CN104011171B - Use based on containing C24 Guerbet-, C26 Guerbet-, the method for the surfactant exploitation mineral oil of the mixture of C28 Guerbet-hydrocarbon alcoxylates - Google Patents

Abstract

The present invention relates to a kind of surfactant mixture, it comprises at least three kinds with regard to hydrocarbyl moieties (R¹)(R²)‑CH‑CH₂For different and there is the ionic surfactant of logical formula (I), wherein R¹、R²、A⁰, defined in k, X, o, Y, a, b, M specification and claims the most freely.The invention still further relates to its Use and preparation method, and relate to the aqueous surfactant preparaton containing described mixture, relate to the method by Winsor type III microemulsion flooding exploitation mineral oil, wherein described aqueous surfactant preparaton is injected in mineral oil reservoir via injecting well, and from described oil reservoir, extract crude oil out via extraction well.

Description

Use based on containing C24 Guerbet-, C26 Guerbet-, C28 Guerbet-hydrocarbon alkane The method of the surfactant exploitation mineral oil of the mixture of epoxide compound

The present invention relates to a kind of surfactant mixture, relate to its Use and preparation method, and relate to containing described The aqueous surfactant preparaton of mixture, relates to the method by Winsor type III microemulsion flooding exploitation mineral oil, Wherein described aqueous surfactant preparaton is injected in mineral oil reservoir via injecting well, and via extraction well from described oil reservoir Middle extraction crude oil.

In natural minerals oil reservoir, mineral oil is present in the hole of porous reservoir rock, its towards side, ground by not Layer is sealed thoroughly.Described hole can be superfine hole, capillary tube, hole etc..Pore neck such as can have the diameter of the most about 1 μm. In addition to mineral oil (including gas component), oil reservoir also comprises and has or the water of high or low salt content.

In mineral oil is exploited, it is generally divided into primary recovery, secondary recovery and tertiary recovery.In primary recovery, mineral Oil due to the self-generated pressure of oil reservoir, after oil reservoir probing starts through by boring automatic flowing to surface.

Therefore after primary recovery, use secondary recovery.In secondary recovery, except the boring, i.e. for exploiting mineral oil Outside so-called extraction well, in the stratum containing mineral oil, also pierce other boring.Via these so-called injection wells to oil reservoir Middle injection water is to maintain pressure or to make it again raise.Owing to injecting the event of water, mineral oil is by the direction injecting well extraction well Slowly it is pressed in stratum via hole.But, this only hole be filled with oil completely and more viscous oil by water promote advance In the case of just work.The penetration by water hole once moved, it flows along the path that now resistance is minimum, i.e. flows through formation Passage, and no longer promote oil advance.

Primary recovery and secondary recovery the most only can exploit the about 30-35% of the mineral oil mass in the presence of described oil reservoir.

Known mineral oil yield can be improved further by tertiary oil recovery measure.The summary of tertiary oil recovery can be found in such as " Journal of Petroleum Science of Engineering19 (1998) ", the 265-280 page.Tertiary oil recovery bag Include such as by the use of thermal means, wherein hot water or steam are injected in oil reservoir.This makes oil viscosity reduce.Flow media used equally may be used For gas, such as CO₂Or nitrogen.

Three mineral oil exploit the method also including wherein using suitable chemicals as oil recovery auxiliary agent.These can be used for Affect the situation of water flow end, and be therefore also used for exploiting the mineral oil being the most firmly held in rock stratum.

In neighbouring secondary recovery latter stage, viscous force and capillary force act on and are trapped on the mineral oil preserving in petrosal foramen, The ratio that wherein both power is relative to each other depends on that microcosmic is separating of oil.These power are by dimensionless group, the most so-called capillary Pipe number describes.Viscous force (viscosity of speed × driving phase) is to capillary force (moistening of the interfacial tension × rock between profit) Ratio:

$N_c=\frac{\mathrm{\μ\ν}}{\mathrm{\σ}\cos \mathrm{\θ}}$

In the formula, μ is the viscosity of the fluid ordering about mineral oil motion, and ν is Darcy velocity (flow of unit are), σ For ordering about the interfacial tension between liquid and the mineral oil that mineral oil moves, and θ is the contact angle between mineral oil and rock (C.Melrose, C.F.Brandner, J.Canadian Petr.Techn.58, the 10-12 month in 1974).Capillary number is the highest, The mobility of oil is the highest, and therefore oil removal degree is the biggest.

The capillary number that known neighbouring secondary mineral oil exploits latter stage is about 10^-6, it is necessary to make capillary number be increased to about 10^-3-10^-2Such that it is able to make extra mineral oil move.

To this end, the flooding method that can implement particular form is referred to as Winsor type III microemulsion flooding.At Winsor In type III microemulsion flooding, the surfactant of injection should form Winsor III with the aqueous phase in the presence of oil reservoir and oil phase Type microemulsion.Winsor type III microemulsion not has an emulsion of specific droplet, but the heat of water, oil and surfactant The liquid mixture that mechanics is stable.Its three advantages are:

-extremely low interfacial tension σ that is derived between mineral oil and aqueous phase；

-it is generally of extremely low viscosity and is not trapped by porous matrix；

-it even forms under minimum energy input and can keep within the time of endless stably (the most in contrast, the most often Rule emulsion needs the high shear force not occurred in oil reservoir, and is only dynamic stabilization).

Winsor type III microemulsion is the equilibrium system of excessive water and excessive oil.In these conditions forming microemulsion Under, surfactant covers oil-water interface, and interfacial tension σ is more preferably reduced to < 10^-2MN/m's (ultralow interfacial tension) Value.In order to obtain optimum, under the surfactant of the amount of determination, described water_-Microemulsion_-Microemulsion ratio in oil systems Naturally should be maximum, because this can obtain lower interfacial tension.

(interfacial tension between profit drops in so much to such an extent as to the interface of minimum can to change oil droplet shape in this way State is the most favourable and spherical is no longer preferred), and they can be by displacement of reservoir oil water-driven through capillary pipe opening.

In the presence of excess surface active agent, when all oil-water interfaces are covered by surfactant, form Winsor Type III microemulsion.Therefore it constitute the surfactant reservoir causing the extremely low interfacial tension between oil phase and aqueous phase.Due to Winsor type III microemulsion has low viscosity, and it also migrates across porous reservoir rock (in contrast, emulsion in oil displacement process It is captured in porous matrix and blocks oil reservoir).When Winsor type III microemulsion with not yet covered by surfactant When oil-water interface meets, the surfactant of described microemulsion can significantly reduce the interfacial tension at this new interface, and causes oil fortune Dynamic (such as being deformed by oil droplet).

