Society of ‘Petroleum Engineers FUNDAMENTALS OF ENHANCED OIL RECOVERY Presented by Dr. Larry W. Lake © copyright 1986 society of Petroleum Engineers All rights reserved. This book or any part thereof \nust not be reproduced in ary form without the ‘written permission of the Society of Petri i8:30 9:00 9:30 9:45 10:15 11:00 12:00 1S 1:45 215 2:30 3:30 430 Fundamentals of Enhanced Oil Recovery Module 1 - Defining EOR Module 2 - Reviewing Displacement Fundamentals Break t Module 3 - Understanding Phase Behavior Module 4 - Defining Polymer Flooding Module 5 - Exploring Micellar-Polymer Flooding Lunch Micellar-Polymer (cont.) Module 6 - Using Other Chemical Methods Break Module 7 - Analyzing Thermal Flooding Module 8 - Acquiring Solvent Flooding Basics SummaryFirst Revision COURSE OVERVIEW FUNDAMENTALS OF ENHANCED OIL RECOVERY INSTRUCTOR Larry W. Lake Department of Petroleum Engineering The University of Texas at Austin NEED FOR Enhanced of] recovery (EOR) 1s being used more and COURSE more as companies recognize the need for making the best use of existing resources, and as field tests are proving that it is economically feasible to use EOR methods. As the potential for gain through EOR becomes more recognized, petroleum and chemical engineers will be asked to evaluate the economié and production potential of individual wells, and to make recommendations regarding the most ‘appropriate method. This course Is designed to help engineers make these reconmendations. TARGETED Chemical and petroleum engineers with at least a AUDIENCE 8.5., experienced engineers who want to review or to broaden their area of expertise, Individuals who sell chemicals or services, chemists who Understand the chemistry and want to know how it is applied. EXPECTED © Better understanding of why EOR is used OUTCOMES 0 Greater awareness of the major clas: and subdivisions of each EOR method 0 Increased ability to judge which EOR method is appropriate for a given application © Increased knowledge of how each EOR method works and the problems encountered with each CONTENT This course reviews fundamental principles of SCOPE displacement and phase behavior needed to understand EOR methods. It covers the four major types of EOR, specific chemicals In each category, conditions under which they work, and special problems encountered with each. The course is designed as a fundamentals course and, as such, can only give an overview of each method. COURSE Student time required Is approximately 18 hours, LENGTH of which seven will be used to view the presentations, discussions, and debriefing activities on the video tape. Other student time will be spent in reading workbook materials and working fourteen exercises interspersed throughout the course. Intro-2ABOUT THE INSTRUCTOR Larry W. Lake serves on the petroleum engineering faculty at the University of Texas. His earlier work with Shell Development Company led to his current reputation as an expert in chemical Flooding research. He holds a 8.5. degree from Arizona State University and a Ph.D. from Rice University, both in chemical engineering. ‘ACKNOWLEDGEMENTS Fred |. Stalkup, Arco Research, Plano, Texas Gary A. Pope, University of Texas, Austin, Texas R.S. Schechter, University of Texas, Austin, Texas Margaret Zumr, Associates International, Inc., Dallas, Texas Warner Klapprodt, W.K. Productions, Dallas, Texas Mo Kudchacker, Tenneco Oi! Company, Houston, Texas John R. Waggoner, University of Texas, Austin, Texas Myra A. Dria, University of Texas, Austin, Texas Intron3COURSE OUTLINE FUNDAMENTALS OF ENHANCED OIL RECOVERY INTRODUCT | ON PROCESS OVERVIEW... +005 COURSE OVERVIEW, INSTRUCTOR INFORMATION. COURSE OUTLINE. COURSE MAP..... SI CONVERSION CHART AND’! HINTS: MODULE 1...DEFINING EOR MODULE OVERVIEW. OVERVIEW... 2.05 CURRENT STATUS. WHY EOR?.....04 are COMPARATIVE PEFORMANCES. FORECASTS FOR EOR SUMMARY REFERENCES... +--++eeee EXERCISE 1: WHY EOR?.... MODULE 2...REVIEWING DISPLACEMENT FUNDAMENTALS MODULE OVERVIEW...-.---+ FACTORS AFFECTING OIL RECOVERY AREAL SWEEP EFFICIENCY... VERTICAL SWEEP EFFICIENCY DISPLACEMENT SWEEP EFFICIENCY SWEEP EFFICIENCY SUMMARY... TRAPPED OIL SATURATION. REFERENCES... eee EXERCISE 2: CALCULATING CAPILLARY NUMBERS... EXERCISE 3: ANALYZING FACTORS WHICH AFFECT OIL RECOVERY. MODULE 3...UNDERSTANDING PHASE BEHAVIOR MODULE OVERVIEW. . OVERVIEW... Beer PRESSURE-TEMPERATURE DIAGRAMS. PRESSURE-COMPOSITION DIAGRAMS. TERNARY DIAGRAMS. « REPRESENTATIVE SAL. SUMMARY. REFERENCES. Meee EXERCISE 4: SKETCHING A PRESSURE-COMPOSITION DIAGRAM. .. EXERCISE 5: USING A TERNARY DIAGRAM..... Intro=4COURSE OUTLINE FUNDAMENTALS OF ENHANCED OIL RECOVERY MODULE 4...0EFINING POLYMER FLOODING MODULE OVERVIEW... shel USES/TYPES.....++ whe? POLYMER CHEMISTRY. heb POLYMER PROPERTIES. wheB FIELD RESULTS... shel9 FAVORABLE CONDITIONS she 2lt whe whe 27 MODULE 5...EXPLORING MICELLAR-POLYMER FLOODING MODULE OVERVIEW... seeesSel PROCESS DEFINITION. . 5-2 SURFACTANTS...064 5-8 PHASE BEHAVIOR.. +... 5-13 INTERFACIAL TENSION... 5-19 SLUG FORMULATION. ..... 5-23 SURFACTANT RETENTION. 5-25, LAB/FIELD RESULTS. 5-30 SUMMARY... 5-36 REFERENCES... 4. ..04 pee 5-37 EXERCISE 7: ESTIMATING OPTIMAL CONDITIONS... 5-39 EXERCISE 8: DEFINING THE IMPORTANCE OF RETENTION. 5-42 MODULE 6...USING OTHER CHEMICAL METHODS MODULE OVERVIEW. ....206 6-1 FOAM FLOODING. 6-2 FOAM STABILITY. 6-3 CHARACTER! STICS. 265 EFFECTS. ..seeceseeeeee sane 6-6 ALKALINE FLOODING... seen 69 DISPLACEMENT MECHAN! SMS see 6913, ROCK-FLUID INTERACTIONS 6-17 FIELD RESULTS.....-+ 6-21 SUMMARY. « « ooo 6-23 REFERENCES... +. .+00+ eeceeee 6-24 EXERCISE 9: SUMMARIZING ALKALINE AND FOAM FLOODING. 6-27 Intro-5COURSE OUTLINE FUNDAMENTALS OF ENHANCED OIL RECOVERY MODULE 7..-ANALYZING THERMAL FLOODING MODULE OVERVIEW. VISCOSITY REDUCTION. . ENTHALPY OF STEAM. FOUR PROCESS VARIATIONS. OTHER DISPLACEMENT MECHANI SHS. EFFECTS OF LOW STEAM DENSITY HEAT LOSSES.. CALCULATION PROCEDURES. FIELD TESTS SUMMARY. « REFERENCES. EXERCISE 10: ine HOw Viscosity REDUCTION IMPROVES PRODUCTIVITY, EXERCISE 112 CALCULATING HEAT LOSS, wecee eee eeeeeDnhd MODULE 8...ACQUIRING SOLVENT FLOODING BASICS MODULE OVERVIEW. SOLVENT FLOODING FUNDAMENTALS. SOLVENT PROPERTIES...... SOLVENT-CRUDE PHASE BEHAVIOR. SOLVENT DISPLACEMENT CLASSIFICATIONS. ««.+ SOLVENT FLOODING EXPERIEMENTS DISPLACEMENT MECHANISMS. LABORATORY RESPONSE. FIELO RESPONSE...... SUMMARY se eee REFERENCES... EXERCISE 12; USING MINIMUM MiSCIBILITY PRESSURE CORRELATIONS, wee BOIS, EXERCISE 13: MINIMUM MISC GAS DRIVES. ..+seseeereeeees EXERCISE 14: UNDERSTANDING FINGERING... «+ Intro-6COURSE OUTLINE FUNDAMENTALS OF ENHANCED OIL RECOVERY SUMMARY SOLUTION SOLUTION SOLUTION SOLUTION SOLUTION SOLUTION SOLUTION SOLUTION SOLUTION SOLUTION SOLUTION SOLUTION ‘SOLUTION SOLUTION SCREENING GUIDES.....+4.4 GENERAL REFERENCES. Intro-7 EXERCISE EXERC! SE EXERC! SE EXERC! SE EXERCISE EXERCISE EXERCISE EXERCISE 8, EXERCISE EXERCISE EXERCISE EXERCISE EXERCISE EXERCISE + Sum=2u ++ Sum=25 + Sum=28COURSE MAP ACTIVITIES IN EACH MODULE MODULE 1 ‘tape (40) Exercise (10) HOOULE 2 Tape (38) Exercises (30) Course Introduction Module Overview Presentation through EOR Forecasts Reading (1-1 to 1-19) Exercise 1 Debriefing Exercise 1 Module Sunmary Reading (2-1 to 2-16) = Module Overview = Presentation through Trapped 0i1 Saturation = Reading (2-17 to 2-20) - Exercise 2 = Debriefing Exercise 2 = Exercise 3 = Debriefing Exercise 3 = Module Summary = Reading (3-1 to 3-12) MODULE 3 Tape (45) Exercises (40) MODULE & Tape (50) Exercises (20) Module Overview Presentation through Pressure-Composition Diagrams Exercise 4 Debriefing Exer ek = Module Overview ~ Presentation through Mechanical Degradation + Exercise 6 = Debriefing Exercise 6 Presentation= Ternary Diagrams = Presentation through Reading (3-13 to 3-17) Presentation finishing Ternary Diagrams and Representative Salini Exercise 5 Debriefing Exercise 5 Module Summary Reading (4-1 to 4-13) Favorable Conditions = Module Summary - Reading (5-1 to 5-12) Tatro-8COURSE MAP MODULE 5 RODULE 6 Tape (76) Exercises (55) Tape (20) Exercise (15) = Module Overview Module Overview = Presentation through Reading (6-1 to 6-24) Surfactants Exercise 9 then Debrief = Reading (5-13 to 5-24) Module Surmary = Presentation through Slug Formulation Reading (7-1 to 7-6) - Exercise 7 then Debrief = Presentation on Surfactant Retention = Reading (5-25 to 5-36) = Exercise 8 and Debrief = Presentation: Lab/Field Results = Module Summary HOOULE 7 MODULE 8 Tape (60) Exercises (50) Tape (87) Exercises (60) = Module Overview = Module Overview = Presentation through = Presentation through Steaming a Well Solvent Displacement Classifications = Exercise 10 then Debrief = Exercise 12 then Debrief = Presentation through Heat Losses = Exercise 13 then Debrief + Exercise 11 then Debrief = Presentation through Displacement echani sms + Module Surmary = Reading (8-23 to 8-27) = Reading (8-1 to 8-22) = Exercise 14 then Debrief = Presentation on Lab/Field Results and Module Summary = Course Summary Tntro-85In Abridged St Units Guide? ST Base Quantities and Units ST Unit Syrbol SPE Dirensions ("Abbreviation") Syrbol ge Cuantity OF et tne et Use Foman Spisension* a Wpetght) type erisht) Tee Tage ater @ mass Kdlogram kg a tire second : 5 thermodynamic temperature kelvin x t amommt_ of substance: mole’ mol 2 hen the role 1s used, the elementary entities must be specitiedi they may be, atone, then the ions, electrons, other perticles, or specified groups of such particles in Potiole work, the tama *kilogran mole", ‘pound sole", etc., are often erroneously Shortened to “nole*. ‘Same Comon ST Derived Units ‘st Unit Syrbol (abbreviation) , Bante, acceleration area density fpergyr serk force preseure feloctty we Visconity, dyrante Pye Viscosity, Kdneraete ah vise. = ‘to Convert From » mutetply bv 2d acre (0.8. survey! wees ied) 4.046 872 £002 cores Feeiee2) 41386 000 B04 stroephere (standard) feseal (ex) ‘1-013 280 E05 fr Bieca} tye) 2-000 000 £v05 Barrel (for petroleum 42 gal) Bega) geo 672 Eo birmel fee) 5.615 5600 Beieian chemel unit. (International Table) SSalesG) 1.088 086 Esa? earcy Hater?) 9.868 232 E13 Gay ban solar) Second ts) #840 000 0d ane reveog fi) 1-000 000 LoS Gilion 0.8. quid) Pecos) 3.905 412 £03 gan Elloggae, kg) 1-000 000 -03 fectare fetter) 1000 000 E+04 Bie 1.8. survey! eter ta Tens 947 even eeu {ibm svolsepots) Rilogean tkg) 40595 924 5-01 Spool sun km pakke natis conestes eat bien ie & sah mS ee Re} oe ei 4 ae ais ie Geuranen of ie 3 Oe ition ot mo Se Eittionn oe sitianitn 1 Re As, et ale, The SI Heteic System of Units and SPE's Tenta- Intro-9 campbell tive metric Standard, JPr, Dec. 1977, p. 1575.COMMON SI_UNITS USED IN THIS COURSE SI HINTS km? = 1(km)? = 1(10?m)*= 1 X 108m? 1MPa = 147 psi 1K = 1.8F 1k) = 1 Btu 1 um? = 1 Darcy 1ImPa-s= 1p 1mN/m = 1 dyne/cm Intro=10MODULE 1 DEFINING EOR Enhanced O11 Recovery (E0R) is oi! recovery by the Injection of materials not normally found in the reservoir. This module Is an overview to help you analyze the need for EOR, define the major EOR processes, and compare the performance of each. This course focuses on oll recovery, and does not address enhanced gas recovery. Also be aware that only U.S. domestic statistics are cited in this section. OBJECTIVES: During this module you wi 1, Define EOR 2. Analyze the EOR target 3. Discuss the current status of EOR 1), Describe the need for EOR 5. Define incremental oi! recovery 6. Compare performances of chemical, thermal, and solvent processes 7. Examine EOR forecasts OUTLINE: 0 OVERVIEW © CURRENT STATUS 0 WHY EOR? © COMPARATIVE PERFORMANCES : © FORECASTS FOR EOR © SUMMARY ACTIVITIES: During this first section of the course, you will listen toa presentation and discussion, read the reference material in the workbook, and complete an exercise . designed to help you summarize the formation presented. Exercise 1: Why EOR? MATERIALS: Video Tape Hodule 1 Workbook Pages 1-1 to 1-21 TIME: You can expect to take approximately 50 minutes to complete all of the activities in this module in addition to the reading. Tape Time: 40 minutes Exercise: 10 minutes Fundamentals of Enhanced Oi! RecoveryMODULE 1 OVERVIEW DEFINITION Enhanced of! recovery (E0R) is defined as oil recovery by the injection of materials not normally present in the reservo This definition embraces all modes of recovery processes (drive, push-pull, and well treatments), and covers a very large number’ of oi! recovery agents. Most importantly, the definition does not restrict EOR to a particular phase (primary, secondary, or tertiary) in the producing life of a reservoir. Nearly all EOR processes have been at least field-tested as _ secondary displacements. Conmercial primary or secondary thermal floods are common. To be sure, much interest has been focused on tertiary EOR, but the definition does not place any such restriction. DISTINCTIONS The definition does exclude waterflooding and is intended to exclude all pressure maintenance processes. Sometimes the latter distinction is not clear since many pressure maintenance processes have displacement character. Moreover, agents such as methane in a high pressure gas drive or carbon dioxide in a reservoir with substantial resident CO, do not satisfy the definition, yet both are clearly EOR processes. Usually the EOR cases that fall outside of the definition are classified by the intent of the process. 1-2 Fundamentals of Enhanced Oi! RecoveryMODULE 1 OVERVIEW EOR TARGET Much of the interest in £0R centers around the amount of oi] to which it is potentially applicable. Table 1 shows that this "target" oil accounts for 278 billion barrels in the domestic U.S. which represents nearly 70% of the 401 billion barrels of original oil in place. TABLE 1...PRODUCTION, RESERVES AND RESIDUAL OIL IN PLACE U.S. ONSHORE, EXCLUDING ALASKA (from Geffen, 1973) Billions Percent of Category of Barrels Original Oi! In Place Produced 101 25.2 Proved Reserves 22 5. EOR Target 278 63 TOTAL yor 100.0 If EOR could recover only 10% of this amount, it could more than double the proved domestic reserves. 1-3 Fundamentals of Enhanced Oil RecoveryMODULE 1 CURRENT STATUS WHERE WE STAND NOW The possibility of recovering substantial additional oil lies primarily in the future. Recent production trends, Figure 1, show that a steadily growing percentage of the domestic production comes from EOR processes. FIGURE 1 EOR PRODUCTION RATE (from Petroleum Data Book) EOR recovery as % of domestic Production 10.0% 10.0 10.0 9.0% 8.0% 7.0% 6.0% 5.0% 4.0% 3.0% 2.0% 1.0% 0.0% es + © aan es s 3 8g e 8s S&S & Oe ota ee Fundamentals of Enhanced Oil Recovery revised 2/96MODULE 1 CURRENT STATUS ACTIVITY Thermal methods, particularly steam drive and soak (combined on ANALYSIS Table 2) occupy the larges share of EOR projects and have : experienced steady growth between 1971 and 1986. (It has since declined, as all activity in the oil industry has.) PROJECTION Project number measures activity, but oll production rate RATE measures success. Table 3 shows nominal daily oil production rates for the EOR processes. JOMESTIC EOR PRODUCTION RATE BY PROCESS TYPE (from Oil and Gas Journal) TABLE 1982 198419861988 «199019921904 1996 Thermal Methods Steam 288.4 958.1 468.7 455.5 444.1 4540 415.8 419.4 Insitu combustion 102 64 103 65 61 47 25 4s Hot Water 07 29 40 20 a7 03 Total thermal 298.6 364.8 479.7 464.9 454.2 460.7 419.0 424.2 Chemical Micollarpomer 0.928 4.8 458 ° Poymer 29 102 1530288 Akane 06 03 02 0.0 Total chemical 44 18-4 16.9 22.5 11.8 22 41.9 04 Solvent Hycrocarbon miscible 14.4 93.85.8559 118.1 99.7 98.3 C02 miscible 313° 284 643956 145.0 161.5 170.7 C02 immiscible 07 (44 04 ot on Nitrogen 7a) 105 oO) (22.918 eae) | cat 28 Fluogas (miscibleand 298.4281 21.4173 1400 ° immisefble) other 63 0 44 48 Total solvent 83.0 108.2 131.0 190.6 298.0 288.6 299.4 Grand total 903.0 460.9 604.7 618.4 656.6 760.9 709.5 723.7 1-6 Fundamentals of Enhnaced Oil Recovery revised 4/96MODULE 1 CURRENT STATUS ACTIVITY Thermal methods, particularly steam drive and soak ANALYSIS (combined on Table 2), occupy the largest share of EOR projects, and have experienced steady growth since 1971. This growth reflects the long-standing commercial success of steam flooding. The total of all EOR projects has increased steadily, with polymer flooding and carbon dioxide showing explosive growth since 1980.” Of the other processes, only alkaline and micellar-polymer have not experienced some measure of growth over this same time. PROJECTION Project number measures activity, but oil production RATE rate measures success. Table 3 shows nominal daily oil production rates for the EOR processes. TABLE 3...DOMESTIC EOR PRODUCTION RATE BY PROCESS TYPE (from Oil and Gas Journal) Production (barrels/day or 0.159 m3/day) 1980 1982 1984 1986 1988 ‘Thermal methods Steam 243,477 288,996 958,115 468,692 445,484 In situ combustion 12,133 10,228 6445 © 10,272 6.525 Hot water —— 705 __2,896 Total thermal 255,810 206,624 “364,560 478,869 464,905 Chemical Micellar polymer 930 g02 2,892 1,403 1,508 Polymer 924 2,587 10,232 15,313 20,992 Alkaline 60) 500) oad 185 0 Total chemical 2,404 069 «13,998 «= 46.901 22,501 Solvent Hydrocarbon miscible 14,499 33,767 25,985 C02 miscible 21,532 24,983 31,300 28,440,192 CO2 immiscible 702 1,349 420 Nitrogen 7.420 18,510 19,050 Flue gas (miscible and immiscible 29.400 26,150 40,450 Total solvent 74,807* 71,915 * 83,011 108,216 150,047 Grand total 392,821 374,608 460,969 604,786 637,453 “Other solvent methods not separately classified in these years. Fundamentals of Enhanced Oil RecoveryMODULE 1 CURRENT STATUS PRODUCTION RATE Here the preponderance toward steam flooding, about 80% of the total EOR production rate, is even more apparent. Of the remaining EOR production about 80% is by solvent flooding. Careful comparisons of Tables 2 and 3 reveal several details. Polymer flooding production, for example, is quite small for the number of projects reported. This process seems to be preferred for smaller projects or for projects which are producing very little oil at initiation. ‘The production rate per project is nearly equal for steam and carbon dioxide. This indicates that the disparity between their respective production rates is caused mainly by the difference in number of projects. The project rate for micellar-polymer and alkaline flooding indicates the as yet marginal economics of these processes. 1-7 Fundamentals of Enhanced Oil RecoveryMODULE 1 WHY E0R? MAINTAINING Even given the large disparity between the RESERVES commercial success of the various processes, we will need all forms of EOR to maintain reserves at an acceptable level. Reserves are defined as petroleum (crude and condensate) recoverable from known reservoirs under prevailing ‘economics and technology. They are given by the following material balance equation Present = Past + Additions = Production from Reserves Reserves to Reserves _—Reserves ADDING TO Reserves can change because the last two terms can RESERVES, change with time. €0R falls under additions to reserves because of changes in economics and/or technology. Additions to reserves break out into four categories: 1. Discovery of new fields 2. Discovery of new reservoirs 3. Extensions to known reservoirs 4. Redefinition of reserves due to changes in economics of extraction technology. Category 4, EOR, will occupy the remainder of this course. Here we substantiate its importance by a brief discussion of categories 1 through 3. DECLINING Throughout most of U.S. petroleum history, reserves RESERVES increased (Figure 2). Reserves began to decline in the late 1960's, a trend that was abruptly reversed in 1971 with the addition of the 9.6 billion barrels from the Alaskan North Slope. The decline immediately began again at a higher rate, however, helped by instability in foreign petroleum supplies. in the early 1980's the decline has greatly slowed, but has not vanished. The reserve-to-production ratio (Figure 2) was relatively constant until the early 1960's, then declined in the late 1960's and the late 1970's, interspersed by a bump due toAlaska. It is likely that the apparent stabilization beginning in 1980 is real, despite the yearly fluctuations, because of the leveling off of the reserves noted above, and because of a decrease in consumption caused by conservation. A stable reserve-to-production ratio is good, but a declining reserve is a major incentive for EOR. 1-8 Fundamentals of Enhanced 011 RecoveryMODULE 1 WHY EOR? FIGURE 2 CRUDE RESERVES IN THE U.S. (from Petroleum Data Book) (years) RESERVES/PRODUCTION ~— RESERVES AT BEGINNING OF YEAR (billions of barrels)~~-~~ 1920 30 40 50 60 70 80 90 NON-EOR ADDITIONS The question naturally arises about the TO RESERVES probability of adding to reserves through categories 1 through 3, discovery of new fields and new reservoirs, and extensions to known reservoirs. Figure 3 shows that whereas production is a rather smoothly varying function of time, reserve additions through new oi! are more sporadic. This means that, in most years, production will exceed additions even when reserves are fairly constant. Therefore, the reserve decline rate can only be seriously retarded by finding large fields. The probability of finding large fields, however, is declining. Figure 4 shows the rate of discovery of significant (one million barrels or more) fields plotted versus the date of discovery. The figure also shows the average number of exploratory wells drilled in the same year. If correlation existed between the two curves, the drilling curve should lead the discovery curve. The discovery peak in 1960 actually leads the drilling peak in 1961. Such may happen again in the discovery curve in the 1980's (the discovery curve terminates six years before the drilling curve because it takes this long, on average, to verify reserves), but both curves Suggest a poor correlation between the number of wells drilled and the frequency of finding significant fields. 