A New Retarded HF

System

BJ Services Company
 Introduction

This presentation focuses on;

1) Sandstone matrix acidizing.

2) A new retarded HF acid, which

provides several advantages over
conventional HF acid, and the
opportunity for true stimulation.
Presentation Highlights

Matrix Acidizing Concepts

New Retarded HF System
Stim-Lab Test Results
Case Studies
Conclusions
 Goal of Matrix Acidizing

Current- Reduce skin damage

- Restore natural permeability
New View - Increase radial flow capacity

Enlarge and connect pores

ACID ACID
 What is Skin?

Definition - The summation of + & - skins...

= Well test skin.
st = sc + sp + sd + pskins
Problem: Skin is dimensionless, ie. no height
or depth & not specific. Acidizing addresses
sd, formation damage.
sd occurs during all phases of wells life.
Realtime skin has proven useful.
Skin is magnified by the nature of radial flow.
 Skin Effect on Radial Flow
Radial flow results in a bottleneck at the
wellbore. Formation skin in radial flow acts
as a cork on the bottle.

Reservoir
Skin Damage

S=0

S=10

p wf

Radius
 Sandstone Reservoirs

Framework grains Constituents of Sandstone

Cementing Matl. Secondary Quartz
Cement
(Carbonate

Porosity
Qtz.)
*Feldspars
Clays (Pore
Lining,ie.
Pore filling solids Illite) *Chert / Mica

Pore filling
Clays (Pore
Filling,ie.
Kaolinite) Remaining Pore Space

Liquids/Gasses Framew ork

Porosity
Filling *Mud Acid Soluble/Sensitive
Minerals
From Economides et al., 1987

All play a role in matrix acidizing!

Why are Clays So Important?

Clays line the pore network, thus

contact fluids
Clays react much more than quartz
Clays can swell/migrate, causing
damage
Clays cause precipitation

In the majority of field cases, clay dissolution dominates the

response of the formation to HF Shaughnessy et al. 1981
 Clay Structure
Clays are composed of tetrahedral and octahedral
sheets, stacked in layers. Stacking arrangement and
composition determine clay type.

Oxygen

Al, Fe, Mg Hydroxyls

Si

Single Silica Hexagonal Sheet

Tetrahedron Structure Single Octahedral Sheet
Octahedral Unit Structure
 The Clay Family
Chlorite Kaolinite

Iron rich Aluminum rich

Usually Authigenic Usually Authigenic
Rosettes or Coating Booklettes
Problem: HCl sensitive Problem: Migrates
 Clay Family (cont.)
Smectite Illite

Calcium / Sodium rich Potassium rich

Detrital/Authigenic/Mud Detrital/Authigenic
Spongelike Hairlike Fibers
Problem: Swelling Problem: Migrates
 About HCl:HF Acid

HFacid mixtures have the unique

ability to dissolve sand & silicates.

HFis usually mixed with HCl. Excess

HCl is used to keep pH low, reduce
.ppt.

One gallon of 12:3 dissolves 0.23 lbs.

of silicate matl., whereas 15% HCl
dissolves limestone at 1.8 lbs./gal.
 Common
Questions/Misconceptions

Temperature over-rides other factors

in rock reaction?

Can precipitation revert stimulation?

HF is a strong acid.

Does deconsolidation really happen?

 Overall Sandstone
Reaction With HCl:HF

Surface Area:Volume Ratio

Temperature
Mineralogy
Fixed
HF Concentration
HCl Concentration Acid Formulation
Matrix Acidizing Problems
InsufficientAcid Penetration
Acid Precipitation Damage
Deconsolidation of Wellbore

Others: Poor Zonal Coverage!!

Poor Candidate Selection (tight, no
oil!!), Skin Misdiagnosis,
Incompatibilities, Poor Field
Practice (no pickling)
 the Biggest Technical
Problem

Lack of well-specific engineering!!

It worked in Brasil, so it must work

in ____________. cookbook,
rules of thumb, boiler plate designs.
 Other Problem(s)

PerceptionP.R.!!
Expensive, Hazardous, Bulky,
Complicated, ___ % failure rate .

Relative
to other techniques,
unpredictable production increment
results highly dependant on
degree and type of damage present.
 Insufficient HF Penetration
Mineral Surface Area Effect
Clays can have several thousand times the surface
area of sand (2cm2/gm -vs- 700m2/gm), equating
to 100 times faster reaction on average.

the reaction of HF on clays and feldspars is virtually

instantaneous even at low temperatures Gatewood et al. 1970.
 Insufficient HF Penetration
Permeability Surface Area Effect

t 1/2 (sec) = 0.855 * w(ft)

Ra (lbs/ft2/sec)

Ra = HF/Clay Rxn. = 7.66 x 10-6 lbs/ft2/sec @ 80oF

21.30 x 10-6 lbs/ft2/sec @ 150oF.

Eg.; K = 25 md, Using pore d() = k,, then 25 1/2 = 5 microns

5 (0.000003281) = w(ft) = 0.000016, so, t 1/2 = 2 sec,, & = 0.81 sec @150oF
 Acid Precipitation Damage

Si, Ca, Mg, Fe, K, Al, Na are all

potential sources for precipitation.

