Insight into the Chemistry of Surfactant-Based Enhanced Oil Recovery Processes
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history of surfactants used for enhanced recovery in oil and gas and chemicals combinations in surfactants.
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Recent Patents on Chemical Engineering,
2009,
2,
1-10
1 1874-4788/09 $100.00+.00 © 2009 Bentham Science Publishers Ltd.
Insight into the Chemistry of Surfactant-Based Enhanced Oil Recovery Processes
Benyamin Yadali Jamaloei*
Chemical & Petroleum Engineering Department, Schulich School of Engineering, University of Calgary, 2500 University Drive NW, Calgary, Alberta T2N 1N4, Canada
Received: October 14, 2008; Accepted: November 12, 2008; Revised: November 24, 2008
Abstract:
During the past several decades, significant and considerable research has been carried out on secondary and tertiary recovery of trapped residual oil remaining within the producing formations underground despite the efficient, current primary production strategies and methods. Methods have been sought of increasing oil recovery, while revamping and improving the economic viability and efficiency of operations.
One method that has received much attention and intensive study over these past decades is the use of surfactant-based chemical flooding. Initial patents and laboratory tests have shown conclusively that chemical solutions and slugs including surfactants, remove considerable oil from the porous medium normally trapped after initial waterflooding. Oil recovery processes by means of surfactant micellar solutions or microemulsions have included the injection of slugs of varied compositions. Patents on surfactant-based enhanced oil recovery processes (such as dilute surfactant flooding, surfactant/polymer flooding, and alkaline/surfactant/polymer flooding) have been issued, starting from the 1920’s and particularly after the 1960’s, when the technology was put on a scientific basis. These patents were generally concerned with the chemistry of surfactant-based enhanced oil recovery processes including envisioning the use of chemical solutions (slugs) to decrease the surface tension between oil and the flooding medium, screening of surfactants for oil recovery efficiency, chemical (surfactant) slug designs and formulation to mobilize residual oil, documenting petroleum sulfonates useful in surfactant flooding, and other important factors in the chemistry of surfactant-based chemical flooding processes. Moreover, evaluation and determination of optimum chemical systems (slugs) for the best economics for a specific field application have been disclosed and documented in several large oil companies’ patents in the surfactant-polymer area. In this article, a full-fledged review of the patents on different aspects of the chemistry of surfactant-based enhanced oil recovery processes is presented.
Keywords
: Surfactant, enhanced oil recovery, chemistry, chemical slug, patent.
INTRODUCTION
Technically, chemical flooding is regarded as a general term for injection processes that inject chemical solutions (slugs or systems) into the reservoir. Surfactant-based substances, and/or alkali are used in solution to reduce surface tension between oil and water in the reservoir, whereas polymers are deployed to improve displacement sweep efficiency. Micellar-polymer and alkaline flooding are regarded as the two major chemical flooding processes. Micellar flooding (also known as microemulsion flooding or surfactant flooding) is a process in which a surfactant slug is injected into the formation followed by a larger slug of water containing polymer (normally a high-molecular-weight polymer) which improves mobility and sweep efficiency. Different forms of surfactant-based chemical flooding have been reported in the literature (alkali/surfactant/polymer (ASP) flooding, surfactant/polymer (SP) flooding, surfactant flooding, dilute surfactant flooding, etc.). The injection scheme for a surfactant-based chemical flooding includes injecting first a preflush, a chemical solution, a mobility
*Address correspondence to this author at the Chemical & Petroleum Engineering Department, Schulich School of Engineering, University of Calgary, 2500 University Drive NW, Calgary, Alberta T2N 1N4, Canada; Tel: +1 403 543 7917; E-mail: byadalij@ucalgary.ca
