CN117431049A - Shale oil imbibition agent, preparation method thereof and slickwater fracturing fluid - Google Patents
Shale oil imbibition agent, preparation method thereof and slickwater fracturing fluid Download PDFInfo
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- CN117431049A CN117431049A CN202210831723.0A CN202210831723A CN117431049A CN 117431049 A CN117431049 A CN 117431049A CN 202210831723 A CN202210831723 A CN 202210831723A CN 117431049 A CN117431049 A CN 117431049A
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- imbibition
- shale oil
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- 238000005213 imbibition Methods 0.000 title claims abstract description 135
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 129
- 239000003079 shale oil Substances 0.000 title claims abstract description 99
- 239000012530 fluid Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000010521 absorption reaction Methods 0.000 claims abstract description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract description 12
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 23
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 20
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 claims description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 13
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- -1 polyoxy ethylene ether Polymers 0.000 claims description 9
- TYIOVYZMKITKRO-UHFFFAOYSA-N 2-[hexadecyl(dimethyl)azaniumyl]acetate Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CC([O-])=O TYIOVYZMKITKRO-UHFFFAOYSA-N 0.000 claims description 8
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 8
- 229960003237 betaine Drugs 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 6
- 230000035515 penetration Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003961 penetration enhancing agent Substances 0.000 claims description 5
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- 229940051841 polyoxyethylene ether Drugs 0.000 claims 1
- 229920000056 polyoxyethylene ether Polymers 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 51
- 238000011084 recovery Methods 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 description 34
- 239000003921 oil Substances 0.000 description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 239000002994 raw material Substances 0.000 description 13
- 239000002357 osmotic agent Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 230000035699 permeability Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000011148 porous material Substances 0.000 description 9
- 230000001965 increasing effect Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000010779 crude oil Substances 0.000 description 7
- 239000011435 rock Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
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- 230000005012 migration Effects 0.000 description 5
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- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000003204 osmotic effect Effects 0.000 description 3
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- 239000004576 sand Substances 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- 230000001502 supplementing effect Effects 0.000 description 2
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- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
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- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 238000007865 diluting Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000012835 hanging drop method Methods 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2648—Alkali metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
- C09K8/604—Polymeric surfactants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/885—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention relates to the field of shale oil reservoir reformation, in particular to a shale oil imbibition agent, a preparation method thereof and a slickwater fracturing fluid, wherein the shale oil imbibition agent comprises the following components: a) a imbibition main agent, b) an amphoteric surfactant, c) a polycyclic aromatic hydrocarbon, and d) an organic solvent; wherein the imbibition main agent comprises polyoxyalkylene ether; the polyoxyalkylene ether is prepared by reacting trimethylolpropane diallyl ether serving as an initiator with alkylene oxide. The shale oil imbibition agent has the characteristics of quick initial imbibition start, low interfacial tension, high imbibition height within 10 minutes and the like. The shale oil seepage and absorption agent has good compatibility with a slick water system, and good drainage assisting and seepage and absorption performance after gel breaking, and can effectively improve the shale oil recovery ratio.
Description
Technical Field
The invention relates to the field of shale oil reservoir reconstruction, in particular to a shale oil imbibition agent, a preparation method thereof and a slickwater fracturing fluid.
Background
The land shale oil resource amount of China is about 1500 hundred million tons, and the recoverable resource amount is about 30-60 hundred million tons. Shale oil has no natural productivity or commercial exploitation value under natural conditions, and special exploitation technologies such as fracturing and the like are needed. Shale oil exploitation mainly relies on spontaneous imbibition under the dominant of capillary force, gravity and the like. The imbibition rate is related to the permeability of the rock, pore structure, wettability, fluid viscosity, fluid saturation, etc.
At present, under the condition that the reservoir property and the fracturing process are certain, the recovery ratio of shale oil needs to be improved from the aspects of supplementing energy, improving seepage, preventing scaling and improving water injection efficiency, and from the aspect of hydrodynamics, improving oil-water migration capacity, improving sweep efficiency and wash oil efficiency, improving permeability, fully enabling crude oil to enter a main pore canal, improving single well productivity, and achieving the purposes of increasing yield and improving recovery ratio.
