CN112342005B - Environment-friendly efficient thick oil viscosity reducer - Google Patents
Environment-friendly efficient thick oil viscosity reducer Download PDFInfo
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- CN112342005B CN112342005B CN202110005081.4A CN202110005081A CN112342005B CN 112342005 B CN112342005 B CN 112342005B CN 202110005081 A CN202110005081 A CN 202110005081A CN 112342005 B CN112342005 B CN 112342005B
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- stirring
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- constant speed
- azobisisobutyronitrile
- heating
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 35
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 104
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 60
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 21
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 19
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 100
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 238000010438 heat treatment Methods 0.000 claims description 50
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 48
- 239000000047 product Substances 0.000 claims description 43
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- 238000005406 washing Methods 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 31
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 21
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 17
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 17
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 17
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000005642 Oleic acid Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 17
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 17
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 16
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 16
- 239000005751 Copper oxide Substances 0.000 claims description 16
- 229910000431 copper oxide Inorganic materials 0.000 claims description 16
- 235000019253 formic acid Nutrition 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000654 additive Substances 0.000 abstract description 11
- 230000000996 additive effect Effects 0.000 abstract description 10
- 239000003999 initiator Substances 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 238000010556 emulsion polymerization method Methods 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 55
- 230000009467 reduction Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000084 colloidal system Substances 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000007704 transition 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
- 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
-
- 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
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Cosmetics (AREA)
Abstract
The invention belongs to the field of petroleum additives, and particularly discloses an environment-friendly efficient thick oil viscosity reducer which comprises a first polymer and a composite additive; the environment-friendly high-efficiency thick oil viscosity reducer is prepared by the following method: mixing monomers such as butyl acrylate, styrene and toluene, adding azobisisobutyronitrile as an initiator, adding sodium p-styrenesulfonate, preparing a product C by an emulsion polymerization method, wherein the product C is a butyl acrylate-styrene-sodium p-styrenesulfonate copolymer and has excellent hydrophilic and lipophilic properties, and then uniformly mixing the product A and the product C to prepare a first polymer; uniformly mixing the auxiliary agent and the main agent to prepare a composite auxiliary agent; uniformly mixing the first polymer and the composite auxiliary agent to prepare the environment-friendly high-efficiency thick oil viscosity reducer; the viscosity reducer has excellent viscosity reducing performance on thick oil.
Description
Technical Field
The invention relates to a thick oil viscosity reducer, in particular to an environment-friendly efficient thick oil viscosity reducer.
Background
The main difference between the thick oil and other common thin oil is that the thick oil contains more colloid and asphaltene, which is also the main factor of the thick oil with larger viscosity. The colloid and asphaltene molecules are the components with the largest relative molecular mass and the strongest polarity in the thickened oil, and researches show that the asphaltene molecules exist in the crude oil in a three-dimensional association network structure form to form an aggregate with high regularity. The colloidal molecules are adsorbed on the asphaltene aggregates to form a transition layer between the asphaltene particles and the liquid oil, suspending the asphaltene particles in the oil to form a petroleum colloid. When the relative displacement occurs between the crude oil molecules, a large internal friction force is generated, thereby showing the high viscosity of the crude oil.
At present, methods such as heating viscosity reduction and the like are mainly adopted for the exploitation of the super-heavy oil, but certain environmental pollution can be caused due to overhigh energy consumption of heating viscosity reduction, and the requirement of environmental protection cannot be met.
Disclosure of Invention
In order to overcome the technical problems, the invention provides an environment-friendly high-efficiency thick oil viscosity reducer.
The purpose of the invention can be realized by the following technical scheme:
an environment-friendly high-efficiency thick oil viscosity reducer comprises a first polymer and a composite auxiliary agent;
the environment-friendly high-efficiency thick oil viscosity reducer is prepared by the following method:
uniformly mixing the first polymer and the composite auxiliary agent according to the weight ratio of (0.1-0.5) to 3 to prepare the environment-friendly high-efficiency thick oil viscosity reducer;
the first polymer is made by the following method:
step S1, adding stearyl methacrylate into an aqueous solution of sodium hydroxide with the mass fraction of 8-12% to wash until the mixture is colorless, then washing the mixture to be neutral by deionized water, filtering the mixture, and drying the mixture for 18-22h at the temperature of 60-75 ℃ to obtain refined stearyl methacrylate; heating 94-96% ethanol by volume fraction in water bath until boiling, adding azobisisobutyronitrile, stirring at a constant speed until the mixture is dissolved, filtering, cooling and crystallizing to obtain refined azobisisobutyronitrile;
step S2, sequentially adding refined octadecyl methacrylate, vinyl acetate and divinylbenzene into a three-neck flask filled with absolute ethyl alcohol, heating to 60-75 ℃, introducing nitrogen, magnetically stirring at the rotating speed of 150-;
step S3, adding butyl acrylate, styrene and toluene into a beaker, stirring at a constant speed of 80-150r/min for 25-35min, adding refined azobisisobutyronitrile, continuing stirring for 10-20min to prepare a mixed solution B, adding sodium p-styrenesulfonate and deionized water into a three-neck flask, introducing nitrogen, heating to 55-65 ℃, stirring at a constant speed and dropwise adding the mixed solution B at the temperature, controlling the dropwise adding time to be 45-55min, stirring at a constant speed after the dropwise adding is finished, reacting for 8-12h, cooling after the reaction is finished, washing with absolute ethyl alcohol for three times, separating, and drying in vacuum to prepare a product C, and uniformly mixing the product A and the product C according to the weight ratio of 1: 1.8-2.2 to prepare a first polymer;
the composite auxiliary agent is prepared by the following method:
step S11, adding ferric nitrate nonahydrate into a beaker filled with deionized water, stirring at a constant speed for 10-20min, adding a sodium hydroxide solution with the concentration of 0.8-1.2mol/L to adjust the pH value until the pH value is =5-6, continuing stirring at a constant speed, adding oleic acid, heating to 110-;
step S12, adding formic acid into deionized water, heating to 45-60 ℃, stirring at a constant speed for 25-35min at the temperature, adding copper oxide, stirring at a constant speed of 300r/min at 200-.
