CN104277812A - Tertiary oil recovery surfactant and preparation method thereof - Google Patents
Tertiary oil recovery surfactant and preparation method thereof Download PDFInfo
- Publication number
- CN104277812A CN104277812A CN201310286383.9A CN201310286383A CN104277812A CN 104277812 A CN104277812 A CN 104277812A CN 201310286383 A CN201310286383 A CN 201310286383A CN 104277812 A CN104277812 A CN 104277812A
- Authority
- CN
- China
- Prior art keywords
- active agent
- reaction
- tensio
- oil
- propanesulfonic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
- C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
- C08G65/3346—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur having sulfur bound to carbon and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates a tertiary oil recovery surfactant 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 tertiary oil recovery surfactant has the name of 3-(alkylphenol polyoxypropylene ether)-2-( polyoxyethylene ether)propanesulfonate and has the structure shown as a formula (I) in the specification, wherein M is any one of alkali metals and alkali earth metals, n is the molar ratio of M to SO3 group in the formula (I), n is 1 when M is an alkali metal, n is 0.5 when M is an alkali earth metal, R is an C4-C20 alkyl, x=1-10 and y=1-20. The technical scheme relatively well solves the above problem and is applicable to tertiary oil recovery production of oil fields.
Description
Technical field
The present invention relates to a kind of tertiary oil recovery tensio-active agent and preparation method thereof.
Background technology
Tertiary oil recovery utilizes physics, chemistry and the means such as biological, continues the remaining oil of recovery of subterranean, improve the method for oil recovery factor with this.The research that application surface promoting agent recovers the oil in oil production originates in earlier 1930s, is developed so far, and has been the important means improving recovery ratio in oil field, theory and practice has had very large progress.At present, following several injection system has been basically formed: active water drive, foam flooding, the low interfacial tension system displacement of reservoir oil etc.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 tertiary oil recovery tensio-active agent, 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 tertiary oil recovery tensio-active agent 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 tertiary oil recovery tensio-active agent, 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 M and SO in 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=1-10, y=1-20.
In technique scheme, preferred x=2 ~ 6 and y=4 ~ 10.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 tertiary oil recovery tensio-active agent that one of above-mentioned technical problem is described, comprises the following steps:
A) under basic catalyst effect, alkyl phenol and aequum propylene oxide are 85 ~ 180 DEG C in temperature of reaction, and pressure is 0 ~ 1MPa(gauge pressure), react 1 ~ 10 hour, 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, 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 ~ 1MPa(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.Step a) and/or step c) described temperature of reaction is preferably 120 ~ 140 DEG C, and reaction pressure is preferably 0 ~ 0.4MPa, 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), the reaction times is preferably 6 ~ 10 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 tertiary oil production in 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 0-1000mg/L, for the consideration of the aspect such as easy construction, saving water resource, be more preferably oilfield injection water, the Zhongyuan Oil Field M15 block 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 temperature be 80 DEG C, salinity is greater than 40000mg/L, Ca
2+, Mg
2+concentration is still can form 10 with crude oil under the condition of 0-1000mg/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 1mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 0.49mol nonyl phenol poly-oxypropylene (2) ether.
B) by step a) gained nonyl phenol poly-oxypropylene 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 0.61mol 3-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-(nonyl phenol poly-oxypropylene ether (2))-2-hydroxy-propanesulfonic acid salt (0.39mol).
C) by step b) the 3-(nonyl phenol poly-oxypropylene ether (2) that synthesizes)-2-hydroxy-propanesulfonic acid salt, 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 1.58 mol oxyethane, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 3-(nonyl phenol poly-oxypropylene ether (2))-2-(Soxylat A 25-7 (4)) propanesulfonic acid salt (0.39mol).
2. surfactant properties evaluation
Oil-displacing agent is prepared:
Above-mentioned tensio-active agent 1 weight part and Zhongyuan Oil Field M15 block 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, Zhongyuan Oil Field used M15 block 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 Zhongyuan Oil Field M15 block 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 with Zhongyuan Oil Field M15 block 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 propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 130 grams of nonyl phenol poly-oxypropylene (1) ethers.
