CN103965853A - Combined surfactant and its preparation method - Google Patents
Combined surfactant and its preparation method Download PDFInfo
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- CN103965853A CN103965853A CN201310044455.9A CN201310044455A CN103965853A CN 103965853 A CN103965853 A CN 103965853A CN 201310044455 A CN201310044455 A CN 201310044455A CN 103965853 A CN103965853 A CN 103965853A
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Abstract
The invention relates to a combined surfactant and its preparation method, and mainly solves the problems of bad temperature resistance, low interface activity, and failing at reaching 10<-3>mN/m ultralow interface tension force especially at low concentration existing in surfactants used as the main composition of oil displacement agent systems in the prior art. The combined surfactant comprises, by mass, 1 part of a zwitterionic surfactant, 0.01-50 parts of an anionic-nonionic surfactant and 0.1-90 parts of water. The combined surfactant can well solve the problems, and can be used in the tertiary oil recovery production of oilfields. The molecular formula of each of the above surfactants is shown in the specification.
Description
Technical field
The present invention relates to a kind of combined surfactant and preparation method thereof.
Background technology
Along with the increase of world energy sources demand, the rational exploitation and utilization of oil has caused people's very big attention, in the today of being becoming tight energy day, improving recovery ratio has become the key subjects of oil production research, after water drive, approximately there is 2/3 oil to be trapped in capillary channel thinner or that larynx footpath is narrower, in high dispersion state, because of the about 30mN/m of the interfacial tension between profit, want this part oil of displacement, depend merely on increase pressure reduction difficulty very large.Be 9806.7Kpa because driving required pressure reduction, and pressure reduction is only 196.1～392.3Kpa when water filling, much smaller than driving pressure differential.
Chemical flooding is the main method of tertiary oil recovery, and surfactant flooding occupies critical role in chemical flooding, and no matter tensio-active agent is as host or as the auxiliary agent displacement of reservoir oil, all plays immeasurable effect to increasing substantially recovery ratio.The dominant mechanism that uses tensio-active agent can improve oil recovery factor is: enter after high water-cut stage in oil field, surplus oil with discontinuous oil film by trap in the hole of reservoir rocks, two main power that act on oil droplet are viscaps, if select suitable surfactant system, reduce the interfacial tension between profit, make the interfacial tension between oil bearing reservoir profit be down to lower or ultralow value (10 from 20～30mN/m
-3～10
-4mN/m), just can reduce oil droplet when surplus oil is moved and be out of shape the resistance bringing, thereby significantly improve oil displacement efficiency.Surfactant flooding improves oil recovery factor and depends mainly on sweep efficiency and the oil displacement efficiency of tensio-active agent in oil reservoir.
Be Er=E υ Ed
In formula: Er represents recovery ratio, %; E υ represents sweep efficiency, %; Ed represents oil displacement efficiency, %.
Therefore, improving Er must start with from improving Ev and Ed.Promoting agent (comprising tensio-active agent and alkali), owing to having the effects such as the oil water interfacial tension of reduction, can improve Ed (oil displacement efficiency).This effect can be described by combined effect parameter capillary number (N):
Ｅｄ∝Ｎ
N=motivating force/viscous force ∝ μ υ/Y
ow
In formula: μ represents to inject phase viscosity; υ represents to inject phase flow stream velocity; Y
owrepresent interfacial tension between profit.
Practice proves, effectively reduce residual oil saturation, capillary number must be improved to 3～4 orders of magnitude.Due to oil reservoir injection rate and pressure limited, therefore depend merely on that to improve μ and υ be inadequate, but can be by oil water interfacial tension Y
owreduce by 3 or the higher order of magnitude, thereby greatly improve capillary number and Ed (oil displacement efficiency) is significantly improved, this is also the main oil-displacement mechanism of promoting agent.And to improve sweep efficiency, and main way is the mobility that reduces displacing fluid, this point can realize by adding polymkeric substance to increase displacing fluid viscosity.Adopt in operation three, use ASP ternary built composite reservoir oil displacement system, by the ultra low interfacial tension that adds tensio-active agent can obtain between profit, displacement of reservoir oil effect (Ed) rate is increased, improve sweep efficiency (Ev) by injection of polymer to increase injection liquid viscosity, inject alkali to reduce the absorption of tensio-active agent.Make full use of the synergistic combination effect that ASP is useful, improve oil recovery factor (Er).
Surfactant for EOR has anion surfactant at present, as sulfonated petro-leum, alkylsulfonate, alkenyl sulphonate and sulfonated lignin etc.What use cats product also has a report, as Chinese patent CN 1528853, CN 1817431, CN 1066137 etc. have reported that bisamide type is cationic in succession, fluorine-containing cationic type and containing pyridyl cation Gemini surfactant, but because positively charged ion has, absorption loss is large, high in cost of production shortcoming, has limited its use at Oil Field.The microemulsion flooding of foreign study report, as Kraft etc. has investigated at water-mineralizing degree under the condition up to 220 g/L, microemulsion system phase, transformation temperature (PIT) rule and the interfacial tension of 5% Soxylat A 25-7 alkyl sodium carboxymethyl, result shows, this tensio-active agent does not substantially decompose in 3 weeks at 95 DEG C, adsorption losses 0.4 mg/g, and without obvious chromatographic separation, but because tensio-active agent usage quantity is large, cost is high, microemulsion flooding is restricted as oil-displacing agent.
The application of combined surfactant in tertiary oil recovery is mainly negatively charged ion and nonionic combined surfactant, in use often need to add additive alkali, to reach ultralow oil/water interfacial tension, but because non-ionic heat resistance is poor, often ineffective in the time of high temperature.After the combination of different anions tensio-active agent, also there is report as surfactant oil displacement, as Chinese patent CN1458219A discloses the Surfactant/Polymer binary ultra low interfacial tension combination flooding formula that a kind of tertiary oil recovery is applied, the tensio-active agent wherein using is sulfonated petro-leum or adds thinner taking sulfonated petro-leum as host and the combined surfactant of other tensio-active agent combination, 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%, this surface-active agent poor activity, oil displacement efficiency is low, surfactant system is too complicated.(the 3rd phase the 20th volume in 2002 such as Zhang Xueqin, colloid and polymkeric substance, P1～5) study the formation micella ability of anionic (SDS) and zwitterionics lauroylamidopropyl betaine (LMB) and reduced the synergistic function of surface tension ability, find that SDS and the synergism in 7:3 to 3:7 scope of LMB mass ratio are remarkable, it is that surface tension and micelle-forming concentration decline that the inorganic salt of lower concentration can make tensio-active agent molectron.