Further preferably, the first polymer is prepared by the following method:
step S1, adding stearyl methacrylate into 10% sodium hydroxide aqueous solution by mass fraction, washing to be colorless, then washing to be neutral by deionized water, filtering, and drying for 20h at 60-75 ℃ to obtain refined stearyl methacrylate; heating ethanol with volume fraction of 95% in water bath until boiling, then adding azobisisobutyronitrile, stirring at a constant speed until the mixture is dissolved, filtering, cooling and crystallizing to obtain refined azobisisobutyronitrile;
step S2, sequentially adding refined octadecyl methacrylate, vinyl acetate and divinylbenzene into a three-neck flask filled with absolute ethyl alcohol, heating to 60-75 ℃, introducing nitrogen, magnetically stirring at the rotating speed of 150-;
step S3, adding butyl acrylate, styrene and toluene into a beaker, uniformly stirring at a rotating speed of 80-150r/min for 30min, then adding refined azobisisobutyronitrile, continuously stirring for 15min to obtain a mixed solution B, adding sodium p-styrenesulfonate and deionized water into a three-neck flask, introducing nitrogen, heating to 60 ℃, uniformly stirring at the temperature, dropwise adding the mixed solution B, controlling the dropwise adding time to be 50min, uniformly stirring and reacting for 10h after the dropwise adding is finished, cooling after the reaction is finished, washing with absolute ethyl alcohol for three times, separating, and drying in vacuum to obtain a product C, and uniformly mixing the product A and the product C according to a weight ratio of 1: 2 to obtain a first polymer.
Further preferably, the composite auxiliary agent is prepared by the following method:
step S11, adding ferric nitrate nonahydrate into a beaker filled with deionized water, stirring at a constant speed for 15min, adding a sodium hydroxide solution with the concentration of 1mol/L to adjust the pH value until the pH value is =5-6, continuing stirring at a constant speed and adding oleic acid, heating to 110-120 ℃, stirring at a constant speed of 200r/min and reacting for 3h, separating an oil phase and a water phase by using a separating funnel after the reaction is finished, collecting the oil phase, washing the oil phase for three times by using distilled water and n-heptane in sequence, then transferring to a vacuum drying box for drying for 20h, controlling the vacuum degree to be-0.10 MPa and the temperature to be 70-80 ℃, and preparing the auxiliary agent;
step S12, adding formic acid into deionized water, heating to 45-60 ℃, stirring at a constant speed for 30min at the temperature, adding copper oxide, stirring at a constant speed of 200-300r/min, heating to 65-75 ℃, reacting at the temperature for 2h, filtering while hot, placing the filtrate in a vacuum drying oven, drying at 50-70 ℃ for 10h to obtain a main agent, and uniformly mixing the auxiliary agent and the main agent according to the weight ratio of 3: 1 to obtain the composite auxiliary agent.
More preferably, in step S2, the weight ratio of the refined octadecyl methacrylate to the vinyl acetate to the divinylbenzene is controlled to be (2.8-3.2) to 0.5, the dosage of the refined azobisisobutyronitrile is 1.5-2.5 percent of the weight sum of the refined octadecyl methacrylate to the vinyl acetate to the divinylbenzene, the volume ratio of the butyl acrylate to the styrene to the toluene is controlled to be (18-22) to 5 to (18-22) in step S3, and the weight-volume ratio of the sodium p-styrenesulfonate to the deionized water to the mixed solution B is controlled to be 2.5g to (25-35) mL to (45-55) mL.
More preferably, the weight ratio of the refined octadecyl methacrylate, the vinyl acetate and the divinylbenzene is controlled to be 3: 0.5 in the step S2, the dosage of the refined azobisisobutyronitrile is 2% of the weight ratio of the refined octadecyl methacrylate, the vinyl acetate and the divinylbenzene, the volume ratio of the butyl acrylate, the styrene and the toluene is controlled to be 20: 5: 20 in the step S3, and the weight-volume ratio of the sodium p-styrenesulfonate, the deionized water and the mixed solution B is controlled to be 2.5 g: 30 mL: 50 mL.
