CN113136191A - Thin oil foaming agent and preparation method and application thereof - Google Patents
Thin oil foaming agent and preparation method and application thereof Download PDFInfo
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- CN113136191A CN113136191A CN202010067798.7A CN202010067798A CN113136191A CN 113136191 A CN113136191 A CN 113136191A CN 202010067798 A CN202010067798 A CN 202010067798A CN 113136191 A CN113136191 A CN 113136191A
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- 239000004088 foaming agent Substances 0.000 title claims abstract description 157
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000006260 foam Substances 0.000 claims abstract description 91
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000002888 zwitterionic surfactant Substances 0.000 claims abstract description 31
- 239000004094 surface-active agent Substances 0.000 claims abstract description 29
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 24
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229960003237 betaine Drugs 0.000 claims abstract description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 6
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 239000000194 fatty acid Substances 0.000 claims abstract description 6
- 229930195729 fatty acid Natural products 0.000 claims abstract description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims abstract 2
- 125000005313 fatty acid group Chemical group 0.000 claims abstract 2
- 239000003921 oil Substances 0.000 claims description 153
- 235000019198 oils Nutrition 0.000 claims description 152
- 238000002156 mixing Methods 0.000 claims description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- LURQBQNWDYASPJ-UHFFFAOYSA-N hydrazinyl Chemical compound N[NH] LURQBQNWDYASPJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 238000006073 displacement reaction Methods 0.000 claims description 12
- 235000019864 coconut oil Nutrition 0.000 claims description 11
- 239000003240 coconut oil Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 2
- 238000005187 foaming Methods 0.000 abstract description 17
- 239000011435 rock Substances 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 62
- 239000010779 crude oil Substances 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 28
- 230000000694 effects Effects 0.000 description 16
- 239000012071 phase Substances 0.000 description 15
- 239000004604 Blowing Agent Substances 0.000 description 11
- 239000008398 formation water Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- -1 perfluoroalkyl sulfonyl chloride Chemical compound 0.000 description 9
- 239000002280 amphoteric surfactant Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 150000004665 fatty acids Chemical group 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000007112 amidation reaction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000418 atomic force spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- JWAZRIHNYRIHIV-UHFFFAOYSA-N beta-hydroxynaphthyl Natural products C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002193 fatty amides Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 230000002195 synergetic effect Effects 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
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Geochemistry & Mineralogy (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention provides a thin oil foaming agent and a preparation method and application thereof, wherein the thin oil foaming agent comprises the following components in percentage by mass: 21.0-25.5% of zwitterionic surfactant, 1.5-4.5% of stabilizing synergist, 0.6-4.5% of surfactant and the balance of water; the zwitterionic surfactant is fatty acid amide propyl dimethyl betaine shown in formula 1, wherein in the formula 1, R is C8‑C14Alkyl group of (1). The foaming agent for the thin oil is simple in composition, not only can be used for normally foaming in the thin oil, but also can be used for reducing the adsorption retention of foam on the surface of a rock, and effectively improving the foam exploitation efficiency of the thin oil.
Description
Technical Field
The invention relates to a thin oil foaming agent, a preparation method and application thereof, and belongs to the technical field of petroleum exploration and development.
Background
Low permeability (less than or equal to 100X 10) of Tuhaan oil field-3μm2) Low viscosity (less than or equal to 5mPa.s) oil reservoir enters the later stage of water drive development. In order to further excavate the remaining oil and improve the development effect, the foam flooding test has been successively conducted on 5 blocks such as shanshan mountain and Wenmi in the last 3 years.
However, in terms of actual effects, only Wenxie block has a certain oil displacement effect at present, but the effect degree and the actual effects are not ideal. Particularly, when foam flooding is carried out, a large number of molecules of a foaming agent can be dissolved in thin oil, normal foaming cannot be carried out, and therefore the phenomenon that the foaming effect of a foaming agent solution is poor is caused, and in a low-permeability reservoir, the adsorption retention of a foam system on the surface of rock is extremely serious due to the fact that the specific surface of the rock is huge.
Therefore, a low-cost, oil-resistant and adsorption-resistant efficient foam oil displacement system suitable for low-permeability, low-viscosity and high-temperature oil reservoirs needs to be further developed, and the recovery rate and the economic benefit of the low-permeability and low-viscosity oil reservoirs are greatly improved.
Disclosure of Invention
The invention provides a thin oil foaming agent which is simple in composition, can normally form bubbles in thin oil, can lower the adsorption retention amount of foam on the surface of a rock, and effectively improves the foam extraction efficiency of the thin oil.
The invention also provides a preparation method of the heavy oil foaming agent, and the method has the advantages of convenience in operation, safety and high efficiency.
The invention also provides application of the thin oil foaming agent in thick oil foam exploitation.