Described oil droplet can merge with oil reservoir continuously subsequently.This has two advantages:

Firstly, since described continuous oil reservoir is pushed ahead through new porous rock, the oil droplet being contained therein can be with Described reservoir merges.

Oil-water interface is made to be substantially reduced additionally, oil droplet merges formation oil reservoir, and the surface activity that therefore will no longer be required to Agent discharges again.Thereafter, the surfactant discharged as mentioned above can order about the oil droplet motion of residual in stratum.

Therefore, Winsor type III microemulsion flooding is a kind of particularly effective method, and compared with emulsion flooding method Need the surfactant of much less.In microemulsion flooding, generally by optional for surfactant and cosolvent and/or basic salt (optionally in the presence of chelating agen) injects together.Subsequently, the solution of thickening polymer is injected to control mobility.Another program It is to inject thickening polymer, surfactant, cosolvent and/or the mixture of basic salt (optionally together with chelating agen), then Inject the solution of thickening polymer to control mobility.These solution should generally be clarification, to prevent from blocking oil reservoir.

To the requirement of the surfactant for three mineral oil exploitations and to the surface activity for other application scenario There is significant difference in the requirement of agent: the suitable surfactant for tertiary oil recovery answers the interfacial tension between Jiang Shui and oil (logical Often it is about 20mN/m) it is decreased to less than 10^-2The lowest value of mN/m such that it is able to make mineral oil fully flow.This must be logical Often be about the reservoir temperature of 15-130 DEG C and realize in the presence of the water of high content of salt, the most also at calcium at high proportion and/or Realize in the presence of magnesium ion；The most described surfactant also must be soluble in the oil reservoir water of high content of salt.

In order to meet these requirements, the mixture of surfactant, especially anion and nonionic table is proposed often The mixture of face activating agent.

US7,119,125B1 describes a kind of sulphation Guerbet (Guerbet) alcohol alkoxylates in recovering the oil Thing and the mixture of low-molecular-weight sulphation alkyl alkoxylates.The best emulsifiability is owing to bimodal distribution.So And, these emulsifiabilities do not play a major role in Winsor type III microemulsion flooding.The emulsifying of oil needs too much surface Activating agent, and required shearing force exists only in (region except around implanter) in flooding operation.

US-A2008/217064 describes a kind of drilling fluid solution, and it comprises: nonionic surfactant, its by The alkyl ethoxylate composition of at least one branched alkyl ethoxylate and end-blocking；And builder and viscosifier.Institute Stating nonionic surfactant can be C₁₀Guerbet alcohol ethoxylate.

US-A 2009/270281 describes surfactant mixture purposes in mineral oil is exploited, and lives in described surface Property the agent composition surfactant that comprises at least one alkyl with 12-30 carbon atom and there is 6-11 carbon atom The branched cosurfactant of alkyl.Alkyl-branched degree in described cosurfactant is 1-2.5, and therefore it can include 2-ethylhexyl or the Guerbet alcohol of 2-propylheptyl type.Described cosurfactant can be alcohol ethoxylate or the moon from The alcohol ethoxylate (such as alkyl ether sulfate) that son is modified.

Other surfactant mixture is described in WO2011/037975A2, WO2011/110501A1, WO2011/ In 110502A1, WO2011/110503A1 and International Application Serial No. PCT/EP2011/055884 and PCT/EP2011/056325.

Therefore, those skilled in the art are according to condition (such as temperature and salt content) present in given oil reservoir, and regulation should By parameter, the such as type of surfactant used, concentration and mixing ratio relative to each other.

As it has been described above, mineral oil exploitation is proportional to capillary number.Interfacial tension between profit is the lowest, then capillary number The highest.Carbon atom meansigma methods in crude oil is the highest, is the most more difficult to obtain low interfacial tension.For low interfacial tension properly Surfactant be those with long alkyl chain.Alkyl chain is the longest, then the effect that can reduce interfacial tension is the best.So And, this compounds ready availability very limited.

Therefore, it is an object of the invention to provide a kind of particularly efficient surfactant for surfactant flooding or Effective surfactant mixture, and three mineral oil recovery methods of a kind of improvement.Other objects of the present invention are to carry For a kind of method preparing these surfactants or surfactant mixture.

This purpose is realized by a kind of surfactant mixture, and it contains at least three kinds with regard to hydrocarbyl moieties (R¹) (R²)-CH-CH₂For-different and there is the ionic surfactant of below formula (I):

Wherein

R¹It is that there is the straight chain of 10-12 carbon atom or branched saturated or unsaturated aliphatic alkyl；

R²It is that there is the straight chain of 12-14 carbon atom or branched saturated or unsaturated aliphatic alkyl；

Each A⁰It is ethylidene, propylidene (preferably 1,2-propylidene) or butylidene (preferably 1,2-Aden independently of one another Base)；

K is the integer of 1-99；

X is the branched or nonbranched alkylidene with 1-10 carbon atom, and it can be replaced by OH group；O is 0 or 1；

M^b+It it is cation；

Y^a-It is sulfate radical, sulfonate radical, carboxylate radical or phosphate radical (preferably phosphoric acid root or carboxylate radical, more preferably sulfate radical)；

B is 1,2 or 3 (preferably 1)；With

A is 1 or 2 (preferably 1).

Another aspect of the present invention relates to a kind of aqueous surfactant preparaton, and it contains the surface activity of the present invention Agent composition, described surfactant formulatory agent preferably has the total surfactant content of 0.05-5 weight %, based on aqueous The total amount meter of surfactant formulatory agent.

The surfactant of surfactant mixture or the present invention that another aspect of the present invention relates to the present invention is joined Preparation is for the method by Winsor type III microemulsion flooding exploitation mineral oil.

Another aspect of the present invention relates to the method by Winsor type III microemulsion flooding exploitation mineral oil, wherein Via at least one, aqueous surfactant preparaton of the present invention is injected well inject in mineral oil reservoir, thus by between oil and water Interfacial tension be reduced to < 0.1mN/m, and extract crude oil from described oil reservoir out via at least one extraction well.

It thus provides with regard to hydrocarbyl moieties (R¹)(R²)-CH-CH₂At least three kinds of ion-type surfaces different for- The mixture of activating agent, and the method by Winsor type III microemulsion flooding exploitation mineral oil, wherein will be containing with regard to hydrocarbon Based moiety (R¹)(R²)-CH-CH₂The aqueous surfactant of at least three kinds of ionic surfactants different for-is joined Preparation injects well via at least one and injects in mineral oil reservoir, wherein the interfacial tension between oil and water is reduced to < 0.1mN/ M, preferably < 0.05mN/m, more preferably < 0.01mN/m, and extract crude oil from described oil reservoir out via at least one extraction well.

