CN104277808A - Oil-displacement surfactant and preparation method thereof - Google Patents
Oil-displacement surfactant and preparation method thereof Download PDFInfo
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- CN104277808A CN104277808A CN201310286347.2A CN201310286347A CN104277808A CN 104277808 A CN104277808 A CN 104277808A CN 201310286347 A CN201310286347 A CN 201310286347A CN 104277808 A CN104277808 A CN 104277808A
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- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
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- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/09—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton
- C07C309/10—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to an acyclic carbon atom
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Abstract
The invention relates to an oil-displacement surfactant capable of improving crude oil recovery rate and a preparation method thereof, and mainly solves the problem that surfactants in the prior art are low in oil displacement efficiency under the conditions of high temperature and high salt. The employed oil-displacement surfactant capable of improving crude oil recovery rate has the name of 3-(alkylphenol polyoxyethylene ether)-2-(polyoxyethylene ether)propanesulfonate, and has the structure shown as a formula (I) in the specification. In the formula (I), M is any one of alkali metals and alkali earth metals, R is a C4-C20 alkyl, x=1-20 and y=1-20. The technical scheme relatively well solves the above problem and is applicable to enhanced oil recovery production of oil fields.
Description
Technical field
The present invention relates to a kind of surfactant oil displacement improving oil recovery factor and preparation method thereof.
Background technology
After oil field enters high water-cut stage, surplus oil with discontinuous oil film by trap in the hole of reservoir rocks, two the main power acted 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 brought, thus significantly improve oil displacement efficiency.
Maximum still sulfonated petro-leum of oil recovery tensio-active agent application, the tensio-active agent of the oil refining such as heavy alkylbenzene sulfonate by product modification, the feature of this kind of tensio-active agent be draw materials extensive, cheap, but this kind of tensio-active agent can not be applicable to the oil field block of high temperature, high salt.In same molecule, introduce the novel surfactant of multiple active function groups, greatly can improve surfactivity, and may synergy be produced, increase salt resistance.Patent U.S. Pat. No.4436672A alkyl alcohol and Racemic glycidol are obtained by reacting alkyl alcohol polyglycidyl ether, then carry out sulfonation, obtain a kind of anion-nonionic tensio-active agent; Patent U.S.Pat.No.2011015111A1 reacts the ether generated containing chloro base with alhpa olefin and the chloro-2-propyl alcohol of 1,3-bis-, then carry out sulfonation reaction, obtains a kind of novel anion surfactant containing two sulfo groups.Patent U.S. Pat. No.4466891A provides a kind of alkylphenol polyoxyethylene propanesulfonic acid salt, and water-soluble and salt resistance increases.
But existing tensio-active agent has much room for improvement in the oil displacement efficiency of high salt high temperature oil reservoir.
Summary of the invention
One of technical problem to be solved by this invention is that in prior art, tensio-active agent exists the low problem of oil displacement efficiency under high temperature, high salt condition, there is provided a kind of new surfactant oil displacement, this tensio-active agent has the advantages that oil displacement efficiency is high under high temperature, high salt condition.
Two of technical problem to be solved by this invention is to provide a kind of preparation method of the surfactant oil displacement corresponding with one of technical solution problem.
Three of technical problem to be solved by this invention is the application in the displacement of reservoir oil of oil field of the described tensio-active agent of one of technical problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of surfactant oil displacement improving oil recovery factor, and its name is called 3-(alkyl phenol polyethenoxy ether)-2-(Soxylat A 25-7) propanesulfonic acid salt, as shown in the formula (I):
?(I)，
Wherein M to be selected from basic metal, alkaline-earth metal any one, and n is SO in M and formula (I)
3the mol ratio of group, when M is basic metal, n is 1, and when M is alkaline-earth metal, n is 0.5, R is C
4-C
20alkyl, x=1-20, y=1-20.
In technique scheme, preferred x=2 ~ 8 and y=2 ~ 8; More preferably x=y=2 ~ 8.Described alkyl is preferably C
7~ C
10alkane.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation method of the surfactant oil displacement that one of above-mentioned technical problem is described, comprises the following steps:
A) under basic catalyst effect, alkyl phenol and aequum oxyethane are 85 ~ 160 DEG C in temperature of reaction, and pressure is 0 ~ 0.40MPa(gauge pressure), react 1 ~ 10 hour, obtain alkyl phenol polyethenoxy ether;
B) step a gained alkyl phenol polyethenoxy ether is dissolved into C
6~ C
8in aromatic hydrocarbons, add at least one alkali in alkali metal hydroxide or alkaline earth metal hydroxides, the mol ratio of described alkyl phenol polyethenoxy ether and described alkali is 1:1 ~ 3, alkalize 0.5 ~ 3 hour at 30 ~ 60 DEG C, add an alkali metal salt of 3-chlorine-2-hydroxyl propanesulfonic acid, the mol ratio of wherein said alkyl phenol polyethenoxy ether and 3-chlorine-2-hydroxyl propanesulfonic acid an alkali metal salt is 1:1 ~ 4, stirring lower temperature of reaction is 30 ~ 80 DEG C, and the reaction times is within 6 ~ 18 hours, obtain 3-(alkyl phenol polyethenoxy ether)-2-hydroxy-propanesulfonic acid salt;
C) by step b) gained 3-(alkyl phenol polyethenoxy ether)-2-hydroxy-propanesulfonic acid salt, under basic catalyst effect, be 85 ~ 160 DEG C with aequum oxyethane in temperature of reaction, pressure is 0 ~ 0.40MPa(gauge pressure), react 1 ~ 10 hour, obtain described 3-(alkyl phenol polyethenoxy ether)-2-(Soxylat A 25-7) propanesulfonic acid salt.
