CN115595136A - Temperature response type foaming agent for foam drainage gas production and preparation method and application thereof - Google Patents
Temperature response type foaming agent for foam drainage gas production and preparation method and application thereof Download PDFInfo
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- CN115595136A CN115595136A CN202110721348.XA CN202110721348A CN115595136A CN 115595136 A CN115595136 A CN 115595136A CN 202110721348 A CN202110721348 A CN 202110721348A CN 115595136 A CN115595136 A CN 115595136A
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- 239000006260 foam Substances 0.000 title claims abstract description 83
- 239000004088 foaming agent Substances 0.000 title claims abstract description 33
- 230000004044 response Effects 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 36
- 239000004094 surface-active agent Substances 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 23
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 18
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000004064 cosurfactant Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 98
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- 239000002904 solvent Substances 0.000 claims description 46
- -1 alkenyl sulfonate Chemical compound 0.000 claims description 41
- 150000005215 alkyl ethers Chemical class 0.000 claims description 36
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 26
- 238000010992 reflux Methods 0.000 claims description 25
- 150000003512 tertiary amines Chemical class 0.000 claims description 25
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 23
- 238000009833 condensation Methods 0.000 claims description 19
- 230000005494 condensation Effects 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 16
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 238000002390 rotary evaporation Methods 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 13
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 229940043237 diethanolamine Drugs 0.000 claims description 12
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 9
- 235000011152 sodium sulphate Nutrition 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229940043264 dodecyl sulfate Drugs 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 239000004604 Blowing Agent Substances 0.000 claims 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 20
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000005201 scrubbing Methods 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 7
- 239000000693 micelle Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 239000012085 test solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008876 conformational transition Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
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- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- 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
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
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- 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
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
- C09K8/604—Polymeric surfactants
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- Polymers & Plastics (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention provides a temperature response type foaming agent for foam drainage gas production, and a preparation method and application thereof. The temperature response type foaming agent comprises the following components in percentage by mass: 5 to 15 percent of temperature response type surfactant, preferably 6 to 13 percent, and more preferably 7 to 12 percent; 3 to 12 percent of cosurfactant selected from at least one of alpha-alkenyl sulfonate, fatty alcohol-polyoxyethylene ether sulfate and lauryl sodium sulfate, preferably 4 to 10 percent, and more preferably 5 to 9 percent; the balance being water. The air bubble agent composition can utilize the temperature difference to have higher foamability and foam stability when the temperature in a shaft is higher, and the temperature is reduced after the air bubble agent composition reaches the ground, so that the purposes of simplifying a foam drainage process, reducing the cost of foam drainage gas production and expanding the application range of foam drainage gas production are achieved.
Description
Technical Field
The invention relates to the technical field of oilfield chemistry, and particularly provides a temperature response type foaming agent for foam drainage gas production and a preparation method and application thereof.
Background
When the natural gas exploitation enters the later stage, the gas well pressure is low, the liquid discharge capacity is reduced, and the exploitation efficiency is reduced due to a large amount of liquid accumulated in the gas well. The foam drainage gas production process is widely applied to natural gas exploitation due to simple operation and excellent drainage effect. The process is characterized in that a foam discharging agent with a surfactant as a main component is added to the bottom of the well, so that accumulated liquid at the bottom of the well is fully mixed with the foam discharging agent to form a large amount of foam under the stirring of natural gas, the friction loss in an oil pipe of the flowing well and the gravity gradient in the well are reduced, the back pressure at the bottom of the well is effectively reduced, and the liquid is continuously lifted. The foams have strong regeneration capacity, and when the aqueous solution of the foams is brought to a pipeline and a separation device on the ground through airflow, the aqueous solution is repeatedly and continuously stirred, and more or less foams are accumulated in the separator. This phenomenon is particularly serious when the foam discharging agent is excessive or the generated foam is too stable, and a large amount of foam can be brought into the gathering pipeline to cause blockage, so that the gathering pressure is increased. Therefore, aiming at the phenomenon, a defoaming agent is required to be injected into the inlet of the separator, and the defoaming agent and the gas-water mixture enter the separator to achieve the purposes of defoaming, inhibiting foam regeneration and facilitating gas-water separation. The addition of the defoaming agent can limit the recycling of the foaming agent, and the introduction of the defoaming device increases the process link, and the measures can increase the development cost. For some gobi and cold areas, the foam-type drainage process supporting facilities are seriously lacked, so that the application range of the foam-type drainage process is limited.
In conclusion, the performance of the foam discharging agent is the key to the success of the drainage and gas production process, and at present, the conventional foam discharging agent needs to be subjected to defoaming treatment after construction, and a synthetic temperature response type surfactant needs to be designed, so that the defoaming link in the traditional foam discharging process is omitted, the foam discharging process is simplified, and the gas reservoir recovery ratio is improved.
