Miscible-Type Waterflooding: Oil Recovery with Micellar Solutions Ww. Gogasrr ‘we & TOScH MEsBERS AIME Abstract A new recovery process for producing oil under both secondary and tertiary conditions uillizes the unique prop- erties of micellar solutions (also known as microemulsions, swollen micelles, and soluble oils). These solutions, which displace 100 percent of the oll in the reservoir con- tacted, can be driven through the reservoir with water ‘and are stable in the presence of reservoir water and rock. Basic components of micellar solutions are surfactant. hydrocarbon and water. They may also contain small amounts of electrolytes and co-surfactants such as alcohols. The specific reservoir application dictates the type and con: ‘centration of each component. A salient feature of the process Is the capability for mobility control. Micellar Solution slug mobility, by way of viscosity control, is ‘made equal 10 or less than the combined oil and water mobility. Mobility control continues with a mobility buffer, that prevents drive water from contacting the micellar solution. Laboratory and field flooding have proven that the process is technically feasible and that surfactant lasses by adsorption om porous media are small. Introduction Projects are under way to recover the maximum amount of oll under the most favorable economic conditions." ‘New techniques are being developed to increase oil re covery.* Polymer solutions are becoming an important means of controlling mobility in a waterflood. Thermal methods such as in-situ combustion and steam injection are being used in reservoirs containing highly viscous corudes, Surfactant flooding is receiving attention as a method of reducing interfacial tension to increase recov- ery?® Exotic recovery processes have been considered primarily for secondary operations. Economics are un- favorable in most cases for tertiary recovery. Studies at the Denver Research Center of the Marathon Oil Co, have led to a new oil recovery method.* Micellar solutions (sometimes called microemulsions, swollen mi celles, and soluble oils) are used to recover oil by miscible type waterflooding. Basically, these solutions contain sur- factant, hydrocarbon, and water, The method can be used in either secondary or tertiary operations. Ges! seampin of SI JOA anf SPR 180-8 rece SSRN Sin hee cigta! ape eee OTe, Be Pa ie erie eae Mitac? of atte, Meialrgtal, and etsieee Bngloeers Tne ime “Maratood” (trademark of Marathon O11 Co) ll recovery MARATHON lL co. LiTTterON, Coto. First, the concept of the process is considered in terms ‘of the requirements for an effective miscible waterflooding ‘operation. Next, micellar solution. properties are de: scribed including structure, composition, and phase be: hhavior with reservoir fluids. Fluid characteristics are then considered as related to mobility control, and, finally, lab. oratory and fleld results are presented to illustrate the efficiency of the process. Concept of the Process Unit displacement efficiency and conformance determine the effectiveness of any oil recovery mechanism. In theory. 1 miscible waterfiood should be capable of a 100-percent unit displacement efficiency with correspondingly high conformance. Requirements for the slug of a miscible wwaterflood include (1) 100-percent displacement of oil in the reservoir contacted. (2) controllable mobility, (3) the capability of being driven through the reservoir with water, (4) a low unit cost to enhance economics, and (5) the ability to remain stable in the presence of reservoir water and rock, Micellar solutions satisfy requirements for the slug of ‘a miscible waterflood process. Our discovery that these solutions acted as though they were miscible by displacing all fluids in the reservoir and by being displaced by water solved the miscibility problem. Adequate mobility control is possible by variations in solution viscosity through com- positional changes. Economic requirements are met since Iicellar solution costs below $6/bbI appear possible Micellar solutions stabilize surfactant in the presence of reservoir rock and water, thus reducing the importance of the problem of surfactant loss by adsorption. Fig. 1 illustrates schematically how these solutions are used. Operations start with injection of @ micellar solution slug that serves as the oil displacing agent. Next, a mobility buffer of either a water-external emulsion or water sol tion containing polymer (thickened water) is injected to protect the slug from water invasion. Finally. drive water (water used in a regular waterflood) is injected to propel the slug and mobility buffer through the reservoir. Reservoir oil and water are displaced ahead of the slug, and a stabilized oil and water bank develops as shown in Fig. I. Stabilized bank saturations