1-9 Fundamentals of Enhanced 0i1 RecoveryMODULE 1 WHY EOR? FIGURE 3 CONTRIBUTION OF NEW OIL TO U.S. RESERVES (from Petroleum Data Book) 10, BAY MARCHAND PRUDHOE BAY 7 KELLY-SNYDER 6 SOUTH PASS a 36 / 2o4 WEST DELTA 73 @ 2 ra s 3 Tame 3 Hath & CRe at ge2 Ze u 5 $4 3 8 = 3 6 Bs, 10 1950 1960 1970 1980 FIGURE 4 DISCOVERY RATE AND DRILLING (from Petroleum Data Book) 120 SIGNIFICANT FIELDS 100 2 1 million barrels recoverable oil (thousands) ~~ NUMBER OF SIGNIFICANT FIELDS NUMBER OF EXPLORATORY WELLS 1940-1950. «196019701980 1-10 Fundamentals of Enhanced 0i1 RecoveryMODULE 1 WHY EOR? SUMMARY We can summarize the need for EOR, then, from Figures 2 through 4, in the following manner: 1, The U.S. domestic reserves are declining slowly. 2. From the viewpoint of exploration, the rate of decline can only be affected by discovering large fields, and 3. The rate of discovery of large fields does not correlate with the number of wells drilled. These observations suggest that techniques other than drilling and exploration are needed to maintain U.S. reserves. Given the large target, these other techniques center around EOR. ett Fundamentals of Enhanced Oil RecoveryMODULE 1 COMPARATIVE PERFORMANCES TECHNICAL, A universal technical measure of an EOR process STANDARD is the amount of "incremental oil" recovered. OF success Figure 5 defines incremental oil. Imagine a Field, reservoir, or well whose oil rate is declining as from A to 8. At B an EOR project is initiated and, if successful, the rate should show a deviation from the projected decline at some time after 8. Incremental oil is the difference between what was actually recovered, 8 to D, and what would have been recovered had the process not been initiated, B to C. This is the shaded area in Figure 5. Clearly, an accurate evaluation of incremental oil requires a careful estimate of the continued decline. This is a major source of evaluation difficulty particularly for projects whose response is not large. Nevertheless, the correct technical measure of the success of an EOR project ‘is the amount of incremental oil recovered, usually reported as a percent of some reference quantity. FIGURE 5 DEFINITION OF INCREMENTAL OIL (from Prats, 1982) EOR Operation OIL PRODUCTION RATE TIME 212 Fundamentals of Enhanced Oil RecoveryMODULE 14 PREDICTING INCREMENTAL OIL RECOVERY DECLINE Techniques to predict incremental oil recovery range CURVES from numerical simulation to pilot testing. Probably the simplest procedure is based on decline curve analysis, a portion of which we apply here. The following defines decline rate and summarizes the different types. DECLINE CURVES... Decline rate = a [=] time’ 1 da a=- od constant — exponential ay @) harmonic aj (¢y hyperbolic In this figure q is the oil rate and the subscript i refers to a quantity evaluated at the beginning of a decline period. The decline rate period begins when a well-established, extrapolatable decline in the oil rate is evident. The rate itself may apply to a single well, a project, a field or even an entire producing area, but decline curve analysis will not apply if a decline period does not exist. The reader can show that exponential and harmonic declines are special cases of hyperbolic declines where n=0 and 1, respectively. All decline curve models are empirically-based, lacking fundamental physical basis. EXPONENTIAL Exponential declines are sometimes called constant DECLINE percentage declines and they are by far the most often used. They are the most useful for EOR purposes. For the exponential decline the following relationships hold between the oil rate qand time t and between the rate and the cumulative oil produced Np: EXPONENTIAL DECLINE . q=qe rate-time q=qi-aNp rate-cumulative 1-13.41 Fundamentals of Enhanced Oil RecoveryMODULE 1 ESTIMATING INCREMENTAL OIL RECOVERY We show the last idealized case to emphasize that rate-cumulative curves can be misleading. The figure below shows a case where the process did not cause an initial increase in rate but merely retarded the decline. DEACCELERATED PRODUCTION... q Project P Begins At first glance this is highly desirable because it apparently greatly increases 1OR. However, recall from the rate-time plot that such behavior will also greatly prolong the project life, perhaps so much so that the present worth of the incremental production will not be enough to pay for the EOR agent. Also, IOR in this circumstance will be very sensitive to the choice of economic limit. 1-13.6 Fundamentals of Enhanced Oil RecoveryMODULE 1 ESTIMATING INCREMENTAL OIL RECOVERY APPLICATION We conclude by showing these applications to a set of .__fea|.data in the figure below upon which the data points have been restored. 300 250 200 = 150 100 50 ee 0 10 20 30 40 50 60 70 60 80 100 110 120 130 140 ° 1000 BbL This is field data from a mid-continent reservoir which initiated an infill drilling program at about 50,000 barrels of oil produced. There are several perturbations of the decline at later times but we will discuss only the obvious large one. The most important departure in this data from the ideal behavior is that the exponential deciine does not reassert itself immediately after the process began. When the decline does begin, however, it extrapolates to the same mobile oil as did the data before the drilling, We conclude from this behavior that the infill drilling program primarily accelerated production but did not expose any new oil. The infill program was successful, but the reservoir is of sufficient continuity that it could be adequately drained, given enough time, with only a few wells. 113.7 Fundamentals of Enhanced Oil RecoveryMODULE 1 ESTIMATING INCREMENTAL OIL RECOVERY IDEALIZED Rate-cumulative plots are simple yet informative tools for CASES interpreting EOR processes because they allow estimates of incremental oil recovery (IOR) by distinguishing between recoverable and mobile oil. We illustrate how this comes about through four idealized cases. In the figure below we show a rate-cumulative plot for a project having an exponential decline just prior to and immediately after the initiation of an EOR process. INCREASED MOBILE OIL... q Project a ear Pp Begins Incremental Mobile Oil We have replaced the data points with the models only for ease of presentation. Placing both periods on the same horizontal axis is permissible because of the scaling arguments mentioned above. In this case, the EOR process did not accelerate the production because the decline rates in both periods are the same; however, the process did increase the amount of mobile oil which in turn caused some incremental oil production. In this case the incremental recoverable and mobile oil are the same. Such idealized behavior would be characteristic of thermal, micellar- polymer and solvent processes. 1-13.4 Fundamentals of Enhanced Oil RecoverMODULE 1 ESTIMATING INCREMENTAL OIL RECOVERY The figure below shows another extreme where production is only accelerated. ACCELERATED PRODUCTION ... a Begins Now the curves extrapolate to a common mobile oil, but with still a non-zero IOR. We expect correctly that processes which behave as this will produce less oil than ones that increase mobile oil, but they can still be profitable, particularly if the agent used to bring about this result is inexpensive. Processes which ideally behave in this manner are ‘polymer floods and polymer gel processes which do not affect residual oil saturation. The figure below shows are rather bad case where the process actually reduced the mobile oil. ACCELERATED PRODUCTION .. . 4 Projet Begins Such behavior is undesirable, but it could stil be profitable if, as is the case above, the accelerated production offsets the loss of mobile oil enough so that IOR is still not zero. Behavior like this probably indicates a target for a future application. 1213.5 Fundamentals of Enhanced Oil RecoveryMODULE 1 ESTIMATING INCREMENTAL OIL RECOVERY RATE- These equations suggest a semi-log relationship TIME between rate and time as illustrated below. RATE-TIME... decline period 7 begins The figure schematically illustrates a set of data (points) which begin an exponential decline at the ninth point where, by definition t = 0. The solid line represents the fit of the decline curve model to the data points. qj is the rate given by the model at t=0, not necessarily the measured rate at this point. The slope of the model is the negative of the decline rate divided by 2.303 since the semi-log graph paper plots base 10 rather than natural logarithms. The model being a straight line, it can be extrapolated (dotted line in the above figure) to some future rate. ‘If we let EL designate the economic limit of the entity under consideration then where the model extrapolation attains EL is an estimate of the project's (of wall's, etc.) economic life. The economic limit is a nominal measure of the rate at which the revenues become equal to operating expenses plus overhead. EL can vary tremendously depending-te the operating conditions. On 113.2 Fundamentals of Enhanced Oil RecoveryMODULE 1 ESTIMATING INCREMENTAL OIL RECOVERY RATE- The frequency of exponential declines is evident CUMULATIVE from how often we see oil rate data automatically plotted on a semi-log axis. But the rate-cumulative plot actually contains more information that is useful in EOR. The figure below shows a typical plot. RATE-CUMULATIVE a ° acorns) ~Nebinot ‘oh First of all, note that the cumulative oil being plotted on the horizontal axis of this figure is based on the oil rate data, not the decline curve. If this were not 0 there would be no additional information in the rate-cumulative plot. Calculating Np normally requires a numerical integration via something like the trapezoid rule. At the onset of the decline period the data again start to follow a straight line through which can be fit a linear model. In effect, what has occurred with this plot is that we have replaced time with cumulative oil produced, but there is one very important distinction: both axes are now linear. This has three important consequences 1. The slope of the model is now -a since no correction for log-scales is required. 2. The origin of the model can be shifted in either direction by simple additions, and 3. The rate can now be extrapolated to zero. Point 2 simply means that we can plot the cumulative oil produced for all periods prior to the decline curve period (or for previous decline curve periods) on the same rate-cumulative plot. Point 3 means that we can extrapolate the model to find the total mobile oil rather than simply the recoverable oil. 1-13.3 Fundamentals of Enhanced Oil RecoveryMODULE 1 COMPARATIVE PERFORMANCES SPECIFIC PROCESS How do the EOR processes compare? We will spend ‘COMPAR! SONS the majority of this course covering basics and a few details of each process. It's useful at this point, however, to introduce some ideas which will be developed further later on, and to give comparative performances. The latter Is represented as typical oil recoveries (100x incremental ofl/original oi! in place) and by various utilization factors based on actual experience. Tables 4 through 6 compare chemical, thermal, and solvent processes, respectively. CHEMICAL FLOODING Chemical flooding EOR processes, Table 4, are united by their sensitivity to high salinities (total dissolved solids should be less than 100,000 g/cubic meter). Chemical agents are susceptible to loss through rock-fluid Interactions. Maintaining adequate Injectivity is a persistent problen. Historically, oi] recoveries have ranged from small to moderately large. Chemical utilization factors must be viewed with respect to the costs of the individual agents. Polymer, for example, is usually 3 to 4 times as expensive per unit mass as surfactant. TABLE 4...CHEMICAL EOR PROCESSES Typical* Typical Agent Process Recovery Mechanism Issues Recovery (%) Utilization Polymer Improves volumetric Injectivity = 5 2-3 Ib sweep by mobility polymer/bb1 reduction Retention oi! produced Hicellar- Same as polymer Same as 15 15-25 1b Polymer plus reduces surfactant/ capillary forces bbl of! produced and high salinities Alkaline- Same as micellar- Same as 5 35-45 Ib polymer polymer plus o micellar- chemical/ solubilization and polymer plus bbl oi! wettability oi! produced alteration composition * from Taber and Martin, 1983. Fundamentals of EnhancedMODULE 1 COMPARATIVE PERFORMANCES THERMAL FLOODING Table 5 shows a similar comparison for thermal processes. Recoveries are generally higher for these processes compared to the chemical methods. Again, the issues are similar within a given category, centering around heat losses, override and air pollution. The latter issue occurs because steam is usually generated by burning a portion of the produced ofl. If this burning is done on the surface, the emission Products contribute to air pollution. If the burning is done in Situ, production wells can be @ source of pollutants. TABLE 5...THERMAL EOR PROCESSES Typical* — Typical Agent Process Recovery Mechanism Issues Recovery (3) Utilization Steam Reduces oi! Depth 50-65 0.5 bbl oil (drive viscosity consumed/ and soak) Heat Losses bbl of! Vapor ization produced of light ends Override Pollution Same as steam Same as 10-15 10 MCF air/ plus cracking steam plus bbl oi! control of produced combust ion *from Taber and Martin, 1983. Fundamentals of Enhanced O11 RecoveryMODULE 1 COMPARATIVE PERFORMANCES SOLVENT FLOODING Table 6 compares the solvent flooding processes. There are only two groups in this category corresponding to whether or not the solvent develops miscibility with the oil. Oil recoveries are generally lower than, micellar-polymer, but the solvent utilization factors (and the respective cost of the solvents) have brought these processes, particularly carbon dioxide flooding, to commercial application. The distinction between a miscible and an immiscible process is slight on Table 6. TABLE 6...SOLVENT EOR PROCESSES Typical — Typical Agent Process Recovery Mechanism Issues Recovery (%) Utilization Immiscible Reduces of! Stability 5-10 10 MCF viscosity solvent/bb1 Override oil produced O11 swelling Supply Solution gas Miscible Same as Same as 5-15 10 MCF immiscible cible solvent/ plus bbl oi} development produced of miscible displacement *from Taber and Martin, 1983. Fundamentals of Enhanced Oi! RecoveryMODULE 1 FORECASTS FOR EOR WHAT'S IN Forecasting such risky processes in @ highly volatile STORE? economic scene is dubious at best. Nevertheless, prediction of EOR trends have abounded. Figure 7 gives a forecast made by the National Petroleum Council (NPC) in 1984. These forecasts assume a base oi! price of $30/bbl and a minimum rate of return on investment of 10%. Implemented technology, that attainable without additional development, shows that thermal recovery has the largest potential, trailed narrowly by solvent flooding, then chemical flooding. The entire EOR projection is 14.5 billion barrels. represents a dismaying small 5% of the total target of! given in Table 1. One purpose of the remainder of this course is to explain why this is so low and to indicate what must be done to improve it. FIGURE 7 EOR FORECAST (from National Petroleum Council, 1984) LEGENO FE thermal Solvent Chemical “ADVANCED TECHNOLOGY IMPLEMENTED TECHNOLOGY (27.5 Billion Barrels) (14.5 Billion Barrels) Technological advancements can dramatically alter this picture. Figure 7 also shows an advanced technology case wherein the thermal potential has nearly doubled and the chemical increased by more than a factor of four. In the chemical flooding case, where micellar-polymer alone represents 10 billion barrels, technological improvements can change it from the process with the least potential to that with the greatest. Solvent flooding, on the other hand, is believed to be fairly well developed. The 27.5-billion-barrel advanced technology potential represents more than 10% of the EOR target, and is larger than the proved reserves listed in Table 1. 1-17 Fundamentals of Enhanced O11 RecoveryMODULE 1 FORECASTS FOR EOR DECLINE OF Lest we underestimate the difficulties in attaining TARGET O|L the advanced technology case, we end this section on a sobering issue. We have continually discussed the EOR target as though it will remain constant. That this is not the case Is indicated by Figure 8 which is a projection into the next century of the three types of reserves in Table 1. The EOR target is the amount between the first and second lines. This figure says that the OR target will actually contract rather rapidly with time, being pinched from below by actual production and from above by abandoned oil. Abandoned oil can come about by a variety of economical ly-driven causes like mechanical deterioration and lease reversion. When a reservoir is actually abandoned, it's not likely that EOR can be successful because few processes can bear the expense of drilling new wells. This, incidentally, is an advantage of EOR over exploratory drilling. We know where the oi! is and much of the equipment is already in place. FIGURE 8 EOR TARGET OIL DECLINES WITH TIME (from Claridge, 1982) Reprinted with permission © 1982 Society of Automotive Engineers, Inc. 450 ABANDONED OIL voor (unless entanced ol reavery [ iprocemes are apiea) soo} | uNPRooucED on t Minbetve ff fies) 200 Ao SECONDARY PRODUCTION PRIMARY PROOUCTION | 0 1380 198s 19991995 2000 2005 YEAR 1-18 Fundamentals of Enhanced Oi! RecoveryMODULE 1 SUMMARY SUMMARY The EOR literature says relatively little about 2 shrinking target, but it introduces a sense of urgency to the implementation of E0R. To avoid this we must diligently seek opportunities for EOR, and then pursue them to successful completion. Doing this requires substantial technical sophistication from all phases of the producing community. To provide this sophistication. is one of the purposes of this course. 1-19 Fundamentals of Enhanced Oi! RecoveryMODULE 1 REFERENCES Claridge, E.L., "Prospects for Enhanced Recovery of O11 in U.S.5!! Paper #825168, 17th Entersociety Energy Conversion Engineering Conference, Aug. 8-12, 1982, Los Angeles, Calif., 981-587. Oil Recovery= An Anal of Potential for Enhanced Oi1 Recovery from known Flelds in the United States- 1976 to 2000, National Petroleum Council, December 1976 and June 19% Geffen, Ted, "Improved Recovery Could Help Ease Energy Shortage," World Oil, vol. 177, no. 5, October 1973, 84-88. katz, Marvin L., "Enhanced 011 Recovery Perspective and Prospects," bresented at the Dallas Section of the Society of Petroleum Engineers of AIME Continuing Education Seminar, Dallas, Texas, May 20, 1980. Qi} and Gas Journal Biennial Survey since 1972, Penn -Well Publishers, Tulsa, Oklahoma. Petroleum Data Book, Dallas Petroleum Engineering Co., ed. Hed Struth, Annually since 1947. Prats, M., Thermal Recovery, Society of Petroleum Engineers of AIME, Henry L. Doherty Series, Monograph, vol. 7, 1982. Taber, J.J. and Mar Enhanced Recovery of Oi F.D., "Technical Screening Guides for the {SPE 12069, presented at the S8th Annual Conference held in San Francisco, California, October 5-8, 1983. Fundamentals of Enhanced 0i1 RecoveryMODULE 1 EXERCISE 1 PURPOSE UTILITY PROCESS WHY EOR? © To summarize the need for EOR © To review the major concepts presented in this module Before going on to the next module, this exercise should help you capsulize the salient points upon which the rest of the course is built. After reading the material in this module and listening to the discussion on tape, consider the following questions and record your answers. ist two of four categories for adding to reserves: 2. Define "incremental © and indicate the major 3. Why is the target for EOR diminishing? 1-21 Fundamentals of Enhanced 0i1 RecoveryMODULE 2 REVIEWING DISPLACEMENT FUNDAMENTALS This course is taught from @ reservoir engineering perspective. Hence, s important that a conmon basis for concepts to which’ we will continually refer be established at the outset. Indeed, many times it is difficult to distinguish an EOR course from one in advanced fluid flow in permeable media. This module briefly reviews the basic concepts dealing with displacements in permeable media. OBJECTIVES: During tl module you will: 1. Define the basic oi! recovery equation 2. Define dimensionless time 3. Define mobility rat 4. Review areal sweep efficiency iscuss vertical sweep efficiency 6. Review displacement efficiency 7. Explore the causes of trapped of! saturation OUTLINE: © FACTORS AFFECTING OIL RECOVERY © AREAL SWEEP EFFICIENCY © VERTICAL SWEEP EFFICIENCY © DISPLACEMENT SWEEP EFFICIENCY © SWEEP EFFICIENCY SUMMARY TRAPPED OIL SATURATION ACTIVITIES: Ouring this module, you will listen to the taped Presentation, read the reference material the workbook, surmarize in writing the relative importance of several factors to the three sweep efficiencies, and work an exercise dealing with trapped oil saturation. Exercise 2: Calculating Capillary Numbers Exercise 3: Analyzing Factors Which Affect Oil Recovery MATERIALS: Video Tape Module 2 Workbook Pages 2-1 to 2-24 Notebook Paper Calculator TIME: You can expect to take approximately 65 minutes to complete all of the activities in this module in addition to the reading. Tape Time: 38 minutes —Exerci es: 30 minutes Fundamentals of Enhanced 011 RecoveryMODULE 2 FACTORS AFFECTING OIL RECOVERY BASIC OIL Based on overall material balances on cumulative RECOVERY oi! recovered in standard volumes, N, may be EQUATION written as o os v,/8, a) ip EnFvSoYp/Po where Ey is the volumetric sweep efficiency reservolr volumes of oil contacted by displacing agent a= (2 ally In place reservoir volumes of of! ori and Ep is the microscopic or displacement sweep efficiency reservoir volumes of oi! mobilized by EOR agent & es eeecereeseeeesaeee = (3) reservoir volumes of of! contacted by EOR agent Since the term $V./B. represents the oil in place at the start of the °! P © displacement in standard volumes, we can define a recovery efficiency Ep as — —__ a from Equation (1). The volumetric sweep efficiency can be decomposed into the product of an areal sweep efficiency and a vertical sweep efficiency by + Ee (5) The definition of the areal sweep efficiency is area contacted by displa (6) total area 2-2 Fundamentals of Enhanced Oi] RecoveryMODULE 2 FACTORS AFFECTING OIL RECOVERY USING EQUATION 1 To use Equation (1) we must have independent estimates of Ey and E,. For certain very special cases (confined displacements in’ areally homogeneous regular patterns with no or very good vertical communication), estimates are available to us through correlation or calculation. When these conditions are not met, must be estimated through scaled laboratory experiments or \ numerical simulation. In the latter case, though It is certainly possible to obtain sweep efficiency estimates, the oil recovery itself may be obtained directly, and Equation (1) is unnecessary. Nevertheless, the equation’ provides a better understanding of sweep efficiency concepts, and of the factors necessary to maximize Ey than does simulation alone. 