SPE 59290 Enhancement of Oil Recovery Using a Low Concentration of Surfactant to Improve Spontaneous and Forced Imbibition in Chalk

E. A. Spinler, D. R. Zornes, D. P. Tobola, A. Moradi-Araghi/Phillips Petroleum Co.

Copyright 2000, Society of Petroleum Engineers Inc. This paper was prepared for presentation at the 2000 SPE/DOE Improved Oil Recovery Symposium held in Tulsa, Oklahoma, 35 April 2000. 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, as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material, as presented, does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Papers presented at SPE meetings are subject to publication review by Editorial Committees of the Society of Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper for commercial purposes 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 where and by whom the paper was presented. Write Librarian, SPE, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.

Abstract A study was undertaken with the objective of evaluating the use of low concentrations of surfactant to improve oil recovery. Various concentrations of commercial surfactants were screened for long term stability at high temperature in seawater. Cloud points, precipitation, and the stability of surface tension were used as screening criteria. Spontaneous imbibition tests at ambient and reservoir temperatures were conducted using reservoir chalk plugs that were moderately water-wet. A selected surfactant, when added at low concentrations (100 to 500 parts per million of active surfactant) to the imbibition water reduced the residual oil saturation over imbibition tests conducted without surfactant. Acceleration of spontaneous imbibition was observed in tests that had improved oil recovery. Forced imbibition tests for viscous displacement were conducted by flow tests. Although low concentrations of surfactant did not lower oil-water interfacial tension below single digits, a reduction in residual oil saturation was obtained in the forced imbibition tests over tests without surfactant. Measurement of surfactant adsorption indicated that low adsorption at reservoir conditions could be obtained below the critical micelle concentration (CMC) of some surfactants. The combination of improved recovery with low adsorption suggests that the addition of surfactant to injected water may improve the economics of surfactantenhanced waterflooding under appropriate conditions. Introduction Surfactants have long been considered for improving oil recovery from oil reservoirs. Although many pilot tests and a few field tests have been conducted, the economics of

surfactant injection have rarely been favorable. Most surfactant studies focused on the injection of a high concentration of surfactant to create ultralow interfacial tension between oil and water via microemulsions followed by a slug of polymer designed to mobilize the surfactant bank and oil. The front end cost of such a process was only favorable if residual oil saturations could be reduced to near zero, surfactant adsorption was not excessive, the sweep efficiency was excellent and oil prices were high. In contrast, consideration herein was given to improving the economics by a process that used only a dilute amount of surfactant to minimize adsorption and to recover only a portion of the residual oil. Published field tests1,2 show that it is possible to have an economic surfactant process at low surfactant concentrations. Others have examined in the laboratory, the possibility of dilute surfactant flooding for improving oil recovery3,4,5. This paper will focus on improvements observed in the displacement of oil in the laboratory and the approach to minimize surfactant losses. Description and Application of Equipment and Processes Preparation of Materials. Kansas outcrop chalk and field reservoir chalk were used in this study. Field reservoir plugs were extracted by alternation of toluene and methanol soaks until no hydrocarbon discoloration was observed (1-2 months). All plugs were one inch in diameter and up to 3.5 inches in length. The wettability of the Kansas outcrop plugs was altered by aging under field crude oil at initial water saturation using established methods6 and then extracted like the field reservoir plugs. Spontaneous imbibition tests were used to establish a baseline measurement and to select moderately waterwet plugs for further testing. The field stock-tank crude oil was centrifuged to remove paraffins that were solid at near-ambient temperatures. Ndecane of 99+% purity was used and filtered through a silica gel column before use. The brines were equilibrated with chalk material and filtered before use. Other fluids were used as purchased. Surfactants were commercially available products. They were diluted with synthetic North Sea water to desired concentrations before use.