buffer and, finally, a driving fluid, which displaces the chemicals and the developed oil bank towards producer. In general, surfactant slugs are composed of a hydrocarbon phase, surfactant, cosurfactant and an aqueous phase. The literature contains numerous ternary diagram representations for these components. These phase diagrams reveal the various phases that may form and develop in the reservoir as residual oil is mobilized and displaced towards production well. In the literature, surfactant slug has also been referred to as micellar solutions, microemulsions, soluble oils, swollen micelles, etc. The primary purpose of a surfactant slug is to lower interfacial tension and displace the trapped residual oil normally after reservoir has been flooded by water. The technical and patent literature contains a number of surfactant slug designs and formulations and variety of techniques that are used to screen surfactant slugs for use as potential oil recovery agents. Adsorption of surfactants within surfactant slug on minerals is an important aspect of any surfactant-based chemical flooding. It is regarded as a major cause of surfactant retention and slug breakdown. This has been one of the active research areas in chemical enhanced oil recovery. Regarding the above general discussion on surfactant slug, one would expect a seriously complex chemistry for the design and implementation of the chemical slug in all
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Recent Patents on Chemical Engineering,
2009
, Vol. 2, No. 1 Benyamin Yadali Jamaloei
surfactant-based enhanced oil recovery processes. This becomes even severe when considering that chemistry of petroleum sulfonates is extremely complex. Since a petro-leum feedstock contains variety of chemical structures. Moreover, individual components of a chemical slug vary in composition, with many patented micellar formulas. Hence, evaluations to determine which chemical slug offers the best economics for a specific field application are often complex since an infinite array of chemical variables must be considered for this evaluation task. Petroleum sulfonates and useful chemical slugs in surfactant flooding have been disclosed in several patents. However, virtually there is not enough detailed information in the non-patent technical literature. In the subsequent sections, a brief overview of some important patents on the chemistry of surfactant-based chemical flooding is presen-ted. These patents have focused on the proper formulation of chemical slugs and appropriate design of surfactant-based chemical flooding processes.
EARLY PATENTS
In the patent history of surfactant-based chemical enhanced oil recovery (EOR), for the first time, in 1927, a patent was issued to Atkinson. In that patent, he proposed that surface tension between crude oil and reservoir rock can be reduced using soap or other aqueous solutions [1]. The technical and patent literature bears several surfactant slug design methods and formulations in the area of surfactant-based enhanced oil recovery processes. Most of these patents described different formulations of chemical solutions including surfactant, cosurfactant, hydrocarbon-water and or salt concentrations which result in specific slug design and property [2-9]. In 1959, Holm and Bernard [10] proposed that surfactant adsorption in water-wet porous medium can be reduced by injecting 0.1-0.3% concentration of surfactant dissolved in a hydrocarbon solvent with a low viscosity. In l961, Csaszar [11] documented the use of a mixture of an anhydrous soluble oil and a nonaqueous solvent containing up to 12% surfactant. In 1962, Gogarty and Olson [12] cited the use of microemulsions in a new miscible-type recovery process known as Maraflood. The Gogarty and Olson patent suggested the injection of a small fraction of the pore volume of micellar solution containing a surfactant concentration greater than about 5%. Patents have been issued to Jones [13, 14], in 1967, claiming the use of high-water-content, oil-external microemulsions and water-external micellar dispersions in oil recovery. In a relatively different ground, Harvey [15] patented a process using dead bacterial and/or yeast cells to carry nonionic surfactants [poly(ethylene oxide) ethers or thioethers] as EOR slugs through the reservoir. Using such slugs in laboratory sand column reservoir models, he obtained 20-30% recovery of residual oil.
PATENT SURVEY 1970-1989
Novel cost-efficient design of chemical slugs for EOR purposes has been always of particular concern over the past decades. What was disclosed in the early patents was continuously followed to be covered in the next several decades with the basic difference that some other modern methods for chemical slug design started to emerge. Roszelle [16] discussed a process in which a water-external micellar dispersions contacts with air or nitrogen to form (in-situ or on the surface) a stable foam. This micellar dispersion contained hydrocarbon, surfactant, and water (50-95% by volume). In the same year, new combinations of surfactants and bacteria were suggested for use in EOR drive fluids. Wagner and Stratton [17] and Hitzman [18] suggested that the commercial surfactant-treated dead bacterial cells can be deployed in EOR drive fluids by eliminating the requirement for injecting live bacterial cells into a reservoir for effective channeling of the injection water. Also, some novel EOR chemical processes and methods were started to emerge in the number of patents in the chemical EOR area in 1970’s. A process for the recovery of oil from an oil reservoir was proposed by Burdyn
et al.