It is further preferable that the molar ratio of the iron nitrate to the oleic acid is controlled to 1: (1.8-2.2) in step S11, and the molar ratio of the formic acid to the copper oxide is controlled to 2: (0.8-1.2) in step S12.
Still more preferably, the molar ratio of ferric nitrate to oleic acid is controlled to 1: 2 in step S11, and the molar ratio of formic acid to copper oxide is controlled to 2: 1 in step S12.
The invention has the beneficial effects that:
(1) the invention relates to an environment-friendly high-efficiency thick oil viscosity reducer which is prepared by mixing a first polymer and a composite auxiliary agent according to the weight ratio of (0.1-0.5) to 3, wherein in the preparation process of the first polymer, octadecyl methacrylate and azobisisobutyronitrile are respectively refined in step S1 for removing residual polymerization inhibitor in the octadecyl methacrylate and preventing the product from being influenced, then in step S2, refined octadecyl methacrylate, vinyl acetate and divinylbenzene are uniformly mixed and added with refined azobisisobutyronitrile as an initiator to prepare a product A, the molecule of the product A can penetrate into an asphaltene-colloid stacking structure in thick oil, the stacking structure is damaged by the aid of strong hydrogen bond forming capacity of a polar group, and wrapped light components are released to form a more dispersed structure and reduce viscosity, and in step S3, butyl acrylate and composite auxiliary agent are mixed, Styrene, toluene and other monomers are mixed, azobisisobutyronitrile is added as an initiator, sodium p-styrenesulfonate is added, a product C is prepared by an emulsion polymerization method, the product C is a butyl acrylate-styrene-sodium p-styrenesulfonate copolymer and has excellent hydrophilic and oleophilic properties, and then the product A and the product C are uniformly mixed according to the weight ratio of 1: 2 to prepare a first polymer, and the first polymer has excellent viscosity reduction performance.
(2) After the composite auxiliary agent is contacted with the heavy oil, iron ions and copper ions in the composite auxiliary agent can be contacted with heavy components in the oil, so that colloid in the heavy oil is subjected to series chain fracture, hydrogenation and denitrification, sulfur and other reactions, and further the aromatic ring structure is damaged, the macromolecule aggregation state is more dispersed, and further the large component is promoted to be converted to the small component, and further the viscosity is reduced, in addition, an oleic acid ligand can also enable the light component to be subjected to partial emulsification, the dispersing capacity for the heavy component is further increased, the viscosity is further reduced, and the viscosity reduction effect on the super-viscous oil can be improved and the using amount of a first polymer can be reduced by adding the composite auxiliary agent, the use of aromatic hydrocarbon substances is reduced, and the environment-friendly effect is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An environment-friendly high-efficiency thick oil viscosity reducer comprises a first polymer and a composite auxiliary agent;
the environment-friendly high-efficiency thick oil viscosity reducer is prepared by the following method:
the first polymer and the compound additive are uniformly mixed according to the weight ratio of 0.1: 3 to prepare the environment-friendly high-efficiency thick oil viscosity reducer.
The first polymer is made by the following method:
step S1, adding stearyl methacrylate into 10% sodium hydroxide aqueous solution by mass fraction, washing to be colorless, then washing to be neutral by deionized water, filtering, and drying for 20h at 60 ℃ to obtain refined stearyl methacrylate; heating ethanol with volume fraction of 95% in water bath until boiling, then adding azobisisobutyronitrile, stirring at a constant speed until the mixture is dissolved, filtering, cooling and crystallizing to obtain refined azobisisobutyronitrile;
step S2, adding refined octadecyl methacrylate, vinyl acetate and divinylbenzene into a three-neck flask filled with absolute ethyl alcohol in sequence, heating to 60 ℃, introducing nitrogen, magnetically stirring for 30min at the rotating speed of 150r/min, adding refined azobisisobutyronitrile after stirring, stirring at a constant speed and reacting for 4h to obtain a crude product, performing suction filtration, washing unreacted refined azobisisobutyronitrile with absolute ethyl alcohol, and then drying at 45 ℃ for 12h to obtain a product A, wherein the weight ratio of the refined octadecyl methacrylate to the vinyl acetate to the divinylbenzene is controlled to be 3: 0.5, and the dosage of the refined azobisisobutyronitrile is 2% of the sum of the weights of the refined octadecyl methacrylate, the vinyl acetate and the divinylbenzene;
step S3, adding butyl acrylate, styrene and toluene into a beaker, uniformly stirring at a rotating speed of 150r/min for 30min, then adding refined azobisisobutyronitrile, continuously stirring for 15min to obtain a mixed solution B, adding sodium p-styrenesulfonate and deionized water into a three-neck flask, introducing nitrogen, heating to 60 ℃, stirring at a constant speed and dripping the mixed solution B at the temperature, controlling the dripping time to be 50min, stirring at a constant speed and reacting for 10h after the dripping is finished, cooling after the reaction is finished, washing for three times by using absolute ethyl alcohol, separating and drying in vacuum to obtain a product C, uniformly mixing the product A and the product C according to the weight ratio of 1: 2 to obtain a first polymer, controlling the dosage ratio of butyl acrylate, styrene and toluene to be 20 mL: 5 mL: 20mL, the dosage ratio of the sodium p-styrene sulfonate, the deionized water and the mixed solution B is 2.5 g: 30 mL: 50 mL.
