CN118703186B - Nano imbibition oil displacement agent for improving recovery ratio - Google Patents
Nano imbibition oil displacement agent for improving recovery ratio Download PDFInfo
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- 238000006073 displacement reaction Methods 0.000 title claims abstract description 63
- 238000011084 recovery Methods 0.000 title claims abstract description 39
- 238000005213 imbibition Methods 0.000 title claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000003921 oil Substances 0.000 claims abstract description 68
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 64
- 229920006322 acrylamide copolymer Polymers 0.000 claims abstract description 44
- 125000002091 cationic group Chemical group 0.000 claims abstract description 39
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 35
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 35
- -1 sodium carboxylate Chemical class 0.000 claims abstract description 33
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 26
- 239000011734 sodium Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- IMOLAGKJZFODRK-UHFFFAOYSA-N 2-phenylprop-2-enamide Chemical compound NC(=O)C(=C)C1=CC=CC=C1 IMOLAGKJZFODRK-UHFFFAOYSA-N 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 17
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 17
- 235000019270 ammonium chloride Nutrition 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- WHUUTDBJXJRKMK-UHFFFAOYSA-N glutamic acid Chemical compound OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- NNCCQALFJIMRKB-UHFFFAOYSA-N 4-[(dimethylamino)methyl]aniline Chemical compound CN(C)CC1=CC=C(N)C=C1 NNCCQALFJIMRKB-UHFFFAOYSA-N 0.000 claims description 6
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 5
- 229940073608 benzyl chloride Drugs 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims 1
- 238000001953 recrystallisation Methods 0.000 claims 1
- 238000010008 shearing Methods 0.000 abstract description 10
- 239000012530 fluid Substances 0.000 abstract description 8
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical group C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 abstract description 6
- 230000001965 increasing effect Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 150000007942 carboxylates Chemical class 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- SUSANAYXICMXBL-UHFFFAOYSA-N 4-prop-2-enylmorpholine Chemical compound C=CCN1CCOCC1 SUSANAYXICMXBL-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C09K8/588—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 polymers
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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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/10—Nanoparticle-containing well treatment fluids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of oil displacement agents for oil exploitation, and discloses a nano imbibition oil displacement agent for improving recovery ratio, which comprises 100 parts by weight of cationic acrylamide copolymer and 5-25 parts by weight of sodium carboxylate modified nano silicon dioxide; after organically modifying, the nano silicon dioxide is uniformly dispersed in the oil displacement agent solution of the cationic acrylamide copolymer, and the solution shows rheological property of nano fluid, has a certain viscosity increasing effect, and is beneficial to improving the apparent viscosity of the oil displacement agent solution. The nano silicon dioxide contains a large amount of carboxylate, can form acid-base interaction with quaternary ammonium salt in the cationic acrylamide copolymer to generate a betaine group, and has good shearing resistance. The total recovery ratio of the nano imbibition oil displacement agent reaches 47.6-53.5%, and the nano imbibition oil displacement agent has excellent oil displacement efficiency.
Description
Technical Field
The invention belongs to the technical field of oil displacement agents for oil reservoir exploitation, and particularly relates to a nano imbibition oil displacement agent for improving recovery ratio.
Background
At present, in oil reservoirs in China, the occupation amount of low-permeability oil reservoirs is large, the method for exploiting the low-permeability oil reservoirs is an aqueous phase displacement method, and the stratum pressure is increased by injecting water, so that the crude oil recovery ratio is improved. However, with the continuous increase of the exploitation degree, the pressure of the oil layer is rapidly reduced, the water content of the produced liquid is rapidly increased, and the crude oil recovery ratio is seriously affected.
Enhanced oil recovery by chemical flooding is an effective method for improving the recovery ratio of crude oil. The polymer flooding enhanced oil recovery has the advantages of high recovery efficiency, low cost and the like, and has great development and application prospects. The polyacrylamide oil displacement agent is most widely applied; the acrylamide is copolymerized with monomers such as acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, dimethyl diallyl ammonium chloride, N-allyl morpholine and the like, so that the heat resistance, shearing resistance and the like of the polyacrylamide oil displacement agent are improved, and the oil displacement agent can be applied to the complex oil reservoir environments such as high temperature, high salt and the like.