are independ ent of original oil and water saturations. This means that. for a particular type of reservoir. the displacement mech anism is the same under secondary and tertiary recovery conditions. Oil is produced first in a secondary operation For tertiary conditions, water is produced first ‘Movement of the slug through the reservoir is stabilized by the mobility buffer. An unfavorable mobility ratio ‘usually exists at the interface between the buffer and drivewater, Others have reported that fingering caused by an adverse mobility ratio can be reduced by grading or feathering.” By using a semilogarithmic relationship for ‘grading as illustrated in Fig. 2, viscosity ratios are made equal between all zones and instability in the system is, decreased Micellar Solutions Micellar solutions are the key to our oil recovery meth ‘od, These solutions are surfactant-stabilized dispersions of, ‘water in hydrocarbon. The structure and composition of these fluids led to their use as oil recovery agents. Miscible- type waterflooding is possible with the solutions because of their phase behavior with reservoir fluids Nomenciature and Structore How the micellar solutions function as recovery media is best appreciated if their liquid structure is understood. ‘SECONDARY wicron nono |DRIVE; MOBILITY Lo f eRe) oh eNeee) (hl ‘wepTION ct PRooUETIN [DRIVES MOBILITY ot Rares) BBR on elsiaiaiela “~ Wie Teraneo woercity aurreR ad \ _ gue i + 8 80(— __— — = | Ba | | 1 bave 684 ware BATCH DUFF Fig. 2—Grading the mobility buffer. This structure gives the wo paramount requirements needed in an oil recovery agent: control of viscosity (hence mobility) and attainment of miscibility Oil and water do not mix unless a third component — ‘a surfactant — is added. A surfactant or soap molecule has fan affinity for both oil and water and acts as a bridging lagent between the two when mixed in proper proportions under certain conditions It was recognized in the early 1900's that when soap is dissolved in water, at sufficient concentrations. the soap molecules form aggregates that are termed micelles." For some time it was felt that micelles existed only in aqueous systems, However, aggregates have since been found in non-aqueous solvents as well." Fig. 3 shows schematic drawings of these two micellar conditions. Miccllar aggregates as depicted in Fig. 3 are capable of solubilizing, or dissolving, appropriate fluids into their centers. When this occurs, the micelle is swollen to accom: modate the solubilized fluid —oil or water, as the case may be.*"* Fig. 4 shows these two situations. These struc tures depict those forms postulated to be contained in the slug utilized in our process where a fluid is solubilized in micelle cores, ‘The spherical micelles shown in Fig. 4 are reminiscent of oil-in-water and water-in-oil emulsions, The difference is one of size: emulsions have particle sizes in the range ‘of 10 mm diameter and larger, while swollen micelles are in the range of about 10 to 10* mm." Emulsions fare not translucent. are heterogeneous. and are phase- unstable (they tend to phase-separate). Swollen micelles, on the other hand, are transparent to translucent. essen: tially homogeneous, and are stable to phase-separation. Systems similar to swollen micelles have been referred to by other names. Hoar and Schulman referred to a water-in-oil transparent dispersion as an “oleopathic hhydro-micelle”* They also noted that “The transparer oil-continuous systems are familiar as ‘soluble-oil” Schulman and co-workers did extensive work on swol len micelles using the name of “transparent oil-water dis persions”."""* With Boweott," Schulman pointed out that ho ‘Spheres Mic Bee a Fig. 3—Micelle types.10 to 40 percent soap concentration was needed to produce isotropic transparent fluids. Further, he noted that if soap micelle interfaces were penetrated by alcohol molecules, the micelles “are able {0 swell almost unlimitedly both with oil and water...". Schulman later referred to these systems as “microemulsions”, noting that the particle sizes, could reach diameters of 1.5% 10" mm." We have chosen to refer to our fluids as micellar solu- tions primarily to distinguish them from emulsions and solutions of surfactant in water or hydrocarbon. Composition and Effects of Components Micellar solutions contain three, four, or more com: ponents. The three basic components are hydrocarbon, surfactant, and water. The hydrocarbon can range from liquefied petroleum gas (LPG) through different refinery streams to crude oil. Alkyl aryl sulfonates are effective surfactants. Other surfactant types may be used." These three components by themselves are sufficient to form micellar solutions Alcohol as a fourth component (co-surfactant) can be added; this increases the latitude in