E. A. SPINLER, D. R. ZORNES, D. P. TOBOLA, A. MORADI-ARAGHI

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Thermal Screening. Forty-six surfactants, comprising the major surfactant classes, were screened for long-term thermal stability at 149 C, which was more severe than the average reservoir temperature of 131 C. Surfactants were used as received and diluted to concentrations of 50 to 3000 parts per million (ppm) active surfactant. Sealed glass ampules of surfactant solution were aged at temperature for periods ranging from 1 day to 16 months. Cloud points, the onset of precipitation, and surface tension measurements were used to evaluate stability. Cloud points were measured with a turbidometer specially designed for high temperature measurements7. Surface tensions were obtained using the maximum differential bubble pressure method. Selected surfactants were evaluated by further testing. The Wilhelmy plate technique was used to evaluate the interaction of the surfactant on water-wet and oil-wet surfaces. The effect of surfactant on interfacial tension between brine and oil at ambient temperature and pressure was measured by pendant drop and by a modified drop-weight method and at elevated temperatures by captive drop measurements. Imbibition Tests. Baseline tests were conducted on the benchtop using n-decane desaturated (by centrifuge) plugs at initial water saturation. Deionized water was allowed to spontaneously imbibe into all faces of the plug for 1-2 weeks and produced volumes of n-decane were measured. This established the wettability behavior and the spontaneous imbibition end-point for a plug. The plug was then dried in preparation for further testing. Benchtop screening of surfactants was carried out in plugs resaturated to initial water saturation with North Sea water and n-decane. An imbibition test was conducted like the baseline test, but with surfactant in the North Sea water. Forced imbibition with surfactant in the seawater on selected plugs followed the spontaneous imbibition test. Most plugs were Dean-Stark extracted for confirmation of water saturation. Measurements of the complete imbibition capillary pressure curve were made with the Direct Measurement of Saturation method8. Octadecane and deionized water were used for the fluids. A centrifuge was used to establish a saturation profile in a chalk plug and this profile was measured by magnetic resonance imaging. Reservoir temperature tests were conducted using stocktank crude oil and North Sea water. A group of plugs as a set was desaturated to initial water saturation. All the plugs in the set were to be handled identically. One plug of the set was designated as a control plug. The control plug was used to monitor for thermal effects, artifacts from the handling procedure or wettability changes caused by the crude oil. A centrifuge was used to establish initial water saturation and then the plugs were quickly placed in pressured imbibition cells containing surfactant in North Sea water and raised to reservoir temperature. No imbibition was observed until after the cells had reached temperature. Following 2 weeks of spontaneous imbibition, the produced oil volumes were noted and the plugs extracted by the Dean-Stark method for water saturation. Thermal corrections were made.

Mechanistic Flow Tests. Oil displacement tests were performed on whole diameter (2-5/8 inch) core material of 4 to 6 inches in length. The samples were cleaned by alternating toluene and methanol in a Soxhlet extractor for 2 weeks followed by flowing alternate slugs at 49 C for 6 to 8 weeks. All experiments were conducted in a Hassler cell at 124 C with a confining pressure of 1000 psig and a maximum differential pressure of 0.5 psig. Fluids used in the test were ndecane and North Sea water with or without surfactant. Initial water saturation was established by flowing n-decane to displace North Sea water. Adsorption Tests. These tests were conducted using Kansas outcrop and reservoir plugs either at 100% water saturation or at residual oil saturation (prepared by centrifuge). Comparisons between the use of reservoir chalk core plugs or Kansas outcrop chalk plugs showed no significant difference in adsorption. The plugs were confined in a Hassler cell under 500-1000 psig pressure. Tests were conducted at ambient to reservoir temperatures. Surfactant in North Sea water was injected into the plugs at concentrations of either 300 or 2000 ppm active. The injection rate was six milliliters per hour, which corresponded to a reservoir rate of 3 feet per day (91 cm per day). Surfactant input and effluent concentrations were measured by differential refractometer. Effluent samples were collected and the surfactant effluent concentration was determined by Total Organic Carbon analysis as a check on the refractometer readings. Adsorption isotherms were developed from matching the surfactant effluent profiles with a one-dimensional convectivedispersive single-phase miscible displacement model9,10. The CMC of surfactants in North Sea water was obtained at ambient conditions by measurement of interfacial tension or by Wilhelmy Plate measurement at various surfactant concentrations and at elevated temperatures by dynamic foam height measurement11. The surface area of the chalk was based on an average of nitrogen adsorption measurements. The molecular adsorption area of the surfactants at surface saturation was based on the Gibbs slope from surface tension measurements as a function of surfactant concentration. Presentation of Data and Results The evaluation window for this laboratory study was approximately three years. To expedite the process, a number of measures were taken. 1. Preliminary economics were run to define the variables to be measured in the laboratory that were important to further economic evaluation. 2. Only commercially available surfactants were evaluated. 3. Surfactant screening tests were performed as much as possible in parallel. Three key variables that affect the economics were incremental oil recovery, surfactant loss, and surfactant injection cost. The appropriate use of these variables also assumed that a mechanistically correct model of surfactant propagation would be available for scaling laboratory oil recoveries and surfactant losses to the reservoir scale. The

