Morrow, Norman R., SPE, New Mexico Petroleum Recovery Research Center Petroleum Recovery Research Center Lim, Hau T., SPE, New Mexico Petroleum Recovery Research Center Ward, Jill S., SPE, New Mexico Petroleum Recovery Research Center Summary Displacements in strongly water-wet cores; are compared with results of similar tests for a mixed wettability condition induced by a selected crude oil. Cores exposed to crude oil showed weakly water-wet imbibition behavior and 30 to 65% improvement in microscopic displacement efficiency. Other characteristics included clean breakthrough and low relative permeability to water at residual oil saturation. Flow visualization experiments with crude oil in micromodels showed improved oil recovery from pore bodies with oil trapping in pore throats. Capillary numbers for mobilization of residual oil from weakly water-wet systems were higher than for strongly water-wet systems. Contact-angle measurements showed that adsorbed transition metal ions at a high-energy surface could have a dominant effect on wetting behavior. Introduction Determination of reservoir wettability and its effect on oil recover are long-standing problems in reservoir engineering. Many researchers maintain that waterflood oil recovery is greatest under strongly water-wet conditions. Owens and Archer predicted steadily decreasing oil recovery as the water advancing contact angle increases. Other work has shown that wetting conditions other than strongly water-wet are frequently encountered and may actually be preferable. In 1955, Richardson et al. reported low residual saturations of kerosene to waterflooding in fresh cores from the East Texas field. Repeated alteration of oil- and waterfloods resulted in increased waterflood residual oil saturation (Sor) that was further increased by extraction between displacement tests. Water imbibition results indicated that a change in wetting behavior had occurred and that the extracted cores were more strongly water-wet than the fresh samples. Salathiel explained the phenomenon of fresh core behavior by postulating a mixed-wettability condition. Strongly oil-wet paths through the rock are generated at those parts of the pore surface in contact with crude oil, while the remainder stays strongly water-wet. Salathiel concluded that these paths are connected in consolidated media and allow oil to continue to flow even at very low oil saturations. Laboratory-prepared, mixed-wettability systems gave low Sor by extended waterflooding. Salathiel noted that the low Sor reported for the East Texas cores was achieved after flooding with 40 PV of water, a point not mentioned by Richardson et al. Salathiel did not report imbibition results for his mixed-wettability cores; thus, comparison with those of the fresh East Texas cores is not possible. The anomalously low Sor found for the East Texas field was ascribed to long-term gravity drainage rather than direct displacement by water-flooding. Low Sor for crude-oil displacements was reported by Rathmell et al. Imbibition tests established that most of the systems that gave decreased all trapping were weakly water-wet. Clean water breakthrough with little or no subsequent oil recovery was observed. Amott also found that Sor for weakly water-wet Berea cores was lower than for strongly wetted cores. The variation in oil recovery with wettability change is of interest for a number of reasons. Three of the most important are:prediction of oil recovery in the course of making economic evaluations of waterflooding,determination of the magnitude of Sor which is critical to the economic evaluation of tertiary oil recovery processes; andimprovement of waterflood recovery and perhaps tertiary recovery that may be achieved by wettability alteration. However, systematic and unambiguous studies of the effects of wettability are not easy to design or carry out. A major difficulty in working with oil/water interfaces at high-energy mineral surfaces is creation of well-characterized wetting situations. Several attempts have been made to relate wettability change to extent of reaction with silanizing agents, but none of the published procedures has gained general acceptance as a means of procedures has gained general acceptance as a means of providing a range of known wettability conditions. providing a range of known wettability conditions. Relationships between oil/water contact angles at solid surfaces and concentration levels of known compounds other than silanes are also available. However, difficulties in reproducing reported contact-angle measurements indicate that these systems are not likely to provide reliable wettability control in porous media, especially considering the added complexity that the pore surfaces may not correspond well to the carefully selected and prepared smooth mineral surfaces generally used for prepared smooth mineral surfaces generally used for contact angle measurements. Several studies have shown the importance of crude-oil components, especially the asphaltenes, in altering the wettability of mineral surfaces. SPEFE p. 89

Use of a high-speed centrifuge for capillary pressure measurements on low-permeability sandstones has been investigated. Curvatures for air/brine and air/decane displacements are compared. Capillary pressures of up to about 800 psi [5516 kPa] for gas displacing brine were extended Over an order of magnitude by measurement of isotherms for desorption of water. Capillary pressures measured by high-speed centrifuge merged satisfactorily with results derived from the desorption isotherms. No distinct irreducible water saturation was observed. Permeabilities to gas at various levels of water saturation were also measured and found to be generally consistent with previous relative-permeability measurements.

No abstract

Synthetic sulfonates for application in enhanced oilrecovery are of increasing interest. Because of the needto explore the range of candidates potentially available atvarious costs from the petrochemical industry, a series ofnine samples was prepared for distribution with financial suppose of the U.S. DOE. This paper briefly describesthe samples and, in more detail, the characterization ofthe samples for oil recovery. The characterization included determination of optimal salinity, stability ofaqueous dispersions in brines containing sodium chlorideand calcium ion, and oil recovery and loss of sulfonate in1-ft (0.305-m) Berea cores. Introduction Most current work in surfactant systems for enhanced oilrecovery is based on sulfonates, either petroleum(natural) or synthetic. The synthetic sulfonates discussedin this paper are those made by alkylation of an aromatic hydrocarbon with a selected olefin, followed by sulfonationof this alkylate. Interest in these synthetic sulfonatesis evident from numerous patents and publications fromseveral laboratories. The major published work in this area, by Reed andHealy, stems from earlier studies that generated seriousquestions as to the effect of fractionation of petroleumsulfonates when used in reservoirs. Interest in andwork with synthetic sulfonates has increased steadily inthe Sun Co. laboratories over the past years because offavorable experimental results. However, availablesamples of synthetic sulfonates have been limited; theydid not include agents that probably would be thelowest cost materials available from current petrochemicaloperations. With the question of cost effectiveness inmind and with the expressed interest of a number of oilrecovery laboratories, Sun approached the Energy R and DAdmin. with the following proposal:Sun wouldprepare large samples of a representative set of syntheticsulfonates,the New Mexico Petroleum RecoveryResearch Center would distribute the samples tointerested laboratories and would receive and distributeinformation from these groups, andthis informationwould include characterization studies on the sampleswith preliminary studies by the New Mexico and Sun laboratories. This work has now been completed. The Sun Applied R and D group in Marcus Hook, PA, did the preparative work. The samples are describedbriefly in a following section; complete description isavailable in Ref. 5. This paper describes characterization of the synthetic sulfonates by optimal salinityexperiments, studies of aqueous dispersions in selectedsodium chloride and calcium chloride concentrations, and oil-recovery experiments in 1-ft (0.305-m) Bereacores. Plans for this work required a decision on the levelof concentration of sulfonate to use. One philosophyexemplified in published work is that the level should below so that, for an acceptable total amount of sulfonate, the %PV of the slug could be as large as possible. Thisapproach is an advantage in efforts to improve theoverall conformance of the recovery system in areservoir. Some interesting results have been obtained with synthetic sulfonates at the level of 2% active concentration.In studies of the stability of aqueous dispersions asin the salinity grids, 1.5% sulfonate was used. Thisvalue is expressed in terms of the aqueous phase; nosignificant oil phase was present. SPEJ P. 226^

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