In a preferred embodiment, R¹It is that there is the straight chain of 10 or 12 carbon atoms or branched, saturated or unsaturated Aliphatic hydrocarbyl, R²It is that there is the straight chain of 12 or 14 carbon atoms or branched, saturated or undersaturated aliphatic hydrocarbyl.

In an especially preferred embodiment, R¹It is straight chain saturated or unsaturated with 10 or 12 carbon atoms The aliphatic hydrocarbyl of (the most saturated)；R²It is the fat of saturated or unsaturated (the most saturated) of the straight chain with 12 or 14 carbon atoms Race's alkyl, and be therefore particularly present the ionic surfactant of at least three kinds of logical formula (I), its with have 24 carbon atoms, 26 carbon atoms and the alkyl of 28 carbon atoms.When a mole total amount is to be formed from these three surfactant, more preferably There is the C of logical formula (I)₂₄Surfactant, in the range of 40-60%, has the C of logical formula (I)₂₆Surfactant is at 30- In the range of 50%, there is the C of logical formula (I)₂₈Surfactant is in the range of 1-20%, based on described total amount meter.The most excellent Choosing, gross weight meter based on surfactant mixture of the present invention, the part by weight of three kinds of ionic surfactants is More than 50 weight %, more preferably greater than 60 weight %, even more preferably greater than 70 weight %, even more preferably greater than 80 weights Amount %, most preferably greater than 90 weight %.

Preferably, k is the integer of 4-50.

Preferably, (OX) in formula (I)_oY^a-Group is OS (O)₂O^-、OCH₂CH₂S(O)₂O^-、OCH₂CH(OH)CH₂S(O)₂O^-、O(CH₂)₃S(O)₂O^-、S(O)₂O^-、CH₂C(O)O^-Or CH₂CH(R‘)C(O)O^-, wherein R ' is hydrogen or has 1-4 carbon atom Alkyl (such as methyl).

In formula (I), alkylidene epoxide (AO) group OA⁰, it occurs k time, can be identical or different.If they Different, then they can according to random, alternately or block fashion arrangement, i.e. according to 2,3,4 or more blocks rows Row.

Therefore, (OA) in formula (I)_kN Aden's epoxide (BuO), m sub-propoxyl group (PO) and l Asia can be represented Ethyoxyl (EO), wherein n, m, l be include 0 natural number, and n+m+l=k.

Preferably, n Aden's epoxide, m sub-propoxyl group and l inferior ethoxyl be at least in part according to block arrangement ( In mathematical term, preferably at least 50%, more preferably at least 60%, even more desirably at least 70%, more preferably at least 80%, more excellent Choosing at least 90%, the most all).

In the present invention, " according to block arrangement " represents that at least one AO has the most identical adjacent AO group, These at least two AO are made to form block.

Preferably, (the R in formula (I)¹)(R²)-CH-CH₂After-group, it is expressed as (OA)_k: there is n Aden's oxygen Aden's epoxide block of base, followed by has the sub-propoxy block of m sub-propoxyl group, and is finally to have l inferior ethoxyl Inferior ethoxyl block.

Preferably, m is the integer (more preferably 5-9) of 4-15, and/or l is the integer (more preferably 4-15) of 0-25, and/or n is The integer (more preferably 5-9) of 2-15.

In a further preferred embodiment, the present invention relates to a kind of with regard to hydrocarbyl moieties (R¹)(R²)-CH-CH₂- For the different mixture of three kinds of ionic surfactants and application thereof, wherein m be 4-15, n be 0-15, Y^a-Selected from sulphuric acid Root, sulfonate radical and carboxylate radical, wherein BuO, PO and EO group with the degree more than 80% in from (R¹)(R²)-CH-CH₂Start for The block form of BuO, PO and EO order exists, and l+m+n sum is 5-49.

One particularly preferred embodiment be wherein n be 2-15, m be 5-9, Y^a-Selected from sulfate radical, sulfonate radical and carboxylic acid Root, wherein A and B group with the degree more than 80% in from (R¹)(R²)-CH-CH₂Start the block shape for BuO, PO and EO order Formula exists, and l+m+n sum is 4-50, and BuO block more than 80% by 1,2-Aden epoxide is constituted.

A kind of preferably surfactant mixture of the present invention is possibly together with the surfactant of lower formula (II) He (III):

Wherein R¹、R²、A⁰、X、Y^a-、M^b+, k, o, a and b be each as defined formula (I) above.

Preferably, formula (I) surfactant is 80-relative to the ratio of formula (I), (II) and (III) surfactant total amount 99 weight %.

In an especially preferred embodiment, in logical formula (II), R¹It it is the straight chain with 10 or 12 carbon atoms Radical of saturated aliphatic alkyl, and in logical formula (III), R²It it is the straight chain radical of saturated aliphatic alkyl with 12 or 14 carbon atoms.

In the said method of the present invention by Winsor type III microemulsion flooding exploitation mineral oil, use and comprise at least Three kinds with regard to hydrocarbyl moieties (R¹)(R²)-CH-CH₂For-different and have logical formula (I) surfactant containing water surface Activating agent preparaton.Additionally, it can also comprise other surfactants and/or other components.

In the inventive method being carried out tertiary recovery mineral oil by Winsor type III microemulsion flooding, use this Bright surfactant mixture the interfacial tension between profit is reduced to < 0.1mN/m, preferably < 0.05mN/m, more preferably < The value of 0.01mN/m.Therefore, the interfacial tension between profit is down to 0.1-0.0001mN/m, preferably 0.05-0.0001mN/m, The value of more preferably 0.01-0.0001mN/m.

Logical formula (I) can contain described with regard to hydrocarbyl moieties (R¹)(R²)-CH-CH₂Three kinds of surface activitys different for- Agent.This difference can produce due to carbon atom number, unsaturated bond number, branch frequency and/or the degree of branching.More particularly, institute State surfactant at R¹And R²Given chain long side is distinct.Such as, R¹/R²For having 10/12,10/13,10/14,11/ 12, the hydrocarbyl chain of 11/13,11/14,12/12,12/13,12/14 carbon atom, preferably have 10/12,10/14,12/12, The hydrocarbyl chain of 12/14 carbon atom.For preparation reason, described surfactant formulatory agent also can exist more than three kinds of differences The surfactant of described formula.Preferably at hydrocarbyl moieties (R¹)(R²)-CH-CH₂There are 24,26 and 28 carbon former in- Three kinds of surfactants of son constitute the key component of surfactant mixture of the present invention.Its ratio is to live based on described surface Property agent composition gross weight is calculated as preferably at least 25 weight %, more preferably at least 30 weight %, more preferably at least 40 weight %, more Preferably at least 50 weight %.