In technique scheme, step a) and step c) at least one in described basic catalyst preferred alkali metal hydroxide, the oxyhydroxide of alkaline-earth metal or the oxide compound of alkaline-earth metal, at least one more preferably in sodium hydroxide or potassium hydroxide.Temperature of reaction described in step a) is preferably 120 ~ 140 DEG C, and the reaction times is preferably 6 ~ 8 hours.The mol ratio of alkyl phenol polyethenoxy ether described in step b) and 3-chlorine-2-hydroxyl propanesulfonic acid an alkali metal salt is preferably 1:1 ~ 2.Temperature of reaction described in step c) is preferably 120 ~ 140 DEG C, and the reaction times is preferably 6 ~ 8 hours.
For three the technical solution used in the present invention solving the technology of the present invention problem are as follows: the application of the described tensio-active agent of one of above-mentioned technical problem in the displacement of reservoir oil of oil field.
In technique scheme, the concrete grammar of described application can inject oil-bearing formation for comprising 1 part, the described tensio-active agent of one of the technology of the present invention problem with weight parts with the oil-displacing agent of 100 ~ 2000 parts, water.The water wherein adopted can be deionized water, river, underground water, seawater, and being preferably total mineralization scope is 10000-50000mg/L, Ca
2++ Mg
2+for the water of 500-2000mg/L, for the consideration of the aspect such as easy construction, saving water resource, be more preferably oilfield injection water, Jiang-Han Area Bamianhe Oilfield that the such as embodiment of the present invention adopts injects water.In order to increase oil displacement efficiency, small molecule alcohol, DMSO, diethanolamine, CTAC etc. that this area is conventional in oil-displacing agent of the present invention, can also be comprised.
Key problem in technology of the present invention is that tensio-active agent have employed novel anion-nonionic tensio-active agent, propanesulfonic acid salt groups is wherein positioned in the middle of two oxygen ethene segments, compared with the anion-nonionic tensio-active agent only connected with an oxygen ethene segment in prior art, the tensio-active agent that the present invention adopts substantially increases anti-salt, anticalcium magnesium ability, thus can be used for the oil reservoir displacement of reservoir oil of high salinity, comparatively high temps, there is very high theory significance, and be with a wide range of applications and practical significance.
Tensio-active agent of the present invention is greater than 30000mg/L, Ca in Bamianhe Oilfield formation temperature 80 DEG C, salinity
2+, Mg
2+concentration is still can form 10 with crude oil under the condition of 500-2000mg/L
-3the ultra low interfacial tension of the mN/m order of magnitude, thus drive crude oil, improve recovery ratio more than 10%, achieve good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
1. tensio-active agent preparation
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 110 grams of nonyl phenols and 1.5 grams of sodium hydroxide and 15 grams of water are added, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, then use nitrogen purging 4 times with the air in removing system, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 132 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 235 grams of Nonyl pheno (6) ethers.
B) by step a) gained 235 grams of polyoxyethylene nonylphenol ethers (6) join in the reactor that whipping appts, condensation reflux unit and division box are housed, add 250 milliliters of benzene and 40 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 147 grams of 3-chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, drip excessive hydrochloric acid and the pH of system is transferred to 2, be extracted with ethyl acetate, after oil phase steams and desolventizes, with sodium hydroxide solution neutralization, then at volume ratio acetone: ethanol: water is that in the mixed solvent of 2:1:1, recrystallization obtains 3-(polyoxyethylene nonylphenol ether (6))-2-hydroxy-propanesulfonic acid salt 254 grams.
C) by step b) the 3-(polyoxyethylene nonylphenol ether (6) that synthesizes)-2-hydroxy-propanesulfonic acid salt 254 grams, join in the reactor that condensing works, whipping appts and gas distributor are housed, add 2 grams of sodium hydroxide and 20 grams of water, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, with nitrogen purging 4 times, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 36 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (6))-2-(Soxylat A 25-7 (2)) propanesulfonic acid salt 288 grams.
2. surfactant properties evaluation
Oil-displacing agent is prepared:
Above-mentioned tensio-active agent 1 weight part and Bamianhe Oilfield are injected the transparent oil-displacing agent that water 500 weight part is mixed to get and be used for interfacial tension evaluation and oil displacement experiment.Wherein in all embodiments of the present invention and comparative example, Bamianhe Oilfield used injects the composition of water in table 1.For ease of comparing, the composition of oil-displacing agent is listed in table 2.
A) interfacial tension evaluation
Adopt Texas ,Usa university to produce TX-500C to rotate and drip an interfacial tensimeter, at 80 DEG C, rotating speed is under 4500 revs/min of conditions, and the interfacial tension between the dewatered oil measuring above-mentioned oil-displacing agent and Bamianhe Oilfield extraction the results are shown in Table 3.