Above-mentioned research does not relate to the combined system of zwitter-ion and anion-nonionic tensio-active agent, although negatively charged ion/zwitter-ion combined surfactant that SDS/LMB forms has certain effect for reduction surface tension, synergy, but result of study does not relate to performances such as reducing oil water interfacial tension, may cannot estimate the application of high-temperature low salt oil reservoir yet.Therefore,, for the LOW PERMEABILITY RESERVOIR of high-temperature low salt, invented one Stability Analysis of Structures under formation temperature, and can form 10 with crude oil
-3～10
-4the combined surfactant of mN/m ultra low interfacial tension, and preparation tensio-active agent water both can be tap water and also can be salt brine solution, usage quantity that can fresh-water-saving.This combined surfactant that is applicable to high-temperature low salt LOW PERMEABILITY RESERVOIR and preparation method thereof just of the present invention.
Summary of the invention
One of technical problem to be solved by this invention is to have that heat resistance is poor, interfacial activity is low, especially cannot reach 10 when the lower concentration as the tensio-active agent of oil-displacing agent system chief component in prior art
-3the problem of mN/m ultra low interfacial tension value, provides a kind of new combined surfactant.For high-temperature low salt LOW PERMEABILITY RESERVOIR, with the aqueous solution of this combined surfactant preparation, in the concentration range of 0.005 ~ 0.3wt%, crude oil is formed to 10
-3～10
-4mN/m ultra low interfacial tension, thus the oil displacement efficiency of oil-displacing agent system improved.
Two of technical problem to be solved by this invention is to provide the preparation method of the described combined surfactant of one of above-mentioned technical problem.
In order one of to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of combined surfactant, comprises following component in mass fraction:
The zwitterionics of (1) 1 part;
The anion-nonionic tensio-active agent of (2) 0.01 ~ 50 parts;
The water of (3) 0.1 ~ 90 parts;
Wherein the general molecular formula of (1), (2) component is:
（1）
（2）
In formula, R
1and R
5be selected from independently of one another C
8～C
30alkyl, by C
4～C
20the phenyl that alkyl replaces; A and c are the adduction number of the PO of propoxy-group, and span independent of one another is 1～15; B and d are the adduction number of ethoxy group EO, and value independent of one another is 1～30; R
2and R
3be selected from independently of one another C
1～C
5alkyl or hydroxyalkyl, R
4and R
6be selected from independently of one another C
1～C
5alkylidene group or hydroxyl substituted alkylene; X
-for-COO
-or-SO
3 -, Y is-COOM or-SO
3n, M and N are selected from basic metal or ammonium independently of one another.
In technique scheme, R
1and R
5independently of one another preferably from C
12～C
24alkyl or by C
8～C
12the phenyl that alkyl replaces; A and c preferably value independent of one another is that 2～12, b and d preferably value independent of one another is 1～10; R
2,r
3be preferably independently of one another methyl, ethyl or hydroxyethyl, R
4and R
6independently of one another preferably from C
1～C
3alkylidene group or hydroxyl replace propylidene; M and N are preferably sodium or potassium, more preferably sodium independently of one another.
The crucial effective constituent of combined surfactant of the present invention is (1) and (2), those skilled in the art will know that, consider for the ease of aspects such as transport and storage or on-the-spot uses, can adopt various supply forms, for example water-free solid-state form, or moisture solid-state form, or moisture paste form, or aqueous solution form; Aqueous solution form comprises that water is made into the form of concentrated solution, is directly made into the solution form of on-the-spot displacement of reservoir oil desired concn, and the solution that for example crucial active constituent content is 0.005～0.3wt% is by weight the comparatively suitable form of the on-the-spot displacement of reservoir oil.Wherein, water not being had to particular requirement, can be deionized water, tap water, and oil field stratum water or oilfield injection water, can also be inorganic salt solution, for example, the inorganic salt solution of 1 ~ 30wt%, the especially inorganic salt solution of 1 ~ 15wt%; Inorganic salt are preferably at least one in sodium-chlor, Repone K or ammonium chloride, more preferably at least one in sodium-chlor or Repone K.
Combined surfactant of the present invention, can also comprise the displacement of reservoir oil component that this area is conventional, for example Polymer Used For Oil Displacement, displacement of reservoir oil foaming agent, the displacement of reservoir oil comprises the small molecules organic amines such as sodium hydroxide, sodium carbonate, sodium bicarbonate, diethanolamine or trolamine with solid or liquid base, organic molecule auxiliary agent comprises short chain fatty alcohol, low carbon chain ketone, DMSO etc.
For solve the problems of the technologies described above two, the technical solution adopted in the present invention is as follows: the preparation method of combined surfactant described in technique scheme, comprises the following steps:
1) preparation of zwitterionics:
I. be 1 by alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether in molar ratio with sulfur oxychloride: mix (1 ~ 3), under 50 ~ 120 DEG C of conditions of temperature of reaction, react 3 ~ 15 hours, after reaction finishes, obtain after treatment chloro alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether;
Ii. the chloro alkyl alcohol of synthesized in i or alkylphenol polyoxyethylene polyoxypropylene ether are mixed with dialkylamine, water and low-carbon alcohol, be 40 ~ 100 DEG C in temperature and carry out tertiary amination reaction 3 ~ 20 hours, continue to drip the aqueous solution of sulphonating agent or carboxylating agent, dropwise and continue at reflux temperature and carry out quaterisation 5 ~ 30 hours, steam low-carbon alcohol and excessive dialkylamine, removal salt, obtain alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether carboxylic acid or sulfonate betaine; Wherein, dialkylamine is dimethylamine, diethanolamine, and sulphonating agent is an alkali metal salt of 3-chlorine-2-hydroxyl propanesulfonic acid, an alkali metal salt or the PS of 2-monochloroethane sulfonic acid, and carboxylating agent is Mono Chloro Acetic Acid or chloroacetic an alkali metal salt, and low-carbon alcohol is selected from C
1~ C
3fatty alcohol, the mol ratio of chloro alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether, dialkylamine and sulphonating agent or carboxylating agent is 1: (1～3): (1～3);
2) preparation of anion-nonionic tensio-active agent:
Alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether are mixed by required proportioning with sulphonating agent or carboxylating agent, alkali metal hydroxide solid and solvent, at 50～130 DEG C of temperature of reaction, react 3～15 hours, after reaction finishes, obtain alkane alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether sulfonate or carboxylate salt through aftertreatment; Wherein, the mol ratio of alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether, sulfonated reagent or carboxylation reagent and alkali metal hydroxide is 1: (1～4): (1～5), sulphonating agent is 3-chlorine-2-hydroxyl propanesulfonic acid an alkali metal salt, 2-monochloroethane sulfonic acid alkali metal salts or 1,3-N-morpholinopropanesulfonic acid lactone, carboxylating agent is Mono Chloro Acetic Acid or Mono Chloro Acetic Acid an alkali metal salt, and solvent is selected from least one in acetone, benzene, toluene or dimethylbenzene;
3) alkyl alcohol of aequum or alkylphenol polyoxyethylene polyoxypropylene ether carboxylic acid or sulfonate betaine, alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether sulfonate or carboxylate salt, water and low-carbon alcohol are added in mixing vessel, being warming up to 40 ~ 100 DEG C stirs 1～4 hour, pressure reducing and steaming low-carbon alcohol, obtains required combined surfactant; In mass fraction, the proportioning of alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether carboxylic acid or sulfonate betaine, alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether sulfonate or carboxylate salt, low-carbon alcohol and water is 1 part: 0.01 ~ 50 part: 0.1 ~ 90 part: 0.1 ~ 90 part, low-carbon alcohol is selected from C
1~ C
3fatty alcohol.
