CN103380208B - For generation of the composition comprising alkyl alkoxy sulfonate of high-temperature stable foam - Google Patents

For generation of the composition comprising alkyl alkoxy sulfonate of high-temperature stable foam Download PDF

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Publication number
CN103380208B
CN103380208B CN201280009626.8A CN201280009626A CN103380208B CN 103380208 B CN103380208 B CN 103380208B CN 201280009626 A CN201280009626 A CN 201280009626A CN 103380208 B CN103380208 B CN 103380208B
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foam
aqueous composition
alkoxyl group
hydrogen
preferred
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CN103380208A (en
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G·阿尔瓦雷斯-于尔根森
G·奥特
V·库尔卡尔-西伯特
M·莱诺索加西亚
S·施泰因
G·绍博
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C09K8/02—Well-drilling compositions
    • C09K8/38—Gaseous or foamed well-drilling 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
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/592—Compositions used in combination with generated heat, e.g. by steam injection
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/594—Compositions used in combination with injected gas, e.g. CO2 orcarbonated gas
    • 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
    • C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
    • C09K8/703—Foams
    • 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
    • C09K8/92—Compositions for stimulating production by acting on the underground formation characterised by their form or by the form of their components, e.g. encapsulated material
    • C09K8/94—Foams
    • C11D2111/42—

Abstract

The present invention relates to the purposes of alkyl alkoxy sulfonate for generation of foam stable under high temperature (as about 250 DEG C at the most).In addition, the present invention relates to a kind of by use comprise at least one straight chained alkyl alkoxyl group sulfonate can foaming aqueous composition and produce the method for high-temperature stable foam.

Description

For generation of the composition comprising alkyl alkoxy sulfonate of high-temperature stable foam
The present invention relates to alkyl alkoxy sulfonate in generation at high temperature, such as, purposes in stable at about 250 DEG C at the most foam.In addition, the present invention relates to a kind of by use comprise at least one straight chained alkyl alkoxyl group sulfonate foaming aqueous composition can produce the method for high-temperature stable foam.
Tensio-active agent is generally used in makeup, medicine and washing composition, and wherein use temperature is usually less than 100 DEG C.For the known surface promoting agent washing at about 10-100 DEG C temperature, clean and foaming is applied, there is at least one C usually 8- 16alkyl chain is as hydrophobic part.With regard to this object, often use is little and have lower interfacial activity under these conditions for the tensio-active agent having compared with long alkyl chain.
Some use temperatures have at least one at least C higher than the tensio-active agent of 100 DEG C 18alkyl chain to improve in residence time of interface.Especially, the typically used of stable at 150-250 DEG C of temperature high-temperature stable tensio-active agent is the high temperature emulsification of such as polymer melt, hot wash, oil recovery application and Drilling additives.
A kind of important application of tensio-active agent is used as pore forming material (also referred to as lathering surfactant), and it can promote formation of foam.Foam is generally the composition of air inclusion and liquid, and it is formed by the bubble in catch liquid (as water), and wherein said bubble is separated by the liquid film (i.e. so-called thin layer) be connected.The foam layer comprising liquid (as water) is shown into the surfactants stabilize of film properties usually by least one.In some cases, described foam can be described as gas soliquid in a liquid.
Usually known pore forming material or lathering surfactant, when being dissolved in liquid phase, time particularly to dissolve on a small quantity, can promoting formation of foam and improve the colloidal stability of foam by suppressing bubble coalescence.Can think that lathering surfactant is gathered into stable foam layer in interface with monolayer adsorption.The interfacial viscosity improved provides thinning to film and the mechanical resistance of breaking.Be such as sodium lauryl sulphate (SDS), Texapon Special (ALS), Zetesol NL (SLES) and betaines for temperature lower than the usually known lathering surfactant of 100 DEG C.
Pore forming material, particularly can the pore forming material of stable foam at high temperature and pressure can be used in various application.The important applied field of high-temperature stable foam is field use, if the probing, particularly tertiary oil recovery technology of acid volume increase, underground heat reservoir is as hot radical oil recovery technique (such as SAGD, " gravity drainage that steam is auxiliary "; CSS, " steam stimulation "), this needs to improve performance under the high temperature conditions.Also be used for application-specific by the foam composition of the temperature raised as demonstrated high stability at higher than 150 DEG C, as in intermetallic composite coating (such as punching press, stretching, shaping, bending, rolling, cutting, grinding, punching, saw, hobbing, fraising, wire drawing, extrude trepanning, embossing, forging), the probing of underground heat reservoir, extraordinary cleaning applications and flame-retardant foam.
Propose various tensio-active agent and surfactant mixture to be used for field use, especially at high temperature used in the field use of foam.
