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1. (WO2018124872) COMPOSITION WITH FOAMING PROPERTIES
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COMPOSITION WITH FOAMING PROPERTIES

Technical Field

The present invention generally relates to a composition with foaming properties. The present invention also relates to the use of said composition in enhanced oil recovery techniques, such as foam-assisted water-alternating-gas processes.

Background

Crude oil is a vital source of energy for the world and makes a major contribution to the world economy.

Conventional oil production strategies have followed primary depletion, secondary recovery and tertiary recovery processes. During the primary depletion stage, reservoir drive uses a number of natural mechanisms to displace oil from porous rocks. Recovery factor during the primary recovery stage may average 5-20%. At some point, there will be insufficient underground pressure to force oil to the surface. Secondary recovery methods are then applied wherein the oil is subjected to immiscible displacement with injected fluids such as water or gas. Typical recovery factor after primary and secondary oil recovery operations may be between 30-50%. Much of the remaining oil is trapped in porous media. Tertiary, or enhanced oil recovery (EOR) methods, increase the mobility of oil in order to increase extraction.

There are currently several different methods for EOR, including steam flood and water flood injection and hydraulic fracturing. One method is through a water alternating-gas (WAG) process. WAG injection consists of injection of intermittent slugs of water and gas to improve gas sweep efficiency in the reservoir. However, a problem with this technique is the tendency of the injected gas to sweep oil from only a limited area of the reservoir because the viscosity of gas used is much lower than that of most oils, which will limit sweep efficiency. Due to the effects of density and gravity, gas will tend to move at the upper reservoir while water moves at the bottom reservoir, thereby leaving unswept oil in the middle.

Foam has been used to improve sweep efficiency by controlling gas mobility, gas front and early gas breakthrough in foam assisted water-alternating gas (FAWAG) processes. This is achieved by increasing the effective viscosity and decreasing the relative permeability of the gas.

While foam has been used in EOR processes before, the use of conventional foaming and foam stabilizing mixtures has been problematic. For example, foam compositions in general tend to destabilize when contacted by oil. Accordingly, when used in oil recovery applications, these foam compositions may prematurely destabilize resulting in an undesired loss of sweep efficiency .

Another problem with conventional foaming and foam stabilizing mixtures is their tendency to destabilize under more severe reservoir conditions such as high temperatures (>95°C) . The use of seawater in FAWAG also creates conditions of high salinity (>35,000 ppm) which is also not conducive to the life span of foams.

Known foaming and foam stabilizing mixtures may also exhibit high adsorption rates on reservoir rock, thereby limiting their function in oil recovery applications.

This is disadvantageous in oil recovery applications because foams that dissipate quickly diminish the effectiveness of FAWAG techniques and therefore limiting oil recovery.

There is a need to provide a foam composition that overcomes, or at least ameliorates, one or more of the disadvantages described above.

There is a need to provide a foam composition with a relatively long life span.

There is further a need to provide a foam composition that maintains good foam generation and stability under severe reservoir conditions of high temperature and high salinity.

There is a need to provide a foam composition that has a low adsorption rate on reservoir rock.

Summary

According to a first aspect, there is provided a composition with foaming properties comprising an acrylic copolymer amphiphilic surfactant, and at least one compound selected from the group consisting of olefin sulfonate, sulfo-betaine and betaine.

According to a second aspect, there is a provided a composition with foaming properties according to the first aspect, when used as a foam.

Advantageously, the disclosed composition with foaming properties may be useful to generate stable foams at high temperature and salinity.

Further advantageously, the above components may display synergistic activity and result in an improved composition with foaming properties. The olefin sulfonate may reduce adsorption on reservoir rock and impart foam stability at high temperature and in the presence of hard water. Betaine and/or sulfo-betaine may be a foam booster and increase foam generation. The acrylic copolymer amphiphilic surfactant may be a foam stabilizer by improving the surface viscosity of foam lamellae, thereby increasing affinity to crude oil.

According to a third aspect, there is provided a composition with foaming properties according to the first aspect, when used in oil recovery processes.

According to a fourth aspect, there is provided a method for recovering oil from a subterranean oil-containing formation comprising:

(a) introducing a composition with foaming properties according to the first aspect into the su t rranean oi1-containing formation

(b) introducing a gas into the subterranean oil- containing formation, wherein the presence of the composition with foaming properties lowers the gas mobility within said format ncl

(c) recovering oil from, the formation.

According to a fifth aspect, there is provided a method for recovering oil from a subterranean oil-containing formation comprising:

(a) injecting a composition with foaming properties according to the first aspect into the subterranean oil-containing formation through one or more injection wells;

(b) introducing a gas into the subterranean oil- containing formation, wherein the presence of the composit ion with foaming propert ies 1owers the gas mobility within said formation;

(c) extracting oil from the formation through one or more production wells.

Advantageously, the composition with foaming properties may be used to generate a foam that exhibits good foam generation and stability under severe reservoir conditions of high temperatures (>95°C), high salinity (>35, 000 ppm) and in the presence of crude oil and a foaming gas .

Further advantageously, the composition with foaming properties may be used to generate foam that has a low adsorption rate on reservoir rock.

Advantageously, the composition with foaming properties may be used to generate a foam that displays a high Mobility Reduction Factor (MRF) within a reservoir. The MRF may be >10. The lowered gas mobility advantageously results in improved sweep efficiency.

Further advantageously, the composition with foaming properties may display regeneration capability and may be used to generate foam even after multiple contacts with a foaming gas .

Definitions

Unless otherwise defined herein, scientific and technical terms used in this application shall have the meanings that are commonly understood by those of ordinary skill in the art. Generally, nomenclature used in connection with, and techniques of, chemistry described herein, are those well-known and commonly used in the art.

Unless the context requires otherwise or specifically stated to the contrary, integers, steps, or elements of the invention recited herein as singular integers, steps or elements clearly encompass both singular and plural forms of the recited integers, steps or elements .

As used herein, unless otherwise specified, the following terms have the following meanings, and unless otherwise specified, the definitions of each term (i.e. moiety or substituent) apply when that term is used individually or as a component of another term (e.g., the definition of aryl is the same for aryl and for the aryl portion of arylalkyl, alkylaryl, arylalkynyl, and the like) .

As used herein, the term "acrylic copolymer" refers to a copolymer which is obtained by copolymerizing a monomer mixture containing at least one selected from acrylate esters and methacrylate esters, and it may include graft copolymers or copolymers of an acrylic ester monomer and a non-acrylic monomer such as styrene, vinyl acetate, ethylene, ethylene oxide, propylene, propylene oxide, butylene, butylene oxide, and the like.

As used herein, the term "graft copolymer" refers to the macromolecule formed when polymer or copolymer chains are chemically attached as side chains to a polymeric backbone. Generally, the side chains are of different composition than the backbone chain.

As used herein, the term "amphiphilic" refers to a compound having affinity for two different environments -for example a molecule with hydrophilic (polar) and lipophilic (non-polar) regions.

As used herein, the term "amphiphilic surfactant" refers to compounds that lower the surface tension (or inte facial tension) between two liquids or between a liquid and a solid, and further have affinity for two different environments, for example hydrophilic (polar) ana lipophilic (non-polar) regions.

As used herein, the term "acrylic copolymer amphiphilic surfactant" refers to a surfactant comprising a copolymer which is obtained by copolymerizing a monomer mixture containing at least one selected from acrylate esters and methacrylate esters, which may include graft copolymers or copolymers of an acrylic ester monomer and a non-acrylic monomer such as styrene, vinyl acetate, ethylene, ethylene oxide, propylene, propylene oxide, butylene, butylene oxide, and the like. The surfactant further lowers the surface tension (or interfacial tension) between two liquids or between a liquid and a solid, and further have affinity for two different environments, for example hydrophilic (polar) and lipophilic (non-polar) regions.

As used herein, the term "alkyl" includes within its meaning monovalent ("alkyl") and divalent ("alkylene") straight chain or branched chain saturated aliphatic groups having from 1 to 20 carbon atoms, eg, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. For example, the term alkyl includes, but is not limited to, methyl, ethyl, 1-propyl, isopropyl, 1-butyl, 2-butyl, isobutyl, tert-butyl, amyl, 1 , 2-dimethylpropyl , 1 , 1-dimethylpropyl , pentyl, isopentyl, hexyl, 4-methylpentyl , 1-methylpentyl, 2-methylpentyl , 3-methylpentyl , 2 , 2-dimethylbutyl , 3,3-dimethylbutyl , 1 , 2-dimethylbutyl , 1 , 3-dimethylbutyl , 1 , 2 , 2-trimethylpropyl , 1 , 1 , 2-trimethylpropyl , heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicodecyl and the like. Alkyl groups may be optionally substituted.

