SOCIETYOF PETROLEHMENGINEERSOF AIME 6200 North CentralExpressway Dallas,Texas 75206

~&R

SPE

5634

THIS PRESENTATION SUBJECTTO CORRECTION IS

Restoration

of

the

Natural m

State

of

Core

Samples

L. E. Cuiec, InstitutFrancaisdu P&.role @Copyright 97S 1 AmerIcanlnstltute ofMhdng,Me tallurgical ,andPetroleum Engineers, inc. This paper was preparedfor the 50th Annual Fall Meetingof the Societyof Petroleum Engineersof AIME, to be held in Dallas,Texas, Sept, 28-oct.1, 1975. Permissionto copy is restricted an abstractof not more than 300 words. Illustrations to may not be copied. The abstractshouldcontainconspicuous acknowledgment f where and by wh~m the paper is o presented. Publicationelsewhereafterpublicationin the JOURNALOF PETROLEUMTECHNOLOGY or the SOCIETYOF PETROLEUMENGINEERSJOURNALis usuallygrantedupon requestto the Editor of the appropriate journalprovidedagreementto give proper.credit made. is Discussionof this paper is invited. Three copiesof any discussionshouldbe sent to the Societyof PetroleumEngineersoffice. Such discussions may be presentedat the above meetingand, with the paper, may be considered for publicationin one of the two SPE aagazines. INTRODUCTION

Nonetheless, these precautions are not sufficient preventa temperature to and pressur drop when the sampleis being broughtup. This The wettabil.ity a reservoirrock plays of an importantrole in oil recoveryduring a wate~ drop may change the distribution fluidson of the surfaceof pores and be accompanied the by drive. It influences the residualoil saturadepositionof asphaltenes other heavy or tion, the relativepermeabilities and the to capillarypressure. Since it is impossible fractions. measureall these parametersin situ,laboratoq In summary,the preservation techniqueas experiments are used, thus raisingthe problem of the representivity f samples. o is now practicedis far from being perfect. Likewise,only modest confidence generally is placedon the qualityof presei~ation. Most scientists workingor. the problem have concludedthat it is difficultto obtain It would be tilus advantageous have to valid measurements without operatingunder conditions close as possibleto those in the anothermethod that couldbe appliedwhetherth as samplehad or had not been coredwith precautic reservoir. and protectedfrom any contamination, fidation o It is easy to reproducereservoirtempera- fluid loss, etc., or whetheror not it had in ture and pressureconditions the laboratory. alreadybeen used for physicalmeasurements in It is also possibleto obtain reservoirfluids. the laboratory. Unfortunately, obtainingporous-medium samples The restoration methodmeets these require that are representative rom the standpoint f of the surfacestateis more delicate. ments. It consistsof two steps: (1) cleaning the surfaceof the solidto removeas much as possibleif not all the productsthat had becom To obtain such samples,we can try either fixed there,whetherthey came from crude oil. o to preservethe originalsurfacestate or else to restoreit. At the moment the formermethod mud. It is not possibleto separatethe productsinitiallyadsorbedon the.rockin the is the most widely used, but requiresspecial precautions while the sampleis being taken.1-3 reservoirfrom those that had become fixed ther of afterward. (2) introduction reservoirfluid Referencesand illustrations end of paper. at

RESTORATION THE NATU OF by saturation with brine followedby sn oilflood to simulatethe conditions the inflow of of oil into the reservoir, agingunder and reservoirtemperature and pressureconditions durtigthe ttie requiredfor the adsorption equilibria become established to correctly. In the bibliography, there sre some result showingthat it is reasonableto hope for such a valid result in representi.ag surface the stateof the solid by preservingor restoring 4.-6 its originalstate. In this paper, we proposeto examinea few problemsraisedby using such a method. For this, two porous media from quarries,respectively,sandstoneand limestone, were used, Their initialsurfacestate,calledreference state,was carefullyanalyzed. Then their aging in the presenceof reservoirfluidswas studiedalongwith their cleaningafter this Pollution. The surfacepropertiesof the porous medi: in their referencestateor after any treatment were evaluatedby a nettability test basec on the one proposedby Amott.2 These investigations evealedthe imporr tance of the nature of the solid surfaceas well as that of the crude oil, whetherfrom th( standpoint adsorption desorptionof the of or productsfrom a crufle oil on a solid. GENE3ALCONSIDERATIONS Description the Porous-Media of Surface Reservoirsare mainlymade up of ssndstoneflimestoneand clay. The presenttivestigationconcernsonly the first two types of surface. Case of Sandstone . It has long been admittedthat silica, which makes up sandstone, has a surfaceof the acid typeOT More recentresearch,moreover? has confirmedthis. For example,Block and Sin_ms8 ave observedthatoctadecylamine h is stronglyadsorbedon the surfaceof glass, whereas stearicacid is hardly adsorbedat all Likewise,McCsfferyand Mungsn9have made the same observation with quartz. To better definethe surfaceof this material,the originof its acidityshouldbe described. Vacuum crushedquartzhas a surfacemade of positivesites (silicaSi+ ions) and negati sites (oxygen0- ions).lo Hence, the over-all chargeis nil or very weak. Steam placed on this materialis separated under the effectof the field of forcesof the solid,and it forms silsnolgroups= Si - Oil. This water is

STATE OF CORE SAMPLES

SPE ~

stronglyattachedand is desorbedonly by heatingto temperatures greaterthan 3000C in high vacuum.

This phenomenoncan be represented th by followingreactionscheme: o-0-Si -t I o I +H20~-O-Si-Oli I 0 I OH I

The silsnolgroups are weak acids capabl they of settinga proton free. Consequently, are Bronstedacids, We have: =SiOH ~-SiO+H+ pKz 7.

If there is enoughwater, other molecul may be adsorbedwith energiesbetweenthose observedrespectively for adsorptions the of physicalor chemicaltype. The adsorption sites for these moleculessre hydroxylsin tl silanolgroups.lo-ll The acid nature,howev is preserved.

It is quite probablethat the surfacecd sandstonefrom quarriesor oil reservoirs ha: been in contactwith water before,possibly it containingother fluids. Therefore, must coveredby silanolgroups snd adsorbedwater molecules.

In addition,silicamay containimpurit in particular,aluminum12 whose presencein I Si 02 network enhancesthe acidityof the sw face becausethis metal tends to pick up a p; of electronsto completeits orbitals. This createsa Lewis acid site,or if water is present,aBronted acid site.ll Nonetheless, the amountof Al observed here is small comparedwith what is found in the silico-aluminates used in catalysis. Case of Limestone

Carbonaterocks have long been consider to have a surfacewith a basic nature.T Con sequently,acids cen react with them. For example,McCafferyand Mungan9have shownth stearicacid becomes stronglyattachedto calcite. Lfiewise,bwe et al.13 estimatet acid productsin crude oi~ =come attached the basic surfacesof carbonaterocks and fo a chemisorbed Pilm of the corresponding calr salt.

Morrow14has also observedthat octenoi acid affectsdolomite,while other acid prod do not. It is possiblethat the basicityis of

xi! ,=

f-%-al.
.

