CN102791824A - Method for producing crude oil using surfactants based on butylene oxide-containing alkyl alkoxylates - Google Patents
Method for producing crude oil using surfactants based on butylene oxide-containing alkyl alkoxylates Download PDFInfo
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- CN102791824A CN102791824A CN2011800130921A CN201180013092A CN102791824A CN 102791824 A CN102791824 A CN 102791824A CN 2011800130921 A CN2011800130921 A CN 2011800130921A CN 201180013092 A CN201180013092 A CN 201180013092A CN 102791824 A CN102791824 A CN 102791824A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—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
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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
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/06—Ether- or thioether carboxylic acids
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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
- C11D1/29—Sulfates of polyoxyalkylene ethers
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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
- C11D1/34—Derivatives of acids of phosphorus
- C11D1/345—Phosphates or phosphites
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/935—Enhanced oil recovery
- Y10S507/936—Flooding the formation
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for producing crude oil by means of Winsor type III microemulsion flooding, wherein an aqueous surfactant formulation which comprises at least one ionic surfactant of general formula R1-O-(D)n-(B)m-(A)I-XY-M+ is forced though injection wells into a mineral oil deposit and crude oil is removed from the deposit through production wells.
Description
The present invention relates to a kind of method through Winsor III type microemulsion flooding exploitation MO; The aqueous surfactant preparaton that wherein will comprise the ionogenic surfactant of at least a following general formula injects the mineral oil reservoir via injecting well, and from said oil reservoir, extracts crude oil out via the extraction well:
R
1-O-(D)
n-(B)
m-(A)
l-XY
-M
+
The invention further relates to the ionogenic surfactant and the reoovery method thereof of said general formula.
In the natural mineral oil reservoir, MO is present in the hole of porous reservoir rock, its towards ground one side by not thoroughly the layer seal.Said hole can be superfine hole, kapillary, hole etc.The pore neck for example can only have the diameter of about 1 μ m.Except MO (comprising gas component), oil reservoir also comprises and has or the water of high or low salts contg.
In the MO exploitation, be divided into primary recovery, secondary recovery and tertiary recovery usually.In primary recovery, MO is because the autogenous pressure of oil reservoir is drilled beginning after flow to the surface automatically by boring at oil reservoir.
Therefore after primary recovery, use secondary recovery.In secondary recovery, except the boring (so-called extraction well) that is used to exploit MO, also in containing the stratum of MO, pierce other boring.Inject water to keep pressure or it is raise once more via these so-called injection wells to oil reservoir.Because inject the event of water, MO slowly is pressed into the stratum by the direction of injecting well extraction well via hole.Yet, this only hole filled by oil fully and more heavy-gravity oil promoted just to work under the progressive situation by water.In case the penetration by water hole of motion, it is along the minimum path flow of resistance this moment, the passage of promptly flowing through and forming, and no longer promote oil and advance.
Primary recovery and secondary recovery only can be exploited about 30-35% of existing mineral oil mass in the said oil reservoir usually.
Known MO output can further improve through the TOR measure.The summary that adopts for three times can be referring to for example " Journal of Petroleum Science of Engineering 19 (1998) ", 265-280 page or leaf.TOR comprises for example by the use of thermal means, wherein hot water or steam is injected oil reservoir.This reduces oil viscosity.Used flow media can be gas such as CO equally
2Or nitrogen.
Three MO exploitations also comprise wherein uses the method for suitable chemical as the oil recovery auxiliary agent.These can be used for influencing the terminal situation of water flows, and therefore also are used for exploiting the MO that firmly remains in the rock stratum.
In contiguous secondary recovery latter stage, viscous force and capillary force act on and are captured on the MO that preserves in the petrosal foramen, and wherein these two kinds of power ratios respect to one another depend on that microcosmic is separating of oil.These power are by non-dimensional parameter, and promptly so-called capillary number is described.Viscous force (viscosity of speed * driving phase) is to the ratio of capillary force (IT * rock between the profit wetting):
In this formula; μ is the fluidic viscosity of ordering about the MO motion, and v is Darcy velocity (flow of unit surface), and σ orders about the liquid of MO motion and the IT between the MO; And θ is the contact angle (C.Melrose between MO and the rock; C.F.Brandner, J.Canadian Petr.Techn.58, the 10-12 month in 1974).Capillary number is high more, and the mobility of oil is just high more, and therefore oily removal degree is also just big more.
The capillary number that known contiguous secondary MO is exploited latter stage is about 10
-6, must make capillary number be increased to about 10
-3-10
-2Thereby, can make extra MO motion.
For this reason, can implement the flooding method of particular form-be called Winsor III type microemulsion flooding.In Winsor III type microemulsion flooding, the tensio-active agent of injection should form Winsor III type microemulsion with existing water of oil reservoir and oil phase.Winsor III type microemulsion is not the emulsion with small droplets, but the thermodynamically stable liquid mixture of water, oil and tensio-active agent.Its three advantages are:
-obtain the utmost point low interfacial tension σ between MO and the water thus;
-therefore it has extremely low viscosity usually and is not captured by porous matrix;
-itself in addition forming under the minimum energy input and can keep stable (in contrast, conventional emulsions needs the common high shear that in oil reservoir, not occur, and only is dynamic stabilizationization) in the time at endless.
Winsor III type microemulsion is the equilibrium system of excessive water and excessive oil.Under these conditions that form microemulsion, tensio-active agent covers oil-water interface, and IT σ is low more, and is then right<10
-2The value of mN/m (ultra low interfacial tension) is favourable more.In order to obtain optimum, under true quantitative tensio-active agent, the microemulsion ratio in said water-microemulsion-oil body system should be peak naturally, because this can obtain lower IT.
Can change oil droplet shape (to such an extent as to the IT between the profit reduce to the minimum interfacial state of degree like this no longer favourable and spherical no longer favourable) in this way, and they can be owing to displacement of reservoir oil water-driven is passed through capillary pipe opening.
In the presence of excess surface active agent, when oil-water interface is covered by tensio-active agent, form Winsor III type microemulsion.Therefore it constitute the tensio-active agent reservoir that causes the utmost point low interfacial tension between oil phase and the water.Because Winsor III type microemulsion has LV, it also moves through porous reservoir rock (in contrast, emulsion can capture in porous matrix and stop up oil reservoir) in oil displacement process.When Winsor III type microemulsion when not met as yet by the oil-water interface that tensio-active agent covered, the tensio-active agent of said microemulsion can significantly reduce the IT at this new interface, and causes oil motion (for example because the oil droplet distortion).
Said oil droplet can merge with continuous oily reservoir subsequently.This has two advantages:
At first, because said continuous oily reservoir is pushed ahead through new porous rock, the oil droplet that is present in wherein can merge with said reservoir.