In technique scheme, 1) in i step the mol ratio of alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether and sulfur oxychloride be preferably 1: 1.2～2.0, preferably 79 DEG C of temperature of reaction, the reaction times is preferably 4 ~ 10 hours; 1) ii sulphonating agent is preferably 3-chlorine-2-hydroxyl propanesulfonate or 2-monochloroethane sodium sulfonate, carboxylating agent is preferably sodium chloroacetate, low-carbon alcohol is preferably to ethanol, n-propyl alcohol or Virahol, the mol ratio of chloro alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether, dialkylamine and sulphonating agent or carboxylating agent is preferably 1: 1.1～and 1.8: 1～2, tertiary amine temperature of reaction is preferably 65 ~ 85 DEG C, time and is preferably 5 ~ 15 hours, and quaterisation is preferably reflux temperature, time and is preferably 6 ~ 20 hours; 2) in step, the mol ratio of alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether, sulfonated reagent or carboxylating agent and alkali metal hydroxide is preferably 1:: (1～1.5): (1.5～3.0), temperature of reaction is preferably 50～110 DEG C, and the reaction times is preferably 5～12 hours.
Combined surfactant prepared by the present invention, after anion-nonionic and zwitterionics combination, can present the advantage such as decline, solubilising effect of surface-active increase, micelle-forming concentration.This is because the hydrophilic group in the moon-nonsurfactant and the positive charge in zwitterionics exist electrostatic attraction effect, can reduce the repulsive interaction between solution surface like charges, and also has certain hydrophobic interaction between the hydrophobic group hydrocarbon chain of the two, impel different surfaces active agent molecule to take arrangement mode more closely, thereby there is higher surfactivity, simultaneously due to strong electrical function, two tensio-active agents can form after new " associated complex ", in solution, more easily form micella, thereby lower the micelle-forming concentration of combined surfactant, and the introducing of nonionic polyoxyalkylene group in the moon-nonsurfactant both can increase the wetting ability of combined surfactant, simultaneously because steric effect has weakened strong interaction between composition to avoid the liquid-crystalization of tensio-active agent, the generation of the phenomenons such as precipitation.Two tensio-active agents in combined surfactant are ionic, and composition also shows the feature of ionic surface active agent, i.e. good heat resistance.Therefore, this tensio-active agent had both had good heat-resisting property, had again excellent interfacial activity, can solve tensio-active agent and cannot reach 10 in the time of lower concentration
-3the problem of mN/m ultra low interfacial tension value, makes tensio-active agent in the migration process of down-hole, still can keep ultralow oil water interfacial tension, thereby can improve oil displacement efficiency even if concentration is lower.
In the present invention, relate to the occasion of the concentration of combined surfactant, all refer to contain the total concn of (1) and (2) in technique scheme.
Adopt the combined surfactant prepared of the present invention, by percentage to the quality, in the scope that consumption is 0.005～0.3wt%, can be used for formation temperature and be 60 ~ 90 DEG C, salinity 500～10000 mg/litre, Mg
2++ Ca
2+the on-the-spot water of Jiangsu oilfield and the crude oil of 10 ~ 100 mg/litre, measured the dynamic interface tension value between this water phase surfactant mixture and crude oil, can reach 10
-3～10
-4the ultra low interfacial tension of mN/m, has obtained good technique effect.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of alkylphenol polyoxyethylene polyoxypropylene ether sulfonate type trimethyl-glycine.
Fig. 2 is the infrared spectrogram of alkyl alcohol polyoxyethylene polyoxypropylene ether hydroxy-propanesulfonic acid salt.
Application U.S. Nicolet-5700 spectrograph, adopts liquid-film method or pressed disc method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), determine the chemical structure of sample, to reach the Infrared Characterization to compound of the present invention.As shown in Figure 1,1600cm
-1left and right place is phenyl ring, 1250cm
-1place is aryl oxide C-O-C, 1060 ~ 11700cm
-1there are the characteristic peak of ehter bond in ethylene oxide propylene oxide, 1080-~ 1190cm in place
-1place is the stretching vibration of C-N, 1179,1030,620 cm
-1for-SO
3absorption peak, prove that the synthetic product of the present invention is alkylphenol polyethenoxy ether polyethenoxy ether sulphonate type beet alkali surface activator really.As shown in Figure 2, wave number 2914cm
-1, 2860cm
-1for methyl on alkyl chain and the flexible characteristic peak of methylene radical C-H, at wave number 726 cm
-1there is the characteristic peak waving in chain alkyl C-H face; 1350cm
-1peak, left and right is the characteristic peak of sulfonate, is because antisymmetric stretching vibration and the vibration of skeleton carbon of S=O cause; Wave number 1108cm
-1for the absorption peak of C-O-C key, prove that the synthetic product of the present invention is alkyl alcohol polyoxyethylene polyoxypropylene ether sulfonate type the moon-nonsurfactant really.
Fig. 3 is the interfacial tension figure of different concns oilfield injection water combined surfactant solution to dewatered oil.
Fig. 4 is that the oil water interfacial tension of 0.1wt% oilfield injection water combined surfactant solution is with the variation diagram of digestion time.
Fig. 5 is the interfacial tension figure of different concns oil field stratum water combined surfactant solution to dewatered oil.
Fig. 6 is that the oil water interfacial tension of 0.05wt% oil field stratum water combined surfactant solution is with the variation diagram of digestion time.
The interfacial tension figure of the combined surfactant injected water solution that Fig. 7 is prepared for the different sequence polyethers of same polymeric degree of comparing with [embodiment 1] to dewatered oil.
The interfacial tension figure of the combined surfactant local water solution that Fig. 8 is prepared for the different sequence polyethers of same polymeric degree of comparing with [embodiment 2] to dewatered oil.
The interfacial tension figure of the combined surfactant local water solution that Fig. 9 is prepared for the same polymeric degree random copolymerization polyethers of comparing with [embodiment 3] to dewatered oil.
