CN115960592A - Foaming agent composition for thickened oil thermal recovery plugging adjustment and preparation method and application thereof - Google Patents
Foaming agent composition for thickened oil thermal recovery plugging adjustment and preparation method and application thereof Download PDFInfo
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- CN115960592A CN115960592A CN202111172420.4A CN202111172420A CN115960592A CN 115960592 A CN115960592 A CN 115960592A CN 202111172420 A CN202111172420 A CN 202111172420A CN 115960592 A CN115960592 A CN 115960592A
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- 239000000203 mixture Substances 0.000 title claims abstract description 76
- 239000004088 foaming agent Substances 0.000 title claims abstract description 74
- 238000011084 recovery Methods 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003921 oil Substances 0.000 claims abstract description 62
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 43
- 229920000570 polyether Polymers 0.000 claims abstract description 43
- 239000004094 surface-active agent Substances 0.000 claims abstract description 34
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 32
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical class [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000295 fuel oil Substances 0.000 claims abstract description 26
- 229960003237 betaine Drugs 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002888 zwitterionic surfactant Substances 0.000 claims abstract description 9
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims abstract 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 48
- 229920001223 polyethylene glycol Polymers 0.000 claims description 48
- 125000000217 alkyl group Chemical group 0.000 claims description 41
- 239000006260 foam Substances 0.000 claims description 39
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- SWGZAKPJNWCPRY-UHFFFAOYSA-N methyl-bis(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](C)O[Si](C)(C)C SWGZAKPJNWCPRY-UHFFFAOYSA-N 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 23
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 20
- 150000002148 esters Chemical class 0.000 claims description 19
- -1 ammonium ions Chemical class 0.000 claims description 18
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 16
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- 150000007942 carboxylates Chemical class 0.000 claims description 7
- 125000005189 alkyl hydroxy group Chemical group 0.000 claims description 6
- 229940117986 sulfobetaine Drugs 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940073507 cocamidopropyl betaine Drugs 0.000 claims description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000002923 metal particle Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920001522 polyglycol ester Polymers 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 11
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000005465 channeling Effects 0.000 description 10
- 238000005187 foaming Methods 0.000 description 10
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 230000033558 biomineral tissue development Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- 239000011575 calcium Substances 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 230000000638 stimulation Effects 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000009671 shengli Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- 238000006073 displacement reaction Methods 0.000 description 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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- 229910001415 sodium ion Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention relates to a foaming agent composition for heavy oil thermal recovery plugging regulation and a preparation method and application thereof. The foaming agent composition for thickened oil thermal recovery plugging regulation consists of the following components in parts by weight: 0.2-10 parts of polyether anionic surfactant; 0.2-10 parts of polyether modified trisiloxane gemini surfactant; 0.1-5 parts of betaine type zwitterionic surfactant; 75 to 99.5 portions of water. The preparation method of the foaming agent composition for thickened oil thermal recovery plugging adjustment comprises the following steps: (1) Synthesizing polyether modified trisiloxane type bi-surfactant; (2) And uniformly mixing the polyether anionic surfactant, the polyether modified trisiloxane gemini surfactant, the betaine type zwitter-ion surfactant and water according to the formula ratio to obtain the foaming agent composition for heavy oil thermal recovery plugging regulation. The invention also discloses application of the foaming agent composition in the thermal recovery plugging regulation process of the heavy oil reservoir.
Description
Technical Field
The invention belongs to the field of thickened oil recovery, and particularly relates to a foaming agent composition for thickened oil thermal recovery plugging regulation, and a preparation method and application thereof.
Background
China has abundant resources and reserves of thick oil, is influenced by high viscosity, high condensation point and the like of the thick oil, and mainly adopts thermal recovery. With the development progress, most of the heavy oil reservoirs in the oil fields of victory, xinjiang, liaohe and the like enter a high-round huff and puff stage. After multiple rounds of huffing and puff, the steam is seriously overlayed and is influenced by heterogeneous oil reservoirs and the like, and the steam is easy to migrate along a high-permeability strip to cause low oil-steam ratio and even form steam channeling. Statistical data show that the oil field is victory for more than 6 periods of approximately 30% oil well throughput, the oil-gas ratio of the period is lower than 0.3, and the economic benefit is poor. And in the current stage, the average recovery ratio of steam huff and puff is less than 20%, a large amount of residual oil is not extracted, auxiliary measures are urgently needed to be found to adjust the steam absorption profile, improve the steam sweep, improve the reservoir utilization degree and further improve the development effect.
The blockage adjusting technology is one of the main technologies of adjusting a steam suction section, blocking a steam channeling channel and improving the multi-round throughput effect. The foam system can enter the deep part of the stratum due to good injectability, and selective plugging is realized, so that the plugging is large and small, the water plugging and oil plugging are not performed, and the engineering risk is small, so that the foam system becomes the dominant process of thermal recovery plugging regulation.
