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WO2014201367A1 - Procédés et compositions de stimulation de la production d'hydrocarbures à partir de formations souterraines - Google Patents

Procédés et compositions de stimulation de la production d'hydrocarbures à partir de formations souterraines Download PDF

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Publication number
WO2014201367A1
WO2014201367A1 PCT/US2014/042326 US2014042326W WO2014201367A1 WO 2014201367 A1 WO2014201367 A1 WO 2014201367A1 US 2014042326 W US2014042326 W US 2014042326W WO 2014201367 A1 WO2014201367 A1 WO 2014201367A1
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WO
WIPO (PCT)
Prior art keywords
solvent
microemulsion
branched
group
carbon atoms
Prior art date
Application number
PCT/US2014/042326
Other languages
English (en)
Inventor
Randal M. Hill
Lakia M. CHAMPAGNE
Nathan L. LETT
Keith Ingram DISMUKE
David GERMACK
Nicole MAST
Melinda SOEUNG
Original Assignee
Cesi Chemical, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US13/918,155 external-priority patent/US9321955B2/en
Priority claimed from US13/918,166 external-priority patent/US20140371115A1/en
Application filed by Cesi Chemical, Inc. filed Critical Cesi Chemical, Inc.
Priority to EP14811591.8A priority Critical patent/EP3008283A4/fr
Priority to CN201480002623.0A priority patent/CN104769214B/zh
Priority to AU2014278002A priority patent/AU2014278002B2/en
Priority to CA2915351A priority patent/CA2915351C/fr
Publication of WO2014201367A1 publication Critical patent/WO2014201367A1/fr
Priority to AU2017261565A priority patent/AU2017261565B2/en

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Classifications

    • 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
    • E21B43/162—Injecting fluid from longitudinally spaced locations in injection well
    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/64—Oil-based compositions
    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/72—Eroding chemicals, e.g. acids
    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/82—Oil-based compositions
    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds

Definitions

  • the present invention generally provides methods and compositions for stimulating the production of hydrocarbons (e.g., formation crude oil and/or formation gas) from subterranean formations.
  • hydrocarbons e.g., formation crude oil and/or formation gas
  • stimulation generally refers to the treatment of geological formations to improve the recovery of liquid hydrocarbons (e.g., formation crude oil and/or formation gas).
  • Common stimulation techniques include well fracturing and acidizing operations.
  • Oil and natural gas are found in, and produced from, porous and permeable subterranean formations.
  • the porosity and permeability of the formation determine its ability to store hydrocarbons, and the facility with which the hydrocarbons can be extracted from the formation.
  • Hydraulic fracturing is commonly used to stimulate low permeability geological formations to improve the recovery of hydrocarbons.
  • the process can involve suspending chemical agents in a well-treatment fluid (e.g., fracturing fluid) and injecting the fluid down the wellbore.
  • fracturing fluid e.g., fracturing fluid
  • the assortment of chemicals pumped down the well can cause damage to the surrounding formation by entering the reservoir rock and blocking the pore throats. It is known that fluid invasion can have a detrimental effect on gas permeability and can impair well productivity.
  • fluids may become trapped in the formation due to capillary end effects in and around the vicinity of the formation fractures.
  • additives have been incorporated into well- treatment fluids.
  • the composition of additives comprises multi-component chemical substances and compositions that contain mutually distributed nanodomains of normally immiscible solvents, such as water and hydrocarbon-based organic solvents, stabilized by surfactants (e.g., microemulsions).
  • surfactants e.g., microemulsions.
  • the incorporation of additives into well-treatment fluids can increase crude oil or formation gas, for example by reducing capillary pressure and/or minimizing capillary end effects.
  • hydrocarbons e.g., formation crude oil and/or formation gas
  • methods of selecting a composition for treating an oil or gas well having a wellbore comprising determining whether displacement of residual aqueous treatment fluid by formation crude oil or displacement of residual aqueous treatment fluid by formation gas is preferentially stimulated for the oil or gas well having a wellbore; and selecting an emulsion or a microemulsion for injection into the wellbore to increase formation crude oil or formation gas production by the well, wherein the emulsion or the microemulsion comprises water, at least a first type of solvent, and a surfactant, wherein the solvent is selected from the group consisting of unsubstituted cyclic or acyclic, branched or unbranched alkanes having 6-12 carbon atoms, unsubstituted acyclic branched or unbranched alkenes having one or two double bonds and 6-12 carbon atoms, cyclic or acyclic, branched or unbranched alkanes having 9-12 carbon atoms and substituted with only
  • methods of treating an oil or gas well having a wellbore comprising injecting an emulsion or a microemulsion into the wellbore of the oil or gas well to stimulate displacement of residual aqueous treatment fluid by formation crude oil and increase production of formation crude oil by the well, wherein the emulsion or the microemulsion comprises water, at least a first type of solvent, and a surfactant; and wherein the solvent is selected from the group consisting of unsubstituted cyclic or acyclic, branched or unbranched alkanes having 6-12 carbon atoms,
  • branched or unbranched alkenes having one or two double bonds and 6-12 carbon atoms
  • cyclic or acyclic, branched or unbranched alkanes having 9-12 carbon atoms and substituted with only an -OH group
  • branched or unbranched dialkylether compounds having the formula C n H 2n+ iOC m H 2m+ i, wherein n + m is between 6 and 16, and aromatic solvents having a boiling point between about 300-400 °F.
  • methods of treating an oil or gas well having a wellbore comprising injecting an emulsion or a microemulsion into the wellbore of the oil or gas well to stimulate displacement of residual aqueous treatment fluid by formation gas and increase production of formation gas by the well, wherein the emulsion or the microemulsion comprises water, at least a first type of solvent, and a surfactant; and wherein the solvent is selected from the group consisting of cyclic or acyclic, branched or unbranched alkanes having 8 carbon atoms and substituted with only an -OH group and aromatic solvents having a boiling point between about 175-300 °F.
  • compositions for injecting into a wellbore comprising an aqueous carrier fluid and an emulsion or a microemulsion, wherein the emulsion or the microemulsion is present in an amount between about 0.1 wt and about 2 wt versus the total composition, and wherein the emulsion or microemulsion comprises an aqueous phase, a surfactant, a freezing point depression agent, and a solvent comprising an alpha-olefin.
  • Figure 1 shows an exemplary plot for determining the phase inversion
  • the present invention generally relates to methods and well-treatment compositions (e.g., emulsions or microemulsions) for stimulating of the production of liquid hydrocarbons (e.g., formation crude oil and/or formation gas) from subterranean formations.
  • the compositions comprise an emulsion or a microemulsion, as described in more detail herein.
  • the emulsions or the microemulsions may include water, a solvent, a surfactant, and optionally a freezing point depression agent or other components.
  • the solvent comprises more than one type of solvent (e.g., a first type of solvent and a second type of solvent).
  • the methods relate to stimulating displacement of residual aqueous treatment fluid by formation crude oil or formation gas to increase production of liquid hydrocarbons, as described in more detail below.
  • methods of selecting an emulsion or a microemulsion comprising a solvent are provided, wherein the emulsion or the microemulsion is selected so as to increase liquid hydrocarbon production.
  • methods of selecting an emulsion or a microemulsion comprising a solvent are provided, wherein the emulsion or the microemulsion is selected so as to increase gaseous hydrocarbon production.
  • the solvent is a hydrocarbon solvent comprising between 6 and 12 carbon atoms.
  • the hydrocarbon may be a linear, branched, or cyclic hydrocarbon, including aromatics, and may be optionally substituted with various functional groups, as described herein.
  • microemulsions or emulsions comprising certain solvents increase the displacement (e.g., flowback) of residual aqueous treatment fluid by liquid hydrocarbons (e.g., crude oil) as compared to other solvents.
  • emulsions or microemulsions comprising certain solvents increase the displacement of residual aqueous treatment fluid by gaseous hydrocarbons as compared to other solvents.
  • Laboratory tests may be conducted, as described herein, to determine the displacement of residual aqueous treatment fluid by liquid hydrocarbons and/or gaseous hydrocarbons of an emulsion or a microemulsion
  • Petroleum is generally recovered from subterranean reservoirs through the use of drilled wells and production equipment.
  • Wells are "stimulated” using various treatments (e.g., fracturing, acidizing) of geological formations to improve the recovery of liquid hydrocarbons.
  • Oil and natural gas are found in, and produced from, porous and permeable subterranean formations. Based on techniques known in the art, as well as the preference for the desired product isolated (e.g., formation crude oil or formation gas), it may be preferential to stimulate either crude oil production or gas production from each well.
  • a well drilled into a subterranean formation may penetrate formations containing liquid or gaseous hydrocarbons or both, as well as connate water or brine.
  • the gas-to-oil ratio is termed the GOR.
  • the operator of the well may choose to complete the well in such a way as to produce (for example) predominantly liquid hydrocarbons (crude oil). Alternatively, the operator may be fracturing a tight gas shale formation containing predominantly gaseous hydrocarbons.
  • incorporation of the emulsions or the microemulsions described herein into well-treatment fluids can aid in reducing fluid trapping, for example, by reducing capillary pressure and/or minimizing capillary end effects.
  • incorporation of the emulsions or the microemulsions described herein into well-treatment fluids can promote increased flowback of aqueous phases following well treatment, and thus, increase production of liquid and/or gaseous hydrocarbons.
