CN104232047A - Surface active agent composition for tertiary oil recovery and preparation method and application thereof - Google Patents
Surface active agent composition for tertiary oil recovery and preparation method and application thereof Download PDFInfo
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- CN104232047A CN104232047A CN201310237576.5A CN201310237576A CN104232047A CN 104232047 A CN104232047 A CN 104232047A CN 201310237576 A CN201310237576 A CN 201310237576A CN 104232047 A CN104232047 A CN 104232047A
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- 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
Abstract
The invention relates to a surface active agent composition for tertiary oil recovery, and a preparation method and application thereof, and mainly solves the problems of poor displacement efficiency of the surface active agent of the prior art in a tertiary oil recovery process, and harm to the stratum and the oil field, corrosion of equipment and pipeline and difficult demulsification due to oil inorganic alkali contained in displacement system. The invention adopts the surface active agent composition comprising a cationic surface active agent and an anionic-non-ionic surface active agent in the molar ratio of 1:0.01-1:100. The cationic surface active agent is at least one selected from the group consisting of quaternary ammonium salt and quaternary ammonium alkali; and the anionic-non-ionic surface active agent is represented by a molecular general formula shown as below, wherein M and N are independently selected from one of an alkali metal, alkaline earth metal and ammonium. The technical scheme well solves the above problems, and can be used in tertiary oil recovery process.
Description
Technical field
The present invention relates to three employing surfactant compositions, preparation method and the application in tertiary oil recovery thereof.
Background technology
Along with the increase of world energy sources demand, the rational exploitation and utilization of oil has caused the very big attention of people, to the produced quantity of oil and the requirement of production efficiency also more and more higher.Realize the high-efficiency mining of hydrocarbon resources, not only there is realistic meaning for raising crude production rate, have more important strategic importance.1/3 of the general only extraction oil in-place of conventional oil production method (once with secondary method), also have an appointment 2/3 crude oil fail extraction, therefore when energy day is becoming tight, improve the key subjects that tar productivity has become oil production research.Tertiary oil recovery technology is then a kind of method of effective raising tar productivity, can be divided into four large classes: one is that heating power drives, and comprises steam flood, combustion in situ etc.; Two is that mixed phase drives, and comprises CO
2mixed phase, hydrocarbon mixed phase and other rare gas element mixed phases drive; Three is chemical floodings; Four is microbe oil productions, comprises biological polymer, MICROBIAL SURFACTANT is driven.Chemical flooding is extremely important in intensified oil reduction and the extensive technology implemented, and comprises the multiple combination technology of polymer flooding, surfactant flooding, caustic waterflooding etc. and polymkeric substance, alkali, tensio-active agent.The effect of chemical flooding is the result of physical action and chemical action, and what physical action referred to displacing fluid involves effect, and chemical action refers to the microcosmic oil drive effect of displacing fluid.The core of chemical action reduces the interfacial tension of displacing fluid and crude oil.Tensio-active agent is owing to having oleophylic (hydrophobic) and hydrophilic (oleophobic) character concurrently, and when tensio-active agent is water-soluble, molecule is mainly distributed on water-oil interface, significantly can reduce oil water interfacial tension.The reduction of oil water interfacial tension means that surfactant system can overcome the force of cohesion between crude oil, and larger oil droplet is dispersed into little oil droplet, thus improves the percent of pass of crude stream when pore throat.The oil displacement efficiency of tensio-active agent also shows the effects such as the wettability of rock surface making oleophylic reverses, emulsification of crude oil, raising surface charge density and oil droplet coalescence, and this is the reason that tensio-active agent plays very important effect in chemical flooding technology.
Current surface active agent for tertiary oil recovery adopts Recompounded multielement system mostly, comprises nonionic surface active agent and ionogenic surfactant simultaneously, also adds the auxiliary agent such as alkali and alcohol in part formulation.As patent CN101024764A provides a kind of tensio-active agent of oil-field thick-oil well, this promoting agent is made up of water, sheet alkali, ethanol, oleic acid, alkylphenol polyoxyethylene, Sodium dodecylbenzene sulfonate.For another example patent CN1458219A discloses the surfactant polymer pure binary ultra low interfacial tension combination flooding formula of a kind of tertiary oil recovery application, the tensio-active agent wherein used is sulfonated petro-leum or is the complexed surfactant that host adds thinner and other surfactant compound with sulfonated petro-leum, the weight percent of its component is sulfonated petro-leum 50 ~ 100%, alkylsulfonate 0 ~ 50%, carboxylate salt 0 ~ 50%, alkylaryl sulphonate 0 ~ 35%, low-carbon alcohol 0 ~ 20%.And for example patent CN1394935 has invented a kind of chemical oil displacement agent, and it mainly comprises sodium octylbenzene sulfonate anion surfactant, surfactant adjuvant, tensio-active agent synergistic agent, surface active agent solubilization agent.This oil-displacing agent can reduce the structural viscosity of viscous crude significantly, can reduce oil water interfacial tension simultaneously, thus improves oil recovery factor.
But above-mentioned surface active agent for tertiary oil recovery still exists more problem, mainly surfactant activity is poor, oil displacement efficiency is low, simultaneously because surfactant system is too complicated, and thus Produced Liquid breakdown of emulsion difficulty, sewage disposal difficulty is large; In addition because flooding system is containing mineral alkali, formation and oil well bring injury, cause the problem such as etching apparatus and pipeline, and due to the serious viscosity reducing polymkeric substance of mineral alkali meeting, have to greatly improve the working concentration of polymkeric substance for reaching required viscosity, oil recovery comprehensive cost is improved; The high temperature resistance of tensio-active agent, high salt tolerance, anti-high salinity limited in one's ability.
As everyone knows, anion surfactant, as sulfonated petro-leum, petroleum carboxylate, alkylbenzene sulfonate etc. are widely used in tertiary oil recovery process at present, and cats product is easily adsorbed by stratum because of it or produce precipitation, therefore reduce the ability of oil water interfacial tension, be generally not used in tertiary oil recovery.Because when cationic and anionic surfactant mixes close to equal proportion, its aqueous solution easily forms precipitation, thus cause cationic and anionic surfactant mixed system not only to become incompatibility in the application, and correlation theory research is also more delayed.Research in recent years finds, the cationic and anionic surfactant mixed system aqueous solution has a lot of anomalous property, as there is the interaction between strong electrostatic interaction and hydrophobic carbon chain in aqueous due to cationic and anionic surfactant, facilitate the interionic association of two kinds of different charged surfactant of band, be easy in the solution form micella, produce the surfactivity higher than single tensio-active agent.In addition, cationic and anionic surfactant mixed system obviously can reduce the absorption loss of cats product on rock core, thus significantly can reduce the inherent defect of cats product.
Gong Yujun etc. (see volume the 1st phase Northwest University's journal in February the 30th (natural science edition) in 2000,28 ~ 31) research thinks that cetyl trimethylammonium bromide (CTAB) and sodium lauryl sulphate (SDS) mixed system have solublization.In oil production process, utilize solublization can " displacement of reservoir oil ", by under the oil wash that sticks on the sandstone of rock stratum, thus improve oil recovery.Huang Hongdu etc. (see oil and gas journal volume the 4th phase August the 29th in 2007,101 ~ 104) have studied the anion surfactants such as sulfonated petro-leum, petroleum carboxylate, alkylbenzene sulfonate and cetyl trimethylammonium bromide, alkali compound system interfacial tension and draw to draw a conclusion: adding of cats product makes the interfacial activity of petroleum carboxylate, alkylbenzene sulfonate, sulfonated petro-leum improve.
