AIM Lj! [4 PETROLEUM TRANSACTIONS & Reverse-Wetting Logging JOHN W. GRAHAM. JUNIOR MEMBER AINE HUMBLE OIL & REFINING CO, T.P. 8041 INTRODUCTION The most common method of identifying hydzocar- bon-bearing strata in a well that penetrates many difler- tent formations involves measurement and interpretation of the electrical properties of the formations as deter- mined by electrical logs, Even though this method is used extensively, and even though in a great many in stances itis capable of indicating presence of oil or gas, situations atise for which it is extremely difficult, if not impossible, to deduce the presence of hydrocarbons. These situations may involve the following. 1, A thin formation, bounded by highly resistive formations, in which it is impossible to obtain the ac- tual resistivity of the uninvaded zone with existing log sing devices. 2. A formation in which invasion has been so oxten- sive that a value for the uninvaded zone resistivity can- not be obtained. 3. A very shaly formation in which the resistivity in dex, 1, is lower than that usually associated with ‘pro ductive formations, 4. Laminated formations comprised of thin produc- tive sands separated by thin shale streaks in which the individual sand and shale streaks are too thin to per- rit measurement of uninvaded-zone resistivity with ex- isting logging devices. ‘5S. Productive formations in which the water satura tion is high To extend the utility of electric Jog interpretation to identification of hydrocarbons in all types of formations, there is strong incentive to find a method not subject to these limitations, Some time ago, in connection with research on the wettability of reservoir rock, an investigation was con- ducted in which the resistivities of cores were measured shortly after they were removed from a core barrel, and again after they had been extracted and restored to their original oil and brine saturation.’ The resistivities 1g: BB, Pane arearatod at thet Anptal Bal Meine of Soe of Patria Teckyaeoy. hay dincasion eet hee SPE 1116-G after extraction were generally lower, Other tests made fon the cores indiested that they were more nearly water wet after they were extracted; thus, it was assumed that the observed changes in resistivities were due to a change in wettability of the cores. Other experiments have shown that resistivities of rock samples are sharply dependent on wettability. These experiments have shown that oil-wet samples are more resistive than water-wet samples. To obtain an understanding of how the wetting prop- crligs of the surfaces of core material affect electrical resistivity, a series of experiments was conducted, Two groups of core samples were prepared for testing. One group contained brine, but no residual oil. The other group was saturated with brine, flooded with oil to a Jow water saturation, then flooded with brine to a final residual of] saturation, Resistivity. measurements were made on each group. Both groups were then flooded ‘with the original brine to which a chemical had been added that renders sand and clay surfaces preferentially oil wet, a so-called reverse-wetting agent. Very little change in resistivity was observed in cores containing only water. The group containing residual oil, however, showed resistivity increases of 100 to 200 per cent, ‘These experiments showed that the resistivity of a core containing oi could be altered by changing wet- tability of the core. Moreover, the possibility was in troduced that reverse-wetting agents might be employed as the basis for a logging method for identification of oil-bearing strata. Since behavior of a porous rock con: taining gas and water might be expected to be similar to that of a rock containing oil and water, such a meth- od should also be applicable to identification of gas- bearing zones. In principle the wettability of the invaded zone could be reversed without altering conductivity of the interstitial water or the hydrocarbon. saturation therein, Those strata showing significantly increased in- vvaded-zone resistivities would, therefore, contain hydro- carbons; those with no sigsificant change would be filed only with water. ‘Addition of a reverse-wetting agent to a hydrocarbon- bearing zone which is, by nature, already preferentially cil wet would not result in an enhancement of its re- sistivity. It is. generally belioved, however, that mast hydrocarbon-bearing strata are preferentially water wet(The possibility exists, of course, that some reservoirs ‘may be preferentially oil wet. In either the oil-wet or Water-wet case, the