CN104232045B

CN104232045B - Composite surface active agent composition and preparation method and application thereof

Info

Publication number: CN104232045B
Application number: CN201310237545.XA
Authority: CN
Inventors: 李应成; 顾松园; 沈之芹; 张卫东; 鲍新宁
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2013-06-17
Filing date: 2013-06-17
Publication date: 2017-02-15
Anticipated expiration: 2033-06-17
Also published as: CN104232045A; NO347784B1; NO20160047A1

Abstract

The invention relates to a composite surface active agent composition, and a preparation method and application thereof, and mainly solves the problems of poor displacement efficiency 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 composite 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 to 1:100. The cationic surface active agent is at least one selected from the group consisting of quaternary ammonium salt or quaternary ammonium alkali; and the anionic-non-ionic surface active agent is represented by a molecular general formula shown as below, wherein M represents one of an alkali metal, an alkaline earth metal and ammonium. The technical scheme well solves the above problems, and can be used in tertiary oil recovery process.

Description

Compound surfactant composition, preparation method and application

Technical field

The present invention relates to compound surfactant composition, preparation method and its application in tertiary oil recovery.

Background technology

With the increase of world energy sources demand, the rational exploitation and utilization of oil has caused the very big attention of people, to oil Yield and production efficiency requirement also more and more higher.Realize the high-efficiency mining of petroleum resources, for raising crude output not Only there is realistic meaning, with more important strategic importance.Conventional oil production method（Once with secondary method）Normally only produce former The 1/3 of oily oil in place, the crude oil that there is also about 2/3 fails extraction, therefore in the case that energy day is becoming tight, improves tar productivity The key subjects of oil exploitation research are become.Tertiary oil recovery technology is then a kind of effective method improving tar productivity, can divide For four big class：One is that heating power drives, including steam drive, combustion in situ etc.；Two is that mixed phase drives, including CO₂Mixed phase, hydrocarbon mixed phase and other Inert gas mixed phase drives；Three is chemical flooding；Four is microbe oil production, drives including biopolymer, MICROBIAL SURFACTANT.Change Learning drive is technology that is extremely important in intensified oil reduction and implementing on a large scale, including polymer flooding, surfactant flooding, caustic waterflooding etc. And the multiple combination technology of polymer, alkali, surfactant.The effect of chemical flooding is the knot of physical action and chemical action Really, physical action refers to the effect that involves of displacing fluid, and chemical action refers to the microcosmic oil drive effect of displacing fluid.Chemical action Core is to reduce the interfacial tension of displacing fluid and crude oil.Surfactant is due to having oleophylic concurrently（Hydrophobic）With hydrophilic（Oleophobic）Property Matter, when surfactant is dissolved in water, molecule is mainly distributed on oil-water interfaces, can significantly reduce oil water interfacial tension.Oil The reduction of water interfacial tension means that surfactant system can overcome the cohesive force between crude oil, and larger oil droplet is dispersed into little oil Drip, thus improving crude oil to flow through percent of pass during pore throat.The oil displacement efficiency of surfactant is also manifested by making the rock table of oleophylic Face wettability reversal, emulsification of crude oil, the raising effect such as surface charge density and oil droplet coalescence, this is surfactant in chemical flooding The reason play very important effect in technology.

Surface active agent for tertiary oil recovery adopts Recompounded multielement system mostly at present, comprises non-ionic surfactant simultaneously Agent and ionic surfactant, are additionally added the auxiliary agents such as alkali and alcohol in part formulation.As patent CN101024764A provides one The surfactant of kind of oil-field thick-oil well, this activating agent be by water, piece alkali, ethanol, oleic acid, APES, ten Dialkyl benzene sulfonic acids sodium forms.For another example patent CN1458219A discloses a kind of surfactant polymer of tertiary oil recovery application Pure binary ultralow interfacial tension combination flooding formula, used in it, surfactant is petroleum sulfonate or with petroleum sulfonate is Host adds diluent and the complexed surfactant of other surfactant compound, and the percentage by weight of its component is mahogany acid Salt 50～100%, alkylsulfonate 0～50%, carboxylate 0～50%, alkylaryl sulfonates 0～35%, low-carbon alcohols 0～20%.Again As patent CN1394935 has invented a kind of chemical oil displacement agent, it mainly includes sodium octylbenzene sulfonate anion surfactant, table Face activity agent aid, surfactant synergist, surface active agent solubilization agent.This oil displacement agent can significantly reduce the knot of viscous crude Structure viscosity, can reduce oil water interfacial tension simultaneously, thus improving oil recovery factor.

However, above-mentioned surface active agent for tertiary oil recovery still suffers from more problem, mainly surfactant activity is poor, drive Oily efficiency is low, simultaneously because surfactant system is excessively complicated, thus Produced Liquid breakdown of emulsion is difficult, and sewage disposal difficulty is big；Separately Outward because oil displacement system contains inorganic base, injury is brought to stratum and oil well, causes the problems such as etching apparatus and pipeline, and due to Inorganic base can seriously reduce the viscosity of polymer, have to greatly improve the concentration of polymer for reaching required viscosity, make Oil recovery integrated cost improves；The high temperature resistance of surfactant, high salt tolerance, anti-high salinity limited in one's ability.

It is known that anion surfactant, such as petroleum sulfonate, petroleum carboxylate, alkylbenzenesulfonate etc. are at present During being widely used in tertiary oil recovery, and cationic surfactant is easily adsorbed or produced by stratum precipitation because of it, therefore fall The ability of low oil water interfacial tension, is generally not used for tertiary oil recovery.Because cationic and anionic surfactant mixes close to equal proportion During conjunction, its aqueous solution easily forms precipitation, thus lead to cationic and anionic surfactant mixed system not only to become in the application joining 5 taboos, and correlation theory research is also more delayed.Research in recent years finds, cationic and anionic surfactant mixed system The aqueous solution has a lot of anomalous properties, such as because cationic and anionic surfactant has strong electrostatic interaction in aqueous Interaction and between hydrophobic carbon chain, promotes two kinds of band difference interionic associations of charged surfactant, in the solution It is readily formed micella, the higher surface-active of the single surfactant of producing ratio.Additionally, cationic and anionic surfactant mixing System can obviously reduce absorption loss on rock core for the cationic surfactant, thus cation surface activating can be significantly reduced The inherent shortcoming of agent.

Gong Yujun etc.（See 2 months the 1st phases Northwest University's journal (natural science edition) of volume 30 in 2000,28～31）Research Think cetyl trimethylammonium bromide（CTAB）With lauryl sodium sulfate（SDS）Mixed system has solubilization.In stone In oily recovery process, using solubilization can " displacement of reservoir oil ", under the oil wash that will stick on the sandstone of rock stratum, thus improve oil adopting Yield.Huang Hongdu etc.（See petroleum gas journal in August, 2007 the 4th phase of volume 29,101～104）Have studied petroleum sulfonate, The anion surfactants such as petroleum carboxylate, alkylbenzenesulfonate and cetyl trimethylammonium bromide, alkali compound system Interfacial tension simultaneously draws to draw a conclusion：The addition of cationic surfactant makes petroleum carboxylate, alkylbenzenesulfonate, oil sulphur The interfacial activity of hydrochlorate is improved.

