US20130150269A1 - Light co-solvent compositions - Google Patents

Light co-solvent compositions Download PDF

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US20130150269A1
US20130150269A1 US13/714,163 US201213714163A US2013150269A1 US 20130150269 A1 US20130150269 A1 US 20130150269A1 US 201213714163 A US201213714163 A US 201213714163A US 2013150269 A1 US2013150269 A1 US 2013150269A1
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unsubstituted
light
methyl
solvent
independently hydrogen
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Upali P. Weerasooriya
Gary A. Pope
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University of Texas System
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University of Texas System
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Assigned to BOARD OF REGENTS, THE UNIVERSITY OF TEXAS SYSTEM reassignment BOARD OF REGENTS, THE UNIVERSITY OF TEXAS SYSTEM ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: POPE, GARY A., WEERASOORIYA, UPALI P.
Priority to US15/365,170 priority patent/US10106725B2/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/594—Compositions used in combination with injected gas, e.g. CO2 orcarbonated gas
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons

Definitions

  • EOR Enhanced Oil Recovery
  • 40-60% of the reservoir's original oil can typically be extracted compared with only 20-40% using primary and secondary recovery (e.g. by water injection or natural gas injection).
  • Enhanced oil recovery may also be referred to as improved oil recovery or tertiary recovery (as opposed to primary and secondary recovery).
  • Enhanced oil recovery may be achieved by a variety of methods including miscible gas injection (which includes carbon dioxide flooding), chemical injection (which includes polymer flooding, alkaline flooding and surfactant flooding), microbial injection, or thermal recovery (which includes cyclic steam, steam flooding, and fire flooding).
  • miscible gas injection which includes carbon dioxide flooding
  • chemical injection which includes polymer flooding, alkaline flooding and surfactant flooding
  • microbial injection or thermal recovery (which includes cyclic steam, steam flooding, and fire flooding).
  • thermal recovery which includes cyclic steam, steam flooding, and fire flooding.
  • the injection of various chemicals has been used to improve oil recovery.
  • Injection of alkaline or caustic solutions into reservoirs with oil that has organic acids or acid precursors naturally occurring in the oil will result in the production of soap (i.e. in situ generated soap) that may lower the interfacial tension enough to increase production.
  • soap i.e. in situ generated soap
  • Dilute solutions of surfactants such as petroleum sulfonates may be injected to lower the interfacial tension or capillary pressure that impedes oil droplets from moving through a reservoir.
  • Special formulations of oil, water and surfactant microemulsions have also proven useful. Application of these methods is usually limited by the cost of the chemicals and their adsorption and loss onto the rock of the oil containing formation.
  • Some unrefined petroleum contains carboxylic acids having, for example, C 11 to C 20 alkyl chains, including napthenic acid mixtures.
  • the recovery of such “reactive” oils may be performed using alkali (e.g. NaOH or Na 2 CO 3 ) in a surfactant composition.
  • the alkali reacts with the acid in the reactive oil to form soap in situ.
  • These in situ generated soaps serve as an additional source of surfactants enabling the use of much lower level of surfactants initially added to effect enhanced oil recovery (EOR).
  • EOR enhanced oil recovery
  • the added alkali causes precipitation of cations, such as Ca +2 or Mg +2 .
  • an expensive chelant such as EDTA may be required in the surfactant composition.
  • expensive water softening processes may be used.
  • compositions provided herein include a light co-solvent, an alkali agent and a water-soluble polymer and are particularly useful for oil recovery under a broad range of reservoir conditions (e.g. high to low temperatures, high to low salinity, highly viscous oils).
  • reservoir conditions e.g. high to low temperatures, high to low salinity, highly viscous oils.
  • the non-surfactant aqueous compositions according to the embodiments provided herein are highly versatile and cost effective.
  • the present invention provides a non-surfactant aqueous composition including a light co-solvent, a water-soluble polymer and an alkali agent.
  • an emulsion composition including an unrefined petroleum phase and a non-surfactant aqueous phase.
  • the non-surfactant aqueous phase includes a light co-solvent and an alkali agent.
  • a method of displacing an unrefined active petroleum material in contact with a solid material includes contacting an unrefined active petroleum material with a non-surfactant aqueous composition, wherein the unrefined active petroleum material is in contact with a solid material.
  • the unrefined active petroleum material is allowed to separate from the solid material thereby displacing the unrefined active petroleum material in contact with the solid material.
  • a method of converting an unrefined active petroleum acid into a surfactant includes contacting an unrefined active petroleum material with the non-surfactant aqueous composition, thereby forming an emulsion in contact with the unrefined active petroleum material. An unrefined active petroleum acid within the unrefined active petroleum material is allowed to enter the emulsion, thereby converting the unrefined active petroleum acid into a surfactant.
  • FIG. 1 Phase behavior activity (1.5% n-butyl-5EO) plot with Oil #1 @ 38° C.
  • FIG. 2 Phase behavior activity (1% sec-butanol) plot with Oil #2 @ 65° C.
  • FIG. 3 (A) Phase behavior activity (1% iso-butyl-1EO) plot with Oil #2 at 85° C. (B) Phase behavior activity (1% iso-butyl-1EO) plot with Oil #2 at 65° C.
  • FIG. 4 Phase behavior activity (1% iso-butyl-1EO) plot with Oil #2 at 85° C.
  • FIG. 5 Phase behavior activity plot (1% TEGBE) with Oil #3 at 55° C.
  • FIG. 6 (A) Oil recovery profile and (B) pressure drop plot for Oil 1 core flood.
  • FIG. 7 (A) Oil recovery profile and (B) pressure drop plot for Oil 2 core flood.
  • FIG. 8 (A) Oil recovery profile and (B) pressure drop plot for Oil 3 core flood.
  • FIG. 9 (A) Oil recovery profile and (B) pressure drop plot for Oil 4 core flood.
  • FIG. 10 (A) Oil recovery profile and (B) pressure drop plot for Oil 5 core flood.
  • FIG. 11 (A) Oil recovery profile and (B) pressure drop plot for Oil 6 core flood.
  • substituent groups are specified by their conventional chemical formulae, written from left to right, they equally encompass the chemically identical substituents that would result from writing the structure from right to left, e.g., —CH 2 O— is equivalent to —OCH 2 —.
  • alkyl by itself or as part of another substituent, means, unless otherwise stated, a straight (i.e. unbranched) or branched chain which may be fully saturated, mono- or polyunsaturated and can include di- and multivalent radicals, having the number of carbon atoms designated (i.e. C 1 -C 10 means one to ten carbons).
  • saturated hydrocarbon radicals include, but are not limited to, groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, homologs and isomers of, for example, n-pentyl, n-hexyl, n-heptyl, n-octyl, and the like.
  • An unsaturated alkyl group is one having one or more double bonds or triple bonds.
  • unsaturated alkyl groups include, but are not limited to, vinyl, 2-propenyl, crotyl, 2-isopentenyl, 2-(butadienyl), 2,4-pentadienyl, 3-(1,4-pentadienyl), ethynyl, 1- and 3-propynyl, 3-butynyl, and the higher homologs and isomers.
  • Alkyl groups which are limited to hydrocarbon groups are termed “homoalkyl”.
  • An alkoxy is an alkyl attached to the remainder of the molecule via an oxygen linker (—O—).
  • alkylene by itself or as part of another substituent means a divalent radical derived from an alkyl, as exemplified, but not limited, by —CH 2 CH 2 CH 2 CH 2 —.
  • an alkyl (or alkylene) group will have from 1 to 24 carbon atoms, with those groups having 10 or fewer carbon atoms being preferred in the present invention.
  • a “lower alkyl” or “lower alkylene” is a shorter chain alkyl or alkylene group, generally having eight or fewer carbon atoms.
  • heteroalkyl by itself or in combination with another term, means, unless otherwise stated, a stable straight or branched chain or combinations thereof, consisting of at least one carbon atom and at least one heteroatom selected from the group consisting of O, N, P, Si and S.
  • the heteroatom(s) O, N, P and S and Si may be placed at any interior position of the heteroalkyl group or at the position at which the alkyl group is attached to the remainder of the molecule.
  • Examples include, but are not limited to, —CH 2 —CH 2 —O—CH 3 , —CH 2 —CH 2 —NH—CH 3 , —CH 2 —CH 2 —N(CH 3 )—CH 3 , —CH 2 —S—CH 2 —CH 3 , —CH 2 —CH 2 , —S(O)—CH 3 , —CH 2 —CH 2 —S(O) 2 —CH 3 , —CH ⁇ CH—O—CH 3 , —Si(CH 3 ) 3 , —CH 2 —CH ⁇ N—OCH 3 , —CH ⁇ CH—N(CH 3 )—CH 3 , O—CH 3 , —O—CH 2 —CH 3 , and —CN.
