CN105273704A - Salt-resistant oil-displacing surfactant and preparation method thereof - Google Patents
Salt-resistant oil-displacing surfactant and preparation method thereof Download PDFInfo
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- CN105273704A CN105273704A CN201410328886.2A CN201410328886A CN105273704A CN 105273704 A CN105273704 A CN 105273704A CN 201410328886 A CN201410328886 A CN 201410328886A CN 105273704 A CN105273704 A CN 105273704A
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Abstract
The invention relates to a salt-resistant oil-displacing surfactant and a preparation method thereof to mainly overcome the problem that a conventional surfactant has low oil-displacing efficiency under the condition of hypersalinity. The salt-resistant oil-displacing surfactant, named as 3-(alkylphenol polyoxyethylene ether)-2-(hydroxypropylsulfonic acid polyoxypropylene ether)propanesulfonate, has a structural formula (I) as described in the specification. In the formula (I), M1 and M2 are independently selected from alkali metal and alkaline earth metal, wherein n1 is 1 if M1 is the alkali metal, n1 is 0.5 if M1 is the alkaline earth metal, n2 is 1 if M2 is the alkali metal, and n2 is 0.5 if M2 is the alkaline earth metal; R is a C4-20 alkyl group; x is in a range of 1 to 20; and y is in a range of 1 to 10. The salt-resistant oil-displacing surfactant perfectly overcomes the above-mentioned problem and can be applied to production for improving crude oil recovery efficiency of an oil field.
Description
Technical field
The present invention relates to a kind of salt tolerant oil displacement surfactant 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, it is stable not that this kind of tensio-active agent also also exists performance, salt tolerant is the series of problems such as poor-performing of resistance to divalent cation especially, 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.4466891A provides a kind of alkylphenol polyoxyethylene propanesulfonic acid salt; 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.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 salt tolerant oil displacement surfactant, this tensio-active agent has the advantages that oil displacement efficiency is high under high salinity condition.
Two of technical problem to be solved by this invention is to provide a kind of preparation method of the salt tolerant oil displacement surfactant corresponding with one of technical solution problem.
Three of technical problem to be solved by this invention is that the described tensio-active agent of one of technical problem improves the application in oil recovery factor in oil field.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: salt tolerant oil displacement surfactant, its name is called 3-(alkyl phenol polyethenoxy ether)-2-(hydroxypropyl sulfonic acid polyethenoxy ether) propanesulfonic acid salt, and structure is such as formula shown in (I):
Wherein M
1and M
2independently be selected from in basic metal, alkaline-earth metal any one, work as M
1for n during basic metal
1be 1, work as M
1for n during alkaline-earth metal
1be 0.5, work as M
2for n during basic metal
2be 1, work as M
2for n during alkaline-earth metal
2be 0.5, R be C
4~ C
20alkyl, x=1 ~ 20, y=1 ~ 10.
In technique scheme, preferred x=2 ~ 8, y=2 ~ 4.
In technique scheme, described alkyl is preferably C
7~ C
10alkyl.
In technique scheme, as the most preferred technical scheme: described alkyl is C
8~ C
9alkyl, x=4 ~ 6, y=2-3.