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specific reservoir for which these studies were conducted is a highly fractured chalk believed to have zones that range from moderate to highly water-wet. Commercial availability of a surfactant was a prime criterion for surfactant selection because surfactant costs could be determined up-front and used in the screening process. Thermal tests were used to identify surfactants that were stable for long periods under adverse salinity and temperature conditions. Imbibition and flow tests were employed to recognize which surfactants enhanced oil production. Adsorption tests were needed to determine surfactant losses. The combination of laboratory results along with surfactant cost enabled a selection of a preferred surfactant with desirable characteristics. This paper focuses solely on the experimental results for this particular surfactant. This surfactant was an ammonium salt of ethoxylated and sulfated alcohols (C8-C10 alkyl ethers). It was designated as surfactant A for identification in this paper. Thermal Stability Tests. Surfactant A was tested at two concentrations, 300 and 3000 ppm active (Table 1). At the active concentration of 300 ppm, a white precipitate was observed after 4 months of aging at 149 C. However, during the thermal stability tests, a precipitate was also observed in ampules containing only seawater. This precipitation was believed to be an interaction between seawater and the glass walls of the ampules that can occur over extended time at high temperatures. It was not determined if the observed precipitate was due solely to the glass-seawater interaction. At the higher concentration of 3000 ppm active, the onset of a cloud point was observed for surfactant A after 1 week of aging at 149 C. This was not observed at the lower concentration. A cloud point could indicate surfactant degradation. Surface tension was used as measure of the surfactant activity. The measurement required an ampule to be opened. Thus, several ampules were prepared for each surfactant concentration to allow for this test during the thermal aging process. An initial measurement of each surfactant concentration was made before tests began. Subsequent measurements of the contents of the ampules were made at room temperature. The surface tension of 36.1 milliNewtons/meter (mN/m) for the 300 ppm active concentration of surfactant A remained unchanged after thermal aging for 4 months. Surface tension was not measured for the higher concentration of surfactant after thermal aging. The onset of precipitation, the formation of cloud point, and the increase in surface tension are measures of surfactant instability. In this case, surfactant A was considered stable for extended periods at high temperature if used at low concentrations, the area of interest in this study. Spontaneous Imbibition Tests. Tests were conducted with reservoir core plugs ranging from 19 to 36 % porosity. The results of the tests are tabulated in Table 2. An initial Amott water index or Spontaneous Imbibition Index12 for wettability was measured before contact with surfactant. The additional pore volume (PV) recovery is the PV percentage increase in