US4,201,678 mixtures describing a kind of both sexes trimethyl-glycine, linear aliphatic or alkylated aromatic sulfonic acid salt and optional non-neutralization of ammonia.This mixture can be used as the pore forming material in foam drilling and works in the hot hole of temperature higher than 200 DEG C.
WO94/18431 relates to the oil recovery for improving at 38-120 DEG C of temperature and comprises C 10-16alkene sulfonic acid salt surfactant and compatibilizing compound are to improve the Efferescent compositions of salt tolerance.
CN-A1927993 describes high-temperature stratum from Efferescent compositions and the application in viscous oil exploitation thereof.Said composition comprises sulfonated α-olefin or dialkyl diphenyl ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate as pore forming material.
Document US5,193,618 disclose a kind of method using auxiliary (EOR) technology recovery of hydrocarbons from oil reservoir of recovering the oil of steam, and wherein composition comprises foam GO TO table surface-active agent, particularly alkyl aromatic sulfonates, and comprise sulfonated α-olefin dimeric precipitation control additive.
US2005/0137114 describes a kind of foam composition in about 80-160 ℉ (27-70 DEG C) temperature range, it comprises at least one anion surfactant, at least one cats product and one or more zwitterionic compounds, and wherein said anion surfactant is selected from ether sulfate or ether sulfate ammonium, alkylether sulfonate, alkylaryl sulphonate and composition thereof.
Alkyl alkoxy sulfonate and preparation method thereof is that prior art is known.Document DE-A3622439 describes C 8-18the purposes of alkylether sulfonate in cosmetic applications.Document US4,088,189 describe and assist the alkyl in oil-extraction method to gather alkoxyalkyl sulfonate for tensio-active agent and alkylaryl gathers alkoxyalkyl sulfonate.
But be starved of the excellent lathering surfactant and foam composition with high thermal stability, it easily can be prepared and form foam under being used in the temperature of 100-250 DEG C.Special needs at higher than 150 DEG C for some application as in foam drilling application or the application of thermal recovery oil.In addition, in some application, importantly tensio-active agent and produced foam demonstrate enough stability to higher salt concentrations and contact with oil phase usually.
The object of this invention is to provide the tensio-active agent of improvement and the method for foam composition, particularly water-based foam stable under being prepared in high temperature (such as 150-250 DEG C).These foam composition should in long-time, particularly at the most 1 day, preferably at the most 10 days, usually demonstrates high-temperature stability (such as at the most 100 DEG C) at the most in 60 days, and also demonstrate high stability when contacting with hydrocarbon phase.In addition, need tensio-active agent to have chemical stability at 250 DEG C of temperature at the most, and at room temperature have good water-soluble, this is as solution pumped into the prerequisite in well in some application.Except high thermal resistance, described pore forming material should not welding, should not produce residue and can easily obtain with low cost.
Be surprisingly found out that containing having 14-36 carbon atom, particularly 20-30, the linear alkyl chain of a preferred 22-28 carbon atom and have 1-20 oxyalkyl units, the specific sulfonate of a preferred 1-10 oxyalkyl units is chemically stable and produces foam at the temperature of 250 DEG C at the most.Further discovery salt (such as Repone K) improves froth stability.The optimum quantity of stand-by salt depends on surfactant structure.Also mixture that is long and short alkyl chain surfactants can be used for regulating solvability, surfactivity and froth stability.
The straight chained alkyl alkoxyl group sulfonate that the present invention relates at least one formula (I) is used at 100-250 DEG C, and preferred 150-250 DEG C is also the purposes producing foam at the temperature of 180-250 DEG C, preferred 200-250 DEG C usually:
Wherein:
R 1for having 14-36, preferred 20-30, preferred 22-30, preferred 22-28, the more preferably linear alkyl chain of 24-28 carbon atom;
R abe hydrogen or methyl separately independently for n oxyalkyl units;
R bbe hydrogen or methyl separately independently for n oxyalkyl units;
Condition is for n oxyalkyl units separately, at least one R aor R bbe not hydrogen;
M is the number of 0-10, preferred 1-8;
N is the number of 0-10, preferred 1-8;
P is the number of 0-20, preferred 1-8;
Condition is m+n+p>0;
X is selected from Na +, K +, Mg 2+and NH 4 +,
Y is the integer of 1 or 2.
In addition, the present invention relates to formula as above (I) straight chained alkyl alkoxyl group sulfonate produces high-temperature stable foam purposes as tensio-active agent.
" foam " of the present invention or " foam composition " are air inclusion, the composition of liquid and the tensio-active agent as layer stablizer, it is by the bubble formation in catch liquid (such as water), and wherein said bubble is separated by the liquid film (so-called thin layer) be connected.Comprise liquid if the foam lamellae of water is usually by least one surfactants stabilize, it shows into film properties.In some cases, described foam can be described as gas soliquid in a liquid.Described thin layer connects via intersection and forms the network intersected.Described bubble can be spherical and has weak interaction-particularly when gas volume fraction is less than about 74%.
