IPTC 10506

A Laboratory Study Investigating Methods for Improving Oil Recovery in Carbonates

K.J. Webb, C.J.J. Black, and G. Tjetland, BP Exploration

Copyright 2005, International Petroleum Technology Conference

saturation change in the spontaneous imbibition phase of the
This paper was prepared for presentation at the International Petroleum Technology test between simulated formation and sea waters.
Conference held in Doha, Qatar, 21–23 November 2005.

This paper was selected for presentation by an IPTC Programme Committee following review
of information contained in an proposal submitted by the author(s). Contents of the paper, as
Background
presented, have not been reviewed by the International Petroleum Technology Conference Some recent publications 6 7 show oil recovery in carbonates is
and are subject to correction by the author(s). The material, as presented, does not necessarily
reflect any position of the International Petroleum Technology Conference, its officers, or increased by the addition of sulphate to the injection water.
members. Papers presented at IPTC are subject to publication review by Sponsor Society
Committees of IPTC. Electronic reproduction, distribution, or storage of any part of this paper
These tests describe corefloods which have generally been
for commercial purposes without the written consent of the International Petroleum Technology performed at ambient or reduced conditions using dead fluids
Conference is prohibited. Permission to reproduce in print is restricted to an abstract of not
more than 300 words; illustrations may not be copied. The abstract must contain conspicuous and show that the addition of sulphate at concentrations that
acknowledgment of where and by whom the paper was presented. Write Librarian, IPTC, P.O.
Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.
are present in sea water, modify the rock wettability to
increased water wet behaviour.
Abstract
Previous studies have shown that waterflood recovery is Imbibition capillary pressure characteristics are key to
dependent on the composition of injection brine in clastic describing recovery characteristics in fractured carbonates as
reservoirs 1 2 3 4 5 . they control fracture matrix interactions as well as oil drainage
from oil wet pore surfaces. Any wettability modification to a
Some researchers have also shown that oil recovery from more water wet system will therefore be identifiable in the
carbonates is dependent on the ionic composition of the imbibition capillary pressure data.
injection water 6 7. These studies have however been generated
at laboratory conditions which are not representative of the A study was therefore designed to compare recovery from a
reservoir, and therefore it is uncertain whether these IOR North Sea carbonate core sample using sulphate free formation
benefits are applicable to actual reservoir waterflood oil simulated brine, with sea water, which contains sulphate.
recovery.
Description of the Equipment
A reservoir condition coreflood study was therefore performed These studies utilised coreflood facilities which operate at full
on core from a North Sea carbonate field (Valhall) to reservoir conditions, up to 150oC and 10,000 psi, (Figure 1).
determine whether the recovery benefits seen in reduced The equipment utilises gamma-ray attanuation in-situ
condition experiments, were also obtained from full reservoir saturation monitoring 8 and uses live fluids both for ageing and
condition tests, using live crude oil and brine. In these fluid flow. A schematic of the in-situ saturation equipment is
reservoir condition tests, two reservoir core plugs were given in Figure 2. Volumetric production is measured at full
selected from the same reservoir layer and were similar in reservoir conditions with an in-line separator, and saturations
reservoir properties so that comparisons could be drawn at the end of the flood are assured by performing aqueous
between the experiments. Samples were prepared to give dispersions with a doped phase.
initial water saturations which were uniformly distributed and
volumetrically matched to the height above the oil water
contact of the samples in the reservoirs. The initial water
saturation composition was based upon the simulated
formation brine composition of the field. The plugs were then
aged in live crude oil to restore wettability. Imbibition
capillary pressure tests were then performed at full reservoir
conditions, with live oil and brine, using the semi dynamic
method. The first experiment utilised a simulated formation
water and the second test utilised a simulated sea water,
respectively, as the displacing water.

The resultant data showed that the sea water used in the
capillary pressure test modified the wettability of the
carbonate system, changing the wettability of the rock to a
more water wet state. This was indicated by comparing the Figure 1: Typical Reservoir Condition Facility
2 IPTC 10506

Figure 2: In-situ Saturation Monitoring Equipment Acquisition of Initial Water Saturations.