the final water saturation with surfactant following imbibition compared to the baseline final water saturation without surfactant. Spontaneous imbibition tests 12 and 13 were conducted at reservoir temperature using field crude oil. Tests 16 and 17 were obtained from capillary pressure measurements at 35 C. All of the other results were spontaneous imbibition tests conducted with n-decane at ambient conditions. A contour map of all tabulated data (Figure 1) by a least squares fit, helped to sort out many of the variations in recovery of the tabulated data. All of the data was included because the number of tests was limited and the goal was to define recovery behavior that was global in nature. The contour map indicated that better oil recovery occurred for less water-wet chalk cores. Greater improvements in oil recovery from spontaneous imbibition should be expected to correlate with less water-wet chalk if the wettability was altered to a more water-wet state. The greatest improvement in oil recovery occurred near or above the 100 ppm active surfactant concentration as indicated by the maxima in the contour data. This improvement in recovery took place well below the CMC of surfactant A (see Table 3). At these concentrations, only partial coverage of the chalk surface by surfactant probably occurred13, but it may be enough to alter the less water-wet pore surfaces to water-wet. When oil production versus time data was collected, spontaneous imbibition tests with surfactant showed an apparent increase in the oil production rate over baseline tests without surfactant. Test 14 of Figure 2 shows one example of such a test for 300 ppm active surfactant. An IFT reduction from 52 to 8.8 mN/m (Table 4) normally would be expected to result in a decrease in the oil production rate from a reduction in the IFT contribution to capillary forces. Others14 have shown that under appropriate circumstances, the imbibition rate can increase. In this case, the observed increase in rate possibly resulted from wettability alteration of some of the pore surfaces to a more water-wet state by the surfactant. If the impact from wettability alteration was greater than that from the IFT reduction, a higher production rate could result. The results for spontaneous imbibition test 17 came from a comparison of capillary pressure measurements of the imbibition curves for highly water-wet chalk with and without 300 ppm active surfactant (Figure 3). A reduction in residual oil and the reduction in the breakover pressure (point at which the imbibition curve begins to go vertical) is evident from the plot. The relatively close match in the capillary pressure curves at higher pressures is surprising, suggesting that reductions expected from the change in interfacial tension were offset by changes in wettability. Forced Imbibition Tests. The forced imbibition test results are tabulated in Table 5. All of these test results are based on flow experiments in chalk plugs. The concentration of surfactant in seawater was kept below the CMC, which varied with temperature (Table 3). Tests 18 and 19 were conducted at reservoir temperature and tests 20-22 were conducted at ambient temperature. For tests 18, and 20-22, both the brine

E. A. SPINLER, D. R. ZORNES, D. P. TOBOLA, A. MORADI-ARAGHI

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flood and the surfactant flood were conducted from initial water saturation. Test 19 was a waterflood to residual oil followed immediately by a surfactant flood starting from residual oil saturation. These tests indicated that increasing oil recovery would occur with increasing surfactant concentration (Figure 4) for viscous displacement even starting late in a waterflood. This is consistent with a change in the capillary number as increasing concentrations of surfactant further lower the IFT (Table 4). Adsorption Tests. Laboratory tests were conducted to measure the chalk matrix adsorption/retention of surfactant A under dynamic conditions. Dynamic tests have been shown to be an effective means to obtain adsorption numbers quickly9. Tests with chalk plugs at and above ambient temperature were conducted by injecting 2000 ppm active solution of surfactant A and additional tests at ambient conditions were conducted by injecting 300 ppm active. The 2000 ppm active solution was to provide data for adsorption isotherms over an extended concentration range. The 300 ppm active solution provided detailed data near the surfactant concentration range of most interest (low concentrations) and eliminated an experimental artifact. Near ambient temperatures, there was evidence that an artifact occurred for high surfactant concentrations. A gel film was noted on the inlet face of chalk plugs for some tests. This resulted in an apparent high adsorption. However, tests conducted at 300 ppm active showed no indication of gel film formation. Results for an injected 2000 ppm surfactant slug profile into a 100% brine saturated reservoir chalk core plug and the resultant effluent profile at reservoir temperature are shown in Figure 5. Maximum adsorption of surfactant A was obtained after 7 to 8 injected pore volumes. This is evident in the curve showing the difference between injected and effluent concentrations. In contrast, for 300 ppm injected surfactant profile (into a 100% brine saturated Kansas chalk plug) and the resultant effluent profile at ambient temperature (Figure 6) showed that after 8 pore volumes, adsorption was continuing, but decreasing. Both the reservoir temperature test and the ambient temperature test were conducted below the CMC of the surfactant (see Table 3) because the CMC varied with temperature. The apparently different adsorption behavior could be explained treating adsorption as having both a fast and slow component, that are dependent upon time and surfactant concentration. Similar nonequilibrium behavior has been reported by Austad, et al.15 for sandstone, who proposed that slow adsorption in porous rock was attributed to a longtime, diffusion-controlled adsorption of surfactant monomers into the micropores of clays. For the particular Kansas outcrop chalk used in these tests, the clay content typically measured as 2.5 weight percent. The fast component to adsorption would be expected to take place at readily accessible pore and clay mineral surfaces. For injection at 2000 ppm, the concentration of surfactant appeared sufficient to satisfy even the slow adsorption component in the chalk within the time frame of