  • Residual aqueous treatment fluids may include those fluids employed for fracturing (e.g., pumped into the well), as well as residual aqueous fluids originally present in the well.
  • methods of treating an oil or gas well comprise injecting an emulsion or a microemulsion into the wellbore of the oil or gas well to stimulate displacement of residual aqueous treatment fluid by formation crude oil or formation gas, and increase production of liquid or gaseous hydrocarbons by the well.
  • methods are provided for selecting a composition for treating an oil or gas well.
  • the inventors have discovered that certain solvents are more effective at stimulating displacement of residual aqueous treatment fluid by formation crude oil and others are more effective for stimulating displacement of residual aqueous treatment fluid by formation gas for the oil or gas well.
  • the microemulsion may be diluted and/or combined with other liquid component(s) prior to and/or during injection.
  • the microemulsion is diluted with an aqueous carrier fluid (e.g., water, brine, sea water, fresh water, or a well-treatment fluid (e.g., such as a fluid comprising an acid, a fracturing fluid comprising polymers, sand, etc., slickwater) prior to and/or during injection into the wellbore.
  • an aqueous carrier fluid e.g., water, brine, sea water, fresh water
  • a well-treatment fluid e.g., such as a fluid comprising an acid, a fracturing fluid comprising polymers, sand, etc., slickwater
  • a composition for injecting into a wellbore comprising a microemulsion as described herein and an aqueous carrier fluid, wherein the microemulsion is present in an amount between about 0.1 and about 50 gallons per thousand gallons of dilution fluid ("gpt"), or between about 0.5 and about 10 gpt, or between about 0.5 and about 2 gpt.
  • gpt dilution fluid
  • microemulsion does not result in the breakdown of the microemulsion.
  • emulsions or microemulsion are provided.
  • the terms should be understood to include emulsions or microemulsions that have a water continuous phase, or that have an oil continuous phase, or microemulsions that are bicontinuous.
  • the term "emulsion” is given its ordinary meaning in the art and refers to dispersions of one immiscible liquid in another, in the form of droplets, with diameters approximately in the range of 100 1,000 nanometers. Emulsions may be thermodynamically unstable and/or require high shear forces to induce their formation.
  • the term "microemulsion” is given its ordinary meaning in the art and refers to dispersions of one immiscible liquid in another, in the form of droplets, with diameters approximately in the range between about 1 and about 1000 nm, or between 10 and about 1000 nanometers, or between about 10 and about 500 nm, or between about 10 and about 300 nm, or between about 10 and about 100 nm.
  • Microemulsions are clear or transparent because they contain particles smaller than the wavelength of visible light.
  • microemulsions are homogeneous thermodynamically stable single phases, and form spontaneously, and thus, differ markedly from thermodynamically unstable emulsions, which generally depend upon intense mixing energy for their formation.
  • Microemulsions may be characterized by a variety of advantageous properties including, by not limited to, (i) clarity, (ii) very small particle size, (iii) ultra-low interfacial tensions, (iv) the ability to combine properties of water and oil in a single homogeneous fluid, (v) shelf life stability, and (vi) ease of preparation.
  • the microemulsions described herein are stabilized microemulsions that are formed by the combination of a solvent- surfactant blend with an appropriate oil-based or water-based carrier fluid.
  • the microemulsion forms upon simple mixing of the components without the need for high shearing generally required in the formation of ordinary emulsions.
  • microemulsion is a thermodynamically stable system, and the droplets remain finely dispersed over time.
  • the average droplet size ranges from about 10 nm to about 300 nm.
  • the emulsion or microemulsion is a single emulsion or microemulsion.
  • the emulsion or microemulsion comprises a single layer of a surfactant.
  • the emulsion or microemulsion may be a double or multilamellar emulsion or microemulsion.
  • the emulsion or microemulsion comprises two or more layers of a surfactant.
  • the emulsion or microemulsion comprises a single layer of surfactant surrounding a core (e.g., one or more of water, oil, solvent, and/or other additives) or a multiple layers of surfactant (e.g., two or more concentric layers surrounding the core).
  • the emulsion or microemulsion comprises two or more immiscible cores (e.g., one or more of water, oil, solvent, and/or other additives which have equal or about equal affinities for the surfactant).
  • a microemulsion comprises water, a solvent, and a surfactant.
  • the microemulsion may further comprise additional components, for example, a freezing point depression agent. Details of each of the components of the microemulsions are described in detail herein.
  • the components of the microemulsions are selected so as to reduce or eliminate the hazards of the microemulsion to the environment and/or the subterranean reservoirs.
  • the microemulsion generally comprises a solvent.
  • the solvent, or a combination of solvents may be present in the microemulsion in any suitable amount.
  • the total amount of solvent present in the microemulsion is between about 2 wt and about 60 wt , or between about 5 wt and about 40 wt , or between about 5 wt and about 30 wt , versus the total microemulsion composition.
  • the water to solvent ratio in a microemulsion may be varied.
  • the ratio of water to solvent, along with other parameters of the solvent may be varied so that displacement of residual aqueous treatment fluid by formation gas and/or formation crude is preferentially stimulated.
  • the ratio of water to solvent is between about 15: 1 and 1: 10, or between 9: 1 and 1:4, or between 3.2: 1 and 1:4.
  • the solvent when displacement of residual aqueous treatment fluid by formation crude oil is preferentially stimulated, is selected from the group consisting of unsubstituted cyclic or acyclic, branched or unbranched alkanes having 6- 12 carbon atoms, unsubstituted acyclic branched or unbranched alkenes having one or two double bonds and 6-12 carbon atoms, cyclic or acyclic, branched or unbranched alkanes having 9-12 carbon atoms and substituted with only an -OH group, branched or unbranched dialkylether compounds having the formula C n H 2n+ iOC m H 2m+ i, wherein n + m is between 6 and 16, and aromatic solvents having a boiling point between about 300- 400 °F.
  • the solvent is an unsubstituted cyclic or acyclic, branched or unbranched alkane having 6-12 carbon atoms.
  • the cyclic or acyclic, branched or unbranched alkane has 6-10 carbon atoms.
  • unsubstituted acyclic unbranched alkanes having 6-12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, and dodecane.
  • Non-limiting examples of unsubstituted acyclic branched alkanes having 6-12 carbon atoms include isomers of methylpentane (e.g., 2-methylpentane, 3-methylpentane), isomers of dimethylbutane (e.g., 2,2-dimethylbutane, 2,3-dimethylbutane), isomers of methylhexane (e.g., 2- methylhexane, 3 -methylhexane), isomers of ethylpentane (e.g., 3-ethylpentane), isomers of dimethylpentane (e.g., 2,2,-dimethylpentane, 2,3-dimethylpentane, 2,4- dimethylpentane, 3,3-dimethylpentane), isomers of trimethylbutane (e.g., 2,2,3- trimethylbutane), isomers of methylheptane (e.g
  • trimethylpentane e.g., 2,2,3-trimethylpentane, 2,2,4-trimethylpentane, 2,3,3- trimethylpentane, 2,3,4-trimethylpentane
  • isomers of ethylmethylpentane e.g., 3- ethyl-2-methylpentane, 3-ethyl-3-methylpentane.
  • unsubstituted cyclic branched or unbranched alkanes having 6-12 carbon atoms include cyclohexane, methylcyclopentane, ethylcyclobutane, propylcyclopropane,
  • the unsubstituted cyclic or acyclic, branched or unbranched alkane having 6-12 carbon is selected from the group consisting of heptane, octane, nonane, decane, 2,2,4-trimethylpentane (isooctane), and propylcyclohexane.
  • the solvent is an unsubstituted acyclic branched or unbranched alkene having one or two double bonds and 6-12 carbon atoms. In some embodiments, the solvent is an unsubstituted acyclic branched or unbranched alkene having one or two double bonds and 6-10 carbon atoms.
  • Non-limiting examples of unsubstituted acyclic unbranched alkenes having one or two double bonds and 6-12 carbon atoms include isomers of hexene (e.g., 1-hexene, 2-hexene), isomers of hexadiene (e.g., 1,3-hexadiene, 1,4-hexadiene), isomers of heptene (e.g., 1-heptene, 2-heptene, 3- heptene), isomers of heptadiene (e.g., 1,5-heptadiene, 1-6, heptadiene), isomers of octene (e.g., 1-octene, 2-octene, 3-octene), isomers of octadiene (e.g., 1,7-octadiene), isomers of nonene, isomers of nonadiene, isomers of decene, isomers
  • the acyclic unbranched alkene having one or two double bonds and 6-12 carbon atoms is an alpha-olefin (e.g., 1-hexene, 1-heptene, 1-octene, 1-nonene, 1- decene, 1 -undecene, 1 -dodecene).
  • alpha-olefin e.g., 1-hexene, 1-heptene, 1-octene, 1-nonene, 1- decene, 1 -undecene, 1 -dodecene.
  • Non-limiting examples unsubstituted acyclic branched alkenes include isomers of methylpentene, isomers of dimethylpentene, isomers of ethylpentene, isomers of methylethylpentene, isomers of propylpentene, isomers of methylhexene, isomers of ethylhexene, isomers of dimethylhexene, isomers of methylethylhexene, isomers of methylheptene, isomers of ethylheptene, isomers of dimethylhexptene, and isomers of methylethylheptene.
