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SPE 124215

Improved Oil Recovery From Combining Well Stimulation With Novel


Surfactant Technologies
Sandra L. Berry, SPE, Kern Smith, SPE, and Jennifer L. Cutler, SPE, BJ Services Company, and
Leonard Kalfayan, SPE, Hess Corporation

Copyright 2009, Society of Petroleum Engineers


This paper was prepared for presentation at the 2009 SPE Annual Technical Conference and Exhibition held in New Orleans, Louisiana, USA, 47 October 2009.
This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers 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 acknowledgment of SPE copyright.

Abstract
Oil and natural gas will continue to be the primary sources of energy for the foreseeable future. However, with respect to oil,
field recovery rates are low (35 percent or less) and access to proven reserves is diminishing. New and better chemical
technologies to maximize oil recovery are called for especially for enhancing response from conventional well treatments in
mature fields.
Enhancing oil recovery rate even fractionally can pay enormous dividends. Sandrea and Sandrea1, reported that a one percent
increase in global recovery efficiency could yield an additional 88 billion barrels of oil a volume sufficient to replace about
three years of current worldwide production. Thus, very modest improvements in well performance on a global basis could
substantially elevate production and unlock vast amounts of oil reserves from reservoirs already in exploitation. Beneficial
consequences would be reduced dependence on new drilling and reliance on new discoveries. Clearly, within this context,
technologies that can be readily and economically applied to improve oil recovery from existing wells are very attractive.
This paper introduces a novel concept in which certain surfactants with enhanced oil recovery (EOR) properties can be
combined with traditional stimulation fluids; that is, production well treatments are used to deliver EOR surfactant chemistry
to the formation. This concept would enable extraction of additional oil through a spontaneous imbibition process. Combined
stimulation / EOR applications include propped fracturing, acid fracturing, matrix stimulation, and scale inhibitor squeeze
treatments.
The paper presents laboratory data demonstrating the efficacy of two new surfactant chemistries designed to enhance both
stimulation and oil recovery in naturally fractured carbonate and diatomite reservoirs. Specifically, data will be provided to
show the highly synergistic effect of combining a particular EOR surfactant with carbonate acidizing.
Finally the paper discusses the applications and deployment of this EOR surfactant-aided, production enhancement concept.

Introduction
Reserve recovery rates from various oil-bearing rock formations have been reported to be very low during the primary
recovery operation. For example, it has been reported that 60% of the worldwide reservoirs are located in carbonate
reservoirs but the estimated total oil recovery does not generally exceed 10% of the OOIP2 (Akbar and Alghamdi, 2001).
Likewise, the giant diatomaceous oil fields in California, Lost Hills and Belridge contain some 10 billion bbls of oil with
estimated oil recovery of only 5% original oil in place. Therefore, enhancing oil recovery rates even modestly can be very
advantageous in elevating production via increased recovery of oil from reservoirs already in production.
This paper introduces a novel concept in which enhanced oil recovery (EOR) surfactants can be combined with traditional
stimulation fluids to enhance oil recovery rates. Such applications enable extraction of additional oil through a spontaneous
imbibition process in the formation. Application of the EOR surfactants could include propped fracturing, acid fracturing,
matrix stimulation, and inhibitor squeeze treatments.

SPE 124215

After introduction of the EOR surfactant into the oil-bearing formation by traditional carbonate stimulation treatments, the
surfactant would further enhance oil recovery by the spontaneous imbibition process in the formation matrix. Spontaneous
imbibition of water-based products only occurs when the pore surfaces are effectively water-wet: Water imbibes into the rock
matrix and oil is expelled into the fractures, where it can be flushed out to the wellbore and produced to surface. Surfactants
have been utilized to alter carbonate rock surfaces to a more water-wet state in order to promote the imbibition of water into
the formation matrix.
The focus of this project was to investigate the use of EOR surfactants in carbonate and diatomite formations, and the ability
of the surfactants to modify the wettability of reservoir rock and produce additional oil via imbibition.