composition through which’ micellar solutions can be made. Isopropyl alcohol (IPA) serves as a good example. Fig. 5 shows pseudo- ternary diagram for a four-component system in terms of volume percent. The presence of a definite interface defines the two-phase region. In the single-phase region, for ex: ample, at high water and low alcohol concentrations, solu- tions are milky, but they show no phase separation after standing for several days, Water containing dissolved electrolytes may be used in preparing micellar solutions, Salts, as a fifth component, allow even additional control in attaining the proper vis. cosity required for mobility control. ‘When water is added to the solution denoted as “S” in Fig. 5 to give a 25 percent water containing micellar solu- tion designated by A, a fluid results that is definitely oil external. This fluid is miscible with hydrocarbon; hence, ‘one of the requirements for an effective oil recovery agent is satisfied. Water will dilute Fluid A as indicated by the line con necting A in Fig. $ with the apex representing pure water. Fluid A remains oilexternal when diluted with water to Bive the solution designated by H. With continued dil Solubiized oi! Solublized Weter Spherical Micelles Be Sei we Ee Fig. 4Swollen micelles. TABLE 1—-COMPOSITIONS OF MICELLAR SOLUTIONS (Wolume Percent) A Hc De FF Sulfonate Tyee 8° SLT OK KOS, Petroleum Sulfonate 143 14 129 13 103 86 Isopropyl Alcohol 137 (30 '20 107 06 43 Water’ 25.0 400 117 200 273 342 Pentane 57.0 436 Crude Column Overhead 734 ©80 618 Stabilized Light Straight Run Gasoline 529 Soditim Sulfate O21 *Manutactured by Shell Chemical Co, *?Manufactured by Bryton Chemical Co. *°Prepared in the laboratory. ‘Weight percent based on water. tion, the oil-external system inverts to a water-external emulsion denoted as B in Fig. 5. The phase diagram indi ‘cates that Fluid B ig “miscible” with both Fluid A and water. In essence, these conditions form the basis for our process. An oil-bearing reservoir is flooded by frst inject ing a slug of A, then following this with a buffer of ‘matched mobility B, and finally by injecting drive water Oil mixes readily with the micellar solution slug, inter faces normally being non-existent immediately following mixing. Mixtures of slug, emulsion, and water (see Fig. 5) are in the single-phase region so’ that the displacement takes place without interfaces. Because of these conditions, the slug is moved effectively through the reservoir. Table 1 gives some typical compositions of micellar solutions, The crude column overhead (CCO) and straight rum gasoline indicated in the table are hydrocerbon streams from an atmospheric crude column. Distilled water with no electrolytes added was used in making all the solutions shown except Solution F. System H in this table illustrates 2 composition that results when System A is diluted with ‘water. The compositions of Fluids A and H in Fig. 5 are given by Systems A and H in Table 1, respectively. ‘The effect that some components have on micellar solu: tions canbe appreciable. For example, straight and branched alkane hydrocarbons require relatively small con- centrations of IPA to produce stable solutions. Unsatw rates and aromatics require large concentrations of IPA. Saturated eyclics are unique in that the range of IPA wean | , Fig. S—Pseudo-ternary phase diagram for pentane- sulfonate-IPA-water.needed to produce stable solutions is quite broad. Mixtures, of pure hydrocarbons fall in an intermediate region Salts, too, have their effect not only in viscosity control bbut also in making phase-stable solutions. Besides the commonly-thought-of salts such as NaCI or Na,SO,.. many other electrolytes have been used effectively. Acids and bases and polyvalent salts are equally as effective as NaCl. To a first approximation, the salt effect is @ function of jon concentration and not of ion type. This generalization falters somewhat with strong mineral acids where slightly less is needed on a molar ion hasis to impart similar results, Tonic strength has been found as a useful means for predicting the phase behavior effects of micellar solutions. Solutions were prepared using FeCl,. Pb(NO,)... and CrCl, as electrolytes. Values of ionic strength were calculated using 15 = % ¥evz., where IS is the ionic strengths z is the ionic charge of the cation; and c is the coneentration. ‘The approximate center of a single-phase region of a phase diagram was used as the reference point for these calcula- tions. Table 2 shows the results, along with the maximum jon concentration at which each salt can produce phase stable fluids. The close agreement of ionic strength in the table suggests its use for predicting concentrations of other salts ‘Two important side effects of using salts in micellar