Shale reservoirs are the main object of future further exploitation, which can be exploited in relation to the fracture systems present in their reservoirs. The matrix rock mass plays a role in oil storage, and the crack plays a role in oil guiding. For a fractured low-permeability oil reservoir, the main mechanism of oil displacement is to promote water in the fracture to be absorbed into a matrix through imbibition, and replace crude oil to perform oil extraction. Thus, for shale reservoirs, the imbibition aid is a key aid for pressure flooding extraction.
Imbibition is defined. Imbibition occurs in porous media and is an effective method for exploiting matrix rock and low permeability interval crude oil. Imbibition is also called self-priming, i.e., spontaneous imbibition, and refers to the process of automatically sucking water into a core and driving out crude oil without pressurization. Generalized imbibition includes pressurized imbibition and spontaneous imbibition. Pressurized imbibition is the so-called water-flooding oil recovery, also called forced imbibition. The term "imbibition" is used to refer to self-priming and does not include pressurized imbibition. The imbibition divides single-side contact imbibition, double-side contact imbibition and surrounding contact imbibition. The unilateral imbibition is that the core is unilaterally contacted with water, and the water is absorbed into the core under the traction of capillary pressure, and the oil in the core is discharged. This imbibition is also known as capillary pressure imbibition.
It is generally believed that during secondary migration of hydrocarbon, capillary forces are the resistance to hydrocarbon migration when the radius of curvature of the opposite end of the continuous hydrocarbon (gas) is greater than the front end due to pore structure changes; and when the radius of curvature of the opposite end of the continuous oil (gas) is smaller than that of the front end, capillary force is the motive force of oil and gas migration. Capillary forces always tend to cause the non-wetting phase to occupy a relatively large pore space, with intermittent movement of oil (gas) under the combined action of buoyancy, hydrodynamic forces and capillary forces, as demonstrated in physical simulation experiments. In practice, there are 3 capillary forces in the capillary. The first direction and the second direction are parallel to the extending direction of the capillary, and the third direction is perpendicular to the wall of the capillary and indicates a non-wetting phase; the third type of capillary forces primarily serves to increase the frictional resistance between the non-wetting phase and the pore throat wall, which is often ignored in media with a thicker pore throat (e.g., reservoirs). To migrate the oil and gas, the force along its forward direction must exceed the capillary and frictional resistance in that direction. One view is that capillary forces are considered to be important dynamics in the primary migration of oil and gas from the source rock to the reservoir, so that under water-wet conditions, the oil and gas phases will automatically move from small pores and fine throats into larger, coarser pores and throats under capillary forces.
An important factor that depends on the development efficiency of oil and gas reservoirs is oil-water permeability, and especially for some low-permeability reservoirs, the permeability determines the productivity of the oil and gas well.
In addition, from a green chemistry perspective, oilfield development has reached an efficiency driving stage. The efficiency of the production element configuration is improved, wherein the water is used for supplementing the capability, and meanwhile, more crude oil is replaced by the same water, so that good benefits are obtained, and the oil reservoir is protected, energy is saved, and the environment is protected. The imbibition yield increasing technology is designed and developed in consideration of the problems. Firstly, the wettability of the rock can be changed, so that the rock is converted into hydrophilicity, the imbibition effect is enhanced, the crude oil in the pore canal is replaced, and the recovery ratio is improved. And secondly, the agent is safe and environment-friendly, protects the oil reservoir and can be reused.
The imbibition technology is designed and developed specifically for imbibition problem by replacing crude oil in cracks through a high-efficiency imbibition extractant with a new structure and related auxiliary agents.
The imbibition enhanced recovery yield increasing technology developed aiming at the characteristic of low permeability of the shale oil reservoir is used for solving the problems of low shale oil exploitation efficiency, high cost, unobvious oil increasing effect and the like, is a technology which can be widely developed, remarkably reflects the characteristics of protecting the oil reservoir, reducing pressure and increasing injection, being simple and convenient to operate, being obvious in benefit and the like, and has very feasible operability.
Disclosure of Invention
The invention aims to solve the problems of low exploitation efficiency, high cost and insignificant oil increasing effect of the existing shale oil, and provides a shale oil imbibition agent, a preparation method thereof and a slickwater fracturing fluid. The shale oil seepage and absorption agent has good compatibility with a slick water system, and good drainage assisting and seepage and absorption performance after gel breaking, and can effectively improve the shale oil recovery ratio.