In the steam huff and puff process, the development characteristics of the temperature field show that the temperature of the near wellbore region is 300-150 ℃, the temperature of the deep part of the oil reservoir is gradually reduced to 80-150 ℃, and a great temperature difference exists between the near wellbore region and the deep part of the oil reservoir. The handling process experiences such a large temperature difference, and a wide temperature application range is provided for the foam blockage adjusting method. Besides the temperature, in the later period of heavy oil exploitation, the reservoir heterogeneity is more and more serious, the requirements on the plugging strength and migration strength of foam are higher and higher, the regeneration and stability of the foam in a porous medium greatly influence the plugging validity period, and further influence the multi-round application effect.
The prior foaming agent for heavy oil thermal recovery channeling sealing in China cannot be suitable for a wide temperature area from the deep part of an oil reservoir to a near-wellbore area due to the deterioration of the stability of the structure and the performance at high temperature. And as the heavy oil reservoir enters the later stage of steam injection and steam huff and puff for multiple times, the heterogeneity of the stratum is intensified, the plugging strength of the traditional foaming agent is relatively weak, the back wave and the efficiency of the steam huff and puff for multiple times are reduced, the first cycle generally has obvious plugging adjusting effect in field implementation, and when the second cycle and the third cycle are repeatedly implemented subsequently, the obvious effect is not achieved, and the subsequent plugging steam channeling channel is weak.
Chinese patent application CN201210392988.1 discloses a foam channeling sealing composition and a preparation method and application thereof, the foam channeling sealing composition mainly solves the gas channeling problem in the gas displacement process, but the foam channeling sealing composition provided by the invention cannot resist the high temperature of 200-300 ℃, and cannot be applied to the multiple-round heavy oil reservoir channeling sealing process.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects of the prior art, the invention discloses a foaming agent composition for thickened oil thermal recovery plugging regulation, a preparation method and application thereof, and the foaming agent composition can be used for plugging a steam channeling channel and improving steam sweep in the thickened oil thermal recovery process. The foaming agent composition can quickly form small and uniform foam with a foam resistance factor of 80-600 at the temperature of 80-300 ℃; the system can resist the temperature of 80-300 ℃, and the foaming and foam stabilizing capability of the foaming agent is basically unchanged after the system is aged for 10 days at high temperature; the system is applicable to the mineralization degree of more than 50000mg/L, wherein, the calcium and magnesium ions are more than 3000mg/L; when the system is applied in the process of heavy oil thermal recovery, the system can be injected in a preposed manner and can be injected along with steam.
The technical scheme is as follows: the foaming agent composition for thickened oil thermal recovery plugging regulation consists of the following components in parts by weight:
0.2-10 parts of polyether anionic surfactant;
0.2-10 parts of polyether modified trisiloxane gemini surfactant;
0.1-5 parts of betaine type zwitterionic surfactant;
75 to 99.5 portions of water.
Further, the polyether anionic surfactant is one of fatty alcohol-polyoxyethylene ether sulfonate and fatty alcohol-polyoxyethylene ether carboxylate.
Furthermore, the structure of the fatty alcohol polyoxyethylene ether sulfonate is shown as the formula (1):
wherein M is 1 Is at least one of alkali metal ion, alkaline earth metal ion or ammonium ion, preferably K + 、 Na + 、NH 4 + At least one of;
R 1 is C8-C24 aliphatic group or long-chain aryl group, preferably C12-C18 aliphatic group or long-chain aryl group;
R 2 is one of methyl, ethyl, propyl and isopropyl, preferably one of ethyl, propyl and isopropyl;
m is any integer of 3 to 20, preferably any integer of 3 to 10.
Furthermore, the structure of the fatty alcohol polyoxyethylene ether carboxylate is shown as the formula (2):
wherein M is 2 At least one of alkali metal particles, alkaline earth metal ions and ammonium ions, preferably K + 、 Na + 、NH 4 + At least one of;
R 3 is a C8-C24 long-chain alkyl group, preferably a C12-C18 long-chain alkyl group;
R 4 is C1-C5 alkyl, preferably C2-C3 alkyl;
n is any integer of 3 to 20, preferably any integer of 3 to 10.
Further, the structure of the polyether modified trisiloxane type bi-surfactant is shown as a formula (3):
wherein p is 0 or 1, preferably p =0;
q is any integer or decimal of 8 to 30, preferably q is any integer or decimal of 10 to 18, and more preferably q is any integer or decimal of 12 to 16.
Further, the betaine type zwitterionic surfactant is selected from one of cocamidopropyl betaine, alkyl sulfobetaine and alkyl hydroxy sulfopropyl betaine.
Further, the structure of the alkyl betaine is shown as the formula (4):
wherein R is 5 Is a C12-C24 long-chain alkyl group, preferably a C12-C18 long-chain alkyl group.
Further, the alkyl sulfobetaine has a structure represented by formula (5):
wherein R is 6 Is a C12-C24 long-chain alkyl group, preferably a C12-C18 long-chain alkyl group;
R 7 is C2-C3 alkyl.
More particularly, the structure of the alkyl hydroxy sulfopropyl betaine is shown as the formula (6):
wherein R is 8 Is a C12-C24 long-chain alkyl group, preferably a C12-C18 long-chain alkyl group.
The molar ratio of the polyether anionic surfactant to the polyether modified trisiloxane type bi-surfactant is (0.5-20): 1, preferably (0.5-5): 1.