As used herein, the term "alkenyl" refers to divalent straight chain or branched chain unsaturated aliphatic groups containing at least one carbon-carbon double bond and having from 2 to 20 carbon atoms, eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. For example, the term alkenyl includes, but is not limited to, ethenyl, propenyl, butenyl, 1-butenyl, 2-butenyl, 2-methylpropenyl , 1-pentenyl, 2-pentenyl, 2-methylbut-l-enyl , 3-methylbut-l-enyl, 2-methylbut-2-enyl , 1-hexenyl, 2-hexenyl, 3-hexenyl, 2 , 2-dimethyl-2-butenyl , 2-methyl-2-hexenyl, 3-methyl-l-pentenyl , 1 , 5-hexadienyl , heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl , pentadecenyl , hexadecenyl, heptadecenyl , octadecenyl, nonadecenyl, eicodecenyl and the like. Alkenyl groups may be optionally substituted . As used herein, the term "olefin" refers to alkenyl with one carbon-carbon double bond. An "alpha-olefin" refers to an olefin having a double bond at the primary or alpha position .

As used herein, the term "alkynyl" refers to divalent straight chain or branched chain unsaturated aliphatic groups containing at least one carbon-carbon triple bond and having from 2 to 20 carbon atoms, eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. For example, the term alkynyl includes, but is not limited to, ethynyl, propynyl, butynyl, 1-butynyl, 2-butynyl, 2-methylpropynyl , 1-pentynyl, 2-pentynyl, 2-methylbut-l-ynyl , 3-methylbut-l-ynyl, 2-methylbut-2-ynyl , 1-hexynyl, 2-hexynyl, 3-hexynyl, 2 , 2-dimethyl-2-butynyl , 2-methyl-2-hexynyl, 3-methyl-l-pentynyl , 1 , 5-hexadiynyl , heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl , pentadecynyl , hexadecynyl, heptadecynyl , octadecynyl, nonadecynyl, eicodecynyl and the like. Alkynyl groups may be optionally substituted.

The term "carbocycle" , or variants such as

"carbocyclic ring" as used herein, includes within its meaning any stable 3, 4, 5, 6, or 7-membered monocyclic or bicyclic or 7, 8, 9, 10, 11, 12, or 13-membered bicyclic or tricyclic, any of which may be saturated, partially unsaturated, or aromatic. The term "carbocycle" includes within its meaning cycloalkyl, cycloalkenyl and aryl groups. Examples of such carbocycles include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, cyclooctyl, [3.3.0] bicyclooctane, [4.3.0] bicyclononane ,

[ 4.4.0 ] bicyclodecane (decalin) , [2.2.2 ] bicyclooctane, fluorenyl, phenyl, naphthyl, indanyl, adamantyl, or tetrahydronaphthyl (tetralin) . Preferred carbocycles, unless otherwise specified, are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, and indanyl. Carbocycles may be optionally substituted.

The term "cycloalkyl" as used herein refers to a non-aromatic mono- or multicyclic ring system comprising about 3 to about 10 carbon atoms. The cycloalkyl can be optionally substituted with one or more "ring system substituents " which may be the same or different, and are as defined herein. Non-limiting examples of suitable monocyclic cycloalkyls include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and the like. Non-limiting examples of suitable multicyclic cycloalkyls include 1 -decalinyl, norbornyl, adamantyl and the like. Further non-limiting examples of cycloalkyl include the following :


The term " cycloalkenyl " as used herein refers to a non-aromatic mono or multicyclic ring system comprising about 3 to about 10 carbon atoms which contains at least one carbon-carbon double bond. Non-limiting examples of suitable monocyclic cycloalkenyls include cyclopentenyl , cyclohexenyl , cyclohepta-1 , 3-dienyl , and the like. Non-limiting example of a suitable multicyclic cycloalkenyl is norbornylenyl , as well as unsaturated moieties of the examples shown above for cycloalkyl. Cycloalkenyl groups may be optionally substituted.

The term "aryl", or variants such as "aromatic group" or "arylene" as used herein refers to monovalent ("aryl") and divalent ("arylene") single, polynuclear, conjugated or fused residues of aromatic hydrocarbons having from 6 to 10 carbon atoms. Such groups include, for example, phenyl, biphenyl, naphthyl, phenanthrenyl , and the like. Aryl groups may be optionally substituted.

The term "halogen", or variants such as "halide" or "halo" as used herein, includes within its meaning fluorine, chlorine, bromine and iodine.

The term "heteroaryl" as used herein refers to an aromatic monocyc1 ic or mu11icyc1 ic ririg syste , comprising about 5 to about 14 ring atoms, preferably about 5 to about 10 ring atoms, in which one or more of the ring atoms is an element other than carbon, for example nitrogen, oxygen or sulfur, alone or in combination. "Heteroaryl" may also include a heteroaryl as defined above fused to an aryl as defined above. NOR- limiting examples of suitable heteroaryls include pyridyl, pyrazinyl, furanyl, thienyl, pyrimidinyl, pyridone (including N-substituted pyridon.es), isoxazolyl , i sothiazoly1 , oxazolyl, thiazolyl, pyrazolyl, furazanyl, pyrrolyl, pyrazolyl, triazolyl, 1 , 2 , 4-thiadiazolyl , pyrazinyl, pyridazinyl, quinoxalinyl , phthalazinyl , oxindolyl, imidazo[l , 2-a] pyridinyl, imidazo[2,l -b] thiazolyl, benzofurazanyl , indolyl, azaindolyl, benz imidazolyl , benzothienyl , quinolinyl, imidazolyl, thienopyridyl , quinazolinyl , thienopyrimidyl , pyrrolopyridyl , imidazopyridyl, isoquinolinyl , benzoazaindolyl , 1 , 2, 4-triazinyl, benzothiazolyl and the like. The term "heteroaryl" also refers to partially saturated heteroaryl moieties such as, for example, tetrahydroisoquinoly1 , tetrahydroquinolyl and the like. Heteroaryl groups may be optionally substituted.

The term "heterocycle " as used herein, refers to a group comprising a covalently closed ring herein at least one atom forming the ring is a carbon atom and at least one atom forming the ring is a heteroatom. Heterocyclic rings may be formed by three, four, five, six, seven, eight, nine, or more than nine atoms, any of which may be saturated, partially unsaturated, or aromatic. Any number of those atoms may be heteroatoms (i.e., a heterocyclic ring may comprise one, two, three, four, five, six, seven, eight, nine, or more than nine heteroatoms) . Herein, whenever the number of carbon atoms in a heterocycle is indicated (e.g., C1-C6 heterocycle) , at least one other atom (the heteroatom) must be present in the ring. Designations such as "C1-C6 heterocycle" refer only to the number of carbon atoms in the ring and do not refer to the total number of atoms in the ring. It is understood that the heterocylic ring will have additional heteroatoms in the ring. In heterocycles comprising two or more heteroatoms, those two or more heteroatoms may be the same or different from one another. Heterocycles may be optionally substituted. Binding to a heterocycle can be at a heteroatom or via a carbon atom. Examples of heterocycles include heterocycloalkyls (where the ring contains fully saturated bonds) and heterocycloalkenyls (where the ring contains one or more unsaturated bonds) such as, but are not limited to the following:


wherein D, Ε, F, and G independently represent a heteroatom. Each of D, E, F, and G may be the same or different from one another.

The term "optionally substituted" as used herein means the group to which this term refers may be unsubstituted, or may be substituted with one, two, three or more groups other than hydrogen provided that the indicated atom' s normal valency is not exceeded, and that the substitution results in a stable compound. Such groups may be, for example, halogen, hydroxy, oxo, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, aryl alkoxy, alkylthio, nydroxyalkyl , alkoxyalkyl, cycloalkyl, cycloalkylalkoxy, alkanoyl, alkoxycarbonyl , a1ky1su1fony1 , a1ky1su1fony1oxy, a1ky1su1fony1a1ky1 , ary1su1 fony1 , ary1su1fony1oxy, ary1su1fony1a1ky1 , alkylsulfonamide alkylamido, alkylsuIfonamidoalkyl , alky1amidoaIky1 , arylsuIfonamido , arylcarboxamido , arylsulfonamidoalkyl , arylcarboxamidoalkyl , aroyl , aro l4alkyl, ary1alkanoyl , acyl, aryl, aryl alkyl, alkylaminoalkyl , a group RxRyN~, Rx0C0(CH2)m,

RxC0N (Ry) (CH2) RxRY C0 (CH2) m, RxRYNS02 (CH2) m or

RxS02 RY (CH2) m (where each of Rx and RY is independently selected from hydrogen or alkyl , or where appropriate RXRY forms part of carbocylic or heterocyclic ring and m is O, 1 , 2, 3 or 4), a group RxRYN(CH2)p- or RXRYN (CH2) p0— (wherein p is 1 , 2 , 3 or 4) ; wherein when the substituent is RXRYN (CH2) p- or RXRYN (CH2) pO, Rx with at least one Cf-2 of the (CHoJp portion of the group may also form a carbocyclyl or heterocyclyl group and Ry may be hydrogen, alkyl .

The word "substantially" does not exclude "completely" e.g. a composition which is "substantially free" from Y may be completely free from Y. Where necessary, the word "substantially" may be omitted from the definition of the invention.

Unless specified otherwise, the terms "comprising" and "comprise", and grammatical variants thereof, are intended to represent "open" or "inclusive" language such that they include recited elements but also permit inclusion of additional, unrecited elements.

As used herein, the term "about", in the context of concentrations of components of the formulations, typically means +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/-3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value .