The studies above result shows anions and canons Surfactant Mixing Systems for reduction oil water interfacial tension, raising Oil displacement efficiency has certain effect.But the former result of study shows that its interface performance still has much room for improvement, and the latter is in system Still employ alkali, thus alkali cannot be avoided to bring injury, etching apparatus and pipeline and breakdown of emulsion difficulty etc. to ask on stratum and oil well Topic.In addition above-mentioned system is easier to generate precipitation, is unfavorable for practical application.

For this reason, one aspect of the present invention absorbs has used for reference forefathers with regard to anions and canons Surfactants mixed system research knot Really, on the other hand adopt Anionic-nonionic surfactant to replace traditional anion surfactant, overcome yin, yang The shortcomings of ionic surface active agent easily precipitates when compounding, has invented the cation surface activating for improving oil recovery factor Agent and Anionic-nonionic surfactant compound surfactant composition.

Content of the invention

One of the technical problem to be solved is existing surfactant oil displacement efficiency during tertiary oil recovery Difference, simultaneously because oil displacement system contains inorganic base, brings injury, etching apparatus and pipeline and breakdown of emulsion difficult to stratum and oil well Problem, provides a kind of new compound surfactant composition, and said composition has that interfacial activity is high, washing oil ability is strong, body System is simple, will not bring injury to stratum and oil well, will not etching apparatus and pipeline and the advantage not resulting in breakdown of emulsion difficulty.

The two of the technical problem to be solved are to provide a kind of surface corresponding with solving technical problem one to live The preparation method of property agent composition.

The three of problem to be solved by this invention are the described surface activator compositions of one of above-mentioned technical problem at three times Application in oil recovery.

For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows：Compound surfactant combines Thing, including cationic surfactant and Anionic-nonionic surfactant, described cationic surfactant with cloudy from The mol ratio of son-nonionic surfactant is 1: 0.01～1: 100, and its cationic surfactant is selected from quaternary ammonium salt or season At least one in amine base, Anionic-nonionic surfactant is by following general molecular formula（A）、（B）、（C）Or（D）Represent：

（A）、(B)、

（C）、（D）；

Wherein M is any one in alkali metal, alkaline-earth metal or ammonium root, and R is H, C₁~C₂₀Alkyl, C₆~C₁₀Aryl Or any one in substituted aryl, m and n independence value is any one integer or decimal in 0～100；R is C₁～C₁₀ Alkylidene；R is M and SO in general molecular formula₃Group or the mol ratio of M and COO group, the r=when M is for alkali metal or ammonium root 1, when M is for alkaline-earth metal, r=0.5；R₁For C₁~C₅₀Alkyl or alkenyl.

Preferable m in technique scheme>0；For general molecular formula（C）With（D）Live in shown Anionic-nonionic surface Property agent optional m further>0 and n>0.

Cationic surfactant described in technique scheme preferably is selected from tetra-alkyl ammonium chloride or tetra-alkyl ammonium hydroxide In at least one.Carbon number in described cationic surfactant molecule is preferably 4 ~ 40.Described Anionic-nonionic Surfactant cationic M preferably is selected from Na, K, Mg, Ca or NH₄In any one.R is preferably H, C₅～C₁₅Alkyl or Aryl.R₁It is preferably C₅～C₂₀Alkyl, thiazolinyl.R is preferably C₁～C₅Alkylidene.

In technique scheme, m and n is preferably any one integer in 0～50 or decimal.

Cationic surfactant described in technique scheme is excellent with the mol ratio of Anionic-nonionic surfactant Scope is selected to be 1: 0.1～1: 10.

For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：One of above-mentioned technical problem is described Described in technical scheme, the preparation method of compound surfactant composition, comprises the following steps：

A) by alkyl phenol polyoxyethylene polyoxypropylene ether, catalyst according to mol ratio 1:(1～5) add reactor, in room Temperature～100^oC alkalizes 1～10 hour, then adds sulfonated reagent or carboxylating reagent, wherein alkyl phenol polyoxyethylene polyoxypropylene Ether：The mol ratio of sulfonated reagent or carboxylating reagent is 1：(1～4), is warming up to 50～100^oC reacts 1～20 hour, post-treated Obtain alkyl phenol polyoxyethylene polyoxypropylene ether sulfonate or alkyl phenol polyoxyethylene polyoxypropylene ether carboxylate；Described post processing Preferably include to use acidic aqueous solution（For example aqueous hydrochloric acid solution, aqueous sulfuric acid, phosphate aqueous solution, sodium bisulphate solution or Aqueous potassium hydrogen sulfate）Adjust to pH=1 ~ 3, carry out water-oil separating, oil phase adds alkali lye to be neutralized to pH=7 ~ 9；Described The preferred base catalyst of catalyst, described catalyst is more preferably alkali metal hydroxide, in most preferably NaOH or KOH at least A kind of；Described sulfonated reagent is preferably hydroxyl sulfoacid and its salt or halogenosulfonic acid and its salt；Described carboxylating reagent is preferably Halogenated carboxylic acid and its salt；

B) by cationic surfactant and the Anionic-nonionic surfactant that obtains according to step a) is molten respectively In Xie Yushui, then mix according to mol ratio (1: 0.1)～(1: 10), obtain described surface activator composition.

For solving the three of above-mentioned technical problem, technical scheme is as follows：Any one of one of technical problem technology Application in tertiary oil recovery for the compound surfactant composition described in scheme.

The compound surfactant composition one side of the present invention is due to anions and canons surfactant opposite charges pole Property base between strong electrostatic attraction effect so that surfactant molecule adsorbed on interfaces amount increase, critical micelle concentration Significantly reduce, thus having the incomparable high surface of single surfactant；Simultaneously because compound surfactant The interfacial activity of superelevation, its aqueous solution can form ultralow interfacial tension with crude oil, thus effectively overcoming the cohesive force between crude oil, has Beneficial to the outflow of crude oil, and then oil displacement efficiency is greatly improved.Another aspect compound surfactant composition can change oil Cationic surfactant in the wetability of layer surface, such as composition is by the electronegative base on a solid surface with absorption Group interacts so as to be desorbed, and makes glossy wet structure change into neutral wetting or water-wet surface, reduces crude oil in solid The adhesion work on surface, thus be conducive to the stripping of crude oil.Anions and canons surfactant mixed solution has increasing to crude oil simultaneously Molten effect, can wash down sticking to the crude oil on the sandstone of rock stratum further, improve oil recovery factor.

Adopt compound surfactant composition of the present invention during tertiary oil recovery, there is interfacial activity high：Compound Surface activator composition consumption be 0.01～0.05wt% under the conditions of remain to and underground crude oil formed 10^-3～10^-4MN/m Ultralow interfacial tension；Washing oil ability is strong：Compound surfactant composition is to the washing oil rate of crude oil more than 40%；Surface-active Agent composition system is simple.Because system does not contain inorganic base, thus the wound that when avoiding scene application, inorganic base causes to stratum Evil, the corrosion that equipment is caused and the problem of the breakdown of emulsion difficulty thus causing, achieve preferable technique effect.

Below by embodiment, the present invention is further elaborated.