Disclosure of Invention
In view of this, in order to solve the problems in the background art, the present invention provides a temperature-responsive foaming agent for foam drainage gas production, and a preparation method and an application thereof, wherein the temperature-responsive foaming agent has high foamability and foam stability when the temperature in a wellbore is high due to a temperature difference, and reduces the temperature after reaching the ground to automatically defoam, so as to achieve the purposes of simplifying a foam drainage process, reducing the cost of foam drainage gas production, and expanding the application range of foam drainage gas production.
According to a first aspect of the present invention, there is provided a temperature-responsive foaming agent comprising, in mass fraction:
5 to 15 percent of temperature response type surfactant, preferably 6 to 13 percent, and more preferably 7 to 12 percent;
3 to 12 percent of cosurfactant selected from at least one of alpha-alkenyl sulfonate, fatty alcohol-polyoxyethylene ether sulfate and dodecyl sulfate, preferably 4 to 10 percent, and more preferably 5 to 9 percent;
the balance being water.
According to some embodiments of the invention, the temperature responsive surfactant is:
n is an arbitrary number from 4 to 6, preferably an arbitrary number from 4 to 5; r is alkyl, preferably C 1 ～C 20 One or more of alkyl groups, more preferably C 6 ～C 12 An alkyl group;
specifically, the alpha-olefin sulfonate comprises sodium alpha-olefin sulfonate, which satisfies the formula:
R'-HC＝CH-CH 2 -SO 3 Z
wherein R' is C 5 ～C 30 At least one of alkyl groups of (a);
z is at least one of alkali metal ions, preferably sodium ions; and/or
The fatty alcohol-polyoxyethylene ether sulfate comprises fatty alcohol-polyoxyethylene ether sodium sulfate with a molecular formula of R' O (CH) 2 CH 2 O)m-SO 3 Na, wherein m is 2 or 3, R' is C 12 ～C 15 At least one of alkyl groups.
The lauryl sulfate salt comprises sodium lauryl sulfate.
According to some embodiments of the invention, the temperature responsive surfactant is 5 to 15% by mass; 3 to 10 percent of alpha-sodium alkenyl sulfonate; and/or sodium fatty alcohol-polyoxyethylene ether sulfate 4-12%; and/or sodium dodecyl sulfate 4-11%; the balance being water.
According to a second aspect of the present invention, there is also provided a method of preparing a temperature-responsive foaming agent as described above, comprising the steps of:
mixing a temperature response type surfactant, a cosurfactant selected from at least one of alpha-alkenyl sulfonate, fatty alcohol-polyoxyethylene ether sulfate and dodecyl sulfate and water to prepare the temperature response type foaming agent.
Preferably, the temperature-responsive surfactant is prepared via a process comprising the steps of:
step a) dissolving polyoxyethylene alkyl ether in a solvent I, dropwise adding thionyl chloride, then heating in the presence of a catalyst for reaction, and removing the solvent after the reaction to obtain a chlorinated polyoxyethylene alkyl ether intermediate.
Further, 1 to 5g of polyoxyethylene alkyl ether and 50 to 100ml of solvent I are sequentially added into a three-neck reaction flask with a condensation reflux device. Adding 10-30 ml of thionyl chloride (SOCl) into a constant-pressure dropping funnel 2 ) Make SOCl 2 Slowly dropping into a three-neck flask, adding 1-2 drops of DMF (dimethyl formamide) serving as a catalyst into a reaction system after the dropping is finished, and heating to 60-80 ℃ for reaction. Introducing N in the reaction process 2 HCl and SO generated in the reaction system 2 The gas is brought out, and the side reaction is avoided. Stopping the reaction after 6 to 12 hours, carrying out rotary evaporation on the reaction solution at the temperature of between 50 and 70 ℃, and removing the solvent and unreacted SOCl 2 Obtaining light yellow oily liquid, namely a chlorinated polyoxyethylene alkyl ether intermediate.
And step b) dissolving the chlorinated polyoxyethylene alkyl ether intermediate prepared in the step a) and diethanol amine in a solvent II, heating, carrying out condensation reflux reaction, and removing the solvent to prepare a tertiary amine intermediate.
Specifically, the chlorinated polyoxyethylene alkyl ether intermediate prepared in the step a) and diethanol amine are added into a three-neck reaction flask according to the molar ratio of 1-1. Heating to 50-80 ℃, condensing and refluxing for reaction, taking out reaction liquid after the reaction market is 6-18 hours, decompressing and rotary-steaming at 50-70 ℃ to remove the solvent, washing with water for layering, and separating out the diethanol amine which is used as the reaction to obtain the tertiary amine intermediate.
And c) dissolving the tertiary amine intermediate prepared in the step b) and sodium chloroacetate in a solvent III, heating, carrying out condensation reflux reaction, removing the solvent, and then filtering and drying to prepare the temperature response type surfactant.
Specifically, dissolving the tertiary amine intermediate obtained in the step b) and sodium chloroacetate in a solvent III, adding the solution into a three-neck reaction flask, heating to 50-90 ℃, performing condensation reflux reaction, stopping the reaction after 9-18 hours of reaction market, and performing reduced pressure rotary evaporation on the reaction solution at 40-60 ℃ to remove the solvent.