The invention provides a thin oil foaming agent which comprises the following components in percentage by mass: 21.0-25.5% of zwitterionic surfactant, 1.5-4.5% of stabilizing synergist, 0.6-4.5% of surfactant and the balance of water;
the zwitterionic surfactant is fatty acid amide propyl dimethyl betaine shown in formula 1, wherein in the formula 1, R is C8-C14Alkyl groups of (a);
the thin oil foaming agent as described above, wherein the stabilizer synergist is alkanolamide represented by formula 2, and R in formula 2 is C8-C18Alkyl groups of (a);
the thin oil foaming agent as described above, wherein the interfacial activityThe agent is perfluoroalkyl sulfonyl chloride and NH2NH(CH2)3N+(CH3)2CH2COO-Refluxing for 5-8 h.
The thin oil foaming agent as described above, wherein the perfluoroalkyl sulfonyl chloride and NH2NH(CH2)3N+(CH3)2CH2COO-Is 652: 161.
The thin oil foaming agent as described above, wherein the surfactant is C11F23SO2NH(CH2)3N+(CH3)2CH2COO-。
A thin oil foaming agent as described above, wherein coconut oil acid is mixed with NH2NH(CH2)3N+(CH3)2CH2COO-Mixing, heating to 60-80 ℃, and reacting for 4-6 h to obtain the zwitterionic surfactant.
The thin oil foaming agent as described above, wherein the coconut oil acid is NH2NH(CH2)3N+(CH3)2CH2COO-In a molar ratio of 1: 1.
the thin oil foaming agent comprises the following components in percentage by mass: 23.4 percent of zwitterionic surfactant, 3.6 percent of stabilizing synergist, 3.0 percent of surfactant and the balance of water.
The invention also provides a preparation method of any one of the above thin oil foaming agents, which is characterized in that the thin oil foaming agent is obtained by uniformly mixing the zwitterionic surfactant, the stabilizing synergist, the surfactant and water.
The invention also provides an application of any one of the thin oil foaming agents as a foam oil displacement agent in thin oil foam exploitation.
The implementation of the invention has at least the following advantages:
1. the thin oil foaming agent disclosed by the invention not only can normally bubble in thin oil, but also can lower the adsorption retention amount of foam on the surface of rock, and effectively improves the foam exploitation efficiency of the thin oil;
2. the thin oil foaming agent has good compatibility stability with media such as formation water and the like, and can be widely applied to foam fracturing technology, oil and gas co-production and gas and water co-production well oil extraction, gas production and drainage;
3. the thin oil foaming agent has simple composition and low production cost, and is suitable for large-scale popularization and application in enterprises;
4. the preparation method of the thin oil foaming agent has the characteristics of simple conditions, feasible process, safety and high efficiency, and is convenient for practical popularization and large-scale application.
Drawings
FIG. 1 is a graphical comparison of the interfacial tension between crude oils at different concentrations for the thin oil frother of the present invention and a comparative thin oil frother;
FIG. 2 is a graph comparing the plugging force curves of the thin oil frother of the present invention and a comparative thin oil frother at different concentrations;
FIG. 3 is a graph comparing the concentration curves of amphoteric surfactants at different concentrations for the thin oil frother of the present invention and the comparative thin oil frother.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a thin oil foaming agent which comprises the following components in percentage by mass: 21.0-25.5% of zwitterionic surfactant, 1.5-4.5% of stabilizing synergist, 0.6-4.5% of surfactant and the balance of water;
the zwitterionic surfactant is fatty acid amide propyl dimethyl betaine shown in formula 1, wherein in the formula 1, R is C8-C14Alkyl groups of (a);
the thin oil foaming agent of the invention can be used for exploiting thin oil, and the thin oil of the invention refers to hypotonic (less than or equal to 100 x 10)-3μm2) Low viscosity (less than or equal to 5mPa.s) crude oil. For example, West blocks of Tuoha oil fields are typical of high-temperature thin oil reservoirs, the viscosity of the underground crude oil is 0.7 mPas, and the permeability of the oil layer is 59 x 10-3μm2The oil layer temperature was 84.2 ℃.
The thin oil foaming agent is prepared by mixing the zwitterionic surfactant, the stabilizing synergist, the surfactant and water according to a certain proportion, wherein the zwitterionic surfactant is shown in a formula 1.
Among them, the stabilizing synergist is used for a substance that improves foamability and increases foam stability.
According to the technical scheme provided by the invention, the thin oil foaming agent can reduce the interfacial tension of an oil-water interface, enhance the foaming capacity in the thin oil, remarkably reduce the retention amount of foam on the surface of a rock, and effectively improve the foam flooding efficiency of the thin oil. The inventors have analyzed based on this phenomenon and considered that it is possible to: the raw material (fatty acid amide propyl dimethyl betaine) for preparing the thin oil foaming agent has stronger electron cloud power supply effect, is beneficial to improving the temperature resistance of the thin oil foaming agent, and the combination of different carbon chains in the raw material ensures that a hydrophobic group and a hydrophilic group of the thin oil foaming agent are not single any more, but form a synergistic effect, thereby greatly improving the foaming capacity of the thin oil foaming agent in the thin oil and improving the retention phenomenon of foam on the surface of rock.