Zwitter-ion, the anion-nonionic tensio-active agent injected water solution interfacial tension figure to dewatered oil of Figure 10 for comparing with [embodiment 1].
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
1) synthetic [a=8, b=2, the R of nonyl phenol poly-oxypropylene Soxylat A 25-7 trimethyl-glycine
2=CH
3, R
3=CH
3, R
4=CH
2cH (OH) CH
2, X
-=SO
3 -]
I. add nonyl phenol poly-oxypropylene Soxylat A 25-7 (a=8 to being equipped with in the dry four-hole reaction flask of stirring, condensation and device for absorbing tail gas, b=2) 463.2 grams (0.6 mole), 107.1 grams of sulfur oxychlorides (0.9 mole), be heated to reflux, keep back flow reaction 6 hours, after reaction finishes, change water distilling apparatus into and boil off excessive sulfur oxychloride, obtain chloro nonyl phenol poly-oxypropylene Soxylat A 25-7 (a=8, b=2) 467.2g, yield 98.5%.
Ii. by the chloro nonyl phenol poly-oxypropylene Soxylat A 25-7 (a=8 of i synthesized, b=2) 237.2 g(0.3 mole) add with reflux condensate device, temperature is taken into account in the four-hole boiling flask of agitator, and add 33wt% dimethylamine agueous solution 61.4g(0.45 mole), water 30g and Virahol 90g mix mutually, being heated to 80 DEG C reacts, in reaction process, add the hydrogen chloride gas that 30wt% aqueous sodium hydroxide solution generates with absorption reaction, and to keep pH value of reaction system be 7.5 ~ 9, react after 8 hours, to 255.5 grams of the aqueous solution (0.39 mole) that continue to drip 30wt% 3-chlorine-2-hydroxyl propanesulfonate in reaction solution, dropwise in reflux temperature reaction 15 hours.After reaction result, the salt solution of point sub-cloud, upper organic phase steams Virahol and excessive dimethylamine, and 60 DEG C of vacuum-dryings obtain nonyl phenol poly-oxypropylene Soxylat A 25-7 trimethyl-glycine [a=8, b=2, R
2=CH
3, R
3=CH
3, R
4=CH
2cH (OH) CH
2, X
-=SO
3 -].
2) synthetic [c=2, d=4, the R of octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium
6=CH
2cH (OH) CH
2, Y=SO
3na]
By octadecyl polyoxyethylene polyoxypropylene ether (c=2, d=4) 281 grams (0.5 mole) and 40 grams of (1 mole) sodium hydroxide, 147.4 grams of (0.75 mole) 3-chlorine-2-hydroxyl propanesulfonates, 12.9 grams of Tetrabutyl amonium bromides and 900 milliliters of benzene are mixed in to be furnished with mechanical stirring, in the four-hole reaction flask of 2000 milliliters of thermometer and reflux condensing tube, to be heated to 75 DEG C of reactions 8 hours.Cooling, with the hcl acidifying of 15wt% to water layer pH=2 ~ 3, branch vibration layer, organic layer is concentrated except desolventizing, with the neutralization of 40wt% aqueous sodium hydroxide solution, 60 DEG C of vacuum-dryings, obtain octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium [c=2, d=4, R
6=CH
2cH (OH) CH
2, Y=SO
3na].
To synthetic nonyl phenol poly-oxypropylene Soxylat A 25-7 trimethyl-glycine [a=8, b=2, R
2=CH
3, R
3=CH
3, R
4=CH
2cH (OH) CH
2, X
-=SO
3 -] carrying out Infrared spectroscopy, Fig. 1 is the infrared spectrum recording; To synthetic octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium [c=2, d=4, R
6=CH
2cH (OH) CH
2, Y=SO
3na] carry out infrared analysis, Fig. 2 is the infrared spectrum recording.
3), in mass parts, get 1) synthetic nonyl phenol poly-oxypropylene Soxylat A 25-7 trimethyl-glycine [a=8, b=2, R
2=CH
3, R
3=CH
3, R
4=CH
2cH (OH) CH
2, X
-=SO
3 -] 30 parts, 2) synthetic octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium [c=2, d=4, R
6=CH
2cH (OH) CH
2, Y=SO
3na] 15 parts, 55 parts of ethanol and 60 parts of 3wt% sodium chloride aqueous solutions add in reaction flask successively, are warming up to 75 DEG C and stir 2 hours, and ethanol is removed in underpressure distillation, obtains the combined surfactant that concentration is 45.2wt%.
[embodiment 2]
1) synthetic [a=6, b=2, the R of dodecyl phenol polyoxyethylene polyoxypropylene ether trimethyl-glycine
2=cH
2cH
2oH, R
3=CH
2cH
2oH, R
4=CH
2cH
2, X
-=SO
3 -]
I. add 4-dodecylphenol polyoxyethylene polyoxypropylene ether (a=6 to being equipped with in the dry four-hole reaction flask of stirring, condensation and device for absorbing tail gas, b=2) 418.8 grams (0.6 mole), 121.4 grams of sulfur oxychlorides (1.02 moles), be heated to reflux, keep back flow reaction 7 hours, reaction finishes rear with [embodiment 1] aftertreatment, obtain chlorinated dodecane base phenol polyoxyethylene polyoxypropylene ether (a=6, b=2) 418.7g, yield 97.4%.
Ii. by the chlorinated dodecane base phenol polyoxyethylene polyoxypropylene ether (a=6 of i synthesized, b=2) 215.0 g(0.3 mole) add with reflux condensate device, temperature is taken into account in the four-hole boiling flask of agitator, and add diethanolamine 34.7g(0.33 mole), water 20g and ethanol 60g mix mutually, being heated to 75 DEG C reacts, in reaction process, add the hydrogen chloride gas that 30wt% aqueous sodium hydroxide solution generates with absorption reaction, and to keep pH value of reaction system be 7.5 ~ 9, react after 10 hours, in reaction solution, add 83.0 grams of hydration 2-monochloroethane sodium sulfonates and (0.45 mole) water 150g, reinforced complete in reflux temperature reaction 20 hours, reaction finishes rear with [embodiment 1] aftertreatment, obtain dodecyl phenol polyoxyethylene polyoxypropylene ether trimethyl-glycine [a=6, b=2, R
2=cH
2cH
2oH, R
3=CH
2cH
2oH, R
4=CH
2cH
2, X
-=SO
3 -].