Further, the reaction mixture was washed with ethanol and filtered to remove unreacted sodium chloroacetate. And recrystallizing and purifying the filtrate by using a mixed solution of ethanol and diethyl ether, and drying in vacuum to finally obtain the temperature response type surfactant.
According to some embodiments of the present invention, the solvent I in step a) comprises chloroform, and the mass ratio of the polyoxyethylene alkyl ether to the chloroform is 1 to 10%, preferably 2 to 9%, more preferably 3 to 8%; and/or
The molar ratio of the thionyl chloride to the polyoxyethylene alkyl ether in step a) is from 1; and/or
The catalyst in step a) comprises N, N-dimethylformamide, and the molar ratio of the catalyst to the polyoxyethylene alkyl ether is 1; and/or
The reaction temperature in the step a) is 60-80 ℃, nitrogen is introduced in the reaction process, and after the reaction, the reaction liquid is subjected to rotary evaporation at 50-70 ℃ to remove the solvent, so as to prepare the chlorinated polyoxyethylene alkyl ether intermediate.
According to some embodiments of the invention, the molar ratio of the chloropolyoxyethylene alkyl ether intermediate to diethanolamine in step b) is 1 to 1, preferably 1 to 1, 2.5, more preferably 1.5 to 1; and/or
The solvent II comprises a mixture of ethanol and water, and the volume ratio of the ethanol to the water is (3): 1; and/or
In the step b), the temperature of the condensation reflux reaction is 50-80 ℃ and the time is 6-18 hours; and/or
After the condensation reflux reaction in the step b), carrying out reduced pressure rotary evaporation at 50-70 ℃ to remove the solvent, thus obtaining the tertiary amine intermediate.
According to some embodiments of the invention, the molar ratio of the tertiary amine intermediate to the sodium chloroacetate in step c) is 1; and/or
The solvent III comprises a mixture of ethanol and water, and the volume ratio of the ethanol to the water is 3: 1; and/or
The temperature of the condensation reflux reaction in the step c) is 50-90 ℃ and the time is 9-18 hours; and/or
After the condensation reflux reaction in the step c), carrying out reduced pressure rotary evaporation at 40-60 ℃ to remove the solvent, thus obtaining the temperature response type surfactant.
According to some embodiments of the invention, the temperature responsive foaming agent comprises: 5 to 15 percent of temperature response type surfactant, preferably 6 to 13 percent, and more preferably 7 to 12 percent;
3 to 12 percent of alpha-alkenyl sodium sulfonate, preferably 3 to 10 percent, and more preferably 4 to 10 percent; and/or
3 to 12 percent of fatty alcohol-polyoxyethylene ether sodium sulfate, preferably 4 to 10 percent, and more preferably 5 to 9 percent; and/or
3 to 12 percent of sodium dodecyl sulfate, preferably 4 to 9 percent of sodium dodecyl sulfate, and more preferably 5 to 9 percent of sodium dodecyl sulfate;
the balance being water.
Specifically, the temperature response type surfactant, alpha-alkenyl sodium sulfonate and/or fatty alcohol polyoxyethylene ether sodium sulfate and/or lauryl sodium sulfate are slowly added into a stainless steel reaction kettle according to a proportion, then solvent-deionized water is added, the mixed solution is heated to 40-60 ℃, and the mixed solution is stirred at a low speed for 10-40 minutes to obtain the temperature response type foaming agent.
According to a third aspect of the present invention, there is provided a use of the temperature-responsive foaming agent as described above or the method of preparing the temperature-responsive foaming agent as described above in the field of oilfield chemistry.
According to some embodiments of the invention, the application comprises use in a process for foam drainage.
The invention has the beneficial effects that:
(1) The temperature response type foaming agent provided by the invention can adjust the stability of foam within the temperature range of 20-80 ℃, the foam can be rapidly broken at low temperature, and the foam has stability at high temperature.
(2) Temperature-regulated foam stability is achieved by conformational transition of the frother molecules upon thermal stimulation, resulting in a change in the morphology of the assembled body. The surfactant has the advantages of simple preparation process, low cost and environmental friendliness.
Drawings
Fig. 1 is a flow chart of a chemical formula of a temperature responsive surfactant according to an exemplary embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
A foam is a heterogeneous dispersion of small bubbles of gas dispersed in a liquid, which coalesce together. In the petroleum industry, foam is often referred to as water-based foam (aquous foam), i.e., the liquid phase in the foam system is water. Common water-based foam systems consist of a gas phase, a liquid phase and a surfactant, wherein the gas is the dispersed phase (discontinuous phase) and the liquid is the continuous phase, and the surfactant enables the foam to form by reducing the surface tension and can be adsorbed on the foam liquid film to form a double adsorption layer to stabilize the foam. Since the foam system itself is a thermodynamically metastable system, it begins to decay as soon as it is produced and is more susceptible to destabilization and collapse under adverse circumstances. Temperature responsive foam refers to foam whose stability can be controlled by temperature. The foam drainage gas production technology enters an individualized application stage, foam is endowed with intelligent responsiveness, and foams are generated at the temperature of a shaft and defoams at the temperature of the ground, so that the purposes of removing a defoaming link in the conventional foam drainage process and simplifying the foam drainage process are achieved, and the foam drainage gas production technology has important research values for reducing the cost of foam drainage gas production and expanding the application range of foam drainage gas production. The foaming agent is the most important and basic component in the foam system, so the core for constructing the temperature-sensitive foam system is the temperature-sensitive foaming agent.