In order to achieve the above object, an aspect of the present invention provides a shale oil osmotic absorbent comprising: a) a imbibition main agent, b) an amphoteric surfactant, c) a polycyclic aromatic hydrocarbon, and d) an organic solvent; wherein the imbibition main agent comprises polyoxyalkylene ether; the polyoxyalkylene ether is prepared by reacting trimethylolpropane diallyl ether serving as an initiator with alkylene oxide.
The second aspect of the invention provides a preparation method of the shale oil permeation absorbent, which comprises the following steps: the shale oil permeation and absorption agent is obtained by uniformly mixing the permeation and absorption main agent, the amphoteric surfactant, the polycyclic aromatic hydrocarbon and the organic solvent.
The third aspect of the invention provides a slick water fracturing fluid containing the shale oil permeation and absorption agent.
The shale oil imbibition agent has the characteristics of quick initial imbibition start, low interfacial tension, thorough imbibition and the like.
The shale oil permeation and absorption agent can effectively reduce the fracturing cost, improve the fracturing yield increasing efficiency, improve the integral water injection oil displacement efficiency and remarkably improve the shale oil recovery ratio.
The slickwater fracturing fluid flowback fluid can be recycled after simple treatment, and can be reused for single well blocking removal and yield increase, and the reservoir oil displacement is injected back.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a shale oil seepage and absorption agent, which comprises the following components: a) a imbibition main agent, b) an amphoteric surfactant, c) a polycyclic aromatic hydrocarbon, and d) an organic solvent; wherein the imbibition main agent comprises polyoxyalkylene ether; the polyoxyalkylene ether is prepared by reacting trimethylolpropane diallyl ether serving as an initiator with alkylene oxide.
According to a particularly preferred embodiment of the present invention, the shale oil penetration enhancer contains, in 100 parts by weight: 20-40 parts by weight of a imbibition main agent, b) 10-20 parts by weight of an amphoteric surfactant, c) 3-8 parts by weight of polycyclic aromatic hydrocarbon, d) 32-67 parts by weight of an organic solvent.
According to a preferred embodiment of the present invention, the alkylene oxide is one or more of ethylene oxide, propylene oxide, butylene oxide.
In order to further improve the permeability and the imbibition efficiency of the imbibition agent in shale oil, the imbibition agent molecule is designed to be of a multi-branched structure, and according to a preferred embodiment of the invention, the polyoxyalkylene ether is polyoxyethylene polyoxypropylene ether.
According to a preferred embodiment of the present invention, the method for preparing polyoxyethylene polyoxypropylene ether comprises: under the action of alkali metal hydroxide as catalyst, trimethylol propane diallyl ether is used as initiator to react with ethylene oxide and propylene oxide.
In the present invention, the conditions of the reaction in the process for producing a polyoxyethylene polyoxypropylene ether may be a conventional choice in the art, as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the conditions of the reaction include: the reaction temperature is 120-130 ℃, the reaction pressure is 0.2-0.4 MPa, and the reaction time is 1-4 hours.
In order to further increase the permeability of the infiltrant in shale oil, according to a preferred embodiment of the invention, the weight ratio of initiator, ethylene oxide, propylene oxide and catalyst is (1.5-5): (250-400): (120-220): 1.
according to a particularly preferred embodiment of the invention, the weight ratio of initiator, ethylene oxide, propylene oxide and catalyst is (2.5-4): (300-350): (150-200): 1.
in the present invention, the amphoteric surfactant may be a conventional choice in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the amphoteric surfactant includes alkyl betaines, which are one or more of dodecyl betaine, dodecyl dihydroxyethyl betaine, octadecyl dihydroxyethyl betaine, hexadecyl betaine. By adopting the preferable scheme, the surface interfacial tension of the osmotic agent can be further reasonably adjusted, and the osmotic start speed is improved.
