
CC 3.4.60 REL. PERM. EXPONENT OF PHASES 1,2,AND 3 AT HIGH CAPILLARY NO.
*---- e13c e23c e31c
1 1 1
CC water oil
0.80 81.3195 0
CC
0.5
1.9
0.0
0.0
0.0
CC
*---- AP1 AP2 AP3
55
550
300
CC
CC 3.4.82 PARAMETER TO COMPUTE CSEP,MIN. CSEP, AND SLOPE OF LOG VIS. VS.
LOGCSEP
1 0.01 -0.33
CC
3.97 10 2.0
CC
1
1
1 100 0.04
CC 3.4.85 SPECIFIC WEIGHT FOR COMPONENTS 1,2,3,7,8 ,
0.44 0.4065 0.4065 0.42 0.346 0
2
*----- ISTB
1
CC 3.4.94 FORMATION VOLUME FACTOR CC
water oil
me
*----- FVF(I), I=1 TO MXP (IGAS=0 MXP=3,IGAS=1 MXP=4)
1.00265
1.057
1
CC
*---- COMPC(1)
372
0.0000033
0.0000234
0
0
0
FLAG
*---- ICPC IEPC IOW
0
0 0
CC
*---- CPC0
0.0
CC
*---- EPC0
0.0
CC
*---- D(KC,1),KC=1,N
0
0
0
0
0
0
0
0
0
0
0
0
CC
*---- D(KC,2),KC=1,N
0
0
0
0
0
0
0
0
0
0
0
0
CC
*---- D(KC,3),KC=1,N
0
0
0
0
0
0
0
0
0
0
0
0
CC
0.16
0.04
CC
0.16
0.04
CC
0.16
0.04
CC
0
CC
1.9 0.1 1000. 0.0 0.0 100.
0
0 0 700.
CC
0
0 0
804
2 1
7 13 13 0.1
373
0.25 0.35
5 10 0 2 0 1
5 1 4 6
3 2 0 0 1
0 0 0
4
-2.00
SODIUM
1.00
HYDROGEN (REACTIVE)
1.00
Oleic acid
-1.00
-1.00
HYDROGEN ION
SODIUM ION
CARBONATE ION
HAo
WATER
AOHHCO3H2CO3
HAw (* FLDSPS *)
SORBED HYDROGEN ION
2
0. 0. 1. 0. 0. 0. 0. 1. 1. 0.
0. 1. 0. 0. 0. 0. 0. 0. 0. 0.
1. 0. 0. 1. 2. 0. 1. 1. 2. 1.
0. 0. 0. 1. 0. 1. 0. 0. 0. 1.
0. 0.
0. 1.
1. 0.
0. 0.
1.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 1.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 1.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 1.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 1.0 0.0 0.0
-1.0 0.0 0.0 1.0 0.0 0.0 0.0
-1.0 0.0 0.0 0.0 0.0 0.0 0.0
1.0 0.0 1.0 0.0 0.0 0.0 0.0
2.0 0.0 1.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 1.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 1.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 1.0
1.0 1.0 -2.0 0.0 0.0 -1.0 -1.0 -1.0 0.0 0.0
1.0 1.0
0.1000000000000E+01 0.1000000000000E+01 0.1000000000000E+01
0.1000000000000E+01 0.1000000000000E+01 0.5111109189239E-12
0.1460000000000E-13 0.2110000000000E+11 0.4890000000000E+17
0.5111109189239E-04
0.2700000000000E+07
-1.0 1.0 0.0 0.0 0.0 1.0 -1.0
374
0.0
0.3314998194551E-01
0.3250000000000E+00 0.0000000000000E+00
0.2000000000036E-02
0.3255849484789E+00
0.1109874150515E+03
0.1089260793651E-05
0.2063731180133E-01
0.3060460680743E-06 0.3255849484789E+00 0.9058995723128E-07
0.1099891073921E-01 0.5548749995229E+02
0.2378020355988E-01 0.9369778385637E-02
0.9999994553699E+00 0.9897867313046E+00
0.1000000000000E-07 0.5000000000000E+03
CC
CC*******************************************************************
CC
*
CC 3.7 WELL DATA
*
CC
*
CC*******************************************************************
CC
CC
CC 3.7.1 FLAG FOR SPECIFIED BOUNDARY AND ZONE IS MODELED
*---- IBOUND IZONE
0 0
CC 3.7.5 TOTAL NUMBER OF WELLS, WELL RADIUS FLAG, FLAG FOR TIME OR
COURANT NO.
CC IRO=2 for Peaceman. ITIME=0 for days; =1 for CN for min&max tstep size
4 2
1
4
CC 3.7.6a WELL ID,LOCATIONS,AND FLAG FOR SPECIFYING WELL TYPE, WELL RADIUS,
SKIN
CC
=3 for press. inj. =2for y horiz. well
*---- IDW IW ZW IFLAG RW SWELL IDIR JFIRST JLAST IPRF
1 6 1
1 0.35 0 3 12
12 0
CC
CC 3.7.6c WELL NAME
*---- WELNAM
INJ1
CC
51000.
CC 3.7.6d ICHEK , MAX. AND MIN. ALLOWABLE BOTTOMHOLE PRESSURE AND RATE
*---- ICHEK PWFMIN PWFMAX QTMIN
QTMAX
0
0
6000. 0
102000.
SKIN
CC
=4 for rate prod.
=2for y horiz. well
*---- IDW IW ZW IFLAG RW SWELL IDIR IFIRST ILAST IPRF
2 18 1
4 0.35 0
3 1 1 0
CC
CC 3.7.6c WELL NAME
*---- WELNAM
PROD1
375
CC if ICHEK = 0 then no check for limits