T,. f!lKRc E.
. -. -----

Arrhenius-Os+,wald type, e.g., becauseof - Ca ofthe Lewis type becauseof the OH grOUpS, .I electron pairs in the o~gen of the C03 group. But we must be contentwith assumptions because much less researchhas been done on carbonates then on silicaor silico-aluminates. Nature of AdsorbableProducts A great deal of researchhas been done to identifythe productscontainedin crude oils. Whiteheadand Breger have made a bibliographic review. 15 The number of such productsis considerable. Whereas differences may be found from one crude to anotheror from one familyof crudesto snother~there are nonetheless seve al major categories compounds. These of ~el % : normal and branchedparaffins? naphthenes, naphtheno-sromatics~ heterocyclicsf and asphaltenes. Paraffinsand naphthenesare inert or relatively inactivewith regard to the surface of porousmedia. Possiblebonds sre of the Van der Waals type and, hence, are weak. Aromaticsor naphtheno-aromatics are usuallyless than the precedingones in quality,but are necessarily more activewith regardto solid surfaces. Indeep,they may participate n bonds with solids. in Other productssuch as heterocyclics snd asphaltenes,which containoxygen$nitrogen~ sulfur,metallicatoms, etc., as weil as carbon and hydrogen,are often polar, acid,basic and are quite possiblythe most activewith regard to the acid or basic sites of solids. Adsorption may then occur by covalentbonds,hydrogen bonds or interactions betweendipolesand electriccharges. Nonetheless, these latterproducts,which sre probablythe most importsntin adsorption phenomenonon rocks, are also the ones about which the least is known. Some analysesconcerningacid and basic productsin crude oils have showrt at the h followingfamiliesof productsare probably alwaysrepresentedlT:

Becauseof their great number,weak concentrationand complexformulation, there is not much chanceof identifying them easilyand accurately. The most we can obtainis some indications to their amountand nature on as the basis of over-allanalyses. For example,the acidityof the crude oil is measuredby the acid number given in mg K3H/g of crude. This number generallyvaries from 0.1 to 7. The total nitrogencontentaverages0.3 to 0.6 percentweight and may be as much as 1 percent. The basic nitrogen/total itrogenratio n is usuallybetween0.25 and 0.35.17 Accordingto what was said above,a crude oil containsall the more adsorbable products as it containsmore heterocyclic compoundsand asphaltenes.Characterizing crude oil by its a acid number and its basic nitrogencontentin order to examineits affinitywith regard to a given type of solid appearsto be interesting at the moment. However,considering that the preceding titrationsare over-allones, no consideration has been given to the structure the molecules of that containthe acid or basic groups. We csn assumethat, with identicalacidityor basicity,any changein the surfaceproperties of a given solidwill dependon the place occupiedby adsorbedmolecules. In addition,sincewe how that crude oils are oxidizable differingdegrees!for a to given crude oil there will be more or less oxidizable productsin contactwith sir to form new polar productsthat are also adsorbableand to ,modify the surfacestateof the solid. Therefore,dependingon the crude oil end matrix considered, there will be more or less adsorbedproductsthat will make portionsof the originally hydrophilesolid surfaceoleophile. The pollutionof reservoirrock samplesby some drillingmud productsoccursfrequentlyanc must not be neglected. However,this point has not been tsken up in this study.

It is also probablethat the water normalQ 1. Acid products: aliphatict naphthenic~ coveringthe surfaceof reservoirrocks before aromatic,sulfonicand other sulfur-containhg migrationof oil must not preventthe adsorption of certainoil products. Indeed,some of these acids;phenols. products (phenols, pyridines)are partially 2. Basic products: pyridines,quinolines solublein water, and we must assumethat all , the polar productswill have anon-nil volubilisoquinokines, substituted pyrroles. ity in such a highlypolar fluid as water. 3. Non-basicnitrogen-containing product s: carbazoles, tidoles,pyrroles.

RBTORATION OF THE NATURAL STATE 01 CORE SAMPLES Choice of CleaningFluids In the petroleumliterature, very few resultsare found concerning the efficiency of solventsin cletig porous-medium reservoir samples,and the solventsusuallyused are not always efficientto clean a pollutedporous medium.2#18~lg To clean a porous medium,the pores must be emptiedof their Iiqtidor solid content? and the film adsorbedon the solidmust be removed. To empty the pores, a suitablesolventor solventsmust be chosenwhile bearingin mind that a given solventis all the more capableof solubilizing solidproductor of becoming a misciblewith snotherliquid as their respectiv formulasare more similaror as their polarity or polarizability natures are close together. The desorption productsfixed on the of solid is more difficultto achieveend depends on the type of adsorbate-adsorbant bonds.

SPE 563L

Blonstedbases possiblycontainedin crude oils and representedby B are placedin the presence of this solid,the followingreactionis possible: SSi OH + J3~N5iO--+HB .

Ec@libriumismore or less advsnced dependingon the respectiveforcesof the acid and the base. A weak-acidsalt forms, end it shouldbe possibleto destroythis salt by the actionof an acid strongerthen Si O H, e.g., aceticacid.

The weak acid is then removedfrom its salt accordingto:

-1

(+

coo---

lIB ,

If low energybonds (Van der Waals bonds) are responsible for adsorption phenomena a sweep by a Limitedseriesof solventsor even by a singlecarefullychosen solventmay succee in extracting the crude oil from the pores and If Lewis bases are in contactwith the in removingthe adsorbedproductsby mechanical silica,they can also be strorlgly fixed on the entrainment. surface. Substituted Pyridinesproducethe formationof pyridiniumions, which will be The hydrogenand m bonds can also be electrostat.icly bonded to the surfaceaccording destroyedin this way, even thoughthe energies to \ involvedare greater. / ---A >: In all these cases we can restorethe surfacestateby a continuous displacement of the equilibrium:
~4 / \

The equilibrium displacedfar tr the is right, and the acetategoes into solution. If acetic acid circulatesin the porous medium? progressively as CH3 COO- %+S is eliminated it is formed,end the two precedingequilibria must move toward the right until exhaustion is achievedso as to restorethe surfacestateof the silica.

The attackof this systemby an acid strongerthan Si OH, e.g., acetic acid, gives . product solubilize productfixed on ~ \, the solid in the solver$ =i 0--- HN -~=i OH If the phenomenainvolvehigh-energy bonds 0 / rangingup to covalentbonds, a chemical-type reactioncould be necessaryto destroythe bond betweenthe adsorbedproductand the solid.

Consideringthe respectively acid or basic nature of the ssndstoneand limestonesurface and the existenceof acid and basic productsin crude oils, the existenceof high-energy bonds of the acid-basic type is possible, apriori. We will look at the possibility destroying of such bonds by acid or basic solvents. What we are about to say has the value of an assumptionand does not rule out the possibility that other high-energy bonds etist betweenthe solid and the adsorbedproducts. The surfaceof siliceousrocks has a more or less markedBronstedacid nature. If the

is soluble,a continuoussweepof acetic acid can once agah restorethe surfacestate of the silica. In the case of silicaon which aBronsted or Lewis base has been adsorbed,the systemcan also be attackedby a base providedthat it is capableof replacingthe one precedinglyadsorbed. This is theoretically possibleif this replacement brings in the systemin a weaker

w 563L

L. E. CUIEX

energy state. However,the newly fixed base Fontainebleau sandstoneand Rouffach limestone. must be able to be easily eliminated later. If In the sandstone, the surfaceavailableto the vapor tensionof this base is sufficiently high, vacuumpumpingand heatingmight be effec- fluidsis of the almostpure siliceoustype witl tive. 60 pg/g Fe and 180pg/gAl. In the case of calcite,if this basicity is due to Ca OH groups,a Bronstedacid may form the corresponding salt on the surface.13 - CaO]~+Fl COOR ~~Ca COOR +1420.

