Nettability Literature Survey Part 1: Rock/OiVBrine Interactions and the Effects of Core Handling on Wettabiiity

William G. Anderson, SPE, Conoco Inc. s

Summary. Nettability is a major factor controlling the location, flow, +d .@stributiOn Of fl~d? @ a reservoir. The wettabdity of a core will affect almost all types of core analyses, including capillary pressure, refative permeability, waterflood behavior, electrical properties, and simulated tertiary recovery. The most accurate resuks are obtained when natiye- or restored-state cOr~ Me ~ with native cmde Oil~d brine at reservoir temperattrre and pressure. Such conditions provide cores that have the same wettab~ky as the . reservoir. ~. The wettabih@ of, ori&lly water-yet reservoir rock can be altered by the adsorption of polar com~ounds and/or the deposition of organic materiaf that was originally in tie crude oil. The degree of alteration is determined by the interaction of the oil constituents, the mineral su~ace,. and tie brine chefi$~. The PrO:~ures for obtaining native-irate, clesned, and rsstored-state cores are diSCUSSe4ss we~ aS the eff@s Of cOnng, preservation, and experimental conditions on nettability. Also reviewed are methods for artificially controlling the wetmbflity during laboratory experiments. htrodirotion This paper is the first of a series of literature surveys covering the effectsof nettability on core analysis. 1-3 Changes in nettability have been shown to affect capilIq pressure, relative permeability, waterflood behavior, dispersion of tracers, simulated terdaiy recovery, imedncible water saturation (IWS), residual 01 saturation (ROS), and electilcal properties. 4-26 For core analysis to predict the behavior of a reservoir accurately, the nettability of a core must be the same as tbe nettability of the undisturbed reservoir rock. A seriousproblem occurs because many aspects of core handling can drastically affect nettability. Water-Wet, Oil-Wet, and Neutrafly Wet. Wettabfity is defined as the tendency of one fluid to spread on or adhere to a solid surface in the presence of other irmniscible fluids. 7 In a rock/oif/brine system, it is a measure of the preference that tie rock has for either the oil or water. When the rock is water-wet, there is a tendency for water to occupy the smsll pores and to contact the majority of the rock surface. Siarly, in an oil-wet system, the rock is preferentially in contact with the oil; the location of the two fluids is reversed from the water-wet case, and oil will occupy the small pores and con~ct tie majority of the rock surface. It is importunt to note, however, that the teim wettabWy is used for the wetting preference of the rockand does not necessarily refer to the fluid that is in contact with tie rock at any given time. For example, consider a clean sandstone core that is saturated with a refined ofl. Even though the rock surface is coated with oil, the sandstone core is still preferentially water-wet. Thk wetting preference can be coP&h!1986society.+Pe!role.mEngineers
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demonstmted by allowing water to imbibe into the core. The water will displace the oil from the rock ,surface, ~dicating that the,rock suiface prefers? to be in contact with water rather than oil. Simjkwly, a cow samra!ed with water is oil-wet if oil will imbibe into the core and displace water from the rock surfuce. Depending on the specitic interactions of rock, oil, and Mne, the wwab@ of a system can range from itrongly water-wet to str022gIy oil-wet. When the rock his no strong preference for either oif or water, the system is said to be of neufml (or intermediate) wettabfi~. Besides strong and neutkd nettability, a third ~pe is fracdonsl nettability, where different areas of the core have different wibing preferences. 27 The wettabfity of the rocklfluid system is impoitant because it is a major factor controlling the location, flow, snd distribution of fluids in a reservoir. .Jn general, one of the flizids in a porous medium of uniform wettabilky that contis at least two immiscible fluids will be the wetting fluid. When the system is iu equilibrium, the wetting fluid will completely OCCUPY smsllest pores and the be in contact with a majoriv of the rock s~face (ass~ing, of course, that the saturation of the weting fluid is sufficiently high). The nonwetting fluid will occupy tie centers of the larger pores and form globules that extend over several pores. In the remainder of this survey; the terms wetdizg snd nonwetting fluid wilf be used in addkion to water-ivet and oil-wet. This will help us to draw conclusions about a SYStern with the oppositi wetibility. The behavior of oif in a water-wet system is very similar to tle behavior of water in an oil-wet one: For exmuple, it is generally assumed that for a system with a strong wetting prefererice, the tietting-phase relative permeab~ky is only a function of 1125

of Petmlc.mTechnology, October19S6

ABLE 1DISTRIBUTION OF RESERVOIR WETTABILITIES BASED ON CONTACT ANGLE34 Contact Angle (degrees) o to 75 75 to 105 105to 180 Silicate Resewoirs 13 1: 30 Carbonate Reservoirs 2. A 25 Total Reservoirs 15 3; 55

Water-wet Intermediate wet Oil-wet Total

. .

its own saturation-i. e., it shows no, hysteresis. 7,12,28 Owens and Arch&28 measured the gas/oil drainage permea.bflily, where the oif was the strongly wetting fluid, and compared it with the water/ofi imbibition relative pormeahii@, where the water was tie strongly wetting fluid. The water-imbibkioi reIative permeability (strongly water-wet system) was a continuation of the oil-drainage relative permeability (strongly oif-wet system), demonstrating the amdogy between systems of opposite wettabilities. Historically, afl petroleum reservoirs were believed to be strongly water-wet. This was based on tyo mjor fac~. Fust, almost allclean sedentary rocks are strongly water-wet. Second, sandstone reservoirs were deposited in aqueous erivironments into which oil later migrated. It was assumed that the comate water woufd prevent the oil from touching the rock surfaces. In 1934, Nuttingzg realized that some producing reservoirs were, in fact, ac@ally strongly oil-wet. He found that the quaitz surfaces of the Tensleep sandstone in Wyoming had adsorbed heavy hydrocmbons in layers about 0.7pm tldck (about 1,000 molecules) so fdy that they could not be removed by gasoline or vzrious solvents.When $e hydrocarbon film was removed by ,fuing the core, the film could be restored by soaking the cores in crude oil overnight. Examples of other reservoirs that are genertiy recog- , nized as sirongly oil-wet are the Bradford sands.of the Bmdford pool,, Pennsylvania, 30-32 and the Ordovicisrr ssmds of the Okkiborns City field. 33 More recentfy, Treiber et aL % used the water advancing contact angle to eiamine the wettabdity of 55 oil reservoirs. fn this procedure, deoxygenated synthetic fofmation brine and dead anaerobic crudes were tested on quartz and calcite c~stafs at rescrvom temperamre. COnta~. angles (mea.+. ured through the water) fromOto750 [0 to 1.3 rad] were dipmed water:we~ from .75 to 105 [1.3 t6 1.83 rad], intermediate wet; and from 105 to 180 [1.83 to 3:14 red], oil-wet. As summarized in Table 1, 37 of the reservoirs tested were classified as oil-wet, 3 were of intemnetilate wegabtity, and 15 were water-w.et. Most of the oil-wet reservoirs were mildly oil-wet, with a contact angfe betieen 120 and 140 [2:1 and 2.4 rad]. Of the carbonate resemoirs included, 8 % were water-wet, 8 % were intermediate, and S4% were oil-wet. Most of the carbonate reservoim were from the west Texas area, however, so there is a geographical bias in the data. Treiber et al. cautioned that these tindlngs could not be considered representative of a trufy random samplhzg of petroleum reservoirs. The sainples were bkmed because (1) all were operations for the sarnb company, (2) most were being considered for some type of flooding, and (3) some of the reservoirs had demonstrated unusual behavior. A fourth consideration is how much the use of degassed fluids rather than the real formation fluids af1126

fected the wettsbflity behavior in the contsct-migle tests. As ,iiscussed later, this probably causes amoverestimaticm of the oil-wetness. Therefore, the large percentage of reservoirs found tobe ol-wet is less significant than the general indications that not all reservoirs are waterwet and that the r&ervoir wettabilky varies widely. Contact-sngJe measurements made by Clilingm snd Yen35 suggest that most carbonate reservoirs ramge fiorn neutrally to oif-wet. They measured the we~bdity of 161 limestone, dolomitic liiestone, calcitic dolomite, arid dolomite cores. The cores tested included (1) 90 cores from Asrnari limestones and dolomites from tie Mid$e EasG (2) 15 dolotite cores from west Texas; (3)3 cores of Madison liiestone from Wyoming; (4) 4 cirbonate cores from Mexican oil fields; (5)4carbonate cores from the Rengiuoil field in the Peoples Republic of China; (6) 16 csrbonate cores from Albe~ (7) 19 chalk cores from tie North.,SeT (8) 5 samples from India+ amd (9) 5 samples from Soviet oil fields in the Urals-Volga region. Table2 shows the distribution of wettsbfities with 80% of the reservoirs either oil-wet or strongly oil-wet. Some. of the strongly oil-wet reservoirs were oil-wet bew+se of a bitumen coating. Note that the range of contact angles considered to be neutrslly wet is smaller thari the range given in Table 1. This demonstrates the variation from paper to paper of the cutoff angles between ?Je different wetting statea. As discussed iu more detiril later, reservoir rock can change from its &iginal, strongly water-wet condition by adsorption of polar compounds and/or the de ositjon of orgsnic matter originally in the crude oil. 7,3P Some 6-42 crude oils make a rock oil-wet by depositing a thick organic film on the mineral surfaces. Ofher crude oils conti pOlar compounds that cm be adsorbed to make the rock more oif+vet. Some of these compounds are srrfficiently water soluble to pass throu~ the aqueous phase to the rock. Fractiormf Wettabilfty. The retilzation that rock wettabflity can be akercd by adsorbable crude oil components lexito tie idea that heterogeneous forma of wettabiity exist in reservoir rock. Generally, the intend surface of re.servoir rock is composed of many minerals with different surface chemistry and adsorption properties, which may lead to variations in nettability. Fractional nettability slso called heterogeneous, spotted, or fhlmation wettabifky-was proposed by Brown and Fatt27. aud others. 43* fn fkactioml wegsbdity, crude oif components are strongly adsorbed in certain areas of the rock, so a portion of the rock is strongly oil-wet, whie the rest @strongly water-wet. Note tit this is cqncepty+fly different from intermediate wettsbtity, which assumes that all portioim of the rock surfsce have a slight but equal preference to being wetted by water or oil. lomnalof PetmlaunTechmlo8y,@to&r 1986

Factors Affecting the Original Reservoir Wenabiiity The &igiaal strong wa~r-wetness of most, rcservoi ~nerals csn be altered by the adsorption of polar compounds. and/or the deposition of qr tic matter that was origi$ nally in the crude oil. 7,20,3,32,36+155-63 fhe surfaceactive agents io the oil aze generally believed to be p+w com ounds that contsin oxygen, nitrogen, andlor SU1-.. ,@r. ! 6,37,40,41,SS,56,W68 These compounds con@in both a polar and i hydrocmbon end. The polar end adsorbs on the rock surface, exposing the hydrocsrbqz end and making the s+face more oil-wet. Experiments haveshown fhat some.of these aaturaf surfacfants are sut%cientfysoluble iizwater to adsorb onto tic rock surface aftcrpassing through a thin layer of water. 42,60S69-71 In addition to the oif composition, the degree to.which the wettabllity is aftcred by fhese surfactants is also determinqi by the pressure, tcmpermmc, mineml surface, and Native-State, Cleaned, and ReStored-State Coraa. brine chemistry, including ionic composition and PH. The Cores in three different stitei .of ,presepatioh are used effects of pressure and temperature will be discussed Mcr in core anafysis: native .Xaie,cleaned, and restored state. @the section on experimental conditions. The importance The best results for mrrftiphase-type flow mialyses are obof the mineral surface is shown by the contact-angle @easklincd with mtive-ststi cmes, where alterations to the wettabfity of the un@rrbed reservoir rock are minimized. . orementa +cbssed esrlier, ,3s in which a large majority of tie carbonate reservoirs tested were. oil-wet, while Ii thk set of paper~ the term native-state is used for Many.of the sandstone reservoirs were water-wet: Seveml niry core that was obtained and stored by methods that researchers have found that some polar compounds afpreserve the Nettability of the reservoir. No distinction fect the wettabilky of sandstone and carbmaitc surfaces is made between cores taken with oil- or water-baked in ~lfferent ~ays, 37,+42,6672-76 The. chemistiy of the fluids, as long as the native wektabflity is maintained. Be brine can also alter the. wettabtity. Mrdtivafent cations aware, however, that some papers dktin=gish on tie basometimes enhance the adsorption of surfactants on the sis of drilliig fluid (e.g., see Treiber et al. 34), In these finer~ ~rface. %77-s3 fhe brine pH is also impOrt8nt papers, native-state refers only to cores taken with a in determination of the nettability and other interfacisf suit8bIe ofl-fjjhte.t~e rhill:mg,mud, which nrtintains the properties of the cmdelbrinelrock system. 6Z26,~In afkaoriginal connate water saturation. :Fresh:state refers Iine floodmE, for example, allmhne chemicals can react to a core with unaltered wettabtity that was taken with with some c-fides to pr~duce surfactqts that sfter wett?a water-base d@ling mud that cbntsins no compounds that b~lty, 6,26 can alter core tiettabdity. Here, the term native-state is !. used for both cases. The second type of core is the cleaned core, where an Surface-Active Compormda in Crude Oil. ~ie the attempt is made to remove all the fluids and adsorbed or-. surface-acfive components of crude tie found in a wide ganic msterid by flowing solvents through the cores. ~ge ofWrolem fractions, 41 they are more prevalent Cleared cores are ususlly strongly water-wet and should m gze heavier fractions of cmde, such as re$ina and \ 1:127 Journalof Petroleum Technology, October19S6

hfi@ Wettibifity. Salatfrie147 introduced the term ririxed wettabilby for a special type of fractional nettability iri which the oil-wet surfaces form continuous paths through tie larger porca. 48-50The smafler pores remain water-wet and contsin no oil. The fact that sll of the oil in a miixed-wettabflity core is located in the lager oiftvet pores causes a.smdlbut finite oil permeabtlty to ?xist down to very low oil sahrrdtiom. T@ in mm pertits the drainage of oil during a waterflood to continue until verj low oil saturations are reached. Note that the main distirrction betywen mixed md fractional wettsbtity is that @.elatter, implies neither specitic locations for the oil-wet surfaces nor continuous oil-wet paths. SalatMet visualizes the generation of mixed nettability ih,,tie following manner, When od yufially invaded an ciiiginilly water-wet reservoir, it displaced waler from the larger pores, while the smaller pores remained water-fi!kd becairse 6f capillary forces. A mixed-tiettabihty condl-: tion occuried if the oif deposited a layer of oil-wet organic, material ody on those rock surfaces tliat were in direct contsct with the oil but not on Me brine-covered surfaces. Oil-wet deposits would not be formed in the small water-ffled. pores, snowing them to remain waterwet. The question that Salatliel did not address was how the oil first came into direct contact with the rock. As the oil moyes into the larger pores, a tfdn layer of interstitial water remains on @pore walls, preventing the oil from contacting the rock. Under certain conditions, however, @e waterfdrn separating the crude and the mineml surface cm mpture. Hall et al. 51 sad Melrose52 recently developed a theoretical model for the stability of these thiri water films that shows fiat the water ftis become thiier and thinner as more oil enters the rock. The water fim is $tabflized by electrostatic forces arising from the eIectficaf double layers at the oillwater and wateif rock interfaces. 5154As tie water fifmthickness is further reduced, a critical tlickness is reached where the water films in the larger pores become unstable. The films rupture and are dkplaced, aflowing oil to contact ~e rock.

TABLE 2DiStribUtiOn OF dARBONATE RESERVOIR WETTABILITIES35

contact
Water-wet Intermediate wet oil-wet Strongly oil-wet Angle (degreas) O to 80 .80 to 100 100to 160 160 to 180

Percent of Reservoirs . a : 15

be used. only for such measurements as, porosity and air permeability where the wettab~lty will not affect the results. The third type of core is the restored-state core, in which the mtive nettability is restored by a three-step process. The core. is cleaned and then satrmtcd with brine, followed by crude oil. F,@ally, @e core is aged at reservoir temperature for about 1,000 hours. The methods used to obtain the.three different types of cnres will be discussed in more detail later.