[19]. Surfactants are formed within the reservoir by injection of an aqueous alkaline solution (and optionally followed by a second alkaline slug containing a thickening agent) and neutralizing the organic acids in the reservoir oil. The injected solution contained sufficient alkaline agent to create a pH within the range of 11.5-13 and a monovalent salt within the range of 0.5–2.0 weight percent. Screening of petroleum sulfonates- which are generally known as the most available and commercial types of surfactants- and manipulation of their combination in a chemical slug has been always of particular interest to the researchers. Plummer
et al.
[20] invented an aqueous petroleum sulfonate mixture which contained, at least, two different petroleum sulfonates. The implemented sulfonates had an average equivalent weight within the range of about 390–450. The hydrocarbon portion of the sulfonate had an average aliphatic to aromatic proton ratio within the range of about 4–20 moles per mole. Use of some hydrocarbon solvents together with some colloidal materials in a given chemical slug has been also presented in some patents. Specifically, in 1976, a method was invented by Christopher
et al.
[21] for recovering oil from reservoirs which contained both oil and an aqueous phase. According to the proposed method, fluid included a slug of a mixture of hydrocarbon solvent, colloidal silica, water and a high molecular weight polymer. This slug of chemical mixtures then is followed by another fluid which can drive the chemical solution (slug) within the porous medium. They also invented a novel displacing fluid design for the above-cited process. Use of sacrificial systems in chemical EOR, was disclosed in some patents. In one of these important patents, recovery of oil from a reservoir by use of an alkaline agent-sulfonate surfactant system in conjunction with the injection of a sacrificial system- which contains an inorganic polyphosphate and an alkali metal carbonate- was proposed by Chang’s patent [22] in 1976. An aqueous initiation slug and an alkaline are injected into the reservoir. Aqueous initiation slug contained an inorganic polyphosphate, and alkali selected from the group consisting of alkali metal and ammonium hydroxides. In this invention, the pre-flush slug is followed by the injection of surfactant slug which contains an alkaline agent and a sulfonate surfactant. After injection
Chemical Aspects of Surfactant-based EOR Recent Patents on Chemical Engineering,
2009,
Vol. 2, No. 1
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of the surfactant slug, an aqueous driving fluid is injected in order to displace the oil toward a production system [22]. Some patents have focused on use of chemical slugs to specifically alter the wettability of formations in order to enhance the oil recovery. As a particular instance, in 1977, Needham
et al.
[23] filed for a patent specifying a newly designed process according to which the quantity of oil recoverable from an already waterflooded predominantly oil-wet formation could be increased. This can be achieved by passing a first solution through the formation to change the formation from its oil-wet to a water-wet state. The first solution then is followed by passing a second solution which has high interfacial tension with the oil throughout the formation. This will force the oil from the small pores of the formation into larger ones. Finally, a third solution is passed which has low interfacial tension with the oil in the reservoir. They also cited that passing a mobility buffer-solution through the reservoir to prevent viscous fingering and consequent channeling, and finally passing the driving fluid through the formation completes this new chemical EOR process design [23]. Recovery of oil from oil reservoirs by waterflooding employing an alkaline agent and a sulfonate surfactant had been commonly in research market for several decades. Burdyn
et al.
[24] filed for a patent in which a similar but modified version of such process has been expounded. They described that an aqueous initiation slug (preflush) is injected into the reservoir which contains an alkaline agent and ammonium hydroxides. This preflush slug is then follo-wed by an aqueous surfactant slug (containing a sulfonate surfactant and an alkaline agent). Subsequent to injection of the surfactant slug, oil is displaced by an aqueous flooding medium whose portion may contain a thickening agent for mobility control [24]. Some patents have accentuated some biochemistry aspects of a certain chemical EOR process. As an instance, for the first time, in 1980, a waterflood process was described in detail by Chang [25]. In this process, a slug of biopolymer is injected into a formation before injection of the synthetic polymer slug to prevent the synthetic polymer from degradation when it contacts formation brine or surfactants present in the reservoir. Patents have been issued which are particularly on synthesis of novel chemicals useful in a certain chemical EOR process. A novel methodology for isolation of native petroleum surfactants for lowering interfacial tensions in aqueous-alkaline systems was explained by Yen
et al.