In order to further improve the starting speed of the osmotic agent, the alkyl betaine is a mixture of dodecyl betaine and hexadecyl betaine, and the weight ratio of the dodecyl betaine to the hexadecyl betaine is (0.5-2): 1.
in the present invention, the polycyclic aromatic hydrocarbon may be a conventional choice in the art as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the polycyclic aromatic hydrocarbon is one or more of fluorene, naphthalene, anthracene, phenanthrene. By adopting the preferable scheme, the permeability of the osmotic agent to shale oil at the interface can be improved, and the stripping of heavy components in the shale oil can be increased.
In the present invention, the organic solvent includes a benzene solvent, preferably one or more of xylene, toluene, and trimethylbenzene.
According to a preferred embodiment of the present invention, the organic solvent is a mixed solvent of xylene and dimethyl sulfoxide. By adopting the preferable scheme, the good mutual dissolution uniformity of the components of the osmotic agent can be improved, and the osmotic agent is convenient to store and apply.
In order to further improve the good mutual dissolution uniformity of the components of the osmotic agent, according to a preferred embodiment of the invention, the weight ratio of dimethyl sulfoxide to dimethylbenzene is (1-6): 1.
in the present invention, the shale oil imbibition agent having the aforementioned characteristics can achieve the object of the invention, and the preparation method of the catalyst is not particularly limited, and the catalyst can be prepared by mixing the imbibition main agent, the amphoteric surfactant, the polycyclic aromatic hydrocarbon and the organic solvent raw materials under the condition that the raw materials are uniformly mixed.
The invention provides a slick water fracturing fluid which contains the shale oil seepage and absorption agent.
In the invention, the slickwater fracturing fluid is fracturing fluid which can effectively reduce the friction of the fracturing fluid, has certain viscosity and meets certain sand carrying performance, and the specific composition is not limited and can be selected according to the needs.
When the shale oil seepage and absorption agent is used, the shale oil seepage and absorption agent can be added into a slick water fracturing fluid system, or each component of the shale oil seepage and absorption agent can be directly added into the slick water system, and the addition sequence of each component is not limited.
According to a preferred embodiment of the invention, the slickwater fracturing fluid contains 0.05 to 1 weight percent of shale oil penetration and absorption agent.
The shale oil imbibition agent provided by the invention can effectively improve the shale oil recovery ratio and has the characteristics of quick initial imbibition start, low interfacial tension, thorough imbibition and the like. Meanwhile, the shale oil seepage and absorption agent has good compatibility with a slick water system, and good drainage assisting and seepage and absorption performance after gel breaking.
The present invention is further illustrated by the following specific examples, the scope of which is not limited to the examples, and the reagents used in the present invention are commercially available unless otherwise specified:
preparing a slick water fracturing fluid system: 0.3wt% of emulsion resistance reducing agent (SFFR, model number is made by middle petrochemical land frame Co., ltd.), 0.1wt% of efficient cleanup additive (SFCU, model number is made by middle petrochemical land frame Co., ltd.), 0.3wt% of clay stabilizer (SFCS, model number is made by middle petrochemical land frame Co., ltd.) and 99.27wt% of water are mixed, then 0.03wt% of gel breaker (SFCP, model number is made by middle petrochemical land frame Co., ltd.) is added, gel is broken at 90 ℃ for 1 hour, and then the mixture is cooled to room temperature to obtain a gel-breaking slick water fracturing fluid system.
The test method related by the invention comprises the following steps:
1. compatibility of the osmotic agent with the slick hydraulic fracturing fluid System
The sample and the slickwater fracturing fluid formula are prepared into a slickwater fracturing fluid product, the components are mutually compatible, and the slickwater fracturing fluid product has no layering, no precipitation, no turbidity and no color change phenomenon, and is marked as good, otherwise, the slickwater fracturing fluid product is bad.
And (3) excessive experiment verification: the product is prepared according to the formula, and is compatible with other products in the system, the addition of all additives in the system is enlarged by 10 times, and the phenomena of layering, precipitation, turbidity and color change are avoided.
2. Surface tension test
The surface tension and interfacial tension test method under the water system comprises the following steps: weighing 0.6000g of the osmotic absorbent sample into a 200mL clean volumetric flask by a ten-thousandth balance, diluting to a scale by deionized water to prepare a solution with 0.3 weight percent, and detecting the surface tension of the solution at 25 ℃ by a surface interfacial tensiometer by using a 'hanging drop method'; the interfacial tension value with dehydrated 3# aviation kerosene was measured.