B) oil displacement experiment evaluation
According to the composite oil-displacing system physical simulation flooding test measure of merit in SY/T6424-2000 composite oil-displacing system performance test methods, at 80 DEG C, length is 30cm, and diameter is 2.5cm, and rate of permeation is 1.5 m
2rock core on carry out imitation oil displacement experiment experiment.First inject water by Bamianhe Oilfield and carry out water drive to moisture 98%, after water drive terminates, metaideophone 0.3pv(rock pore volume) above-mentioned oil-displacing agent, then water drive is to moisture 98%, improves oil recovery factor and the results are shown in Table 4.
[embodiment 2]
1. tensio-active agent preparation
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 110 grams of nonyl phenols and 1.5 grams of sodium hydroxide and 15 grams of water are added, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, then use nitrogen purging 4 times with the air in removing system, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 22 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 130 grams of Nonyl pheno (1) ethers.
B) step a) gained 130 grams of polyoxyethylene nonylphenol ethers (1) are joined in the reactor that whipping appts, condensation reflux unit and division box are housed, add 250 milliliters of benzene and 40 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 138 grams of 3-chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, drip excessive hydrochloric acid and the pH of system is transferred to 2, be extracted with ethyl acetate, after oil phase steams and desolventizes, with sodium hydroxide solution neutralization, then at volume ratio acetone: ethanol: water is that in the mixed solvent of 2:1:1, recrystallization obtains 3-(polyoxyethylene nonylphenol ether (1))-2-hydroxy-propanesulfonic acid salt 158 grams.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (1))-2-hydroxy-propanesulfonic acid salt 158 grams, join in the reactor that condensing works, whipping appts and gas distributor are housed, add 1.5 grams of sodium hydroxide and 1.5 grams of water, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, with nitrogen purging 4 times, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 115 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (1))-2-(Soxylat A 25-7 (7)) propanesulfonic acid salt 268 grams.
2. surfactant properties evaluation
Except oil-displacing agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing, the composition of oil-displacing agent is listed in table 2, evaluation result is listed in table 3 and table 4.
[embodiment 3]
1. tensio-active agent preparation
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 110 grams of nonyl phenols and 1.5 grams of sodium hydroxide and 15 grams of water are added, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, then use nitrogen purging 4 times with the air in removing system, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 44 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 148 grams of Nonyl pheno (2) ethers.
B) step a) gained 148 grams of polyoxyethylene nonylphenol ethers (2) are joined in the reactor that whipping appts, condensation reflux unit and division box are housed, add 250 milliliters of benzene and 40 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 140 grams of 3-chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, drip excessive hydrochloric acid and the pH of system is transferred to 2, be extracted with ethyl acetate, after oil phase steams and desolventizes, with sodium hydroxide solution neutralization, then at volume ratio acetone: ethanol: water is that in the mixed solvent of 2:1:1, recrystallization obtains 3-(polyoxyethylene nonylphenol ether (2))-2-hydroxy-propanesulfonic acid salt 175 grams.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (2))-2-hydroxy-propanesulfonic acid salt 175 grams, join in the reactor that condensing works, whipping appts and gas distributor are housed, add 1.5 grams of sodium hydroxide and 1.5 grams of water, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, with nitrogen purging 4 times, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 34 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (2))-2-(Soxylat A 25-7 (2)) propanesulfonic acid salt 201 grams.
2. surfactant properties evaluation
Except oil-displacing agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing, the composition of oil-displacing agent is listed in table 2, evaluation result is listed in table 3 and table 4.
[embodiment 4]
1. tensio-active agent preparation
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 110 grams of nonyl phenols and 1.5 grams of sodium hydroxide and 15 grams of water are added, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, then use nitrogen purging 4 times with the air in removing system, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 88 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 192 grams of Nonyl pheno (4) ethers.
B) by step a) gained 192 grams of polyoxyethylene nonylphenol ethers (4) join in the reactor that whipping appts, condensation reflux unit and division box are housed, add 250 milliliters of benzene and 40 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 142 grams of 3-chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, drip excessive hydrochloric acid and the pH of system is transferred to 2, be extracted with ethyl acetate, after oil phase steams and desolventizes, with sodium hydroxide solution neutralization, then at volume ratio acetone: ethanol: water is that in the mixed solvent of 2:1:1, recrystallization obtains 3-(polyoxyethylene nonylphenol ether (4))-2-hydroxy-propanesulfonic acid salt 210 grams.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (4))-2-hydroxy-propanesulfonic acid salt 210 grams, join in the reactor that condensing works, whipping appts and gas distributor are housed, add 2 grams of sodium hydroxide and 20 grams of water, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, with nitrogen purging 4 times, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 66.5 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (4))-2-(Soxylat A 25-7 (4)) propanesulfonic acid salt 268 grams.
2. surfactant properties evaluation
Except oil-displacing agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing, the composition of oil-displacing agent is listed in table 2, evaluation result is listed in table 3 and table 4.
[embodiment 5]
1. tensio-active agent preparation
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 110 grams of nonyl phenols and 1.5 grams of sodium hydroxide and 15 grams of water are added, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, then use nitrogen purging 4 times with the air in removing system, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 176 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 281 grams of Nonyl pheno (8) ethers.