  • the unsubstituted acyclic unbranched alkene having one or two double bonds and 6-12 carbon atoms is selected from the group consisting of 1-octene and 1,7-octadiene.
  • the solvent is a cyclic or acyclic, branched or unbranched alkane having 9-12 carbon atoms and substituted with only an -OH group.
  • Non-limiting examples of cyclic or acyclic, branched or unbranched alkanes having 9-12 carbon atoms and substituted with only an -OH group include isomers of nonanol, isomers of decanol, isomers of undecanol, and isomers of dodecanol.
  • the cyclic or acyclic, branched or unbranched alkane having 9-12 carbon atoms and substituted with only an -OH group is selected from the group consisting of 1 -nonanol and 1- decanol.
  • the solvent is a branched or unbranched dialkylether compound having the formula C n H2 n+1 OC m H 2m+1 wherein n + m is between 6 and 16. In some cases, n + m is between 6 and 12, or between 6 and 10, or between 6 and 8.
  • Non- limiting examples of branched or unbranched dialkylether compounds having the formula C n H2n + iOC m H 2 m + i include isomers of C3H7OC3H7, isomers of C 4 H 9 OC3H7, isomers of CsHnOC ⁇ H ?
  • the branched or unbranched dialklyether is an isomer C 6 H 13 OC 6 H 13 (e.g., dihexylether).
  • an emulsion or microemulsion comprises an aromatic solvent.
  • the aromatic solvent includes, but is not limited to, aryl compounds including at least one aromatic carbocyclic groups.
  • the aromatic solvent comprises an optionally substituted phenyl ring.
  • the aromatic solvent comprises a Ce- t o aromatic hydrocarbon.
  • the solvent is an aromatic solvent having a boiling point between about 300-400 °F.
  • aromatic solvents having a boiling point between about 300-400 °F include butylbenzene, hexylbenzene, mesitylene, light aromatic naphtha, and heavy aromatic naphtha.
  • the solvent is selected from the group consisting of cyclic or acyclic, branched or unbranched alkanes having 8 carbon atoms and substituted only with an -OH group and aromatic solvents having a boiling point between about 175-300 °F.
  • the solvent is a cyclic or acyclic, branched or unbranched alkane having 8 carbon atoms and substituted with only an -OH group.
  • cyclic or acyclic, branched or unbranched alkanes having 8 carbon atoms and substituted with only an -OH group include isomers of octanol (e.g., 1-octanol, 2- octanol, 3-octanol, 4-octanol), isomers of methyl heptanol, isomers of ethylhexanol (e.g., 2-ethyl-l-hexanol, 3-ethyl-l-hexanol, 4-ethyl-l-hexanol), isomers of dimethylhexanol, isomers of propylpentanol, isomers of methylethylpentanol, and
  • the cyclic or acyclic, branched or unbranched alkane having 8 carbon atoms and substituted with only an -OH group is selected from the group consisting of 1-octanol and 2-ethyl-l-hexanol.
  • the solvent is an aromatic solvent having a boiling point between about 175-300 °F.
  • aromatic liquid solvents having a boiling point between about 175-300 °F include benzene, xylenes, and toluene.
  • the solvent is not xylene.
  • the microemulsion comprises a first type of solvent and a second type of solvent.
  • the first type of solvent to the second type of solvent ratio in a microemulsion may be present in any suitable ratio.
  • the ratio of the first type of solvent to the second type of solvent is between about 4: 1 and 1:4, or between 2: 1 and 1:2, or about 1: 1.
  • the first type of solvent and the second type of solvent are different and are selected from the group consisting of unsubstituted cyclic or acyclic, branched or unbranched alkanes having 6-12 carbon atoms, unsubstituted acyclic branched or unbranched alkenes having one or two double bonds and 6-12 carbon atoms, cyclic or acyclic, branched or unbranched alkanes having 9-12 carbon atoms and substituted with only an -OH group, branched or unbranched dialkylether compounds having the formula C n H 2n+ iOC m H 2m+ i, wherein n + m is between 6 and 16, and aromatic solvents having a boiling point between about 300-400 °F.
  • the first type of solvent and the second type of solvent are different and are selected from the group consisting of cyclic or acyclic, branched or unbranched alkanes having 8 carbon atoms and substituted with only an - OH group and aromatic solvents having a boiling point between about 175-300 °F.
  • At least one solvent present in the microemulsion is a terpene or terpenoid.
  • the first type of solvent is selected from the group consisting of unsubstituted cyclic or acyclic, branched or unbranched alkanes having 6-12 carbon atoms, unsubstituted acyclic branched or unbranched alkenes having one or two double bonds and 6-12 carbon atoms, cyclic or acyclic, branched or unbranched alkanes having 9-12 carbon atoms and substituted with only an -OH group, branched or unbranched dialkylether compounds having the formula C n H 2n+ iOC m H 2m+ i, wherein n + m is between 6 and 16, and aromatic solvents having a boiling point between about 300-400 °F and the second type of solvent is a terpene or terpenoid.
  • the terpene or terpenoid may be selected so as to preferentially stimulate displacement of residual aqueous treatment fluid by formation crude oil.
  • the terpene or terpenoid for preferentially stimulating displacement of residual aqueous treatment fluid by formation crude oil may have a phase inversion temperature greater than 109.4 °F, as determined by the method described herein.
  • the first type of solvent is selected from the group consisting of cyclic or acyclic, branched or unbranched alkanes having 8 carbon atoms and substituted with only an -OH group and aromatic solvents having a boiling point between about 175-300 °F and the second type of solvent is a terpene or terpenoid.
  • the terpene or terpenoid may be selected so as to preferentially stimulate displacement of residual aqueous treatment fluid by formation gas.
  • the terpene or terpenoid for preferentially stimulating displacement of residual aqueous treatment fluid by formation gas may have a phase inversion
  • microemulsions comprising more than two types of solvents may be utilized in the methods, compositions, and systems described herein.
  • the microemulsion may comprise more than one or two types of solvent, for example, three, four, five, six, or more, types of solvents.
  • the microemulsion may comprise one or more solvents selected from the group consisting of unsubstituted cyclic or acyclic, branched or unbranched alkanes having 6-12 carbon atoms, unsubstituted acyclic branched or unbranched alkenes having one or two double bonds and 6-12 carbon atoms, cyclic or acyclic, branched or unbranched alkanes having 9-12 carbon atoms and substituted with only an -OH group, branched or unbranched dialkylether compounds having the formula C n H 2n+ iOC m H 2m+ i, wherein n + m is between 6 and 16, and aromatic solvents having a boiling point between about 300-400 °F and one or more terpenes or terpenoids.
  • solvents selected from the group consisting of unsubstituted cyclic or acyclic, branched or unbranched alkanes having 6-12 carbon atoms, unsubstitute
  • the microemulsion may comprise one or more solvents selected from the group consisting of cyclic or acyclic, branched or unbranched alkanes having 8 carbon atoms and substituted with only an - OH group and aromatic solvents having a boiling point between about 175-300 °F and one or more terpenes or terpenoids.
  • At least one of the solvents present in the microemulsion is a terpene or a terpenoid.
  • the terpene or terpenoid comprises a first type of terpene or terpenoid and a second type of terpene or terpenoid.
  • Terpenes may be generally classified as monoterpenes (e.g., having two isoprene units), sesquiterpenes (e.g., having 3 isoprene units), diterpenes, or the like.
  • terpenoid also includes natural degradation products, such as ionones, and natural and synthetic derivatives, e.g., terpene alcohols, aldehydes, ketones, acids, esters, epoxides, and hydrogenation products (e.g., see Ullmann's Encyclopedia of Industrial Chemistry, 2012, pages 29-45, herein incorporated by reference). It should be understood, that while much of the description herein focuses on terpenes, this is by no means limiting, and terpenoids may be employed where appropriate. In some cases, the terpene is a naturally occurring terpene.
  • the terpene is a non-naturally occurring terpene and/or a chemically modified terpene (e.g., saturated terpene, terpene amine, fluorinated terpene, or silylated terpene).
  • a chemically modified terpene e.g., saturated terpene, terpene amine, fluorinated terpene, or silylated terpene.
  • the terpene is a monoterpene.
  • Monoterpenes may be further classified as acyclic, monocyclic, and bicyclic (e.g., with a total number of carbons between 18 and 20), as well as whether the monoterpene comprises one or more oxygen atoms (e.g., alcohol groups, ester groups, carbonyl groups, etc.).
  • the terpene is an oxygenated terpene, for example, a terpene comprising an alcohol, an aldehyde, and/or a ketone group.
  • the terpene comprises an alcohol group.
  • Non-limiting examples of terpenes comprising an alcohol group are linalool, geraniol, nopol, a-terpineol, and menthol.
  • the terpene comprises an ether-oxygen, for example, eucalyptol, or a carbonyl oxygen, for example, menthone.
  • the terpene does not comprise an oxygen atom, for example, d-limonene.
  • Non-limiting examples of terpenes include linalool, geraniol, nopol, a-terpineol, menthol, eucalyptol, menthone, d-limonene, terpinolene, ⁇ -occimene, ⁇ -terpinene, a-pinene, and citronellene.
  • the terpene is selected from the group consisting of a-terpeneol, a-pinene, nopol, and eucalyptol.
  • the terpene is nopol.