23 Fundamentals of Enhanced 011 RecoveryMODULE 2 FACTORS AFFECTING OIL RECOVERY DIMENSIONLESS Two other definitions will be used throughout TIME this section and the remainder of the course. The first definition is that of dimensionless time, which for incompressible flow, is the cumulative volume of fluid injected divided by a reference pore volume, Table 1. The denominator of the definition is variously defined depending upon the application, Table 1. To be sure the numerical values of both the numerator’ and denominator can be uncertain, but their definitions are clear. Dimensionless time 1s the most important scaling between the laboratory and the field because it can be defined precisely in both cases. TABLE 1. DIMENSIONLESS TIME.. THE FUNDAMENTAL SCALING VARIABLE REFERENCE USAGE VOLUME ‘Area x Length x Porosity Corefloods ‘Area x Thickness x Porosity General (en vp Total pore volume) Vp x Volumetric Sweep Ef jiency Micellar Polymer (px £,= Floodable pore volume = Vpq) Floods Ver &Sq™ Movable Pore Volume Waterlloods Ver x So = Hydrocarbon Pore Volume Miscible Floods avery Fundamentals of Enhanced 011 RecoveryMODULE 2 FACTORS MOBILITY RATIO behind gradient: several 2. If Mot, displace AFFECTING OIL RECOVERY The second definition is that of mobility ratio. The most general definition of this quantity is the ratio of the pressure gradient ahead of and ‘a piston-like front (Prats, 1982). Once the pressure s are eliminated with Darcy's law, the definition takes on more useful special cases: If the displacement is incompressible (volumetric Flux constant across the front), the mobility ratio is the ratio of mobility of the displacing fluid divided by that of the displaced fluid. This special case gives the name to the mobility ratio and is the one we apply to polymer and ellar-polymer floods. The definition must be altered to account for composition gradients on either side of the front. If there are no gradients, the mobility ratio Is the end-point mobility ratio. If the displacement is incompressible and miscible, the mobility ratio is the ratio of the displaced fluid viscosity to that of the displacing fluid. This definition is most useful in solvent flooding. If the mass flux is constant across the front, the mobility ratio becomes the kinematic mobility ratio where the viscosities in the two previous definitions are replaced by the kinematic viscosity. The kinematic viscosity Is the dynamic viscosity divided by the fluid density. The condition of constant mass flux is roughly approximated in steam floods and floods with compressible gases. the displacement is “unfavorable. If M<1, the ment is “favorable! Fundamentals of Enhanced Oil RecoveryMODULE 2 FACTORS AFFECTING OIL RECOVERY AREAL SWEEP The upper figure in Figure 1 shows a schematic of EFFICIENCY a highly-idealized piston-like displacement in a four-layer heterogeneous reservoir. The lower figure is an areal view of the upper layer. Based on definition (6), £, is the doubly cross-hatched area (at t,) divided by the total cfoss-hatched area. FIGURE 1 SWEEP EFFICIENCY SCHEMATIC UNSWEPT SWEPT ZONE AREAL Fundamentals of Enhanced 0i1 RecoveryMODULE 2 AREAL SWEEP EFFICIENCY AREAL SWEEP Though areal sweep efficiency may be determined MCORRELATIONS" through simulation, or by analytical methods, the most common source of areal sweep efficiency data is from displacements in scaled physical models. Figures 2-4 present three of these sweep ‘‘correlations" for three different regular well patterns, Several more correlations are in the literature. For the patterns indicated in the lower right corner of each figure, Figures 2 through # plot E, on the y-axis versus the reciprocal mobility ratio on the axis with time as a parameter. Since mobility ratio and pattern type are Fixed for a given displacement, time is actually the dependent variable E, = E, (dimensionless time). The dimensionless time (V4) “in Floures 2 through 4 is cumulative displaceable pore volumes of displacing agent injected...the fourth definition in Table 1. These correlations are for piston-like displacements in regular, homogeneous, confined patterns. When the well patterns are unconfined, the total area in definition (6) can be much larger and E, smaller. From the correlations, E, increases with increasing time, or throughput, and decreasing § mobility ratio. At a fixed mobility ratio E, is equal to the displaceable pore volumes injected until bfeakthrough, and then given by the indicated curves thereafter. E, also increases as the pattern type more closely approaches linear flow, but this sensitivity of E, is not great for more common patterns. Large mobility ratios “are detrimental to both areal and displacement sweep. 2-7 Fundamentals of Enhanced 011 RecoveryMODULE 2 AREAL SWEEP EFFICIENCY FIGURE 2 AREAL SWEEP EFFICIENCY FOR A CONFINED FIVE-SPOT PATTERN (from Craig, 1971 courtesy of SPE-AIME) 100, 90 80 70 % AREA SWEPT 60 50 1010.20 0.414 08 Gig 1.0m ema ee getI0 RECIPROCAL OF MOBILITY RATIO FIGURE 3 AREAL SWEEP EFFICIENCY FOR A CONFINED DIRECT LINE DRIVE (from Craig, 1971 courtesy of SPE-AIME) 100 90 20 70 60 % AREA SWEPT so 40 ‘Ot 02 04 06931 2 4 6 810 2030 RECIPROCAL OF MOBILITY RATIO Fundamentals of Enhanced 0i1 RecoveryMODULE 2 AREAL SWEEP EFFICIENCY FIGURE 4 AREAL SWEEP EFFICIENCY FOR A STAGGERED LINE DRIVE PATTERN (from Craig, 1971 courtesy SPE-AIME) 100, % AREA SWEPT 20°30 0102 04 OSgqt 2 4 6 810 RECIPROCAL OF MOBILITY RATIO 2-9 Fundamentals of Enhanced 011 RecoveryMODULE 2 AREAL SWEEP EFFICIENCY MOBILITY RATIO A more instructive way to plot AS A PARAMETER E,-correlations is with mobility ratio as as “parameter. Figure 5 shows that displacing fluid breakthrough (BT) decreases as M increases. Prior to BT, all curves are the same. However, after BT the larger Nts are clearly undesirable. All curves will approach complete sweep-out, Ex = 1, with enough throughput. FIGURE 5 FIVE-SPOT AREAL SWEEP 100 =1 80 60 M=100 40 AREAL SWEEP EFFICIENCY 20 0 0 05 10 «#15 «(2.0 MOVABLE PORE VOLUMES INJECTED 2-10 Fundamentals of Enhanced RecoveryMODULE 2 AREAL SWEEP EFFICIENCY VISCOUS FINGERING The main reason £, decreases as increases is becausé the displacement front becomes unstable. Figure 6 shows this effect, The "fingering" results in early displacing fluid breakthrough and prolonged injection to sweep-out (compare to Figure 5). We will return to this important phenomenon in Module 8. FIGURE 6 VISCOUS FINGERING 211 Fundamentals of Enhanced RecoveryMODULE 2 VERTICAL SWEEP EFFICIENCY DEFINITION An equally important contributor to poor oi! recovery, Equation (1), is vertical sweep efficiency, E,. £, is_ defined in Equation (7). It is the double hatched area IX Figure 7 divided by the single hatched area. cross-sectional area contacted by displacing agent - (7) total cross-section E, is quite complex and consequently difficult to generalize. It d&pends on these four factors: heterogeneity, gravity, mobility ratio, capillary forces (and ratios thereof) and throughput. We discuss only the first three. HETEROGENEITY The dependency on heterogeneity is in Figure 7. This is a uniformly stratified reservoir with varlable permeabilities ky > ky > ky > kao, Because of the permeability contrast, displacing fluid’ will? 8T early in layer 1, and the entire cross-section will achieve sweep-out late, when layer 2 breaks through. FIGURE 7 VERTICAL SWEEP EFFICIENCY UNSWEPT. SWEPT ZONE UNSWEPT, it ie ff if a SWEPT ZONE UNSWEPT 2-12 Fundamentals of Enhanced Oi! RecoveryMODULE 2 VERTICAL SWEEP EFFICIENCY GRAVITY EFFECT Gravity can compound the effect of heterogeneity, but it can be important even in a homogenous reservoir. Figure 8 shows this effect. If the displacing fluid is less dense than what is being displaced, it will flow to the top (tongue over) of the reservoir and bypass fluid below. If-the densities are reversed, the displacing fluid will tongue under. Gravity will be important when vertical communication is good and gravity forces are strong compared to viscous forces, The First condition is satisfied when RL is large where L (ky \* Ri== *) walt (8) The second condition holds when the gravity number N. is large where g (9) k = absolute permeability vertical permeability mobility of displacing fluid u = superficial velocity and 4p Paisplacing ~ Pdisplaced Both R, and Ny are dimensionless. Fundamentals of Enhanced Oi! RecoveryMODULE 2 VERTICAL SWEEP EFFICIENCY GRAVITY EFFECT Although similar in many respects, gravity continued tonguing is not the same as viscous fingering. Tonguing can occur if M<1, as long as R, and N, are large. By the same token, gravity tonguing does “ not require a dipping reservoir (although dip can be used to advantage when gravity 1s important). Gravity tonguing is important in solvent flooding and especially in steam flooding. It will be discussed further in Modules 7 and 8 FIGURE 8 GRAVITY EFFECT DENSITIES: DISPLACING 5 a & > 8 o W & g > 214.5 Fundamentals of Enhanced Oil Recovery revised 1/92MODULE 2 VERTICAL SWEEP EFFICIENCY HETEROGENEITY The bypassing displacement type actually continued consist of two types. A displacement is fingering if the fluid bypassing is caused by a viscous instability. It is channeling if the bypassing is caused by heterogeneity. Here we can begin to see the interplay between fingering and heterogeneity. Note that the displacements in Fig. 10 and the classification in Fig. 11 call bypassing channeling since fingering can't ocour in M=1 displacements. Figure 12 shows concentration contours for unstable M=10 displacements. The displacements in the panels in the upper right remain more-or-less dispersive. Considering both Figs. 10 and 12, evidently the absence of continuity can defeat both fingering and channeling. Waggoner et al. (1991) showed that this effect persisted up to M=100. The lower right panels continue to be bypassing, although the adverse mobility ratio has exacerbated the extent of the channeling. The displacements on the left (small heterogeneity) are the most affected by the adverse mobility ratio. Here there are clearly defined bypassing zones. These zones must be fingers since they disappear when the Mzt. Figure 13 shows the classification at adverse mobility ratio. FIGURE 13 CLASSIFICATION OF DISPLACEMENT TYPES Dimensionless Critical Correlation Length Dykstra-Parsons coatficient From Waggoner et al. (1991) Fingering occurs only at small heterogeneity and dispersive behavior is the boundary between the two. 214.6 Fundamentals of Enhanced Oil Recovery revised 1/82MODULE 2 VERTICAL SWEEP EFFICIENCY FIGURE 12 CONCENTRATION CONTOURS OF M=10 DISPLACEMENTS 214.7 Vop = 0.54 Vp = 0.86 Vpp = 0.01 tn So 0 S H 4 = From Waggoner et al. (1991) Fundamentals of Enhanced Oil Recovery revised 1/02MODULE 2 VERTICAL SWEEP EFFICIENCY EFFECT OF LATERAL All of the above runs were cases where the COMMUNICATION lateral communication was very good. Figure 14 shows, for completeness, a case where the lateral communication was very poor (RL=0). The mobility ratio is again adverse M=10. For no lateral communication there is no fingering; bypassing is exclusively by channeling. Moreover, channeling appears to be controlled mainly by heterogeneity and the continuity determines the extent of channeling. Obviously there is a large difference between the contours of Figs. 12 and 14, illustrating the importance of lateral communication in displacement performance. Most reservoirs tend to the RL large limit, unless there is a clear-cut barrier to flow. EFFECT OF GRAVITY Chang et al. (1991) performed a similar set of simulations that showed the effects of gravity and partial miscibility on displacement classification. One of their results, is shown in Fig. 15. FIGURE 15 DISPLACEMENT CLASSIFICATION FOR CASES WITH GRAVITY Dimensionless Correlation Length 0 02 04 0.8 08 1 Dykstra-Parsons Coefficient From Chang et al. (1991) 214.8 Fundamentals of Enhanced Oil Recovery revised 1/92MODULE 2 VERTICAL SWEEP EFFICIENCY FIGURE 14 CONCENTRATION CONTOURS FOR NO LATERAL COMMUNICATION K a a °o oO cr w w 1 < < = From Waggoner et al. (1991) |], - 0.67 2-14.9 Fundamentals of Enhanced Oil Recovery revised 1/92MODULE 2 VERTICAL SWEEP EFFICIENCY The gravity number was Ng = 0.049 and lateral communication was good. Under these conditions the fingering regions disappears entirely to be replaced by a gravity dominated override region as discussed above. Chang et al. (1991) used a definition of gravity number that is the product of Ng, defined above, and RL. Another thing remarked upon by Chang et al. (1991) is that the first- contact miscible displacement simulated above represents a worst-case displacement. All additional complexities dealing with phase behavior, capillary pressure and other petrophysical properties tend to lessen the degree of both channeling and fingering. SUMMARY The interplay among vertical communication, continuity, mobility ratio and heterogeneity is probably more complicated than discussed here. However, there are several insights which seem to qualitatively make sense. Conclusions . . . Fingering and channeling are distinct Fingering requires lateral communication Heterogeneity and gravity can defeat — fingering Fingering occurs only at small © — heterogeneity Bypassing on field-scale is mainly — channeling The first is these conclusions is simply a common-sense definition, but the others are more controversial. That channeling prevails, almost regardless of mobility ratio, on the field scale follows from typical values of VDP taken from cores. The importance of viscous fingering is considerably decreased--except that adverse mobility ratios still cause lower sweep efficiency--because it is overpowered by heterogeneity (specifically, continuity) and, under some circumstances, gravity. Some of the things we will notice as we cover the remainder of this manual are that (a) oil recovery in the field is always much lower than recovery in the laboratory, and (b) recoveries are low for all EOR processes (the nonthermal ones, that is), regardless of mobility ratio. The fact that most displacements are dominated by a competition between heterogeneity and continuity is that main reason that this is so. 2-14.10 Fundamentals of Enhanced Oil Recovery revised 1/92MODULE 2 OISPLACEMENT SWEEP EFFICIENCY MOBILITY RATIO The last efficiency in Equation (1) is the local AND Ey displacement efficiency, Ep, defined as volume of of] mobilized Eos (10) volume of 011 contacted E, is what is measured in a core flood where Ey = 1. 18 is also what is calculated by fractional Flow or Buckley-Leverett theory. Figure 9 shows two water saturation profiles at the same time t, for two different mobility ratios M, and M) in a waterflood.” Actually, E) is a function of throughput? wettability, dip and even’ N.2 However, it is also a function of mobility ratio, and 9 the lower M's give higher Ey. For an inmiscible displacement, Ey is bounded by 2 residual pRase saturation for the displaced phase” S._. FIGURE 9 EFFECT OF MOBILITY RATIO ON Ep WATER SATURATION DISTANCE > 2-15, Fundamentals of Enhanced Oi! RecoveryMODULE 2 SWEEP EFFICIENCY SUMMARY SWEEP EFFICIENCIES The key features of summarized her! are Increase all sweep efficiencies by decreasing M Decrease M by? Lowering g;) or kay Increasing or Pater Keo Oil recovery is still limited by residual or trapped oi! saturation. 2-16 Fundamentals of Enhanced 0i1 RecoveryMODULE 2 TRAPPED OIL SATURATION OVERVIEW A residual nonwetting phase saturation is somewhat paradoxical. The nonwetting phase Mabhors! the rock surfaces and, given enough contact time, all of the nonwetting phase would be expelled from the medium. Repeated experimental evidence has shown this not to be the case. In fact, under most conditions the residual nonwetting phase saturation is as large as the residual wetting phase saturation. The residual nonwetting phase is trapped in the larger pores in "globules" that are several pore diameters in length. CAPILLARY The most common experimental observation of DESATURATION trapping in real permeable media has been that of CURVE a relationship between trapped nonwetting or wetting phase saturations and a local capillary number. We will call this relationship the capillary desaturation curve (cDC). A common definition for the local capillary number Ny. is N= (10) where u_ = displacing fluid superficial velocity b= displacing fluid viscosity 1 = interfacial tension between displacing and displaced Fluids Ny_ is dimensionless. 2-17 Fundamentals of Enhanced 0i1 RecoveryMODULE 2 TRAPPED OIL SATURATION ANALYSIS Figure 10 shows a schematic CDC curve. FIGURE 10 Typically, such curves are plots of residual (non-flowing) saturation for the nonwetting (Sywr)_and/or wetting (S,,) phases on the y-axis versus a capillary number of a“ logarithmic x-axis. The capillary number (NV) is a dimensionless ratio of viscous to local capillary “© forces, variously defined. At low N/., both Sand Sy, are roughly constant at "plateau!" ““ values neo ana Swe) At some oN, designated as the "criticat” capillary “" number, a "kNGel! in the curves occurs and the residual saturations begin to decrease. Frequently, the two COC curves are normalized by their respective plateau values. FIGURE 10 CAPILLARY DESATURATION CURVES 30 Wetting Phase 20 10 % RESIDUAL OIL OR WATER SATURATION Nonwetting Phase 0 0s 0c 10e 0 10) 10°72 101 2-18 Fundamentals of Enhanced Oil RecoveryMODULE 2 TRAPPED OIL SATURATION CONCLUSIONS Experimental data suggest the following about CDCs: 1 2-19 Wettability is quite Important. The extreme wetting phase normalized CDC curves is 2-3 factors of ten to the right of nonwetting phase COC curve, Figure 10. However, Intuition demands that the two CDC curves should approach each other at some intermediate wetting condition. Pore size distribution also important, Figure 11. The critical-total N range should increase with increasing pore size “© distribution for both wetting and nonwetting phases. The critical-total N, range for the nonwetting phase should be greater than for the wetting phase with, again, a continuous shift between wettability extremes. FIGURE 11 IMPORTANCE OF PORE SIZE DISTRIBUTION Wide Pore Size Distribution ‘arbonates ypical Sandstone 10) Assumed Nonwetting ‘% RESIDUAL OIL SATURATION 107 10% 105 104 «109102104 Nye Fundamentals of Enhanced Oil RecoveryMODULE 2 TRAPPED OIL SATURATION RELEVANCE TO EOR COCs. are important to EOR, particularly the chemical flooding methods Modules 4 through 6. Two important observations to carry forward are: > Most waterfloods are at low N,. , well upon the plateau portion of the COC. + It requires 2-4 factors of ten increase in Nj, above the waterflood value to cause —_lowered! oil saturation. The only way this can be done is through lowered IFT. 2-20 Fundamentals of Enhanced Oil RecoveryMODULE 2 REFERENCES Chang, Yih-bor, M.T. Lim, G.A. Pope, and K. Sepehrnoori, "Carbon Dioxide Flow Patterns Under Multiphase Flow, Heterogeneous Field Scale Conditions," paper SPE 22654, presented at the 1991 Annual Technical Conference and Exhibition, Dallas, TX , Oct. 6-9. Collins, R.E., Flow of Fluids through Porous Materials, PennWell Publishing Company, 1976. Craig, F.F., The Reservoir Engineering Aspects of Waterflooding, SPE Monograph, 1971. Dake, L.P., Fundamentals of Reservoir Engineering, Elsevier, 1978.