In one embodiment, the thin oil foaming agent of the present invention comprises, by mass: 23.4 percent of zwitterionic surfactant, 3.6 percent of stabilizing synergist, 3.0 percent of surfactant and the balance of water.
Among them, the zwitterionic surfactant of the present invention can be obtained commercially or can be prepared by the following method.
Specifically, coconut oil acid (coconut oil fatty acid) is mixed with NH2NH(CH2)3N+(CH3)2CH2COO-Mixing (commercially available), heating to 60-80 ℃, and reacting for 4-6 h to obtain the zwitterionic surfactant shown in the formula 1.
Further, coco acid with NH2NH(CH2)3N+(CH3)2CH2COO-In a molar ratio of 1: 1.
the stabilizing synergist can be alkanolamide shown in formula 2, wherein in the formula 2, R is C8-C18Alkyl groups of (a);
the stabilizing synergist contains hydrophilic groups such as hydroxyethyl, so that the electron cloud enables the combination of molecules to be tighter while providing more power supply effect, the addition of the hydrophilic groups also improves the adaptability of the thin oil foaming agent to the use environment, such as the pH value of the environment, different mineralization degrees and the like, and in addition, due to the introduction of the side chain hydrophilic groups, the foam film wall formed when the thin oil foaming agent foams is thicker and more elastic, so that the foam stability of the thin oil foaming agent is improved.
The alkanolamides of formula 2 are commercially available or can be prepared by the following method. Specifically, coco oil acid is reacted with NH (CH)2CH2OH)2(diethanolamine) is mixed according to the molar ratio of 1:1, heated to 60-80 ℃ and reacted for 4-6 h, and amidation reaction is carried out to generate alkanolamide.
Further, the surfactant is composed of perfluoroalkyl sulfonyl chloride and NH2NH(CH2)3N+(CH3)2CH2COO-Refluxing for 5-8h to obtain the product, wherein perfluoroalkyl sulfonyl chloride and NH are used for ensuring high efficiency of reaction2NH(CH2)3N+(CH3)2CH2COO-Is 652: 161. Wherein, the carbon atom of the purified perfluoroalkyl sulfonyl chloride on the market can be selectedThe number of carbon atoms of the perfluoroalkyl sulfonyl chloride is preferably 11 (which is directly available commercially) for use in the surfactant of the present invention, in the range of from 8 to 12.
Theoretically, perfluoroalkyl sulfonyl chlorides and NH2NH(CH2)3N+(CH3)2CH2COO-React to form CnF2n+ 1SO2NH(CH2)3N+(CH3)2CH2COO-Where n is 8 to 12, preferably 11.
The sulfo group contained in the surfactant can enable the structure of the zwitterionic surfactant to be more compact and the binding degree to be higher, further improve the temperature resistance of the thin oil foaming agent and simultaneously have salt resistance (Ca)2+、Mg2+) And (4) sex.
The invention also provides a preparation method of any one of the thin oil foaming agents, which comprises the following steps: uniformly mixing the zwitterionic surfactant, the stabilizing synergist, the surfactant and water to obtain the thin oil foaming agent.
The proportions of the amphoteric surfactant, the stabilizing synergist, the surfactant and the water are the same as those described above, and are not described herein again.
The invention also provides an application of any one of the thin oil foaming agents as a foam oil displacement agent in thin oil foam exploitation.
When nitrogen foam fluid is used for oil displacement in an injection well, due to the fact that dirt and other conditions often exist on the pipe wall of a well deep zone and a zone close to the well, the traditional ground foaming device can only mix and foam on the ground, the quality of foam generated at the bottom of the well cannot be guaranteed, the treatment on an oil layer is not very ideal, the two-phase liquid of gas and liquid at the bottom of the well cannot be guaranteed to be in a high-speed turbulent flow state, continuous and stable high-quality foam is generated, and the oil displacement effect is not very ideal. Therefore, a downhole foam generator is used for downhole foaming to overcome the above-mentioned disadvantages.
Hereinafter, the thin oil foaming agent and the preparation method thereof according to the present invention will be described in detail by way of specific examples.
Example 1
Uniformly mixing a zwitterionic surfactant, a stabilizing synergist, a surfactant and water to obtain the thin oil foaming agent No. 1 of the embodiment;
wherein, the mass content of the zwitterionic surfactant is 23.4 percent, the mass content of the stabilizing synergist is 3.6 percent, the mass content of the surfactant is 3.0 percent, and the balance is water.
The zwitterionic surfactant is fatty amide propyl dimethyl betaine and is prepared by the following method:
mixing coconut oil acid with NH2NH(CH2)3N+(CH3)2CH2COO-Mixing according to a molar ratio of 1:1 (coconut oil acid is a mixture, the molecular weight of the coconut oil acid is between 158-238, and the molecular weight is 158 in practical application), heating to 60 ℃, refluxing for 4h, and carrying out amidation reaction to obtain the zwitterionic surfactant.
The stabilizing synergist is alkanolamide and is prepared by the following method:
mixing cocoanut oil acid with NH (CH)2CH2OH)2(diethanolamine) mixing according to the ratio of 1:1 (coconut oil acid is a mixture, the molecular weight of the coconut oil acid is 158-298), heating to 80 ℃, refluxing for 6h, and carrying out amidation reaction to obtain alkanolamide.