solutions should be mentioned. One is that radioactive water-soluble tracers are incorporated in hydrocarbon media.” The other is that salts in the solubilized water of oll-external fluids can be used as in-situ tracers. to monitor slug movement and flow behavior in interpreting flooding data. We have used NaNO, for this purpose by analyzing for NO,” in the effluent fluids. Proper choice of co-surfactants can also impart dramatic effects on micellar solutions. Systems using methanol as the co-surfactant seem to be unusually sensitive to. tem: perature changes. Much less methanol (relative to IPA) is needed at elevated temperatures than at room tempera ture. Glycerin generates rather thick micellar solutions and requires fairly large quantities (greater than about 7 percent by volume). Resides the five fundamental components discussed other desirable additives may be incorporated in micellar solutions without deleterious effects. Certain bactericides such as formaldehyde (1 percent in water), HgCl, (25 ppm in water), and CuSO; (25 ppm in water) may be added to these solutions. Thickening agents, both oil- and water-soluble, can also be used in these fluids as viscosity ‘enhancers. Phase Rehavior with Reservolr Fluids To achieve high unit displacement in oil recovery. the displacing medium must be miscible with the displaced fluids, The oil-external character of the micellar solutions makes them compatible with crude oil. This compatibility between crude oil and micellar solution slug represents the first important phase relationship in the process, and constitutes a real advantage over displacements using aqueous systems such as water containing a water-soluble surfactant or a water-external emulsion, Compatibility be- tween oil and a slug of micellar solution depends upon micellar solution components and composition. Oil-soluble alcohols, for instance, enhance crude compatibility. The ‘humerous degrees of freedom in slug design suggest that compatibitity with almost any crude is possible. Micellar solutions have been made that are compatible with many different crudes, including volatile, black, and the so-called green paralfin crudes. Simple laboratory mixing tests using varying proportions of one fluid to another are sufficient to demonstrate the phase behavior of slugs with erudes. ‘True miscibility between the slug and crude is often lack ing in the scientific sense; ie., a zer0 interfacial tension with no phase-separation after long periods of time for all combinations of the slug and crude oil is not observed. ‘Another important fluid relationship that must be con sidered is phase behavior between micellar solutions and connate water. Depending on the salinity of the water in place, water may be either solubilized by or removed from the micellar solution, For a given slug composition, the solubilization decreases as the salinity of the brine in- creases. Brine compatibility is a function of surfactant type and concentration, It is also a function of alcohol content. We have made micellar solutions that are com: patible with brines of 50,000 ppm total dissolved solids ‘A third uid relationship that should be considered is that between slug* and mobility buffers. Buffers of either water-external emulsion or thickened water mix extremely ‘well with oil-external micellar solutions. Again, there is some dependence on the particular systems involved. For example. IPA makes the slug more hydrophilic and thus ‘more compatible with the bulfers. Mobility Control Adequate mobility control is an important requirement for any miscible-waterflood process, Without this control. slug integrity is jeopardized, and large pore volumes of slug are required. Mobility control for the process. is based on the total mobility of the oil and water owing ahead of the slug in a stabilized bank” Ideally. the slug mobility is made equal to or less than that of the bank. Mobility control continues with the buifer's mobility being ‘made equal to or less than that of the slug. How slug and buffer mobilities are controlled through solution properties is the subject of this section, Micellar Solution Slug Mobility Slug represents a significant cost. Every effort is made to reduce the slug size while maintaining its integrity. With adequate mobility contro! behind the slug. the pore volume ‘of micellar solution is minimized. Under normal opera- tions, a 3 to 15 percent PV is sullcient Micellar solutions typically exhibit the rheological char acter shown in Fig. 6." System D of Table Iwas used t0 obtain these data. As shown, fluid behavior is Newtonian fat low shear rates, Increasing shear causes the fluid t0 ‘become non-Newtonian, the apparent viscosity being re lated to the shear rate by a power law function. Normally, flow rates in a reservoir are