It was essential that plug samples had representative Swi
values which were matched to the height above the oil water
70 Cross-Section of GASM Apparatus contact in the reservoir. For these cleaned plug samples,
60 initial water saturations were achieved by porous plate de-
saturation, using the strongly non wetting gas nitrogen. Once
50 East these initial water saturations were acquired, the samples were
40 Coreholder Collimator Minature
West loaded into hydrostatic coreholders and saturated by flowing
Lead
NaI refined oil under back pressure.
30 North
Detector
Collimator
20 In-situ saturation monitoring was used to provide distributed
10 saturation data to aid interpretation of experimental results.
Gamma This technique was based on the linear attenuation of γ-rays.
0
Ray Source Each source/detector pair viewed a slice of core 4 mm wide.
1st Qtr 2nd Qtr 3rd Qtr 4th Qtr A linear relationship between the log of counts (transmitted
flux) and water saturation existed. Therefore, by employing
careful calibration procedures for each source/detector
assembly, fluid saturations were calculated. A number of
In-Situ
100 Saturation Monitoring Schematic these assemblies were mounted along the core plug samples
so that water saturation was monitored at fixed positions 5
80 Gamma Source
versus time/throughput during the waterfloods. The accuracy
60 of these measurements was ~1% of a pore volume.
East
dP dP
Inlet 40 Outlet
West Two sets of calibration data were collected for each
PLUG
source/detector pair at the end of each capillary pressure test.
20 North 100% brine saturation calibrations were recorded at the end of
0 the cleaning stage. 100% oil saturation calibrations were
1st 2nd 3rd 4th NaI measured with the core 100% saturated with live crude oil.
Qtr Qtr Qtr QtrDetectors
In these experiments it was necessary to replace chloride ions
in the simulated formation brine and the sea water with iodide
ions so that the contrast between the aqueous and oleic phases
Description of Procedures was increased. This reduced the noise to signal ratio, and
improved the accuracy of the calculated in-situ saturations.
Core Preparation. Plug samples, nominally 7.5 cm long by The molarity of the doped brine was kept the same as the un-
3.77 cm in diameter were used for this study. All samples doped brine to ensure that no adverse rock/fluid interactions
were selected from the same well and the same reservoir occurred.
interval. Mercury injection and mineralogical characterics
were similar for all samples. Plug samples were cut from Ageing Process. Samples were loaded into reservoir
preserved whole core pieces by using depolarized kerosene as condition coreholders and slowly raised in pressure and
cutting lubricant (Core samples were extracted from the temperature to reservoir conditions. Reservoir temperature
reservoir with oil based mud). Whole core samples were X- was 90oC, and reservoir pressure (pore) 3998 psi with a
Ray CT scanned prior to plugging (to select plugging confining pressure of 5880 psi.
locations). Plug samples were also scanned prior to use. This
ensured that samples used in coreflood tests were free from The refined oil was miscibly displaced at full reservoir
any hetreogenities which could impact fluid flow at the plug conditions by first toluene (to ensure no asphaltene
scale. precipitation) and then live crude oil to constant gas/oil ratio.
When the differential pressure was stable, the live crude oil
All samples used for this study were restored i.e. samples viscosity and effective permeability to live crude oil were
were cleaned to as water wet condition as possible by measured. All samples were aged in live crude oil for two to
miscible solvents. After cleaning, samples were saturated three weeks. During the ageing period the crude oil was
with the simulated formation water by flowing under a back replaced every few days. A minimum of one pore volume
pressure. After c. 10 pore volumes of brine throughput, was injected and a sufficient amount was used to achieve a
samples were removed from the hydrostatic coreholders and constant pressure drop across the sample and a constant gas
initial water saturations were set up using the procedures oil ratio.
described below.
IPTC 10506 3

Imbibition Capillary Pressure Measurement Figure 4: Schematic of Semi Dynamic Capillary Pressure
The semi dynamic technique is a technique which can measure Measurement
both positive and negative capillary pressures at full reservoir
Water -
conditions with live fluids. Wettability and fluid IFT should Oil -
therefore be representative of the reservoir. The technique is Flow Across Positive Pc
Outlet Decreasing
based on a novel approach which was developed by IFP in Flow
Oil Out
France9 This technique allows development of full cycle
Pc=Po-Pw
drainage and imbibition capillary pressure functions by
flowing oil across one face and brine across the other plug
Water - Oil -
face. A schematic of the flow diagram of the reservoir Pc=0
Flow across Flow across
condition capillary pressure rig using the semi dynamic outlet face outlet face
technique is given in Figure 3.
Pc=0

Figure 3: Semi Dynamic Pc Schematic Oil -

Water -
Decreasing
Negative Pc
Increasing Flow
Flow
Water Out

Pc=Po-Pw

The final saturation data are interpreted from the in-situ

saturation data measured at the oil end of the plug sample (for
positive capillary pressures) and the water end of the core (for
the negative capillary pressures). This allows saturations to be
measured at as near as possible to the location where the
capillary pressure measurement is made. These saturation
data are then confirmed by volumetric change in the separator
and single phase dispersion tests at the end of the test.