The molar ratio of the polyether anionic surfactant to the betaine type zwitterionic surfactant is (0.2-10): 1, preferably (1 to 5) is 1.
The preparation method of the foaming agent composition for thick oil thermal recovery plugging regulation comprises the following steps:
(1) Synthesis of polyether modified trisiloxane gemini surfactant
(11) Under the protection of nitrogen, dissolving polyethylene glycol in dichloromethane, stirring for 0.5-3 h at 40-70 ℃ to obtain a mixed solution, then respectively adding p-toluenesulfonic acid, dicarboxylic acid or maleic anhydride into the mixed solution, heating to 120-140 ℃ to react for 2-6 h to obtain a reaction solution, then separating the reaction solution by using ethyl acetate, washing and drying to obtain an intermediate diacid polyethylene glycol ester; wherein
The mass ratio of polyethylene glycol to dichloromethane is 1: (5-20);
(12) Under the protection of nitrogen, mixing the intermediate diacid polyethylene glycol ester with a catalyst and isopropanol, activating at 40-80 ℃ for 10-60 min, then heating to 90-120 ℃, continuously dropwise adding 1,1,1,3,5,5,5-heptamethyltrisiloxane, reacting for 2-24 h, adsorbing and removing the catalyst by using activated carbon, and removing byproducts by reduced pressure distillation to obtain the polyether modified trisiloxane gemini surfactant, wherein the mass ratio of 1,1,1,3,5,5,5-heptamethyltrisiloxane to isopropanol is 1: (5-20);
(2) Preparation of foaming agent composition for thickened oil thermal recovery plugging adjustment
And uniformly mixing the polyether anionic surfactant, the polyether modified trisiloxane gemini surfactant, the betaine type zwitter-ion surfactant and water according to the formula ratio to obtain the foaming agent composition for heavy oil thermal recovery plugging regulation.
Further, the dicarboxylic acid in the step (11) is one of maleic acid and 2-hexene-1,6-diacid; the number average molecular weight of the polyethylene glycol in the step (11) is 400-1500.
Further, the catalyst in the step (12) is one of chloroplatinic acid, platinum siloxane complex, carbonyl iron, palladium/alumina and palladium/calcium carbonate.
Furthermore, the molar ratio of the dicarboxylic acid or maleic anhydride to the polyethylene glycol is (1.1-1.4): 2, preferably (1.2-1.3): 2.
Further, the mass ratio of the p-toluenesulfonic acid to the polyethylene glycol in the step (11) is (1.5-2): 100, preferably 1.8.
Furthermore, the molar ratio of the intermediate diacid polyethylene glycol ester to 1,1,1,3,5,5,5-heptamethyltrisiloxane is (1.1-1.4), preferably (1.2-1.3) to 1.
Further, the mass ratio of the catalyst to 1,1,1,3,5,5,5-heptamethyltrisiloxane is (0.12-0.2): 100, preferably (0.15 to 0.18) 100.
Further, the structure of the dicarboxylic acid in step (11) is shown as formula (7):
wherein p is 0 or 1.
Further, the structure of the intermediate diacid polyethylene glycol ester is shown as the formula (8):
wherein p is 0 or 1,q is any integer or decimal number from 8 to 30.
Further, the 1,1,1,3,5,5,5-heptamethyltrisiloxane has the structure shown in the formula (9):
the foaming agent composition is applied to the thermal recovery plugging regulation process of the heavy oil reservoir.
The method comprises the following specific steps: and injecting the foaming agent composition and gas into the stratum from the shaft under the proper injection timing, blocking a hypertonic channel and improving steam sweep.
The injection time is one of pre-injection or steam-accompanied injection.
The gas is nitrogen, air, CO 2 And flue gas.
The reaction equation for preparing the polyether modified trisiloxane gemini surfactant is as follows:
the polyether anionic surfactant in the foaming agent composition for heavy oil thermal recovery plugging has the advantages of good water solubility, strong surface activity, good hydrothermal stability, good compatibility and the like, and can quickly foam in a porous medium;
the polyether modified trisiloxane gemini surfactant is a synthetic organic silicon gemini surfactant, can greatly reduce CMC of the foaming agent, simultaneously improves the separation pressure of a foam liquid film, further increases the foam stability and the blocking strength, and is a foam stabilizer capable of resisting high temperature and high salt;
the betaine type zwitterionic surfactant can increase the charge density of a gas-liquid interface, and has good foaming performance, foam stabilizing performance and compatibility. The synergistic effect of the three components enables the foam system to quickly foam and block at high strength within the range of 80-300 ℃ by regulating and controlling the electrostatic attraction in the interface layer, the electrostatic repulsion between layers and the hydration, greatly improves the foam performance and the temperature resistance of the foam system, and has better popularization prospect in heavy oil reservoirs which are huffed and puff for multiple times.