Above-mentioned result of study shows that anions and canons Surfactant Mixing Systems has certain effect for reduction oil water interfacial tension, raising oil displacement efficiency.But the former result of study shows its interface performance still to have much room for improvement, and the latter still have employed alkali in system, thus alkali formation and oil well cannot be avoided to bring injury, etching apparatus and the problem such as pipeline and breakdown of emulsion difficulty.Above-mentioned system ratio is easier to generate precipitation in addition, is unfavorable for practical application.
For this reason, one aspect of the present invention absorbs has used for reference forefathers about anions and canons Surfactants mixed system result of study, Anionic-nonionic tensio-active agent is adopted to replace traditional anion surfactant on the other hand, the shortcoming such as easily to precipitate when overcoming cationic anionic surfactant combination, invented for cats product used for tertiary oil recovery and Anionic-nonionic surfactant composition.
Summary of the invention
One of technical problem to be solved by this invention is that existing tensio-active agent oil displacement efficiency in tertiary oil recovery process is poor, simultaneously because flooding system contains mineral alkali, formation and oil well bring injury, the problem of etching apparatus and pipeline and breakdown of emulsion difficulty, provides a kind of three employing surfactant compositions newly.Said composition has that interfacial activity is high, washing oil ability is strong, system is simple, formation and oil well can not bring injury, can not etching apparatus and pipeline and can not cause the advantage of breakdown of emulsion difficulty.
Two of technical problem to be solved by this invention is to provide a kind of preparation method of the surfactant composition corresponding with technical solution problem one.
Three of technical problem to be solved by this invention is that one of technical problem described three adopts the application of surfactant composition in tertiary oil recovery.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: three adopt surfactant composition and preparation method thereof, comprise cats product and Anionic-nonionic tensio-active agent, the mol ratio of described cats product and Anionic-nonionic tensio-active agent is 1: 0.01 ~ 1: 100, its cationic surfactant is selected from least one in quaternary ammonium salt or quaternary amine alkali, and Anionic-nonionic surfactant molecule general formula is:
Wherein M and N is independently selected from any one in basic metal, alkaline-earth metal or ammonium root; F is M and SO in general molecular formula
3the mol ratio of group, when M be basic metal or ammonium root time f=1, the f=0.5 when M is alkaline-earth metal; G is the mol ratio of N and COO group in general molecular formula, when N be basic metal or ammonium root time g=1, the g=0.5 when M is alkaline-earth metal; R is H, C
1~ C
20alkyl, C
6~ C
10aryl or substituted aryl in any one, R ' and R " independently take from C
1~ C
10alkylidene group, a, b, m, n independently take from any one integer in 0 ~ 20, and c, d, x, y independently take from any one integer in 0 ~ 100 or decimal.
In technique scheme, at least one is non-vanishing for optional x or c.
In technique scheme, described cats product preferred version is selected from tetra-alkyl ammonium chloride or tetra-alkyl ammonium hydroxide, and the carbonatoms in cats product molecule is preferably 4 ~ 40.Described Anionic-nonionic tensio-active agent cationic M or N preferred version are selected from Na, K, Mg, Ca or NH
4in any one.R preferred version is H, C
5~ C
15alkyl, any one in aryl." preferred version is C to R ' or R
1~ C
5alkylidene group.Described a, b, m, n are preferably any one integer in 0 ~ 10.C, x, d or y are preferably any one integer in 0 ~ 50 or decimal.
The mol ratio preferred version of cats product described in technique scheme and Anionic-nonionic tensio-active agent is 1: 0.1 ~ 1: 10.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: described in any one of one of above-mentioned technical problem technical scheme, three adopt the preparation method of surfactant compositions, comprise the following steps:
A) unsaturated fatty acids 1, an acidic catalyst and aromatic hydrocarbon are added reactor, in 50 ~ 150
oc addition reaction 1 ~ 20 hour, wherein unsaturated fatty acids: aromatic hydrocarbons mol ratio is 1:(0.5 ~ 1.0); After reaction terminates, in temperature 100 ~ 300
oc, pressure 10 ~ 100kg/cm
2hydrogenation reaction 1 ~ 10 hour, thus aryl is obtained carboxylic acid and be reduced into aryl substituted alcohols; Aryl substituted alcohols, basic catalyst and required propylene oxide, oxyethane are added reactor, in 100 ~ 200
oc carries out etherification reaction 1 ~ 20 hour; Then add sulfonated reagent in 50 ~ 100
oc reaction carries out sulfonation reaction in 1 ~ 20 hour, and wherein aryl replaces fatty alcohol polyoxypropylene Soxylat A 25-7: the mol ratio of sulfonated reagent is 1:(1 ~ 4); After reaction terminates, pH=1 ~ 3 are adjusted to acidic aqueous solution (such as aqueous hydrochloric acid, aqueous sulfuric acid, phosphate aqueous solution, sodium bisulphate solution or aqueous potassium hydrogen sulfate), carry out oily water separation, it is aryl monosubstituted fatty alcohol polyoxypropylene polyoxyethylene ether sulfonic acid that oil phase obtains sulfonated products; Then add in aforementioned sulfonated products by unsaturated fatty acids 2, repeat addition-reduction-etherificate, the etherate obtained and carboxylating reagent are in 50 ~ 100
oc reaction carries out carboxylation reaction in 1 ~ 20 hour, described etherate: the mol ratio of carboxylating reagent is 1:(1 ~ 4), after reaction terminates, pH=1 ~ 3 are adjusted to acidic aqueous solution (such as aqueous hydrochloric acid, aqueous sulfuric acid, phosphate aqueous solution, sodium bisulphate solution or aqueous potassium hydrogen sulfate), carry out oily water separation, oil phase adds alkali lye and is neutralized to pH=7 ~ 9, obtains the aryl two replacement fatty alcohol polyoxypropylene Soxylat A 25-7 sulfoacid carboxylic acid salt anionic-nonionogenic tenside shown in above-mentioned general formula;
B) be dissolved in the water respectively by cats product and according to the Anionic-nonionic tensio-active agent that step a) obtains, then mix according to mol ratio 1: 0.1 ~ 1: 10.
In technique scheme, an acidic catalyst of step a) described addition reaction is perchloric acid, ClSO
3at least one in H, p-methyl benzenesulfonic acid.
In technique scheme, step a) described in etherification reaction described in the preferred preferred alkali metal hydroxide of basic catalyst, at least one most preferably in NaOH or KOH.
In technique scheme, step a) described in sulfonated reagent be preferably hydroxyl sulfoacid and salt thereof or halogenosulfonic acid and salt thereof.
In technique scheme, step a) described in carboxylating reagent be preferably halogenated carboxylic acid and salt thereof.
In technique scheme, hydrogenation reaction is reaction well known in the art, and usually adopt hydrogenation catalyst to promote reaction, conventional hydrogenation catalyst has Pd/C catalyzer, Pt/C catalyzer, Raney's nickel catalyst etc.Pd/C or Pt/C catalyst noble metal content is not key of the present invention, and such as Pd or Pt content can be 0.5 ~ 5wt%.Pd or the Pt content adopted in embodiment is 0.5wt%.
For solve the problems of the technologies described above three, technical scheme of the present invention is as follows: according to any one of one of above-mentioned technical problem technical scheme, three adopt the application of surfactant composition in tertiary oil recovery.