Surface tension test: the drop was a sample solution, the external environment was air, and the solution and air were measured to form a "liquid-gas" surface tension value.
Interface tension test: the drop is a sample solution, the external environment is 3# aviation kerosene, and the drop and the 3# aviation kerosene are measured to form a liquid-liquid interfacial tension value.
The testing method of the surface tension and interfacial tension testing method under the slick hydraulic fracturing fluid system comprises the following steps: the test was carried out by the same method as above, except that a slickwater fracturing fluid was prepared with 0.3wt% of the osmotic agent.
3. Capillary imbibition test
Capillary preparation for imbibition: the capillary specification, standard capillary inner diameter 0.3mm, was sonicated with chromic acid wash for 3 hours to remove surface organic material. Then sequentially carrying out ultrasonic cleaning by using hydrochloric acid solution (volume ratio is 1:10) and hydrofluoric acid solution (concentration is 10wt%) to roughen and activate the surface of the capillary for 30min. And then ultrasonically cleaning with deionized water to remove residual acid until the pH is more than 6.5 and drying at 105 ℃. Preparing ageing oil according to a proportion, wherein the ageing oil comprises the following components: 3# aviation kerosene: 90# pitch = 2:5:3 (mass ratio). The treated capillary was completely immersed in the aging oil and aged at 60℃for 4 weeks. Taking out the capillary, cleaning asphalt on the outer wall of the capillary by using kerosene, placing the capillary in a closed environment at 60 ℃ for drying to obtain an oil wet capillary, and preserving the oil wet capillary for later use.
The method for testing the liquid level height under the water system for 10min comprises the following steps: preparing 0.3% of liquid to be measured (the mass content of the imbibition agent sample in water) by using deionized water, keeping the temperature of the liquid to be measured at 25 ℃, pouring the liquid to be measured into a colorimetric tube, and enabling a scale to cling to the rear wall and stand at the rear. And vertically placing the treated capillary tube in a colorimetric tube, reading the liquid level height in a recording tube, and recording the liquid level height in 10 minutes.
The method for testing the liquid level height of the slick fracturing fluid system in 10 minutes comprises the following steps: the test was carried out by the same method as above, except that a slickwater fracturing fluid was prepared with 0.3wt% of the osmotic agent.
4. Test of flowback Rate
The testing method comprises the following steps: adopting a 20-40 mesh quartz sand filling pipe to simulate and test the flowback rate, filling 20-40 mesh quartz sand into a sand filling pipe with the length of 25cm and the diameter of 2.5cm, vibrating up and down for 200 times to basically keep the permeability of each time consistent, injecting a mixed solution of a sample to be tested (the addition amount is 0.3wt% of the mixed solution) and a slickwater fracturing fluid system into the sand filling pipe at room temperature, wherein the use amount of the slickwater fracturing fluid is 0.5wt% of the quartz sand, then injecting a gel breaker (manufactured by China-petrochemical land frame company, model SFCP), the use amount of the gel breaker is 0.03wt% of the quartz sand, opening a lower valve to enable the liquid to flow out under the action of gravity, recording the outflow amount, and calculating to obtain the flowback rate (the flowback rate=outflow amount/injection mixed liquid amount is 100%); the blank group replaced the sample with an equal volume of water.
Example 1
Preparation of a imbibition main agent: respectively adding ethylene oxide and propylene oxide into a No. 1 tank and a No. 2 tank, metering according to a certain proportion, and then entering a No. 3 tank; adding a certain amount of trimethylolpropane diallyl ether and KOH into a dried high-pressure reaction kettle, after the high-pressure reaction kettle is assembled, replacing the air in the kettle with nitrogen for 3-5 times, purging a device pipeline, heating, continuously and slowly adding a mixture of metered ethylene oxide and propylene oxide when the temperature in the kettle is raised to 75 ℃, controlling the pressure to be 0.2MPa and the temperature to be 120 ℃, and continuing to react for 3 hours after the feeding is finished. And then cooling, and purging residual gas in the pipeline and the reaction kettle by using nitrogen to obtain the imbibition main agent.
The raw materials of the imbibition main agent are as follows: 0.3 part by weight of trimethylolpropane diallyl ether, 70 parts by weight of ethylene oxide, 30 parts by weight of propylene oxide and 0.2 part by weight of potassium hydroxide.