Has the advantages that: compared with the prior art, the invention has the following beneficial effects:
(1) The foaming agent composition has strong foaming capacity and high plugging strength, can form small-size and uniform foam at the temperature of 80-300 ℃, and has a resistance factor of 80-600; the system has a suitable degree of mineralization of more than 50000mg/L, wherein calcium and magnesium ions are 0-3000 mg/L;
(2) The foaming agent composition can resist the temperature of 80-300 ℃, and the foaming and foam stabilizing capability of the foaming agent is basically unchanged after the foaming agent composition is aged for more than 10 days at high temperature; the pre-injection can be carried out in the heavy oil thermal recovery, and the injection can be carried out along with the steam;
(3) The foam agent composition has small adsorption loss in a reservoir and can be transported in a deep part.
Drawings
FIG. 1 is a resistance factor curve of a foaming agent composition G2 for thick oil thermal recovery plugging adjustment at 80 ℃ after aging at 300 ℃.
FIG. 2 is a production dynamic curve of a single well F in a certain area of a victory oil field before and after using the foaming agent composition for heavy oil thermal recovery plugging.
The specific implementation mode is as follows:
the present invention is described in further detail below with reference to specific examples and with reference to the data. It will be understood that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
Example 1
The foaming agent composition G1 for thickened oil thermal recovery plugging regulation consists of the following substances in parts by mass:
further, the fatty alcohol-polyoxyethylene ether sulfonate has the following molecular formula:
wherein M is 1 Is sodium ion; r is 1 Is a C12 fatty group; r 2 is-CH 2 CH 2 -, m is 15.5.
The molecular formula of the polyether modified trisiloxane gemini surfactant S1 is as follows:
wherein p =0; q is 9.5.
The preparation method of the foaming agent composition G1 for thickened oil thermal recovery plugging adjustment comprises the following steps:
(1) Synthesis of polyether modified trisiloxane gemini surfactant S1
(11) Under the protection of nitrogen, dissolving polyethylene glycol in dichloromethane, stirring for 0.5h at 70 ℃ to obtain a mixed solution, then respectively adding p-toluenesulfonic acid and maleic anhydride into the mixed solution, heating to 120 ℃ to react for 6h to obtain a reaction solution, then separating the reaction solution by using ethyl acetate, washing and drying to obtain an intermediate diacid polyethylene glycol ester; wherein
The mass ratio of polyethylene glycol to dichloromethane is 1:20;
(12) Under the protection of nitrogen, mixing the intermediate diacid polyethylene glycol ester with a catalyst and isopropanol, activating at 40 ℃ for 60min, heating to 120 ℃, continuously dropwise adding 1,1,1,3,5,5,5-heptamethyltrisiloxane, reacting for 2h, adsorbing and removing the catalyst by using activated carbon, and removing by-products by reduced pressure distillation to obtain the polyether modified trisiloxane type bi-surfactant S1, wherein
1,1,1,3,5,5,5-heptamethyltrisiloxane to isopropanol in a mass ratio of 1:10;
(2) Preparation of foaming agent composition G1 for thick oil thermal recovery plugging adjustment
The fatty alcohol-polyoxyethylene ether sulfonate, the polyether-modified trisiloxane gemini surfactant S1, the cocamidopropyl betaine and water in the formula amount are uniformly mixed to obtain the foaming agent composition G1.
Further, the number average molecular weight of the polyethylene glycol in the step (11) is 400.
Further, the catalyst in the step (12) is chloroplatinic acid.
Further, the molar ratio of the maleic anhydride to the polyethylene glycol is 1.2.
Further, the mass ratio of the p-toluenesulfonic acid to the polyethylene glycol in the step (11) is 1.5:100.
further, the molar ratio of the intermediate diacid polyethylene glycol ester to 1,1,1,3,5,5,5-heptamethyltrisiloxane is 1.2.
Further, the mass ratio of the catalyst to 1,1,1,3,5,5,5-heptamethyltrisiloxane is 0.12: 100.
Further, the structure of the intermediate diacid polyethylene glycol ester is shown as the formula (8):
wherein p is 0,q is 10.
The 1,1,1,3,5,5,5-heptamethyltrisiloxane has the structure shown in formula (9):
the foaming agent composition G1 is applied to the thermal recovery plugging regulation process of the heavy oil reservoir.
Under the condition of preposed injection, the foaming agent composition G1 for heavy oil thermal recovery plugging regulation and nitrogen are injected into a stratum from a shaft, a high-permeability channel is plugged in the thermal recovery process, and steam sweep is improved.
Example 2
The foaming agent composition G2 for thickened oil thermal recovery plugging regulation consists of the following components in parts by mass:
further, the fatty alcohol-polyoxyethylene ether carboxylate has the following molecular formula:
wherein, M 2 Is potassium ion; r 3 Is C8 long chain alkyl; r 4 is-CH 2 CH 2 -, m is 10.
The molecular formula of the polyether modified trisiloxane gemini surfactant S2 is as follows:
wherein p =0; q is 17.
Further, the alkyl betaine has the following molecular formula:
wherein R5 is C12 long-chain alkyl.