And along with the amazing intelligent temperature response type bubble of defoaming when low temperature, foaming when high temperature arranges the agent and can utilize the temperature difference to reach the effect of foaming in the shaft bottom, ground defoaming to can remove the defoaming link in traditional bubble row technology from. Therefore, the temperature-responsive surfactant molecules are designed and synthesized, the temperature-sensitive foam scrubbing agent is developed, and the method has important significance for simplifying the foam scrubbing process and improving the gas reservoir recovery ratio.
In view of this, the present invention provides a temperature-responsive foaming agent comprising a temperature-responsive surfactant, wherein Ethoxy (EO) is a typical type of thermo-sensitive group: in a low-temperature environment, hydrogen bonds are formed between the ethoxy groups and water molecules, so that the water solubility of the epoxy resin is enhanced, and the epoxy resin shows the characteristic of hydrophilic groups; and as the temperature is increased, hydrogen bonds are broken, and the ethoxy group is dehydrated, so that the characteristics of the hydrophobic group are presented. And, this transition temperature increases with increasing ethoxy segment length. And the surface active agent molecules containing EO units with certain lengths are dehydrated along with the increase of temperature, and the area of the hydrophilic head group of the surface active agent is reduced and the length of the hydrophobic chain segment is increased. According to the theory of stacking parameters, the change can promote the growth of the micelle, so that the original spherical micelle is gradually increased into a rod-shaped micelle and a worm-shaped micelle. Compared with spherical micelles, the interaction between rod-shaped micelles and wormlike micelles can increase the viscosity of the solution, so that the liquid film drainage rate in a corresponding foam system is greatly reduced, and the foam is more stable. In summary, the surfactant molecular design will start with long chain molecules containing ethoxy segments.
The increase in temperature has a non-negligible negative effect on the foam system in its metastable state, which needs to be stable in a harsh environment of high temperature and high salt, thus placing higher demands on the stability of the surfactant. Nonionic surfactants such as polyoxyethylene alkyl ether and the like have excellent salt tolerance, but have cloud points, namely the solubility is reduced after a certain temperature is reached to influence the performance; although anionic surfactants and cationic surfactants do not have a cloud point, high salt ion concentration also affects intermolecular forces. Therefore, the zwitterionic surfactant which has better comprehensive performance and is easier to compound is selected as the target foaming agent.
The following describes in detail a specific embodiment of the present invention with reference to specific examples.
It should be noted that the reagents used in the examples of the present invention are all conventional products that are commercially available, and all of the reagents are analytically pure or chemically pure.
Preparation example 1
Fig. 1 is a flow chart of a chemical formula of a temperature responsive surfactant according to an exemplary embodiment of the present invention.
Step a) preparation of a chlorinated polyoxyethylene alkyl ether intermediate
1g of polyoxyethylene alkyl ether (CAS No.: 9004-98-2, molecular weight: 709, chemical purity, same in lower Dimuyu) and 50ml of chloroform (Beijing chemical reagent works, chemical purity, CAS No.: 67-66-3, same in the following preparation examples) were sequentially charged into a three-necked reaction flask with a condensing reflux unit, and 10ml of thionyl chloride (SOCl) was charged into a constant pressure dropping funnel 2 ) (Beijing chemical Co., ltd., chemical purity, CAS number: 7719-09-7, same as in the following preparation examples) by reacting SOCl 2 Slowly dropping into a three-neck flask. After the completion of the dropwise addition, 1 to 2 drops of DMF (chemical purity, CAS number: 68-2-2, the same as in the following preparation examples) was added as a catalyst to the reaction system, and the temperature was raised to 60 ℃ to effect a reaction. Introducing N in the reaction process 2 HCl and SO generated in the reaction system 2 The gas is brought out, and the occurrence of side reaction is avoided. Stopping the reaction after 6-12 h, carrying out rotary evaporation on the reaction liquid at 50 ℃, and removing the solvent and unreacted SOCl 2 Obtaining light yellow oily liquid, namely a chlorinated polyoxyethylene alkyl ether intermediate.
Step b) preparation of Tertiary amine intermediate
1 (mol/mol) of a chloropolyoxyethylene alkyl ether intermediate was added to a three-necked reaction flask with diethanolamine (beijing carbofuran technologies ltd., analytical purity, CAS No. 111-42-2, same as in the following preparation) and a mixture of ethanol and water (v/v = 3) was added as a solvent. And then heating to 50 ℃, carrying out condensation reflux for reaction, taking out reaction liquid after 6h of reaction, carrying out decompression rotary evaporation at 50 ℃ to remove the solvent, washing with water for layering, and separating out unreacted diethanolamine to obtain the tertiary amine intermediate.