2) synthetic [c=8, d=6, the R of nonyl phenol poly-oxypropylene Soxylat A 25-7 ethyl sulfonic acid potassium
6=CH
2cH
2, Y=SO
3k]
Except pressing nonyl phenol poly-oxypropylene Soxylat A 25-7 (c=8, d=6), the mol ratio of a hydration 2-monochloroethane sodium sulfonate and sodium hydroxide is 0.5:: react at 0.75: 1, toluene is that solvent was in 100 DEG C of reactions 5 hours, substitute the sodium hydroxide neutralization of 40wt% with the potassium hydroxide of 40wt%, other operation is with [embodiment 1], obtain nonyl phenol poly-oxypropylene Soxylat A 25-7 ethyl sulfonic acid potassium [c=8, d=6, R
6=CH
2cH
2, Y=SO
3k]
3), in mass parts, get 1) synthetic dodecyl phenol polyoxyethylene polyoxypropylene ether trimethyl-glycine [a=6, b=2, R
2=cH
2cH
2oH, R
3=CH
2cH
2oH, R
4=CH
2cH
2, X
-=SO
3 -] 50 parts, 2) synthetic nonyl phenol poly-oxypropylene Soxylat A 25-7 ethyl sulfonic acid potassium [c=8, d=6, R
6=CH
2cH
2, Y=SO
3k] 20 parts, 30 parts of Virahols and 35 parts of deionized water solutions add in reaction flask successively, are warming up to 80 DEG C and stir 2 hours, and Virahol is removed in underpressure distillation, obtains the combined surfactant that concentration is 70.3wt%.
[embodiment 3]
1) synthetic [a=4, b=8, the R of tetradecyl polyoxyethylene polyoxypropylene ether trimethyl-glycine
2=cH
3, R
3=CH
3, R
4=CH
2cH
2, X
-=SO
3 -]
I. add tetradecyl polyoxyethylene polyoxypropylene ether (a=4 to being equipped with in the dry four-hole reaction flask of stirring, condensation and device for absorbing tail gas, b=8) 478.8 grams (0.6 mole), 85.7 grams of sulfur oxychlorides (0.72 mole), be heated to reflux, keep back flow reaction 8 hours, reaction finishes rear with [embodiment 1] aftertreatment, obtain chloro-tetradecane base polyoxyethylene polyoxypropylene ether (a=4, b=8) 478.6g, yield 97.7%.
Ii. by the chloro-tetradecane base polyoxyethylene polyoxypropylene ether (a=4 of i synthesized, b=8) 245.0 g(0.3 mole) add with reflux condensate device, temperature is taken into account in the four-hole boiling flask of agitator, and add 33wt% dimethylamine agueous solution 73.6g(0.54 mole), water 30g and n-propyl alcohol 90g mix mutually, being heated to 85 DEG C reacts, in reaction process, add the hydrogen chloride gas that 30wt% aqueous sodium hydroxide solution generates with absorption reaction, and to keep pH value of reaction system be 7.5 ~ 9, react after 6 hours, in reaction solution, add 88.6 grams of hydration 2-monochloroethane sodium sulfonates and (0.48 mole) water 150g, reinforced complete in reflux temperature reaction 18 hours, reaction finishes rear with [embodiment 1] aftertreatment, obtain tetradecyl polyoxyethylene polyoxypropylene ether trimethyl-glycine [a=4, b=8, R
2=cH
3, R
3=CH
3, R
4=CH
2cH
2, X
-=SO
3 -].
2) synthetic [c=2, d=4, the R of octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium
6=CH
2cH (OH) CH
2, Y=SO
3na]
Except pressing octadecyl polyoxyethylene polyoxypropylene ether (c=2, d=4), the mol ratio of 3-chlorine-2-hydroxyl propanesulfonate and potassium hydroxide is 0.5:: react at 0.6: 1.5, acetone is that solvent was in 55 DEG C of reactions 12 hours, other operation is with [embodiment 1], obtain octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium [c=2, d=4, R
6=CH
2cH (OH) CH
2, Y=SO
3na].
3), in mass parts, get 1) synthetic tetradecyl polyoxyethylene polyoxypropylene ether trimethyl-glycine [a=4, b=8, R
2=cH
3, R
3=CH
3, R
4=CH
2cH
2, X
-=SO
3 -] 40 parts, 2) synthetic octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium [c=2, d=4, R
6=CH
2cH (OH) CH
2, Y=SO
3na] 10 parts, 50 parts of Virahols and 55 parts of 5wt% sodium chloride aqueous solution water add in reaction flask successively, are warming up to 80 DEG C and stir 3 hours, and Virahol is removed in underpressure distillation, obtains the combined surfactant that concentration is 49.8wt%.
[embodiment 4]
1) synthetic [a=4, b=4, the R of octadecyl polyoxyethylene polyoxypropylene ether trimethyl-glycine
2=cH
2cH
2oH, R
3=CH
2cH
2oH, R
4=CH
2cH (OH) CH
2, X
-=SO
3 -]
I. add octadecyl polyoxyethylene polyoxypropylene ether (a=4 to being equipped with in the dry four-hole reaction flask of stirring, condensation and device for absorbing tail gas, b=4) 406.8 grams (0.6 mole), 107.1 grams of sulfur oxychlorides (0.9 mole), be heated to reflux, keep back flow reaction 6 hours, reaction finishes rear with [embodiment 1] aftertreatment, obtain chlorooctadecane base polyoxyethylene polyoxypropylene ether (a=4, b=4) 410.0g, yield 98.1%.
Ii. by the chlorooctadecane base polyoxyethylene polyoxypropylene ether (a=4 of i synthesized, b=4) 209.0g(0.3 mole) add with reflux condensate device, temperature is taken into account in the four-hole boiling flask of agitator, and add diethanolamine 34.7g(0.33 mole), water 20g and n-propyl alcohol 60g mix mutually, being heated to 85 DEG C reacts, in reaction process, add the hydrogen chloride gas that 30wt% aqueous sodium hydroxide solution generates with absorption reaction, and to keep pH value of reaction system be 7.5 ~ 9, react after 6 hours, to 353.7 grams of the aqueous solution (0.54 mole) that continue to drip 30wt% 3-chlorine-2-hydroxyl propanesulfonate in reaction solution, reinforced complete in reflux temperature reaction 12 hours, reaction finishes rear with [embodiment 1] aftertreatment, obtain octadecyl polyoxyethylene polyoxypropylene ether trimethyl-glycine [a=4, b=4, R
2=cH
2cH
2oH, R
3=CH
2cH
2oH, R
4=CH
2cH (OH) CH
2, X
-=SO
3 -].
2) synthetic [c=8, d=6, the R of nonyl phenol poly-oxypropylene Soxylat A 25-7 ethyl sulfonic acid potassium
6=CH
2cH
2, Y=SO
3k]
Except pressing nonyl phenol poly-oxypropylene Soxylat A 25-7 (c=8, d=6), the mol ratio of a hydration 2-monochloroethane sodium sulfonate and sodium hydroxide is 0.5:: react at 0.6: 1.5, benzene is that solvent was in 75 DEG C of reactions 10 hours, substitute the sodium hydroxide neutralization of 40wt% with the potassium hydroxide of 40wt%, other operation is with [embodiment 1], obtain nonyl phenol poly-oxypropylene Soxylat A 25-7 ethyl sulfonic acid potassium [c=8, d=6, R
6=CH
2cH
2, Y=SO
3k].
