Wettability and Its Effect on Oil Recovery

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1 Wettability and Its Effect on Oil Recovery Norman R. Morro, SP, Ne Mexico Petroleum Recovery Research Center, Ne MexIco Inst. of Mining & Technology Introduction Reservoir ettability is determined by complex interface boundary conditions acting ithin the pore space of sedimentary rocks. These conditions have a dominant effect on interface movement and associated oil displacement. Wettability is a significant issue in multiphase flo problems ranging from oil migration from source rocks to such enhanced recovery processes as alkaline flooding or alternate injection of CO 2 and ater. In this paper, ettability ill be discussed mainly in the context of recovery of light Oo-viscosity) oils by aterflooding. Waterflooding has been idely applied for more than half a century; secondary recovery by aterflooding presently accounts for more than one-half of current U.S. oil production. Many research papers have addressed the effect of ettability on aterflood recovery during this period. For much of the past 50 years, hoever, a large body of reservoir engineering practice has been based on the assumption that most reservoirs are very strongly ater-et (VSWW); i.e., the reservoir-rock surface alays maintains a strong affmity for ater in the presence of oil. The rationale for assuming VSWW conditions as that ater originally occupied the reservoir trap; as oil accumulated, ater as retained by capillary forces in the fmer pore spaces and as films on pore surfaces overlain by oil. Wettability behavior other than VSWW as observed for reservoir core samples, but as often ascribed to artifacts related to core recovery and testing procedures. The majority of reservoir engineering measurements have been made on cleaned core ith refined oil or air as the nonetting phase to give results for, or equivalent to, VSWW conditions. Examples of such measurements are laboratory aterfloods, determination of electrical resistivity vs. ater saturation relationships, and capillary pressure measurements for determination of reservoir connate ater saturation. Mounting evidence on the effects of crude oil on etting behavior l has no led to Copyright 1990 Society of Petroleum Engineers 1476 ide acceptance of the conclusion that most reservoirs are at ettability conditions other than VSWW. This conclusion has led to a resurgence of interest in satisfactory procedures for measuring reservoir ettability and determining its effect on oil recovery, especially ith respect to aterflooding. Determination of reservoir ettability and its effect on oil recovery by methods that involve core samples ill be referred to as advanced core analysis for ettability (ACAW). Reservoir ettability is not a simply defined property. Classification of reservoirs as ater-et or oil-et is a gross oversimplification. Various procedures for measuring ettability have been proposed. To methods of quantifying ettability based on rocklbrine/oil displacement behavior, the modified Amott test 2 and the USBM test, 3 are in common use. Each method depends on ater saturation measurements and related capillary pressures or flo conditions to define a ettability scale. The tests sho that reservoir ettability can cover a broad spectrum of etting conditions that range from VSWW to very strongly oil-et. Within this range, complex mixed-ettability conditions given by combinations of preferentially ater-et and oil-et surfaces have been identified. In this paper, the 'adopted scales of reservoir ettability and their relationships to interface boundary conditions are considered together ith the dramatic effects that ettability can have on oil recovery. Contact Angles, Spreading, and Adhesion Contact Angle and Spreading. Contact angle is the most universal measure of the ettability of surfaces. Fig. 1 shos idealized examples of contact angles at smooth solid surfaces for oil and ater of matched density. Early studies of etting phenomena shoed that the etting properties of a solid are dominated by the outermost layer of molecules. (Films that result from spreading and other thin adsorbed films are not indicated in Fig. 1.) Large change in the ettability of a surface, such as quartz, can be achieved by adsorption of a monolayer of polar molecules so that the outermost part of the surface is composed of hydrocarbon chains. Extreme change in ettability (see Fig. 1), such as from a or b to e or f, or vice versa, is called ettability reversal. Adsorption of polar compounds from crude oil plays a critical role in determining the etting properties of reservoir-rock surfaces. Many early studies of etting behavior, even for comparatively simple systems, ere plagued by problems of reproducibility. Aside from surface contamination, other forms of heterogeneity in chemical composition, surface roughness, and static and dynamic interface properties contribute to the complexity of observed etting phenomena. Large differences in contact angles, depending on hether an interface as advanced or receded, called into question the validity of attempting to describe ettability by a single-valued equilibrium contact angle. Successful systematic studies of closely reproducible equilibrium-contact-angle measurements have been summarized by Zisman. 4 By use of smooth (often polymeric), solid surfaces and pure liquids, contact-angle hysteresis as limited to ithin 1 or 2. In contrast, contact-angle hysteresis is observed almost invariably for crude-oillbrine systems. Fig. 2 shos examples of contact angles that exhibit small and large hysteresis. Receding angles are generally lo ( < 30 ) and seldom exceed 60, hereas a ide range of advancing angles is observed. The shaded regions in Fig. 2 sho the range of possible contact-angle values for a fixed position of the three-phase line of contact. Contact-angle measurements on reservoircrude-oillbrine systems provide one approach to measuring reservoir ettability. For the most extensive set of data yet reported,5 contact angles for crude oil and simulated reservoir brine ere measured at reservoir temperature and ambient pressure. Choice of mineral substrate, usually quartz or calcite, as based on hat as judged from petrographic examination to be the predominant mineral at pore surfaces. (There are obvious limitations to representing the rock surface by a single mineral.) To determine contact angles, to parallel mineral plates are submerged in brine and December 1990 JPT