B) by step a) gained 281 grams of polyoxyethylene nonylphenol ethers (8) join in the reactor that whipping appts, condensation reflux unit and division box are housed, add 500 milliliters of benzene and 40 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 144 grams of 3-chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, drip excessive hydrochloric acid and the pH of system is transferred to 2, be extracted with ethyl acetate, after oil phase steams and desolventizes, with sodium hydroxide solution neutralization, then at volume ratio acetone: ethanol: water is that in the mixed solvent of 2:1:1, recrystallization obtains 3-(polyoxyethylene nonylphenol ether (8))-2-hydroxy-propanesulfonic acid salt 289 grams.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (8))-2-hydroxy-propanesulfonic acid salt 289 grams, join in the reactor that condensing works, whipping appts and gas distributor are housed, add 2 grams of sodium hydroxide and 20 grams of water, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, with nitrogen purging 4 times, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 139 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (8))-2-(Soxylat A 25-7 (8)) propanesulfonic acid salt 420 grams.
2. surfactant properties evaluation
Except oil-displacing agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing, the composition of oil-displacing agent is listed in table 2, evaluation result is listed in table 3 and table 4.
[embodiment 6]
1. tensio-active agent preparation
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 110 grams of nonyl phenols and 1.5 grams of sodium hydroxide and 15 grams of water are added, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, then use nitrogen purging 4 times with the air in removing system, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 88 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 192 grams of Nonyl pheno (4) ethers.
B) by step a) gained 192 grams of polyoxyethylene nonylphenol ethers (4) join in the reactor that whipping appts, condensation reflux unit and division box are housed, add 250 milliliters of benzene and 40 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 142 grams of 3-chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, drip excessive hydrochloric acid and the pH of system is transferred to 2, be extracted with ethyl acetate, after oil phase steams and desolventizes, with sodium hydroxide solution neutralization, then at volume ratio acetone: ethanol: water is that in the mixed solvent of 2:1:1, recrystallization obtains 3-(polyoxyethylene nonylphenol ether (4))-2-hydroxy-propanesulfonic acid salt 210 grams.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (4))-2-hydroxy-propanesulfonic acid salt 210 grams, join in the reactor that condensing works, whipping appts and gas distributor are housed, add 2 grams of sodium hydroxide and 20 grams of water, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, with nitrogen purging 4 times, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 66.5 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (4))-2-(Soxylat A 25-7 (4)) propanesulfonic acid salt 268 grams.
2. oil-displacing agent performance evaluation
Except oil-displacing agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing, the composition of oil-displacing agent is listed in table 2, evaluation result is listed in table 3 and table 4.
[embodiment 7]
1. tensio-active agent preparation
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 110 grams of nonyl phenols and 1.5 grams of sodium hydroxide and 15 grams of water are added, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, then use nitrogen purging 4 times with the air in removing system, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 88 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 192 grams of Nonyl pheno (4) ethers.
B) by step a) gained 192 grams of polyoxyethylene nonylphenol ethers (4) join in the reactor that whipping appts, condensation reflux unit and division box are housed, add 250 milliliters of benzene and 40 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 142 grams of 3-chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, drip excessive hydrochloric acid and the pH of system is transferred to 2, be extracted with ethyl acetate, after oil phase steams and desolventizes, with sodium hydroxide solution neutralization, then at volume ratio acetone: ethanol: water is that in the mixed solvent of 2:1:1, recrystallization obtains 3-(polyoxyethylene nonylphenol ether (4))-2-hydroxy-propanesulfonic acid salt 210 grams.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (4))-2-hydroxy-propanesulfonic acid salt 210 grams, join in the reactor that condensing works, whipping appts and gas distributor are housed, add 2 grams of sodium hydroxide and 20 grams of water, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, with nitrogen purging 4 times, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 66.5 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (4))-2-(Soxylat A 25-7 (4)) propanesulfonic acid salt 268 grams.
2. surfactant properties evaluation
Except oil-displacing agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing, the composition of oil-displacing agent is listed in table 2, evaluation result is listed in table 3 and table 4.
[embodiment 8]
1. tensio-active agent preparation
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 110 grams of nonyl phenols and 1.5 grams of sodium hydroxide and 15 grams of water are added, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, then use nitrogen purging 4 times with the air in removing system, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 44 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 146 grams of Nonyl pheno (2) ethers.
B) by step a) gained 146 grams of polyoxyethylene nonylphenol ethers (2) join in the reactor that whipping appts, condensation reflux unit and division box are housed, add 250 milliliters of benzene and 40 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 141 grams of 3-chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, drip excessive hydrochloric acid and the pH of system is transferred to 2, be extracted with ethyl acetate, after oil phase steams and desolventizes, with sodium hydroxide solution neutralization, then at volume ratio acetone: ethanol: water is that in the mixed solvent of 2:1:1, recrystallization obtains 3-(polyoxyethylene nonylphenol ether (2))-2-hydroxy-propanesulfonic acid salt 178 grams.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (2))-2-hydroxy-propanesulfonic acid salt 178 grams, join in the reactor that condensing works, whipping appts and gas distributor are housed, add 1.5 grams of sodium hydroxide and 15 grams of water, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, with nitrogen purging 4 times, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 67 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (2))-2-(Soxylat A 25-7 (4)) propanesulfonic acid salt 240 grams.
2. surfactant properties evaluation
Except oil-displacing agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing, the composition of oil-displacing agent is listed in table 2, evaluation result is listed in table 3 and table 4.
[embodiment 9]
1. tensio-active agent preparation
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 110 grams of nonyl phenols and 1.5 grams of sodium hydroxide and 15 grams of water are added, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, then use nitrogen purging 4 times with the air in removing system, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 88 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 192 grams of Nonyl pheno (4) ethers.