In other situations of higher gas volume fraction, bubble shape can be polyhedron distortion.In actual foam, bubble normally unordered and there is various foam size (polydispersion foam).
Especially, for the present invention, tensio-active agent (lathering surfactant), for be dissolved in liquid phase, promotes the tensio-active agent of formation of foam when particularly dissolving on a small quantity.Pore forming material or lathering surfactant improve the colloidal stability of foam by suppressing the coalescent of bubble.
" foam of high-temperature stable " of the present invention means lather volume at 100 DEG C at the most (especially at 150 DEG C at the most, usually at 150-250 DEG C) temperature under at 100 seconds or longer (preferably greater than 200 seconds, preferably greater than 300 seconds) after reduce be less than for 10% (be preferably less than 5%, be more preferably less than 2%).Froth stability can be caved in by can be observed foam (foam layer fracture), and the front time describes.
Preferably, the radicals R in formula (I) 1for having 14-36, preferred 20-30, also preferred 22-30, preferred 22-28, the more preferably linear alkyl chain of 24-28 carbon atom.Generally speaking, straight chained alkyl alkoxyl group sulfonate of the present invention preferably can be prepared by the alkoxylate of commercially available alcohol (such as fatty alcohol) or alcohol mixture in mode known in principle.Therefore, radicals R herein 1carbonatoms can to represent in known manner in described alkyl alkoxy sulfonate and the mean number of existing carbon atom represent the maximum distribution of carbonatoms in alkyl chain respectively.
The present invention's straight chained alkyl alkoxyl group sulfonate used usually demonstrate have formula (I) to the block structure of general structure.The present invention's straight chained alkyl alkoxyl group sulfonate used comprises m general formula-O-(C usually 4h 8) butoxy, a n general formula-O-CH 2-CH (CH 3)-propoxy-and p general formula-O-CH 2cH 2-oxyethyl group.
Herein, propoxy-formula-O-CH 2-CH (CH 3)-is clearly intended to also comprise formula-O-CH (CH 3)-CH 2)-unit, therefore in described straight chained alkyl alkoxyl group sulfonate containing reverse alkoxyl group.These two kinds of orientations can be present in surfactant molecule usually.Depend on reaction conditions (such as alkali or acid catalysis), usually main oxyalkyl units (such as propoxy-) to be introduced in one of above-mentioned orientation.In addition, after the polymerization of such as oxybutylene, described butoxy can be straight chain or branching.Preferred described butoxy is branching.
The present invention's straight chained alkyl alkoxyl group sulfonate used can be prepared in mode known to the person skilled in the art in principle.Usual use alkoxylating catalyst makes alcohol R 1-OH and oxyalkylene (such as ethylene oxide, propylene oxide, oxybutylene) react.Described synthesis also can be initial by the alkyl alcohol mixture with the distribution of certain alkyl chain length, wherein usually mentions maximum chain length distribution (such as C 24/ 26alkyl alcohol or C 16/ 18alkyl alcohol).The method implementing alkoxylation is known to the person skilled in the art.The molecular weight distribution of those skilled in the art's it is also known that alcoxylates can be subject to the impact of reaction conditions, particularly catalyst choice.Subsequently, alcohol alcoxylates and such as thionyl chloride (such as in chlorobenzene) can be made to react to obtain chloride product.Subsequently, can react with such as S-WAT, this obtain needed for sulfonate.
Number m, n, p refer to the mean value of alkoxyl group (such as butoxy, propoxy-, oxyethyl group) existing in described alkyl alkoxy sulfonate, and wherein this mean value is non-essential is natural number, but also can be rational number required arbitrarily.
The sum (m+n+p) of oxyalkyl units is in particular 1-20, the number of preferred 1-10.In preferred embodiments, m=0, n=0, and p is 1-20, preferred 1-10, the number of preferred 1-8.In another preferred embodiment of the present, m=0, n are the number of 1-10, preferred 1-8, and p is the number of 1-10, preferred 1-8.In another preferred embodiment of the present, m is the number of 1-8, and n is the number of 1-8, and n is the number of 1-8.
In another embodiment of the present invention, use formula (I) the straight chained alkyl alkoxyl group sulfonate comprising ethoxy unit more more than propoxy unit, wherein propoxy unit is in particular 0-1 with the ratio (n/p) of ethoxy unit.
In one embodiment of the invention, the straight chained alkyl alkoxyl group sulfonate of at least one formula (I) is used, wherein R 1for having 20-30, the straight chained alkyl of a preferred 22-28 carbon atom, and wherein m+n+p is the number of 1-20, preferred 1-10.