The nano fluid oil displacement agent system has the performances of temperature resistance, salt resistance, polymer swelling improvement and the like, can control the rheological property of injection fluid, and is beneficial to improving the recovery ratio. The Chinese patent CN113717709B discloses a nano fluid permeation and absorption agent, a preparation method and application thereof, and adopts amphiphilic grafting modified nano silicon dioxide particles, betaine type surfactant, nonionic surfactant and the like as main components of the nano fluid permeation and absorption agent, so that the oil-water interface property can be changed, the permeation and absorption displacement rate of gel breaking liquid to compact oil is increased, but the nano fluid permeation and absorption agent does not show good high temperature resistance and shearing resistance.
Disclosure of Invention
The technical problems to be solved are as follows: the invention provides a nano imbibition oil displacement agent for improving recovery ratio, which solves the problems of poor high temperature resistance, poor shearing resistance and lower recovery ratio of polyacrylamide oil displacement agents.
(II) technical scheme: a nano-imbibition oil displacement agent for improving recovery ratio comprises 100 parts by weight of cationic acrylamide copolymer and 5-25 parts by weight of sodium carboxylate modified nano-silica.
The preparation method of the cationic acrylamide copolymer comprises the following steps: adding water, acrylamide, acrylic acid, 4- (dimethyl alkyl ammonium chloride) phenyl acrylamide and an emulsifier OP10 into a reaction container, heating to a reaction temperature, adding ammonium persulfate and sodium bisulfite in a nitrogen atmosphere, cooling after reaction, adding ethanol to separate out precipitate, extracting, drying and crushing to obtain the cationic acrylamide copolymer.
4- (Dimethylalkylammonium chloride) phenylacrylamide has the structural formula (I):
Formula (I).
The preparation method of the sodium carboxylate modified nano silicon dioxide comprises the following steps: carrying out surface modification on nano silicon dioxide by using hexamethylene diisocyanate to obtain HDI modified silicon dioxide; then adding the HDI modified silicon dioxide into a reaction vessel, adding a toluene solvent, stirring and dispersing, adding DL-glutamic acid, adding sodium hydroxide to adjust the pH value to 9-10 after the reaction, centrifugally separating, washing with water and ethanol, and drying to obtain the sodium carboxylate modified nano silicon dioxide.
Preferably, in the preparation method of the cationic acrylamide copolymer, the mass ratio of acrylamide to acrylic acid to 4- (dimethyl alkyl ammonium chloride) phenyl acrylamide is 100 (70-100): 3-10.
Preferably, in the preparation method of the cationic acrylamide copolymer, the reaction temperature is 50-60 ℃ and the reaction time is 5-7h.
Preferably, in the preparation method of the sodium carboxylate modified nano-silica, the mass ratio of the HDI modified silica to the DL-glutamic acid is 100 (150-400).
Preferably, in the preparation method of the sodium carboxylate modified nano silicon dioxide, the reaction temperature is 60-80 ℃ and the reaction time is 4-8h.
Preferably, the preparation method of the 4- (dimethyl alkyl ammonium chloride) phenyl acrylamide comprises the following steps:
And (1) adding methylene dichloride, 4- (dimethylaminomethyl) aniline, triethylamine and acryloyl chloride into a reaction container under ice bath, stirring, reacting for 4-6 hours at room temperature, distilling under reduced pressure, washing a product with saturated sodium chloride, and recrystallizing in ethanol to obtain 4- (dimethylaminomethyl) phenyl acrylamide.
And (2) adding acetonitrile and benzyl chloride with the mass ratio of 100 (60-82) of 4- (dimethyl aminomethyl) phenyl acrylamide into a reaction container provided with a condensing reflux pipe, heating to 75-85 ℃, reacting for 24-36h, distilling under reduced pressure, washing the product with petroleum ether, and recrystallizing in ethanol to obtain the 4- (dimethyl alkyl ammonium chloride) phenyl acrylamide.