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 described salt tolerant oil displacement surfactant of one of above-mentioned technical problem, comprises the following steps:
A) under basic catalyst effect, alkyl phenol and aequum reacting ethylene oxide obtain alkyl phenol polyethenoxy ether; Temperature of reaction is preferably 85 ~ 160 DEG C, and pressure is preferably 0 ~ 0.40MPa (gauge pressure), and the reaction times is preferably 1 ~ 10 hour;
B) by step a) gained alkyl phenol polyethenoxy ether be dissolved into C
6~ C
8in aromatic hydrocarbons, add at least one alkali in alkali metal hydroxide or alkaline earth metal hydroxides, alkalize 0.5 ~ 3 hour at 30 ~ 60 DEG C, add an alkali metal salt of 3-chlorine-2-hydroxyl propanesulfonic acid, under stirring, be obtained by reacting 3-(alkyl phenol polyethenoxy ether)-2-hydroxy-propanesulfonic acid salt; The mol ratio of described alkyl phenol polyethenoxy ether and described alkali is preferably 1:(1 ~ 3); The mol ratio of wherein said alkyl phenol polyethenoxy ether and 3-chlorine-2-hydroxyl propanesulfonic acid an alkali metal salt is preferably 1:(1 ~ 4); Temperature of reaction is preferably 30 ~ 80 DEG C; Reaction times is preferably 6 ~ 18 hours;
C) by step b) gained 3-(alkyl phenol polyethenoxy ether)-2-hydroxy-propanesulfonic acid salt, under basic catalyst effect, obtain described 3-(alkyl phenol polyethenoxy ether)-2-(polyethenoxy ether) propanesulfonic acid salt with aequum propylene oxide reaction; Temperature of reaction is preferably 85 ~ 160 DEG C; Reaction pressure is preferably 0 ~ 0.40MPa (gauge pressure); Preferably 1 ~ 10 hour reaction times;
D) by step c) gained 3-(alkyl phenol polyethenoxy ether)-2-(polyethenoxy ether) propanesulfonic acid salt, be dissolved into C
6~ C
8in aromatic hydrocarbons, add at least one alkali in alkali metal hydroxide or alkaline earth metal hydroxides, alkalize 0.5 ~ 3 hour at 30 ~ 60 DEG C, add an alkali metal salt of 3-chlorine-2-hydroxyl propanesulfonic acid, under stirring, be obtained by reacting 3-(alkyl phenol polyethenoxy ether)-2-(hydroxypropyl sulfonic acid polyethenoxy ether) propanesulfonic acid salt; The mol ratio of described 3-(alkyl phenol polyethenoxy ether)-2-(polyethenoxy ether) propanesulfonic acid salt and described alkali is preferably 1:(1 ~ 3); The mol ratio of an alkali metal salt of described 3-(alkyl phenol polyethenoxy ether)-2-(polyethenoxy ether) propanesulfonic acid salt and 3-chlorine-2-hydroxyl propanesulfonic acid is preferably 1:(1 ~ 4); Temperature of reaction is preferably 30 ~ 80 DEG C; Reaction times is preferably 6 ~ 18 hours.
In technique scheme, step a) and/or step c) at least one in described basic catalyst preferred alkali metal hydroxide or alkaline earth metal hydroxides.Step b) mol ratio of described alkyl phenol polyethenoxy ether and 3-chlorine-2-hydroxyl propanesulfonic acid an alkali metal salt is more preferably 1:(1 ~ 2), the reaction times is more preferably 6 ~ 10 hours.Step a) and/or step c) at least one of described basic catalyst more preferably in sodium hydroxide or potassium hydroxide.Step a) and/or step c) described temperature of reaction is more preferably 120 ~ 140 DEG C, the reaction times is more preferably 6 ~ 8 hours.
For solving the technology of the present invention problem three, the technical solution used in the present invention is as follows: the described tensio-active agent of one of above-mentioned technical problem is improving the application in oil recovery factor.
In technique scheme, the concrete grammar of described application can for inject oil-bearing formation by 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 80000-300000mg/L, Ca
2++ Mg
2+for the water of 1000-6000mg/L, for the consideration of the aspect such as easy construction, saving water resource, be more preferably oilfield injection water, water is injected in the Pu Chengxi District, Zhongyuan Oil Field that the such as embodiment of the present invention adopts.In order to increase oil displacement efficiency, the additive that this area is conventional can also be comprised in oil-displacing agent of the present invention, such as small molecule alcohol, DMSO, diethanolamine, CTAC etc.
Key problem in technology of the present invention is that tensio-active agent have employed novel anion-nonionic tensio-active agent, and containing multiple hydrophilic radical, two sulfonic acid groups lay respectively at the centre of molecule segment and polyoxyethylene and polyoxypropylene segment.Simultaneously because the synergy of multiple group considerably increases the anti-salt of tensio-active agent and the performance of anti-divalent cation, compared with anion-nonionic tensio-active agent of the prior art, the tensio-active agent salt resistance ability that the present invention adopts is stronger, can be used for the oil reservoir displacement of reservoir oil of high salinity, 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 at Pu Chengxi District, Zhongyuan Oil Field formation temperature 85 DEG C, salinity 80000-300000mg/L, Ca
2+, Mg
2+concentration is still can form 10 with this block dewatered oil under the condition of 1000-6000mg/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, 0.5mol nonyl phenol 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 1.5mol oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 0.49mol Nonyl pheno (3) ether.
B) by step a) gained polyoxyethylene nonylphenol ether (3) 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 0.61mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 8 hours.After reaction terminates, dropping concentration is that the pH of system is transferred to 2 by the hydrochloric acid of 6M, 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 (3))-2-hydroxy-propanesulfonic acid salt (0.39mol).