Step c) preparation of temperature-responsive surfactant
The obtained tertiary amine intermediate and sodium chloroacetate were dissolved in a mixture of ethanol and water (v/v = 3. After 9h, the reaction was stopped, and the reaction mixture was rotary evaporated at 40 ℃ under reduced pressure to remove the solvent. The reaction mixture was washed with ethanol and filtered to remove unreacted sodium chloroacetate. And recrystallizing and purifying the filtrate by using a mixed solution of ethanol and diethyl ether, and drying in vacuum to finally obtain a target product.
Preparation example 2
Step a) preparation of a chlorinated polyoxyethylene alkyl ether intermediate
2g of polyoxyethylene alkyl ether (same as preparation example 1) and 60ml of chloroform were sequentially charged into a three-necked reaction flask equipped with a condensing reflux apparatus, and 15ml of thionyl chloride (SOCl) was charged into a constant-pressure dropping funnel 2 ) Make SOCl 2 Slowly dropping into a three-neck flask. After the dropwise addition is finished, adding 1-2 drops of DMF (dimethyl formamide) serving as a catalyst into the reaction system, and heating to 65 ℃ for reaction. Introducing N in the reaction process 2 HCl and SO generated in the reaction system 2 The gas is brought out, and the side reaction is avoided. After 7.5h, the reaction was stopped, the reaction solution was rotary evaporated at 55 ℃ to remove the solvent and unreacted SOCl 2 Obtaining light yellow oily liquid, namely a chlorinated polyoxyethylene alkyl ether intermediate.
Step b) preparation of Tertiary amine intermediate
A 1. And then heating to 60 ℃, carrying out condensation reflux for reaction, taking out reaction liquid after 9h of reaction, carrying out decompression rotary evaporation at 55 ℃ to remove the solvent, washing with water for layering, and separating out unreacted diethanol amine to obtain a tertiary amine intermediate.
Step c) preparation of temperature responsive surfactant
The obtained tertiary amine intermediate and sodium chloroacetate were dissolved in a mixture of ethanol and water (v/v = 4. After 11 hours, the reaction was stopped, and the reaction mixture was rotary evaporated under reduced pressure at 45 ℃ to remove the solvent. The reaction mixture was washed with ethanol and filtered to remove unreacted sodium chloroacetate. And recrystallizing and purifying the filtrate by using a mixed solution of ethanol and diethyl ether, and drying in vacuum to finally obtain a target product.
Preparation example 3
Step a) preparation of a chlorinated polyoxyethylene alkyl ether intermediate
3g of polyoxyethylene alkyl ether (same as preparation example 1) and 75ml of chloroform were sequentially charged into a three-necked reaction flask equipped with a condensing reflux apparatus, and 20ml of thionyl chloride (SOCl) was charged into a constant pressure dropping funnel 2 ) Make SOCl 2 Slowly dropping into a three-neck flask. After the dropwise addition is finished, adding 1-2 drops of DMF (dimethyl formamide) serving as a catalyst into the reaction system, and heating to 70 ℃ for reaction. Introducing N in the reaction process 2 HCl and SO generated in the reaction system 2 The gas is brought out, and the occurrence of side reaction is avoided. Stopping the reaction after 9h, rotary evaporating the reaction solution at 60 ℃, and removing the solvent and unreacted SOCl 2 Obtaining light yellow oily liquid, namely a chlorinated polyoxyethylene alkyl ether intermediate.
Step b) preparation of Tertiary amine intermediate
A 1. And then heating to 65 ℃, carrying out condensation reflux for reaction, taking out reaction liquid after 12h of reaction, carrying out decompression rotary evaporation at 60 ℃ to remove the solvent, washing with water for layering, and separating out unreacted diethanol amine to obtain a tertiary amine intermediate.
Step c) preparation of temperature-responsive surfactant
The obtained tertiary amine intermediate and sodium chloroacetate were dissolved in a mixture of ethanol and water (v/v = 6. After 14 hours, the reaction was stopped, and the reaction mixture was rotary evaporated under reduced pressure at 50 ℃ to remove the solvent. The reaction mixture was washed with ethanol and filtered to remove unreacted sodium chloroacetate. And recrystallizing and purifying the filtrate by using a mixed solution of ethanol and diethyl ether, and drying in vacuum to finally obtain a target product.
Preparation example 4
Step a) preparation of a chlorinated polyoxyethylene alkyl ether intermediate
4g of polyoxyethylene alkyl ether (same as preparation example 1) and 90ml of chloroform were sequentially charged in a three-necked reaction flask equipped with a condensing reflux unit, and 25ml of thionyl chloride (SOCl) was charged in a constant pressure dropping funnel 2 ) Make SOCl 2 Slowly dropping into a three-neck flask. After the dropwise addition is finished, adding 1-2 drops of DMF (dimethyl formamide) serving as a catalyst into the reaction system, and heating to 75 ℃ for reaction. Introducing N in the reaction process 2 HCl and SO generated in the reaction system 2 The gas is brought out, and the side reaction is avoided. After 10.5h, the reaction was stopped, the reaction solution was rotary evaporated at 65 ℃ to remove the solvent and unreacted SOCl2, and a pale yellow oily liquid, i.e., a chloropolyoxyethylene alkyl ether intermediate, was obtained.