The preparation method of the foaming agent composition G2 for thickened oil thermal recovery plugging adjustment comprises the following steps:
(1) Synthesis of polyether modified trisiloxane gemini surfactant S2
(11) Under the protection of nitrogen, dissolving polyethylene glycol in dichloromethane, stirring for 3 hours at 40 ℃ to obtain a mixed solution, then respectively adding p-toluenesulfonic acid and maleic anhydride into the mixed solution, heating to 140 ℃ to react for 2 hours to obtain a reaction solution, then separating the reaction solution by using ethyl acetate, washing and drying to obtain an intermediate diacid polyethylene glycol ester; wherein
The mass ratio of polyethylene glycol to dichloromethane is 1:10;
(12) Under the protection of nitrogen, mixing the intermediate diacid polyethylene glycol ester with a catalyst and isopropanol, activating at 60 ℃ for 30min, heating to 100 ℃, continuously dropwise adding 1,1,1,3,5,5,5-heptamethyltrisiloxane, reacting for 12h, adsorbing and removing the catalyst by using activated carbon, and removing by-products by reduced pressure distillation to obtain the polyether modified trisiloxane gemini surfactant, wherein the polyether modified trisiloxane gemini surfactant is prepared
1,1,1,3,5,5,5-heptamethyltrisiloxane to isopropanol in a mass ratio of 1:5;
(2) Preparation of foaming agent composition G2 for thickened oil thermal recovery plugging adjustment
The fatty alcohol-polyoxyethylene ether carboxylate, the polyether modified trisiloxane gemini surfactant S2, the alkyl betaine and water in the formula amount are uniformly mixed to obtain the foaming agent composition G2 for heavy oil thermal recovery plugging regulation.
The molar ratio of the maleic acid to the polyethylene glycol is 1.1.
The mass ratio of the p-toluenesulfonic acid to the polyethylene glycol is 1.8:100.
the molar ratio of the intermediate diacid polyethylene glycol ester to 1,1,1,3,5,5,5-heptamethyltrisiloxane is 1.4.
The mass ratio of the catalyst to 1,1,1,3,5,5,5-heptamethyltrisiloxane is 0.15:100.
the intermediate diacid polyethylene glycol ester has the following molecular formula:
wherein p =0; q is 18.
Further, the catalyst in the step (12) is platinum siloxane complex.
Further, the 1,1,1,3,5,5,5-heptamethyltrisiloxane has the structure shown in formula (9):
the foaming agent composition G2 is applied to the thermal recovery plugging regulation process of the heavy oil reservoir.
The method comprises the following specific steps: under the condition of steam accompanied injection, the foaming agent composition and air are injected into the stratum from a shaft, a high-permeability channel is blocked in the thermal recovery process, and steam sweep is improved.
Example 3
The foaming agent composition G3 for thickened oil thermal recovery plugging regulation consists of the following components in percentage by mass:
further, the fatty alcohol-polyoxyethylene ether sulfonate has the following molecular formula:
wherein M is 1 Is potassium ion; r 1 Is a C8 long chain aryl group; r 2 Is a propyl group; m is 5.
Further, the polyether modified trisiloxane gemini surfactant S3 has the following molecular formula:
wherein p =1; q is 23.
Further, the alkyl sulfobetaine has the following molecular formula:
wherein R is 6 Is C12 long chain alkyl; r is 7 Is ethyl.
The preparation method of the foaming agent composition G3 for thickened oil thermal recovery plugging regulation comprises the following steps:
(1) Synthesis of polyether modified trisiloxane gemini surfactant S3
(11) Under the protection of nitrogen, dissolving polyethylene glycol in dichloromethane, stirring for 2 hours at 60 ℃ to obtain a mixed solution, then respectively adding p-toluenesulfonic acid and dicarboxylic acid into the mixed solution, heating to 130 ℃ to react for 4 hours to obtain a reaction solution, then separating the reaction solution by using ethyl acetate, washing and drying to obtain an intermediate diacid polyethylene glycol ester; wherein
The mass ratio of polyethylene glycol to dichloromethane is 1:5;
(12) Under the protection of nitrogen, mixing the intermediate diacid polyethylene glycol ester with a catalyst and isopropanol, activating at 80 ℃ for 10min, heating to 90 ℃, continuously dropwise adding 1,1,1,3,5,5,5-heptamethyltrisiloxane, reacting for 24h, adsorbing and removing the catalyst by using activated carbon, and removing by-products by reduced pressure distillation to obtain the polyether modified trisiloxane gemini surfactant, wherein the polyether modified trisiloxane gemini surfactant is prepared
1,1,1,3,5,5,5-heptamethyltrisiloxane to isopropanol mass ratio of 1:20;
(2) Preparation of foaming agent composition G3 for thick oil thermal recovery plugging adjustment
And uniformly mixing the fatty alcohol polyoxyethylene ether sulfonate, the polyether modified trisiloxane gemini surfactant S3, the alkyl sulphobetaine and water according to the formula ratio to obtain the foaming agent composition G3.
Further, the dicarboxylic acid in step (11) is 2-hexene-1,6-diacid. In one embodiment the dicarboxylic acid in step (11) is maleic acid.
Further, the catalyst in the step (12) is palladium/alumina.
Further, the molar ratio of the dicarboxylic acid to the polyethylene glycol is 1.4.
Further, the structure of the dicarboxylic acid in step (11) is shown as formula (7):
wherein p is 0. In another embodiment, the dicarboxylic acid has the formula wherein p is 1.