In one embodiment, at least one formula as above (I) straight chained alkyl alkoxyl group sulfonate can be used, wherein R 1for having 20-30, the linear alkyl chain of a preferred 22-28 carbon atom, m=0, n=0, and p is the number of 2-8.
In one embodiment, at least one formula as above (I) straight chained alkyl alkoxyl group sulfonate can be used, wherein R 1for having 20-30, the linear alkyl chain of a preferred 22-28 carbon atom, m=0, n are the number of 2-8, and p is the number of 2-8.
Preferably, the present invention relates to comprise at least one formula as above (I) straight chained alkyl alkoxyl group sulfonate aqueous composition for generation of the purposes of foam as above.
In embodiments, the present invention relates to the aqueous composition comprising at least one formula (I) straight chained alkyl alkoxyl group sulfonate to be used at 100-250 DEG C, preferred 150-250 DEG C, preferred 180-250 DEG C, produce the purposes of foam under the pressure of the more preferably temperature of 200-250 DEG C and 1-100 bar.
Especially, the aqueous composition that the present invention is used can comprise following material (or being made up of following material):
The water of 10-99.99% (w/w), preferred 90-99.99% (w/w),
0.01-10% (w/w), preferred 0.01-5% (w/w), more preferably 0.01-1% (w/w), more preferably at least one formula as above (I) the straight chained alkyl alkoxyl group sulfonate of 0.05-0.5% (w/w)
Other additives of at least one of 0-25% (w/w).
Unless hereinafter separately had definition, otherwise all amount % (w/w) given all relate to whole composition.
Described composition is usually by 90-99% (w/w) water, and 0.01-10% (w/w) at least one alkyl alkoxy sulfonate is formed.Other additives (at the most 25%) can be added in said composition.
Unless otherwise defined, otherwise all amount % (w/w) given all relate to whole aqueous composition.
In embodiments, above-mentioned aqueous composition comprises 0.01-10% (w/w), preferred 0.01-5% (w/w), more preferably 0.01-1% (w/w), more preferably at least one formula as above (I) the straight chained alkyl alkoxyl group sulfonate of 0.05-0.5% (w/w).
In one embodiment, above-mentioned aqueous composition can comprise the mixture of at least two kinds of formula as above (I) straight chained alkyl alkoxyl group sulfonate.
Other additives of the aqueous composition that the present invention is used can such as be selected from:
I) water-soluble inorganic salt (such as sodium-chlor, Repone K, magnesium chloride);
Ii) cosolvent, it is selected from alcohol, ethoxylated alcohol, such as butyldiglycol, ether and ester;
Iii) other tensio-active agents (cosurfactant);
Iv) thickening material, such as stratiform silicon-dioxide.
Especially, the amount of other additives is 0.01-25% (w/w), preferred 0.01-10% (w/w), preferred 0.1-5% (w/w).
In embodiments of the invention, above-mentioned aqueous composition comprises its amount is that at least one water-soluble inorganic salt of 0.01-25% (w/w), preferred 0.01-10% (w/w) is as other additives.Especially, described water-soluble inorganic salt is selected from sodium-chlor, Repone K and magnesium chloride.For the present invention, " water-soluble cpds " means the compound of the solubleness under standard temperature (such as 25 DEG C) in water higher than 10g/l.
Especially, above-mentioned aqueous composition can comprise cosolvent further, and it can be selected from polar water-miscible solvent.Especially, described cosolvent can be selected from alcohol, particular methanol, ethanol, Virahol, butanols, butyl one glycol, butyldiglycol, butyltriglycol; Ether, preferred dme, diethyl ether, dipropyl ether, methyl ethyl ether, methyl-propyl ether, ethyl propyl ether; Glycol ethers and ester, ethyl acetate, n-butyl acetate, propylidene base diol ester.Suitable cosolvent also can be mixture or the combination of above-mentioned solvent.
In embodiments of the invention, above-mentioned aqueous composition can comprise 0.01-25% (w/w), preferred 0.01-10% (w/w), preferred 0.1-5% (w/w) at least one is selected from the cosolvent of alcohol, ether and ester as other additives.