Specific embodiment

【Embodiment 1a】

By alkyl phenol polyoxyethylene polyoxypropylene ether, NaOH according to mol ratio 1：5 addition reactors, in 100^oC alkalization 1 is little When, then according to alkyl phenol polyoxyethylene polyoxypropylene ether：Chloromethylsulfonic acid mol ratio 1：4 addition sulfonated reagents, are cooled to 50^oC continues reaction 20 hours.After reaction terminates, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 1, and stratification divides and goes Aqueous phase, oil phase is neutralized to pH value 7 with the 10 wt %NaOH aqueous solution, and vacuum removal moisture obtains alkyl phenol polyoxypropylene polyoxy second Alkene ether sulfonic acid sodium.

Alkyl phenol polyoxyethylene polyoxypropylene ether sulfonic acid sodium table by hexadecyltrimethylammonium chloride and present invention preparation Face activating agent is dissolved in water, stir 30 minutes, be configured to the 0.3wt% aqueous solution, then by above-mentioned surfactant according to Cation：Anionic-nonionic surfactant molar ratio 1: 0.3 mixes, and obtains compound surfactant composition 1a, its composition, structure are shown in Table 1a.

【Embodiment 2a】

By alkyl phenol polyoxyethylene polyoxypropylene ether, KOH according to mol ratio 1：1 addition reactor is little in room temperature alkalization 10 When, then according to alkyl phenol polyoxyethylene polyoxypropylene ether：Sodium isethionate mol ratio 1：3 addition sulfonated reagents, are warming up to 70^oC continues 10 hours.After reaction terminates, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2.5, and stratification divides and removes water Phase, oil phase is neutralized to pH value 9 with 10 wt % ammoniacal liquor, and vacuum removal moisture obtains alkyl phenol polyoxyethylene polyoxypropylene ether sulfonic acid Ammonium.

Lived in the alkyl phenol polyoxyethylene polyoxypropylene ether sulfonic acid ammonium surface of benzyltriethylammoinium chloride and present invention preparation Property agent be dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun Ion：Anionic-nonionic surfactant molar ratio 1: 0.1 mixes, and obtains compound surfactant composition 2 A, its composition, structure are shown in Table 1 a.

【Embodiment 3a】

By alkyl phenol polyoxyethylene polyoxypropylene ether, KOH according to mol ratio 1：1.5 addition reactors, in 30^oC alkalization 8 is little When, then according to alkyl phenol polyoxyethylene polyoxypropylene ether：Chlorine amyl group sodium sulfonate mol ratio 1：2 addition sulfonated reagents, are warming up to 60^oC continues 15 hours.After reaction terminates, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification divides and removes water Phase, oil phase is with 10 wt %Ca (OH)₂Aqueous suspension is neutralized to pH value 8, and vacuum removal moisture obtains alkyl phenol polyoxypropylene polyoxy Vinethene sulfoacid calcium.

Alkyl phenol polyoxyethylene polyoxypropylene ether sulfonic acid calcium table by phenyl trimethicone ammonium chloride and according to present invention preparation Face activating agent is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then presses above-mentioned surfactant According to cation：Anionic-nonionic surfactant molar ratio 1: 1.2 mixes, and obtains compound surfactant 3 a, Its composition, structure are shown in Table 1 a.

【Embodiment 4a】

By alkyl phenol polyoxyethylene polyoxypropylene ether, NaOH according to mol ratio 1：2 addition reactors, in 50^oC alkalization 6 is little When, then according to alkyl phenol polyoxyethylene polyoxypropylene ether：3- chlorine-2-hydroxyl propanesulfonate mol ratio 1：2 addition sulfonated reagents, It is warming up to 80^oC continues 8 hours.After reaction terminates, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, stratification, point Remove aqueous phase, oil phase is with 10 wt %Mg (OH)₂Aqueous suspension is neutralized to pH value 8, and vacuum removal moisture obtains alkyl phenol polyoxypropylene APEO sulfonic acid magnesium.

Alkyl phenol polyoxyethylene polyoxypropylene ether by stearyl dimethyl benzyl ammonium chloride and according to present invention preparation Sulfonic acid magnesium surfactant is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then by above-mentioned surface Activating agent is according to cation：Anionic-nonionic surfactant molar ratio 1: 2.0 mixes, and obtains compound surface and lives Property agent 4 a, its composition, structure be shown in Table 1 a.

【Embodiment 5a】

By alkyl phenol polyoxyethylene polyoxypropylene ether, NaOH according to mol ratio 1：3 addition reactors, in 60^oC alkalization 5 is little When, then according to alkyl phenol polyoxyethylene polyoxypropylene ether：Monoxone mol ratio 1：1 addition carboxylating reagent, is warming up to 100^oC continues Continuous 1 hour.After reaction terminates, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification divides and removes aqueous phase, oil phase is used The 10 wt %NaOH aqueous solution are neutralized to pH value 8, and vacuum removal moisture obtains alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid sodium.

Alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid sodium by decyl triethylammonium hydroxide and according to present invention preparation Surfactant is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant According to cation：Anionic-nonionic surfactant molar ratio 1: 10 mixes, and obtains compound surfactant 5 a, Its composition, structure are shown in Table 1 a.

【Embodiment 6a】

By alkyl phenol polyoxyethylene polyoxypropylene ether, NaOH according to mol ratio 1：4 addition reactors, in 80^oC alkalization 2 is little When, then according to alkyl phenol polyoxyethylene polyoxypropylene ether：Chloropropionic acid mol ratio 1：1.5 addition carboxylating reagent, are cooled to 50^oC Continue 18 hours, then add hydrochloric acid to be neutralized to pH<3, and carry out water-oil separating, oil phase adds 10%Ca (HCO₃)₂It is neutralized. After reaction terminates, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification point removes aqueous phase, and oil phase is with 10 wt % Ca(OH)₂Aqueous suspension is neutralized to pH value 8, and vacuum removal moisture obtains alkyl phenol polyoxyethylene polyoxypropylene ether calcium carboxylates.

Alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid by DTAC and according to present invention preparation Calcium surfactant is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then by above-mentioned surface-active Agent is according to cation：Anionic-nonionic surfactant molar ratio 1: 0.9 mixes, and obtains compound surfactant 6 A, its composition, structure are shown in Table 1 a.

【Embodiment 7a】

By alkyl phenol polyoxyethylene polyoxypropylene ether, KOH according to mol ratio 1：1 addition reactor is little in room temperature alkalization 10 When, then according to alkyl phenol polyoxyethylene polyoxypropylene ether：Sodium chloroacetate mol ratio 1：3 addition carboxylating reagent, are warming up to 80^oC Continue 8 hours.After reaction terminates, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification divides and removes aqueous phase, oil phase It is neutralized to pH value 8 with the 10 wt %KOH aqueous solution, vacuum removal moisture obtains alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid potassium.

Alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic by dioctadecyl dimethyl ammonium chloride and according to present invention preparation Sour potassium surfactant is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then lives in above-mentioned surface Property agent is according to cation：Anionic-nonionic surfactant molar ratio 1: 4 mixes, and obtains compound surfactant 7 A, its composition, structure are shown in Table 1 a.