The mass ratio of the p-toluenesulfonic acid to the polyethylene glycol is 2:100.
the molar ratio of the intermediate diacid polyethylene glycol ester to 1,1,1,3,5,5,5-heptamethyltrisiloxane is 1.1.
The mass ratio of the catalyst to 1,1,1,3,5,5,5-heptamethyltrisiloxane is 0.2:100.
the intermediate diacid polyethylene glycol ester has the following molecular formula:
wherein p =1; q is 22.
The foaming agent composition G3 is applied to the thermal recovery plugging regulation process of the heavy oil reservoir.
The method comprises the following specific steps: under the condition of steam accompanied injection, the foaming agent composition and the flue gas are injected into the stratum from a shaft, a high-permeability channel is blocked in the thermal recovery process, and the steam sweep is improved.
Performance evaluation of foaming agent compositions G1, G2 and G3 for thickened oil thermal recovery plugging adjustment
Test example 1
The experimental water is produced water in a certain block F of the Shengli oil field, the total mineralization is 23561mg/L, wherein, ca 2+ Content 2479Mg/L, mg 2+ The content is 201mg/L.
The foaming agent compositions G1, G2 and G3 for thick oil thermal recovery plugging control prepared in examples 1 to 3 and the commercial foaming agents RYM-1 and RYM-2 were aged at a high temperature of 300 ℃ for 1 day, and the foaming volume, the foam half-life period and the resistance factor at 80 ℃ and 200 ℃ of the treated 5 foaming agents were evaluated. Foaming volume, foam half-life period and resistance factor test methods refer to Q/SH10202052-2010 foaming agent for conventional foam flooding, and the results are shown in Table 1.
TABLE 1 Performance test results for foam compositions G1, G2, G3 and commercial foams RYM-1 and RYM-2 for heavy oil thermal recovery profile control
Wherein the change curve of the resistance factor of the foaming agent composition G2 for thick oil thermal recovery plugging adjustment at 80 ℃ after aging at 300 ℃ is shown in figure 1.
According to the evaluation results, the foaming agent compositions G1, G2 and G3 for thick oil thermal recovery plugging have strong foaming and stability performance at the temperature of 80 ℃ and 200 ℃ after aging, and have good high-temperature stability. The foaming volume of the foaming agent compositions G1, G2 and G3 for thick oil thermal recovery plugging regulation at the temperature of 80 ℃ is more than 276mL, the foam half-life period reaches more than 360min, and the foaming volume of the commercially available foaming agents RYM-1 and RYM-2 is less than 270mL, the foam half-life period is less than 230min, and the foaming volume is obviously lower than that of the foaming agent compositions; the resistance factors of the foaming agent compositions G1, G2 and G3 of the invention reach more than 460, the highest resistance factor of G2 reaches 550, while the resistance factors of the commercial foaming agents RYM-1 and RYM-2 are 388 and 296 respectively, which are obviously lower than that of the invention; the similar change rule is realized under the condition of 200 ℃. The foaming agent compositions G1, G2 and G3 all meet the relevant requirements of oil fields, have excellent comprehensive performance compared with a commercial foaming agent, and can meet the requirements of multiple times of heavy oil reservoir development.
Test example 2: in situ application testing
The experiment aims at a single well F in a certain block of the Shengli oil field, the oil reservoir temperature is 65 ℃, the crude oil viscosity is 13665mPa.s, the emulsified water content is 24.3 percent, the total mineralization degree of formation water is 23561mg/L, wherein Ca 2+ The content of 2479Mg/L, mg 2+ The content is 201mg/L. The reservoir is fine sandstone and siltstone, and the oil reservoir permeability is 2620md.
In the early stage, 9 rounds of steam stimulation are carried out, in order to improve the development effect, in the month 5 in 2020, a foam plugging regulating and steam stimulation measure test is carried out on the foam plugging regulating and steam stimulation measure composition G2 for thick oil thermal recovery prepared in the example 2, wherein the daily fluid before the measure is 52.6t/d, the daily oil is 1.9t/d, the water content is 96.4 percent, the daily fluid after the measure is 35.9t/d, the daily oil is 13.7t/d, the water content is 61.8 percent, the daily fluid of the current single well is 36.8t/d, the daily oil is 5.2t/d, and the water content is 85.9 percent. The production dynamics are shown in FIG. 2.