R¹Group is to have the straight chain of 10-12 carbon atom or branched saturated or unsaturated aliphatic alkyl.R²Group is tool There are the straight chain of 12-14 carbon atom or branched saturated or unsaturated aliphatic alkyl.R¹With R²Identical, or R¹Preferably there is ratio R²Less less than two carbon atoms (the most just lacking two carbon atoms).

At branched R¹Or R²In the case of group, R¹Or R²In the degree of branching be preferably 0.1-5 (preferably 0.1-1.5). With regard to branched aliphatic hydrocarbyl (R¹)(R²)-CH-CH₂For, this obtains the degree of branching of 1.2-11 (preferably 1.2-4).

Term " degree of branching " subtracts 1 with the methyl number that known mode is defined as in alcohol molecule in principle at this.Average Change degree is the assembly average of the degree of branching of all molecules in a sample.

It is preferable, however, that embodiment is to use the saturated of straight chain or the undersaturated R with 10 or 12 carbon atoms¹Group Or there is the R of 12 or 14 carbon atoms²Group.Particularly preferably use the R that straight chain is saturated¹And R²Group.With regard to aliphatic hydrocarbyl (R¹) (R²)-CH-CH₂For, which achieving the degree of branching is 1.

In formula defined above, l, m and n individually include the natural number of 0, i.e. 0,1,2 etc..But, to poly-alkane For the technical staff in epoxide compound field, it is evident that this definition is the definition of single surfactant in each case.? There are surfactant mixture or the feelings of surfactant formulatory agent comprising the multiple surfactant with described formula Under condition, number l and m each represents the meansigma methods of all molecules of described surfactant, this is because in each case, alcohol and oxygen The alkoxylation changing ethylene and/or propylene oxide and/or butylene oxide provides the chain length with certain distribution.This distribution Can describe by polydispersity index D in known mode in principle.D=Mw/Mn, is equal mole of matter of weight-average molar mass and number The business of amount.Polydispersity index can be measured by method known to those skilled in the art, such as, surveyed by gel permeation chromatography Fixed.

Preferably, l is 0-99, preferably 1-40, more preferably 1-20.

Preferably, m is 0-99, preferably 1-20, more preferably 4-15.

Preferably, n is 0-99, preferably 1-20, more preferably 2-15.

According to the present invention, l+m+n (=k) sum is the number of the number in the range of 1-99, preferably 5-50, more preferably 8-39.

In formula (I), X is the branched or nonbranched alkylidene with 1-10 carbon atom, preferred 2-4 carbon atom, It can be replaced by OH group.Alkylidene is preferably methylene, ethylidene or propylidene.More particularly, X is preferably CH₂CH₂, CH₂CH(OH)CH₂,(CH₂)₃,CH₂Or CH₂(R '), wherein R ' is hydrogen or the alkyl with 1-4 carbon atom (such as methyl) to CH. (o=1) can be there is or there is not (o=0) in X.

In general formula, Y^a-For sulfonate radical, sulfate radical, carboxylate radical or phosphate radical (preferably sulfonate radical, sulfate radical or carboxylic acid Root, especially sulfate radical and carboxylate radical).Therefore, a can be 1 or 2.

In general formula, M⁺For cation, it is preferably selected from Na⁺、K⁺、Li⁺、NH₄ ⁺、H⁺、Mg²⁺And Ca²⁺(preferably Na⁺、K⁺Or NH₄ ⁺) cation.In a word, b can have the value of 1,2 or 3.

It is used as to prepare the alcohol (R of the initial compounds of surfactant of the present invention¹)(R²)-CH-CH₂-OH can such as pass through R¹CH₂CH₂OH and R²Alcohol two coalescence of OH type elimination of water simultaneously and prepare.

Therefore, another aspect of the present invention is a kind of method preparing surfactant mixture of the present invention, described side Method comprises the steps:

A () has formula R-CH by condensation at least two₂-CH₂The mixture of the primary alconol of-OH and prepare and there is logical formula (IV) (R¹)(R²)-CH-CH₂Guerbet (Guerbet) alcohol of OH (IV), wherein R is to have the straight chain of 10-12 carbon atom or prop up Saturated or the unsaturated aliphatic alkyl changed, wherein R¹And R²The most as hereinbefore defined,

B () makes the alcohol obtained in processing step (a) carry out alkoxylate,

C () makes alcohol alkoxylates and the Y obtained in processing step (b)^a-Radical reaction, is optionally formed spacer groups OX。

In processing step (a), there is logical formula (IV) (R¹)(R²)-CH-CH₂The preparation method of the Guerbet alcohol of OH is Known to the person skilled in the art.

During Guerbet reaction, primary alconol final two is polymerized to β-branched primary alcohol in the presence of suitable catalyst.By The Primary product that described alcohol is formed is aldehyde, its dimerization by aldol condensation elimination of water subsequently, then hydrogenates thus obtains saturated Alcohol.If the hydrogenation of double bond is incomplete, then in addition to primary product, the most described Guerbet alcohol, it is also possible to form different by-products The most undersaturated β-the branched primary alcohol of thing；If the reaction being hydrogenated to Guerbet alcohol is incomplete, then can also be formed saturated Alpha-branched aldehyde, or it is particularly formed in side chain or main chain the β-branched primary alcohol with additional branch.

Formula R-CH₂CH₂The dimerization reaction of-OH alcohol can form the mixture of alcohol.These mixture can include C₁₂C₁₄Fat Alcohol mixture (straight chain is saturated), there is the C of the Ziegler alcohol of 12 and 14 carbon atoms₁₂C₁₄Mixture, C₁₂C₁₄Fatty alcohol mixes Thing (straight chain and part are undersaturated) or C₁₂C₁₄The mixture of oxo alcohol.

In a preferred embodiment of the invention, formula R-CH₂CH₂The dimerization reaction of-OH alcohol, wherein R be have 10 or The straight chain of 12 carbon atoms or branched saturated or unsaturated aliphatic alkyl, be provided that the lattice with 24,26 and 28 carbon atoms That Bert alcohol.

In an especially preferred embodiment, R is straight chain saturated or unsaturated with 10 or 12 carbon atoms The aliphatic hydrocarbyl of (the most saturated).

In order to prepare Guerbet alcohol in processing step (a), the mixture of alcohol (II) is made to be condensed.Preferably, wherein R=10 The ratio of alcohol be 60-80 mole of %, wherein the ratio of the alcohol of R=12 is 20-40 mole of %.Particularly preferably make about 70 moles of % The alcohol of wherein R=10 and the alcohol reaction of wherein R=12 of about 30 moles of %.