[26]. They explained the petroleum synthesis with the capability of surface tension reduction at high pH values. Surfactant fraction of the petroleum can be extracted by petroleum distillation in the temperature range of 100–200ºC. This fraction is concentrated by removing its benzene-soluble components. The resulted fraction can be injected as a slug into the oil reservoir to enhance alkaline/water flooding process. It is also possible to mix the obtained fraction with petroleum, or enrich it with the residue, or alternatively the residue can be mixed with petroleum. Each of these combinations can be injected as slug to help alkali/water flooding process. Yen
et al.
mentioned that:” amenability of a reservoir for alkaline flooding can be determined by separating the native surfactant fraction and measuring its interfacial tension with water at the proposed alkalinity of the floodwater.” [26]. In 1980, a novel aqueous surfactant-containing fluid appropriate for use in general surfactant- based oil recovery flooding processes, and an oil recovery process using the above-cited fluid was disclosed by Carlin
et al.
[27]. This fluid contained petroleum sulfonates alone or in combination with solubilizing cosurfactants such as ethoxylated alkyl or alkylaryl compounds, alkyl or alkylaryl polyethoxy sulfates, or alkyl or alkylaryl polyethoxy sulfonates. The aforementioned synthetic petroleum sulfo-nate was a mixture of petroleum sulfonates of varying equivalent weights ranging from 250 to 700, with an average equivalent weight between 325 and 425 [27]. In some previously published patents, researchers tried to present novel processes and chemical slug designs suitable for specific circumstances of formation temperature, salinity, etc. This has become a major concern over these decades. Shupe
et al.
[28] documented an oil recovery process suitable for use in formations with temperature from 70 to 300ºF, and water salinity of 70,000 to 220,000 parts per million total dissolved solids. In this process, a viscous emulsion, microemulsion or micellar dispersion fluid is injected into the reservoir to recover the oil. The author clearly stated that [28]:” proposed emulsion contained at least two surfactants such as an alkylpolyalkoxyalkylene sulfonate or alkylarylpolyalkoxyalkylene sulfonate and also a nonionic surfactant which is individually insoluble in the cosolvent (alkanol, or ethoxxylated alkylphenol).” Regarding salinity issues, a water-external phase viscous emulsion was designed by Cardenas
et al.
[29]. This emulsion contained a water soluble and/or dispersible alkylpolyalkoxyalkylene sulfonate or alkylarylpolyalkoxyalkylene sulfonate and a water-dispersible and/or soluble petroleum sulfonate as a phase-stabilizing additive. They explained in detail that this is an effective fluid for flooding formations containing brine whose salinity is from 70,000 to 220,000 parts per million total dissolved solids and also having temperatures up to 300ºF. They also showed that designed emulsion is phase-stable over a wide range of formation temperatures and water salinities and hardness values [29]. Synthesis of new chemicals useful in chemical EOR processes from industrial chemical effluents has been documented in some published patents. Especially, in 1982, Johnson
et al.
[30] filed for a patent in which the synthesis of a sacrificial or competitive adsorbate for surfactants contained in chemical flooding emulsions was disclosed. Adsorption of surfactant on the rock surfaces is reduced by injection of this adsorbate prior to or concurrent with the chemical emulsion. This reduction is allotted to the adsorp-tion of this adsorbate on the mineral surfaces within the formation. In a different mode, surfactant can be displaced from the mineral surface by injection of the adsorbate immediately after chemical flood. This adsorbate was a caustic effluent from the bleach stage or the weak black liquor from the digesters and pulp washers of the Kraft pulping process [30]. Also, proper combination of alcohols and other chemicals to synthesize new cosurfactants (cosolvent) for surfactant-based EOR processes was one of the major