reverse-wetting technique may be useful in determining in situ wettability.) More impor- tant, those strata dificult to identify from the electric log by virtue of their high water saturations and cor- respondingly low resistivity are almost certainly preferen- tially water wet. Consequently, the reverse-wetting tech- nique should be a useful logging method for detecting the presence of hydrocarbon-bearing zones containing even small amounts of oil oF gas. With the objective of developing a useful logging technique, a laboratory investigation was initiated for development of a more complete understanding of the reverse-wetting phenomenon, and tests of the technique as a hydrocarbon-locating method were then made in the field, LABORATORY INVESTI ‘A number of points pertinent to use of the reverse wetting technique in locating hydrocarbon-bearing strata were explored in laboratory investigation. These points include type of reservoir rock amenable 10 the treat- ‘ment, nature and amount of the agent required, rate of altainment of increased resistivity and its persis- tence, effect of characteristics of oil in the rock on the resistivity inerease, and influence of temperature on the enhancement of resistivity. Experiments designed to elucidate these points are described in following sec- tions. GATION ‘Tyres of Reservoir Rock AMENABLE ro TREATMENT. To investigate the type of reservoir rock in which resistivity could be increased by addition of a reverse- wetting agent, 2 number of samples of sandstone, shaly sand, limestone and artificially prepared quartz cores \were prepared fo contain residual oil and brine. Another group of similar samples was saturated with brine only. Resistivities of corresponding samples in the two groups Were measured, Wetting characteristics of the samples were then changed from predominantly water wet to predominantly oil wet by flooding the samples with » dilute solution of a reverse-wetting agent dissolved in brine of the same resistivity as that used in saturating the cores originally. Resistivity of each sample was agsin measured. Results of these experiments are shown in Tables 1 and 2. Table 1 contains results obtained with samples ‘completely saturated with brine. It can be seen that only ant change resulted from contact with the agent. Table 2 shows the results obtained with cores containing brine and residual oil. In all eases the re- sistvity was increased significantly, From these experiments it can be expected that the resistivity of reservoir rock containing brine and residual oil is increased by addition of reverse-wetting agent re- sardless of the type of reservoir rock. NATURE AND AMOUNT OF AGENT REQUIRED As illustrated in Table 2 all reverse-wetting agents tested resulted! in an increase in resistivity of the cores containing brine and residual oil. From this it appears that the pertinent characteristic of the agent is its abil ity to render the rock surface preferentially wet to the hydrocarbon. An auxiliary experiment demonstrated that the action of the reverse-wetting agent in increasing re- sistivity is not due 10 a reduction in interfacial tension ieee tom Meory elening sald by gia Sola per se. A core containing residual oil was treated with 4 non-ionic surfactant, and it was observed that the ‘ore was not made oil wet. Resistivity of the core after {treatment with this agent’ was slighily lower than its original resistivity. In the experiments, tabulated in Tables 1 and 2, con- centration of reverse-wetting agent utilized was in each cease in the range of 2 to 5 per cent. Although no ex tensive investigation was conducted to determine per- missible limits of concentration, it was concluded on the basis of laboratory experiments that about 2 per Cent concentration of the reverse-wetting agent is proba- bly adequate. RATE OF ATTAINMENT OF INCREASED RESISTIVITY To study rate of attainment of the resistivity increase brought about by alteration of wettability, a Berea core containing residual oil and brine was placed in a con- ventional waterflooding apparatus so that the core re-sistivity could be measured while flooding was in prog- ress. Brine containing reverse-wetting agent was then flooded through the core at a rate of one pore volume every 140 seconds, Resistivity measurements were made periodically Results of this test are shown graphically in Fig. 1. There appeared to be no appreciable time lag between time of contact with the agent and the subsequent re- sistivity increase. Shown in Fig. 1 are transient effects duting periods of no flow. Resistivity under static