In addition, oil droplet merges the oily reservoir of formation significantly reduces oil-water interface, and the tensio-active agent that therefore will no longer need discharges once more.Thereafter, the tensio-active agent that discharges as stated can order about oil droplet motion residual in the stratum.
Therefore, Winsor III type microemulsion flooding is a kind of special effective means, and compares the tensio-active agent that needs much less with the emulsion flooding method.In microemulsion flooding, usually that tensio-active agent is optional with solubility promoter and/or basic salt (optional with sequestrant) injection.Subsequently, the polymers soln that injects thickening is to control flowability.Another program is the mixture that injects thickening polymer, tensio-active agent, solubility promoter and/or basic salt (optional with sequestrant), and the solution that injects thickening polymer then is to control flowability.It is clarifying that these solution should be usually, to prevent to stop up oil reservoir.
There is significant difference in the exploitation of three MO with the requirement of tensio-active agent and to the requirement of the tensio-active agent that is used for other application scenario: the suitable surfactant that is used for TOR answers the IT (being generally about 20mN/m) between Jiang Shui and the oil to reduce to less than 10
-2The low especially value of mN/m, thus can make MO fully mobile.This must realize in the presence of reservoir temperature that is generally about 15-130 ° C and the water at high content of salt, is more particularly also realizing in the presence of calcium and/or the mg ion at high proportion; Therefore said tensio-active agent also must dissolve in the oil reservoir water of high content of salt.
In order to satisfy these requirements, surfactant mixtures is proposed often, especially the mixture of negatively charged ion and nonionogenic tenside.
US3,890,239 disclose organic sulfonate and C
8-C
20-AO-H type (AO=has the oxyalkylene of 2-6 carbon atom) alkyl alkoxylates and C
8-C
20-AO-vitriol or C
8-C
20The combination of-AO-sulfonate type aniorfic surfactant.Oxyalkylene is very usually described in the context of 890,239 disclosures only at US3.Yet, only have the instance that comprises EO.
US4,448,697 require protection C
1-C
6-(AO)
1-40-EO
>=10The purposes of-H type alkyl alkoxylates and AS combination.AO can be 1,2-oxybutylene or 2,3-oxybutylene.
US4,460,481 have described alkylaryl alkoxy sulfate or sulfonate surfactant.Oxyalkylene can be ethylene oxide, propylene oxide or oxybutylene.Condition is the major part that ethylene oxide accounts for oxyalkylene.Oxybutylene is not described in more detail.
Therefore, those skilled in the art regulate application parameter, for example surfactant types, concentration and ratio of mixture respect to one another according to the condition that exists in the given oil reservoir (for example temperature and salts contg).
As stated, the MO exploitation is proportional with capillary number.IT between the profit is low more, and then capillary number is high more.Carbon atom MV in the crude oil is high more, then is difficult to obtain lower IT more.The suitable surfactant that is used to reduce IT is to have those of chain alkyl.Alkyl chain is long more, and the effect that then can reduce IT is just good more.Yet the being easy to get property of this compounds is very limited.
Therefore, the purpose of this invention is to provide a kind of especially effectively tensio-active agent of surfactant flooding and modification method of tertiary recovery MO of being used for.
Therefore; A kind of method through Winsor III type microemulsion flooding tertiary recovery MO is provided; The aqueous surfactant preparaton that wherein will comprise at least a ionogenic surfactant injects well via at least one and injects the mineral oil reservoir so that the IT between the profit is reduced to the < value of 0.1mN/>m; Preferred < the value of 0.05mN/>m; More preferably the value of 0.01mN/m, and from said oil reservoir, extract crude oil out via at least one extraction well, wherein said tensio-active agent preparaton comprises the tensio-active agent of at least a following general formula:
R
1-O-(D)
n-(B)
m-(A)
l-XY
-M
+
Wherein
R
1Be straight chain with 8-30 carbon atom or branching, saturated or unsaturated aliphatic and/or aromatic hydrocarbyl,
A is an inferior ethoxyl,
B is inferior propoxy-,
D is inferior butoxy,
L is 0-99,
M is 0-99,
N is 1-99,
X is alkyl or the alkylene with 0-10 carbon atom,
M
+Be positively charged ion,
Y
-Be selected from sulfate radical, sulfonate radical, carboxylate radical and phosphate radical,
But wherein A, B and D group random distribution, alternately distribute or be two, three, four or more a plurality of block form of random order, the l+m+n sum is 3-99,1, the ratio of 2-oxybutylene is at least 80% based on the oxybutylene total amount.
A kind of surfactant mixt that is used to exploit MO also is provided, its comprise at least a such as preceding text the ionogenic surfactant of definition general formula.
The hereinafter reply the present invention specify:
In aforesaid method of the present invention, use the aqueous surfactant preparaton of the tensio-active agent that comprises at least a said general formula through Winsor III type microemulsion flooding exploitation MO.In addition, it can comprise other tensio-active agents and/or other components.
Through in the inventive method of Winsor III type microemulsion flooding tertiary recovery MO, use tensio-active agent of the present invention IT between the profit to be reduced to < 0.1mN/>m, preferred < 0.05mN/>m, the more preferably < value of 0.01mN/>m.Therefore, the IT between the profit is reduced to 0.1-0.0001mN/m, preferred 0.05-0.0001mN/m, the more preferably value of 0.01-0.0001mN/m.
General formula R
1-O-(D)
n-(B)
m-(A)
l-XY
-M
+Can contain at least a tensio-active agent.Owing to the preparation reason, also can there be the tensio-active agent of multiple different said general formula in the said tensio-active agent preparaton.
R
1Group is for having 8-30 carbon atom, preferred 9-30 carbon atom, the more preferably aliphatic hydrocarbyl of the straight chain of 10-28 carbon atom or branching and/or aromatic hydrocarbyl.
In special preferred embodiment of the present invention, R
1Group is different C
17H
35Or by straight chain C
16H
33And C
18H
37The commercially available fatty alcohol mixture of forming or derived from commercially available C
16Guerbet alcohol 2-hexyl last of the ten Heavenly stems-1-alcohol or derived from commercially available C
24Guerbet alcohol 2-decyl tetradecanol or derived from commercially available C
28Guerbet alcohol 2-dodecyl cetyl alcohol.
More preferably, in straight chain alcohol, n=3-10 and m=5-9, and in branching alcohol, n=2-10 and m=5-9.This moment in each case, preferred D be greater than 80% 1,2-oxybutylene, and begin by alcohol, oxyalkylene has D-B-A in proper order.Being block form greater than 90% oxyalkylene arranges.