Preparation of shale oil seepage and absorption agent: according to the weight parts, 30 weight parts of the imbibition main agent, 15 weight parts of dodecyl betaine, 6 weight parts of naphthalene, 12 weight parts of dimethylbenzene and 37 weight parts of dimethyl sulfoxide are uniformly mixed under stirring, and the shale oil imbibition agent is obtained.
The results of testing the relevant properties in a water system with a shale oil imbibition agent content of 0.3wt% are shown in Table 1, and the relevant properties in a slick water fracturing fluid system with a shale oil imbibition agent content of 0.3wt% are shown in Table.
Example 2
Preparation of a imbibition main agent: as in example 1.
The raw materials of the imbibition main agent are as follows: 0.4 part by weight of trimethylolpropane diallyl ether, 65 parts by weight of ethylene oxide, 35 parts by weight of propylene oxide and 0.2 part by weight of potassium hydroxide.
Preparation of shale oil seepage and absorption agent: according to the weight parts, 20 weight parts of a seepage and absorption main agent, 10 weight parts of dodecyl betaine, 3 weight parts of naphthalene, 10 weight parts of dimethylbenzene and 57 weight parts of dimethyl sulfoxide are uniformly mixed under stirring, so that the shale oil seepage and absorption agent is obtained.
The results of testing the relevant properties in a water system with a shale oil imbibition agent content of 0.3wt% are shown in Table 1, and the results of testing the relevant properties in a slick water fracturing fluid system with a shale oil imbibition agent content of 0.3wt% are shown in Table 2.
Example 3
Preparation of a imbibition main agent: as in example 1.
The raw materials of the imbibition main agent are as follows: 0.6 part by weight of trimethylolpropane diallyl ether, 60 parts by weight of ethylene oxide, 40 parts by weight of propylene oxide and 0.2 part by weight of potassium hydroxide.
Preparation of shale oil seepage and absorption agent: according to the weight parts, 40 weight parts of a imbibition main agent, 10 weight parts of dodecyl betaine, 10 weight parts of hexadecyl betaine, 8 weight parts of naphthalene, 15 weight parts of dimethylbenzene and 17 weight parts of dimethyl sulfoxide are uniformly mixed under stirring, and the shale oil imbibition agent is obtained.
The results of testing the relevant properties in a water system with a shale oil imbibition agent content of 0.3wt% are shown in Table 1, and the results of testing the relevant properties in a slick water fracturing fluid system with a shale oil imbibition agent content of 0.3wt% are shown in Table 2.
Example 4
Preparation of a imbibition main agent: as in example 1.
The raw materials of the imbibition main agent are as follows: 0.5 part by weight of trimethylolpropane diallyl ether, 67 parts by weight of ethylene oxide, 33 parts by weight of propylene oxide and 0.2 part by weight of potassium hydroxide.
Preparation of shale oil seepage and absorption agent: according to the weight parts, 40 weight parts of a imbibition main agent, 20 weight parts of dodecyl betaine, 8 weight parts of naphthalene, 15 weight parts of dimethylbenzene and 17 weight parts of dimethyl sulfoxide are uniformly mixed under stirring, and the shale oil imbibition agent is obtained.
The results of testing the relevant properties in a water system with a shale oil imbibition agent content of 0.3wt% are shown in Table 1, and the results of testing the relevant properties in a slick water fracturing fluid system with a shale oil imbibition agent content of 0.3wt% are shown in Table 2.
Example 5
Preparation of a imbibition main agent: same as in example 4.
The raw materials of the imbibition main agent are as follows: same as in example 4.
Preparation of shale oil seepage and absorption agent: according to the weight parts, 40 weight parts of the imbibition main agent, 20 weight parts of hexadecyl betaine, 8 weight parts of fluorene, 15 weight parts of toluene and 17 weight parts of dimethyl sulfoxide are uniformly mixed under stirring, so that the shale oil imbibition agent is obtained.
The results of testing the relevant properties in a water system with a shale oil imbibition agent content of 0.3wt% are shown in Table 1, and the results of testing the relevant properties in a slick water fracturing fluid system with a shale oil imbibition agent content of 0.3wt% are shown in Table 2.