  • heteroalkylene by itself or as part of another substituent means a divalent radical derived from heteroalkyl, as exemplified, but not limited by, —CH 2 —CH 2 —S—CH 2 —CH 2 — and —CH 2 —S—CH 2 —CH 2 —NH—CH 2 —.
  • heteroatoms can also occupy either or both of the chain termini (e.g., alkyleneoxy, alkylenedioxy, alkyleneamino, alkylenediamino, and the like).
  • cycloalkyl and heterocycloalkyl represent, unless otherwise stated, cyclic versions of “alkyl” and “heteroalkyl,” respectively. Additionally, for heterocycloalkyl, a heteroatom can occupy the position at which the heterocycle is attached to the remainder of the molecule. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-cyclohexenyl, 3-cyclohexenyl, cycloheptyl, and the like.
  • heterocycloalkyl examples include, but are not limited to, 1-(1,2,5,6-tetrahydropyridyl), 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-morpholinyl, 3-morpholinyl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, 1-piperazinyl, 2-piperazinyl, and the like.
  • a “cycloalkylene” and a “heterocycloalkylene,” alone or as part of another substituent means a divalent radical derived from a cycloalkyl and heterocycloalkyl, respectively.
  • aryl means, unless otherwise stated, a polyunsaturated, aromatic, hydrocarbon substituent which can be a single ring or multiple rings (preferably from 1 to 3 rings) which are fused together (i.e. a fused ring aryl) or linked covalently.
  • a fused ring aryl refers to multiple rings fused together wherein at least one of the fused rings is an aryl ring.
  • heteroaryl refers to aryl groups (or rings) that contain at least one heteroatom (e.g. N, O, or S), wherein the nitrogen and sulfur atoms are optionally oxidized, and the nitrogen atom(s) are optionally quaternized.
  • heteroaryl includes fused ring heteroaryl groups (i.e. multiple rings fused together wherein at least one of the fused rings is a heteroaromatic ring).
  • a 5,6-fused ring heteroarylene refers to two rings fused together, wherein one ring has 5 members and the other ring has 6 members, and wherein at least one ring is a heteroaryl ring.
  • a 6,6-fused ring heteroarylene refers to two rings fused together, wherein one ring has 6 members and the other ring has 6 members, and wherein at least one ring is a heteroaryl ring.
  • a 6,5-fused ring heteroarylene refers to two rings fused together, wherein one ring has 6 members and the other ring has 5 members, and wherein at least one ring is a heteroaryl ring.
  • a heteroaryl group can be attached to the remainder of the molecule through a carbon or heteroatom.
  • Non-limiting examples of aryl and heteroaryl groups include phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 2-imidazolyl, 4-imidazolyl, pyrazinyl, 2-oxazolyl, 4-oxazolyl, 2-phenyl-4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-benzothiazolyl, purinyl, 2-benzimidazolyl, 5-indolyl, 1-isoquinoly
  • arylene and heteroarylene alone or as part of another substituent means a divalent radical derived from an aryl and heteroaryl, respectively.
  • oxo as used herein means an oxygen that is double bonded to a carbon atom.
  • Each R-group as provided in the formulae provided herein can appear more than once. Where a R-group appears more than once each R group can be optionally different.
  • contacting refers to materials or compounds being sufficiently close in proximity to react or interact.
  • the term “contacting” includes placing an aqueous composition (e.g. chemical, surfactant or polymer) within a hydrocarbon material bearing formation using any suitable manner known in the art (e.g., pumping, injecting, pouring, releasing, displacing, spotting or circulating the chemical into a well, well bore or hydrocarbon bearing formation).
  • aqueous composition e.g. chemical, surfactant or polymer
  • unrefined petroleum and “crude oil” are used interchangeably and in keeping with the plain ordinary usage of those terms.
  • “Unrefined petroleum” and “crude oil” may be found in a variety of petroleum reservoirs (also referred to herein as a “reservoir,” “oil field deposit” “deposit” and the like) and in a variety of forms including oleaginous materials, oil shales (i.e. organic-rich fine-grained sedimentary rock), tar sands, light oil deposits, heavy oil deposits, and the like.
  • “Crude oils” or “unrefined petroleums” generally refer to a mixture of naturally occurring hydrocarbons that may be refined into diesel, gasoline, heating oil, jet fuel, kerosene, and other products called fuels or petrochemicals. Crude oils or unrefined petroleums are named according to their contents and origins, and are classified according to their per unit weight (specific gravity). Heavier crudes generally yield more heat upon burning, but have lower gravity as defined by the American Petroleum Institute (API) and market price in comparison to light (or sweet) crude oils. Crude oil may also be characterized by its Equivalent Alkane Carbon Number (EACN).
  • EACN Equivalent Alkane Carbon Number
  • Crude oils vary widely in appearance and viscosity from field to field. They range in color, odor, and in the properties they contain. While all crude oils are mostly hydrocarbons, the differences in properties, especially the variation in molecular structure, determine whether a crude oil is more or less easy to produce, pipeline, and refine. The variations may even influence its suitability for certain products and the quality of those products. Crude oils are roughly classified intro three groups, according to the nature of the hydrocarbons they contain. (i) Paraffin based crude oils contain higher molecular weight paraffins, which are solid at room temperature, but little or no asphaltic (bituminous) matter. They can produce high-grade lubricating oils.
  • Asphaltene based crude oils contain large proportions of asphaltic matter, and little or no paraffin. Some are predominantly naphthenes and so yield lubricating oils that are sensitive to temperature changes than the paraffin-based crudes.
  • Mixed based crude oils contain both paraffin and naphthenes, as well as aromatic hydrocarbons. Most crude oils fit this latter category.
  • Reactive crude oil as referred to herein is crude oil containing natural organic acidic components (also referred to herein as unrefined petroleum acid) or their precursors such as esters or lactones. These reactive crude oils can generate soaps (carboxylates) when reacted with alkali. More terms used interchangeably for crude oil throughout this disclosure are hydrocarbon material or active petroleum material.
  • An “oil bank” or “oil cut” as referred to herein, is the crude oil that does not contain the injected chemicals and is pushed by the injected fluid during an enhanced oil recovery process.
  • Unrefined petroleum acids as referred to herein are carboxylic acids contained in active petroleum material (reactive crude oil).
  • the unrefined petroleum acids contain C 11 to C 20 alkyl chains, including napthenic acid mixtures.
  • the recovery of such “reactive” oils may be performed using alkali (e.g. NaOH or Na 2 CO 3 ) in a non-surfactant composition.
  • the alkali reacts with the acid in the reactive oil to form soap in situ. These in situ generated soaps serve as a source of surfactants enabling efficient oil recovery from the reservoir.
  • polymer refers to a molecule having a structure that essentially includes the multiple repetitions of units derived, actually or conceptually, from molecules of low relative molecular mass.
  • the polymer is an oligomer.
  • bonded refers to having at least one of covalent bonding, hydrogen bonding, ionic bonding, Van Der Waals interactions, pi interactions, London forces or electrostatic interactions.
  • productivity refers to the capacity of a well to produce hydrocarbons (e.g. unrefined petroleum); that is, the ratio of the hydrocarbon flow rate to the pressure drop, where the pressure drop is the difference between the average reservoir pressure and the flowing bottom hole well pressure (i.e., flow per unit of driving force).
  • solubility in general refers to the property of a solute, which can be a solid, liquid or gas, to dissolve in a solid, liquid or gaseous solvent thereby forming a homogenous solution of the solute in the solvent.
  • Solubility occurs under dynamic equilibrium, which means that solubility results from the simultaneous and opposing processes of dissolution and phase joining (e.g. precipitation of solids).
  • the solubility equilibrium occurs when the two processes proceed at a constant rate.
  • the solubility of a given solute in a given solvent typically depends on temperature. For many solids dissolved in liquid water, the solubility increases with temperature.
  • solubility and solubilization is the property of oil to dissolve in water and vice versa.
  • Viscosity refers to a fluid's internal resistance to flow or being deformed by shear or tensile stress. In other words, viscosity may be defined as thickness or internal friction of a liquid. Thus, water is “thin”, having a lower viscosity, while oil is “thick,” having a higher viscosity. More generally, the less viscous a fluid is, the greater its ease of fluidity.
  • salinity refers to concentration of salt dissolved in a aqueous phases. Examples for such salts are without limitation, sodium chloride, magnesium and calcium sulfates, and bicarbonates. In more particular, the term salinity as it pertains to the present invention refers to the concentration of salts in brine and surfactant solutions.
  • a “light co-solvent” refers to a compound having the ability to increase the solubility of a solute in the presence of an unrefined petroleum acid. Light co-solvents are not surfactants. Light co-solvents have a hydrophobic portion having no more than 6 carbons bound together, a hydrophilic portion (e.g. an alcohol or carboxylate) and optionally an alkoxy portion. Light co-solvents as provided herein include light alcohols, light alkoxy alcohols and light alkoxy carboxylates.
