Surfactant-enhanced alkaline flooding

The focus of more recent work has been the use of relatively low concentrations of additives in other oil recovery processes. Of particular interest is the use of surfactants (qv) as CO2 (4) and steam mobiUty control agents (foam). Combinations of older EOR processes such as surfactant-enhanced alkaline flooding and alkaline—surfactant—polymer flooding show promise of improved cost effectiveness. 

Including a surfactant in the caustic formulation (surfactant-enhanced alkaline flooding) can increase optimal salinity of a saline alkaline formulation. This can reduce iaterfacial tension and increase oil recovery (255,257,258). Encouraging field test results have been reported (259). Both nonionic and anionic surfactants have been evaluated in this appHcation (260,261). 

Surfactants evaluated in surfactant-enhanced alkaline flooding include internal olefin sulfonates (259,261), linear alkyl xylene sulfonates (262), petroleum sulfonates (262), alcohol ethoxysulfates (258,261,263), and alcohol ethoxylates/anionic surfactants (257). Water-thickening polymers, either xanthan or polyacrylamide, can reduce injected fluid mobiHty in alkaline flooding (264) and surfactant-enhanced alkaline flooding (259,263). The combined use of alkah, surfactant, and water-thickening polymer has been termed the alkaH—surfactant—polymer (ASP) process. Cross-linked polymers have been used to increase volumetric sweep efficiency of surfactant—polymer—alkaline agent formulations (265). 

In buffered surfactant-enhanced alkaline flooding, it was found that the minimum in interfacial tension and the region of spontaneous emulsification correspond to a particular pH range, so by buffering the aqueous pH against changes in alkali concentration, a low interfacial tension can be maintained when the amount of alkali decreases because of acids, rock consumption, and dispersion [1826]. 

T. R. French and C. B. Josephson. Surfactant-enhanced alkaline flooding with weak alkalis. US DOE Rep NlPER-507, NIPER, February 1991. 

Both nonionic and anionic surfactants have been evaluated in this application (488,489) including internal olefin sulfonates (487, 490), linear alkylxylene sulfonates (490), petroleum sulfonates (491), alcohol ethoxysulfates (487,489,492). Ethoxylated alcohols have been added to some anionic surfactant formulations to improve interfacial properties (486). The use of water thickening polymers, either xanthan or polyacrylamide to reduce injected fluid mobility mobility has been proposed for both alkaline flooding (493) and surfactant enhanced alkaline flooding (492). Crosslinked polymers have been used to increase volumetric sweep efficiency of surfactant - polymer - alkaline agent formulations (493). 

Surface wave, 17 422. See also S-wave Surfactant adsorption, 24 119, 133-144 at the air/liquid and liquid/liquid interfaces, 24 133-138 approaches for treating, 24 134 measurement of, 24 139 at the solid/liquid interface, 24 138-144 Surfactant blends, in oil displacement efficiency, 13 628-629 Surfactant-defoamers surface tension, <5 244t Surfactant-enhanced alkaline flooding,... 

The point at which, supposedly, 50% of the acid species is transformed in salt corresponds to the half-neutrahzation, i.e., when half the alkahne required to reach the equivalence point has been added. This position corresponds to a buffer zone in which the variation of pH is small with respect to the amoimt of added neutralization solution (Fig. 14 left plot). Hence, in this region a very slight variation of pH can produce a very large variation of neutralization (Fig. 14 right plot), i.e., a considerable alteration of the relative proportion of AH and A . Far away from this pH, the opposite occurs. Consequently, the pH could be used to carry out a formulation scan, but the scale is far from hnear and the variation of pH does not render the variation of the characteristic parameter of the actual surfactant mixture that is at interface [77,78]. The appropriate understanding of the behavior of this kind of acid-salt mixture is particularly important in enhanced oil recovery by alkaline flooding [79,80] and emulsification processes that make use of the acids contained in the crude oils [81-83]. 

Liu Q, Dong M, Ma S, Tu Y (2007) Surfactant enhanced alkaline flooding for western canadan heavy oil recovery. Colloids Surf A 293 63-71... 

The use of chemicals to coax more oil out of the ground has been investigated for many years. Chemically enhanced methods are of three major types (1) polymer flooding (2) surfactant flooding and (3) alkaline flooding. 

Phase Behavior. The use of phase-behavior diagrams in surfactant-enhanced alkaline flooding is more complicated than in micellar-polymer flooding for several reasons. One reason is that phase behavior is very sensitive to the water-to-oil ratio employed. From surfactant mixing rules, varying the amount of oil present will vary the amount of petroleum soap... 

This book is written mainly for petroleum professionals. Because overwhelming parameters are needed to describe a chemical EOR process, it is not practical to measure every one of them therefore an effort has been made to collect, synthesize, and suimnarize available data, especially Chinese information that is inaccessible in Western literature. An effort has also been made to cover comprehensively the fundamental theories and practices related to alkaline (A), surfactant (S), and polymer (P) flooding processes, especially alkaline-surfactant-polymer (ASP) flooding that has barely been discussed in any enhanced oil recovery book in English. 

This paper presents observations on the difference in behavior of emulsification processes which can occur during surfactant and caustic flooding in enhanced recovery of petroleum. Cinephotomicrographic observations on emulsion characteristics generated at the California crude oil-alkaline solution interface as well as in the Illinois crude oil-petroleum sulfonate system are reported. The interdroplet coalescence behavior of oil-water emulsion systems appear to be quite different in enhanced oil recovery processes employing various alkaline agents as opposed to surfactant/polymer systems. 