2 spedistinguished Author SERIES then a drop of oil is introduced beteen the plates. When the plates are moved relative to each other, advancing and receding conditions can be observed. Water-advancing contact angles, (J A' are reported as defining ettability because these are considered relevant to aterflooding. 5 Figs. 3a and 3b sho the distribution of advancing contact angles observed for quartz and calcite, respectively. (a) e = 0 (ater spreading) (b) e = 25 (c) e = 600 Adhesion Behavior of Crude-Oil/Brine/ Solid Systems. Because of problems in making definitive contact-angle measurements, a simpler approach to characterization of the etting behavior of crude oils has recently been adopted. 6-8 Smooth mineral surfaces are first pre-equilibrated for about 7 days ith brine. A drop of oil is contacted ith a surface overlain by brine for a standardized time of 2 minutes. The oil drop maintains a lo ater-receding angle during enlargement. Upon ithdraal, one of to extremes of behavior are usually observed. Either the drop detaches from the surface (nonadhesion) or the interface boundary remains pinned at the three-phase line of contact (adhesion) (see Fig. 4). For adhesion, the contact angle generally increases during ithdraal of oil until the liquid bridge ruptures because of capillary instability; after rupture, a drop of oil still remains on the solid surface. In some instances, an excess of surfactant, caused by a decrease in interface surface area after rupture, causes the oillbrine interface to become rigid. The interface eventually returns to its normal appearance ith a fe minutes (see Fig. 4). The area over hich the oil drop remains attached to the solid is usually very strongly etted by oil. Thus, adhesion corresponds to large hysteresis of contact angle (Figs. 2 and 4). The angle at hich the liquid-bridge rupture occurs is not necessarily the maximum advancing contact angle. In testing the adhesion properties of 22 crude oils as a function of brine composition and ph, remarkable similarities in results ere obtained for 20 oils, ith ph being the dominant factor. 8 To examples of ph vs. salinity mapping shon in Fig. 5 indicate the general form of these plots. The to oils that did not conform gave adhesion at both JPT December 1990 WATER mjfifl;)l7nm!flm OIL. OIL J11IJ1II1IIIIJJJlllllj'llllljjjj)lIj)llfllI (d) e = 100 (e) e = 160 (f) e = 180 (oil spreading) Fig. i-idealized examples of contact angles and spreading. (a) Small Hysteresis (b) Large Hysteresis Fig. 2-Possible ranges of stable contact angle, 8, for small and large hysteresis of contact angle, ith location of oil Indicated for 8 A' lo and high ph. In comparable tests on refined oil, adhesion as not observed at any of the tested ph levels. The transition ph for nearly all the crude oils tested fell ithin the narro ph band of about 6.5 ±2. For a given oil, only slight changes in ph at close-to-neutral conditions can cause a drastic change in adhesion behavior. This may explain the problems often experienced in obtaining reproducible crudeoillbrine/mineral etting behavior. A crude oil recovered and tested for adhesion behavior under anaerobic conditions gave results similar to those obtained after deliberate exposure to oxygen. Thus, the general form of the adhesion behavior is not an artifact of oxidation. 8 "Contact angle is the most universal measure of the ettability of surfaces." 1477

3 Non-adhesion Adhesion f! J '5 E z " f! 12 0 Q) 10 II> Q) a: '5 8 E 6 Z " 0-20 Water Advancing Contact Angle (a) Quartz eo.eo < eo-18O Water Advancing Contact Angle (b) Calcite Fig. 3-Distribution of contact angles for crude-oil/brine systems on (a) quartz (29 measurements), and (b) calcite (30 measurements) (after Treiber et al. 5 ). The similarity in effect of brine properties or etting behavior observed for all but to crude oils provides a case for the use of crude oil rather than a refined oil as a reasonably definitive and certainly, for reservoir engineering purposes, a more relevant model for the oleic phase. Note that the advancing contact angle values for crude oil/brine on quartz (see Fig. 3a) fall into to classes that seem to be consistent ith observed adhesion tests conducted on glass or silica surfaces. In spite of the chemical complexity of crude oils, a distinct possibility exists that crude oils ill give consistent results ith respect to other phenomena that depend on etting properties. Stability of Thin Films. The outcome of adhesion tests depends on the stability of the ater film beteen the solid and the oil drop. Stabilization of the thin film by electrostatic repulsion requires that the charge at the brine/solid interface and the net charge of the brine/oil interface have the same sign. Film thickness, generally much less than 100 nm, is determined by a balance beteen van der Waals attractive forces and repulsion by electrostatic and hydration forces. 9 The much-less-understood hydration forces come into play in the stabilization of very thin ater films at high ionic strength. The highcontact-angle values shon in Fig. 3b are consistent ith adhesion occurring more readily on calcite than quartz because, under comparable conditions, calcite has a more positive surface charge. It follos that the types and distribution of minerals such as carbonate cements or clay minerals at the surface of pore alls, even if they make up only a minor part of the total mineral constituents ofthe rock, also play an important role in ho crude oil alters etting properties. With respect to the effect of ph in the reservoir, rock minerals ill tend to buffer reservoir ph at some fixed characteristic value that is close to neutral Because ph cutoff values are also close to neutral, adhe- NONADHESION.. LOW RECEDING ANGLE «30 ) ADHESION j =.----, LOW ADVANCING ANGLE BEFORE DETACHMENT «ad' ) /.. TEMPORARY ADHESION AFTER DETACHMENT HIGH ADVANCING ANGLE (>9<1') TYPICAL DROP SHAPE IF RIGID FILM FORMS UPON RUPTURE AFTER RUPTURE OF OIL BRIDGE DROP SHAPE JUST BEFORE DETACHMENT Fig. 4-lIIustrations of interface configurations for adhesion and nonadhesion of crude oil December 1990 JPT