【Embodiment 8a】

By alkyl phenol polyoxyethylene polyoxypropylene ether, NaOH according to mol ratio 1：3 addition reactors, in 65^oC alkalization 2 is little When, then according to alkyl phenol polyoxyethylene polyoxypropylene ether：Chloropropionic acid mol ratio 1：2 addition carboxylating reagent, are warming up to 75^oC continues Continuous 9 hours.After reaction terminates, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification divides and removes aqueous phase, oil phase is used The 10 wt %NaOH aqueous solution are neutralized to pH value 8, and vacuum removal moisture obtains alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid sodium.

Live by four octyl group ammonium chlorides and according to the alkyl phenol polyoxyethylene polyoxypropylene ether carboxylic acid sodium surface of present invention preparation Property agent be dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun Ion：Anionic-nonionic surfactant molar ratio 1: 6 mixes, and obtains compound surfactant 8 a, its composition, Structure is shown in Table 1 a.

【Embodiment 9a】

By the 0.30wt% compound surfactant of embodiment 3 a preparation and 0.15wt% polyacrylamide (molecular weight 26000000) aqueous solution mixes, and obtains a kind of Polymer Used For Oil Displacement-surfactant complex.

Table 1a compound surfactant composition composition and structure

【Embodiment 10 a】Compound surfactant composition interface performance is tested

Measure compound surfactant composition and Shuanghe Oil Field with TX-500C rotating interfacial tensimeter5- 11 series of strata oil water interfacial tensions.Temperature of the measurement is 81^oC, stratum water is NaHCO₃Type, salinity is 7947mg/L, chloride ion content 2002 mg/L, Ca²⁺Content 20 mg/L, Mg²⁺Content 12.2 mg/L, compound surfactant composition consumption is 0.3 wt %.

Table 2a compound surfactant composition and Shuan He oil field5-11 series of strata oil water interfacial tension

Embodiment	Interfacial tension (mN/m)
		1 a	0.0071
2 a	0.0087
		3 a	0.0002
4 a	0.0004
		5 a	0.0059
6 a	0.0068
		7 a	0.0007
8 a	0.0062
		9 a	0.0051

From table 2a, the compound surfactant of embodiment 1a～8a preparation has good boundary for Henan Oil Field Face performance.Embodiment 9a shows, after the surfactant of present invention preparation is compounded with polymer, its interface performance is still good.

The compound surfactant of embodiment 3a preparation is configured to variable concentrations, respectively test and Shuanghe Oil Field5-11 series of strata oil water interfacial tension, the results are shown in Table 3a.

Table 3a variable concentrations surface activator composition 3a and Shuanghe Oil Field5-11 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)	0.006	0.003	0.001	0.0006	0.0004	0.0002

The above results show, compound surfactant composition of the present invention has very high oil for Henan Oil Field crude oil Water termination activity.

With TX-500C rotating interfacial tensimeter measure again embodiment 4 a preparation compound surfactant with Former oil extraction in oil field three factory's oil water interfacial tension.Temperature of the measurement is 80^oC, formation water salinity is 79439mg/L, Ca²⁺Content 592 Mg/L, Mg²⁺Content 2871mg/L, dosage of surfactant is 0.3 wt %.Oil water interfacial tension is 0.003mN/m, shows this The surfactant of invention not only for low mineralization oil reservoir, still has good interface characteristics simultaneously for high temperature and high salt oil deposit Can, have the advantages that the scope of application is wide.

【Embodiment 11a】Compound surfactant composition washing oil aptitude tests

Take Shuanghe Oil Field5-11 series of strata oil-sand, according to oil：Sand=1：4 (weight ratios) are 81^oAging 7 days of C, every 2 is little When stir 5 minutes；Then take out above-mentioned aging after oil-sand 5g, press oil-sand with the surfactant solution of 0.3 wt %：Solution Weight ratio=1：10 mix, and after aging 48 hours under reservoir temperature, with the crude oil in petroleum ether extraction solution, use 50ml Colorimetric cylinder constant volume, spectrophotometer colorimetric analysis at wavelength 430nm.Using calibration curve gauging surface activator solution Central Plains Oil concentration.

Table 4a compound surfactant composition washing oil result

Embodiment	Washing oil rate %
		1 a	63.8
2 a	61.4
		3 a	45.8
4 a	59.2
		5 a	41.5
6 a	53.5
		7 a	58.9
8 a	46.7

【Embodiment 12 a】Compound surfactant composition Oil Displacing Capacity is studied

It is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is 1.5 microns²Rock core on carry out oil displacement test.First Use Shuanghe Oil Field5-11 series of strata stratum water drive produces to oil-free, the compound table of metaideophone 0.3PV (rock pore volume) After the surfactant composition of face, then water drive produces to oil-free, improves oil recovery factor and the results are shown in Table 5 a.

Table 5a compound surfactant composition oil displacement test result

Surfactant sequence number	Improve recovery ratio %
		1 a	6.3
2 a	5.9
		3 a	6.1
4 a	6.7
		5 a	5.2
6 a	5.5
		7 a	6.9
8 a	5.3

【Comparative example 1a】

According to Northwest University's journal (natural science edition) 2 months the 1st phases of volume 30 in 2000, the method such as 28～31 Gong Yu armies Cetyl trimethylammonium bromide (CTAB) and lauryl sodium sulfate (SDS) are configured to mixed system (mol ratio 1：1.5), Test it respectively in 0.3 wt % consumption and Shuanghe Oil Field5-11 series of strata crude oil oil water interfacial tension, washing oil rate and drive Oiliness energy, result is as follows：

Table 6a reference oil displacement agent performance

Interfacial tension (MN/m)	Washing oil rate %	Improve recovery ratio %
			0.03	45.6	2.8

【Comparative example 2a】

According to petroleum gas journal in August, 2007 the 4th phase of volume 29, Huang Hong degree etc. (101～104) method etc. is by 0.01 Wt % cetyl trimethylammonium bromide and 0.02 wt % anion surfactant petroleum sulfonate and 1.8 wt %Na₂CO₃ It is configured to mixed system, test it respectively in 0.3 wt % consumption and Shuanghe Oil Field5-11 series of strata crude oil oil-water interfaces Tension force, washing oil rate and Oil Displacing Capacity, result is as follows：

Table 7a reference oil displacement agent performance

Interfacial tension (MN/m)	Washing oil rate %	Improve recovery ratio %
			0.008	56.3	4.2

【Embodiment 1b】

By APES, NaOH according to mol ratio 1：5 addition reactors, in 100^oC alkalizes 1 hour, then According to APES：Chloromethylsulfonic acid mol ratio 1：4 addition sulfonated reagents, are cooled to 50^oIt is little that C continues reaction 20 When, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification divides and removes aqueous phase, oil phase is water-soluble with 10 wt %NaOH Liquid is neutralized to pH value 8, and vacuum removal moisture obtains APES sodium sulfonate.

APES sulfonate surfactants by hexadecyltrimethylammonium chloride and present invention preparation It is dissolved in water, stir 30 minutes, be configured to the 0.3wt% aqueous solution, then by above-mentioned surfactant according to cation： Anionic-nonionic surfactant molar ratio 1: 0.3 mixes, and obtains compound surfactant composition 1 b, its group Become, structure is shown in Table 1 b.