0
0
9999. 0
-17040.
SKIN
CC
=4 for rate prod.
=2for y horiz. well
3 30 1
4 0.35 0
3 1 1 0
CC
CC 3.7.6c WELL NAME
*---- WELNAM
PROD2
0
0
9999. 0
-17040.
SKIN
CC
=4 for rate prod.
=2for y horiz. well
4 42 1
4 0.35 0
3 1 1 0
CC
CC 3.7.6c WELL NAME
*---- WELNAM
PROD3
0
0
9999. 0
-17040.
CC
CC 3.7.7a ID,INJ. RATE AND INJ. COMP. FOR RATE CONS. WELLS FOR EACH PHASE
(L=1,3)
1
5100 0.997 0. 0.003 0.3 0.325 0. 0. 0. 0.188 0.514 111 0.0001
1
0.
0. 0. 0. 0.
0. 0. 0. 0.
0. 0. 0. 0.
1
0.
0. 0. 0. 0.
0. 0. 0. 0.
0. 0. 0. 0.
CC
CC 3.7.7d ID, Total Production Rate FOR RATE CONSTRAINT WELL (IFLAG=1 OR 4)
*---- ID Q in Ft3/day. Note: this value needs to be input as negative number.
2 -1700.
CC
3 -1700.
CC
4
-1700
CC 3.7.8 CUM. INJ. TIME , AND INTERVALS (PV OR DAY) FOR WRITING TO OUTPUT
FILES
CC
profilesPROF prodPROF prodHIST maps
recovery
*---- TINJ CUMPR1 CUMHI1
WRHPV WRPRF
RSTC
376
750.0
150.0 150.0
1.0
150.0
750.0
CC
CC 3.7.11 FOR IMES=2 ,THE INI. TIME STEP,CONC. TOLERANCE,MAX.,MIN. courant numbers
*---- DT
DCLIM CNMAX CNMIN
0.000001
12*0.01 0.1
0.02
CC
CC 3.7.14 FLAG FOR INDICATING BOUNDARY CHANGE
*---- IBMOD
0
CC
CC 3.7.19 IRO, ITIME, NEW FLAGS FOR ALL THE WELLS
2
1
1 4 4 4
CC
CC 3.7.20 NUMBER OF WELLS CHANGES IN LOCATION OR SKIN OR PWF
*---- NWEL1
0
CC
CC 3.7. NUMBER OF WELLS WITH RATE CHANGES, ID
*---- NWEL2 ID
1
1
CC
CC 3.7.7a ID,INJ. RATE AND INJ. COMP. FOR RATE CONS. WELLS FOR EACH PHASE
(L=1,3)
1
5100 1.0 0. 0.0 0.30 0.325 0. 0. 0. 0.001 0.325 111 0.0001
1
0. 0. 0. 0. 0.
0.
0. 0. 0.
0. 0. 0. 0.
1
0. 0. 0. 0. 0.
0.
0. 0. 0.
0. 0. 0. 0.
CC 3.7.8 ***********************************************************************
CC
profilesPROF prodPROF prodHIST maps
recovery
*---- TINJ CUMPR1 CUMHI1
WRHPV WRPRF
RSTC
3000. 150.0 150.0
5.0
150.0 3000.0
CC
CC 3.7.11 FOR IMES=2 ,THE INI. TIME STEP,CONC. TOLERANCE,MAX.,MIN. courant numbers
*---- DT
DCLIM CNMAX CNMIN
0.000001
12*0.01 0.1
0.02
11. UTCHEM Input File for Coreflood BM-07 in Chapter 7

CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
*
CC SURFACTANT POLYMER FLOODING
*
CC
*
CC LENGTH (FT) :
PROCESS : chemical FLOODING
*
377
CC THICKNESS (FT) :
*
CC WIDTH (FT) :
COORDINATES :
*
CC POROSITY :
*
*
CC DATE :
*
CC
*
CC*******************************************************************
CC
CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
CC
*----RUNNO
BM-07
CC
CC
*----HEADER
High pH surfactant/polymer coreflood
using sandstone core
***********************************************************
CC
CC SIMULATION FLAGS
1 4 3 0 0 2 0 1 0 0 0 0
CC
SIZE
1 1 100 0
0
CC
*----DX
DY
DZ
0.1665 0.1665
0.04
CC
11 0 0 0 3 0 0
CC
CC
WATER
OIL
SURFACTANT
POLYMER
ANION
CALCIUM
alc1
alc2
CARBOBATE
378
SODIUM
HYDROGEN
CC
1 1 1 1 1 1 1 0 1 1 1
CC
CC*******************************************************************
CC
*
CC OUTPUT OPTIONS
*
CC
*
CC*******************************************************************
CC
CC
1
1 0
CC
1 1 1 1 1 1 1 0 1 1 1
CC
1 1 1 0 0 0 1 0
0
CC
1 1 0 0 1 0 0
0
CC
1 0 1 1
CC
CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
CC
*---- TMAX
2.0
CC
*----COMPR PSTAND
0. 0.
CC
PERMEABILITY
379
0 0 3 3 0
0
CC
*----PORC1
.165
CC
*----PERMX
1297
CC
1
CC
1
CC
0
0
0 -1
CC
*----D111
0.
CC
*----PINIT DEPTH
14.7 0.0
CC
*----SWI
0.65
CC
*----C50
C60
0.0396 0.0
CC
CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
CC
0. 1. .001 0
CC
*---- IFGHBN
0
380
CC FOR ALCOHOL 1
0.0
0.035 0.14 0.024 0.0 0.035
CC FOR ALCOHOL 2
0
0
0
0
0
0
CC
0.11
0.19 0
0
CC
0 2.81
0
CC
1 0.0
0.0
0
0
CC
*---- nalmax epsalc
20
0.0001
CC
3.
1.76
90 35.31 0.172
CC
0
0
0 0
0
cc
cc
*--- ift
1
CC
*----CHUH
AHUH
0.3 10
CC
*----XIFTW
1.48
CC
*---- IMASS ICOR
0 0
CC
*----ITRAP T11
T22
T33
2
1865. 59000 364.2
381
CC
*---- IPERM
0
CC
*----ISRW IPRW IEW
0 0 0
CC
.38 .35 .38
CC
*----P1RW P2RW P3RW
.05 .85 .05
CC
*----E1W E2W E3W
2.0 1.7
2.0
CC
*----S1RC S2RC S3RC
.0 .0 .0
CC
*----P1RC P2RC P3RC
1.0 1.0 1.0
CC
*----E13CW E23C E31C
1. 1. 1.0
CC
0.370 8.0 0.0
CC
0.2 2.0 0.0 0.0 0.0
CC
*----AP1 AP2 AP3
40 200. 300.
CC
1. .01 -0.40
CC
*----GAMMAC GAMHF POWN IPMOD
4.0 35. 1.5 0
382
CC
*----IPOLYM EPHI3 EPHI4 BRK CRK rkcut
1
1.0 0.85 100. 0.04 10
CC
.433 .390 0.397 .42 .346 0. 2
CC
*-----ISTB
1
CC
1 1 1
CC
0.
0.
0.
0.
0.
CC
*----ICPC IEPC IOW
0
0 0
CC
*----CPC
0.
CC
*---- EPC
2.
CC
*----D(1) D(2) D(3) D(4) D(5) D(6)
0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0.
CC
*----D(1) D(2) D(3) D(4) D(5) D(6)
0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0.
CC
*----D(1) D(2) D(3) D(4) D(5) D(6)
0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0.
CC
0.08
0.002
CC
0.08 0.002
383
CC
0.08 0.002
CC
*----IADSO
0
CC
3.0 0.1 1000. 1.0 0. 100. 0 0 0 0
CC
*----QV
XKC XKS EQW
0.16 0.25 0.4 429.
21
7 13 13 0.1
5 11 0 3 0 1
5 1 5 0
4 3 1 0 2
0 0 0
CALCIUM
2.00
-2.00
SODIUM
1.00
HYDROGEN (REACTIVE)
1.00
-1.00
HYDROGEN ION
SODIUM ION
CALCIUM ION
CARBONATE ION
WATER
CA (HC03) +
HYDROXIDE ION
BICARBONATE ION
DISSOLVED CARBON MONOHYDROXIDE
AQUEOUS CALCIUM CARBONATE (* FL
SORBED HYDROGEN ION
SORBED SODIUM ION
SORBED CALCIUM ION (* SORBSPS *
3
0. 0. 1. 0. 0. 1. 1. 0. 0. 0. 1.
0. 0. 0. 1. 0. 0. 1. 0. 1. 1. 1.
0. 1. 0. 0. 0. 0. 0. 0. 0. 0. 0.
1. 0. 0. 0. 2. 1. 1. 1. 1. 2. 0.
0. 0. 1.
0. 0. 0.
0. 1. 0.
1. 0. 0.
1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 1.0 0.0 0.0 0.0 0.0 0.0 0.0
384
0.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0