4 14 14 Moutray Crude, 50 C NS-3,50 C 12...,.,....,...,...':'...: , I a. 2 o. Noriad.hesion. Nonkdhesion Adtlpsloo......!... i... x... Adhi,sion......:..., : H cutoff 1 ;::::;:1;::::::::[:: r x :.'.: ;.... ; "1 1.,0 101 Molar Concentration of Na + (a) 10 I a i ph cutoff + -::::r:::;;::f :: :::.::.:: ::::J::::::::::::::::::::r:::::::::::::::::r::::::::::::::::::.. :. : Molar Concentration of Na + (b) Fig. 5-Adheslon maps (ph vs. NaCI brine concentration) for to crude oils (after Buc.kley and MorroS). sion tests may not provide a definite prediction of the etting condition that crude oil ill establish itl1in a rock. Just as the outcome of the adhesion test depends on the stability of thin ater films, maintenance of ater-etness in a reservoir depends on the stability of thin ater films at pore alls. If the ater films are unstable, crude oil has access to solid surface in the region of contact and adsorption of polar compounds can drastically, and often permanently, alter the etting properties of the solid. The adhesion test studies sho adsorption to be specific to the area contacted by oil. This type of adsorption gives rise to. hat is knon as mixed ettability because the surface etting properties of the contacted area are distinctly different from the neighboring surface. Differences in adhesion and adsorption behavior at different mineral surfaces, together ith the effects of rnicroporosity and surface roughness, ill obviously contribute to the complexity of mixed-ettability systems. Asphaltenes. Wettability alteration has often been ascribed to the adsorption of highmolecular-eight colloidal particles knon as asphaltenes suspended in crude oil. 10 Asphaltenes are operationally defined as the precipitate resulting from adding a large volume of lo-molecular-eight hydrocarbon to the crude oil (typically 40 volumes of pentane). Their role in ettability alteration as further confirmed by the observation that deasphalted crude oil no longer exhibited adhesion in the lo-ph range. 8 Stabilization of ater films by electrical double-layer repulsion in the Athabasca tar sands explains the strong ater-etness often observed for this sand. 11 When a sample of freshly mined Athabasca tar sand is kneaded under ater, an abundance of clean sand grains fall from the sample. Thus, even though the tar sands have very high (+ve) Primary DRAINAGE /(FOrced) ii:" 6 Secondary DRAINAGE >- 60 (Forced) a: IMBIBITION > (spontaneous) 0 0 a: 0...J I 6. Ss 6 40 = -- AS WI It.Sos IMBIBITION (F=edi I 0 = 4S t (-ve) / IAH=l lo Secondary / 20 DRAINAGE N (USBM) = log A1 A2 (Spontaneous) 0 S,,'" CURVE IAH WATER INJECTED Vp Fig. 6-Relatlonshlp of ettablllty measurement by Amott and USBM tests to Pc curves for a mlxed-ettability system. Fig recovery vs. brine injected for COBR systems ith Amott-Harvey ettability Index ranging from 1.0 to (after Jadhunandan and Morro 15 ). JPT December

5 16 G z G u:: U W I Z W ::;; W Cl. (Jl is > a: o 0 W 0.5 (; W Kyt8 at al. (1961)23 Donaldson at at (1969)' SalalhulIl (1973)24 Wang (1986)21 Rathme!1 at al. (1973)n r-:=-- : COBR Systems (s8e Fig.7) lauooncr\jd:"e o;;-;-, (.\...: : c:::= ? '() _ vs /REFERENCE..:,. \<ssnexas..._--- \ \, _ LCONVENT10NAL CORE -. 10% SILICON :-:J. _.".., '_._._._. _._._. _._._.-. -'._.-' OII o WATER INJECTED Vp en Q) () C Q)... :::J () () o '0... Q).0 E :::J Z o o Residual Oil, percent Fig. B-Effect of ettability on laboratory aterfloods relative to recovery at strongly ater et conditions. Fig. 9-ROS measured by the single-ell tracer test for 112 reservoirs. asphaltene contents (about 15%), the sand remains strongly ater-et over geologic time. Perfect Wetting and the Effect of Capillary Pressure on Thin Films and Contact Angles. Under the early orking assumption that reservoir rocks ere VSWW, the rock surface as often discussed and illustrated as if a drained rock surface ere still overlain by a thick film of ater. Even hen ater spreads, hoever, retained ater films at drained solid surfaces that are in equilibrium ith the neighboring bulk ater ill be extremely thin relative to typical pore dimensions. Perfect etting, or spreading, is the most extreme ettability condition that can be expressed by contact angle-0 for ater or 180 for oil (see Fig. I). As a general rule, liquids such as ater or hydrocarbons ill spread against air on the surface of a mineral such as quartz or calcite. Systems exhibiting ater spreading and oil spreading ill be called perfectly ater-et, PWW, and perfectly oil-et, POW, respectively. PWW systems are a special subset of VSWW systems because the latter can include systems of lo, but fmite, contact angle. Even though a PWW condition may be difficult to achieve for crude-oil/brine systems, it provides a useful reference state. Contact angles cannot be measured directly for porous media, and it may not alays be possible to distinguish PWW (0 contact angle) and VSWW (lo, finite contact angle) systems by their displacement behavior. In mathematical treatments of capillarity, a common practice is to neglect the thick ness of drained films, even though their presence is of crucial importance to etting behavior. If an adsorbed film is at equilibrium ith the bulk liquid at its prevailing capillary pressure, the film's thickness ill depend on the combined effect of the capillary pressure of the bulk liquid and the curvature of the solid overlain by the film. A disjoining pressure, IT, hich for a zerocurvature solid surface is equal to the prevailing capillary pressure, is identified ith the film. 9 If the adsorbed film thickness changes ith capillary pressure"then, in principle, the contact angles can also change. Then, scaling of displacement pressure ill not be. exactly linear ith respect to pore size. While the theory of equilibrium relationships beteen capillary liquid, thin films, and vapor have been the subject of numerous scientific publications, as yet no consistent body of experimental evidence shos that such effects produce measurable changes in the etting properties of porous media. Thus, it can be assumed for most practical purposes that the boundary conditions that determine ettability are independent of the prevailing capillary pressure. Measurement of WettabUlty of OIl/Brine/Rock Systems Capillary Pressure Behavior of Crude Oil/Brine/Rock Systems. Understanding the relationships beteen ettability, capillary pressure, and the distribution of oil and ater in pore spaces is a necessary step in the difficult problem of quantifying ettability and its relation to oil recovery. Basic relationships beteen capillary pressure, surface curvature, and interfacial tension (1FT) and the use of contact angle in describing boundary conditions in cylindrical pores are ell knon. For crude-oil/brine/rock (COBR) systems, relationships beteen ettability and capillary displacement pressures are complicated by the complex pore structure and mineralogy of reservoir rocks and the effects of adsorbed organic components from the crude oil. Fig. 6 shos an augmented sketch 12 of relationships beteen primary drainage, imbibition, and secondary drainage; a full data set for all the curves shon is not available for COBR systems. (The curves in Fig. 6 are not representative of all types of COBR behavior. For example, imbibition capillary pressures sometimes fall close to zero, but then the rock continues to imbibe ater very sloly.) The curves shon are useful in comparing the three commonly used methods of measuring ettability for COBR systems: the Amott test,2 the USBM test,3 and imbibition rate measurements. 