,,

aaphaftenes. These surfactants are believed to be polar compounds that contain oxygen, nit@gen, and/or suffer. The oxygen compounds, which are usually acidic, include the phenols and a bwge number of different carboxylic acids. 67$5,86Seifert mid Howellsw showed that the carboxylic acids are titerfaciilfy active at alkaline PH. The sulfor compounds include the sulfides and tilophenes, with smaller amounts of other compormda, such as mer~ap~s ~d polysulfides. 87,88The nitrogen compo~da are generaUy either basic or neutral and include csrbaxoles, tides, pyridenes, quinoliies, and porphy~~. 40.s7-90me pVhYtis camf&m imerfadly active metal/porphyrin complexes with a number of dii%erent > m tds, including nickel, vanadium, iron, coppr, tic, titanium, calcium, aud mirgnesinm. 9*-95 Because the .9zrfactarrts in cnrde oil are composed of a lsrge number of very complex chemicals that represent onfy a small fraction of the,crude, identi@g which compounds are im ortam in aftering the wettabtity has not beeipossible 6 h addkion, attempts to correlate bulk crude propert;ei with the abflity of the crude to ~ter wettabiliw have been unauccessf+ McGhee et al. 62 satnrated Berek cores with brink, od flooded them to IWS with different cnides, then incubated them at 140F [60C] for 1,0+30hours to allow the wet@bfity to reach equilibrium. .The U.S. BWearr of Mines (USBIvf)wettsbllily index wasthen meaaured and compared with bulk propwties of the crude. They found no correlation between the USBM index and interfaci.d tension (IFT), organic acid content, percerit nitrogen, or percent suIfnr of the cnrde. oCuiec96 measured the Arnott nettability index of restored-stnte cor6s and found no correlation between ivettabilky and amonnta of acids, basea, aromatics, resins, nitrogen, or srdfur. In all cases, when the restored-state cores were water-wet, the crndes bad low sapha.ftenesnd anffur contents., However, other low-asphaftenexnd lowmdtirr c@des rendered cores neutrally or oil-wet. Experiments that determined the general mtnre of the surfactxnts xnd the crude oil fractions in which they are concentrated without attempting ~ determine exactly which compounds cause wet@bifity alteration have been more success~. Jolwnsen and Danningw,9s found that asphzdtenea were responsible for changing some cmdeoiWwater/glass systems from water-wet to oil-wet. The system ,was oil-wet when the cmde was used but wat&rwet when the deasphalted crude was used; The addkion of a very small amount (0.25%) of the whole crude to Ozedeasphalted crnderestored the oif-wettingness of the system. Donafdsbn aud Crocker55 and Donafdson56 measured wepabilky alte@ion caused by the polar coinpoaada extracted from aeveml different mincmf oifa. First, the nettability of a series of uizcontanzinated Berea plugs was mcasnredwith brine agd a refied mineral oiL The average USBM wettabilky iizdex was 0.81, or strongly water-wit. After cleanirig, the USBM nettability index of the plugs was measured with brine and a 5 % mixture of the extracted polar organic componnda in the retined mineral oil., The phtgs were significantly leas water-wet, with USBM wettabtity indices ranging from 0.45 (waterwet) to -0.W (xretitmlfy. et), demonstrating that polar w compmmda in cnide can alter the wettabtity. Note that there was appsfentfy no aging time with the polar cOmponnds in the plugs, so equilibrium wettxbifities may be more strongly oil-wet. /., 112s

Several researchers 57,5s analyzed wetkbiliw-afterirw compounds extracted from cor~. Jennings58 r~moved ~ portion of the nettability-altering cornpotirids by extracttig a non-water-wet core with tolnene,, followed by a cfdorofordmethanol mixiure. An imblbitioiz test showed tbst some of the wettabil@-idtering compounds had been removed during the s~ond extraction because the core was more water-wet. The material remo+ed dtiring the second extraction contained porphytis ~d bigh-moledorweight pamffinic and aromatic cbmpoiihds. Denekaa et al, 41 used a d~tiflntion pro;exs to separate cmde oifs into fractions of different molecular weight. A clean, dry core wax saturated with the crude oil fraction to be tested, then aged for 24 hotii:. An imbibition test based on the relative rate of imbibkion waa nsed to determine the wettxbility Alteration..1.1 The originxl crqde oil and the heaviest residue left a,fterdistillation had the greatest effect on the nettability; they were the only fluids that nzadetbe rock oil-wet.fhia fiplies that a considerable portion of the surfact+ds, in the crude oiI had a large molecular weight. Many of the lower-molecular-, weight fractions, however, also debreaaed the waternettability, demonstrating that the surfactants in crude have a broad range of molecufa.r weights. Cuiecg6 obtained similar results. Note that Denekas et al. and Cuiec botlr used@ cores and that idso~tiob of the w&ttnbilityif .ikering cOnzpoundswoufd probably have been iltered the cores contained brine during tie aging process.. A number of roaearchera have examined the i@rfacinUy active materiak that are cOncentrat&dat the Oil/water interface. Generalfy, these materi~s can iilso be adsorb@ on tie rock surface to sfter wettsblli~. 3.7,8~g9-*m Bartell and Nlederhauser 103managed @ sepirate these, materials from ~e crude oil dqd f6und that they, formed a hxfd, black. noncrys@fline substxnce tit was sapI@tic in nature. . . Adsorption Through Water F~s. Experiments hove shown tfiat nataml surfactants. ii cimde.are often sufflcienify soluble in water to a&sorb onto the rock surface ,&r passing tbrougb a thin ld~er. of water. 42,60>69-71 Meaauremerits comparing aaphd~ene a+orption in cores with and without water show tlwt m many. caaes a water film wiUreduce but not completely ir@it =pk+lterfendsowtion. 6M9,70 Be&use the wa~ei .qzd asphaltenes wM coadsorb, however, the wat4.r film may alter tie detailed adsorption mechanism. 70,1w Lyutin @d Burdynm found that the asphalt&e adsorption f$orn A&h ,crude in an ynconsolidated sandpack wai about 80% of the dry y~ue at a water saturation of 107. PV, decreasing to 40 % when the water sapration was incrth+ed to 30% PV. Berezin the et al. 69 exmzzizzed adsorption of .&phalten&s&d ;exins from crude onto cleaned sandstone cores. With Tuimazy crude, a water,satnration of about 17% reduced the adaozption by about a factor. of three. With two other crndes, a water saturation of about 20% completely. inhibited the adsorption. Such complete inhibition by tie, water fifm woidd be expected in reservoirs that remain water-wet, with no significant ,adsorption:from the cmde. Reisberg ad Doscherbs aged clean glaas slides in c~de ofi.floating above brine and observed the formation of oif-wet fti. The formation i.nd s~bility of the oif-wet fti on the slide was observed by lowering .!-be slide into the brine and observing whether the brine disJoumalof Petroleum Technology, October1986

oxygen compounds gave higher airgles on dolumite.tbsn quartz, up to 145 [2.5 rad] for. octanoic acid [CH3(CH2)6COOHJ and up to 165 [2.9 rad] foc lawic acid [CH3 (CH2),0 COOH]. Note, however, that tbe uxygen-containing acidic compounds appesr to react gradualfy with the dolomite, so the contacf angles ae unstable and the sy$em gadu?dly becomes more water-wet. Cram if.ail noted that none of the relatively simple compounds they tested could create a stcble, oil-wet yuface. There fure, they cuncluded that the compounds respomi-. blefor wettabihty alteration in crude were higher-weight Sandston& mrd Carbonate Surfaces. The types of minpolar compounds and other po+ons of the asphaltenes eral surfaces irr a reservoti are also im ortarrt in determi@rg wettabfity. Both Treiber et cd. E and ClriHngai and resins. ad Yen35 found that carbonate reservoirs are wpi@y. In the inure complex crudeibrinelrock systems, the nriner# surface will not necessarily have a preference for more oil-wet than sandstone ones. Two other sets of excompounds of the opposite acidhy. The simple systems periments show that the mineral surface interacts with the dkcussed here tested each surfactcrd individpaUy and recmde oil imposition to detefine wettabWy. The first moved the effects of brine chemismy. @ tke section on set e~nes the adsorption onto silica and cmbonatesurbrine chemistry, it will be shown thnt multivalent cations faces of relatively simple polar crrmpoundy the second cnn promote the adsorption of surfactants with the same set exnmines the adsorption of crirde. acidigi as the surfcqe. fir addition, the adsorption of auy Simple Pokr Compounds. Whsin the effects of brine single surfactant in the crude might be enhanced or chemistry are removed, silica tends to adsorb simple orgtic bases, wh~e the carbonates tend to adsorb simple depressed by the adsorpion of other compounds. ~rgaic tilds. 37,Q83 This occurs because silica normallY Adsor@on From Crude. A nnmber of researchers found differences in the adsorption of crude oil cumhas a negatively charged, weakly acidic surface in water nenr neutral pH, while the carbonates have positively punerits onto dry sandstone and carbonate surfaces. 41,72-74, l@,110Denekss et al. 41 sepmated out the charged, weakly bssie surfaces. 37,@,83, 105 acidic and basic orgaric compounds from crude arrd testThese surfaces will preferentially adsorb compounds ed them in initially clean, dry cores by tie method deof the opposite polarity (acidity) by m acidbase reaction. scribed earlier. They found that the wettabfity of Wettabili~ of silica will be more strongly affected by the snndstone was altered by both the acidic and basic comorganic bases, whfie the carbonates will be more strongpounds, while the Iiiestone was more sensitive to the baly affected by the organic acids. This was found to be the sic nitrogenous orgmric compounds. CW+in experiments on the adsorption and nettability alSeveral experimenters have compared the adsorption te~tion of refntively simple polar ,compormds oir sandstone and carbonates. The compounds were dksolved in of asphnbenes from crude onto initially clean, dry sazrdpacks composed of either quartz or disaggregared core a nonpolm oil, and the contact angkeof the oillwatcrhninmaterial that contained both quartz and carbonate. 72,110 eral system was measured on mr initially km, strongly They found that adsorption was greater in disaggregate water-wet aystal surface. &xreraHy, adsorption mrd wetcore material. Tumasyan and Babclyan 110. easured the m tabifity nkemtion occurred with basic compounds on the adsorption, of asphaltenes from Kyarovdag cmde onto acidic silici surfaces and acidic compounds on the basic quartz and cleaned, disaggregate Kynrovdag core m~ccrbomte surfaces. Acidic compounds had very little efterial @atconticd 10.4 % carbonate. The adsorption wnc fect. on sifica, and basic com ounds had litde effect on fo~l~ fieCabonat=. 37 42,66.7S.7J. however, that about 8x 104 mg/cm2 for qumtz nnd about 18x 104 A Note, mglcmz for the core material, mr iacrease of more than most of the ,adsorbed compounds chmrged the wettabfiV a factor of two: Abdurashitoi ef al. 72 meaarzzedthe adonly from strongly to mildly water-wet, rather than to sorption of asphnftenes nto sida-sized fractions of pure o oil-wet. quartz samds and sends containing both quartz and carThe acidic compounds that adsorbed and nftered the wettab~l~ of the carbonates in preference to silica in- bonate. They found that the adsorption on the qunrtz sands was as much as an order of magnimde lower Own the adcluded naphtherric acid 37.109mrd a number of carbox$; sorption on the sands containing both minerals. These re- ic acids (RCOOH), including capryfic (octanoic , 2 psfmitic (.hexadecarroic), 42 stearic (@adecanoic), 10 ,10s srrks are very qualitative, however, because the speCXc surface arei of the quartz packs was lower dum the area and oleic (cis-9-octadecnnoic) acids. 42 Basic compounds of the mixed mineral smrdpacks, which afso reduces the that adsorbed on the acidic silica surfaces included isoqrdno~ne37and octadccykmzine [CH3(CH~17NH~. 1ffi,108 ~onnt of adsorption. @mz40 and Morrow ei al. 66 exded dze adsorption and wettabilhy alteration on quartz imddolomite of a num- Brine Chemistry. The salhrity nrzdpH of brine ae very ber of relatively low-molecukw-weight compounds found imw-t in determining wettabiilg because they strongly in crude oils. Basic nitrogen compounds gave advancing affect the surface charge on the rock surface and fluid incontact angles up to 66 [1.15 rad] (water-wet), with terfaces, which in turn can affect the adsorption of .srrrhigher angles for qrrnrtz than dolumite. Sulfur compounds factants. o,m Positively charged, cationic srrrfactanta tested provided arzgfes of 40 [0.7 rad] or less with wifl be attracted to negatively chnrged surfaces, while rto systematic dlffercrrces between the two surfaces, The negatively charged, anionic surfactcnts will be attracted contact angles either were stable or decreased with time to positively charged sin-faces. The surface charge of Q. (i.e., the system became more water-wet). The acidic ica and ccfcite in water is positive at low pH, but nega-

placed alf of the cmde ofl from the slide. They first aged a clean glass slide in crude mrdfound that a film, d6posited over several days, made the slide moderately oil-wet. They modified the experiment by immersing the slide in water before aging it in crude. Surprisingly, the oil-wet fti formed much more rapidly. when a NaCl solution was used instead of water, the slide also became oil-wet, but it was necessary to age the slide for a longer period of time.

Journd of Petml..m T-hnology,

October 1986

1129

tive at high PH. For sifica, the surface becomes negatively char ed when the pH is increased above about 2 to 3.7, ! 3,105 whfle calcite does not become negatively char ed untif the pH is greater than about 8 to 9.5. &,05.111As discussed in the previous section, silica is negatively charged near neutral pH and tends to adsorb organic acids, whiIe cafcite is positively charged and tends to adaorb organic bsaes. Calcite will adsorb cationic smf@mJts rather than anionic surfactants., however, if the pH of the solution iJJ which it is immersed is increased above 9.111 The pH also affects the iotiation of the snrface-active organic acids and basea in the crude.. fn afkahe waterflooiling, a relatively inexpensive caustic chemical typically sodium hydroxide or sndium ofiosificate-is added to the injection ,water. 112The hydroxide ion mscts with organic acids in acidic crude oils to produce surfactanta that after the wettabiti~ ador adsorb at the oilhine interface to lower f.FT. Seifert and How.ells85 exsmined the interfaciafly active materials in a California cnrde oil. They found that the crude contained. a large mount Of carbnxylic acids that form soaps it ilkaline PH. The possibfity of EOR during amalkaline flocaldepcnda on the pH and salinity of the brine, the a.sidi of the crude, ? and the origiwd wettabtity of the system. 2,113,114Cooke et al. 6 discussed the effects of salkhy nn wettxb~ky in alkaline flonds where the soaps are formed by the interaction of the alkaline water with the acidic crude oil. In relatively fresh water, the snaps that are formed are sohtble in water; promoting water-wetness. If the system is initially oif-wet, EOR may occur b a wettabdity rever, ~~ from ~fi..wet to ~a~r-wet. 17.2.? 114J 15 On the ~ther hand, in high-salinity systems, EOR may occur as, a result nf awater-wet-to-oil-wet wettnbifky reveraaf. Aa the saliniw is increased; the soaps become almost in.duble, adsorb on the rock surfaces, and. promote oil~en~g, 6.113If the system is initially water-wet, COok et al. ststf that EOR in a highly sshme ~ystem may oc,cur by a water-wet-to-oil-wet tiettability reversaf mech~sm.6 ,113,114

In silkdoillbrine systems, multivalent metsl cations in @ebrine can reduce the solubilky of the crude surfactants andlor promote adsorption at the mineraf surfaces, causin the system to become more oil? .116,117Multivalent metal ions that have wet. 6,W,77,79,8 altered the wettabifity of such systems include Ca 2, Ni2, and Fe3. Treiber et al. 34 examMg2, Cu2, ificd the effects of trace metalions in the brine on the wettab~hy. They meakured the contact angles on quartz of dead Werobic cmdes in deoiygenated synthetic fofmation brine and found that as little as 10 ppm of Cu2 or Ni2 coufd change the wettab~ky fcom watdr-wet to oiIwet. Brown and Neusta.dterm placed cmde oil droplets in a contact-angle apparatus tilled with dktifled water. They found that Oreaddition of.less than 1 ppm of Ca2 or Mg2 would alter the nettability, making the system more oil-wet. The addition of trace amounta of Fe2 also changed the wettabiIity with some of the crudes tested. The.$emultivalent ions have SISO been ahown to incresae the od wetness of soils stab~ied with cut-back xaphalt..11S,119 (Cutback ~~~t is ml MPildt ==ted iti an inexpensive solvent, such as gasoline, to reduce the Seved strongly water-wet viscosi~.) HaiIcnck 11s soils with cut-back asphalt. He fokd that the oil wetness
,.
1130

of the anil after the.asphalt tre@zent waa greatly increaaed by pretreating the soif with a solution of ferric or @miIJU222 sulfate. Morrow et al. xl aged glass sfidca in Moutray crude, waahed the slides to remove the bufk crude, and then used isooctafre and distilled water. to meaaure tie wateradvancing angle. They fonnd that the wettabifity strongly depended on the sfnount of trace ions iJJthe system. When the glaas slide was extremely clean, no residual fb was depnsited by the crnde, and the system was waterwet. Next, they treated the glass with femic (Fe3 ) or orler transition metal ions before exposing it to drecnide. They obtained contact angles up to 120 to 140 [2.1to 2.4 rad], with the angle dependent on the choice of ion and its c&rcentration. Theferric ion was pxrticulady effective in altering the wettabilky. There appexr to be two related reasons for ~e effects of these mnftiv#ent ions on the wettabili~. Fiiat, they ~, can reduce the snlubility of the surfactants in the crude andbrine, helping to promote oil-wetting. 6,113Second, they behave as activators for the smfactants in the crnde. Acdvator .la a term used in the floption industry for ions or cnmpounds thst, while not snrfact@ themselves, enhance surfactant adsorption on the mizreraf smface snd increase the flnatabifity. Generally, the activators act like a bridge between the mineraI surface and tie adsorbing surfactant, helping tn bmd the snrfactant to the NIffsce. go AS shown previously, clean @J~ haa a negatively charged surface nnd tends to adsorb @ositively charged) orgnnic bases from solution. The (negatively chsrged) acida in solution will not adsorb on the surface because they will be repelled by the like charge on the quartz surface. For example, clean quartz is not floated by fatty acids, ideating that tie quartz remains water-wet. At the proper pH conditions, however, the wettabfity can be changed and the quartz can be floated by the additidn of smafl nmounts of marry multivalent metalfic cations, including Ca2, Ba 2, Cu2, Al3 i ad Fe +3. WT%Q.107These ions adsorb on tie qun3t2 surface, providing positively char.r@ sites for the adso% ,-. tion of&e fstty ;~ds. -. For exam 1. Ga.din and Chang7s imdGaudm and Fuerstemm% staled the adsorption of laurnte ions on auartz. When sodium Iaurate, CHa (CH2.) toCOONa, is ~ded to the water, it dissociates @~ a ne~ati;ely charged laumte ion and a positively charged Na ion. Because quartz develops a negative surface charge as a result of the dissociation of H + ions from the Si-OH groups on ihe silica surface, the negatively charged laurate ion is repelled ffom tie negatively charged quartz surface. Hence no adsorption occurs. However, adsorption occurs when, for example, divafent Ca2 or Ba2 ions are added aa the activator. These positive djwdent ions can adsorb on the surface, allowing the negatively chmged surfaciant (in this caae, the laurate ions) to adaorb in association wia them. Researchers with other experimental systems also state that divalent ions can bind to a negatively chargedsurfactant to fogn a positive, cationk surfactant/metal ~mplex, w.bich is then attracted to and adsorbs on the negatively charged quartz snrf?ce, 116,117 CIays. Several researchers have studied tie adsorption of aiphaftcnis Wd resipa onto clays, and found that.ad- ; sorption can make the clays more oil-wet. 70,76.1~, 120-133 Journalof Pmol&m Technology, October1986