An observation a thin sectionof of RouffachWestone showedthat it is made up of quartz and calcitegranulescementedby crystal Line calciteand that the porous surfaceis amost entirelycelciticin nature. The sampleplugs are cut out with water am then dried h a partialvacuum at 8500. Fluids

It might be possibleto introducea strongerbase than - CaOH, e.g.,NaOH, to remove the salt from the weak base by
+

Ca COOR Na COOli

+NaO1;

>

- Ca OH

The wettabili.ty test is performedwith the pair of fluids consistingof brine with 100 gm/ liter of Na Cl and MayolineBayol 50 oil. Both and to restorethe surfacestateof the calcite, fluids are used after the gas has been removed from them. So as to have substances capable However,if the Bronstedacidspresenton of changingtheir surfacepropertiesinside these porous media, crude oils containing difthe calciteare sufficiently strong,they may ferent amountsof acid or basic productsare attackto set free the C02 and H20. used. Actually,Oils A and B are obtainedby lightening the original.toragecrude by means s If the basicityof the calciteis a Lewis of a Mght cut from the same crude (OilA) or b~ basicity,on accountof the electronpairs of kerosene (OilB). Oil C is a storagecrude. the oxygensin the C03 group,it is possible All these crude oils have been in contactwith that the Lewis acids may adsorbon these air* o~gens. The fixationof such en acid represented by A can be written: Some propertiesof these fluids sre given in Table 1. The solventsused for cleaningthe porous media are pure productsavailablein laboratories. An attackwith a Lewis base strongerthan the surfacebase can remove acid A from the salt. For example,with pyridinethe reaction can be written: Description NettabilityTest of

To evaluatethe nettabilityof porousmedi and to followits evolutionwith the treatment undergoneby these solids,a test based on forced end spontaneous displacement measuremen of one fluid by the other was adopted.

No matterwhat type of acid is adsorbedon calcite,it is also possibleto attackthe systemby an acid capableof replacingthe one previouslyfixed on and capableof subsequently being easily eliminated. Nonetheless, the fact that calcitemay be decomposed Br6nsted by acids does not facilitate the searchfor such a solution. In so far as this type of acid-base bonds does occur,we can hope to destroythem by chosingthe suitablesolvents. ExPERImTAL ?orousMedia The followingporousmedia were chosen:

For a drying-oven dried sample,the fluids are introducedby saturating the porousmedium with brine snd then sweepingit with about 15 PV of Mayoline.

When the sampleis first saturatedwith crude oil, a light sweepis performedwith Mayoline (to replacethe crude oil by refined oil and measurethe intrinsicpermeability to oil); then it is sweptwith brine, and finally swept lightlyagainwith Mayoline. During each of the two Maydine sweeps,only three pore volumesare made to circulateso as to limit th subsequent desorption the productsadsorbed of on the rock. The nettability test includesthe foliofi

~ucce~~ive stages: (1) ~mbibitionin brine, (2) displacement brine, (3) imbibitionin by Mayoline,and (4) displacement Mayo~e~ by

The imbibition are done in pyrex-glass cellsunder thermostated ambientconditionsof Ag5ruz Rock-FluidSystems 20 * loC. The cylindrically shapedsamples,40 of ~ in diameterend 55 to 150 ZWI lwt kept ~ After crude oil has been introduced into a verticalposition?with the cylindrical. face coveredby a teflon stripswhich in turn is held the sampleswith or withoutresidualwater, the are placedin a cell filledwith crude oil and in place by a Viton sleeve. preservedat 85% under a pressureof about len@h of time. The lengthof time of imbibitionuntil the 1,000psi for a predetermined asymptoteis reachedvaries from a few hours to OperatingConditionsof Cleaning more than 2 months. Sweep displacements are done in a Hassler cell.

water is stronger. If the solidis oil-wet,thl valuesof rl end r2 are inverted. Lastly,in the case of a porousmediumwith neutralor intermediate wettabil.ity, two ratios have the very low valuesor are even zero.

Insteadof using the Soxhletflask,becaus we could never be sure that it would be effective insidethe sample,the techniqueof forced displacement was adopted. It is performedat To limit the influenceof permeability s heterogeneity the residualsaturation on values, 600c with a downstreamcounterpressure o as to the pressuredifference used for all the sweeps keep the solventin the liquidphase. performedon each sampleis chosen so that the RESULTS ratio of the viscosityand capillarity forces is equal to a fixed value. Validityof the Test The sweepvolumeof the two displacements Prior to any study,a check shouldbe made in the test is also arbitrarily fixed at 15 PV. to see that the nettability test chosengives The totaltime of the sweepby Mayotie enc resultsthat csn be consideredidenticalin the case of samplescomingfrom the same block or its standingin th5s oil before imbibition is approximately hours. The amount of fluid differentblocks and having the same surface 50 properties. displacedduringimbibition end displacements state and petrophysical is volumetrically easuredto within 0.025 cc. m Case of Sandstone Amott2used arbitrary imbibitionperiods The test was performedon a great many of 20 hours and displacements centrifuging. by samplescomingfrom differentblocks. Their The test chosenfor this projectis surfacestate after havingbeen cut outt dried$ and saturated with brine and Mayolineis conslightlydifferentend includesthe followhg Soi\ measurements:initialoil saturation, sideredas a referencestate. imbibitioncurve in briue and total amount recovered, ratio r of the emountof oil disThe petrophysical propertiesvary conside placed spontaneous by the brine to the total iy ably in this porousmedium For example,the permeability between 1.9 and 3,850 md. The is amountrecoverable spontaneous by anl forced displacements, value of ~w at Sor, imbibition @ - k correlation obtainedis in good agreemen curve in oil and total amountrecovered,ratio with the one found by Jacquim 20 r2 of the emountof brine spontaneously displacedby oil to the amountrecoverable by The resultsobtainedfor some of samples spontaneous end forceddisplacements, and value studiedare given in Table 2. We can see that of ~. at SW. (1) Soi does not dependonk, and (2) this medium is clearlypreferentially water wet in All the aboveparameters depend on the its referencestate. surfacepropertiesof the porous mediumwith Fig. 1 givesthe curvesfor oil recovery1 regardto the pair of fluids,but they are more imbibition brine, in percentPV, vs dimenin or less sensitive any changein these to properties. sionlesstime ~~21 with: The use of the ratiosrl and r2 was proposed by Amott.2 It can be predicted,and was confirmedby Amott, that in the case of a preferentially water-wetsolid,r2 will be zero and rl will have a positivevalue that is all. the nearer to one as the preferential affinityfor n=t fJ;-, r .- (0 ~L2

The over-allresultsobtainedshow that samplesfrom the same block and having similar