Above-mentioned aqueous composition can comprise the tensio-active agent (cosurfactant) except the straight chained alkyl alkoxyl group sulfonate described in formula (I) as other additives further, this cosurfactant is compared with the straight chained alkyl alkoxyl group sulfonate described in formula (I) especially, demonstrates more hydrophilic character.Especially, described cosurfactant can be at least one and is selected from alkylsulfonate (such as cumene sulfonate, dodecane sulfonate), alkyl-sulphate (such as dodecyl sulfate, myristyl sulfate, palmityl vitriol, stearin-based sulfate), alkylaryl sulphonate, alkyl aryl sulfate, alkyl alkoxy sulfonate, alkyl alkoxy sulfate, alkylaryl alkoxyl group sulfonate, alkylaryl alkoxy sulfate, alcohol ethoxylate, alkyl phosphate, alkyl acid phosphate alkoxy ester, the tensio-active agent of alkyl polyglucoside and sorbitan fatty acid ester.Except the cosurfactant more hydrophilic than described straight chained alkyl alkoxyl group sulfonate, more not hydrophilic tensio-active agent also can be a part for described aqueous composition, as saturated or unsaturated C 5-20alcohol (such as amylalcohol, hexanol, decyl alcohol, dodecanol, oleyl alcohol, C 16/18alcohol), there is C 8-C 18the salt (such as stearic sodium salt) of the alkylamine of alkyl chain length, lipid acid (such as oleic acid and stearic acid) and lipid acid.Especially, above-mentioned cosurfactant comprises C 8-20alkyl chain.Above-mentioned tensio-active agent can preferably add with its salt such as its basic metal or alkaline earth metal salt.
In preferred embodiments, the aqueous composition that the present invention is used comprises at least one and is selected from the cosurfactant of following material as other additives: C 8-20alkylsulfonate, C 8-20alkyl-sulphate, C 8-20alkylaryl sulphonate, C 8-20alkyl aryl sulfate, C 8-20alkyl alkoxy sulfonate, C 8-20alkyl alkoxy sulfate, C 8-20alkylaryl alkoxyl group sulfonate, C 8-20alkylaryl alkoxy sulfate, more preferably at least one C 8-20alkylaryl sulphonate or C 8-20alkylaryl alkoxyl group sulfonate.
Especially, the aqueous composition that the present invention is used comprises its amount for 0.01-10% (w/w), preferred 0.01-1% (w/w), at least one cosurfactant of preferred 0.1-0.9% (w/w).
In another embodiment, described aqueous composition comprises the alkyl alkoxy sulfonate of described formula (I) as unique tensio-active agent.
In preferred embodiments, the present invention relates to such use, wherein said foam is used for washing and cleans, and forms microemulsion, Metal Production or application of recovering the oil.
In addition, the present invention relates to a kind of generation foam, the particularly method of high-temperature stable foam, it comprises the steps:
A) aqueous composition is prepared by being added in (being such as dissolved in) water by the straight chained alkyl alkoxyl group sulfonate of at least one formula (I):
Wherein:
R 1for having 14-36 carbon atom, preferred 20-30, preferred 22-30, preferred 22-28, the more preferably linear alkyl chain of 24-28 carbon atom;
R abe hydrogen or methyl separately independently for n oxyalkyl units;
R bbe hydrogen or methyl separately independently for n oxyalkyl units;
Condition is for n oxyalkyl units separately, R aor R bin at least one is not hydrogen;
M is 0-10, preferred 0-8, the number of preferred 1-8;
N is the number of 0-10, preferred 1-8;
P is the number of 0-20, preferred 1-8;
Condition is m+n+p>0;
X is selected from Na +, K +, Mg 2+and NH 4 +,
Y is the integer of 1 or 2;
B) optionally other additives of at least one are added in described aqueous composition;
C) described aqueous composition (if in step a or properly acquisition in stepb) is made to contact with gas;
Wherein said method is at 100-250 DEG C, and preferred 150-250 DEG C, usually at 180-250 DEG C, more preferably carries out at the temperature of 200-250 DEG C.
At least one step of aforesaid method, preferred steps c is usually at 100-250 DEG C, and preferred 150-250 DEG C, usually at 180-250 DEG C, more preferably carries out at the temperature of 200-250 DEG C.
In another embodiment, step c) can carry out at the temperature of 15-30 DEG C, then by described aqueous composition (respectively, described foam) rise to 100-250 DEG C, preferred 150-250 DEG C, usual 180-250 DEG C, the more preferably temperature of 200-250 DEG C.
In a preferred embodiment of the invention, described aqueous composition (if step a) in or properly in step b) in obtain) with the contact (step c) of gas by being undertaken in aqueous composition described in gas inject.
Aforesaid method, preferred steps c can implement especially under the pressure of 1-100 bar.
Preferably, the method for described generation foam is at 100-250 DEG C, and preferred 150-250 DEG C, carries out usually at the temperature of 180-250 DEG C.More preferably, the contact (step c) of described aqueous composition and gas is at 100-250 DEG C, and preferred 150-250 DEG C, usually at 180-250 DEG C, more preferably carries out at the temperature of 200-250 DEG C.
Other additives described can be selected from water-soluble inorganic salt and cosolvent, cosurfactant and thickening material.With regard to other additives that the inventive method is used, also applicable with straight chained alkyl alkoxyl group sulfonate for generation of the above-mentioned preferred embodiment that the purposes of foam is relevant.