Clementz %120,121 eximined adsorption under mhydroua conditions of the heafl endsthe nonvolndle, highmolecuiar-weight fraction-of cmde oil, which are primarily asphal~nes snd resins. He found that rhe compounds adsorbed rapidly onto montmorillonhe, forming a stable clay/organic compound and chsnging the nettability from water-wet to oil-wet. Clementz also looked at adsorption under anhydrous coiiditions of the heavy ends onto Berwcorca that contain significant amounts of kaolinite. The adsorption of tie heavy ends made the core neutrally wet as determined by an imblbhion test. The adsorption also,reduced the expansion of swelling clays, clay surface area, cation exchange capacity, and water sensitivity. The materials that adsorbed onto both the montmorillonite and kaolinite were difficult to remove, although most of them could be exmacted with a chloroformlacetone mixture. Clementzused dry cores and clays. As discussed C& er, the presence of a water fdm will gen@ly reduce the adsorption of wettabfity-altering materials, typically by a factor of two to four, although in some cases, it will completely inhibk adsorption. >@ Collins and Melmse70 measured the adsorption onto kaolinite of asphaltenes dksolved in tolucne. The dry clay adsorbed a maximum of about 30 mg asphaltene/g clay. The addkion of 6.6% water t? the clay reduced the adsorption to 13 mg/g. In addition to reducing the adsorption, the water l@ may alter the d:tied mechanism of asphaltene adsor@on because the asphaltenes and water will coadaorb. 7 For example, in contrast to his work with anhydrous cores, ClemenE found that the adsorption of asphaltene onto Berea cores in the presence of water dld not reduce the water sensitivity of the kaoliidte. lW Non-Water-Wet Mineral.% When all of the surface contaminants are carefully removed, most minerals, including quartz, carbonates, and sulfates, are wrongly water-wet. go,1o7,lx From flotation studies, however, a few minerals have been found that are naturally but weakly water-wet or even oil-wet. These minerals include sulfnr; graphite, talc, coal, snd msny sulfides. Pyrophyllhe and other talc-like silicates (sificates with a sheet-liie also neutrally wet to Oil&rncture) are ~obably ~ese finer~~ ~ ~OW~ tO be SO~e~et, 30,107,134-12 what hydrophobic because air can be used to float them on water ir3froth flotation, implying a large waterlairhnineral contact angle. Because they are non-water-wet with air, it is probable that they are also oil-wet. On the bsais of core-cleaning attempts in a limited number of reservoirs, it appears that cores containing conl are sometimes na.tur@ly neutrally wet because they can be cleaned only to a neutfsll wet condition rsther than a z ~Uon lY wa~r.wet one. 1 a,129 Cuiec96 and Cuicc et 8 al. 13 cleaned unpreserved cores with different solvents and then measured wettabdity. In four cases where cores contained large ixnounts of unexmactable organic carbon, they were able to clean the cores only ti neutmf nettability. Wendel et al. 12s cleaned core from the Hutton reserv6ii contaminated with an invefi-oil-emulsion drilling mud. Core from most zones in thk reservoir could be cleaned to a water-wet state. However, in one zone that contained si=tilcant amounts of coal, the core was neutrally wet after cleaning. About 50% of the rock surface in tie neutrally wet zone was covered by a thin layer of organic matter less than 300 ~ [30 mn] thick. ThIS fayer Journalof Petroleum Technology, October1986 --

may be a:rcauft of dif3i3si0n organic cmnpounda released of during diagenesis from the small, organic, detrital pardcles of cod scattered throughout the zone. Unforhmately, this is unclear at present. Thin sections from both water-wet and neutrally wet (tier clcaqing) zones show that both contain approqtely equal amounts and dis-. @bution of woody coal; algae coal, and pyrite. Consequently, it is unknown what causes the postcleaning neutral tiettability of this neutrally wet zone. Boneauand Cfampitt 131and Trantham and Cknnpitt 132 stite that the oil wetness of the North Burbank unit is caused by a coating of chamosite clay (Fe3Al zSi2O IO . 3HzO) on the pore surfaces rather than the more common, strongly adsorbed organic coating. The chamosite clay, which is iron rich, covers about 70% of the rock surfaces It seems plausible that tbe chamosite cfay renders the core oil-wet because, as discussed earlier, iron ions are strong activators, promoting o~-weufng. Cl~pitt* states that unpubliahti contact-angle measurements made with all of the ~emls inthe No&Burbank core ahowed that chamosite M naturally oil-wet. Artificial Variation of Wettabifity Aadescribed previously, a native-state core contains a cmmplex mixture of different compounds that can adsorb and deaorb, possibly altering the wettabdity during an experiment. Msny re8esrchers have tried to simpfify their experiments by artificially control~mg the wettabfii~ to some constant, uniform value. The three methods most commonly used are (1) treabnent of a clean, dry core with various chemicals, generally orgWOcMOrOsfl~es fOr. sandstone cores and naphtienic adds fOrwbOnat~ core~ (2) using sintered cores witi, pure fluids; and (3) adding surfacthnts to the fluids. A sintered tdlon core with pure fluids is the preferred method to obtain a uniformly wetted core because tic wetrabili~ of these coma is constant snd reproducible. The fiettabilhy of cores treatid with brganochlorosilan:s, naphthenic acids, or stirfactanta is much more variable because it afso depends on such variablesas the chemical uked, the concentration, tie treatment time, the rock surface, and the brine PH. These treatments have advantages, however, when he~rOgen~ous wettabtity or wettsbil~ alter~tion is studied. Organochlorosffanes and Other Core Tr&dmMa. One. method of making a sandatone core uniformly non-watcrwet is to treat it with a solution conpining an OrganO~~oro~~e ~ompond, 133-139vm~tiom of ~~ tf~~tment have also been used to create fractionally wetted ~mdpacf&&+$50.1@h!2~d mixed-wet cores. 143me ~rganosilane compounds contain silicon molecules with attached chlorines and non-water-wet organic groups, with. the general formufa RnSiC14-n where R is usually methyl or phenyl and n =0, 1, 2, or 3.133 These substances ,react with the hydroxyl (OH) groups on silicon dioxide surfsces, exposing the organic groups and rendering the surface non-water-wet. For example, dimerhyldichlorosilane, (CH3)2SiC12 (Drifilm@ or Teddol@ ), chemisorbs on the outside of the sificate lattice of glass, eliminating HC1 and exposing CH groups, which reduce h of the surface 1 Other compounds il3the wata-wetness clude heximethyldkilazane 138 and trimethyMdo!Osikme. 145The wettabfily of the core is altered by flowing Ptiltip Petroleum, BaII[esville K, O .P.rsmtic.nnm.nimtimwithR.L.Clmnpiu,
Dac.1S83. 1131

that contact an~es sa large aa 154 [2.7 rad] could be obtained for aK1casurfaces mated with different conqamations of methylsilOxane polymer, but these contact angles tended to decrease towsrd 90 [1.6 rid] as they aged. Memwat $?ral. l@ tmatcd silica surfaces with various concentrations of four different organochlorosilanes and obtnincd contact angles ffom 75 to 160 [1.3 to 2.8 rad] with water and xylene on the treated surfaces. Depcndmg on the specific treatment, they found that the contact angle could gradually chlorosilmies sre mixed witkuntrcated; water-wet sands. The fraction of oil-wet surface is aasumed to be the sb.me increase or decrcaae aa the system aged. Because&e wetas the fraction of orgnndcblorosilane-treated sand. One tabtity of cores treated with organosikmes can range from problem, however, is that some of the organocblorosimildly water-wet to strongly oil-wet depending on the Spe: lane is known to be transferred to the water-wet sand cific treatment, the Amott or USBM method shoufd be used to determine the wettabllity of the treated core. grains, likely changing their wettabtity.43 Auother method of obtaining fractioml nettability is to form tie Quilon@ treatments are mother method that has been porous medium from water-wet (gkMs)beads and oil-wet used to alter the wettabiIity of sandstofie cores. Tiffii hnd (tcflon) beads. 146 Yellig 149treated Berea cores with Quiion-C@ to render Moh~~ ad s~tcr 143have reqedfy publiahcd a techthem uniformly oil-wet. Workers at tie Petroleum Recovery Inst. have used Quilon-S@, i related comnique to generate mixed-nettability cores so that the large compounds consist of a chrome ~md, 15~153 me won pores have continuous water-ivet surfacca, leaving the complex containing a hydrophobic fatty acid group in an smalf pores ofi-wet. Note that in these cores, the nettaisopropyl alcohol solution. When @iiori is injected into bility is reversed from Salatbiels47 mixed-wettability tie core, the molecules bmd to the surface, expose the cores. Cleaned cores are first treated witi orgagosikmes fatty acid group, and render the rock surface oil-wet. 1X to render them uniformly oil-wet. The treated cores are Note that wettabtity of the treated core probably v~ies, saturated with oil, flooded with heptadecane to dkplace depending on concentration, tfcatment time, etc., so it the oil, and then flooded with brine to ROS. Because the core is oil-wet, the large pores are fdlcd with brine, but should be meaaured with the USBM or Amott metbnds. In many crises, the treated core is probably OIIIY neutralthe small ones are fdled with oil. Brine and heptadecane ly to mildly oil-wet. IMY then be injected simu&aneously to alter the fraction These trcatmerita have been used on sandatone core with of pores ffled with oil or water. After the desired saturathe chemical binding to the s~Ica surfaces. Orgsno-. tion is reached, the core is fust placed in a cold water bath (50F [1OC])to freeze the heptsdecane, then an 11.5 chlorosikme treatments, which adsorb on silica surfaces by reacting with the hydro+yl grou$a, are generally not pH sodium hydroxide solution is injected to diapfimc the effective on carbonate surfacea. 1 5,1% A number of brine. Mohanty and Sslter state that the alkaline solution 109.155-157bWe used m hthenic acids to ~Wche~~ removes the orgnnosilane coating from the lnrger, brinerender carbomtc cores more ofl-wet. ?7 The naphtle~c tilled pores, leaving them strongly water-wet, while the acids react with the calcium carbonate to form cslcium frozen heptadecane prevents auy change in nettability in tie small oiLffled, oil-wet pores. Folly, t+e alksdine so- naphthenates, which are ofi-tiening. 109 Note that naphthenic acida will not nlter the wettabtity of saudatone. lutiori is displaced with brine, arid all of the fluids are res~faces. w moved, leaving a mixed-wet@ ility core. After this Sharma and Wuuderlich15s altered the nettability of treatment, the cores imbibed both oil and water, indicatBerea pIugs by saturating them with au asphaltic crude: ing that areas of the. core were both water- and oil-wet. Unfortunately, Moh&y and Salter did not test the cores Drv Dlum were vacuum-saturated with isrhaltic cmde oil, : by oil flooding them to determine whether they had a very th&fl~shed with pentane, which ten& to precipita~ low water.saturation after tie injection of manyPVs of asphakenca onto the pore walls. 67 The pentane wasreoil. This would have verified the formation of continumoved in a vacuum, kwiug behind a layer of asphaltenes. ous water-wet paths through the large pores, which would Tim plugs probably had mixed wettnb~ky after Ecatmenc be analogous to oil-wet paths in Sala~eli cores. boti,oil snd water would imbibe spontaneously. 3 An advsutage of thk method is that it uses com@mda found One problem with orgamochlorosilane treatments is that the nettability of the tmatcd core varirs depending on such natnrslly in the resetioir and ,pight be a more realktic ticatrnent than the other trcahnenta discussed above. Note, variables as the orgtiocidorosil~e used, the concentration, the treatment iiine, the time elapsed since the surhowever, that it is necessary to verify tiat the crude is face was treated, and the pH of the brine. 147 No compatible with the pentie because some cmdes will plug dependable treatment has been reported for acgeving a the core when pentane is injeded. given: core wettahilhy. Note that many organosilanetreated cores ze only neutrally to mildly oil-wet, instead Artificial Coma. Several rcaearchera have used artificial of strongly ofl-wet. Coley et al. 134used General Eleccores and pure fluida to control wettab~hy. The uniform tric Co. s~lcone fluid No. 99 in concentrations ranging composition of tie core and the absence of surfactimts from 0.002sto 2.0% and were nhle to vmythe contact combine to give a constant; uniform, and reproducible angle, in. glass capillaries only from 95 to 115 [1.7 to nettability. The most popular material for the artificial 2 fad]. RathnieO et al. 137found that cores treated with core baa been polytetiafluoroethylene (teflon). Stegemeier dmethyldichlorosikme would still slowly imbibe water, fid Jess&n159used porous packa of tcflon particles. More indicating that the cores were at most neutrslly wet. In recent experiments hsve used consolidated teflon a solution of the organosilane through it, snowing a sufficient time for the reaction to occur, and then flushing the unreacfed compound from the core. Some control of the change in we,ttabifi~ can be achieved by variation in the concentration of organosilsne in the solution. For a complete description of the method, see Ref. 134. In addition tu unifoqnly treating cores, organocldorosikmca are used to prepare fractionally wetted sandPacks, 43,46.50,140-142 Sand gtins txeated with 6rgm30~onmt, Newcombe et d. 136 stated 1132 Journal of Pekole.m Technology, October 1986

,.
cores, 160-68 which are prepared by compressing teflon powder and sintering it at elevated temperatures to produce a consolidated core. Mungan 167 completely describes the process. Lefebvr.e du Prey lm has 81s0us<d Sinter.Sd5tifle88 8tee] and altina cores. ~, Teflon is preferred for two reaaons: it is chemically inert and has a low surface energy. 16g Most minerals found in reservoir rock have ahigh sutface energy, soabn08t all liquid8 will spread,,op and wet them against $r. The w&abiMy of such high-energy solids must bec$mtroUed with either adsorbed fti on the solid 8urface or 8urfactants in the fluids. Both of these inethod8 raise the problem of changes in the wettab~ty during the experiment as a result of adsorptionldesorption phenomena. On the other hand, the surface energy of teflOn iS low enouti. that a wide range of contact angles can be obtained with various combinations of pure fluids that do not contain surfactants. The u8e of pwe flbids with teflon also avoids difflcukies with contact-angle hysteresis associated with adsorption/desorption equilibrium and the problems associated with contact angle and IFT aging phenomena. Thisis dlscus8ed in more detail in Ref. 1. fiany experiments in tetlon cores use air or Nz anfl various fluida to va~ the contact angle. Contact angles from Oto 1080 [0 to 1.9 rad] can be obtained by the proper ChOiCe liqof ui~gas pati8. 161For ~x~ple, an air/water/teflOn sYstern hasa contact angle through the water of 108 [1.9 rad]. Lefebvre du Prey 160 used mixtures of water, glycerol, glycol, and alcohols to represent the water pbaae and mixtures of pure hydrowbons for the oil phaae. Contact angles through the oil phase of from O to 168 [Oto. 2.9 rad] were reported for hk teflm, steel, and alumina cores. wet

when, water conta.inhg a mild acid is injected. The most cofnrnonly used amines have been hexylamine and n-@ylamine. Mungan 174measured the water-advancing cOnmct a@ on a siliii, syficc u8ing water, nhexylamine, and a refined bid. Tbe contact angle with no aminca present was about 60 [1 rad], or water-wet. As the concentration of tines tias increaaed, tie contact angle gradually changed to about 120 [2.1. rad], or mildly oil-wet. In addition to iltering the wettab~ky, the amines partition between the oil and water and lower IFT.