The composite additive is prepared by the following method:
step S11, adding ferric nitrate nonahydrate into a beaker filled with deionized water, stirring at a constant speed for 15min, adding a sodium hydroxide solution with the concentration of 1mol/L to adjust the pH value until the pH value is =5, continuing stirring at a constant speed and adding oleic acid, heating to 110 ℃, stirring at a constant speed of 150r/min and reacting for 3h, separating an oil phase and a water phase by using a separating funnel after the reaction is finished, collecting the oil phase, washing the oil phase for three times by using distilled water and n-heptane in sequence, then transferring to a vacuum drying oven to dry for 20h, controlling the vacuum degree to be-0.10 MPa and the temperature to be 70 ℃, preparing an auxiliary agent, and controlling the molar ratio of ferric nitrate to oleic acid to be 1: 2;
step S12, adding formic acid into deionized water, heating to 45 ℃, stirring at constant speed for 30min at the temperature, adding copper oxide, stirring at constant speed of 200r/min, heating to 65 ℃, reacting for 2h at the temperature, filtering while hot, placing the filtrate in a vacuum drying oven, drying at 50 ℃ for 10h to obtain a main agent, uniformly mixing the auxiliary agent and the main agent according to the weight ratio of 3: 1 to obtain a composite auxiliary agent, and controlling the molar ratio of formic acid to copper oxide to be 2: 1.
Example 2
An environment-friendly high-efficiency thick oil viscosity reducer comprises a first polymer and a composite auxiliary agent;
the environment-friendly high-efficiency thick oil viscosity reducer is prepared by the following method:
the first polymer and the compound additive are uniformly mixed according to the weight ratio of 0.2: 3 to prepare the environment-friendly high-efficiency thick oil viscosity reducer.
The first polymer is made by the following method:
step S1, adding stearyl methacrylate into an aqueous solution of sodium hydroxide with the mass fraction of 8% to wash until the mixture is colorless, then washing the mixture to be neutral by deionized water, filtering the mixture, and drying the mixture for 20 hours at the temperature of 60 ℃ to obtain refined stearyl methacrylate; heating ethanol with volume fraction of 95% in water bath until boiling, then adding azobisisobutyronitrile, stirring at a constant speed until the mixture is dissolved, filtering, cooling and crystallizing to obtain refined azobisisobutyronitrile;
step S2, adding refined octadecyl methacrylate, vinyl acetate and divinylbenzene into a three-neck flask filled with absolute ethyl alcohol in sequence, heating to 60 ℃, introducing nitrogen, magnetically stirring for 30min at the rotating speed of 150r/min, adding refined azobisisobutyronitrile after stirring, stirring at a constant speed and reacting for 4h to obtain a crude product, performing suction filtration, washing unreacted refined azobisisobutyronitrile with absolute ethyl alcohol, and then drying at 45 ℃ for 12h to obtain a product A, wherein the weight ratio of the refined octadecyl methacrylate to the vinyl acetate to the divinylbenzene is controlled to be 3: 0.5, and the dosage of the refined azobisisobutyronitrile is 2% of the sum of the weights of the refined octadecyl methacrylate, the vinyl acetate and the divinylbenzene;
step S3, adding butyl acrylate, styrene and toluene into a beaker, uniformly stirring at a rotating speed of 150r/min for 30min, then adding refined azobisisobutyronitrile, continuously stirring for 15min to obtain a mixed solution B, adding sodium p-styrenesulfonate and deionized water into a three-neck flask, introducing nitrogen, heating to 60 ℃, stirring at a constant speed and dripping the mixed solution B at the temperature, controlling the dripping time to be 50min, stirring at a constant speed and reacting for 10h after the dripping is finished, cooling after the reaction is finished, washing for three times by using absolute ethyl alcohol, separating and drying in vacuum to obtain a product C, uniformly mixing the product A and the product C according to the weight ratio of 1: 2 to obtain a first polymer, controlling the dosage ratio of butyl acrylate, styrene and toluene to be 20 mL: 5 mL: 20mL, the dosage ratio of the sodium p-styrene sulfonate, the deionized water and the mixed solution B is 2.5 g: 30 mL: 50 mL.