  • Examples of a light co-solvent include, but are not limited to C 1 -C 6 alcohols, C 1 -C 6 alkoxy alcohols, C 1 -C 6 diols, C 1 -C 6 alkoxy diols, C 1 -C 6 alkoxy carboxylates, and C 1 -C 6 alkoxy di-carboxylates.
  • alkali agent is used according to its conventional meaning and includes basic, ionic salts of alkali metals or alkaline earth metals.
  • Alkali agents as provided herein are typically capable of reacting with an unrefined petroleum acid (e.g. the acid in crude oil (reactive oil)) to form soap (a surfactant salt of a fatty acid) in situ. These in situ generated soaps serve as a source of surfactants causing a reduction of the interfacial tension of the oil in water emulsion, thereby reducing the viscosity of the emulsion.
  • Examples of alkali agents useful for the provided invention include, but are not limited to, sodium hydroxide, sodium carbonate, sodium silicate, sodium metaborate, and EDTA tetrasodium salt.
  • a “microemulsion” as referred to herein is a thermodynamically stable mixture of oil, water, light co-solvent and alkali agent that may also include additional components such as polymers (e.g. water-soluble polymers) and a salt.
  • a “macroemulsion” as referred to herein is a thermodynamically unstable mixture of oil and water that may also include additional components.
  • non-surfactant aqueous compositions and methods of using the same for a variety of applications including enhanced oil recovery.
  • the non-surfactant aqueous compositions provided herein may be used with broad oil concentrations, and at a wide range of salinities, including high salinities such as hard brine.
  • the non-surfactant aqueous compositions according to the embodiments provided herein further promote the formation of emulsions and reduce the viscosity (interfacial viscosity as well as bulk viscosity) of such emulsions, resulting in high oil recovery efficiencies.
  • For the recovery of heavy oils e.g. oils with less than 20° API gravity or a viscosity of more than 400 mPa s
  • heavy oils e.g. oils with less than 20° API gravity or a viscosity of more than 400 mPa s
  • high temperatures are required to decrease the viscosity of the crude oil.
  • the present invention provides a non-surfactant aqueous composition including a light co-solvent, a water-soluble polymer and an alkali agent.
  • a non-surfactant aqueous composition as provided herein refers to a composition which does not include a surface active agent having an alkyl chain with more than six carbons.
  • the non-surfactant aqueous compositions provided herein do not include large hydrophobic alkoxy carboxylates, where the hydrophobic portion has at least 8 and up to 150 carbons bound together, a hydrophilic portion (e.g. a carboxylate) and alkoxy portion including up to 210 alkoxy groups bound together, as disclosed in the international application having international application number PCT/US2011/049617.
  • the non-surfactant aqueous compositions provided herein may include more than one light co-solvent.
  • the non-surfactant aqueous composition includes a plurality of different light co-solvents.
  • the different light co-solvents can be distinguished by their chemical (structural) properties.
  • the non-surfactant aqueous composition may include a first light co-solvent, a second light co-solvent and a third light co-solvent, wherein the first co-solvent is chemically different from the second and the third light co-solvent, and the second light co-solvent is chemically different from the third co-solvent.
  • the plurality of different light co-solvents includes at least two different light alcohols (e.g. a C 1 -C 6 alcohol and a C 1 -C 4 alcohol).
  • the non-surfactant aqueous composition includes a C 1 -C 6 alcohol and a C 1 -C 4 alcohol.
  • the plurality of different light co-solvents includes at least two different alkoxy alcohols (e.g. a C 1 -C 6 alkoxy alcohol and a C 1 -C 4 alkoxy alcohol).
  • the non-surfactant aqueous composition includes a C 1 -C 6 alkoxy alcohol and a C 1 -C 4 alkoxy alcohol.
  • the plurality of different light co-solvents includes at least two different alkoxy carboxylates (e.g. a C 1 -C 6 alkoxy carboxylate and a C 1 -C 4 alkoxy carboxylate).
  • the non-surfactant aqueous composition includes a C 1 -C 6 alkoxy carboxylate and a C 1 -C 4 alkoxy carboxylate.
  • the plurality of different light co-solvents includes at least two light co-solvents selected from the group consisting of light alcohols, alkoxy alcohols and alkoxy carboxylates.
  • the plurality of different light co-solvents may include a light alcohol and an alkoxy alcohol, a light alcohol and an alkoxy carboxylate, or a light alcohol, an alkoxy alcohol and an alkoxy carboxylate.
  • the light co-solvent has the formula
  • R 1A is unsubstituted C 1 -C 6 alkylene, unsubstituted phenylene, unsubstituted cyclohexylene, unsubstituted cyclopentylene or methyl-substituted cyclopentylene.
  • R 2A is independently hydrogen, methyl or ethyl.
  • R 3A is independently hydrogen or
  • R 4A is independently hydrogen, methyl or ethyl.
  • n is an integer from 0 to 30, and m is an integer from 0 to 30. In one embodiment, n is an integer from 0 to 25. In one embodiment, n is an integer from 0 to 20. In one embodiment, n is an integer from 0 to 15. In one embodiment, n is an integer from 0 to 10. In one embodiment, n is an integer from 0 to 5. In one embodiment, n is 1. In other embodiments, n is 3. In one embodiment, n is 5. In one embodiment, m is an integer from 0 to 25. In one embodiment, m is an integer from 0 to 20. In one embodiment, m is an integer from 0 to 15.
  • m is an integer from 0 to 10. In one embodiment, m is an integer from 0 to 5. In one embodiment, m is 1. In other embodiments, m is 3. In one embodiment, m is 5.
  • each of R 2A and R 4A can appear more than once and can be optionally different. For example, in one embodiment where n is 2, R 2A appears twice and can be optionally different. In other embodiments, where m is 3, R 4A appears three times and can be optionally different.
  • the light co-solvent has the formula
  • R 1B is unsubstituted C 1 -C 6 alkylene, unsubstituted phenylene, unsubstituted cyclohexylene, unsubstituted cyclopentylene or methyl-substituted cyclopentylene.
  • R 2B is independently hydrogen, methyl or ethyl.
  • R 3B is independently hydrogen or methyl.
  • the symbol q is an integer from 0 to 30 and r is 1 or 2. In one embodiment, q is an integer from 0 to 25. In one embodiment, q is an integer from 0 to 20. In one embodiment, q is an integer from 0 to 15. In one embodiment, q is an integer from 0 to 10. In one embodiment, q is an integer from 0 to 5. In one embodiment, q is 1. In other embodiments, q is 3. In one embodiment, q is 5.
  • R 4B is independently hydrogen or
  • R 5B is independently hydrogen, methyl or ethyl.
  • R 6B is independently hydrogen or methyl.
  • the symbol s is an integer from 0 to 30, and t is 1 or 2. In one embodiment, s is an integer from 0 to 25. In one embodiment, s is an integer from 0 to 20. In one embodiment, s is an integer from 0 to 15. In one embodiment, s is an integer from 0 to 10. In one embodiment, s is an integer from 0 to 5. In one embodiment, s is 1. In other embodiments, s is 3. In one embodiment, s is 5. In formula (II) each of R 2B , R 3B , R 5B , and R 6B can appear more than once and can be optionally different.
  • R 2B appears twice and can be optionally different.
  • R 5B appears three times and can be optionally different.
  • R 3B appears three times and can be optionally different.
  • R 1A may be linear or branched unsubstituted alkylene.
  • R 1A of formula (I) is linear unsubstituted C 1 -C 6 alkylene.
  • R 1A of formula (I) is branched unsubstituted C 1 -C 6 alkylene.
  • R 1A of formula (I) is linear unsubstituted C 2 -C 6 alkylene.
  • R 1A of formula (I) is branched unsubstituted C 2 -C 6 alkylene.
  • R 1A of formula (I) is linear unsubstituted C 3 -C 6 alkylene.
  • R 1A of formula (I) is branched unsubstituted C 3 -C 6 alkylene. In other embodiments, R 1A of formula (I) is linear unsubstituted C 4 -C 6 alkylene. In other embodiments, R 1A of formula (I) is branched unsubstituted C 4 -C 6 alkylene. In other embodiments, R 1A of formula (I) is linear unsubstituted C 4 -alkylene. In other embodiments, R 1A of formula (I) is branched unsubstituted C 4 -alkylene.
  • R 1B may be linear or branched unsubstituted alkylene.
  • R 1B of formula (II) is linear unsubstituted C 1 -C 6 alkylene.
  • R 1B of formula (II) is branched unsubstituted C 1 -C 6 alkylene.
  • R 1B of formula (II) is linear unsubstituted C 2 -C 6 alkylene.