【Embodiment 2b】

By APES, KOH according to mol ratio 1：1 addition reactor, alkalizes 10 hours in room temperature, then presses According to APES：Sodium isethionate mol ratio 1：3 addition sulfonated reagents, are warming up to 70^oC continuation 10 hours, so Being neutralized to pH value with 5wt% aqueous hydrochloric acid solution afterwards is 2, and stratification divides and removes aqueous phase, oil phase is neutralized to pH value with 10 wt % ammoniacal liquor 8, vacuum removal moisture obtains APES ichthyodin.

By the APES sulfonic acid ammonium surfactant of benzyltriethylammoinium chloride and present invention preparation respectively It is dissolved in the water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to cation：Cloudy Ion-nonionic surfactant mol ratio 1: 0.1 mixes, and obtains compound surfactant composition 2 b, its group Become, structure is shown in Table 1 b.

【Embodiment 3b】

By APES, KOH according to mol ratio 1：1.5 addition reactors, in 30^oC alkalizes 8 hours, then According to APES：Chlorine amyl group sodium sulfonate mol ratio 1：2 addition sulfonated reagents, are warming up to 60^oC continues 15 hours, Then being neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification point removes aqueous phase, and oil phase is with 10 wt %Ca (OH)₂Water Suspension is neutralized to pH value 8, and vacuum removal moisture obtains APES sulfoacid calcium.

APES sulfoacid calcium surfactant by phenyl trimethicone ammonium chloride and according to present invention preparation Be dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun from Son：Anionic-nonionic surfactant molar ratio 1: 1.2 mixes, and obtains compound surfactant 3 b, its composition, Structure is shown in Table 1 b.

【Embodiment 4b】

By APES, NaOH according to mol ratio 1：2 addition reactors, in 50^oC alkalizes 6 hours, then presses According to APES：3- chlorine-2-hydroxyl propanesulfonate mol ratio 1：2 addition sulfonated reagents, are warming up to 80^oIt is little that C continues 8 When, being then neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification point removes aqueous phase, and oil phase is with 10 wt %Mg (OH)₂'s Aqueous suspension is neutralized to pH value 8, and vacuum removal moisture obtains APES sulfonic acid magnesium.

APES sulfonic acid magnesium table by stearyl dimethyl benzyl ammonium chloride and according to present invention preparation Face activating agent is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then presses above-mentioned surfactant According to cation：Anionic-nonionic surfactant molar ratio 1: 2.0 mixes, and obtains compound surfactant 4 b, Its composition, structure are shown in Table 1 b.

【Embodiment 5b】

By APES, NaOH according to mol ratio 1：3 addition reactors, in 60^oC alkalizes 5 hours, then presses According to APES：Monoxone mol ratio 1：1 addition carboxylating reagent, is warming up to 100^oC continues 1 hour, Ran Houyong It is 2 that 5wt% aqueous hydrochloric acid solution is neutralized to pH value, and stratification divides and removes aqueous phase, and oil phase is neutralized with the aqueous suspension of 10 wt %NaOH To pH value 8, vacuum removal moisture obtains APES carboxylic acid sodium.

APES carboxylic acid sodium surface-active by decyl triethylammonium hydroxide and according to present invention preparation Agent is dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun from Son：Anionic-nonionic surfactant molar ratio 1: 10 mixes, and obtains compound surfactant 5 b, its composition, Structure is shown in Table 1 b.

【Embodiment 6b】

By APES, NaOH according to mol ratio 1：4 addition reactors, in 80^oC alkalizes 2 hours, then presses According to APES：Chloropropionic acid mol ratio 1：1.5 addition carboxylating reagent, are cooled to 50^oC continues 18 hours, Ran Houyong It is 2 that 5wt% aqueous hydrochloric acid solution is neutralized to pH value, and stratification point removes aqueous phase, and oil phase is with 10 wt %Ca (OH)₂Aqueous suspension It is neutralized to pH value 8, vacuum removal moisture obtains APES calcium carboxylates.

Live by DTAC and according to the APES calcium carboxylates surface of present invention preparation Property agent be dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun Ion：Anionic-nonionic surfactant molar ratio 1: 0.9 mixes, and obtains compound surfactant 6 b, its group Become, structure is shown in Table 1 b.

【Embodiment 7b】

By APES, KOH according to mol ratio 1：1 addition reactor, alkalizes 10 hours in room temperature, then presses According to APES：Sodium chloroacetate mol ratio 1：3 addition carboxylating reagent, are warming up to 80^oC continues 8 hours, Ran Houyong It is 2 that 5wt% aqueous hydrochloric acid solution is neutralized to pH value, and stratification divides and removes aqueous phase, oil phase is neutralized to pH with the 10 wt %KOH aqueous solution Value 8, vacuum removal moisture obtains APES carboxylic acid potassium.

APES carboxylic acid potassium surface by dioctadecyl dimethyl ammonium chloride and according to present invention preparation Activating agent is dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to Cation：Anionic-nonionic surfactant molar ratio 1: 4 mixes, and obtains compound surfactant 7 b, its group Become, structure is shown in Table 1 b.

【Embodiment 8b】

By APES, NaOH according to mol ratio 1：3 addition reactors, in 65^oC alkalizes 2 hours, then presses According to APES：Chloropropionic acid mol ratio 1：2 addition carboxylating reagent, are warming up to 75^oC continues 9 hours, then uses 5wt% It is 2 that aqueous hydrochloric acid solution is neutralized to pH value, and stratification divides and removes aqueous phase, oil phase is neutralized to pH value 8 with the 10 wt %NaOH aqueous solution, Vacuum removal moisture obtains APES carboxylic acid sodium.

APES carboxyl acid natrium surfactant difference by four octyl group ammonium chlorides and according to present invention preparation It is dissolved in the water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to cation：Cloudy Ion-nonionic surfactant mol ratio 1: 6 mixes, and obtains compound surfactant 8 b, and its composition, structure are shown in Table 1 b.

【Embodiment 9b】

By the 0.30wt% compound surfactant of embodiment 3 b preparation and 0.15wt% polyacrylamide (molecular weight 26000000) aqueous solution mixes, and obtains a kind of Polymer Used For Oil Displacement-surfactant complex.

Table 1b compound surfactant composition composition and structure

【Embodiment 10 b】Compound surfactant composition interface performance is tested

Table 2b compound surfactant composition and Shuan He oil field5-11 series of strata oil water interfacial tension

Embodiment	Interfacial tension (mN/m)
		1 b	0.0080
2 b	0.0096
		3 b	0.0004
4 b	0.0006
		5 b	0.0068
6 b	0.0075
		7 b	0.0011
8 b	0.0075
		9 b	0.0062

From table 2 b, the compound surfactant of embodiment 1 b～8 b preparation has well for Henan Oil Field Interface performance.Embodiment 9 b shows, after the surfactant of present invention preparation is compounded with polymer, its interface performance is still Well.

The compound surfactant of embodiment 3 b preparation is configured to variable concentrations, respectively test and Shuanghe in Henan's oil Field5-11 series of strata oil water interfacial tension, the results are shown in Table 3 b.