conditions increased appreciably; it was 43 per cent higher than resistivity during flow. To clucidate this unexpected transient be- havior, another experiment was conducted with a water- wet Berea core containing residual kerosene in which the static and dynamic resistivities were determined when brine containing no reverse-wetting agent was passed through the core, For the latter case it was ob- served that the static value was only 13 per cent higher than the dynamic value. Hence, it was concluded that alteration of wettability leads to a considerable mag- nification of this transient effect ‘AS a result of this investigation it was concluded that, for all practical purposes, the resistivity increase associated with reversal of wettability is attained almost instantaneously after introduction of the agent. Persistence oF INDUCED RESISTIVITY INCREASE To determine length of time that the resistivity in- crease brought shout by a reverse-wetting agent per sists, use was made of @ Berea sandstone core contain- ing brine and residual kerosene. Resistivity of this core was measured. The core was then flooded with a few Pore volumes of a solution of 2 per cont coco amine acetate in brine, after which core resistivity was meas- ured periodically for several days. Results of this experiment are shown in Fig. 2, where core resistivity is plotted as a function of elapsed time. The resistivity increase in Berea sandstone associated with reverse wetting persisted for at least 79 days Another factor affecting persistence was studied, namely the influence of prolonged flushing with brine containing no additive on the resistivity increase induced by introduction of a reverse-wetting agent into an oil- bearing rock, A Berea core containing Lohmvm brine and residual Kerosene was treated with reverse-wetting ‘agent and then flushed with a copious volume of brine containing no agent, Core resistivity was measured pet- ‘odically. Results of resistivity measurements are shown in Fig. 3 as a function of the amount of brine flushed through the core. After 74 pore volumes of brine had been flowed through the core resistivity was reduced from a high of 99 to 64 ohm.m, which was still twice the resistivity before wettability of the core was altered ‘These observations indicate that increased resistivity resulting from introduction of a reverse-wetting agent persists over long periods of time, and that the effect persists even after extended flushing of treated rock with fan agent-free solution, Errect oF Type or HYDROCARRON ow Resistiviry INCREASE, ‘As a matter of convenience, all experiments discussed previously employed kerosene as the residual hydrocar- bon phase, To determine whether the same results could be obtained with crude oil as the residual hydrocarbon, aan experiment was performed using crude oil from the Conroe field, Monigomery County, Tex., in a Berea sandstone cote. Treatment of the core, which contained brine and Conroe crude at residual oil saturation, with a reverse-wetting agent resulted in a threefold resistivity increase; this demonstrated that results obtained with kerosene should be applicable to reservoir rocks which contain crude oil No experiments comparable to those described in preceding sections were performed in which gas was substituted for oil as the residual hydrocarbon phase. In auxiliary experiments, however, visual observation was made of the wettability behavior of glass surfaces treated by reverse-wetting agents and it was evident that re- verse-wetting agents in aqueous solution produce prefer- ential gas wettability. It is thus likely that treatment of & reservoir rock containing brine and gas at residual saturation would result in increased resistivity, EFFECT oF Hicit TEMPERATURE ow Restsriviry INCREASE Al experiments discussed previously were conducted at room temperature, approximately 70°F. To exam- ine effect of increased temperature on resistivity. in- crease, a Berea core containing brine and residual kero- sene was flushed with several pore volumes of a 1 per cent solution of coco amine acetate in brine, Resistivity of the core was measured. The core was then placed in a container filled with reverse-wetting solution and heated to approximately 150°F for five days, Resistivity at the end of this period was essentially the same as that before heating, indicating that no deleterious ef- fects on the resistivity increase were introduced by higher temperature, THEORY ‘Through laboratory experience we may postulate a ‘mechanism which aecounts for the increase in resis: tivity of an oi-containing porous