Throughout this disclosure, certain embodiments may be disclosed in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3,

from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.

Certain embodiments may also be described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the disclosure. This includes the generic description of the embodiments with a proviso or negative limitation removing any subject matter from the genus, regardless of whether or not the excised material is specifically recited herein.

Detailed Description of the Disclosure In one aspect, there is provided a composition with foaming properties. In one embodiment, the composition with foaming properties comprises a foam stabilizer. The composition may be used to generate a foam that displays enhanced stability.

In another aspect, there is provided a composition with foaming properties comprising an acrylic copolymer amphiphilic surfactant, and at least one compound selected from the group consisting of olefin sulfonate, sulfo-betaine and betaine.

In one embodiment, the composition with foaming properties comprises an olefin sulfonate and an acrylic copolymer amphiphilic surfactant.

In another embodiment, the composition with foaming properties comprises a sulfo-betaine and an acrylic copolymer amphiphilic surfactant.

In another embodiment, the composition with foaming properties comprises a betaine and an acrylic copolymer amphiphilic surfactant.

In a further embodiment, the composition with foaming properties comprises an olefin sulfonate, a sulfo-betaine, and an acrylic copolymer amphiphilic surfactant .

In yet another embodiment, the composition with foaming properties comprises an olefin sulfonate, a betaine, and an acrylic copolymer amphiphilic surfactant.

In another embodiment, the composition with foaming properties comprises olefin sulfonate, sulfo-betaine, betaine, and acrylic copolymer amphiphilic surfactant.

In the above embodiments, the acrylic copolymer amphiphilic surfactant may be a foam stabilizer.

In one embodiment, the olefin sulfonate may be sodium alpha-olefin sulfonate. The alpha-olefin group may be selected from C3 to Cis alpha olefin, such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl or 1-decenyl, 1-undecenyl, 1-dodecenyl, 1-tridecenyl , 1-tetradecenyl , 1-pentadecenyl , 1-hexadecenyl , 1-heptadecenyl , 1-octadecenyl , 1-nonadecenyl or 1-eicosenyl. The alpha-olefin group may be a Ci to Ci6 alpha olefin. The olefin sulfonate may be of the formula CnH2n-iS03M, wherein n is an integer of 14, 15, or 16, and M is a counterion, such as Na+.

In one embodiment, the olefin sulfonate may be a compound of Formula (I) :


Formula (I) wherein R1 is an optionally substituted alkyl, alkenyl or alkynyl and M+ is sodium. In a preferred embodiment, R1 may be optionally substituted C10 to C12 alkyl, alkenyl or alkynyl .

In a compound of Formula (I) , R1 may be selected from optionally substituted alkyl, alkenyl or alkynyl . R1 may be selected from an optionally substituted alkyl group selected from optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or eicodecyl. R1 may be substituted or unsubstituted , The optional substituents on R1 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl , hydroxyl, carboxylic acid, cyano or halogen. R may be C10 to C-12 alkyl, R may be Cio or C12 alkyl.

The olefin sulfonate may be selected from the group consisting of the following compounds:



In one embodiment, the sulfo-betaine may be any neutral compound with a positively charged cationic group and a negatively charged functional group which is a sulfo- group. The sulfo-betaine may be of the formula (CnH2n+i) -CONH (CH2) 3N+ (CH3) 2CH2CH (OH) CH2S03~, wherein n is an integer of 11, 12 or 13. The sulfo-betaine may be a compound of Formula (II) :

Formula (II) wherein R2 is optionally substituted alkylene, alkenylene or alkynylene;

R3 is optionally substituted alkyl, alkenyl or alkynyl and

R5 and R6 each are independently optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, heterocyclyl .

In a compound of Formula (II) , R2 may be selected from optionally substituted alkylene, alkenylene or alkynylene. R2 may be selected from an optionally substituted alkylene group selected from optionally substituted methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, or eicodecylene . R2 may be substituted or unsubstituted . The optional substituents on R2 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl? Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbony1 , ary1 , heteroary1 , carbocyc1y1 , or heterocyc1y1 , hydroxyl, carboxylic acid, cyano or halogen. may be an optionally substituted alkylene. R" may be an alkylene group substituted with a hydroxygroup . R may be a methylene, ethylene, propylene or butylene substituted with hydroxy. R2 may be - (CH2) 2-CH (OH) -, -CH2-CH (OH) -CH2-or -CH (OH) - (CH2) 2- .

In a compound of Formula (II) , R3 may be selected from optionally substituted alkyl, alkenyl or alkynyl. R3 may be selected from an optionally substituted alkyl

group selected from optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or eicodecyl. R3 may be substituted or unsubst ituted . The optional substituents on R3 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, neteroaryl, carbocyclyl, or heterocyclyl , hydroxyl, carboxylic acid, cyano, halogen or alkylamido. R3 may be an optionally substituted alkyl. R^ may be an alkyl substituted with alkylamido. R3 may be [Cu-13 alkyl] -C (0) NH- (CH2) 3- · R3 may be [Cn or 13 alkyl] -C (0) NH-(CH2)3-.

In a compound of Formula (II) , R5 and R6 may each be selected from optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, heterocyclyl. R5 and R6 may each be alkyl selected from methyl, ethyl, propyl, butyl, pentyl or hexyl. R5 and R6 may each be alkenyl selected from ethenyl, propenyl, butenyl, pentenyl or hexenyl . R5 and R6 may each be alkynyl selected from ethynyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl or 3-methyl-l-pentynyl . R5 and R6 may each be aryl selected from phenyl or naphthyl . R5 and R6 may each be heteroaryl selected from pyrroline, pyrrolidine, imidazoline, imidazolidine, pyrazoline, pyrazolidine, pyrane, piperidine, morpholine, thiomorpholine, piperazine or hydrofuran. R5 and R6 may each be substituted or unsubst ituted . The optional substituents on R5 or R6 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl, hydroxyl, carboxylic acid, cyano or halogen, R5 and R6 may each independently be

optionally substituted alkyl . R5 and R6 may each independently be methyl, ethyl or propyl.

In another embodiment, the sulfo-betaine may be an alkyl amidopropyl hydroxy sulfo-betaine of formula (IIA) :

CH3

I

R4-CO-NH-(CHfe - 4· CNrCH-CHrS03"

! !

C¾ ^ Formula (IIA)

wherein R4 is an optionally substituted alkyl, alkenyl or alkynyl .

In a compound of Formula (IIA), R4 may be selected from optionally substituted alkyl, alkenyl or alkynyl. R4 may be selected from an optionally substituted alkyl group selected from optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or eicodecyl. R4 may be substituted or unsubstituted . The optional substituents on R4 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl , hydroxyl, carboxylic acid, cyano or halogen. R4 may be an optionally substituted alkyl group. R4 may be optionally substituted Cn to C13 alkyl. R4 may be optionally substituted Cn or C13 alkyl.

The sulfo-betaine may be a compound selected from the group consisting of the following compounds:


In one embodiment, the betaine may be of Formula

(III) :


Formula (III) wherein R7 is optionally substituted alkylene, alkenylene or alkynylene;

R10 is optionally substituted alkyl, alkenyl or alkynyl; and

R8 and R9 each are independently optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, heterocyclyl .

In a compound of Formula (III), R7 may be selected from optionally substituted alkylene, alkenylene or alkynylene. R7 may be selected from an optionally substituted alkylene group selected from optionally substituted methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, or eicodecylene . R7 may be substituted or unsubstituted . The optional substituents on R7 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl, hydroxyl, carboxylic acid, cyano or halogen. R7 may be an optionally substituted alkylene. R7 may be optionally substituted methylene, ethylene, propylene or butylene.

In a compound of Formula (III), R10 may be selected from optionally substituted alkyl, alkenyl or alkynyl . R10 may be selected from an optionally substituted alkyl group selected from optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or eicodecyl. R10 may be substituted or unsubstituted . The optional substituents on R10 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl , hydroxy1, carboxylic acid, cyano, halogen or alkyla ido. R10 may be an optionally substituted alkyl. R may be an alkyl substituted with alkylamido. R" may be [Cii-13 alkyl ] -C (0) NH- (CH2) 3- . RxJ may be [Cn 0r 13 alkyl] -C (0) NH- (CH2) 3- .

In a compound of Formula (III) , R8 and R9 may each be selected from optionally substituted alkyl, alkenyl,

Q

alkynyl, aryl, heteroaryl, carbocyclyl, heterocyclyl. R and R9 may each be alkyl selected from methyl, ethyl, propyl, butyl, pentyl or hexyl. R8 and R9 may each be alkenyl selected from ethenyl, propenyl, butenyl, pentenyl or hexenyl . R8 and R9 may each be alkynyl selected from ethynyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl or 3-methyl-l-pentynyl . R8 and R9 may each be aryl selected from phenyl or naphthyl . R8 and R9 may each be heteroaryl selected from pyrroline, pyrrolidine, imidazoline, imidazolidine, pyrazoline, pyrazolidine, pyrane, piperidine, morpholine, thiomorpholine, piperazine or hydrofuran. R8 and R9 may each be substituted or unssubstituted . The optional substituents on R8 or R9 may

be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl , hydroxyl, carboxylic acid, cyano or halogen. R8 and R9 may each independently be optionally substituted alkyl. R8 and R9 may each independently be methyl, ethyl or propyl.