13 In discussing capillary pressure curves and ettability, uncertainty can arise in hat is meant by the terms drainage and imbibition. For the nomenclature used in Fig. 6, drainage is defined as a decrease in ater saturation and imbibition as an increase. The forced drainage mechanism is characterized by larger pores tending to empty before smaller pores. The spontaneous imbibition mechanism is characterized by smaller pores filling before larger pores. For systems in hich capillary pressure changes sign, as hen spontaneous imbibition is folloed by forced displacement, a further increase in December 1990 JPT

6 ater saturation occurs by a drainage mechanism. Similarly, a system can exhibit spontaneous imbibition of oil, hich by definition is a spontaneous drainage process (see Fig. 6). Amott Test. In the Amott test,2 ater is first displaced by oil by centrifuging or by use of a high floing pressure gradient. Pressure levels and time taken to reach initial ater saturation, Si, are somehat arbitrary. The aim should be to begin at the same ater saturation as in the reservoir. The core at Si is then immersed in ater to allo spontaneous imbibition. Spontaneous imbibition of ater ceases at some change in ater saturation, s, hen the oil/ater surface curvature falls to zero. Further oil can usually be recovered by forced displacement to give an overall increase in ater saturation, t' by floing ater at a high pressure gradient or centrifuging. Fig. 6 shos the relationships of saturation changes to capillary-pressurevs.-saturation curves. The ettability index to ater, I, is given by I=sft.... (1) An analogous index (see Fig. 6) can then be measured for oil such that Io=osfl.... (2) The difference, I-I o ' is often used to characterize ettability by a single number, I AH, knon as the Amott-Harvey index. Several points should be noted. Cessation of spontaneous imbibition of either ater or oil occurs hen the relevant interfacial curvatures fall to zero. (The generally minor effect of buoyancy is neglected.) In practice, this exact condition can be difficult to identify if imbibition rates become very lo. An operational definition for the endpoints for spontaneous imbibition is then needed, such as alloing a period of 1 eek or so. The use of CAT scanning 14 to check on the uniformity of distributions obtained by spontaneous imbibition could provide especially valuable information on the character of spontaneous imbibition behavior in mixedettability systems.. The endpoints achieved for forced displacement sometimes change ith each displacement cycle and may be somehat arbitrary in any case. Waterflooding of mixed-ettability systems is often characterized by continued production of oil don to lo residual oil saturations (ROS's). If forced displacement is performed at excessive capillary number, the residual oil obtained ill be loer than that given by normal laboratory aterflooding procedure. When the Amott tests are used, even though the ettability may be expressed as a single value, IAH =(/-Io)' it is better to report all/ and 10 values (one of hich is often zero) and associated saturations as part of the ettability result. Each time saturation data are converted to ettability indices and the difference beteen the indices is used to obtain a ettability number, valuable information is lost. In quoting indices, JPT December 1990 saturation values from hich they ere derived should also be provided together ith operational details of ho Si' s. t. os, and ot ere determined. A eakness of the Amott test is its failure to distinguish beteen important degrees of strong ater-etness, all of hich ill give an I of, or very close to, unity. USBM Method. In the USBM method, 3 drainage and imbibition capillary pressures are measured, usually by centrifuging. As ith the Amott test, the method as developed from observation of COBR displacement behavior. The ettability number is defined (see Fig. 6) by N=log(AI/A2)'... (3) here A 1 =area under the secondary aterdrainage curve (drainage from residual oil) and A2 =area under the imbibition curve falling belo the zero-pc axis. The chief advantages of this method are the speed and simplicity of the procedure and its adaptation to relative permeability measurements. Points to note, ith respect to this interpretation, are that corrections must be applied to the average saturations measured by centrifuging, the claimed thermodynamic basis for the method that equates ork of displacement to change in surface free energy does not recognize the effects of irreversibility in capillary pressure relationships, and systems that imbibe to give positive A 2, for example VSWW systems, are not recognized in the proposed interpretation. Imbibition Rates. The driving force for spontaneous imbibition rates is proportional to the imbibition capillary pressure. Measurements of spontaneous imbibition rate 13 provide an especially useful supplement to Amott indjces or USBM ettability numbers. Whereas the Amott test depends mainlyon the saturation at hich imbibition capillary pressure falls to zero, spontaneous imbibition rate depends on the magnitude of the imbibition capillary pressure. Measurements of imbibition rates are of special value as a sensitive measure of etting in the range here the Amott index is at or close to unity. Quantitative interpretation obviously ill be aided by having reference results obtained at or very close to perfect etting conditions. Improved interpretation of spontaneous imbibition behavior for COBR systems is likely to provide an important advance in ettability characterization. Measurements of imbibition rates also provide information on dynamic IFf and etting phenomena that may be important in the reservoir but are not reflected by Amott or USBM ettability