Alteration of the OrighraI Wettabflity As mentioned previously, alterations in nettability can affect the iesuks of moat core analyses. IdcaOy, tieie @yse8 shordd be mu with core wettabfity that is identical to the nettability of the undisturbed reservoir rock. Unfortunately, many factors can significantly alter *i. wettabilky of thecore. The8e factors can be divided into two general categories (1) tho8e that influenc&core wettsbik ity before testing, such as drilliig fluit is, packaging, preservation, and cleanin% and.(2) those that influence wettabiitv dtig testing, such m test fluids, temperahue, and pres&re. - The wettabili~of a.core can be altered during the drilling process by the flushhg aitionsof driig fluids, particularly if the fluid contsim 8urfactimts 128>75or ha8 a 1 pH~~.1i~.1?6 different 1% that of the reservoir fluids. The w@@biiv may also be changed by the pressure and temperature drop that occurs as the core is brought to the surface. This action expels fluids, particularly the light ends, and changes the spatial dkribution of the fluids. In addition, asphaltenes and other heavy ends may deposit on the rock suifaces, making them more oil-wet. The techniques used in ba@.ling, packaging, and preserving the Surface-Active Agents. The use of clean cores and pure core & slso alter the .wettability through a 10SSof light tkdd8 with various C0nCenmati013Sf a SiJigle Surfactant ends, deposition of heavy ends, and ofidation. The laboo isthe third way that re8e81Cher8have controlled the netratory procedures for cleaning and preparing the core cm tability of cores: Owens ,and Archerzs used biwium change the wettabfity by altering the amount and type of dlnonyl 8ulfonate in the oil and reported stable contsct material adsorbed on tie rock surface. angles up to 180 [3.1 rad] on a quartz crystal. Morrow Factors that can alter wettabfity diuing testing include et al. 66 were uriable to reproduce this work, finding a the test temperature and pressure. Generally, cores nm strong time dependence for the contact angle. They tried at atmospheric coiidition8 are more oil-wet than those mn to control the wetfabtity with octanoic acid, obtaining@at ,reservoir conditiom becau8e of.the reduction iri SOIU-. gles from Oto 155 [0 to 2.7rad] on dolomite. They found bility of wettabfity-akering compotindi. An additional that the wettabflity could be maintained for less than a factor iMuencing -he wettabfl~ is the choice Of test day, however, after which tlesystem became increa.$ingly fluids; certain migerd oils camalter the wettqbility. Core water-wet as tie octanoic acid 81OWIY reacted with the analyses ze sometimes run with air/brine or airlmercudolomite. v,in place of ofl and brine. ,These analyses ~nplicitly ashaVe I18Sd 8mkJeS, sume that wetfabfity effects are unimportant. A number of res&hers 17,26. 17&174 R-NH2, to study EOR caused by Wettab~hy dtemtion iII Currently, three different *of cores ae used in core laboratory &#.wflmds. Wwtability reversal from Ofi-wet analysis: (1) the mtive-state ,core, where every effort is to water-wet and. from water-wet tooil-wet are two of made to maintiin the nettability Of the in-situ roch (2) the proposed mechanism for enhanced recove~ during the cleaned core, where the intent is to remove all of the alkaline waterflooding. 114 In Oiese laborato~ 8tudies, adsorbed compounds from the rock and to leave the core clean core, a refined oil, and ibrine containing mines strongly water-we! and (3) the restored-state mm, where were used. The wettabili~ was rever8ed by changing the the core is first cleaned apd ~en returned toits original pH from alkaline. to acidic. When the PH was alkalime, wettabti~. These definitions are used in the majority of the amine group physically adsorbed on tie rock surface, the more recent literature. However, in some papers, parexposing t& hydrocwhn cl@ to make the sUrfaCe0~ticuk@y older ones, the term restored-state is used for wet. 173The wettabilhy was altered when the PH became what are actually cleaned cores (e.g., see Craig7 ). The acidic because tie mines formed water-soluble salts that work with native- and restored-state core is at either mm rapidly desorbed from the rock surfaces, leaving thern- bient or reservoir temperature and pressure, i.idfe cleaned water-wet, Hence a core that is oil-wet becomes watercores are usually tested at ambient temperature.
Jownd of PetJolam Technology, October 1986 1133

Native.State Core Coring. In a nativi-stite (fresh) core, every precaution is taken to minimtie changes from the undkturbed reservoir nettability condhion, starting when the core ig frost flushed by the dr~g mud. In pyticukw, a mid with s~factants or a pH that differs greatly from the reservoir fluids must be avoided. Ofl-based-emulsion muds ?nd other muds containing surfactaits, caustics, mud thinners, organic coriosion, in&itors, and lign@fonates must be avoided. 175,177 Note that, @hIle they probably exist, no commercially available oil-based muds have been m rted P thatcan preserve the reservoir nettability. 175>17178 The different coring fluids for obtaining native-stati cye have been recomriended. (1) synthetic formation brine, (2).unoxidized lease crude oil, or (3) a water-breed mud with a miniznuin of addhives. Bobek et al. 175recommend coring with brine and noadditives. If ,.hk is not possible, a water-based mud containing only bentonite, cnrboxymeibyl cellulose, rock salt,, and barite should be used. This is recommended b~ause they found that this would not alter the wembfiity of strongly water-wet cores. Note, however, that the carboxymethyl celkdose,may ~ter the wettabfit of oil-wet cores, rendering them more 2 water-wet, 15 .~75 Bbrlich and Wygsl 179 recommend a synthetic formation brine coritaining CaC12 powder for fluid loss control and no o~er additives. Mungait 180recotiends coriug with lease crude oil. Note f.hatthere are tio possible problems with the use of crude oil: (1) it is flammable, and (2) surfactams can be formed by oxidation. of the cmde, which could alter tie wettabili@. ,103 rhfortummly, very MtIe work has been published about the effects of individual drilling mud components cmwettabiihy, particularly for oif-wet cores. Burkhardt .r al. 176 exaniined the effects of mud filtrate flushing on restored,stitecores snd found no significant effects. Unfortunately, the cores were in contact with the crude oil for only 12 to 16.hours, so it is doubtfol that the wettabtity was restored before testing. Bobek ei al. 175 tested several dit%r<nt drillkm mud componerits used in water-baaemuds on both wat~r-wet and oil-wet pings The drilling mud :omp6nen@ to be tested were dksolved in or leachdwith distied water then the resulting solntion was filtcreii. Concentrations of the compamds were chosen to duplicate those encountered in the field: Water-wet limestone and s~dstone plugs were saturated .wltb the test solution and wetibflity alteration monitored by the irgblbkion method., As,dkcussed earlier,.theyfonnd flat rock salt, carboxymethyl celhdose,. bentonite, and bake had ho effect on tie wetmbfli~ Of these initially water-wet plugs. Starch, lime, tetmsoditirn phosphate, and calcium lignosujfomte altered the wettabtity of the sandstone and/or limestone plugs. Drilhg components that, did not.affect the water-wet plugs were tested on oil-wet sandstone plugs. The dry, initially water-wet plugs were made oil-wet before testing by saturation with Elk Basin crude and aging for one day. Notethit becanse of the short duration of the aging, the wettabiity may not have been in equilibri~. The aged cores were flushed witi a drilling mud component fkraW, then the wettabfity was measured. by the imbibition method. .Sa.kdid not affect the wettabfity, whfle carboxymethyl cellulose made. the plugs more water-wet (bariti was not tested). Bobck et al. found that the PH ,. 1134

of the filtrates was an iinpotit factor in we~bdity alteration. The origti bentonite filtrate changed me wettzbtity from oil-wet to water-wet. When the pH was lowered into the neutml or acidic rsnge, however, no wettabtitjI reversaIoccurr+. Sharma snd Wunderlich 158meaaurcd the wettabi!.iwafteration caused by different drilliig mu@components in water-wet and oif-wet Berea plugs. The oil-wet Berea plugs were prepared by treatmentwiti an asphaltic crude and pcntane, as discussed previously. Dry plugs were saturated with brine, injected with 10 to 12 PVs of the drilling fluid component, aged for 15 hours; tien flushed with 5 to 6 PVs of brine. Wettabilky was measurd after contamination by a combined USBM/Aniotl method developed by Shagna and Wunderlich 158and compared with the we~bility of control samples. The driiing components tested included bentonite,, carboxymethyl cellulose, Dextrid@ (an organic polymer), D~spac@ (a polyanionii ceflukiwe polymer), hydroxyetbylcelhdose, pregelatinized starch, and xanthm gum. These components are generally considered relatively bltid, with onfy small effects on the wettiibilky. None of the components affected the nettability of ~e water-wet plugs. However, N of the components, with the exception.of the bentonite fdtrate, made the oil-wet plugs significantly less oil-wet. This indicat&stie need for further rese~ch on acceptable drillings muds for obtaining native-state core. Several researchers have attempted unsuccessfully to fmd suitable commercially available oil-based muds for ~btig ~tive.sate core, 175, 177, 178,~ of tie ~fi.ba~~ drilling mud iiltrates tesied made water-wet cores more oil-wet. Unfortunately,. none of the reports identify tlze specific drilling mud components used. ,
Cm-e Packaging and Preierv&ion. Once the core is brought to the surface, it must be protected from wetW btity alteration caused by the loss of light ends or deposition snd oxkldion of heavy ends., On exposure to air, . subticei k crizdecan rapidly okidize to form wkw products that are surfactants, altering ihe wettabili,W,34,73,103,115,175,181,182 M ad&tiOn, a tick ofl-w@

residue from the crude will be deposited on &e rock surface if the core is allowed to dry out. To prevent wetEbility alteration, Bobek et al. 175 recommended two sltemitive packaging procedure: that are now gene@y used for native-state cores. The fwst ia to wrap the cores at the weUii@in polyethylene or polyvinylidene film and then in aluminum foil. The wrapped cores we then sealed with a thick layer of paraffin or a special plastic sealer designed to exclnde oxygen aid prevent evaporation. The second, preferred method is to immerse the cores at tip wellsite in deoxygenated formation or synthetic brine in a glass-lined steel or plastic tube, which is then seafid to prevent leakage and the entrance of oxygen. ImbibG tion wettabihw tests showed that the nettability of core packaged by either of these WO methods was unchanged from the wettabfily mesaimed at the wellsite. Instid of deoxygenated brine, Mungari180 recommended tit the cores be cut and stored in degassed l&ae crude oil. Morgan and Gordan 183and McGhee et al. 62 recommended that the cores be stored in their wetting fluid, either forntstion brine or crude oil. Thewettabiky would be,determined by an imblbhion test at the wellsite. Finally, not? that cores taken in a robber sleeve, fiberglass, or PVC Journalof Petroleum Tedmo108y, Octpber 1986

TABLE 3EFFECTS OF EXPOSURE TO AIR AND PARTIAL DRYING ON NATIVE-STATE CORE Number of Cores Tested 2 3 2 4 Average . Dlsplacementby-Water Ratio 0,97 0.63 0.42 0.18 Average Oisplacementby-oi Ratio 0,00 0.00 0.00 0.00

iescriplion Native state Exposed to air at 70 to 100nF for 1 day Exposed to air at 75F for 60 days Exposed to air at 225F for 7 days

Cay$btdnedbyuse ofthe Amattwellafl~v,,s, natNeNatecorefrom0,! Zone8., Sterling Conly,

liner can be DESeNed if the ends are cappedand sealed. A number-of experiments have dem&strated that exposure to air and drying cao alter the nettability of core. As discussed earlier, Treiber et al. w measured the. nettability of 50 reservoirs usfig deoxygemted synthetic formation brine and anaerobic crude. In some cases, the contact angle showed that the reservoir was water-wet. For some of those cnrdes, exposure to oxygen changed the wettabili~ to ofi-wet. Bartell mrd Niederhauser103 stodied interracially active materials in crude, which concentrate and form solid fflms at the oil/water interface. These materiils can also be adsorbed on the rock surface, rendering it oil-wet. Crodes and brines were obteined and stored without exposure to oxygen. Most of these crudes showed very little interfaciel activity. On exposure to air, the cmdes developed moderate-to-strong fdrn-fomning tendencies, while the oil/water IFT was lowered by as much as 50 %, indicating that surfactants were formed by oxidatiori of the crude... Richadson et al. 1s2 stored core from a mixedwettability reservoir47 using four different methods. Oxidation snd drying of the core tiere prevented with the first two methods: (1) core wrapped in foil and scaled in paraffh and (2) core stored in evacuated (deoxygenated) formation water. The other methods were (3) core stored in aerated formation water and (4) core stored in cloth core bags. The cores were oilflooded with kerosene to IWS and then waterflooded. The average ROS for the samples protected from oxidation and drying (Methods 1 and2) was about 13%; forthesamples submergedin aerated water, about 24%; and for the samples storedin core bags, about 25%. Bobciket al. 175used the imbibition method to compare the nettability of native-state cores at the wellsite, cores allowed to weather, and cores stored by the two recommended metiods discnssed above. The nettability of the cores stored by either of the two recommended methods was the same as the nettability measured at the wellsite, while most of the weathered cores became more oil-wet. Am0tt177 used bismethtidt ocomparith ewettabihy of native-state cores with similar cores that were exposed tooxygen ayd~owed to partially dry, asshownin Table 3. The native-stste cores were strongly water-wet, with a dkplacement-by -water ratio of 0.97. In the Amott test, the displacement-by-water ratio is the ratio of the oil volume displaced by spontaneous imbibition to the total oil volume displaced by .botb imbibition and forced displacement. Itiszero forneuqally mdofl-wetcO~~s aod J&mal of Petroleum .Tecbnology, October 1986

approaches one as the water-wetness increases. Siniiiar: ly~ the displacement-by-oil ratio is zero for neutrally and water-wetcores aod approaches one as the oil-wetness increases. The cores became more oil-wet as they were either exposed to the air for longer periods of time, o! at higher temperatures. Similar tests on an initially weakly water-wet core showed elmost no change. On the other hand, Mungan 115used the imbibition method to measure the wettabilhy of native-state cores. In contrast to tie experiments discussed above, cores preserved in deaerated water were oil-wet, but becsore water-wet when exposed to ti for 1 week. Chfingar and Yen35 have also reported that some cores became more water-wet on exposure to sir, indicating that it is bnpossible to predict how the wetfsbtity will be altered by tie oxidation of tie cmde. Mungao 180recnmmendsflushing native-state core with five erode oil before sny flow studies are startsd. After native-state cores .havc been prepared, they are usually nm at reservoir conditions with crude oil and brine. Probably the greatest, uncontrollable problem with nstive-state core is the alteration of nettability as the core is brought m the surface., When the pressure is lowered to atmospheric, light ends are lost from the erode, changing its properties. In addition, heavy components cm come out of solution and deposit on the rock, making it more oil-wet. 137 The decrease in temperature wilf also decrease the solubili~ of some wettebfli~-altering compounds. Pressure coring prevents tie loss of light .erids. However, the cores are frozen before removal, so wetta.bflity-altering compounds W deposit. Unfortunately, there is no experimental work avsilableon wettabflity alteration as the core is brought to the surface. .. . Cleaned Core The second type of core used in core aoalyais is the cleaned core. Cr&ig7 recommends that cleaned core be used for multiphase flow measurements only when the reservoir is known to be strongly water-wet because errors iq the core am.lysis will be introduced otiimvise. There are two main reasons to clean wre. The first is to remove all liquids fromthe core so that. porosity, permeability, and fluid saturations can be measured. Core cleaning for these roudoe core measurements will not be considered in this paper. The second reason for cleaning is to obtain a strongly water-wet core, generally as a first step in restoring the wettabfity of a contaminated core. 1135