C) by step b) 3-(polyoxyethylene nonylphenol ether (3))-2-hydroxy-propanesulfonic acid salt that synthesizes, 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 0.39mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (3))-2-(polyethenoxy ether (1)) propanesulfonic acid salt (0.39mol).
D) by step c) 3-(polyoxyethylene nonylphenol ether (3))-2-(polyethenoxy ether (1)) the propanesulfonic acid salt (0.39mol) that synthesizes joins and whipping appts is housed, in the reactor of condensation reflux unit and division box, add 200 milliliters of benzene and sodium hydroxide (0.78mol), alkalize 2 hours at 60 DEG C, add 0.47mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 5 hours, obtain 3-(polyoxyethylene nonylphenol ether (3))-2-(hydroxypropyl sulfonic acid polyethenoxy ether (1)) propanesulfonic acid salt (0.36mol).
2. surfactant properties evaluation
Oil-displacing agent is prepared:
Above-mentioned tensio-active agent 1 weight part and Pu Chengxi District 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, the composition of water is injected in table 1 in Pu Chengxi District used.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 85 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 the extraction of Pu Chengxi District 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 85 DEG C, length is 30cm, and diameter is 2.5cm, and rate of permeation is 1.5m
2rock core on carry out imitation oil displacement experiment experiment.First inject water with Pu Chengxi District 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, 0.5mol nonyl phenol 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 0.5mol 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) by step a) gained 0.5mol polyoxyethylene nonylphenol ether (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 0.6mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 8 hours.After reaction terminates, dropping concentration is that the pH of system is transferred to 2 by the hydrochloric acid of 6M, 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 0.38mol.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (1))-2-hydroxy-propanesulfonic acid salt 0.38mol, 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 1.52mol propylene oxide, control pressure≤0.40MPa reaction; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (1))-2-(polyethenoxy ether (4)) propanesulfonic acid salt 0.37mol.
D) by step c) 3-(polyoxyethylene nonylphenol ether (1))-2-(polyethenoxy ether (4)) the propanesulfonic acid salt (0.37mol) that synthesizes joins and whipping appts is housed, in the reactor of condensation reflux unit and division box, add 200 milliliters of benzene and sodium hydroxide (0.74mol), alkalize 2 hours at 60 DEG C, add 0.45mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 5 hours, obtain 3-(polyoxyethylene nonylphenol ether (1))-2-(hydroxypropyl sulfonic acid polyethenoxy ether (4)) propanesulfonic acid salt (0.35mol).
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, 0.5mol nonyl phenol 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 1.0mol oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 0.49mol Nonyl pheno (2) ether.
B) by step a) gained 0.49mol polyoxyethylene nonylphenol ether (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 0.59mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 8 hours.After reaction terminates, dropping concentration is that the pH of system is transferred to 2 by the hydrochloric acid of 6M, 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 0.38mol.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (2))-2-hydroxy-propanesulfonic acid salt 0.38mol, 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 0.76mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (2))-2-(polyethenoxy ether (2)) propanesulfonic acid salt 0.36mol.
D) by step c) 3-(polyoxyethylene nonylphenol ether (2))-2-(polyethenoxy ether (2)) the propanesulfonic acid salt (0.36mol) that synthesizes joins and whipping appts is housed, in the reactor of condensation reflux unit and division box, add 200 milliliters of benzene and sodium hydroxide (0.72mol), alkalize 2 hours at 60 DEG C, add 0.42mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 5 hours, obtain 3-(polyoxyethylene nonylphenol ether (2))-2-(hydroxypropyl sulfonic acid polyethenoxy ether (2)) propanesulfonic acid salt (0.33mol).
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, 0.5mol nonyl phenol 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 2.0mol oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 0.49mol Nonyl pheno (4) ether.
B) by step a) gained 0.49mol polyoxyethylene nonylphenol ether (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 0.58mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 8 hours.After reaction terminates, dropping concentration is that the pH of system is transferred to 2 by the hydrochloric acid of 6M, 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 0.38mol.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (4))-2-hydroxy-propanesulfonic acid salt 0.38mol, 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 0.76mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (4))-2-(polyethenoxy ether (2)) propanesulfonic acid salt 0.37mol.