tests. Advances in interpretation of spontaneous imbibition results ill depend on improved methods of scaling and comparison of results from one system to another. Effects of WettabllHy on 011 Recovery-Laboratory Waterfloods The effects of ettability on oil recovery have been investigated through laboratory displacement tests. Wettability of COBR systems is usually characterized by the Amott test or the USBM method. Results for VSWW conditions are commonly used as a reference state. Reported changes in recovery as systems become less ater-et range from being much loer to being much higher than those given by VSWW conditions. Important goals of ettability research are to provide rational and consistent explanations of these apparent inconsistencies and to identify optimum conditions for oil recovery. In revieing ettability effects, oil recovery ill be described by displacement efficiency, ED, defined as ED=[(Soi-.tT)1 Soi]100%,... (4) here Soi is the initial oil saturation and SOT is the ROS of the core sample. When the ROS continues to decrease ith Vp throughput, SOT and ED are functions of Vp:.. ED()={[Soi-.tT(Jj,)]1 Soi} 100%.... (5) Plots of ED() vs. Vp of ater injected provide a convenient ay of comparing results of laboratory aterflood tests. Several early examples of laboratory aterfloods sho oil recovery decreasing ith decreasing ater-etness. This is consistent ith the intuitive notion that strong etting preference of the rock for ater and associated strong capillary imbibition forces give the most efficient oil displacement: Hoever, an increasing number of examples of improved recovery ith shift from strongly ater-et conditions are being reported for eakly ater-et or intermediate etting condition, particularly for COBR systems. (These results generally involve displacement of crude oils or refined oils from cores in hich organic films have been deposited from crude oil.) Fig. 7 shos averaged results 15 for an extensive COBR data set. In preparation of these samples, it as found that an increase in aging temperature, a decrease in ater saturation, and to a lesser extent, aging time, au tended to make the cores less ater-et. Recovery is seen to pass through a maximum hen I AH is close to zero. If E Ds is the displacement efficiency at strongly ater-et conditions and Eoo is the ettability at some other global etting condition, e, then the effects of ettability on recovery curves can be conveniently compared by plotting the relative displacement efficiency, Eoo()=(EooIEDs)100%,.... (6) against the number of Vp injected, as shon in Fig. 8. The selected results sho that a shift toard less ater-et conditions can range from being highly adverse to being highly beneficial to oil recovery. The validity of the E Ds data is obviously an important aspect of this interpretation. Reservoir Residual 011 The greatest practical significance of ettability is its effect on oil recoveries achieved in the reservoir by aterflooding. The need 1481

7 for accurate ROS measurements as stimulated by the prospect of tertiary recovery. Many methods of measuring residual oil have been proposed. The single-ell tracer test, hich measures ROS for a radius of about 10 m around the ellbore, has been idely applied to reservoirs vieed as likely candidates for tertiary recovery. 20 Results for 114 reservoirs are plotted as a histogram in Fig. 9. ROS's remaining after aterflooding range from as lo as 4 % to more than 40%. The results sho that lo values of residual oil that can be achieved in the laboratory are also commonly observed in atered-out reservoirs. Obvious goals in ettability research are to explain hy high aterflood recoveries are observed in some oil reservoirs and ho they might be obtained in others. Pore-Level Displacement Mechanisms The results presented in Fig. 7 sho that departure from VSWW conditions can give distinctly reduced oil entrapment. Floexperiments in 2D pore netorks (micromodels) permit observation of pore-level displacement mechanisms that affect displacement efficiency. Under VSWW conditions in systems of high aspect ratio (high ratio of pore body to throat size) believed to be typical of reservoir rocks, residual oil is trapped as disconnected blobs in pore bodies. Numerous theoretical and experimental investigations 2l have been reported on mechanisms of entrapment (snap-off) and mobilization of oil blobs at VSWW. Simulated aterfloods of crude oil from micromodels have also been made at various ettability conditions achieved by changes in brine ph and salinity. While a great variety of distributions have been observed, no crude-oillbrine system shoed the extensive trapping of oil in pore bodies that is characteristic of VSWW systems. * Overall, the most important observation ith respect to crude oil displacement as that the process by hich oil becomes disconnected (snap-off) tended to be inhibited. Furthermore, the oil phase often maintained continuity through capillary structures ith oil/ater surface boundaries that ere pinned at the solid surface. Local (porelevel) changes in saturation and capillary pressure ere accommodated by changes in contact angle ithin the range permitted by hysteresis. Lo advancing angles and high receding angles ere seen to coexist, even for capillary structures ithin a single pore. The most important difference beteen refined oil and crude oil displacements in micromodels as that displacement of crude oil from at least some of the pore bodies alays made a significant contribution to overall recovery. Experimental studies by Li and Wardla 22 shoed that snap-off in simple pore models of rectangular cross sections can be inhibited if the ater-advancing con- "These results ere provided by Charles T. Carlisle, Chemical Tracers Inc., Houston, and Harry A. Deans, U. of Wyoming, Laramie tact angle exceeds about 60. Further important advances in theoretical and experimental accounts of snap-off mechanisms ill continue to be made through study of capillary pressure and instability behavior in pores that have comers and are of nonuniform cross section. During the past lo years, there has been a notable revival in analysis of pore netorks for modeling displacement processes in porous media. The relevance of results given by such models depends on the validity of the rules adopted in the analysis. The choice of rules to account for ettability effects in netork models is a problem that has only just begun to be explored. Advanced Core Analysis for WeUablllty