Surfactants for Improving Oil Recovery


The use of surfactants for improving oil recovery is not new. The earliest reference to the use of surfactants dates back to
1929, when De Groot was granted a patent for use of a water-soluble surfactant to improve oil recovery. Since then, there
have been many advancements in surfactant chemistries and methods of using them to release trapped oil from formation
matrices.
Unlike most sandstone formations, carbonate formations are prevalently naturally fractured. Similarly, and unlike sandstone
reservoirs which are commonly water-wet, most carbonate reservoirs tend to exhibit oil-wet or mixed-wet characteristics.
Both of these factors are primary contributors to the poor oil recovery factors in carbonates. Recent work by Yongfu et al.3
demonstrated the effectiveness of surfactant solutions in enhancing oil recovery in naturally fractured carbonate reservoirs.
The enhanced oil recovery (EOR) mechanism described is one whereby the surfactant solution alters the wettability of the
carbonate surfaces, making it more water-wet. This process has the effect of allowing the wetting aqueous phase to imbibe
into the rock matrix spontaneously and expel oil from the matrix into the natural fracture network (Figure 1).
Diatomites are another class of low-permeability rock that may benefit from water imbibition into the matrix and subsequent
oil displacement. Although most prior work has focused on imbibition in carbonaceous rocks, there have been studies by
Schembre7 et al. in diatomites. Diatomites are a hydrous form of silica or opal composed of the remains of microscopic
shells of diatoms, which are single-celled aquatic plankton. They are typically very porous. Porosities are in the range of 50
to 70%. However, permeabilities are low, in the range of 0.1 to 1 md. Given this unique combination of high porosity and
low permeability, diatomite reservoirs usually have high initial oil saturation (up to 70%) and thus the potential to be
productive through wells completed with hydraulic fracturing. However, these diatomite formations also tend to have largescale faults and natural fracture systems, which most likely increase their size and connectivity when the pore pressure
changes during production or stimulation activity. So the complexity of the flow paths in diatomite offers challenges similar
to those in naturally fractured carbonate reservoirs.

Carbonate EOR Studies


The objective of these studies was to evaluate the potential benefit of incorporating EOR surfactants in traditional carbonate
stimulation fluid systems.
1. Spontaneous Imbibition Studies
Laboratory spontaneous imbibition experiments were conducted to investigate the mechanism of oil recovery from naturally
fractured carbonate cores, at negligible pressure gradient, with various EOR surfactants. Tests compared the rate of oil
recovery in various solutions to qualitatively assess their performance. Although capillary force is the dominant driving
mechanism for spontaneous imbibition and the rate of oil recovery depends on many factors, this study does not include a
rigorous evaluation of all such parameters.
Laboratory tests were performed using two different West Texas carbonate formation core samples and two crude oils.
Different types and concentrations of surfactants added to aqueous fluid systems were compared to a base case 2% potassium
chloride solution. The following are further details of the laboratory procedure and materials used:
Laboratory Procedure Limestone cores were saturated with crude oil. Spontaneous imbibition with base brines with or
without EOR surfactant was evaluated. The test procedure for the spontaneous imbibition studies is as follows:
1) Vacuum saturate core with crude oil at ambient temperature for 24 hrs, (Swi = 0)
2) Remove from vacuum and drain excess oil for approximately 15 minutes

SPE 124215

3)
4)
5)
6)
7)
8)

Determine the weight of oil-saturated core. Use to calculate the volume of oil in the core
Place the oil-saturated core in the Amott cell (Figure 2)
Add test solutions through the top of the burette to the 1.0-ml level on the burette
Seal the top of the burette and the top seal of the junction of the burette and base with Parafilm
Record the volume of oil expelled by the core and collected in the burette against time
Determine the oil recovered as % of Original Oil in Place (OOIP) versus time