Especially preferred straight chain or branched aliphatic alkyl are especially for having the straight chain or the branched aliphatic alkyl of 10-28 carbon atom.
The degree of branching of branched aliphatic alkyl is generally 0.1-5.5, preferred 1-3.5.Here, term " degree of branching " subtracts 1 with the methyl number that known mode in principle is defined as in the pure molecule.The average degree of branching is the statistical average value of all branchign of molecule degree in the sample.
In following formula, A means inferior ethoxyl.B means inferior propoxy-and D means inferior butoxy.
In the defined general formula of preceding text, l, m and the n integer of respectively doing for oneself.Yet as far as the technician in poly-alkoxylation thing field, clearly this is defined in and is the definition of single tensio-active agent under every kind of situation.Comprise in existence under the situation of surfactant mixt or tensio-active agent preparaton of tensio-active agent of multiple said general formula; Respectively the do for oneself MV of said all molecules of tensio-active agent of number l, m and n, this is because alcohol and the alkoxylate of ethylene oxide and/or propylene oxide and/or oxybutylene obtain to have the chain length of certain distributed in each case.This distribution can be described by polymolecularity D with known mode in principle.D=Mw/Mn is the merchant of weight-average molar mass and mumber average molar mass.Polymolecularity can known by one of skill in the art method, for example passes through gel permeation chromatography.
In above-mentioned general formula, l is 0-99, preferred 1-40, more preferably 1-20.
In above-mentioned general formula, m is 0-99, preferred 1-20, more preferably 5-9.
In above-mentioned general formula, n is 1-99, preferred 2-30, more preferably 2-10.
According to the present invention, the l+m+n sum is 3-99, preferred 5-50, the more preferably number of 8-39.
According to the present invention, 1, the ratio of the inferior butoxy of 2-be at least 80% based on inferior butoxy (D) total amount, preferably at least 85%, preferably at least 90%, more preferably at least 95% 1,2-Asia butoxy.
Inferior ethoxyl (A), inferior propoxy-(B) and inferior butoxy (D) be random distribution, alternately distribute or be two, three, four, five or more a plurality of block form of random order.
In a preferred embodiment of the invention, in the presence of a plurality of different alkylene oxide group blocks, the order of R1 is preferably inferior butoxy block, inferior propoxy-block, inferior ethoxyl block.Used inferior butoxy should comprise >=80% 1, the 2-oxybutylene, preferred>90% 1, the 2-oxybutylene.
In above-mentioned general formula, X is for having 0-10, the alkylidene group or the alkylene group of preferred 0-3 carbon atom.Alkylidene group is preferably methylene radical, ethylidene or propylidene.
In the prior art of being quoted, there is not C usually
4The specific descriptions information of epoxide.This can mean 1 usually, 2-oxybutylene, 2, the mixture of 3-oxybutylene, different oxybutylene and these compounds.This composition depends on used C usually
4Alkene, and be somewhat dependent upon method for oxidation.
In above-mentioned general formula, Y is sulfonate radical, sulfate radical, carboxylate radical or phosphate radical.
In above-mentioned general formula, M
+Be positively charged ion, be preferably and be selected from Na
+, K
+, Li
+, NH
4 +, H
+, Mg
2+And Ca
2+Positively charged ion.
The tensio-active agent of said general formula can be with known mode in principle, through correspondent alcohol R
1The alkoxylate preparation of-OH.Be that those skilled in the art institute is known on this oxyalkylated implementation principle.The MWD of the same known alcoxylates of those skilled in the art can receive reaction conditions, especially the influence of catalyzer selection.
The tensio-active agent of said general formula can be preferably through the alkoxylate preparation of base catalysis.In this case, can be in pressurized reactor, with pure R
1-OH mixes with alkali metal hydroxide (preferred Pottasium Hydroxide) or alkali metal alcoholates (for example sodium methylate).Can and/or improve temperature (30-150 ° of C) and remove the water that still is present in the said mixture by decompression (for example < 100 millibars).Thereafter, said alcohol exists with the form of corresponding alkoxide.Then, with rare gas element (for example nitrogen) inerting and the temperature of 60-180 ° of C and at the most 10 the crust pressure under progressively add oxyalkylene.In preferred embodiments, at first under 130 ° of C, be metered into oxyalkylene.In reaction process, temperature rises to 170 ° of C, and this is because due to the reaction release of heat.In other preferred embodiments of the present invention, at first under the temperature of 135-145 ° of C, add oxybutylene, under the temperature of 130-145 ° of C, add propylene oxide then, under the temperature of 125-145 ° of C, add ethylene oxide then.When reaction finishes, for example can pass through to add acid (like acetate or phosphoric acid) catalyst neutralisation, and the words that need are with its filtering.
Yet, said pure R
1The alkoxylate of-OH also can be passed through additive method, for example carries out through acid catalyzed alkoxylate.In addition, for example can use described double-hydroxide clay, perhaps can use DMC catalysts (dmc catalyst) like DE4325237A1.Suitable dmc catalyst for example is disclosed in DE10243361A1, especially [0029]-[0041] section with the document wherein quoted in.For example, can use Zn-Co type catalyzer.In order to implement this reaction, can be with said pure R
1-OH and said catalyst mix can make the dehydration of said mixture and as described and reactions of alkylene oxide as stated.Usually use the catalyzer that is no more than 1000ppm based on this mixture, because should be a small amount of, said catalyzer can remain in the product.Catalytic amount usually can be less than 1000ppm, for example 250ppm or still less.
At first introduce anionic group.Those skilled in the art institute is known in principle for this.Under the situation of sulfate radical, for example can use and the reaction in falling film reactor, carried out of sulfuric acid, chlorsulfonic acid or sulphur trioxide, with post neutralization.Under the situation of sulfonate radical, for example can use the reaction with propane sultone, subsequently with the butyl sultone neutralization, neutralize with vinyl sulfonic acid sodium salt or 3-chloro-2-hydroxy-propanesulfonic acid sodium salt subsequently.Under the situation of carboxylate radical, available oxygen oxidation alcohol and for example with post neutralization, perhaps with the sodium chloroacetate reactant salt.
Other tensio-active agents
Except the tensio-active agent of above-mentioned general formula, said preparaton can be chosen extra other tensio-active agents that comprises wantonly.These for example are alkylaryl sulphonate or alkene sulfonate (sulfonated or internal olefin sulphonates) type AS and/or alkylethoxylate or alkyl polyglucoside type nonionogenic tenside.These other tensio-active agents especially also can be oligopolymer or polymeric surfactant.Advantageously use this class in polymer type cosurfactant to reduce the amount that forms the required tensio-active agent of microemulsion.Therefore, this class in polymer type cosurfactant is also referred to as " microemulsion auxiliary agent ".The instance of this class in polymer type tensio-active agent comprises amphiphilic block copolymer, and it comprises at least one hydrophilic block and at least one hydrophobic block.The example comprises polyoxytrimethylene-polyethylene oxide block copolymer; Polyisobutene-polyethylene oxide block copolymer; And the comb copolymer with ethylene oxide side chain and hydrophobic main chain, wherein said main chain preferably comprises alkene or (methyl) propenoate basically as monomer.Here, term " polyoxyethylene " should comprise like the defined polyoxyethylene block that comprises propylene oxide unit of preceding text in each case.The further details of this type tensio-active agent is disclosed among the WO2006/131541A1.