D) by step c) 3-(polyoxyethylene nonylphenol ether (2))-2-(polyethenoxy ether (2)) the propanesulfonic acid salt (0.36mol) that synthesizes joins and whipping appts is housed, in the reactor of condensation reflux unit and division box, add 200 milliliters of benzene and sodium hydroxide (0.72mol), alkalize 2 hours at 60 DEG C, add 0.42mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 5 hours, obtain 3-(polyoxyethylene nonylphenol ether (2))-2-(hydroxypropyl sulfonic acid polyethenoxy ether (2)) propanesulfonic acid salt (0.33mol).
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, 0.5mol nonyl phenol 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 3.0mol oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 0.49mol Nonyl pheno (6) ether.
B) by step a) gained 0.49mol polyoxyethylene nonylphenol ether (6) 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 0.58mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 8 hours.After reaction terminates, dropping concentration is that the pH of system is transferred to 2 by the hydrochloric acid of 6M, 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 0.39mol.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (6))-2-hydroxy-propanesulfonic acid salt 0.39mol, 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 1.18mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (6))-2-(polyethenoxy ether (3)) propanesulfonic acid salt 0.38mol.
D) by step c) 3-(polyoxyethylene nonylphenol ether (6))-2-(polyethenoxy ether (3)) the propanesulfonic acid salt (0.38mol) that synthesizes joins and whipping appts is housed, in the reactor of condensation reflux unit and division box, add 200 milliliters of benzene and sodium hydroxide (0.76mol), alkalize 2 hours at 60 DEG C, add 0.44mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 5 hours, obtain 3-(polyoxyethylene nonylphenol ether (6))-2-(hydroxypropyl sulfonic acid polyethenoxy ether (3)) propanesulfonic acid salt (0.35mol).
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
Use the tensio-active agent that embodiment 5 is synthesized, difference is compound concentration.
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
Use the tensio-active agent that embodiment 5 is synthesized, difference is compound concentration.
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, 0.5mol nonyl phenol 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 4.0mol oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 0.49mol Nonyl pheno (8) ether.
B) by step a) gained 0.49mol polyoxyethylene nonylphenol ether (8) 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 0.58mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 8 hours.After reaction terminates, dropping concentration is that the pH of system is transferred to 2 by the hydrochloric acid of 6M, 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 0.39mol.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (8))-2-hydroxy-propanesulfonic acid salt 0.39mol, 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 1.17mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (8))-2-(polyethenoxy ether (3)) propanesulfonic acid salt 0.38mol.
D) by step c) 3-(polyoxyethylene nonylphenol ether (8))-2-(polyethenoxy ether (3)) the propanesulfonic acid salt (0.38mol) that synthesizes joins and whipping appts is housed, in the reactor of condensation reflux unit and division box, add 200 milliliters of benzene and sodium hydroxide (0.76mol), alkalize 2 hours at 60 DEG C, add 0.44mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 5 hours, obtain 3-(polyoxyethylene nonylphenol ether (8))-2-(hydroxypropyl sulfonic acid polyethenoxy ether (3)) propanesulfonic acid salt (0.35mol).
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, 0.5mol nonyl phenol 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 2.0mol oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 0.49mol Nonyl pheno (4) ether.
B) by step a) gained 0.49mol polyoxyethylene nonylphenol ether (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 0.58mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 8 hours.After reaction terminates, dropping concentration is that the pH of system is transferred to 2 by the hydrochloric acid of 6M, 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 0.39mol.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (4))-2-hydroxy-propanesulfonic acid salt 0.39mol, 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 0.39mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (4))-2-(polyethenoxy ether (1)) propanesulfonic acid salt 0.39mol.
D) by step c) 3-(polyoxyethylene nonylphenol ether (4))-2-(polyethenoxy ether (1)) the propanesulfonic acid salt (0.39mol) that synthesizes joins and whipping appts is housed, in the reactor of condensation reflux unit and division box, add 200 milliliters of benzene and sodium hydroxide (0.78mol), alkalize 2 hours at 60 DEG C, add 0.48mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 5 hours, obtain 3-(polyoxyethylene nonylphenol ether (4))-2-(hydroxypropyl sulfonic acid polyethenoxy ether (1)) propanesulfonic acid salt (0.36mol).
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, 0.5mol nonyl phenol 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 6.0mol oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 0.5mol Nonyl pheno (12) ether.