Example 6
Preparation of a imbibition main agent: same as in example 4.
The raw materials of the imbibition main agent are as follows: same as in example 4.
Preparation of shale oil seepage and absorption agent: according to the weight parts, 40 weight parts of the imbibition main agent, 20 weight parts of dodecyl betaine, 2 weight parts of naphthalene, 15 weight parts of dimethylbenzene and 17 weight parts of dimethyl sulfoxide are uniformly mixed under stirring, and the shale oil imbibition agent is obtained.
The results of testing the relevant properties in a water system with a shale oil imbibition agent content of 0.3wt% are shown in Table 1, and the results of testing the relevant properties in a slick water fracturing fluid system with a shale oil imbibition agent content of 0.3wt% are shown in Table 2.
Example 7
Preparation of a imbibition main agent: same as in example 4.
The raw materials of the imbibition main agent are as follows: same as in example 4.
Preparation of shale oil seepage and absorption agent: according to the weight parts, 40 weight parts of a imbibition main agent, 20 weight parts of dodecyl betaine, 8 weight parts of naphthalene, 15 weight parts of dimethylbenzene and 10 weight parts of dimethyl sulfoxide are uniformly mixed under stirring, and the shale oil imbibition agent is obtained.
The results of testing the relevant properties in a water system with a shale oil imbibition agent content of 0.3wt% are shown in Table 1, and the results of testing the relevant properties in a slick water fracturing fluid system with a shale oil imbibition agent content of 0.3wt% are shown in Table 2.
Example 8
Preparation of a imbibition main agent: same as in example 4.
The raw materials of the imbibition main agent are as follows: same as in example 4.
Preparation of shale oil seepage and absorption agent: according to the weight parts, 40 weight parts of the imbibition main agent, 20 weight parts of dodecyl betaine, 8 weight parts of naphthalene and 32 weight parts of dimethyl sulfoxide are uniformly mixed under stirring, and the shale oil imbibition agent is obtained.
The results of testing the relevant properties in a water system with a shale oil imbibition agent content of 0.3wt% are shown in Table 1, and the results of testing the relevant properties in a slick water fracturing fluid system with a shale oil imbibition agent content of 0.3wt% are shown in Table 2.
Comparative example 1
Preparation of a imbibition main agent: the starting material trimethylolpropane diallyl ether was replaced by propylene glycol, and the imbibition main agent was obtained in the same manner as in example 4.
The raw materials of the imbibition main agent are as follows: same as in example 4.
Preparation of shale oil seepage and absorption agent: same as in example 4.
The results of testing the relevant properties in a water system with a shale oil imbibition agent content of 0.3wt% are shown in Table 1, and the results of testing the relevant properties in a slick water fracturing fluid system with a shale oil imbibition agent content of 0.3wt% are shown in Table 2.
Comparative example 2
Preparation of a imbibition main agent: same as in example 4.
The raw materials of the imbibition main agent are as follows: same as in example 4.
Preparation of shale oil seepage and absorption agent: according to the weight parts, 40 weight parts of the imbibition main agent, 8 weight parts of naphthalene, 15 weight parts of dimethylbenzene and 17 weight parts of dimethyl sulfoxide are uniformly mixed under stirring, and the shale oil imbibition agent is obtained.
The results of testing the relevant properties in a water system with a shale oil imbibition agent content of 0.3wt% are shown in Table 1, and the results of testing the relevant properties in a slick water fracturing fluid system with a shale oil imbibition agent content of 0.3wt% are shown in Table 2.
Comparative example 3
Preparation of a imbibition main agent: same as in example 4.
The raw materials of the imbibition main agent are as follows: same as in example 4.
Preparation of shale oil seepage and absorption agent: according to the weight parts, 40 weight parts of the imbibition main agent, 20 weight parts of dodecyl betaine, 15 weight parts of dimethylbenzene and 17 weight parts of dimethyl sulfoxide are uniformly mixed under stirring, and the shale oil imbibition agent is obtained.
The results of testing the relevant properties in a water system with a shale oil imbibition agent content of 0.3wt% are shown in Table 1, and the results of testing the relevant properties in a slick water fracturing fluid system with a shale oil imbibition agent content of 0.3wt% are shown in Table 2.