  • R 1B of formula (II) is branched unsubstituted C 2 -C 6 alkylene.
  • R 1B of formula (II) is linear unsubstituted C 3 -C 6 alkylene.
  • R 1B of formula (II) is branched unsubstituted C 3 -C 6 alkylene. In other embodiments, R 1B of formula (II) is linear unsubstituted C 4 -C 6 alkylene. In other embodiments, R 1B of formula (II) is branched unsubstituted C 4 -C 6 alkylene. In other embodiments, R 1B of formula (II) is linear unsubstituted C 4 -alkylene. In other embodiments, R 1B of formula (II) is branched unsubstituted C 4 -alkylene.
  • R 1A is linear or branched unsubstituted alkylene (e.g. branched unsubstituted C 1 -C 6 alkylene)
  • the alkylene is a saturated alkylene (e.g. a linear or branched unsubstituted saturated alkylene or branched unsubstituted C 1 -C 6 saturated alkylene).
  • R 1A is linear or branched unsubstituted saturated alkylene.
  • R 1A of formula (I) is linear unsubstituted saturated C 1 -C 6 alkylene. In one embodiment, R 1A of formula (I) is branched unsubstituted saturated C 1 -C 6 alkylene. In other embodiments, R 1A of formula (I) is linear unsubstituted saturated C 2 -C 6 alkylene. In other embodiments, R 1A of formula (I) is branched unsubstituted saturated C 2 -C 6 alkylene. In other embodiments, R 1A of formula (I) is linear unsubstituted saturated C 3 -C 6 alkylene.
  • R 1A of formula (I) is branched unsubstituted saturated C 3 -C 6 alkylene. In other embodiments, R 1A of formula (I) is linear unsubstituted C 4 -C 6 alkylene. In other embodiments, R 1A of formula (I) is branched unsubstituted saturated C 4 -C 6 alkylene. In other embodiments, R 1A of formula (I) is linear unsubstituted saturated C 4 -alkylene. In other embodiments, R 1A of formula (I) is branched unsubstituted saturated C 4 -alkylene.
  • R 1B is linear or branched unsubstituted alkylene (e.g. branched unsubstituted C 1 -C 6 alkylene)
  • the alkylene is a saturated alkylene (e.g. a linear or branched unsubstituted saturated alkylene or branched unsubstituted C 1 -C 6 saturated alkylene).
  • R 1B is linear or branched unsubstituted saturated alkylene.
  • R 1B of formula (II) is linear unsubstituted saturated C 1 -C 6 alkylene. In one embodiment, R 1B of formula (II) is branched unsubstituted saturated C 1 -C 6 alkylene. In other embodiments, R 1B of formula (II) is linear unsubstituted saturated C 2 -C 6 alkylene. In other embodiments, R 1B of formula (II) is branched unsubstituted saturated C 2 -C 6 alkylene. In other embodiments, R 1B of formula (II) is linear unsubstituted saturated C 3 -C 6 alkylene.
  • R 1B of formula (II) is branched unsubstituted saturated C 3 -C 6 alkylene. In other embodiments, R 1B of formula (II) is linear unsubstituted C 4 -C 6 alkylene. In other embodiments, R 1B of formula (II) is branched unsubstituted saturated C 4 -C 6 alkylene. In other embodiments, R 1B of formula (II) is linear unsubstituted saturated C 4 -alkylene. In other embodiments, R 1B of formula (II) is branched unsubstituted saturated C 4 -alkylene.
  • R 1A of formula (I) is substituted or unsubstituted cycloalkylene or unsubstituted arylene.
  • R 1A of formula (I) is W A -substituted or unsubstituted cyclopropylene, wherein W A is C 1 -C 3 alkyl.
  • R 1A of formula (I) is R 8A -substituted or unsubstituted cyclobutylene, wherein R 8A is C 1 -C 2 alkyl.
  • R 1A of formula (I) is R 9A -substituted or unsubstituted cyclopentylene, wherein R 9A is C 1 -alkyl.
  • R 1A of formula (I) is R 10A -substituted or unsubstituted cyclopentylene, wherein R 10A is unsubstituted cyclohexyl.
  • R 1A of formula (I) is unsubstituted phenylene, unsubstituted cyclohexylene, unsubstituted cyclopentylene or methyl-substituted cyclopentylene.
  • R 1B of formula (II) is substituted or unsubstituted cycloalkylene or unsubstituted arylene.
  • R 1B of formula (II) is R 7B -substituted or unsubstituted cyclopropylene, wherein R 7B is C 1 -C 3 alkyl.
  • R 1B of formula (II) is R 8B -substituted or unsubstituted cyclobutylene, wherein R 8B is C 1 -C 2 alkyl.
  • R 1B of formula (II) is R 9B -substituted or unsubstituted cyclopentylene, wherein R 9B is C 1 -alkyl.
  • R 1B of formula (II) is R 10B -substituted or unsubstituted cyclopentylene, wherein R 10B is unsubstituted cyclohexyl.
  • R 1B of formula (II) is unsubstituted phenylene, unsubstituted cyclohexylene, unsubstituted cyclopentylene or methyl-substituted cyclopentylene.
  • —R 1A —R 3A of formula (I) is C 1 -C 6 alkyl, unsubstituted phenyl, unsubstituted cyclohexyl, unsubstituted cyclopentyl or a methyl-substituted cycloalkyl.
  • the light co-solvent has the structure of formula
  • R 11A is C 1 -C 6 alkyl, unsubstituted phenyl, unsubstituted cyclohexyl, unsubstituted cyclopentyl or a methyl-substituted cycloalkyl.
  • n and m are independently 1 to 20. In other embodiments, n and m are independently 1 to 15. In other embodiments, n and m are independently 1 to 10. In one embodiment, n and m are independently 1 to 6. In one embodiment, n and m are independently 1. In one embodiment, q and s are independently 1 to 20. In other embodiments, q and r are independently 1 to 15. In other embodiments, q and r are independently 1 to 10. In one embodiment, q and r are independently 1 to 6. In other embodiments, q and r are independently 3.
  • the light co-solvent included in the compositions provided herein may be a monohydric or a dihydric alkoxy alcohol (e.g. C 1 -C 6 alkoxy alcohol or C 1 -C 6 alkoxy diol). Where the light co-solvent is a monohydric alcohol, the light co-solvent has the formula (I) and R 3A is hydrogen. Where the light co-solvent is a diol, the light co-solvent has the formula (I) and R 3A is
  • R 1A is linear unsubstituted C 4 alkylene and n is 3.
  • the light co-solvent is triethyleneglycol butyl ether. In other embodiments, the light co-solvent is tetraethylene glycol. In further embodiments, m is 3. In one embodiment, R 1A is linear unsubstituted C 4 alkylene and n is 5. In one embodiment, the light co-solvent is pentaethyleneglycol n-butyl ether. In further embodiments, m is 5. In one embodiment, R 1A is branched unsubstituted C 4 alkylene and n is 1. In one embodiment, the light-co-solvent is ethyleneglycol iso-butyl ether.
  • m is 1.
  • R 1A is branched unsubstituted C 4 alkylene and n is 3.
  • the light co-solvent is triethyleneglycol iso-butyl ether.
  • m is 3.
  • the light co-solvent is ethylene glycol or propylene glycol.
  • the light co-solvent is ethylene glycol alkoxylate or propylene glycol alkoxylate.
  • the light co-solvent is propylene glycol diethoxylate or propylene glycoltriethoxylate.
  • the light co-solvent is propylene glycol tetraethoxylate.
  • R 3A may be hydrogen or
  • R 3A is
  • the light co-solvent of the compositions provided herein may be an alkoxy carboxylate or an alkoxy dicarboxylate (e.g. C 1 -C 6 alkoxy carboxylate or C 1 -C 6 alkoxy dicarboxylate).
  • the light co-solvent is an alkoxy carboxylate
  • the light co-solvent has the formula (II)
  • R 4B is hydrogen.
  • the light co-solvent is an alkoxy dicarboxylate
  • the light co-solvent has the formula (II) and R 4B is
  • R 1B is linear unsubstituted C 4 alkylene and q is 3. In some further embodiments, s is 3. In other embodiments, R 1B is linear unsubstituted C 4 alkylene and q is 5. In some further embodiments, s is 5. In one embodiment, R 1B is branched unsubstituted C 4 alkylene and q is 1. In some further embodiments, s is 1. In one embodiment, R 1B is branched unsubstituted C 4 alkylene and q is 3. In some further embodiments, s is 3.
  • —R 1B —R 4B of formula (II) is C 1 -C 6 alkyl, unsubstituted phenyl, unsubstituted cyclohexyl, unsubstituted cyclopentyl or a methyl-substituted cycloalkyl.