Recently we have carried out laboratory tests (17, 18, 19) in which the sodium silicate was added directly to a dilute surfactant solution to recover oil. Such a process would be akin to alkaline flooding processes where a dilute surfactant is formed in-situ. In this case however the crude is lighter and does not contain the natural acids necessary to form surfactants in-situ. Therefore surfactant is injected and protected or enhanced by the sodium silicate such that a low tension waterflood is assured. Such a system is less complex and therefore more widely applicable than micellar/polymer techniques thus filling the void between the alkaline and micellar/polymer EOR processes. 

Alkaline flooding is based on the reaction that occurs between the alkaline water and the organic acids, naturally occurring in some crudes, to produce in-situ surfactants or emulsifying soaps at the oil/water interface. Recent literature (i-J.) summarizes several proposed mechanisms by which alkaline water-flooding will enhance oil recovery. These mechanisms include emulsification and entrapment, emulsification and entrainment, and wettability reversal (oil-wet to water-wet or water-wet to oil-wet). Depending on the initial reservoir and experimental conditions with respect to oil, rock and injection water properties, one or more of these proposed mechanisms may be controlling. 

Enhanced oil recovery by alkaline flooding was proposed some years ago as an inexpensive way to take advantage of the acid components that occur naturally in some crude oils [80,81]. The stabilization of oil-in-water emulsions can also be attained this way. In these cases the carboxylic acid contained in the crude oil adsorbs at the O/W interface, where it is neutralized into a carboxylic salt with surfactant properties such as interfacial tension lowering or emulsification. Fatty amines and their cationic counterparts at low pH are routinely used to stabilize asphalt emulsions for roads and pavement. 

In the alkaline flood process, the surfactant is generated by the in situ chemical reaction between the alkali of the aqueous phase and the organic acids of the oil phase The surface-active reaction products can adsorb onto the rock surface to alter the wettability of the reservoir rock and/or can adsorb onto the oil-water interface to lower the interfacial tension. At these lowered tensions (1-10 dyne/cm), surface or shear-driven forces promote the formation of stable oil-in-water emulsions or unstable water-in-oil emulsions the nature of the emulsion phase depends on the pH, temperature, and electrolyte type and concentration. These different paths of the surface-active reaction products have created different recovery mechanisms of alkaline flooding. The four alkaline recovery mechanisms which have been cited in the recent literature are (i) Emulsification and Entrainment, (ii) Emulsification and Entrapment, (iii) Wettability Reversal from Oil-to Water-Wet, and (iv) Wettability Reversal from Water- to Oil-Wet. These four mechanisms are similar in that alkaline flooding enhances the recovery of acidic oil by two-stage processes. 

Uses Interfadal tension reducing agent for use In alkaline surfactant polymer flooding for enhanced oil recovery... 

Krumrine, P.H. Ailin-Pyzik, I.B. Falcone, J.S., Jr. Campbell, T.C. "Surfactant Flooding III The Effect of Alkaline Chemicals on the Adsorption of Anionic Surfactants by Clays", presented at the "ACS Symposium on the Chemistry of Enhanced Oil Itecovery", Atlanta, GA, April 2, 1981. Hazel, J.F. J. Phys. Chem. 1945, 520. 

In chemical flooding processes for enhanced oil recovery, alkaline chemicals can be useful for hardness ion suppression or removal, reaction with acidic crude oils to generate surface-active species, reduction in surfactant adsorption on reservoir rock surfaces, changes in interfacial phase properties, mobility control and increased sweep efficiency, oil wettability reversal and increased emulsification. 

There are two additional types of chemical flooding systems that involve surfactants which are briefly mentioned here. One of these systems utilizes surfactant-polymer mixtures. One such study was presented by Osterloh et al. [72] which examined anionic PO/EO surfactant microemulsions containing polyethylene glycol additives adsorbed onto clay. The second type of chemical flood involves the use of sodium bicarbonate. The aim of the research was to demonstrate that the effectiveness of sodium bicarbonate in oil recovery could be enhanced with the addition of surfactant. The surfactant adsorption was conducted in batch studies using kaolinite and Berea sandstone [73]. It was determined that the presence of a low concentration of surfactant was effective in maintaining the alkalinity even after long exposures to reservoir minerals. Also, the presence of the sodium bicarbonate is capable of reducing surfactant adsorption. 

It also reduces adsorption of the (mostly anionic) surfactant on the reservoir rock, essentially by enhancing the negative surface charge. In some cases (alkaline-polymer floods), where there are high levels of saponifiable crude oil acids present in the crude oil (high acid number) added surfactant is not even required. The polymer is present to assist in mobility control and to ensure that the injected chemical slug remains intact and promotes the formation of an oil bank ahead of it. 

Recent laboratory studies have demonstrated the potential utility of borates as alkaline agents in chemical enhanced oil recovery. Compared with existing alkalis, sodium metaborate has an unusually high tolerance toward the hardness ions, Ca + and Mg +, paving the way for the implementation of alkali-surfactant-polymer floods for the large number of high-hardness saline carbonate reservoirs. In the absence of surfactants, borate solutions exhibit a strong tendency for spontaneous imbibition, or uptake into oil-wet or mixed-wet carbonate cores, with consequently improved recovery of oil compared with solutions of other salts and alkalis. 

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