B) step a) gained 0.5mol nonyl phenol poly-oxypropylene ether (1) is 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 0.6mol 3-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-(nonyl phenol poly-oxypropylene ether (1))-2-hydroxy-propanesulfonic acid salt 0.38mol.
C) by step b) synthesize 3-(nonyl phenol poly-oxypropylene 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 2.68mol oxyethane, control pressure≤0.40MPa reaction; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 3-(nonyl phenol poly-oxypropylene ether (1))-2-(Soxylat A 25-7 (7)) propanesulfonic acid salt 0.37mol.
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 2.0mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 0.49mol nonyl phenol poly-oxypropylene (4) ether.
B) step a) gained 0.49mol nonyl phenol poly-oxypropylene ether (4) is 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 0.59mol 3-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-(nonyl phenol poly-oxypropylene ether (4))-2-hydroxy-propanesulfonic acid salt 0.38mol.
C) by step b) synthesize 3-(nonyl phenol poly-oxypropylene ether (4))-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 reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 3-(nonyl phenol poly-oxypropylene ether (4))-2-(Soxylat A 25-7 (4)) 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 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 1.5mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 0.49mol nonyl phenol poly-oxypropylene (3) ether.
B) by step a) gained 0.49mol nonyl phenol poly-oxypropylene 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 0.58mol 3-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-(nonyl phenol poly-oxypropylene ether (3))-2-hydroxy-propanesulfonic acid salt 0.38mol.
C) by step b) synthesize 3-(nonyl phenol poly-oxypropylene ether (3))-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 2.28mol oxyethane, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 3-(nonyl phenol poly-oxypropylene ether (3))-2-(Soxylat A 25-7 (6)) propanesulfonic acid salt 0.37mol.
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 2.0mol oxyethane, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 0.49mol nonyl phenol poly-oxypropylene (4) ether.
B) by step a) gained 0.49mol nonyl phenol poly-oxypropylene ether (4) 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 0.58mol 3-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-(nonyl phenol poly-oxypropylene ether (4))-2-hydroxy-propanesulfonic acid salt 0.39mol.
C) by step b) synthesize 3-(nonyl phenol poly-oxypropylene 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 3.14mol oxyethane, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 3-(nonyl phenol poly-oxypropylene ether (4))-2-(Soxylat A 25-7 (8)) propanesulfonic acid salt 0.38mol.
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 0.5mol propylene oxide, control pressure≤0.40MPa carries out propoxylation reaction; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 0.49mol nonyl phenol poly-oxypropylene (1) ether.
B) by step a) gained 0.49mol nonyl phenol poly-oxypropylene 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 0.58mol 3-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-(nonyl phenol poly-oxypropylene ether (1))-2-hydroxy-propanesulfonic acid salt 0.39mol.
C) by step b) synthesize 3-(nonyl phenol poly-oxypropylene ether (1))-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 7.8mol oxyethane, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 3-(nonyl phenol poly-oxypropylene ether (1))-2-(Soxylat A 25-7 (20)) propanesulfonic acid salt 0.38mol.
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 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 2.0mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 0.49mol octyl phenol polyoxyethylene (4) ether.
B) by step a) gained 0.49mol octyl phenol polyethenoxy ether (4) 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 0.58mol 3-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-(octyl phenol polyethenoxy ether (4))-2-hydroxy-propanesulfonic acid salt 0.38mol.
C) by step b) synthesize 3-(nonyl phenol poly-oxypropylene ether (4))-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 1.52mol oxyethane, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 3-(octyl phenol polyethenoxy ether (4))-2-(Soxylat A 25-7 (4)) propanesulfonic acid salt 0.38mol.
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 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 0.51mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 0.5mol octylphenol polyethylene oxypropylene (1) ether.
B) by step a) gained 0.5mol octyl phenol polyethenoxy 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 0.6mol 3-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-(octyl phenol polyethenoxy ether (1))-2-hydroxy-propanesulfonic acid salt 0.38mol.
C) by step b) synthesize 3-(octyl phenol polyethenoxy 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 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 1.9mol oxyethane, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 3-(octyl phenol polyethenoxy ether (1))-2-(Soxylat A 25-7 (5)) propanesulfonic acid salt 0.38mol.