B) by step a) gained 192 grams of polyoxyethylene nonylphenol ethers (4) join in the reactor that whipping appts, condensation reflux unit and division box are housed, add 400 milliliters of benzene and 38 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 142 grams of 3-chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, drip excessive hydrochloric acid and the pH of system is transferred to 2, be extracted with ethyl acetate, after oil phase steams and desolventizes, with sodium hydroxide solution neutralization, then at volume ratio acetone: ethanol: water is that in the mixed solvent of 2:1:1, recrystallization obtains 3-(polyoxyethylene nonylphenol ether (4))-2-hydroxy-propanesulfonic acid salt 210 grams.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (4))-2-hydroxy-propanesulfonic acid salt 210 grams, join in the reactor that condensing works, whipping appts and gas distributor are housed, add 2 grams of sodium hydroxide and 20 grams of water, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, with nitrogen purging 4 times, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 166 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (4))-2-(Soxylat A 25-7 (10)) propanesulfonic acid salt 367 grams.
2. surfactant properties evaluation
Except oil-displacing agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing, the composition of oil-displacing agent is listed in table 2, evaluation result is listed in table 3 and table 4.
[embodiment 10]
1. tensio-active agent preparation
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 110 grams of nonyl phenols and 1.5 grams of sodium hydroxide and 15 grams of water are added, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, then use nitrogen purging 4 times with the air in removing system, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 440 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 541 grams of Nonyl pheno (20) ethers.
B) by step a) gained 541 grams of polyoxyethylene nonylphenol ethers (20) join in the reactor that whipping appts, condensation reflux unit and division box are housed, add 800 milliliters of benzene and 40 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 144 grams of 3-chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, drip excessive hydrochloric acid and the pH of system is transferred to 2, be extracted with ethyl acetate, after oil phase steams and desolventizes, with sodium hydroxide solution neutralization, then at volume ratio acetone: ethanol: water is that in the mixed solvent of 2:1:1, recrystallization obtains 3-(polyoxyethylene nonylphenol ether (20))-2-hydroxy-propanesulfonic acid salt 536 grams.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (20))-2-hydroxy-propanesulfonic acid salt 536 grams, join in the reactor that condensing works, whipping appts and gas distributor are housed, add 2 grams of sodium hydroxide and 20 grams of water, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, with nitrogen purging 4 times, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 19 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (20))-2-(Soxylat A 25-7 (1)) propanesulfonic acid salt 288 grams.
2. surfactant properties evaluation
Except oil-displacing agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing, the composition of oil-displacing agent is listed in table 2, evaluation result is listed in table 3 and table 4.
[embodiment 11]
1. tensio-active agent preparation
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 103 grams of octyl phenols and 1.5 grams of sodium hydroxide and 15 grams of water are added, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, then use nitrogen purging 4 times with the air in removing system, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 66 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 160 grams of octyl phenol polyoxyethylene (3) ethers.
B) by step a) gained 160 polyoxyethylene octylphenol ether (3) join in the reactor that whipping appts, condensation reflux unit and division box are housed, add 300 milliliters of benzene and 38 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 140 grams of 3-chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, drip excessive hydrochloric acid and the pH of system is transferred to 2, be extracted with ethyl acetate, after oil phase steams and desolventizes, with sodium hydroxide solution neutralization, then at volume ratio acetone: ethanol: water is that in the mixed solvent of 2:1:1, recrystallization obtains 3-(polyoxyethylene octylphenol ether (3))-2-hydroxy-propanesulfonic acid salt 176 grams.
C) by step b) synthesize 3-(polyoxyethylene octylphenol ether (3))-2-hydroxy-propanesulfonic acid salt 176 grams, join in the reactor that condensing works, whipping appts and gas distributor are housed, add 1.5 grams of sodium hydroxide and 15 grams of water, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, with nitrogen purging 4 times, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 47 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene octylphenol ether (3))-2-(Soxylat A 25-7 (3)) propanesulfonic acid salt 218 grams.
2. surfactant properties evaluation
Except oil-displacing agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing, the composition of oil-displacing agent is listed in table 2, evaluation result is listed in table 3 and table 4.
[embodiment 12]
1. tensio-active agent preparation
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 103 grams of octyl phenols and 1.5 grams of sodium hydroxide and 15 grams of water are added, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, then use nitrogen purging 4 times with the air in removing system, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 22 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 121 grams of octyl phenol polyoxyethylene (1) ethers.
B) by step a) gained 121 grams of polyoxyethylene octylphenol ethers (1) join in the reactor that whipping appts, condensation reflux unit and division box are housed, add 250 milliliters of benzene and 40 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 142 grams of 3-chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, drip excessive hydrochloric acid and the pH of system is transferred to 2, be extracted with ethyl acetate, after oil phase steams and desolventizes, with sodium hydroxide solution neutralization, then at volume ratio acetone: ethanol: water is that in the mixed solvent of 2:1:1, recrystallization obtains 3-(polyoxyethylene octylphenol ether (1))-2-hydroxy-propanesulfonic acid salt 158 grams.