Of the present invention three adopt surfactant composition on the one hand due to electrostatic attraction effect strong between anions and canons tensio-active agent opposite charges polar group, surfactant molecule is increased in adsorbed on interfaces amount, micelle-forming concentration significantly reduces, thus has the incomparable high surface of single tensio-active agent; Simultaneously due to the interfacial activity of surfactant composition superelevation, its aqueous solution can form ultra low interfacial tension with crude oil, thus effectively overcomes the force of cohesion between crude oil, is conducive to former oil-out, and then significantly improves oil displacement efficiency.Surfactant composition can change oil reservoir wettability of the surface on the other hand, as the cats product in composition by with absorption electronegative Interaction of substituents on a solid surface, its desorption is got off, glossy wet structure is made to change into intermediate wet or water-wet surface, reduce the work of adhesion of crude oil at solid surface, thus be conducive to the stripping of crude oil.Anions and canons tensio-active agent mixing solutions has solublization to crude oil simultaneously, can be washed down by the crude oil sticked on the sandstone of rock stratum further, improves oil recovery factor.
Adopt surfactant composition of the present invention in tertiary oil recovery process, there is interfacial activity high: compound surfactant composition consumption is still can form 10 with underground crude oil under 0.01 ~ 0.05wt% condition
-3~ 10
-4mN/m ultra low interfacial tension; Washing oil ability is strong: surfactant composition to the washing oil rate of crude oil more than 40%; Surfactant composition system is simple.Because system is not containing mineral alkali, the injury that when thus avoiding rig-site utilization, mineral alkali formation causes, the corrosion caused equipment and the problem of breakdown of emulsion difficulty caused thus, achieve good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1a]
By CH
3(CH
2)
10cH=CH (CH
2)
8cOOH, pentadecyl benzene and perchloric acid add reactor, pass into N
2be 35kg/cm to pressure
2, in 200
oc reacts 2 hours, wherein CH
3(CH
2)
10cH=CH (CH
2)
8cOOH: pentadecyl benzene: perchloric acid mol ratio is 1:1:0.1.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 1%, 100
oc, 100kg/cm
2pressure hydrogenation reaction 10 hours, then by Pd/C catalyst filtration; Aryl abovementioned steps obtained replaces fatty alcohol and NaOH adds reactor according to mol ratio 1:1.5, stirs and adds required propylene oxide, in 150 after 30 minutes
oc reacts 5 hours; Then add the oxyethane of aequum, in 200
oc reacts 1 hour, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: ClCH
2sO
3na mol ratio 1:3 adds sulfonated reagent, is warming up to 70
oc reacts 10 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
2=CHCOOH and perchloric acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: sodium chloroacetate: NaOH mol ratio 1:1.5:1.5 adds carboxylating reagent, is warming up to 80
oc reacts 6 hours.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 2 wt %Ca (OH)
2be neutralized to pH value 8, vacuum removal moisture, obtain target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent phenyl trimethicone ammonium chloride and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3wt% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 0.6 mixes, obtain surfactant composition 1a, its composition, structure are in Table 1a.
[embodiment 2a]
By CH
3(CH
2)
2cH=CHCOOH, octyl group benzene and ClSO
3h adds reactor, passes into N
2be 100kg/cm to pressure
2, in 50
oc reacts 20 hours, wherein CH
3(CH
2)
2cH=CHCOOH: octyl group benzene: ClSO
3h mol ratio is 1:1:0.25.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 0.2%, 120
oc, 120kg/cm
2pressure hydrogenation reaction 8 hours, then filters Pd/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and KOH adds reactor according to mol ratio 1:1.5, stirs and adds required propylene oxide, in 120 after 30 minutes
oc reacts 7 hours; Then add the oxyethane of aequum, in 160
oc reacts 4 hours, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: sodium isethionate mol ratio 1:2.5 adds sulfonated reagent, is warming up to 90
oc reacts 8 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3(CH
2)
2cH=CHCOOH and ClSO
3h adds reactor, repeats aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: 3-chloropropionic acid: KOH mol ratio 1:1.5:2.5 adds carboxylating reagent, is warming up to 80
oc reacts 6 hours.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 5 wt %NaOH are neutralized to pH value 8, and vacuum removal moisture obtains target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent decyl triethylammonium hydroxide and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 0.1 mixes, obtain surfactant composition 2 a, its composition, structure are in table 1 a.
[embodiment 3a]
By CH
2=CHCOOH, amylbenzene and p-methyl benzenesulfonic acid add reactor, pass into N
2be 50kg/cm to pressure
2, in 120
oc reacts 15 hours, wherein CH
2=CHCOOH: amylbenzene: p-methyl benzenesulfonic acid mol ratio is 1:1:0.15.After reaction terminates, add the Pt/C catalyzer of fatty acid wt 0.2%, 300
oc, 100kg/cm
2pressure hydrogenation reaction 1 hour, then filters Pt/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and CsOH adds reactor according to mol ratio 1:1.5, stirs and adds required propylene oxide, in 100 after 30 minutes
oc reacts 20 hours; Then add the oxyethane of aequum, in 200
oc reacts 1 hour, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: hydroxyl amyl group sodium sulfonate mol ratio 1:4 adds sulfonated reagent, is warming up to 50
oc reacts 20 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3(CH
2)
10cH=CH (CH
2)
8cOOH and p-methyl benzenesulfonic acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: 3-bromocaproic acid: CsOH mol ratio 1:1.5:2.5 adds carboxylating reagent, is warming up to 100
oc reacts 1 hour.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 5 wt %KOH are neutralized to pH value 8, and vacuum removal moisture obtains target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent etamon chloride and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 1.2 mixes, obtain surfactant composition 3 a, its composition, structure are in table 1 a.
[embodiment 4a]
By CH
3(CH
2)
4cH=CH (CH
2)
2cOOH, benzene and perchloric acid add reactor, pass into N
2be 80kg/cm to pressure
2, in 150
oc reacts 1 hour, wherein CH
3(CH
2)
4cH=CH (CH
2)
2cOOH: benzene: perchloric acid mol ratio is 1:1:0.10.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 0.2%, 100
oc, 10kg/cm
2pressure hydrogenation reaction 10 hours, then filters Pd/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and KOH adds reactor according to mol ratio 1:1.5, stirs and adds required propylene oxide, in 140 after 30 minutes
oc reacts 10 hours; Then add the oxyethane of aequum, in 180
oc reacts 3 hours, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: hydroxypropyl azochlorosulfonate acid sodium mol ratio 1:2 adds sulfonated reagent, is warming up to 70
oc reacts 8 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3(CH
2)
4cH=CH (CH
2)
2cOOH and p-methyl benzenesulfonic acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: 4-chloro-butyric acid sodium: NaOH mol ratio 1:1.5:2.0 adds carboxylating reagent, is warming up to 80
oc reacts 6 hours.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 2 wt %Mg (OH)
2be neutralized to pH value 7, vacuum removal moisture, obtain target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent benzyltriethylammoinium chloride and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 4.7 mixes, obtain surfactant composition 4 a, its composition, structure are in table 1 a.
[embodiment 5a]
By CH
3(CH
2)
8cH=CHCOOH, benzene and perchloric acid add reactor, pass into N
2be 40kg/cm to pressure
2, in 120
oc reacts 5 hours, wherein CH
3(CH
2)
8cH=CHCOOH: benzene: perchloric acid mol ratio is 1:1:0.12.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 0.2%, 150
oc, 30kg/cm
2pressure hydrogenation reaction 8 hours, then filters Pd/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and NaOH adds reactor according to mol ratio 1:2, stirs and adds required propylene oxide, in 150 after 30 minutes
oc reacts 5 hours; Then add the oxyethane of aequum, in 150
oc reacts 8 hours, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: hydroxyl butyl sulfonic acid sodium mol ratio 1:2 adds sulfonated reagent, is warming up to 70
oc reacts 8 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3(CH
2)
4cH=CHCOOH and p-methyl benzenesulfonic acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: 4-chloro pentane acid sodium: NaOH mol ratio 1:1.5:2.0 adds carboxylating reagent, is warming up to 80
oc reacts 8 hours.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase is with 10 wt% ammonia neutralizations to pH value 8, and vacuum removal moisture, obtains target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent tetrabutylammonium chloride and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 10 mixes, obtain surfactant composition 5 a, its composition, structure are in table 1 a.