Examples 4 to 10
Is substantially the same as example 1 except that: m in fatty alcohol-polyoxyethylene ether sulfonate 1 、R 1 、 R 2 M is different:
examples 11 to 14
Substantially the same as example 1, except that: the number average molecular weight of polyethylene glycol and the type of catalyst are different:
| number average molecular weight of polyethylene glycol | Kind of catalyst | |
| Example 11 | 500 | Platinum siloxane complex |
| Example 12 | 1200 | Carbonyl iron |
| Example 13 | 1000 | Palladium/alumina |
| Example 14 | 800 | Palladium/calcium carbonate |
Examples 15 to 18
Substantially the same as example 1, except that: the molar ratio of maleic anhydride to polyethylene glycol and the mass ratio of p-toluenesulfonic acid to polyethylene glycol are different:
examples 19 to 22
Substantially the same as example 1, except that: the molar ratio of the intermediate diacid polyethylene glycol ester to 1,1,1,3,5,5,5-heptamethyltrisiloxane and the mass ratio of the catalyst to 1,1,1,3,5,5,5-heptamethyltrisiloxane are different:
examples 23 to 26
Substantially the same as example 2, except that: m in molecular formula of fatty alcohol-polyoxyethylene ether carboxylate 2 、R 3 、；R 4 M is different;
| M 2 | R 3 | R 4 | m | |
| example 23 | K + | C24 Long chain alkyl | -CH 2 CH 2 CH 2 - | 3 |
| Example 24 | Na + | C12 Long chain alkyl | -CH 2 CH 2 CH 2 CH 2 - | 20 |
| Example 25 | Na + | C18 Long chain alkyl | -CH 2 - | 12 |
| Example 26 | NH 4 + | C16 Long chain alkyl | -CH 2 CH 2 CH 2 CH 2 CH 2 - | 8 |
Examples 27 to 29
Substantially the same as example 2, except that: r in alkyl betaines 5 Different;
| R 5 | |
| example 27 | C18 Long chain alkyl |
| Example 28 | C24 Long chain alkyl |
| Example 29 | C14 Long chain alkyl |
Examples 30 to 33
Substantially the same as example 3, except that: r in the formula of alkyl sulphobetaines 6 And R 7 The difference is as follows:
| R 6 | R 7 | |
| example 30 | C24 Long chain alkyl | Ethyl radical |
| Example 31 | C18 Long chain alkyl | N-propyl radical |
| Example 32 | C14 Long chain alkyl | Isopropyl group |
| Example 33 | C16 Long chain alkyl | N-propyl radical |
Examples 34 to 37
Substantially the same as example 3, except that: replacing alkyl sulfobetaine with alkyl hydroxy sulfopropyl betaine, wherein the structure of the alkyl hydroxy sulfopropyl betaine is shown as the following formula:
wherein, the substituent R in the structure of the alkyl hydroxy sulfopropyl betaine in the examples 8 The situation is as follows:
| R 8 | |
| example 34 | C14 Long chain alkyl |
| Example 35 | C18 Long chain alkyl |
| Example 36 | C24 Long chain alkyl |
| Example 37 | C12 Long chain alkyl |
Examples 38 to 40
Substantially the same as example 3, except that: the molar ratio of dicarboxylic acid to polyethylene glycol was different:
| molar ratio of dicarboxylic acid to polyethylene glycol | |
| Example 38 | 1.1:2 |
| Example 39 | 1.2:2 |
| Example 40 | 1.6:2 |
The embodiments of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (20)
1. The foaming agent composition for thickened oil thermal recovery plugging regulation is characterized by comprising the following components in parts by weight:
0.2-10 parts of polyether anionic surfactant;
0.2-10 parts of polyether modified trisiloxane type gemini surfactant;
0.1-5 parts of betaine type zwitterionic surfactant;
75 to 99.5 portions of water.
2. The foaming agent composition for thick oil thermal recovery plugging regulation of claim 1, wherein the polyether anionic surfactant is one of fatty alcohol-polyoxyethylene ether sulfonate and fatty alcohol-polyoxyethylene ether carboxylate.
3. The foaming agent composition for thickened oil thermal recovery plugging control as claimed in claim 2, wherein the fatty alcohol-polyoxyethylene ether sulfonate has a structure shown in formula (1):
wherein M is 1 Is at least one of alkali metal ion, alkaline earth metal ion or ammonium ion, preferably K + 、Na + 、NH 4 + At least one of;
R 1 is C8-C24 aliphatic group or long-chain aryl group, preferably C12-C18 aliphatic group or long-chain aryl group;
R 2 is one of methyl, ethyl, propyl and isopropyl, preferably one of ethyl, propyl and isopropyl;
m is any integer of 3 to 20, preferably any integer of 3 to 10.
4. The foaming agent composition for thick oil thermal recovery plugging regulation according to claim 2, wherein the structure of the fatty alcohol-polyoxyethylene ether carboxylate is shown as the formula (2):
wherein, M 2 Is at least one of alkali metal particles, alkaline earth metal ions and ammonium ions, preferably K + 、Na + 、NH 4 + At least one of (a);
R 3 is a C8-C24 long-chain alkyl group, preferably a C12-C18 long-chain alkyl group;
R 4 is C1-C5 alkyl, preferably C2-C3 alkyl;
n is any integer of 3 to 20, preferably any integer of 3 to 10.
5. The foaming agent composition for heavy oil thermal recovery plugging control of claim 1, wherein the polyether modified trisiloxane-based gemini surfactant has a structure shown in formula (3):
wherein p is 0 or 1, preferably p =0;
q is any integer or decimal of 8 to 30, preferably q is any integer or decimal of 10 to 18, and more preferably q is any integer or decimal of 12 to 16.
6. The foam composition for thickened oil thermal recovery plugging according to claim 1, wherein the betaine type zwitterionic surfactant is one selected from the group consisting of cocamidopropyl betaine, alkyl sulfobetaine, and alkyl hydroxysulfopropyl betaine.