Preferably, in the step (1), the mass ratio of the 4- (dimethylaminomethyl) aniline, the triethylamine and the acryloyl chloride is 100 (66-75) to 60-70.
(III) technical effects: the invention takes the cationic acrylamide copolymer and sodium carboxylate modified nano silicon dioxide as components of an oil displacement agent, wherein 4- (dimethyl alkyl ammonium chloride) phenyl acrylamide is taken as a functional monomer to carry out polymerization reaction with acrylamide and acrylic acid, and a plurality of benzene ring structures are introduced into a molecular chain of the acrylamide copolymer, so that the structural stability of the polymer at high temperature can be improved, the temperature resistance of an oil displacement system is improved, and the polymer still has higher apparent viscosity at high temperature. And the 4- (dimethyl alkyl ammonium chloride) phenyl acrylamide contains amide groups, has good hydrophilicity, and does not influence the hydrophilicity and water solubility of the acrylamide copolymer due to the introduction of a benzene ring structure after polymerization.
After being organically modified, the nano silicon dioxide is uniformly dispersed in the oil displacement agent solution of the cationic acrylamide copolymer, and the solution shows rheological property of nano fluid, has a certain viscosity increasing effect, and is beneficial to improving the apparent viscosity of the oil displacement agent solution. The nano silicon dioxide contains a large amount of carboxylate, and carboxylate anions (COO -) of the nano silicon dioxide interact with quaternary ammonium salt N + cations in the cationic acrylamide copolymer to form a betaine group, so that the nano silicon dioxide has good shearing resistance. Still has higher apparent viscosity at high shear rates.
The invention uses the cationic acrylamide copolymer and sodium carboxylate modified nano silicon dioxide as the components of the nano imbibition oil displacement agent, the total recovery ratio of the secondary oil displacement agent solution after oil displacement reaches 47.6-53.5%, and the excellent oil displacement efficiency is shown. Has good practical application in the fields of chemical flooding enhanced oil recovery and oil reservoir exploitation.
Detailed Description
The present invention will be further described in conjunction with specific examples and comparative examples to facilitate a more complete, accurate and thorough understanding of the present invention by those skilled in the art.
The preparation method of the HDI modified silicon dioxide comprises the following steps: 30mL of toluene, 1g of nano silicon dioxide and 2.4g of hexamethylene diisocyanate are added into a reaction vessel, the temperature is raised to 80 ℃, the reaction is carried out for 12 hours, centrifugal separation is carried out, the toluene is washed, and the HDI modified silicon dioxide is obtained after drying; the reaction formula is as follows:
Example 1
(1) Adding 40mL of toluene solvent and 1g of HDI modified silicon dioxide into a reaction vessel, stirring and dispersing, adding 4g of DL-glutamic acid, heating to 60 ℃, stirring and reacting for 8 hours, adding sodium hydroxide to adjust the pH to 9, centrifugally separating, washing with water and ethanol, and drying to obtain the sodium carboxylate modified nano silicon dioxide. The reaction formula is as follows:
(2) 40mL of methylene chloride, 4g of 4- (dimethylaminomethyl) aniline, 2.64g of triethylamine and 2.8g of acryloyl chloride were added to the reaction vessel under ice bath, the mixture was stirred and reacted at room temperature for 4 hours, distilled under reduced pressure, and the product was washed with saturated sodium chloride and then recrystallized from ethanol to give 4- (dimethylaminomethyl) phenylacrylamide. The reaction formula is as follows:
(3) To a reaction vessel equipped with a condensate reflux tube, 80mL of acetonitrile, 5g of 4- (dimethylaminomethyl) phenylacrylamide, 4.1g of benzyl chloride were added, the temperature was raised to 75℃and the reaction was stirred for 24 hours, distilled under reduced pressure, and the product was washed with petroleum ether and then recrystallized from ethanol to give 4- (dimethylalkylammonium chloride) phenylacrylamide. The reaction formula is as follows:
(4) 90mL of water, 10g of acrylamide, 7g of acrylic acid, 0.5g of 4- (dimethyl alkyl ammonium chloride) phenylacrylamide and 0.3g of emulsifier OP10 are added into a reaction vessel, then the temperature is raised to 60 ℃,30mg of ammonium persulfate and 30mg of sodium bisulfite are added into the reaction vessel under the nitrogen atmosphere to react for 5 hours, the reaction vessel is cooled, ethanol is added to separate out precipitate, the precipitate is extracted, dried and crushed, and the cationic acrylamide copolymer is obtained.