In one embodiment, the betaine may be of formula (IIIA) :

CH::

I

t

Formula (IIIA) wherein R11 is an optionally substituted alkyl, alkenyl or alkynyl .

In a compound of Formula (IIIA), R11 may be selected from optionally substituted alkyl, alkenyl or alkynyl. R11 may be selected from an optionally substituted alkyl group selected from optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or eicodecyl. R11 may be substituted or unsubstituted . The optional substituents on R11 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl, hydroxyl, carboxylic acid, cyano or halogen. R11 may be an optionally substituted alkyl group. R11 may be optionally substituted Cn to C13 alkyl. R11 may be optionally substituted Cn or C13 alkyl.

The betaine may be selected from the group consisting of the following compounds:


In one embodiment, the acrylic copolymer amphiphilic surfactant may be an acrylic graft copolymer. The acrylic graft copolymer may comprise or consist of a poly (methyl methacrylate) backbone and poly (ethylene oxide) or poly (propylene oxide) side chains.

The poly (methyl methacrylate) backbone may be:


wherein y is an integer of 1 to 100.

The acrylic graft copolymer may comprise or consist of a poly (methyl methacrylate) backbone and poly (ethylene oxide) or poly (propylene oxide) side chains.

The acrylic copolymer amphiphilic surfactant may be of formula (IVa) or formula (IVb) :

Formula (IVb)

wherein y is an integer of 1 to 100;

n is an integer of 5 to 100; and

R12 is hydrogen or optionally substituted alkyl, alkenyl or alkynyl.

In a compound of Formula (IVa) or (IVb) , y may be integer of 1 to 100, 5 to 100, 10 to 100, 20 to 100, 30 to 100, 40 to 100, 50 to 100, 60 to 100, 70 to 100, 80 to 100, 90 to 100, 1 to 90, 1 to 80, 1 to 70, 1 to 60, 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 10, 1 to 5, or 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 or any integer or range falling within 1 to 100.

In a compound of Formula (IVa) or (IVb) , n may be an integer of 5 to 100, 10 to 100, 20 to 100, 30 to 100, 40 to 100, 50 to 100, 60 to 100, 70 to 100, 80 to 100, 90 to 100, 5 to 90, 5 to 80, 5 to 70, 5 to 60, 5 to 50, 5 to 40, 5 to 30, 5 to 20, 5 to 10, or 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 or any integer or range falling within 5 to 100.

In a compound of Formula (IVa) or (IVb) , R12 may be selected from optionally substituted alkyl, alkenyl or alkynyl . R12 may be selected from an optionally substituted alkyl group selected from optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or eicodecyl. R12 may be substituted or unsubst ituted . The optional substituents on R12 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl , hydroxyl, carboxylic acid, cyano or ha1ogen .

The disclosed acrylic copolymer amphiphilic surfactant may have a molecular weight of at least 5000, at least 6000, at least 7000, at least 8000, at least 9000, at least 10,000, at least 11,000, at least 12,000, at least 13,000, at least 14,000, at least 15,000, at least 16,000, at least 17,000, at least 18,000, at least 19,000, at least 20,000, or any range or integer falling within 5000 to 20,000. In one embodiment, the acrylic copolymer surfactant may have a molecular weight of between 5000 and 20,000, between 5000 and 19,000, between 5000 and 18,000, between 5000 and 17,000, between 5000 and 16,000, between 5000 and 15,000, between 5000 and 14,000, between 5000 and 13,000, between 5000 and 12,000, between 5000 and 11,000, between 5000 and 10,000, between 5000 and 9000, between 5000 and 8000, between 5000 and 7000, between 5000 and 6000, between 6000 and 20,000, between 7000 and 20,000, between 8000 and 20,000, between 9000 and 20,000, between 10,000 and 20,000, between 11,000 and 20,000, between 12,000 and 20,000, between 13,000 and 20,000, between 14,000 and 20,000, between 15,000 and 20,000, between 16,000 and 20,000, between 17,000 and 20,000, between 18,000 and 20,000, or between 19,000 and 20,000.

In one embodiment, the quantity of active acrylic copolymer amphiphilic surfactant in the disclosed composition may range from 0.2 to 0.46 wt%, 0.2 to 0.4 wt%, 0.2 to 0.36 wt%, 0.2 to 0.32 wt%, 0.2 to 0.28 wt%, 0.2 to 0.24 wt%, 0.24 to 0.46 wt%, 0.28 to 0.46 wt%, 0.32 to 0.46 wt%, 0.36 to 0.46 wt%, 0.4 to 0.46 wt%, or any range or integer falling within 0.2 to 0.46 wt%.

In one embodiment, the quantity of active olefin sulfonate in the disclosed composition may range from 8.0-15.0 wt%, 8.0-14.0 wt%, 8.0-13.0 wt%, 8.0-12.0 wt%, 8.0-11.0 wt%, 8.0-10.0 wt%, 8.0-9.0 wt%, 9.0-15.0 wt%, 10.0-15.0 wt%, 11.0-15.0 wt%, 12.0-15.0 wt%, 13.0-15.0 wt%, 14.0-15.0 wt% or any range or integer falling within 8.0-15.0 wt%.

In one embodiment, the quantity of active sulfo-betaine in the disclosed composition may range from 3.0-5.0 wt%, 3.5-5.0 wt%, 4.0-5.0 wt%, 4.5-5.0 wt%, 3.0-4.5 wt%, 3.0-4.0 wt%, 3.0-3.5 wt%, or any range or integer falling within 3.0-5.0 wt%.

In one embodiment, the quantity of active betaine may range from 1.5-11.0 wt%, 2.5-11.0 wt%, 3.5-11.0 wt%, 4.5-11.0 wt%, 5.5-11.0 wt%, 6.5-11.0 wt%, 7.5-11.0 wt%, 8.5-11.0 wt%, 9.5-11.0 wt%, 10.5-11.0 wt%, 1.5-10.5 wt%, 1.5-10.0 wt%, 1.5-9.5 wt%, 1.5-9.0 wt%, 1.5-8.5 wt%, 1.5-8.0 wt%, 1.5-7.5 wt%, 1.5-7.0 wt%, 1.5-6.5 wt%, 1.5-6.0 wt%, 1.5-5.5 wt%, 1.5-5.0 wt%, 1.5-4.5 wt%, 1.5-4.0 wt%, 1.5-3.5 wt%, 1.5-3.0 wt%, 1.5-2.5 wt%, 1.5-2.0 wt%, or any range or integer falling within 1.5-11.0 wt%.

In one embodiment, the composition with foaming properties comprises cocaamido propyl hydroxy sulfo-betaine of Formula (II) or Formula (IIA), cocaamido propyl betaine of Formula (III) or Formula (IIIA), C14-C16 alpha olefin sulfonate of Formula (I); and acrylic copolymer amphiphilic surfactant.

In another embodiment, the composition with foaming properties comprises cocaamido propyl hydroxy sulfo-betaine of Formula (II) or Formula (IIA), cocaamido propyl betaine of Formula (III) or Formula (IIIA), C14-C16 alpha olefin sulfonate of Formula (I); and acrylic copolymer amphiphilic surfactant comprising or consisting of a poly (methyl methacrylate) backbone and poly (ethylene oxide) side chains.

In another embodiment, the composition with foaming properties comprises cocaamido propyl hydroxy sulfo-betaine of Formula (II) or Formula (IIA), cocaamido propyl betaine of Formula (III) or Formula (IIIA), C14-C16 alpha olefin sulfonate of Formula (I) ; and acrylic copolymer amphiphilic surfactant comprising or consisting of a poly (methyl methacrylate) backbone and poly (propylene oxide) side chains.

In another embodiment, the composition with foaming properties comprises cocaamido propyl hydroxy sulfo-betaine of Formula (II) or Formula (IIA), cocaamido propyl betaine of Formula (III) or Formula (IIIA), C14-C16 alpha olefin sulfonate of Formula (I) ; and acrylic copolymer amphiphilic surfactant of Formula (IVa) .

In another embodiment, the composition with foaming properties comprises cocaamido propyl hydroxy sulfo-betaine of Formula (II) or Formula (IIA), cocaamido propyl betaine of Formula (III) or Formula (IIIA), C14-C16 alpha olefin sulfonate of Formula (I); and acrylic copolymer amphiphilic surfactant of Formula (IVb) .

In one embodiment, the disclosed composition with foaming properties may be useful to generate stable foams at high temperature and salinity.

In yet another embodiment, the disclosed composition with foaming properties may be useful to generate stable foams at a temperature of 90-105°C, 95-105°C, 97-105°C, 98-105°C, 99-105°C, 100-105°C, 90-100°C, 90-99°C, 90-98°C, 97-105°C, 95-105°C, or any range or integer falling within 90-105°C.