0.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0
-1.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0
1.0 0.0 1.0 1.0 0.0 0.0 0.0 0.0
-1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
1.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0
2.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0
0.0 0.0 1.0 1.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 1.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 1.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.0
1.0 1.0 2.0 -2.0 0.0 1.0 1.0 -1.0 -1.0 0.0 0.0
1.0 1.0 2.0
0.1000000000000E+01 0.1000000000000E+01 0.1000000000000E+01
0.1000000000000E+01 0.1000000000000E+01 0.1560000000000E-10
0.5080000000000E+12 0.3210000000000E-12 0.1660000000000E+11
0.3900000000000E+17 0.1580000000000E+04
0.1538461538462E+03 0.1000000000000E+05
0.0 2.0 -1.0 0.0 0.0 0.0 -2.0 1.0
-1.0 1.0 0.0 0.0 0.0 1.0 -1.0 0.0
-1.0 0.0
0.1690000000000E-01
0.4200000000000E-01 0.2223714496884E-03
0.2000000012034E-04
0.4177928466057E-01
0.1109999983439E+03
0.1213454901761E-05 0.4177928466057E-01 0.1111754459562E-03
0.1288004203807E-09 0.5549998973404E+02
0.3251076471666E-02 0.1119346497063E-01 0.1227729278851E-02
CC
CC*******************************************************************
CC
*
CC WELL DATA
*
CC
*
CC*******************************************************************
CC
CC
*---- IBOUND IZONE
0 0
CC
2 2 1 2
CC
1 1 1 1 .003
0. 3 100 100 0
CC
CC WELL NAME
*---- WELNAM
385
INJECTOR
CC
0 0.0 5000. 0.0 50000.
CC
2 1 1 2
.003 0. 3 1
1
0
CC
CC WELL NAME
*---- WELNAM
PRODUCER
CC
0 0.0 5000. 0.0 50000.
CC
1 0.0247 0.9447 0. 0.02 .25 0.0209
0.0001 0.0353 0. 0.187 0.235 111
1 0.
0. 0. 0. 0. 0.
0. 0. 0. 0. 0. 0.
1 0.
0. 0. 0. 0. 0.
0. 0. 0. 0. 0. 0.
CC
CC ID,
*----ID PWF
2 14.7
CC
0.15 0.05 0.05
0.05 0.05
0.1
CC
0.0001 11*0.01 0.1 0.01
CC
CC
*--- IBMOD
0
CC34567890---------2---------3---------4---------5---------6---------7---------8
2 1 1 2
CC
*----NWEL1
0
CC
*----NWEL1 Id
1
1
CC
386
1 0.0247 0.9824 0.0 0. .22 0.02167
0.0001 0.0176 0.0 0.156 0.159 111
1 0.
0. 0. 0. 0. 0.
0. 0. 0.0 0. 0. 0.
1 0.
0. 0. 0. 0. 0.
0. 0. 0.0 0. 0. 0.
CC
0.30 0.02 0.02
0.02 0.02
0.5
CC
0.0001 11*0.01 0.1 0.01
CC
CC
*--- IBMOD
0
CC34567890---------2---------3---------4---------5---------6---------7---------8
2 1 1 2
CC
*----NWEL1
0
CC
*----NWEL1 Id
1
1
CC
1 0.0247 1.0
0.0 0. .18 0.022
0.0001 0. 0. 0.036 0.0398 111.
1 0.
0. 0. 0. 0. 0.
0. 0. 0. 0. 0. 0.
1 0.
0. 0. 0. 0. 0.
0. 0. 0. 0. 0. 0.
CC
2.0 0.02 0.02
0.02 0.02
0.2
CC
0.0001 11*0.01 0.1 0.01
387
APPENDIX E
Alkali Consumption for a Reservoir Rock
The purpose of this study is to see how each reaction consumes alkali and how
much each of them retards the pH front in a sandstone reservoir rock. Therefore, a 1D
coreflood simulation similar to the coreflood M1 in Chapter 7 (Tables E.1 and E.2)
was conducted. In this example, reactions such as cation exchange and quartz
dissolution are studied separately to qualitatively and quantitatively investigate the
effect on the pH front. The rock and fluid properties are given in Table E.1. The
chemical flood design is summarized in Table E.2. The core is initially filled with 3
wt% NaCl. 1 wt% Na2CO3 is added to 19000 ppm NaCl during the slug and polymer
drive. The slug and polymer drive contain 2500 ppm polymer. Synthetic surfactant
(0.3 wt%) is injected for 0.1 PV.
The rock contains the following minerals:
80 wt% Quartz
13 wt% K feldspar (Albite NaAlSi3O8)
<1 wt% Siderite (FeCO3)
6 wt% Clay (Kaolinite and illite)
No Calcite
Table E.3 lists the elements and species used to model the fluid injection into
the sandstone rock. The aqueous reactions are as listed below:
388
H 2O H + + OH
Na + + H 2O NaOH + H +
Ca 2+ + H 2O Ca(OH)+ + H +
H + + CO32 HCO3
Na + + CO32 NaCO3
Ca 2+ + CO32 CaCO3
Na + + H + + CO32 Na(HCO3 )
Ca 2+ + H + + CO32 Ca(HCO3 ) +
2H + + CO32 H 2CO3
Al3+ + 4H 2O Al(OH)4 + 4H +
H 4SiO4 H + + H3SiO4
NaH3SiO 4 Na + + H3SiO4
Solids such as calcite were added to the geochemistry description to test if