B) by step a) gained 0.5mol polyoxyethylene nonylphenol ether (12) join in the reactor that whipping appts, condensation reflux unit and division box are housed, add 400 milliliters of benzene and 40 grams of sodium hydroxide, alkalize 2 hours at 60 DEG C, add 0.6mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 8 hours.After reaction terminates, dropping concentration is that the pH of system is transferred to 2 by the hydrochloric acid of 6M, 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 (12))-2-hydroxy-propanesulfonic acid salt 0.38mol.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (12))-2-hydroxy-propanesulfonic acid salt 0.38mol, 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 3.8mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (12))-2-(polyethenoxy ether (10)) propanesulfonic acid salt 0.38mol.
D) by step c) 3-(polyoxyethylene nonylphenol ether (12))-2-(polyethenoxy ether (10)) the propanesulfonic acid salt (0.38mol) that synthesizes joins and whipping appts is housed, in the reactor of condensation reflux unit and division box, add 200 milliliters of benzene and sodium hydroxide (0.76mol), alkalize 2 hours at 60 DEG C, add 0.45mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 5 hours, obtain 3-(polyoxyethylene nonylphenol ether (12))-2-(hydroxypropyl sulfonic acid polyethenoxy ether (10)) propanesulfonic acid salt (0.35mol).
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, 0.5mol octyl phenol 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 1.5mol oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 0.49mol octyl phenol polyoxyethylene (3) ether.
B) by step a) gained 0.49mol 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 0.58mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 8 hours.After reaction terminates, dropping concentration is that the pH of system is transferred to 2 by the hydrochloric acid of 6M, 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 0.38mol.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (3))-2-hydroxy-propanesulfonic acid salt 0.38mol, 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 1.2mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene octylphenol ether (3))-2-(polyethenoxy ether (3)) propanesulfonic acid salt 0.38mol.
D) by step c) 3-(polyoxyethylene octylphenol ether (3))-2-(polyethenoxy ether (3)) the propanesulfonic acid salt (0.38mol) that synthesizes joins and whipping appts is housed, in the reactor of condensation reflux unit and division box, add 200 milliliters of benzene and sodium hydroxide (0.76mol), alkalize 2 hours at 60 DEG C, add 0.44mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 5 hours, obtain 3-(polyoxyethylene octylphenol ether (3))-2-(hydroxypropyl sulfonic acid polyethenoxy ether (3)) propanesulfonic acid salt (0.34mol).
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, 0.5mol gram of octyl phenol 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 4.2mol oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 0.5mol octyl phenol polyoxyethylene (8) ether.
B) by step a) gained 0.5mol polyoxyethylene octylphenol ether (8) 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 0.6mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 8 hours.After reaction terminates, dropping concentration is that the pH of system is transferred to 2 by the hydrochloric acid of 6M, 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 (8))-2-hydroxy-propanesulfonic acid salt 0.38mol.
C) by step b) synthesize 3-(polyoxyethylene octylphenol ether (8))-2-hydroxy-propanesulfonic acid salt 0.38mol, 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 2.0mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene octylphenol ether (8))-2-(polyethenoxy ether (5)) propanesulfonic acid salt 0.38mol.
D) by step c) 3-(polyoxyethylene octylphenol ether (8))-2-(polyethenoxy ether (5)) the propanesulfonic acid salt (0.38mol) that synthesizes joins and whipping appts is housed, in the reactor of condensation reflux unit and division box, add 200 milliliters of benzene and sodium hydroxide (0.76mol), alkalize 2 hours at 60 DEG C, add 0.45mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 5 hours, obtain 3-(polyoxyethylene octylphenol ether (8))-2-(hydroxypropyl sulfonic acid polyethenoxy ether (5)) propanesulfonic acid salt (0.35mol).
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, 0.5mol amylic 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 2.6mol oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 0.5mol amylic phenol polyoxyethylene (5) ether.
B) by step a) gained 0.5mol amylic phenol polyoxyethylene (5) ether 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 0.6mol3-chlorine-2-hydroxyl propanesulfonate, 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 0.36mol3-(amylic phenol polyoxyethylene (5) ether)-2-hydroxy-propanesulfonic acid salt.
C) by step b) 3-(amylic phenol polyoxyethylene (5) the ether)-2-hydroxy-propanesulfonic acid salt 0.35mol that synthesizes, 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 0.72mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(amylic phenol polyoxyethylene (5) ether)-2-(polyoxypropylene (2) ether) propanesulfonic acid salt 0.35mol.