The composite additive is prepared by the following method:
step S11, adding ferric nitrate nonahydrate into a beaker filled with deionized water, stirring at a constant speed for 15min, adding a sodium hydroxide solution with the concentration of 1mol/L to adjust the pH value until the pH value is =5, continuing stirring at a constant speed and adding oleic acid, heating to 110 ℃, stirring at a constant speed of 150r/min and reacting for 3h, separating an oil phase and a water phase by using a separating funnel after the reaction is finished, collecting the oil phase, washing the oil phase for three times by using distilled water and n-heptane in sequence, then transferring to a vacuum drying oven to dry for 20h, controlling the vacuum degree to be-0.10 MPa and the temperature to be 70 ℃, preparing an auxiliary agent, and controlling the molar ratio of ferric nitrate to oleic acid to be 1: 2;
step S12, adding formic acid into deionized water, heating to 45 ℃, stirring at constant speed for 30min at the temperature, adding copper oxide, stirring at constant speed of 200r/min, heating to 65 ℃, reacting for 2h at the temperature, filtering while hot, placing the filtrate in a vacuum drying oven, drying at 50 ℃ for 10h to obtain a main agent, uniformly mixing the auxiliary agent and the main agent according to the weight ratio of 3: 1 to obtain a composite auxiliary agent, and controlling the molar ratio of formic acid to copper oxide to be 2: 1.
Example 3
An environment-friendly high-efficiency thick oil viscosity reducer comprises a first polymer and a composite auxiliary agent;
the environment-friendly high-efficiency thick oil viscosity reducer is prepared by the following method:
the first polymer and the compound additive are uniformly mixed according to the weight ratio of 0.4: 3 to prepare the environment-friendly high-efficiency thick oil viscosity reducer.
The first polymer is made by the following method:
step S1, adding stearyl methacrylate into 10% sodium hydroxide aqueous solution by mass fraction, washing to be colorless, then washing to be neutral by deionized water, filtering, and drying for 20h at 60 ℃ to obtain refined stearyl methacrylate; heating ethanol with volume fraction of 95% in water bath until boiling, then adding azobisisobutyronitrile, stirring at a constant speed until the mixture is dissolved, filtering, cooling and crystallizing to obtain refined azobisisobutyronitrile;
step S2, adding refined octadecyl methacrylate, vinyl acetate and divinylbenzene into a three-neck flask filled with absolute ethyl alcohol in sequence, heating to 60 ℃, introducing nitrogen, magnetically stirring for 30min at the rotating speed of 150r/min, adding refined azobisisobutyronitrile after stirring, stirring at a constant speed and reacting for 4h to obtain a crude product, performing suction filtration, washing unreacted refined azobisisobutyronitrile with absolute ethyl alcohol, and then drying at 45 ℃ for 12h to obtain a product A, wherein the weight ratio of the refined octadecyl methacrylate to the vinyl acetate to the divinylbenzene is controlled to be 3: 0.5, and the dosage of the refined azobisisobutyronitrile is 2% of the sum of the weights of the refined octadecyl methacrylate, the vinyl acetate and the divinylbenzene;
step S3, adding butyl acrylate, styrene and toluene into a beaker, uniformly stirring at a rotating speed of 150r/min for 30min, then adding refined azobisisobutyronitrile, continuously stirring for 15min to obtain a mixed solution B, adding sodium p-styrenesulfonate and deionized water into a three-neck flask, introducing nitrogen, heating to 60 ℃, stirring at a constant speed and dripping the mixed solution B at the temperature, controlling the dripping time to be 50min, stirring at a constant speed and reacting for 10h after the dripping is finished, cooling after the reaction is finished, washing for three times by using absolute ethyl alcohol, separating and drying in vacuum to obtain a product C, uniformly mixing the product A and the product C according to the weight ratio of 1: 2 to obtain a first polymer, controlling the dosage ratio of butyl acrylate, styrene and toluene to be 20 mL: 5 mL: 20mL, the dosage ratio of the sodium p-styrene sulfonate, the deionized water and the mixed solution B is 2.5 g: 30 mL: 50 mL.
The composite additive is prepared by the following method:
step S11, adding ferric nitrate nonahydrate into a beaker filled with deionized water, stirring at a constant speed for 15min, adding a sodium hydroxide solution with the concentration of 1mol/L to adjust the pH value until the pH value is =5, continuing stirring at a constant speed and adding oleic acid, heating to 110 ℃, stirring at a constant speed of 150r/min and reacting for 3h, separating an oil phase and a water phase by using a separating funnel after the reaction is finished, collecting the oil phase, washing the oil phase for three times by using distilled water and n-heptane in sequence, then transferring to a vacuum drying oven to dry for 20h, controlling the vacuum degree to be-0.10 MPa and the temperature to be 70 ℃, preparing an auxiliary agent, and controlling the molar ratio of ferric nitrate to oleic acid to be 1: 2;
step S12, adding formic acid into deionized water, heating to 45 ℃, stirring at constant speed for 30min at the temperature, adding copper oxide, stirring at constant speed of 200r/min, heating to 65 ℃, reacting for 2h at the temperature, filtering while hot, placing the filtrate in a vacuum drying oven, drying at 50 ℃ for 10h to obtain a main agent, uniformly mixing the auxiliary agent and the main agent according to the weight ratio of 3: 1 to obtain a composite auxiliary agent, and controlling the molar ratio of formic acid to copper oxide to be 2: 1.