The nano imbibition displacement agent for improving the recovery ratio consists of 1g of cationic acrylamide copolymer and 0.05g of sodium carboxylate modified nano silicon dioxide.
Example 2
(1) Adding 30mL of toluene solvent and 1g of HDI modified silicon dioxide into a reaction vessel, stirring and dispersing, adding 3.2g of DL-glutamic acid, heating to 70 ℃, stirring and reacting for 5 hours, adding sodium hydroxide to adjust the pH to 9, centrifugally separating, washing with water and ethanol, and drying to obtain the sodium carboxylate modified nano silicon dioxide.
(2) 50ML of methylene chloride, 4g of 4- (dimethylaminomethyl) aniline, 2.64g of triethylamine and 2.4g of acryloyl chloride were added to the reaction vessel under ice bath, the mixture was stirred and reacted at room temperature for 6 hours, distilled under reduced pressure, and the product was washed with saturated sodium chloride and then recrystallized from ethanol to give 4- (dimethylaminomethyl) phenylacrylamide.
(3) 60ML of acetonitrile, 5g of 4- (dimethylaminomethyl) phenylacrylamide, 3g of benzyl chloride, and a reaction vessel equipped with a condensing reflux tube were added, the temperature was raised to 85℃and the reaction vessel was stirred for 24 hours, distilled under reduced pressure, the product was washed with petroleum ether and then recrystallized from ethanol to give 4- (dimethylalkylammonium chloride) phenylacrylamide.
(4) 90ML of water, 10g of acrylamide, 8g of acrylic acid, 0.3g of 4- (dimethyl alkyl ammonium chloride) phenylacrylamide and 0.28g of emulsifier OP10 are added into a reaction vessel, then the temperature is raised to 60 ℃,30mg of ammonium persulfate and 30mg of sodium bisulfite are added into the reaction vessel under the nitrogen atmosphere to react for 5 hours, the reaction vessel is cooled, ethanol is added to separate out precipitate, the precipitate is extracted, dried and crushed, and the cationic acrylamide copolymer is obtained.
The nano imbibition displacement agent for improving the recovery ratio consists of 1g of cationic acrylamide copolymer and 0.12g of sodium carboxylate modified nano silicon dioxide.
Example 3
(1) Adding 30mL of toluene solvent and 1g of HDI modified silicon dioxide into a reaction vessel, stirring and dispersing, adding 2.4g of DL-glutamic acid, heating to 60 ℃, stirring and reacting for 6 hours, adding sodium hydroxide to adjust the pH to 10, centrifugally separating, washing with water and ethanol, and drying to obtain the sodium carboxylate modified nano silicon dioxide.
(2) 4- (Dimethylalkylammonium chloride) phenylacrylamide was prepared as in example 1.
(3) 100ML of water, 10g of acrylamide, 8g of acrylic acid, 1g of 4- (dimethyl alkyl ammonium chloride) phenyl acrylamide and 0.3g of emulsifier OP10 are added into a reaction vessel, then the temperature is raised to 60 ℃,30mg of ammonium persulfate and 30mg of sodium bisulfite are added into the reaction vessel under the nitrogen atmosphere to react for 6 hours, the reaction vessel is cooled, ethanol is added to separate out sediment, the sediment is extracted, dried and crushed, and the cationic acrylamide copolymer is obtained.