[embodiment 6a]
By CH
3(CH
2)
8cH=CH (CH
2)
4cOOH, ethylbenzene and perchloric acid add reactor, pass into N
2be 50kg/cm to pressure
2, in 140
oc reacts 3 hours, wherein CH
3(CH
2)
8cH=CH (CH
2)
4cOOH: ethylbenzene: perchloric acid mol ratio is 1:1:0.15.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 0.2%, 200
oc, 50kg/cm
2pressure hydrogenation reaction 6 hours, then filters Pd/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and NaOH adds reactor according to mol ratio 1:2, stirs and adds required propylene oxide, in 150 after 30 minutes
oc reacts 5 hours; Then add the oxyethane of aequum, in 150
oc reacts 8 hours, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: ClCH
2sO
3na mol ratio 1:2 adds sulfonated reagent, is warming up to 85
oc reacts 5 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3(CH
2)
8cH=CH (CH
2)
4cOOH and perchloric acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: sodium chloroacetate: NaOH mol ratio 1:1.5:2.0 adds carboxylating reagent, is warming up to 100
oc reacts 1 hour.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 10 wt% Mg (OH)
2be neutralized to pH value 8, vacuum removal moisture, obtain target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent prepared by four octyl group ammonium chlorides and the present invention is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 1.5 mixes, obtain surfactant composition 6 a, its composition, structure are in table 1 a.
[embodiment 7a]
By CH
3(CH
2)
7cH=CH (CH
2)
2cOOH, biphenyl and p-methyl benzenesulfonic acid add reactor, pass into N
2be 50kg/cm to pressure
2, in 100
oc reacts 5 hours, wherein CH
3(CH
2)
7cH=CH (CH
2)
2cOOH: biphenyl: p-methyl benzenesulfonic acid mol ratio is 1:1:0.15.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 0.2%, 160
oc, 40kg/cm
2pressure hydrogenation reaction 8 hours, then filters Pd/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and KOH adds reactor according to mol ratio 1:2, stirs and adds required propylene oxide, in 120 after 30 minutes
oc reacts 8 hours; Then add the oxyethane of aequum, in 150
oc reacts 6 hours, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: ClCH
2sO
3na mol ratio 1:2 adds sulfonated reagent, is warming up to 80
oc reacts 6 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3(CH
2)
7cH=CH (CH
2)
2cOOH and perchloric acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: sodium chloroacetate: NaOH mol ratio 1:1.5:2.0 adds carboxylating reagent, is warming up to 75
oc reacts 10 hours.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 10 wt% NaOH are neutralized to pH value 8, and vacuum removal moisture obtains target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent palmityl trimethyl ammonium chloride and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 1.9 mixes, obtain surfactant composition 7 a, its composition, structure are in table 1 a.
[embodiment 8a]
By CH
3(CH
2)
2cH=CHCOOH, benzene and p-methyl benzenesulfonic acid add reactor, pass into N
2be 50kg/cm to pressure
2, in 130
oc reacts 6 hours, wherein CH
3(CH
2)
2cH=CHCOOH: benzene: p-methyl benzenesulfonic acid mol ratio is 1:1:0.10.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 0.2%, 160
oc, 40kg/cm
2pressure hydrogenation reaction 8 hours, then filters Pd/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and KOH adds reactor according to mol ratio 1:2, stirs and adds required propylene oxide, in 120 after 30 minutes
oc reacts 8 hours; Then add the oxyethane of aequum, in 150
oc reacts 6 hours, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: sodium isethionate mol ratio 1:2 adds sulfonated reagent, is warming up to 80
oc reacts 6 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3(CH
2)
2cH=CHCOOH and p-methyl benzenesulfonic acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: 3-chloropropionic acid sodium: NaOH mol ratio 1:1.5:2.0 adds carboxylating reagent, is warming up to 75
oc reacts 10 hours.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 10 wt% NaOH are neutralized to pH value 8, and vacuum removal moisture obtains target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent distearyl dimethyl ammonium chloride and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 3.6 mixes, obtain surfactant composition 8 a, its composition, structure are in table 1 a.
[embodiment 9a]
By CH
3(CH
2)
6cH=CH (CH
2)
3cOOH, isopropyl benzene and p-methyl benzenesulfonic acid add reactor, pass into N
2be 50kg/cm to pressure
2, in 120
oc reacts 5 hours, wherein CH
3(CH
2)
6cH=CH (CH
2)
3cOOH: isopropyl benzene: p-methyl benzenesulfonic acid mol ratio is 1:1:0.20.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 0.2%, 170
oc, 40kg/cm
2pressure hydrogenation reaction 8 hours, then filters Pd/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and KOH adds reactor according to mol ratio 1:2, stirs and adds required propylene oxide, in 140 after 30 minutes
oc reacts 8 hours; Then add the oxyethane of aequum, in 150
oc reacts 7 hours, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: ClCH
2sO
3na mol ratio 1:2 adds sulfonated reagent, is warming up to 80
oc reacts 6 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3(CH
2)
6cH=CH (CH
2)
3cOOH and p-methyl benzenesulfonic acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: sodium chloroacetate: NaOH mol ratio 1:1.5:2.0 adds carboxylating reagent, is warming up to 75
oc reacts 10 hours.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 10 wt% NaOH are neutralized to pH value 8, and vacuum removal moisture obtains target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent Dodecyl trimethyl ammonium chloride and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 10 mixes, obtain surfactant composition 9 a, its composition, structure are in table 1 a.
[embodiment 10 a]
By CH
3cH
2cH=CH (CH
2)
2cOOH, nonyl benzene and p-methyl benzenesulfonic acid add reactor, pass into N
2be 50kg/cm to pressure
2, in 160
oc reacts 8 hours, wherein CH
3cH
2cH=CH (CH
2)
2cOOH: nonyl benzene: p-methyl benzenesulfonic acid mol ratio is 1:1:0.15.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 0.2%, 170
oc, 60kg/cm
2pressure hydrogenation reaction 8 hours, then filters Pd/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and NaOH adds reactor according to mol ratio 1:2, stirs and adds required propylene oxide, in 160 after 30 minutes
oc reacts 8 hours; Then add the oxyethane of aequum, in 150
oc reacts 8 hours, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: sodium isethionate mol ratio 1:2 adds sulfonated reagent, is warming up to 80
oc reacts 6 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3cH
2cH=CH (CH
2)
2cOOH and perchloric acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: 3-chloropropionic acid sodium: NaOH mol ratio 1:1.5:2.0 adds carboxylating reagent, is warming up to 75
oc reacts 10 hours.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 10 wt% NaOH are neutralized to pH value 8, and vacuum removal moisture obtains target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent tetrabutylammonium chloride and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 7.5 mixes, obtain surfactant composition 10 a, its composition, structure are in table 1 a.
[embodiment 11 a]
The 0.30wt% surfactant composition prepare embodiment 5 a and 0.15wt% polyacrylamide (molecular weight 2,600 ten thousand) aqueous solution evenly, obtain a kind of Polymer Used For Oil Displacement-surfactant complex.