The MO reoovery method
In MO reoovery method of the present invention, the suitable aqueous formulation of said general formula tensio-active agent is injected well via at least one inject the mineral oil reservoir, and from said oil reservoir, extract crude oil out via at least one extraction well.In context of the present invention, term " crude oil " does not mean single phase certainly, and is meant common crude oil-water miscible liquid.Generally speaking, oil reservoir has several injection wells and several extraction wells usually.
The IT that mainly the acting as of tensio-active agent reduced between the water oil-desirable is to reduce to significantly＜value of 0.1mN/m.Injecting said tensio-active agent preparaton (being called " surfactant flooding ") or preferred Winsor III type " microemulsion flooding " afterwards, can be through water (" water drive ") or more high viscosity water solution (" polymer flooding ") the injection stratum that preferably has a polymkeric substance of remarkable thickening effectiveness be keep-uped pressure.Yet, the also known technology of Action of Surfactant that wherein at first make in the stratum.Another known technology is the solution that injects tensio-active agent and thickening polymer, injects thickening polymer solution then.Those skilled in the art know the details of the industrial implementation of " surfactant flooding ", " water drive " and " polymer flooding ", and use suitable technique according to the oil reservoir type.
As far as the inventive method, use the aqueous formulation of the tensio-active agent of said general formula.Outside dewatering, said preparaton also can be chosen wantonly and comprise water miscibility or organic substance or other materials of water dispersible at least.This type additive is particularly useful in storage or surface of stability activator solution during being transported to the oil field.Yet the amount of other solvents of this type should be no more than 50 weight % usually, preferred 20 weight %.In the particularly advantageous embodiment of the present invention, only water is used for preparation.The instance of water miscibility solvent comprises that especially alcohol is like methyl alcohol, ethanol, propyl alcohol, butanols, sec-butyl alcohol, amylalcohol, butyl glycol, butyldiglycol or butyl triglycol.
According to the present invention, the ratio of the existing all surface promoting agent of said general formula surfactant comprise (being the tensio-active agent and the optional tensio-active agent that exists of said general formula) is at least 30 weight %.Preferred this ratio is at least 50 weight %.
Can the mixture that the present invention is used be preferred for the surfactant flooding of oil reservoir.Be particularly suited for Winsor III type microemulsion flooding (in Winsor III scope the displacement of reservoir oil or have the displacement of reservoir oil in the bicontinuous microemulsions phase scope).The technology of microemulsion flooding is described in detail at the beginning part.
Except said tensio-active agent, said preparaton also can comprise other components, for example C
4-C
8Alcohol and/or basic salt (so-called " displacement of reservoir oil of basic surface promoting agent ").This type additive for example can be used for reducing the delay in the stratum.Yet based on the ratio of the alcohol of used tensio-active agent total amount be at least usually 1:1-, also can use significantly excessive alcohol.The amount of basic salt can be 0.1-5 weight % usually.
Wherein use the oil reservoir of said method to have usually and be at least 10 ° of C, for example the temperature of 10-150 ° of C preferably has the temperature of at least 15 ° of C to 120 ° of C.All surface promoting agent total concn together is 0.05-5 weight % based on said aqueous surfactant preparaton total amount, is preferably 0.1-2.5 weight %.Those skilled in the art especially make appropriate selection according to the condition in the said mineral oil reservoir according to desired properties.At this moment, it will be apparent for a person skilled in the art that said surfactant concentrations can be owing to this preparaton can mix with local water after injecting the stratum, perhaps tensio-active agent also can be absorbed on the solid surface on stratum and changes.The huge advantage of the used mixture of the present invention is that said tensio-active agent causes good especially interfacial tension lowering effect.
Certainly and preferably at first prepare the enriched material of diluted on site only to the desired concn that is used for injecting the stratum.Tensio-active agent total concn in this enriched material is generally 10-45 weight %.
Hereinafter embodiment is intended to set forth in detail the present invention:
Part I: tensio-active agent synthetic
Universal method 1: through KOH catalysis alkoxylate (being applicable to EO, PO and/or 1, the situation of 2-BuO used)
In the 2L autoclave, will treat oxyalkylated alcohol (1.0 equivalent) and the KOH aqueous solution that comprises 50 weight %KOH.The amount of KOH is 0.2 weight % of product to be prepared.Under agitation, with this mixture in 100 ° of C and 20 millibars dehydration 2 hours down.Then, use N
2Purge 3 times, set up the N of about 1.3 crust
2Intake pressure, and temperature risen to 120-130 ° of C.So that remaining on the mode of 125-135 ° of C (under the situation of ethylene oxide) or 130-140 ° of C (under the situation of propylene oxide) or 135-145 ° of C (1, under the situation of 2-oxybutylene), temperature is metered into oxyalkylene.Restir 5 hours under 125-145 ° of C is used N then
2Purge, be cooled to 70 ° of C, and empty reaction kettle.By in the acetate with alkaline crude product.Perhaps also available commercially available Magnesium Silicate q-agent neutralizes, then with its filtering.By at CDCl
3In
1H-NMR spectrum, GPC and OH pH-value determination pH characterize light product, and measure productive rate.
Universal method 2: through DMC catalysis alkoxylate (2, under the situation of 3-oxybutylene)
In the 2L autoclave, under 80 ° of C, will treat that oxyalkylated alcohol (1.0 equivalent) and DMC catalysts (for example available from BASF Zn-Co type dmc catalyst) are mixed.For deactivated catalyst, under 80 ° of C, apply about 20 millibars 1 hour.The amount of DMC accounts for 0.1 weight % of product to be prepared or still less.Then, use N
2Purge 3 times, set up the N of about 1.3 crust
2Intake pressure, and temperature risen to 120-130 ° of C.So that remaining on the mode of 125-135 ° of C (under the situation of ethylene oxide) or 130-140 ° of C (under the situation of propylene oxide) or 135-145 ° of C (2, under the situation of 3-oxybutylene), temperature is metered into oxyalkylene.Restir 5 hours under 125-145 ° of C is used N then
2Purge, be cooled to 70 ° of C, and empty reaction kettle.By at CDCl
3In
1H-NMR spectrum, GPC and OH pH-value determination pH characterize light product, and measure productive rate.