Table 3b variable concentrations surface activator composition 3 b and Shuanghe Oil Field5-11 series of strata oil water interfacial tension

Dosage of surfactant (%)	0.01	0.02	0.05	0.1	0.2	0.3
							Interfacial tension (MN/m)	0.009	0.007	0.004	0.002	0.0007	0.0004

With TX-500C rotating interfacial tensimeter measure again embodiment 4 b preparation compound surfactant with Former oil extraction in oil field three factory's oil water interfacial tension.Temperature of the measurement is 80^oC, formation water salinity is 79439mg/L, Ca²⁺Content 592 Mg/L, Mg²⁺Content 2871mg/L, dosage of surfactant is 0.3 wt %.Oil water interfacial tension is 0.003mN/m, shows this The surfactant of invention not only for low mineralization oil reservoir, still has good interface characteristics simultaneously for high temperature and high salt oil deposit Can, have the advantages that the scope of application is wide.

【Embodiment 11 b】Compound surfactant composition washing oil aptitude tests

Take Shuanghe Oil Field5-11 series of strata oil-sand, according to oil：Sand=1：4 (weight ratios) are 81^oAging 7 days of C, every 2 is little When stir 5 minutes；Then take out above-mentioned aging after oil-sand 5g, press oil-sand with the surfactant solution of 0.3 wt %：Solution= 1：10 (weight ratios) mix, and after aging 48 hours under reservoir temperature, with the crude oil in petroleum ether extraction solution, use 50ml Colorimetric cylinder constant volume, spectrophotometer colorimetric analysis at wavelength 430nm.Using calibration curve gauging surface activator solution Central Plains Oil concentration.

Table 4b compound surfactant composition washing oil result

Embodiment	Washing oil rate %
		1 b	62.5
2 b	60.1
		3 b	44.3
4 b	58.1
		5 b	40.8
6 b	52.4
		7 b	57.6
8 b	45.5

【Embodiment 12b】Compound surfactant composition Oil Displacing Capacity is studied

It is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is 1.5 microns²Rock core on carry out oil displacement test.First Use Shuanghe Oil Field, to aqueous 92 wt %, metaideophone 0.3pv's (rock pore volume) is compound for 5-11 series of strata stratum water drive After surface activator composition, water drive to aqueous 100%, improves oil recovery factor and the results are shown in Table 5 b.

Table 5b compound surfactant composition oil displacement test result

Surfactant sequence number	Improve recovery ratio %
		1 b	5.5
2 b	5.1
		3 b	5.2
4 b	5.9
		5 b	4.4
6 b	4.7
		7 b	6.1
8 b	4.5

【Embodiment 1c】

By C₅H₁₁OH, NaOH are according to mol ratio 1：5 and, stir 30 minutes, then add required expoxy propane, in 140^oC reacts 10 hours, then adds required oxirane, in 140^oC reaction is reacted 1 hour again；Then according to C₅H₁₁OH With sodium chloroacetate mol ratio 1：1 addition carboxylating reagent, in 50^oC continues reaction 20 hours, then uses 5wt% aqueous hydrochloric acid solution to neutralize It is 2 to pH value, stratification, divides and removes aqueous phase, oil phase is neutralized to pH value 8 with the 10 wt %NaOH aqueous solution, and vacuum removal moisture obtains To Anionic-nonionic surfactant.

The Anionic-nonionic surfactant of phenyl trimethicone ammonium chloride and present invention preparation is dissolved separately in water In, stir 30 minutes, be configured to the 0.3wt% aqueous solution, then by above-mentioned surfactant according to cation：Anionic-nonionic Surfactant molar ratio 1: 10 mixes, and obtains surface activator composition 1 c, and its composition, structure are shown in Table 1 c.

【Embodiment 2c】

By fatty alcohol C₂₀H₄₁OH, KOH are according to mol ratio 1：2.5, stirring adds required expoxy propane after 30 minutes, in 100^oC reacts 10 hours；Then add the desired amount of oxirane, in 140^oC reacts 10 hours, then according to fatty alcohol polyoxy Propylene APEO：ClCH₂CH₂COOH mol ratio 1：1.5 addition carboxylating reagent, in 100^oC continues reaction 1 hour, Ran Houyong It is 2 that 5wt% aqueous hydrochloric acid solution is neutralized to pH value, and stratification divides and removes aqueous phase, oil phase is neutralized to pH with the 10 wt %KOH aqueous solution Value 8, vacuum removal moisture obtains Anionic-nonionic surfactant fatty alcohol polyoxypropylene APEO carboxylic acid potassium.

Fatty alcohol polyoxypropylene APEO carboxylic acid potassium surface by decyl triethylammonium hydroxide and present invention preparation Activating agent is dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to Cation：Anionic-nonionic surfactant molar ratio 1: 7 mixes, and obtains surface activator composition 2 c, its group Become, structure is shown in Table 1 c.

【Embodiment 3c】

By fatty alcohol C₁₄H₂₉OH, NaOH are according to mol ratio 1：4, stirring adds required expoxy propane after 30 minutes, in 140^oC reacts 5 hours；Then add required oxirane, in 160^oC reacts 6 hours；Then according to fatty alcohol polyoxypropylene APEO：ClCH₂COOH mol ratio 1：1.5 addition carboxylating reagent, in 70^oC continues reaction 8 hours, then uses 5wt% hydrochloric acid It is 2 that the aqueous solution is neutralized to pH value, and stratification point removes aqueous phase, and oil phase is with 10 wt %Mg (OH)₂Aqueous suspension is neutralized to pH value 8, vacuum removal moisture obtains Anionic-nonionic surfactant fatty alcohol polyoxypropylene APEO carboxylic acid potassium.

Fatty alcohol polyoxypropylene APEO carboxylic acid potassium surfactant by etamon chloride and present invention preparation Be dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun from Son：Anionic-nonionic surfactant molar ratio 1: 1.3 mixes, and obtains surface activator composition 3 c, its composition, Structure is shown in Table 1 c.

【Embodiment 4c】

By fatty alcohol C₁₆H₃₃OH, NaOH are according to mol ratio 1：5 and, stir 30 minutes, then add required epoxy third Alkane, in 140^oC reacts 1 hour, then adds required oxirane, in 140^oC reaction is reacted 4 hours again；Then according to fat Fat alcohol polyoxyethylene polyoxypropylene ether：ClCH₂COOH mol ratio 1：2 addition carboxylating reagent, in 80^oC continues reaction 5 hours, then Being neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification point removes aqueous phase, and oil phase is with 10 wt %Ca (OH)₂Aqueous suspension It is neutralized to pH value 8, vacuum removal moisture obtains Anionic-nonionic surfactant fatty alcohol polyoxypropylene APEO carboxylic Sour calcium.

Lived in the fatty alcohol polyoxypropylene APEO calcium carboxylates surface of benzyltriethylammoinium chloride and present invention preparation Property agent be dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun Ion：Anionic-nonionic surfactant molar ratio 1: 5 mixes, and obtains surface activator composition 4 c, its composition, Structure is shown in Table 1 c.

【Embodiment 5c】

By fatty alcohol C₁₀H₂₁OH, NaOH are according to mol ratio 1：5, stirring adds required expoxy propane after 30 minutes, in 140^oC reacts 10 hours, then adds required oxirane, in 150^oC reacts 8 hours again；Then according to fatty alcohol polyoxy Propylene APEO：ClCH₂COONa mol ratio 1：2 addition carboxylating reagent, are then neutralized to pH value with 5wt% aqueous hydrochloric acid solution For 2, stratification, point removes aqueous phase, oil phase is neutralized to pH value 8 with 10 wt % ammoniacal liquor, vacuum removal moisture obtains anion-non- Ionic surface active agent fatty alcohol polyoxypropylene APEO carboxylic acid ammonium.

