Patrick J. Shuler

An experimental study of wetting behavior and surfactant EOR in carbonates with model compounds

This study focuses on the mechanisms responsible for enhanced oil recovery (EOR) from fractured carbonate reservoirs by surfactant solutions, and methods to screen for effective chemical formulations quickly. One key to this EOR process is the surfactant solution reversing the wettability of the carbonate surfaces from less water-wet to more water-wet conditions. This effect allows the aqueous phase to imbibe into the matrix spontaneously and expel oil bypassed by a waterflood. This study used different naphthenic acids (NA) dissolved in decane as a model oil to render calcite surfaces less water-wet. Because pure compounds are used, trends in wetting behavior can be related to NA molecular structure as measured by solid adsorption; contact angle; and a novel, simple flotation test with calcite powder. Experiments with different surfactants and NA-treated calcite powder provide information about mechanisms responsible for sought-after reversal to a more water-wet state. Results indicate this flotation test is a useful rapid screening tool to identify better EOR surfactants for carbonates. The study considers the application of surfactants for EOR from carbonate reservoirs. This technology provides a new opportunity for EOR, especially for fractured carbonate, where waterflood response typically is poor and the matrix is a high oil-saturation target.

Branched Alkyl Alcohol Propoxylated Sulfate Surfactants for Improved Oil Recovery

Abstract This investigation considers branched alkyl alcohol propoxylated sulfate surfactants as candidates for chemcial enhanced oil recovery (EOR) applications. Results show that these anionic surfactants may be preferred candidates for EOR as they can be effective at creating low interfacial tension (IFT) at dilute concentrations, without requiring an alkaline agent or cosurfactant. In addition, some of the formulations exhibit a low IFT at high salinity, and hence may be suitable for use in more saline reservoirs. Adsorption tests onto kaolinite clay indicate that the loss of these surfactants can be comparable to or greater than other types of anionic surfactants. Surfactant performance was evaluated in oil recovery core flood tests. Selected formulations recovered 35–50% waterflood residual oil even with dilute 0.2 wt% surfactant concentrations from Berea sandstone cores.

A computational approach to predicting the formation of iron sulfide species using stability diagrams

A program has been developed for generating stability diagrams that combine the principles of the Pourbaix E-pH diagrams with a rigorous and predictive thermodynamic model for multicomponent, nonideal aqueous solutions. Since the diagrams are based on a realistic model for the aqueous phase, they are referred to as real-solution stability diagrams. They are valid for solutions ranging from dilute to concentrated (up to 30 mol kg−1) at temperatures up to 300 °C and pressures up to 1 kbar. The stability diagrams are used to predict the conditions that favor the stability of various iron sulfide species. For this purpose, the applicability of the diagrams is extended to include the prediction of both stable and metastable products. The diagrams indicate that the formation of iron monosulfide follows the FeHS+ → amorphous FeS → mackinawite → pyrrhotite replacement sequence. It is predicted that a transformation of iron monosulfides to pyrite may occur through greigite and/or marcasite. Greigite is predicted to be absent in strictly reducing environments. The predictions are in agreement with experimental data on iron sulfide formation in solution and/or at the iron/solution interface.

Evaluation of Effects of Selected Wax Inhibitors on Paraffin Deposition

Abstract Deposition from decane solutions of model paraffins such as n-C24H50 (C24), and n-C36H74 (C36), as well as a mixture of n-alkanes (C21 to C44) was examined with and without chemical wax deposition inhibitors. The device used to produce the deposits investigated was a “Cold Disk” Wax Deposition Apparatus (CoDWaD) capable of producing field like deposits with relatively small volumes of oil in minutes. It was found that most of commercial wax inhibitors tested could decrease the deposition of low molecular weight paraffins (C34 and below), while having little effect on the wax deposition for high molecular weight paraffins (C35–C44). In many cases, although the total amount of wax formed on the cold plate was reduced, the absolute amount of deposition for high molecular wax was actually increased. Therefore, the net effect of many commercial inhibitors is to make even harder wax under the tests conditions studied here. One intriguing result was that the addition of an oleic imidazoline c rrosion inhibitor improved the performance of two wax inhibitors tested. It was also observed that there are subtle differences in inhibitor performance depending on whether the test solutions are binary mixtures, synthetic wax mixtures, or crude oil.

Alkyl Polyglycoside-Sorbitan Ester Formulations for Improved Oil Recovery

Abstract We measured interfacial tensions (IFT) of aqueous alkyl polyglucoside (APG) systems formulated with sorbitan ester-type cosurfactants against n-octane. The study focused on low to ultra-low IFT systems which are relevant for enhanced oil recovery (EOR). In addition, we measured equilibrium adsorption concentrations of these surfactants and cosurfactants onto kaolinite clay, commonly found in oil reservoirs. We present one surfactant EOR laboratory flood experiment with one selected APG-sorbitan ester formulation with which we recovered 94% of initial oil in place (IOIP).