E5t5%!L
~z,

L, E. CUIXZ With ssndstot<e, examination an was made with two seriesof samples,one with low and the other with high permeabil.ity (Table4-A). In both cases,a considerable changeh the nettability- found. was

petrophysical properties behave in almostthe same way duringthe test. When they come from differentblocks,reproducibility s slightly i less good. The influenceof permeability oil on recoveryby imbibition brine for the entire in set of referencesamplesis given in Fig. 2. A singlecorrelation obtained. The accuracy is hoped for in predictingthe behaviorof a samplemust be evaluatedin keepingwith the complexnature of porousmedia and the difficulty encountered obtaininga similarbein haviorwith two presumablyidenticalsamples. The decreasein oil trappingwhen permeabilityincreasesmay explainth& increasein oil recoverywith permeability. The value of the rl ratio is all the closerto one as the permeability the sample of is high. Case of Limestone In this case, the test was also performed on severalsamples,once agsin taken in their referencestate, The resultsobtainedare propgroupedin Table 3. The petrophysical ertiesvary less than in the precedingcase. The test resultsare well grouped, especially for the first block. The mean behaviorof this block was calculated. The dispersion relationto this mean is slight. in The curvesof oil recoveryby imbibition h brine are given in Fig. 3. So, and especially because all the sample s used afterwardcame from the first block, all the indications providedby the test are correctlyrepeatedfrom one sampleto the next, exceptfor a deviationof the imbibition curve in brine, even despitethe use of a dimensionless time, In the variationzone examined, there was no influenceof permeabilityon the behaviorof this medium In addition,a prior examination showed that dryingin a dryingoven at 85C did not chsngethe surfacepropertiesof the porous media. Changein Nettabilityby AtiE with a Crude Oil Influenceof Aging Time To obtain a mccdmumeffect,the operation is performedwithoutresidualwater and with the most polar oil, i.e., Oil A. After imposing a determinedaging time, awettability test is performedwith the Mayoline-brine system.

With Iimestcneand for aging times of a few hours, an intermediate nettability was attained, while there was a reversalof the wettabili.ty longer aging times (Table5-A). for In the remainderof the project,when we had changedthe surfacepropertiesof the sample with a crude oil, an aging time of 96 hours was adopted. Influenceof the Presenceof ResidualWater on the Efficiencyof the Crt e Oil Aping Treatment It was assumedthat the oil had migrated from the sourcerock to the reservoirrock. Therefore,it was importantto examinethe case of brine-saturated samplesbefore titroductionof crude oil. In the case of ssndstone the behaviorof Sample F 75(Table4-B) shows that the residualwater origtiallycovering the surfaceof the sandstonedid not prevent some substances the oil from becoming in adsorbedon the surface. In the case of limestone(Table5-B),the effectobtsinedin 96 hours of agingwith residualwater is equivalent that obtained to in a few hours withoutresidualwater. In summary,the water film coveringthe rock is probablymerely a way of slowingdown the adsorption polar compoundsin crude of oils, but not of preventingit. Influenceof the Nature of Crude Oil The aging treatmentwas also performed with two other crude oils. On sandstone: The changein wettabil.it increases(compared with the referencestate Y h the followingorder (Table4-C): oil11+ oilC. ~ oilA .

Since sandstonehas an acid surface,the basic productsin crudes shouldbe adsorbed there, and the changein surfacepropertiesof the solid shoulddependon the amountof basic nitrogen. based on this reasoning,the precedingorderwould have been: oilC~oilll~oilA. Hence, it is probablytoo simplistic to reason in this manner. Indeed,crudescontain adsorbable productsthat are neitherbasic nor acid. Furthermore, the amountof basic

RESTORATIONOF THE NATURALSTATE OF CORE SAMPLES nitrogen-containing productsdoes not specify the nature of the organicradical. hat must t play a role for reasonsof sterichhirance, for example. On limestone: An identicalexperiment was made with this medium,and the results (Table5-C) show that in the importanceof the effectobtainedthe order is as follows: oilA . oilR ..;* oilC .-+>. Limestonehas a basic type of surfaceand a crude oil shouldchangethe propertiesof such a surfaceall the more readilyif it contains more acid products. The resul+.s obtained,moreover,are in agreementwith the order of the valuesof the acid numbersof the crudesstudied. Case of Mayoline However,it can be seen that the acid numbersof Mayolineand Crude Oil C are similar,and so we examinedthe case of aging of both types of rock with Mayoline. We found that wfith limestone(It 73, Table 5<) the amountof oil recoveredby imbibition in brine 5s reducedby half when comparedwith the referencebehavior(Table3), This is similarto the resultsobtainedwith both lowacid crudes. With sandstone(F 83, Table 44), the result conformsto the one p~edictedfor a referencesampleha.cing same permeability. the A 96-houraging treatmentwith Mayoline g not containin any basic nitrogenthus had no effecton the acid surfaceof sandstone. On the contrary, with a non-nilacid number,an influencewas found with limestone. In the presentstate of our researchand in the absenceof more completeresults?it is difficultto affirmthat solelythe acid number and amountGf basic nitrogenare sufficient for predictingthe behaviorof a given solid surfaceand a given oil. Furthermore, the literature containscontradictory resdts in the field of adsorption crude oil polar of compoundson solids.lt23-25 Influenceof Solventson the Matrix of &ndstone and Limestone So es to work in conditionssimilarto those in which solventsare used in the case of pollutedsamples,we operatedas follows: cuttingout a plug and dryingit, saturating the mediumby the consideredsolvent,aging in the same solventfor 48 hours at 6CPC under slightpressure,dryingh a vacuum drying

SPE .-. 563L

oven at 85C, saturation with brine, then sweepby Mayolineuntil %, and nettability test. We investigated the influenceof chloroform, ethanol,pyridineand hydrogenperotide on both porous media and with aceticend hydrochloricacidswith sandstonealone. . The resultsobtainedshow that in the nettabilitytest both sandstoneand limestone behave in a way that is similarto what can be predictedfor referencesampleshavingthe same permeability, ClesnirwPreviouslyPollutedSamples Case of Sandstone Numeroustests were performed. Only part of the resultsobtainedis given in Table 4 end Fig. 4. To get an idea of a given cleaning process,a comparison was made with results obtainedfor referencesampleshaving the same permeability. Usual Solvents Chloroform,a commonlyused solventof the acid-apolar type? was used on severalpreviously treatedsampleswith one of the crude oils. We found that even after long-duration sweephaving. large volume in relationto the a pore volume [approximately 00 PV) polluted 3 ssmplesdid not regain their initialsurface properties, matterwhat crude oil was used. no Indeed,the behaviorduring imbibitionin brtie and hence the value of the rl ratio show that the samplesconsideredare considerably less wettableto water than they must have been beforepollution. Tolueneand benzeneare also commonlyused solvents. They are apolar,but with t,? presenceof an aromaticnucleus,they .re highlypolarizable polar moleculesare in if their vicinity. They are too good solventsfor aromatics,and becauseof the number of carbon atoms containedin their molecules,they should be better than chloroformfor solubiliztig long molecules. The behaviorof the samples(F 109) during imbibition I.xine the value of the rl in end ratio indicatethat the cleaningthat was performedwas not very efficient. Series or Mixtureof Solvents Series of solventscent siningone or severalrepresentatives f alkanes,cycloo alkanes,aromatics, basic productsand acid

SPE 563L productswere also used.