Alcohol (II) is condensed into the reaction of Guerbet alcohol and is preferably being calculated as 0.5-10 weight % alkali metal hydrogen based on described alcohol Carry out in the presence of oxide or alkaline earth metal hydroxide, such as Lithium hydrate, sodium hydroxide, Cesium hydrate. or hydroxide Potassium, preferably potassium hydroxide.For the secondary component of high reaction rate and small scale, described alkali metal hydroxide or alkaline earth gold Belong to hydroxide will to use with the concentration being 3-6 weight % based on described alcohol.Described alkali metal hydroxide or alkaline earth gold Belong to hydroxide can (lamellar, powder) use in solid form, or use with the aqueous solution form of 30-70%, preferably 50%.

In a preferred embodiment, formula (II) alcohol is made to be condensed in the presence of NaOH and/or KOH.

Suitably catalyst is catalyst known in the art, for example, see US 3119880 (nickel salt, lead salt), US 35558716 (oxides of copper, lead, zinc, chromium, molybdenum, tungsten and manganese), US 3979466 (palladium complex) or US 3864407 (join by silver Compound).ZnO is preferably used as the catalyst for dimerization.

Described catalyst preferably comprises ZnO catalyst, generally adds it to the mixture for preparing Guerbet alcohol In.

The mixture of Guerbet alcohol can be prepared by the known method described in DE 3901095A1.

In a preferred embodiment of the invention, described Guerbet alcohol in processing step (a) at 150-320 DEG C, at a temperature of preferred 180-280 DEG C and synthesize the most in the presence of one or more catalysts.

The surfactant of described formula can be corresponding by making in processing step (b) in known mode in principle Alcohol (R¹)(R²)-CH-CH₂-OH alkoxylate and prepare.On the implementation principle of this alkoxylate be those skilled in the art institute Know.Those skilled in the art are it is also known that the molecular weight distribution of alcoxylates can be selected by reaction condition, especially catalyst The impact selected.

The surfactant of described formula is preferably prepared by the alkoxylate of base catalysis in processing step (b).? In this case, can be in pressure reactor, by alcohol (R¹)(R²)-CH-CH₂-OH and alkali metal hydroxide, preferred hydroxide Potassium or mix with alkali metal alcoholates, such as Feldalat NM.Can be by decompression (such as < 100 millibars) and/or improve temperature (30-150 DEG C) remove the water being still in described mixture.Thereafter, described alcohol is presented in corresponding alkoxide.Then, indifferent gas is used Body (such as nitrogen) inerting, and 60-180 DEG C temperature and at most less than 10 bars maximum pressure under be gradually added oxidation Alkene.In preferred embodiments, first at 130 DEG C, metering adds oxyalkylene.In course of reaction, anti-due to discharge Should be hot, temperature is increased to 170 DEG C.In another preferred embodiment of the present invention, first add at a temperature of 125-145 DEG C Butylene oxide, then adds propylene oxide at a temperature of 130-145 DEG C, then adds oxidation at a temperature of 125-155 DEG C Ethylene.At the end of reaction, such as by adding acid (such as acetic acid or phosphoric acid) catalyst neutralisation, and can be filtered if necessary Remove.

But, described alcohol (R¹)(R²)-CH-CH₂The alkoxylate of-OH is also by additive method, such as pass through acid catalysis Alkoxylate carry out.Additionally, the double-hydroxide clay as described in DE 4325237A1 such as can be used, or can use double Metal cyanide catalyst (dmc catalyst).Suitably dmc catalyst e.g., as disclosed in DE 10243361A1, especially the [0029] in-[0041] section and wherein cited document.Such as, Zn-Co type catalyst can be used.In order to implement this reaction, Can be by described alcohol (R¹)(R²)-CH-CH₂-OH mixes with described catalyst, and described mixture can be made as mentioned above to be dehydrated, and such as institute With reactions of alkylene oxide as stating.Generally use the catalyst being less than 1000ppm based on this mixture meter, owing to this is a small amount of, Described catalyst can remain in the product.The amount of catalyst may be typically smaller than 1000ppm, such as 250ppm or less.

Processing step (c) relates to alcohol alkoxylates and the Y obtained in processing step (b)^a-The reaction of group, optionally Form spacer groups OX.

For example, it is possible to introduce sulfate radical and phosphate groups (optionally in activation by them and alcohol direct reaction Afterwards).Sulfonate group can be passed through vinyl addition, substitution reaction or aldol reaction and introduce, and hydrogenates the most subsequently, obtains Obtain interval base OX accordingly.Or, alcohol can also change into chloride in advance, and it subsequently can be with Direct Sulfonation.Carboxylate radical is permissible Such as by with chloroacetate root, propylene acid group or substituted propylene acid group H₂C=(R ') C (O) O^-Reaction obtains, and wherein R ' is hydrogen Or there is the alkyl of 1-4 carbon atom.

In principle, anionic group Y^a-It is by functional group Y^a-And interval base OX composition, wherein functional group Y^a-For sulfate radical, Sulfonate radical, carboxylate radical or phosphate radical, interval base OX can be singly-bound (o=0) in the simplest situations.Situation at sulfate radical Under, such as can use the reaction carried out in falling film reactor with sulphuric acid, chlorosulfonic acid or sulfur trioxide, neutralize subsequently.At sulfonic acid In the case of root, such as, can use the reaction with propane sultone, neutralize with butyl sultone subsequently, use vinyl sulfonic acid subsequently Sodium salt or 3-chlorine-2-hydroxyl propane sulfonic acid sodium salt neutralize.In order to prepare azochlorosulfonate acid compound, phosgene or thionyl chloride also can be such as used to incite somebody to action OH end group changes into chloride, the most such as, react with sulphite.In the case of carboxylate radical, such as available oxygen oxidation alcohol And neutralize subsequently, or with sodium chloroacetate reactant salt.Carboxylate also can such as pass through the Michael of (methyl) acrylic acid or ester Addition obtains.Phosphoric acid compound can such as be obtained by the esterification with phosphoric acid or phosphorus pentachloride.