All brines used for the waterflood tests were pre-equilibrated

with separator gas used to recombine the live oil to the
reservoir pore pressure used during the experiment. This
The test rig utilises an air bath for ensuring live oil and brine ensured that no gas transfer from oil to water phases resulted
vessels, together with the in line separator are maintained at in oil shrinkage during the reservoir condition tests.
reservoir temperature. The carbon fibre core holder is situated
outside of the air bath and is maintained at full reservoir Preparation of Injection Brines
conditions by externally heating the coreholder with an Brines were prepared by dissolving salts in deionised water.
internal heater mat and trace heating external lines. In-situ Doped simulated formation water (sulphate free) was utilised
saturation source/detector pairings are then mounted on the for setting up initial conditions in the samples and injection
coreholder. fluid for the sulphate free brine. Doped sea water was selected
as injection fluid to determine impacts of sulphate on the
Capillary Pressure measurements in homogeneous samples are imbibition capillary pressure and hence oil recovery. The
made by utilising differential pressure measurement devices brines were doped keeping the molarity between undoped
with the positive pressure linked to the fluid flowing through brines and doped brines ther same. The brine analyses for
the sample and the negative side connected to the fluid each of the fluids are given in Table 1.
sweeping the outlet face. Therefore during an imbibition
(water saturation increasing) experiment, oil is flowed through
the sample whilst water is flushed across the fluid outlet face
during the measurement of positive capillary pressure and vice
versa during measurement of negative capillary pressure.
During the measurement of positive capillary pressure, the
flow of oil is decreased from a high value and water is allowed
to imbibe from the sweeping face into the plug. During the
measurement of negative capillary pressure, the flow of brine
is increased from a low value and water is allowed to displace
oil in the plug sample. These steps are represented in the
schematic in Figure 4.
4 IPTC 10506

Table 1: Brine Analyses Table 3: Zero Sulphate Pc Characteristics

Ionic Simulated Simulated Sw Pc
Species Formation Sea Water 0.056 200
Water 0.058 36.9
(mg/l) (mg/l)
0.073 9.3

Na +
24332 9287 0.112 5.06
Mg++ 162 1258 0.137 3.56
Ca++ 726 399 0.176 1.46
K+ 215 374
Cl- 27686 5232 0.232 0.5
I- 42333 42333 0.28 0
SO4-- 0 2648
HCO- 0 140 0.503 -0.8
0.606 -1.13
Plug Details 0.698 -2
Plug details are given in Table 2. Both samples were taken 0.768 -3
from the same reservoir intervals and had similar 0.793 -4
porosity/permeability characteristics and mercury injection 0.81 -5
pore size distributions (Figure 5). 0.827 -13
0.84 -31.4
Table 2: Plug Details
0.857 -79.3
Plug Porosity Permeability
Number (mD)
1 0.41 2.2
Figure 6: Reservoir Condition Capillary Pressure:
2 0.41 2.3 Sulphate Free (Low Capillary Pressures)
Imbibition Pc
Figure 5: Comparison of Pore Size Distribution 5
Characteristics between Samples
4
350
3
300 Plug 1 Sulphate free
Plug 2 2
250
1
200
Pc

0
PSD

0 0.2 0.4 0.6 0.8 1

150 Plug 1 -1

100 -2

50 -3

0 -4
0.001 0.01 0.1 1 10
-5
Mean Pore Diameter
Sw

Imbibition Capillary Results with Sulphate free

Injection Brine
Results from the reservoir condition capillary pressure using
simulated formation brine (sulphate free) are given in Table 3.
Results are also presented in Figure 6 (low capillary pressure
region) and Figure 7 (all data). At zero capillary pressure
(spontaneous imbibition saturation) the sample has imbibed
from a saturation of 0.056 (Swi) to 0.28. At the end of the
capillary pressure test(-80psi), the remaining oil saturation was
0.143. Summary in-situ saturation data are shown in Figure
8.
IPTC 10506 5

Figure 7: Reservoir Condition Capillary Pressure Table 4: Sea Water Pc Characteristics

(Sulphate Free) Sw Pc
Imbibition Pc
0.073 249
100
0.085 45
80
0.09 15
60 Plug 1 Sulphate free
0.131 8
40 0.197 3.33
20 0.23 2.22
0.25 1.79
Pc