Step b) preparation of Tertiary amine intermediate
A 1. And then heating to 70 ℃, carrying out condensation reflux for reaction, taking out reaction liquid after 15h of reaction, carrying out reduced pressure rotary evaporation at 65 ℃ to remove the solvent, washing with water for layering, and separating out unreacted diethanolamine to obtain the tertiary amine intermediate.
Step c) preparation of temperature-responsive surfactant
The obtained tertiary amine intermediate and sodium chloroacetate were dissolved in a mixture of ethanol and water (v/v = 7. After 16h, the reaction was stopped, and the reaction mixture was rotary evaporated under reduced pressure at 55 ℃ to remove the solvent. The reaction mixture was washed with ethanol and filtered to remove unreacted sodium chloroacetate. And recrystallizing and purifying the filtrate by using a mixed solution of ethanol and diethyl ether, and drying in vacuum to finally obtain a target product.
Preparation example 5
Step a) preparation of a chlorinated polyoxyethylene alkyl ether intermediate
Sequentially arranged at three ports with a condensing reflux deviceA flask was charged with 5g of polyoxyethylene alkyl ether (same as preparation example 1) and 100ml of chloroform, and 30ml of thionyl chloride (SOCl) was added to a constant pressure dropping funnel 2 ) Make SOCl 2 Slowly dropping into a three-neck flask. After the dropwise addition is finished, 1-2 drops of DMF (dimethyl formamide) serving as a catalyst are added into the reaction system, and the temperature is raised to 80 ℃ for reaction. Introducing N in the reaction process 2 HCl and SO generated in the reaction system 2 The gas is brought out, and the side reaction is avoided. Stopping the reaction after 12h, rotary evaporating the reaction solution at 70 ℃, and removing the solvent and unreacted SOCl 2 Obtaining light yellow oily liquid, namely a chlorinated polyoxyethylene alkyl ether intermediate.
Step b) preparation of Tertiary amine intermediate
A 1. And then heating to 80 ℃, carrying out condensation reflux for reaction, taking out reaction liquid after reacting for 18h, carrying out reduced pressure rotary evaporation at 70 ℃ to remove the solvent, washing with water for layering, and separating out unreacted diethanol amine to obtain a tertiary amine intermediate.
Step c) preparation of temperature-responsive surfactant
The obtained tertiary amine intermediate and sodium chloroacetate were dissolved in a mixture of ethanol and water (v/v = 8. After 18 hours the reaction was stopped, the reaction mixture was rotary evaporated at 60 ℃ under reduced pressure to remove the solvent. The reaction mixture was washed with ethanol and filtered to remove unreacted sodium chloroacetate. And recrystallizing and purifying the filtrate by using a mixed solution of ethanol and diethyl ether, and drying in vacuum to finally obtain a target product.
The yield of the target product obtained in preparation example 4 was the highest, and the temperature-responsive foaming agent was prepared using the temperature-responsive surfactant prepared in preparation example 4 in each of the following examples.
Example 1
Slowly adding 5% of temperature-responsive surfactant and 3% of alpha-sodium alkenyl sulfonate (Huashi chemical technology Co., ltd., chemical purity, CAS number: 68439-57-6, the same as in the following examples) into a stainless steel reaction kettle, adding solvent-deionized water, heating the mixed solution to 40 ℃, and stirring at low speed for 10min to obtain the target temperature-responsive foam scrubbing agent.
Example 2
Slowly adding 10% of temperature-responsive surfactant and 8% of alpha-sodium alkenyl sulfonate into a stainless steel reaction kettle, adding solvent-deionized water, heating the mixed solution to 50 ℃, and stirring at a low speed for 20min to obtain the target temperature-responsive foam scrubbing agent.
Example 3
Slowly adding 15% of temperature-responsive surfactant and 12% of alpha-sodium alkenyl sulfonate into a stainless steel reaction kettle, adding solvent-deionized water, heating the mixed solution to 60 ℃, and stirring at a low speed for 40min to obtain the target temperature-responsive foam scrubbing agent.
Example 4
Slowly adding 5% of temperature-responsive surfactant and 3% of sodium fatty alcohol polyoxyethylene ether sulfate (Beijing Bailingwei science and technology Co., ltd., chemical purity, CAS No. 9004-82-4, the same as in the following examples) into a stainless steel reaction kettle, adding solvent-deionized water, heating the mixed solution to 40 ℃, and stirring at low speed for 10min to obtain the target temperature-responsive foam-discharging agent.
Example 5
Slowly adding 10% of temperature-responsive surfactant and 8% of fatty alcohol-polyoxyethylene ether sodium sulfate into a stainless steel reaction kettle, adding solvent-deionized water, heating the mixed solution to 50 ℃, and stirring at a low speed for 20min to obtain the target temperature-responsive foam scrubbing agent.