Example 4
An environment-friendly high-efficiency thick oil viscosity reducer comprises a first polymer and a composite auxiliary agent;
the environment-friendly high-efficiency thick oil viscosity reducer is prepared by the following method:
the first polymer and the compound additive are uniformly mixed according to the weight ratio of 0.5: 3 to prepare the environment-friendly high-efficiency thick oil viscosity reducer.
The first polymer is made by the following method:
step S1, adding stearyl methacrylate into 10% sodium hydroxide aqueous solution by mass fraction, washing to be colorless, then washing to be neutral by deionized water, filtering, and drying for 20h at 60 ℃ to obtain refined stearyl methacrylate; heating ethanol with volume fraction of 95% in water bath until boiling, then adding azobisisobutyronitrile, stirring at a constant speed until the mixture is dissolved, filtering, cooling and crystallizing to obtain refined azobisisobutyronitrile;
step S2, adding refined octadecyl methacrylate, vinyl acetate and divinylbenzene into a three-neck flask filled with absolute ethyl alcohol in sequence, heating to 60 ℃, introducing nitrogen, magnetically stirring for 30min at the rotating speed of 150r/min, adding refined azobisisobutyronitrile after stirring, stirring at a constant speed and reacting for 4h to obtain a crude product, performing suction filtration, washing unreacted refined azobisisobutyronitrile with absolute ethyl alcohol, and then drying at 45 ℃ for 12h to obtain a product A, wherein the weight ratio of the refined octadecyl methacrylate to the vinyl acetate to the divinylbenzene is controlled to be 3: 0.5, and the dosage of the refined azobisisobutyronitrile is 2% of the sum of the weights of the refined octadecyl methacrylate, the vinyl acetate and the divinylbenzene;
step S3, adding butyl acrylate, styrene and toluene into a beaker, uniformly stirring at a rotating speed of 150r/min for 30min, then adding refined azobisisobutyronitrile, continuously stirring for 15min to obtain a mixed solution B, adding sodium p-styrenesulfonate and deionized water into a three-neck flask, introducing nitrogen, heating to 60 ℃, stirring at a constant speed and dripping the mixed solution B at the temperature, controlling the dripping time to be 50min, stirring at a constant speed and reacting for 10h after the dripping is finished, cooling after the reaction is finished, washing for three times by using absolute ethyl alcohol, separating and drying in vacuum to obtain a product C, uniformly mixing the product A and the product C according to the weight ratio of 1: 2 to obtain a first polymer, controlling the dosage ratio of butyl acrylate, styrene and toluene to be 20 mL: 5 mL: 20mL, the dosage ratio of the sodium p-styrene sulfonate, the deionized water and the mixed solution B is 2.5 g: 30 mL: 50 mL.
The composite additive is prepared by the following method:
step S11, adding ferric nitrate nonahydrate into a beaker filled with deionized water, stirring at a constant speed for 15min, adding a sodium hydroxide solution with the concentration of 1mol/L to adjust the pH value until the pH value is =5, continuing stirring at a constant speed and adding oleic acid, heating to 110 ℃, stirring at a constant speed of 150r/min and reacting for 3h, separating an oil phase and a water phase by using a separating funnel after the reaction is finished, collecting the oil phase, washing the oil phase for three times by using distilled water and n-heptane in sequence, then transferring to a vacuum drying oven to dry for 20h, controlling the vacuum degree to be-0.10 MPa and the temperature to be 70 ℃, preparing an auxiliary agent, and controlling the molar ratio of ferric nitrate to oleic acid to be 1: 2;
step S12, adding formic acid into deionized water, heating to 45 ℃, stirring at constant speed for 30min at the temperature, adding copper oxide, stirring at constant speed of 200r/min, heating to 65 ℃, reacting for 2h at the temperature, filtering while hot, placing the filtrate in a vacuum drying oven, drying at 50 ℃ for 10h to obtain a main agent, uniformly mixing the auxiliary agent and the main agent according to the weight ratio of 3: 1 to obtain a composite auxiliary agent, and controlling the molar ratio of formic acid to copper oxide to be 2: 1.
Comparative example 1
This comparative example compares to example 1, where a first polymer was made from product a, and was prepared as follows:
step S1, adding stearyl methacrylate into 10% sodium hydroxide aqueous solution by mass fraction, washing to be colorless, then washing to be neutral by deionized water, filtering, and drying for 20h at 60 ℃ to obtain refined stearyl methacrylate; heating ethanol with volume fraction of 95% in water bath until boiling, then adding azobisisobutyronitrile, stirring at a constant speed until the mixture is dissolved, filtering, cooling and crystallizing to obtain refined azobisisobutyronitrile;
and step S2, adding refined octadecyl methacrylate, vinyl acetate and divinylbenzene into a three-neck flask filled with absolute ethyl alcohol in sequence, heating to 60 ℃, introducing nitrogen, magnetically stirring for 30min at the rotating speed of 150r/min, adding refined azobisisobutyronitrile after stirring, stirring at a constant speed and reacting for 4h to obtain a crude product, performing suction filtration, washing unreacted refined azobisisobutyronitrile with absolute ethyl alcohol, and drying at 45 ℃ for 12h to obtain a product A, wherein the weight ratio of the refined octadecyl methacrylate to the vinyl acetate to the divinylbenzene is controlled to be 3: 0.5, and the dosage of the refined azobisisobutyronitrile is 2% of the sum of the weights of the refined octadecyl methacrylate, the vinyl acetate and the divinylbenzene.