  • the terpene is eucalyptol.
  • the terpene is not limonene (e.g., d-limonene).
  • the emulsion is free of limonene.
  • the terpene is a non-naturally occurring terpene and/or a chemically modified terpene (e.g., saturated terpene). In some cases, the terpene is a partially or fully saturated terpene (e.g., p-menthane, pinane). In some cases, the terpene is a non-naturally occurring terpene.
  • Non-limiting examples of non-naturally occurring terpenes include, menthene, p-cymene, r-carvone, terpinenes (e.g., alpha- terpinenes, beta-terpinenes, gamma-terpinenes), dipentenes, terpinolenes, borneol, alpha- terpinamine, and pine oils.
  • the terpene may be classified in terms of its phase inversion temperature (" ⁇ ").
  • phase inversion temperature is given its ordinary meaning in the art and refers to the temperature at which an oil in water microemulsion inverts to a water in oil microemulsion (or vice versa).
  • the PIT values described herein were determined using a 1: 1 ratio of terpene (e.g., one or more terpenes):de-ionized water and varying amounts (e.g., between about 20 wt and about 60 wt ; generally, between 3 and 9 different amounts are employed) of a 1: 1 blend of surfactant comprising linear C 12 -C 15 alcohol ethoxylates with on average 7 moles of ethylene oxide (e.g., Neodol 25-7):isopropyl alcohol wherein the upper and lower temperature boundaries of the microemulsion region can be determined and a phase diagram may be generated.
  • terpene e.g., one or more terpenes
  • de-ionized water varying amounts (e.g., between about 20 wt and about 60 wt ; generally, between 3 and 9 different amounts are employed) of a 1: 1 blend of surfactant comprising linear C 12 -C 15 alcohol ethoxylates with on average
  • phase diagram e.g., a plot of temperature against surfactant concentration at a constant oil-to-water ratio
  • fish a plot of temperature against surfactant concentration at a constant oil-to-water ratio
  • the temperature at the vertex is the ⁇ .
  • An exemplary fish diagram indicating the PIT is shown in Figure 1.
  • PITs for non-limiting examples of terpenes determined using this experimental procedure outlined above are given in Table 1.
  • Table 1 Phase inversion temperatures for non-limiting examples of terpenes.
  • the terpene has a PIT greater than and/or less than 43 °C, as determined by the method described herein. In some embodiments, the terpene has a PIT greater than 43 °C, as determined by the method described herein. In some embodiments, the terpene has a PIT less than 43 °C, as determined by the method described herein. In some embodiments, the terpene has a PIT greater than 32 °C, as determined by the method described herein. In some embodiments, the terpene has a PIT less than 32 °C, as determined by the method described herein.
  • the PIT is between about -10 °C and about 70 °C, or between about -4 °C and about 60 °C, as determined by the method described herein. In some embodiments, the minimum PIT is -10 °C, or -4 °C, as determined by the method described herein. In some embodiments, the maximum PIT is 70 °C, or 60 °C, as determined by the method described herein.
  • the terpene may be selected to have a phase inversion temperature greater than 109.4 °F, as determined by the method described herein.
  • the terpene may be selected to have a phase inversion temperature less than 109.4 °F, as determined by the method described herein.
  • the solvent utilized in the emulsion or microemulsion herein may comprise one or more impurities.
  • a solvent e.g., a terpene
  • a natural source e.g., citrus
  • impurities present from the extraction process.
  • the solvent comprises a crude cut (e.g., uncut crude oil, for example, made by settling, separation, heating, etc.).
  • the solvent is a crude oil
  • the solvent is a citrus extract (e.g., crude orange oil, orange oil, etc.).
  • the terpene may be present in the microemulsion in any suitable amount. In some embodiments, terpene is present in an amount between about In some
  • terpene is present in an amount between about 2 wt and about 60 wt , or between about 5 wt and about 40 wt , or between about 5 wt and about 30 wt , versus the total microemulsion composition.
  • the terpene is present in an amount between about 1 wt and about 99 wt%, or between about 2 wt and about 90 wt %, or between about 1 wt and about 60 wt%, or between about 2 wt and about 60 wt%, or between about 1 wt and about 50 wt%, or between about 1 wt and about 30 wt%, or between about 5 wt and about 40 wt%, or between about 5 wt and about 30 wt%, or between about 2 wt and about 25 wt%, or between about 5 wt and about 25 wt%, or between about 60 wt and about 95 wt%, or between about 70 wt or about 95 wt%, or between about 75 wt and about 90 wt%, or between about 80 wt and about 95 wt%, versus the total microemulsion composition.
  • the water to terpene ratio in a microemulsion may be varied.
  • the ratio of water to terpene by weight is between about 3: 1 and about 1:2, or between about 2: 1 and about 1: 1.5.
  • the ratio of water to terpene is between about 10: 1 and about 3: 1, or between about 6: 1 and about 5: 1.
  • the microemulsion comprises an aqueous phase comprising water.
  • the water may be provided from any suitable source (e.g., sea water, fresh water, deionized water, reverse osmosis water, water from field production).
  • the water may be present in any suitable amount.
  • the total amount of water present in the microemulsion is between about 1 wt about 95 wt , or between about 1 wt about 90 wt , or between about 1 wt and about 60 wt , or between about 5 wt and about 60 wt or between about 10 and about 55 wt , or between about 15 and about 45 wt , versus the total microemulsion composition.
  • At the emulsion or microemulsion may comprise mutual solvent which is miscible together with the water and the non-aqueous solvent.
  • the mutual solvent is present in an amount between about at 0.5 wt to about 30% of mutual solvent.
  • suitable mutual solvents include ethyleneglycolmonobutyl ether (EGMBE), dipropylene glycol monomethyl ether, short chain alcohols (e.g., isopropanol), tetrahydrofuran, dioxane, dimethylformamide, and dimethylsulfoxide.
  • the microemulsion comprises a surfactant.
  • the microemulsion may comprise a single surfactant or a combination of two or more surfactants.
  • the surfactant comprises a first type of surfactant and a second type of surfactant.
  • surfactant is given its ordinary meaning in the art and refers to compounds having an amphiphilic structure which gives them a specific affinity for oil/water-type and water/oil-type interfaces which helps the compounds to reduce the free energy of these interfaces and to stabilize the dispersed phase of a microemulsion.
  • surfactant encompasses cationic surfactants, anionic surfactants, amphoteric surfactants, nonionic surfactants, zwitterionic surfactants, and mixtures thereof.
  • the surfactant is a nonionic surfactant.
  • Nonionic surfactants generally do not contain any charges.
  • Amphoteric surfactants generally have both positive and negative charges, however, the net charge of the surfactant can be positive, negative, or neutral, depending on the pH of the solution.
  • Anionic surfactants generally possess a net negative charge.
  • Cationic surfactants generally possess a net positive charge.
  • Zwitterionic surfactants are generally no pH dependent, not pH dependent.
  • a zwitterion is a neutral molecule with a positive and a negative electrical charge, though multiple positive and negative charges can be present. Zwitterions are distinct from dipole, at different locations within that molecule.
  • the surfactant is an amphiphilic block copolymer where one block is hydrophobic and one block is hydrophilic. In some cases, the total molecular weight of the polymer is greater than 5000 daltons.
  • the hydrophilic block of these polymers can be nonionic, anionic, cationic, amphoteric, or zwitterionic.
  • surface energy is given its ordinary meaning in the art and refers to the extent of disruption of intermolecular bonds that occur when the surface is created (e.g., the energy excess associated with the surface as compared to the bulk).
  • surface energy is also referred to as surface tension (e.g., for liquid-gas interfaces) or interfacial tension (e.g., for liquid-liquid interfaces).
  • surfactants generally orient themselves across the interface to minimize the extent of disruption of intermolecular bonds (i.e. lower the surface energy).
  • a surfactant at an interface between polar and non-polar phases orient themselves at the interface such that the difference in polarity is minimized.
  • the surfactant(s) are matched to and/or optimized for the particular oil or solvent in use.
  • the surfactant(s) are selected by mapping the phase behavior of the microemulsion and choosing the surfactant(s) that gives the desired range of stability.
  • the stability of the microemulsion over a wide range of temperatures is targeted as the microemulsion may be subject to a wide range of temperatures due to the environmental conditions present at the subterranean formation and/or reservoir.
  • the surfactant is an alkyl polyglycol ether, for example, having 2-250 ethylene oxide (EO) (e.g., or 2-200, or 2-150, or 2-100, or 2-50, or 2-40) units and alkyl groups of 4-20 carbon atoms.
  • the surfactant is an alkylaryl polyglycol ether having 2-250 EO units (e.g., or 2-200, or 2- 150, or 2-100, or 2-50, or 2-40) and 8-20 carbon atoms in the alkyl and aryl groups.
  • the surfactant is an ethylene oxide/propylene oxide (EO/PO) block copolymer having 2-250 EO or PO units (e.g., or 2-200, or 2-150, or 2-100, or 2-50, or 2-40).
  • the surfactant is a fatty acid polyglycol ester having 6-24 carbon atoms and 2-250 EO units (e.g., or 2-200, or 2-150, or 2-100, or 2-50, or 2-40).
  • the surfactant is a polyglycol ether of hydroxyl-containing triglycerides (e.g., castor oil).