C) by step b) synthesize 3-(polyoxyethylene octylphenol ether (1))-2-hydroxy-propanesulfonic acid salt 158 grams, join in the reactor that condensing works, whipping appts and gas distributor are housed, add 1.5 grams of sodium hydroxide and 15 grams of water, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, with nitrogen purging 4 times, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 85 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene octylphenol ether (1))-2-(Soxylat A 25-7 (5)) propanesulfonic acid salt 237 grams.
2. surfactant properties evaluation
Except oil-displacing agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing, the composition of oil-displacing agent is listed in table 2, evaluation result is listed in table 3 and table 4.
[embodiment 13]
1. tensio-active agent preparation
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 82 grams of amylic phenols and 1 gram of sodium hydroxide and 10 grams of water are added, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, then use nitrogen purging 4 times with the air in removing system, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 110 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 186 grams of amylic phenol polyoxyethylene (5) ethers.
B) by step a) gained 186 grams of amylic phenol polyoxyethylene (5) ethers join in the reactor that whipping appts, condensation reflux unit and division box are housed, add 500 milliliters of benzene solvents and 40 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 136 grams of 3-chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, drip excessive dilute hydrochloric acid and the pH of system is transferred to 2, be extracted with ethyl acetate, after oil phase steams and desolventizes, with sodium hydroxide solution neutralization, then at volume ratio acetone: ethanol: water is that in the mixed solvent of 2:1:1, recrystallization obtains 213 grams of 3-(amylic phenol polyoxyethylene (5) ethers)-2-hydroxy-propanesulfonic acid salt.
C) by step b) 3-(amylic phenol polyoxyethylene (5) ether that synthesizes)-2-hydroxy-propanesulfonic acid salt 213 grams, join in the reactor that condensing works, whipping appts and gas distributor are housed, add 1.5 grams of sodium hydroxide and 15 grams of water, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, with nitrogen purging 4 times, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 35 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 242 grams of 3-(amylic phenol polyoxyethylene (5) ethers)-2-(polyoxyethylene (2) ether) propanesulfonic acid salt.
2. surfactant properties evaluation
Except oil-displacing agent composition difference, method of evaluating performance is with embodiment 1.For ease of comparing, the composition of oil-displacing agent is listed in table 2, evaluation result is listed in table 3 and table 4.
[embodiment 14]
1. tensio-active agent preparation
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 150 grams of 4-dodecylphenols and 1.5 grams of sodium hydroxide and 15 grams of water are added, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, then use nitrogen purging 4 times with the air in removing system, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 50 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 192 grams of dodecyl phenol polyethenoxy (2) ethers.
B) by step a) gained 192 grams of dodecyl phenol polyethenoxy (2) ethers join in the reactor that whipping appts, condensation reflux unit and division box are housed, add 400 milliliters of benzene solvents and 30 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 146 grams of 3-chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, drip excessive hydrochloric acid and the pH of system is transferred to 2, be extracted with ethyl acetate, after oil phase steams and desolventizes, with sodium hydroxide solution neutralization, then at volume ratio acetone: ethanol: water is that in the mixed solvent of 2:1:1, recrystallization obtains 223 grams of 3-(dodecyl phenol polyethenoxy (2) ethers)-2-hydroxy-propanesulfonic acid salt.
C) by step b) synthesize 3-(dodecyl phenol polyethenoxy (2) ether)-2-hydroxypropionate sodium 223 grams, join in the reactor that condensing works, whipping appts and gas distributor are housed, add 1.5 grams of sodium hydroxide and 15 grams of water, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, with nitrogen purging 4 times, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 77 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 292 grams of 3-(dodecyl phenol polyethenoxy (2) ether)-2-(polyoxyethylene (4) ether) sulfonate.
2. surfactant properties evaluation
Method of evaluating performance is with embodiment 1.For ease of comparing, the composition of oil-displacing agent is listed in table 2, evaluation result is listed in table 3 and table 4.
[embodiment 15]
1. tensio-active agent preparation
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 115 grams of hexadecyl phenol and 1 gram of sodium hydroxide and 10 grams of water are added, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, then use nitrogen purging 4 times with the air in removing system, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 80 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 190 grams of hexadecyl phenol polyethenoxy (5) ethers.
B) by step a) gained 190 grams of hexadecyl phenol polyethenoxy (5) ethers join in the reactor that whipping appts, condensation reflux unit and division box are housed, add 400 milliliters of benzene solvents and 26 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 130 grams of 3-chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, drip excessive hydrochloric acid and the pH of system is transferred to 2, be extracted with ethyl acetate, after oil phase steams and desolventizes, with sodium hydroxide solution neutralization, then at volume ratio acetone: ethanol: water is that in the mixed solvent of 2:1:1, recrystallization obtains 208 grams of 3-(hexadecyl phenol polyethenoxy (5) ethers)-2-hydroxy-propanesulfonic acid salt.
C) by step b) synthesize 3-(hexadecyl phenol polyethenoxy (5) ether)-2-hydroxy-propanesulfonic acid salt 208 grams, join in the reactor that condensing works, whipping appts and gas distributor are housed, add 1 gram of sodium hydroxide and 10 grams of water, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, with nitrogen purging 4 times, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 66 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 267 grams of 3-(hexadecyl phenol polyethenoxy (5) ethers)-2-(polyoxyethylene (5) ether) propanesulfonic acid salt.