Fatty alcohol polyoxypropylene APEO carboxylic acid ammonium surfactant by tetrabutylammonium chloride and present invention preparation Be dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun from Son：Anionic-nonionic surfactant molar ratio 1: 0.4 mixes, and obtains surface activator composition 5 c, its composition, Structure is shown in Table 1 c.

【Embodiment 6c】

By fatty alcohol C₁₈H₃₇OH, NaOH are according to mol ratio 1：5, stirring adds required expoxy propane after 30 minutes, in 140^oC reacts 10 hours, then adds required oxirane, in 160^oC reacts 8 hours；Then according to fatty alcohol polyoxypropylene APEO：Chloromethylsulfonic acid mol ratio 1：4 addition sulfonated reagents, in 75^oC continues reaction 8 hours, then uses 5wt% hydrochloric acid It is 2 that the aqueous solution is neutralized to pH value, and stratification divides and removes aqueous phase, oil phase is neutralized to pH value 8, vacuum with the 10 wt %NaOH aqueous solution Removing moisture obtains Anionic-nonionic surfactant fatty alcohol polyoxypropylene sodium sulfonate of ethoxylated.

Fatty alcohol polyoxypropylene sodium sulfonate of ethoxylated surfactant by four octyl group ammonium chlorides and present invention preparation Be dissolved in water, stir 30 minutes, be configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant according to sun from Son：Anionic-nonionic surfactant molar ratio 1: 1.6 mixes, and obtains surface activator composition 6 c, its composition, Structure is shown in Table 1 c.

【Embodiment 7c】

By fatty alcohol C₁₂H₂₃OH, NaOH are according to mol ratio 1：4, stirring adds required expoxy propane after 30 minutes, in 140^oC reacts 7 hours, then adds required oxirane, in 160^oC reacts 5 hours；Then according to fatty alcohol polyoxypropylene APEO：Sodium isethionate mol ratio 1：3 addition sulfonated reagents, in 80^oC continues reaction 8 hours, then uses 5wt% salt It is 2 that aqueous acid is neutralized to pH value, and stratification point removes aqueous phase, and oil phase is with 10 wt %Ca (OH)₂Aqueous suspension is neutralized to pH Value 8, vacuum removal moisture obtains Anionic-nonionic surfactant fatty alcohol polyoxypropylene APEO sulfoacid calcium.

Fatty alcohol polyoxypropylene APEO sulfoacid calcium table by hexadecyltrimethylammonium chloride and present invention preparation Face activating agent is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then presses above-mentioned surfactant According to cation：Anionic-nonionic surfactant molar ratio 1: 2 mixes, and obtains surface activator composition 7 c, its Composition, structure are shown in Table 1 c.

【Embodiment 8c】

By fatty alcohol C₈H₁₇OH, NaOH are according to mol ratio 1：4, stirring adds required expoxy propane after 30 minutes, in 140^oC reacts 4 hours, then adds required oxirane, in 160^oC reacts 2 hours；Then according to fatty alcohol polyoxypropylene APEO：3- chlorine-2-hydroxyl propanesulfonate mol ratio 1：4 addition sulfonated reagents, in 80^oC continues reaction 8 hours, then Being neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification point removes aqueous phase, and oil phase is with 10 wt %Mg (OH)₂Aqueous suspension It is neutralized to pH value 8, vacuum removal moisture obtains Anionic-nonionic surfactant fatty alcohol polyoxypropylene APEO sulphur Sour magnesium.

Fatty alcohol polyoxypropylene APEO sulfonic acid magnesium by dioctadecyl dimethyl ammonium chloride and present invention preparation Surfactant is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then by above-mentioned surfactant According to cation：Anionic-nonionic surfactant molar ratio 1: 3 mixes, and obtains surface activator composition 8 c, Its composition, structure are shown in Table 1 c.

【Embodiment 9c】

By fatty alcohol C₁₈H₃₅OH, NaOH are according to mol ratio 1：4, stirring adds required expoxy propane after 30 minutes, in 140^oC reacts 5 hours, then adds required oxirane, in 160^oC reacts 5 hours；Then according to fatty alcohol polyoxypropylene APEO：Chlorine amyl group sodium sulfonate mol ratio 1：4 addition sulfonated reagents, in 80^oC continues reaction 10 hours, then uses 5wt% It is 2 that aqueous hydrochloric acid solution is neutralized to pH value, and stratification divides and removes aqueous phase, oil phase is neutralized to pH value 8 with the 10 wt %NaOH aqueous solution, Vacuum removal moisture obtains Anionic-nonionic surfactant fatty alcohol polyoxypropylene sodium sulfonate of ethoxylated.

Fatty alcohol polyoxypropylene sodium sulfonate of ethoxylated table by DTAC and present invention preparation Face activating agent is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then presses above-mentioned surfactant According to cation：Anionic-nonionic surfactant molar ratio 1: 0.1 mixes, and obtains surface activator composition 9 c, Its composition, structure are shown in Table 1 c.

【Embodiment 10 c】

By fatty alcohol C₁₈H₃₃OH, NaOH are according to mol ratio 1：5, stirring adds required expoxy propane after 30 minutes, in 140^oC reacts 3 hours, then adds required oxirane, in 160^oC reacts 3 hours；Then according to fatty alcohol polyoxypropylene APEO：3- chlorine-2-hydroxyl propanesulfonate mol ratio 1：4 addition sulfonated reagents, in 80^oC continues reaction 10 hours, then Being neutralized to pH value with 5wt% aqueous hydrochloric acid solution is 2, and stratification divides and removes aqueous phase, oil phase is neutralized to the 10 wt %NaOH aqueous solution PH value 8, vacuum removal moisture obtains Anionic-nonionic surfactant fatty alcohol polyoxypropylene sodium sulfonate of ethoxylated.

Fatty alcohol polyoxypropylene polyoxyethylene ether sulfonic acid by stearyl dimethyl benzyl ammonium chloride and present invention preparation Natrium surfactant is dissolved in water, and stirs 30 minutes, is configured to the 0.3 wt % aqueous solution, then by above-mentioned surface-active Agent is according to cation：Anionic-nonionic surfactant molar ratio 1: 4 mixes, and obtains surface activator composition 10 C, its composition, structure are shown in Table 1 c.

【Embodiment 11c】

By the 0.30wt% compound surfactant of embodiment 10c preparation and 0.15wt% polyacrylamide (molecular weight 26000000) aqueous solution mixes, and obtains a kind of Polymer Used For Oil Displacement-surfactant complex.

Table 1c surface activator composition composition and structure

【Embodiment 12c】Surface activator composition interface performance is tested

Measure surfactant oil displacement composition and Shuanghe Oil Field with TX-500C rotating interfacial tensimeter5- 11 series of strata oil water interfacial tensions.Surface activator composition consumption：0.3 wt %, temperature of the measurement is 81^oC, stratum water is NaHCO₃ Type, salinity is 7947mg/L, chloride ion content 2002 mg/L, Ca²⁺Content 20 mg/L, Mg²⁺Content 12.2 mg/L.