Gas used in step c is preferably selected from nitrogen, carbonic acid gas, steam, water vapour, Sweet natural gas, methane, ethane, propane, fuel gas, air and composition thereof, is preferably selected from air, steam, carbonic acid gas, nitrogen and composition thereof.Described gas is more preferably selected from air, steam, carbonic acid gas, nitrogen and composition thereof.
Especially, can preferably by above just for generation of foam purposes described at least one formula (I) straight chained alkyl alkoxyl group sulfonate be used for generation foam of the present invention method in.
Especially, above with regard to formula (I) straight chained alkyl alkoxyl group sulfonate in the method for preferred embodiment generation foam used in the present invention producing the aqueous composition described in the purposes in foam.
Preferably, the present invention relates to a kind of method of above-mentioned generation foam, wherein 0.01-10% (w/w) at least one cosurfactant is added in described aqueous composition as other additives.Suitable cosurfactant is described above.
In embodiments, the present invention relates to a kind of method producing foam, it comprises the steps:
A) aqueous composition is prepared by being added in (being such as dissolved in) water by least one formula (I) the straight chained alkyl alkoxyl group sulfonate of 0.01-10% (w/w):
Wherein:
R 1for having 20-30, preferred 22-30, preferred 22-28, the more preferably linear alkyl chain of 24-28 carbon atom;
R abe hydrogen or methyl separately independently for n oxyalkyl units;
R bbe hydrogen or methyl separately independently for n oxyalkyl units;
Condition is for n oxyalkyl units separately, at least one R aor R bbe not hydrogen;
M is 0-10, preferred 0-8, the number of preferred 1-8;
N is the number of 0-10, preferred 1-8;
P is the number of 0-20, preferred 1-8;
Condition is m+n+p>0;
X is selected from Na +, K +, Mg 2+and NH 4 +,
Y is the integer of 1 or 2;
B) measured as 0.01-10% (w/w), at least one cosurfactant of preferred 0.01-1% (w/w), preferred 0.1-0.9% (w/w) adds in described aqueous composition;
C) at 100-250 DEG C, preferred 150-250 DEG C, preferred 180-250 DEG C, more preferably at the temperature of 200-250 DEG C and preferably under the pressure of 1-100 bar, by in aqueous composition described in gas inject (in step a, obtaining in stepb if appropriate).
In another aspect, the present invention relates to a kind of aqueous composition bubbled, it comprises:
The water of 10-99.99% (w/w), preferred 90-99.9% (w/w),
At least one formula (I) the straight chained alkyl alkoxyl group sulfonate of 0.01-10% (w/w):
Wherein:
R 1for having containing 20-36, preferred 22-30, preferred 24-30, preferred 25-30, the linear alkyl chain of a preferred 25-28 carbon atom;
R abe hydrogen or methyl separately independently for n oxyalkyl units;
R bbe hydrogen or methyl separately independently for n oxyalkyl units;
Condition is for n oxyalkyl units separately, at least one R aor R bbe not hydrogen;
M is 0-10, preferred 0-8, the number of preferred 1-8;
N is the number of 0-10, preferred 1-8;
P is the number of 0-20, preferred 1-8;
Condition is m+n+p>0;
X is selected from Na +, K +, Mg 2+and NH 4 +,
Y is the integer of 1 or 2;
Other additives of at least one of 0-25% (w/w).
Described composition is made up of 90-99% (w/w) water, 0.01-10% (w/w) at least one alkyl alkoxy sulfonate usually.Other additives (at the most 25%) can be added in said composition.
Unless otherwise defined, otherwise all amount % (w/w) given all relate to whole aqueous composition.
Preferably, the above-mentioned aqueous composition bubbled comprises 0.01-10% (w/w), preferred 0.01-5% (w/w), more preferably 0.01-1% (w/w), more preferably at least one formula (I) the straight chained alkyl alkoxyl group sulfonate of 0.05-0.5% (w/w).
In addition, above just at high temperature produce the aqueous composition of foam purposes described in preferred embodiment be also applicable to the invention described above can foaming aqueous composition.
The present invention is elaborated further by Examples below.
Embodiment 1: forming foam at 200 DEG C at the most
Before use and the back side has the autoclave of window, thus by cameras observe as the whipability of temperature and time function, foamy structure and froth stability.Temperature is regulated by electric heater unit.Photo and short-sighted frequency is used to carry out record.Nitrogen is used to apply the peak pressure of 80 bar thus make solution keep liquid.Foam produces by nitrogen being injected the water phase surfactant mixture (50ml) of mechanical stirring (1300rpm).The concentration of tensio-active agent is 1g/l.Be that the frit of 2 μm is placed in jet pipe end to produce small bubbles by aperture.After nitrogen injection, stop stirring and detecting froth stability.
Under the differing temps of 200 DEG C at the most, record can be observed the time (y-axis see Fig. 1) during the first sign of foam collapses.