such that micellar solutions behave as Newtonian fluids TERGa gy Bis ape Oe tow Say” cay fe aeamel wet ‘a eee gi TTT. CAPILLARY VISCOMETER SF * CONE @ PLATE VISCOMETER. Bt el = 0 100 i000 8000 SHEAR RATE (SEC) Fig. 6—Rheological properties of a micellar solutionSiug viscosity is a function of composition and can be controlled to fit a specific application, Micellar solutions can be made having viscosities from that of kerosene to that of a gel-like paste. Furthermore, any of a number of, methods usually may be used to obtain the desired vis cosity. A few of the parameters that can be varied to control viscosity are the amount of water, the electrolyte concentration, the hydrocarbon and surfactant type, and the use of co-surfactants, Fig. 7 illustrates how water content affects the viscosity of a micellar solution. In this figure 76, 19, and 5 percent solutions of pentane, sulfonate, and IPA, respectively, are grouped together and represent one component; water is the other component. Points A, H, and B on this figure are the same compositions as given in Table 1 and Fig. 5. As the solid line indicates, the addition of water to the hydro: carbon, surfactant, and alcohol solution causes the viscos- ity to rise to about 10 ep at 25 percent water. With addi tional water, the solution viscosity increases exponentially to a point of about 45 percent water. This is the inversion point where the oil-external character of the Muid gives Way to the waterexternal system, Fig. 7 also shows how the use of electrolytes helps to control viscosity. With the addition of salt, the micellar solution takes up more water but maintains the same viscosity. Table 3 gives an example of an even more striking reduction in viscosity when salt is added, Two orders of magnitude reduction in viscosity are achieved by adding less than 0.3 percent NaSO,. The table also demonstrates that salt can be used to bring about phase stability in an otherwise unstable fluid. 100] Capi to {| _| ‘As one would expect, hydrocarbon type also has a bearing on micellar solution viscosity. Generally, the more viscous the hydrocarbon the more viscous the resulting micellar solution, The effect of surfactant concentration fon viscosity is shown in the data of Table 4. Note that the SLSRG concentrations in Table 4 are not constant. These changes are not so consequential to viscosity as the changes in sulfonate concentration, For example, on the basis of Percent water, System E should have a higher viscosity than System C (Fig. 7). Since the reverse is true, the effect ‘must be due to the difference in sulfonate concentration. Co-surfactants usually cause a reduction in micellar solution viscosity. Specific data are not given here since the effect actually seen is so strongly a function of the ‘other variables in the system. Usually an order of magni- tude reduction in viscosity is not uncommon when I or 2 percent of either isopropyl or normal butyl alcohol is added, after Mobility ‘The mobility buffer furnishes protection at the trailing edge of the slug. Table 5 shows how composition affects the viscosity of these fluids. Both the emulsions and thickened water exhibit non-Newtonian behavior. The emulsions in Table 5 are of the type whose viscosity is shown in Fig. 7 with water concentrations above 45 per: cent. With the capability of adjusting viscosity as indicated in the table, the buffer’s mobility can be made less than ‘oF equal to the slug. In practice, a thickened water buffer is more economical than an oil-in-water emulsion. High molecular weight, par tially hydrolyzed, polyacrylamide polymers. such as Dow's Pusher, are effective for preparing the thickened water Polymers of this type were used to prepare the solutions listed in Table 5. With these high molecular weight poly: mers, mobility control depends on both permeability re duction and viscosity” COIN TABLE 2—IONIC STRENGTH AND CONCENTRATION ‘OF IONS FOR POLYVALENT SALTS IN MICELLAR SOLUTIONS Concentrations of fons in | tonie ‘Moles/titer of Water strength in the Miceior Sotions jaf] 0.068 0.042 : $ 8865 See § of La fh a S68 Bee posit ifsc z _ & £ % TABLE 3—VISCOSITY REDUCTION IN MICELLAR =| is s SoLUONS A8/A FONCTION OF SALT CONCENTRATION pos 6 Micellar gm NaSO, Added per Stability Viscosity z,¢ 2 solutions Eter Miesar Soiution Comments \tep) i 1 ° $2009 hy % 1 Ys Sear Stier | % 1 @ Hazy, Unstable > 2000 7 % i 28 Clear, Stable 87 mW ° Hazy, Unstable Gel | i 26 Sein Sete” “loo vA ‘TABLE 4—VISCOSITY AS & FUNCTION OF ow 20-3 4 50 G0 70 80 90 100 ‘SULFONATE CONCENTRATION % Water A=Oil-External Slug(See Tobie! and Figure 5) H=Oil-External Solution (See Table! and Figure 5) B= Water-External Emulsion (See Figure 5) $C= Salt-Contoining Micellor Solution Ts Inversion Point between Oil-and Water-External Slugs Fig. Viscosity vs percent water. (Wolume Percent) H,0 sulfonate SLSRG* Viscosity System (percent) (percent) (percent) _ (ep). a 40 10 50 62 8 40 18 45 a & 40 20 40 eae D 45 10 45 118, E a3 15 40 256 ‘Stabilized light straight run gasoline.