Except above-mentioned logical formula (I), (II) and the surfactant of (III), described preparaton can the most additionally comprise other Surfactant.These e.g. alkylaryl sulfonates, petroleum sulfonate or alkene sulfonate (alpha-alkene sulfonate or interior alkene Sulfonated hydrocarbon) anionic surfactant of type, and/or alkyl ethoxylate or the nonionic of alkyl polyglucoside type Surfactant.Beet alkali surface activator can also be used.These other surfactants are especially alternatively oligomer or poly- Compound surfactant.Advantageously use this class in polymer type cosurfactant to reduce the surface formed needed for microemulsion The amount of activating agent.Therefore, the cosurfactant of this class in polymer type is also referred to as " microemulsion auxiliary agent ".This kind of polymer type surface The example of activating agent includes amphiphilic block copolymer, and it comprises at least one hydrophilic block and at least one hydrophobic block.In fact Example includes polypropylene oxide-polyethylene oxide block copolymer, polyisobutylene-polyethylene oxide block copolymer, and has Ethylene oxide side chain and the comb copolymer of hydrophobic main chain, wherein said main chain comprises alkene or (methyl) acrylic acid the most substantially Ester is as monomer.Herein, term " polyethylene glycol oxide " should include as defined above comprising propylene oxide in each case The polyethylene oxide block of unit.The further detail below of this kind of surfactant is disclosed in WO2006/131541A1.

In the mineral oil recovery method of the present invention, by the appropriate aqueous preparaton of described formula surfactant via extremely A few injection well injects in mineral oil reservoir, and extracts crude oil from described oil reservoir out via at least one extraction well.In the present invention In context, term " crude oil " is not intended to single phase certainly, and refers to common Crude oil-water emulsion.It is said that in general, oil reservoir leads to Often there is several injection well and several extraction well.

The Main Function of surfactant is that the interfacial tension reduced between water oil wishes to be reduced to notable ＜ 0.1mN/m Value.Injecting described surfactant formulatory agent (referred to as " surfactant flooding ") or preferred Winsor type III " microemulsion The liquid displacement of reservoir oil " after, can be by the more high viscosity water solution by water (" water drive ") or the polymer preferably with notable thickening effect (" polymer flooding ") injects and keeps pressure in stratum.But, it is also known that first make Action of Surfactant in stratum Technology.Another known technology is the solution injecting surfactant with thickening polymer, is then injected into thickening polymer solution.This Skilled person knows the details of the industrial implementation of " surfactant flooding ", " water drive " and " polymer flooding ", and according to oil reservoir Type uses suitable technology.

For methods of the present invention, the aqueous formulation containing described logical formula (I) surfactant is used.In addition to water, Described preparaton also can optionally comprise water miscibility or at least organic substance of water dispersible or other materials.This kind of additive is outstanding It is for storing or transport is to surface of stability activator solution during oil field.But, the amount of other solvents this kind of generally should not More than 50 weight %, preferably more than 20 weight %.In a particularly advantageous embodiment of the present invention, only water is used for Preparation.The example of water-miscible solvent especially includes alcohol such as methanol, ethanol, propanol, butanol, sec-butyl alcohol, amylalcohol, butyl second two Alcohol, butyldiglycol or butyltriglycol.

In a preferred embodiment of the invention, described three kinds with regard to hydrocarbyl moieties (R¹)(R²)-CH-CH₂-and Say that different logical formula (I) surfactants should constitute the master of all surface activating agent in the final preparaton injected in oil reservoir Want component.They preferably comprise at least 25 weight % of all surface activating agent used, more preferably at least 30 weight %, even more Preferably at least 40 weight %, even more preferably at least 50 weight %.

Mixture used by the present invention can be preferred for the surfactant flooding of oil reservoir.It is particularly suited for Winsor III Type microemulsion flooding (displacement of reservoir oil or the displacement of reservoir oil in the range of there is bicontinuous microemulsions phase in the range of Winsor III).Microemulsion drives The technology of oil describes in detail at the beginning part.

Except described surfactant, described preparaton also can comprise other components, such as C₄-C₈Alcohol and/or basic salt (so-called " alkaline surfactant's displacement of reservoir oil ").This kind of additive such as can be used for reducing the delay in stratum.Based on table used The ratio of the alcohol of face activating agent total amount meter is generally at least 1:1 it is also possible, however, to use significant excess of alcohol.The amount of basic salt is led to Chang Kewei 0.1-5 weight %.Optionally can add chelating agen (such as EDTA), usually 0.03-5 weight in basic salt Amount %.

The oil reservoir wherein using described method is generally of at least 10 DEG C, and the temperature of such as 10-150 DEG C preferably has The temperature of at least 15 DEG C to 120 DEG C.All surface activating agent total concentration together is to prepare based on described aqueous surfactant Agent total amount is calculated as 0.05-5 weight %, preferably 0.1-2.5 weight %.Those skilled in the art are according to desired properties, especially Suitable selection is made according to the condition in described mineral oil layer.Now, described in it will be apparent for a person skilled in the art that The concentration of surfactant can change after injecting stratum, and this is owing to this preparaton can mix with formation water, or Person's surfactant also can be absorbed on the surface of solids on stratum.The huge advantage of mixture used by the present invention is described table Face activating agent causes particularly preferred interfacial tension reducing effect.

It is of course possible to and can advise first preparing concentrate, it is diluted to the most at the scene needed for injecting in stratum Concentration.Surfactant total concentration in this concentrate is usually 10-45 weight %.

Embodiment

Part I: the synthesis of surfactant

Universal method 1: prepare Guerbet alcohol

In 1L flask, it is initially introduced into alcohol (1 equivalent), and suitably melts at 50 DEG C.Under agitation, KOH powder is added (0.24 equivalent) and zinc oxide (5 weight %, based on initiator alcohol).Described reactant mixture is heated to 180-as quickly as possible 230 DEG C, and the reaction water of generation is distilled off via distillating mouth.In order to remove reaction water as quickly as possible, optionally use aluminium foil Make described glass flask adiabatic.Again described reactant mixture is stirred 6-30 hour at a given temperature.The alcohol mixture formed Analyzed by gas chromatography, and further work-up is not just used for alkoxylate subsequently.

Universal method 2: carry out alkoxylate (being directed to use with EO, PO and/or 1,2-BuO) by KOH catalysis

In 2L autoclave, by the most water-soluble with the KOH comprising 50 weight %KOH for the alcohol (1.0 equivalent) treating alkoxylate Liquid mixes.The amount of KOH is 0.2 weight % of product to be prepared.Under agitation, this mixture is taken off under 100 DEG C and 20 millibars Water 2 hours.Then, N is used₂Purge 3 times, set up the N of about 1.3 bars₂Admission pressure, and temperature is risen to 120-130 DEG C.So that Temperature is maintained at 125-155 DEG C (in the case of ethylene oxide) or 130-145 DEG C (in the case of propylene oxide) or 125- The mode of 145 DEG C (in the case of 1,2-butylene oxides) measures addition oxyalkylene.Then at 125-145 DEG C, it is stirred for 5 little Time, use N₂Purging, is cooled to 70 DEG C, and empties reactor.Alkaline coarse product acetic acid neutralizes.Or also can use commercially available magnesium silicate It is neutralized, is then filtered.By at CDCl₃In¹H-NMR spectrum, gel permeation chromatography and OH pH-value determination pH characterize light color Product, and measure productivity.