  • the surfactant is an ethylene oxide/propylene oxide block copolymer having 2-250 EO or PO units (e.g., or 2-200, or 2-150, or 2-100, or 2-50, or 2-40).
  • the surfactant is a fatty acid polyglycol ester having 6-24 carbon atoms and 2-250 EO units (e.g., or 2-200, or 2-150, or 2-
  • the surfactant is a fatty ester of glycerol, sorbitol, or pentaerythritol.
  • the surfactant is an amine oxide (e.g., dodecyldimethylamine oxide).
  • the surfactant is an alkyl sulfate, for example having a chain length of 8-18 carbon atoms, alkyl ether sulfates having 8-18 carbon atoms in the hydrophobic group and 1-40 ethylene oxide (EO) or propylene oxide (PO) units.
  • EO ethylene oxide
  • PO propylene oxide
  • the surfactant is a sulfonate, for example, an alkyl sulfonate having 8-18 carbon atoms, an alkylaryl sulfonate having 8-18 carbon atoms, an ester or half ester of sulfosuccinic acid with monohydric alcohols or alkylphenols having 4-15 carbon atoms, or a multisulfonate (e.g., comprising two, three, four, or more, sulfonate groups).
  • the alcohol or alkylphenol can also be ethoxylated with 1 250 EO units (e.g., or 2-200, or 2-150, or 2-100, or 2-50, or 2-40).
  • 1 250 EO units e.g., or 2-200, or 2-150, or 2-100, or 2-50, or 2-40.
  • the surfactant is an alkali metal salt or ammonium salt of a carboxylic acid or poly(alkylene glycol) ether carboxylic acid having 8-20 carbon atoms in the alkyl, aryl, alkaryl or aralkyl group and 1-250 EO or PO units (e.g., or 2-200, or 2-150, or 2- 100, or 2-50, or 2-40).
  • the surfactant is a partial phosphoric ester or the corresponding alkali metal salt or ammonium salt, e.g., an alkyl and alkaryl phosphate having 8-20 carbon atoms in the organic group, an alkylether phosphate or alkarylether phosphate having 8-20 carbon atoms in the alkyl or alkaryl group and 1-250 EO units (e.g., or 2-200, or 2-150, or 2-100, or 2-50, or 2-40).
  • the surfactant is a salt of primary, secondary, or tertiary fatty amine having 8-24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid, and phosphoric acid.
  • the surfactant is a quaternary alkyl- and alkylbenzylammonium salt, whose alkyl groups have 1-24 carbon atoms (e.g., a halide, sulfate, phosphate, acetate, or hydroxide salt).
  • the surfactant is an alkylpyridinium, an alkylimidazolinium, or an alkyloxazolinium salt whose alkyl chain has up to 18 carbons atoms (e.g., a halide, sulfate, phosphate, acetate, or hydroxide salt).
  • the surfactant is amphoteric or zwitterionic, including sultaines (e.g., cocamidopropyl hydroxy sultaine), betaines (e.g., cocamidopropyl betaine), or phosphates (e.g., lecithin).
  • sultaines e.g., cocamidopropyl hydroxy sultaine
  • betaines e.g., cocamidopropyl betaine
  • phosphates e.g., lecithin
  • Non limiting examples of specific surfactants include a linear C12-C15 ethoxylated alcohols with 5-12 moles of EO, lauryl alcohol ethoxylate with 4-8 moles of EO, nonyl phenol ethoxylate with 5-9 moles of EO, octyl phenol ethoxylate with 5-9 moles of EO, tridecyl alcohol ethoxylate with 5-9 moles of EO, Pluronic® matrix of EO/PO copolymers, ethoxylated cocoamide with 4-8 moles of EO, ethoxylated coco fatty acid with 7-11 moles of EO, and cocoamidopropyl amine oxide.
  • the surfactant is a siloxane surfactant as described in U.S. Patent Application Serial No. 13/831,410, filed March 14, 2014, herein incorporated by reference.
  • the surfactant is a Gemini surfactant.
  • Gemini surfactants generally have the structure of multiple amphiphilic molecules linked together by one or more covalent spacers.
  • the surfactant is an extended surfactant, wherein the extended surfactats has the structure where a non-ionic hydrophilic spacer (e.g. ethylene oxide or propylene oxide) connects an ionic hydrophilic group (e.g.
  • the surfactant is an alkoxylated polyimine with a relative solubility number (RSN) in the range of 5-20.
  • RSN values are generally determined by titrating water into a solution of surfactant in l,4dioxane. The RSN values is generally defined as the amount of distilled water necessary to be added to produce persistent turbidity.
  • the surfactant is an alkoxylated novolac resin (also known as a phenolic resin) with a relative solubility number in the range of 5-20.
  • the surfactant is a block copolymer surfactant with a total molecular weight greater than 5000 daltons.
  • the block copolymer may have a hydrophobic block that is comprised of a polymer chain that is linear, branched, hyperbranched, dendritic or cyclic.
  • monomeric repeat units in the hydrophobic chains of block copolymer surfactants are isomers of acrylic, methacrylic, styrenic, isoprene, butadiene, acrylamide, ethylene, propylene and norbornene.
  • the block copolymer may have a hydrophilic block that is comprised of a polymer chain that is linear, branched, hyper branched, dendritic or cyclic.
  • monomeric repeat units in the hydrophilic chains of the block copolymer surfactants are isomers of acrylic acid, maleic acid, methacrylic acid, ethylene oxide, and acrylamine.
  • the surfactant has a structure as in Formula I:
  • R 12 is hydrogen or Ci_6 alkyl. In some embodiments, for a compound of Formula (I), R 12 is H, methyl, or ethyl. In some embodiments, for a compound of Formula (I), R 12 is H.
  • the surfactant has a structure as in Formula II:
  • X + is a metal cation or N(R 13 ) 4 , wherein each R 13 is independently selected from the group consisting of hydrogen, optionally substituted alkyl, or optionally substituted aryl.
  • X + is NH 4 .
  • Non-limiting examples of metal cations are Na + , K + , Mg +2 , and Ca +2 .
  • Y " is -O " , -S0 2 0 ⁇ , or -OS0 2 0 ⁇ .
  • the surfactant has a structure as in Formula III:
  • Z + is N(R 13 ) 3 , wherein each R 13 is independent selected from the group consisting of hydrogen, optionally substituted alkyl, or optionally substituted aryl.
  • Ar is phenyl.
  • each m is 1.
  • each m is 2.
  • n is 6-100, or 1-50, or 6-50, or 6-25, or 1-25, or 5-50, or 5-25, or 5-20.
  • the surfactant(s) are matched to and/or optimized for the particular oil or solvent in use.
  • the surfactant(s) are selected by mapping the phase behavior of the microemulsion and choosing the surfactant(s) that gives the desired range of stability.
  • the stability of the microemulsion over a wide range of temperatures is targeting as the microemulsion may be subject to a wide range of temperatures due to the environmental conditions present at the subterranean formation.
  • the emulsion or microemulsion may comprise one or more additives in addition to water, solvent (e.g., one or more types of solvents), and surfactant (e.g., one or more types of surfactants).
  • the additive is an alcohol, a freezing point depression agent, an acid, a salt, a proppant, a scale inhibitor, a friction reducer, a biocide, a corrosion inhibitor, a buffer, a viscosifier, a clay swelling inhibitor, an oxygen scavenger, and/or a clay stabilizer.
  • the surfactant may be present in the microemulsion in any suitable amount. In some embodiments, the surfactant is present in an amount between about 10 wt and about 70 wt , or between about 15 wt and about 55 wt versus the total
  • the surfactant is present in an amount between about 0 wt and about 99 wt , or between about 10 wt and about 70 wt , or between about 0 wt and about 60 wt , or between about 1 wt and about 60 wt , or between about 5 wt and about 60 wt , or between about 10 wt and about 60 wt , or between 5 wt and about 65 wt , or between 5 wt and about 55 wt , or between about 0 wt and about 40 wt , or between about 15 wt and about 55 wt , or between about 20 wt and about 50 wt , versus the total microemulsion composition.
  • the microemulsion comprises an alcohol.
  • the alcohol may serve as a coupling agent between the solvent and the surfactant and aid in the stabilization of the microemulsion.
  • the alcohol may also lower the freezing point of the microemulsion
  • the microemulsion may comprise a single alcohol or a combination of two or more alcohols.
  • the alcohol is selected from primary, secondary and tertiary alcohols having between 1 and 20 carbon atoms.
  • the alcohol comprises a first type of alcohol and a second type of alcohol.
  • Non-limiting examples of alcohols include methanol, ethanol, isopropanol, n-propanol, n-butanol, i-butanol, sec-butanol, iso-butanol, and t-butanol.
  • the alcohol is ethanol or isopropanol.
  • the alcohol is isopropanol.
  • the alcohol may be present in the emulsion in any suitable amount. In some embodiments, the alcohol is present in an amount between about 0 wt and about 50 wt , or between about 0.1 wt and about 50 wt , or between about 1 wt and about 50 wt , or between about 5 wt and about 40 wt , or between about 5 wt and 35 wt , versus the total microemulsion composition.
  • the microemulsion comprises a freezing point depression agent.
  • the microemulsion may comprise a single freezing point depression agent or a combination of two or more freezing point depression agents.
  • the freezing point depression agent comprises a first type of freezing point depression agent and a second type of freezing point depression agent.