3), in mass parts, get 1) synthetic octadecyl polyoxyethylene polyoxypropylene ether trimethyl-glycine [a=4, b=4, R
2=cH
2cH
2oH, R
3=CH
2cH
2oH, R
4=CH
2cH (OH) CH
2, X
-=SO
3 -] 15 parts, 2) synthetic nonyl phenol poly-oxypropylene Soxylat A 25-7 ethyl sulfonic acid potassium [c=8, d=6, R
6=CH
2cH
2, Y=SO
3k] 20 parts, 35 parts of ethanol and 62 parts of 8wt% sodium chloride/potassium chloride aqueous solution add in reaction flask successively, are warming up to 75 DEG C and stir 3 hours, and ethanol is removed in underpressure distillation, obtains the combined surfactant that concentration is 35.0wt%.
[embodiment 5]
1) synthetic [a=10, b=1, the R of docosyl polyoxyethylene polyoxypropylene ether trimethyl-glycine
2=cH
2cH
2oH, R
3=CH
2cH
2oH, R
4=CH
2, X
-=COO
-]
I. add docosyl polyoxyethylene polyoxypropylene ether (a=10 to being equipped with in the dry four-hole reaction flask of stirring, condensation and device for absorbing tail gas, b=1) 570 grams (0.6 mole), 142.8 grams of sulfur oxychlorides (1.2 moles), be heated to reflux, keep back flow reaction 4 hours, reaction finishes rear with [embodiment 1] aftertreatment, obtain chloro docosyl polyoxyethylene polyoxypropylene ether (a=10, b=1) 572.9g, yield 98.6%.
Ii. by the chloro docosyl polyoxyethylene polyoxypropylene ether (a=10 of i synthesized, b=1) 290.6g(0.3 mole) add with reflux condensate device, temperature is taken into account in the four-hole boiling flask of agitator, and add diethanolamine 34.7g(0.33 mole), water 20g and ethanol 60g mix mutually, being heated to 65 DEG C reacts, in reaction process, add the hydrogen chloride gas that 30wt% aqueous sodium hydroxide solution generates with absorption reaction, and to keep pH value of reaction system be 7.5 ~ 9, react after 6 hours, to 96.1 grams of the aqueous solution (0.33 mole) that continue to drip 40wt% sodium chloroacetate in reaction solution, reinforced complete in reflux temperature reaction 7 hours, reaction finishes rear with [embodiment 1] aftertreatment, obtain docosyl polyoxyethylene polyoxypropylene ether trimethyl-glycine [a=10, b=1, R
2=cH
2cH
2oH, R
3=CH
2cH
2oH, R
4=CH
2, X
-=COO
-].
2) synthetic [c=2, d=4, the R of octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium
6=CH
2cH (OH) CH
2, Y=SO
3na]
Except pressing octadecyl polyoxyethylene polyoxypropylene ether (c=2, d=4), the mol ratio of 3-chlorine-2-hydroxyl propanesulfonate and sodium hydroxide is 0.5:: react at 0.55: 1.5, toluene is that solvent was in 110 DEG C of reactions 16 hours, other operation is with [embodiment 1], obtain octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium [c=2, d=4, R
6=CH
2cH (OH) CH
2, Y=SO
3na].
3), in mass parts, get 1) synthetic docosyl polyoxyethylene polyoxypropylene ether trimethyl-glycine [a=10, b=1, R
2=cH
2cH
2oH, R
3=CH
2cH
2oH, R
4=CH
2, X
-=COO
-] 25 parts, 2) synthetic octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium [c=2, d=4, R
6=CH
2cH (OH) CH
2, Y=SO
3na] 5 parts, 35 parts of n-propyl alcohols and 75 parts of 10wt% sodium chloride aqueous solutions add in reaction flask successively, are warming up to 85 DEG C and stir 2 hours, and n-propyl alcohol is removed in underpressure distillation, obtains the combined surfactant that concentration is 31.1wt%.
[embodiment 6]
1) synthetic [a=6, b=2, the R of docosyl polyoxyethylene polyoxypropylene ether trimethyl-glycine
2=cH
3, R
3=CH
3, R
4=CH
2, X
-=COO
-]
I. add docosyl polyoxyethylene polyoxypropylene ether (a=6 to being equipped with in the dry four-hole reaction flask of stirring, condensation and device for absorbing tail gas, b=2) 457.2 grams (0.6 mole), 121.4 grams of sulfur oxychlorides (1.02 moles), be heated to reflux, keep back flow reaction 10 hours, reaction finishes rear with [embodiment 1] aftertreatment, obtain chloro docosyl polyoxyethylene polyoxypropylene ether (a=6, b=2) 453.8g, yield 96.9%.
Ii. by the chloro docosyl polyoxyethylene polyoxypropylene ether (a=6 of i synthesized, b=2) 234.2g(0.3 mole) add with reflux condensate device, temperature is taken into account in the four-hole boiling flask of agitator, and add 33wt% dimethylamine agueous solution 53.2g(0.39 mole), water 30g and ethanol 90g mix mutually, being heated to 80 DEG C reacts, in reaction process, add the hydrogen chloride gas that 30wt% aqueous sodium hydroxide solution generates with absorption reaction, and to keep pH value of reaction system be 7.5 ~ 9, react after 8 hours, in reaction solution, add 36.9 grams of Mono Chloro Acetic Acids (0.39 mole) and 40wt% aqueous sodium hydroxide solution 40g, reinforced complete in reflux temperature reaction 10 hours, reaction finishes rear with [embodiment 1] aftertreatment, obtain docosyl polyoxyethylene polyoxypropylene ether trimethyl-glycine [a=6, b=2, R
2=cH
3, R
3=CH
3, R
4=CH
2, X
-=COO
-].
2) synthetic [c=2, d=4, the R of octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium
6=CH
2cH (OH) CH
2, Y=SO
3na]
Except pressing octadecyl polyoxyethylene polyoxypropylene ether (c=2, d=4), the mol ratio of 3-chlorine-2-hydroxyl propanesulfonate and sodium hydroxide is 0.5:: react at 0.75: 0.75, toluene is that solvent was in 95 DEG C of reactions 7 hours, other operation is with [embodiment 1], obtain octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium [c=2, d=4, R
6=CH
2cH (OH) CH
2, Y=SO
3na].