\ Mayer-Gurr, A., Petroleum Engineering (Geology of Petroleum Series Volume 3) John Wiley & Sons, 1976, Muskat, M., IE Homogens ids thre Media, J.W. Edwards, Inc., 1946. Pats, M., Thermal Recovery, Society of Petroleum Engineers of AIME, Henry L. Doherty Series, Monograph, Vol 7, 1982. Timmerman, E.H., Practical Reservoir Engineering |, PennWell Publishing Company, 1982. Timmerman, E.H., Practical Reservoir Engineering Il, PennWell Publishing Company, 1982. Waggoner, J.R., J.L. Castillo, and L.W. Lake, "Simulation of EOR Processes in Stochastically Generated Permeable Media,” paper SPE 21237, presented at the 1991 SPE Symposium on Reservoir Simulation, Anaheim, CA, February 17-20 2-24 Fundamentals of Enhanced Oil Recovery revised 192MODULE 2 EXERCISE 2 PURPOSE UTILITY PROCESS CALCULATING CAPILLARY NUMBERS © To calculate typical values of ca lary number 0 To estimate typical swept-zone oi! saturations for a low interfacial tension process © To gain experience in SI units The effect of lowering the interfacial tension ina displacement may be represented by the capillary number concept. With this calculated, you will be able to estimate the degree of detrapping possible in the swept zone of a displacement. Follow the steps listed on the next page. You will need the following formulas: The steady-state median superficial velocity in a balanced 5-spot is ear Fin (w-008) where u, = superficial water velocity [=] L/t k = absolute permeability [=] 1? Ke end-point water relative permeability AP = injector-producer pressure drop [=] F/L? A= pattern area [=] L tance [=] d= injector-producer well radius [=] L, and In means natural logarithm. In the above, [=] means "has units oft’. The ten in this formula arises because the problem asks for the median velocity. Fundamentals of Enhanced 0i1 RecoveryMOOULE 2 EXERCISE 2 PROCESS (continued) STEP 1 STEP 2 STEP 3 STEP 4 STEP 5 CALCULATING CAPILLARY NUMBERS The appropriate capillary number definition is Uwby 5 Me™ In these equations and throughout the course, u means superficial or Darcy velocity and v is the interstitial or front velocity. u is the velometric flow rate divided by the area open to flow. v is the rate at which a tracer propagates in a porous medium. They are related by v = u/o where o is the porosity. You will need the following data: 2 k= 0.25 um b= 0.6 mPa-s Ke = 03 A= 0,162 km? = 15am AP = 20 MPa Tyo" 30 AN/m tance d. Calculate the injector-producer Calculate the super: the given formula. cial velocity uy using Calculate a water= 1 capillary number No. If the water-oi1 interfacial tension number were reduced to 1 wN/m, calculate the capillary number. If of! is the nonwetting phase, estimate the residual oil saturation for both cases in the swept zone from the capillary desaturation curve (Figure 10, p.2-17). Fundamentals of Enhanced Oi! RecoveryMODULE 2 EXERCISE 3 ANALYZING FACTORS WHICH AFFECT OIL RECOVERY PURPOSE UTILITY PROCESS 9 To investigate aspects of of] recovery efficiency not explicitly treated in the lectures To develop a qualitative understanding of the sensitivity of several phenomena to sweep efficiencies and oil trapping © To summarize oi! recovery concepts OR rests on understanding basic concepts of displacements in permeable media. Many times a qualitative understanding of the effects of various factors is as important as being able to represent them quantitatively. Fill in the table below with "strong", "moderate", or Nglight! to indicate the sensitivity of the quantities in the left column to those across the top. Although the exercise does not ask for jit, you should be able to substantiate your answers. QUANTITY Sweep Efficiencies Residual Oi! Areal | Vertical | Displacement Saturation Throughput Mobility Ratio Gravity Capillary Forces Heterogeneity Relative Perms Well Pattern Spacing 2-24 Fundamentals of Enhanced Oi! RecoveryMODULE 3 UNDERSTANDING PHASE BEHAVIOR With the exception of polymer Flooding, all of EOR relies on phase behavior to define, classify, and even design. Phase behavior, in this course, Is the pictorial representation of the number and type of equilibrium phases at a given intensive state of a fluid system. This module reviews those qualitative aspects of phase behavior that will be useful in the remainder of the course. ~ OBJECTIVES: During this module you will: 1. Review pure component phase behavior 2. Review mixture phase behavior 3. Construct @ pressure-composition diagram 4. Construct @ ternary diagram + Use a ternary diagram { Ilustrate representative salinities OUTLINE: OVERVIEW PRESSURE-TEMPERATURE DIAGRAMS PRESSURE-COMPOSITION DIAGRAMS TERNARY DIAGRAMS REPRESENTATIVE SALINITIES SUMMARY © 00000 ACTIVITIES: During this module, you will read the reference material, listen to the presentation and discussion, and work two exercises. Exercise 4: Sketching a Pressure-Composition Diagram Exercise 5: Using a Ternary Diagram MATERIALS: Video Tape Module 3 Workbook Pages 3-1 to 3-26 Calculator Linear Graph Paper Ruler Tine You can expect to take approximately 95 minutes to complete all of the activities in this module in addition to the reading. 45 minutes Exercises: 40 minutes Tape Tim Fundamentals of Enhanced Oi] RecoveryMODULE 3 OVERVIEW IMPORTANCE The phase behavior of crude oil, water, and EOR OF PHASE fluids is a common base for understanding the BEHAVIOR displacement mechanisms of £0R processes. Such behavior includes the two- and three-phase behavior ‘of surfactant-brine-oi! systems, the two or more phases formed in crude ofl- miscible solvent systems, and the gas-oil-brine phases of steam flooding. Because of its importance, we devote an entire section to the more Important qualitative aspects of phase behavior. Complete treatments can be found in a variety of references in the literature (Burcik, 1957; Francis, 1963; McCain, 19733 Schneider, 1970). DEFINITIONS In all discussions of phase behavior it is of paramount importance to understand the difference between a component and a phase. a homogenous region of matter. —'"Homogenous" means that it is possible to move from any point in the region to any other without detecting a discontinuous change in a property. If such a change is observed, we have crossed an interface, and the system consists of more than one phase. The three types of phases are gas, liquid, and’ solid. Component: any identifiable chemical entity. This definition is broad enough to distinguish among all types ‘of chemical isomers, or even among chemical species that are different only by the substitution of a radioactively-tagged elegent. Examples are: H,0, CH,» Teghee tase Waly. Gefhy and Ogee atural? aysteds cotts’n many components, and we aré commonly forced to combine several components into "pseudo-components" to simplify phase behavior representation and subsequent calculations. Fundamentals of Enhanced Oil RecoveryMODULE 3 PRESSURE-TEMPERATURE DIAGRAMS PURE COMPONENT Figure 1 shows 2 schematic P-T plot for a pure PHASE component in thermodynamic equilibrium. “The lines BEHAVIOR on the diagram represent temperatures and pressures at which phase transitions occur, and, therefore, separate the diagram into regions in which the system is single phase. Specifically the phase boundary separating the solid and liquid phases is the fusion or melting curve, that between the solid and gas phases is the sublimation curve, and that between the liquid and vapor phases is the vapor pressure curve. Based on our earlier definition of a phase, we expect @ discontinuous change in system properties when a phase boundary is crossed. FIGURE 1 PURE COMPONENT P-T DIAGRAM SOLID] LIQUID FLUID Zz P Zz e CRITICAL POINT 6 VAP a PRESS' z uN ‘BUBBLE/DEW POINT CURVE TRIPLE POINT GAS SUBLIMATION LINE It is possible for a fluid ina particular phase to momentarily exist at a P-T coordinate corresponding to another phase. This condition is not permanent, however, as the material would eventually revert to the appropriate stable equilibrium state. 33 Fundamentals of Enhanced Oi! RecoveryMODULE 3 PRESSURE-TEMPERATURE DIAGRAMS TRIPLE POINT Three phases can coexist at only a single point P-T space. This single point, the triple point, is shown on Figure 1 as the point where the three phase boundaries intersect. For pure components, no more than three phases can form at any temperature and pressure. CRITICAL POINT Of more interest to us Is the critical point at the termination of the vapor pressure curve. The coordinates of the critical point on a P-T plot are the critical temperature and critical pressure, respectively. The critical pressure is the pressure above which a liquid cannot be vaporized regardless of the temperature. The definition of the critical temperature is the temperature above which a gas cannot be condensed regardless of the pressure. The critical point is the point where gas and liquid are identical. Since the region above the critical point is neither clearly a liquid nor a gas, it i sometimes called the supercritical fluid. QUALITATIVELY The behavior shown in Figure 1 for a pure CORRECT component is qualitatively correct though with less detail than what can be observed. There can exist, in fact, more than one triple point where solid-solid-liquid equilibria is’ observed (water is a familiar example of a pure component that has, this behavior). Such nuances are not our concern. Here we emphasize gas- and liquid-liquid equilibria. In fact, in further discussions of phase behavior we ignore triple points and solid phase equilibria. Even with these omitted, the P-T diagrams in this module are only qualitatively correct since the critical point and the vapor pressure curve vary greatly among components. See Figure 2 for quantitative comparisons. 34 Fundamentals of Enhanced Oi RecoveryMODULE 3 PRESSURE-TEMPERATURE DIAGRAMS FIGURE 2 VAPOR PRESSURE OF PURE SUBSTANCES PRESSURE (MPa) i asl, -200 100 0 100 200300 TEMPERATURE (°C) Fundamentals of Enhanced 011 RecoveryMODULE 3 PRESSURE~TEMPERATURE DIAGRAMS PHASE BEHAVIOR Since the purpose of EOR is to recover crude OF MIXTURES oil, an unrefined product, we will rarely deal with the phase behavior of pure components except as an aid to understanding mixtures. We use this and the next section to compare the phase behavior of mixtures to pure components and to introduce two pictorial representations of mixture phase behavior that are common in EOR literature--the pressure composition (Pez) and ternary diagrams. TWwO-PHASE For a multicomponent mixture, two (or more) COEXISTENCE phases can coexist in a planer region in P-T space. Compared to the single component case, where two phases coexist only along a line in P+T space, for mixtures two phases are present ina region or envelope In P-T space, Figure 3. FIGURE 3 HYDROCARBON MIXTURES (CONSTANT COMPOSITION) uquio FLUID -ERICONDENBAR. |ECRICONDENTHERM 3-6 Fundamentals of Enhanced Oi! RecoveryMODULE 3 PRESSURE-TEMPERATURE DIAGRAMS CONSTANT Consider In conjunction with Figure 3 a change in COMPOSITION Pressure at constant temperature. The phase EXPANSION envelope is fixed for constant overall composition. Since the indicated change is usually brought about by changing the volume of a pressure cell at constant composition and temperature, the process is a constant composition expansion. BUBBLE POINTS At the highest pressure, the material in the cell is a single liquid phase. At a certain pressure, we begin to see a small amount of vapor phase formed. The upper boundary of the phase envelope passing through this point is the bubble point curve, and the y-coordinate at this point is the bubble point pressure at the fixed temperature. When the pressure falls again, successively more gas is formed as the liquid vaporizes. Note that this vaporization takes place over a finite pressure range in contrast to the behavior of a pure component. If we were to continue the constant composition expansion to pressure lower than Pg, we would eventually reach a pressure where the liquid phase would? disappear, appearing only as drops in the cell just before this point. DEW POINTS The pressure at which the liquid vanishes is the dew_point pressure at the fixed temperature, and the lower boundary of the phase envelope is the dew point curve. For a pure component, Figure 1, the dew and bubble point curves coincide. Quality lines exist, within the two-phase envelope, which indicate constant relative amounts of liquid and vapor. The composition of the liquid and gas phases is different at each point within the envelope, and both change continuously as the pressure decreases. 7 Fundamentals of Enhanced Oi! RecoveryMODULE 3 PRESSURE-TEMPERATURE DIAGRAMS CRITICAL POINT Phase compositions are not shown on the P-T plot. FOR MIXTURES We do know, however, that the liquid and gas phases are saturated (can dissolve no more of the other phase) with respect to each other in the two-phase envelope. Hence, at any T and P within the region, the liquid phase is at its bubble point and the gas phase at its dew point. The quality lines converge to a common point at the critical point of the mixture, though this point does not, in general, occur at extreme values of the temperature and pressure on the phase envelope boundary. The maximum pressure on the phase envelope boundary is the cricondenbar, the pressure above which a liquid cannot vaporize. The maximum temperature on the phase envelope is the gricondentherm, the temperature above which a gas cannot be ‘condensed. These definitions are the same as for the critical point in pure component systems. Hence, the best definition of the critical point for mixtures is the temperature and pressure at which the two phases become identical. 3-8 Fundamentals of Enhanced Oi! RecoveryMODULE 3 PRESSURE-TEMPERATURE DIAGRAMS CHANGES IN Since €0R processes are highly dependent on OVERALL composition, the behavior of the P-T envelope as COMPOSITION the overall composition of the mixture changes is highly important. Consider the dilution of a crude of] M, with a more volatile pure component A as shown in Figure 4. As’ the overall mole fraction of A increases, the phase envelope migrates toward the vertical axis, increasing the size of the single-phase gas region. Simultaneously, the phase envelope shrinks as it approaches the vapor pressure curve of the pure component A. There are, of course, an infinite number of mixtures (Figure 4 shows only three) of the crude oi] with component A. Each mixture has its respective critical point in P=T space, which also migrates to the critical point of the pure component on a critical locus. The overall composition of a mixture at a critical the critical mixture at that temperature and pressure. FIGURE 4 HYDROCARBON MIXTURES (VARIABLE COMPOSITION) Schematic dilution of a crude oil by a more volatile pure substance INCREASING ‘MOLE FRACTION A 9 Con, Pg (cRUE Fundamentals of Enhanced Oi! RecoveryMODULE 3 PRESSURE~COMPOSITION DIAGRAMS Paz PLOT In order to show composition information directly, let us show the phase behavior of the dilution in Figure 4 ona plot of mole fraction of component A (z,) versus pressure at fixed temperature. Such @ plot is a” pressure composition plot (Pz). The P=z plot for the sequence of ‘tures in Figure 4 is on Figure 5. Since the P-T diagram of Figure 4 shows only three mixtures, and does not show quality lines, we can only represent phase envelope boundaries at 2 relatively few points on Figure 5. FIGURE 5 PRESSURE-COMPOSITION PLOT FOR THE DILUTION IN FIGURE 4 Ps MOLE FRACTION A Fundamentals of Enhanced Oi! RecoveryMODULE 3 PRESSURE-COMPOSITION DIAGRAMS ANALYS 1S If we start at some high pressure on Figure 4 and FIGURES 4,5 follow a line of constant temperature as pressure is reduced, we encounter a dew point curve for mixture M, at pressure Pe. Since this mixture Is rich in component A,! this point plots ° nearest the right vertical axis on Figure 5 at the pressure coordinate Py. Continuing down the constant temperature line, at Ps the critical point for mixture M, is encountered (mixture M, is” the critical composition at this” temperature and pressure). But, this point is also a second dew point for mixture M,. Hence, Ps plots at the same vertical coordinate for both ‘mixtures on "Figure 5, but with different horizontal coordinates. At Py there is @ bubble point for mixture My and a dew point’ for Mj. These points again define the > corresponding phase boundaries of the P-z plot in Figure 5. The process Continues to successively lower pressures in the same manner. Each pressure below the critical is simultaneously a bubble point and 3 dew point pressure for mixtures of different overall compositions. The pressures P, and P, are.the bubble and dew point pressures of the undiluted” crude | oil. The two-phase envelope in Figure 5 does not intersect the right vertical axis since the fixed temperature is above the critical temperature of the pure component A. We have sketched in the closure of the two-phase envelope as well as a few quality lines. You should recall that the entire P-z diagram is at constant temperature. Thus, we cannot represent the phase dehavior at other temperatures unless we show several diagrams. More importantly, the compostion plotted on the horizontal axis of the P-z plot is the overall composition, not either of the phase compositions. Thus, horizontal lines do not connect equilibrium mixtures. Such ie lines do exist, but are, in general, oriented on a horizontal Tine in a hyperspace whose coordinates are the phase compositions. For binary mixtures, however, the tie lines are in the plane of the Pez plot, and the critical point is necessarily located at the top of the two-phase region. Finally, though Figure 5 is schematic, it bears qualitative similarity to an actual P-z diagram in Figure 6. 3 Fundamentals of Enhanced O11 RecoveryMODULE 3 PRESSURE-COMPOSITION DIAGRAMS PRESSURE (psia) FIGURE 6 ACTUAL P=z DIAGRAM (from Simon et al., 1978, courtesy SPE) 5000 Bubble Point Pressure ___Dew Point Region 4000) 3000 Critical Point Volume % Liquid | 2000 1000 (OF 2040 res CO Oe 00) MOL % CO; IN RESERVOIR A Fundamentals of Enhanced Oil RecoveryMODULE 3 TERNARY DIAGRAMS INTRODUCTION On a P=z plot we sacrifice a degree of freedom, temperature, to obtain compositional information. P-z diagrams, however, can show only the composition of one component, and this representation is many times insufficient for the multitude of compositions that can form in an EOR displacement. A plot that represents more composition information is the ternary diagram. DESCRIPTION Imagine a mixture, at fixed temperature and Pressure, consisting of three components 1, 2, and 3. The components may be pure components, or, more commonly in EOR, they are pseudo-components, themselves consisting of several components. The composition of the mixture will be a point on a plot of the mole fraction of component 3 versus that of component 2. In fact, this entire two-dimensional space is made up of points which represent the component concentrations of all possible mixtures. We need only plot the concentrations of two of the components, however, since the concentration of the third may always be obtained by subtracting the sum of the mole fractions of 2 and 3 from one. This fact means that all possible compositions will plot into a right triangle whose hypotenuse is a line from the 1.0 on the y-axis to 1.0 on the x-axis. Though ternary diagrams are on occasion shown this way (see Figure 12), they are most commonly plotted so that the right triangle is shifted to an equilateral triangle as in Figure 7. 3613 Fundamentals of Enhanced Oi! RecoveryMODULE 3 TERNARY DIAGRAMS FIGURE 7 TERNARY DIAGRAM O PERCENT 3 ANALYSIS AI possible ternary compositions fall on the interior of the equilateral triangle. The boundaries of the triangle represent binary mixtures (the component at the apex opposite to the particular side is absent), and the apexes represent pure components. Thus, point M, on Figure 7 isa mixture having 20, 50, and 308 1, 2, and 3, ‘respectively. Point My is @ binary mixture of 70% 1 and 303 3." Point M, is 100% 2. Representing the compositions in this manner is possfble for any concentration variable (mole fraction, volume fraction, mass fraction) that sums to a constant. 3-14 Fundamentals of Enhanced Oil RecoveryMODULE 3 TERNARY DIAGRAMS SIMULTANEOUS Ternary diagrams ere extremely useful tools in REPRESENTATION EOR because they can simultaneously represent phase, end overall compositions, and relative amounts. To demonstrate this, we show the correspondence of the P-T diagram to the ternary diagram in Figures 8 and 9 in the same fashion as was done for the P-z diagram in Figures 4 and 6. Here we consider a ternary system consisting of components 1, 2, and 3. Consider the dilution of mixtures having constant ratios of components 2 and 3 by component 1. Each dilution represents a line corresponding to a fixed ratio on the ternary of Figure 9. We want to follow the formation and disappearance of phases on the ternary diagram at the fixed temperature and pressure indicated by the box on Figure 8. == For the dilution of component 3 by component 1, the reference temperature and pressure is above the critical locus in the upper left panel. This dilution does not encounter a phase change. The C,-C, binary dilution (upper right panel), does encounter phase! 7 changes, and in fact, the reference temperature and pressure is a bubble point for a mixture of 25% C, and a dew point for a mixture of 85% C,. These phase | transitions are shown on the C.-C, axis of the! ternary. =+ The dilution shown in the middle-left panel of Figure 7 shows phase transitions at 82 and 21%, respectively, which are also plotted on the ternary. For the dilution of the 1:3 mixture the critical locus passes through the fixed temperature and pressure, and this composition, 24%C,, is the critical composition of the ternary mixture. | This composition is indicated on the ternary diagram of Figure 9 as a plait point after the more common designation of the critical mixture in liquid-liquid phase equilibria. s- Note that at the fixed temperature and pressure, there can exist a second phase transition-- a dew point at 67% C, =- at the same temperature and pressure. After making several’ dilution passes through the ternary diagram, one can connect the points where there are phase transitions. This defines a closed curve in Figure 9, the binodal curve, which separates regions of one- and two-phase behavior. Two phases exist within the region enclosed by the binodal curve. Outside this region all components are mutually miscible in a single phase. 