Alkaline flooding emulsification

Huang and Yu (2002) observed that emulsification was not completely reversible. When the dynamic IFT reached ultralow, emulsification occurred. Even when dynamic IFT went up, emulsified oil droplets did not easily coalesce. In alkaline flooding, emulsification is instant, and emulsions are very stable. From this emulsification point of view, the dynamic minimum IFT plays an important role in enhanced oil recovery. From the low IFT point of view, we may think we should use equilibrium IFT because reservoir flow is a slow process. However, the coreflood results in the Daqing laboratory showed that when the minimum dynamic IFT reached 10 mN/m level and the equilibrium IFT was at 10 mN/m the ASP incremental oil recovery factors were similar to those when the equilibrium IFT was 10 mN/m (Li, 2007). One explanation is that once the residual oil droplets become mobile owing to the instantaneous minimum IF F, they coalesce to form a continuous oil bank. This continuous oil bank can be move even when the IFT becomes high later. Then for this mechanism to work, the oil droplets must be able to coalesce before the IFT becomes high. It can be seen that it will be more difficult for such a mechanism to function in field conditions rather than in laboratory corefloods. This mecha-... 

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]. 

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]. 

From the previous discussions, we can see that ultralow IFT cannot be reached in alkaline flooding. The incremental oil recovery is not correlated with the IFT or crude acid number. The low IFT mechanism may not be the dominant mechanism. However, a reasonably low IFT is required for emulsification to occur, which is another proposed mechanism and summarized in the previous section. 

In ASP flooding, alkaline, surfactant, and polymer have different effects on relative permeabilities. Table 13.2 shows our attempt to summarize these effects compared with waterflood. From Table 13.2, we can see that the effect of alkaline flood in terms of emulsification is similar to the polymer effect, whereas its effect in terms of IFT is similar to the surfactant effect. Less rigorously, we may say that only polymer reduces k, and only surfactant reduces IFT. In ASP flooding, the viscosity of the aqueous phase that contains the polymer is multiplied by the polymer permeability reduction factor in polymer flooding and the residual permeability reduction factor in postpolymer water-flooding to consider the polymer-reduced k effect. Then we can use the k curves (water, oil, and microemulsion) from surfactant flooding or alkaline-surfactant flooding experiments without polymer. 

Chapter 10 on alkaline flooding lists emnlsiflcation as one important mechanism in oil recovery. Experiments showed that if the color of produced fluid was dark brown, and the water color was dark yellow, the oil was emulsified. In these experiments, the oil recovery was in the range of 18 to 22%. If water and oil came out of the core alternately, and the water was clear, the oil was not emulsified. In these cases, the oil recovery was in the range of 14 to 16% (Cheng et al., 2001). In other words, emulsification increased the oil recovery factor by abont 5%. Many wells in Daqing ASP applications showed that if the produced fluids were more emulsifled, the decrease in water cut would be higher. 

Greater improvements in Enhanced Oil Recovery by alkaline flooding occurred in linear core floods where more in-situ emulsification was observed ... 

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. 

The recovery of naturally acidic oils by alkaline flooding fits into the phase alteration category. The recovery mechanisms of these floods are varied since the surface active salts, which are formed by the in situ acid-base reaction, can adsorb onto the oil-water interface to promote emulsification or can absorb onto the rock surface to alter wettability. The exact recovery mechanism, recently reviewed by Johnson (3) depends on the pH and salinity of the aqueous phase, acidity of the organic phase and wettability of the rock surface (4,5). In this study an additional alkaline recovery mechanism is explored. This mechanism. Emulsification and Coalescence, depends on the valency of the electrolyte as well as the pH and salinity of the aqueous phase. The Emulsification and Coalescence mechanism for the recovery of acidic oils is similar to the Spontaneous Emulsification mechanism suggested by Schechter et al. (6) for the recovery of nonacidic oils with petroleum sulfonate solutions. 

Mechanistic interpretations The results of the dynamic and equilibrium displacement experiments are used to evaluate and further define mechanisms by which alkaline floods increase the displacement and recovery of acidic oil in secondary mode and the tertiary mode floods. The data sets used in the mechanistic interpretations of alkaline floods are (a) overall and incremental recovery efficiencies from dynamic and equilibrium displacement experiments, (b) production and effluent concentration profiles from dynamic displacement experiments, (c) capillary pressure as a function of saturation curves and conditions of wettability from equilibrium displacement experiments, (d) interfacial tension reduction and contact angle alteration after contact of aqueous alkali with acidic oil and, (e) emulsion type, stability, size and mode of formation. These data sets are used to interpret the results of the partially scaled dynamic experiments in terms of two-stage phase alteration mechanisms of emulsification followed by entrapment, entrainment, degrees and states of wettability alteration or coalescence. 