precipitates formed during the alkaline injection. The PHREEQC softwarewas used to
predict which solid is precipitated in the presence of these minerals and alkali
solution. The chemistry of these solids is included as below;
CaCO3
K1sp = [Ca 2 + ][CO32 ]
SiO2 (Silica)
K 2sp = [H 4SiO4 ]
Al2Si2O5 (OH)4 (Kaolinite)
K 3sp = [H + ]6 [Al3 + ]2 [H 4SiO4 ]2
The cation exchange reaction between the sodium and hydrogen is also
included. Cation exchange capacity is about 1.8 meq/100 g rock. The reactions
responsible for alkali consumption are studied. Insoluble salt formations by the
389
reaction with hardness ions and exchange with the rock surfaces are not studied
because of small divalent concentrations present.
The effect of hydrogen/sodium cation exchange on alkali consumption at 1.0
PV is shown in Figure E.1. We observe that cation exchange is a major consumer of
alkali and delays the pH front compared to the surfactant. The cation exchange
capacity is relatively large at 1.8 meq/100g rock. As demonstrated in Figure E.1, pH
and surfactant are not moving together. This means there is no benefit from the
increase of pH for surfactant adsorption reduction. Figure E.2 shows that clay
hydrogen sites are replaced by sodium during the cation exchange reaction. Hydrogen
is desorbed and sodium is adsorbed when alkaline is injected. The amount of alkali
consumption by hydrogen and sodium exchange reaction from this plot is calculated:
eqOH
mole
0.145(
sodium adsorbed or hydrogen desorbed) 1(
)
litPV
1molesodium adsorbed or hydrogen removed
(0.485 fraction of PVsodium adsorbed or hydrogen removed) 0.075444 liter PV = 0.005306 eqOH
To express this consumption as meq/100 g rock:
0.485 fraction of rock influenced by this reaction 852 g mass of core = 413.22 g
1000meq
0.005306 eq OH- consumed
1 eq
100 = 1.28 meq

100grock
413.22 g
During the cation exchange reaction, 0.145 mole/L PV hydrogen is replaced
by sodium (Reading from Figure E.2). The fraction of PV affected by this cation
exchange reaction is 0.485 which is read from the Figure E.2. The pore volume of this
390
core is 0.075444 . Alkali consumption from the hydrogen/sodium exchange reaction

is 1.28 meq/100 g rock.
The blue curve shows the pH front for the cation exchange reaction in Figure
E.3 and the green curve shows the pH front for both cation exchange and congruent
dissolution of silica. Dissolution of silica reduces the pH from 10.8 to 10.4, but it
does not affect the pH front. The following two reactions are responsible for alkali
consumption.
H 4SiO 4 + OH H 2O + H3SiO4
H 4SiO 4 + Na + + OH H 2O + NaH3SiO 4
H3SiO4- and NaH3SiO4 are the products of the congruent dissolution of silica.
As shown in Figure E.4, their concentrations increase due to these reactions. The
readings from the Figure E.4 are: 0.0243 mole/L NaH3SiO4 H3SiO4-, 0.00708 mole/L
and a pore volume fraction of 0.475, for a consumption of:
(0.0243 + 0.00708) (
eqOH
mole
H3SiO4- and NaH3SiO4 ) 1(
)
L
1mole H3SiO4- and NaH3SiO4
(0.475 fraction of PVinf luenced by these species) 0.075444 liter PV = 0.001125 eqOH
To express this consumption as meq/100 g rock:
0.475 fraction of rock influenced by this reaction 852 g mass of core = 404.7 g
1000meq
0.001125 eq OH-
1 eq
100 = 0.27 meq

100grock
404.7 g
391
Table E.4 shows the contribution of each of these reactions on the

consumption of alkali. The major consumption of alkali is due to cation exchange
reaction.
392
Table E.1: Rock and fluid properties for example coreflood similar to coreflood M1
Porosity
0.19
Permeability, md
448
Length, ft
0.32
0.35
Endpoint oil relative perm.
0.35
Endpoint water relative perm
0.08
Water viscosity (85oC), cp
0.37
Oil viscosity (85oC), cp
3.0
Table E.2: Chemical flood design of example coreflood similar to coreflood M1