L. E. CUIIi?2 Series 0? Solvents A seriesof solventssimilarto the one used on sandstonealso succeededin correctly cleaninglimestone(R 30). A seriescontainingonly pentsne,heptane,cyclohexene, benzene,ethanolwas efficient, too. Basic or Acid Solvents Basic solventsused directly(R 35, R 8b, R 74 or precededby a miscibleslug (R 76, R 781 clesnedthe limestonecorrectly. Acid solvents(R 80, R 81, R 86) proved to be less effective. The most importantresult is doubtless the findingthat solventsof the acid or basic type have a specificeffecton Loth sandstone and limestonemedia. This agreeswith the hypothesesput fcrwsrdwith relationto the nature of the adsorbate-adsorbant bond and the way this bond was destroyedby the displacementof the adsorptionequilibria. The fact that a seriesof solventscontainingone or severalrepresentatives f o differentfamiliesof the productscontsined in crude oils succeededin correctlycleaning the surfacedoes not gainsaythe preceding hypotheses. Indeed,if adsorption reactions are balancedreactions,these equilibria can be displacedin the directionof desorption by circulating various solventsin which the adsorbedproductsare more or less soluble, The circulation a singlesolventof the of chloroform toluenetype, neitherof which or has a marked acid or basic nature,nonetheless has less chsnceof solubilizing all types of adsorbedcompoundsand hence of displacing the adsorptionequilibria. This agreeswith the fact that sweepswith such solventsdid not prove to be effective,especially when the solid surfaceshad been pollutedby the most polar crude oil. In summary,we found that i% is not useless to try to obtain samplesthat are representative the surfacestateof a of reservoirby means of restoration. However,the problem stillremainsof studyingargillaceous rocks for which solidfluid interactions couldwell be greater. In addition,the cleaningof porous media pollutedby drillingmud additivesshouldalso be investigated. This project as a whole has demonstrated that a theoretical. approachto hteractions betweenrock types, crude-oilcomponents and differentsolventsis en effective way of tacklingthe problemof cleaningporousmedia

This type of cleaningproved to be effec. tive (F 60). We also tried to combineseverti solventshaving differentcharacteristicsn i the same phase. For this, a mixtureof methanol,acetoneand toluene (MAT)was used in the proportions15-15-70. This mixturewa~ made up of an acid solvent?a basic polar solventsnd an aromaticsolvent. However,the resultsobtained(F 12b) : are hardly satisfactory.Indeed, imbibition brine is abnormally weak, as is the rl ratio. Basic or Acid Solvents The use of solidswith a basic naturewa~ done under the followingconditions: ethyl acetate (100 cc), ethyl ether (950 cc), pyridhe (1,000cc) followedby ethanol (550 cc , benzene (6(x) cc) followedby pyridine (6( cc), and chloroform(lCO cc followedby dimethylformsmide1,000cc1. This proved to ( be insufficiently effective. Only a seriesof solventscontaining1 N NaOH proved efficient. A few resultspertainingto these clesnfi operationsare given in Table 6. Solventshaving an acid characterwere used directlywhen they were misciblein crude oil (F 104, F 115, F 119) or precededb: a misciblesolventin the other cases (F 61, F 106, F 21). In all cases and even with small volumesand short cleaningtimes, cleaningproved to be effective. However,wh( the aceticacid could not reach easilythe surfaceof the pores, its effectiveness was clearlydiminished(F 111). Case of Limestone A great many cleaningtests were performf and some of the resultsobtainedare given in the effecTable 7 and Fig. 5. For evaluating tivenessof a cleaningoperation,a comparison was made with the resultswith reference samples. Usual Solvents Cleaningby chloroform proved to be effe[ tive for the two least polar crude oils (R 26 andR 29). In the case of Oil A (R 3 b) we did not find the referencebehavior. In the case of the samplecleanedwith toluene (R 87), a comparison with the mean preference behaviordid not concludein good cleaningefficiency.

10

RESTORATION THE NATURAL STATE OF CORE SAMFiES OF and could prove to be useful in guidingthe choiceof eventualadditivesto be used for secondary tertiaryrecovery. or CONCLUSIONS du P&role.

SPE 563L

I am indebtedto the ti~o companiesfor permissionto publishthis paper. I am indebtedalso to Mrs. FrengoiseGallsnd,who obtsinedmuch of the experimental data.

A nettability test based on spontaneous REFERENCES and forceddisplacement experiments has provedto be correctly reproducible from one 1. BobektJ. E., Mattax,C. C., and Denekas, sampleto anotherfor both sandstoneand limesM. O.: Weservoir Rock Wettabilitv Its tone when the petrophysical propertiesare Significance and Evaluation, Tra&s.,AIME it similar. (l:;:)$, 155* 2. tObservations Relatingto the The surfacepropertiesof sendstoneand Wetta~ility PorousRock,t! of Trans.,AIME limestonemay be greatlymodifiedby contact (1959)216, 156. with a crude oil under reservoirconditions. A The changeproduceddependson the crude oil 3* Keelan,~ K.: tCore nalysisTechniques and Applications,tf Paper 4160 SPE end may go all the way to reversingthe presentedat Meeting,Colmbus, Nov. 1972. nettability the case of a crude oil rich in in Effects L. Mungan,N.: ?~cert~ Nettability polar products. in Laboratory Waterfloods,t Pet. Tech. J. (Feb. 1966) 247. Solid-crude oil adsorptionequilibria appearto be established quickly,and perhaps 5* Mungsn,Necmettin: RelativePermeability Measurement Using ReservoirFluids,~~ot. S more quicklywith sandstone than with limePet. EnE. J. (Oct. 1972)398-402. stone ~ 6. Ruhl, W., SchmidtCf., and Wissmsnn,W.: !Displacements Tests With PorousRock The presenceof residualwater does not SamplesUnder ReservoirConditions,~I World preventa polar crude oil from changingthe Pet. Cong., Frankfurt(1963) SectionII, surfacepropertiesof a porous medium. paper 11, P.D. 6. Chloroform, ethanol,pyritineand hydro7. Benner,F. C., and Bertell,F. E.: ~The Effect of Polar Impurities Upon Capillary gen peroxidedoes not changethe surfacepropand SurfacePhenomenah PetroleumProclucertiesof the virginporous media studied. tion,tt rill. and Prod. Prac.,API, New D Likewise,hydrochloric and acetic acids have York (19L1)3.41. no effecton the surfacepropertiesof sandt?. BlockTA~,-~d Simms,B. B.: ~Desorption stone. and Exchangeof AdsorbedOctadecylamine snd StearicAcid on Steel and Glass,t. ~ With regard to pollutionby polar crude of Coil. and Interf.Sci. (1967) ~, 514. oils, standardsolventssuch as chloroformand F. 9* MacCaffery, G., snd Mungen,N.: toluenecsnnotbe used in cleaningporous !Icontact ngle A and Interracial Tension media. Studiesof Some Hydrocarbon Water Solid tt Systems, Jo Cdn, Pet. Tech. (July-Sept. A seriesof solventsappearsto be effec1970) 185. tive in cleeningboth types of porous media. 100 Cases, J:: ltPoint chargenulle et de structuredes silicates,tl Chim. Phys. J. For cleaningby a singleproduct,solvent (1969)66, No. 10, 1602. having sn acid nature tend to be quite effec11. Tanabe,K.: Solid Acids and Bases, Their tive for ssndstone, and solventswith a basic Cat ic Properties, AcademicPress, nature are effectivefor limestone. This &ha, New York (1970)65. would appearto confirmthe theoretical 12. Pascal,P.: NouveauTrait6de Chimie hypothesesformulatedat the beginningof this mindrale,VIII, 68-69. paper. 13. Lowe, A. C., Phillips,M. C., and Rid&ford, A. C,: t~ the Wettingof NOMENCLATURE CarbonateSurfacesby Oil snd Water,!. ~ Cdn. Pet. Tee&. (AprilAune 1973)33. The symbolsare those adoptedby the 1,!+. Morrow,N. R., Cram, P. J., end Societyof Petroleum&gineers of AIME. Studiesin Dolomite F. G.: !l)isplacernent with Nettability Controlby OctanoicAcidt ACKNOWLEMWNTS paper SPE3993 presentedat SPl&AIME Annual Fall Meettig,San Antonio,Oct. The researchfrom which this paper was 1972. derivedwas carriedout under a cooperative 15. Whitehead,W. L., and Breger,I. A.: agreement betweenthe Soci6t&Nationaledes P&roles d~Aquitaine and the InstitutFrancais Ormnic Chemietry-Geochemistry of
q

SPE 563L

L. E. CUIEC

11 -.