3-15 Fundamentals of Enhanced Oi! RecoveryMODULE 3 TERNARY DIAGRAMS FIGURE 8 SCHEMATIC EVOLUTION OF P-T DIAGRAM IN THREE COMPONENT SYSTEMS DILUTION WITH PURE COMPONENTS DILU 3-16 cy Bubbie Pt Dew rt. < Cheve Curve 1 ea Y Pl fh T T TION WITH BINARY MIXTURES. Gn Fundamentals of Enhanced 011 RecoveryMODULE 3 TERNARY DIAGRAMS FIGURE 9 SCHEMATIC TERNARY DIAGRAM OF DILUTION ON FIGURE 8 susste POINT i Cr BINARY DILUTION Fundamentals of Enhanced RecoveryMODULE 3 TERNARY DIAGRAMS USEFUL FEATURE One very useful-- and potentially confusing: feature of ternary diagrams is that it is possible to represent the composition of the phases as well as the overall composition on the same diagram. Consider an overall composition on the inside of the binodal curve as shown in Figure 10. C= Ci, 8, + C49 S, io) uW 2 where C,, is the concentration of component i in phase J, and $, ‘Jis the relative amount of phase j. Sy convention, we take / phase 1 to be the C,-rich phase and 2 to be the Cprlean phase. Since Ss; + $, 21, we can eliminate $, from two of the “equations in '(1) 2 to give 23 7 S31 . Pri eo a ANALYSIS This equation says that a line through the EQUATION 2 composition of phase 1 and the overall composition has the same slope as a line passing through the composition of phase 2 and the overall composition. Both lines, therefore, are merely segments of the same straight line which passes through both phase compositions and the overall composition. The intersection of these tie lines with the binodal curve gives the phase compositions as shown on Figure 10. Furthermore, Equation (2) implies, by @ similar triangle argunent, that the length of the line segment between and C,, ‘divided the length of the segment between C,» and C, the ‘relative amount §,. This, of course, is the |* well ‘Rnown inverse lever rule which” can also be derived for S, as well. The tie lines must vanish as the plait point is approached since all phase compositions are equal at this point. There are, of course, no tie lines in the single phase region. By holding constant and allowing C, to vary, we can construct s. qfality lines, as indicated in! Figure 10, which must also converge to the plait point. 3-18, Fundamentals of Enhanced Oi! RecoveryMODULE 3 TERNARY DIAGRAMS FIGURE 10 TWO-PHASE TERNARY EQUILIBRIA 3-RICH PHASE ‘COMPOSITION OVERALL’ COMPOSITION BINODAL CURVE S-LEAN PHASE : COMPOSITION Fundamentals of Enhanced Oi] RecoveryMODULE 3 TERNARY DIAGRAMS THREE-PHASE For regions in the ternary diagram where three REGIONS phases form, the state of the system is entirely determined. It follows that three-phase regions are represented on ternary diagrams as smaller sub-triangles bedded within the larger ternary triangle, Figure 11, The phase compositions of any overall composition within the sub-triangle are given by the apexes or invariant points of the sub-triangle, there being no tie lines in three-phase regions. The relative amounts of the three phases present are given by the graphical construction indicated on Figure 11. A point on @ non-apex side of the sub-triangle may be regarded as being simultaneously in the three-phase region or in a two-phase region. Thus, the sub-triangle must always be bounded on a non-apex side by a two-phase region for which the side of the sub-triangle is a tie line, The adjoining two-phase regions can be quite small, however. By the same argument, the apexes of the sub-triangle must adjoin a single-phase region. FIGURE 11 THREE-PHASE TERNARY DIAGRAM 3 3-20 Fundamentals of Enhanced 011 RecoveryMODULE 3 REPRESENTATIVE SALINITIES EFFECTS OF For liquid. systems (e.g, micellar-polymer), SALINITY salinity affects phase behavior more than pressure. "Salinity" is the total dissolved solids (TDS) content of the aqueous phase. Typical values are shown in Figure 12. Virtually all chemical flooding properties depend on the concentrations of specific ions rather than salinity only. It is particularly Important to separately monitor the aqueous phase's total divalent cation content (hardness) as the latter are usually more critical to chemical flood properties than the same TDS concentration. Figure 12 also shows typical brine hardness. Brine salinity and hardness also affect many polymer properties. FIGURE 12 SALINITIES FROM REPRESENTATIVE OILFIELD BRINES (from Gash et al., 1981, courtesy SPE) LABORATORY TEST BRINES AREAS 4 Texas © Gulf Coast © Rocky Mountain 10,000 HARDNESS (mg/l, Cat++mgt+) 3 3 8 10,000 100,000 TOTAL DISSOLVED SOLIDS (mg/1) Fundamentals of Enhanced Oi! RecoveryMODULE 3 UNDERSTANDING PHASE BEHAVIOR SUMMARY We touch on only the bare essentials of phase behavior in this module. If you're interested in more, see the references. The important concepts that you should carry forward to the next modules aret Critical p Critical temperature and pressure P-z diagram (Constant T) Ternary diagram (Constant T and P) How the above change with T and/or P = Salinity and hardness. Fundamentals of Enhanced 0 RecoveryMODULE 3 REFERENCES Burcik, E.J., Properties of Petroleum Reservoir Fluids, John Wiley & Sons, Inc., 1957. Francis, Alfred W., Liquid-Liquid Equilibriums, Interscience Be sO ore ee a i Gash, 8.H., Griffith, T.D., and Chan, A.F., "Phase Behavior Effects on the Oil Displacement Mechanisms of Broad Equivalent Weight Surfactant Systems," SPE 9812, presented at the Second Joint Society of Petroleum Engineers/Department of Energy Symposium fon Enhanced Oil Recovery, Tulsa, Oklahoma, April 5-8, 1981. McCain, W.0., The Properties of Petroleun Fluids, Petroleum Publishing Co., 1973. Schneider, G.M., Phase Equilibria in Fluid Mixtures at High Pressures, Advances in Chemical Physics, edited by I. Prigogine| and Stuart A. Rice, Volume 17, Interscience Publishers, New York, 1970. Simon, Ralph, Rosman, A., and Zana Properties of C0,-Reservoir (February 1978) 20-36. Erdine, "Phase Behavior Systems," SPEJ, 18(1), SPE Reprint Series No. 15 Phase Behavior, 1981 edition, published by Society of Petroleum Engineers. 3-23 Fundamentals of Enhanced Oi! RecoveryMODULE 3 EXERCISE 4 SKETCHING A PRESSURE-COMPOSITION DIAGRAM PURPOSE 0 To define the —relation pressure-temperature and pressure-compos/tion diagram 0 To determine the effect of temperature pressure-composition diagram o To justify a qualitative trend miscibility pressure and temperature UTILITY Visualization is one of the most effective ways to teach concepts. This exercise is intended to force a degree of visualization that will pressure-temperature and —_pressure=composition diagrams. PROCESS Follow both steps: as indicated, Make your diagrams as clear as possible, and put both diagrams on the same figure. Some interpretation is required on the quality lines. STEP 1 Figure 13, on page 3-25, shows the hypothetical change in’ the pressure-temperature envelope of a crude ofl as it Is diluted with a more volatile component (C0. in this case). pressure-composifion diagrams at 340 K (152 F) and 356K (181 F). Include as many quality lines as possible. STEP 2 The pressure required to attain increases with the maximum two-phase pressure on a pressure-diagram. Sased on your plot, whether you expect that the miscibi ity pressure will increase or decrease with temperature. Fundamentals of Enhanced Oi! RecoveryMODULE 3 EXERCISE 4 SKETCHING A PRESSURE-COMPOSITION DIAGRAM FIGURE 13 CHANGE IN CRUDE OIL P-T WITH DILUTION BY CO, 3500 60 Mole % CO2 40 Mole %CO2 3000 BS 2500 20 Mole %CO2 = Z 2000 % 1500 Sude = & 1000 500 60 80 100 120 140 160 180 200 220 240 TEMPERATURE (°F) Fundamentals of Enhanced Oil RecoveryMODULE 3 EXERCISE 5 PURPOSE UTILITY PROCESS USING A TERNARY DIAGRAM © To-gain experience in reading ternary diagrams 0 To define the use of the inverse lever rule Solvent flooding classifications, and the entire basis for designing a micellar-polymer flood, rests on ternary representations of phase equilibria. By completing this exercise, you will have a better understanding of how these tools are used. This is a one-step exercise which involves repeated reading of points from a ternary diagram and execution of the inverse lever rule. Use your ruler to apply the lever rule. The results should be put in tabular form. Consider the three-component system represented on Figure 11 (page 3-20). Calculate the composition(s) and relative amounts present at overall compositions A-E, Note that you must sketch on grid lines in Figure 11. Fundamentals of Enhanced Oi! RecoveryMODULE 4 DEFINING POLYMER FLOODING Polymer flooding recovers oi! by improving displacement and volumetric sweep efficiencies through lowered water mobility. In this module, we see how polymer lowers water mobility, and to what extent this can produce incremental ofl. OBJECTIVES: During this module you will: 1. List uses of polymer in of! production 2. List popular polymer types and give the chemical origin of their properties 3. Illustrate the importance of shear rate on viscosity 4. Summarize mobility reduction with polymers 5. Define inaccesible pore volume and retention 6. Summarize polymer degradation mechanisms 7. Compare properties of polyacrylamides and polysaccharides 8. Give representative polymer flood performances 9. Describe favorable conditions for polymer use USES/TYPES POLYMER CHEMISTRY POLYMER PROPERTIES FIELD RESULTS FAVORABLE CONDITIONS eo 0000 ACTIVITIES: During this module, you will read the reference material, listen to the presentation and debriefing, and work an exercise. Exercise 6: Calculating Shear Rates MATERIALS: Video Tape Module 4 Workbook Pages i=1 to 4-28 Calculator TIME: You can expect to take approximately 70 minutes to complete all of the activities in this module in addition to the reading. Tape Time: 50 minutes Exercise: 20 minutes Fundamentals of Enhanced Oi! RecoveryMODULE 4 USES/TYPES THREE USES Polymers have been used in oi! produc wayst nin three s-- as near-well treatments to improve the performance of water injectors or high watercut producers by blocking off high conductivity zones --- as agents which may be cross-linked in situ to plug high conductivity zones at depth in the reservoir (Needham et al., 1974). These processes require that polymer be injected with an inorganic metal cation which will cross-link subsequently injected polymer molecules with ones already bound to solid surfaces. s-- as agents to lower the displacing fluid mobility or mobility ratio. You will recall from Module 2 that lowering M increases all displacement efficiencies. The first mode is not truly a chemical flooding process since the actual oil-displacing agent is not the polymer. The overwhelming majority of polymer EOR projects have been in the third mode which is the one emphasized here. TYPICAL POLYMER Figure 1 shows a schematic of @ typical polymer FLOOD INJECTION flood injection sequence: 1. a preflush usually consisting of a low salinity brine 2. an oil "bank" 3. the polymer solution itself 4, a fresh water buffer to protect the polymer solution from backside dilution 5. chase or drive water Many times the fresh water buffer contains polymer in decreasing amounts (a grading or taper) to lessen the unfavorable mobility ratio between the chase water and the polymer solution. Because of the driving nature of the process, polymer floods are always done through separate sets of injection and production wells. Fundamentals of Enhanced 01! RecoveryMODULE & USES/TYPES FIGURE 1 TYPICAL POLYMER FLOOD INJECTION SEQUENCE (Drawing by Joe Lindley, U.S. Department of Energy, Bartlesville, Oklahoma) CHEMICAL FLOODING (Polymer) “Te method shown requires 2 pets ic condton te resanos, he recon of a poymer Sree eatay cores tse Gameng ara a Sten M0 (to 1 ve Feber sakson ord fesung of bark toproaicion weds. SR Tike nag noe re (Sgn SP owe SS SRS SSS = bs ESS Pie SEES SS Fundamentals of Enhanced Oil RecoveryMODULE 4 USES/TYPES CHEMICAL FLOODING Mis lowered in a polymer flood by injecting PROPERTIES water which contains a high molecular weight, water-soluble polymer. Since the water is usually a dilution of an oilfield brine, interactions with salinity are important, particularly for certain classes of polymers. Salinity" here is the total dissolved solids (TDS) content of the aqueous phase. Typical values are shown in Module 3. Virtually all chemical flooding properties depend on the concentrations of specific ions rather than salinity only. It is particularly important to separately monitor the aqueous phase's total divalent cation content (hardness) as the latter are usually more critical to chemical flood properties than the same TDS concentration. Because of the high molecular weight ( 1 to 3 ymillion is typical) only a small amount (typically about 500 g/m’) of polymer will bring about a substantial increase in water viscosity. Furthermore, several types of polymers lower mobility by lowering water relative permeability in addition to increasing the water viscosity. How polymer lowers mobility, and the interactions with salinity may be qualitatively illustrated with some discussion of polymer chemistry. dod Fundamentals of Enhanced 0i1 RecoveryMODULE 4 USES/TYPES POLYMER Several polymers have been considered for polymer TYPES Flooding: Xanthan gum = hydrolyzed polyacrylamide (HPAM) = copolymers of acrylic acid and acrylamide = copolymers of acrylamide and 2-acrylamide-2 methyl! propane sulfonate (AM/AMPS) = hydroxyethylcel lulose (HEC) = carboxymethyl hydroxyethycel lulose (CHHEC) = polyacrylamide (PAK) = polyacrylic acid = glucan = dextran polyethyleneoxide (PEO) = polyvinylalcoho! Only the first three have actually been field tested. However, the variety of entries in this partial listing emphasizes that there are many potentially suitable chemicals, some of which may prove to be more effective than those currently used. Nevertheless, virtually all of the commercially attractive polymers fall into two generic classes: polyacrylamides and polysaccharides (biopolymer or Xanthan gum), The remainder of this discussion deals with these exclusively. Representative molecular structures fare in Figures 2 and 3 from Willhite and Dominguez (1977). "hes Fundamentals of Enhanced Oil RecoveryMODULE 5 EXPLORING MICELLAR=POLYMER FLOODING Micellar-polymer flooding is widely believed to be the most complex EOR process. Certainly, this is true from the point of view of the choices involved in its design. The emphasis of this module is to present enough of the fundamentals of micellar-polymer flooding that you will understand the basis for design and reasons for how it performs. OBJECTIVES: During this module you will: 1. Recognize the terminologies 2. Identify process variations 3. Define the chemical bases for surfactants 4. Identify types of phase behavior 5. Describe the importance of lowering interfacial tension 6. Define and use optimal salinity 7. Identify the causes of retention 8. Examine how a core flood performs 9. Analyze how field tests have performed OUTLINE: PROCESS DEFINITION SURFACTANTS PHASE BEHAVIOR INTERFACIAL TENSION SLUG FORMULATION SURFACTANT RETENTION LAB/FIELD RESULTS e 000000 ACTIVITIES: After reading the material in the workbook and listening to the instructor's presentation and discussion with on-screen students, you will work two exercises. Exercise Exercise Estimating Optimal Conditions Defining the Importance of Retention MATERIAL: Video Tape Module 5 Workbook Pages 5-1 to 5-43 Calculator Semi-log (3-4 cycles) graph paper TIME: You can expect to take approximately 130 minutes to to complete all of the activities in this module in addition to the reading. Tape Time: 76 minutes Exercises: 55 minutes Fundamentals of Enhanced Oil RecoveryMODULE 5. PROCESS DEFINITION INTRODUCTION From the earliest days it was recognized that capillary forces caused large quantities of of! to be left behind in well-swept zones of waterflooded oi! reservoirs. Capillary forces are the consequence of the interfacial tension (IFT) between the oi! and water phases which resists externally applied viscous forces and causes the Injected and banked-up connate waters to locally bypass ofl, “By the same token, early efforts on enhanced of! recovery (EOR) have striven to displace this of! by decreasing the oil-water IFT. Though many techniques have been proposed and field tested, the predominant EOR technique for achieving low IFTs is micellar-polymer (MP) flooding. Today the commercial realization of HP flooding is largely in the future. However, the intense research interest in the past 30 years has brought about several technical advances in the Understanding of the process. The purpose of this module is to describe many of these technical advances. TERMINOLOGY MP flooding has appeared the technical literature under many names: detergent, surfactant, lowetension, soluble of!, microemulsion, and chemical flooding. We are using the term micellar-polymer flooding (MP) since it is the least ambiguous (chemical flooding, for example, could describe all non-thermal EOR processes), and most comprehensive (no other name implies the polymer component). There are also several generic names which imply a specific sequence and type of injected fluids as well as the specific nature of the oil-recovering MP slug itself. Though there are differences among generic processes, this module emphasizes the similarities since the common aspects are more numerous and important. MP FLOODING MP flooding is any process which injects a surface-active agent (a surfactant) to bring about improved oi! recovery. This definition eliminates alkaline flooding where the surfactant is generated in situ, and other EOR processes where lowering the capillary forces is not the primary means of oil recovery. Successfully recovering oi! in this manner is the task of an elaborate formulation and design procedure which is undergoing almost daily revision as more becomes known. Fundamentals of Enhanced 0i1 RecoveryMODULE 5. PROCESS DEFINITION FIGURE 1 TYPICAL MICELLAR-POLYMER FLOOD Preflush FIGURE 1 An idealized version of an MP flooding sequence ANALYSIS is in Figure 1. The process is invariably applied to tertiary floods (those producing at high water-oil ratios during waterfloods), and is always implemented in the drive mode (not cyclic nor huff'n puff). The entire process consists of: Chase water Mobility Buffer Producer Injector —— > Preflush A volume of brine whose purpose is to change (usually lower) the salinity of the resident brine so that mixing with the surfactant will not cause the loss of interfacial activity. Preflushes have ranged from from 0 to 100% of the Floodable pore volume (V,) of a reservoir. In some processes a sacrificial Pagent is added to lessen the subsequent surfactant retention. MP Slug ‘This volume, ranging from 5 to 20% V, in field applications, contains the main oil-recovEring agent, the primary surfactant, in concentrations ranging from 1 to 20 volume percent. Several other chemicals, Figure 1, are usually necessary to meet the criteria for efficient oi! recovery. The exact purpose of these chemicals is discussed in more detail later. This slug lowers IFT and recovers residual oil. Because of this, the target oi! for an MP flood (the residual oi!) is different from that of a polymer flood--the remaining oil in excess of the residual oil. Fundamentals of Enhanced Oi! RecoveryMODULE 5 PROCESS DEFINITION Mobility Buffer This fluid is a dilute solution of a water-soluble polymer whose purpose is to drive the MP slug and banked-up fluids to the production wells. Much of polymer flooding technology carries over to designing and implementing the mobility buffer. Figure 2 compares the various types of MP slugs. These range from aqueous slugs A (surfactant dissolved in water) to oleic slugs $ (surfactant dissolved in oil). Practical use has seen all variations in between these extremes, | and M. FIGURE 2 COMPARING HP SLUGS SURFACTANT ‘SINGLE-PHASE MICROEMULSION at ‘\ AQUEOUS SOLUBLE SURFACTANT ea 7 oll A ee \ MULTIPHASE WATER s ol IMMISCIBLE MICROEMULSION 5-4 Fundamentals of Enhanced 011 RecoveryMODULE 5 PROCESS DEFINITION ity Buffer Chase Water This is a volume of brine containing a concentration of polymer grading between that. of the mobility buffer at the front and zero at the back. The gradual concentration decrease mitigates the effect of the adverse mobility ratio between the mobility buffer and chase water. The purpose of the chase water is simply to reduce the expense of continually injecting polymer. If the taper and mobility buffer have been designed properly, the MP slug will be produced before it Is penetrated by the chase water. Fundamentals of Enhanced Oi] RecoveryMODULE 5 PROCESS DEFINITION MP FLOODING Generally, three objectives must be met to to SUCCESS recover ofl efficiently through micellar-polymer CRITERIA flooding (Gilliland and Conley, 1975): 1. The MP surfac interfacially act ¢ slug must be propagated in an e mode. 2. Enough surfactant must be injected so that some of it is unretained by the permeable media surfaces. The MP displacement must be designed so that the active surfactant sweeps a large portion of the reservoir ithout excessive dissipation because of dispersion, or channeling. The first of these objectives is met through the formulation step of the MP design procedure. The second two objectives are met through scale-up. Though there is considerable overlap, the formulation step consists mainly of test tube experiments and core floods, and the scale-up step of core floods and numerical simulations. Fundamentals of Enhanced Oi! RecoveryMODULE 5. PROCESS DEFINITION CAPILLARY The basic tool for illustrating how lowering DESATURATION IFT reduces residual oi! saturation is the ‘CURVE capillary desaturation curve (CDC). This was discussed in some detail in Hodule 3. The COC a plot of nonwetting or wetting phase residual saturation on the y-axis versus a dimensionless ratio of viscous to local capillary forces on a logarithmic x-axis. The ratio of viscous to local capillary forces is the capillary number Ny Nemes a For a waterflood u and g are the superficial velocity and viscosity of the displacing water, and Y is the IFT between the water and oi! phases. Of the three quantities in Equation (1) only the IFT can be changed drastically, enough to reduce S.A typical. value for causing_,good residual of! saturation °° reduction “is in the range of 10°72 mN/m, a value that can be obtained only with a surface-active material. 