The surfactant is C11F23SO2NH(CH2)3N+(CH3)2CH2COO-The preparation method comprises the following steps:
reacting perfluoroalkyl sulfonyl chloride (purified product with 11 carbon atoms, available directly from market) with NH2NH(CH2)3N+(CH3)2CH2COO-Mixing according to the mass ratio of 652:161, heating to 80 ℃, and refluxing for 8h to obtain the surfactant.
Example 2
Uniformly mixing a zwitterionic surfactant, a stabilizing synergist, a surfactant and water to obtain the thin oil foaming agent 2# of the embodiment;
wherein, the mass content of the zwitterionic surfactant is 25.5 percent, the mass content of the stabilizing synergist is 3.6 percent, the mass content of the surfactant is 3.0 percent, and the balance is water.
The above raw materials were the same as those in example 1.
Example 3
Uniformly mixing the zwitterionic surfactant, the stabilizing synergist, the surfactant and water to obtain the thin oil foaming agent # 3 in the embodiment;
wherein, the mass content of the zwitterionic surfactant is 23.0 percent, the mass content of the stabilizing synergist is 2.7 percent, the mass content of the surfactant is 4.3 percent, and the balance is water.
The above raw materials were the same as those in example 1.
Example 4
Uniformly mixing the zwitterionic surfactant, the stabilizing synergist, the surfactant and water to obtain the dilute oil foaming agent No. 4 of the embodiment;
wherein, the mass content of the zwitterionic surfactant is 21.2 percent, the mass content of the stabilizing synergist is 3.3 percent, the mass content of the surfactant is 3.5 percent, and the balance is water.
The above raw materials were the same as those in example 1.
Comparative example
The thin oil foaming agent of this comparative example was purchased from the Douwanghe chemical plant under the trade name XHY-4.
Test example 1
The foaming agent is an essential component for forming foam, and as a foaming agent, the most important properties are its foam properties (including foaming ability and stability of the generated foam), and the quality of the foam properties of the foaming agent is one of the most important factors for use in a foam system. However, the foaming properties of various foaming agents are different and have certain difference. Therefore, the present test example evaluates the foaming properties of the foaming agent. Since the foaming agent is required to have as high foaming ability and foam stability as possible in the development process, the foam properties of the foaming agent are evaluated from both the foaming ability and the foam stability.
The foaming agent solution is prepared by using formation water, oilfield injection water, oilfield produced water, clear water and crude oil respectively, and a foam performance evaluation experiment is carried out.
1. Effect of formation water on blowing agent Performance
The thin oil foaming agent prepared in example 1 and the foaming agent of comparative example were prepared into foaming agent solutions with a concentration of 0.01% to 0.2% using formation water, respectively, and the foam volume, the half-life of the solution, the half-life of the foam, the defoaming time, the apparent viscosity, and the like of each foaming agent solution were measured at 84.2 ℃ under normal pressure (Waring-Blender method), and the measurement results are shown in tables 1 and 2.
TABLE 1 Performance parameters of the thin oil frother of example 1
TABLE 2 Performance parameters of the thin oil foam 4 of the comparative examples
2. Effect of oilfield injection water on foamer Performance
The thin oil foaming agent prepared in example 1 and the foaming agent of comparative example were prepared into foaming agent solutions having a concentration of 0.01% to 0.2% by using oilfield injection water, and the foam volume, the half-life of the solution, the half-life of the foam, the defoaming time, the apparent viscosity, etc. of each foaming agent solution were measured at 84.2 ℃ under normal pressure (Waring-Blender method), and the results of the measurements are shown in tables 3 and 4.
TABLE 3 Performance parameters of the thin oil frother of example 1
| Concentration/% (effective) | 0.01 | 0.02 | 0.04 | 0.06 | 0.08 | 0.10 | 0.15 | 0.20 |
| Foam volume/mL | 430 | 490 | 540 | 600 | 660 | 720 | 810 | 870 |
| Half life t of liquid1/2/s | 21 | 38 | 75 | 83 | 103 | 110 | 121 | 150 |
| Half-life of foam t1/2/s | 225 | 765 | 1215 | 1354 | 1395 | 1575 | 1365 | 1382 |
| Defoaming time/min | 90 | 92 | 90 | 98 | 102 | 108 | 105 | 105 |
| Foam characteristic value/number | 0.5349 | 0.5918 | 0.6296 | 0.6667 | 0.6970 | 0.7222 | 0.7531 | 0.7701 |
| Comprehensive index/(mL. s) | 96750 | 374850 | 656100 | 812400 | 920700 | 1134000 | 1105650 | 1202340 |
| Apparent viscosity/(mPa. s) | 205 | 239.9 | 389.9 | 409.9 | 464.9 | 484.9 | 539.9 | 559.9 |
TABLE 4 Performance parameters of the thin oil blowing agent of the comparative examples
3. Effect of oilfield produced Water on foamer Performance
The thin oil foaming agent prepared in example 1 and the foaming agent of the comparative example were prepared into foaming agent solutions with a concentration of 0.01% to 0.2% respectively using oilfield produced water, and the foam volume, the half-life of the solution, the half-life of the foam, the defoaming time, the apparent viscosity, and the like of each foaming agent solution were measured at 84.2 ℃ under normal pressure (Waring-Blender method), and the measurement results are shown in tables 5 and 6.