Universal method 3: through the chlorsulfonic acid sulfation
In the 1L round-bottomed flask, will treat that Sulfated alkyl alkoxylates (1.0 equivalent) is dissolved in the methylene dichloride (based on weight %) of 1.5 times of amounts and is cooled to 5-10 ° of C.So that temperature be no more than the mode of 10 ° Cs drip chlorsulfonic acid (1.1 equivalent) thereafter.Make this mixture get warm again after a cold spell to room temperature and under this temperature at N
2Stirred 4 hours in the stream, being up under 15 ° of C, above-mentioned reaction mixture is dropped in the NaOH aqueous solution of half volume then.The amount of calculating NaOH is excessive for a little based on used chlorsulfonic acid to obtain.Gained pH value is about pH9-10.Being up under 50 ° of C, under gentle vacuum, removing methylene dichloride on the rotatory evaporator.
Product is used
1H-NMR characterizes, and measures the water cut (about 70%) of this solution.
Following alcohol is used to synthesize.
Performance test
Use the gained tensio-active agent to test as follows, whether be suitable for tertiary recovery MO to evaluate it.
Testing method is described
SP
*Measurement
A) measuring principle:
IT between the water oil is in a known way through measuring solubilization parameter SP
*And measure.Through measuring solubilization parameter SP
*And the method for measuring IT is the method that is used for the approximate test IT that industrial circle is accepted.Solubilization parameter SP
*Sign is dissolved in the mL number of the oil in the tensio-active agent that every mL is used for microemulsion (Winsor III type).If use isopyknic water and oil, then IT σ (IFT) can pass through rough and ready formula IFT ≈ 0.3/ (SP thus
*)
2Calculate (C.Huh, J.Coll.Interf.Sc., the 71st volume the 2nd phase (1979)).
B) program
In order to measure SP
*, in 100mL has the test cylinder of magnetic stirring bar, charge into 20mL oil and 20mL water.To wherein adding certain density specific surfactant.Then, make temperature progressively be increased to 90 ° of C, observe the temperature window that forms microemulsion by 20 ° of C.
But the evaluation of the formation vision of microemulsion is perhaps by conductivity measurement.Form three-phase system (upper oil phase, middle level micro emulsion liquid phase, lower floor's water).When the upper and lower have same size mutually and in 12 hours, do not change, then record the optimum temps (T that forms microemulsion
Best).Measure the middle level phase volume.From this volume, deduct the tensio-active agent volume that is added.Then with income value divided by 2.Then with this volume divided by the tensio-active agent volume that is added.The result counts SP
*
Be used to measure SP
*The type of oil and water confirm according to system to be detected.Can use MO itself or simulated oil, like decane.Used water can be pure water and salt solution to simulate the condition in the MO stratum better.The composition of water for example can be regulated based on the composition of specific oil reservoir water.
The specific descriptions that the information of used water and oil phase can vide infra and test.
Test result
The mixture of 1:1 decane and NaCl solution is mixed with butyldiglycol (BDG).Butyldiglycol (BDG) is as solubility promoter and be not included in SP
*Calculated value in.To wherein adding the surfactant mixt that constitutes by 3 parts of alkyl alkoxy sulfates and 1 part of dodecylbenzene sulfonate (Lutensit A-LBN 50 is available from BASF).The total concn of said tensio-active agent is in the weight % of TV.
In addition, the mixture with 1:1 decane and NaCl solution mixes with butyldiglycol (BDG).Butyldiglycol (BDG) is as solubility promoter and be not counted in SP
*The surfactant mixt that interpolation is made up of 3 parts of alkyl alkoxy sulfates and 1 part of secondary alkyl sulfonate (Hostapur SAS 60 is available from BASF).In the said tensio-active agent total concn of weight % with respect to water.
In addition, the crude oil (33 ° of API) of 1:1 southern German and the mixture of NaCl solution are mixed with butyldiglycol (BDG).Butyldiglycol (BDG) is as solubility promoter and be not included in SP
*Calculating in.To wherein adding the surfactant mixt that constitutes by 3 parts of alkyl alkoxy sulfates and 1 part of dodecylbenzene sulfonate (Lutensit A-LBN 50 is available from BASF).The total concn of said tensio-active agent is in the weight % of TV.
In two other tests, the crude oil available from southern German (33 ° of API) of 1:1 and the mixture of NaCl solution or the mixture of 1:1 or Canadian crude oil (14 ° of API) and NaCl solution are mixed with butyldiglycol (BDG) separately.Butyldiglycol (BDG) is as solubility promoter and be not counted in SP
*Add the surfactant mixt that constitutes by 3 parts of alkyl alkoxy sulfates and 1 part of secondary alkyl sulfonate (Hostapur SAS 60 is available from Clariant) separately.Separately in the said tensio-active agent total concn of weight % with respect to water.
Tensio-active agent result based on straight chain alcohol and branching alcohol is shown among the table 1-7.
Table 1 is based on straight chain C
16C
18The tensio-active agent of alcohol
Obvious by the Embodiment C of table 11 and C3 or C2 and C4, C
16C
18-7PO-vitriol and C
16C
18The SP of-9PO-vitriol
*There is little difference.Thus, it should be noted should be at similar T
BestUnder compare to get rid of temperature effective.Under the situation of the tensio-active agent with nonionic composition, these can produce considerable influence.
The C that contains BuO when use
16C
18During-alkoxy sulfate, has surprising result.Embodiment 5 and 6 is illustrated in C
16C
18Introduce two 1 between-Fatty Alcohol(C12-C14 and C12-C18) and seven propylene oxide units, no matter 2-oxybutylene unit causes all obtaining surprising stable SP still being 47 ° of C under under 62 ° of C
*=16.When the total concn of tensio-active agent reduced, similar situation can appear.In embodiment 11, SP
*Under 72 ° of C, be 15.Variation with containing of identical degree of alkoxylation of pure PO compound is big (C3 and C4) more, perhaps when the tensio-active agent total concn reduces, and SP
*The reduction degree is big (C9 and C10) slightly.
In contrast, as in control Example C7 and C8, between propylene oxide block and sulfate radical, have 1, the 2-oxybutylene is arranged so not favourable.SP
*Be in low-level slightly and when considering temperature not simultaneously, its variation is more obvious.
Use 2, the 3-oxybutylene is significantly poorer.By finding out SP among the C12
*Be essentially half the (SP
*=8), therefore poorer than alkyl propoxy-vitriol (C9) with identical degree of alkoxylation.Surprisingly, not only carbonatoms but also its spatial disposition have very big influence to the ability that said tensio-active agent reduces IT.As 2, under the situation of 3-oxybutylene, in fact unfavorable arrangement can produce destructive effects and obtain than poorer value under the situation of the respective surfaces promoting agent that does not contain the oxyalkylene with 4 carbon atoms.US3890239 or US4448697 do not describe this.