In obtaining a cleaned core, an attempt is made to remove all of the fluids and adsorbed material, leaving a clean rock surface. Gant aid Anderson 129 discuss the meibcdsused,tu clean core. One common method is reflux extraction (l)ean-Stark or Soxhfet) with a solvent such as toluene, sometimes followed by extraction with cfdoroform or methanol. Alternatively, a flow-through system where the solvents are injected under pressure is sometimes used. 57,&,65lf the cleaning procedure is successful, the core is left strongly water-wet. Cuiec$5 mid others 57,1w discussed the chemicalreactions involved in the cleanin process. Cui&ca,& compared me efficiency of different solvents in flow-through core cleaning. Initially water-wet outcrop sandstone and limestone cores were saturated with different cntdes (sometimes the cores also contained brine), then aged. The aged cores ivere ncyrmfly neutr~- to oil-wet, as determined. by the Amott wettabflity test. The cores were then cletied with dlffererit solvents, and the Amott test was used to determine cleauing efficiency. Cuiec found that he could clean both sandstone and liiestone cores by flowing the f?ll@ig seven solvents through the core: pdarte, hexane, heptane, cyclobexane, beuzene, pyridine, and ethanol. Chloroform, tohtene, and methanol used singly were not very effective. Cuiec also looked at several dtiercnt acidic and basic solvents used individually and found that the acidic solvents tended to be more effective in cleaning sandstone, whiie the basic solvents were better in cleaning Iimcstone. This difference was attributed to the acidic nature of the sandstone surface and the basic mture of the limestone surface. For examplei because sandstone (silica) has a weakly acidic surface, it tends to adsorb bases from tie crude oif. When a stronger acid flows through the sys@m, it will gradually react with and strip off the adsorbed bases, Ieaviug a clean silica surface. G@ and Anderson 129 surveyed most of the corecleouing experiments in the literature. They found that the best choice of solvents depends heavily on the cmde ~d the mineral surfaces becavse they help determine the amount and @pe of nettability-altering compounds adsorbed. Solvents that give good results with some cores and cmdes often faif in other cases. For example, Grist et al. 1s4 and Holbrook and Beruard45 both found that they could clean core to a strongly water-wet state using a cliloroformfmerhanol mixture, while Jennings5s repOrted. fiat thk was unsuccessful. For cleaning for routine core analysis, API 1s5 reports that cbfom form is excellent for many midcontinent .ctudes,wh~e toluene is us6ful for asphaltic cntd:s.. hi many cases, it appears that any single solvencis relatively ineffective in core cleaning and that much better results can be obtained wiih a mixtttfe or series of solvents. 129 The followhg solvents have, been rCpOfied for specflc binbinations of crude and core to give pcor resufts when used alone: chloroform, ,65 benzene, 5S,1M,120~=bon di~~fide, lU,120 ~~mol, @ ~d toluene.5@.@.65 .1~.120,1T.l~,1s6 Many of the researchers cited above have found that toluene used alone is one of the least effective solvents. However, when combined with other solvents, such as methanol (CHs OH) 184 or ethanol (CH3 CH zOH), 61 toluene is often ve~ effective. The toluene is effective in removing the hydrocarbons, including asphal1136

tenes 130JW some of the weakly polar compcmmi.s,W and l wbiletbe more,spongly polar methanol (ethanol) qcmoves the strongly adsorbed polar compounds that are often responsible for altering wettabilky. In addition to toluenelmethanol and tolueneletbonol, successful cleaning has ako been reported with cbforoforndacetone 1wZ120. and cfdorofordmetfranol, 1s4 as well as 1= a number of different series of solvents. ,65 CuieCand his coworkers made the most extensive study of core cleaning for nettability restoration. In a recent paper, Cuiec et az. 130statkd that their core cleaning always begins with a toluene flush to remove hydrocarbons and asphaltenes. A number of solvents are then.tested to determine the most effective, including (1) a series of nonpolar solvents, e.g., cyclohexane or heptane; (2) acidic solvents, e.g., cblorofonn, ethanol, or metbanoh (3) basic solventi, e.g., dioxane or pyridine; ond (4) mixtures of solvents, e.g., methanollacetoneltoluene. When none of these procedures are effective, other tests are performed by combining the above procedural, using otler solvents, ad incremfig the Circdatiog time. Tohtene is generally not a very effective solvent, but it canalter the nettability of some core. Jennings 186 cleaned sever,d cores by toluene extraction and found that the wettabilities and relative penn.eabilities were not changed. He stoted that this indicated that tolueneextmcted core retoined the reservoir wettabi!ity and coufd be used for relative p+mneabtity rneosurements, However, this generally is not the case. Aftbough it is less et%cient than other solvents, we have found that toluene extraction can alter the wettabili@ and relative penneabtitics of native-state core. fn some cases, neutmlly wet or tidly oil-wet mtive-state core becomes strongly water-wet titer extraction witi toluene. The relative permeability cume~ ~~o ~E,fi. AMOU177 ako found that toluene extraction can clean some cores, while it had Wt3e effect for other ones, such as the strongly oil-wet Bradford cores. Therefore, because tolueneextraction will alter the wettabilky and relative permeability of many. native-state cores, m%uremcnts shouId be tie on mtive-state cores before toluene extinction. One problem with a cleaned core is that it is sometimes difficult, if not impossible, to remove all of the adsorbed material. If this occurs, the wetta.bfity of tie cleaned core wifl be left in some indefinite staie, causing variations in core analyses. Grist et al. lW cleaned cores by three curently used methods and then examined how ROS and endpoint effective permeabilities vtied after a waterflood. ROS was very similar for W methods. However, the endpoint effectiye water permeability varied by more than a factor of three betwtin different cleaning methods. Their explanation for this behavior was that some methods were able to extract more of the adsorbd. components, leaving.the rock more water-wet. In the more water-wet cores, the rwidti oil had a greater tendency to form trapped droplets, blocking pore throats and lowering water permeabtity. The least effective of the three cleaniug me~ods was overnight reflux extinction with toluene. More effective was reflux extraction with toluene followed by 2 days of extraction with a mixture of cbloroforin oud methanol. Finally, tie most efficient method was reflux extraction with tcduene followed by 3 weeks of extraction with chloroform and methanol. In the last stage of cleaning, methanol was used alone. Journalof Petroleum Technology, October1986

Another draivback of cleaned cores is that it is occassionafly possible for cIeaning to change an originally water-wet rock to an ofi-wet one. The extraction process may quickfy boil off the connate water, allowing the remaining oif to contact the rock surface and form oil-wet deposits that are afmost impossible to remove. 187 The cleaning experiments discussed examine the best methods to remove. cmde oil constituents from the pore walk. In many cases, core is also contaminated with drilling mud surfactits, which mustalso be removed before the wettabifity of acore can be restored. 12ar129 The best choice of solvents depends on the crude, the mineraf s~rfaces, and the drilfiig mud surfactsnts. Gant and Anderson 129cleaned Berea sandstone and Guelph (Baker) dolomite plugs contaminated with an invert-oilemufsion rfrifling mud. filtrate. The best solvent fOr bOfh rock types was a 50/50 mixture of toluene/methanol, oi the equivalent, containing 1% ammonium hydroxide. A three-step method (three successive Dean-Stark extractions-toluene, foffowed by glacial acetic acid, followed by ethanol) was the second best choice for Berea, while 2-methoxyetiyl ether was the second best choice for dolomite, demonstrating that the choice of solvents can depend O? the mineral surfaces in the core. Restored-State Core , If one conld be positivethat the original reservoir wettabilhy hadizotbeen inadvertently modified, a native-state core would give resnks closest to those of the reservoir. However, riative-st@ecores present scveraf problems. The necessary procedures to preserve the wettabtiq are troublesome and time-consuming. Even when sll of the precautions iwe tsken, there is still a possibility that the nettability has been chtiged through oxidation or through deposition as tie temperature and pressure dropped when the core was brought to the surface. In addition, tic question arisesabout tie procedure to follow to obtah the most reliable information from cores in which the nettability WaS aftered When onfy core with alt&ed wei@bfity is available, the best possible mukiphase measurements ore obtained by resto& the resefioir wettabfi~ with a three-step ~roces~. 47,F0,64,65.,96,115,128,130,1S0,18SThe f~st ste~ is to ~leaa the core to rernoVeall compounds from th~ rock surface. After the core is cleaned, the second step is to flow reservoir fluids into the core sequentially. F~y, the core is aged at the reservoir temperamre for a suKLcient dine b establish adsorption equilibrium. Seversl experimenters have compared measurements made on core in the native, cleaned, and rsatored states. In each experiment, measurements in the restored state were slmost identical to the,previous mtive-sta.te ones,demons@atin that this procedure will restore nettability. 50,115s0;18~ J ~,, The first and most @fficult step in nettability restoration is to clean the contaminated core by use of the methods described to remove all compounds adsorbed on the surfaces and to make the core as water-wet as possible. All compounds must be removed from the core because we have no knowledge of which compounds were adsorbed on the undisturbed reservoir rock and which were deposited afterward. The USBM or Amott nettability measurements are used to verify that the core is strongly water-wet., Unforttzmtely, detemining which solvent wiII successfoffy clean the core is still a trial-andIourmt of Petroleum Technology, October 1986

Fig. 1Wettabitity changes for a restored-state core and the effects of flushing restored-state cores with refined OIIS. Berea core and Big Muddy crude. error process because the best choice of solvents depends heavily on the crude oil, the mineraf surfaces, and any &idling mud contaminant. Further discussion can be foundin Ref. 129. In the second step, sequentially flowing reservoir fftids btto the core, the core is saturated with deoxygenated synthetic or formation brine and then flooded with crnde oil to simnla.tsthe intlow of oil into the resemoir. When cmde oil for wettahifity restoration is obtained, precautions should be taken to minimize alterations to the crude. The hnple must be taken before tiy Sm&ct.mrts or Ofier chemicals ae added to treat the crude. It should be taken as Iong as possibIe after any wefl treatments to aIIow time for these chemicafs to be flushed from the well. Finally, the cmde should be sealed in air:tight containers as soon as possible to minimize oxidation and the 10SS of light. ends. The fired step in wettsbfity restoration is to age tie core at the reservoir temperature for a stilcient time to establish adso~tion e&libzium. The aging time required to re-eatabfish reservoir nettability varies, depending on the crude, brine, and reservoir rock. Generally, we feel &at core shoufd be aged for 1,000 hours (40 days) at the reservoir temperature. 128This a&ng period was chrken for two reasons several experiments have shown that up to 1,000 hours is required to reach wetting equilibrium ~$s. 115, 89-lgl and 1,000 hours is roughly the length 1 of ~me required for the contact ~gle measnred on a flat surface to approach its equilibrium value. 7>26,34.191 III some cases, the restoration time can be significantly less than l,OW hours. MunganlsO was able to restore the wettabilky after aging for 6 days, while the nettability of the rocfuoilhine system used by Schmid50 and Riibl et ~. lss was restord after only 3 days. Salathie147was able to restore a mixed-wettabilhy qate to samples after 3 days. Cuiec et al. 130describes two reservoirs in which the wettabtity was restored after only a few hours, with no fur, ther cbamges in tie wettabiIity for aging times as long as 1,000 ho;rs. There are two basic options to determine the aging time to restore wettabllitv. We feel that it is ,most convenient to age afl cores for l:W hours, which is roughly the mmimum time that the experiments discussed previously required to achieve wetting equilibrium. While cores may 1137

<

be aged for a period longer than the minimum necessary, thk is not a serious drawback because the aging cores require minimal attention. Another possibtity is to determine the minizhtzmaging time by measuring the wetrabfity of the core with the USBM or Amen methods at frequent intervals during the aging period. The aging is stopped when the wettabflity reaches its cquilibtium value. Although this minimizes aging time, it is much less convenient because it is labor intensive nnd requires frequent disturbances to the plug. The core is aged at either the reservoir pressure with live cmdeso, 180,188,191 r ambient pressure with dead o cmde. 115.128.190 When live crude oils a~d the reservoir pressure are used, the solubflities of the wettabilhyaltering compounds should have their reservoir values. It is possible that the nettability will differ when dead cmdes .at nmblent pressure are used. At the present time, however; it is not known whether the difference is importazm Fig. 1 shows the chsnges in the USBM wettabfity index as a core was restored. * A series of Berea plugs was saturated with brine and driven to IWS by centrifugation in crude oil. Each core was aged in dead crude for a different period, of time, after which the USBM wettabtity was measured. As can be seen, the wettabilky changed from water-wet (W =0.8) to moderately oil-wet ( W= O.3) over a 40-day period. The plugs flushed with Soltrol@ and Blnndol@ will be dkcussed later. Lorcnzetal. 190and Cuiec65 found tbatitissometknes possible to speed up the approach to wetting equilibrium by saturating.thecore with oil alone. The approach to equilibrium is fastix because the polar compounds no longer have to dlffase across a water layer to adsorb on the rock. This procedure should be avoided, however, because it can give iriaccuratc results. For example, consider the restoration of a core that originally had Salatbiels47 mixed wettab~ity, where &e large pores are oil-wet nndthesma!.l ones are water-wet. During tbeaging process, thesmall pores must contain comate.water to prevent the deposition of au oil-wet fiim, leaving them water-wet. Onthe other hand, ifaclcan core is saturated only with oil, tbe entire core, includlu gtbesmallpores, will become uniforndy oil-wet, whlchis the wrong wettability. Anaddhionalp roblemw ithsaturadngt iec ore solely with oil istbat the effects of brine chemistry are ignored. As discussed previously, the wettabtity of the core depends on the ionic composition and pH of the brine. Finally, Clementz10?.120,121$howedtbat flowing cntde oiltbrougha dry core camcause tbeformition of very stable oil-wet, claylorganic complexes. Thepresenceof an initial water film on the clay surfaces haa been shown to reduce but not completely inhibit the adsorption of the nettability-akering materkds. @@.70 The effects of brine OtI wearability make it necesssry to saturate the core with

brine, then oil, during the nettability restoration process. Experimental Conditions Once a mtive or restored-state core is obtained, core analyses can be performed. These tests can be mn with either crude or refined oil at ambient or reservok temperature and pressure. Because wettabfity effects are being igPersonalc.mmlcati.nwl,hD..J. endel, e!r.aleum W P TestingSeMceS,Smta Fe SPringS, CA,No.19S0. 1138

nored, cleaned cores are generally mn with refined oif (or even mercury or air) at room temperature and pressure. From the viewpoint of titaining the nettability, the best laboratory tests should be mn with native or restored cores at reservoir conditions with live cntde oil and brine because this is the best simulation of reservoir conditions possible. Cor~ are generally more water-wet .at rese~oir conditions tbzn they are at rooin temperature ad pressure, 62,180,192-195he effects of the following T experimental conditions on nettability will be dkcussed: (1) rcaervoir vs. room temperature, (2) live vs. &ad cmde at reservoir pressure, and (3) refined vs. crude oils. Changing the temperature has two different effects, both of wtich tend to make the core mom water-wet at higher temperamres. First, an increase in temperature tends to increase the solubtity of wettabtity-altering cOmpounds. 196 some of ~eSe compounds will even desorb from the surface as the temperature increases. Second, the IFT and the contact angle measured through -bewater will decreaae as the temperate increases. This effect has been noted in experiments with cleaned cores, minernl oil, and brine, where it was found that cores at higher temperatures were more water-wet even though there were no compounds that could adsorb and desorb. 19-2? For example, McCaffery201 measured the wateradvancing contact angle on qWrtz of n-tetradecane and brine. The amglewas about 40 [0.7 rad] at 77F [25C], but decreased to about 15. [0.3 rad] as the temperature was raised to 300F [150 C]. when live crude oils at the reservoir pressure and temperature are used, the solubilities of.dzewettabfity-afteting compounds have their reservoir values. The use of dead crude at ambient or reservoir prcasure may change the nettability kmzse the properties of the crude are altered. Light ends are lost from the crude, while the heavy ends are, less soluble, which may make the core more oil-wet. However, the effects of pressure are not known at present. The two reported experiments found that ressure is much less important than temperature. 18~,1~ meland and Lamondo 192 found little difference in contact angles measured using stock-tank vs. live cmde at the reservoir temperature (190F 88C]) and pressure i (3,800 psi [26.2 MPa]). Mtmgan 10 measured a wateradvancing contact angle ,of $7 [1.5 rad] using live reservoir crude and synthetic formation brine at resemok temperikurc (138F [59C]) and pressure (1,200, psi [g.3 MPa]). The water-advwcing contact angle was almost identical, 85 [1.48 rad], using degassed crude and brine at ambient pressure and reservoir temperamre. Because refined oifs are much easier to work with tlum cmde, it is a common laboratory practice to flush nativeor restored-state cores with refined oil before testing. However, there is a possibilky that this idters the nettability. Craig7 poshdated that it would be possible, once the original wettabtity was restored, to use refined nzineml oil in place of crude oil in laboratory tests without adversely affecting the wetk+bility. Test times are shor! compared with the time it takes to achieve adsorption equilibrium and obtain native wettsbtity (about 1,000 hours). Craig hypothesized that the desorption of wettabilityMbzencing materials would require a correspondingly long period of time. If this is correct, @e orig@l wettabtity wotdd be unchanged if laboratory tests using refined oil and brine were conducted quickly enough.
Hje~.