Alkaline/Surfactant/Polymer Slug
0.1 PV
3.0 wt% IOS C20-24 (batch#26519844-2) with 1.0 wt% n-Pentanol and 1.0 wt% SBA
1.0 wt% Na2CO3 added to 19,000 ppm NaCl
2500 ppm AN125 polymer (lot#UB 4558)
flow rate: 0.5 ml/min
Polymer Drive
1.6 PV
2500 ppm AN125 polymer (lot#UB 4558)
10,000 ppm NaCl
1.0 wt% Na2CO3
frontal velocity: 0.5 ml/min
front adv:8 ft/day
393
Table E.3: Elements and species simulated for case study

Elements or
pseudo-elements

Calcium, Aluminum, Silicon, Oxygen, Carbonate,
Chlorine, Iron
Independent aqueous
H+, Na+, Ca2+, Fe2+, Al3+, CO32-, Cl-, HAo, H2O, H4SiO4
or oleic species
Al(OH)4-, H3SiO4-, HAw, A-
Dependent aqueous
or oleic species
Cation exchange
H+, Na+
Solid species
SiO2 (Silica), Al2Si2O5(OH)4 (Kaolinite),

CaCO3
Table E.4: Contribution of each reaction on alkali consumption

Reaction
Consumption
Cation Exchange
1.28 meq/100g rock
H + Na + + OH Na + H2O
Dissolution of quartz
+
H 4SiO 4 H + H3SiO4
0.27 meq/100g rock
NaH3SiO 4 Na + + H3SiO4
394
0.030
10
0.025
0.020
0.015
0.010
0.005
0.000
0
0.2
0.4
0.6
0.8
surfactant concentration, vol fraction
pH
12
Adsorbed cation concentration, mol/L PV
Figure E.1: pH and surfactant concentration at 1.0 PV

0.20
0.18
Sodium
0.16
0.14
Hydrogen
0.12
0.10
0.08
0.06
0.04
0.02
0.00
0
0.2
0.4
0.6
Figure E.2: Adsorbed cation concentration (1.0 PV)
395
0.8
12
pH decrease is due to dissolution of silica.
11
10
pH
9
8
7
6
5
0
0.2
0.4
0.6
0.8
Figure E.3: Effect of silica dissolution on the pH front (1.0 PV)
solution species concentration, mol/L
0.030
0.025
NaH3SiO4
0.020
0.015
0.010
H3SiO4-
0.005
0.000
0
0.2
0.4
0.6
Figure E.4: Solution species concentration (1.0 PV)
396
0.8
APPENDIX F
Modeling the Effect of Co-solvent on the Phase Behavior
This appendix is written as a continuation to Appendix B of Glen Anderson's
thesis (2006) to provide information on how to obtain the phase behavior parameters
when co-solvent is present.
Co-solvents are added to the surfactant solution to improve the coalescence
times and help speed up the equilibration time. They can cause a shift in the optimum
salinity and a reduction in solubilization parameters. In the example case studied,
cosolvent increases the optimum salinity and reduces the solubilization ratio.
Therefore, the change of optimum salinity and solubilization ratio as a function of
cosolvent concentration needs to be measured in order to accurately model the effect
on the phase behavior. The cosolvent partition coefficient for this example was
measured to be 0.31 with the crude oil and reservoir brine (Dwarakanath et al., 2008).
Dwarakanath et al. (2008) used
the partition model of Provoust to match the
cosolvent partitioning data where the input paramteres akwc7, akws7, akm7, ak7, pt7
found to be 3., 1.76, 90, 35.31, and 0.172, respectively. The formulation of this
surfactant mixture contains 2 wt% surfactant, 3 wt% co-solvent and electrolyte
(Na2CO3) at 85oC. See Chapter 7 (Section 7.3) for more detail on the surfactant
formulation.
397
Effect on Optimum Salinity

As shown in Equation 2-65 (Chapter 2), the effective salinity is affected by
divalent cations and cosolvents. The effect of cosolvent on the effective salinity uses
a slope factor a. In the following equation, we replace a in Equation 2-65 with 7.
The 7th component in UTCHEM is the first cosolvent.
CSE =
C51
( F 1)
(1 + 7 f 7S )
where CSE is the effective salinity and C51 is the brine salinity.
The CSEL and CSEU, the limits of Winsor's Type III with no cosolvent, are first
obtained as outlined by Anderson (2006) (Refer to UTCHEM Technical
Documentation for more details on the phase behavior modeling). We then need to
find 7 to calculate the shift in optimal salinity for different co-solvent concentrations.
The UTCHEM batch input file is used to estimate the 7 (BETA7 input parameter)
using the following process: Different batch input files with different co-solvent
concentrations and salinities are run iteratively to match the measured optimum
salinities with one value of 7. The 7 value is found to be 2.89 (Figure F.1) for this
formulation. Provoust's model for cosolvent partitioning was used. The phase
behavior results were calibrated with UTCHEM using the methodology developed by
Satoh (1984). The co-solvent input parameters for UTCHEM (akwc7, akws7, akm7,
ak7, pt7) of this formulation are 3., 1.76, 90, 35.31, and 0.172, respectively. The
example batch input file is attached to this appendix.
398
Effect on Solubilization Ratio

After finding the parameter 7, the next step is to find the effect of co-solvent
concentration on the solubilization ratio. The following linear relationship between
the height of the binodal curve ( C3 max ) and f 7S is for the case with one co-solvent:
C3 max,7m = m7m f 7S + C7m
for m = 0 ,1 , 2
( F 2)
where m = 0 for zero salinity, 1 at optimal salinity, and 2 at twice the optimal salinity.
m7m is the slope for the maximum height of binodal curve vs. fraction of co-solvent
associated with the surfactant pseudocomponent at the salinity m. C7m is the intercept
of maximum height of the binodal curve at zero fraction of cosolvent associated with
the surfactant pseudocomponent at the salinity m. Parameters m7m and C7m are
obtained by matching the volume fraction diagrams corresponding to at least three
different total chemical (co-solvent + surfactant) compositions.
For the first iteration, the slope parameters are set to zero in the UTCHEM
batch input file (HBNS70, HBNS71, HBNS72) and the intercept parameters are
adjusted ( HBNC70, HBNC71, HBNC72) in order to obtain a reasonable match of the
volume fraction diagrams as explained in Anderson (2006). Then the slope
parameters are obtained. For example, in this case we first match the phase behavior
parameters for the data without co-solvent. Then the slope parameter is changed at
different cosolvent concentrations until one value best representing the range of data
is determined (Figure F.2). Therefore, the HBNS71 variable which reflects the effect
399
of cosolvent on the optimal solubilization ratio is found. The variables HBNC70,