Cores Limestone cores with permeability ranging from 20 to 25 md were utilized for this part of the study. The cores were
approximately 1.5 inches in diameter and 2 inches in length. The mineralogical analysis of the cores indicated 98 to 100%
carbonate. Prior to testing, residual hydrocarbon and other contaminants were removed from the core plugs through toluene
extraction until the fluid in contact with the core plug was visibly clear. The plugs were further cleaned with methanol. After
cleaning, the plugs were dried in an oven until stable weights were achieved.
Crude oil Two West Texas crude oils were utilized in the spontaneous imbibition tests to evaluate the effect of various
surfactant mixtures on their ability to release crude oil from the carbonate cores. The crude oil properties are shown in Table
1.
EOR Surfactants One of the major technical hurdles of surfactant EOR technology is the need to custom-design a
surfactant for a specific crude oil in a specific reservoir, in which the formation brine salinity, temperature, pressure and clay
content are important considerations. In general, the performance of EOR surfactants is limited within a narrow salinity
range, and surfactant effectiveness may depend on the rock mineralogy, on which ionic exchange is dependent.
A series of carbonate EOR surfactants were pre-screened using different outcrop and formation core materials with a West
Texas crude oil sample. The surfactants chosen for this study are EOR surfactants that provide greater than 50% oil recovery
over a wide range of imbibition tests.
I. Surfactant A - surfactant with best performance in pre-screening studies
II. Surfactant B - surfactant with moderate performance in pre-screening studies
Treatment Solutions A series of different carrier solutions were utilized in the imbibition tests to better understand the
efficacy of the EOR surfactants, specifically in relation to stimulation of carbonate formations.
a)

2% KCl brine base fluid test fluid to evaluate the effect of the EOR surfactant only in improving oil recovery from
oil saturated cores
b) Non-Acid Stimulation (NAS) fluid water-based fluid system containing surfactants (apart from the EOR
surfactant) and other chemical additives designed to effectively disperse mud solids, break emulsions and water
blocks, and lower the viscosity of drilling muds. This stimulation fluid may be used for treating deep, hightemperature formations where excessive corrosion of tubular goods is considered to be a potential problem.
c) Dilute 0.5% acetic acid test fluid to evaluate the combined effect of the EOR surfactant and an acid system to
improve the oil recovery. A very dilute (slow-reacting) system was used to prevent dissolution of the carbonate core
by acid.

Note: Emulsion testing was performed by mixing the oil samples and the treatment solutions, to ensure fluid compatibility
(see Table 3 for a typical result).
2. Core Flow Studies
In order to investigate the application of EOR surfactants in carbonate acid stimulation, core flow experiments were
conducted to determine regain oil permeability. For these tests, a 10% acetic acid stimulation fluid system was evaluated with
and without surfactant A. This was an extension of the imbibition test with the dilute 0.5% acetic acid. In addition, the tests
assessed the potential benefit of shutting in the treatment for a few hours.
Cores Limestone cores with permeability ranging from 1.4 to 2.7 md were utilized for this part of the study. The cores were
approximately 1 inch in diameter and 2 inches in length. The mineralogical analysis of the cores indicated calcium carbonate
content of 98%, magnesium carbonate content of 0.4%, and remaining material (silica or quartz) content of 1.6%.
Prior to testing, residual hydrocarbon and other contaminants were removed from the plugs via toluene extraction until the
fluid in contact with plugs was visibly clear. The plugs were further cleaned with methanol. After cleaning, the plugs were
dried in an oven until stable weights were achieved.
Oil A clear mineral oil, Isopar-L, was used as the oil phase in regain permeability testing.

SPE 124215

EOR Surfactants Only surfactant A was evaluated. Surfactant A was the best performing surfactant in prior imbibition
studies.
Treatment Solutions The acid system evaluated consisted of 10% acetic acid in a 5% ammonium chloride solution
containing a non-ionic non-emulsifier. This base fluid system was evaluated for stimulation performance with and without
the EOR surfactant A , and with and without a shut-in period.
The following is a summary of the conditions for these series of tests:
I.
II.
III.
IV.

10% acetic acid system, with no shut-in period


10% acetic acid system + 0.5 % surfactant A, with no shut-in period
10% acetic acid, with shut-in period of 20 hrs
10% acetic acid system + 0.5 % surfactant A, with shut-in period of 20 hrs