the test. Higher temperatures also probably increased the rate of adsorption. At the lower 300 ppm concentration, the slow component would be expected, as measured, to require additional time or pore volumes of throughput to reach adsorption equilibrium. One advantage to the tests run at the lower concentration tests and at ambient temperatures was that these conditions would be more similar to proposed injection concentrations and cooler temperatures found near field water injection wells16. The resulting adsorption isotherms are inclusive of both the fast and slow adsorption components from modeling the effluent profiles for reservoir, intermediate and ambient temperature tests (Figure 7). Adsorption at the CMC concentration and above varies because the CMC changed with temperature (Table 3). Below the CMC of the lower temperature test, the adsorption isotherms show little difference. Tests at other intermediate temperatures, not reported herein, had similar behavior. The presence of residual oil during an adsorption test appeared to slightly reduce the adsorption of surfactant A. The lack of additional surfactant adsorption in the presence of oil has also been observed by Mannhardt17. One possible explanation is that the loss of surfactant to the oil/brine interface was less than the loss to the chalk pore surfaces and the oil may be partially shielding the chalk pore surfaces from surfactant. Discussion Field Application. Important to the possible implementation of a surfactant flood in the field is the understanding of how the measurements made in the laboratory may realize oil recovery in the field. Ultimately, a numerical model would be necessary to integrate all of the laboratory and field data. However, some things can be inferred directly from the laboratory data. Additional oil recovery in the laboratory was obtained for both spontaneous and forced imbibition at low concentrations of surfactant A. This appeared to be due to wettability alteration and/or to an increase in the capillary number from IFT reduction. In a highly fractured reservoir for which this process was originally designed, there are apt to be zones that are capillary dominated and other zones that recover oil viscously. Ideally, it would be expected that the reservoir near the injection wells would see benefit from viscous displacement with higher pressure gradients and higher concentrations of surfactant. Areas further away would realize improved spontaneous imbibition from lesser surfactant concentrations as the surfactant is depleted by adsorption, etc. Consequently, benefits from both wettability alteration and capillary number improvement are possibly realized by the use of lower concentrations of surfactant. Injection of water over long periods of time can cause significant temperature variations in a reservoir. As seawater is injected, cooling occurs near the injection well and a thermal front moves through the reservoir. Table 6 tabulates the IFT change that occurs with temperature change for

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ENHANCEMENT OF OIL RECOVERY USING A LOW CONCENTRATION OF SURFACTANT TO IMPROVE SPONTANEOUS AND FORCED IMBIBITION IN CHALK

surfactant A. As the temperature increases, the IFT increases. Lower IFTs for the cooler zones would benefit viscous displacement near an injection well. Far from the injection well, where spontaneous imbibition may dominate displacement, the increase in IFT from hotter temperatures does not appear to have a negative effect. This was evident from recovery for reservoir temperature tests with crude oil, tests 12 and 13, of Table 2. The propagation of surfactant through a reservoir is limited by its retention. Adsorption of surfactant on reservoir surfaces is normally the major reason for surfactant retention. Some loss also does occur at oil-water interfaces. However, minimization of adsorption must be a primary consideration in surfactant selection. Surfactant A has low adsorption characteristics because as an anionic surfactant it does not adsorb on the negatively charged surfaces of chalk minerals. Most adsorption for surfactant A would be expected to occur on positively charged clay particulate edges and on hydrophobic films coating pore surfaces. The maximum adsorption occurs for the CMC and higher concentrations. Adsorption levels decrease rapidly below the CMC. Adsorption for different concentrations of surfactant A (as determined from the isotherms) are listed in Table 7. These adsorption levels are particularly low because generally, the concentrations are well below the CMC of surfactant A. Economic Considerations. The third key variable affecting the economics of enhancing oil recovery using a low concentration of surfactant is the cost of injecting surfactant. This cost includes facilities, operating expenses and surfactant expense. Low to high concentrations of surfactant A (up to 100,000 ppm) was observed to readily dissolve in cold seawater (2 C) with minimal mixing indicating that facilities and operating expenses may be reasonable. Currently, for surfactant A, the price for large quantities was under $1.50 per pound active surfactant. At 300 ppm active, this translates to an injection cost of about $0.16 per barrel of seawater. Although this may not seem like much cost, it must be compared to the incremental recovery of oil to evaluate the economic feasibility. One potential application is the longterm injection of low concentrations of surfactant. In the application herein, the mobility of oil and water with surfactant was approximately one, indicating no major additional chemical expense associated with mobility control was needed. Ultimately, the economics of this process must compete with other enhanced oil recovery methods. Those considerations were beyond the scope of this paper.