What is interesting is, in straight chain C
16C
18In the Fatty Alcohol(C12-C14 and C12-C18), in case 1,2-oxybutylene unit content is three or more a plurality of, then unexpected improvement can take place.In embodiment 13, introduce three this type unit and cause SP
*Rise to 23.5.This in addition can be able to further raising (embodiment 14-16) through reaching 5 unit.At this moment, SP
*Even be higher than 30.
Table 2 is based on the different C of branching
17The tensio-active agent of alcohol
Similar situation is present in the table 2.At this moment, use based on the different C of branching
17There is the influence that can not be attributable simply to straight chain alcohol in the alkyl alkoxy sulfate of-alcohol with checking.
Control Example C1 most clearly is illustrated in the tensio-active agent with identical degree of alkoxylation with embodiment 2, uses 1,2-oxybutylene and not use propylene oxide obviously be favourable.Under similar temperature, SP
*It is three times high.1,2-BuO directly is arranged on the alkyl structure part (embodiment 5 and 6) and has also obtained than the lower IT of different arrangements (for example embodiment 4).
Table 3 is based on branching C
16The tensio-active agent and the C of Guerbet alcohol
16C
18The contrast of-pure based surfactants
Can find out by table 3, similar situation also occur.If the tensio-active agent based on straight chain alcohol comprises above 21 2-BuO unit, then SP
*Obviously rise sharply, therefore reduce IT.Compare with embodiment 3 and 4, embodiment 2 has shown based on straight chain C
16C
18-alcohol tensio-active agent with based on branching C
16Difference between the Guerbet alcohol.In the Guerbet based surfactants, introduce 21,2-oxybutylene unit has obtained than based on the remarkable better SP of straight chain alcohol and tensio-active agent with similar chain length
*Yet can be found out by embodiment 5, under the situation of straight chain alcohol, introduce 1 of volume more, the 2-oxybutylene can obtain the SP roughly the same with embodiment 4
*
Can find out by embodiment 6, between sulfate radical and PO block, introduce the extra hydrophobicity that 10 EO can remedy the 7-BuO block basically; Therefore, its can be under conditions of similarity (similar salts contg, similar temperature T
Best) compare with control Example C1.
Can find out that by control Example C7 and C8 do not introducing 1, under the 2-oxybutylene, said tensio-active agent is merely the average surface promoting agent.Embodiment 11 demonstrates and introduces 1 normally 1, and 2-BuO is only to a certain degree improving SP down
*At C
16Under the situation of Guerbet based surfactants (embodiment 3), only introduce 2 equivalents 1,2-BuO, SP
*Be able to remarkable improvement.
Table 4 uses the test of southern German crude oil
Can find out by table 4, compare, use crude oil also to obtain essentially identical situation with the test of using the decane simulated oil.Under suitable temperature, control Example C1 obtains than containing significantly lower SP of BuO tensio-active agent among the embodiment 2
*, therefore obtain higher IT.Control Example C3 and embodiment 4 demonstrate 1 of similar fashion, the advantage of 2-oxybutylene.
Table 5 uses the decane test under similar temperature and salinity
Clearly, with BDG blended water phase surfactant mixture at top condition (salinity, T
Best, it obtains 3 phase systems (Winsor III type) through adding oil) under be soluble.As shown in table 5, top condition (salinity, T
Best) very close.Shown in embodiment 2, correctly finely tune degree of alkoxylation obtain to have with EXAMPLE V 1 in the tensio-active agent of the similar hydrophilic-hydrophobic balance of tensio-active agent.SP among the embodiment 2
*Higher.Therefore IT is much lower.
Table 6 uses the test of crude oil (33 ° of API) under similar temperature and salinity available from Germany
Clearly, with BDG blended water phase surfactant mixture at top condition (salinity, T
Best, it is soluble through adding under oil acquisition 3 phase systems (Winsor III type).As shown in table 6, top condition (salinity, T
Best) very approaching.Shown in embodiment 2, correctly finely tune degree of alkoxylation obtain to have with EXAMPLE V 1 in the tensio-active agent of the similar hydrophilic-hydrophobic balance of tensio-active agent.SP among the embodiment 2
*Also much higher.Therefore IT is much lower.
Table 7 is available from the test of Canadian crude oil (API 14) under similar temperature and salinity
Clearly, with BDG blended water phase surfactant mixture at top condition (salinity, T
Best, it obtains 3 phase systems (Winsor III type) through adding oil) under be soluble.As shown in table 7, top condition (salinity, T
Best) very close.Shown in embodiment 2, correctly finely tune degree of alkoxylation obtain to have with EXAMPLE V 1 in the tensio-active agent of the similar hydrophilic-hydrophobic balance of tensio-active agent.SP among the embodiment 2
*Also much higher.Therefore IT is much lower.
Claims (16)
1. one kind is passed through the method that Winsor III type microemulsion flooding is exploited MO; To be used for wherein the IT between the profit is reduced to that < the aqueous surfactant preparaton that comprises at least a ionogenic surfactant of 0.1mN/>m injects well via at least one and injects the mineral oil reservoir; And from said oil reservoir, extract crude oil out via at least one extraction well, wherein said tensio-active agent preparaton comprises the tensio-active agent of at least a following general formula:
R
1-O-(D)
n-(B)
m-(A)
l-XY
-M
+
Wherein
R
1Be straight chain with 8-30 carbon atom or branching, saturated or unsaturated aliphatic and/or aromatic hydrocarbyl,
A is an inferior ethoxyl,
B is inferior propoxy-,
D is inferior butoxy,
L is 0-99,
M is 0-99,
N is 1-99,
X is alkyl or the alkylene with 0-10 carbon atom,
M
+Be positively charged ion, and
Y
-Be selected from sulfate radical, sulfonate radical, carboxylate radical and phosphate radical, wherein
But A, B and D group random distribution, alternately distribute or be two, three, four or more a plurality of block form of random order, the l+m+n sum is 3-99, and 1, the ratio of 2-oxybutylene is at least 80% based on the oxybutylene total amount.
2. according to the process of claim 1 wherein that the l+m+n sum is 5-50.
3. according to the method for claim 1 or 2, wherein 1, the ratio of 2-oxybutylene is at least 90% based on the oxybutylene total amount.
4. according to each method among the claim 1-3, the tensio-active agent of wherein said general formula comprises 2-15 1,2-oxybutylene unit.