  • the light co-solvent has the structure of formula
  • R 12B is C 1 -C 6 alkyl, unsubstituted phenyl, unsubstituted cyclohexyl, unsubstituted cyclopentyl or a methyl-substituted cycloalkyl.
  • R 4B may be independently hydrogen or
  • R 4B is
  • the light co-solvent provided herein may be an alcohol or diol (C 1 -C 6 alcohol or C 1 -C 6 diol). Where the light co-solvent is an alcohol, the light co-solvent has a structure of formula (I), where R 3A is hydrogen and n is 0. Where the light co-solvent is a diol, the light co-solvent has a structure of formula (I), where R 3A is
  • R 1A is linear or branched unsubstituted C 1 -C 6 alkylene. In other embodiments, R 1A is linear or branched unsubstituted C 2 -C 6 alkylene. In one embodiment, R 1A is linear or branched unsubstituted C 2 -C 6 alkylene. In one embodiment R 1A is linear or branched unsubstituted C 3 -C 6 alkylene. In other embodiments, R 1A is linear or branched unsubstituted C 4 -C 6 alkylene. In one embodiment, R 1A is linear or branched unsubstituted C 4 -alkylene. In one embodiment, R 1A is branched unsubstituted butylene. In one embodiment, the light co-solvent has the structure of formula
  • the light co-solvent has the structure of formula
  • the light co-solvent has the structure of formula
  • the light co-solvent as used herein is a compound within the non-surfactant aqueous composition that may function as an interfacial viscosity agent when the aqueous composition is in contact with a crude oil (e.g. an unrefined petroleum).
  • An “interfacial viscosity agent” as provided herein is an agent that together with an alkali agent of the non-surfactant aqueous composition facilitates the formation of soap in situ from carboxylic acids contained in the unrefined oil (also referred to herein as unrefined oil acid). By contacting the alkali agent with the carboxylic acid in the crude oil (e.g.
  • the light co-solvent facilitates the generation of soap in situ.
  • the formation of soap in situ promotes the formation of emulsions (both microemulsion and macroemulsion) providing for efficient production of the crude oil by lowering the interfacial tension between the water and the crude oil.
  • the light co-solvent provided herein may further allow for the formation of microemulsions between the unrefined petroleum and the non-surfactant aqueous composition.
  • the light co-solvent may decrease the interfacial viscosity and thus help transform highly viscous macroemulsions to less viscous microemulsions.
  • the light co-solvent may further break the macroemulsoins or prevent the formation of macroemulsion entirely.
  • the light co-solvent having the formula (I), (II), (III), (IV), (V), (VI) or (VII) provided herein may act to increase the flow of crude oil through the solid material (e.g. solid rock) toward production wells.
  • the light co-solvents according to the embodiments provided herein may also be referred to herein as “light co-solvents provided herein” or “the light co-solvent of the present invention.” Any one or combination of a light co-solvent of formulas (I), (II), (III), (IV), (V), (VI) or (VII) is useful in the methods and compositions provided herein.
  • the alkali agent is NaOH. In other embodiments, the alkali agent is Na 2 CO 3 .
  • the light co-solvent is present in an alkali stabilizing amount.
  • An “alkali stabilizing amount” means that the light co-solvent is present in an amount in which the alkali agent degrades at a slower rate in the presence of the light co-solvent than in the absence of the light co-solvent.
  • the rate of degradation may be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100% slower. In one embodiment, the rate of degradation is 2, 3, 4, 5, 6, 7, 8, 9 or 10 times slower.
  • the light co-solvent is present in a soap-solubilizing amount.
  • a “soap-solubilizing amount” means that the light co-solvent is present in an amount in which the soap formed in situ by the alkali agent and the acid in the crude oil (e.g. unrefined pretoleum acid) is more soluble in the presence of the light co-solvent than in the absence of the light co-solvent.
  • the solubilization may be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100% higher. In some embodiment, the solubilization is 2, 3, 4, 5, 6, 7, 8, 9 or 10 times higher.
  • the light co-solvent is present in an amount sufficient to increase the solubility of the in situ generated soap in the non-surfactant aqueous composition relative to the absence of the light co-solvent. In other words, in the presence of a sufficient amount of the light co-solvent, the solubility of the in situ generated soap in the non-surfactant aqueous composition is higher than in the absence of the light co-solvent.
  • the light co-solvent may increase or decrease the optimum salinity of the non-surfactant aqueous composition. In one embodiment, the light co-solvent may reduce the sensitivity of the optimum salinity to the oil concentration.
  • the non-surfactant aqueous composition includes a gas.
  • the gas may be combined with the non-surfactant aqueous composition to reduce its mobility by decreasing the liquid flow in the pores of the solid material (e.g. rock).
  • the gas may be supercritical carbon dioxide, nitrogen, natural gas or mixtures of these and other gases.
  • the gas e.g. methane
  • the gas and the light co-solvent are present in a synergistic viscosity decreasing amount.
  • a “synergistic viscosity decreasing amount” as used herein, means that a light co-solvent and a gas are present in amounts in which the viscosity decreasing activity of the light co-solvent and the gas combined is greater than the additive viscosity decreasing activity of the light co-solvent individually and the gas individually.
  • the viscosity decreasing activity of the light co-solvent and the gas combination is 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100% more than the additive viscosity decreasing activity of the light co-solvent individually and the gas individually.
  • the viscosity decreasing activity of the light co-solvent and the gas combination is 2, 3, 4, 5, 6, 7, 8, 9 or 10 times more than the additive viscosity decreasing activity of the light co-solvent individually and the gas individually.
  • the non-surfactant aqueous compositions provided herein are particularly useful for the recovery of viscous oils (e.g. oils with a viscosity of more than about 40 mPa s and less than about 400 mPa s) and heavy oils (e.g. oils with less than less than 20° API gravity or a viscosity of more than about 400 mPa s).
  • viscous oils e.g. oils with a viscosity of more than about 40 mPa s and less than about 400 mPa s
  • heavy oils e.g. oils with less than less than 20° API gravity or a viscosity of more than about 400 mPa s.
  • high temperatures may be required in order to decrease the viscosity of the unrefined petroleum as well as of the emulsions.
  • Some surfactants are unstable at high temperatures, resulting in loss of interfacial activity and thus less oil recovery.
  • the light co-solvents included in the non-surfactant aqueous compositions provided herein are stable at high (i.e. viscosity decreasing) temperatures.
  • a viscosity decreasing temperature as referred to herein is a temperature decreasing the viscosity of a crude oil relative to its naturally occurring viscosity in the reservoir.
  • the non-surfactant aqueous composition has a viscosity decreasing temperature. In some further embodiments, the viscosity decreasing temperature is equal to or less than about 200° C.
  • the light co-solvents provided herein are nonionic. In one embodiment, the light co-solvents provided herein are not sensitive to hardness and salinity compared to typical anionic surfactants commonly used.
  • the non-surfactant aqueous composition has a salinity of about 250,000 ppm. The total range of salinity (total dissolved solids in the brine) may be 100 in saturated brine (about 260,000 ppm).
  • the non-surfactant aqueous composition may include seawater, brine from an aquifer, river or lake.
  • the aqueous combination may further include salt to increase the salinity.
  • the salt is NaCl, KCl, CaCl 2 , MgCl 2 , Na 2 SO 4 or Na 2 CO 3 .
  • the non-surfactant aqueous composition may include more than 10 ppm of divalent cations combined. In one embodiment, the aqueous composition includes more than 10 ppm of Ca 2+ and Mg 2+ combined. The non-surfactant aqueous composition may include more than 100 ppm of divalent cations combined. In one embodiment, the non-surfactant aqueous composition includes more than 1000 ppm of Ca 2+ and Mg 2+ combined. In one embodiment, the non-surfactant aqueous composition includes more than 3000 ppm of Ca 2+ and Mg 2+ combined.
  • the non-surfactant aqueous composition includes more than 10 ppm of cations such as divalent cations. In other embodiments, the non-surfactant aqueous composition includes more than 100 ppm of cations such as divalent cations. In one embodiment, the non-surfactant aqueous composition includes more than 1000 ppm of cations such as divalent cations. In one embodiment, the divalent cations are Ba 2+ , Fe 2+ , Ca 2+ and Mg 2+ .
  • the non-surfactant aqueous composition has an acid neutralizing pH.
  • An acid neutralizing pH is a pH that allows for the formation of soap in situ from the acids contained in the crude oil and the alkali agent present in a non-surfactant aqueous composition.
  • the neutralizing pH is approximately equal to or higher than pH 8. In other embodiments, the neutralizing pH is at least 9.0.
  • non-surfactant aqueous composition includes hard brine
  • chelating agents may be included to prevent the divalent cations from precipitating the soap.