Precipitation occurs in Primary,

Secondary and even Tertiary
reactions.

Some have defined matrix acidizing as; pumping an acid in

hopes of creating more stimulation than damage
How We Tried To Fix It?

Precipitation- Increase Preflush

/Overflush, Organic:HFmixtures,
Retarded Acids, Increase HCl ratio.
Penetration - Use more acid volume,
Use weaker or Retarded Acids.
Deconsolidation - Use less acid volume,
Use weaker or Retarded Acids.

Cost of Retarded Acid Systems are +/- 2x RMA!! (Corrosion + HCl).

We need a more cost effective and technically efficient solution.
 History of Retarded HF

System Primary Ingredient Mechanism

SGMA Organic Esters Slow Release of HF

Clay Acid HBF4 Slow Generation of HF

RHF AlCl3 Slow Release of HF

RMS Hexafluophosphoric Acid Slow Generation of HF

New HF System:
BJ Sandstone AcidTM
Two Working Mechanisms

Limits Clay Reaction

Delayed Release of HF
 Limits Clay Reaction

Phosphonate reacts with

clays to form Al-
Al-Si
Si--Ph film
Film has low sol. in weak
acid, eg. HF
Film limits further reaction
of clays and is removed by
an acidic Overflush
EDAX confirms presence of
Phosphonate film.
 Delayed Release of HF

Phosphonate - contains 5 Hydrogens

which dissociate at different
stoichiometric conditions.
NH4 F2
At surface - two hydrogens will
hydrolyze, producing a % of the HO OH OH
total HF vol.
HO P ---C - -- P OH
At formation - as HF spends and pH
rises, additional H- dissociates, O CH2 O
combining with F+ to form HF.
NH4 F2

Same dissolving power (HF%) as conventional Mud Acid

Stim-Lab Test Results
 Testing and Apparatus

Z-1 Z-2 Z-3 Z-4

1.25 2.5 2.5 3.25

Injection CS PD CS PD CS PD
1.5 0.5 1.5 0.5 1.5 0.5
Face
Core-1 Core-2

1/2 Strength HF Comparison @ 150 deg. F.

100 md Berea Cores (82%QTZ., 9%F9%FSpar
Spar,, 4% Ill., 3% Kaol
Kaol..
Flow: PD-
PD-3pv NH4Cl, ID-
ID-5pv NH4Cl, ID=-
ID=-5pv HCl,
ID--10pv
ID 10pv--HF, ID-
ID-5pv HCl, ID-
ID-5 pv NH4Cl, PD-
PD-3pv NH4Cl
 Compressive Strength

6000

5000

4000

3000

2000

1000

0
Control Injection End Middle Production End

1/2 Strength Sandstone Acid 1/2 Strength Mud Acid

 Core Flow Tests

88.3
100
69.2
80

60

40

20 0
-14.1
0

-20
% Retained Fmtn. Strength @ 3" % Improved Perm. @ 9.5"

Mud Acid Sandstone Acid

 Pore Size Distribution

40 36

Sandstone Acid
Frequency Largest Pore(%)
35
increases the 30 22 19
frequency and 25
size of largest 20
pores. 15
34

10 13 13 13 13

0
Injection Middle Pr oduction

Control Mud Acid SSA

 Effluent Analysis

HV retards/limits HF 14,000

spending so less Si, Al 12,000 RMA

in solution during the 10,000

critical early time

mg / L
8,000
reactions. 6,000

4,000
SSA
HV has a high chelating 2,000
capacity and interferes 0
with crystal growth, 2.5 pv 4.5 pv 6.5 pv

which reduces .ppt of Si, Al Si Al Si

Al, Ca, Fe, Na, Mg. Pv = Pore Volume of HF Stage

 Effluent Analysis

1.6
Delayed and limited
1.4
reaction on clays
1.2
leaves more HF 1

% HF
available for deeper 0.8
penetration. 0.6
0.4
0.2
0
2.5 pv 4.5 pv 6.5 pv
SSA RMA
Pv = Pore Volume of HF Stage
 Clay Solubility Analysis
Kaolinite
100
SSA has slower
reaction with 80
Smectite, Kaolinite,

%Sol.
60
Illite, Chlorite (ie.
slope of curve). 40

20
Limited reaction due
0
to clay coating (ie. 0.5 5 30 50
flatness of curve). min min min min

SSA RMA
 Testing Summary

EDAX shows that HV reacts with clays to

form protective film.

Dynamic Solubility tests show that HV:HF

has limited solubility with clay.

Pore size distribution shows increase in %

and size of average pore -vs- RMA.
 Test Summary (Cont.)
Compressive strength tests show
deeper, more uniform penetration.

Core flows show better distribution

of stimulation and indicate that HCl
postflush reverses clay film effect.

Effluent analysis indicates HV:HFs

ion chelation ability and limited clay
reaction minimizes .ppt.
 Other Features of HV:HF

Very low corrosion compared to

equal HF strength systems (very low
HCl content)
HV is a strong water wetter
Scale inhibition potential
Ideal for liquid automated system
(10% non-H2O system -vs- 50%)
 Conclusions

Sandstone Acid provides the following;

Deep and Uniform HF Stimulation

Limits and Retards Clay Reaction
Less Precipitation By -products
High Working Temperature Range