Comparative example 2
Compared with example 1, the composite additive is not added in the comparative example.
Comparative example 3
The comparative example is a LDPS heavy oil viscosity reducer sold in the market.
The viscosity-reducing properties of examples 1 to 4 and comparative examples 1 to 3 were examined;
seven groups of thick oil with the viscosity of 40000 mPas and 50000 mPas are weighed respectively and 100g of each thick oil is added with the thick oil viscosity reducer prepared in the examples 1-4 and the comparative examples 1-3 and 1.3mL of toluene with the total mass of the thick oil being 0.5wt%, the viscosity of the thick oil after viscosity reduction is measured, and the viscosity reduction rate is calculated, and the results are shown in the following tables 1 and 2:
the viscosity reduction was carried out on thick oil having a viscosity of 40000 mPas, and the results are shown in the following Table 1:
TABLE 1
The viscosity reduction was carried out on a viscous oil having a viscosity of 50000 mPas, and the results are shown in the following Table 2:
TABLE 2
As can be seen from the above table, the viscosity reduction rate of the thick oil having a viscosity of 40000 mPas was 57.25 to 57.75% for examples 1 to 4, and 53.0 to 54.5% for comparative examples 1 to 3; the viscosity reduction rate of the thick oil with the viscosity of 50000 mPas is 64.2-64.4% in examples 1-4, and is 62.2-62.5% in comparative examples 1-3; the molecule of the product A can permeate into an asphaltene-colloid stacking structure in thick oil, the stacking structure is damaged by the strong hydrogen bond forming capability of a polar group, the wrapped light component is released, a dispersed structure is formed, the viscosity is reduced, monomers such as butyl acrylate, styrene and toluene are mixed in the step S3, azobisisobutyronitrile is added as an initiator, sodium styrene sulfonate is added, and a product C is prepared by an emulsion polymerization method, wherein the product C is a butyl acrylate-styrene-sodium styrene sulfonate copolymer and has excellent hydrophilic and lipophilic properties, and then the product A and the product C are uniformly mixed according to the weight ratio of 1: 2 to prepare a first polymer which has excellent viscosity reduction performance.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (6)
1. An environment-friendly efficient thick oil viscosity reducer is characterized by comprising a first polymer and a composite auxiliary agent;
the environment-friendly high-efficiency thick oil viscosity reducer is prepared by the following method:
uniformly mixing the first polymer and the composite auxiliary agent according to the weight ratio of (0.1-0.5) to 3 to prepare the environment-friendly high-efficiency thick oil viscosity reducer;
the first polymer is made by the following method:
step S1, adding stearyl methacrylate into an aqueous solution of sodium hydroxide with the mass fraction of 8-12% to wash until the mixture is colorless, then washing the mixture to be neutral by deionized water, filtering the mixture, and drying the mixture for 18-22h at the temperature of 60-75 ℃ to obtain refined stearyl methacrylate; heating 94-96% ethanol by volume fraction in water bath until boiling, adding azobisisobutyronitrile, stirring at a constant speed until the mixture is dissolved, filtering, cooling and crystallizing to obtain refined azobisisobutyronitrile;
step S2, adding refined octadecyl methacrylate, vinyl acetate and divinyl benzene into a three-neck flask filled with absolute ethyl alcohol in sequence, heating to 60-75 ℃, introducing nitrogen, magnetically stirring at the rotating speed of 150 plus 200r/min for 25-35min, adding refined azobisisobutyronitrile after stirring, stirring at constant speed and reacting for 3-5h to obtain a crude product, performing suction filtration, washing unreacted refined azobisisobutyronitrile with absolute ethyl alcohol, and then drying at the temperature of 45-60 ℃ for 11-13h to obtain a product A, wherein the weight ratio of the refined octadecyl methacrylate to the vinyl acetate to the divinyl benzene is controlled to be (2.8-3.2) to 0.5, and the dosage of the refined azobisisobutyronitrile is 1.5-2.5% of the sum of the weight of the refined octadecyl methacrylate to the vinyl acetate to the divinyl benzene;
s3, adding butyl acrylate, styrene and toluene into a beaker, stirring at a constant speed of 80-150r/min for 25-35min, adding refined azobisisobutyronitrile, continuing stirring for 10-20min to prepare a mixed solution B, adding sodium p-styrene sulfonate and deionized water into a three-neck flask, introducing nitrogen, heating to 55-65 ℃, stirring at a constant speed and dropwise adding the mixed solution B at the temperature, controlling the dropwise adding time to be 45-55min, stirring at a constant speed after dropwise adding and reacting for 8-12h, cooling after the reaction is finished, washing with absolute ethyl alcohol for three times, separating, drying in vacuum to prepare a product C, uniformly mixing the product A and the product C according to the weight ratio of 1: 1.8-2.2 to prepare a first polymer, controlling the volume ratio of the butyl acrylate, the styrene and the toluene to be (18-22) to 5: 18-22), the weight volume ratio of the sodium p-styrene sulfonate, the deionized water and the mixed solution B is 2.5g to (25-35) mL to (45-55) mL;
the composite auxiliary agent is prepared by the following method:
step S11, adding ferric nitrate nonahydrate into a beaker filled with deionized water, stirring at a constant speed for 10-20min, adding a sodium hydroxide solution with the concentration of 0.8-1.2mol/L to adjust the pH value until the pH value is =5-6, continuing stirring at a constant speed, adding oleic acid, heating to 110-;
step S12, adding formic acid into deionized water, heating to 45-60 ℃, stirring at a constant speed for 25-35min at the temperature, adding copper oxide, stirring at a constant speed of 300r/min at 200-.