TABLE 5 thin oil frother of example 1
| Concentration/% (effective) | 0.01 | 0.02 | 0.04 | 0.06 | 0.08 | 0.10 | 0.15 | 0.20 |
| Foam volume/mL | 430 | 460 | 530 | 590 | 650 | 700 | 820 | 880 |
| Half life t of liquid1/2/s | 15 | 30 | 70 | 80 | 82 | 90 | 105 | 124 |
| Half-life of foam t1/2/s | 200 | 445 | 740 | 1174 | 1285 | 1160 | 1105 | 1135 |
| Defoaming time/min | 85 | 89 | 90 | 95 | 95 | 93 | 96 | 94 |
| Foam characteristic value/number | 0.5349 | 0.5652 | 0.6226 | 0.6610 | 0.6923 | 0.7143 | 0.7561 | 0.7727 |
| Comprehensive index/(mL. s) | 86000 | 204700 | 392200 | 692660 | 835250 | 812000 | 906100 | 998800 |
| Apparent viscosity/(mPa. s) | 209.9 | 259.9 | 354.9 | 389.9 | 484.9 | 469.9 | 509.9 | 569.9 |
TABLE 6 Performance parameters of the thin oil blowing agent of the comparative example
| Concentration/% (effective) | 0.01 | 0.02 | 0.04 | 0.06 | 0.08 | 0.10 | 0.15 | 0.20 |
| Foam volume/mL | 350 | 410 | 530 | 580 | 630 | 680 | 730 | 800 |
| Half life t of liquid1/2/s | 18 | 30 | 58 | 71 | 80 | 85 | 100 | 122 |
| Half-life of foam t1/2/s | 192 | 450 | 630 | 900 | 1065 | 1095 | 1168 | 1038 |
| Defoaming time/min | 84 | 90 | 88 | 92 | 90 | 88 | 92 | 90 |
| Foam characteristic value/number | 0.4286 | 0.5122 | 0.6226 | 0.6552 | 0.6825 | 0.7059 | 0.7260 | 0.7500 |
| Comprehensive index/(mL. s) | 67200 | 184500 | 333900 | 522000 | 670950 | 744600 | 852640 | 830400 |
| Apparent viscosity/(mPa. s) | 239.9 | 259.9 | 359.9 | 424.9 | 475.9 | 469.9 | 514.9 | 549.9 |
4. Effect of clean water on blowing agent Performance
The thin oil foaming agent prepared in example 1 and the foaming agent of comparative example were prepared into foaming agent solutions having a concentration of 0.01% to 0.2% respectively using clean water, and the foam volume, the half-life of the solution, the half-life of the foam, the defoaming time, the apparent viscosity, etc. of each foaming agent solution were measured at 84.2 ℃ under normal pressure (Waring-Blender method), and the results of the measurements are shown in tables 7 and 8.
TABLE 7 thin oil frother of example 1
TABLE 8 thin oil frother of comparative example
| Concentration/% (effective) | 0.01 | 0.02 | 0.04 | 0.06 | 0.08 | 0.10 | 0.15 | 0.20 |
| Foam volume/mL | 280 | 370 | 490 | 540 | 600 | 660 | 710 | 780 |
| Half life t of liquid1/2/s | 26 | 40 | 62 | 75 | 94 | 107 | 120 | 129 |
| Half-life of foam t1/2/s | 137 | 377 | 639 | 1089 | 1189 | 1210 | 1183 | 1129 |
| Defoaming time/min | 82 | 87 | 90 | 92 | 95 | 98 | 93 | 94 |
| Foam characteristic value/number | 0.2857 | 0.4595 | 0.5918 | 0.6296 | 0.6667 | 0.6970 | 0.7183 | 0.7436 |
| Comprehensive index/(mL. s) | 38360 | 139490 | 313110 | 588060 | 713400 | 798600 | 839930 | 880620 |
| Apparent viscosity/(mPa. s) | 239.9 | 334.9 | 449.9 | 449.9 | 504.9 | 499.9 | 509.9 | 541.9 |
5. Effect of crude oil on blowing agent Performance
By usingCrude oil with concentration of 0.5% (volume concentration of crude oil after mixing with formation water is 0.5%, crude oil density is 0.8231g/cm3Viscosity of 5.2mPa · s) the thin oil foaming agent prepared in example 1 and the foaming agent of comparative example were prepared into foaming agent solutions having a concentration of 0.01% to 0.2%, respectively, and the foam volume, the half-life of the solution, the half-life of the foam, the defoaming time, the apparent viscosity, and the like of each foaming agent solution were measured at 84.2 ℃ under normal pressure (Waring-Blender method), and the results of the measurements are shown in tables 9 and 10.