  • freeze point depression agent is given its ordinary meaning in the art and refers to a compound which is added to a solution to reduce the freezing point of the solution. That is, a solution comprising the freezing point depression agent has a lower freezing point as compared to an essentially identical solution not comprising the freezing point depression agent.
  • suitable freezing point depression agents include primary, secondary, and tertiary alcohols with between 1 and 20 carbon atoms. In some embodiments, the alcohol comprises at least 2 carbon atoms, alkylene glycols including polyalkylene glycols, and salts.
  • Non-limiting examples of alcohols include methanol, ethanol, i-propanol, n-propanol, t-butanol, n-butanol, n-pentanol, n-hexanol, and 2-ethyl-hexanol.
  • the freezing point depression agent is not methanol (e.g., due to toxicity).
  • alkylene glycols include ethylene glycol (EG), polyethylene glycol (PEG), propylene glycol (PG), and triethylene glycol (TEG).
  • the freezing point depression agent is not ethylene oxide (e.g., due to toxicity).
  • salts include salts comprising K, Na, Br, Cr, Cr, Cs, or Bi, for example, halides of these metals, including NaCl, KC1, CaCl 2 , and MgCl.
  • the freezing point depression agent comprises an alcohol and an alkylene glycol.
  • the freezing point depression agent comprises a carboxycyclic acid salt and/or a di-carboxycylic acid salt.
  • Another non-limiting example of a freezing point depression agent is a combination of choline chloride and urea.
  • the microemulsion comprising the freezing point depression agent is stable over a wide range of temperatures, for example, between about 25 °F to 150 °F, or between about 50 °F to 200 °F.
  • the freezing point depression agent may be present in the microemulsion in any suitable amount. In some embodiments, the freezing point depression agent is present in an amount between about 1 wt and about 40 wt , or between about 3 wt and about 20 wt , or between about 8 wt and about 16 wt , versus the total microemulsion composition.
  • the freezing point depression agent is present in an amount between about 0 wt and about 70 wt , or between about 1 wt and about 40 wt , or between about 0 wt and about 25 wt , or between about 1 wt and about 25 wt , or between about 1 wt and about 20 wt , or between about 3 wt and about 20 wt , or between about 8 wt and about 16 wt , versus the total microemulsion composition.
  • additives include proppants, scale inhibitors, friction reducers, biocides, corrosion inhibitors, buffers, viscosifiers, clay swelling inhibitors, paraffin dispersing additives, asphaltene dispersing additives, and oxygen scavengers.
  • proppants include grains of sand, glass beads, crystalline silica (e.g., Quartz), hexamethylenetetramine, ceramic proppants (e.g., calcined clays), resin coated sands, and resin coated ceramic proppants.
  • crystalline silica e.g., Quartz
  • ceramic proppants e.g., calcined clays
  • resin coated sands e.g., calcined clays
  • resin coated ceramic proppants e.g., resin coated ceramic proppants.
  • Other proppants are also possible and will be known to those skilled in the art.
  • Non-limiting examples of scale inhibitors include one or more of methyl alcohol, organic phosphonic acid salts (e.g., phosphonate salt), polyacrylate, ethane- 1,2-diol, calcium chloride, and sodium hydroxide.
  • organic phosphonic acid salts e.g., phosphonate salt
  • polyacrylate e.g., polyacrylate
  • ethane- 1,2-diol calcium chloride
  • sodium hydroxide sodium hydroxide
  • Non-limiting examples of buffers include acetic acid, acetic anhydride, potassium hydroxide, sodium hydroxide, and sodium acetate.
  • Other buffers are also possible and will be known to those skilled in the art.
  • Non-limiting examples of corrosion inhibitors include isopropanol, quaternary ammonium compounds, thiourea/formaldehyde copolymers, propargyl alcohol and methanol.
  • Other corrosion inhibitors are also possible and will be known to those skilled in the art.
  • biocides include didecyl dimethyl ammonium chloride, gluteral, Dazomet, bronopol, tributyl tetradecyl phosphonium chloride, tetrakis
  • Non-limiting examples of clay swelling inhibitors include quaternary ammonium chloride and tetramethylammonium chloride. Other clay swelling inhibitors are also possible and will be known to those skilled in the art.
  • friction reducers include petroleum distillates, ammonium salts, polyethoxylated alcohol surfactants, and anionic polyacrylamide copolymers. Other friction reducers are also possible and will be known to those skilled in the art.
  • oxygen scavengers include sulfites, and bisulfites. Other oxygen scavengers are also possible and will be known to those skilled in the art.
  • paraffin dispersing additives and asphaltene dispersing additives include active acidic copolymers, active alkylated polyester, active alkylated polyester amides, active alkylated polyester imides, aromatic naphthas, and active amine sulfonates.
  • Other paraffin dispersing additives are also possible and will be known to those skilled in the art.
  • the other additives are present in an amount between about 0 wt about 70 wt , or between about 0 wt % and about 30 wt , or between about 1 wt and about 30 wt , or between about 1 wt and about 25 wt , or between about 1 and about 20 wt , versus the total microemulsion composition.
  • the microemulsion comprises an acid or an acid precursor.
  • the microemulsion may comprise an acid when used during acidizing operations.
  • the microemulsion may comprise a single acid or a combination of two or more acids.
  • the acid comprises a first type of acid and a second type of acid.
  • acids or di-acids include
  • the microemulsion comprises an organic acid or organic di-acid in the ester (or di-ester) form, whereby the ester (or diester) is hydrolyzed in the wellbore and/or reservoir to form the parent organic acid and an alcohol in the wellbore and/or reservoir.
  • esters or di-esters include isomers of methyl formate, ethyl formate, ethylene glycol diformate, a,a-4-trimethyl-3-cyclohexene-l-methylformate, methyl lactate, ethyl lactate, ⁇ , ⁇ -4- trimethyl 3-cyclohexene-l-methyllactate, ethylene glycol dilactate, ethylene glycol diacetate, methyl acetate, ethyl acetate, a,a,-4-trimethyl-3-cyclohexene-l-methylacetate, dimethyl succinate, dimethyl maleate, di(a,a-4-trimethyl-3-cyclohexene-l- methyl) succinate, l-methyl-4-(l-methylethenyl)-cyclohexylformate, l-methyl-4-(l- ethylethenyl)cyclohexylactate, 1 -methyl-4- ( 1 -methylethenyl
  • the microemulsion comprises a salt.
  • the presence of the salt may reduce the amount of water needed as a carrier fluid, and in addition, may lower the freezing point of the microemulsion.
  • the microemulsion may comprise a single salt or a combination of two or more salts.
  • the salt comprises a first type of salt and a second type of salt.
  • Non-limiting examples of salts include salts comprising K, Na, Br, Cr, Cs, or Li, for example, halides of these metals, including NaCl, KC1, CaCl 2 , and MgCl 2 .
  • the microemulsion comprises a clay stabilizer.
  • the microemulsion may comprise a single clay stabilizer or a combination of two or more clay stabilizers.
  • the salt comprises a first type of clay stabilizer and a second type of clay stabilizer.
  • Non-limiting examples of clay stabilizers include salts above, polymers (PAC, PHPA, etc.), glycols, sulfonated asphalt, lignite, sodium silicate, and choline chloride.
  • the other additives are present in an amount between about 0 wt about 70 wt , or between about 1 wt and about 30 wt , or between about 1 wt and about 25 wt , or between about 1 and about 20 wt , versus the total microemulsion composition.
  • the components of the microemulsion and/or the amounts of the components may be selected so that the microemulsion is stable over a wide-range of temperatures.
  • the microemulsion may exhibit stability between about -40 °F and about 400 °F, or between about -40 °F and about 300 °F or between about -40 °F and about 150 °F.
  • the lower boundary may be determined by the freezing point and the upper boundary may be determined by the cloud point and/or using spectroscopy methods.
  • Stability over a wide range of temperatures may be important in embodiments where the microemulsions are being employed in applications comprising environments wherein the temperature may vary significantly, or may have extreme highs (e.g., desert) or lows (e.g., artic).
  • emulsions or microemulsions comprising water, a solvent, and a surfactant, wherein the solvents and surfactants may be as described herein.
  • the solvent comprises more than one type of solvent, for example, two, three, four, five, six, or more, types of solvents.
  • At least one solvent is selected from the group consisting of unsubstituted cyclic or acyclic, branched or unbranched alkanes having 6-12 carbon atoms, unsubstituted acyclic branched or unbranched alkenes having one or two double bonds and 6-12 carbon atoms, cyclic or acyclic, branched or unbranched alkanes having 9-12 carbon atoms and substituted with only an -OH group, branched or unbranched dialkylether compounds having the formula C n H2 n+1 OC m H 2m+1 , wherein n + m is between 6 and 16, and aromatic solvents having a boiling point between about 300-400 °F.
  • At least one solvent is selected from the group consisting of cyclic or acyclic, branched or unbranched alkanes having 8 carbon atoms and substituted with only an -OH group and aromatic solvents having a boiling point between about 175-300 °F.
  • at least one solvent is a terpene.
  • the microemulsion may further comprise addition components, for example, a freezing point depression agent.