Petroleum,PergamonPress,Internat.Series of Monogr.in Earth Sciences,Ed. I.A. Breger, 248-333. M. 16. Byramjee,R. S., and Bestougeff, A.: Etude sur les transformationshysiqueset p chimiquesde p6troleen liaisonavec les conditionsgdologiques! Adv. in Org. Geochem. Int. Ser. of Monogr.in Earth , Sciences (1966)~ 129. 17. Lmhte, H. L.t and Littmann,E. R.: ~ PetroleumAcidsand Bases, Chemical PublishingCo., Inc., Newyork (1955). of 18. Jennings,H. Y.: SurfaceProperties Naturai &d S theticPorousMedia,Prod. r (1957 27 No 51 20 19. Reisberg,J., and Drosher,T. M.: lnterracial~henornenan Crude Oil-Water i Systems,Prod. Monthl~ (Nov. 1956).43. entre la 20. Jacquin,C.: I!Corr&lationS perm6abili.t4 les caracl%ristiques et g~omdtriques Gr&s de Fonta5neoleau, du Revue de lInstitut Frsncaisdu P6trole, (July-Augu&t 196A) 921.

21. Mattax$C. C., and Kyte, J. R.: Imbibition Oil Recoveryfrom FracturedWater Drive Reservoirs, paper SPE 187 presentedat SPE-AIME36th AnnualFall Meeting,Dallast Oct. 1961. 22. Morgan,J. T., and Gordon,D. T.: influence of Pore Geometryon Water-OilRelative Permeability, aper SPE 2588 presentedat p SPE-AIMEUth Annual Fall Meeting,Denver, Sept.-Ott.1969. Recoveryby Surface 23, Salathiel, A.: t~oil R. Film Drainagein Mixed Nettability Rock, paper SPE 4104 presentedat SPE-AIMEAnnual Fall Meeting,San Antonio,Oct. 1972. 24. Treiber,L. E., Archer,D. L., and Owens, w. w.: Laboratory Evaluation the of Nettability 50 Oil Producing of Reservoirs, paper SPE 3526 presentedat Meeting,New Orleans,Oct. 19710 25. Denekas,M. O., Mattax,C. C., and Davis, o G. T.: ~?Effectf Crude Oil Componentson Rock Nettability, Trans.,mm (1959)u, 330.

TABLE 1 - FLUID CHARACTERISTICS

Brine Fluid

Mayoiine

Bayol

50

Oil A

Oil B

oil c

b ~ {Z2C) g/cm3
p 22*C) CPO

100 g/1 NaCl

(from EsSO)
0.835 11.1 0.834 12 0,852 12.6 0.824 2.77 (15*C) (21-C)

1.065 1,14

Acid Number
mg

KOH/g

0.02

i.55

0.06

0.03

Baaic

Nitrogen

PP

non measurable

435

231

85

Total Nitrogen Pv <1 1,455 935

630

Basic Nitrogen Total Nitrogen

0.30

0.25

0.135

Sulfur
Weight

V.

<50

ppm

0.59

0.19

0.24

TABLE 2 - FONTAINEBLEAU SANDSTONEREFERENCETESTS Dimpl~cement ImbibitionDisplacement rine with B Imbibition Di~plaCement with Block Sample
Number Number with Mayoline 9 % 8.5 ~w k+. ~~= Soi in Brine s Oil displaced 0, %Pv % Oil displaced s r k;w in Mav. Brine displaced Kine dicpl. Mavoline S = Io&.s k at 1 2

F7

. F4

md 41

% 79

%Pv
9.5

%
51.5

sat or
.05

18

61

% Pv % Pv %Pfr s ~ 0 38.5 90 .27 .61 0 27 77 .36 .64

9 88 .55

9.2
5.7

95
8.2 -

.61

79
83.5

21
5

38
78.5

8
2.5

50
76

.014 0 .05
,.01 .01

.72 .66
.28

0 0
0

----------------------------------------------------------------------------------------------------------11 F 20

0
0 0

----------------------------------------------------------------------------------------------------------F 31 Iv F 34 7.3 34 .82 82 13 69 9 60 6.4 12 .67 97 5 92 13 79

20 22.5
27.5

80 88
93

.68 .42 ,63 1

.59 .35
.8

0 0
0 0

----------------------------------------------------------------------------------------------------------F 50 v F 69 F 66 6, ? 8.8 12.7 17.5 96 560 . ?7 .5 .56 78.5 85.5 85 4.5 16 37 74 69.5 48 8.5 4 0 65.5 65.5 48

.03
.01 ,.08

0
0 0-

----------------------------VI F93 5.7 1.9 .58

-----------------------------------------------------------------------------88, 5 5 83.5 7.5 76 .01 0 10 86 .6 .4 0

----------------------------------------------------------------------------------------------------------VII F 102 16.3

I#470
260

.5
.44

87
80.5

49.5 37.5
42.5 38

0
0

37.5
38

.1
.26

0
0

46.5
54.5

84
92.5

.38
.86

L
1

o
0

----------------------------------------------------------------------------------------------------------VIH F131 11.7

-----------------------------------------------------------------------------------------------------------F135 Ix F134 23.6 3p50 .65 85 59 26 .5 25.5 .43 0 66.5 92 .68 .99 0 23.5 ?#Oo .44 71 49 22 0 22 .32 0 47 69 .41 1 o

----------------------------------------------------------------------------------------------------------x F 201 15.3

900

.34

79

35.5 43.5

43.5

.2

43

86.5

.44 1

TABLE 3 - ROUFFACHLIMESTONEREFERENCETESTS with B Imbibition Ditplscemant ImbibitionDiapl~cament rine Displacement with Brine with~yoline in M in May. Mayoline k Brine Brine So= Oil SOY k Oil s s. k ro 01 di-placed displaced atrw displaced 100-Swr atro diepl. 0 qt 7LPV % s Swr % Pv %Pv %Pv $ % Pv swr % or
.78 .84 .75 ,.79 .48 .79 .78 I, 72 .58 .66 .84 ..67 .73 64.5 62 61.5 56.5 64 60.5 63 60 57 54.5 58. ) 15.5 15 15 15.5 15 15 12 14 15 12.5 15.5 49 47 46.5 41 49 45.5 51 46 42 42 43 2 1.5 2 0.5 44 40.5 40 42.5 .017 .029 .03 .029 0 0 0 0 17 24 20 22.5 61 64.5 60 65 .55 .70 ..81 ,.71 .87 ., 9? .87 .97 0 o 0 0 4 2 4 37 47 41.5 .018 .018 .015 0 0 0 21 23 22.5 58 70 64 .76 .48 .56 .79 .88 .79 0 0 0 5 4 44 43 .012 .027 0 0 21 24.5 65 67.5

Block

Sample

Number Number
. R 17 R] R 84 R. 10 R 15 1 R 13 R 90 R 16 R 1> R 69 R 18 . % 17.9 19.4 18.6 18.6 18.4 18.5 18.7 17.8 18.3 18.3 18.9 .

k w md 5.3 7.5 7.5 9.1 9.1 10.3 11.0 12.7 12.9 13.4 19.2

1
. .76 .?9

0 o

---------------------------Averase .75

------------------59.5 14.5 45

-----------------------3 42 .03 0

-------------------------------21.5 63.5 .69 .85 0.