In another embodiment, the disclosed composition with foaming properties may be useful to generate stable foams at salinity of more than 30, 000 ppm, more than 35, 000 ppm, more than 40, 000 ppm, more than 45, 000ppm, more than 50, 000 ppm, more than 60, 000 ppm, more than 70, 000 ppm, more than 80, 000 ppm, more than 90, 000 ppm, up to 100,000 ppm, or any range or integer falling within 30, 000 to 100, 000 ppm.

The disclosed composition with foaming properties may be able to generate stable foams at 5-25% oil saturation, 5-20%, 10-20%, 15-20%, 5-15%, 5-10% or any range or integer falling within 5-25% of oil saturation.

In an embodiment, the composition with foaming properties may be used as a foam.

In one embodiment, the composition with foaming properties further comprises water and a foaming gas. The water may be distilled water, double distilled water or sea water. The foaming gas may be any gas that imparts foaming properties to the composition such as nitrogen, oxygen, carbon dioxide, natural gas, methane, propane, butane, and mixtures thereof. The foaming gas may generate a stable foam with said composition upon contact. The stability of the generated foam may be sustained after multiple contacts with a foaming gas.

The composition with foaming properties may further comprise an alkali pH buffer for regulating the pH of the composition. The alkali pH buffer may be a borate buffer, ammonium chloride solution or triethylamine hydrochloride solution .

In another embodiment, the composition with foaming properties may further comprise an aqueous medium. The aqueous medium may be water optionally comprising one or more salts. The aqueous medium may be seawater.

In one embodiment, the amount of aqueous medium in a composition with foaming properties may be present in about 90.0 wt%, 85.0 wt%, 80.0 wt%, 75.0 wt%, 70.0 wt%, 65.0 wt%, 60.0 wt%, 55.0 wt%, 50.0 wt% or any range or integer falling within the scope of 50.0 to 90.0 wt% of the composition with foaming properties. The corresponding amount of active surfactant in said composition may be present in about 10.0 wt%, 15.0 wt%, 20.0 wt%, 25.0 wt%, 30.0 wt%, 35.0 wt%, 40.0 wt%, 45.0 wt%, 50 wt% or any range or integer falling within 10.0 to 50 wt% of the composition with foaming properties.

In one embodiment, the amount of aqueous medium in a composition with foaming properties may be present in about 90 wt%, about 85 wt%, about 80 wt%, about 75 wt%, about 70 wt%, about 65 wt%, about 60 wt%, about 55 wt%, or about 50 wt%, and the amount of active surfactant may be present in about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, or any range or integer falling within 50 to 90 wt% of the composite on with foaming properties. In such an embodiment, the amount of aqueous medium in a composition with foaming properties may be present in about 80 wt%, and the amount of active surfactant may be present in about 20 wt% of the composition with foaming properties.

In another aspect, there is provided a composition with foaming properties according to the present disclosure when used in oil recovery processes.

In another aspect, there is provided the use of a composition with foaming properties according to the present disclosure in oil recovery processes.

In one embodiment, the composition with foaming properties is used as a foam.

In a further aspect, there is provided a method to enhance the recovery of oil from a subterranean oil-containing formation utilising a foam stabiliser-according to the present disclosure.

In another aspect, there is provided a method to enhance the recovery of oil from a subterranean oil-containing formation comprising the use of a composition with foaming properties according to the present disclosure, comprising:

(a) introducing a composition with foaming properties according to the present disclosure into the subterranean oil-containing formation; (b) introducing a gas into the subterranean oil- containing formation, wherein the presence of the composition with foaming properties lowers the gas mobility within said formation; and (c) recovering oil from the formation.

In another aspect, there is provided a method to enhance the recovery of oil from a subterranean oil-containing formation comprising the use of a composition with foaming properties according to the present disclosure, comprising:

(a) injecting a composition with foaming properties according to the present disclosure into the subterranean oil-containing formation through one or more injection wells;

(b) introducing a gas into the subterranean oil- containing formation, wherein the presence of the composition with foaming properties lowers the gas mobility within said formation;

(c) extracting oil from the formation through one or more production wells.

The composition with foaming properties may be part of a package introduced into a subterranean oil-containing formation by itself or with another fluid.

In one embodiment, the disclosed composition with foaming properties may be used as a fire fighting foam, foam cleaner, industrial foam, agricultural foam or foam used in home and personal care products.

In another aspect, there is provided a foam composition. In one embodiment, the foam composition comprises a foam stabilizer. The composition may be used to generate a foam that displays enhanced stability.

In another aspect, there is provided a foam composition comprising an acrylic copolymer amphiphilic surfactant, and at least one compound selected from the group consisting of olefin sulfonate, sulfo-betaine and betaine .

In one embodiment, the foam composition comprises an olefin sulfonate and an acrylic copolymer amphiphilic surfactant .

In another embodiment, the foam composition comprises a sulfo-betaine and an acrylic copolymer amphiphilic surfactant.

In another embodiment, the foam composition comprises a betaine and an acrylic copolymer amphiphilic surfactant. In yet another embodiment, the foam composition comprises an olefin sulfonate, a sulfo-betaine, and an acrylic copolymer amphiphilic surfactant. In yet another embodiment, the foam composition comprises an olefin sulfonate, a betaine, and a acrylic copolymer amphiphilic surfactant.

In another embodiment, the foam composition comprises olefin sulfonate, sulfo-betaine, betaine, and acrylic copolymer amphiphilic surfactant.

In the above embodiments, the acrylic copolymer amphiphilic surfactant may be a foam stabilizer.

In one embodiment, the olefin sulfonate may be sodium alpha-olefin sulfonate. The alpha-olefin group may be selected from C3 to Ci8 alpha olefin, such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl or 1-decenyl, 1-undecenyl, 1-dodecenyl, 1-tridecenyl , 1-tetradecenyl , 1-pentadecenyl , 1-hexadecenyl , 1-heptadecenyl , 1-octadecenyl , 1-nonadecenyl or 1-eicosenyl. The alpha-olefin group may be a Ci4 to Ci6 alpha olefin.

In one embodiment, the olefin sulfonate may be a compound of Formula (I) :


Formula (I) wherein R1 is an optionally substituted alkyl, alkene or alkynyl and M+ is sodium. In a preferred embodiment, R1 may be optionally substituted Ci o to C12 alkyl, alkene or alkynyl .

In a compound of Formula (I) , R1 may be selected from optionally substituted alkyl, alkenyl or alkynyl. R1 may be selected from an optionally substituted alkyl group selected from optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or eicodecyl. R1 may be substituted or unsubstituted . The optional substituents on R1 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbony1 , ary1 , heteroary1 , carbocyc1y1 , or heterocyc1y1 , hydroxyl, carboxylic acid, cyano or halogen. R1 may be Ci o to C12 alkyl. R may be Ci o or C12 alkyl.

The olefin sulfonate may be selected from the group consisting of the following compounds:



In one embodiment, the sulfo-betaine may be any neutral compound with a positively charged cationic group and a negatively charged functional group which is a sulfo- group. The sulfo-betaine may be of the formula (CnH2n+i) -CONH (CH2) 3N+ (CH3) 2CH2CH (OH) CH2S03_, wherein n is an integer of 11, 12, or 13.

The sulfo-betaine may be a compound of Formula (II) :


Formula (II)

wherein R2 is optionally substituted alkylene, alkenylene or alkynylene;

R3 is optionally substituted alkyl, alkenyl or alkynyl; and

R5 and R6 each are independently optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, heterocyclyl .

In a compound of Formula (II) , R2 may be selected from optionally substituted alkyl, alkenylene or alkynylene. R2 and R3 may each be selected from an optionally substituted alkylene group selected from optionally substituted methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, or eicodecylene . R2 may be substituted or unsubstituted . The optional substituents on R2 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl, hydroxyl, carboxylic acid, cyano or halogen. R' may be an optionally substituted alkylene. R2 may be an alkylene group substituted with a hydroxy group. R may be a methylene, ethylene, propylene or butylene substituted

with hydroxy. R2 may be - (CH2) 2~CH (OH) -, -CH2-CH (OH) -CH2-or -CH (OH) - (CH2) 2- .

In a compound of Formula (II) , R3 may be selected from optionally substituted alkyl, alkenyl or alkynyl . R3 may be selected from an optionally substituted alkyl group selected from optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or eicodecyl. R may be substituted or unsubstituted . The optional substituents on R3 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, ca bonyl, aryl, heteroaryl, carbocyclyl, or heterocycly1 , hydroxy!, carboxylic acid, cyano, halogen or alkylamido. R3 may be an optionally substituted alkyl. R^ may be an alkyl substituted with alkylamido. R3 may be [Cn-13 alkyl] -C (0) NH- (CH2) 3- . R3 may be [Cn or 13 alkyl] -C (0) NH-(CH2)3-.