57 Fundamentals of Enhanced Oi] RecoveryMODULE 5 SURFACTANTS INTRODUCTION To fully understand the role of surfactants in MP flooding, we must define their physical properties, how they affect phase behavior, and how phase behavior and interfacial tension are correlated. Because of the voluminous literature on surfactant properties, this discussion is only a précis. For more on oil-recovering surfactants, see Akstinat (1981) upon which much of this discussion is based. MOLECULAR A typical surfactant monomer is composed of a STRUCTURE nonpolar portion or moiety (lypophile) and a polar (hydrophile) moiety. The entire monomer is sometimes called an amphiphile because of this dual nature. Figure 3 shows the molecular structure of two common surfactants (top two panels) and illustrates a shorthand notation for surfactant monomers: the monomer is represented by a "tadpole'’ symbol with the nonpolar moiety being the tail and the polar being the head. FIGURE 3 SURFACTANT MOLECULAR STRUCTURE SODIUM DODECYL SULFATE NAR AMAR AN, 1 ‘0-S—O" Nat b TEXAS NO. 1 SULFONATE QR RS. LN NINN, CAnca can . ¢ ~D) ° R= HYDROCARBON GROUP (non-polar) Fundamentals of Enhanced Oi! RecoveryMODULE 5 ‘SURFACTANTS FOUR CLASSES Anionics Cationics Won-ionics Amphoterics Surfactants are classified into four groups depending on their polar moieties, Table 1. These are: As required by electroneutrality, the anionic surfactant molecule is uncharged with an inorganic metal cation (usually sodium) associated with the monomer. In an aqueous solution the molecule ionizes to free cations and the anionic monomer. Anionic surfactants are the most common in MP flooding because they are good surfactants, relatively resistant to retention, stable, and can be made relatively cheaply. Surfactants whose polar moiety is positively charged are cationic surfactants. In this case, the surfactant molecule contains an inorganic anion to balance the charge. Cationic Surfactants have little use in MP flooding because they are highly adsorbed by the anionic surfaces of interstitial clays. The non-ionics are a class of surfactants that have seen extensive MP use, mainly as co-surfactants but increasingly as primary surfactants. This class of surfactant does not form ionic bonds, but when dissolved in aqueous solutions, exhibits surfactant properties simply by electronegativity contrasts among _its constituents. Non-ionics are much more tolerant of high salinities than anionics, and, as a rule, are poorer surfactants. A final class of surfactants are those which contain aspects of two or more of the previous classes. For example, an amphoteric may contain both an ai group and a nonpolar group. These surfactants have not been used in oil recovery. 5-9 Fundamentals of Enhanced Oi RecoveryMODULE 5 SURFACTANTS TABLE 1...CLASSIFICATION OF SURFACTANTS AND EXAMPLES (from Akstinat, 1982) ele UNey Ave) Cationics “Amphoterics Sulfonates, quart, Ammonium, Aminocarboxylic Alkyl, Alkyl sulfates, pyridinu acids, aryl, acyl carboxylates, imidazolinium, others acylamingo, phosphates, _piperidinium, acylaminepoly- ee. sulfononium, Bycol ethers, compounds, polyol ethers, others atkanolamides, and others POTENTIAL Note that within any one class there is @ huge VARIATIONS variety of possible surfactants. Figure 3 shows some of this variety by illustrating differences in nonpolar molecular weight (C,, _ for the sodium dodecy! sulfate -SDS- versus C,, for '* Texas No.1), polar moiety identity (sulfate versus sulfonate), and tail branching (straight chain for SDS versus two tails for Texas No. 1), all within the same class of anionic surfactants. In addition to these, there are variations in the position of the polar moiety attachment, and the number of polar moieties (monosulfonates versus disulfonates, for example). Even small variations can change surfactant properties drastically. For example, sulfates tend to be less thermally stable than sulfonates. 5-10 Fundamentals of Enhanced Oi! RecoveryMODULE 5 ‘SURFACTANTS SURFACTANTS Most MP slugs contain distributions of surfactants IN WATER and even surfactant types which further adds to the complexity of describing slug behavior. In the following, we ignore distinctions between surfactant types by simply treating the surfactant as the tadpole structure (Figure 3). If an anionic surfactant is dissolved in an aqueous solution the surfactant disassociates into a cation and @ monomer. If the surfactant concentration is then increased, the lypophilic moieties of the surfactant begin to associate among themselves to form aggregates or micelles containing several monomers each. A plot of surfactant monomer concentration versus total surfactant Concentration, Figure 4, would show a curve that begins at the origin, increases monotonically with unit slope, then levels off at the critical micelle concentration (CMC). Above the CMC, all further increases in surfactant concentration cause increases in the micelle concentration only. Since CMCs are typically quite small, the surfactant is predominantly in micelle form at nearly all practical concentrations for MP flooding. Hence, the name micellar-polymer flooding. FIGURE 4 SURFACTANTS IN WATER [MONOMERS Pets o 6 ee = _ hes 33 oun MICELLES ae en SURFACTANT MONOMER CONCENTRATION CRITICAL MICELLE '— CONCENTRATION TOTAL SURFACTANT CONCENTRATION 5-11 Fundamentals of Enhanced 0i1 RecoveryMODULE 5 SURFACTANTS SURFACTANTS When the surfactant solution contacts an oleic AT INTERFACES phase (the term oleic phase indicates that this phase can contain more than oil), the surfactant tends to accumulate at the intervening interface. | The lypophilic moiety "dissolves" in the oleic phase, and the hydrophilic in the aqueous phase. The surfactant prefers the interface over the micelle. However, only small surfactant concentrations are necessary to saturate the former. It Is clear why the dual nature of the surfactant is encouraged since the accumulation at the interface causes the IFT between the two phases to lower, The interface blurs in much the same manner as do the interfaces in vapor-liquid equilibria near a critical point. The surfactant itself and the attending conditions should be adjusted to maximize this effect. However, in doing so the solubility of the surfactant in the bulk oleic and aqueous phases is also affected. Since this solubility also impinges on the mutual solubility of brine and oil, which also affects IFTs, this discussion leads naturally to the topic of surfactant-oil-brine phase behavior. Curiously, and this is true of many micellar properties, the surfactant concentration itself plays a rather minor role in what follows compared to the temperature, brine salinity, and brine hardness. Fundamentals of Enhanced Oi! RecoveryMODULE 5 PHASE BEHAVIOR EFFECT OF MP phase behavior is strongly affected by the SALINITY salinity of the brine pseudocomponent. Consider the sequence of phase diagrams, Figures 5-7, as the brine salinity is increased. Salinity describes some measure of the electrolytic strength of the brine such as total dissolved solids. The phase behavior about to be described was originally given by Winsor (195i) and adapted to MP flooding later (Healy et al., 1976). 5-13 Fundamentals of Enhanced Oi! RecoveryMODULE 5 PHASE BEHAVIOR TYPE 11 (-) At low brine salinity, typical MP surfactant SYSTEM will exhibit good aqueous phase solubility and poor oi] phase solubility. Thus, an overall composition near the brine-oil boundary of the ternary will split into two phases: an excess oi! phase that is essentially pure oil, and a (water external) microemulsion phase that contains brine surfactant, and some solubilized oil. The solubilized oil occurs when globules of oil occupy the central core of the swollen micelles. The tie lines within the two-phase region have a negative slope. This type of phase environment is variously called a Winsor type | system, a lower phase microemulsion I! (~) system. The latter terminology is adopted here-- I! means that no more than two phases can (not necessarily will) form, and (-) means that the tie lines have negative slope, Figure 5. The plait point in such a system P, is usually located quite close to the oil apex. Any overall "composition above the binodal curve is single phase. FIGURE 5 TYPE 11(-) SYSTEM § AQUECUS a\ SWOLLEN $ MICELLE WATER EXTERNAL MICROEMUGSION, EXCESS ‘OIL COMPOSITION 5-14 Fundamentals of Enhanced 0i1 RecoveryMODULE 5 PHASE BEHAVIOR TYPE 11(+) For high brine salinities, Figure 6, electrostatic SYSTEM forces drastically decrease the surfactant's solubility in the aqueous phase. An overall composition within the two-phase region will now split into an excess brine phase and an (oi! external) microemulsion phase which contains most of the surfactant and some solubilized brine. The brine is solubilized through the formation of inverted swollen micelles, Figure 6, with brine globules at their cores. The phase environment is’ a Winsor type I! system, an upper phase microemulsion, or a type I! (+) system. The plait point, P,, is now close to the brine apex. FIGURE 6 TYPE 11 (+) SYSTEM SWOLLEN, MICELLE excess SRINE (Olt EXTERNAL MICROEMULSION, 8 0 LOvERALL COMPOSITION 5-15 Fundamentals of Enhanced Oi! RecoveryMODULE 5 PHASE BEHAVIOR TyPE 111 At salinities between those of Figures 5 and 6, SYSTEM ‘there must be a continuous change between type 11(-) and 11(+) systems. The obvious change of a counterclockwise tie line rotation and corresponding plait point migration is Incorrect. There is no salinity where the solubilities of the surfactant for the brine- and oil-rich phases are exactly equal. There is a range of salinities, however, where 2 third surfactant-rich phase is formed, Figure 7. An overall composition within the three-phase region separates into excess oi! and. brine phases as in the type I1(-) and 11 (+) environments, and into a microemulsion phase whose composition is represented by an invariant point. This environment is called a Winsor type III, @ middle phase microemulsion, or a type II! system. Above and to the right and left of the three-phase region are type II(-) and I1(+) lobes wherein two phases will form as before. In the three-phase region there are now two IFTs between the microemulsion and Oi} gg and microemulsion-water 7, FIGURE 7 TYPE 111 SYSTEM EXCESS MIDOLE PHASE BRINE MICROEMULSION OVERALL, COMPOSITION 5-16 Fundamentals of Enhanced Oi] RecoveryMODULE 5 PHASE BEHAVIOR SHIFTS IN PHASE Figure 8, a "prism diagram, shows the entire ENVIRONMENT progression of phase environments from type 1i(=) to I1(+). Over the type Ill salinity range, the invariant H point migrates from near the oi! apex to near ‘the brine apex before disappearing at a critical tie line. Equally important, as the migration takes place, the surfactant concentration in the microemulsion phase goes through a minimum where the brine-oil ratio at the invariant point becomes one. The migration of the invariant point implies essentially unlimited solubility of brine and of! in a single phase. This has generated an intense research Interest into the nature of the type Il! microemulsion. More importantly for oi! recovery, the type Ill environment is the phase environment where all IFTs are the lowest. . In much the same manner as the Ideal Gas Law approximates the behavior of real gases, Figures 5-7 are approximations to actual MP phase behavior. Several variables other than salinity can bring about the Figure 8 phase environment shifts. in general, changing any condition that enhances the surfactant's oil solubility will cause the shift from type II(-) to II(+). Some of the more important are: Decreasing temperature Increasing surfactant molecular weight Decreasing tail branching Decreasing of] specific gravity Increasing concentration of high molecular weight alcohols. Decreasing the surfactant's oi! solubility will cause the reverse change. Thus, Figure 8 could be redrawn with any of the above variables (and several others) on the base of the prism with the variable Cee increasing in the direction of increased oil solubility.°© These observations have occupied a very great share of the MP literature. Their utility will become apparent under the discussion of IFTS. Fundamentals of Enhanced Oil RecoveryMODULE 5 PHASE BEHAVIOR FIGURE 8 HOW PHASE BEHAVIOR CHANGES WITH SALINITY SURFACTANT + 5-18 Fundamentals of Enhanced 011 RecoveryMODULE 5 INTERFACIAL TENS! ON IFTs AND You are no doubt wondering what this belabored PHASE BEHAVIOR discussion of HP phase behavior has to do with the goal of recovering of! through lowered IFT. Early MP flooding literature contains considerable information about the techniques of measuring IFT and what causes them to be low. IFTs were found to vary with the types and concentration of surfactant, co-surfactant, electrolyte, oil, polymer, and with temperature. However, in one of the most significant advances in all of MP. technology, all IFTs have been shown to directly correlate with the MP phase behavior (Healy and Reed, 1974). Two practical benefits of this correlation are immediately realized: observations of MP phase behavior can immediately be translated to IFTs, and relatively difficult measurements of IFTs can be largely supplanted by relatively easy phase behavior measurements. SOLUBILIZATION To Investigate further the relation between IFTS PARAMETERS and phase behavior, let V., V,, and V, be the volume fractions of oi1,° brite, and “surfactant in the microemulsion phase. According to Figure 8, three quantities are well-defined and continuous. Considering the type II(=) behavior of Figure 5, for example, Vj, V,, and V, are the coordinates of the microemulsion phase ° comBosition of the binodal curve. 5-19 Fundamentals of Enhanced Oi! RecoveryMODULE 5 INTERFACIAL TENSION SOLUBILIZATION Solubilization parameters between —the PARAMETERS microemulsion-oleic phases S,, , for type (continued) 11(=) and 111 phase behavior,”> and between the microemulsion-aqueous phases S,,, for type 11(+) and 111 are defined as Sno Yo / Vs (2a) eee Vee (2) The interfacial tensions between the corresponding phases, tro 24 Tyr are Functions only of |S, and Sys Figure 9 shows typical correlation. FIGURE 9 HIGH SOLUBILIZATION PARAMETERS MEAN LOW IFT (Healy et al., 1976, courtesy SPE) 107 107 107} INTERFACIAL TENSION (mN/m) Oe 2p nee omeo 1098 120 14s oS 2022, SOLUBILIZATION PARAMETER 5-20 Fundamentals of Enhanced 0i1 RecoveryMODULE 5 INTERFACIAL TENSION OPTIMAL SALINITY The corresponding behavior of the solubilization parameters and IFTs are shown in Figure 10 in a different manner. Consider a locus at constant oil, brine, and surfactant overall concentrations in Figure 8, but with a variable salinity. If the non-ideal effects are unimportant and the locus at low surfactant concentration and termediate brine-oil ratios, 7%, will be defined from low salinity up to Coey and #P8m Coe, to high salinities. Both 1FTs are thé towest in™ the threSphase type II! region between Coz, and Coey where both solubilization ratios are also. large. © There isp further, a precise_ysalinity where both IFTs are equal at values low enough (10°? mN/m) for good oi! recovery. This salinity Is the optimal salinity for th particular surfactant, brine, oi! combination. The common IFT the optimal IFT. Optimal salinities have been defined on the bas of ‘equal {Ffs, as in Figure 10, equal solubilization ratios, maximum oi] recovery in core floods, and equal contact angles. All definitions give roughly the same value. Hence, since optimal phase behavior salinity is the same as maximum ol! recovery linity, generating an interfacially active MP slug translates into generating this optimal salinity in situ in the presence of the surfactant material. FIGURE 10 DEFINING OPTIMAL SALINITY (Healy et al., 1976, courtesy SPE) 107 [1169 eft f-—$ ti >} = » A g fo 2 af 3 107 Ymw a é 5 if S y a = 103] 2 Optimal w Salinity, Sy Zz z ‘e (Of Oe Rete dees see ose zg SALINITY (YeNaCl) Fundamentals of Enhanced Oi! RecoveryMODULE 5 INTERFACIAL TENSION OPTIMAL SALINITY Optimal salinities can vary greatly depending cont Inued on the nature of the surfactant and brine pseudocomponents. It is dismaying, however, that for most commercially attractive surfactants In most HP candidate reservoirs, the optimal salinity is smaller then the resident brine salinity. Optimal. salinities can Be raised by adding to the slug any chemical, a cosurfactant, which reases the primary surfactant's brine solubility. Adding co-surfactants to the MP slug normally increases the optimal IFT. 5-22 Fundamentals of Enhanced 0i1 RecoveryMODULE 5 ‘SLUG FORMULATION TECHNIQUES Historically there have been three techniques for 1 generating optimal conditions in MP displacement. Each relates to propagating optimal salinity. Raise the MP slug optimal salinity to that of the resident brine salinity in the candidate reservoir. This procedure is philosophically the most satisfying of the three design procedures, and usually the most difficult. Though it has been the subject of intensive research, surfactants that have high optimal salinities that are not, at the same time, unstable at reservoir conditions, excessively retained by the solid surfaces, or expensive, have not yet been discovered. Recent field successes with synthetic surfactants have demonstrated, however, the technical feasibility of this approach (Bragg et al., 1982). A second way to make the optimal salinity of «the HP formulation equal to the resident brine salinity is to add co-surfactant. This approach Is the most successful implementation to date. However, there are penalties in surfactant/co-surfactant separation and, as mentioned above, loss of interfacial activity. Lower the resident salinity of a candidate reservoir to match the MP slug's optimal salinity. This also very common approach is the main purpose of the preflush step illustrated in Figure 1. A successful preflush is appealing because, with the resident salinity lowered, the MP slug would displace oil wherever it goes in the reservoir and retention would be low also. Preflushes generally require quite large volumes to significantly lower the resident salinity owing to mixing effects and cation exchange. With some planning, the function of preflush could be accomplished during the waterflooding preceding the MP flood. 5-23 Fundamentals of Enhanced 011 RecoveryMODULE 5 SLUG FORMULATION TECHNIQUES continued 5-24 The most recent technique for generating active MP slugs in situ is the salinity gradient design (Nelson, 1983). This technique attempts to dynamically lower the resident salinity to optimum during the course of the displacement by sandwiching the MP slug between the over optimal resident brine and an under-optimal mobility buffer salinity. The success of this procedure relies on it being necessary that only a portion of the HP slug be in the active region for good oil recovery. For salinity gradient floods, the salinity of the mobility buffer is the most significant factor in bring about good oi! recovery. The salinity gradient design has several other advantages in being resilient to design and Process uncertainties, in providing a favorable environment for the - polymer in the mobility buffer, minimizing retention, and being indifferent to the surfactant dilution effect. Fundamentals of Enhanced 011 RecoveryMODULE 5 SURFACTANT RETENTION INTRODUCTION The second criterion for successful MP flooding is to inject enough surfactant so that some of it will bring about optimal conditions. Surfactant retention is probably the most significant barrier to the commercial application of HP flooding. The problem here is, in a sense, one of selectivity. The surfactants should be designed for good selectivity for oil/water interfaces, but poor selectivity for Fluid/solid interfaces. MECHANI SHS Surfactants are retained through one of at least four mechanism: 1. On metal oxide surfaces, Figure 11, the surfactant monomer will physically adsorb through hydrogen bonding and micelle-like associations with the monomer tails, and ionically bond with cationic surface sites. At higher surfactant concentrations, this association includes tail-to-tail interactions with the solution monomers resulting in proportionally greater adsorption, At and above the CMC, the supply of monomers becomes constant as does the retention. The Langmuir-type adsorption isotherm of adsorption versus overall surfactant concentration bears resemblance to the CMC plot of Figure 4. FIGURE 11 ADSORPTION ON METAL OXIDE SURFACES (From Harwell, 1983) Chemical Adsorption RSO3 + +e et surface RSO3 Concentration 5-25 Fundamentals of Enhanced Oi! RecoveryMODULE 5 SURFACTANT RETENTION MECHANISMS continued 2. In hard brines the prevalence of divalent cations causes the formation of surfactant-divalent complexes which have a low solubility in brine. Precipitation of this surfactant-divalent complex will lead to retention though, when oi! present, this effect is lessened by the surfactant's solubility In the oleic phase. 