5. according to each method among the claim 1-4, wherein all surface promoting agent concentration together is 0.05-5 weight % based on said aqueous surfactant preparaton total amount.
6. according to each method among the claim 1-4, wherein:
M is 5-9,
N is 2-10, and
Y
-Be selected from sulfate radical, sulfonate radical and carboxylate radical, wherein
In A, B and the D group greater than 80% degree with by R
1Begin to be the block form existence of D, B, A order, the l+m+n sum is 7-49,1, and the ratio of 2-oxybutylene is at least 90% based on the oxybutylene total amount in the molecule.
7. according to the method for claim 6, R wherein
1For straight-chain fatty alcohol and n with 16 or 18 carbon atoms is 3-10.
8. tensio-active agent preparaton that comprises the ionogenic surfactant of at least a following general formula:
R
1-O-(D)
n-(B)
m-(A)
l-XY
-M
+
Wherein
R
1Be straight chain with 8-30 carbon atom or branching, saturated or unsaturated aliphatic and/or aromatic hydrocarbyl,
A is an inferior ethoxyl,
B is inferior propoxy-,
D is inferior butoxy,
L is 0-99,
M is 0-99,
N is 1-99,
X is alkyl or the alkylene with 0-10 carbon atom,
M
+Be positively charged ion, and
Y
-Be selected from sulfate radical, sulfonate radical, carboxylate radical and phosphate radical, wherein
But A, B and D group random distribution, alternately distribute or be two, three, four or more a plurality of block form of random order, the l+m+n sum is 3-99, and 1, the ratio of 2-oxybutylene is at least 80% based on the oxybutylene total amount.
9. according to Claim 8 tensio-active agent preparaton, wherein:
M is 5-9,
N is 2-10, and
Y
-Be selected from sulfate radical, sulfonate radical and carboxylate radical, wherein
In A, B and the D group greater than 80% degree with by R
1Begin to be the block form existence of D, B, A order, the l+m+n sum is 7-49, and 1, the ratio of 2-oxybutylene is at least 90% based on the oxybutylene total amount in the molecule.
10. according to the tensio-active agent preparaton of claim 9, R wherein
1For straight-chain fatty alcohol and n with 16 or 18 carbon atoms is 3-10.
11. each tensio-active agent preparaton according to Claim 8-10, wherein all surface promoting agent concentration together is 0.05-5 weight % based on said aqueous surfactant preparaton total amount.
12. the tensio-active agent of a following general formula,
R
1-O-(A)
l-(B)
m(D)
n-XY
-M
+
Wherein
R
1Be straight chain with 8-30 carbon atom or branching, saturated or unsaturated aliphatic and/or aromatic hydrocarbyl,
A is an inferior ethoxyl,
B is inferior propoxy-,
D is inferior butoxy,
L is 0-99,
M is 0-99,
N is 1-99,
X is alkyl or the alkylene with 0-10 carbon atom,
M
+Be positively charged ion, and
Y
-Be selected from sulfate radical, sulfonate radical, carboxylate radical and phosphate radical, wherein
But A, B and D group random distribution, alternately distribute or be two, three, four or more a plurality of block form of random order, the l+m+n sum is 3-99, and 1, the ratio of 2-oxybutylene is at least 80% based on the oxybutylene total amount.
13. according to the tensio-active agent of claim 12, wherein the l+m+n sum is 3-49.
14. according to the tensio-active agent of claim 12 or 13, wherein 1, the ratio of 2-oxybutylene is at least 90% based on the oxybutylene total amount.
15. according to each tensio-active agent among the claim 12-14, wherein R
1Be straight chain with 10-30 carbon atom or branching, saturated or unsaturated aliphatic and/or aromatic hydrocarbyl.
16. according to each tensio-active agent among the claim 12-15, wherein:
R
1For having the straight-chain fatty alcohol of 16 or 18 carbon atoms,
M is 5-9,
N is 3-10, and
Y
-Be selected from sulfate radical, sulfonate radical and carboxylate radical,
Wherein in A, B and the D group greater than 80% degree with by R
1Begin to be the block form existence of D, B, A order, the l+m+n sum is 7-49, and 1, the ratio of 2-oxybutylene is at least 90% based on the oxybutylene total amount in the molecule.
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| EP10002488.4 | 2010-03-10 | ||
| PCT/EP2011/053321 WO2011110503A1 (en) | 2010-03-10 | 2011-03-04 | Method for producing crude oil using surfactants based on butylene oxide-containing alkyl alkoxylates |
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| CN201510041875.0A Pending CN104726084A (en) | 2010-03-10 | 2011-03-04 | Method for producing crude oil using surfactants based on butylene oxide-containing alkyl alkoxylates |
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| EP (1) | EP2545136A1 (en) |
| JP (1) | JP2013528720A (en) |
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| CN111566183A (en) * | 2017-05-30 | 2020-08-21 | 巴斯夫欧洲公司 | Method for extracting petroleum from underground oil reservoir with high temperature and salinity |
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| JP6063879B2 (en) | 2011-03-18 | 2017-01-18 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Integrated circuit device, optical device, micromachine, and method for manufacturing mechanical precision device having patterned material layer having a line width of 50 nm or less |
| WO2013060622A1 (en) | 2011-10-24 | 2013-05-02 | Basf Se | Method for producing mineral oil using surfactants based on a mixture of c28-guerbet-, c30-guerbet-, c32-guerbet-containing hydrocarbon alkoxylates |
| US9475978B2 (en) * | 2011-10-24 | 2016-10-25 | Basf Se | Process for producing mineral oil using surfactants based on a mixture of C24 guerbet-, C26 guerbet-, C28-guerbet containing hydrocarbyl alkoxylates |
| US9475979B2 (en) * | 2011-10-24 | 2016-10-25 | Basf Se | Process for producing mineral oil using surfactants based on a mixture of C20 Guerbet-, C22 Guerbet-, C24 Guerbet-containing hydrocarbyl alkoxylates |
| EP2771427B1 (en) | 2011-10-24 | 2016-07-06 | Basf Se | Method for producing mineral oil using surfactants based on a mixture of c20-guerbet-, c22-guerbet-, c24-guerbet-containing hydrocarbon alkoxylates |