In a compound of Formula (II) , R5 and R6 may each be selected from optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, heterocyclyl . R5 and R6 may each be alkyl selected from methyl, ethyl, propyl, butyl, pentyl or hexyl. R5 and R6 may each be alkenyl selected from ethenyl, propenyl, butenyl, pentenyl or hexenyl . R5 and R6 may each be alkynyl selected from ethynyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl or 3-methyl-l-pentynyl . R5 and R6 may each be aryl selected from phenyl or naphthyl . R5 and R6 may each be heteroaryl selected from pyrroline, pyrrolidine, imidazoline, imidazolidine, pyrazoline, pyrazolidine, pyrane, piperidine, morpholine, thiomorpholine, piperazine or hydrofuran. R5 and R6 may each be substituted or unsubstituted . The optional substituents on R5 or R6 may

be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, heteroaryl, carbocyciyl, or heterocyclyl , hydroxyl, carboxylic acid, cyano or halogen. R5 and R6 may each independently be optionally substituted alkyl. R5 and R6 may each independently be methyl, ethyl or propyl.

In another embodiment, the sulfo-betaine may be an alkyl amidopropyl hydroxy sulfo-betaine of formula (IIA) :

CH3

1

R4 «C0«NH-{O¾ - N+- GHrCH-CHrSO

! I

Un-J vn Formula (IIA)

wherein R4 is an optionally substituted alkyl, alkenyl or alkynyl .

In a compound of Formula (IIA), R4 may be selected from optionally substituted alkyl, alkenyl or alkynyl. R4 may be selected from an optionally substituted alkyl group selected from optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicodecyl. R4 may be substituted or unsubstituted . The optional substituents on R4 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, heteroaryl, carbocyciyl, or heterocyclyl, hydroxyl, carboxylic acid, cyano or halogen. R4 may be an optionally substituted alkyl group. R4 may be optionally substituted Cn to C13 alkyl. R4 may be optionally substituted Cn or C13 alkyl.

The sulfo-betaine may be a compound selected from the group consisting of the following compounds:

In one embodiment, the betaine may be of Formula (III) :


Formula (III) wherein R' is optionally substituted alkylene, alkenylene or alkynylene;

R10 is optionally substituted alkyl, alkenyl or alkynyl; and

R8 and R9 each are independently optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, heterocyclyl .

In a compound of Formula (III), R7 may be selected from optionally substituted alkylene, alkenylene or alkynylene. R7 may be selected from an optionally substituted alkylene group selected from optionally substituted methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, or eicodecylene . R7 may be substituted or unsubstituted . The optional substituents on R7 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl , hydroxy1, carbox lic acid, cyano or halogen. R7 may be an optionally substituted alkylene. R7 may be optionally substituted methylene, ethylene, propylene or butylene.

In a compound of Formula (III), R10 may be selected from optionally substituted alkyl, alkenyl or alkynyl . R10 may be selected from an optionally substituted alkyl group selected from optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or eicodecyl. R10 may be substituted or unsubstituted . The optional substituents on R10 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl , hydroxy1, carboxylic acid, cyano, halogen or alkylamido. R10 may be an optionally substituted alkyl. R may be an alkyl substituted with alkylamido. R may be [Cii-13 alkyl ] -C (0) H- (CH2) 3- . RJ may be [Cn or 13 alkyl] -C (0) NH- (CH2) 3- .

In a compound of Formula (III) , R8 and R9 may each be selected from optionally substituted alkyl, alkenyl,

Q

alkynyl, aryl, heteroaryl, carbocyclyl, heterocyclyl. R and R9 may each be alkyl selected from methyl, ethyl, propyl, butyl, pentyl or hexyl. R8 and R9 may each be alkenyl selected from ethenyl, propenyl, butenyl, pentenyl or hexenyl . R8 and R9 may each be alkynyl selected from ethynyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl or 3-methyl-l-pentynyl . R8 and R9 may each be aryl selected from phenyl or naphthyl . R8 and R9 may each be heteroaryl selected from pyrroline, pyrrolidine, imidazoline, imidazolidine, pyrazoline, pyrazolidine, pyrane, piperidine, morpholine, thiomorpholine, piperazine or hydrofuran. R8 and R9 may each be substituted or unssubstituted . The optional substituents on R8 or R9 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl , hydroxyl, carboxylic acid, cyano or halogen. R8 and R9 may each independently be optionally substituted alkyl. R8 and R9 may each independently be methyl, ethyl or propyl.

In one embodiment, the betaine may be of formula (IIIA) :

CM*

1

R11-€0*HC'H¾ -^CHsCOGf

I

Formula (IIIA) wherein R11 is an optionally substituted alkyl, alkenyl or alkynyl .

In a compound of Formula (IIIA), R11 may be selected from optionally substituted alkyl, alkenyl or alkynyl. R11 may be selected from an optionally substituted alkyl group selected from optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or eicodecyl. R11 may be substituted or unsubstituted . The optional substituents on R11 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, heteroaryl, carbocyclyl, or hete ocyclyl, hydroxyl, carboxylic acid, cyano or halogen. R11 may be an optionally substituted alkyl group. R11 may be optionally substituted Cn to C13 alkyl . R may be optionally substituted Cn or C13 alkyl.

The betaine may be selected from the group consisting of the following compounds:


In one embodiment, the acrylic copolymer surfactant may be an acrylic graft copolymer. The acrylic graft copolymer may comprise or consist of a poly (methyl methacrylate) backbone and poly (ethylene oxide) or poly (propylene oxide) side chains.

The poly (methyl methacrylate) backbone may be:


wherein y is an integer of 1 to 100.

The acrylic graft copolymer may comprise or consist of a poly (methyl methacrylate) backbone and poly (ethylene oxide) or poly (propylene oxide) side chains.

The acrylic copolymer amphiphilic surfactant may be of formula (IVa) or formula (IVb) :


Formula (IVa)

wherein y is an integer of 1 to 100;

n is an integer of 5 to 100; and

R12 is hydrogen or optionally substituted alkyl, alkenyl or alkynyl.

In a compound of Formula (IVa) or (IVb) , y may be integer of 1 to 100, 5 to 100, 10 to 100, 20 to 100, 30 to 100, 40 to 100, 50 to 100, 60 to 100, 70 to 100, 80 to 100, 90 to 100, 1 to 90, 1 to 80, 1 to 70, 1 to 60, 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 10, 1 to 5, or 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 or any integer or range falling within 1 to 100.

In a compound of Formula (IVa) or (IVb) , n may be an integer of 5 to 100, 10 to 100, 20 to 100, 30 to 100, 40 to 100, 50 to 100, 60 to 100, 70 to 100, 80 to 100, 90 to 100, 5 to 90, 5 to 80, 5 to 70, 5 to 60, 5 to 50, 5 to 40, 5 to 30, 5 to 20, 5 to 10, or 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 or any integer or range falling within 5 to 100.

In a compound of Formula (IVa) or (IVb) , R12 may be selected from optionally substituted alkyl, alkenyl or alkynyl. R12 may be selected from an optionally substituted alkyl group selected from optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or eicodecyl. R12 may be substituted or unsubstituted . The optional substituents on R12 may be Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, amino, sulfinyl, sulfonyl, carbonyl, aryl, heteroaryl, carbocyclyl, or neterocyclyl , hydroxyl, carboxylic acid, cyano or halogen. The disclosed acrylic copolymer amphiphilic surfactant may have a molecular weight of at least 5000, at least 6000, at least 7000, at least 8000, at least 9000, at least 10,000, at least 11,000, at least 12,000, at least 13,000, at least 14,000, at least 15,000, at least 16,000, at least 17,000, at least 18,000, at least 19,000, at least 20,000, or any range or integer falling within 5000 to 20,000. In one embodiment, the polyacrylamide surfactant may have a molecular weight of between 5000 and 20,000, between 5000 and 19,000, between 5000 and 18,000, between 5000 and 17,000, between 5000 and 16,000, between 5000 and 15,000, between 5000 and 14, 000, between 5000 and 13, 000, between 5000 and 12,000, between 5000 and 11,000, between 5000 and 10,000, between 5000 and 9000, between 5000 and 8000, between 5000 and 7000, between 5000 and 6000, between 6000 and 20,000, between 7000 and 20,000, between 8000 and 20,000, between 9000 and 20,000, between 10,000 and 20,000, between 11,000 and 20,000, between 12,000 and 20,000, between 13,000 and 20,000, between 14,000 and 20,000, between 15,000 and 20,000, between 16,000 and 20,000, between 17,000 and 20,000, between 18,000 and 20,000, or between 19,000 and 20,000.

In one embodiment, the quantity of active acrylic copolymer amphiphilic surfactant in the disclosed composition may range from 0.2 to 0.46 wt%, 0.2 to 0.4 wt%, 0.2 to 0.36 wt%, 0.2 to 0.32 wt%, 0.2 to 0.28 wt% , 0.2 to 0.24 wt%, 0.24 to 0.4 wt%, 0.28 to 0.4 wt%, 0.32 to 0.4 wt%, 0.36 to 0.4 wt%, or any range or integer falling within 0.2 to 0.46 wt%.

In one embodiment, the quantity of active olefin sulfonate in the disclosed composition may range from 8.0-15.0 wt%, 8.0-14.0 wt%, 8.0-13.0 wt%, 8.0-12.0 wt%, 8.0-11.0 wt%, 8.0-10.0 wt%, 8.0-9.0 wt%, 9.0-15.0 wt%, 10.0-15.0 wt%, 11.0-15.0 wt%, 12.0-15.0 wt%, 13.0-15.0 wt%, 14.0-15.0 wt%, or any range or integer falling within 8.0-15.0 wt%.