2. surfactant properties evaluation
Oil-displacing agent is prepared:
By above-mentioned steps c) 3-(hexadecyl phenol polyethenoxy (5) ether that synthesizes)-2-(polyoxyethylene (5) ether) propanesulfonic acid salt 1 weight part, methyl-sulphoxide (DMSO) 0.5 weight part and Jiang-Han Area Bamianhe Oilfield inject water 500 weight part mix and blend 1 hour, obtains a kind of oil-displacing agent of homogeneous transparent.Other method of evaluating performance is with embodiment 1.For ease of comparing, the composition of oil-displacing agent is listed in table 2, evaluation result is listed in table 3 and table 4.
[comparative example 1]
1. tensio-active agent preparation
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 110 grams of nonyl phenols and 1.5 grams of sodium hydroxide and 15 grams of water are added, while lead to nitrogen limit when being heated to 85 DEG C, stirring reaction 1 hour.Open vacuum system, at 90 DEG C of temperature, vacuumize dehydration 1 hour, then use nitrogen purging 4 times with the air in removing system, then system temperature of reaction is adjusted to 150 DEG C and slowly passes into 176 grams of oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 281 grams of Nonyl pheno (8) ethers.
B) by step a) gained 281 grams of polyoxyethylene nonylphenol ethers (8) join in the reactor that whipping appts, condensation reflux unit and division box are housed, add 500 milliliters of benzene and 40 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 144 grams of 3-chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, drip excessive hydrochloric acid and the pH of system is transferred to 2, be extracted with ethyl acetate, after oil phase steams and desolventizes, neutralize with sodium hydroxide solution, then at volume ratio acetone: ethanol: water is that in the mixed solvent of 2:1:1, recrystallization obtains 3-(polyoxyethylene nonylphenol ether (8))-2-hydroxy-propanesulfonic acid salt 289 grams, structure is as follows:
2. surfactant properties evaluation
3-(polyoxyethylene nonylphenol ether (8) by above-mentioned synthesis)-2-hydroxy-propanesulfonic acid salt 1 weight part and Jiang-Han Area Bamianhe Oilfield inject water 500 weight part mix and blend 1 hour, obtains oil-displacing agent solution.
A) interfacial tension evaluation
Adopt Texas ,Usa university to produce TX-500C to rotate and drip an interfacial tensimeter, at 80 DEG C, rotating speed is under 4500 revs/min of conditions, and the interfacial tension between the dewatered oil measuring above-mentioned oil-displacing agent and Bamianhe Oilfield extraction the results are shown in Table 5.
B) oil displacement experiment evaluation
According to the composite oil-displacing system physical simulation flooding test measure of merit in SY/T6424-2000 composite oil-displacing system performance test methods, at 80 DEG C, length is 30cm, and diameter is 2.5cm, and rate of permeation is 1.5 m
2rock core on carry out imitation oil displacement experiment experiment.First inject water by Bamianhe Oilfield and carry out water drive to moisture 98%, after water drive terminates, metaideophone 0.3pv(rock pore volume) above-mentioned oil-displacing agent, then water drive is to moisture 98%, improves oil recovery factor and the results are shown in Table 5.
[comparative example 2]
1. tensio-active agent preparation
According to the method described in patent U.S. Pat. No.4466891A, synthesize the tensio-active agent of following structure:
2. surfactant properties evaluation
Above-mentioned tensio-active agent 1 weight part and Jiang-Han Area Bamianhe Oilfield are injected water 500 weight part mix and blend 1 hour, obtains a kind of oil-displacing agent of homogeneous transparent.Other is with comparative example 1, will the results are shown in table 5 for ease of comparing.
[comparative example 3]
1. tensio-active agent preparation
Following structure is synthesized according to patent U.S.Pat.No.2011015111A1 method:
Tensio-active agent.
2. surfactant properties evaluation
Above-mentioned tensio-active agent 1 weight part and Jiang-Han Area Bamianhe Oilfield are injected water 500 weight part mix and blend 1 hour, obtains a kind of oil-displacing agent of homogeneous transparent.Other is with comparative example 1, will the results are shown in table 5 for ease of comparing.
[comparative example 4]
1. tensio-active agent preparation
Following structure is synthesized according to patent U.S. Pat. No.4466891A method:
Tensio-active agent.
2. surfactant properties evaluation
Above-mentioned tensio-active agent 1 weight part and Jiang-Han Area Bamianhe Oilfield are injected water 500 weight part mix and blend 1 hour, obtains a kind of oil-displacing agent of homogeneous transparent.Other is with comparative example 1, will the results are shown in table 5 for ease of comparing.
Table 1 Bamianhe Oilfield injects water
| Project | Na ++K + | Mg 2+ | Ca 2+ | Cl - | SO 4 2- | HCO 3 - | TDS |
| mg/L | 9776.0 | 294.3 | 1499.1 | 17003.2 | 2055.2 | 167.0 | 30794.8 |
Table 2 embodiment 1-16 oil-displacing agent forms
Table 3 embodiment 1-16 oil-displacing agent interfacial tension performance
Table 4 embodiment 1-16 oil displacement experiment result
Table 5 comparative example 1-4 the performance test results
| Comparative example | Interfacial tension (mN/m) | Improve recovery ratio % |
| 1 | 0.0082 | 3.3 |
| 2 | 0.013 | 2.5 |
| 3 | 0.041 | 1.7 |
| 4 | 0.113 | 0.9 |
Claims (10)
1. improve a surfactant oil displacement for oil recovery factor, its name is called 3-(alkyl phenol polyethenoxy ether)-2-(Soxylat A 25-7) propanesulfonic acid salt, structure as shown in the formula (I):
（I）
Wherein M be in basic metal, alkaline-earth metal any one, n is SO in M and formula (I)
3the mol ratio of group, when M is basic metal, n is 1, and when M is alkaline-earth metal, n is 0.5, R is C
4~ C
20alkyl, x=1 ~ 20, y=1 ~ 20.