Journal

of Petroleum Technology, October1986

The onfy experinient to teat this hypothesis that we are aware of was conducted by Wendel. * He aged ,Blg Muddy crude in Berea sandstone at IWS to develop his restorer-state cores. The cores. were flushed with one of two refinkdoik, Soltrol 170 or Bkmdol, to detexmine how they affected the wettabfily. The results&e show in Fig. 1. Bkmdol did not si@ficantly affect the we~btity, while Soltml 170 changed tbe core from oil-wetto neutrally wet. The wettabdity: alteration could be caused by either surface-atilve impurities in the Soltrol 175or desorption of previously depositwj oti-wetdng crude compounds from the pore walls into tie Soltrol. It i; not known which explanation is correct. Wendel did not attempt to fflter the refined oils tfmugh a cbromatogmphic coltmm tn remove surface-active compounds. These contamiim ts are known to have a large effect on corit.w-migle measurements, which are extremely seyitive to small amounts of contaminants. Wettabifity measurements in core should be less sensitive, however, because the ratio of smface area to volume is much higher. Conc133sioris

1. The nettability of a rsaeryoir ample affects ita capillmy pressure, relative pe,rmwbtity, waterflood behavior, dispersion, mid electrical properties. fn addhion, simulated teftiary recovery can be 51ter,cd.The tcfi,~ recove~ PrOcesses affected by we~biE~ include hot-water, surfactant, miscible, aid caustm floodlng. 2. Cleaned, strongly water-wet cores should be used onfy in such c6re analyses as porosity. and air permeability, where the wettabilky is unhpportmrt. h addition, they may be used in other tests when the reservoir is known to be strongly water-wet. 3. The nettability of originally water-wet mineral sgrfaces can be altered by the adsorption of pokw compounds aui/or the deposition of orgariic rnattertlmtwas origiMUY in the crude oil. Fmrfactants in the crude oil are generally believed to ,be polar compounds that contain oxygen, nitrogen, ,mdlor sulfur. These compounds ~ most prevalent in the heavier fractions of crude oil, such as the resins and asphaltenes. 4. Nettability alteration is determined by the interaction of the oil constituents, the mineral surface, and the brine chemistfy, including ionic composition and pH. In siIicafoiVbrine systems, trace amounts of mukivalent meM. cations can alter *e nettability. The catiom can reduce the solubti~ of crude oil surfactants and/or activate the adsorption of aniotiic surfactants onto the silks. Mfdtivalent ions :$tathave altered tie wettabfity of sihcafoil/brine systems tnclude Ca2, .Mg2, Cu2, Ni2, and Fe3. 5. Work on mineral flotation indicatca that coal, Acknowledgments graphite, sulfur, talc, the talc-liie silicates, and many sultidca are probably naturally,neutrally wet to oil-wet. Most I w grateful to Jeff Meyers for hk many helpful suggesother minerals-includhg quartz, carbonates, and tions and comments. I also thank the management of sulfatesare strongly water-wet in their natural s@.te. Conoco h.c. for permission to publish this paper, 6. Contact-angle measurements suggest ti.at most carbonate reservoirs range frpm neutralIy to oil-wet as a re- References sult of the adsorption of surfactimts from the crude oil. 1. Andemm, W, G.: < Weuabitily Literature Survey-Parr 2 Wet7. Very little work has been reported about the changes Iabitim Measurenimt,, to be published in JPT (Nov. 19S6). in wetibility caused by drioiig mud addhives. Three 2. Anderson, W.G.: .Wetmbili~ Literature SUrvey-PaX % The Efdifferent Cciring.flrtids ave been recommended to obtain h fects of Watabtity on,the E2ectrkaJProperties of Porous Media,>, to be published in JPT (Dec. 1986), native-state core: (1) synthetic formation brine, (2) un-Pemmalmmmunlcatim wilhD,J.Wend.at, Petroleum TestingS6wkeS,Santa Fe SP,ingS, A,N.. 19S0, G 3. Anderson, W.G.: WemabilityLiterature SmyPmt 4: The Effects of We@ilify m CapiUaIY Pressure,,xpaper SPE 15271waifable at SPE, E?icbardsm, TX.

oxidized lease crude oil, or (3) a water-based mud with a minimum of iddkives. B&use of surfactits in the SYStern, no conimercitiy available oil-based or oil-ernukion muds are khown that preserve the native wt?ttability. 8. The wetr?bility of a native-state core. cambe altered by loss of light ,ends and/or the deposition aid oxidation of heayy ends. TWOalternative pac@ging procedures cam be used to miniinize these effects. The first is to immerse the corei in deoxygenatdd formation or synthetic brine and place !hem in a glass-lined steel or plastic tube, which is then seaIed against leakage aud the entrance of oxygen. An alteinaiive procedure is to wrap the cores at the welksite in polyethylene or pglyvinylidene fdm and tien. in ihunirimn foil. The wrapped pore is tlyn coated with i+thick layer of paraffin or a plastic sealer. 9. Because of the increased solublky of the wettabilityaltering compounds at the higher temperature spd pressure, the cmde-odtbrinetcore system is usually more water-wet at reservoir condition than at ambient con&tions. In addition, the contact angle measured tluough the water will generslly decrease as the tempetatufe is increased, and the system will become more water-wet, even if no surfactauts are present. 10. Extraction with toluene cti alter the wettabil.ity of some iiative-state cores, causing someinitially neutrally wet or qikfly oil-wet cores to become strongly water-wet. Measurements on native-state iorei should be made before toluene extraction. 11. During the attempted restoration of a cleaned core to ita orig$al wetrabtity, the core should be saturated with brine, @lflooded, md then aged at the reservoir corrditiom for 1,COO hours. This will embie a inixed-wettabtity condhkin to be restored, if thk was the original wettabdity. In addition, it will allow the brine chemistry to influence tie r~tored nettability. An alternative procedure, which completely saruratea the core with cmde oil, should, be avoided., 12. The three commonly used methods for artificially conrrolEng wettabfity during laboratory experiments are (1) treatment of the core with chemicals, generally orghocblorosilane solutions for sandstone. cores and naphtbenic acids for carbonate cores; (2) using sintered teflon cores with pure fluids; and (3) adding surfacmnts to the fluids. To obtain a uniformly wetted core, a sinteredteflon core with pure fluids is preferred because its nettability is more constant and re reducible than the wetof cores treated WI organochlorosilanes, tabilby # naphthenic acids, or smfactants. However, these treatments have advantages when heterogeneous wettabllity or nettability alteration isstudied.

4. Bartell, F,E. and Miller, F, L.: .Degree of Wefdng of Silica by Crude Petroleum Oils, 1, lmi. Eng. Chem (July 192S) 20, No. ,7, 738-42. 5. Bw&Y, J.P.: Towards Understanding Wctu.bilily Effects on on Oil Recovery, Intl. Energy Agency Workshop EOR, Bartlesville~mrgy Technology Center, (April 24, 1980) CONFSW4M0,. u. S.DOE (Feb. 1981) 11643. 6. cook., C.E,. Williams, R.E., and Kolodzie, P. A.: Oil Recovery by Alkalie. Waterfloodig, 3, JPT (1974) 1365-74. 7. Craig, F, F.: % Resemoir Engineering Aspecz3 of Wafecfloodixg, Monograph Series, SPE, Richardson, TX (1971)3. 8. Dbdd, C.G.: The Problem of Determining Petroleum Resewou Rock Wet@iliIy, p?per SPE 1480Givaihble at SPB, Richardson. TX. 9. Donaldson, E. C., Thomas, R. D., and Lorenz, P.B.: cWeffability Deleimination and Its Effect on Recovery Efficiency, SPEJ (March 1969) 13-20. . M 10. Domldsm, E.C. and Thomas, R.D.: C< icroscopic Observations of Oil Displacement i Water-Wet and O&Wet Systems,zSpaper SPE 3555 presemed at the 1971 SPE lumuaf Meeting, New Orleans, Oct. 3-6. 11. Donaldson, E.C. and Kayser, M. B.: .Thrc&Phase Fluid Flow in Porous Media, Bartlewille Energy Technology Center, reForl DOE/BETC/IC-80/4, U.S. DOE (APrii 1981). 12, D.Uien, F. A.L.: Porous J&ii.: Fluid TransForIand Pore Stmctfue, Academic Press, New York Chy (1979). 13. Hjelme~d, 0.s. ~d TO~aet~r, 0.: ~~bii, tie Key tO Proper Laboratog Watefloodmg Expenmmd% ln~. Energy Agency Workshop on EOR, BarOesviUe Energy Technology Center (April 24, 19S0) CONF-8@1140, U.S. DOE (Feb. 19S1) 1-24. 14, Icmescue, E, and Mini, B,B,: ;<AReview of Laboratory Techniques for Measuring Wel@biliii of Pefmleum Reservoir Rocks, Petroleum Recovery JIM. report 1983-3, Calgary (Oct. 1983]. in 15. Xinmy, P.T. and Nid.sm, R. F.: C&Wetfability Oil Recovery, World Oil (March 1951) 132, No. 4, 145-54., 16, Kremesec, V..J. and Treiber, L. E.: Effects of System We.nabtiiw m Oil Displacement by Micellar Flooding, S,JPT (Jan. 1978) .52-60. : 17. Leach, R,O. a al.: A Laboratow and Field Study of WenabilifyAdjuw.mmtin Watertlmling, ,, JPT(Feb. 1962)2S-$12 Tmns., AIME, 225, 18. M?mden, S.S.: ,Wenabilitj-lts Measurement and Applimtion to Wateflwdiw,,, J. .@. Assoc. Pet. Tech. (Jan. 1965)30, .No. 1, 1-10, 19. Marsden, S.S.: !TVeoabiliq?The Elusive Key 02WaWfM+ing, Pet. Ens. (April 1965) 37, No. 4, 82-87. 20. McGee, J., Crocker, M, E., and Marchin, L. M.: Nettability: State-of-the-An. A Review of the Literature, Natl. Imt: for Petrnlemn Resemch. mnort NIPER-58, Bartlesville, Ang. 1985. Recovery Using .Water.S . Driv21. mna and Oil Recovery: Wet22.

,,----

,...% . . . .. . . . . ..-. -, . . . .

23. Pra{s, M.: 7 l?zermalRecoveV, Monograph Series, SPE, Richardson, TX (1982) ?T,55-57. 24. %za. S.H.. Trei be,, L.E. . and Archer, D.L, : .Wettabiiky of R6ervoir Rocks and Its ,E&lua,tion;, Producers Mon:hly (APfl 196S) 32, No. 4, 2-7.. 25, Schoenberger, K.: The Role of Tenability i Oil Reservoir .Recovery, Erdoel-Erdgas 2eirschrifi (April 1982) 98, No, 4, 130-35. Er@i.sbWn?Jadonavaifable from the John Crerar Libray, Translation No, 85- 102d4 (*BLL) 48A. 26. Wagner, O.R. md Leach, R. O.: Improving Oil Displacement EmimcY by Wettabilky Adjusbnent,zTrans.,@ME (1959)216, 65-72. 2T. Brown, R.J.S. and Fatt, 1.:< Measuremem of Fractional WettabiJity of Oti Field Rocks by the Nuclear Magmti. Relaxation Method,>, Tram. , ASME (1956) 2W, 262-64. 2s. Owens, W, W. and Archer., D.L.: .Thc Effect oTRock Wettabflity on Od-Water Relative Permeability Reladmships,, IFT (July 1971) S73-78; Trans., AJME, 251. 29. Nutting, PG.: Some Physical and chemical Properties of Reservoir Rocks Bearhg on the AccunudatioII md Discharge of Oil, W Prob[ans of Petroleum G.O1OSY, .E. Wrafimr.md F.H. ~ee (cd,.), AAPG, Tulsa (1934) 825-32. 1140

30. Andresen, K. H:: Dkcssia of Natureand Impm+ame of Surface Forces in Pmductim of Petroleum,>, Drill. a@P~od, Pm.., API, New York Ciiy (1939) 442-48. 31. Marsdea, S.S. and Nikias, PA.:. The WettabifiW of the Bradford S.md. L,13Producers Monthly (May 1962) 26, No. 5,2-5.. 32. Marsdcn, S.S. and Khan, S.: &TheWettabiJiv of the Bradford Sand, U; Pymlysk CbmmatogsaphySmdiis, Producers Monrhly, (Jun. 1965) 29, No. 6, 10-14. 33...W.LZ,D. L.: ,Possibilities of .%wndaiy Recovery for the .Okfa-, honia City Wilcox Sand,> Tram,, MME (1942) 146, 28+3. 34. Treiber, L.E., Archer, D. L., andOwens. W. W.: A f.aboratory Evaluation of the Wet!abiMy of Fitly Oil Prodncing R.=voirs,x, SPEJ (D..: 1972) 53lJKJ Tram., ASME, 253 35. Chilingm, G.V. and Yen, T, F.: <SomeNotes cmWctfabitity and Relative Penneabiifies of CarbonateReservoir Rocks, IL Ene?gy SOurccs (1983) 7, No. 1, 67-75. .36. Benner, F. C., Riches, W.W., and BmteU, F, E.: bNa&md Im; F.xIance of Surface Forces in Production of Petroleum, ! Drill. and Prod. Prac., API, New York City (1939) 44243. 37. Benmr, F.C. ad BarteO, F. E.: 3%. Effect of Polar Zmpurkies UPOII iPiLaIY SurfacePhenomenain lwrokum Prcd.,don,>> C and Drill. and Prod. Pra.., API, New York City (1942) 34143. 38. Benner, F. C., Dcdd, C.G., and Bartell,.F.E.: DisplacementPressures for PemoletunOii-Water3ilica Systems, Oil& GasJ. (Nov. 12, 1942) 41, No. 27, 199-20S. 39. Bemer, F.C., Dodd, C.G., and BarteU, F. E.: Ewluation of EffectiveDisplmemerdPressures for Petroleum Oif-Wat@iica Syiterns,>, Fun&menfal Research on Occurrence and Recovecv .f Perroltwm, API, New York Cily (1943) 85-93. 40. Cram, P.S.: ,?Weitability Studies With NowHydr.xarbori Constituents of Ciude Oil,, Petroleum. Recovety Research Inst., research repor! RR-17 fDe.. 1972). 41. Den&.s, M.O., MalOix,C.C., and Davis, G,T.: Effect of Crude OJ Componentson Rock Wettabiiv? Tram, AIME (195?) 216, 330-33,. 42. l-row, A.C,, PhiJIips, M.C,, and Riddiford, A. C;: -On tie W.tting of Carbonate Surfaces by Od and Water, J. Crfn.Per.,T.cL (April-Jum 1973) 12, No. 44, 3340. 43. Fan, L and Kfikoff, W, A.: Effecr of Fmctiond Wetlabifily on MuMph& F@ Tlmmgh Porous Media: , Tram. , AfME (1959) 216, 426-32. 44. G-tudiov, S.K.: The Namre of the Surface of Minerals of Oil-Bearinz Rocks.,, 1... Vwsh. ffcheb. .Znwrdenii,NeJt i Gaz (1963) 6, k 7, 37-42., 45. Holbmok, O.C: and Bernard, G. C.: Determination of WettahiJitv hv Dve Adsomtion. Tram,. AfMf? (1958) 213,261-64. 46. Iw&k&, i. N.: ~ Co& Imion oi lnt&sd&J tiateT iattuation and Heterogme.ms Tenability,>> Producers Monthly (Oct. 1960) 24, No. 12, 1S-26. 47. Sdathiel, R.A.: Ofl Recovery by Surface Film Dr&ge in Mixed-Wettab~ity Rocks,, JPT (Od. 1973) 121!$24 Trans., ADKE, 255. 4S. Nba,P.: Di&&sio m Effect OfFrictiorialW.uability on Muldphase Flow Thin@ Porous Media, , Tram. , AfME (1958) 216, .,6-2, ..- . . . 49. MrJore, J.: cLaboratory Dctqniined Ele&ric Logging Paranw rms of the BradfordThird Sand,, ProducersMonthly (Mxch 1958) 22, No. 3, 30-39. 50.. Schmid, C.: aThe SVetMbiliWof Petroleum Rocks and Results of E%Paimentsto Smdy the Effects of Variidons in WefmbiliT of Core Samplcs,,SErdoel zmdKohle-Erdzu-PelroAmie (1964) 17, No. S, 605-09, English translation available from the John Crerar Library, Translation No. TT-65-U404. 51. Hall, A.C., Collins, S.H., and Melmse, J.C.: ,tibiliv of Aqneow Weldng Films in Afhabasca Tar Sands, xSP=(April 1983) 23, No.2, i49-59. 52. Melmse, J.C. ! Tmmpmtatim of Mixed Wcttabilily St?ses.in Reserwir Rocks,, paper SPE 10971 presented at the 19S2 SPE .4mumlTechnical Conf&me and ExhibhioL New Orleans, Sept. 26=29. 53. Blake, T.D. md Kitchener, J. A.: Sfability of Aque&s Fi&s on Hydrophobic Methylated Silk.,, S3. Chan Sot., Faraday Trans. 1 (1977 68, 1435+42. 7J 54. Takamnra, K. md chow. R.S.: GAMechanism for fnhiation of L.-- ... ... ..B!mmen Displacement Fmm Oil Sand, J. Cd.. Pet. Tech. iNov.-Dex. 1983) 22, No. 6, 22-30. 55. Dcmddson, E.C. and Crock.,, M. E.: CChmacterizatioof the Cmde Oif Polar Compound Extract, Bartfesyille Energy TechJournal of Pecrolewn Technology, October 19S6

..