In one embodiment, the quantity of active sulfo-betaine in the disclosed composition may range from 3.0-5.0 wt%, 3.5-5.0 wt%, 4.0-5.0 wt%, 4.5-5.0 wt%, 3.0-4.5 wt%, 3.0-4.0 wt%, 3.0-3.5 wt%, or any range or integer falling within 3.0-5.0 wt%.

In one embodiment, the quantity of active betaine may range from 1.5-11.0 wt%, 2.5-11.0 wt%, 3.5-11.0 wt%, 4.5-11.0 wt%, 5.5-11.0 wt%, 6.5-11.0 wt%, 7.5-11.0 wt%, 8.5-11.0 wt%, 9.5-11.0 wt%, 10.5-11.0 wt%, 1.5-10.5 wt%, 1.5-10.0 wt%, 1.5-9.5 wt%, 1.5-9.0 wt%, 1.5-8.5 wt%, 1.5-8.0 wt%, 1.5-7.5 wt%, 1.5-7.0 wt%, 1.5-6.5 wt%, 1.5-6.0 wt%, 1.5-5.5 wt%, 1.5-5.0 wt%, 1.5-4.5 wt%, 1.5-4.0 wt%, 1.5-3.5 wt%, 1.5-3.0 wt%, 1.5-2.5 wt%, 1.5-2.0 wt%, or any range or integer falling within 1.5-11.0 wt%.

In one embodiment, the foam composition comprises cocaamido propyl hydroxy sulfo-betaine of Formula (II) or Formula (IIA), cocaamido propyl betaine of Formula (III) or Formula (IIIA), C14-C16 alpha olefin sulfonate of Formula (I), and acrylic copolymer amphiphilic surfactant.

In another embodiment, the foam composition comprises cocaamido propyl hydroxy sulfo-betaine of Formula (II) or Formula (IIA), cocaamido propyl betaine of Formula (III) or Formula (IIIA), C14-C16 alpha olefin sulfonate of Formula (I) ; and acrylic copolymer amphiphilic surfactant comprising or consisting of a poly (methyl methacrylate ) backbone and poly (ethylene oxide) side chains.

In another embodiment, the foam composition comprises cocaamido propyl hydroxy sulfo-betaine of Formula (II) or Formula (IIA), cocaamido propyl betaine of Formula (III) or Formula (IIIA), C14-C16 alpha olefin sulfonate of Formula (I); and acrylic copolymer amphiphilic surfactant comprising or consisting of a poly (methyl methacrylate ) backbone and poly (propylene oxide) side chains.

In one embodiment, the disclosed foam composition may be useful to generate stable foams at high temperature and salinity.

In another embodiment, the foam composition comprises cocaamido propyl hydroxy sulfo-betaine of Formula (II) or Formula (IIA), cocaamido propyl betaine of Formula (III) or Formula (IIIA), C14-C16 alpha olefin sulfonate of Formula (I); and acrylic copolymer amphiphilic surfactant of formula (IVa) .

In another embodiment, the foam composition comprises cocaamido propyl hydroxy sulfo-betaine of Formula (II) or Formula (IIA), cocaamido propyl betaine of Formula (III) or Formula (IIIA), C14-C16 alpha olefin sulfonate of Formula (I); and acrylic copolymer amphiphilic surfactant of formula (IVb) .

In yet another embodiment, the disclosed foam composition may be useful to generate stable foams at a temperature of 90-105°C, 95-105°C, 97-105°C, 98-105°C, 99-105°C, 100-105°C, 90-100°C, 90-99°C, 90-98°C, 90-97°C, 90-95°C, or any range or integer falling within 90-105°C.

In another embodiment, the disclosed foam composition may be useful to generate stable foams at salinity of more than 30, 000 ppm, more than 35, 000 ppm, more than 40, 000 ppm, more than 45, 000ppm, more than 50, 000 ppm, more than 60, 000 ppm, more than 70, 000 ppm, more than 80,000ppm, more than 90,000 ppm, up to 100,000ppm, or any range or integer falling within 30,000 to 100, 000 ppm.

The disclosed foam composition may be able to generate stable foams at 5-25% oil saturation, 5-20%, 10-20%, 15-20%, 5-15%, 5-10%, or any range or integer falling within 5-25% of oil saturation.

In one embodiment, the foam composition further comprises water and a foaming gas. The water may be distilled water, double distilled water or sea water. The foaming gas may be any gas that imparts foaming properties to the composition such as nitrogen, oxygen, carbon dioxide, natural gas, methane, propane, butane, and mixtures thereof. The foaming gas may generate a stable foam with said composition upon contact. The stability of the generated foam may be sustained after multiple contacts with a foaming gas.

The foam composition may further comprise an alkali pH buffer for regulating the pH of the composition. The alkali pH buffer may be a borate buffer, ammonium chloride solution or triethylamine hydrochloride solution.

In another embodiment, the foam composition may further comprise an aqueous medium. The aqueous medium may be water optionally comprising one or more salts. The aqueous medium may be seawater.

In one embodiment, the amount of aqueous medium in the disclosed composition may be present in about 90.0 wt%, 85.0 wt%, 80.0 wt%, 75.0 wt%, 70.0 wt%, 65.0 wt%, 60.0 wt%, 55.0 wt%, 50.0 wt%, or any range or integer falling within 50.0 to 90.0 wt% of the foam composition. The corresponding amount of active surfactant in said composition may be present in about 10.0 wt%, 15.0 wt%, 20.0 wt%, 25.0 wt%, 30.0 wt%, 35.0 wt%, 40.0 wt%, 45.0 wt%, 50 wt%, or any range or integer falling within 10.0 to 50 wt% of the foam composition.

In one embodiment, the amount of aqueous medium in a composition with foaming properties may be present in about 90 wt%, about 85 wt%, about 80 wt%, about 75 wt%, about 70 wt%, about 65 wt%, about 60 wt%, about 55 wt%, or about 50 wt%, and the amount of active surfactant may be present in about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, or any range or integer falling within 50 to 90 wt%, of the composition with foaming properties. In such an embodiment, the amount of aqueous medium in a composition with foaming properties may be present in about 80 wt%, and the amount of active surfactant may be present in about 20 wt% of the composition with foaming properties.

In another aspect, there is provided a foam composition according to the present disclosure when used in oil recovery processes.

In another aspect, there is provided the use of a foam composition according to the present disclosure in oil recovery processes.

In a further aspect, there is provided a method to enhance the recovery of oil from a subterranean oil-containing formation utilising a foam stabiliser-according to the present disclosure.

In another aspect, there is provided a method to enhance the recovery of oil from a subterranean oil-containing formation comprising the use of a foam composition according to the present disclosure, comprising :

(a) introducing a foam composition according to the present disclosure into the subterranean oil- containing formation;

(b) introducing a gas into the subterranean oil- containing formation, wherein the presence of the foam composition lowers the gas mobility within said formation; and

(c) recovering oil from the formation.

In another aspect, there is provided a method to enhance the recovery of oil from a subterranean oil- containing formation comprising the use of a foam composition according to the present disclosure, comprising :

(a) injecting a foam composition according to the present disclosure into the subterranean oil- containing formation through one or more injection wells ;

(b) introducing a gas into the subterranean oil- containing formation, wherein the presence of the foam composition lowers the gas mobility within said formation;

(c) extracting oil from the formation through one or more production wells.

The foam composition may be part of a package introduced into a subterranean oil-containing formation by itself or with another fluid.

In one embodiment, the disclosed foam composition may be used as a fire fighting foam, foam cleaner, industrial foam, agricultural foam or foam used in home and personal care products.

Brief Description of Drawings

The accompanying drawings illustrate a disclosed embodiment and serves to explain the principles of the disclosed embodiment. It is to be understood, however, that the drawings are designed for purposes of illustration only, and not as a definition of the limits of the invention.

Fig. 1 shows the foam volumes of compositions comprising sodium alpha-olefin sulfonate and alkyl amidopropyl hydroxy sulfo-betaine with and without an acrylic copolymer amphiphilic surfactant.

Fig. 2 shows the foam volumes of compositions comprising sodium alpha-olefin sulfonate and alkyl amidopropyl hydroxy sulfo-betaine with an acrylic copolymer amphiphilic surfactant after four successive contacts with methane.

Examples

Non-limiting examples of the invention and a comparative example will be further described in greater detail by reference to specific Examples, which should not be construed as in any way limiting the scope of the invention .