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 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 5.0mol oxyethane, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 0.5mol amylic phenol polyoxypropylene (10) ether.
B) by step a) gained 0.5mol amylic phenol polyoxypropylene (10) 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 0.6mol 3-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 0.36mol 3-(amylic phenol polyoxypropylene (10) ether)-2-hydroxy-propanesulfonic acid salt.
C) by step b) 3-(amylic phenol polyoxypropylene (10) ether that synthesizes)-2-hydroxy-propanesulfonic acid salt 0.35mol, 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 4.2mol oxyethane, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 3-(amylic phenol polyoxypropylene (10) ether)-2-(polyoxyethylene (12) ether) 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 12]
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 2.0mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 0.5mol 4-dodecylphenol polyoxypropylene (4) ether.
B) by step a) gained 0.5mol 4-dodecylphenol polyoxypropylene (4) 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 0.6mol 3-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-(4-dodecylphenol polyoxypropylene (4) ether)-2-hydroxy-propanesulfonic acid salt 0.36mol.
C) by step b) synthesize 3-(4-dodecylphenol polyoxypropylene (4) 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 3.6mol oxyethane, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 3-(4-dodecylphenol polyoxypropylene (4) ether)-2-(polyoxyethylene (10) ether) sulfonate 0.36mol.
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 13]
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 2.0mol propylene oxide, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 0.49mol hexadecyl phenol polyoxypropylene (4) ether.
B) by step a) gained 0.49mol hexadecyl phenol polyoxypropylene (4) 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 0.58mol 3-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 polyoxypropylene (4) ether)-2-hydroxy-propanesulfonic acid salt 0.36mol.
C) by step b) synthesize 3-(hexadecyl phenol polyoxypropylene (4) 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 2.9mol oxyethane, control pressure≤0.40MPa reacts; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 3-(hexadecyl phenol polyoxypropylene (4) ether)-2-(polyoxyethylene (8) ether) propanesulfonic acid salt 0.35mol.
2. surfactant properties evaluation
Oil-displacing agent is prepared:
By above-mentioned steps c) tensio-active agent 1 weight part, methyl-sulphoxide (DMSO) 0.5 weight part and the Zhongyuan Oil Field M15 block that synthesize 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 reaction 4 hours, then passes into 1.5mol propylene oxide, continues reaction 4 hours; After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, 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 0.58mol 3-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, structure is as follows:
2. surfactant properties evaluation
3-(Nonyl pheno (6) polyoxypropylene (3) ether by above-mentioned synthesis)-2-hydroxy-propanesulfonic acid salt 1 weight part and Zhongyuan Oil Field M15 block 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 Zhongyuan Oil Field M15 block 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 with Zhongyuan Oil Field M15 block 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, with Glacial acetic acid neutralization after cooling, 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 0.58mol 3-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, structure is as follows:
2. surfactant properties evaluation
Above-mentioned tensio-active agent 1 weight part and Zhongyuan Oil Field M15 block 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 the mixture be made up of 3.0mol oxyethane and 1.5mol propylene oxide, control pressure≤0.40MPa reacts 6 hours.After reaction terminates, use nitrogen purging system, with Glacial acetic acid neutralization after cooling, obtain 0.49mol Nonyl pheno (6) polyoxypropylene (3) copolyether.