‘The buffer's mobility is lower than that of the drive water. Under these conditions, drive-water_ movement through the reservoir is more rapid than that of the mobility buffer. Sufficient buffer is required to prevent drive water from reaching the slug before its effectiveness is lost; but, because of buffer cost, the volume used is, kept as small as possible. Depending on the design mo: bility and reservoir conditions, the mobility buffer pore volume can range between 30 and 60 percent. Efficiency of the Process Both laboratory and field testing have been undertaken to evaluate the technical feasibility of the process. Labora tory and field results are given here as an indication of efficiency. With other processes using surfactant, loss by adsorption is reported as a problem Results given in this section indicate that surfactant loss by adsorption ‘minimal with micellar solutions. Laboratory The effectiveness of micellar solutions as displacing agents is illustrated in Table 6 by results obtained with infinite slugs. Results indicate that recovery is not affected by initia saturations. Injection of the micellar solution in these runs caused a stabilized oil and water bank to develop. The length of this bank depended upon the initial core saturations, but the bank saturation in each run was indevendent of the initial saturation. The high recoveries at less than 1 PV injection indicate the high unit displace- ‘ment efficiencies characteristic of flooding with micellar solutions. Displacement results with micellar solutions in ‘consolidated cores and glass micromodels are available." ‘The effect on recovery of using a micellar solution stug is seen by comparing results in Tables 7 and 8. Without any slug (Table 7), the average oil recovery was about 59 percent after injecting 2 PV of water. By using a TABLE 5 MOBILITY BUFFERS OWL-IN-WATER-EMULSIONS Composition (Volume percent) Fluid Fluid 2 Pentane, 33930 6 and a 12-percent slug (Table 8). the oil recovery after 2 PV of total uid injection equalled 67.5 and 92.0 percent, respectively. Table 8 shows that the recovery was about the same with the 12- and 20-percent slugs. These results indicate a minimum slug size between 6 and 12 percent. Fresh water was injected to complete the floods listed in Table & after injecting the pore volume of slug indicated. Slug viscosities used to obtain the results in Tables 6 and 8 were about 11 cp at 72P. To prevent gravity segre. gation, frontal velocities were 82 ft/day. Blackhawk “E” sand was used for both cores and fell in a size range of =80 to +120 mesh, Cores had a permeability of about 8 darcies and a porosity of 37 percent. The oil viscosity was 85 ep at 72F. ‘The question of adsorption is always present with oil recovery methods using surfactants, In our opinion, the problem appears inconsequential in this process. Appar- cently, the interaction between the surfactant, hydrocarbon, and water reduces adsorption. Static tests have shown high adsorption losses in both surfactant hydrocarbon and surfactant-water solutions Table 9 shows the surfactant remaining in laboratory cores after flooding with water. Results are encouraging in light of the losses experienced with other processes using surfactants. For the experiments, 4-ft X 2-in, diameter Berea cores were: (1) saturated with water containing about 3 percent total dissolved solids; (2) flooded with 08 PV of micellar solution slug; and (3) flooded with 2.0 PV of thickened water. Sulfonate remaining in the ores was determined by material balances, which were accurate to ==3 percent. Correspondingly, the values in TABLE 7—RECOVERIES FROM WATERFLOODING Recoveries Initiat Saturations (Percent of Oil in Place) (Percent of PV) ‘Water Inlected. Run “Ol Water Gas LOPV 15 PV 20PY 1 557 137 306 417 500 567 2 547 212 287 = 492578 27 3 847 56 297 424 508 576 iameter sand pack ‘Tyoe S Sutonate 33 pe Care 10 x Yon Ieropn Aloha go gf ster 3 3 NE ope TABLE RECOVERIES WITH DIFFERENT SIZE Viscosity, em 100 38 MHEELLAR SOLUTION SLUGS THICKENED WATER Composition of Micellar Solution Slug Composition (opm) Fuld) Fwd? ula 8 Comper Glumeperent) Polymer concentration 150 Pentane 535 Totai'sat concentration =o ga Type § Sultonate 102 Vinci op mo sso “Bs Isopropyl Acahot 33 ‘Monsuted at» shear rate of 8 sec", water 330 Recoveries TABLE 6—RECOVERIES WITH DIFFERENT (Percent of Oi in Pace) tug size Initial Soturatons “Tota Sug and Water INITIAL SATURATIONS Soest barcent of by injected Composition ofthe Micellar Solution fun "ev" “On Water TOW 1s ZOPT volime-percend oo —-—_testumesereent) 