Example 6
Slowly adding 15% of temperature-responsive surfactant and 12% of fatty alcohol-polyoxyethylene ether sodium sulfate into a stainless steel reaction kettle, adding solvent-deionized water, heating the mixed solution to 60 ℃, and stirring at low speed for 40min to obtain the target temperature-responsive foam-scrubbing agent.
Example 7
Slowly adding 5% of temperature-responsive surfactant and 3% of sodium dodecyl sulfate into a stainless steel reaction kettle, adding solvent-deionized water, heating the mixed solution to 40 ℃, and stirring at a low speed for 10min to obtain the target temperature-responsive foam scrubbing agent.
Example 8
Slowly adding 10% of temperature-responsive surfactant and 8% of sodium dodecyl sulfate into a stainless steel reaction kettle, adding solvent-deionized water, heating the mixed solution to 50 ℃, and stirring at low speed for 20min to obtain the target temperature-responsive foam scrubbing agent.
Example 9
Slowly adding 15% of temperature-responsive surfactant and 12% of sodium dodecyl sulfate into a stainless steel reaction kettle, adding solvent-deionized water, heating the mixed solution to 60 ℃, and stirring at low speed for 40min to obtain the target temperature-responsive foam scrubbing agent.
Example 10
Slowly adding 15% of temperature-responsive surfactant, 4% of alpha-sodium alkenyl sulfonate and 6% of sodium dodecyl sulfate into a stainless steel reaction kettle, adding solvent-deionized water, heating the mixed solution to 60 ℃, and stirring at low speed for 40min to obtain the target temperature-responsive foam scrubbing agent.
Example 11
Slowly adding 15% of temperature-responsive surfactant, 5% of alpha-alkenyl sodium sulfonate and 7% of fatty alcohol-polyoxyethylene ether sodium sulfate into a stainless steel reaction kettle, adding solvent-deionized water, heating the mixed solution to 60 ℃, and stirring at low speed for 40min to obtain the target temperature-responsive foam scrubbing agent.
[ temperature-responsive foaming agent Performance test ]
In order to verify the foaming ability, foam stabilizing ability and temperature responsiveness of the foaming agent for foam drainage and gas production of the present invention, a roche foam tester was used to perform a number of tests on the temperature-responsive foaming agent prepared in examples 1 to 9, the test procedures being as follows:
foaming capacity (maximum height of foam, H) of the foam was measured at 20 ℃,40 ℃,60 ℃,80 ℃ respectively max ) And foam stabilizing ability (half-life, t) 1/2 ). Taking two surfactant samples, respectively preparing 0.5% (w/w) solution, preheating, testingThe test procedure was as follows:
(1) setting a constant-temperature water bath kettle as a test temperature, and successively moistening and washing the inner wall of the graduated tube by using pure water and test solution;
(2) injecting 50mL of test solution preheated to a set temperature into the graduated tube;
(3) sucking 200mL of preheated test solution by using a dropping liquid tube, and placing the test solution on a pipe frame at a fixed position;
(4) allowing the solution in the drip tube to flow down naturally, recording the maximum height of the foam Hmax and the time t when the foam decays to half of the maximum foam height 1/2 。
The test results are shown in table 1, and the degree of mineralization in the test solution is 100000mg/L (CaCl 2: naCl =4 (w/w).
Table 1 shows the foaming ability, foam stabilizing ability and foam properties at different temperatures of the temperature responsive foaming agents of examples 1 to 11.
TABLE 1
As can be seen from table 1, the temperature-responsive foaming agents prepared in examples 1 to 9 have poor foaming and foam-stabilizing properties at a low temperature (20 ℃), and the initial bubble height and half-life period of the foaming agent gradually increase with increasing temperature, which proves that the foaming agent has a temperature-responsive type, because the synthesized temperature-responsive surfactant molecules can realize a conceptual transformation under thermal stimulation, thereby causing the appearance of the assembly to change and realizing the stability of the foam regulated by temperature.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent variations and modifications can be made by those skilled in the art in light of the technical teaching provided by the present invention, and should be considered as the protection scope of the present invention.
Claims (10)
1. A temperature response type foaming agent for foam drainage gas production is characterized by comprising the following components in percentage by mass:
5 to 15 percent of temperature response type surfactant, preferably 6 to 13 percent, and more preferably 7 to 12 percent;
3 to 12 percent of cosurfactant selected from at least one of alpha-alkenyl sulfonate, fatty alcohol-polyoxyethylene ether sulfate and dodecyl sulfate, preferably 4 to 10 percent, and more preferably 5 to 9 percent;
the balance being water.