-------11

-----------------------R3a It 303 22.2 22.5 197 385 .32 .63

-----59 61

---------------------------14.5 18 44.5 43 6 0 38.5 43 .11 .043

--------0 0

-----26.5 25.5

---------65 68.5 ,.44 .62

-------.7 1

------0 0

SANDSTuNE TABLE 4 - FONTAINEBLEAU Part - Influence Time Crudeil A of .4ging with O A

Sample Number . F 10 ?? 11 F 12 F 125 F 126 F 113 F 118 0 % 8.25 7.1 7.35 15.2 14.8 15.0 15.4 k 0 Aging Time hours 1 4.5 96 2 16 96 96* .4 .37 .39 .4 Displacement with Brine at S k rw s ; . or . .13 .14 42 52.5 52 31 34 24.5 24.5 Diaplscement with MaVoline k at s ro Swr .08 .05 .05 .23 ..16 .21 .27 7: 72 74.5 60 79 77.5 71 83.5 Imbibition in Brine s AS 70 0 0 0 8.5 2.5 9.5 6.5 Di.placemer_t with Brine AS krw at s or .001 .001 .17 .17 .19 f.14 ~.16 SO % 61, 5 67.5 47.5 42.5 42.5 34 47.5 imbibition in Mayoline AS so %P; 1 1 1.5 ,?. 5 1 0 1 % 62.5 68.5 49 45 43.5 34 48.5 Displacement with Mayoline 4tSk*t S ro %P: s ; wr 4 3.5 3 41.5 37.5 39.5 38.5 .37 .36 .01 I. 29 .22 *. 19 ,.11 66.5 ;2 52 86.5 81 73.5 87

1 . 0 o 0 .24 .07 .26 .18

rnd 41.5 6.1 12 810 795 990 930

;.
72 74. 5 60 70.5 75 61.5 (7

%P; IG. 5 7 14.5 28 32.5 27.5 29.5

.2 .29 .33 .06 .025 0 .023

--------------------------------------------------* + 120 day-

------------------------------------

> --------------------------------------

in atmospheric conditions
Part B Influence of Swr

-----------------------------------------------------------------------------------------------------------------------------Brine 7 .07 65.5 F 75 6.1 96 ------------------------------------------------------------------------------------------------------------------------------

65.5

.002

2.5

9.5

,.11

.21

Part C ----F 57 F 59 F 83 -----------------9 10.75 8.45 89 255 35.7

Influence of Oil Nature

~_____________________________________________________________________________________________________ Crude 011 B 7? 73,5 f. 5 .006 .12 .16 6 31.5 79.5 96 Crude Oil C 12.5 2.5 .006 .34 .12 72.5 ?0 57.5 30.5 96 Mayoline 71 13.5 0 .06 71 .04 53.5 .39 84.5 96

o 0 0

73 57.5 71 .

19 11 Z3.5

..26 .26 .47

92 68.5 94.1 I

.87 .17

0 0 o

TABLE 5 - ROUFFACHLIMESTONE of Aging Part - lmfluance Time with Crude A

Displacement with Brine ~ qt S rw So .18 .22 .08 .09 .2 .29 ..06 .25 Y 44 38 43 43 51 46 59.5 50 Dieplzcement with Mayoline krO qt S SW= .12 ,.15 .41 /.21 J. 08 1. 1 ..14 .061 ; . 71 66 72.5 60 61 69 71.5 71 ----------4 1, 5 2.5 0 0 0 0 0 Imbibition in Brine &SO SO % Pv . 67 64.5 70 60 61 69 71.5 71 % . 24.5 27 28.5 20 29 26 28 28 Displacement with Brine Skatb ASO % Pv . 42.5 37.5 41.5 40 32 43 43.5 41 .13 .12 .12 .42 .12 .1 .09 ;

Oil A

Sampl. Number . 3t3 R8 R9 R5 R6 R? R 71 R 79 ~ % 17.9 19.2 19.1 19.6 18.1 18.5 19.3 19.4 kO md 15.7 19.6 15.8 14.7 9.5 9.9 28.3 34.5 q

Aging Time hours 1 4 8 20 48 120 432 96 * -------

rw Sor

Imbibition in Mayolinc S s % :V 1 1.5 1.5 4 2.5 2.5 3.5 5.5 --------------7: 43.5 39 43 44 34.5 45.5 47 46.5

Displacement with Mayoline 4 so so kr~ % Pv 32.5 24 27 25.5 ?3 19 8.5 10 % Swr .55 .16 .35 L 29 .20 .21 .32 .15

1 1.13 ,.04 J.09 0 0 0 0 0

76 63 70 69.5 57.5 64.5 55.5 56, 5

.022 .062 .07 .13 ,.08 .12 .29 ,.36

-------------------

----------------------

------------------------

----------------------------

+ 120 d~ys in lab. conditions Part B Influence of Sw ~

------------R 37 -----------------18.9

-------Brine 20

---------96 ----------

--------------------

-------------------.41 54.5 2.5 -------------------------

----------------------------------52 27.5 -----------24.5 r. 036 -----2.5 -----27

--------------28.5 55.5 ---------------

---------.. % ..09 ----------------------

-------.085

Part;C

Influence of Oil Nature

-------R 25 R 27 R 73

----19.1 18.9 17.3

---------20 20 5.2

,=--- ------------------------------.09 .05 .02 45 40.5 52.5 .47 .30 .48 71.5 65 67.5 9 10 a

----62.5 55 59.5

-------------------8.5 ?. 5 1.5 54 47.5 58 .03 .025 .011

---------.5 0 0 53.5 47.5 5a

-----

---------------------------23.5 20 13.5 77 67.5 71.5 .55 .47 .48 .5 .57 .83 0 0 .022

Crude 011 B 96 Crude Oil C 96 Mayoline 96

I
1

SANDSTONE STUDY OF CLEANINGAFTER POLLUTIONWITH CRUDE OIL A TABLE 6 - FONTAINEBLEU Solvent Clemnng
Sample Number F llb F 109 Chloroform Benz?ne L 800 1,200 Cleaning Solvent cc hour. 90 48 25 ,. ,, ,. ,. ,, ,. 50 50 4 48 24 24 5 5 40 1 md 14.2 1, 380 Volume Time
k