D) by step c) 3-(amylic phenol polyoxyethylene (5) ether)-2-(polyoxypropylene (2) ether) the propanesulfonic acid salt (0.35mol) that synthesizes joins and whipping appts is housed, in the reactor of condensation reflux unit and division box, add 200 milliliters of benzene and sodium hydroxide (0.70mol), alkalize 2 hours at 60 DEG C, add 0.40mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 5 hours, obtain 3-(amylic phenol polyoxyethylene (5) ether)-2-(hydroxypropyl sulfonic acid polyoxypropylene (2) ether) propanesulfonic acid salt (0.31mol).
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, 0.5mol 4-dodecylphenol 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 1.1mol oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 0.5mol dodecyl phenol polyethenoxy (2) ether.
B) by step a) gained 0.5mol dodecyl phenol polyethenoxy (2) ether 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 0.6mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 8 hours.After reaction terminates, dropping concentration is that the pH of system is transferred to 2 by the hydrochloric acid of 6M, 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-(dodecyl phenol polyethenoxy (2) ether)-2-hydroxy-propanesulfonic acid salt 0.36mol.
C) by step b) synthesize 3-(dodecyl phenol polyethenoxy (2) ether)-2-hydroxypropionate sodium 0.36mol, 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 1.5mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(dodecyl phenol polyethenoxy (2) ether)-2-(polyoxypropylene (4) ether) sulfonate 0.36mol.
D) by step c) 3-(dodecyl phenol polyethenoxy (2) ether)-2-(polyoxypropylene (4) ether) sulfonate (0.36mol) that synthesizes joins and whipping appts is housed, in the reactor of condensation reflux unit and division box, add 200 milliliters of benzene and sodium hydroxide (0.72mol), alkalize 2 hours at 60 DEG C, add 0.42mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 5 hours, obtain 3-(dodecyl phenol polyethenoxy (2) ether)-2-(hydroxypropyl sulfonic acid polyoxypropylene (4) ether) sulfonate (0.33mol).
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, 0.5mol hexadecyl phenol and 2 grams of sodium hydroxide and 20 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 2.5mol oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 0.49mol hexadecyl phenol polyethenoxy (5) ether.
B) by step a) gained 0.49mol hexadecyl phenol polyethenoxy (5) ether 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 0.58mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 8 hours.After reaction terminates, dropping concentration is that the pH of system is transferred to 2 by the hydrochloric acid of 6M, 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-(hexadecyl phenol polyethenoxy (5) ether)-2-hydroxy-propanesulfonic acid salt 0.36mol.
C) by step b) synthesize 3-(hexadecyl phenol polyethenoxy (5) ether)-2-hydroxy-propanesulfonic acid salt 0.36mol, 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 1.8mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(hexadecyl phenol polyethenoxy (5) ether)-2-(polyoxypropylene (5) ether) propanesulfonic acid salt 0.35mol.
D) by step c) 3-(hexadecyl phenol polyethenoxy (5) ether)-2-(polyoxypropylene (5) ether) the propanesulfonic acid salt (0.35mol) that synthesizes joins and whipping appts is housed, in the reactor of condensation reflux unit and division box, add 200 milliliters of benzene and sodium hydroxide (0.70mol), alkalize 2 hours at 60 DEG C, add 0.40mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 5 hours, obtain 3-(hexadecyl phenol polyethenoxy (5) ether)-2-(hydroxypropyl sulfonic acid polyoxypropylene (5) ether) propanesulfonic acid salt (0.31mol).
2. surfactant properties evaluation
Oil-displacing agent is prepared:
By above-mentioned steps c) 3-(hexadecyl phenol polyethenoxy (5) ether)-2-(polyoxypropylene (5) ether) propanesulfonic acid salt 1 weight part that synthesizes, diethanolamine 0.5 weight part and Pu Chengxi District 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, 0.5mol nonyl phenol 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 3.0mol oxyethane, control pressure≤0.40MPa carries out ethoxylation 4 hours, then passes into 1.5mol propylene oxide, continues reaction 4 hours; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 0.49mol Nonyl pheno (6) polyoxypropylene (3) ether.