Fig. 1 shows the time t (in second) when to observe the first foam collapses (y-axis) under temperature T (in DEG C) (x-axis) of 120-200 DEG C, wherein:
Open squares () represents C16/C18-6PO-2EO-SO 3na,
Black triangle (▲) represents C12 phenol-6PO-2EO-SO 3na, and
Solid diamond (◆) represents iC17-6PO-2EO-SO 3na tensio-active agent.
EO represents ethoxy unit, and PO represents propoxy unit and BO represents butoxyl unit.With the alkyl chain of the C description surface promoting agent of numeral, such as C16 means the alkyl chain with 16 carbon atoms, and iC17 means the iso-alkyl chain with 17 carbon atoms.
As can be seen from the result of Fig. 1, compared with having the different surfaces active agent structures of almost identical C atomicity in hydrophobic molecular moieties, the performance of linear alkyl chain is very good.Expection branching causes the tensio-active agent tap density of air/water interface to reduce, and this makes foam layer unstability.
As seen from Figure 1, C16/C18-6PO-2EO-SO is comprised 3the foam of Na is stablized about 400 seconds at 150 DEG C, and comprises contrast surface promoting agent C12 phenol-6PO-2EO-SO 3na and iC17-6PO-2EO-SO 3the foam of Na caved at the temperature of 150 DEG C after 2 and 5 seconds.At the temperature of 120 DEG C, comprise C16/C18-6PO-2EO-SO 3the foam of Na caved in after 500 seconds, comprised C12 phenol-6PO-2EO-SO 3the foam of Na caved in after 35 seconds, and comprised iC17-6PO-2EO-SO 3the foam of Na caved in after 3 seconds.
Embodiment 2: form foam at 250 DEG C
At the temperature of 250 DEG C, to have different ethoxy unit (EO) number the sodium salt of straight chain C 24/26 polyethoxye sulfonate and the foaming behavior under different Repone K (KCI) concentration compare.Foam is to produce with the same way described in embodiment 1.Froth stability (foam starts the time before the caving in) mode according to embodiment measures.The concentration of tensio-active agent is 1g/l.Result is shown in Table 1.
Table 1: foam starts to cave at 250 DEG C
As can be seen from the result of table 1, froth stability depends on the quantity (EO number) of ethoxy unit.Add the electric charge that salt can protect anion sulfoacid root, this causes piling up more closely in air/water interface.Can expect that in the presence of salt, the froth stability of foam is improved.
At C22-2EO-SO 3when Na, find the increase that froth stability measure along with KCl and continue rising, and reaching the maximum of about 100g/l.But, in certain situation as C22-5EO-SO 3na or C24/26-4EO-SO 3under Na, find that froth stability experiences maximum value along with the increase of salt amount.This effect may be relevant with salting-out effect, and this depends on that EO unit, alkyl chain length and potential coordination phenomenon are (at C22-5EO-SO 3when Na).
Embodiment 3: alkyl chain length is on the impact of froth stability
At 200-250 DEG C of temperature as described in Example 2, measure the froth stability comprising the foam of the alkyl alkoxy sulfonate with different alkyl chain length, wherein the concentration of tensio-active agent is 1g/l.The results are summarized in table 2.
Table 2: foam starts to cave at 200 DEG C and 250 DEG C
Find that froth stability improves along with the alkyl chain length increase of tensio-active agent.
Embodiment 4: the froth stability using surfactant mixture
At 200-250 DEG C of temperature as described in Example 2, measure in varing proportions with alkylaryl alkoxyl group sulfonate (C12 phenol-6PO-2EO-SO 3na) C combined 24/26-4EO-SO 3the froth stability of Na, wherein the total concn of tensio-active agent is 1g/l.The weight ratio of tensio-active agent is 9:1 and 8:2.The results are summarized in table 3.
Table 3: foam starts to cave at 200 DEG C and 250 DEG C
Result display foam stabilization effect is also by using the surfactant mixture acquisition containing alkyl alkoxy sulfonate and at least one with other tensio-active agents of shorter hydrophobic chain.
Embodiment 5: the impact of additive
At 200-250 DEG C of temperature as described in Example 2, the C22-2EO-SO combined with stratiform silica clays mineral and salt is measured 3the froth stability of Na tensio-active agent, wherein the concentration of tensio-active agent is 1g/l.The composition relevant with froth stability at T=200 DEG C and T=250 DEG C and the results are summarized in table 4.LaponiteRD is used as stratiform silicon-dioxide, and Repone K (KCl) is as salt.
Table 4: foam starts to cave at 200 DEG C and 250 DEG C
Clay mineral can aqueous phase between thickening foam layer thus reduce drainage and improve froth stability.Clay mineral (LaponiteRD) demonstrates foam stabilization effect.