2. surfactant oil displacement according to claim 1, is characterized in that x=2 ~ 8, y=2 ~ 8.
3. surfactant oil displacement according to claim 2, is characterized in that x=y.
4. surfactant oil displacement according to claim 2, is characterized in that described alkyl is C
7~ C
10alkane.
5. the preparation method of surfactant oil displacement according to claim 1, comprises the following steps:
A) under basic catalyst effect, alkyl phenol and aequum oxyethane are 85 ~ 160 DEG C in temperature of reaction, and pressure is 0 ~ 0.40MPa(gauge pressure), react 1 ~ 10 hour, obtain alkyl phenol polyethenoxy ether;
B) step a gained alkyl phenol polyethenoxy ether is dissolved into C
6~ C
8in aromatic hydrocarbons, add at least one alkali in alkali metal hydroxide or alkaline earth metal hydroxides, the mol ratio of described alkyl phenol polyethenoxy ether and described alkali is 1:1 ~ 3, alkalize 0.5 ~ 3 hour at 30 ~ 60 DEG C, add an alkali metal salt of 3-chlorine-2-hydroxyl propanesulfonic acid, the mol ratio of wherein said alkyl phenol polyethenoxy ether and 3-chlorine-2-hydroxyl propanesulfonic acid an alkali metal salt is 1:1 ~ 4, stirring lower temperature of reaction is 30 ~ 80 DEG C, and the reaction times is within 6 ~ 18 hours, obtain 3-(alkyl phenol polyethenoxy ether)-2-hydroxy-propanesulfonic acid salt;
C) by step b) gained 3-(alkyl phenol polyethenoxy ether)-2-hydroxy-propanesulfonic acid salt, under basic catalyst effect, be 85 ~ 160 DEG C with aequum oxyethane in temperature of reaction, pressure is 0 ~ 0.40MPa(gauge pressure), react 1 ~ 10 hour, obtain described 3-(alkyl phenol polyethenoxy ether)-2-(Soxylat A 25-7) propanesulfonic acid salt.
6. the preparation method of surfactant oil displacement according to claim 5, is characterized in that step a) and step c) described basic catalyst is at least one in alkali metal hydroxide, the oxyhydroxide of alkaline-earth metal or the oxide compound of alkaline-earth metal.
7. the preparation method of surfactant oil displacement according to claim 6, is characterized in that described basic catalyst is at least one in sodium hydroxide or potassium hydroxide.
8. the preparation method of surfactant oil displacement according to claim 5, it is characterized in that temperature of reaction described in step a) is 120 ~ 140 DEG C, the reaction times is 6 ~ 8 hours.
9. the application of tensio-active agent described in claim 1 in the displacement of reservoir oil of oil field.
10. application according to claim 9, is characterized in that application method is will comprise 1 part, described tensio-active agent with weight parts to inject oil-bearing formation with the oil-displacing agent of 100 ~ 2000 parts, water.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106590579A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Oil displacing composition for oil reservoir with high salinity and preparation method thereof |
| CN106590584A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Oil-displacement surfactant for high-salt oil reservoirs |
| CN110872357A (en) * | 2019-11-06 | 2020-03-10 | 中国石油天然气股份有限公司 | Polypeptide surfactant and preparation and application thereof |
| CN111088014A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Yin-yang composite surfactant for oil extraction, preparation method thereof and oil displacement method |
| CN111088013A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Anion-cation composite oil displacement surfactant, preparation method thereof and oil displacement method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106590579A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Oil displacing composition for oil reservoir with high salinity and preparation method thereof |
| CN106590584A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Oil-displacement surfactant for high-salt oil reservoirs |
| CN106590584B (en) * | 2015-10-20 | 2019-05-14 | 中国石油化工股份有限公司 | Oil displacement surfactant for high salinity reservoir |
| CN106590579B (en) * | 2015-10-20 | 2019-06-11 | 中国石油化工股份有限公司 | For high salinity reservoir displacement composition and preparation method thereof |
| CN111088014A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Yin-yang composite surfactant for oil extraction, preparation method thereof and oil displacement method |
| CN111088013A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Anion-cation composite oil displacement surfactant, preparation method thereof and oil displacement method |
| CN111088014B (en) * | 2018-10-23 | 2022-02-01 | 中国石油化工股份有限公司 | Yin-yang composite surfactant for oil extraction, preparation method thereof and oil displacement method |
| CN111088013B (en) * | 2018-10-23 | 2022-07-12 | 中国石油化工股份有限公司 | Anion-cation composite oil displacement surfactant, preparation method thereof and oil displacement method |
| CN110872357A (en) * | 2019-11-06 | 2020-03-10 | 中国石油天然气股份有限公司 | Polypeptide surfactant and preparation and application thereof |
| CN110872357B (en) * | 2019-11-06 | 2021-04-30 | 中国石油天然气股份有限公司 | Polypeptide surfactant and preparation and application thereof |
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