TABLE 1 shale oil imbibition agent Performance test results
As can be seen from Table 2, the osmotic agent of the present invention can effectively reduce the surface tension and increase the imbibition height for 10 min. Because of the simulated oil and capillary wall adsorption, pure water is difficult to overcome the adsorption work driving oil, i.e. no obvious imbibition occurs. The osmotic agent is contained and then imbibition occurs due to the low interfacial tension of the osmotic agent. Therefore, the imbibition agent has better imbibition effect.
Table 2 results of the slick fracturing fluid Performance test
As can be seen from Table 2, the mutual compatibility between the seepage and absorption agent and the slick water fracturing fluid system is good, and the seepage and absorption agent has no layering, no precipitation, no turbidity and no color change phenomenon. The slickwater fracturing fluid obtained by mixing the seepage and absorption agent and the slickwater fracturing fluid system has relatively low surface tension and interfacial tension, relatively high seepage and absorption height and flow-back rate, and good seepage and absorption effect.
Claims (10)
1. A shale oil imbibition agent, characterized in that the shale oil imbibition agent comprises: a) a imbibition main agent, b) an amphoteric surfactant, c) a polycyclic aromatic hydrocarbon, and d) an organic solvent;
wherein the imbibition main agent comprises polyoxyalkylene ether;
the polyoxyalkylene ether is prepared by reacting trimethylolpropane diallyl ether serving as an initiator with alkylene oxide.
2. The shale oil penetration and absorption agent according to claim 1, wherein the shale oil penetration and absorption agent comprises, on a 100 weight part basis: 20-40 parts by weight of a imbibition main agent, b) 10-20 parts by weight of an amphoteric surfactant, c) 3-8 parts by weight of polycyclic aromatic hydrocarbon, d) 32-67 parts by weight of an organic solvent.
3. The shale oil penetration absorber of claim 1 or 2, wherein the alkylene oxide is one or more of ethylene oxide, propylene oxide, butylene oxide; and/or
The polyoxy ethylene ether is polyoxyethylene polyoxypropylene ether;
preferably, the preparation method of the polyoxyethylene polyoxypropylene ether comprises the following steps: under the action of an alkali metal hydroxide serving as a catalyst, trimethylol propane diallyl ether serving as an initiator is reacted with ethylene oxide and propylene oxide to prepare the catalyst;
more preferably, the weight ratio of the initiator, ethylene oxide, propylene oxide and catalyst is (1.5-5): (250-400): (120-220): 1, preferably (2.5-4): (300-350): (150-200): 1.
4. a shale oil penetration enhancer as claimed in any of claims 1-3, wherein said amphoteric surfactant comprises an alkyl betaine; the alkyl betaine is one or more of dodecyl betaine, dodecyl dihydroxyethyl betaine, octadecyl dihydroxyethyl betaine and hexadecyl betaine; preferably, the alkyl betaine is a mixture of dodecyl betaine and hexadecyl betaine, and the weight ratio of the dodecyl betaine to the hexadecyl betaine is (0.5-2): 1.
5. the shale oil penetration enhancer of any of claims 1-4, wherein the polycyclic aromatic hydrocarbon is one or more of fluorene, naphthalene, anthracene, and phenanthrene.
6. The shale oil penetration enhancer of any of claims 1-5, wherein the organic solvent comprises a benzene-based solvent, preferably one or more of xylene, toluene, trimethylbenzene.
7. The shale oil penetration and absorption agent as claimed in claim 6, wherein the organic solvent is a mixed solvent composed of xylene and dimethyl sulfoxide, more preferably the weight ratio of dimethyl sulfoxide to xylene is (1-6): 1.
8. a method of preparing a shale oil penetration enhancer as claimed in any of claims 1 to 7, comprising: and uniformly mixing the imbibition main agent, the amphoteric surfactant, the polycyclic aromatic hydrocarbon and the organic solvent to obtain the shale oil imbibition agent.
9. A slickwater fracturing fluid comprising the shale oil penetration/absorption agent of any one of claims 1-7.
10. The slickwater fracturing fluid of claim 9 wherein,
in the slickwater fracturing fluid, the shale oil seepage and absorption agent accounts for 0.05 to 1 weight percent.
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