Example 1: Preparation of sodium C14-16 alpha olefin sulfonate

Isomerized C14-16 alpha olefin was first pre-heated by means of a heat exchanger and catalyst bed with temperatures ranging between 187° C and 190° C. The alpha olefin was then sulfonated in a vertical falling film reactor using concurrent sulfur trioxide ( SO3) /nitrogen down flow. A portion of the acid was cooled at a cyclone separator and recycled to the bottom of the falling film reactor. The acid was then digested by passing through a water- j acketed, plug flow vessel at 40°C with mechanical agitation. The resulting crude acid was then neutralized by the addition of 50 wt% aqueous sodium hydroxide (NaOH) for approximately 45 minutes to 80 minutes at between 35 and 40°C followed by passing the neutralized acid through a high shear mixer or using mechanical stirring at 85-90°C. After neutralization, the sodium olefin sulfonate was then subjected to hydrolysis conditions. The general hydrolysis procedure involves weighing 30 grams of the sodium olefin sulfonate into a 50 mL mechanically stirred pressure reactor adding a specified amount of 50 wt% aqueous NaOH, initiating stirring of approximately 200 rpm and increasing the temperature to the desired hydrolysis temperature (120-160°C) for 15-25 minutes, holding the reactor contents at the desired temperature, followed by cooling to room temperature. The product or contents (sodium C14-16 alpha olefin sulfonate) from the reactor was collected and stored or analyzed for conversion rate.

Example 2 : Preparation of coca amido sulfo-betaine

In a first step, coconut fatty acids, predominantly lauric acid (C12) , was reacted with excess dimethylaminopropylamine in aqueous solution at 200° C for seven hours to convert it to its corresponding amide, dimethylaminopropyl cocoamide. The resultant amide was then dissolved in anhydrous acetone with boiling under reflux. 1 , 2^-sultone was then added dropwise within about twenty seconds. After boiling for five hours under reflux, the acetone was distilled off and the product, coca amido sulfo-betaine, was dried in a hot desiccator.

Example 3: Preparation of coca amido propyl betaine

In a first step, coconut fatty acids, predominantly lauric acid (C12) , was reacted with excess dimethylaminopropylamine in aqueous solution at about 160 °C to convert it to the corresponding amide. The resultant dimethylaminopropyl cocoamide was than reacted with sodium chloroacetate and water in a 100 mL round bottom flask with a magnetic stir bar and a condenser. The reaction mixture was heated at 98°C for 8 hours and the pH was kept basic by the addition of 50 wt% NaOH . Upon completion of the reaction, the mixture was neutralized with 1 M HC1 and allowed to cool. The reaction mixture was filtered to obtain the product, coca amido propyl betaine as a 45 % solution in water.

Example 4 : Preparation of acrylic copolymer amphiphilic surfactant

The acrylic graft copolymer was synthesized by the free radical dispersion polymerization technique. Into a round bottom flask equipped with a magnetic stirrer and containing a binary solvent system (ethanol : water in appropriate ratio), monomer methyl metacrylate (6.0 12.0 mmol), monomer polyethylene oxide, and initiator azobisisobutyronitrile were added. The flask was sealed and the reaction mixture was then bubbled with a moderate flow of nitrogen gas for 15 minutes, before heated to 60 °C in a water bath. The copolymerization was allowed to proceed overnight with continuous flow of nitrogen gas. On the completion of the reaction, the product - a translucent liquid, was dialyzed in water. The resulting liquid was concentrated to a viscous syrup using a vacuum rotating evaporator, and then freeze-dried up to a solid state. The copolymer was stored in vials at 4°C.

Example 5 : Protocol for foam generation and foam stability tests

The protocol consists of sparging gas through a surfactant (in seawater) , measuring the height of the produced foam (either foam half-life or full foam degradation) over time.

200 mL of aqueous surfactant solution is decanted into a lOOOmL graduated cylinder. A gas dispersion tube is inserted fully into the surfactant and the graduated cylinder is stoppered. The cylinder is placed in a water bath and the surfactant is allowed to acclimatize to the test temperature for 5 minutes.

A rotometer is set to a constant gas flow rate (e.g. 10) the timer is started. The foam will rise to the top of the graduated cylinder. The timer is stopped when the foam reaches the top of the graduated cylinder. The time is recorded and the time taken for the foam to reach the top of the graduation cylinder is the surfactant's foam generation ability.

The sparging is then shut off (switch rotometer to zero) and the timer is started again. The time taken for the foam to decay to half of the cylinder is taken as the foam's half-life.

The time taken for the foam column to break up completely (i.e. only one level of bubbles on the surface of the test fluid) is taken as the full foam degradation over time.

The foam test is repeated three times for each surfactant concentration.

Example 6 : Preparation of composition with foaming properties

An acrylic copolymer amphiphilic surfactant solution was first prepared by preparing 1.0% of acrylic copolymer amphiphilic surfactanti . e . 1 mL in 100 mL double distilled water. The solution was stirred and subsequently allowed to stand for 24 hours.

In a separate beaker, the following surfactants were blended: C1 to Ci6 alpha-olefin sulfonate, cocaamido propyl sulfo-betaine, cocaamido propyl betaine and Sodium tetraphenylborate (STPB) (by Sigma-Aldrich, using an overhead stirrer at 400 rpm until consistency is seen (Total : 100 mL) .

Then, 100 mL of acrylic copolymer amphiphilic surfactant (that has been left to stand for 24 hrs) and 100 mL of the surfactant blend were blended in a ratio of 1:1 using an overhead stirrer at <400 rpm. 200 mL of double distilled water was added during blending until a homogenous solution is obtained.

The formulation was left to stand overnight.

Example 7 : Composition with foaming properties

The following is an example of a composition with foaming properties of the present disclosure.


The best (optimized) formulation has an active concentration of 20%, with the rest made up of double distilled water (-80%) .

Example 8 : Comparative foam stability study

The foam stability comparison between foam compositions with and without an acrylic copolymer amphiphilic surfactant is shown.

Testing is carried out at 90°C, in the presence of crude oil (10 v/v% saturation) and in the presence of methane gas (99.99%) .

The foam stability protocol set out in Example 2 was used. The foam stability was measured as foam half-life

(duration taken for foam to decay from 1000cm 3 to 500cm3) or full foam decay time (duration taken for foam to decay from 1000 cm3 to 250 cm3) .

Composition 1: 0.46 wt% C14-C16 alpha olefin sulfonate, 0.25 wt% cocaamido propyl hydroxy sulfo-betaine, 0.27 wt% cocaamido propyl betaine and 0.02 wt% STPB or distilled water. Total 0.5 wt% of total active diluted in 200 mL seawater.

Composition 2: 0.46 wt% C14-C16 alpha olefin sulfonate, 0.25 wt% cocaamido propyl hydroxy sulfo-betaine, 0.27 wt% cocaamido propyl betaine, and 0.02 wt% acrylic copolymer amphiphilic surfactant (graft copolymer of poly (methyl methacrylate ) backbone and poly (propylene oxide) side chains) . Total 0.5 wt% of total active diluted in 200 mL seawater.

Table 2


Fig. 1 shows the results of the foam stability test. Results show an increase in foam stability when the acrylic copolymer amphiphilic surfactant is added to a foam composition. Therefore, the acrylic copolymer amphiphilic surfactant proved to be efficient at stabilizing foam when used in foam compositions.

Example 9: Foam regeneration capability

The regeneration capability of a foam composition containing an acrylic copolymer amphiphilic surfactant is shown, including the stability of the foam at each run.

Testing is carried out at 90°C, in the presence of crude oil (10 v/v% saturation) and in the presence of methane gas (99.99%) .

The foam stability protocol set out in Example 1 was used. The foam stability was measured as foam half-life

(duration taken for foam to decay from 1000cm 3 to 500cm3) or full foam decay time (duration taken for foam to decay from 1000 cm3 to 250 cm3) .

Composition 3: 0.46 wt% C14-C16 alpha olefin sulfonate, 0.25 wt% cocaamido propyl hydroxy sulfo-betaine, 0.27 wt% cocaamido propyl betaine, 0.02 wt% acrylic copolymer amphiphilic surfactant (graft copolymer of poly (methyl methacrylate ) backbone and poly (propylene oxide) side chains) . Total 0.5 wt% of total active diluted in 200 mL seawater.

Table 3


Fig. 2 shows the results of the regeneration of foam tests. Results show that the foam volume of a foam composition comprising acrylic copolymer amphiphilic surfactant was sustained over 4 successive contacts with methane gas (bubbled) and in the presence of crude oil (10 v/v%) .

Results show an increase in foam stability when the acrylic copolymer amphiphilic surfactant is added to a foam composition. Therefore, the acrylic copolymer amphiphilic surfactant prove to be efficient at stabilizing foam when used in foam compositions.

Applications

The disclosed composition with foaming properties advantageously comprises an acrylic copolymer amphiphilic surfactant that may be an efficient foam stabilizer.

Advantageously, the composition with foaming properties may be used to generate a foam that exhibits good foam generation and stability under severe reservoir conditions of high temperatures, high salinity and in the presence of crude oil.

Therefore advantageously, the disclosed composition with foaming properties may be used in improved oil recovery methods .

There is therefore also provided a method for recovering oil from a subterranean oil-containing formation .

The composition with foaming properties advantageously may be used to generate foam which exhibits a low adsorption rate on reservoir rock and high Mobility Reduction Factor. The lowered gas mobility advantageously results in improved sweep efficiency.

Further advantageously, the composition with foaming properties may be used to generate a stable foam even after repeated contacts with a foaming gas.

It will be apparent that various other modifications and adaptations of the invention will be apparent to the person skilled in the art after reading the foregoing disclosure without departing from the spirit and scope of the invention and it is intended that all such modifications and adaptations come within the scope of the appended claims.