Universal method 3: carry out alkoxylate by DMC catalysis

In 2L autoclave, by treat the alcohol (1.0 equivalent) of alkoxylate and DMC catalysts (such as available from The Zn-Co type dmc catalyst of BASF) mix at 80 DEG C.In order to activate described catalyst, at 80 DEG C, apply about 20 millibar 1 Hour.The amount of DMC is 0.1 weight % of product to be prepared or less.Then, N is used₂Purge 3 times, set up the N of about 1.3 bars₂Air inlet Pressure, and temperature is risen to 120-130 DEG C.So that temperature be maintained at 125-135 DEG C (in the case of ethylene oxide) or Mode under 130-140 DEG C (in the case of propylene oxide) or 135-145 DEG C (in the case of 1,2-butylene oxide) is measured Add oxyalkylene.Then it is stirred at 125-145 DEG C 5 hours, uses N₂Purging, is cooled to 70 DEG C, and empties reactor.By At CDCl₃In¹H-NMR spectrum, gel permeation chromatography and OH pH-value determination pH characterize light color product, and measure productivity.

Universal method 4: carry out sulfonation by chlorosulfonic acid

In 1L round-bottomed flask, will treat that the alkyl alkoxylates (1.0 equivalent) of sulfonation is dissolved in the dichloromethane of 1.5 times amount In (based on weight %) and be cooled to 5-10 DEG C.Thereafter, so that the temperature mode less than 10 DEG C drips chlorosulfonic acid, (1.1 work as Amount).This mixture is made to get warm again after a cold spell to room temperature and at such a temperature at N₂Stream stirs 4 hours, then by upper at being up to 15 DEG C State in the NaOH aqueous solution that reactant mixture drops to half volume.Calculate the amount of NaOH to obtain based on chlorosulfonic acid used as slightly Micro-excess.Resulting ph is about 9-10.At being up to 50 DEG C, on the rotary evaporator and remove dichloromethane under gentle vacuum Alkane.

Product is used¹H-NMR characterizes, and measures the water content (about 70%) of this solution.

In order to synthesize, use following alcohol.

Alcohol	Describe
		C12C14	By straight chain C12H25-OH and C14H29The commercially available fatty alcohol mixture that-OH is constituted
C24Guerbet	Commercially available C24Guerbet alcohol (the 2-decyl tetradecane-1-alcohol), purity > 98%
		C28Guerbet	Commercially available C28Guerbet alcohol (2-dodecyl hexadecane-1-alcohol), purity > 98%

Performance test

Gained surfactant is used to test as follows, to evaluate its suitability for tertiary recovery mineral oil.

Method of testing describes

The measurement of SP*

A) measuring principle

Interfacial tension between water oil is to measure in known manner by measuring solubilization parameter SP*.Increased by mensuration Molten parameter SP* and to measure the method for interfacial tension be the method for approximate test interfacial tension that industrial circle is accepted.Increase Molten parameter SP* represents the mL number of the oil being dissolved in every mL surfactant in microemulsion (Winsor type III).If Use isopyknic water and oil, then interfacial tension σ (IFT) can be from there through approximate formula IFT ≈ 0.3/ (SP*)²Calculate (C.Huh, J.Coll.Interf.Sc., the volume 71 the 2nd phase (1979)).

B) program

In order to measure SP*, the 100mL test cylinder have magnetic stirring bar is filled with 20mL oil and 20mL water.Xiang Qi The certain density specific surfactant of middle addition.Then, make temperature be stepped up to 90 DEG C by 20 DEG C, observe and form microemulsion Temperature window.

The formation of microemulsion can be by visual assessment or by conductivity measurement.Formed three-phase system (upper oil phase, in Layer microemulsion liquid phase, lower floor's aqueous phase).When upper strata phase have mutually with lower floor same size and when 12 is little interior do not change time, then Obtain being formed the optimum temperature (T of microemulsion_{Most preferably}).Measure the volume of middle level phase.Added surface activity is deducted from this volume Agent volume.Then by income value divided by 2.Then by this volume divided by the surfactant volume added.Result is expressed as SP*。

The type of oil and water for measuring SP* determines according to system to be detected.Mineral oil itself or simulation can be used Oil, such as decane.Water used can be that pure water and saline are preferably to simulate the condition in mineral oil stratum.The composition of aqueous phase is such as Can regulate according to the composition of specific oil reservoir water.

The details of aqueous phase used and oil phase can be found in the specific descriptions hereafter tested.

Test result

The 1:1 mixture of decane and NaCl solution is mixed with butyldiglycol (BDG).Butyldiglycol (BDG) is used as Cosolvent and not included in the value of calculation of SP*.To this end, be added to by 3 parts of alkyl alkoxy sulfates and 1 part of oil sulphur The surfactant mixture that hydrochlorate is constituted.The total concentration of described surfactant represents according to weight % of aqueous phase.

Result is shown in Table 1.

Table 1 uses decane to test

From table 1, it is not required that control sample C1 (the two kinds of tables prepared from the mixture of commercially available Guerbet alcohol of protection Face activating agent) provide the good interface tension force for decane.But, from embodiment 2 and 3, surprisingly can obtain Obtain even lower value.Here, it is thus achieved that ultralow interfacial tension.This is especially in the situation of heavy oil (API gravity is less than 20 °) Under be important.These systems are only capable of difficulty reach low interfacial tension.So, under these oil conditions, only The surfactant used should be to have turned out those that can reach ultralow interfacial tension in the oil that other is lighter.

It addition, use the embodiment of oil reservoir containing heavy oil to carry out following research:

-crude oil has about 16 ° of API,

-reservoir temperature is about 20 DEG C,

-and oil reservoir water there is about 16100ppm TDS (the salt total amount of dissolving).

NaHCO to NaCl and 4100ppm containing 12000ppm₃Solution add 0.25% Na₂CO₃, 0.08% C₂₄C₂₆C₂₈-Guerbet-7BuO-7PO-10EO-sulfate, Petrostep S3B (the interior alkene from Stepan of 0.02% Sulfonated hydrocarbon), the butyldiglycol of 0.05% and 0.07%PA20 (polyacrylic acid sodium salt), or The Na of 0.25%₂CO₃, 0.07%C₂₄C₂₆C₂₈-Guerbet-7BuO-7PO-10EO-sulfate, the Petrostep of 0.03% S3B (from the internal olefin sulphonates of Stepan), the butyldiglycol of 0.05% and 0.07%PA20 is (poly- Acrylic acid sodium salt).Total surfactant concentration and Na₂CO₃Amount relate to active substance, and as the weight percent of aqueous phase Than row in the following table.