Laboratory Procedure The test procedure for the regain oil permeability study was as follows:
1) Initial KoSwi Each sample was evacuated and pressure saturated with tap water. Each test sample was loaded into a
preheated Hassler coreholder and approximately 1000 psi of confining stress applied. Mineral oil was injected against 200
psi backpressure in an arbitrary formation-to-wellbore direction. Differential pressure and flow rate were monitored and
an effective permeability to oil at irreducible water (KoSwi) saturation was calculated.
2) Preflush (all samples) 5 pore volumes 3% ammonium chloride (NH4Cl) solution
3) Treatment 2 pore volumes treatment solution @ 0.3 cc/min (with or without 20 hours shut-in period)
4) Postflush (all samples) Minimum 5 pore volumes 3% NH4Cl solution
5) Final KoSwi - Immediately after postflush, mineral oil was injected against 200 psi backpressure in the original
formation-to-wellbore flow direction. Differential pressure and flow rate were monitored and an effective permeability to
oil at irreducible water (KoSwi) saturation was calculated.
6) Each sample was unloaded from the coreholder and remaining hydrocarbons and salts were extracted. After sufficient
drying, the permeability to air was measured again to confirm permeability stimulation.
3. Results and Interpretation
Evaluation of the spontaneous water imbibition studies in Texas limestone cores with the two West Texas crude oil samples
showed that Surfactant A provides the greater enhanced oil recovery. In case of the 2% KCl brine base fluid (Table 2 and
Figure 3), it is evident that the use of EOR surfactants (A & B) improves the release of crude oil from the internal limestone
core surfaces. It is evident that the imbibition rate of Surfactant A into the limestone cores is initially very slow (i.e., the first
3 to 6 hours). However, the rate of release of the test oil from within the core increases thereafter, and continues through the
seven-day test period. The improvement in the oil recovery of the OOIP (compared to the base fluid with no surfactant)
ranged from 206 to 226%. These studies indicated very good enhanced recovery of the OOIP with addition of 0.5% by
volume of Surfactant A.
Results of the spontaneous imbibition studies with Surfactant A in Non-Acid Stimulation fluid are shown in Table 4 and
Figure 4. Overall, the addition of Surfactant A provided an enhanced stimulation fluid that increased oil recovery from the
cores. However, in additional testing, it was observed that the system could be further optimized by removing one of the
NAS treatment components and using less surfactant to yield even better oil recovery. The NAS and modified NAS
treatments with surfactant A showed improvements of 94 to 129% and 25 to 286%, respectively.
Results of the spontaneous imbibition studies conducted with the dilute 0.5% acetic acid are shown in Table 5 and Figure 5.
As mentioned, the purpose of this test was to evaluate the combined effect of the EOR surfactant and an acid system to
improve oil recovery. A very dilute (slow-reacting) acid system was used to prevent the carbonate core material from being
dissolved significantly by acid during the nine-day test period. The spontaneous imbibition studies showed that the percent
oil recovery rates at 9 days for the 0.5% acetic acid system with Surfactant A were 53% of the OOIP as compared to 5.4% for
the base 0.5% acetic acid treatment with no Surfactant A.
The Core Flow testing results (Figures 6 and 7) indicate greatly increased oil permeability values after the 10% acetic acid +
Surfactant A treatment with and without a 20-hour shut-in period. Without a shut-in period, the treatment containing
Surfactant A provided approximately 50% stimulation in KoSwi over the treatment without Surfactant A. In the tests with a
20-hour shut-in, both resulted in major stimulation or wormholing. The test with the treatment containing Surfactant A
promoted significant wormholing while the test without Surfactant A promoted minor or smaller wormholes. Both tests
containing Surfactant A indicate the ability of the surfactant to promote increased oil production.

SPE 124215

Diatomite EOR Studies


As mentioned previously, the Lost Hills and Belridge diatomaceous oil fields in California contain some 10 billion barrels of
oil, with recovery estimated at just 5% of the original oil in place. The average depth of the productive interval is 2000 feet,
with the major portion of the oil in diatomaceous rocks. These rocks consist of mostly diatom skeletons, clay and sand. A
diatom skeleton has many small pores with diameters less than two microns, resulting in very high porosity. However, the
mixing of the diatom skeletons, clay, and sands create very complex pore structures leading to potentially low permeability.
Figure 10 shows a Scanning Electron Microscopy (SEM) image of the diatomite obtained from a quarry in California for use
in this enhanced oil recovery surfactant study.
The primary objective of these studies was to evaluate the potential benefit of incorporating EOR surfactants in traditional
diatomite stimulation fluid systems.
1. Spontaneous Imbibition Studies
Laboratory spontaneous imbibition experiments were conducted to investigate the mechanism of oil recovery from diatomite
cores, at negligible pressure gradient, with a specially blended Surfactant C.
Cores In this study, spontaneous imbibition studies were conducted with Surfactant C in treatment fluids on diatomite earth
core material obtained from a quarry in California. The quarry is located on the California coast west of the Sisquoc and
Monterey formations. Analysis of the diatomite core material by x-ray diffraction showed it to be composed of 93% Opal A
(sourced from the diatoms), 3% plagioclase feldspar and 3% quartz.
Crude oil Two California crude oils were utilized in the spontaneous imbibition test to evaluate Surfactant Cs ability to
release crude oil from diatomite formation cores. The properties of the main crude oils used in these tests are shown in Table
1 (labeled Oil # 3 and #4). Oil #3 is relatively thin with an API gravity of 32o and Oil #4 is thick, with an API gravity of 15o.
Laboratory Procedure The test procedure for the diatomite spontaneous imbibition studies was similar to the carbonate
core studies previously described. In the studies with diatomite cores, the horizontal endfaces of the plugs were blocked off
with epoxy to determine if spontaneous imbibition would occur in the vertical direction. This core preparation was conducted
because diatomaceous formations tend to be horizontally layered, with permeability higher along bedding planes.