  • at least one solvent is selected from the group consisting of butylbenzene, heavy aromatic naphtha, light aromatic naphtha, 1-nonanol,
  • propylcyclohexane 1-decanol, dihexylether, 1,7-octadiene, hexylbenzene, nonane, decane, 1-octene, isooctane, octane, heptane, mesitylene, xylenes, toluene, 2-ethyl-l- hexanol, 1-octanol.
  • At least one solvent is selected from the group consisting of butylbenzene, heavy aromatic naphtha, light aromatic naphtha, 1-nonanol, propylcyclohexane, 1-decanol, dihexylether, 1,7-octadiene, hexylbenzene, nonane, decane, 1-octene, isooctane, octane, heptane, mesitylene, toluene, 2-ethyl-l -hexanol, 1- octanol.
  • the at least one solvent is not xylene.
  • at least one solvent is an alpha-olefin.
  • composition for injecting into a wellbore comprising an aqueous carrier fluid, and an emulsion or a microemulsion as described herein, wherein the emulsion or the microemulsion is present in an amount between about 0.1 wt and about 2 wt versus the total composition.
  • the emulsion or microemulsion comprises an aqueous phase, a surfactant, a freezing point depression agent, and a solvent as described herein.
  • the solvent is as described herein.
  • the solvent comprises an alpha-olefin, for example, having between 6-12 carbon atoms.
  • the solvent comprises a cyclic or acyclic, branched or unbranched alkane having 8-12, or 9-12, or 8, or 9, or 10, or 11, or 12 carbon atoms and substituted with only an -OH group.
  • the total amount of solvent present in the emulsion or microemulsion is between about 2 wt and about 60 wt and/or the ratio of the aqueous phase to solvent in the emulsion or microemulsion is between 15: 1 and 1: 10.
  • the composition may comprise more than one type of solvent.
  • the solvent comprises an alpha- olefin and a terpene.
  • the solvent comprises a cyclic or acyclic, branched or unbranched alkane having 8-12 carbon atoms and substituted with only an -OH group and a terpene.
  • microemulsions described herein may be formed using methods known to those of ordinary skill in the art.
  • the aqueous and non-aqueous phases may be combined (e.g., the water and the solvent(s)), followed by addition of a surfactant(s) and optionally other components (e.g., freezing point depression agent(s)) and agitation.
  • a surfactant(s) and optionally other components e.g., freezing point depression agent(s)
  • agitation e.g., freezing point depression agent(s)
  • the strength, type, and length of the agitation may be varied as known in the art depending on various factors including the components of the microemulsion, the quantity of the microemulsion, and the resulting type of microemulsion formed.
  • Agitation may be provided by any suitable source, for example, a vortex mixer, a stirrer (e.g., magnetic stirrer), etc.
  • any suitable method for injecting the microemulsion e.g., a diluted microemulsion
  • microemulsion into a wellbore
  • the microemulsion may be injected into a subterranean formation by injecting it into a well or wellbore in the zone of interest of the formation and thereafter pressurizing it into the formation for the selected distance.
  • Methods for achieving the placement of a selected quantity of a mixture in a subterranean formation are known in the art.
  • the well may be treated with the microemulsion for a suitable period of time.
  • the microemulsion and/or other fluids may be removed from the well using known techniques, including producing the well.
  • experiments may be carried out to determine displacement of residual aqueous treatment fluid by formation crude oil or formation gas by a microemulsion (e.g., a diluted microemulsion).
  • a microemulsion e.g., a diluted microemulsion
  • displacement of residual aqueous treatment fluid by formation crude oil may be determined using the method described in Example 2 and/or displacement of residual aqueous treatment fluid by formation gas may be determined using the method described in Example 3.
  • Certain compounds of the present invention may exist in particular geometric or stereoisomeric forms.
  • the present invention contemplates all such compounds, including cis- and iraws-isomers, R- and S-enantiomers, diastereomers, (D)-isomers, (L)- isomers, the racemic mixtures thereof, and other mixtures thereof, as falling within the scope of the invention.
  • Additional asymmetric carbon atoms may be present in a substituent such as an alkyl group. All such isomers, as well as mixtures thereof, are intended to be included in this invention.
  • Isomeric mixtures containing any of a variety of isomer ratios may be utilized in accordance with the present invention. For example, where only two isomers are combined, mixtures containing 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 96:4, 97:3, 98:2, 99: 1, or 100:0 isomer ratios are all contemplated by the present invention. Those of ordinary skill in the art will readily appreciate that analogous ratios are contemplated for more complex isomer mixtures.
  • aliphatic includes both saturated and unsaturated, nonaromatic, straight chain (i.e., unbranched), branched, acyclic, and cyclic (i.e., carbocyclic) hydrocarbons, which are optionally substituted with one or more functional groups.
  • aliphatic is intended herein to include, but is not limited to, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and cycloalkynyl moieties.
  • alkyl includes straight, branched and cyclic alkyl groups.
  • alkenyl alkynyl
  • alkynyl alkenyl
  • alkynyl alkynyl
  • aliphatic is used to indicate those aliphatic groups (cyclic, acyclic, substituted, unsubstituted, branched or unbranched) having 1-20 carbon atoms.
  • Aliphatic group substituents include, but are not limited to, any of the substituents described herein, that result in the formation of a stable moiety ⁇ e.g., aliphatic, alkyl, alkenyl, alkynyl, heteroaliphatic, heterocyclic, aryl, heteroaryl, acyl, oxo, imino, thiooxo, cyano, isocyano, amino, azido, nitro, hydroxyl, thiol, halo, aliphaticamino, heteroaliphaticamino, alkylamino, heteroalkylamino, arylamino, heteroarylamino, alkylaryl, arylalkyl, aliphaticoxy, heteroaliphaticoxy, alkyloxy, heteroalkyloxy, aryloxy, heteroaryloxy, aliphaticthioxy, heteroaliphaticthioxy, alkylthioxy, heteroalkylthioxy, arylthioxy, heteroarylthioxy,
  • alkane is given its ordinary meaning in the art and refers to a saturated hydrocarbon molecule.
  • branched alkane refers to an alkane that includes one or more branches, while the term “unbranched alkane” refers to an alkane that is straight-chained.
  • cyclic alkane refers to an alkane that includes one or more ring structures, and may be optionally branched.
  • acyclic alkane refers to an alkane that does not include any ring structures, and may be optionally branched.
  • alkene is given its ordinary meaning in the art and refers to an unsaturated hydrocarbon molecule that includes one or more carbon-carbon double bonds.
  • branched alkene refers to an alkene that includes one or more branches, while the term “unbranched alkene” refers to an alkene that is straight-chained.
  • cyclic alkene refers to an alkene that includes one or more ring structures, and may be optionally branched.
  • acyclic alkene refers to an alkene that does not include any ring structures, and may be optionally branched.
  • aromatic is given its ordinary meaning in the art and refers to aromatic carbocyclic groups, having a single ring (e.g., phenyl), multiple rings (e.g., biphenyl), or multiple fused rings in which at least one is aromatic (e.g., 1,2,3,4- tetrahydronaphthyl, naphthyl, anthryl, or phenanthryl). That is, at least one ring may have a conjugated pi electron system, while other, adjoining rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls and/or heterocyclyls.
  • aryl is given its ordinary meaning in the art and refers to aromatic carbocyclic groups, optionally substituted, having a single ring (e.g., phenyl), multiple rings (e.g., biphenyl), or multiple fused rings in which at least one is aromatic (e.g.,
  • At least one ring may have a conjugated pi electron system, while other, adjoining rings can be
  • aryl group may be optionally substituted, as described herein.
  • Substituents include, but are not limited to, any of the previously mentioned substitutents, i.e., the substituents recited for aliphatic moieties, or for other moieties as disclosed herein, resulting in the formation of a stable compound.
  • an aryl group is a stable mono- or polycyclic unsaturated moiety having preferably 3-14 carbon atoms, each of which may be substituted or unsubstituted.
  • microemulsions in Table 2 were prepared by mixing 46 parts by weight of this blend with 27 parts by weight a solvent as shown in Table 2 and 27 parts by weight of water, with the exception of nonane and decane, which were prepared by mixing 50 parts of the blend with 25 parts by weight of solvent and 25 parts per weight of water.
  • Two emulsions were also prepared using the same method comprising a mixture of a hydrocarbon solvent and a terpene (1: 1 ratio of hydrocarbon:terpene). The solvents were obtained through commercial sources.
  • the heavy aromatic naphtha employed was Exxon Aromatic 150 Fluid which comprises C 10-12 alkyl benzenes and has a distillation temperature between 363-396 °F and the light aromatic naphtha employed was Exxon Aromatic 100 Fluid which comprises C ⁇ o dialkyl and trialkylbenzenes and has a distillation temperature between 322-340 °F.
  • the mixtures were identified as a microemulsion based on the spontaneous formation with minimal mechanical energy input to form a clear dispersion from an immiscible mixture of water and solvent upon addition of an appropriate amount of surfactant.
  • the order of mixing of this and other compositions described in this example were not necessary, but for convenience, a procedure was generally followed in which a mixture of the surfactant and the isopropyl alcohol was first prepared then combined that with a mixture of the solvent and water. With small samples, in the laboratory, a few seconds of gentle mixing yielded a transparent dispersion.
  • gallons per thousand (gpt) dilutions of the microemulsions were prepared and tested.
  • the dilutions comprise 0.2 wt% of the microemulsion in 2 wt% KC1 solution.