Table 2c surface activator composition and Shuan He oil field5-11 series of strata oil water interfacial tension

Embodiment	Interfacial tension (mN/m)
		1 c	0.0075
2 c	0.0062
		3 c	0.0040
4 c	0.0003
		5 c	0.0075
6 c	0.0005
		7 c	0.0008
8 c	0.0054
		9 c	0.0006
10 c	0.0001
		11 c	0.0008

From table 2 c, the compound surfactant of embodiment 1 c～10 c preparation has well for Henan Oil Field Interface performance.Embodiment 11 c shows, after the surfactant of present invention preparation is compounded with polymer, its interface performance is still Well.

The surface activator composition of embodiment 10 c preparation is configured to variable concentrations, respectively test and Shuanghe in Henan's oil Field5-11 series of strata oil water interfacial tension, the results are shown in Table 3 c.

Table 3c variable concentrations surface activator composition 10 c and Shuanghe Oil Field5-11 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	0.002	0.0003	0.0002	0.0001

With TX-500C rotating interfacial tensimeter measure again embodiment 8 c preparation compound surfactant with Former oil extraction in oil field three factory's oil water interfacial tension.Temperature of the measurement is 80^oC, formation water salinity is 79439mg/L, Ca²⁺Content 592 Mg/L, Mg²⁺Content 2871mg/L, dosage of surfactant is 0.3 wt %.Oil water interfacial tension is 0.001mN/m, shows this The surfactant of invention not only for low mineralization oil reservoir, still has good interface characteristics simultaneously for high temperature and high salt oil deposit Can, have the advantages that the scope of application is wide.

【Embodiment 13 c】Surface activator composition washing oil aptitude tests

Take Shuanghe Oil Field5-11 series of strata oil-sand, according to oil：Sand=1：4 (weight ratios) are 81^oAging 7 days of C, every 2 is little When stir 5 minutes；Then take out above-mentioned aging after oil-sand 5g, press oil with the surface activator composition solution of 0.3 wt % Sand：Solution=1：10 (weight ratios) mix, after aging 48 hours under reservoir temperature, with former in petroleum ether extraction solution Oil, with 50ml colorimetric cylinder constant volume, spectrophotometer colorimetric analysis at wavelength 430nm.Using calibration curve gauging surface activity Agent solution Central Plains oil concentration.

Table 4c surface activator composition washing oil result

Embodiment	Washing oil rate %
		1 c	64.0
2 c	59.4
		3 c	55.9
4 c	65.1
		5 c	52.9
6 c	60.8
		7 c	62.3
8 c	63.0
		9 c	64.2
10 c	67.6

【Embodiment 14 c】Surface activator composition Oil Displacing Capacity is studied

It is 30 centimetres in length, a diameter of 2.5 centimetres, permeability is 1.5 microns²Rock core on carry out oil displacement test.First Use Shuanghe Oil Field5-11 series of strata stratum water drive is to oil-free, the surfactant group of metaideophone 0.3PV (rock pore volume) After compound, then water drive, to oil-free, improves oil recovery factor and the results are shown in Table 5 c.

Table 5c surface activator composition oil displacement test result

Embodiment	Improve recovery ratio %
		1 c	6.9
2 c	6.2
		3 c	6.0
4 c	8.1
		5 c	5.3
6 c	7.2
		7 c	8.0
8 c	7.4
		9 c	8.8
10 c	10.3

Claims

1. compound surfactant composition, including cationic surfactant and Anionic-nonionic surfactant, institute The mol ratio of the cationic surfactant stated and Anionic-nonionic surfactant is 1: 0.01～1: 100, its middle-jiao yang, function of the spleen and stomach from Sub- surfactant is selected from least one in quaternary ammonium salt or quaternary amine alkali, and Anionic-nonionic surfactant is by following molecule Formula (A), (B), (C) or (D) represents：

Wherein M is any one in alkali metal, alkaline-earth metal or ammonium root, and R is H, C₁～C₂₀Alkyl, C₆～C₁₀Aryl or Any one in substituted aryl, m and n independence value is any one integer or decimal in 0～100；R ' is C₁～C₁₀'s Alkylidene；R is M and SO in general molecular formula₃Group or the mol ratio of M and COO group, the r=1 when M is for alkali metal or ammonium root, When M is for alkaline-earth metal, r=0.5；R₁For C₁～C₅₀Alkyl or alkenyl.

2. according to claim 1 compound surfactant composition it is characterised in that m>0；For general molecular formula (C) and (D) the optional m further of the Anionic-nonionic surfactant shown in>0 and n>0.

3. compound surfactant composition according to claim 1 or claim 2 is it is characterised in that described cation surface activating Agent is selected from least one in tetra-alkyl ammonium chloride or tetra-alkyl ammonium hydroxide.

4. according to compound surfactant composition described in claim 1 or 2 it is characterised in that described cationic surfactant Carbon number in molecule is 4～40.

5. compound surfactant composition according to claim 1 or claim 2 is it is characterised in that R is H, C₅～C₁₅Alkyl.

6. compound surfactant composition according to claim 1 or claim 2 is it is characterised in that R₁For C₅～C₂₀Alkyl, alkene Base.

7. compound surfactant composition according to claim 1 or claim 2 is it is characterised in that R ' is C₁～C₅Alkylidene.

8. according to claim 1 compound surfactant composition it is characterised in that m and n is any one in 0～50 Individual integer or decimal.

9. the preparation method of compound surfactant composition described in claim 1, comprises the following steps：

A) by alkyl phenol polyoxyethylene polyoxypropylene ether, catalyst according to mol ratio 1:(1～5) add reactor, room temperature～ 100 DEG C alkalize 1～10 hour, then add sulfonated reagent or carboxylating reagent, wherein alkyl phenol polyoxyethylene polyoxypropylene ether：Sulphur Changing reagent or the mol ratio of carboxylating reagent is 1：(1～4), is warming up to 50～100 DEG C and reacts 1～20 hour, post-treated alkane Base phenol polyoxyethylene polyoxypropylene ether sulfonate or alkyl phenol polyoxyethylene polyoxypropylene ether carboxylate；Described catalyst is alkali Property catalyst；Described sulfonated reagent is hydroxyl sulfoacid and its salt or halogenosulfonic acid and its salt；Described carboxylating reagent is halo Carboxylic acid and its salt；

B) by cationic surfactant and the Anionic-nonionic surfactant that obtains according to step a) is dissolved separately in In water, then mix according to mol ratio (1: 0.1)～(1: 10), obtain described surface activator composition.

10. the preparation method of compound surfactant composition according to claim 9, is characterized in that described post processing Adjust to pH=1～3 including with acidic aqueous solution, carry out water-oil separating, oil phase adds alkali lye to be neutralized to pH=7～9.

The preparation method of 11. compound surfactant compositions according to claim 9, is characterized in that described base catalysis Agent is alkali metal hydroxide.

12. according to claim 11 compound surfactant composition preparation method, it is characterized in that described alkali metal Hydroxide is at least one in NaOH or KOH.

Application in tertiary oil recovery for the compound surfactant composition any one of 13. claims 1 to 8.