2. Rheological Testing
The objective of this series of experiments was to determine the fracturing stimulation fluid compatibility with the proposed
EOR Surfactant C. The fracturing fluid tested was a high-yielding, refined, natural guar gelling agent crosslinked at high pH
by a borate complexor. The rheological properties of the system were determined at 125 deg F with and without 0.5% of
Surfactant C. The target fluid stability is a minimum viscosity of 100 cP at 100 sec-1 for 30 minutes at temperature of 125
deg F.
Laboratory Procedure The fracturing fluid was prepared by first hydrating 1 liter of linear gel fluid for 30 minutes in tap
water using a standard Servodyne mixer with a high-efficiency paddle at 1500 rpm. The base gel viscosity was measured on
an OFITE 900 using a R1-B1 rotor-bob configuration @ 511s-1 to ensure full hydration. Afterward, the fully crosslinked
sample was tested in the HPHT rheometer (using a R1-B5 rotor-bob configuration) by initially shearing it at 100 sec-1
followed by a shear rate sweep of 100, 80, 60, and 40 s-1 to calculate the power law indices n and K. The fluid was sheared
at 100 s-1 between shear rate sweeps, and the shear rate sweep was repeated every 30 minutes for 1.5 hours.
Results and Interpretation
The results of the spontaneous imbibition studies on the diatomite formation cores indicate that Surfactant C can enhance the
release of crude oil from core material (see Tables 6 and 7; and Figures 8 and 9). From this testing it is evident that the
imbibition rate of the Surfactant C into the diatomite cores is initially very slow, as also in the case with carbonates.
However, the rate of release of the test oil from the internal surface of the core increases over the 7-day test period. The
improvement in the oil recovery of the OOIP (compared to the base fluid with no surfactant) ranged from 39 to 102% for the
thin oil and 125 to 242% for the thick oil. It is interesting to note that greater benefit was observed with the higher-viscosity
oil. Results indicate the need to perform some initial pilot tests with representative formation cores and oils, if available, to
allow optimization of the surfactant concentration.
These studies show the Surfactant C treatments will imbibe into the diatomite core material in both vertical and horizontal
directions. The studies were conducted with diatomite cores having both the horizontal and vertical face open and with the
horizontal face of the core sealed with epoxy before the test study. Finally, the rheological testing indicated that the addition

SPE 124215

of Surfactant C had some effect on the breaker package (oxidative and enzyme breakers) used in the fracturing fluid. As
shown in Figure 10, the addition of 0.5% of Surfactant C resulted in a more stable fluid over time. It was determined from
further testing that the surfactant was affecting the performance of the oxidative breaker in the package. However, it was
possible to optimize the break profile and obtain an acceptable fracturing fluid by modifying the oxidative breaker
concentration.

Conclusions

These studies show that the utilization of production well treatments to deliver EOR surfactant chemistry can enable
extraction of additional oil through a spontaneous imbibition process in the formation.

EOR surfactants can be combined synergistically with conventional stimulation fluid systems to enhance oil recovery.

It is demonstrated that an EOR surfactant (Surfactant A) combined with conventional acid (acetic) treatment in matrix or
fracturing applications can improve oil production from carbonate formations.