HBNC71, HBNC72 and HBNS71 are 0.035, 0.024, 0.035 and 0.14 for the case
studied, respectively. We did not model the effect of co-solvent on the limits of the
Winsor's Type III salinity window because data were not available. Therefore,
HBNS70 and HBNS72 parameters remain zeros.
400
1.2
Optimal Salinity, S* (wt% Na2CO3)
1.1
1.0
0.9
0.8
0.7
0.6
S*
0.5
UTCHEM
0.4
0.3
0.2
0.1
0.0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
% EGBE
Figure F.1: The effect of cosolvent concentration on optimal salinity (formulation

containing the EGBE)
20
SP
18
Not Equilibrated
Optimal Solubilization, SP
16
Linear (UTCHEM)
14
12
10
8
6
4
2
0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
% EGBE
Figure F.2: The effect of cosolvent concentration on optimum solubilization ratio

(formulation containing the EGBE)
401
BATCH INPUT Example of Surfactant/Cosolvent Phase Behavior

CC*******************************************************************
CC
*
CC BRIEF DESCRIPTION OF DATA SET : UTCHEM (VERSION 9.82 )
*
CC
*
CC*******************************************************************
CC
*
CC batch calculation to obtain UTCHEM phase behavior with cosolvent
*
CC
*
CC LENGTH (FT) :
PROCESS : SURFACTANT/COSOLVENT
*
CC THICKNESS (FT) :
INJ. RATE (FT3/DAY) :
*
CC WIDTH (FT) :
*
CC POROSITY :
*
CC GRID BLOCKS : 5x 1x1
*
CC DATE :
*
CC
*
CC*******************************************************************
CC
CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
CC Run number
*---- RUNNO
UTBATC
CC
*---- title(i)
get the hand's parameter from batch samples (with pCE)
surfactant and cosolvent
NO Correct fluid properties, only match of phase behavior parameters
CC
CC SIMULATION FLAGS
1 2 0 0 0 0 0 1 0 0 0 0
CC
CC no. of gridblocks,flag specifies constant or variable grid size,unit
5 1 1 0 0
CC
CC constant grid block size in x,y,and z
*---- dx1
dy1
dz1
1
1
1
CC
CC total no. of components,no. of tracers,no. of gel components
*----n no ntw nta ngc ng noth
7 0 0 0 0 0 0
CC
CC Name of the components
402
*----spname(i) for i=1 to n

Water
Oil
Surf.
Polymer
Chloride
Calcium
Alcohol 1
CC
CC flag indicating if the component is included in calculations or not
*----icf(kc) for kc=1,n
1 1 1 0 1 1 1
CC
CC*******************************************************************
CC
*
CC OUTPUT OPTIONS
*
CC
*
CC*******************************************************************
CC
CC
CC FLAG TO WRITE TO UNIT 3,FLAG FOR PV OR DAYS TO PRINT OR TO STOP THE RUN
0
0
0
CC
1 1 1 0 1 1 1
CC
CC FLAG FOR PRES.,SAT.,TOTAL CONC.,TRACER CONC.,CAP.,GEL, ALKALINE PROFILES
0 0 0 0 0 0 0 0 0
CC
CC FLAG FOR WRITING SEVERAL PROPERTIES TO UNIT 4 (Prof)
0 0 0 0 0 0 0 0
CC
CC FLAG for variables to PROF output file
0 0 0 0
CC
CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
CC
CC MAX. SIMULATION TIME ( DAYS)
*---- TMAX
250
CC
403
*---- COMPR
PSTAND
0
0
CC
PERMEABILITY
0 1 1 0 0
CC
CC CONSTANT POROSITY FOR WHOLE RESERVOIR
*---- PORC1
1
CC
*---- PERMX(K),K=1,NZ
1000000
CC
CC CONSTANT Y-PERMEABILITY (MILIDARCY) FOR LAYER K = 1,NZ
*---- PERMY(K),K=1,NZ
1000000
CC
CC CONSTANT Z-PERMEABILITY FOR WHOLE RESERVOIR
*---- PERMZC
1000000
CC
CC FLAG FOR CONSTANT OR VARIABLE DEPTH, PRESSURE, WATER
SATURATION,INITIAL AQUEOUS PHASE cOMPOSITIONS
0
0 0 -1
CC
*---- D111
0
CC
CC CONSTANT PRESSURE (PSIA)
*---- PRESS1
1
CC
CC CONSTANT INITIAL WATER SATURATION
*---- SWI
1
CC
CC BRINE SALINITY AND DIVALENT CATION CONCENTRATION (MEQ/ML)
*---- C50
C60
0.149 0.0
CC
CC*******************************************************************
CC
*
*
CC
*
CC*******************************************************************
CC
CC
404
0 1 0.001 0
CC
CC flag indicating type of phase behavior parameters
*---- ifghbn
0
CC FOR ALCOHOL 1
0.0
0.035
0.14
0.024
0.0
0.035
CC FOR ALCOHOL 2
0. 0. 0. 0. 0. 0.
CC
0.11 0.19 0
0
CC
0 2.89
0
CC
1 0.0
0.0
0
0
CC
*---- nalmax epsalc
20
0.0001
CC
3.
1.76
90 35.31 0.172
CC
0
0
0 0
0
CC
CC ift model flag
*---- ift
1
CC
*---- chuh ahuh
0.3
13
CC
*---- xiftw
1.5
CC
405
CC ORGANIC MASS TRANSFER FLAG