The nano imbibition displacement agent for improving the recovery ratio consists of 1g of cationic acrylamide copolymer and 0.18g of sodium carboxylate modified nano silicon dioxide.
Example 4
(1) Adding 30mL of toluene solvent and 1g of HDI modified silicon dioxide into a reaction vessel, stirring and dispersing, adding 1.5g of DL-glutamic acid, heating to 80 ℃, stirring and reacting for 4 hours, adding sodium hydroxide to adjust the pH to 9, centrifugally separating, washing with water and ethanol, and drying to obtain the sodium carboxylate modified nano silicon dioxide.
(2) 4- (Dimethylalkylammonium chloride) phenylacrylamide was prepared as in example 1.
(3) 90ML of water, 10g of acrylamide, 7g of acrylic acid, 0.5g of 4- (dimethyl alkyl ammonium chloride) phenylacrylamide and 0.28g of emulsifier OP10 are added into a reaction vessel, then the temperature is raised to 50 ℃,30mg of ammonium persulfate and 30mg of sodium bisulfite are added into the reaction vessel under the nitrogen atmosphere to react for 7 hours, the reaction vessel is cooled, ethanol is added to separate out precipitate, the precipitate is extracted, dried and crushed, and the cationic acrylamide copolymer is obtained.
The nano imbibition displacement agent for improving the recovery ratio consists of 1g of cationic acrylamide copolymer and 0.25g of sodium carboxylate modified nano silicon dioxide.
Comparative example 1
(1) A cationic acrylamide copolymer was prepared as in example 1.
The imbibition displacement agent for improving the recovery ratio consists of 1g of cationic acrylamide copolymer.
Comparative example 2
(1) A cationic acrylamide copolymer was prepared as in example 1.
The nano imbibition oil displacement agent for improving the recovery ratio consists of 1g of cationic acrylamide copolymer and 0.05g of HDI modified silicon dioxide.
Comparative example 3
(1) 90ML of water, 10g of acrylamide, 7g of acrylic acid and 0.3g of emulsifier OP10 are added into a reaction vessel, then the temperature is raised to 60 ℃,30mg of ammonium persulfate and 30mg of sodium bisulphite are added into the reaction vessel under the nitrogen atmosphere to react for 5 hours, cooling, ethanol is added to precipitate, extraction, drying and crushing are carried out, and the acrylamide copolymer is obtained.
The nano imbibition displacement agent for improving the recovery ratio consists of 1g of acrylamide copolymer and 0.05g of sodium carboxylate modified nano silicon dioxide.
Comparative example 4
(1) 90ML of water, 10g of acrylamide, 7g of acrylic acid, 0.5g of dimethyl diallyl ammonium chloride and 0.3g of emulsifier OP10 are added into a reaction vessel, then the temperature is raised to 60 ℃,30mg of ammonium persulfate and 30mg of sodium bisulphite are added into the mixture under nitrogen atmosphere to react for 5 hours, the mixture is cooled, ethanol is added to precipitate, and the mixture is extracted, dried and crushed to obtain the cationic acrylamide copolymer.
The nano imbibition displacement agent for improving the recovery ratio consists of 1g of cationic acrylamide copolymer and 0.05g of sodium carboxylate modified nano silicon dioxide.
Adding the nano imbibition oil displacement agent for improving the recovery ratio into 2L of stratum water (mineralization degree is 14692 mg/L) to prepare an oil displacement agent solution, heating the oil displacement agent solution to 25-85 ℃, and testing the apparent viscosity of the oil displacement agent solution by adopting a rheometer, wherein the shearing rate is 170s -1. The test results are shown in Table 1.
TABLE 1 temperature resistance test of nano-imbibition displacement agent
The apparent viscosity of the oil displacement agent solution is tested by adopting a rheometer, the temperature is 25 ℃, and the shearing rate is 400-1000s -1. The test results are shown in Table 2.