Using crude oil with concentration of 1% (the volume concentration of crude oil is 1% after mixing with formation water, the density of crude oil is 0.8231g/cm3Viscosity of 5.2mPa · s) the thin oil foaming agent 1# obtained in example 1 and the foaming agent of comparative example were prepared into foaming agent solutions having a concentration of 0.01% to 0.2%, respectively, and the foam volume, the half-life of the solution, the half-life of the foam, the defoaming time, the apparent viscosity, and the like of each foaming agent solution were measured at 84.2 ℃ under normal pressure (Waring-Blender method), and the results of the measurements are shown in tables 11 and 12.
TABLE 9 Performance parameters for comparative example thin oil foaming agent with 0.5% crude oil addition
TABLE 10 Performance parameters of the thin oil frother of example 1 with 0.5% crude oil addition
| Concentration/% (effective) | 0.01 | 0.02 | 0.04 | 0.06 | 0.08 | 0.10 | 0.15 | 0.20 |
| Foam volume/mL | 220 | 250 | 290 | 440 | 500 | 580 | 670 | 740 |
| Half life t of liquid1/2/s | 3 | 5 | 15 | 43 | 74 | 102 | 133 | 120 |
| Half-life of foam t1/2/ |
6 | 8 | 20 | 199 | 505 | 850 | 950 | 1031 |
| Defoaming time/min | 85 | 90 | 92 | 90 | 93 | 98 | 92 | 94 |
| Foam characteristic value/number | 0.0909 | 0.2 | 0.3103 | 0.5455 | 0.6 | 0.6552 | 0.7015 | 0.7297 |
| Comprehensive index/(mL. s) | 1320 | 2000 | 5800 | 87560 | 252500 | 493000 | 636500 | 762940 |
| Apparent viscosity/(mPa. s) | 209.9 | 257.9 | 294.9 | 326.9 | 379.9 | 424.9 | 519.9 | 579.9 |
TABLE 11 Performance parameters for comparative example thin oil frother with 1% crude oil addition
TABLE 12 Performance parameters of the thin oil frother of example 1 with 1% crude oil addition
| Concentration/% (effective) | 0.01 | 0.02 | 0.04 | 0.06 | 0.08 | 0.10 | 0.15 | 0.20 |
| Foam volume/mL | 220 | 230 | 270 | 300 | 410 | 490 | 620 | 680 |
| Half life t of liquid1/2/s | 3 | 6 | 11 | 16 | 29 | 62 | 89 | 100 |
| Half-life of foam t1/2/ |
4 | 7 | 15 | 24 | 170 | 373 | 870 | 1000 |
| Defoaming time/min | 80 | 82 | 85 | 87 | 85 | 89 | 92 | 95 |
| Foam characteristic value/number | 0.0909 | 0.1304 | 0.2593 | 0.3333 | 0.5122 | 0.5918 | 0.6774 | 0.7059 |
| Comprehensive index/(mL. s) | 880 | 1610 | 4050 | 7200 | 192700 | 182770 | 539400 | 680000 |
| Apparent viscosity/(mPa. s) | 216.9 | 267.9 | 309.9 | 359.9 | 409.9 | 484.9 | 524.9 | 564.9 |
As can be seen from tables 1 to 12:
the thin oil foaming agent disclosed by the embodiment of the invention has excellent foaming capacity and foam stability in the environments of formation water, oilfield injection water, oilfield produced water, clear water and crude oil.
Test example 2
The thin oil foaming agent prepared in example 1 was prepared into foaming agent solutions with a concentration of 0.04% to 0.1% using oilfield produced water, and the foam volume, foam half-life, and the like of each foaming agent solution were measured at 84.2 ℃ under pressures of 0.1MPa, 5MPa, 10MPa, and 15MPa, respectively, and the measurement results are shown in table 13.
The thin oil foaming agent of the comparative example is respectively prepared into foaming agent solutions with the concentration of 0.04-0.1% by utilizing the produced water of the oil field, the foam volume, the foam half-life period and the like of each foaming agent solution are detected under the conditions that the temperature is 84.2 ℃ and the pressure is 0.1MPa, 5MPa, 10MPa and 15MPa respectively, and the detection results are shown in Table 14.
Watch 13
TABLE 14
From a comparison of tables 13 and 14, it can be seen that: the thin oil frother of example 1 had superior foaming performance at different pressures than the comparative thin oil frother.
Test example 3
1. Determination of interfacial tension
The foaming agent is actually a surfactant, and is bound to generate adsorption on a contact interface of crude oil and an aqueous solution, so that the oil-water interfacial tension is reduced, and the oil displacement efficiency is improved. Therefore, the interfacial tension between the crude oil and the thin oil frother of example 1 was measured.
Specifically, the thin oil foaming agent XHY-6 obtained in example 1 and the foaming agent of comparative example XHY-4 were prepared into foaming agent solutions having a concentration of 0.025% to 0.2% using formation water, respectively, and interfacial tensions between the respective foaming agent solutions and the crude oil were measured at 84.2 ℃ and 15MPa in the oil layer of the Tuohwenxi three-well area.