1 20 557 165 278 930 985 Pontane 578 2 2 HL 88 28 SS 535 ype" sulfonate 133 3% 89 Be ot 23 ers Ieborony coho 28 Core: 104% x Yin. diameter sand pack. Ol Recovered TABLE 9 SURFACTANT LOSS IN LABORATORY CORES Throughout “it iaieatee Saturtions "Ypereent* Throughput Suriactant Remalning in Core Water Gas Pv" ercanth Run (Percent of Surfactant Injected) 235 20 928 : 18 Bia 288 338 3 os a 2 58 3 ot Core: 6 x 0.35, diameter sand pack. a 80Table 9 are accurate to 0.05. The slug for each run had a slightly different co-surfactant and electrolyte composi tion. The average composition of CCO, Type K sulfonate, IPA, and water was 55.5, 104, 25, and 31.6 percent by volume, respectively. Fiela Field testing was started in 1962 in the Eastern Ilinois oilfield area." One secondary and two tertiary tests have been completed. These tests have demonstrated the tech: nical feasibility of the process. A larger scale tertiary project is under way in this area to determine economic potential. A test is being conducted in the Bradford Dis- trict of Pennsylvania in a reservoir producing Penn grade crude. It is a joint project of Pennzoil United, Ine., and Marathon Oil Co. Current evaluation is aimed at deter mining process economics and the range of reservoir types amenable to the method. ‘The production behavior of the most recent test is plotted in Fig. 8. This test was conducted in a waterflood. depleted interval of the old Eastern Illinois field. Residual oil saturation at the start of the test was 35 to 40 percent. ‘Two isolated, inverted five-spot patterns were used for the test. In both patterns, the micellar solution slug was followed by thickened water. Pattern 1 received a larger volume of the micellar solution than did Pattern 2. At the start of the test, both patterns were producing at very th WOR’s, typical of the late stages of a waterflood. ‘As the producing wells began to respond, oil cuts. in creased, with one of the eight wells showing a 50 percent oll cut, Pattern 1 reached an over-all oil eut of 36 percent, and Pattern 2 reached a maximum cut of about 19 percent Fig. 9 shows actual core samples taken from this last test reservoir. The composite on the left is made from samples taken through the reservoir section after the res- ervoir was waterflooded but prior to the injection of slug, ‘The composite on the right is from a core taken behind the slug front at a distance of about 40 ft from the injec tion well. This core was analyzed and found to be com pletely devoid of any oil saturation. Oil samples from the field have shown the passage of surfactant through the reservoir. Cores taken behind the slug front revealed no adsorbed surfactant. In making these determinations, we extracted crushed cores with benzene in a Soxhlet, and concentrated the solutions by boiling off the benzene, then we examined for surfactant with an infrared spectrophotometer. Conclusions 1. A new oil recovery method has been developed that utilizes the unique properties of micellar solutions. PATTERN 1 Wen FER MAR APR MAY NE UOTE Fig. 8Field production behavior. ° wo Oke 2. Properties of micellar solutions depend upon the types and composition of the basic components used in their formulation. Hydrocarbon, surfactant, and water are ‘basic to the solutions. Small ‘concentrations of co-sur- factants and electrolytes alter the properties of the micellar solutions 3. The constituent in smallest concentration that imparts the greatest change in micellar solution properties is salt. Salts affect the viscosity and phase stability and are also ‘useful as in-situ tracers 4, Micellar solution slugs can be made with different surfactants and hydrocarbons. 5. Fluid compositions are formulated to achieve misci bility throughout the process. Micellar solutions are misc ble with the mobility buffer, which in turn is miscible with drive water. 6. Tonic strength can be used to predict the effect of salts on micellar solution phase behavior. 7. Mobility control is possible with the process. Viscosi ties are fixed by judicious selection of the slug composi- tion. Oil-in-water emulsions and thickened water are satis. factory as buffers, their mobilities being controlled by composition. BEFORE FLOODING AFTER FLOODING RESERVOIR i Fig. 9—Field cores: before and after flooding.8, Rheofogically, the micellar solutions may behave as ‘Newtonian fluids at low shear rates. At high shear rates, the fluids are non-Newtonian and follow a power law relationship. 9. Micellar solutions used in the process are effective agents in miscible-type floods and displace 100 percent of the oil in the reservoir contacted. 10. In a 10-ft sand pack, a slug between 6 and 12 per: ‘cent PV recovers essentially all of the oil when driven by fresh water, 11, Field data show the process to be technically feasible. 