| JP5961274B2 (en) * | 2011-10-24 | 2016-08-02 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Process for producing mineral oil using a hydrocarbyl alkoxylate mixed surfactant containing C28 gel, C30 gel and C32 gel |
| US9475977B2 (en) * | 2011-10-24 | 2016-10-25 | Basf Se | Process for producing mineral oil using surfactants based on a mixture of C28 Guerbet, C30 Guerbet, C32 Guerbet-containing hydrocarbyl alkoxylates |
| CN104736228B (en) * | 2012-09-29 | 2017-08-18 | 陶氏环球技术有限责任公司 | Anionic surfactant compositions and its purposes |
| WO2014064152A1 (en) * | 2012-10-26 | 2014-05-01 | Basf Se | Process for mineral oil production using surfactants at least comprising a secondary alkanesulphonate and an alkyl ether sulphate/sulphonate/carboxylate/phosphate |
| WO2014063933A1 (en) * | 2012-10-26 | 2014-05-01 | Basf Se | Process for mineral oil production using surfactants based on anionic alkyl alkoxylates which have been formed from glycidyl ethers |
| US9555385B2 (en) | 2013-03-08 | 2017-01-31 | Dow Global Technologies Llc | Anionic surfactant compositions and use thereof |
| US11390794B2 (en) | 2017-09-21 | 2022-07-19 | Basf Se | Robust alkyl ether sulfate mixture for enhanced oil recovery |
| CN113801316B (en) * | 2020-06-15 | 2024-01-26 | 中国石油化工股份有限公司 | Alkoxy block polyether sulfonate anionic surfactant and preparation method thereof |
| CN113797842B (en) * | 2020-06-15 | 2023-08-29 | 中国石油化工股份有限公司 | Hydrocarbyl aryl anionic nonionic surfactant and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3843706A (en) * | 1969-05-23 | 1974-10-22 | Us Agriculture | Long chain ether alcohol sulfates from propylene oxide and 1,2-butylene oxide |
| US4395364A (en) * | 1979-11-16 | 1983-07-26 | Kao Soap Co., Ltd. | Detergent composition containing sulfonate surfactant and polyoxyalkylene alkyl or alkenyl sulfuric acid ester salt |
| US4460481A (en) * | 1980-09-29 | 1984-07-17 | Texaco Inc. | Surfactant waterflooding enhanced oil recovery process |
| US4592875A (en) * | 1984-06-25 | 1986-06-03 | Atlantic Richfield Company | Alkoxylated ether sulfate anionic surfactants from plasticizer alcohol mixtures |
| CN1197449A (en) * | 1995-08-04 | 1998-10-28 | 韦特科公司 | Reducing estrogenicity of alkoxylated compounds and products thereof |
| CN1292255A (en) * | 1999-09-29 | 2001-04-25 | 欧莱雅 | Keratin material detergent composition containing washing surfactant, dialkyl diallyl ammonium homopolymer and acrylic ternary copolymer |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3890239A (en) | 1973-02-01 | 1975-06-17 | Sun Oil Co | Surfactant compositions useful in oil recovery processes |
| US4393935A (en) * | 1980-05-30 | 1983-07-19 | Basf Wyandotte Corporation | Stimulation of gas wells with phosphate ester surfactants |
| US4448697A (en) | 1982-01-22 | 1984-05-15 | Texaco Inc. | Secondary recovery process |
| DE4325237A1 (en) | 1993-07-28 | 1995-02-02 | Basf Ag | Process for the preparation of alkoxylation products in the presence of mixed hydroxides modified with additives |
| CN1091085C (en) * | 1999-12-03 | 2002-09-18 | 山东淄博新华－肯孚制药有限公司 | Process for recovering nitrogen-contained organic alkali |
| DE10243361A1 (en) | 2002-09-18 | 2004-04-01 | Basf Ag | Alkoxylate mixture used in laundry and cleaning detergents for washing and cleaning textiles contains alkoxylates of alkanols with different chain lengths with ethylene oxide and optionally other alkylene oxide(s) |
| DE102005026716A1 (en) | 2005-06-09 | 2006-12-28 | Basf Ag | Surfactant mixtures for tertiary mineral oil production |
| WO2009084729A1 (en) * | 2007-12-28 | 2009-07-09 | Kao Corporation | Laundry detergent composition |
-
2011
- 2011-03-04 WO PCT/EP2011/053321 patent/WO2011110503A1/en active Application Filing
- 2011-03-04 EP EP11706292A patent/EP2545136A1/en not_active Withdrawn
- 2011-03-04 KR KR1020127026526A patent/KR20130016266A/en not_active Application Discontinuation
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- 2011-03-09 AR ARP110100729A patent/AR080479A1/en not_active Application Discontinuation
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3843706A (en) * | 1969-05-23 | 1974-10-22 | Us Agriculture | Long chain ether alcohol sulfates from propylene oxide and 1,2-butylene oxide |
| US4395364A (en) * | 1979-11-16 | 1983-07-26 | Kao Soap Co., Ltd. | Detergent composition containing sulfonate surfactant and polyoxyalkylene alkyl or alkenyl sulfuric acid ester salt |
| US4460481A (en) * | 1980-09-29 | 1984-07-17 | Texaco Inc. | Surfactant waterflooding enhanced oil recovery process |
| US4592875A (en) * | 1984-06-25 | 1986-06-03 | Atlantic Richfield Company | Alkoxylated ether sulfate anionic surfactants from plasticizer alcohol mixtures |
| CN1197449A (en) * | 1995-08-04 | 1998-10-28 | 韦特科公司 | Reducing estrogenicity of alkoxylated compounds and products thereof |
| CN1292255A (en) * | 1999-09-29 | 2001-04-25 | 欧莱雅 | Keratin material detergent composition containing washing surfactant, dialkyl diallyl ammonium homopolymer and acrylic ternary copolymer |
Non-Patent Citations (1)
| Title |
|---|
| 姚光裕: "自动乳化的消泡剂", 《中华纸业》, no. 03, 25 April 2001 (2001-04-25) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111566183A (en) * | 2017-05-30 | 2020-08-21 | 巴斯夫欧洲公司 | Method for extracting petroleum from underground oil reservoir with high temperature and salinity |
Also Published As
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|---|---|
| AR080479A1 (en) | 2012-04-11 |
| WO2011110503A1 (en) | 2011-09-15 |
| MX340884B (en) | 2016-07-29 |
| MX2012010276A (en) | 2012-09-28 |
| CN104726084A (en) | 2015-06-24 |
| CN102791824B (en) | 2016-03-02 |
| AU2011226215A1 (en) | 2012-09-20 |
| CA2791119C (en) | 2018-05-22 |
| EA201401362A1 (en) | 2015-05-29 |
| KR20130016266A (en) | 2013-02-14 |
| RU2563642C2 (en) | 2015-09-20 |
| CA2791119A1 (en) | 2011-09-15 |
| ECSP12012146A (en) | 2012-10-30 |
| BR112012022670A2 (en) | 2020-08-11 |
| EP2545136A1 (en) | 2013-01-16 |
| RU2012142936A (en) | 2014-04-20 |
| MY161638A (en) | 2017-04-28 |
| JP2013528720A (en) | 2013-07-11 |
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