2. The environment-friendly efficient thick oil viscosity reducer as claimed in claim 1, wherein the first polymer is prepared by the following method:
step S1, adding stearyl methacrylate into 10% sodium hydroxide aqueous solution by mass fraction, washing to be colorless, then washing to be neutral by deionized water, filtering, and drying for 20h at 60-75 ℃ to obtain refined stearyl methacrylate; heating ethanol with volume fraction of 95% in water bath until boiling, then adding azobisisobutyronitrile, stirring at a constant speed until the mixture is dissolved, filtering, cooling and crystallizing to obtain refined azobisisobutyronitrile;
step S2, sequentially adding refined octadecyl methacrylate, vinyl acetate and divinylbenzene into a three-neck flask filled with absolute ethyl alcohol, heating to 60-75 ℃, introducing nitrogen, magnetically stirring at the rotating speed of 150-;
step S3, adding butyl acrylate, styrene and toluene into a beaker, uniformly stirring at a rotating speed of 80-150r/min for 30min, then adding refined azobisisobutyronitrile, continuously stirring for 15min to obtain a mixed solution B, adding sodium p-styrenesulfonate and deionized water into a three-neck flask, introducing nitrogen, heating to 60 ℃, uniformly stirring at the temperature, dropwise adding the mixed solution B, controlling the dropwise adding time to be 50min, uniformly stirring and reacting for 10h after the dropwise adding is finished, cooling after the reaction is finished, washing with absolute ethyl alcohol for three times, separating, and drying in vacuum to obtain a product C, and uniformly mixing the product A and the product C according to a weight ratio of 1: 2 to obtain a first polymer.
3. The environment-friendly efficient thick oil viscosity reducer as claimed in claim 1, wherein the compound auxiliary is prepared by the following method:
step S11, adding ferric nitrate nonahydrate into a beaker filled with deionized water, stirring at a constant speed for 15min, adding a sodium hydroxide solution with the concentration of 1mol/L to adjust the pH value until the pH value is =5-6, continuing stirring at a constant speed and adding oleic acid, heating to 110-120 ℃, stirring at a constant speed of 200r/min and reacting for 3h, separating an oil phase and a water phase by using a separating funnel after the reaction is finished, collecting the oil phase, washing the oil phase for three times by using distilled water and n-heptane in sequence, then transferring to a vacuum drying box for drying for 20h, controlling the vacuum degree to be-0.10 MPa and the temperature to be 70-80 ℃, and preparing the auxiliary agent;
step S12, adding formic acid into deionized water, heating to 45-60 ℃, stirring at a constant speed for 30min at the temperature, adding copper oxide, stirring at a constant speed of 200-300r/min, heating to 65-75 ℃, reacting at the temperature for 2h, filtering while hot, placing the filtrate in a vacuum drying oven, drying at 50-70 ℃ for 10h to obtain a main agent, and uniformly mixing the auxiliary agent and the main agent according to the weight ratio of 3: 1 to obtain the composite auxiliary agent.
4. The environment-friendly high-efficiency viscosity reducer for thick oil as claimed in claim 1, wherein the weight ratio of the refined stearyl methacrylate, the vinyl acetate and the divinylbenzene is controlled to be 3: 0.5 in step S2, the dosage of the refined azobisisobutyronitrile is 2% of the total weight of the refined stearyl methacrylate, the vinyl acetate and the divinylbenzene, the volume ratio of the butyl acrylate, the styrene and the toluene is controlled to be 20: 5: 20 in step S3, and the weight-volume ratio of the sodium p-styrenesulfonate, the deionized water and the mixed solution B is 2.5 g: 30 mL: 50 mL.
5. The environment-friendly efficient viscosity reducer for thick oil according to claim 3, wherein the molar ratio of ferric nitrate to oleic acid is controlled to be 1: 1.8-2.2 in step S11, and the molar ratio of formic acid to copper oxide is controlled to be 2: 0.8-1.2 in step S12.
6. The environment-friendly efficient viscosity reducer for thick oil according to claim 3, wherein the molar ratio of ferric nitrate to oleic acid is controlled to be 1: 2 in step S11, and the molar ratio of formic acid to copper oxide is controlled to be 2: 1 in step S12.
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