Conclusions 1. Oil recovery can be improved with low concentrations of surfactant for both spontaneous and forced imbibition of water. 2. Surfactant adsorption can be reduced to very low levels if the surfactant concentration is kept below the CMC. 3. The combination of significant additional oil recovery with very low surfactant adsorption should improve the economics of waterflooding. Acknowledgments The author acknowledges permission to publish the above paper from Phillips Petroleum Company Norway and Coventurers, including Fina Exploration Norway S.C.A., Norsk Agip A/S, Elf Petroleum Norge AS, Norsk Hydro Produksjon a.s, TOTAL Norge A.S and Den norske stats oljeselskap a.s. All opinions expressed herein are solely those of the authors. Nomenclature CMC Critical micelle concentration IFT Interfacial tension PV Pore volume References
1. Inks, C. G., et al.: Controlled Evaluation of a Surfactant in Secondary Recovery, paper SPE 2110, 1968. 2. Downs, H. H., et al.: Enhanced Oil Recovery by Wettability Alteration, Oil-Field Chemistry Enhanced Recovery and Production Stimulation, American Chemical Society, Washington , DC (1989) 577-595. 3. Michels, A. M., et al..: Enhanced Water Flooding Design Using Dilute Surfactant Concentrations for North Sea Conditions, paper SPE/DOE 35372 presented at the 1996 Symposium on Improved Oil Recovery, Tulsa, April 21-24. 4. Bondor, P. L.: Dilute surfactant flooding for North Sea application: technical and economic considerations, presented at the 6th Europe Impr. Oil Recovery Symp.m Stavanger, Norway, 1991. 5. Fjelde, I., et al.: Efficiency of Surfactants, A Norwegian Research Program on Improved Oil Recovery Program Summary, Norwegian Petroleum Directorate, Stavanger (1996) 375-386. 6. Jia, D., et al.: Control of Core Wettability with Crude Oil. paper SPE 21041 presented at SPE International Symposium on Oilfield Chemistry, Anaheim, Califormia, Febr. 20-22, 1991. 7. Moradi-Araghi, A., et al.: Pressurized apparatus for measuring the cloud points of polymer solutions, Rev. Sci. Instrum. (Sept. 1986) 57 (9). 8. Spinler, E. A. and Baldwin, B. A., Capillary Pressure Scanning Curves by Direct Measurement of Saturation, paper SCA 9705 presented at the 1997 International Symposium of the SCA, Calgary, Canada, Sept. 7-10. 9. Mannhardt, K. and Norosad, J. J.: Modeling Adsorption of Foam-foaming Surfactants, presented at the 4th European Sumposium on Enhanced Oil Recovery, Hamberg, Germany, Oct 27-29, 1987.

E. A. SPINLER, D. R. ZORNES, D. P. TOBOLA, A. MORADI-ARAGHI

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10. Mannhardt, K. and Norosad, J. J.: Chromatographic Movement of Surfactant Mixtures in Porous Media, Chemical Engineering Science, Vol 46, No 1, (1991) 75-83. 11. Morrison, C., et al.: A dynamic foam method for the estimation of critical micelle concentrations at elevated temperatures and pressures, JPS&E (1996) 15. 12. Spinler, E. A.: Determination of In-Situ Wettability from Laboratory and Well Log Measurements for Carbonate Field, paper SPE 38733 presented at the 1997 SPE Annual Technical Conference and Exhibition, San Antinio, Texas, Oct. 5-8. 13. Somasundaran, P. and Fuerstenau, D. W.: J. Phys. Chem. (1966) 90. 14. Al-Lawati, S. and Saleh, S. T.: paper SPE 36688 presented at the 1996 Annual Technical Conference and Exhibition, Denver, Colorado, Oct. 1996. 15. Austad, T., et al.: Adsorption II. Nonequilibrium adsorption of surfactants onto three reservoir cores from the Norwegian Continental Shelf. The effects of clay minerals, J. Petro. Sci and Engr. (1991) 125-135 (6). 16. Van DeVerg, P.E., et al.: Water Saturation in Breakthrough Intervals, Ekofisk Field, Norway paper LL presented at the SPWLA 40th Annual Logging Symposium SPWLA, Oslo, Norway, May, 1999. 17. Mannhardt, K. and Novosad, J. J.: The Effects of Wettability and Residual Oil on Adsorption of FoamFoaming Surfactants, In Situ (1994) 18 (2).