  • examples of chelating agents useful herein are without limitation, EDTA (ethylenediaminetetraacetic acid), EDTA sodium salt, and tetrasodium iminodisuccinat.
  • the non-surfactant aqueous composition further includes a chelating agent.
  • the non-surfactant aqueous composition further includes a hard brine.
  • an emulsion composition including an unrefined petroleum phase and a non-surfactant aqueous phase.
  • the non-surfactant aqueous phase includes a light co-solvent and an alkali agent.
  • the light co-solvent is a compound according to the embodiments provided herein (e.g. a compound of formula (I), (II), (III), (IV), (V), (VI) or (VII)).
  • the non-surfactant aqueous phase includes the components set forth in the non-surfactant aqueous composition provided above.
  • the aqueous phase contains a light co-solvent and an alkali agent.
  • the aqueous phase may include a combination of one or more light co-solvents.
  • the viscosity of the emulsion composition is less than the viscosity in the absence of the light co-solvent.
  • the viscosity of the emulsion composition is less than 3 times the viscosity of an unrefined petroleum (e.g. the unrefined petroleum which makes up the unrefined petroleum phase of the emulsion composition).
  • the viscosity of the emulsion composition is less than 30 centipoise. In other embodiments, the viscosity of the emulsion composition is less than 200 centipoise.
  • the light co-solvents present in the non-surfactant aqueous phase transform (break down) the initially formed macroemulsion into stable microemulsions thereby allowing for efficient recovery of the crude oil in the petroleum phase.
  • the emulsion composition is a microemulsion.
  • the oil and water solubilization ratios are insensitive to the combined concentration of divalent metal cations (e.g. Ca +2 and Mg +2 ) within the non-surfactant aqueous phase. In other embodiments, the oil and water solubilization ratios are insensitive to the salinity of the water or to all of the specific electrolytes contained in the water.
  • the term “insensitive” used in the context of this paragraph means that the solubilization ratio tends not to change (e.g. tends to remain constant) as the concentration of divalent metal cations and/or salinity of water changes.
  • the change in the solubilization ratios are less than 5%, 10%, 20%, 30%, 40%, or 50% over a divalent metal cation concentration range of 10 ppm, 100 ppm, 1000 ppm or 10,000 ppm. In another embodiment, the change in the solubilization ratios are less than 5%, 10%, 20%, 30%, 40%, or 50% over a salinity concentration range of 10 ppm, 100 ppm, 1000 ppm or 10,000 ppm.
  • the emulsion composition further includes a water-soluble polymer.
  • the water-soluble polymer may be a biopolymer such as xanthan gum or scleroglucan, a synthetic polymer such as polyacryamide, hydrolyzed polyarcrylamide or co-polymers of acrylamide and acrylic acid, 2-acrylamido 2-methyl propane sulfonate or N-vinyl pyrrolidone, a synthetic polymer such as polyethylene oxide, or any other high molecular weight polymer soluble in water or brine.
  • the water-soluble polymer is a partially (e.g. 20%, 25%, 30%, 35%, 40%, 45%) hydrolyzed anionic polyacrylamide.
  • the water-soluble polymer has a molecular weight of approximately about 8 ⁇ 10 6 . In some other further embodiment, the water-soluble polymer has a molecular weight of approximately about 18 ⁇ 10 6 .
  • Non-limiting examples of commercially available polymers useful for the invention including embodiments provided herein are Florpaam 3330S and Florpaam 3336S.
  • the light co-solvent is present in an amount sufficient to increase the solubility of in situ generated soap in the non-surfactant aqueous phase relative to the absence of the light co-solvent.
  • the solubility of in situ generated soap in the non-surfactant aqueous composition is higher than in the absence of the light co-solvent.
  • the solubility of the in situ generated soap may be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100% higher. In one embodiment, the solubilization is 2, 3, 4, 5, 6, 7, 8, 9 or 10 times higher.
  • the light co-solvent provided herein may increase the solubility of the water-soluble polymer in the non-surfactant aqueous composition needed to thicken it to prevent an unstable displacement (e.g. fingers) and thus to efficiently displace the oil through the rock.
  • the light co-solvent is present in an amount sufficient to increase the solubility of the water-soluble polymer in the emulsion composition relative to the absence of the light co-solvent. In other words, in the presence of a sufficient amount of the light co-solvent, the solubility of the polymer in the emulsion composition is higher than in the absence of the light co-solvent.
  • the polymer is more soluble in the presence of the light co-solvent than in the absence of the light co-solvent.
  • the solubility of the polymer in the emulsion composition may be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100% higher. In one embodiment, the solubilization is 2, 3, 4, 5, 6, 7, 8, 9 or 10 times higher.
  • the emulsion composition containing a light co-solvent and an alkali agent may further include a water-soluble polymer and/or a gas.
  • the emulsion composition includes a polymer or a gas.
  • the emulsion composition further includes a gas.
  • the emulsion composition includes a polymer and a gas.
  • the emulsion composition has a viscosity decreasing temperature.
  • the emulsion composition includes at least one light co-solvent, an alkali agent and a polymer.
  • the emulsion composition a gas.
  • the emulsion composition has a viscosity decreasing temperature.
  • the viscosity decreasing temperature is equal to or less than about 200° C. In one embodiment, the viscosity decreasing temperature is equal to or less than about 150° C. In one embodiment, the viscosity decreasing temperature is equal to or less than about 100° C. In one embodiment, the viscosity decreasing temperature is equal to or less than about 80° C. In one embodiment, the viscosity decreasing temperature is equal to or less than about 60° C.
  • the emulsion composition has a salinity of about 300,000 ppm. In other embodiments, the emulsion composition has a salinity of about 250,000 ppm. In one embodiment, the emulsion composition has a salinity of about 200,000 ppm. In other embodiments, the emulsion composition has a salinity of about 150,000 ppm. In one embodiment, the emulsion composition has a salinity of about 100,000 ppm. In one embodiment, the emulsion composition has a salinity of about 50,000 ppm.
  • the emulsion composition has an acid neutralizing pH. In further embodiments, the acid neutralizing pH is approximately equal to or higher than pH 8. In one embodiment, the emulsion composition further includes a chelating agent. In some further embodiments, the emulsion composition includes a hard brine. In one embodiment, the unrefined petroleum phase includes a heavy oil. In some further embodiments, the viscosity of the heavy oil is equal to or more than 40 mPa s.
  • the emulsion composition of the present invention include light co-solvents according to the embodiments described above.
  • the light co-solvent has a structure according to formula (I), (II), (III), (IV), (V), (VI) or (VII).
  • the light co-solvent has the formula (I).
  • the light co-solvent has the formula (III).
  • the light co-solvent has the formula (IV).
  • the light co-solvent has the formula (V).
  • the light co-solvent has the formula (VI).
  • the light co-solvent has the formula (VII).
  • a method of displacing an unrefined active petroleum material in contact with a solid material includes contacting an unrefined active petroleum material with a non-surfactant aqueous composition, wherein the unrefined active petroleum material is in contact with a solid material.
  • the unrefined active petroleum material is allowed to separate from the solid material thereby displacing the unrefined active petroleum material in contact with the solid material.
  • the non-surfactant aqueous composition includes a light co-solvent (as described herein) and an alkali agent.
  • the non-surfactant aqueous composition further includes a water-soluble polymer.
  • the light co-solvent has the formula (I).
  • the light co-solvent has the formula (II). In one embodiment, the light co-solvent has the formula (III). In one embodiment, the light co-solvent has the formula (IV). In one embodiment, the light co-solvent has the formula (V). In one embodiment, the light co-solvent has the formula (VI). In one embodiment, the light co-solvent has the formula (VII).
  • the light co-solvent may be present in a non-surfactant aqueous composition or an emulsion composition as described above.
  • the solid material may be a natural solid material (i.e. a solid found in nature such as rock).
  • the natural solid material may be found in a petroleum reservoir.
  • the method is an enhanced oil recovery method.
  • the natural solid material is rock or regolith.
  • the natural solid material may be a geological formation such as clastics or carbonates.
  • the natural solid material may be either consolidated or unconsolidated material or mixtures thereof.
  • the unrefined active petroleum material may be trapped or confined by “bedrock” above or below the natural solid material.
  • the unrefined active petroleum material may be found in fractured bedrock or porous natural solid material.
  • the regolith is soil.
  • an emulsion forms after the contacting.
  • the emulsion thus formed may be the emulsion composition as described above.
  • the method includes allowing an unrefined petroleum acid within the unrefined petroleum material to enter into the emulsion (e.g. emulsion composition), thereby converting the unrefined petroleum acid into a surfactant.
  • the emulsion e.g. emulsion composition
  • the oil may be mobilized and therefore separated from the solid material.
  • a method of converting an unrefined active petroleum acid into a surfactant includes contacting an unrefined active petroleum material with the non-surfactant aqueous composition, thereby forming an emulsion in contact with the unrefined active petroleum material.