rock on addition of a reverse-wetting ageat. Besa ingadaty Ki Cones | % Fic. 1—Resisrivry oF Bersa_ Cont Conatsine Rrsiwosi On (a) ‘Witte Fuowine. Ravensr wernine Soxtimon Tunaten Cone, ano (n) DOe "xe Pmcons oF No Frow, fe neta || T TT L Rovere lina Pegsisrence or Revense-vernine Resisrivery Txcxease' prea oh N= t cheaters TA Tey stop cnn [| | a nto ine lowed Tash Care Poe lanes Fro, 3-Eprecr of Bnixe Froooixe os Troween Restsriviny The increase in resistivity is caused by a redistribution of the liguids within the pores brought about by a change in the wetting of the surfaces (see Fig. 4). Fig. da shows a cluster of sand grains containing brine and a residual oil globule. Since brine js the wet ting phase and oll the non-wetting phase, «thin film of water separates the oi globule from the nearest sand grains, When a potential gradient is applied across this assemblage, current flows in the maze of capillaries con- taining brine ‘After passage of the roverse-wetting solution, the capillaries originally filled with brine ate costed with a layer of adsorbed ions which render sand surfaces oil wet, The oil globule is now able to grasp, s0 10 speak, the sand grains, and. moves into a new equilibrium configuration consistent with the new wettability con- dition. Such a configuration is shown in Fig. 4b. Now the oil ean more sharply restrict the flow of eurrent in the capillaries than it could when the matrix was com- pletely water wet. Thus, electic resistivity is increased Tn a shaly sample the adsorption of a cationic agent upon the shale surfaces may: sharply reduce the ef- fect of double-layer conductivity. This may inerease the resistivity of the sample slightly. However, laboratory work has shown that the change caused by this phe- nomenon is small when compared to the change caused by reverse wetting in a similar sample containing an oil saturation. FIELD TESTS Since the laboratory investigation demonstrated that the resistivity of porous rock containing brine and oil at residual saturation could be increased several-fold by addition of a reverse-wetting agent, plans were made for field testing the technique of locating hydrecarbon- Dearing strata by use of a reverse-wetting agent. ‘Two ways in which the reverse-wetting agent might be used were considered. One procedure consisted of (1) drilling through a suspected hydrocarbon-bearing zone with ordinary mud, (2) running an appropriate log, (3) displacing the original mud with a new mud for Tiquid containing a reverse-wetting agent, (4) dis- turbing the filter cake on the wall of the hole so that the agent might penetrate porous strata, and (5) run- ning a second log. Strata containing hydrocarbons were expected to exhibit an appreciably higher resistivity af- ter introduction of the agent. ‘Another method of employing the reverse-wetting technique consisted of adding the agent to the fluid used during drilling into a zone which might contain hydro- carbons. In this case there is not available for compari- son a log made without the use of the reverse-wetting agent, but on the other hand, the high resistivity in- oe (0) Resi Gaal in are Send (0 Na Ea Cogan Rss Sta es Potten Saat Fic, ¢-Mrctavisw of Revense-werrixe Tstervity, INCHvAst duced by the agent in the invaded zone should produce characteristic features on short-spacing logs. ‘Use was made of both of the foregoing methods in {esting reverse-wetting logging in the field. ‘A test conducted in California followed the procedure employing before and after logging. In this test the well ‘was drilled to total depth with natural mud; then the zone of interest was reamed with a reverse-wetting mud. Logs were run both before and after using the special mud. ‘A test was condueted in North Texas with the “sin- le-stage” procedure. In this procedure the reverse-wet- ting agent was added to the mud used in drilling the zone of interest, These two tests are described in the following sections. CauiFORNIA Fusco Test ‘The California well chosen for a field test was to be completed in an interval that had produced in the area for a number of years. In previous wells drilled in this field, great difficulty was experienced in delineating ‘the zones which would produce oil in commercial quan- tities and those which would produce only water. The electric logs were of limited use in this delineation be- ‘cause throughout the zone the water saturations caleu- lated from data obtained with the induction and Micro- [Log ranged from 75 to 100 per cont. It was hoped that completely oilfree sands could be detected by use of the