Table 2 test of shear resistance of nano-imbibition displacement agent
As can be seen from tables 1 and 2, examples 1-4, which use cationic acrylamide copolymer and sodium carboxylate modified nano silica as components of the oil displacement agent, have the characteristic of high apparent viscosity, and still have higher apparent viscosity at high temperature and high shear rate, and exhibit good heat resistance and shear resistance. This is due to the fact that 4- (dimethyl alkyl ammonium chloride) phenyl acrylamide is used as a functional monomer, and is polymerized with acrylamide and acrylic acid, and a plurality of benzene ring structures are introduced into the molecular chain of the copolymer, so that the structural stability of the polymer at high temperature can be improved, and the temperature resistance of an oil displacement system can be improved. And the 4- (dimethyl alkyl ammonium chloride) phenyl acrylamide contains amide groups, has good hydrophilicity, and does not influence the hydrophilicity and water solubility of the acrylamide copolymer due to the introduction of a benzene ring structure after polymerization.
Meanwhile, after the nano silicon dioxide is organically modified, the nano silicon dioxide is uniformly dispersed in the oil displacement agent solution of the cationic acrylamide copolymer, the solution shows rheological property of nano fluid, has a certain viscosity increasing effect, and is beneficial to improving the apparent viscosity of the oil displacement agent solution. The nano silicon dioxide contains a large amount of carboxylate, and carboxylate anions (COO -) of the nano silicon dioxide interact with quaternary ammonium salt N + cations in the cationic acrylamide copolymer to form a betaine group, so that the nano silicon dioxide has good shearing resistance.
The imbibition displacement agent of comparative example 1 is free of nano silicon dioxide and has smaller apparent viscosity.
The HDI modified silicon dioxide of comparative example 2 does not contain sodium carboxylate groups, can not form acid-base interaction with the cationic acrylamide copolymer, does not generate betaine groups, has shearing resistance of the oil displacement agent, and has a large reduction range of apparent viscosity of the oil displacement agent solution under high shearing rate.
Comparative example 3 an acrylamide copolymer was prepared without adding 4- (dimethylalkylammonium chloride) phenylacrylamide, the polymer did not contain a heat-resistant benzene ring structure, the oil-displacing agent solution had poor temperature resistance, the apparent viscosity was greatly reduced at high temperature, the polymer also did not contain quaternary ammonium salt cations, acid-base interaction with the cationic acrylamide copolymer was not formed, no betaine groups were formed, the anti-shear properties of the imbibition oil-displacing agent were exhibited, and the apparent viscosity of the oil-displacing agent solution was greatly reduced at high shear rate.
Comparative example 4A cationic acrylamide copolymer was obtained by polymerizing dimethyl diallyl ammonium chloride as a cationic monomer, and the polymer did not contain a heat-resistant benzene ring structure, and the oil-displacing agent solution was poor in temperature resistance and large in apparent viscosity drop at high temperature.
Core displacement and crude oil recovery testing: adding the nano-permeability oil displacement agent for improving the recovery ratio into 2L of stratum water (mineralization degree is 14692 mg/L) to prepare an oil displacement agent solution; saturating the crude oil for the sand filling pipe after saturation of stratum water (mineralization degree is 14692 mg/L) for 72h, wherein the inner diameter of the sand filling pipe is 3 cm, the length of the sand filling pipe is 40 cm, and the porosity is about 23.1%; displacing the reservoir oil with stratum water until the water content is 95%, and injecting the reservoir oil with the injection rate of 0.2mL/mL and the injection amount of 1PV; and finally, displacing the mixture by using an oil displacement agent solution until the water content is 95%, the injection rate is 0.2mL/mL, and the injection amount is 1PV. The test results are shown in Table 3.
Table 3 core displacement and oil recovery testing of nano-imbibition displacement agents
From Table 3, it is clear that in examples 1-4, the cationic acrylamide copolymer and the sodium carboxylate modified nano silica are used as components of the oil displacement agent, and the total recovery ratio after oil displacement by the secondary oil displacement agent solution reaches 47.6-53.5%. Exhibits excellent oil displacement efficiency.