The decision to investigate the ettability of a reservoir and the level of effort expended in ACA W ork to match reservoir conditions should be based on the level of significance these results ill have on making reservoir decisions. Determination of reservoir ettability and measurement of valid relative permeability curves are both very difficult problems. The time and expense of making reservoir-condition tests result in fe being performed on anyone reservoir. Although there is no guaranteed prescription for measurement of reservoir ettability, its effect on reservoir performance may be of sufficient importance that the effort to obtain the best possible data is orthhile. The basic problem in ACA W is knoing hether the nature and distribution of surface properties and fluid phases as they occur in the reservoir are maintained or restored. Within the general topic of ACA W many areas can be identified: (1) recovery of cores; (2) core handling at the ellsite and core storage; (3) core cleaning; (4) restoration of reservoir ettability, including the correct connate ater saturation; (5) measurement of ettability; (6) measurement of aterflood displacement behavior and associated relative permeabilities; and (7) ef-. fect of ettability on electrical resistivity. Each of these topics has an extensive literature; useful bibliographies have been provided by Anderson ACA W procedures are usually influenced by the character of the particular reservoir under study and experience gained in orking ith that reservoir. API core analysis procedures for ettability determination are no recognized to be largely outdated. Attention currently is being turned to the greater standardization of ACA W ithin the industry. Recovery of Reservoir Cores. Alteration of the ettability of core samples from their reservoir state during cutting, surfacing, and subsequent handling can occur for a number of reasons. These include (1) drillingfluid contamination, (2) temperature and pressure reduction effects on crude oil composition such as asphaltene precipitation or ax deposition, (3) oxidation, (4) drying, and (5) flashing of connate ater ith pressure reduction. When coring ith ater-based drilling fluids, emphasis has been placed on the use of s<xalled bland muds. Because particulates from the mud are retained mainly at the surface of the cut core, studies of ettability alteration caused by flushing are made ith the mud filtrates. Early ork concentrated mainly on identifying mud compositions that caused no alteration in the ettability of strongly ater-et cores. More recently, attention has been given to changes in mixed- and oil-et cores. Cores cut ith reservoir crude, diesel, or other oil-based drilling muds of lo ater content as the drilling fluid have the distinct advantage (because of the importance of the amount and distribution of connate ater to etting behavior) that the connate ater is left relatively undisturbed. Drilling conditions and other safety considerations may often preclude this approach. Increased use of oil-based (emulsion) muds has resulted in special attention being given to cleaning oil-based cores and restoring them to reservoir ettability conditions. Wunderlich 29 has given a detailed revie of the various options and comparisons in recovering cores ith unaltered ettability. Core Handling and Storage. There may commonly be long time delays beteen core recovery and core testing during hich cores must be stored. Cores are commonly preserved in mud filtrate or brine. They are generally protected from oxygen, evaporation, light,. and extreme temperature changes. Unconsolidated cores are usually subjected to freezing as part of the recovery process. In ACA W ork, preserved cores are generally called fresh cores, even though testing may continue for several years after the cores ere taken. Core CIeaoing. The usual objective of core cleaning by flo of organic solvents or extraction is to remove all organic compounds ithout altering the basic pore structure of the rock. 23,30 A ide range of combinations and/or sequences of solvents have been proposed. The type of crude oil and core lithology are used for guidance in selection of solvents, but procedures are far from standardized. 1 Methods commonly used in judging that the cleaned cores give a completely ateret condition may be inadequate ith respect to the requirement that all adsorbed organic material be removed. For example, achievement of an Amott index of unity for refined oil, after cleaning, does not necessarily mean that all the adsorbed organic material has been removed or that a VSWW system has been achieved. More reliable checks on removal of adsorbed hydrocarbons ould be provided by measurement of spontaneous imbibition rates for displacement of refined oil. In early core analysis ork, the objective of core cleaning as to restore the core to a VSWW condition that ould represent the December 1990 JPT

8 ettability believed to pertain in the reservoir. Subsequent displacement tests, such as relative permeability measurement, ere performed ith brine and a refined oil. With groing recognition that VSWW conditions are not common, core cleaning in ACA W ork is no a first step in restoring the core sample to reservoir etting conditions. Restoration of Reservoir Wettability. In restoration procedures, the objective is to re-establish reservoir ettability conditions by contacting the core ith reservoir crude oil. More idespread acceptance of the importance of reservoir ettability has resulted in special attention being given to adopting ACA W restoration procedures to old core samples that have been alloed to age and eather ith little attention to the storage enviromnent. An important step in ettability restoration is to establish an Si that corresponds to the reservoir. This requires knoledge of the reservoir ater saturation and a method of establishing this initial saturation in the core. Determination of reservoir connate ater, aside from problems of ettabiiity, is much more difficult than sometimes assumed. 