Table 1 a tri-adopts surfactant composition to form and structure
[embodiment 12 a] three adopts the test of surfactant composition interface performance
Rotate with TX-500C and drip interfacial tensimeter mensuration surfactant composition and Shuanghe Oil Field
5-11 series of strata oil water interfacial tension.Dosage of surfactant consumption: 0.3 wt %, measuring temperature is 81
oc, local water is NaHCO
3type, salinity is 7947mg/L, chloride ion content 2002 mg/L, Ca
2+content 20 mg/L, Mg
2+content 12.2 mg/L.
Table 2 a tri-adopts surfactant composition and Shuan He oil field
5-11 series of strata oil water interfacial tension
| Embodiment | Interfacial tension (mN/m) |
| 1 a | 0.0043 |
| 2 a | 0.0069 |
| 3 a | 0.0033 |
| 4 a | 0.0075 |
| 5 a | 0.0022 |
| 6 a | 0.0002 |
| 7 a | 0.0007 |
| 8 a | 0.0036 |
| 9 a | 0.0049 |
| 10 a | 0.0009 |
| 11 a | 0.0048 |
From table 2 a, compound surfactant prepared by embodiment 1 a ~ 10 a has good interface performance for Henan Oil Field.Embodiment 11 a shows, tensio-active agent prepared by the present invention and polymkeric substance composite after, its interface performance is still good.
Surfactant composition prepared by embodiment 6 a is mixed with different concns, respectively test and Shuanghe Oil Field
5-11 series of strata oil water interfacial tension, the results are shown in Table 3 a.
Table 3 a different concns surfactant composition 6 and Shuanghe Oil Field
5-11 series of strata oil water interfacial tension
| Dosage of surfactant (wt %) | 0.01 | 0.02 | 0.05 | 0.1 | 0.2 | 0.3 |
| Interfacial tension (MN/m) | 0.005 | 0.003 | 0.001 | 0.0003 | 0.0002 | 0.0002 |
The above results shows, the present invention three adopts surfactant composition to have very high interfacial activity for Henan Oil Field crude oil.
Rotate with TX-500C and drip interfacial tensimeter and again measure surfactant composition prepared by embodiment 6 a and Zhongyuan Oil Field and to recover the oil three factory's oil water interfacial tensions.Measuring temperature is 80
oc, formation water salinity is 79439mg/L, Ca
2+content 592 mg/L, Mg
2+content 2871mg/L, dosage of surfactant is 0.3 wt %.Oil water interfacial tension is 0.002mN/m, shows tensio-active agent of the present invention not only for low mineralization oil reservoir, still has good interface performance simultaneously, have the advantage that the scope of application is wide for high temperature and high salt oil deposit.
[embodiment 13 a] three adopts the aptitude tests of surfactant composition washing oil
Get Shuanghe Oil Field
5-11 series of strata oil-sand, according to oil: sand=1:4 (weight ratio) is 81
oaging 7 days of C, stirs 5 minutes for every 2 hours; Then take out above-mentioned aging after oil-sand 5g, with the surfactant soln of 0.3 wt % by oil-sand: solution=1:10 (weight ratio) mixes, under reservoir temperature after aging 48 hours, with the crude oil in petroleum ether extraction solution, with 50ml colorimetric cylinder constant volume, spectrophotometer is in wavelength 430nm place's colorimetric analysis.Utilize typical curve gauging surface activator solution Crude Oil concentration.
Table 4 a tri-adopts surfactant composition washing oil result
| Embodiment | Washing oil rate % |
| 1 a | 63.4 |
| 2 a | 64.9 |
| 3 a | 57.5 |
| 4 a | 63.4 |
| 5 a | 54.3 |
| 6 a | 66.0 |
| 7 a | 68.6 |
| 8 a | 63.7 |
| 9 a | 59.5 |
| 10 a | 65.8 |
[embodiment 14 a] three adopts the research of surfactant composition Oil Displacing Capacity
Be 30 centimetres in length, diameter is 2.5 centimetres, and rate of permeation is 1.5 microns
2rock core on carry out oil displacement test.First use Shuanghe Oil Field
5-11 series of strata local water is driven to without oil, and after the surfactant composition of metaideophone 0.3PV (rock pore volume), water drive, to moisture 100%, improves oil recovery factor and the results are shown in Table 5 a.
Table 5 a tri-adopts surfactant composition oil displacement test result
| Embodiment | Improve recovery ratio % |
| 1 a | 7.3 |
| 2 a | 6.7 |
| 3 a | 6.1 |
| 4 a | 4.8 |
| 5 a | 5.5 |
| 6 a | 10.1 |
| 7 a | 10.4 |
| 8 a | 8.1 |
| 9 a | 7.3 |
| 10 a | 9.4 |
[comparative example 1a]
According to Northwest University's journal (natural science edition) volume the 1st phase February the 30th in 2000, cetyl trimethylammonium bromide (CTAB) and sodium lauryl sulphate (SDS) are mixed with mixed system (mol ratio 1:1.5) by the methods such as 28 ~ 31 Gong Yu armies, test it respectively when 0.3 wt % consumption and Shuanghe Oil Field
5-11 series of strata crude oil oil water interfacial tension, washing oil rate and Oil Displacing Capacity, result is as follows:
Table 6 a reference oil-displacing agent performance
| Interfacial tension (MN/m) | Washing oil rate % | Improve recovery ratio % |
| 0.03 | 45.6 | 2.8 |
[comparative example 2a]
According to oil and gas journal volume the 4th phase August the 29th in 2007, Huang Hongdu etc. (101 ~ 104) method etc. are by 0.01wt% cetyl trimethylammonium bromide and 0.02 wt % anion surfactant sulfonated petro-leum and 1.8 wt %Na
2cO
3be mixed with mixed system, test it respectively when 0.3 wt % consumption and Shuanghe Oil Field
5-11 series of strata crude oil oil water interfacial tension, washing oil rate and Oil Displacing Capacity, result is as follows:
Table 7 a reference oil-displacing agent performance
| Interfacial tension (MN/m) | Washing oil rate % | Improve recovery ratio % |
| 0.008 | 56.3 | 4.2 |
[embodiment 1b]
By CH
3(CH
2)
10cH=CH (CH
2)
8cOOH, pentadecyl benzene and perchloric acid add reactor, pass into N
2be 35kg/cm to pressure
2, in 200
oc reacts 2 hours, wherein CH
3(CH
2)
10cH=CH (CH
2)
8cOOH: pentadecyl benzene: perchloric acid mol ratio is 1:1:0.1.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 1%, 100
oc, 100kg/cm
2pressure hydrogenation reaction 10 hours, then by Pd/C catalyst filtration; Aryl abovementioned steps obtained replaces fatty alcohol and NaOH adds reactor according to mol ratio 1:1.5, stirs and adds required propylene oxide, in 150 after 30 minutes
oc reacts 5 hours; Then add the oxyethane of aequum, in 200
oc reacts 1 hour, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: ClCH
2sO
3na mol ratio 1:3 adds sulfonated reagent, is warming up to 70
oc reacts 10 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
2=CHCOOH and perchloric acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: sodium chloroacetate: NaOH mol ratio 1:1.5:1.5 adds carboxylating reagent, is warming up to 80
oc reacts 6 hours.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 2 wt %Ca (OH)
2be neutralized to pH value 8, vacuum removal moisture, obtain target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent phenyl trimethicone ammonium chloride and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3wt% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 0.6 mixes, obtain surfactant composition 1 b, its composition, structure are in table 1 b.