2. The temperature-responsive foaming agent of claim 1, wherein the temperature-responsive surfactant is:
n is an arbitrary number from 4 to 6, preferably an arbitrary number from 4 to 5;
r is alkyl, preferably C 1 ～C 20 One or more of alkyl groups, more preferably C 6 ～C 12 An alkyl group; and/or
The alpha-olefin sulfonate comprises sodium alpha-olefin sulfonate, which satisfies the formula:
R′-HC＝CH-CH 2 -SO 3 Z
wherein R' is C 5 ～C 30 At least one of alkyl groups of (a); z is at least one of alkali metal ions, preferably sodium ions; and/or
The fatty alcohol-polyoxyethylene ether sulfate comprises fatty alcohol-polyoxyethylene ether sodium sulfate; preferably, it has the formula R' O (CH) 2 CH 2 O)m-SO 3 Na, wherein m is 2 or 3, R' is C 12 ～C 15 At least one of alkyl groups; and/or
The lauryl sulfate salt comprises sodium lauryl sulfate.
3. The temperature-responsive blowing agent of claim 2, wherein the temperature-responsive blowing agent comprises, in mass fraction:
5 to 15 percent of temperature response type surfactant;
3 to 10 percent of alpha-sodium alkenyl sulfonate; and/or 4-12% of fatty alcohol-polyoxyethylene ether sodium sulfate; and/or sodium dodecyl sulfate 4-11%;
the balance being water.
4. A method of preparing the temperature responsive blowing agent of any of claims 1-3 comprising the steps of: mixing a temperature response type surfactant, a cosurfactant selected from at least one of alpha-alkenyl sulfonate, fatty alcohol-polyoxyethylene ether sulfate and dodecyl sulfate and water to prepare a temperature response type foaming agent;
preferably, the temperature-responsive surfactant is prepared via a process comprising the steps of:
step a) dissolving polyoxyethylene alkyl ether in a solvent I, dropwise adding thionyl chloride, heating in the presence of a catalyst for reaction, and removing the solvent after the reaction to prepare a chlorinated polyoxyethylene alkyl ether intermediate;
step b) dissolving the chlorinated polyoxyethylene alkyl ether intermediate prepared in the step a) and diethanol amine in a solvent II, heating, carrying out condensation reflux reaction, and removing the solvent to prepare a tertiary amine intermediate;
and c) dissolving the tertiary amine intermediate prepared in the step b) and sodium chloroacetate in a solvent III, heating, carrying out condensation reflux reaction, removing the solvent, and then filtering and drying to prepare the temperature response type surfactant.
5. The process according to claim 4, wherein the solvent I in step a) comprises chloroform, and the mass ratio of the polyoxyethylene alkyl ether to the solvent I is 1% to 10%, preferably 2% to 9%, and more preferably 3% to 8%; and/or
The molar ratio of the thionyl chloride to the polyoxyethylene alkyl ether in step a) is from 1; and/or
The catalyst in step a) comprises N, N-dimethylformamide, and the molar ratio of the catalyst to the polyoxyethylene alkyl ether is 1; and/or
The reaction temperature in the step a) is 60-80 ℃, nitrogen is introduced in the reaction process, and after the reaction, the reaction liquid is subjected to rotary evaporation at 50-70 ℃ to remove the solvent, so as to prepare the chlorinated polyoxyethylene alkyl ether intermediate.
6. The process according to claim 4 or 5, characterized in that the molar ratio of the chloropolyoxyethylene alkyl ether intermediate to diethanolamine in step b) is 1:1 to 1:3, preferably 1; and/or
The solvent II comprises a mixture of ethanol and water, and the volume ratio of the ethanol to the water is 3: 1; and/or
The temperature of the condensation reflux reaction in the step b) is 50-80 ℃, and the time is 6-18 hours; and/or
After the condensation reflux reaction in the step b), carrying out reduced pressure rotary evaporation at 50-70 ℃ to remove the solvent, thus obtaining the tertiary amine intermediate.
7. The process according to any one of claims 4 to 6, characterized in that the molar ratio of the tertiary amine intermediate to the sodium chloroacetate in step c) is 1; and/or
The solvent III comprises a mixture of ethanol and water, and the volume ratio of the ethanol to the water is 3: 1; and/or
The temperature of the condensation reflux reaction in the step c) is 50-90 ℃ and the time is 9-18 hours; and/or
After the condensation reflux reaction in the step c), carrying out reduced pressure rotary evaporation at 40-60 ℃ to remove the solvent, thus obtaining the temperature response type surfactant.
8. The method of any of claims 4 to 7, wherein the temperature responsive blowing agent comprises: 5 to 15 percent of temperature response type surfactant, preferably 6 to 13 percent, and more preferably 7 to 12 percent;
3 to 12 percent of alpha-sodium alkenyl sulfonate, preferably 3 to 10 percent, and more preferably 4 to 10 percent; and/or 3-12% of fatty alcohol-polyoxyethylene ether sodium sulfate, preferably 4-10%, more preferably 5-9%; and/or sodium dodecyl sulfate 3% -12%, preferably 4% -9%, more preferably 5% -9%;
the balance being water.
9. Use of a temperature responsive foaming agent according to any of claims 1 to 3 or a method of preparing a temperature responsive foaming agent according to any of claims 4 to 8 in the field of oilfield chemistry.
10. Use according to claim 9, in a foam drainage process.
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