31 If a satisfactory determination of Si has been made, displacement procedures are designed to achieve this value in the laboratory core sample. This may involve flooding at high pressure, sometimes ith a high-viscosity refined oil, centrifuging, or removal of ater by desaturation by means of a porous plate or partial drying. The core is flushed ith crude oil and then aged at reservoir temperature for about 1 to 4 eeks. The objective of the aging process is to re-establish adsorption equilibrium beteen the rock surface and the crude oil that had been established in the reservoir over geologic time. Various degrees of sophistication can be used.in the restoration procedure to achieve systems that are more closely representative of reservoir conditions. IdentifIcation of the key parameters that affect ettability in COBR systems ill obviously lead to much greater confidence in design of ACA W procedures. Comparison of Fresh Core and Restored State Results. A major concern in ACA W ork is that there is no sure ay to check the validity of results. Comparison of results for fresh cores to restored-state results for the same cores provides the closest approach. 1 The best possible indication that the results are valid is that the to data sets agree. If they do not, the various possible causes of disagreement are revieed in deciding hich data set is likely to be more reliable. Measurement of Relative Permeabilities. Having obtained a reservoir core sample andlor fluids, ith careful attention being paid to maintenance or restoration of reservoir conditions, laboratory tests are conducted to obtain relative permeability JPT December 1990 measurements These measurements are used in reservoir simulation to obtain production forecasts. Design of surface facilities is often tied to these forecasts. The most commonly used and convenient method of measuring relative permeability is by the unsteady-state method. This method as originally developed and applied ith strongly etted systems and high displacement rates. It is no idely recognized that such an approach cannot be expected to simulate conditions of intermediate or mixed ettability. Hoever, if tests are run at reservoir rates, the results may be influenced by capillary end effects (mainly holdup of oil at the outflo face). Coreflood simulation can be used to correct for end effects. There is groing evidence that end effects for aterfloods at reservoir rates in mixed-ettability systems can be quite small. In-situ measurements of saturation by X -ray adsorption or CAT scanning to check for end effects and general uniformity of fluid distributions provide for improved confidence in procedures and results. Reservoir Wettability and Electrical Resistivity. Electric logging is the most idely used method of identifying hydrocarbon-bearing intervals in a ellbore. Standard methods of relating oil saturation to electrical resistivity are based on measurements of brine in cleaned cores, usually ith air as the nonetting phase. These measurements ill generally correspond to VSWW conditions. Most investigations of the effect of ettability on resistivity shoed increases in resistivity ith decreases in ater-etness that ere often too large to be reasonable. Hoever, most of these results ere for systems in hich ettability change as induced by artificial means, such as silane treatment of cores. Relatively little information is available on saturation exponents for COBR systems. Sanson 33 and Longeron et at. 34 shoed that Archie saturation exponents ere only moderately higher for COBR systems than for a clean core and refined oil. Further systematic study of electrical resistivity of COBR systems is needed, ith special attention being given to ettability variation and obtaining data at lo ater saturations. Remarks A practical solution commonly suggested for ACA W is to measure relative permeability and other parameters that enter reservoir simulation at conditions that duplicate the reservoir. Hoever, the understanding of ettability gained by this approach and the overall value of data specific to a piece of core are very limited. Even more serious is the inability to check the validity of the data. With greater attention being paid to mixedettability systems and the use of CAT scanning to obtain direct measurements of fluid distribution, uncertainties in relative permeability measurement are being identified. Interpretation of relative permeability curves in terms of interface behavior and fluid distributions is still fairly primitive. Rules of thumb commonly used in the interpretation of the effect of ettability on relative permeability behavior should be treated ith caution. Mechanistic accounts of the effect of ettability on capillary pressure, fluid distribution, and oil retention provide a more direct approach to understanding interactions beteen ettability and pore geometry and a logical starting point for developing a fuller understanding of relative permeability relationships. Conclusions 1. Reservoir ettability can cover a ide spectrum of conditions. Systems of intermediate or mixed ettability are quite common, hereas VSWW systems may be a rarity. 2. Contact-angle behavior of crude-oill brine systems falls into to main classes distinguished by either small or large hysteresis. 3. Adhesion behavior of crude oils is strongly dependent on ph. 4. Methods in most general use for measuring the ettability of COBR systems (the Amott test, the USBM test, and imbibition rate measurements) are strongly dependent on capillary pressure. In all three tests,. decrease in interface curvature to zero is a key condition. 5. Laboratory aterfloods on COBR systems sho that oil recovery is optimum at neutral ettability. 6. Agreement in results for fresh core ith those for restored core provides the best indication that reservoir ettability has been duplicated in the laboratory. 7. ROS values obtained in the laboratory for mixed-ettability systems and those determined by in-situ measurements sho that it is possible for aterfloods to achieve very high displacement efficiencies. Nomenclature A 1 = area under secondary drainage curve A2 = area under imbibition curve falling belo zero-pc axis ED = displacement efficiency E Ds = displacement efficiency at strongly ater-et conditions EDe = displacement efficiency at some global etting condition e IAH = Amott-Harvey ettability index 10 = ettability index (for oil) I = ettability index (for ater) N = ettability number by USBM centrifuge test Pc = capillary pressure Soi = initial oil saturation of core sample Sor = ROS of core sample S = ater saturation Si = initial ater saturation = pore volume A = difference 1483