B) by step a) gained 0.49mol Nonyl pheno (6) polyoxypropylene (3) ether 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 0.58mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 8 hours.After reaction terminates, dropping concentration is that the pH of system is transferred to 2 by the hydrochloric acid of 6M, 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-(Nonyl pheno (6) polyoxypropylene (3) ether)-2-hydroxy-propanesulfonic acid salt 0.38mol, and structure is as follows:
2. surfactant properties evaluation
3-(Nonyl pheno (6) polyoxypropylene (3) ether)-2-hydroxy-propanesulfonic acid salt 1 weight part of above-mentioned synthesis and Pu Chengxi District are injected 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 85 DEG C, rotating speed is under 4500 revs/min of conditions, measures the interfacial tension above-mentioned oil-displacing agent and Pu Chengxi District injected between water and the dewatered oil of extraction and 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 85 DEG C, length is 30cm, and diameter is 2.5cm, and rate of permeation is 1.5m
2rock core on carry out imitation oil displacement experiment experiment.First inject water with Pu Chengxi District 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
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 0.5mol nonyl phenol 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 1.5mol propylene oxide, control pressure≤0.40MPa reacts 4 hours, obtains nonyl phenol poly-oxypropylene (3) ether, then pass into 3.0mol oxyethane, continue reaction 4 hours; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 0.49mol nonyl phenol poly-oxypropylene (3) polyoxyethylene (6) ether.
B) by step a) gained 0.49mol nonyl phenol poly-oxypropylene (3) polyoxyethylene (6) ether 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 0.58mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 8 hours.After reaction terminates, dropping concentration is that the pH of system is transferred to 2 by the hydrochloric acid of 6M, 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-(nonyl phenol poly-oxypropylene (3) polyoxyethylene (6) ether)-2-hydroxy-propanesulfonic acid salt 0.38mol, and structure is as follows:
2. surfactant properties evaluation
Above-mentioned tensio-active agent 1 weight part and Pu Chengxi District 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
A) in the reactor that condensing works, whipping appts and gas distributor be housed, 0.5mol nonyl phenol 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 3.0mol oxyethane, control pressure≤0.40MPa carries out ethoxylation; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 0.49mol Nonyl pheno (6) ether.
B) by step a) gained 0.49mol polyoxyethylene nonylphenol ether (6) 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 0.58mol3-chlorine-2-hydroxyl propanesulfonate, at reflux, react 8 hours.After reaction terminates, dropping concentration is that the pH of system is transferred to 2 by the hydrochloric acid of 6M, 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 0.39mol.
C) by step b) synthesize 3-(polyoxyethylene nonylphenol ether (6))-2-hydroxy-propanesulfonic acid salt 0.39mol, 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 1.18mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain 3-(polyoxyethylene nonylphenol ether (6))-2-(polyethenoxy ether (3)) propanesulfonic acid salt 0.38mol, structure is as follows:
2. surfactant properties evaluation
Above-mentioned tensio-active agent 1 weight part and Pu Chengxi District 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.
Water is injected in Pu Chengxi District, table 1 Zhongyuan Oil Field
| Project | Na ++K + | Mg 2+ | Ca 2+ | Cl - | SO 4 2- | HCO 3 - | TDS |
| mg/L | 85066 | 367 | 3840 | 138006 | 1089 | 282 | 228650 |
Table 2 embodiment 1-15 oil-displacing agent forms
Table 3 embodiment 1-15 oil-displacing agent interfacial tension performance
| Embodiment | Interfacial tension (mN/m) |
| 1 | 0.0065 |
| 2 | 0.0074 |
| 3 | 0.0026 |
| 4 | 0.0018 |
| 5 | 0.0012 |
| 6 | 0.0002 |
| 7 | 0.0065 |
| 8 | 0.0015 |
| 9 | 0.0058 |
| 10 | 0.0073 |
| 11 | 0.0040 |
| 12 | 0.0041 |
| 13 | 0.0235 |
| 14 | 0.0082 |
| 15 | 0.0043 |
Table 4 embodiment 1-15 oil displacement experiment result
| Embodiment | Improve recovery ratio % |
| 1 | 5.8 |
| 2 | 5.3 |
| 3 | 7.4 |
| 4 | 10.5 |
| 5 | 10.1 |
| 6 | 11.8 |
| 7 | 4.6 |
| 8 | 8.1 |
| 9 | 6.9 |
| 10 | 5.0 |
| 11 | 7.5 |
| 12 | 6.4 |
| 13 | 4.3 |
| 14 | 4.4 |
| 15 | 5.9 |
Table 5 comparative example 1-3 the performance test results
| Comparative example | Interfacial tension (mN/m) | Improve recovery ratio % |
| 1 | 0.011 | 4.3 |
| 2 | 0.023 | 4.6 |
| 3 | 0.045 | 3.5 |
Claims (10)
1. salt tolerant oil displacement surfactant, its name is called 3-(alkyl phenol polyethenoxy ether)-2-(hydroxypropyl sulfonic acid polyethenoxy ether) propanesulfonic acid salt, and structure is such as formula shown in (I):
Wherein M
1and M
2independently be selected from in basic metal, alkaline-earth metal any one, work as M
1for n during basic metal
1be 1, work as M
1for n during alkaline-earth metal
1be 0.5, work as M
2for n during basic metal
2be 1, work as M
2for n during alkaline-earth metal
2be 0.5, R be C
4~ C
20alkyl, x=1 ~ 20, y=1 ~ 10.