[embodiment 2b]
By CH
3(CH
2)
2cH=CHCOOH, octyl group benzene and ClSO
3h adds reactor, passes into N
2be 100kg/cm to pressure
2, in 50
oc reacts 20 hours, wherein CH
3(CH
2)
2cH=CHCOOH: octyl group benzene: ClSO
3h mol ratio is 1:1:0.25.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 0.2%, 120
oc, 120kg/cm
2pressure hydrogenation reaction 8 hours, then filters Pd/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and KOH adds reactor according to mol ratio 1:1.5, stirs and adds required propylene oxide, in 120 after 30 minutes
oc reacts 7 hours; Then add the oxyethane of aequum, in 160
oc reacts 4 hours, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: sodium isethionate mol ratio 1:2.5 adds sulfonated reagent, is warming up to 90
oc reacts 8 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3(CH
2)
2cH=CHCOOH and ClSO
3h adds reactor, repeats aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: 3-chloropropionic acid: KOH mol ratio 1:1.5:2.5 adds carboxylating reagent, is warming up to 80
oc reacts 6 hours.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 5 wt %NaOH are neutralized to pH value 8, and vacuum removal moisture obtains target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent decyl triethylammonium hydroxide and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 0.1 mixes, obtain surfactant composition 2 b, its composition, structure are in table 1 b.
[embodiment 3b]
By CH
2=CHCOOH, amylbenzene and p-methyl benzenesulfonic acid add reactor, pass into N
2be 50kg/cm to pressure
2, in 120
oc reacts 15 hours, wherein CH
2=CHCOOH: amylbenzene: p-methyl benzenesulfonic acid mol ratio is 1:1:0.15.After reaction terminates, add the Pt/C catalyzer of fatty acid wt 0.2%, 300
oc, 100kg/cm
2pressure hydrogenation reaction 1 hour, then filters Pt/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and CsOH adds reactor according to mol ratio 1:1.5, stirs and adds required propylene oxide, in 100 after 30 minutes
oc reacts 20 hours; Then add the oxyethane of aequum, in 200
oc reacts 1 hour, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: hydroxyl amyl group sodium sulfonate mol ratio 1:4 adds sulfonated reagent, is warming up to 50
oc reacts 20 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3(CH
2)
10cH=CH (CH
2)
8cOOH and p-methyl benzenesulfonic acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: 3-bromocaproic acid: CsOH mol ratio 1:1.5:2.5 adds carboxylating reagent, is warming up to 100
oc reacts 1 hour.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 5 wt %KOH are neutralized to pH value 8, and vacuum removal moisture obtains target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent etamon chloride and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 1.2 mixes, obtain surfactant composition 3 b, its composition, structure are in table 1 b.
[embodiment 4b]
By CH
3(CH
2)
4cH=CH (CH
2)
2cOOH, benzene and perchloric acid add reactor, pass into N
2be 80kg/cm to pressure
2, in 150
oc reacts 1 hour, wherein CH
3(CH
2)
4cH=CH (CH
2)
2cOOH: benzene: perchloric acid mol ratio is 1:1:0.10.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 0.2%, 100
oc, 10kg/cm
2pressure hydrogenation reaction 10 hours, then filters Pd/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and KOH adds reactor according to mol ratio 1:1.5, stirs and adds required propylene oxide, in 140 after 30 minutes
oc reacts 10 hours; Then add the oxyethane of aequum, in 180
oc reacts 3 hours, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: hydroxypropyl azochlorosulfonate acid sodium mol ratio 1:2 adds sulfonated reagent, is warming up to 70
oc reacts 8 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3(CH
2)
4cH=CH (CH
2)
2cOOH and p-methyl benzenesulfonic acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: 4-chloro-butyric acid sodium: NaOH mol ratio 1:1.5:2.0 adds carboxylating reagent, is warming up to 80
oc reacts 6 hours.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 2 wt %Mg (OH)
2be neutralized to pH value 7, vacuum removal moisture, obtain target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent benzyltriethylammoinium chloride and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 4.7 mixes, obtain surfactant composition 4 b, its composition, structure are in table 1 b.
[embodiment 5b]
By CH
3(CH
2)
8cH=CHCOOH, benzene and perchloric acid add reactor, pass into N
2be 40kg/cm to pressure
2, in 120
oc reacts 5 hours, wherein CH
3(CH
2)
8cH=CHCOOH: benzene: perchloric acid mol ratio is 1:1:0.12.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 0.2%, 150
oc, 30kg/cm
2pressure hydrogenation reaction 8 hours, then filters Pd/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and NaOH adds reactor according to mol ratio 1:2, stirs and adds required propylene oxide, in 150 after 30 minutes
oc reacts 5 hours; Then add the oxyethane of aequum, in 150
oc reacts 8 hours, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: hydroxyl butyl sulfonic acid sodium mol ratio 1:2 adds sulfonated reagent, is warming up to 70
oc reacts 8 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3(CH
2)
4cH=CHCOOH and p-methyl benzenesulfonic acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: 4-chloro pentane acid sodium: NaOH mol ratio 1:1.5:2.0 adds carboxylating reagent, is warming up to 80
oc reacts 8 hours.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase is with 10 wt% ammonia neutralizations to pH value 8, and vacuum removal moisture, obtains target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent tetrabutylammonium chloride and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 10 mixes, obtain surfactant composition 5 b, its composition, structure are in table 1 b.
[embodiment 6b]
By CH
3(CH
2)
8cH=CH (CH
2)
4cOOH, ethylbenzene and perchloric acid add reactor, pass into N
2be 50kg/cm to pressure
2, in 140
oc reacts 3 hours, wherein CH
3(CH
2)
8cH=CH (CH
2)
4cOOH: ethylbenzene: perchloric acid mol ratio is 1:1:0.15.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 0.2%, 200
oc, 50kg/cm
2pressure hydrogenation reaction 6 hours, then filters Pd/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and NaOH adds reactor according to mol ratio 1:2, stirs and adds required propylene oxide, in 150 after 30 minutes
oc reacts 5 hours; Then add the oxyethane of aequum, in 150
oc reacts 8 hours, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: ClCH
2sO
3na mol ratio 1:2 adds sulfonated reagent, is warming up to 85
oc reacts 5 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3(CH
2)
8cH=CH (CH
2)
4cOOH and perchloric acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: sodium chloroacetate: NaOH mol ratio 1:1.5:2.0 adds carboxylating reagent, is warming up to 100
oc reacts 1 hour.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 10 wt% Mg (OH)
2be neutralized to pH value 8, vacuum removal moisture, obtain target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent prepared by four octyl group ammonium chlorides and the present invention is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 1.5 mixes, obtain surfactant composition 6 b, its composition, structure are in table 1 b.
[embodiment 7b]
By CH
3(CH
2)
7cH=CH (CH
2)
2cOOH, biphenyl and p-methyl benzenesulfonic acid add reactor, pass into N
2be 50kg/cm to pressure
2, in 100
oc reacts 5 hours, wherein CH
3(CH
2)
7cH=CH (CH
2)
2cOOH: biphenyl: p-methyl benzenesulfonic acid mol ratio is 1:1:0.15.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 0.2%, 160
oc, 40kg/cm
2pressure hydrogenation reaction 8 hours, then filters Pd/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and KOH adds reactor according to mol ratio 1:2, stirs and adds required propylene oxide, in 120 after 30 minutes
oc reacts 8 hours; Then add the oxyethane of aequum, in 150
oc reacts 6 hours, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: ClCH
2sO
3na mol ratio 1:2 adds sulfonated reagent, is warming up to 80
oc reacts 6 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3(CH
2)
7cH=CH (CH
2)
2cOOH and perchloric acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: sodium chloroacetate: NaOH mol ratio 1:1.5:2.0 adds carboxylating reagent, is warming up to 75
oc reacts 10 hours.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 10 wt% NaOH are neutralized to pH value 8, and vacuum removal moisture obtains target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent palmityl trimethyl ammonium chloride and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 1.9 mixes, obtain surfactant composition 7 b, its composition, structure are in table 1 b.