Analysis of the Influence of Alkyl Polyglycoside Surfactant and Cosolvent Structure on Interfacial Tension in Aqueous Formulations versus n-Octane

Abstract We studied the influence of molecular structural elements of alkyl polyglycoside (APG) surfactants on the interfacial tension (IFT) in aqueous formulations against n-octane. This included the analysis of alkyl and aryl chain length, type and number of sugar-ring head, anomers, addition of cosolvents and effect of salt addition. We found that longer alkyl or aryl chains lead to lower IFT, consistent with data recorded for commercial (mixed) APGs. APGs with only one sugar-ring head had lower IFT than their analog maltose derivates (two-ring head). Intriguingly the stereochemistry of the sugar head (i.e. galactose versus glucose) and the type of anomer showed a significant influence on IFT. The n-octyl-α-D-glucopyranoside anomer had a lower IFT than the corresponding β-anomer. 1-octanol and 1-hexanol were efficient cosolvents consistent with the datasets observed for commercial APGs. Salt addition reduced IFT. Functional groups (aldehyde, amide-methoxy) integrated into the molecular architecture of the APG skeleton were efficient in terms of significantly reducing IFT, suggesting a strategy for the molecular design of advanced APG surfactants. We discuss the results in the context of the hydrophilic-lipophilic deviation (HLD) concept, which we modified so that IFT values are discussed instead of phase behavior.

Dissolution of the barite (001) surface by the chelating agent DTPA as studied with non-contact atomic force microscopy

Abstract DTPA (diethylenetriaminepentaacetic acid) is a chelating agent widely used for removal of barium sulfate (barite) scale in the petroleum industry. In this paper we report ex-situ investigations of barite dissolution in deionized water and in 0.18 M DTPA aqueous solutions. Non-contact atomic force microscopy (NC-AFM) was used to observe dissolution on the BaSO 4 (001) cleavage surface. Dissolution was carried out at room temperature in a 10 ml reactor. Each sample was first etched in solution and dried before examination by NC-AFM. Dissolution on the BaSO 4 (001) surface took place via development of etch pits. In deionized water, triangular etch pits were observed on the (001) terraces at room temperature. And, zigzag shaped etch pits were found at the edges of steps. In DTPA solutions, etch pits on the (001) terraces were observed and these became deeper and longer with increasing time. The geometry of these etch pits was trapezoidal, and/or trapezohedral. To explain this characteristic morphology caused by dissolution we suggest that the active sites of one DTPA molecule bind to two or three Ba 2+ cations exposed on the (001) surface.

Evaluation of Effects of Selected Wax Inhibitors on Wax Appearance and Disappearance Temperatures

Abstract In this investigation, a light transmittance method was used to evaluate the wax appearance temperatures (WAT) and wax disappearance temperatures (WDT) of model paraffin compounds (n-C24H50 (C24) and n-C36H74 (C36)) in n-decane (C10) solutions both with and without wax inhibitors. The change in WAT at different paraffin concentrations in the presence of an inhibitor behaves as though there is a constant amount of paraffin removed by the inhibitor. However, the amount of apparent paraffin reduction by an inhibitor (e.g. 160 g of C24 by one gram of an inhibitor) indicates that the inhibition mechanism cannot easily be explained by a simple “sequestering” effect. Wax inhibitors that decrease the WAT tend to also increase the WDT. Most of the wax inhibitors tested at a dosage of 100 ppm did suppress the WAT of lower molecular weight paraffin (C24) solutions, but had little or no effect for higher molecular weight paraffin (C36) solutions. Side-chain length of polymethacrylate wax inhibitors is an important performance parameter. Of the three polymethacrylate wax inhibitors tested, the one with the longest alkyl side-chain (C18) had the most effect on suppressing the WAT and increasing the WDT of the binary mixtures (n-C10–n-C24 solutions).

Experimental Study of Surfactant Retention on Kaolinite Clay

Abstract We measured equilibrium surfactant retention on kaolinite clay for a large array of surfactants. We demonstrate that the mass balance measurements we used are a rapid way to screen surfactants in terms of their potential to be used in enhanced oil recovery applications. Surfactant classes investigated include: alkyl(aryl) sulfonates, ethylene oxide-propylene oxide copolymers, ethoxylated alkylphenols, alkyl polyglucosides, sorbitan ester ethoxylates, alkyl alcohol propoxylated sulfate sodium salts, gemini surfactants, sulfosuccinates and organo silicone-ethylene oxide-propylene oxide terpolymers. We identified several surfactants which had zero retention under the test conditions and which may therefore be suitable as enhanced oil recovery chemicals in surfactant flooding schemes. We discuss surfactant retention mechanisms on kaolinite clay and analyze surfactant structure-retention relationships for several surfactant classes.

Alkyl Polyglycoside/1-Naphthol Formulations: A Case Study of Surfactant Enhanced Oil Recovery

Abstract We present a case study of surfactant enhanced oil recovery using Alkyl polyglucoside/1-naphthol formulations. Alkyl polyglucosides are a green, non-toxic and renewable surfactant class synthesized out of agricultural raw materials. We measured interfacial tensions versus n-octane and viscosities of these formulations and conducted one coreflood enhanced oil recovery (EOR) experiment where we recovered 82.6 % of initial oil in place demonstrating that these formulations are efficient EOR agents.