nology Center, repori DOE/TJETC&U-8015, U.S. DOE (Oct. 1980). 56. DonaJdson, E, C.: OiJ-Water-Rmk WettahiMy Measurement, P=P~MS. Am.ric=m Che~c~ SOC..Di~. OfPetrole.m. Che~stry [March 29-April 3, 1981) 26, No. 1, 110-22. 57. BaJdtiin, B.A. and Gray, P. R.: .Fluid-Surface Jmeractionsin Oil Reservoir s. pauer SPE 4925 0973) available at SPE, Richardson, TX. 58. Jennings, H. Y,: Swface Properties of Natural and Synthetic Porous Media,,z Producers Monthly (Mach 1957) 21, No. 5, 20-24. 59. Lyutin, L.V. and Oleinik, I. P.: Adsopdon of AsphaJt.nes by QUWIZ,23 Naudin.-Tddm. Sb. PODobycheNeji, Vses. Nefte-Gis. Nauchn.-Isded Jnst. (1962) 16, 7S-81. E@ish translation available fmmlhe Job. Craw Library, Translation No. 65-12831. 60. Lyufi., L.v. and B.rcyn, T,A,: AdSorption if Asphaltenes in a Stratum and Its Effect on Permeability and Oil Productio n,, Tr., vk. Nef2egasov, Nauch.-Issled. Inst. (1970) S3, 117-30. English mindadon available from the John Cram Library, Translation No. 75-10925-081, 61. McCaffeIY, F. G., Signmd, P. M., and Fosti, J. E.: Pore Space aridDwlacement Characteristics of Carbona%wswvou Rcw@.,x 9 Proc. Camdian WdJ Lwsim,?SwieN FormationEvacuationSymposium, CdgaIY (1977)-~ l~B16. 62, McGhee, J..W,, Croc~er, M. E., rmd Dmm12son, E. C.: ReJative Weuig Properties of Crude Oils in Berea Sandstone,,, BartlesviUeEnergy Techmlogy Center, report BETC/RJ-78/9, U.S. DOE (Jan. 1979), 63. TuYbovich, B.1,: Compqison of the Nettability of Core Samples From Water-Petml$mn Pam of Strata and the WaterPetr@Jtn.CollectC,r (Transition) Zone,,x Nejiyanoe KhozJaismo (1972) 50. No. 11.4748. Ew.Jish frandadon available from L.U. Fra~ij Transktli.m No;, L@T-268. 64. Cuie.c,L. E.: Restoration of the Natural State of Core Samples, paps, SPE z634 presented at the 1975SPE .AMwdTechnicalCofermce and Exhibition, DaJlas, Sept. 28-Ott. 1. 65. Cuiec, L, E,: Study of problems Related to fhe Restorati.m of the Naturi.1State of Core Samples,Z, J, Cd., Pet. Tech. (Oct. 33... 1977) 16, No.4, 68-80. ., 66. Morrow, N. R., Cram, P.J., and McCaffery, F. G;: XDisplacement ?,tudi~ in Dol@te With Weftat6Jity Ccmrcd by Octimoic Acid,,, SPEJ (Aug. 1973) 221-32; Trans., AJME, 255. 67. Neumann, H.]. , Paczynska-f-ahme, B., and Seven., D.: CompOSitiOnad pmpemes of pe*.leum, H~s~d ~~% Yew York CiW (1981) 146. 109-113, . . 68. Reisberg, J. and Doscher, T.M,: Jnteficial Phenomenain Crude Oil-Water Systems, ,, Producers Monrhly, 21, No. 1 (Nov. 1956) 43-50. 69. Bwezin, V. M., Y&gin., V. S,, and Du&oviria, N. A.: Adsorption of Asphaltenes and Tar From Petroleum by W.mMme, 37 N@ep?omysl. Del. (19S3) 5, 15-17. E.gUsh tramlati.m avtiable from the John Craw Library, Tm!adm No, 83-1010748G. 70. Collins, S.H. and Melmse, J. C.: Adso@m of Asphalten- and Water 0. Reservoir Rock MineraJs,3, paper SPE 11800 present. ed at tie 1983 SPE Jntl. Symposium on Oilfield and GeotbermaJ chemistry, Denver, Jane I -3. 71. Kusakov, M.M. and Mekenitskaya, L. I.: sA.Study of fhe State of Connate Water in Oil Resemoirs,>> Rewarch in SW@ Forces, B.V. Dery=giri (@.) 12.1S. E@ish translation by Ccmsul!aMS Bureau, New York City (1963). 72. Abdumddtov, S.A., Guesinov, M. F., md Tairov, N.D! Efferl of Different Rock Fmcdons L@m the Adsorption of Ambaltems From Petroleums of the B&khanv-Sa,bunchiR&animk Deposits,,, [s.. V3mh. Ucheb. Zaved. (1j6619, No. 10, 63-65,. English translation avaihble from the John Crerar Library> Translation No. 71-M451-08L 73. Bartmur, F, A.; Barbour, R, V., wd Peters., 1.C.: <ASrudy of AspbaJt-Aggre8ate Imexactims UsiwgImJerse Gas-Liquid Chin-. nmtography,,, J. Appl. Chem, )3ixechnol, (1974) 24,645-54. 74, Emley, ELK., and Scholz, H. A.: CAStudy of AsphaJt:AgSre@e J.teractiom by Heat of Immemiom 3> Inst. Pet. (March 1972) J. 5S, No. 560, 95-101. , 75. Sinmkmt, A,A, and CldJingm,G,V., .Effect of Polarity and Preseme of Carbonate Pmiclm cm ReJati,t Penneabiliy of Rocks A Review,z, 7he Composs of Si&m 3anuna Epsilon (Jan. 1961) 39, No. 2, 115-20. . 76. Somertcm,W.H. and.i?dke, c. J.: .Role of Clays in the Enhanced ~ovev of petroleum, paper SPE S845 presemtedat the 19s0 Journalof Petroleum Technology, October 19S6

SPE/DOE Symposium on Enhanced OiJ Recovery, TnJsa, OK, April 20-23. 77. Bmvm, C.E. ~d Nmstadter, E.L.:. The Wet!ability of OilAVater/Silica Systems With Reference to Oil RecoveIT,,, 3. Cdn. Pet. Tech. (JtdY-Sept. 19S0) 19, No. 3, 10%110. +8. Gaudin, A.M. and Chang, C. S.: Adsorptio! On Q.@.From m Aqueous Solution, of Barium and Jaurate Ions, Trans. i AJfvfE-Mkine Eneineerine (Feb. 1952) 193.193-201. 79. Gmdin, A.M. ;d ~uemcena~,D.W,: 4cQ&rlz ~otation with Anionic,CoU&tors,>Trans., AJMJ-Min@ Engineering(Jan 1955) 202. .. . .. . . . . 66.77. 80. Leja, 1,: Su@ce Chendwy ofroth Flmadcm, Plemrn Rms, New F York City (1982). 81. Morrow, N, R., Lim, H. T., and Ward, J, S.: Effect of Crud? Oihfndnced WeuabiliWChatms on Oil Recovefl,,, SFEFE @b. . 1986) g9-103. S2. Schuhmann, R. md Frakash; B.: Effect of BaC12and Other Activators on Soap Flotation of Quartz, Tram.,. A2ME-Mining Engineering (May 19$0) 187, 591-6@ g3. somasundarm, P.: Clnterfa.id Chemistry of Particulate Flotation.,, Advances in Inrefocial Phenomena of Porlicuhne/Sohrion/@s SJSWI.$; Appkcutions 2. F1.ra;on Research, P. Somasundaran ad R.B. GrieVes (eds.), AJChE Symposium Series (1975) 71, No. 150, 1-15, 84. Stras%er, I. E.: Effect of pH m JntwfaciaJ Fihm md Stability of Crude Ofi-Water Emdsions,3 JPT (March 196S) 303-12; Trcmm.,A?ME, 2!3. SS. Seifert, W.K. and Howells, W. G.: lmerfacially Active Acids in a California Crude OIL .4naIy?icalChendsny (April 1969)41, No. 4, 55&62. 86. MM, w+ d TmW, RIM.: e,3ddmi0 OfPOIYCYCLC ~e matic and Hiremcyclic Crude Oil Carboxylic Acids,,, Amdylical Chemkoy (June 1970) 42, No. 7, 750-58. 87, Snyder, L.R. and BueJl, B.E.: CompositionType Separationand Cla?sificadm of Petroleum by Titration, Im Exchange, and Adsorption,,, J. f%em. Eng. Data (Oct. 1966) 11, No. 4, 545-53. 88. Snyder, L.R.: ;Pe&cdeum Nitrogen timpnmds and OxygenCornpounds, Accounrs of CRemica[Research (Sept. 1970) 3, No. 9, 290-99. 89. McKay, I.F. et td.: Petrolewn Asphaltene Chernimy and Composition, .4mdyficalC&mLmy of Liquid Fuel .%urces:Tar sands; Oil Shale; Coal, and Perroleum, P.C. U&n (cd:), Advances in ~, Chemistry %@.. .&nwican Chem. SCC.,Washi.ston, DC (197S) 170. 12S-42. 90. Speight, J.G. and Moschopdis, S. E.: ..0. tie Molecular Nafure of Petroleum Asphakes, Chemistv of Asplulwws, J.W. Bunger and N.C. Li (eds.), Advances in ChemishySeries, American Chemical S..., Washington, DC (19$30 195, 1-15. 91. Der,das, M.O. et cd.: %faterials Adsorbed,it Crude FetcO1emWatm Jnterface% Isolation and Analysis of Normal Paraff,ns of H,~h Molecular Weisht.l 3hf. Enx. c7Mm. fMaY 1951) 43, No. 5,?165-69. 92. Dodd, C.G., Moore, J.W., .wd Dmekas, M. O.: MetaHiferous Substances Adsorbed at Crude PeImleum-Water fmerfaces; , Id. %/. Ckm (Nov. 1952) 44, No. 11, 2585-90. 93. Dunning, H. N., Moore, J.W., and Denekm, M. O.: lmerk+i?.l Activities +d Porphyrin Cements of Petrolemn Extracts,,, Imi. Eg. Chem. (Aug. 1953) 45, No. 8, 1759-1765. PMpafieSof 94. Dunning, H. N., Moor., J.W., and Myers, A. T.: < Porphyrins in Pemoleum,- Imf. Eg. Ckm. (Sepl:. 1954)46, No. 9,2000-07. 95. Moore, J.W, and Dunning, H. N.: Tnterfa.id Activides and Porphyrin Contents of Oil-Shafe Extracts,,, Ind. fig. C&n. (July 1955) 47, No. 7, 1440-44. 96. Cuiec, L. : RodclCrud~Od Jnteracdom and WetlabfiW An Attempt to .Uderstand Their Interrelation,% paper SPE 13211 P~t~ at the 1984 SPE Ann.aJ Technical Confermm ,ti EX. Idbidon, Hmsm, Sept. 16-19. 97, Johaimri, R,T. and Dmming, H.N.: <RelativeWminS Tendencies of Crude Oil by the Capilhrkmtric Method,, > Froducers ,+Amrhly(Sept. 1959) ?3, No. 1L 20-22. 98. Johmsen, R.T. qd D.I@z, H. N.: .ReJadve WetdDSTendem ties of Cmde Oils by Capilkimelric M&od,>Z U.S. Dept. of the Jnterior, BarOewille Petroleum Research Cent=, BarOesville, USBM rewrf RJ 5752 (1961), 99. Dodd, C;G.: The Rb&lo~cal Behavior of Films at C&de PeUole!un-WaterJ & n f9,,, L <hp. C&m. (May 1960)64, No. 5, 544-50, 1141

100. Hasiba, H,H.andJessen, .W.:cFiJmForming CompoundsFrom F Crude Oils, Intcrfaciti Films and Paraffin Dcposilion,,Z J. cd.. Pa, Tech (Jan-Mamh 1968) 7,, No. L 1-12. 101. Hasiba, H.H. md Jessen, F. W.: C<FJmProperdes of Jnterface Active Compounds Adsorted From Cmde OiJ at fhe OiJIWat~ Jnterf3ce, paper SPE 1747 (1968) avaiJableat SPE, JIEhardson, TX, 102. Kimbler, O.K.,; Red, R.L., and SiJ&rberg, I, H.: Physical Char acteristics of Natural FiJms Formed at Crude Oil-Watw Interfaces, 3SPEI (hue 1966) 153-66 Trims., AJME, 247. 103. Bartell, F.E. md Nkderhauser, D.O.: c+FiJmForming Consdtumts of Crude Petroleum Oils., 3Fwufamenfal Research on Occurrence and Recovery of Petroleum, API, New York City (1946-1947) 57-80. 1C4. Clemenfz, D. M.: Clay .Ya.biliition in SandstonesTbmugh Adsorption of Petroleum Heavy Ends,s JPT (Sept. 1977) 1061-66. 105. SOJnun,W. and Morgm, J.J:: Aquatic Chwnistq, J. Wiley and Sem, New York city (1970). 106, Block, A. and Simm.s, B.B.: C<Deso@ionand Exchange of Adsorbed Ocfadecybmnineand Stearic Acid on Steel and Gfass, J. Colfoid tnreiface Sci. (1967) 25, 514-18. 107, Oaudin, A.M.: F!mtcziom, econd edition, McGraw JiilJ Book Co. s Inc., New York City (1957). 108. McCaffery, F. G. andMungan, N.: cContact Angle md fntcrfacial Tension Studies of .%rne Hydmcar&m-Water,%lid Systems,, J. C&. Per, Tech, (Iuly-SqR. 1970) 9, No, 3, 185-96. 109. Neumann, H.J,: Investigations cmthe Welfablity of Formations and on Oil Mieratiom, >Erdod und KohJe-Erdeas-Petrochemie (March 19.6.6) 9, No: 3, 171-72. English tra~laticm available ~ from Associated TecfudmJ Services, Translation No. 74T93G, 110. Tumasyan, A.B. and Babalyan, GA.: Adsorption of Asp~tsnes During FiftmtioL,, Dokl. .4&d Ncmk Azerb. SSR (1964) 20, No. 9. English translation available from fhe John Crerar Llbrafy, Tran&fion No. 65-14833. 111. Somasundawm, P. rmd Age,, G,E,: :me ~. po~t ~~~hage of CaJcite,,, J. Colloki Inte@oc. SC-i.(Aug. 1967) 24, No. 4, 433-40. 112. Muz., N,: Enhamced Oil Recovmy Using .Wmer as a Driving Fluid Part 4Fudammtals of AlkaJhe Fl?odig,>, Worfd Oil (J. 1981) 192, No. 6, 209-20. 113. Casmr, T. P., Somedon, W.H., and Kelly, J.F.:`` Recoveqf Me&ardsms of AJkahne F200dine., Suhce Phmonwuzin Enhnnced Oil Recovmv.D.O. Shah i&i,). Pien.tn Press. New York Ciw (1981) 249~91 114. Johnmn, C. E.: StimsofCausticm dEmukionM etio&,,,JPT (Jam 1976) 85-92, 115. Mungm, N,: CCetin WethbiliQ Effech.inbborato~ Wakrflmds.,,JPT(Feb. 1966)247-52 T,o.s.. AJME. 237.

don/Gas $s!ems; Applicadonsm Fforadm Research,P. Somasum

127. 128.

129. 130.

131. 132.

133.

134.

135.

damn and R.B. Grieves (eds.) AJChE Symposium Series (1975) 71, No. 150, 183-88. Kfassen, V.I. and Mokrousov, V. A.: A. Introducdon m rhe 7heory of Fkmdon, Bun:nvoti and Co., London (1963). Wmidel, D.J., Anderson, W .G., and Meyers, J. D.: Restored: Stafe Core Anafysis for fhe Hutton Reservoir, paper SPE 14298 presented at the 1985 SPE AnmMJTechnical Conference and Exhibition, Las Vegas, Sept. 22-25. Gant, P.L. and Anderson, W.G.: Core Cleaning for Restoradm of Native Weuabifky,s, pr+w SPE 14875 (Oct. 1985). Available at SPE, Richardson, TX. Cuiec, L. E., Longeron, D. and Pa.sirsz!g, J.: On the Necessity of Respeding Reservoir Coalitions in Laboratory Dispfa.emmt Sfudies,, paper SPE 7785 pm.wded at tie 1979SPE MiddJe East OiJ Techicaf Conference, Bahrain, March 25-29. Bo.can, D.F. md Clampitt, R. L.: <CA Surfac@nt System for IAC Oil-Wet Sandstone of tie North Burbank Unit, JPT flfay 1977) 501-06. TranOmm,J. and Clarnpiti, R. L.: Detemdmtion of Oil SatuC. ration After Waterflooding in an Oil-Wet Reservoir-The NmdI Burbank Unit, Tract 97 Project,,, JPT fMay 1977) 491-SW. Bass, R.L. and Porter, M,R.: Siicones, Wmefproo8ng and Water-RmeIlencv. J.L. MoiUet (cd.). Elsevier Publishing Co.. New Yo~k City (i963) 136-87. Coley, F. H., Marsden, SS., and Calhoun, J.C.: A Study of tie Effect of Wembifiq ondm Behavior of Fluids m SY tnfhetic Pom.s Media,,, Producers Mmrhly (June 1956) 20, No. 8, 29-45. ,, Gateby, W.A. and Marsden, S.S.: Some WeffabiliV Chamcterisdcs of Synthetic Porons Media,x, Pro&cers Mon!hly (Nov.
1957) 22. No, 1.5-12.