[embodiment 8b]
By CH
3(CH
2)
2cH=CHCOOH, benzene and p-methyl benzenesulfonic acid add reactor, pass into N
2be 50kg/cm to pressure
2, in 130
oc reacts 6 hours, wherein CH
3(CH
2)
2cH=CHCOOH: benzene: p-methyl benzenesulfonic acid mol ratio is 1:1:0.10.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 0.2%, 160
oc, 40kg/cm
2pressure hydrogenation reaction 8 hours, then filters Pd/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and KOH adds reactor according to mol ratio 1:2, stirs and adds required propylene oxide, in 120 after 30 minutes
oc reacts 8 hours; Then add the oxyethane of aequum, in 150
oc reacts 6 hours, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: sodium isethionate mol ratio 1:2 adds sulfonated reagent, is warming up to 80
oc reacts 6 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3(CH
2)
2cH=CHCOOH and p-methyl benzenesulfonic acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: 3-chloropropionic acid sodium: NaOH mol ratio 1:1.5:2.0 adds carboxylating reagent, is warming up to 75
oc reacts 10 hours.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 10 wt% NaOH are neutralized to pH value 8, and vacuum removal moisture obtains target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent distearyl dimethyl ammonium chloride and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 3.6 mixes, obtain surfactant composition 8 b, its composition, structure are in table 1 b.
[embodiment 9b]
By CH
3(CH
2)
6cH=CH (CH
2)
3cOOH, isopropyl benzene and p-methyl benzenesulfonic acid add reactor, pass into N
2be 50kg/cm to pressure
2, in 120
oc reacts 5 hours, wherein CH
3(CH
2)
6cH=CH (CH
2)
3cOOH: isopropyl benzene: p-methyl benzenesulfonic acid mol ratio is 1:1:0.20.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 0.2%, 170
oc, 40kg/cm
2pressure hydrogenation reaction 8 hours, then filters Pd/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and KOH adds reactor according to mol ratio 1:2, stirs and adds required propylene oxide, in 140 after 30 minutes
oc reacts 8 hours; Then add the oxyethane of aequum, in 150
oc reacts 7 hours, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: ClCH
2sO
3na mol ratio 1:2 adds sulfonated reagent, is warming up to 80
oc reacts 6 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3(CH
2)
6cH=CH (CH
2)
3cOOH and p-methyl benzenesulfonic acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: sodium chloroacetate: NaOH mol ratio 1:1.5:2.0 adds carboxylating reagent, is warming up to 75
oc reacts 10 hours.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 10 wt% NaOH are neutralized to pH value 8, and vacuum removal moisture obtains target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent Dodecyl trimethyl ammonium chloride and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 10 mixes, obtain surfactant composition 9 b, its composition, structure are in table 1 b.
[embodiment 10 b]
By CH
3cH
2cH=CH (CH
2)
2cOOH, nonyl benzene and p-methyl benzenesulfonic acid add reactor, pass into N
2be 50kg/cm to pressure
2, in 160
oc reacts 8 hours, wherein CH
3cH
2cH=CH (CH
2)
2cOOH: nonyl benzene: p-methyl benzenesulfonic acid mol ratio is 1:1:0.15.After reaction terminates, add the Pd/C catalyzer of fatty acid wt 0.2%, 170
oc, 60kg/cm
2pressure hydrogenation reaction 8 hours, then filters Pd/C catalyzer; Aryl abovementioned steps obtained replaces fatty alcohol and NaOH adds reactor according to mol ratio 1:2, stirs and adds required propylene oxide, in 160 after 30 minutes
oc reacts 8 hours; Then add the oxyethane of aequum, in 150
oc reacts 8 hours, obtains the monosubstituted fatty alcohol polyoxypropylene Soxylat A 25-7 of aryl; Then according to polyethers: sodium isethionate mol ratio 1:2 adds sulfonated reagent, is warming up to 80
oc reacts 6 hours.After reaction terminates, being neutralized to pH value with 5wt% aqueous hydrochloric acid is 2.5, stratification.By oil-phase product, CH
3cH
2cH=CH (CH
2)
2cOOH and perchloric acid add reactor, repeat aforementioned addition-reduction-etherification step.After etherificate terminates, according to polyethers: 3-chloropropionic acid sodium: NaOH mol ratio 1:1.5:2.0 adds carboxylating reagent, is warming up to 75
oc reacts 10 hours.After reaction terminates, be neutralized to pH value 2.5 with 5wt% aqueous hydrochloric acid, stratification, oil phase 10 wt% NaOH are neutralized to pH value 8, and vacuum removal moisture obtains target product Anionic-nonionic tensio-active agent.
Anionic-nonionic tensio-active agent tetrabutylammonium chloride and the present invention prepared is dissolved in the water respectively, stir 30 minutes, be mixed with the 0.3 wt % aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic surfactant molar ratio 1: 7.5 mixes, obtain surfactant composition 10 b, its composition, structure are in table 1 b.
[embodiment 11 b]
The 0.30wt% surfactant composition prepare embodiment 5 b and 0.15wt% polyacrylamide (molecular weight 2,600 ten thousand) aqueous solution evenly, obtain a kind of Polymer Used For Oil Displacement-surfactant complex.
Table 1 b tri-adopts surfactant composition to form and structure
[embodiment 12 b] three adopts the test of surfactant composition interface performance
Rotate with TX-500C and drip interfacial tensimeter mensuration surfactant composition and Shuanghe Oil Field
5-11 series of strata oil water interfacial tension.Dosage of surfactant consumption: 0.3 wt %, measuring temperature is 81
oc, local water is NaHCO
3type, salinity is 7947mg/L, chloride ion content 2002 mg/L, Ca
2+content 20 mg/L, Mg
2+content 12.2 mg/L.
Table 2 b tri-adopts surfactant composition and Shuan He oil field
5-11 series of strata oil water interfacial tension
| Embodiment | Interfacial tension (mN/m) |
| 1 b | 0.0056 |
| 2 b | 0.0082 |
| 3 b | 0.0045 |
| 4 b | 0.0090 |
| 5 b | 0.0032 |
| 6 b | 0.0002 |
| 7 b | 0.0009 |
| 8 b | 0.0049 |
| 9 b | 0.0062 |
| 10 b | 0.0018 |
| 11 b | 0.0062 |
From table 2 b, compound surfactant prepared by embodiment 1 b ~ 10 b has good interface performance for Henan Oil Field.Embodiment 11 b shows, tensio-active agent prepared by the present invention and polymkeric substance composite after, its interface performance is still good.
Surfactant composition prepared by embodiment 6 b is mixed with different concns, respectively test and Shuanghe Oil Field
5-11 series of strata oil water interfacial tension, the results are shown in Table 3 b.
Table 3 b different concns surfactant composition 6 wt and Shuanghe Oil Field
5-11 series of strata oil water interfacial tension
| Dosage of surfactant (wt %) | 0.01 | 0.02 | 0.05 | 0.1 | 0.2 | 0.3 |
| Interfacial tension (MN/m) | 0.009 | 0.009 | 0.004 | 0.0003 | 0.0002 | 0.0002 |
The above results shows, the present invention three adopts surfactant composition to have very high interfacial activity for Henan Oil Field crude oil.