3), in mass parts, get 1) synthetic docosyl polyoxyethylene polyoxypropylene ether trimethyl-glycine [a=6, b=2, R
2=cH
3, R
3=CH
3, R
4=CH
2, X
-=COO
-] 15 parts, 2) eight synthetic alkyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium [c=2, d=4, R
6=CH
2cH (OH) CH
2, Y=SO
3na] 5 parts, 30 parts of Virahols and 85 parts of 15wt% sodium chloride aqueous solutions add in reaction flask successively, are warming up to 85 DEG C and stir 2 hours, and n-propyl alcohol is removed in underpressure distillation, obtains the combined surfactant that concentration is 19.8wt%.
[embodiment 7]
Combined surfactant prepared by [embodiment 1 ~ 6] adds Jiangsu Shanian Oilfield injected water, and (total mineralization TDS is 800 mg/litre, Mg
2++ Ca
2+be 35 mg/litre) in, stir 2 hours in 30 DEG C, obtain 0.3wt% combined surfactant mother liquor, water with same salinity is diluted to different concns, measure the oil water interfacial tension of combined surfactant solution and Jiangsu Shanian Oilfield dewatered oil, probe temperature is 85 DEG C, and in the scope of 0.005～0.3wt%, the dynamic interface tension value between the combined surfactant aqueous solution and crude oil can reach 10
-2～10
-4the ultra low interfacial tension value of mN/m, as shown in Figure 3.The TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
[embodiment 8]
With [embodiment 7], it is each 100 milliliters of 0.1wt% injected water solution that [embodiment 1 ~ 6] synthetic combined surfactant is mixed with to concentration, be respectively charged in the pressurized vessel of 100 milliliters, after sealing, put into the baking oven of 110 DEG C, the oil water interfacial tension (temperature of measuring tension force is still 85 DEG C) while measuring different digestion time.After aging 14 days of 110 DEG C of temperature, the combined surfactant aqueous solution of 0.1wt% and the interfacial tension of dewatered oil still can keep 10
-3～10
-4the ultralow value of mN/m, as shown in Figure 4.
[embodiment 9]
With [embodiment 7], difference preparation tensio-active agent water changes oil field stratum water into, and (total mineralization TDS is 12000 mg/litre, Mg
2++ Ca
2be 45 mg/litre).In the scope of 0.005～0.3wt%, the dynamic interface tension value between the combined surfactant aqueous solution and crude oil can reach 10
-2～10
-4the ultra low interfacial tension value of mN/m, as shown in Figure 5.
[embodiment 10]
With [embodiment 8], change aging temperature into 85 DEG C, adopt the local water preparation 0.05wt% surfactant soln with [embodiment 9], measure the oil water interfacial tension of different digestion times.After aging 90 days of 85 DEG C of temperature, the combined surfactant aqueous solution of 0.05wt% and the interfacial tension of dewatered oil still can keep 10
-3～10
-4the ultralow value of mN/m, as shown in Figure 6.
[comparative example 1]
" nonyl phenol poly-oxypropylene Soxylat A 25-7 (a=8; b=2) " that substitute block copolymerization except " Nonyl pheno (2) polyoxypropylene (8) ether " with block copolymerization, as preparing the starting raw material of zwitterionics, all the other operations are with [embodiment 1].The oil water interfacial tension of measuring different concns injected water solution and Jiangsu Shanian Oilfield dewatered oil with [embodiment 7], probe temperature is 85 DEG C, in the scope of 0.005～0.3wt%, dynamic interface tension value can reach 10
-3mN/m as shown in Figure 7.
[comparative example 2]
" octadecyl polyoxyethylene polyoxypropylene ether (c=2; d=4) " that substitute block copolymerization except " octadecyl polyoxyethylene (4) polyoxypropylene (2) ether " with block copolymerization, as preparing the starting raw material of anion-nonionic tensio-active agent, all the other operations are with [embodiment 1].The oil water interfacial tension of measuring different concns injected water solution and Jiangsu Shanian Oilfield dewatered oil with [embodiment 7], probe temperature is 85 DEG C, in the scope of 0.005～0.3wt%, dynamic interface tension value can reach 10
-2～10
-3mN/m as shown in Figure 7.
[comparative example 3]
" 4-dodecylphenol polyoxyethylene polyoxypropylene ether (a=6; b=2) " that substitute block copolymerization except " dodecyl phenol polyethenoxy (2) polyoxypropylene (6) ether " with block copolymerization, as preparing the starting raw material of zwitterionics, all the other operations are with [embodiment 2].The oil water interfacial tension of measuring different concns local water solution and Jiangsu Shanian Oilfield dewatered oil with [embodiment 9], probe temperature is 85 DEG C, in the scope of 0.005～0.3wt%, dynamic interface tension value can reach 10
-3mN/m as shown in Figure 8.
[comparative example 4]
" nonyl phenol poly-oxypropylene Soxylat A 25-7 (c=8; d=6) " that substitute block copolymerization except " Nonyl pheno (6) polyoxypropylene (8) ether " with block copolymerization, as preparing the starting raw material of anion-nonionic tensio-active agent, all the other operations are with [embodiment 2].The oil water interfacial tension of measuring different concns local water solution and Jiangsu Shanian Oilfield dewatered oil with [embodiment 9], probe temperature is 85 DEG C, in the scope of 0.005～0.3wt%, dynamic interface tension value can reach 10
-2～10
3mN/m as shown in Figure 8.
[comparative example 5]
" tetradecyl polyoxyethylene polyoxypropylene ether (a=4; b=8) " that substitute block copolymerization except " tetradecyl polyoxyethylene (8) polyoxypropylene (4) ether " with random copolymerization, as preparing the starting raw material of zwitterionics, all the other operations are with [embodiment 3].The oil water interfacial tension of measuring different concns local water solution and Jiangsu Shanian Oilfield dewatered oil with [embodiment 9], probe temperature is 85 DEG C, in the scope of 0.005～0.3wt%, dynamic interface tension value can reach 10
-2～10
-3mN/m as shown in Figure 9.
[comparative example 6]
Except substituting " octadecyl polyoxyethylene polyoxypropylene ether (c=2; d=4) " with " octadecyl polyoxyethylene (4) polyoxypropylene (2) ether " of random copolymerization as the starting raw material of preparing anion-nonionic tensio-active agent, all the other operations are with [embodiment 3].The oil water interfacial tension of measuring different concns local water solution and Jiangsu Shanian Oilfield dewatered oil with [embodiment 9], probe temperature is 85 DEG C, in the scope of 0.005～0.3wt%, dynamic interface tension value can reach 10
-2～10
-3mN/m as shown in Figure 9.
[comparative example 7]
Step 1) and 2) with [embodiment 1].
