Adsorption of EOR Chemicals Under Laboratory and Reservoir Conditions, Part III: Chemical Treatment Methods
Authors: Levitt David , Bourrel Maurice 
Published: March 2016

Abstract
This is the final installment in a series of three papers examining iron mineralogy and its effect on surfactant adsorption in reservoir and outcrop rock samples. The goal of these studies is to establish best practices for obtaining surfactant adsorption values representative of those in a reduced oil reservoir, despite performing experiments in an oxidizing laboratory atmosphere.
This article follows two others examining the abundance and form of iron in the reservoir and in core samples (Part I: Levitt et al., 2015), and a proposed core restoration technique utilizing iron-reducing bacteria (Part II: Harris et al., 2015). In this Part III, chemical reduction methods are examined.
Surfactant retention is a leading uncertainty in economic forecasting of chemical EOR, in large part due to the order-of-magnitude effects of artifacts such as improper core preservation. The industry standard is to (a) limit atmospheric contact of cores to the extent feasible, and (b) when necessary, reduce oxidized cores using strong reducing agents such as sodium dithionite, along with buffering and chelating agents such as sodium bicarbonate and EDTA or sodium citrate. However few studies have been performed to determine whether such invasive treatments are necessary, or what unintended effects the use of such reactive chemicals may have.
The most striking conclusion from these studies is the lack of clear evidence of any advantage of electrochemical reduction versus a simpler treatment with chelators such as sodium citrate or EDTA. Wang (1993) suggests that oxidation of reservoir cores leads to higher surfactant adsorption due to the reduction of clays, which yields a more negative surface charge. Static experiments with montmorillonite clay, as well as an oxidized outcrop containing significant clay and iron content, illustrate that rinsing with non-reducing agents such as sodium bicarbonate, EDTA, or sodium citrate can lower adsorption as much as a strong reducing agent such as sodium dithionite. In the case of montmorillonite, cation exchange appears to be the mechanism by which adsorption is lowered, and so NaCl alone is sufficient to lower adsorption to near-zero values. For the iron- and clay-containing outcrop material, initial measurements indicating "adsorption" far in excess of a dense bilayer were due in fact to the precipitation of sulfonate surfactant with calcium, which eluded from the dissolution of small amounts of anhydrite. An alkyl alkoxy sulfonate surfactant showed higher calcium tolerance, and did not yield "multilayer" adsorption when equilibrated with the anhydrite-containing core sample.
While treatment with a citrate-bicarbonate-dithionite solution does indeed lower adsorption several-fold further, solutions of either sodium bicarbonate or EDTA are at least as effective, and sodium citrate is almost as effective. These non-reductive treatments remove small amounts (~0.1% – ~0.2% of rock mass) of Fe and Al, and fines are invariably apparent in treatment fluids, both of which suggest removal of small amounts of trivalent Fe/Al colloids. Wang (1993) suggests reduction or removal of trivalent iron from clay surfaces as a possible mechanism of lowered adsorption under electrochemically reducing conditions. These results suggest that removal of trivalent cations, with concomitant lowering of anionic surfactant adsorption, is possible with non-reductive chelators such as sodium citrate or sodium EDTA. Sodium bicarbonate is equally effective at lowering adsorption, but does not result in elution of Fe or Al, indicating that these are likely reprecipitated. PIPES buffer, which is used in biological applications for its low propensity to form ligands, lowers adsorption as much and no more than a 10% NaCl rinse, suggesting only anhydrite removal and possibly cation exchange with clays occurs.
While these results suggest that non-reductive means may be used to remove artifacts introduced by core oxidation, they come with an important caveat: even rinsing with a brine solution can result in significant alteration of mineralogy. The use of chelating agents will invariably result in dissolution of any soluble minerals present such as gypsum or anhydrite, which can be an important contributor to surfactant (in particular ABS) consumption.
In cases where iron removal is necessary due to polymer degradation issues, PIPES buffer is proposed for use as an alternative to bicarbonate, the latter having a greater tendency for ligand formation. The combination of borohydride and bisulfite is suggested as an alternative to dithionite as a reducing agent, resulting in more complete iron removal under some conditions, and anecdotally less tendency for polymer degradation upon subsequent oxidation, though both of these claims should be verified.