  • the process employed dispensing 200 microliters of the microemulsion into a vortex of a vigorously stirred beaker containing 100 mL of 2 wt% KC1, generally at room temperature (e.g., about 25 °C).
  • Table 2 2 gallons per thousand
  • Tables 3 and 4 provide data related to microemulsions comprising octane wherein the water to oil ratio and the surfactant were varied.
  • the components of the formulation are given in Table 4 and the results are provided in Table 3.
  • the greater efficacy of displacement of residual aqueous treatment fluid for the microemulsions comprising octane by crude oil compared with gaseous hydrocarbon was maintained over the range of water to oil ratio of 3.2: 1 to 1:4 or surf actant/co- solvent concentrations from 40-50.
  • Table 3 Effectiveness of brine displacement by gas and oil using a microemulsion
  • This example described a non-limiting experiment for determining displacement of residual aqueous treatment fluid by formation crude oil.
  • a 25 cm long, 2.5 cm diameter capped glass chromatography column was packed with 77 grams of 100 mesh sand. The column was left open on one end and a PTFE insert containing a recessed bottom, 3.2 mm diameter outlet, and nipple was placed into the other end. Prior to placing the insert into the column, a 3 cm diameter filter paper disc (Whatman, #40) was pressed firmly into the recessed bottom of the insert to prevent leakage of 100 mesh sand. A 2" piece of vinyl tubing was placed onto the nipple of the insert and a clamp was fixed in place on the tubing prior to packing.
  • the columns were gravity-packed by pouring approximately 25 grams of the diluted microemulsions (e.g., the microemulsions described in Example 1, and diluted with 2% KC1, e.g., to about 2 gpt, or about 1 gpt) into the column followed by a slow, continuous addition of sand. After the last portion of sand had been added and was allowed to settle, the excess of brine was removed from the column so that the level of liquid exactly matched the level of sand. Pore volume in the packed column was calculated as the difference in mass of fluid prior to column packing and after the column had been packed. Three additional pore volumes of brine were passed through the column.
  • inner-diameter capped glass chromatography column was filled with approximately 410 + 20 g of 20/40 mesh Ottawa sand and the diluted microemulsions (e.g., the microemulsions described in Example 1, and diluted with 2% KC1, e.g., to about 2 gpt, or about 1 gpt).
  • the diluted microemulsions e.g., the microemulsions described in Example 1, and diluted with 2% KC1, e.g., to about 2 gpt, or about 1 gpt.
  • This example describes a method for determining the phase inversion
  • a solvent e.g., a terpene
  • the methods are described in the literature (e.g., see Strey, Microemulsion micro structure and interfacial curvature. Colloid & Polymer Science, 1994. 272(8): p. 1005-1019; Kahlweit et al., Phase Behavior of Ternary Systems of the Type HiO-Oil-Nonionic Amphiphile (Microemulsions).
  • the phase inversion temperature was determined as the point on the "fish-tail" at which the temperature range of one-phase microemulsion closes to a vertex.
  • the temperature at the vertex was selected as the PIT.
  • An exemplary fish diagram indicating the PIT is shown in Figure 1.
  • the PIT values which were measured using this above-described procedure are shown in Table 1. Those terpenes containing alcohol groups (linalool, geraniol, nopol, a-terpineol and menthol), gave PIT values between -4 °C and 16 °C.
  • Example 2 A series of laboratory tests similar to as described in Example 1 were conducted to characterize the effectiveness of a series of microemulsions incorporating a range of terpenes.
  • the phase inversion temperatures of the terpenes were determined as described in Example 4.
  • Table 5 shows results for displacement of residual aqueous treatment fluid by oil and gas for formulations (e.g., using the experimental procedures outlined in Examples 2 and 3) using dilutions of the microemulsions comprising 46 parts of 1: 1 Neodol 25-7, 27 parts deionized water, and 27 parts terpene solvent).
  • the dilutions were prepared of each microemulsion in 2% KC1, at 2 gpt.
  • Table 5 shows displacement by gas results for the dilutions that demonstrates that terpene solvents with ⁇ values higher than 109.4 °F give approximately 40% recovery, while those with ⁇ values below 109.4 °F give significantly higher recovery.
  • Displacement results for 2 gpt dilution of microemulsions comprising 46:27:27 surfactant:water:terpene + isopropanol formulations.
  • T/S/W stands for terpene weight %/l: l surfactant- IP A weight /deionized water wt
  • a reference to "A and/or B,” when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A without B (optionally including elements other than B); in another embodiment, to B without A (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
  • At least one of A and B can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.

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Abstract

La présente invention concerne des procédés et des compositions de stimulation de la production d'hydrocarbures (par exemple, du pétrole brut d'une formation et/ou du gaz d'une formation) à partir de formations souterraines. Dans certains modes de réalisation, les compositions sont des émulsions ou des microémulsions, qui peuvent comprendre de l'eau, un solvant et un tensioactif. Dans certains modes de réalisation, l'invention concerne des procédés de sélection d'une composition de traitement d'un puits de pétrole ou de gaz.
PCT/US2014/042326 2013-06-14 2014-06-13 Procédés et compositions de stimulation de la production d'hydrocarbures à partir de formations souterraines WO2014201367A1 (fr)

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CN201480002623.0A CN104769214B (zh) 2013-06-14 2014-06-13 用于刺激从地下地层中生产烃类的方法和组合物
AU2014278002A AU2014278002B2 (en) 2013-06-14 2014-06-13 Methods and compositions for stimulating the production of hydrocarbons from subterranean formations
CA2915351A CA2915351C (fr) 2013-06-14 2014-06-13 Procedes et compositions de stimulation de la production d'hydrocarbures a partir de formations souterraines
AU2017261565A AU2017261565B2 (en) 2013-06-14 2017-11-16 Methods and compositions for stimulating the production of hydrocarbons from subterranean formations

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EP2970750A4 (fr) * 2013-03-14 2017-04-19 Flotek Chemistry, LLC Procédés et compositions pour la stimulation de la production d'hydrocarbures à partir de formations souterraines
AU2015227467B2 (en) * 2015-09-17 2018-11-08 Flotek Chemistry, Llc Methods and compositions for use in oil and/or gas wells comprising a terpene alcohol
US10377942B2 (en) 2017-04-06 2019-08-13 Nissan Chemical America Corporation Hydrocarbon formation treatment micellar solutions
US10563117B2 (en) 2017-09-13 2020-02-18 Nissan Chemical America Corporation Crude oil recovery chemical fluids
US10801310B2 (en) 2017-09-26 2020-10-13 Nissan Chemcial America Corporation Using gases and hydrocarbon recovery fluids containing nanoparticles to enhance hydrocarbon recovery
US10870794B2 (en) 2017-11-03 2020-12-22 Nissan Chemical America Corporation Using brine resistant silicon dioxide nanoparticle dispersions to improve oil recovery
US10934478B2 (en) 2018-11-02 2021-03-02 Nissan Chemical America Corporation Enhanced oil recovery using treatment fluids comprising colloidal silica with a proppant

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EP2970750A4 (fr) * 2013-03-14 2017-04-19 Flotek Chemistry, LLC Procédés et compositions pour la stimulation de la production d'hydrocarbures à partir de formations souterraines
WO2015157156A1 (fr) * 2014-04-08 2015-10-15 Fu Xuebing Systèmes et procédés pour accélérer la production d'hydrocarbures visqueux dans un réservoir souterrain avec des émulsions comprenant des agents chimiques
AU2015227467B2 (en) * 2015-09-17 2018-11-08 Flotek Chemistry, Llc Methods and compositions for use in oil and/or gas wells comprising a terpene alcohol
US10975289B2 (en) 2017-04-06 2021-04-13 Nissan Chemical America Corporation Hydrocarbon formation treatment micellar solutions
US10377942B2 (en) 2017-04-06 2019-08-13 Nissan Chemical America Corporation Hydrocarbon formation treatment micellar solutions
US10557078B2 (en) 2017-04-06 2020-02-11 Nissan Chemical America Corporation Brine resistant silica sol
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US10563117B2 (en) 2017-09-13 2020-02-18 Nissan Chemical America Corporation Crude oil recovery chemical fluids
US10801310B2 (en) 2017-09-26 2020-10-13 Nissan Chemcial America Corporation Using gases and hydrocarbon recovery fluids containing nanoparticles to enhance hydrocarbon recovery
US10870794B2 (en) 2017-11-03 2020-12-22 Nissan Chemical America Corporation Using brine resistant silicon dioxide nanoparticle dispersions to improve oil recovery
US11180692B2 (en) 2017-11-03 2021-11-23 Nissan Chemical America Corporation Using brine resistant silicon dioxide nanoparticle dispersions to improve oil recovery
US11274244B2 (en) 2017-11-03 2022-03-15 Nissan Chemical America Corporation Using brine resistant silicon dioxide nanoparticle dispersions to improve oil recovery
US10934478B2 (en) 2018-11-02 2021-03-02 Nissan Chemical America Corporation Enhanced oil recovery using treatment fluids comprising colloidal silica with a proppant

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AU2014278002A1 (en) 2016-01-07
AU2017261565A1 (en) 2017-12-07
EP3008283A1 (fr) 2016-04-20
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CN104769214A (zh) 2015-07-08
CA2915351C (fr) 2020-09-15

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