Crude oil interfacial tension in the presence of surfactant solution be 20 DEG C by rotation drip method from Detection on the SVT20 of DataPhysics.Filled out for this purpose it is proposed, oil droplet is injected at 20 DEG C by surfactant saline solution In the capillary tube filled, and observe drop expansion under about 4500 revs/min, until reaching steady state value.This was typically at 2 hours After situation.Interfacial tension IFT (or σ_II) such as Hans-Dieter"und Kolloid-disperse Systeme [interface and colloidal dispersion system] " Springer Verlag Berlin Described in Heidelberg2002, according to the following formula from drum diameter d_z, angular velocity omega and density contrast (d₁-d₂) calculate:

σ_ll=0.25 d_z ³·ω2·(d₁-d₂)

Result of the test is listed in Table 2.

The experiment that table 2 is carried out with crude oil

From embodiment 4,5 and 6, can also reach very in heavy oil with described surfactant in each case Low interfacial tension (API gravity is less than 20 °).Surfactant solution is clarification in the case of every, and allows to have no Problem ground injects in the porous rock with suitable penetration.

Comparative example C7 and C8 are based on containing being based only on a kind of Guerbet alkyl (C₂₄-Guerbet or C₂₈-Ge Er Bert) the surfactant formulatory agent of surfactant.These surfactants demonstrate under the same conditions and compare the present invention The interfacial tension that surfactant is significantly higher, this can be from embodiment 4 (C₂₄C₂₆C₂₈-Guerbet) and comparative example C7 (C₂₄- Guerbet) and C8 (C₂₈-Guerbet) relatively find out.

Claims (14)

1. a surfactant mixture, it contains at least three kinds with regard to hydrocarbyl moieties (R¹)(R²)-CH-CH₂For-not With and there is the ionic surfactant of below formula (I):

Wherein

R¹It it is the saturated or unsaturated aliphatic alkyl of the straight chain with 10 or 12 carbon atoms；

R²It it is the saturated or unsaturated aliphatic alkyl of the straight chain with 12 or 14 carbon atoms；

Wherein R¹And R²Selection make at least three kinds of logical formula (I) ionic surfactant obtain have 24 carbon atoms, 26 Alkyl (the R of individual carbon atom and 28 carbon atoms¹)(R²)CHCH₂-；Wherein there is the C of logical formula (I)₂₄Surfactant is at 40- In the range of 60%, there is the C of logical formula (I)₂₆Surfactant, in the range of 30-50%, has the C of logical formula (I)₂₈Surface Activating agent is in the range of 1-20%, based on mole total amount meter formed from these three surfactant；

Each A⁰It is ethylidene, propylidene or butylidene independently of one another；

K is the integer of 1-99；

X is the branched or nonbranched alkylene with 1-10 carbon atom, and it can be replaced by OH group；

O is 0 or 1；

M^b+It it is cation；

Y^a-It is sulfate radical, sulfonate radical, carboxylate radical or phosphate radical；

B is 1,2 or 3；With

A is 1 or 2.

Surfactant mixture the most according to claim 1, wherein k is the integer of 4-50.

3. according to the surfactant mixture of claim 1 or 2, wherein (OX) in formula (I)_oY^a-Group is OS (O)₂O^-、 OCH₂CH₂S(O)₂O^-、OCH₂CH(OH)CH₂S(O)₂O^-、O(CH₂)₃S(O)₂O^-、S(O)₂O^-、CH₂C(O)O^-Or CH₂CH(R‘)C(O) O^-, wherein R ' is hydrogen or the alkyl with 1-4 carbon atom.

4. according to the surfactant mixture of claim 1 or 2, wherein (OA) in formula (I)_kRepresent n Aden's epoxide, m Individual sub-propoxyl group and l inferior ethoxyl, wherein n+m+l=k.

Surfactant mixture the most according to claim 4, wherein n Aden's epoxide, m sub-propoxyl group and l sub-ethoxy Base is according to block arrangement.

Surfactant mixture the most according to claim 5, the wherein (R in formula (I)¹)(R²)-CH-CH₂After-group, It is expressed as (OA)_k: there is Aden's epoxide block of n Aden's epoxide, followed by there is the sub-propoxyl group of m sub-propoxyl group Block, and be finally the inferior ethoxyl block with l inferior ethoxyl.

Surfactant mixture the most according to claim 4, wherein m is the integer of 4-15, and/or l is the integer of 0-25, And/or n is the integer of 2-15.

8. according to the surfactant mixture of claim 1 or 2, wherein possibly together with the surface activity of lower formula (II) He (III) Agent:

Wherein R¹、R²、A⁰、X、Y^a-、M^b+, k, o, a and b respectively defined for formula (I) freely.

Surfactant mixture the most according to claim 8, its Chinese style (I) surfactant relative to formula (I), (II) and (III) ratio of surfactant total amount is 80-99 weight %.

10. an aqueous surfactant preparaton, its surfactant mixture containing with good grounds claim 1 or 2.

11. aqueous surfactant preparatons according to claim 10, wherein said surfactant formulatory agent has 0.05- The total surfactant content of 5 weight %, total amount meter based on aqueous surfactant preparaton.

12. 1 kinds of methods by Winsor type III microemulsion flooding exploitation mineral oil, wherein will according to claim 10 or The aqueous surfactant preparaton of 11 injects well via at least one and injects in mineral oil reservoir, thus by the interface between profit Tension force is down to < 0.1mN/m, and extract crude oil from described oil reservoir out via at least one extraction well.

The method of 13. 1 kinds of surfactant mixtures prepared according to claim 1 or 2, described method comprises the steps:

A () has formula R-CH by condensation at least two₂-CH₂The mixture of the primary alconol of-OH and prepare and there is logical formula (IV) (R¹) (R²)-CH-CH₂The Guerbet alcohol of OH (IV), wherein R is to have the straight chain of 10-12 carbon atom or branched saturated or insatiable hunger And aliphatic hydrocarbyl, wherein R¹And R²Defined in each claim 1 or 2 freely,

B () makes the alcohol obtained in processing step (a) carry out alkoxylate,

C () makes alcohol alkoxylates and the Y obtained in processing step (b)^a-Radical reaction, is optionally formed spacer groups OX.

14. surfactant mixtures according to claim 1 or 2 or the surfactant formulatory according to claim 10 or 11 Agent is carrying out the purposes in mineral oil exploitation by Winsor type III microemulsion flooding.