The measurement is carried out by using a JJ2000B rotary drop interfacial tension measuring instrument, wherein the density of the crude oil is 0.82g/cm3The oil-water density difference is 0.18g/cm3The results are shown in FIG. 1.
FIG. 1 is a graphical comparison of the interfacial tension between crude oils at different concentrations for the thin oil frother of the present invention and the comparative thin oil frother. As shown in figure 1, the thin oil foaming agent prepared by the invention generates adsorption on a contact interface between crude oil and an aqueous solution, can effectively reduce the tension of an oil-water interface, and is more beneficial to improving the oil displacement efficiency.
2. Determination of the occlusion capacity (resistance factor):
in the foam displacement process, the foaming agent solution and the gas generate foam by the action of the pore medium such as the seizure and division, and therefore, the foam generation ability and the foam stability are affected by the foaming agent component in the case of the same gas. When the foaming agent seeps in the pore medium, the dilution of underground liquid and the adsorption retention phenomenon with the rock are caused, so that the effective concentration of the foaming agent is influenced to different degrees. Therefore, in the test example, the core displacement test evaluation is performed on the foam performance of the foam system during seepage in the pore medium, so as to determine the plugging rate of the sand-filled pipe of the foam system.
In the core displacement test, the pressure value can be directly tested, so the blocking strength of the foam in the core is generally characterized by a resistance factor Z, namely:
in the formula: z-the drag factor;
ΔPbrinepressure difference between two ends of the rock core during water injection, namely MPa;
ΔPfoamand pressure difference at two ends of the rock core is MPa when foam is injected.
When the foam is exposed to air, the generation and coalescence of the foam are hardly limited by the environmental space, and when the foam is generated in the porous medium of the reservoir, the pore throat of the reservoir influences the existing form of the foam, such as the size, dispersion, coalescence and the like of the foam. The permeability is one of characteristic parameters for characterizing the pore structure and has a main influence on the blocking capacity of the foam.
Specifically, the thin oil foaming agent XHY-6 prepared in example 1 and the foaming agent of comparative example XHY-4 were formulated with formation water into foaming agent solutions having concentrations of 0.05%, 0.075%, 0.1%, 0.125%, and 0.15%, respectively, and the plugging force of each foaming agent solution in the pore medium under the conditions of reservoir permeability was measured at 84.2 ℃ and 25 MPa. In the test, a sand filling pipe with the model of phi 38mm multiplied by 1000mm is used, 100-sand 200-mesh quartz sand is selected, the gas-liquid ratio is 1:1, and the measurement result is shown in figure 2.
FIG. 2 is a graph comparing the plugging force curves of the thin oil frother of the present invention and the comparative thin oil frother at different concentrations. As can be seen from FIG. 2, the thin oil foaming agent prepared by the present invention has a significantly higher plugging capability than the comparative foaming agent.
3. System compatibility test
By adopting a spectrophotometric method, when the pH value of the amphoteric surfactant is less than or equal to 6, the amphoteric surfactant is in a cationic type and can be quantitatively complexed with an anionic acid orange II dye [ p- (beta-naphthol azo) benzenesulfonic acid ], then an organic solvent is used for extraction, and an organic phase is detected to obtain the concentration of the amphoteric surfactant, namely the concentration of the foaming agent.
0.5 percent of crude oil (the volume concentration of the crude oil after the crude oil is mixed with formation water is 0.5 percent, and the density of the crude oil is 0.769g/cm3Viscosity of 0.7 mPas) the dilute oil blowing agent XHY-6 obtained in example 1 and the blowing agent XHY-4 of the comparative example were prepared to a concentration of 0.025% respectively,0.05%, 0.075% and 0.1% foaming agent solutions, while the dilute oil foaming agent XHY-6 obtained in example 1 was formulated with clear water to give nominal foaming agent solutions with concentrations of 0.025%, 0.05%, 0.075% and 0.1%, respectively. The amphoteric surfactant concentration in the frother solution was determined using the method described above. The results are shown in FIG. 3.
FIG. 3 is a graph comparing the amphoteric surfactant concentration curves at different concentrations for the thin oil frother of the present invention and the comparative thin oil frother, with the dashed line being the calibration line for the calibration frother solution.
In fig. 3, the calibration line indicates:
after a calibrated foaming agent solution with the concentration of 0.025 percent is mixed with crude oil for layering, the foaming agent content in the water solution is 250mg/L, and the foaming agent molecular content in the oil phase is 0 mg/L;
mixing and layering a calibrated foaming agent solution with the concentration of 00.05% with crude oil, wherein the content of a foaming agent in an aqueous solution is 500mg/L, and the molecular content of the foaming agent in an oil phase is 0 mg/L;
after a calibrated foaming agent solution with the concentration of 0.075 percent is mixed with crude oil for layering, the foaming agent content in a water solution is 750mg/L, and the foaming agent molecular content in an oil phase is 0 mg/L;
after the calibrated foaming agent solution with the concentration of 0.1 percent is mixed with the crude oil for layering, the foaming agent content in the water solution is 1000mg/L, and the foaming agent molecular content in the oil phase is 0 mg/L.