Hydraulic fracturing fluids can be formulated to include an EOR surfactant (Surfactant C) to provide a viable method to
enhance presently low oil recoveries from diatomite reservoirs.

An EOR surfactant (Surfactant C) is effective in increasing oil recovery from diatomite cores with both heavy and light
crude oils from California.

Spontaneous imbibition of aqueous phase improves oil displacement from within the rock matrix. This is especially true
for formations that have mixed wettability or are oil-wet.

Shut-in period is not required for the EOR surfactants to provide an incremental oil recovery benefit. However, when
used in acid stimulation treatments, a shut-in period may enhance the ultimate oil recovery.

Spontaneous imbibition tests with an EOR surfactant (Surfactant A) in limestone cores yielded an improvement in the oil
recovery of the OOIP (compared to the base fluid with no surfactant) from 206 to 226%.

Spontaneous imbibition tests with an EOR surfactant (Surfactant C) in diatomite cores favorably altered wettability of
the rock surface and enhanced oil recovery.

The authors recommend performing a few simple laboratory tests on formation material (core/or suitable outcrop sample
and oil) at simulated downhole conditions to determine fluid compatibilities, verify performance, and to optimize the
treatment design for field application.

Acknowledgements
The authors thank BJ Services for the privilege to publish this paper and for supporting this research work.
References
1) Sandrea, Ivan, and Sandrea, Raphael. Global Oil Reserves-Recovery Factors Leave Vast Target For EOR
Technologies, Oil and Gas Journal, November 2007.
2) Akbar, M., Vissapragada, B., Alghamdi, A.H., Allen, D., Herron, M., Carnegie, A., Dutta, D., Olesen, J-R.,
Chourasiya, R.D., Logan, D., Stief, D., Netherwood, R., Russel, S.D., and Saxena, K. A Snapshot of Carbonate
Reservoir Evaluation, Oilfield Review, 12 (4), 20-21, (Winter 2000/2001).
3) Yongfu, W., Shuler, P. J., Blanco, M., Tang, Y., Goddard III, W.A... An Experimental Study of Wetting Behavior
and Surfactant EOR in Carbonates with Model Compounds, paper SPE 99612 presented at the 2006 SPE/DOE
Symposium on Improved Oil Recovery, Tulsa, 22-26 April 2006.
4) Tabary, Rene, Fomari, Antoine, et al.: Improved Oil Recovery With Chemicals in Carbonate Formations
paper SPE 121668 presented at the 2009 SPE International Symposium on Oilfield Chemistry , Woodlands, Texas
20-22 April 2009.
5) Weiss, W.W. and Xie, X. : Oilfield Surfactants Improve Recovery by Imbibition, paper SPE 106402 presented at
2007 SPE International Symposium on Oilfield Chemistry , Houston, Texas, 28 February-2 March, 2007.
6) Adibhatia,B. and Mohanty, K.K.: Oil Recovery From Fractured Carbonates by Surfactant-Aided Gravity Drainage:
Laboratory Experiments and Mechanistic Simulations, paper SPE 99773 presented at 2006 SPE/DOE Symposium
on Improved Oil Recovery, Tulsa, Oklahoma, 22-26 April 2006.
7) Schembre, J. M., Akin, S., Castanier, L. M., Kovscek, A. R.:Spontaneous Water Imbibition into Diatomite, paper
SPE 46211 presented at 1998 Western Regional Meeting, Bakersfield, California, 10-13 May 1998.

SPE 124215

8) Barenblatt, et. al: Oil Deposits in Diatomites: A New Challenge for Subterranean Mechanics, paper SPE 75230
presented at SPE/DOE Thirteenth Symposium on Improved Oil Recovery, Tulsa, Oklahoma, 13-17 April 2002.
9) Ikeda, M., Tang, G.Q., Ross, C.M., Kovscek, A.R.:Oil Recovery and Fracture Reconsolidation of Diatomaceous
Reservoir Rock by Water Imbibition at Elevated Temperature, paper SPE 110515 presented at 2007 SPE Annual
Technical Conference and Exhibition, Anaheim, California, U.S.A., 1114 November 2007.
10) Wendel,D.J. et.al.: Waterflood Potential of Diatomite: New Laboratory Methods, paper SPE 17439 presented at
SPE California Regional Meeting, Long Beach, California, 23-25 March, 1988.