  • An unrefined active petroleum acid within the unrefined active petroleum material is allowed to enter the emulsion, thereby converting the unrefined active petroleum acid into a surfactant.
  • the non-surfactant aqueous composition includes a light co-solvent as described herein and alkali agent.
  • the non-surfactant aqueous composition includes a water-soluble polymer.
  • the light co-solvent has the formula (I).
  • the light co-solvent has the formula (II). In one embodiment, the light co-solvent has the formula (III). In one embodiment, the light co-solvent has the formula (IV). In one embodiment, the light co-solvent has the formula (V). In one embodiment, the light co-solvent has the formula (VI). In one embodiment, the light co-solvent has the formula (VII).
  • the non-surfactant aqueous composition is the non-surfactant aqueous composition described above.
  • the emulsion is the emulsion composition described above. An unrefined petroleum acid within the unrefined petroleum material is allowed to enter the emulsion, thereby converting (e.g. mobilizing) the unrefined petroleum acid into a surfactant.
  • the unrefined active petroleum material is a petroleum reservoir.
  • Phase Behavior Screening Phase behavior studies have been used to characterize chemicals for EOR. There are many benefits in using phase behavior as a screening method. Phase Behavior studies are used to determine: (1) the effect of electrolytes; (2) oil solubilization and IFT reduction, (3) microemulsion densities; (4) microemulsion viscosities; (5) coalescence times; (6) optimal light co-solvent/alkali agent formulations; and/or (7) optimal properties for recovering oil from cores and reservoirs.
  • Thermodynamically stable phases can form with oil, water and non-surfactant aqueous mixtures.
  • In situ generated soaps form micellar structures at concentrations at or above the critical micelle concentration (CMC).
  • CMC critical micelle concentration
  • the emulsion coalesces into a separate phase at the oil-water interface and is referred to as a microemulsion.
  • a microemulsion is a surfactant-rich distinct phase consisting of in situ generated soaps, oil and water and light co-solvent, alkali agent and other components. This phase is thermodynamically stable in the sense that it will return to the same phase volume at a given temperature.
  • the phase transition is examined by keeping all variables fixed except for the scanning variable.
  • the scan variable is changed over a series of pipettes and may include, but is not limited to, salinity, temperature, chemical (light co-solvent, alcohol, electrolyte), oil, which is sometimes characterized by its equivalent alkane carbon number (EACN), and light co-solvent structure, which is sometimes characterized by its hydrophilic-lipophilic balance (HLB).
  • the phase transition was first characterized by Winsor (1954) into three regions: Type I—excess oleic phase, Type III—aqueous, microemulsion and oleic phases, and the Type II—excess aqueous phase.
  • phase transition boundaries and some common terminology are described as follows: Type Ito III—lower critical salinity, Type III to II—upper critical salinity, oil solubilization ratio (Vo/Vs), water solubilization ratio (Vw/Vs), the solubilization value where the oil and water solubilization ratios are equal is called the Optimum Solubilization Ratio ( ⁇ *), and the electrolyte concentration where the optimum solubilization ratio occurs is referred to as the Optimal Salinity (S*). Since no surfactant is added, the only surfactant present is the in-situ generated soap. For the purpose of calculating a solubilization ratio, one can assume a value for soap level using TAN (total acid number) and an approximate molecular weight for the soap.
  • TAN total acid number
  • Mass Balance Mass balances are used to measure chemicals for mixtures and determine initial saturation values of cores.
  • Water Deionizer Deionized (DI) water is prepared for use with all the experimental solutions using a NanopureTM filter system. This filter uses a recirculation pump and monitors the water resistivity to indicate when the ions have been removed. Water is passed through a 0.45 micron filter to eliminate undesired particles and microorganisms prior to use.
  • Borosilicate Pipettes Standard 5 mL borosilicate pipettes with 0.1 mL markings are used to create phase behavior scans as well as run dilution experiments with aqueous solutions. Ends are sealed using a propane and oxygen flame.
  • Pipette Repeater An Eppendorf Repeater Plus® instrument is used for most of the pipetting. This is a handheld dispenser calibrated to deliver between 25 microliter and 1 ml increments. Disposable tips are used to avoid contamination between stocks and allow for ease of operation and consistency.
  • Propane-oxygen Torch A mixture of propane and oxygen gas is directed through a Bernz-O-Matic flame nozzle to create a hot flame about 1 ⁇ 2 inch long. This torch is used to flame-seal the glass pipettes used in phase behavior experiments.
  • Convection Ovens Several convection ovens are used to incubate the phase behaviors and core flood experiments at the reservoir temperatures.
  • phase behavior pipettes are primarily kept in Blue M and Memmert ovens that are monitored with mercury thermometers and oven temperature gauges to ensure temperature fluctuations are kept at a minimal between recordings.
  • a large custom built flow oven was used to house most of the core flood experiments and enabled fluid injection and collection to be done at reservoir temperature.
  • pH Meter An ORION research model 701/digital ion analyzer with a pH electrode is used to measure the pH of most aqueous samples to obtain more accurate readings. This is calibrated with 4.0, 7.0 and 10.0 pH solutions. For rough measurements of pH, indicator papers are used with several drops of the sampled fluid.
  • the oil and water solubilization ratios are calculated from interface measurements taken from phase behavior pipettes. These interfaces are recorded over time as the mixtures approached equilibrium and the volume of any macroemulsions that initially formed decreased or disappeared.
  • Phase behavior samples are made by first preparing non-surfactant aqueous stock solutions and combining them with brine stock solutions in order to observe the behavior of the mixtures over a range of salinities.
  • Non-surfactant aqueous stock solutions are based on active weight-percent co-solvent.
  • the masses of light co-solvent, alkali agent and de-ionized water (DI) are measured out on a balance and mixed in glass jars using magnetic stir bars. The order of addition is recorded on a mixing sheet along with actual masses added and the pH of the final solution. Brine solutions are created at the necessary weight percent concentrations for making the scans.
  • Co-solvent Stock The chemicals being tested are first mixed in a concentrated stock solution that usually consisted of light co-solvent, alkali agent and/or polymer along with de-ionized water. The quantity of chemical added is calculated based on activity and measured by weight percent of total solution. Initial experiments are at about 1-3% light co-solvent so that the volume of the middle microemulsion phase would be large enough for accurate measurements assuming a solubilization ratio of at least 10 at optimum salinity.
  • Phase behavior components are added volumetrically into 5 ml pipettes using an Eppendorf Repeater Plus or similar pipetting instrument.
  • Light co-solvent, alkali agent and brine stocks are mixed with DI water into labeled pipettes and brought to temperature before agitation.
  • Almost all of the phase behavior experiments are initially created with a water oil ratio (WOR) of 1:1, which involves mixing 2 ml of the aqueous phase with 2 ml of the evaluated crude oil or hydrocarbon, and different WOR experiments are mixed accordingly.
  • WOR water oil ratio
  • the typical phase behavior scan consisted of 10-20 pipettes, each pipette being recognized as a data point in the series.
  • the desired sample compositions are made by combining the stocks in the following order: (1) Electrolyte stock(s); (2) De-ionized water; (3) light co-solvent stock; (4) alkali agent stock; (5) Polymer stock; and (6) Crude oil or hydrocarbon.
  • the pipettes are blanketed with argon gas to prevent the ignition of any volatile gas present by the flame sealing procedure.
  • the tubes are then sealed with the propane-oxygen torch to prevent loss of additional volatiles when placed in the oven.
  • Pipettes are arranged on the racks to coincide with the change in the scan variable. Once the phase behavior scan is given sufficient time to reach reservoir temperature (15-30 minutes), the pipettes are inverted several times to provide adequate mixing. Tubes are observed for low tension upon mixing by looking at droplet size and how uniform the mixture appeared. Then the solutions are allowed to equilibrate over time and interface levels are recorded to determine equilibration time and light co-solvent/alkali agent performance.
  • Phase behavior experiments are allowed to equilibrate in an oven that is set to the reservoir temperature for the crude oil being tested.
  • the fluid levels in the pipettes are recorded periodically and the trend in the phase behavior observed over time. Equilibrium behavior is assumed when fluid levels ceased to change within the margin of error for reading the samples.
  • the fluid interfaces are the most crucial element of phase behavior experiments. From them, the phase volumes are determined and the solubilization ratios are calculated. The top and bottom interfaces are recorded as the scan transitioned from an oil-in-water microemulsion to a water-in-oil microemulsion. Initial readings are taken one day after initial agitation and sometimes within hours of agitation if coalescence appeared to happen rapidly. Measurements are taken thereafter at increasing time intervals (for example, one day, four days, one week, two weeks, one month and so on) until equilibrium is reached or the experiment is deemed unessential or uninteresting for continued observation.