Rotate with TX-500C and drip interfacial tensimeter and again measure surfactant composition prepared by embodiment 6 b and Zhongyuan Oil Field and to recover the oil three factory's oil water interfacial tensions.Measuring temperature is 80
oc, formation water salinity is 79439mg/L, Ca
2+content 592 mg/L, Mg
2+content 2871mg/L, dosage of surfactant is 0.3 wt %.Oil water interfacial tension is 0.002mN/m, shows tensio-active agent of the present invention not only for low mineralization oil reservoir, still has good interface performance simultaneously, have the advantage that the scope of application is wide for high temperature and high salt oil deposit.
[embodiment 13 b] three adopts the aptitude tests of surfactant composition washing oil
Get Shuanghe Oil Field
5-11 series of strata oil-sand, according to oil: sand=1:4 (weight ratio) is 81
oaging 7 days of C, stirs 5 minutes for every 2 hours; Then take out above-mentioned aging after oil-sand 5g, with the surfactant soln of 0.3 wt % by oil-sand: solution=1:10 (weight ratio) mixes, under reservoir temperature after aging 48 hours, with the crude oil in petroleum ether extraction solution, with 50ml colorimetric cylinder constant volume, spectrophotometer is in wavelength 430nm place's colorimetric analysis.Utilize typical curve gauging surface activator solution Crude Oil concentration.
Table 4 b tri-adopts surfactant composition washing oil result
| Embodiment | Washing oil rate % |
| 1 b | 62.3 |
| 2 b | 63.8 |
| 3 b | 56.3 |
| 4 b | 62.1 |
| 5 b | 52.9 |
| 6 b | 64.8 |
| 7 b | 67.3 |
| 8 b | 62.6 |
| 9 b | 58.4 |
| 10 b | 64.7 |
[embodiment 14 b] three adopts the research of surfactant composition Oil Displacing Capacity
Be 30 centimetres in length, diameter is 2.5 centimetres, and rate of permeation is 1.5 microns
2rock core on carry out oil displacement test.First use Shuanghe Oil Field
after 5-11 series of strata local water is driven to the surfactant composition of moisture 92 wt %, metaideophone 0.3pv (rock pore volume), water drive, to moisture 100%, improves oil recovery factor and the results are shown in Table 5 b.
Table 5 b tri-adopts surfactant composition oil displacement test result
| Embodiment | Improve recovery ratio % |
| 1 b | 6.8 |
| 2 b | 6.2 |
| 3 b | 5.5 |
| 4 b | 4.2 |
| 5 b | 4.8 |
| 6 b | 9.5 |
| 7 b | 9.7 |
| 8 b | 7.5 |
| 9 b | 6.7 |
| 10 b | 8.9 |
Claims (10)
1. one kind three adopts surfactant composition, comprise cats product and Anionic-nonionic tensio-active agent, the mol ratio of described cats product and Anionic-nonionic tensio-active agent is 1: 0.01 ~ 1: 100, its cationic surfactant is selected from least one in quaternary ammonium salt or quaternary amine alkali, and Anionic-nonionic surfactant molecule general formula is:
Wherein M and N is independently selected from any one in basic metal, alkaline-earth metal or ammonium root; F is M and SO in general molecular formula
3the mol ratio of group, when M be basic metal or ammonium root time f=1, the f=0.5 when M is alkaline-earth metal; G is the mol ratio of N and COO group in general molecular formula, when N be basic metal or ammonium root time g=1, the g=0.5 when M is alkaline-earth metal; R is H, C
1~ C
20alkyl, C
6~ C
10aryl or substituted aryl in any one, R ' and R " independently take from C
1~ C
10alkylidene group, a, b, m, n independently take from any one integer in 0 ~ 20, and c, d, x, y independently take from any one integer in 0 ~ 100 or decimal.
2. three adopt surfactant composition according to claim 1, at least one is non-vanishing to it is characterized in that x or c.
3. three employing surfactant compositions according to claim 1 or 2, it is characterized in that described cats product is selected from least one in tetra-alkyl ammonium chloride or tetra-alkyl ammonium hydroxide, the carbonatoms in cats product molecule is 4 ~ 40.
4. three employing surfactant compositions according to claim 1 or 2, is characterized in that R is H, C
5~ C
15alkyl or aryl.
5. three employing surfactant compositions according to claim 1 or 2, it is characterized in that R ' or R " is C
1~ C
5alkylidene group.
6. three employing surfactant compositions according to claim 1 or 2, is characterized in that described a, b, m or n are any one integer in 0 ~ 10.
7. three adopt surfactant compositions according to claim 1, it is characterized in that c, x, d or y are any one integer in 0 ~ 50 or decimal.
8. the preparation method of three employing surfactant compositions according to any one of claim 1 to 7, comprises the following steps:
A) unsaturated fatty acids 1, an acidic catalyst and aromatic hydrocarbon are added reactor, in 50 ~ 150
oc addition reaction 1 ~ 20 hour, wherein unsaturated fatty acids: aromatic hydrocarbons mol ratio is 1:(0.5 ~ 1.0); After reaction terminates, in temperature 100 ~ 300
oc, pressure 10 ~ 100kg/cm
2hydrogenation reaction 1 ~ 10 hour, thus aryl is obtained carboxylic acid and be reduced into aryl substituted alcohols; Aryl substituted alcohols, basic catalyst and required propylene oxide, oxyethane are added reactor, in 100 ~ 200
oc carries out etherification reaction 1 ~ 20 hour; Then add sulfonated reagent in 50 ~ 100
oc reaction carries out sulfonation reaction in 1 ~ 20 hour, and wherein aryl replaces fatty alcohol polyoxypropylene Soxylat A 25-7: the mol ratio of sulfonated reagent is 1:(1 ~ 4); After reaction terminates, be adjusted to pH=1 ~ 3 with acidic aqueous solution, carry out oily water separation, it is aryl monosubstituted fatty alcohol polyoxypropylene polyoxyethylene ether sulfonic acid that oil phase obtains sulfonated products; Then add in aforementioned sulfonated products by unsaturated fatty acids 2, repeat addition-reduction-etherificate, the etherate obtained and carboxylating reagent are in 50 ~ 100
oc reaction carries out carboxylation reaction in 1 ~ 20 hour, described etherate: the mol ratio of carboxylating reagent is 1:(1 ~ 4), after reaction terminates, pH=1 ~ 3 are adjusted to acidic aqueous solution, carry out oily water separation, oil phase adds alkali lye and is neutralized to pH=7 ~ 9, obtains the aryl two replacement fatty alcohol polyoxypropylene Soxylat A 25-7 sulfoacid carboxylic acid salt anionic-nonionogenic tenside described in claim 1 shown in general formula;
B) be dissolved in the water respectively by cats product and according to the Anionic-nonionic tensio-active agent that step a) obtains, then mix according to mol ratio 1: 0.1 ~ 1: 10.
9. three adopt the preparation method of surfactant compositions according to claim 8, it is characterized in that the addition reaction an acidic catalyst used described in step a) is perchloric acid, ClSO
3at least one in H, p-methyl benzenesulfonic acid; Basic catalyst described in etherification reaction is preferred alkali metal hydroxide, at least one more preferably in NaOH or KOH; Described sulfonated reagent is preferably hydroxyl sulfoacid and salt thereof or halogenosulfonic acid and salt thereof; Described carboxylating reagent is preferably halogenated carboxylic acid and salt thereof.
10. three application of employing surfactant composition in tertiary oil recovery according to any one of claim 1 to 7.
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