Figure 1 Example of a naturally fractured carbonate outcrop

Figure 2 Illustration of an Amott cell apparatus used in the imbibition testing

SPE 124215

TABLE 1 - CRUDE OIL CHARACTERISTICS


Description
Oil #1
Oil #2
Oil #3
Oil #4

APIo
30.3
31.5
32
15

Source
West Texas
West Texas
California (light oil)
California (heavy oil)

S.G. @ 72 oF
0.874
0.873
0.820
0.990

TABLE 2 - CARBONATE IMBIBITION TESTS for VARIOUS SURFACTANTS in BRINE


% Oil Recovery of Original Oil in Place (OOIP)
Fluid Description
3 hrs
24 Hrs.
48 Hrs.
72 Hrs.
144 Hrs.
Base Fluid
0.0
2.3
4.5
7.9
15.8
Base Fluid + 0.5 % Surfactant A
3.6
40.9
42.4
43.1
48.4
Base Fluid + 1.0 % Surfactant A
2.6
43.0
46.0
46.8
49.9
Base Fluid + 3.0 % Surfactant A
3.0
48.1
51.2
51.6
51.9
Base Fluid + 1.0 % Surfactant B
3.7
8.0
21.8
31.0
35.6
Base Fluid + 3.0 % Surfactant B
4.6
13.7
28.5
33.1
44.5
Carbonate Cores - Air permeabilities ranged from 20 - 25 md and porosities from 10-15%
Oil Used - Oil #1

60

50

Oil Recovery, % of OOIP

40

30

20

10

0
0

20

40

60

80

100

120

140

160

Incubation Period, hrs

Figure 3 Oil recovery results of imbibition test on carbonate cores with Surfactants A & B in brine.

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TABLE 3 - OIL / SURFACTANT SOLUTIONS EMULSION COMPATIBILITY RESULTS


(50:50 RATIO)
% Fluid Separation after various times at 150F
15 min
30 min
60 min
180 min
Treatment Fluids
2% KCl brine
0
0
NA
NA
Base Fluid*
98
100
100
100
Base Fluid + 1% Surfactant A
95
100
100
100
Base Fluid + 3% Surfactant A
NA
20
40
70
Base Fluid + 1% Surfactant B
90
100
100
100
Base Fluid + 3% Surfactant B
NA
30
60
80
* Base Fluid - Consists of 2% KCl brine + 0.2% non-ionic non-emulsifier

TABLE 4 - CARBONATE IMBIBITION TESTS for SURFACTANT A in NON-ACID STIMULATION FLUID


% Oil Recovery of Original Oil in Place (OOIP)
Fluid Description
24 hrs
72 hrs
144 hrs
164 hrs
188 hrs
212 hrs
Non-Acid Stimulation Fluid (NAF)
3.4
9.1
17.2
17.2
19.4
20.6
NAF + 0.25 % Surfactant A
13.1
24.7
37.1
40.9
44.8
47.1
NAF + 0.50 % Surfactant A
11.7
21.1
31.3
36.8
38.4
40.0
Modified NAF + 0.25 % Surfactant A
25.6
49.7
66.1
72.3
76.9
79.5
Modified NAF + 0.50 % Surfactant A
8.1
14.0
19.9
23.4
24.5
25.7
NAF Formulation - KCl brine + Chelating Agent + Solvent + Cleaning Surfactants
Carbonate Cores - Air permeabilities ranged from 20 - 25 md and porosities from 10-15%
Oil Used - Oil #1

90

80

70

Oil Recovery, % of OOIP

60

50

40

30

20

10

0
0

50

100

150

200

250

Incubation Period, hrs

Figure 4 Oil recovery results of imbibition test on carbonate cores with Surfactant A in a Non-Acid Stimulation
fluid system.