TABLE 3 CRITICAL MICELLE CONCENTRATION (CMC) CMC Active Temperature Concentration (ppm) ( Celsius) 381 23 5569 131 TABLE 4 INTERFACIAL TENSION BEHAVIOR FOR N-DECANE @ 20 C. Active Surfactant Interfacial Tension Concentration (ppm) (mN/m) 0 50 100 300 500 1000 52 21 17 8.8 5.5 4.3

TABLE 1 SURFACTANT THERMAL SCREENING Concentration. (ppm) 3000 300 Stable @ 149 C for 4 months No Yes Surface Tension (mN/m) -36

TABLE 5 FORCED IMBIBITION TEST RESULTS Additional PV Oil Test Active Recovery Concentration (%) (ppm) 18 8 300 19 5 300 20 2 50 21 3 100 22 5 300 TABLE 6 INTERFACIAL TENSION BEHAVIOR FOR CRUDE OIL WITH TEMPERATURE Temperature ( Celsius) North Sea water with no surfactant (mN/m) 27 24 27 29 North Sea water + 300 ppm surfactant (mN/m) 6 6 16 23

TABLE 2 SPONTANEOUS IMBIBITION TEST RESULTS Initial Additional PV Test Active Oil Recovery Concentration Wettability (%) (ppm) 1 13 0.4 50 2 24 0.4 100 3 12 0.4 300 4 19 0.7 300 5 -3 0.9 50 6 6 0.9 100 7 -1 0.9 300 8 -6 0.9 50 9 7 0.9 100 10 3 0.9 300 11 5 0.5 500 12 14 0.6 300 13 11 0.3 300 14 6 0.6 300 15 2 0.6 300 16 7 1.0 300 17 7 1.0 300

25 80 131 180

TABLE 7 ADSORPTION OF SURFACTANT A WITH CONCENTRATION Active Concen. (ppm) 50 100 300 20.3 C 0.016 0.030 0.078 Adsorption (mg/g) at 73.9 C 128.3 C 0.006 0.007 0.011 0.015 0.033 0.044

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1.0 0.9 0.8 W e tta b ility 0.7 0.6 0.5 0.4 0.3 0 100 200 300 400

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Figure 1 A contour map with the contours representing the PV increase in oil recovery from spontaneous imbibition with surfactant concentration and wettability.

Figure 2 Spontaneous imbibition history for Test 14 of Table 1 showing the imbibition rate differences with and without surfactant.

60 50 40 C ap illary P ressu re (p si) 30 20 10 0 0 -10 -20 -30 0.2 0.4

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Figure 3 Comparison of Pc curves for Test 17 of Table 1 showing a decrease in breakover pressure and an increase in oil recovery from the addition of surfactant.

Figure 4 The viscous oil recovery from flowing displacement tests show improving oil recovery with increasing surfactant concentration.

E. A. SPINLER, D. R. ZORNES, D. P. TOBOLA, A. MORADI-ARAGHI

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1 0.8 0.6 C /C 0 0.4 0.2 0 0 2 4 6 8 10 Po re V olum e

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Figure 5 Injected and effluent surfactant profiles at reservoir temperature show that adsorption was satisfied after about 8 pore volumes of surfatant injection at 2000 ppm.

Figure 6 Injected and effluent surfactant profiles at ambient temperature show that adsorption was not satisfied after about 8 pore volumes of surfactant injection at 300 ppm.

0.6 Su rfactan t A d sorption (m g/g ) 0.5 0.4 0.3 0.2 0.1 0 1

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Figure 7 The adsorption isotherms for surfactant A are very similar at low concentrations, but differ significantly at higher concentrations. The shaded area was an estimation of the isotherm profile above the maximum injected concentration of 2000 ppm.