*---- imass icor
0
0
CC
*---- itrap t11
t22
t33
0
1865 59074 364.2
CC
CC FLAG FOR RELATIVE PERMEABILITY AND CAPILLARY PRESSURE MODEL
*---- iperm
0
CC
*---- isrw iprw iew
0 0
0
CC
0 0 0
CC
1
1 1
CC
*---- e1wc e2wc e3wc
1
1
1
CC
1 1 0
CC
CC COMPOSITIONAL PHASE VISCOSITY PARAMETERS
0
0
0
0
0
CC
*---- AP1 AP2 AP3
81 2700 2500
CC
10 0.01 0.17
CC
20
10 1.8
CC
CC CC FLAG FOR POLYMER PARTITIONING, PERM. REDUCTION PARAMETERS
1
1
0.8 1000 0.0186
CC
406
CC SPECIFIC WEIGHT FOR COMPONENTS 1,2,3,7,8 ,Coeffient of oil and GRAVITY FLAG
0.433 0.433 0.433 0.433 0.433 0
2
CC
*----- ISTB
0
CC
*---- COMPC(1) COMPC(2) COMPC(3) COMPC(7) COMPC(8)
0
0
0
0
0
CC
*---- ICPC IEPC IOW
0
0 0
CC
CC CAPILLARY PRESSURE PARAMETER, CPC0
*---- CPC0
0
CC
CC CAPILLARY PRESSURE PARAMETER, EPC0
*---- EPC0
2
CC
*---- D(KC,1),KC=1,N
0
0
0
0
0
0
0
CC
*---- D(KC,2),KC=1,N
0
0
0
0
0
0
0
CC
*---- D(KC,3),KC=1,N
0
0
0
0
0
0
0
CC
0
0
CC
0
0
CC
0
0
CC
CC flag to specify organic adsorption calculation
*---- iadso
0
CC
407

0 0 1000 0.7 0 100 0 0 0 0
CC
0 0 0 419
CC
CC*******************************************************************
CC
*
CC WELL DATA
*
CC
*
CC*******************************************************************
CC
CC
CC FLAG FOR SPECIFIED BOUNDARY AND ZONE IS MODELED
*---- IBOUND IZONE
0 0
CC
2 2
1
2
CC
1 1 1
1 0.5
0
3 1 1 0
CC
CC WELL NAME
*---- WELNAM
INJECTOR
CC
0
0
5000 0
1000
CC
2 5 1
2 0.5
0
3 1 1 0
CC
CC WELL NAME
*---- WELNAM
PRODUCER
CC
0
0
5000 0
50000
CC
*---- ID QI(M,L) C(M,KC,L)
1 0.05 0.95 0 0.02 0 0.21375 0.0 0.03
1 0.05 0 1 0 0 0 0 0
1 0 0 0 0 0 0 0 0
408
CC
CC ID, BOTTOM HOLE PRESSURE FOR PRESSURE CONSTRAINT WELL (IFLAG=2 OR 3)
*---- ID PWF
2 1
CC
*---- TINJ CUMPR1 CUMHI1 WRHPV WRPRF RSTC
500 5
5
0.5 5
50
CC
CC FOR IMES=2 ,THE INI. TIME STEP,CONC. TOLERANCE,MAX.,MIN. courant numbers
*---- DT DCLIM CNMAX CNMIN
0.05
0.003 0.2
0.01
409
Nomenclature
a3, a31,
a32, a33
Constants in surfactant adsorption isotherm
a4, a41,
a42, a43
Constants in polymer adsorption isotherm
ai
Activity of species i
Ap1, Ap2,
Ap3
Polymer viscosity parameters
A-
Chemical symbol for in-situ generated anionic surfactant
b3
Constant in surfactant adsorption isotherm
b4
Constant in polymer adsorption isotherm
Cpc
Capillary pressure parameter
i
C
Overall concentration of component per unit pore volume
CT
n
Total concentration of element n
Cij
Concentration of tracer i in phase j
Cit
Total concentration of tracer i
Cj
Concentration of fluid species j
lk
C
Concentration of solid species k
Ci
Concentration of cation i adsorbed on clay
Cm
Concentration of cation mi adsorbed on micelle surface

410
C A
Concentration of component in phase A
CSE
Effective salinity (eq/L water)
CSE1
Effective salinity below which polymer viscosity is independent of

salinity
CSEP
Effective salinity for polymer
CSEU, CSEL
Upper and lower effective salinity limits for Type (III)

surfactant phase behavior (eq/L water)
C3
Concentration of adsorbed surfactant
Concentration of injected anionic surfactant
Crk
Permeability reduction parameter for polymer
D A
Molecular diffusion of component in phase A
eA
Relative permeability exponent for phase A
e1c, e2c, e3c
Relative permeability exponent for phase 1, 2 and 3 at high capillary

number
e1w, e2w, e3w
Relative permeability exponent for phase 1, 2 and 3 at low capillary

number
f 6s
Fraction of multivalent cations associated with surfactant micelles
f 7s , f8s
Fraction of cosolvents 7 and 8 associated with surfactant micelles
fni
Stoichiometric coefficient of element n in adsorbed cation i
gnk
Stoichiometric coefficient of element n in solid species k
G11, G12,
G13
IFT parameters for water-microemulsion system

411
G21, G22,
G23
IFT parameters for oil-microemulsion system
hnj
Stoichiometric coefficient of element n in solid species j
Number of cations participating in ion exchange on matrix
Number of fluid chemical species participating in reactions
G
k
Absolute permeability tensor
k rA
Relative permeability of phase A
k orA
End-point relative permeability of phase A
Number of solids
Ki
Partition coefficient of tracer i
Ka
Acid dissociation constant of HA
KD
Partition coefficient for HA between water and oil
K eq
r
Reaction equilibrium constant for dependent fluid species r
K sp
k
Solubility product for solid k
K ex
p
Exchange reaction equilibrium constant for reaction p
K exm
q
Equilibrium constant for exchange reaction q on micelle
Kxx, Kyy, etc. Elements of dispersion tensor