10

SPE 124215

TABLE 5 - CARBONATE IMBIBITION TESTS for SURFACTANT A in DILUTE ACID STIMULATION FLUID
% Oil Recovery of Original Oil in Place (OOIP)
Fluid Description
24 hrs
48 hrs
72 hrs
168 hrs
192 hrs
216 hrs
0.5% Acetic Acid Base Fluid
2.3
3.9
4.6
4.6
4.6
5.4
0.5% Acetic Acid + 0.5 % Surfactant A
40.3
46.3
48.0
50.6
51.4
53.3
Carbonate Cores - Air permeabilities ranged from 20 - 25 md and porosities from 10-15%
Oil Used - Oil #1

60

50

Oil Recovery, % of OOIP

40

30

20

10

0
0

50

100

150

200

250

Incubation Period, hrs

Figure 5 Oil recovery results of imbibition test on carbonate cores with and without Surfactant A in a dilute 0.5%
acetic acid stimulation fluid system.
2

Normalized Permeability to Oil, Ko intial/Ko after

1.8
Treatment:
2 PV 10% Acetic Acid
No Shut-In Period

85% Effective Permability Increase

1.6

38% Effective Permability Increase


1.4

1.2

1
Test Temperature = 150 deg F
Core = Indiana Limestone
Porosity = 14.7%
0.8
20

40

60

80

100

120

140

160

180

200

Pore Volumes

Figure 6 Core flow test results of limestone cores with 10% acetic acid with and without EOR Surfactant A (no shutin period after acid injection)

SPE 124215

11

100000
Treatment:
2 PV 10% Acetic Acid
Shut-In Period for 20 hrs

Normalized Permeability to Oil, Ko intial/Ko after

10000
18284% Effective Permability
increase due to wormhole
f
ti
1000
3186% Effective Permability Increase
due to wormhole formation

100

10
Test Temperature = 150 deg F
Core = Indiana Limestone
Porosity = 13.8 - 14.6%
1
0

50

100

150

200

250

0.1
Pore Volumes

Figure 7 Core flow test results of limestone cores with 10% acetic acid with and without EOR Surfactant A (shut in
period for 20 hrs following acid injection)

TABLE 6 - DIATOMITE IMBIBITION TESTS for SURFACTANT C in BRINE


% Oil Recovery of Original Oil in Place (OOIP)
Fluid Description
24hrs
48 hrs
72 hrs
96 hrs
168 hrs
2% KCl Base Fluid
14.6
21.9
31.3
36.5
43.8
2% KCl + 0.2% Non-Emulsifier
24.6
31.6
34.1
37.2
42.3
Base Fluid + 0.5 % Surfactant C
35.5
48.7
49.6
51.0
88.5
Base Fluid + 1.0 % Surfactant C
38.7
51.9
55.4
57.4
61.0
Oil Used - Oil #3 (thin oil)

100

90

80

Oil Recovery, % of OOIP

70

60

50

40

30

20

10

0
0

20

40

60

80

100

120

140

160

180

Incubation Period, hrs

Figure 8 Oil recovery (light oil) results of imbibition test on diatomite cores with Surfactant C in brine.

12

SPE 124215

TABLE 7 - DIATOMITE IMBIBITION TESTS for SURFACTANT C in BRINE @ 125 deg F


% Oil Recovery of Original Oil in Place (OOIP)
Fluid Description
24hrs
96 hrs
120 hrs
144 hrs
168 hrs
Base Fluid
12.7
12.7
12.6
12.6
12.6
Base Fluid + 0.25 % Surfactant C
18.8
23.5
23.5
23.5
28.3
Base Fluid + 0.5 % Surfactant C
37.4
37.4
40.2
43.1
43.1
Base Fluid - 2% KCl containing nonionic non-emulsifier
Oil Used - Oil #4 (thick oil)

50

45

40

Oil Recovery, % of OOIP

35

30

25

20

15

10

0
0

20

40

60

80

100

120

140

160

180

Incubation Period, hrs

Figure 9 Oil recovery (heavy oil) results of imbibition test on diatomite cores with Surfactant C in brine.

SPE 124215

13

App. Viscosity @ 100 s-1

1000

100

Frac Fluid Baseline


Frac Fluid 5.0 gpt Surfactant C
Frac Fluid 1.0 gpt Enzyme, 0.5 ppt GBW
Frac Fluid 1.0 gpt Enzyme, 0.5 ppt GBW, 5.0 gpt Surfactant C
Frac Fluid 1.0 gpt Enzyme, 1.5 ppt GBW, 5.0 gpt Surfactant C

10
0

10

20

30

40

50

60

70

80

Time, min

Figure 10 Hydraulic fracturing fluid design for diatomite formations

Figure 11 SEM photomicrograph of diatomite formation.

90

100