Embodiment 6: chemical stability
At the stored under pressure 1g/lC22-2EO-SO of 12 hours of 250 DEG C and 62 bar 3the Na aqueous solution does not affect foaming behavior.

Claims (13)

1. the straight chained alkyl alkoxyl group sulfonate of at least one formula (I) is used for the purposes producing foam at the temperature of 150-250 DEG C:
Wherein:
R 1for having the linear alkyl chain of 14-36 carbon atom;
R abe hydrogen or methyl separately independently for n oxyalkyl units;
R bbe hydrogen or methyl separately independently for n oxyalkyl units;
Condition is for n oxyalkyl units separately, at least one R aor R bbe not hydrogen;
M is the number of 0-10;
N is the number of 0-10;
P is the number of 0-20;
Condition is m+n+p>0;
X is selected from Na +, K +, Mg 2+and NH 4 +,
Y is the integer of 1 or 2;
Wherein said foam is for application of recovering the oil.
2. purposes according to claim 1, wherein R 1for having the linear alkyl chain of 20-30 carbon atom.
3., according to the purposes of claim 1 or 2, wherein will comprise the aqueous composition of the straight chained alkyl alkoxyl group sulfonate of at least one formula (I) for generation of foam.
4., according to the purposes of claim 1 or 2, wherein use the aqueous composition comprising following component:
The water of 10-99.99% (w/w),
The straight chained alkyl alkoxyl group sulfonate of at least one formula (I) of 0.01-10% (w/w),
Other additives of at least one of 0-25% (w/w).
5. purposes according to claim 4, it is that at least one water-soluble inorganic salt of 0.01-25% (w/w) is as other additives that wherein said aqueous composition comprises its amount.
6. purposes according to claim 4, at least one that wherein said aqueous composition comprises 0.01-25% (w/w) is selected from the cosolvent of alcohol, ether and ester as other additives.
7. purposes according to claim 3, is wherein used for the aqueous composition comprising the straight chained alkyl alkoxyl group sulfonate of at least one formula (I) producing foam under the pressure of the temperature of 150-250 DEG C and 1-100 bar.
8. produce the method for foam, it comprises the steps:
A) aqueous composition is prepared by being added to the water by the straight chained alkyl alkoxyl group sulfonate of at least one formula (I):
Wherein:
R 1for having the linear alkyl chain of 14-36 carbon atom;
R abe hydrogen or methyl separately independently for n oxyalkyl units;
R bbe hydrogen or methyl separately independently for n oxyalkyl units;
Condition is for n oxyalkyl units separately, at least one R aor R bbe not hydrogen;
M is the number of 0-1;
N is the number of 0-10;
P is the number of 0-20;
Condition is m+n+p>0;
X is selected from Na +, K +, Mg 2+and NH 4 +,
Y is the integer of 1 or 2;
B) optionally other additives of at least one are added in described aqueous composition; Wherein said aqueous composition comprises the water of 10-99.99% (w/w), the straight chained alkyl alkoxyl group sulfonate of at least one formula (I) of 0.01-10% (w/w) and other additives of 0-25% (w/w)
C) described aqueous composition is contacted with gas;
Wherein said method is carried out at the temperature of 150-250 DEG C.
9. method according to claim 8, the contact of wherein said aqueous composition and gas is by being undertaken in aqueous composition described in gas inject.
10. the method for according to Claim 8 or 9, gas wherein used in step c is selected from steam, fuel gas and composition thereof.
The method of 11. according to Claim 8 or 9, gas wherein used in step c is selected from nitrogen, carbonic acid gas, water vapour, Sweet natural gas, methane, ethane, propane, air and composition thereof.
The method of 12. according to Claim 8 or 9, wherein adds at least one cosurfactant of 0.01-10% (w/w) in described aqueous composition as other additives.
13. aqueous compositions that can bubble, it comprises:
The water of 10-99.99% (w/w),
The straight chained alkyl alkoxyl group sulfonate of at least one formula (I) of 0.01-10% (w/w),
Wherein:
R 1for having the linear alkyl chain of 20-36 carbon atom;
R abe hydrogen or methyl separately independently for n oxyalkyl units;
R bbe hydrogen or methyl separately independently for n oxyalkyl units;
Condition is for n oxyalkyl units separately, at least one R aor R bbe not hydrogen;
M is the number of 0-10;
N is the number of 0-10;
P is the number of 0-20;
Condition is m+n+p>0;
X is selected from Na +, K +, Mg 2+and NH 4 +,
Y is the integer of 1 or 2;
One or more other additives of 0-25% (w/w), at least one that wherein said additive comprises 0.01-10% (w/w) is selected from C 8-20alkylaryl sulphonate and C 8-20the cosurfactant of alkylaryl alkoxyl group sulfonate.
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