0
0 0.2 0.4 0.6 0.8 1 0.328 0.6
-20
0.38 0
-40
0.5 -0.1
-60 0.6 -0.3
-80 0.7 -0.7
0.8 -2.5
-100
Sw 0.831 -5.8
0.84 -10
0.856 -20
Figure 8: In-situ Saturation Profiles during Reservoir 0.863 -32.2
Condition Capillary Pressure Tests: Formation Water 0.867 -43
(Sulphate free) Injection Brine 0.869 -49.1
0.87 -54.3
1 0.882 -92.8
0.9
0.893 -126.9
0.8
0.895 -142.5
0.7
Swi Distribution
0.899 -167.7
0.6
Saturation

Pc=0 Distribution
0.5 Pc End Distribution 0.901 -250
0.4

0.3

0.2 Figure 9: Reservoir Condition Capillary Pressure: Sea

0.1 Water (Sulphate) Injection Brine (Low Capillary
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Pressures)
Fractional Distance

Sea Water Injection Fluid

Imbibition Capillary Results with Sea Water 5

(Sulphate) 4
Results from the reservoir condition capillary pressure using
3
simulated sea water as injection fluid are given in Table 4 and
in Figure 9 (low capillary pressure region) to Figure 10 (all 2
data). At zero capillary pressure (spontaneous imbibition
1
saturation) the sample has imbibed from a saturation of 0.073
Pc

(Swi) to 0.38. At the end of the capillary pressure test -250 0

0 0.2 0.4 0.6 0.8 1
psi), the remaining oil saturation was 0.099. Figure 11 gives -1
the in-situ water saturation distribution at fixed intervals, at
-2
Swi, Pc=0 and at the end of the test.
-3

-4

-5
Sw
6 IPTC 10506

Figure 10: Reservoir Condition Capillary Pressure: Sea A comparison of oil recovery at Pc=0 and the end of the tests
Water (Sulphate) Injection Brine are given in capillary pressure characteristics between each of
the brines is given in Figure 12. There is clearly an
Sea Water Injection Fluid
improvement in recovery at zero Pc with the sea water,
300
compared with the formation water. At the end of the tests
there was also increased recovery observed for the sulphate
200 injection water.

Figure 12: Comparison of Recovery (fraction of PV) for

100
Formation Water and Sea Water Injections
Pc

0
0.9
0 0.2 0.4 0.6 0.8 1
0.8
-100
0.7

Recovery (Fraction of PV)

0.6
-200 0.5 Pc=0

0.4 Sor

-300 0.3
Sw
0.2

0.1
Figure 11: In-situ Saturation Profiles During Reservoir
0
Condition Capillary Pressure Tests: Sea Water (Sulphate) Formation Water Sea Water
Injection Brine

1
For fractured reservoir systems (or heterogeneous systems) the
0.9
spontaneous imbibition or positive part of the imbibition
0.8
capillary pressure curve are essential for describing imbibition
0.7 Swi Distribution
from fracture to matrix (or high permeability to low
Pc=0 Distribution
0.6
permeability zones). The spontaneous imbibition (i.e Swi to
Saturation

0.5
0.4
0.3
0.2
0.1
0 clearly be seen in Figure 13. In fractured reservoirs the
0 0.1 0.2 0.3 0.4
Fractional Distance
Comparison of Capillary Pressure Characteristics
between Sulphate free Simulated Formation Water
and Sulphate containing Sea Water Injection Fluid
Simulated formation water was used to achieve Swi in both
samples prior to the reservoir condition capillary pressure
tests. The Swi values achieved in both samples were similar;
0.056 for the formation water displacement test and 0.073 for
sea water displacement test. In both instances, the fluid
distribution at Swi was found to be uniform (Table 5). Any
differences observed in the capillary pressure data are not
therefore attributable to Swi.
Pc end Distribution
Sw at 0 psi) is also a good indicator of the water wet nature of
the rock. For the sulphate free injection this volume
corresponded to 0.224 PV, whilst for the Sulphate sea water
injection this corresponded to 0.31 PV, an increase in recovery
at 0psi of 40%. The improvement in the recovery at Pc=0 can
0.5 0.6 0.7 0.8 0.9 1
viscous gradient across matrix blocks depends on the fracture
conductivity and the the matrix dimensions. Recovery is
determined by the viscous gradient overcoming the capillary
pressure retaining the oil in the matrix. Therefore recovery is
fundamentally influenced by not only the spontaneous
imbibition but the negative Pc / Sw relationship. For a given
matrix block size with the viscous gradient across it of say -1
psi the formation brine recovery would be ~45% PV and te sea
water recovery would be ~60% PV. For a range of fracture /
matrix dimensions the sea water capillary pressure curve
obtained implies significantly higher recovery.