In FIG. 3, the curve for the thin oil blowing agent XHY-6 indicates:
mixing an XHY-6 foaming agent solution with the concentration of 0.025 percent with crude oil for layering, wherein the content of a foaming agent in an aqueous solution is 245mg/L, and the molecular content of the foaming agent in an oil phase is 5 mg/L;
mixing an XHY-6 foaming agent solution with the concentration of 0.05 percent with the crude oil for layering, wherein the foaming agent content in the water solution is 485mg/L, and the foaming agent molecular content in the oil phase is 15 mg/L;
mixing 0.075% XHY-6 foaming agent solution with crude oil for layering, wherein the foaming agent content in the water solution is 735mg/L, and the foaming agent molecular content in the oil phase is 15 mg/L;
after 0.1 percent XHY-6 foaming agent solution is mixed with crude oil for layering, the foaming agent content in the water solution is 980mg/L, and the foaming agent molecular content in the oil phase is 20 mg/L.
In FIG. 3, the curve for the comparative example blowing agent XHY-4 represents:
mixing 0.025% XHY-4 foaming agent solution with crude oil for layering, wherein the foaming agent content in the water solution is 125mg/L, and the foaming agent molecular content in the oil phase is 125 mg/L;
mixing an XHY-4 foaming agent solution with the concentration of 0.05 percent with the crude oil for layering, wherein the foaming agent content in the water solution is 310mg/L, and the foaming agent molecular content in the oil phase is 190 mg/L;
after the foaming agent solution with the concentration of 0.075 percent is mixed with the crude oil for layering, the content of the foaming agent in the water solution is 230mg/L, and the molecular content of the foaming agent in the oil phase is 520 mg/L;
after 0.1 percent XHY-4 foaming agent solution and crude oil are mixed and layered, the foaming agent content in the water solution is 270mg/L, and the foaming agent molecular content in the oil phase is 730 mg/L.
When the foaming agent solution is mixed with the oil phase, a part of foaming agent molecules can be dissolved in crude oil, and the foaming effect of the foaming agent is poorer as more foaming agents are dissolved in the crude oil, so that the foaming agent is developed by ensuring that the foaming agent molecules in the oil phase are as less as possible and the foaming agent molecules in the aqueous solution are as more as possible, so that the foaming effect can be ensured.
Therefore, as can be seen from fig. 3: the thin oil blowing agent of example 1 has superior foaming properties compared to the thin oil blowing agent of the comparative example.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The thin oil foaming agent is characterized by comprising the following components in percentage by mass: 21.0-25.5% of zwitterionic surfactant, 1.5-4.5% of stabilizing synergist, 0.6-4.5% of surfactant and the balance of water;
the zwitterionic surfactant is fatty acid amide propyl dimethyl betaine shown in formula 1, wherein in the formula 1, R is C8-C14Alkyl groups of (a);
2. the thin oil frother of claim 1, wherein the stabilizer synergist is an alkanolamide of formula 2, wherein R is C in formula 28-C18Alkyl groups of (a);
3. the thin oil frother of claim 1, wherein the surfactant is selected from the group consisting of perfluoroalkylsulfonyl chloride and NH2NH(CH2)3N+(CH3)2CH2COO-Refluxing for 5-8 h.
4. The thin oil frother of claim 3, wherein the perfluoroalkylsulfonyl chloride is reacted with NH2NH(CH2)3N+(CH3)2CH2COO-Is 652: 161.
5. The thin oil frother of any of claims 1 to 4, wherein the surfactant is C11F23SO2NH(CH2)3N+(CH3)2CH2COO-。
6. The thin oil frother of claim 1, wherein the coconut oil acid is reacted with NH2NH(CH2)3N+(CH3)2CH2COO-Mixing, heating to 60-80 ℃, and reacting for 4-6 h to obtain the zwitterionic surfactant.
7. The thin oil frother of claim 6, wherein the coconut oil acid is reacted with NH2NH(CH2)3N+(CH3)2CH2COO-In a molar ratio of 1: 1.
8. the thin oil foaming agent as claimed in any one of claims 1 to 7, wherein the thin oil foaming agent comprises the following components in percentage by mass: 23.4 percent of zwitterionic surfactant, 3.6 percent of stabilizing synergist, 3.0 percent of surfactant and the balance of water.
9. A method for preparing the thin oil foaming agent as claimed in any one of claims 1 to 8, wherein the thin oil foaming agent is obtained by uniformly mixing a zwitterionic surfactant, a stabilizing synergist, a surfactant and water.
10. Use of the thin oil foaming agent of any one of claims 1 to 8 as a foam oil displacement agent in thin oil foam production.
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| CN116103021A (en) * | 2021-11-10 | 2023-05-12 | 中石化石油工程技术服务有限公司 | Foaming agent for oil-based drilling fluid and preparation method and application thereof |
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