reverse-wetting logging technique. ‘The test well was a fleld development well scheduled for a total depth of 7,450 ft. The well was drilled to 6,600 ft with an 8%-in, bit, At 6,600 ft hole size was reduced to 756 in., and the well was drilled t0 the totaldepth of 7,450 ft. At this point electric logs were run in the natural water-base mud used to drill the well. Following logging of the well, the natural mud was displaced with a starch-stablized mud which was ‘weighted with calcium carbonate, This mud would ac- commodate the reverse-wetting agent, The mud filtrate was designed to have approximately the same resistivity properties as filtrate from the original mud. To effect complete invasion of the reverse-wetting mud filtrate into the formation of interest, the 7%¢-in. hole was reamed with an 8%4-in. bit. (Auxiliary (esis in other wells indicated uniform invasion could not be obtained by disturbing the original mud cake with cementing scratchers in the presence of the reverse-wetting mud.) Following the reaming operation electric logs were run again, Since the reverse-wetting mud was designed to hhave nearly the samo resistivity properties as the natural ‘mud used to drill the hole, the before and after logs ‘could be compared directly. ‘The MicroLog obtained after reaming with reverse- wetting mud was radically different from that obtained before reaming. Portions of both MicroLogs are shown in Fig. 5. Whereas the before log was normal with posi- tive separation, ic., lower resistivity on the 1% 1 in. micro-inverse curve than on the 2-ia. micro-normal ‘curve, the after log revealed large increases in resistivity land negative separation in every permeable zone, (The negative separation, ie., higher resistivity on the 1% 1 in, micro-inverse curve, suggests the adsorption of the reverse-wetting agent in the form of a thin annulus immediately adjacent to the wellbore.) Tn addition, the resistivities shown on beth the 1- and 2-in, electrode- spacing curves were substantially Targer after reaming with the reverse-wetting mud. Resistivity increases i dicated by the 2-in, curves ranged from 80 to 250 per cent. Since a substantial increase in invaded-zone re- sistivity indicates presence of residual oil in the invaded zone, it was concluded that every zone within the reamed section of the hole contained some cil. This conclusion was confirmed by examination of all side- wall cores from the reamed interval. Fig. 6 shows a comparison of the MicroLaterologs obtained before and after reaming with the reverse: wetting mud, As was the case with the MicroLog, the after MicroLaterolog indicated increased invaded-zone resistivity in every permeable stratum within the reamed section of hole. ‘An unexpected result was observed when the be- fore and after potential curves, also shown in Fig. 6, ‘were compared. It was observed that the SP curve was developed in a normal manner when the before logs were run in the original mud. The SP curve obtained on the after logs, however, showed no development, The curve started at the shale base line and remained essen- tially at that value throughout the interval which was reamed with reverse-wetting mud. Upon entering the hole above the reamed section, the SP curve resumed a normal appearance, The reason for this behavior is not clear; however, auxiliary experiments suggest the depressed potential may result, in part, from a change in sign of the streaming potential when the filtrate flows through the cake of the special mud. Since the chemical ‘used was a cationic surface-active agent, adsorption on the clay surfaces could produce this effect. Nori Texas Fit Test In the North Texas fleld chosen for investigation of the single-stage procedure, the productive sand is ex- tremely dificult to delineate by use of electric logs, The potential is usually not well developed, and the resis- livity of the producing sand is virtually the same as that of overlying and underlying shales. Also, water satura tions of above 60 per cent are calculated from induc tion and MicroLogs run in wells in the area. The oil sand is thus not one which would normally be recos- nized as a productive member from examination of the usual electtic Togs alone. Because the productive zone is usually not recogniz~ able from normal electric log data, this field presented an ideal opportunity for testing reverse-wetting logging, ‘The decision was made to incorporate the agent in the ‘mud used in coring the pay and to evaluate results by comparing logs made in the test well with logs of nearby wells drilled with ordinary mud, PROCEDURE ‘The test well was drilled with a conventional water- Fic, 5—Contranison or Brross axo Arvin MicnoLocs, ‘Cattwounta Pista Trek Fie, 6—Conranison oF Lacs Osraiteo Devore ano Arran Reanive wir Revensewernive Me, Cacironvta Frstp Twat.