Table 5: In-situ Saturation Data at Swi

Plug DET 1 DET 2 DET 3 DET 4 DET 5 DET 6 DET 7 DET 8

No.
1 0.056 0.060 0.056 0.060 0.057 0.051 0.060
2 0.073 0.096 0.067 0.069 0.075 0.081 0.075 0.073
IPTC 10506
Figure 13: Recovery Vs Pc (Low negative capillary
pressure)
0 performed. However the positive benefit observed in this
-0.5
-1
Pc
-1.5
-2
-2.5
-3
0 0.2 0.4 0.6 0.8 1
Sw* (Sw-Swi)
For viscous driven and gravity driven waterfloods, the
saturation at any given capillary pressure are important. For
any given capillary pressure, the oil saturation is lower for the
sulphate sea water injection than the sulphate free formation
water.
A comparison of final water saturation achieved during the
tests shows that an oil saturation of 0.14 was achieved for the
sulphate free injection, whilst, ~0.1 was achieved for the
sulphate sea water injection. Whilst this decrease in oil
saturation is small, ~0.04 PV it is still shows that sulphate
containing sea water had higher oil recovery.
Conclusions
Reservoir condition capillary pressure characteristics were
successfully measured at full reservoir conditions using
the semi dynamic technique.
Capillary pressure data representing the full range in
saturation data were successfully measured for both
sulphate free brine and sea water containing sulphate.
From similar Swi values, the water wetting characteristics
of the rock appeared to be increased for the sea water
(sulphate) water injection. This was manifest by an
increase in the positive part of the capillary pressure
curve.
For a given negative capillary pressure, the sea water
injection fluid gave lower oil saturations, compared with
the sulphate free simulated formation water.
For this single comparison, the use of sulphate brine as
injection fluid, gave an oil recovery benefit compared
with the sulphate free simulated formation brine.
7
Recommendations
Currently only a single comparative test has been
single coreflood test, has shown the potential for
improved recovery in carbonates. Further research,
reservoir condition comparative studies and field tests are
required to improve understanding of this potential EOR
process.
References
1: Morrow, N.R., G. Tang, M.Valat, and X. Xie, 1998,
“Prospects of Improved Oil Recovery Related to
Wettability and Brine Composition” J. Pet. Sci. Eng., vol.
20, June, pp. 267-276.
2 Tang, G.Q. and N.R. Morrow, 1997, “Salinity, Temperature,
Oil Composition, and Oil Recovery by Waterflooding,”
SPE Reservoir Engineering, November, pp. 269-276
3: Webb, K.J, Black, C.J.J., Al-Jeel, H “ Low Salinity Oil
Recovery- Log Inject Log” SPE 89379
4: Webb K.J., Black, C.J.J., Edmonds, I.J. “Low Salinity Oil
Recovery- The Role of Reservoir Condition Corefloods”
EAGE Paper C18, Presented at the EAGE EOR
Conference in Budapest, Hungary, April 2005.
5: McGuire, P., Chatham, J.R., Paskvan, F., Sommer, D.,
Carini, F.H. “Low Salinity Oil Recovery: An Exciting
Opportunity for Alaska’s North Slope” SPE 93903
6: Austad, T., Strand, S., Hognesen, E.J., Zhang, P. “Sea
Water as IOR Fluid in fractured Chalk” SPE93000
7: Zhang, P., Austad, T. “Waterflooding in Chalk: relationship
Between Oil Recovery, New Wettability Index, Brine
Composition and Cationic Wettability Modifier”
SPE94209
8: Nicholls, C.I. and Heaviside, J.: "Gamma Ray Absorption
Techniques Improve Analysis of Core Displacement
Tests", SPE 14421 (1985).
9: Lenormond, R., Eisenzimmer, A. and Zarcone, C.: “A
Novel Method for the Determination of Water/Oil
Capillary Pressures of Mixed Wettability Samples”,
Institut Francais du Petrole, SCA Conference 9322 (1993).
Acknowledgements
The authors wish to thank BP and the Valhall partnership (BP
Norge AS, Amerada Hess Norge AS, A/S Norske Shell and
Total E&P Norge AS) for permission to publish this paper.
The results and opinions presented in this paper do not
necessarily reflect the view of the Valhall partnership.
Nomenclature
Pc Capillary Pressure
PV Pore Volume
Sw Water Saturation
Swi Initial Water Saturation