The present embodiment is only for explanation of the present invention and is not to be construed as limiting the present invention, and modifications to the present embodiment, which may not creatively contribute to the present invention as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present invention.
Claims (9)
1. The nano imbibition oil displacement agent for improving the recovery ratio is characterized by comprising 100 parts by weight of cationic acrylamide copolymer and 5-25 parts by weight of sodium carboxylate modified nano silicon dioxide;
The preparation method of the cationic acrylamide copolymer comprises the following steps: adding water, acrylamide, acrylic acid, 4- (dimethyl alkyl ammonium chloride) phenyl acrylamide and an emulsifier OP10 into a reaction vessel; then heating to the reaction temperature, adding ammonium persulfate and sodium bisulphite in nitrogen atmosphere, cooling after reaction, adding ethanol to precipitate, extracting, drying and crushing to obtain the cationic acrylamide copolymer;
The 4- (dimethyl alkyl ammonium chloride) phenyl acrylamide has a structural formula shown in the following formula (I):
Formula (I);
The preparation method of the sodium carboxylate modified nano silicon dioxide comprises the following steps: carrying out surface modification on nano silicon dioxide by using hexamethylene diisocyanate to obtain HDI modified silicon dioxide; then adding the HDI modified silicon dioxide into a reaction vessel, adding a toluene solvent, stirring and dispersing, adding DL-glutamic acid, adding sodium hydroxide to adjust the pH value to 9-10 after the reaction, centrifugally separating, washing and drying to obtain the sodium carboxylate modified nano silicon dioxide.
2. The nano-permeability and oil-displacing agent for enhanced oil recovery according to claim 1, wherein in the preparation method of the cationic acrylamide copolymer, the mass ratio of acrylamide, acrylic acid and 4- (dimethyl alkyl ammonium chloride) phenyl acrylamide is 100:70-100:3-10.
3. The nano-permeability and oil-displacing agent for enhanced oil recovery according to claim 1, wherein in the preparation method of the cationic acrylamide copolymer, the reaction temperature is 50-60 ℃ and the reaction time is 5-7h.
4. The nano-permeability displacement agent for enhanced oil recovery according to claim 1, wherein in the preparation method of sodium carboxylate modified nano-silica, the mass ratio of HDI modified silica to DL-glutamic acid is 100 (150-400).
5. The nano-permeability displacement agent for enhanced oil recovery according to claim 1, wherein in the preparation method of the sodium carboxylate modified nano-silica, the reaction temperature is 60-80 ℃ and the reaction time is 4-8h.
6. The nano-permeability displacement agent for enhanced oil recovery according to claim 2, wherein the preparation method of the 4- (dimethyl alkyl ammonium chloride) phenyl acrylamide is as follows:
Adding dichloromethane, 4- (dimethylaminomethyl) aniline, triethylamine and acryloyl chloride into a reaction container under ice bath, stirring, reacting for 4-6 hours at room temperature, distilling under reduced pressure, washing, and recrystallizing to obtain 4- (dimethylaminomethyl) phenyl acrylamide;
and (2) adding acetonitrile, 4- (dimethyl aminomethyl) phenyl acrylamide and benzyl chloride into a reaction vessel provided with a condensing reflux pipe, performing reduced pressure distillation, washing and recrystallization after the reaction to obtain the 4- (dimethyl alkyl ammonium chloride) phenyl acrylamide.
7. The nano-permeability and oil-displacing agent for enhanced oil recovery according to claim 6, wherein in the step (1), the mass ratio of 4- (dimethylaminomethyl) aniline, triethylamine and acryloyl chloride is 100 (66-75): 60-70.
8. The nano-permeability and oil-displacing agent for enhanced oil recovery according to claim 6, wherein in the step (2), the mass ratio of 4- (dimethylaminomethyl) phenyl acrylamide to benzyl chloride is 100 (60-82).
9. The nano-permeability and oil-displacing agent for enhanced oil recovery according to claim 6, wherein in the step (2), the reaction temperature is 75-85 ℃, and the reaction time is 24-36h.
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