‘base mud. Just above the producing horizon a special ‘mud containing the reverse-wetting agent was placed jn the hole, The mud was composed of ground oyster shells, starch and guar flour in fresh water; the re verse-welting agent was coco amine acetate added in sufficient amount to yield a concentration of about 4 per cent. (This particular wetting agent, though ef- fective, produced a severe foaming problem.) Care was taken to ensure that this mud had very nearly the same resistivity as muds used in drilling other wells in the field. The pay section was cored with this mud in the hole, using a diamond core barrel. Finally, an induc tion-electric log, a MicroLog, and MicroLaterolog were run in the wel Fig. 7 presents comparison of the micro-inverse ‘curves from the test well and the two offset wells. The ‘micro-inverse curves were used because they demon- strate most clearly resistivity in the zone very close to the wellbore. As shown in Fig. 7, the micto-inverse curve shows a marked increase in resistivity opposite the productive zone of the test well. In comparison, the micro-inverse curves of offset wells do not indicate a high resistivity. Fig. 8 shows a comparison of the MicroL.aterolog run in the test well and resistivity values obtained from treated and untreated cores from the producing interval of the test well. To obtain measurements on the cores, it was first necessary to restore the water-wet condi tion which existed before drilling with the special mud. A solution was injected into the cores to restore water wetness. They were then flushed with Kerosene and flooded to residual oil with brine. Once residual oil-brine saturation was established, resistivities were measured. The cores were rendered oil wet with the brine solution containing reverse-wetting agent, and the resistivity measurements repested, The brine solution used was adjusted to have a reiistivity close to the resistivity of the filtrate from the field mud at bottom-hole tem- perature. As shown in Fig. 8 the MicroLaterolog resis- tivity curve falls between the before and after resistivity values obtained with cores from the test well, This po- sition of the curve is expected because the reverse-wet- ting agent is adsorbed on the surfaces of sand nearest the wellbore, and the region farther in the formation will approach normal invaded-zone resistivity. ‘There fore, the MicroLaterolog records a resistivity some- where between the two extremes. In view of results obtained with the MicroLog, the Cae Wat A Tes ans wat 8 Fic, T-Noxrit Texas Fieto Test, 1 11% Micoanvinse Comes, 1939 Fic, 8—Conranisow oF Mictolaremotce wart Boron: axp Arvin Resieniviry Vatets OnraiNr ‘mira Comts rxoat Test Wet, Noxri ‘Texas Fiex Tua, MicroLaterotog and cores from the test well, it is con- cluded that the high resistivity observed in the pay of the test well was attributable to use of the reverse-wet- ting agent. CONCLUSIONS 1. Tt has been demonstrated ia the laboratory that addition of a reverse-wetting agent to a water-wet por- fous rock containing brine and oil at residual saturation results in a marked increase in resistivity of the rock, 2. Field tests have demonstrated that resistivity of cil sands, as measured by short-spacing logs, can be increased’ materially by introduction of reverse-wet- ting agent, 3. The reverse-wetting logging technique may be par- ticularly valuable in identifying hydrocarbons in thin beds, in highly invaded formations, in shaly formations ‘and ‘in formations containing high water saturations, 4. This logging technique may be useful in determin- ing the in situ wettability of earth formations ACKNOWLEDGMENT Significant contributions were made by a number of People who assisted in many phases of the development ‘work and im the successful conduct of the field experi ‘mentation, Among these were J. S. Osoba, F. M, Per kins, Jr, C. L, Prokop and R, A. Salathiel REFERENCES ichardson, J. G. Peskins, F, M., Jty and Owba, J. S Differences in Behasior of Fresh and ‘Aged Bast Texas Woodbine Cores", Trane. AIME. (1955) 20 86, 2 Keller, C. Var “Eiloct of Wettability on the Electrical Re- sistivity of Sand", Oi! and Gas Jour. (Jan. 5, 1988) Sl, 62 3. Licastro, P. H. and Kelle, G. Vor “Resistivity Meature- ments at a Criterion For Determining Fluid Distribution in the Bradford Sand", Prod. Monthly (May, 1993) 17, Tr ek