136. New&mhe. J.. f&Ghee. J.. ad Rms.. M.].: W.ettabilitv Versus Displacement in Wafefflooding k Unconsolidated- Sand Coluws, Trw. , AJME (195:) .204, 227-32. 137. Kadunell,J.J., Bran, P.H., and Pe&ins, T.K.: T@wrv.ir W&flood Rasidual Oil Saturation From Laboratory Tests,,, JPTfPeb, 1973) 175-85; Trans.. ASME. 233. 13g. Singi&l,A.K.&d D~chuk, P:M.:``WeUabiUk Control of Glass Beads,>, C&. J. Chem E.g. fFeb. 1975)53,3-8. 139. Warren, J. E.and CaJho.n, l. C.: .ASmdy of WaterRood Effkciency in Oil-Wet Systems, JPTfTeb. 1955) 222% Tram.,
AfME, 204. ngChar140. Talash, A.W. andCrawford, P.B.:W.xFdmemalF3wdi

116. Fi@o~, P.B,:; A&ovdok of%<&WB orihti~:NaCIVers.s CaCl, Sak Eff-&, J. Colloidkt@ceSci. (J.e19g2) 87, No. 2, 500-17. 117. Somasun&rari, P.and Ham-. H, S.: C<Adsmptioo a, fSlfonates on Resmou Rack, Z> SP~(Aug. 1979)221-3ZT.ons., AJME, 269, 118. Hancock, C,K.: AlutiumS ulfaEadI ronS.lkm~A .xiliaries in Bihmdnons Stabiluation of soils,,, Jnd. EIIg. Chefn. (Nov. 1955) +7, N0. 11,2269-75. 119. Michacls, A. S.:.. `The WaceVroofi"g of Soils a"d Btitig MaL. Mo~ec (&.), terids,,, Wateproofing &Wmer-Repellenq,l. Elsevier Publishing Co., New York City (1963) 339-83. 120. Clementz, D. M.: .Iti~tia of Pewole.m Hea~~& With Montmorillonite, Clays and Clay Minerafs (1976) 24,312-19. 121. C1ememz,D,M.: ,Mtemtion of Rock Pm~wbyAdsoVtio forEnhamed OilRemvof Petmlcum Heavy Ends: fmplicmiom S .ry, PaFer PE 10683presented at III. 19S2SPEIDOE Enhanced Od Recovery Symposium, Tulsa, OK, Apri14-7. 122. Czarnecka, E.and Gillot, J.E.: LFonnafionand Characterization of Clay COnlplCxe$ W,th BitUmm From Athabmca Od Sand,>> C/aysd Cfay Minerats (1980)28, 197-203, 123. Reed, M.G.:~CRitetion of Cmde Ofl B~isby Cby-Cotig Sandstones,,, Cloys od CkzyMin.r.f$ (1968)16, 173-78. 124. GletioSti, V. A., Na,sea. V. I.. ad Pltiti. I. N., Floror;on. ., Primmy Sources, New York Ci~ (1972), 125. Bailey, R, ad Gmy, V. R., CrmtactA gleMeasumments of Water o CmJ,,, J.Appl. Chem. (April 195S)8, 197-202. . 126. Chider, S., Wie, J.M., and FwMemu,D. W.: Ont heNative Flomabflity md Surface properties of Natumfly Hydrophobic Solids,>, Advctncesin Jnte@ciol Phemmma of Pardculme/Solu1142

acteristics of Unconsolidated Sands,,, pafw SPE 36 presented at the 1961 SPE Permian Basin Oil Re=mwem C.xf-ce. Midland. May 65. 141. Talash, A.W. and Crawford, P,B.:`` ExpaimentalFl mdingCharacta-istics of 75-Percem Watir-Wd Sands, 97Producers Monthfy fFeb. 1961) 23, NO. 2,24-26. .; 142. Tafash, A.W.andCrawford, P.B.:Y3xperimeNafFkcding Characterisdcs of S&Percent Water-Wet Sands, Proakcers Monrhfy (Afnil 1962) 26, No. 4, 2-5. 143. Mohmty, K.K. and Salter, S,J.: &MuMphaseF lowinPomusMedix DL OiJ Mobtiatiom Transverse Dispersion. and Wettabi& w, papa SPE 12127pr~ted at the 19ti SPE fiual Technical Conference and Exhibition, San Francisco, Oct. 5-8. M-1. Davies, J.T. and Rideal, E.K.: Jmofacial Phenomena, Academic press, New York City (1961) 36-37. 145. salter, S.J. and Mdmnty, K.K, : .Maltiphase Flow in Porous Media L Macroscopic Observations and Modeling, paper SPE 11017 presented at the 1982 SPE Annual Technicaf Conference and Exhibition, New Orleans, Sept. 26-29. 146. Singhaf, A.K., Mukherjee, D. P., and Somerton, W.H. ZSffect of Heferogemou.s Nettability O Flow of Fluids Through Porous Media,x3J. Cdm Per. Tech, (July-Sept. 1976) 15, No. 3,63-70. 147. Laskowski, J. and Kitchener, J. A.: The HydropbiJicHydmphobic Transition on SiJica,>7 ColfoidZnte@ce So. (April J. 1969) 29. No. 4.670-79. Mmawat; A;, Hemy, J., and Siriwardme, R.: control of Surface Etrgy of Gb.+ by Surface Reacdon% Contact .@e and Stabifity,,, J. Colloid Imetface Sci, (Sept. 1984) 101, No. 1, 110-19. o 149 TiKln, D,L. and Yelfig, W. F.: .GEffectsf Mobile Water on Muftipk Comacf Miscible Gas Dk.placements,>,SPH (June 1983)23, No. 3, 447-55. . 150 Ionescw, E., Batycky, J.P., and Maini, B.B.: M1scibIeDisplac& mmc of Re.siduaJ Oil-Effect of Wembii!y m Dis@on in P.mus Me.2ia,32 Petroleum RecoveTImt., Calgary, rq.mt 19844 (Od. 1984). lo.maf of Petroleum Technology, Ocfob&r1986

151. Maid; B.B., Ionescue, E.; and I%ycky, J,P.: Miscible DwIacement of ResidualOfi-Effe!t of WeUabiJily DsFrsion in Porous on Media, J. Cifn. Pet. Tech. (May-June 1986) 25, No. 3,3641. 152, Novosad. J., Ionesc.-Fomiciov, E., and Mamdmrdt, K.: Polymer Flo@dingin Stratified Cores, paper no. 84-34-42 presented at tie 1984 Petroleum Society of CJM Annual Technicaf Conference, CaJgary, June 10-13. 153. Novosad, J.; The Effect of Rock Heterogeneity and WettabiliQ m Chem@J FJo.+ing, Proc., AGJP, SPA et al. Improved OiJ Recovery European Meedng, Rome (ApriJ 16-18, 1985J 2, 145-53. 154. .JJer, R.J.: Stearato Chromic Cldoride: Izi E.g. Ckem. (ApriJ 1!254)46, No, 4, 766-69. 155, Sweiney, S.A. and Jennings, H.Y.: The Electrical Resistivify of Preferenddlv Water-Wet and FTeferentialhOif-Wet Czbonate Rods, Prod>ers Monthly (May 1960)~, No. 7,29-32. 156. Sweeney, .3A. and Jennings, H.Y.: Effect of Wettabifity on the EJechicd Resisfiviy of Carbonafe Rock from a Petroleum Reservoir, J. Phys. Clwn. (May 1960) 64, 551-53. 157. Zierfuss, H. and Makha, A.: Regad!mg the Relationship Between fhe Formation Resistivity Jndexand fhe OiJRecovew Mwhaism During W aterflooding Procedures, Erd81 und Kohte-&dgas-Perrochemie (1967) 20, 549-52. English mmslation avdable from tie John Crerar Library, Tcamlation No. 6$15700. 158. Sharma, MM. and Wunderlich, R.W.: 4The Alteration of Rock Properties Due to Interactions With DriffingFhid Components, Pap SPE 14302 presenkd at the 1985 SPE Anmrd Tech!dcaf Confemce and Exhibition, Las Vegas, Sept. 22-25. 159, Stegemeier, G. and Jessen, F. W.: The Relationship of Relative Permeability to Contact Angles, Proc., Conference on the Theory of Fluid Flow in Porous Media, U. of OkJahoma, Norman (March 23-24, 1959) 213-29. 160. Lefebvre du Prey, E.J.: Factors Affecting Liquid-Liquid Reladve Penmabilities of a Conw!idatedPom.s Medium,>!SPEJ (Feb. 1973) 39-47. 161. McCaffery, F. G.: The Effect of WettabiJityon Relative Penneabifity and Jmbibifion in Porous Media, PhD fhesis, U., of CaJgaly, Cdgaly, Ah. (1973). 162.. Mccaffmy, F.G. and Bennion, D. W.: The Effect of Wettabfityon Two-PhaseR elativeP ermeabiides,J. Cdm Per. Tech.

...., (@t. -Dec. 1974) 13, N0.4 ,, q-C* . 163. Mwmw,k!R.andM. ninth N,: .% Nettability and CapiJJariV in
164. Porous Media,,, Petroleum Remvery Research Inst., Caf@ry> F@rLRR-7( Jan. 1971). Morrow, N. R.: TbeEffectso fSurfaceR oughnessonC ontact Angle Wifh Special Reference mPelmlenm Recovery,J. cd.. Pet. Te-ck. (Oct.-Dee. 1975) 14, NO. 4,42-53. Momow, N. R.: ~pmPressureC omlatiosf orutifotiY Weti Porous Meda.J. Cdn. Pet. Tech. [Oct.-Dee. 1976) 15(4),49-69. Morrow, J.J.R., and McCaffery, F. G.:`` Displacement Smdiesin uniformly wetted Porou,Media,3, Wem.g,Spreadi.S, andAd6esion, G.F. Padday (cd.), Academic Press, New York Cky (197S) ?x9-31q. Mmrgan,N.:`7n terfaciaJEffecLsinkmnis cibleL@id-Li quidDisplacemem in Porous Media,! SPEJ(Sept. 1966)24753; Tran.s., hfE, 237. Mngam N, and Moor6, E,J.: Certai Wetlabilily Effectson ElecfriwJ Resisfivityin Porous Media, J. Cdn. Per. Tech. (Jm.March 1968) 7, N;. 1,20:25.. Zisman, W.A.: RelationoftheEq.ilibri.mC onIactAngleto Liquid and Solid ComtiNtio., Con&cz Angl., Wermbilitymwi Adhesion, Advmces in Chemistry Series 43, American ChemicaJSoc., Washington, DC (1964) 1-51. Michaels, A.S. and Timmins, R.S.: ,Chromatogsa@dcT innsPrl of Reverse Wetting Agents and 1S Effect on Oil DisplacenmncinPoromMedia,,, Tram., AfME(1960)219, 150-57. Michads, A. S., StanceII, A., and Porter, M. C.: Effect of Chromatographic Transpoti in Hexylandne on Displacement of OiJby Wateri Pom.s Media,, >SPEJ (Sept. 1964) 231-3% Trans., .4M13, 231. Michaels, A.S, and Pmter, M.C.: L`Water-Oil qbicemenmfmm D Porow Media UdJizing Transient Adhesion Tension Akemdom,,, AJChEJ. (MY 1965) 11, NO. 4,617-24. Morris, E.E. and Wieland, D:R.: AMicrmcopicS Ndyof the Effect of Variable Wetfabiliw Condidons on immiscible Fluid Displacement,,, paper SPE 7ti presented at the 1963 SPE AnnuaJ Meeting, New Orleans, Oct. .5-9.

165. 166.

167. 168. 169,

174. Mun@n, N.: Role of Wettabtity and. fnterfaciaJ Temsion in Watefflding,>7SP EJ(June1964)11 5-23;Tr ms.,AfME,23L 175. Bobek, J.E., h4alfax,C. C., and Deneka.s,M. O.:``Re5mokRock WettabiJiiy-lts Significance and Bvahmtion, Trans., AJME (195S) 213, 155-60. 176. Burkhardt,J.A., Wind, M,B., mdMcJ.eam R.H.:``EfftitofCom Surfacing and Mud FiJfrate Flushing on ReJiabtiv of Core AnaJysis Conducted on Fresh Cores, paper SPE 1139-G, presented at tie 195S SPEAnnuaJ M-ring, Houston, Oct. 5-8. 177. Amoft, E.:;` Observations Reladng totic WelfabChYof Porous Rock, >Tram,, ~E (1959)216, 156-62; 178. Jlmm, D.C., JJsing, H., and Menzie, D.E.: EvaJuationofCoie Damage Caused by Ofl-Based DrilJing and Coring J%ids, paper SPE 13097 presented at the 1984 SPE AmuaJ TechnicaJ Conf.rence and Exhibition, Houston, Sept. 16-19. 179. EJufich, R., and WygaJ, R.J.: kkxektio.. ofCmde0llmd Rock Pmties With the Recovery of OiJby Caustic WaterRooding,,SPEJ(Aug. 1977)263-70. 180. Mugm, N.:,Rektive P.mmb%e Mwremeti Using Rmrvoir Fluids, SPEJ(Oct, 1972) 39S-402 Trans., AIME, 253. 181. Boduszynski, M.M.:`` Asphaltenes in PetrolmunA sphaJfSComposition and Connation,'' Chemistry of Asphaltenes, J.W, Bunger and N.C. LI (eds.), American Chemical Sot., Washk@on, DC (1981)195, 119-35. 1S2. Rich.mdson,J. G., Perkins, F. M., and Osoba, J. S.: ``Differences in tie Behavior of Fresh and Aged East Texas Woodbine Cores, JPT(J.ne 1955) 86-91; Trans., AJME,204. 183. Morgan, J.T. and Gordon, D. T.:.` Tntlue.ceo fP01e&om.DY on Water-Oil Relative PermeabiMes, JPT (Oct. 1970) 1199-1208. 184. Grist, D. M., Langley, G, O., and Neusfadfer, E.L.: TheDep&ms of Wafer Permeability on Core CJeaningMethods in the Cascof Some Sandstone Samples,J. Cd.. Pet, Tech. (ApriJune 1975) 14, No, 2, 4&52. 185. API Reco.mendedPmctice forCore-AnalysisP rocedure, API, RP40, fustcdlio,N ewYorkCity( Aug. 1960). 186. Jemdngs, H. Y.:``Effecfs of Labomtow Core Cltingon Wa@rOd ReJativePermeabiliW,'' Producers Monrhly(A.g. l958)Z2, No. 10,26-32. 187. Duyvis, E. M.and Smhs, L.l.M.: ``A Test fortbe WetiifiWof Ca.rbona@Rock?., SPEJ (March 1970) 3-I. 18S. Rthl, W., Scbndd, C., and Wissrnm, W.:``Displaccment TesS With Porous Rink, Samples Under Reservoir Conditions, Proc., Sfi World pet. Cong., Frad=km (1963), Sec. 2, PaFr 11, PD6, 467-S1. 1S9. EhrJich, R., Hasiba, H.H., and Raimondi, P.:``Alkafine Watertlooding for Wetfabiliw Alteration-Evaluating. PotenfiaJ Field .APPJicatiOn, JPT@= 1974) 1335-43. 190. Lorenz, P.B., Domddson,E. C., and Thom2.s,R.D.:`<ti5=of CenmifugaJMeasurements of Wettabtity to Predict Oif Recovery, U.S. Burem of M@, BartJesvilfe Enera Technology cater. repmt7873 (1974). 191. Emery, L.W., M.ngan, N., mdNichoIm", R.W.:``Causti. Sl.s Injection in the Singleton Field,,, JPTfDec. 1970) 1569.76. 192. Hjelmeland, 0.S. and Larmndo, L. E.: ExperimenfaJJnvtigation of the Effects of Temperature, Pressure, and Cmde OiJ Conm.mition o InterfaciaJ Prmerdes. SPERE (JuIY 1986) 193. Colpitm, G.P. and FJmter, D. E.: LaboratoryD kplacementof Oil by Water Under Simulated.Rescmoir Condifions,J. Gfn. PeL Tech. (1964) 3, NO. 2,66-70. 194. EbOg-Economides, C. A.and Economides, M. J.: c$Presmueand Temperamre Dependent Properties of the Rock-Fluid Systems in Petroleum and Geotierrmd Formations, paper SPE S919presentedatfhe 1982 SPEC#lfonda Re.@aJMeed ng,Bakersfield, Mmh 2S-26. 195. Kyte, J.R., Naumann, V.O., mdMatlax, C.C.; ..Eff0=tofReservou Envktimnent on Water-C6iDkrdacemetm. IFT (June 1961) 379-8Z Trans., AJME, 222. 196. Jobnson, R.E. and Deti, R.H.: Wetti+biMyan dConmct&gles,,, .9+.. and CoUoidScience, E. Madjevic (d.), WiJeyhterscieme, New York C@ (1969)2, 85-153. 197. Poston, S.W. eral.:``The Effect of Ternperafure on Imedicibk Water SZurationand Relafive Permeability of Unconsolidated .%@,> SPEJ(Jme 1970) 17180; Tram., AJME, 249. 198. S-ca, B.H. and Guemero, E.T.: TheEffecto fTemperaNre on Dmimge CapiJkuy Pressnre in Rocks Using a Modified Centrifuge,>papm SPE 10153presentedat tie 1981SPE AmwaJTechnical Cofermce and Exh,%ition, San Antonio, Od. 5-7. 1143

170. 171.

172. 173.

Journal of Petroleum Technology, October 1986

199. Sanyal, S,K., Kamey, H.J. Jr., and Mars6en, S.S.: TheEffect of Tempaauue on CapiUW Pressure Pm.verdesof Recks, Proc., SPWL.4 Annual ogging Symposium, Lafayene, LA, MaY6-9, L 1973, N1-N16. 200. Simokiot~A3.~,Rarney,H.J.Jr.,an dMarsde%S. S.: <Effect of Temperature Level Upon Capihy Pressure Curves, SPJ?J (March 1971) 13-22, ZOI. Mc&ffeV, F,G.:<<M~umentofln feCf&ialTemiOm and COntit AngI~ at High Temw#ure and Fmsyre, J. C&. Pet Tech. (J.ly-Sept. 1972) 11, NO. 3,26-32. . ,.

S1 Metric Conversion Factors

degrees F X 1.745329 (F32)/l.8 E.O2 = rad = .0c

m
Ori@.d !m..mdpt (SPE1 3932) recai.ed in the Sociely of Pelrolwn Enginem Dec. %,19%. PW.raCCePted f.r P"bU.atlon J"ly23,'19ffi. Rmn&mm"9CtiPt ceived Feb.3, 1986. oMce Te-

1144

Jomtiof

Pewoleum Te&olo~,

October 1986