9 --... Author... heads the Petrophplce a... CIIien*b'l Group at the Ne IIuIco PeIr6Ieum Recovery All.. ICh Center end.. ell- )unct prot or of peiraieum..... Ing at... IIuIco Tech. He.. euthor or coauthor of more....,... liiiiiniyon CIIpII.tty... IuId poroue medil He hoicie In chemiciii... _ring...,in... PhD 1n...,;.. from the U. of LeecIL He recetnd the 1110 Ne.... TeICh DIItInguIehed A di AWM'd; eerved on c:ommitime for the 1178, 11", end 1tI7 AnnuIII _ Unge; end...".. on the EdItorI8I..... CommIttee. '**'... (J = e contact angle = global etting condition IT = disjoining pressure Subscripts A = advancing i = initial 0= oil r = residual R = receding s = spontaneous t = total (ith saturation change AS') = ater References 1. Cuiec, L.E.: "Evaluation of Reservoir Wettability and Its Effect on Oil Recovery," Interfacial Phenomena in Oil Recovery, N.R. Morro (ed.), Marcell Dekker, Ne York City (1990) Amott, E.: "Observations Relating to the Wettability of Porous Rock," Trans., AIME (1959) 216, Donaldson, E.C., Thomas, R.D., and Lorenz, P.B.: "Wettability Determination and Its Effect on Recovery Efficiency," SPFJ (March 1969) Zisman, W.A.: "Relation of the Equilibrium Contact Angle to Liquid and Solid Constitution," Contact Angle, Wettability and Adhesion, Advances in Chemistry Series 43, American Chemical Soc., Washington, DC (1964) Treiber, L.E., Archer, D.L., and Oens, W.W.: "Laboratory Evaluation of the Wettability of Fifty Oil Producing Reservoirs, " SPFJ (Dec. 1972) Morro, N.R., Lim, H.T., and Ward, I.S.: "Effect of Crude-Oil-Induced Wettability Changes on Oil Recovery," SPEFE (Feb. 1986) Buckley, J.S., Takamura, K., and Morro, N.R.: "Influence of Electrical Surface Charges on the Wetting Properties of Crude Oil," SPERE (Aug. 1989) Buckley, J.S. and Morro, N.R.: "Characterization of Crude Oil Wetting Behavior by Adhesion Tests, " paper SPE presented at the 1990 SPEIDOE Symposium on Enhanced Oil Recovery, Tulsa, April Hirasaki, G.l.: "Wettability: Fundamentals and Surface Forces," paper SPE presented at the 1988 SPEIDOE Symposium on Enhanced Oil Recovery, Tulsa, April Dubey, S.T. and Waxman, M.H.: "Asphaltene Adsorption and Desorption From MineraI Surfaces," paper SPE presented at the 1989 SPE International Symposium on Oilfield Chemistry, Houston, Feb Takamura, K. and Cho, R.S.: "A Mechanism for Initiation.of Bitumen Displacement from Oil Sand," J. Cdn. Pet. Tech. (Nov.Dec. 1983) 22, Sharma, M.M. and Wunderlich, R.W.: "The Alteration of Rock Properties Due to Interactions ith Drilling-Fluid Components," J. Pet. Science & Eng. (Dec. 1987) I, Denekas, M.O., Mattax, C.C., and Davis, G. T.: "Effect of Crude Oil Components on Rock Wettability," JPT(Nov. 1959) ; Trans., AIME, Wellington, S.L. and Vinegar, H.J.: "X-Ray Computerized Tomography," JPT (Aug. 1987) Jadhunandan, P. and Morro, N.R.: "Crude Oil Recovery In Laboratory Water Floods," paper presented at the 1990 IFP Research Conference on Exploration & Production, The Fundamentals of Fluid Transport in Porous Media, Aries, May Kyte, J.R., Naumann, V.O., and Mattax, C.C.: "Effect of Reservoir Environment on Water-Oil Displacements," JPT(luly 1961) ; Trans., AIME, Salathiel, R.A.: "Oil Recovery by Surface Film Drainage in Mixed-Wettability Rocks," JPT (1973) Rathrnell, 1.1., Braun, P.H., and Perkins, T.K.: "Reservoir Waterflood Residual Oil Saturation From Laboratory Tests," JPT (Feb. 1973) ; Trans., AIME, Wang, F.H.L.: "Effect ofwettability Alteration on Water/Oil Relative Permeability, Dispersion, and Floable Saturation in Porous Media," paper SPE presented at the 1986 SPE Permian Basin Oil and Gas Recovery Conference, Midland, March Deans, H.A.: "Single-Well Tracer Methods," Determination of Residual Oil Saturation, Interstate Oil Compact Commission, Oklahoma City (lune 1978) Mohanty, K.K., Davis, H.T., and Scriven, L.E.: "Physics of Oil Entrapment in WaterWet Rock," SPERE (Feb. 1987) Li, Y. and Wardla, N.C.: "The Influence of Wettability and Critical Pore-Throat Size Ratio on Snap-off," J. Colloid Interface Sci. (1986) 109, No.2, Anderson, W.G.: "Wettability Literature Survey-Part 1: RocklOillBrine Interactions and the Effects of Core Handling on Wettability," JPT (Oct. 1986) Anderson, W.G.: "Wettability Literature Survey-Part 2: Wettability Measurement," JPT (Nov. 1986) Anderson, W.G.: "Wettability Literature Survey-Part 3: Effects ofwettability on the Electrical Properties of Porous Media," JPT (Dec. 1986) Anderson, W.G.: "Wettability Literature Survey-Part 4: Effects of Wettability on Capillary Pressure," JPT (Oct. 1987) Anderson, W.G.: "Wettability Literature Survey-Part 5: Effects of Wettability on Relative Permeability," JPT (Nov. 1987) Anderson, W.G.: "Wettability Literature Survey-Part 6: Effects of Wettability on Waterflooding," JPT(Dec. 1987) Wunderlich, R.W.: "Obtaining Samples ith Preserved Wettability," Interfacial Phenomena in Oil Recovery, N.R. Morro (ed.), Marcell Dekker, Ne York City (1990) Hirasaki, G.l., Rohan, J.A., and Dubey, S. T.: "Wettability Evaluation During Restored-State Core Analysis," paper SPE presented at the 1990 SPE Annual Technical Conference and Exhibition, Ne Orleans, Sept Morro, N.R. and Melrose, J.C.: "Applications of Capillary Pressure Data to the Determination of Connate Water Saturation," Interfacial Phenomena in Oil Recovery, N.R. Morro (ed.), Marcell Dekker, Ne York City (1990) Heaviside, 1.: "Measurement of Relative Permeability," Interfacial Phenomena in Oil Recovery, N.R. Morro (ed.), Marcell Dekker, Ne York City (1990) Sanson, B.F.: "RationaIizingthelnfluence of Crude Wetting on Reservoir Fluid Flo With Electrical Resistivity Behavior," JPT (Aug. 1980) Longeron, D.G., Argaud, M.l., and Feraud, J.P.: "Effects of Overburden Pressure, Nature, and Microscopic Distribution of the Fluids on Electrical Properties of Rock Samples," paper SPE presented at the 1986 SPE Annual Technical Conference and Exhibition, Ne Orleans, Oct SI Metric Conversion Factors A x 1.0* E-Ol = om ft x 3,(148* E-Ol = m 'Conversion factor is exact. This paper is SPE Distinguished AutMr SerIes articles are general, descriptive presentations that summarize the state of the art in an area of technology by describing recent developments for readers ho are not specialists in the topics discussed. Written by individuals recognized as experts in the area, these articles provide key references to more definive ork and present specific details only to illustrate the technology. Purpose: To inform the general readership of recent advances in various areas of petroleum engineering. A softbound anthology, SPE Dislinguished Author SOOes: Dec Dec. 1983, is available from SPE's Book Order Dept. JPT December 1990 JPT

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