3. At hardness levels, somewhat lower than those required for precipitation, the preferred multivalent-surfactant will be a monovalent cation which can chemically exchange with cations originally bound to the reservoir clays (Hil! and Lake, 1978). Co-surfactants reduce the density of surfactant molecules at the surface. Hence, adsorption can be reduced by adding a corsurfactant, Figure 12. FIGURE 12 SURFACTANT ADSORPTION ON CLAY oo 0% = 32 = 28 I Ye 7 24 A 2% é x 20) 7 Zo 16 po -p-g———_9 80-1 6% —- 12 § 8 3 10% < 4 0 400 800 1200 1600 2000 EQUILIBRIUM CONCENTRATION ( # mole/liter) Each curve is for the indicated volume percent co-sur factant. 5-26 Fundamentals of Enhanced 0i1 RecoveryMODULE 5 SURFACTANT RETENTION MECHANISMS continued 4. In the presence of oil in a I1(+) phase environment, the surfactant will reside in the oil-external microemulsion phase. Because this region is above the optimum salinity, the IFT is relatively large, Figure 13, and this phase and its dissolved surfactant can be trapped. A similar phase trapping effect does not occur in the II(-) environment because the aqueous mobility buffer miscibly displaces the trapped aqueous-external microemulsion phase without —_ permanent retention. Phase trapping can, thus, be eliminated by using an under-optimal mobility buffer salinity, an integral feature of the salinity gradient design. FIGURE 13 AVOID TYPE 11(+) TO ELIMINATE PHASE TRAPPING (from Glover et al., 1979) 10; | one . Phase Trapping o4 a 2 ecton er (mg/g of rock) 02 SURFACTANT CONCENTRATION ot ay SALINITY (% NaCl) Fundamentals of Enhanced Oi! RecoveryMODULE 5 SURFACTANT RETENTION CLAY CONTENT= Most studies of surfactant retention have not RETENTION made these mechanistic distinctions. Therefore, CORRELATION which mechanism predominates in a given application is not obvious. All mechanisms retain more surfactant at high salinity and hardness, which can, in turn, be attenuated by adding co-surfactants. Precipitation and phase trapping can be eliminated by lowering the mobility buffer salinity at which conditions the chemical adsorption mechanism on the reservoir clays is predominant. There should, therefore, be some correlation of surfactant retention with reservoir clay content. Figure 14 is an attempt to make this correlation by plotting laboratory and field surfactant retention data against clay fraction. The correlation is by no means perfect since it ignores variations in MP formulation and clay distribution as well as salinity effects. However, the figure does capture a general trend that is useful for first-order estimate of retention in a given reservoir. FIGURE 14 SURFACTANT RETENTION INCREASES WITH CLAY CONTENT OField Data Olab Data ACTIVE SULFONATE RETENTION (mmg/e) 0 0.05 0.40 0.15 0.20 WEIGHT FRACTION CLAY 5-28 Fundamentals of Enhanced Oi] RecoveryMODULE 5 SURFACTANT RETENTION OPTIMAL A useful way to estimate the volume of surfactant SLUG SIZES required for an MP slug is through the dimensionless frontal advance Tag D, (Lake et al., 1978), =) (ae) as oo S)E)E fe Where a, is the surfactant retention from Figure 14 (the plateau value on® the appropriate isotherm), is the porosity, C, is the the surfactant concentration in the MP slug, and — and “p. are the rock and surfactant densities, respectively. D. is a fraction and expresses the volume of surfactant retained at its injected concentration as a fraction of the V_. For optimal surfactant usage, the volume of surfactant injectBd should be large enough to contact all of the V., but small enough to prevent excessive production of the surPactant. Besides wasting an expensive chemical, the latter can cause severe produced emulsions. Therefore, the MP slug size (V\_) should be equal to or somewhat larger than D., The volume of SGrfactant required is the product of the slig size and the surfactant concentration VC.. From Equation (3), this quantity is independent of surfa€fatt concentration. Hence, with respect to retention, the amount of surfactant used is independent of surfactant concentration. 5-29 Fundamentals of Enhanced Oi! RecoveryMODULE 5 LAB/FIELD RESULTS INTRODUCTION We conclude this module by reviewing responses of a typical laboratory core and field flood so that you may generally assess the important features and expectations of HP flooding. ‘TYPICAL Figure 15 plots an effluent response of a typical MP FLOOD MP flood i a Berea core showing oi! cut, and produced surfactant (Mahogany AA), co-surfactant (1PA -- isopropyl alcohol), polymer, and chloride anion concentrations. All concentrations have been normalized by respective injected values. The chloride indicates of the ity in this flood. At the top of the figure is the phase environment of the produced fluids. The slug size is V, 0.1, and the horizontal axis is the volume of fluid Pinjected since the start of the slug expressed as a fraction of the core's V.. There was no preflush. Further details of this and similar Bre floods may be found in Gupta (1980). FIGURE 15, HOW A CORE FLOOD PERFORMS (from Gupta, 1980, courtesy SPE) Oil-Water II (+) 1G) 120 ty 100 Vo, 80 \ \ \ 0.50 7.00 7.50 2.00 PORE VOLUMES PRODUCED -* Chloride —=Mahogany AA AUCH! Cut 60 40) 20) OIL CUT (%) PRODUCED/INJECTED CONC. (%) 5-30 Fundamentals of Enhanced Oi! RecoveryMODULE 5 LAB/FIELD RESULTS TYPICAL MP FLOOD Figure 15 shows a typical, though not optimal, oi! recovery experiment. Before surfactant injection, the core was . waterflooded so that initially no oil is produced. Oi! breaks through at about 0.2V. injected with relatively sustained cuts of about 40% until about"0.6 V\, at which point the surfactant begins to be produced. Note thatPabout 60% of the oi! is produced as a clean oi! "bank" that is free of the injected chemicals. That 40% of the oi! is produced with the surfactant indicates a viscous instability apparently caused by unfavorable phase behavior. In a well-designed flood, 80-30% of the oi! is produced ahead of the surfactant. Even here, though, the oil is invariably produced early and at fairly low cuts In laboratory experiments. In Figure 158, surfactant breaks through at 0.6 V., reaches its maximum produced concentration of 30% of the injected?concentration at 0.8V., and ceases at 1.5 V,. The total volume of surfactant produced? is about 50% of that iRjected which indicates substant lal though not excessive retention. The surfactant is preceding both the chloride and polymer by about 0.3 V.. This separation indicates preferential partitioning of the co-surPactant between the aqueous and microemulsion phases (this is a phase behavior non-ideality). Though this did not drastically affect oil recovery (oil recovery is in excess of 90% of the ofl present at the start of the MP slug), the separation is not a favorable indication for this design. A good MP design should show simultaneous production of all HP slug constituents, as well as good oi! recovery. FIGURE 16 HOW A CORE FLOOD PERFORMS WITH INJECTED SURFACTANT (from Gupta, 1980, courtesy SPE) 100 ta injected 90/M Surfactant 809% ==Mahogany AA sof PA ——Polymer 60 50 40! 30 20 10 PRODUCED/INJECTED CONC. (%) 0025050 O75 1.00 125 150 175 2.00 PORE VOLUMES PRODUCED Fundamentals of Enhanced O11 RecoveryMODULE 5 LAB/FIELD RESULTS BELL CREEK Figure 16 shows the produced fluid analyses of well 12-1 in the Bell Creek (Carter and Powder River counties, Montana) MP flood. This flood used a high oi! content MP slug preceded by a preflush containing sodium silicate to lessen surfactant retention and reduce divalent cation concentration. Well 12-1 was a producer in the center of an unconfined single 40-acre 5-spot pattern. Well 12-1 experienced low and declining oi! cuts prior to MP slug injection in February 1979. MP oil response beginning in late 1980 is superimposed on this decline, reaching peak cuts of about 13% about 6 months later. Note that the pre-MP decline must be clearly established for accurate evaluation of the MP oil recovery, a ste that is not necessary in the core flood evaluation. Compared to the coreflood, there is no evident clean oi! production. Surfactant production actually preceded the oi! response at Bell Creek. Simultaneous oi! and surfactant production seems to be the persistent feature of field MP floods probably because of heterogeneities and dispersive mixing. The surfactant precedes the oil in Figure 16 because of excessive content of water-soluble, inactive disulfonate in the MP slug. Other significant features are evident presence of the preflush preceding the MP slug, inferred from the maxima in the pH and silicate concentrations, and the very efficient removal of the calcium cations ahead of the surfactant. When oi production commenced, however, calcium restored roughly to its pre-micellar level. FIGURE 16 BELL CREEK MICELLAR-POLYMER FLOOD (from Holm, 1982, courtesy SPE) OlLCUT (%) SULFONATES. (meq/1) 5-32 Fundamentals of Enhanced Di! RecoveryMODULE 5 LAB/FIELD RESULTS LOUDON SURFACTANT Figures 17 and 18 summarize the Loudon PILOT Surfactant, pilot. This very small 5-spot showed excellent response, recovering about 60% of the remaining oil in place at its conclusion. Part of this response could be due to the large slug used (V,. = 0.4). However, the surfactant clearly became and remained activB® throughout the Flood. FIGURE 17 LOCATION OF LOUDON PILOT (from Bragg et al., 1982, courtesy SPE) FIGURE 18 LOUDON SURFACTANT PILOT RESPONSE (from Bragg et al., 1982, courtesy SPE) sp 70 suk 160 sf 450 40 7 3. bo (SOF RESIDUAD— 750100 oes ome) PORE VOLUMES PRODULFO 5-33 Fundamentals of Enhanced Oi! RecoveryMODULE 5 LAB/FIELD RESULTS FIGURE 19 LOCATION OF MP FIELD TESTS AS OF 1979 (from Lake and Pope, 1979) IMPORTANCE OF Figure 20 shows oil recovery efficiency MOBILITY CONTROL (ultimate oi! produced/oil in place at start of MP process) from a survey of more than 40 NP field tests (Figure 19 indicates locations of the MP field tests as of 1979) correlated as a function of mobility buffer slug size. As of the date of the survey, there were no commercial projects reported. Similar analyses on other process variables showed no or weak correlation (Lake and Pope, 1979). The strong correlation in Figure 20 indicates the Importance of mobility control in MP design. Though this subject has been largely ignored in this module (Gogarty et al., 1970), it is clearly a highly important variable. Note also from this figure that the high oi! content slugs have generally been driven by larger polymer drives than the high water content slugs. Fundamentals of Enhanced Oi! RecoveryMODULE 5 LAB/FIELO TESTS Ultimate of! recovery efficiency averages about 30% in field tests, Figure 20. Since ofl recovery efficiency can be quite high in corefloods, it seems that a 1/3 rule-of-thumb might apply to MP flooding: the peak of! cut an ultimate of! recovery efficiency in an HP flood will average about 1/3 of their respective values in corefloods. FIGURE 20 RECOVERY EFFICIENCY VERSUS MOBILITY BUFFER SIZE (from Lake and Pope, 1979) 5 Moin NO OIL Za oglStUG INSLUG 55 . eo least square line =z os ™_O In Progress _— so 2G 04 22 o€ ge 0.2 2 ol yo 0 04 0.8 1.2 1.6 2.0 3.2 MOBILITY BUFFER SIZE (fraction V,) 5-35 Fundamentals of Enhanced 011 RecoveryMODULE 5 EXPLORING MICELLAR=POLYMER FLOODING SUMMARY Important points stressed, in this module, are the importance of the MP phase behavior in understanding oil recovery, the economic hurdles to be overcome with respect to surfactant retention, and comparisons between corefloods and field responses. On average, MP field tests have produced about 30% of the tertiary oil target, a figure that is marginally attractive at current economic conditions. On the other hand, great advances in the understanding of MP process mechanisms have occurred over the last few years which will almost certainly improve the reliability of the process and will ultimately lead to economically viable processes. Fundamentals of Enhanced 011 RecoveryMODULE 5 REFERENCES Akstinat, M.H., “Surfactants for EOR Process High-salinity Systems, Product Selection and Evaluation," Enhanced Oil Recovery, Elsevier Scientific, New York, New York, 1981. Bragg, J-R., Gale, W.W., McElhannon, W.A., Davenport, 0.W., “Loudon Surfactant. Flood Pilot Test," SPE 10862, presented at the Third Society of Petroleum Engineers Symposium on EOR, Tulsa, Oklahoma, 1982. Gilliand, H.E., and Conley, F.R., "Surfactant Waterflooding,” presented at Symposium on Hydrocarbon Exploration, Drilling, and Production, Paris, France, 1975. Glinsmann, G.R., “Surfactant Flooding with Microemulsions Formed In-Situ - Effect of O71 Characteristics," SPE 8326, presented at the Society of Petroleum Engineers S4th Annual Technical Conference and Exposition, Las Vegas, Nevada, 1975. Glover, C.J., Puerto, M.C., Maerker, J.M., and Sandvik, E.l. “surfactant Phase Behavior and Retention in Porous Media," Society of Petroleum Engineers Journal, 19, (1979) 183-193. Gogarty, W.B., Meabon, H.P., and Milton, H.W., Jr., “Mobility Control Design for Miscible-type Waterfloods Using Hicellar Solutions," Journal of Petroleum Technology, 22, (1970) vat-147, Gupta, S.P., "Compositional effects on displacement mechanisms of the micellar fluid injected in the Sloss Field Test,! SPE 8827, presented at the First Joint Society of Petroleum Engineers/Department of Energy Symposium on Enhanced Oi! Recovery, Tulsa, Oklahoma, 1980. Harwell, J.H., "Surfactant Adsorption and Chromatographic Movement with Application in Enhanced il Recovery," Ph.D. Dissertation, The University of Texas at Austin, Texas, 1983. Healy, R.N., and Reed, R.L., _"Physiochemical Aspects of Microeumulsion Flooding," Society of Petroleum Engineers Journal, 14, (1974) 491-501. Healy, R.N., and Reed, R.L., and Stenmark, D.G., "Multiphase Microemulsion Systems," Society of Petroleum Engineers Journal, 16, (1976) 147-160. 5-37 Fundamentals of Enhanced Oil RecoveryMODULE 5 REFERENCES Hill, Hide, and Lake, L.W., "Cation Exchange in Chemical Flooding: Part’ 3- Experimental," Society of Petroleum Engineers Journal, 18, (1978) 445-456. Holm, L.W., "Design, Performance and Evaluation of the Uniflood Micellar-Polymer Process- Bell Creek Field," SPE 11196, presented at the 57th Annual Fall Technical Conference and Exhibition of the Society of Petroleum Engineers, New Orleans, Louisiana, 1982. Lake, L.W., Stock, L.G., and Lawson, J.B., "Screening Estimation of Recovery Efficiency and Chemical Requirements for Chemical Flooding," SPE 7069, presented at the Society of Petroleum Engineers Fifth Symposium on Improved Methods for Oi] Recovery, Tulsa, Oklahoma, 1978. Lake, L.W., and Helfferich, F., “Cation Exchange in Chemical Flooding, Part Il- The Effect of Dispersion, Cation Exchange, and Polymer/Surfactant Adsorption on Chemical Flood Environment," Society of Petroleum Engineers Journal, 18, (1978) 435-444, Lake, L.W., and Pope, G.A., "Status of Micellar-Polymer Field Tests," Petroleum Engineers International, 51, (1979) 38-69. Nelson, R.C., and Pope, G.A., "Phase Relationships in Chemical Flooding,: Society of Petroleum Engineers Journal, 18, (1978) 325-338. Nelson, R.C., "Effect of Live Crude on Phase Behavior and Gil-Recovery Efficiency of Surfactant Flooding Systems," Society of Petroleum Engineers Journal, 23, No. 3, (1983) 501-520. Winsor, P.A., Solvent Properties of Amphiphilic Compounds. Butterworths, London, 1954. 5-38 Fundamentals of Enhanced Oi] RecoveryMODULE 5 EXERCISE 7 ESTIMATING OPTIMAL CONDITIONS PURPOSE 0 To gain experience in using micellar ternaries © To examine what is meant by a solubilization parameter © To see how solubilization parameters determine Interfacial tension UTILITY Designing a surfactant formulation hinges on generating conditions (salinity) where IFT will be low, and making this IFT as low as possible. In this exercise, you will see how the surfactant-brine-oi! phase behavior will address both issues. PROCESS This exercise requires that you know and understand solubilization ratios. You will calculate these by a simple ratio of phase concentrations which you will read from ternary diagrams. You will then convert the solubilization ratios into IFTs, and from this you can determine optimal salinity STEP 1 Figure 21, on page 5-40, shows the bottom half of six surfactant-brine-oil ternaries ternaries. Calculate and tabulate the solubilization ratios at each salinity. The surfactant concentration is 5 volume percent and the brine-oi! ratio is one. STEP 2 Use the Glinsmann correlation, Figure 22 on page 5-41, to convert these to IFTs. Plot (semi-log) both IFT curves against salinity and the optimal IFT. STEP 3 From this plot, estimate the optimal salinity Sg and the optimal IFT. STEP 4 List as many ways as you can think of to bring about this optimal condition in the reservoir. 5-39 Fundamentals of Enhanced 011 RecoverySURFACTANT CONCENTRATION MODULE 5 EXERCISE 7 ESTIMATING OPTIMAL CONDITIONS FIGURE 21 SURFACTANT CONCENTRATION 02 a Sate SBOE na $063 we NaCt I on on °o 02 0406 08 10 0 0204 06 08 1 02 S08 we % NaCl Smoszmwnact 192 oa on ° o 0020s 0608 10 0 of 04 06 08 10 a set, veemeye ot 002 0406 0810 0 02 04 06 08 vA OIL CONCENTRATION OIL CONCENTRATION 5-40 Fundamentals of Enhanced O11 Recovery SURFACTANT CONCENTRATIONMODULE 5 EXERCISE 7 ESTIMATING OPTIMAL CONDITIONS INTERFACIAL TENSION (mN/m) FIGURE 22 CORRELATION OF SOLUBILIZATION PARAMETERS WITH INTERFACIAL TENSIONS (from Glinsmann, 1979, courtesy SPE) Vols VodVe OIL ‘Ociane °F 107 ow CutBank Crude & 4 mDecane 2 mTridecane 0 MHexadecane © @ NBUCride 102 103 10+} ee ee) Fundamentals of Enhanced Oi! RecoveryMODULE 5 EXERCISE 8 DEFINING THE IMPORTANCE OF RETENTION PURPOSE 0 To gain experience in manipulating concentration units © To define how to calculate the frontal advance lag 0 3 © To identify @ basis for estimating slug sizes UTILITY It is important to generate an optimal IFT, but it is equally important to ensure that this is propagated across the reservoir. This exercise illustrates a simple way to estimate slug size based on a known retention. PROCESS In this exercise, you will estimate retention (which we take here to be solely adsorption) from an existing correlation, and then convert this into a form that is directly comparable to slug size. The formula for the frontal advance lag D, Is a) eas Cy, where = porosity (fraction) B= rock density [=] m/t? pb, = surfactant density {=} m/L? C, = surfactant concentration in slug (volume fraction) 8, * surfactant retention [=] m surfactant/m rock Use the following data: o = 0.2 B= 2.6 fen? = = 3 5 7 9-05 2, = 1 g/em 5-2 Fundamentals of Enhanced Oi! RecoveryMODULE 5 EXERCISE 8 STEP 1 STEP 2 ee STEP & DEFINING THE IMPORTANCE OF RETENTION Estimate the surfactant retention from Figure 14, page 5-28, if the clay fraction is 0.05. Calculate D, based on this value. Estimate the slug size required if the slug size is to be 1.3 0,. The exact fraction depends on economics, but ° 1.3 is typical. The slug in Step 3 causes a 20% OOIP recovery in a reservoir where the initial oi! saturatign is 60%. Estimate the surfactant utilization (kg/m) for this Flood.MODULE 6 USING OTHER CHEMICAL METHODS Foam flooding and alkaline flooding are two other chemical methods Important to EOR. Foams are proposed or are being used as mobility control agents to drive solvent, micellar, or steam slugs. They are rarely used alone. Alkaline flooding Is a surfactant Flood whereby the surfactant is generated by reactions between a water soluble base and acidic components of the crude. This process is an alternative to micellar-polymer flooding because the alkaline agents are much less expensive. During this module, we will briefly cover both methods. OBJECTIVES: During this module you will 1. Ulustrate the role of surfactants in foam stability 2. Identify the causes of foam instability 3. Explain the reasons behind lowered mobility i), List various alkaline agents 5. Explain the acid number concept 6. Deduce the analogy with micellar phase behavior 7. Describe the role of pH loss OUTLINE: FOAM FLOODING FOAM STABILITY CHARACTERISTICS EFFECTS ALKALINE FLOODING DISPLACEMENT MECHANI SHS ROCK-FLUID INTERACTIONS FIELD RESULTS SUMMARY 200000000 ACTIVITIES: This module depends almost exclusively on your reading the material and completing the exercise. You will, however, have an opportunity to listen to 2 brief presentation and debriefing. Exercise 9: Summarizing Alkaline and Foam Flooding MATERIALS: Video Tape Module 6 Workbook Pages 6-1 to 6-28 TIME: You can expect to take approximately 35 minutes to complete all of the activities in this module in addition to the reading. Tape Time: 20 minutes Exercises: 15 minutes 6-1 Fundamentals of Enhanced Oi! RecoveryMODULE 6 FOAM FLOODING OVERVIEW Gas-liquid foams offer an alternative to polymers for providing mobility control in chemical floods, and have been proposed and field tested as mobility contro! agents in steam floods. Foams are dispersions of gas bubbles in liquids. Gas-liquid dispersions are normally unstable and will usually break less than one second. If surfactants are added to the liquid, however, stability is greatly improved so that some foams can persist almost indefinitely. To understand foam properties requires some discussion of surfactants and their classifications. You should review the material in Module 5 for this. Fundamentals of Enhanced Oi] RecoveryMODULE 6 FOAM STABILITY DISCUSSION We can understand the stability of foam by viewing the liquid film separating two gas bubbles in cross-section as in the lower panel of Figure 1. The hydrophiles of the surfactant are oriented into the interior of the film, and the liphophiles toward the bulk gas phase. Suppose that some external force causes