2. salt tolerant oil displacement surfactant according to claim 1, is characterized in that x=2 ~ 8, y=2 ~ 4.
3. salt tolerant oil displacement surfactant according to claim 2, is characterized in that described alkyl is C
7~ C
10alkyl.
4. the preparation method of salt tolerant oil displacement surfactant according to claim 1, comprises the following steps:
A) under basic catalyst effect, alkyl phenol and aequum reacting ethylene oxide obtain alkyl phenol polyethenoxy ether;
B) by step a) gained alkyl phenol polyethenoxy ether be dissolved into C
6~ C
8in aromatic hydrocarbons, add at least one alkali in alkali metal hydroxide or alkaline earth metal hydroxides, alkalize 0.5 ~ 3 hour at 30 ~ 60 DEG C, add an alkali metal salt of 3-chlorine-2-hydroxyl propanesulfonic acid, under stirring, be obtained by reacting 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, obtain described 3-(alkyl phenol polyethenoxy ether)-2-(polyethenoxy ether) propanesulfonic acid salt with aequum propylene oxide reaction;
D) by step c) gained 3-(alkyl phenol polyethenoxy ether)-2-(polyethenoxy ether) propanesulfonic acid salt, be dissolved into C
6~ C
8in aromatic hydrocarbons, add at least one alkali in alkali metal hydroxide or alkaline earth metal hydroxides, alkalize 0.5 ~ 3 hour at 30 ~ 60 DEG C, add an alkali metal salt of 3-chlorine-2-hydroxyl propanesulfonic acid, under stirring, be obtained by reacting 3-(alkyl phenol polyethenoxy ether)-2-(hydroxypropyl sulfonic acid polyethenoxy ether) propanesulfonic acid salt.
5. the preparation method of salt tolerant oil displacement surfactant according to claim 4, it is characterized in that step a) and/or step c) described basic catalyst is at least one in alkali metal hydroxide or alkaline-earth metal.
6. the preparation method of salt tolerant oil displacement surfactant according to claim 4, it is characterized in that step b) mol ratio of described alkyl phenol polyethenoxy ether and 3-chlorine-2-hydroxyl propanesulfonic acid an alkali metal salt is 1:(1 ~ 2), the described reaction times is 6 ~ 10 hours.
7. the preparation method of salt tolerant oil displacement surfactant according to claim 5, it is characterized in that step a) and step c) described basic catalyst is at least one in sodium hydroxide or potassium hydroxide.
8. the preparation method of salt tolerant oil displacement surfactant according to claim 4, it is characterized in that step a) and/or step c) described temperature of reaction is 120 ~ 140 DEG C, the reaction times is 6 ~ 8 hours.
9. tensio-active agent described in claim 1 is improving the application in oil recovery factor.
10. application according to claim 9, is characterized in that application method is inject oil-bearing formation by comprising the oil-displacing agent of 1 part, described tensio-active agent with 100 ~ 2000 parts, water with weight parts.
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| 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 |
| CN111087608A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Oil-displacing surfactant and composition of alkyl phenol polyether bisbenzenesulfonate, and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111087608A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Oil-displacing surfactant and composition of alkyl phenol polyether bisbenzenesulfonate, and preparation method and application thereof |
| 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 |
| CN111087608B (en) * | 2018-10-23 | 2022-08-12 | 中国石油化工股份有限公司 | Oil-displacing surfactant and composition of alkyl phenol polyether bisbenzenesulfonate, and preparation method and application thereof |
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