3), in mass parts, get 1) synthetic nonyl phenol poly-oxypropylene Soxylat A 25-7 trimethyl-glycine [a=8, b=2, R
2=CH
3, R
3=CH
3, R
4=CH
2cH (OH) CH
2, X
-=SO
3 -] 45 parts and 55 parts of 3wt% sodium chloride aqueous solutions add in mixing vessel successively, are warming up to 75 DEG C and stir 2 hours, obtain the zwitterionics that concentration is 45.0wt%.
The oil water interfacial tension of measuring different concns injected water solution and Jiangsu Shanian Oilfield dewatered oil with [embodiment 7], probe temperature is 85 DEG C, in the scope of 0.005～0.3wt%, dynamic interface tension value can reach 10
-2～10
-3mN/m as shown in Figure 10.
[comparative example 8]
Step 1) and 2) with [embodiment 1].
3), in mass parts, get 2) synthetic) synthetic [c=2, d=4, the R of octadecyl polyoxyethylene polyoxypropylene ether hydroxypropionate sodium
6=CH
2cH (OH) CH
2, Y=SO
3na] 45 parts and 55 parts of 3wt% sodium chloride aqueous solutions add in mixing vessel successively, are warming up to 75 DEG C and stir 2 hours, and obtaining concentration is the anion-nonionic tensio-active agent of 45.0wt%.The oil water interfacial tension of measuring different concns injected water solution and Jiangsu Shanian Oilfield dewatered oil with [embodiment 7], probe temperature is 85 DEG C, in the scope of 0.005～0.3wt%, dynamic interface tension value can reach 10
-1～10
-3mN/m as shown in Figure 10.
Claims (9)
1. a combined surfactant, comprises following component in mass fraction:
The zwitterionics of (1) 1 part;
The anion-nonionic tensio-active agent of (2) 0.01 ~ 50 parts;
The water of (3) 0.1 ~ 90 parts;
Wherein the general molecular formula of (1), (2) component is:
（1）
（2）
In formula, R
1and R
5for being selected from independently of one another C
8～C
30alkyl or by C
4～C
20the phenyl that alkyl replaces; A and c are the adduction number of the PO of propoxy-group, and span independent of one another is 1～15; B and d are the adduction number of ethoxy group EO, and value independent of one another is 1～30; R
2and R
3be selected from independently of one another C
1～C
5alkyl or hydroxyalkyl, R
4and R
6be selected from independently of one another C
1～C
5alkylidene group or hydroxyl substituted alkylene; X
-for COO
-or SO
3 -, Y is COOM or SO
3n, M and N are selected from basic metal or ammonium independently of one another.
2. combined surfactant according to claim 1, is characterized in that described R
1and R
5be selected from independently of one another C
12～C
24alkyl or by C
8～C
12the phenyl that alkyl replaces.
3. combined surfactant according to claim 1, is characterized in that described a and c value independent of one another is that 2～12, b and d value independent of one another are 1～10.
4. combined surfactant according to claim 1, is characterized in that described R
2,r
3be selected from independently of one another methyl, ethyl or hydroxyethyl, R
4and R
6be selected from independently of one another C
1～C
3alkylidene group or hydroxyl replace propylidene.
5. combined surfactant according to claim 1, is characterized in that M and N are for being selected from independently of one another sodium or potassium.
6. combined surfactant according to claim 1, is characterized in that described water is the inorganic salt solution of deionized water, tap water or 1 ~ 30wt%.
7. combined surfactant according to claim 6, is characterized in that the inorganic salt solution that described water is 1 ~ 15wt%.
8. combined surfactant according to claim 7, is characterized in that described inorganic salt are at least one in sodium-chlor, Repone K or ammonium chloride.
9. the preparation method of combined surfactant according to claim 1, comprises the following steps:
1) preparation of zwitterionics:
I. be 1 by alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether in molar ratio with sulfur oxychloride: mix (1 ~ 3), under 50 ~ 120 DEG C of conditions of temperature of reaction, react 3 ~ 15 hours, after reaction finishes, obtain after treatment chloro alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether;
Ii. the chloro alkyl alcohol of synthesized in i or alkylphenol polyoxyethylene polyoxypropylene ether are mixed with dialkylamine, water and low-carbon alcohol, be 40 ~ 100 DEG C in temperature and carry out tertiary amination reaction 3 ~ 20 hours, then drip the aqueous solution of sulphonating agent or carboxylating agent, dropwise and continue at reflux temperature and carry out quaterisation 5 ~ 30 hours, steam low-carbon alcohol and excessive dialkylamine, removal salt, obtain alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether carboxylic acid or sulfonate betaine; Wherein, dialkylamine is dimethylamine or diethanolamine, and sulphonating agent is an alkali metal salt of 3-chlorine-2-hydroxyl propanesulfonic acid, an alkali metal salt or the PS of 2-monochloroethane sulfonic acid, and carboxylating agent is Mono Chloro Acetic Acid or chloroacetic an alkali metal salt, and low-carbon alcohol is selected from C
1~ C
3fatty alcohol, the mol ratio of chloro alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether, dialkylamine and sulphonating agent or carboxylating agent is 1: (1～3): (1～3);
2) preparation of anion-nonionic tensio-active agent:
Alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether are mixed by required proportioning with sulphonating agent or carboxylating agent, alkali metal hydroxide solid and solvent, at 50～130 DEG C of temperature of reaction, react 3～15 hours, after reaction finishes, obtain alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether sulfonate or carboxylate salt through aftertreatment; Wherein, the mol ratio of alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether, sulfonated reagent or carboxylation reagent and alkali metal hydroxide is 1: (1～4): (1～5), sulphonating agent is 3-chlorine-2-hydroxyl propanesulfonic acid an alkali metal salt, 2-monochloroethane sulfonic acid alkali metal salts or 1,3-N-morpholinopropanesulfonic acid lactone, carboxylating agent is Mono Chloro Acetic Acid or Mono Chloro Acetic Acid an alkali metal salt, and solvent is selected from least one in acetone, benzene, toluene or dimethylbenzene;
3) alkyl alcohol of aequum or alkylphenol polyoxyethylene polyoxypropylene ether carboxylic acid or sulfonate betaine, alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether sulfonate or carboxylate salt, water and low-carbon alcohol are added in mixing vessel, being warming up to 40 ~ 100 DEG C stirs 1～4 hour, pressure reducing and steaming low-carbon alcohol, obtains required combined surfactant; In mass fraction, the proportioning of alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether carboxylic acid or sulfonate betaine, alkyl alcohol or alkylphenol polyoxyethylene polyoxypropylene ether sulfonate or carboxylate salt, low-carbon alcohol and water is 1 part: 0.01 ~ 50 part: 0.1 ~ 90 part: 0.1 ~ 90 part, low-carbon alcohol is selected from C
1~ C
3fatty alcohol.
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