the film to thin as in the lower janel. Since capillary pressure is inversely proportional to interfacial curvature, the pressure in the thinned portion of the film is lower than in the adjacent flat portion. This causes a pressure difference within the film, liquid flow, and healing. When the foam is static, the gas phase pressure Is constant because of its low density. When the foam is flowing, the gas phase pressure is again constant because of its low density. FIGURE 1. UPPER PANEL: SURFACE TENSION AND ADSORPTION OF A SURFACTANT VERSUS CONCENTRATION LOWER PANEL: GIBS-MARGANGONI EFFECT (from Overbeek, © 1972, Massachusetts Institute of Technology) SURFACE TENSION ADSORPTION! cmc CONC. ui? Thinner, less adsorption, larger surface tension, contraction 6-3 Fundamentals of Enhanced 0i1 RecoveryMODULE 6 FOAM STABILITY ANALYSIS The upper panel in Figure 1 shows that the FIGURE 1 gas-liquid surface tension is @ decreasing Function of surface adsorption as required by the Gibbs theory. According to this view, the thinned portion of the film will have less specific adsorption (since the surface area is locally greater), and a greater surface tension, This locally high surface tension also causes healing. SURFACE TENSION, | Clearly, the surface tension at the gas-lig GAS-LIQUID interfaces plays an important role in film INTERFACES stability. Very low surface tensions would not be favorable. Fortunately, gas-liquid surface tensions are rarely lower than 20 mN/m even with the best foaming agents. In the absence of external forces, the film is at an equilibrium thickness caused by a balance between the repulsion forces of the electrical double layer on the interior of the film boundary and the attractive van der Waal forces between the molecules in the film. If the film becomes substantially smaller than the equilibrium thickness, the free energy barrier between the repulsive and attractive contributions is breached, and the film will collapse. THINNING AND Such thinning can be caused spontaneously by COLLAPSE diffusion of the gas from small to large bubbles, and by gravity drainage. Patton et al. (1982) report on the rate of spontaneous collapse of a large number of foams as a function of surfactant type, temperature, and pH. The half-life of the foam heights reported in their static tests range from 1 to about 45 minutes. Anionic surfactants have greater stability than non-ionics, and the stability of sulfonate foams is greatly affected by water hardness. Foams were generally more unstable at high temperatures, and many could be stabilized by adding a second surfactant. EXTERNAL External effects which may cause the foam to EFFECTS collapse are the presence of a foam breaker {oil or a high electrolyte concentration could do this), local heating, or contact with a hydropholic surface. Fundamentals of Enhanced Oi] RecoveryMODULE 6 CHARACTERISTICS THREE Physically, foams are characterized by three MEASURES measures: quality, texture, and bubble size range. Quality The quality [of a foam is the percentage of the total (bulk) foam volume that is gas volume. The quality can increase with increasing temperature and decreasing pressure both because the gas volume can increase, and also because gas dissolved in the bulk liquid phase can evolve from solution. Foam qualities can be quite high, approaching 97% in many cases. A foam with quality greater than 90% is a dry foam. Texture A second measure is the average bubble size, called the foam texture. The texture determines how the foam will flow through a permeable medium. If the average bubble size is larger than the average pore diameter, the foam flows as a progression of films separating individual gas bubbles. Given typical foam textures and pore sizes, this condition is most nearly realized in permeable flow, particularly for high foam qualities. Bubble Size A third foam measure is the range of bubble sizes. Foams with a large distribution range are more unstable because of the gas diffusion from large to small bubbles. 6-5 Fundamentals of Enhanced Oil RecoveryMODULE 6 EFFECTS MOBILITY Foams can drastically reduce the mobility of a gas LOWERING phase. Figure 2 shows the steady-state mobility of foams of differing quality in Berea cores at three different permeabilities as a function of quality. On the extreme right of this figure (I= 100%), the mobility should approach the respective air permeability divided by the air viscosity. This mobility is 2-3 factors of ten greater than any of the experimental points on the figure. When [TJ= 0 the mobility should approach the water permeability divided by y, . Thus, the mobility of foam is lower than that of either” of its constituents alone. The mobility of the foam decreases with increasing quality until the films between the gas bubbles begin to break and the foam collapses (not shown on Figure 2). Foams are effective in reducing the mobility at all three permeabilities in Figure 2, but the effect of foam quality is more pronounced at the highest ‘permeability. This is a consequence of the contrast between the texture of the foam and the mean pore size of the medium (Fried, 1960). FIGURE 2 EFFECTIVE PERMEABILITY-ViSCOSITY RATIO VERSUS FOAM QUALITY FOR CONSOLIDATED POROUS MEDIA AND 0.1% AEROSOL MA FOAM (from Khan, 1965) eke = 441 um kag = 0.48 pm? Ww kur = 0.26 um? 1.00; um?/mPa-s ° Ss 2 2 60 70 80 90 700 QUALITY OF FOAM (Percent) EFFECTIVE PERMEABILITY - VISCOSITY RATIO Fundamentals of Enhanced 0i1 RecoveryMODULE 6 EFFECTS GAS PHASE The mobility reduction caused by the foam can be PERMEABILITY viewed as an increase in a single phase viscosity, or as a decrease in the gas phase permeability. Representative data of the second type is in Figure 3 which shows the gas phase permeability, both with and without foam, and gas saturation plotted against the liquid injection rate (Bernard et al., 1964). Note that the foam causes a great decrease in gas permeability at the same rate and even the same gas saturation compared to the non-foaming displacement. The analogous analysis performed on the aqueous phase relative permeability shows that neither the gas saturation nor the presence of the foaming agent affects the aqueous phase relative permeability (Bernard et al., 1965). FIGURE 3 EFFECT OF LIQUID FLOW RATE AND GAS SATURATION OF GAS PERMEABILITY WITH AND WITHOUT FOAM (from Bernard and Holm, 1964, courtesy SPE) 1000: Gas, PERMEAGILITY are ATURATION GAS PERMEABILITY (OAS PERMEABILITY, MILLIOARCYS 5 (OAS SATURATION, % PORE SPACE wit Foam without FoaM ou Orasese7eoonaam LIQUID INJECTION RATE, aY/S9. FT. ARELS PER Fundamentals of Enhanced Oi! RecoveryMODULE 6 EFFECTS CAUSES OF LOW The low foam mobilities in permeable media flow FOAM MOBILITY are postulated to be caused by at least two different mechanisms: the formation of or the increase in a trapped residual gas phase saturation, and a blocking of pore throats due to the gas films. From Figure 3 the effect of a trapped gas saturation, which would lower the gas mobility through a relative permeability lowering, Is much smaller than the pore throat blocking effect. The trapped gas phase saturation effect may become important, however, during the later stages of a displacement where the lower pressures could cause more gas to come out of solution. viscosity Several researchers have studied the mobility ENHANCEMENT reduction of foams, viewed as a viscosity enhancement, in capillary tubes (Holbrook et al., 1981). General observations on these data are that foams are generally shear-thinning "fluids" whose power law coefficient increases with the capillary tube radius. Using theoretical arguments based on a Newtonian fluid and an inviscid gas, Hirasal and Lawson (1983) show that the film thickness in a single moving bubble increases as the bubble velocity to the 2/3 power. Since shear stress in @ capillary is inversely proportional to film thickness, the apparent viscosity of a foam in a capillary tube decreases with velocity. Thus, the shear thinning effect observed in capillary tubes is actually a consequence of the film thickening ‘as velocity increases. A second implication in the Hirasaki and Lawson theory is that foam texture occupies as great an importance in determining rheological behavior as does foam quality. FIELD Field tests of foam injection alone have been RESULTS, scarce. Holm (1970) reports on the injection of an air-brine foam into a single well in the Siggins field. Though there was no measurable oi! response, the mobility to both air and brine were significantly reduced, and the injection profile into the central well became more uniform. Fundamentals of Enhanced Oi! RecoveryMODULE 6 ALKALINE FLOODING OVERVIEW The final chemical flooding EOR process is high pH flooding, a schematic of which is shown in Figure 4. As in polymer and MP flooding, there is usually a brine preflush to precondition the reservoir, a finite volume of the oil-displacing chemical, a graded mobility buffer driving agent, and the entire process ‘Is driven by chase water. Moreover, for both high pH and MP flooding, the oil-displacing chemical is a surfactant. However, for MP flooding the surfactant is injected, while in high pH flooding it is generated in situ. HIGH pi High pHs indicate large concentrations of the CHEMISTRY hydroxide anions (0H-). The pH of an ideal aqueous solution is defined as pH= log ioCu* a) where the concentration of hydrogen ions Cy+ is in moles/liter As the concentration of OH is increased, the concentration of H decreases since the two concentrations are related through the dissociation of water (Con (Cn* = Sonne) @) Cr20 . and the water concentration is nearly constant. These considerations suggest two means for introducing high pHs into a reservoir: dissociation of a hydroxyl-containing species, or adding chemicals which preferentially bind hydrogen ions. 6-9 Fundamentals of Enhanced Oi! RecoveryMODULE 6 ALKALINE FLOODING FIGURE 4 SCHEMATIC ILLUSTRATION OF HIGH pH FLOODING PROCESS (Drawing by Joe Lindley, U.S. Department of Energy, Bartlesville, Oklahoma) CHEMICAL FLOODING (Alkaline) ‘Tee met shown ecues a prefush 'ocenton me reservar and econ ofan akan or ahaln coves sion ta ome stars in st relasrg OL Thesis okowed ‘by apotmar souson for moblty cont and a cr fs (war 10 move the chicas {Be resutgo8 Dank t production ws. = ees ff i i Fundamentals of Enhanced 011 RecoveryMODULE 6 ALKALINE FLOODING GENERATING Many chemicals could be used to generate high pHs, HIGH pH but the most commonly used are sodium hydroxide (caustic- Na0H), sodium orthosilicate, and sodium carbonate (Na,CO,). NaOH generates OH by dissociation, the latter two through the formation of weakly-dissociating acids, (silycic and carbonic acid, respectively) which remove free H* ions from solution. High pH chemicals have generally been used in field applications in concentrations up to 5 wt. % (injected pHs of 11 to 13) and with slug sizes up to 20% V,. These result in amounts of chemical which are quite comparable P to the surfactant usage in MP flooding. However, high pH chemicals are substantially less costly. OH” by itself is not a surfactant ice the absence of a lipophilic tail makes it exclusively water-soluble. If the crude oil contains an acidic hydrocarbon component HAS, some of this, HA~, can partition to the aqueous phase where it can react acfording to (Ramakrishnan and Wassan, 1982). (3) HA, SAg+H* The exact nature of HA) is unknown and probably highly dependent ‘on crude oil type. The°deficiency of hydrogen ions in the aqueous phase will cause the extent of this reaction to be to the right. The anionic species A, is a surfactant which can have many of the properties and enter “into most of the phenomena described above For HP flooding. 611 Fundamentals of Enhanced Oi! RecoveryMODULE 6 ALKALINE FLOODING Acid Number If there is no HA, originally present in the crude there can be “little surfactant generated. A useful procedure for characterizing crudes for their attractiveness to high pH flooding is through the acid number. The acid number is the milligrams of potassium hydroxide (KOH) required to neutralize one gram of crude oil. To make this measurement, the crude is extracted with water until the acidic species HA, is removed. The aqueous phase containing HA,» Ay and H* is then brought to pH =7 by adding the KOH. ™“ For” a meaningful value, the crude must be free of acidic additives (scale inhibitor, for example) and acidic gases (CO, or HyS). A good high pH flooding crude will have an acid number’ of * 0.5 mg/g or greater, but acid numbers as Tow as 0.2 mg/g may be candidates since only a small amount of surfactant is required to saturate oil-brine interfaces. Figure 5 presents a histogram of acid numbers based on the work of Jennings (1974). FIGURE 5 HISTOGRAM OF ACID NUMBERS (from Minssieux, 1976, reproduced by kind permission by BP Educational Service) 50 Varied Crude Oils 67.9% of total _—_—— % CRUDE OIL FALLING WITHIN A GIVEN ACID INDEX INTERVAL. 6-12 Fundamentals of Enhanced Oi! RecoveryMODULE 6 DISPLACEMENT MECHAN| SMS INTRODUCTION O11 recovery mechanisms in high pH flooding have been attributed to eight separate mechanics (deZabala et al., 1982). This module concentrates on only the following three: IFT lowering, wettability reversal, and emulsion formation. The last two mechanisms are also present in MP flooding, but are dwarfed by the low IFT effects. With smaller ultimate oi] recoveries, the distinction among effects becomes important in high pH flooding. IFT LOWERING The generated surfactant AZ aggregates at oll-water interfaces which “can lower IFT (Ramakrishan and Wassan, 1982). In general, such lowering is not as pronounced as in HP flooding, but, under certain conditions, can be large enough to produce good ol! recovery. Figure 6 shows IFT measurements of caustic solutions against Long Beach crude oi] at various brine salinities. The IFTs are sensitive to both NaH concentration and salinity, showing minima in the NaOH concentration range of 0.01-0.1 wt.%. The decrease in IFT in these experiments is limited by the spontaneous emulsification of the oil-water mixture when the IFT reaches @ minimum. FIGURE 6 INTERFACIAL TENSIONS FOR CAUSTIC-CRUDE-BRINE SYSTEMS (from Ramakrishnan and Wasson, 1983, courtesy SPE) 107 © 0.25 wi % NaCl = 0,50 wt. % NaCl 41.00 wt. % NaCl 10°} 1FT (mN/m) 10" 107 10107 10" 10? WEIGHT (% NaOH) 6-13 Fundamentals of Enhanced 01 RecoveryMODULE 6 DISPLACEMENT MECHANISMS ANALYSIS There are many similarities in the low IFT effects FIGURE 6 in HP and high-pH flooding. The data in Figure 6 suggest an optimal salinity of about 1.0 wt. % NaCl for a 0.03 wt. % NaOH solution. Indeed, the work of Jennings et al. (1974) has shown that there is an optimal NaOH concentration for a given salinity in oi! recovery experiments. Moreover, the presence of the emulsification effect when IFTs are Tow is ‘exactly what one would expect from an MP system at a surfactant concentration above the Invarient point in surfactant concentration. This suggests that the data in Figure 6 are showing that a type II(-) phase environment at low NaOH concentrations are type (11+) at high. Further work is necessary to establish the connection to MP phase behavior definitively, since the actual surfactant concentration A™ is likely to be much lower in a high-pH system. However, “Nelson et al. (1984) show that a co-surfactant can increase the optimal salinity In a high-pH system much like in MP systems. 6-14 Fundamentals of Enhanced 011 RecoveryMODULE 6 DISPLACEMENT MECHANISMS WETTABILITY Owens and Archer (1971) show that increasing the REVERSAL water wetness increases ultimate oi! recovery. The wettability was reported as decreasing the water-oil contact angle measured on polished synthetic surfaces. This has also been shown by others using high pH chemicals (Wagner and Leach, 1959; Ehrlich et al., 1974). The increased oi! recovery is the result of two mechanisms: a relative permeability effect which causes the mobility ratio of a displacement to decrease, and a shifting of the capillary desaturation curve (Module 2). Cooke et al. (1974) have reported improved of! recovery with increased oi] wetness. Other data show that oil recovery is 2 maximum when the wettability of a permeable medium is neither strongly water-wet nor oil-wet (Lorenz et al., 1974). Given the latter information, the important factor may be the change in the wettability rather than the actual wettability of the final state of the medium. In the original wetting state of the medium, the nonwetting phase occupies large pores and the wetting phase small pores. If the wettability of a medium is reversed, there will exist nonwetting fluid in small pores and wetting fluid in large pores. The resulting fluid redistribution, as the phases attempt to return to their natural state, would make both phases vulnerable to recovery through viscous forces. Fundamentals of Enhanced 011 RecoveryMODULE 6 DISPLACEMENT MECHANISMS EMULSION High pH chemicals can cause improved of! recovery FORMATION through the formation of emulsions. The emulsification produces additional of! In at least two wayst through a mobility ratio lowering since many of these emulsions have a@ substantially increased viscosity, and through solubilization and entrainment of oi! in a flowing aqueous stream. The first mechanism improves displacement and volumetric sweep as does the mobility control agents discussed previously. Local formation of highly viscous emulsions should be discouraged, However, as these would promote viscous fingering from the less viscous’ oil-free high-pH solution, the solubilization and entrainment mechanism would be more important when the IFT between the swollen water phase and the remaining crude is low. Figure 6 shows that for certain conditions, emulsification and low IFTs occur simultaneously. McAuliffe (1973) showed that emulsions injected in a core and those formed in situ give comparable oi] recoveries. 6-16 Fundamentals of Enhanced i! RecoveryMODULE 6 ROCK-FLUID INTERACTIONS THREE ASPECTS Interactions of the high pH chemicals and the permeable media minerals can cause excessive retardation in the propagation of these chemicals throughout the permeable medium. In this module, we discuss three aspects of rock fluid interactions: formation of divalent-hydroxide compounds, cation exchange, and mineral dissolution. Divalent-Hydroxide OH” ions themselves are not appreciably bound Compounds, to the solid surfaces; however, in the presence of multivalent cations they can form hydroxy! compounds M** +x(OH~)SM(OH)x (4) which, being relatively insoluble, can precipitate. from solution. This reaction in turn lowers the pH of the solution, and can also cause formation damage through pore blockage and fines migration. The anionic surfactant species A, can interact with the inorganic cations in solution just as” in HP flooding. However, interactions with the divalent cations usually take precedence particularly in hard brines, or where there are substantial quantities of soluble multivalent minerals. Because of these interactions and those involving surfactants A, , high pH processes are as sensitive to brine salinity and” hardness as are MP processes. Other high-pH rock-fluid interactions are intimately associated with the clay minerals. Clays are hydrous aluminum-silicate compounds which occupy the smallest (less than 2 microns) particle size in typical media. Macroscopically, clays occur as segregated streaks of variable degree of continuity throughout a typical reservoir, or as distributed clays which can line pore walls or fill pore throats. Distributed clays are of most, concern here, since these have quite large surface areas (15-40 m°/g- clay), and can, therefore, ex considerable reactivity (Grim, 1968). Chemically, clays can take on a variety of formulas which differ substantially in their reactivity even though the differences in their molecular formulas are apparently minor. 6-17 Fundamentals of Enhanced 011 RecoveryMODULE 6 ROCK=FLUID INTERACTIONS Cation Exchange The ability of a clay mineral to exchange divalent cations with an aqueous solution can drastically change the lonic environment of a solution with which it is In contact. Clays have excess negative charges caused by the substitution of +2 valence minerals for +3 valence minerals within octahedral or tetrahedral crystal lattice (Brownlow, 1979). The cation exchange capacity Z, is a measure of this excess negative charge. Typical Z/'s ‘are 1-10 meq/100g-clay for kaolinite and 100-180 meq/100g-clay for montmorillonite. These free anionic sites are covered with cations from the solution each of which has a specific degree of selectivity for the particular clay site. In general, H* has high clay selectivity, and divalent cations are more strongly bound than are monovalents. This ,means that the ar sites can be predominantly occupied by H” and/or divalents even when clays are in contact with relatively soft brines. Any subsequent change in the electrolyte environment of the contacting solution can cause the clays to take or give up these cations with a possible detrimental effect on high pH (and MP) flooding. H* cations can exchange on the clay sites with the injected sodium according to Clay-H+Na* =Cay-Na+H* () where "Clay" represents a mineral exchange site (Somerton and Radke, 1980). ,The reversible reaction Equation 5 will clearly cause’ the H* concentration to increase with a resulting pH decline. Figure 7 shows the extent of the OH” retardation caused by cation exchange in laboratory floods. Note that many of the lower pls may require more than 3V, of fluid injection to attain the injected pH. e Fundamentals of Enhanced Oi! Recovery