7. The foaming agent composition for thickened oil thermal recovery plugging control of claim 6, wherein the alkyl betaine has a structure represented by formula (4):
wherein R is 5 Is a C12-C24 long-chain alkyl group, preferably a C12-C18 long-chain alkyl group.
8. The foaming agent composition for thickened oil thermal recovery plugging control of claim 6, wherein the alkyl sulfobetaine has a structure represented by formula (5):
wherein R is 6 Is a C12-C24 long-chain alkyl group, preferably a C12-C18 long-chain alkyl group;
R 7 is C2-C3 alkyl.
9. The foaming agent composition for thick oil thermal recovery plugging regulation according to claim 6, wherein the alkyl hydroxy sulfopropyl betaine has a structure shown in formula (6):
wherein R is 8 Is a C12-C24 long-chain alkyl group, preferably a C12-C18 long-chain alkyl group.
10. The foam agent composition for heavy oil thermal recovery plugging control according to claim 1, wherein the molar ratio of the polyether anionic surfactant to the polyether modified trisiloxane type gemini surfactant is (0.5-20): 1, preferably (0.5-5): 1.
11. The foam agent composition for thick oil thermal recovery plugging regulation according to claim 1, wherein the molar ratio of the polyether anionic surfactant to the betaine zwitterionic surfactant is (0.2-10): 1, preferably (1 to 5) is 1.
12. The preparation method of the foaming agent composition for thickened oil thermal recovery plugging regulation is characterized by comprising the following steps of:
(1) Synthesis of polyether modified trisiloxane gemini surfactant
(11) Under the protection of nitrogen, dissolving polyethylene glycol in dichloromethane, stirring for 0.5-3 h at 40-70 ℃ to obtain a mixed solution, then respectively adding p-toluenesulfonic acid, dicarboxylic acid or maleic anhydride into the mixed solution, heating to 120-140 ℃ to react for 2-6 h to obtain a reaction solution, separating the reaction solution by using ethyl acetate, washing, and drying to obtain an intermediate diacid polyethylene glycol ester; wherein the mass ratio of the polyethylene glycol to the dichloromethane is 1: (5-20);
(12) Under the protection of nitrogen, mixing the intermediate diacid polyethylene glycol ester with a catalyst and isopropanol, activating at 40-80 ℃ for 10-60 min, then heating to 90-120 ℃, continuously dropwise adding 1,1,1,3,5,5,5-heptamethyltrisiloxane, reacting for 2-24 h, adsorbing and removing the catalyst by using activated carbon, and removing by-products by reduced pressure distillation to obtain the polyether modified trisiloxane type gemini surfactant, wherein
1,1,1,3,5,5,5-heptamethyltrisiloxane to isopropanol in a mass ratio of 1: (5-20);
(2) Preparation of foaming agent composition for thickened oil thermal recovery plugging adjustment
The foam agent composition for heavy oil thermal recovery plugging is obtained by uniformly mixing the polyether anionic surfactant, the polyether modified trisiloxane gemini surfactant, the betaine zwitterionic surfactant and water according to the formula ratio.
13. The method of claim 12, wherein the dicarboxylic acid in step (11) is one of maleic acid, 2-hexene-1,6-diacid; the number average molecular weight of the polyethylene glycol in the step (11) is 400-1500.
14. The method for preparing the foam composition for thick oil thermal recovery plugging according to claim 12, wherein the catalyst in the step (12) is one of chloroplatinic acid, platinum siloxane complex, carbonyl iron, palladium/alumina and palladium/calcium carbonate.
15. The method for preparing the foam composition for thick oil thermal recovery plugging according to claim 12, wherein the molar ratio of the dicarboxylic acid or maleic anhydride to the polyethylene glycol is (1.1-1.4): 2, preferably (1.2-1.3): 2;
in the step (11), the mass ratio of the p-toluenesulfonic acid to the polyethylene glycol is (1.5-2): 100, preferably 1.8.
16. The preparation method of the foaming agent composition for thick oil thermal recovery plugging regulation according to claim 12, wherein the molar ratio of the intermediate diacid polyglycol ester to 1,1,1,3,5,5,5-heptamethyltrisiloxane is (1.1-1.4): 1, preferably (1.2-1.3): 1;
the mass ratio of the catalyst to 1,1,1,3,5,5,5-heptamethyltrisiloxane is (0.12-0.2): 100, preferably (0.15 to 0.18) 100.
17. The method for preparing the foaming agent composition for thick oil thermal recovery plugging according to claim 12, wherein the dicarboxylic acid in the step (11) has a structure represented by formula (7):
wherein p is 0 or 1.
18. The preparation method of the foaming agent composition for thick oil thermal recovery plugging regulation according to claim 12, wherein the structure of the intermediate diacid polyglycol ester is shown as the formula (8):
wherein p is 0 or 1,q is any integer or decimal number from 8 to 30.
19. The preparation method of the foaming agent composition for thick oil thermal recovery plugging regulation according to claim 12, wherein the 1,1,1,3,5,5,5-heptamethyltrisiloxane has the structure shown in formula (9):
20. use of the foam composition according to any one of claims 1 to 11 in thermal recovery plug-conditioning of heavy oil reservoirs.
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