B) by step a) gained 0.49mol Nonyl pheno (6) polyoxypropylene (3) copolyether 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 0.58mol 3-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-(Nonyl pheno (6) polyoxypropylene (3) copolyether)-2-hydroxy-propanesulfonic acid salt 0.38mol:
2. surfactant properties evaluation
Above-mentioned tensio-active agent 1 weight part and Zhongyuan Oil Field M15 block 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 Zhongyuan Oil Field M15 block injects water
| Project | Na ++K + | Mg 2+ | Ca 2+ | Cl - | SO 4 2- | TDS |
| mg/L | 6833 | 55 | 310 | 34430 | 538 | 42166 |
Table 2 embodiment 1-14 oil-displacing agent forms
Table 3 embodiment 1-14 oil-displacing agent interfacial tension performance
| Embodiment | Interfacial tension (mN/m) |
| 1 | 0.0038 |
| 2 | 0.0049 |
| 3 | 0.0031 |
| 4 | 0.0021 |
| 5 | 0.0018 |
| 6 | 0.0001 |
| 7 | 0.012 |
| 8 | 0.0083 |
| 9 | 0.0035 |
| 10 | 0.0077 |
| 11 | 0.0071 |
| 12 | 0.0064 |
| 13 | 0.0085 |
Table 4 embodiment 1-14 oil displacement experiment result
| Embodiment | Improve recovery ratio % |
| 1 | 6.8 |
| 2 | 5.3 |
| 3 | 7.8 |
| 4 | 8.7 |
| 5 | 9.5 |
| 6 | 12.3 |
| 7 | 4.5 |
| 8 | 5.1 |
| 9 | 7.5 |
| 10 | 5.5 |
| 11 | 4.8 |
| 12 | 5.3 |
| 13 | 4.8 |
Table 5 comparative example 1-3 the performance test results
| Comparative example | Interfacial tension (mN/m) | Improve recovery ratio % |
| 1 | 0.0092 | 4.4 |
| 2 | 0.013 | 3.5 |
| 3 | 0.021 | 2.6 |
Claims (10)
1. a tertiary oil recovery tensio-active agent, 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 M and SO in 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 ~ 10, y=1 ~ 20.
2. tertiary oil recovery tensio-active agent according to claim 1, is characterized in that x=2 ~ 6, y=4 ~ 10.
3. tertiary oil recovery tensio-active agent according to claim 2, is characterized in that described alkyl is C
7~ C
10alkane.
4. the preparation method of tertiary oil recovery tensio-active agent according to claim 1, comprises the following steps:
A) under basic catalyst effect, alkyl phenol and aequum propylene oxide are 85 ~ 180 DEG C in temperature of reaction, and pressure is 0 ~ 1MPa(gauge pressure), react 1 ~ 10 hour, 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, 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 ~ 1MPa(gauge pressure), react 1 ~ 10 hour, obtain described 3-(alkyl phenol polyethenoxy ether)-2-(Soxylat A 25-7) propanesulfonic acid salt.
5. the preparation method of tertiary oil recovery tensio-active agent according to claim 4, 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.
6. the preparation method of tertiary oil recovery tensio-active agent according to claim 5, is characterized in that described basic catalyst is at least one in sodium hydroxide or potassium hydroxide.
7. the preparation method of tertiary oil recovery tensio-active agent according to claim 4, is characterized in that step a) and/or step c) described temperature of reaction is 120 ~ 140 DEG C, reaction pressure is 0 ~ 0.4MPa reaction times is 6 ~ 8 hours.
8. the preparation method of tertiary oil recovery tensio-active agent according to claim 4, is characterized in that the mol ratio of alkyl phenol polyethenoxy ether described in step b) and 3-chlorine-2-hydroxyl propanesulfonic acid an alkali metal salt is 1:(1 ~ 2), the described reaction times is 6 ~ 10 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310286383.9A CN104277812B (en) | 2013-07-09 | 2013-07-09 | Tertiary oil recovery surfactant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310286383.9A CN104277812B (en) | 2013-07-09 | 2013-07-09 | Tertiary oil recovery surfactant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104277812A true CN104277812A (en) | 2015-01-14 |
| CN104277812B CN104277812B (en) | 2017-05-17 |
Family
ID=52253168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310286383.9A Active CN104277812B (en) | 2013-07-09 | 2013-07-09 | Tertiary oil recovery surfactant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104277812B (en) |
Cited By (4)
| 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 |
| CN106590581A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Salt resistant oil displacement composition and preparation method thereof |
| 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 |
| CN112707945A (en) * | 2020-12-11 | 2021-04-27 | 德仕能源科技集团股份有限公司 | Surfactant for anion-cation oil displacement and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108730A (en) * | 1984-12-06 | 1986-07-09 | 狮子株式会社 | Be used for the micellar that oil reclaims |