  • Oil ID #1 #2 #3 Viscosity, cP 166 @ 38 C. 30-55 @ 90 C. 13.9 @ 55 C. Acid number, ⁇ 5 Not available 6.64 mg KOH/g (highly reactive) API Gravity 19.08° 17.8°-23° 24°
  • a non-surfactant aqueous composition comprising a light co-solvent, a water-soluble polymer and an alkali agent.
  • non-surfactant aqueous composition of embodiment 1 comprising a plurality of different light co-solvents.
  • R 1A is unsubstituted C 1 -C 6 alkylene, unsubstituted phenylene, unsubstituted cyclohexylene, unsubstituted cyclopentylene or methyl-substituted cyclopentylene;
  • R 2A is independently hydrogen, methyl or ethyl;
  • R 3A is independently hydrogen or
  • R 4A is independently hydrogen, methyl or ethyl; n is an integer from 0 to 30, and m is an integer from 0 to 30.
  • R 1B is unsubstituted C 1 -C 6 alkylene, unsubstituted phenylene, unsubstituted cyclohexylene, unsubstituted cyclopentylene or methyl-substituted cyclopentylene;
  • R 2B is independently hydrogen, methyl or ethyl;
  • R 3B is independently hydrogen or methyl;
  • q is an integer from 0 to 30;
  • r is 1 or 2;
  • R 4B is independently hydrogen or
  • R 5B is independently hydrogen, methyl or ethyl; R 6B is independently hydrogen or methyl; s is an integer from 0 to 30, and t is 1 or 2.
  • non-surfactant aqueous composition of any one of embodiments 3 or 5-9 wherein n and m are independently 1 to 20.
  • non-surfactant aqueous composition of any one of embodiments 3 or 5-9, wherein n and m are independently 1 to 6.
  • non-surfactant aqueous composition of any one of embodiments 4-9, wherein q and s are independently 1 to 20.
  • non-surfactant aqueous composition of any one of embodiments 4-9, wherein q and s are independently 1 to 6.
  • non-surfactant aqueous composition of any one of embodiments 3 or 5-11, wherein R 1A is linear unsubstituted C 4 alkylene and n is 3.
  • non-surfactant aqueous composition of any one of embodiments 3 or 5-11, wherein R 1A is linear unsubstituted C 4 alkylene and n is 5.
  • non-surfactant aqueous composition of any one of embodiments 3 or 5-1, wherein R 1A is branched unsubstituted C 4 alkylene and n is 1.
  • non-surfactant aqueous composition of any one of embodiments 3 or 5-11, wherein R 1A is branched unsubstituted C 4 alkylene and n is 3.
  • non-surfactant aqueous composition of any one of embodiments 4-9, 12 or 13, wherein R 1B is linear unsubstituted C 4 alkylene and q is 3.
  • non-surfactant aqueous composition of any one of embodiments 4-9, 12 or 13, wherein R 1B is linear unsubstituted C 4 alkylene and q is 5.
  • Embodiment 26 The non-surfactant aqueous composition of any one of embodiments 4-9, 12 or 13, wherein R 1B is branched unsubstituted C 4 alkylene and q is 1.
  • non-surfactant aqueous composition of any one of embodiments 4-9, 12 or 13, wherein R 1B is branched unsubstituted C 4 alkylene and q is 3.
  • non-surfactant aqueous composition of any one of embodiments 9-32, wherein R 1A is linear or branched unsubstituted C 3 -C 6 alkylene.
  • non-surfactant aqueous composition of any one of embodiments 3-38, further comprising a gas.
  • non-surfactant aqueous composition of any one of the preceding embodiments, wherein the non-surfactant aqueous composition has a viscosity decreasing temperature.
  • non-surfactant aqueous composition of any one of the preceding embodiments, having a salinity of about 250,000 ppm.
  • non-surfactant aqueous composition of any one of the preceding embodiments, having an acid neutralizing pH.
  • non-surfactant aqueous composition of any one of the preceding embodiments, further comprising a chelating agent.
  • non-surfactant aqueous composition of embodiment 46 further comprising a hard brine.
  • Embodiment 48 An emulsion composition comprising an unrefined petroleum phase and a non-surfactant aqueous phase, wherein said non-surfactant aqueous phase comprises a light co-solvent and alkali agent.
  • emulsion composition of embodiment 48 wherein the emulsion composition is a microemulsion.
  • the emulsion composition of embodiment 48 further comprising a water-soluble polymer.
  • emulsion composition of any one of embodiments 48-52, further comprising a gas.
  • emulsion composition of any one of embodiments 48-53, wherein the emulsion composition has a viscosity decreasing temperature.
  • emulsion composition of any one of embodiments 48-58, further comprising a chelating agent.
  • the emulsion composition of embodiment 59 further comprising a hard brine.
  • R 1A is unsubstituted C 1 -C 6 alkylene, unsubstituted phenylene, unsubstituted cyclohexylene, unsubstituted cyclopentylene or methyl-substituted cyclopentylene;
  • R 2A is independently hydrogen, methyl or ethyl;
  • R 3A is independently hydrogen or
  • R 4A is independently hydrogen, methyl or ethyl; n is an integer from 0 to 30, and m is an integer from 0 to 30.
  • R 1B is unsubstituted C 1 -C 6 alkylene, unsubstituted phenylene, unsubstituted cyclohexylene, unsubstituted cyclopentylene or methyl-substituted cyclopentylene;
  • R 2B is independently hydrogen, methyl or ethyl;
  • R 3B is independently hydrogen or methyl;
  • q is an integer from 0 to 30;
  • r is 1 or 2;
  • R 4 is independently hydrogen or
  • R 5B is independently hydrogen, methyl or ethyl; R 6B is independently hydrogen or methyl; s is an integer from 0 to 30, and t is 1 or 2.
  • a method of displacing an unrefined active petroleum material in contact with a solid material comprising: (i) contacting an unrefined active petroleum material with a non-surfactant aqueous composition, wherein said unrefined active petroleum material is in contact with a solid material; (ii) allowing said unrefined active petroleum material to separate from said solid material thereby displacing said unrefined active petroleum material in contact with said solid material.
  • non-surfactant aqueous composition comprises a light co-solvent and alkali agent.
  • non-surfactant aqueous composition further comprises a water-soluble polymer.
  • R 1A is unsubstituted C 1 -C 6 alkylene, unsubstituted phenylene, unsubstituted cyclohexylene, unsubstituted cyclopentylene or methyl-substituted cyclopentylene;
  • R 2A is independently hydrogen, methyl or ethyl;
  • R 3A is independently hydrogen or
  • R 4A is independently hydrogen, methyl or ethyl; n is an integer from 0 to 30, and m is an integer from 0 to 30.
  • R 1B is unsubstituted C 1 -C 6 alkylene, unsubstituted phenylene, unsubstituted cyclohexylene, unsubstituted cyclopentylene or methyl-substituted cyclopentylene;
  • R 2B is independently hydrogen, methyl or ethyl;
  • R 3B is independently hydrogen or methyl;
  • q is an integer from 0 to 30;
  • r is 1 or 2;
  • R 4B is independently hydrogen or
  • R 5B is independently hydrogen, methyl or ethyl
  • R 6 is independently hydrogen or methyl
  • s is an integer from 0 to 30, and t is 1 or 2.
  • a method of converting an unrefined active petroleum acid into a surfactant comprising: (i) contacting an unrefined active petroleum material with the non-surfactant aqueous composition, thereby forming an emulsion in contact with said unrefined active petroleum material; and (ii) allowing an unrefined active petroleum acid within said unrefined active petroleum material to enter said emulsion, thereby converting said unrefined active petroleum acid into a surfactant.
  • non-surfactant aqueous composition comprises a light co-solvent and alkali agent.
  • R 1A is unsubstituted C 1 -C 6 alkylene, unsubstituted phenylene, unsubstituted cyclohexylene, unsubstituted cyclopentylene or methyl-substituted cyclopentylene;
  • R 2A is independently hydrogen, methyl or ethyl;
  • R 3A is independently hydrogen or
  • R 4A is independently hydrogen, methyl or ethyl; n is an integer from 0 to 30, and m is an integer from 0 to 30.
  • R 1B is unsubstituted C 1 -C 6 alkylene, unsubstituted phenylene, unsubstituted cyclohexylene, unsubstituted cyclopentylene or methyl-substituted cyclopentylene;
  • R 2B is independently hydrogen, methyl or ethyl;
  • R 3B is independently hydrogen or methyl;
  • q is an integer from 0 to 30;
  • r is 1 or 2;
  • R 4B is independently hydrogen or
  • R 5B is independently hydrogen, methyl or ethyl; R 6B is independently hydrogen or methyl; s is an integer from 0 to 30, and t is 1 or 2.

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