Diapl~cem,mtimbibition
w with Mayoline k qt so
ro

Dieplac-m*ac
~S with Brine k qt
rw

3mbNdtion
in Mayoline so -bso %Pv 0 0.5 63 40.5 q.

in Brine As. s 7ZPV 0 1.5 %0 78.5 87.5

S 7 63 40

Dtaplac.mont with Mayoline ASO krOat %Pv 22 46.5 wr 0.5 0.31 s

Cleedng

Efficiency SO % 05 87 . 0 0.03 1 0 0.01 2 G . good P= Poor P P

s wr 0.7 0.52

% 78.5 89

%P; 15.5 47, 5

s or 0.01 0.148

F 60

Pentane 500 Hexane Heptane Cyclohexane Betdme Py.ridine * Ethanol M.A. T. Ethanol Ethyl Ac4tate Ethyl
Ether

53

0.9

85

11.5

73.5

24

0.02

49

49

27.5

0.9

76.5

0.32

F 12b F 206 F 207

1,100 1,000 100

11.4

0.32 0.37 0.39 0.51

86 93 95 87.5

0.5 16 23 12.5

85.5 77

27.5 27 14 29

0.01 . 0.07 0.043 0.08

58 30 58 46

0 2.5 1 0

58 52.5 59 46

25.5 29

0.88 0.14 0.11 0.31

83.5 81.5

0.02 0.37 0.63 0.3

0 0.08

P P P P

658 510 1,200

950 600 600 140 140, 1.000 30

72 75

36 47.5

95 93.5

0.03 0

F 05

Bendne Pyridine Chlorof. Ethanel NaOH 1N

Water

F 117

1,130

0.22

89

40.5

48.5

0.126

48.5

48.5

44.5

0.23

93

F 104

Butyric qcid Water Chlorof. +Pb&ol

1,000 100 * zoo

48 4 72 48 24 24 7 7. 25 25 25 48 24 24

1, 191

0.54

90.5

44

46.5

U 5

0.19

38

38

54.5

0.29

92.5

0.84

F115 FI19 F 106 F 121

1,130 1,115 1,050 1, 070

0.26 0.46 0.82 0.48

82.5 90 89 88

41.5 37 45 44

41 53 44 44

2 0 10.5 0

0.2 0.16 0.25 0.15

39 53 33.5 44

0 0 0 0

39 53 33.5 44

57

048 0.39

96 .

0.96 ) 0.81 1

0 0 0 0

G G G G

Benz&ne+ , 000 Benzoic ac id Benz3me Acetic acid Chlorof. Acetic acid Tolu&te Acetic acid Ethanol Acetic acid ToIu&ne Ethanol 600 600 210 210 600 700 550 900 500 300

55 51

0.4. 0.39

88.5 95

F 61

231

0. ?2

85.5

32

53.5

0.04

52.5

52.5

3+. 5

0.8

87

0.96

Fill

1,218

0.43

87

29.5

57.5

19.5

0.1

38

38

49

0.72

87

0.6

TABLE 7 - ROUFFACHLIMESTONESTUDYOF CLEANINGAFTER POLLUTION Solvent Cleaning

Time hours 1, 700
1,800

Sampla Number . R 26 R 29 R 3b R 87

Crude Oil u-cd

Cleaning Solvent

~olwe cc

k w md

Dicplacetnent with Mayoline k so qt

.ro

Imbibition in Brine As. so %Pv 19 19 9.5 11.5 % 49 45 48.5 51

Displacement with Brine As. ?LPv 2 4.5 9.5 7.5 krw at s or ..03 .05 ,, 013 .. 066 so, % 47 40.5 39 43

Imbibition in Mavol.

Displacement with Mavoline

Cleaning efficiency

A sO
% Pv

AsO krO at
%Pv s wr ..58 .63 .65 .58

sO
% 72 71.5 58 69.5

c B A A Chloroform

wr .72 1.73 .77 ,.59

% 68 64 58 62.5

G = good P. poor

60 80 160 30 25 ,, ,, . ,, ,, ,, ,, 50 50 48 4 4 48 4 48 48 4

13.5 21 5.3 25

0 0 0 0

25 31 19 26.5

,91 ,, 81 .5 .61

0 0 0 0

G G P ~P

,.
,,

1,800

Tolu&ie Pentane Hemne Heptane Cyclohexane Benzene Pyridine Ethanol DiOxane Pyridine Ethyl acetate Chlorof. Ethanol N*OH IN Chlorof. D. M. F. ChloroI. + Phenol Chlorof. Benzene + benzoir acid Benzene Butyti.c qcid ChloroL

900 500

R 30

,, ,, ,?

..74

59.5

15.5

44

3.5

1. 03

40.5

25.5

.8

66

.83

R 8b R 35 R 74

A A A

, 100
, 100 ,130 100 100 1, 050 100 1,000 1,200 100

17.5 13.5

t. 67 ;. 72 ,. +2

59 62.5 64.5

14 16.5 23.5

45 46 41

3 4.5 8

,.012 .02

42 41.5 33

o 0 0

17 18.5 30.5

,.53 1. 36 .3

59 60 63.5

.82 .78 .74

0 0 0

G G c

9.3

R 76

20.5

,.6

59

13

46

.033

42

25.5

,. 48

67.5

.77

*G

R 78

32

!. 52

65.5

21

44.5

,.028

41.5

27.5

.47

69

.87

R 80

29

,.55

61

12

49

13

.096

36

25.5

..69

61.5

.48

R 81

700 100 500 250

48 4 20 10

10.5

,. 53

59

9 9.5

50 41

1 11.5

.024 ,.05

49

21

..4

70 62

.88 .44

0 0

R 86

40

). 85

50.5

29.5

32.5

1. 44

F4 l=? F 20 F 31 F 34 F 50 F 69 F66 F 93 F102 F131 F 134 F 135 F 201

/
m

/44
o

/ ~y,w
10 ICY

+
lo3 w ~s id to

Fig. I sandstone

Imbibition reference

data for sampies.

Fontainebleau

4
q

BLOCK 1 II
m m

0
60
A A

50

Y IzI IzE IzlE lx x

Q

40

v v

30

+ 9

20

e OTHERS
u

a q c
1

10
0

0.1

10

,02

,03

,04

PERMEABILITY,
Fig. 2 a function
t2cint-4=+nne

d
as

Imbibition ultimate of permeabi I ity

t-ef-r-n~~

oil for

=amnl~s.

recovery Fontainebleau

R4 R 40 R42 R 43 R 45 R 46 R47 R48 R S9 R 84 R 90

q
(3

II
o

R3a

Q R 303

a
v

A v
q

a +

...-

10

102

103

104

105

in

Fig. 3 I imestone

Imbibition reference

data for samples.

Rouffach

. _.

0
4C
A q

Fllb
F 109 F 60 F 12b F 206 F 207 F 105 F 117

v
El

m
e
0
!ra

1(

L
1

-$.

i.-

data for Fig. 4 - Imbibition sandstone samples previously Polar crude oil and flooded

Fontainebleau pol Iuted by a by various sol-

qIR26 1
1

30

v
a
u

R 87 R 30 R 8b
R 35 R 74 R 76 R 78 R 80 R 81 R86

a o n
A s

10

+ tn

10

105

data for Rouffach Fig. 5 - Imbibition samples previously pol Iuted by a Polar and flooded by various solvents.

limestone crude

u oi I