12. Laboratory and field results show surfactant loss from micellar solutions by adsorption on porous media to be small Acknowledgments ‘The authors express their appreciation to R. W. Olson M. O. Son and C. B. Wenger for their assistance, and to Marathon Oil Co. for permission to publish this paper. References 1. Latimer, J RJ. "Perspective on Improved Oil Recovery”, Pet, Bg. San.. 1963) 39, 62-83. 2 -Rhidfhietion rojas in the U. 8°, Oil and Gar J (Nov. 8, 1965) 145-199. s.spolymer Plats taetng Recor Gap, Ol on Gat. (Gan. 35, 1969) 46-47 4. Howard, J. V.: “Thermal Recovery Comes of Age", World Off Gan, 1965) 98-108 S.Simm, CN. “Thermal Recovery Appraisal” Gian’ 1967) 59-63. 6. Gardner, G. H. F., Henderson, J. H. and Wylie, M. RJ ‘crea Comparten of Mouic enaeenet eto for Improvement of Oil Recovery®, Revue Hos.T8i0, ” 7.Staht. C. sciMe Phase Displacement — A. Survey" Prod, Monty (1965) Nos. I through 3,3, 10,2428, 20 World oit 8. Mungan, N.: “Role of Wettabiity and Interfacial Tension in Water Flooding”, Soc. Pet. Eng. J. (une, 1964) 118-125. 9. Holm, L. W. and Bernard, G. Gu: “Secondary Recovery Waterflogd Process", U.S. Patent No. 3,082,822. (March 26, 1963), 10. Binder, G. G., Irs and Russell, C. D.: "Secondary Oil Recovery Process’,'U."S, Patent’ No, 3,149,669 (Sept. 22, 1964), 11. Csagzar, A. K. “Solvent-Waterload Oil Recovery Process", ‘U.S. Patent No. 3,163,214 (Dec. 28, 1964), 12. Weinaug, C.F, and Ling, D.: “Production of Hydrocarbon Material, U. §. Patent No. 2,867,277 (an. 6, 1955). 13, Sancevie, Z. Au: “BMect of Adverse Mobility Ratios and Graded Viscosity Zones on Viscous Fingering in. Miscible Displacements", MS thesis, The Pennsylvania ‘Stale Us, University Park Gan, 1961). 14, Mysels, K. J.: Introduction f0 Colloid Chemisty, Tntersc- ‘ence Publishers, Ine, New Yerk (1989) 10, 15. The Eneyclopedia of Chemistry, Reinhold Publishing Corp. New York (1957) 398, 16. Recher, P.: Emulsions: Theory and Practice, Reinhold Pub- lishing ‘Corp, New York (1965) 36. 17. Ibid, 46. 18.Jirgensons, B.: Organic Colloids, Elsevier Publishing Co. ‘Amsterdam (1938) 62-63, 19. The Von Nostrand Chemise Dictionary, Van Nostrand Cor, ne, New York (1983) 468. 20. McBain, J. W.: Collold Science, D. C. Heath and Co. Boston (1950) 257 21, Harley, G. S.: “Aqueous Solutions of Parafin-Chain Salts. A’Study in Micelle Formation”, Hermann et Cie, Paris i936) 45. 22. Adamson, A. W.: Physical Chemistry of Surfaces, Tater Science Publishers, Inc, New York (1960) 376. 23. MeBain, J. W.: “Organization of Crystals and Micelles of Soap: Solubilization and Detergeney™, Frontiers in Colloid Chemistry edited by R. BE. Burk and O, Grummit, Inter Science Publishers, Ine, New York (1950) VII, 149151 24. Sumner, C. G.: Clayton's The Theory of Emulsions ond Their Technical Treatment, Chemical Publishing Co., Ine ‘New York (1954) 321. 25. Becher, Pz Principles of Emulsion Technology, Reinhold Pot Book, Reinhold "Pubishing Corp, New Work (1988) 4 26, Rowoott, J. E-and Schulman, I. H.: “Emulsions”, Zets fir Elec. (1985) 89, Heft 4, 285-250. 27. Hoar, T. P. and Schulman, J. H.: "Transparent Water-in- ibe Oteoainic” Hydro cee", Nature 28, Schulman, J. H. and McRoberts, T. S.: “On the Structure of Transparent” Water and Oil Dispersions (Solubilsed its)", Trans. Faraday Society (1946) 428, 165-170 29, Schulman, J. Hand Riley. D. Ps "X-Ray Investigation of the Structure of Transparent Oil-Water Disperse Systems. I", J. Colloid Setence (1948) 3, 383-405 30, Schulman, J. H. and Friend, J. A: “Light Scattering tn- Vestgation on the Structure of Tvansparent-Oil-Water Dis. perse Systems, I, J. Colloid Seience (1949) 4, 497-509 Schulman, J. H,,Stoeckenius, W. and Princs, L.M.: "Mec ‘nisms off Formation. and Siruclure of Micro Emulsions by Electron Microscopy", J. Phys. Chem. (1959) 63, 1677 680. 32, Schulman, J. H.: “Colloid Chemistry”, Annual Revue of Phys. Chem, (1960) 11, 169-186. 33. Stoeckenius, W., Schulman, J. H. apd Prince, L. M.: “The Structure of Myelin Figufes_ sn? Microamulsions as Ob- Served. with the Electron Micronope™, KollZe1. (1960) 4169, Hett 1-2, 170-180. 3Stiman, JH. and Monge, 3, Re, *Fomaton of fit LM, onion 2B Taman Se An a cost 35. Ooqar We Band Qbon, RW "Uw of Miaenins Someta Osan, Wee ot Mirra sit ee Oh eas 6 Teuch, W, Cz ecnion frloororting Wot Ste Fah MC dealer demain, fe Sol TB ai S7.Gopany W Bs Meson, H. Po and Mito, HW. Me Bae Meal Maton Ngan Mn, te a Sea Pa tt Ne ae Me Bas Teale een SSPE ay St.Goqary, W. Be "Mheoele! Proper of Preven Some, Wks SRM! Boreas of Beadewats ra S9.Gorary, Ws "Mobily Cone) with Payne Sole Set a eS TS 40-Tgiee J: “The incon Detergent Sug Water Fol eu REESE ETS Davin JA Se and Jp, 8. Cx “Diplenpent Mace Pa, ing ae Ge TBE, WES; ‘mew Method Sweps Out Of Renanine Aer Wat ose, Mat, Sey Su, OH tsaane x