The emulsification and entrapment mechanism is illustrated in the pressure and production history of the tertiary alkaline flood. 

Emulsification and wettability alteration Increases in the recovery rate and the microscopic mobilization efficiency of residual oil were observed in high pH/high salinity and moderate pH/high salinity alkaline floods. These increases are due to the formation of W/0 emulsions in the presence of a univalent electrolyte. Bulk phase experiments of earlier section indicate that the salt concen-... 

Ultra-low tension In the alkaline flooding of acidic acids, some reduction in interfacial tension (from 30 to approximately 10 1 dynes/cm) is necessary for the emulsification and subsequent mobilization of waterflooded residual oil by the previously discussed phase alteration mechanisms. The residual oil may also be mobilized and produced by a low-tension displacement process which is similar to surfactant flooding if the interfacial tension can be further reduced to ultra-low values (10 to 10 dynes/cm). 

The results of the tertiary and Ca(0H)2 secondary floods are presented in Figures 13 and 14. In the waterflood, breakthrough of the flood water occurred after injection of 0.6 pore volumes of distilled water. The secondary waterflood recovered 71.7 percent of the original oil in place. In the subsequent tertiary mode alkaline flood, oil appeared in the effluent after 1.2 pore volumes of calcium hydroxide were injected into the waterflooded core. The tertiary oil production was delayed because a finite residence time is required for emulsification of the entrapped residual oil, coalescence of the water-in-oil emulsion and subsequent mobilization of the coalesced droplets into an oil bank. 

It was determined from dynamic displacement experiments that alkaline flooding of acidic oils with hydroxides of certain divalent cations increased the production and recovery efficiencies above that obtained by alkaline floods with hydroxides of univalent ions with or without high electrolyte concentration. The increased efficiencies resulted from an Emulsification and Coalescence mechanism. 

Alkaline Floods. Alkaline floods, typically using sodium hydroxide, generate surface active products by an in-situ chemical reaction between the injected alkali and the organic acids of the crude. Four possible mechanisms [95] are responsible for the recovery of oil by alkaline floods (1) emulsification and entrainment, (2) emulsification and entrapment, (3) wettability reversal from oil-wet to water-wet, and (4) wettability reversal from water-wet to oil-wet. One example in the literature of wettability alteration by alkali [96] was reported for an offshore field in the Gulf of Mexico fhat had a low recovery factor from primary production. The wettability of this reservoir was found, using the... 

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. 

The improved production efficiency of the NaOH/NaCl flood resulted from the formation of W/0, water-in-oil, emulsions under the limited shear conditions. The alkaline phase imbibes into the oleic phase as a result of the interfacial chemical reaction. The swollen oil phase, together with its altered configuration, reduces the area available for the passage of the alkaline floodwater. The produced water-oil ratio, WOR, decreases as a result of the lowered water mobility. The consistent presence of a light, emulsion phase at the very end of the oil production stage indirectly confirms the occurrence of the in situ emulsification step. The production efficiency increases with decrease in injection rate because of mass transfer limitations of the interfacial chemical reaction hydrodynamic effects would act in the opposite direction. The degree of in situ emulsification and wettability alteration, and the correspondent mobility reduction, depends on the residence time of the reactants in the core. 

The incremental production of acidic oil by moderate pH (buffered) /high salinity alkaline systems occurred by what is believed to be a complete wettability reversal mechanism. Complete wettability reversal is suggested by the magnitude of the measured contact angle, 170° but not by the wettability index of the porous media. The results of the secondary and tertiary buffered floods appear to confirm the experimental results of Cooke et al. (4) the work of these researchers is discussed in a later section. It will be shown that this mechanism is not a direct extension of the emulsification and partial wettability reversal mechanism. 

Recovery of acidic oils with alkaline agents by an emulsification and coalescence mechanism Calcium hydroxide [Ca(0H)2] was used to verify the emulsification and coalescence concept since, as suggested by the theoretical and experimental evidence of an earlier section, the carboxylic salts of divalent ions form unstable emulsions of water-in-oil. The emulsification and coalescence concept was quantitatively verified by secondary and tertiary flooding of partially oil-saturated sandpacks. A tertiary chemical flood with Ca(0H)2 (pH = 12) recovered 44 percent of the waterflood residual oil from a 3.5-darcy Ottawa sandpack the oil had an acid number of 2 and a viscosity of 1.5 cp. A secondary caustic flood with Ca(0H)2 (pH = 12.32) recovered 82.3 percent of the original oil in place from a 0.25-darcy Ottawa sandpack the oil phase in this secondary flood had the same physical and chemical properties as the oil phase used in the tertiary mode flood. It should be noted that the microscopic mobilization efficiencies of these... 

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. 

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