JG
JG
K A
Dispersion tensor for component in phase A
Number of cations participating in ion exchange on micelles

412
nC
Number of components
nCv
Number of volume occupying components
nP
Number of phases
npc
Exponent in the capillary pressure
Total number of reactive elements
N cA
Capillary number of phase A
Exponent for calculating shear rate dependence of polymer viscosity
PA
Pressure of phase A
pH
Negative logarithm of hydrogen ion concentration (ideal solution)
(pH)c
pH below which adsorption of surfactant is not a function of pH
(pH)t1
pH above which adsorption of surfactant is small constant fraction of

neutral pH value
(pH)t
pH dependent surfactant adsorption parameter
Rate of injection or production of component
Source term for component
Chemical symbol for anionic injected surfactant
SA
Saturation of phase A
SnA
Normalized saturation of phase A
S o
Average oil saturation in the swept pore volume
Sp
Exponent for calculating salinity dependence of polymer solution
SrA
Residual saturation of phase A

413
Time
Tj1, Tj2
Capillary desaturation parameters for phase j
G
uA
Total flux of phase A
u xA , u yA , etc. Flux of phase A in x-direction, y-direction etc.
Vi
The mean residence time of tracer i
Vslug
Volume of tracer slug
x, y, z
Coordinate directions
XD
dimensionless distance from injector
zj
Charge of fluid species j
zm
Charge of the micelle-associated cation m
zi
Charge of the adsorbed cation i
1 , 2 ,
3 , 4 , 5
Compositional microemulsion phase viscosity parameters
LA
Longitudinal dispersivity of phase A
TA
Transverse dispersivity of phase A
exm
q
Coefficient for ion exchange equilibrium q on micelles
6 , 7 , 8
Effective salinity parameters for calcium and up to 2 cosolvents
Effective salinity parameter for polymer viscosity
Shear rate coefficient

414
1/ 2
Shear rate at which polymer viscosity is one-half the value at zero

shear rate
Specific weight of phase A
Viscosity of phase A
wo
IFT between aqueous and oleic phases
AA '
IFT between phase A and A '
Porosity
415
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426
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427
VITA
Hourshad Mohammadi was born in Tehran, Iran on December 19, 1977, the
daughter of Ms. Masoumeh Abrishami and Mr. Gholamali Mohammadi. She
completed her high school diploma in Mathematics & Physics at Hajar High School,
Tehran, Iran in May 1995. She entered Sharif University of Technology in Tehran,
Iran and received a Bachelor of Science degree in Chemical Engineering in
September 1999. She was awarded the degree of Master of Science in Chemical
Engineering from Iran University of Science and Technology in Tehran, Iran in
January 2002. She spent two years as a petroleum engineer in Tehran, Iran. In
January 2004, she entered The University of Texas at Austin as a petroleum
engineering graduate student.
She is married to Renzo Angeles from Peru.
Permanent Address:
506 W. 23rd St.

Houston, TX 77008
This dissertation was typed by the author.
428

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Mechanistic Modeling, Design, and Optimization of

Mechanistic Modeling, Design, and Optimization of

The University of Texas at Austin

Dedicated to my parents and my husband

I would like to express my deepest gratitude to my supervising professors, Dr.

Mechanistic Modeling, Design, and Optimization of

Hourshad Mohammadi, Ph.D.

Supervisors: Gary A. Pope

Alkaline/surfactant/polymer (ASP) flooding is of increasing interest and

These corefloods were performed in different sandstone cores with

1.1 Alkaline/Surfactant/Polymer Flooding.....................................

1.2 Effect of Sodium Carbonate

1.3 Alkalinity Loss Mechanisms...

1.4 Modeling of Alkaline Flooding..

1.4.1 Oil-Alkali Chemistry

1.4.2 Homogeneous Aqueous Reactions..

1.4.3 Dissolution/Precipitation Reactions.

1.4.4 Ion Exchange Reactions with Rock Minerals and

1.5 Basic Assumptions for Modeling Geochemical Reactions.

1.6 Objective of this research

1.7 Review of Chapters.

A Review of UTCHEM Simulator

2.1 General Description of the Simulator.

2.2 Mass Conservation Equations.

2.3 Pressure Equation

2.4 Calculation of Phase Density...

2.5 Modeling of Polymer Properties..

2.5.1 Polymer Solution Viscosity at Zero Shear Rate...

2.5.2 Calculation of Shear Rate.

2.5.3 Polymer Permeability Reduction and Resistance Factor

2.5.4 Polymer Inaccessible Pore Volume..

2.5.5 Polymer Adsorption..

2.6 Surfactant Adsorption..

2.7 Microemulsion Viscosity

2.8 Capillary Pressure

2.9 Relative Permeability Model...

2.10 Capillary Desaturation...

2.11 Interfacial Tension Model..

2.11.1 Healy and Reed's Model.

2.11.2 Chun-Huh's Model......

2.12 Phase Behavior..

2.12.1 Effective Salinity

2.12.2 Flash Calculations..

2.13 Cation Exchange Model

2.14 Effect of Alcohol on Phase Behavior

2.14.1 Alcohol Partitioning

2.14.2 Effective Salinity

2.14.3 Effect of Alcohol on Solubilization Parameters.....

2.15 Mathematical Formulation of Reaction Equilibrium.

2.15.1 Basic Assumptions..

2.15.2 Mathematical Statement of the Reaction Equilibrium

2.15.2.1 Mass Balance Equations......

2.15.2.2 Aqueous Reaction Equilibria Relations...

2.15.2.3 Solubility Product Constraints.

2.15.2.4 Ion Exchange Equilibrium on Matrix

2.15.2.5 Ion Exchange Equilibrium on Micelles.......

2.15.2.6 Partitioning Equilibrium of Acid Component

Alkaline Consumption Studies..........................................................................

3.1 Reactions that Consume Alkaline....................................................

3.2 Alkali Consumption in a Sandstone Rock......................................

3.2.1 Simulation Input Description........................................ ...

3.2.2 Reactions Modeled...........................................................

3.2.2.1 Simulation with no Alkali Consumption