| CN1560178A (en) * | 2004-02-25 | 2005-01-05 | 石油大学(华东) | Anti-salt type thicking oil reducing viscosity agent and preparation process thereof |
| CN101979426A (en) * | 2010-10-09 | 2011-02-23 | 西南石油大学 | Method for synthesizing fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate through olefin addition |
| CN102618239A (en) * | 2011-12-28 | 2012-08-01 | 中国石油天然气股份有限公司 | Salt- and temperature-resistant emulsification viscosity reducer for heavy oil |
-
2013
- 2013-07-09 CN CN201310286383.9A patent/CN104277812B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108730A (en) * | 1984-12-06 | 1986-07-09 | 狮子株式会社 | Be used for the micellar that oil reclaims |
| CN1560178A (en) * | 2004-02-25 | 2005-01-05 | 石油大学(华东) | Anti-salt type thicking oil reducing viscosity agent and preparation process thereof |
| CN101979426A (en) * | 2010-10-09 | 2011-02-23 | 西南石油大学 | Method for synthesizing fatty alcohol (alkylphenol) polyoxyethylene ether sulfonate through olefin addition |
| CN102618239A (en) * | 2011-12-28 | 2012-08-01 | 中国石油天然气股份有限公司 | Salt- and temperature-resistant emulsification viscosity reducer for heavy oil |
Non-Patent Citations (2)
| Title |
|---|
| 孙守双 等: "烷基酚阴离子表面活性剂的合成与应用进展", 《化学研究进展》 * |
| 沈之芹 等: "高活性阴离子-非离子双子表面活性剂合成及性能", 《精细石油化工进展》 * |
Cited By (7)
| 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 |
| CN106590581A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Salt resistant oil displacement composition and preparation method thereof |
| CN106590581B (en) * | 2015-10-20 | 2019-06-11 | 中国石油化工股份有限公司 | Salt tolerant displacement composition and preparation method thereof |
| 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 |
| 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 |
| 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 |
| CN112707945A (en) * | 2020-12-11 | 2021-04-27 | 德仕能源科技集团股份有限公司 | Surfactant for anion-cation oil displacement and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104277812B (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106590582B (en) | Salt tolerant oil displacement surfactant and preparation method thereof | |
| CN102504794B (en) | Hydrophobically associating polymer and mixed surfactant binary compound oil displacement system | |
| CN103421480B (en) | Surfactant oil displacement composition and method of making the same | |
| CN104109519B (en) | Betaine polymer displacement composition and preparation method | |
| CN102464598B (en) | Fatty acid amide polyoxylethylene ether benzene sulfonate and preparation method thereof | |
| CN102703049B (en) | Binary compound oil-flooding composition and application thereof in tertiary oil recovery | |
| CN104277808A (en) | Oil-displacement surfactant and preparation method thereof | |
| CN104277812A (en) | Tertiary oil recovery surfactant and preparation method thereof | |
| CN104277813A (en) | Oil-field oil recovery composition and preparation method thereof | |
| CN111088013B (en) | Anion-cation composite oil displacement surfactant, preparation method thereof and oil displacement method | |
| CN104559988B (en) | Beet alkali surface activator, preparation method and the application in intensified oil reduction | |
| CN105273706A (en) | Oil displacement surfactant suitable for highly mineralized strata | |
| CN105273704A (en) | Salt-resistant oil-displacing surfactant and preparation method thereof | |
| CN105315980A (en) | Oil-displacing composition, and preparation method thereof | |
| CN104559989A (en) | Hydrocarbyl amine polyoxyethylene ether polyoxypropylene ether sulfonate type betaine | |
| CN103540306B (en) | Three adopt surfactant composition and preparation method thereof | |
| CN104277809A (en) | Oil-displacement composition and preparation method thereof | |
| CN106590581B (en) | Salt tolerant displacement composition and preparation method thereof | |
| CN111088014B (en) | Yin-yang composite surfactant for oil extraction, preparation method thereof and oil displacement method | |
| CN104559987A (en) | Amide polyoxyethylene ether sulfonate betaine surfactant | |
| CN105273705B (en) | Salt tolerant displacement composition and preparation method thereof | |
| CN104277810A (en) | Enhanced oil recovery surfactant and preparation method thereof | |
| CN104277815A (en) | Oil-displacement composition and preparation method thereof | |
| CN104276983B (en) | The preparation method of oil recovery tensio-active agent | |
| CN106590584B (en) | Oil displacement surfactant for high salinity reservoir |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |