CN112430459A - Preparation method of high-temperature-resistant thick oil viscosity reducer - Google Patents
Preparation method of high-temperature-resistant thick oil viscosity reducer Download PDFInfo
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- CN112430459A CN112430459A CN202110114344.5A CN202110114344A CN112430459A CN 112430459 A CN112430459 A CN 112430459A CN 202110114344 A CN202110114344 A CN 202110114344A CN 112430459 A CN112430459 A CN 112430459A
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 165
- 238000010438 heat treatment Methods 0.000 claims abstract description 59
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 42
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 27
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 27
- 239000003208 petroleum Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 132
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 102
- 239000000243 solution Substances 0.000 claims description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 69
- 229920001577 copolymer Polymers 0.000 claims description 64
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- 239000000047 product Substances 0.000 claims description 55
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 48
- 239000008367 deionised water Substances 0.000 claims description 47
- 229910021641 deionized water Inorganic materials 0.000 claims description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 38
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 36
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 36
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- 229960001124 trientine Drugs 0.000 claims description 32
- 239000003999 initiator Substances 0.000 claims description 27
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 26
- 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 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 22
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 22
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 239000007795 chemical reaction product Substances 0.000 claims description 20
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000013329 compounding Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 10
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- UFQDKRWQSFLPQY-UHFFFAOYSA-N 4,5-dihydro-1h-imidazol-3-ium;chloride Chemical compound Cl.C1CN=CN1 UFQDKRWQSFLPQY-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000000693 micelle Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 47
- 239000007864 aqueous solution Substances 0.000 description 20
- 239000012141 concentrate Substances 0.000 description 12
- 239000012043 crude product Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
- 239000000295 fuel oil Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000004434 sulfur atom Chemical group 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 229920003118 cationic copolymer Polymers 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
-
- 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
- C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/28—Condensation with aldehydes or ketones
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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (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)
Abstract
The invention belongs to the field of petroleum development, and particularly discloses a preparation method of a high-temperature-resistant thick oil viscosity reducer, which comprises the following raw materials in parts by weight: 15-35 parts of main agent, 10-15 parts of auxiliary agent, 55-80 parts of solvent and 5-10 parts of ethylene-vinyl acetate copolymer; the preparation method comprises the following steps: adding ethylene-vinyl acetate copolymer into a solvent, stirring at a constant speed at 45-55 ℃ until the ethylene-vinyl acetate copolymer is completely dissolved, then sequentially adding a main agent and an auxiliary agent, heating to 60-65 ℃, stirring at a constant speed at the temperature, and ultrasonically dispersing for 4 +/-0.5 h, wherein the ultrasonic power is controlled to be 60-80W, so as to prepare the high-temperature resistant thick oil viscosity reducer; the invention can reduce the particle size of asphaltene micelle, improve the dispersity and further reduce the viscosity of the thickened oil by preparing the assistant containing the amphiprotic high polymer and adding the assistant into the thickened oil.
Description
Technical Field
The invention relates to a thick oil viscosity reducer, in particular to a preparation method of a high-temperature-resistant thick oil viscosity reducer.
Background
The heavy oil is rich in colloid and asphaltene, contains more elements such as sulfur, oxygen, nitrogen and the like and metal compounds such as nickel, vanadium and the like, has low light fraction content, and the light fraction (300 ℃) of crude oil produced by a plurality of heavy oil fields is generally only about 10 percent. The paraffin content in the heavy oil is generally lower, and the paraffin content in the crude oil of most heavy oil fields is only about 5 percent and generally does not exceed 10 percent, so the freezing point is also lower. As the gum and asphaltene content increases, the density and viscosity of the thickened oil increases.
For common oil reservoirs, viscosity reducers, whether of the polymer or surfactant type, have the capacity of large-scale production. However, for a relatively extreme high-temperature oil reservoir, the structure of the chemical agent is very easy to change under an extreme environment, and finally the viscosity reducer cannot achieve the due effect.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a preparation method of a high-temperature-resistant thick oil viscosity reducer.
The purpose of the invention can be realized by the following technical scheme:
the preparation method of the high-temperature-resistant thick oil viscosity reducer comprises the following raw materials in parts by weight: 15-35 parts of main agent, 10-15 parts of auxiliary agent, 55-80 parts of solvent and 5-10 parts of ethylene-vinyl acetate copolymer;
the high-temperature resistant thick oil viscosity reducer is prepared by the following method:
adding ethylene-vinyl acetate copolymer into a solvent, stirring at a constant speed at 45-55 ℃ until the ethylene-vinyl acetate copolymer is completely dissolved, then sequentially adding a main agent and an auxiliary agent, heating to 60-65 ℃, stirring at a constant speed at the temperature, and ultrasonically dispersing for 4 +/-0.5 h, wherein the ultrasonic power is controlled to be 60-80W, so as to prepare the high-temperature resistant thick oil viscosity reducer;
the main agent is prepared by the following method:
step S1, adding maleic anhydride into a reaction container, adding deionized water according to the weight ratio of 1: 9-11, heating to 60-75 ℃, introducing nitrogen into the water, stirring at a constant speed of 200r/min at 150-, then vacuum drying is carried out for 20 plus or minus 2 hours at the temperature of 80 plus or minus 2 ℃, and a product A is prepared; controlling the weight ratio of maleic anhydride, 2-acrylamide-2-methylpropanesulfonic acid to ammonium persulfate to be (1.4-1.6) to 1 to (0.04-0.06);
step S2, adding the mixed solution a into a reaction container, adding ethylenediamine, uniformly stirring for 35-45min, placing the mixture into an ice water bath, dropwise adding carbon disulfide into the reaction container, heating to 30 +/-2 ℃ after dropwise adding, uniformly stirring at a speed of 100 plus or minus one minute at 200r/min at the temperature, reacting for 2 +/-0.5 h, carrying out suction filtration on a reaction product, washing for 2-3 times by using absolute ethyl alcohol, carrying out vacuum drying at 40 +/-2 ℃ to constant weight to obtain a product B, compounding the product A and the product B according to the weight ratio of (4-6) to 1 to prepare a main agent, and controlling the weight ratio of the ethylenediamine to the carbon disulfide to be 1 to (1.8-2.2); the mixed solution a is formed by mixing ethanol and water according to the weight ratio of 1: 1.8-2.2;
the auxiliary agent is prepared by the following method:
step S11, adding dimethyldiallylammonium chloride into deionized water, and stirring at a constant speed to prepare a solution b with the mass fraction of 40 +/-2%; adding acrylamide into deionized water, and stirring at a constant speed to prepare a solution c with the mass fraction of 15 +/-1%; adding the solution b and a half of the solution C into a reaction container, introducing nitrogen to discharge oxygen, heating to 45-65 ℃, uniformly stirring and adding an initiator, uniformly stirring and dropwise adding the rest solution C, controlling the dropwise adding time to be 15 +/-2 min, uniformly stirring and reacting for 4 +/-0.5 h, adding a reaction product into anhydrous acetone after the reaction is finished for precipitation to obtain a copolymer C, and controlling the weight ratio of the dimethyldiallylammonium chloride to the initiator to be (9-11) to (0.45-0.55) to (0.04-0.06);
step S12, adding the copolymer C into deionized water, stirring at a constant speed to prepare a solution D with the mass fraction of 10 +/-1%, then dropwise adding a sodium hydroxide solution with the mass fraction of 15 +/-1% to adjust the pH until the pH is =10 +/-0.5, then adding formaldehyde, heating to 40-60 ℃, stirring at a constant speed to react for 1 +/-0.5 h, adding triethylene tetramine after the reaction is finished, stirring at a constant speed to react for 2 +/-0.5 h to prepare a copolymer D, and controlling the weight ratio of the copolymer C to the formaldehyde to the triethylene tetramine to be (9-11) to (0.09-0.11) to (0.1-0.11);
step S13, cooling the copolymer D prepared in the step S12 to 30 +/-2 ℃, then adding sodium hydroxide, dropwise adding carbon disulfide after uniformly stirring for 30 +/-5 min, controlling the dropwise adding time to be 30 +/-5 min, uniformly stirring at the temperature of 100 plus one year and 150r/min after the dropwise adding is finished, reacting for 4 +/-0.5 h, then heating to 50-60 ℃, uniformly stirring at the speed of 200 plus one year and 300r/min, reacting for 2 +/-0.5 h, adding the product into acetone after the reaction is finished, precipitating, filtering, washing, and performing vacuum drying at 40-60 ℃ for 4 +/-0.5 h to prepare the auxiliary agent; controlling the weight ratio of triethylene tetramine to sodium hydroxide to carbon disulfide to be (1.15-1.25) to 1 to (3-4)
Further, the solvent is composed of petroleum fractions at 140-200 ℃, and is preferably 200# solvent oil.
Further preferably, the main agent is prepared by the following method:
step S1, adding maleic anhydride into a three-neck flask, adding deionized water according to the weight ratio of 1: 10, heating to 60-75 ℃, introducing nitrogen into the water, stirring at a constant speed of 200r/min at 150-, controlling the weight ratio of the maleic anhydride, the 2-acrylamide-2-methylpropanesulfonic acid and the ammonium persulfate to be 1.5: 1: 0.05;
step S2, adding the mixed solution a into a three-neck flask, adding ethylenediamine, stirring at a constant speed for 35-45min, placing in an ice water bath, dropwise adding carbon disulfide into the three-neck flask, heating to 30 ℃ after dropwise adding, stirring at a constant speed of 100 plus one liter of water/min at the temperature, reacting for 2h, performing suction filtration on a reaction product, washing for 2-3 times with absolute ethyl alcohol, performing vacuum drying at 40 ℃ to constant weight to obtain a product B, compounding the product A and the product B according to a weight ratio of 5: 1 to obtain a main agent, and controlling the weight ratio of the ethylenediamine to the carbon disulfide to be 1: 2.
In the step S1, maleic anhydride and 2-acrylamide-2-methylpropanesulfonic acid are mixed in an aqueous solution, ammonium persulfate is added to serve as an initiator, the 2-acrylamide-2-methylpropanesulfonic acid has a sulfonic group, a vinyl group and a secondary amide bond, a sulfur atom electron loss on the sulfonic group can attract anions and multiple electron groups to form a stable conjugated system, so that the heat resistance of a main agent prepared through the maleic anhydride can be improved, the maleic anhydride has a carbon-carbon double bond and an anhydride structure, when the maleic anhydride is mixed with the 2-acrylamide-2-methylpropanesulfonic acid, a polymerization reaction is carried out to generate a product A, the product A has high negative charge density, multi-point adsorption can be formed, the adsorption strength is enhanced, the viscosity of the thick oil is reduced, and then the ethylenediamine and the carbon disulfide are mixed to react in the step S2, and preparing a product B, wherein the product B contains a sulfur atom, a functional group has the characteristic that the sulfur atom presents soft alkali, most heavy metals belong to soft acid or interfacial acid, and the soft acid or interfacial acid and the interfacial acid are combined to form a stable chelate through a coordination bond, so that the main agent can reduce the viscosity of the heavy oil, can also carry out complexation on the metals in the heavy metal heavy oil, and further solves the technical problems of large viscosity of the heavy oil and difficulty in viscosity reduction.
Further, the mixed solution a is formed by mixing ethanol and water according to the weight ratio of 1: 2.
Further preferably, the auxiliary agent is prepared by the following method:
step S11, adding dimethyl diallyl ammonium chloride into deionized water, and stirring at a constant speed to prepare a solution b with the mass fraction of 40%; adding acrylamide into deionized water, and stirring at a constant speed to prepare a solution c with the mass fraction of 15%; adding the solution b and a half of the solution C into a three-neck flask, introducing nitrogen to discharge oxygen, heating to 45-65 ℃, uniformly stirring and adding an initiator, uniformly stirring and dropwise adding the rest solution C, controlling the dropwise adding time to be 15min, uniformly stirring and reacting for 4h, adding a reaction product into anhydrous acetone after the reaction is finished for precipitation to prepare a copolymer C, and controlling the weight ratio of the dimethyl diallyl ammonium chloride to the acrylamide to the initiator to be 10: 0.5: 0.05;
step S12, adding the copolymer C into deionized water, stirring at a constant speed to prepare a solution D with the mass fraction of 10%, then dropwise adding a sodium hydroxide solution with the mass fraction of 15% to adjust the pH until the pH is =10, then adding formaldehyde, heating to 40-60 ℃, stirring at a constant speed to react for 1h, adding triethylene tetramine after the reaction is finished, stirring at a constant speed to react for 2h to prepare a copolymer D, and controlling the weight ratio of the copolymer C to the formaldehyde to the triethylene tetramine to be 10: 0.1;
and S13, cooling the copolymer D prepared in the step S12 to 30 ℃, adding sodium hydroxide, dropwise adding carbon disulfide after uniformly stirring for 30min, controlling the dropwise adding time to be 30min, stirring at a constant speed of 150r/min and reacting for 4h at the temperature after dropwise adding, heating to 50-60 ℃, stirring at a constant speed of 300r/min and reacting for 2h at a constant speed of 200-.
Mixing dimethyldiallylammonium chloride and acrylamide in step S11, adding an initiator, polymerizing the dimethyldiallylammonium chloride and the acrylamide to generate a copolymer C, wherein the copolymer C is a cationic copolymer, then mixing the copolymer C with formaldehyde in an alkaline environment in step S12, adding triethylene tetramine to prepare a copolymer D, the copolymer D is a polymer grafted by the triethylene tetramine, mixing the copolymer D with carbon disulfide under an alkaline condition in step S13, and carrying out xanthation reaction on the copolymer D and the carbon disulfide to prepare an auxiliary agent, wherein the auxiliary agent is an amphoteric polymer and simultaneously contains positive and negative charges; the invention can reduce the particle size of asphaltene micelle, improve the dispersity and further reduce the viscosity of the thickened oil by preparing the assistant containing the amphiprotic high polymer and adding the assistant into the thickened oil.
Further, the initiator is azodiisopropyl imidazoline hydrochloride.
The invention has the beneficial effects that:
(1) the invention relates to a high-temperature-resistant viscosity reducer for thick oil, which comprises a main agent, an auxiliary agent and the like, wherein in the preparation process of the main agent, in a step S1, maleic anhydride and 2-acrylamide-2-methylpropanesulfonic acid are mixed in an aqueous solution, ammonium persulfate is added to serve as an initiator, the 2-acrylamide-2-methylpropanesulfonic acid has a sulfonic acid group, a vinyl group and a secondary amide bond, a sulfur atom electron loss on the sulfonic acid group can attract anions and multi-electron groups to form a stable conjugated system, so that the heat resistance of the main agent prepared by the high-temperature-resistant viscosity reducer can be improved, the maleic anhydride has a carbon-carbon double bond and an anhydride structure, the main agent is subjected to polymerization reaction after being mixed with the 2-acrylamide-2-methylpropanesulfonic acid to generate a product A, the product A has higher negative charge density and can form multi-point adsorption, the adsorption strength is enhanced, the viscosity of the thick oil is further reduced, then in the step S2, ethylenediamine and carbon disulfide are mixed and react to prepare a product B, the product B contains sulfur atoms, the functional group has the characteristic that the sulfur atoms present soft alkali, most heavy metals belong to soft acid or borderline acid, and the soft acid and the borderline acid are combined through coordination bonds to form a stable chelate, so that the main agent can reduce the viscosity of the thick oil and can also complex metals in the heavy metal thick oil, the technical problems that the thick oil containing the heavy metals is high in viscosity and difficult to reduce the viscosity are further solved, and the prepared main agent has excellent heat resistance and endows the prepared viscosity reducer with certain high temperature resistance.
(2) The invention prepares an auxiliary agent, in the preparation process, in step S11, dimethyldiallylammonium chloride and acrylamide are mixed, an initiator is added, dimethyldiallylammonium chloride and acrylamide are polymerized to generate a copolymer C, the copolymer C is a cationic copolymer, then in step S12, the copolymer C is mixed with formaldehyde in an alkaline environment, triethylene tetramine is added to prepare a copolymer D, the copolymer D is a polymer grafted by the triethylene tetramine, in step S13, the copolymer D is mixed with carbon disulfide under an alkaline condition, and the copolymer D and the carbon disulfide generate xanthation reaction to prepare the auxiliary agent, wherein the auxiliary agent is an amphoteric polymer and simultaneously contains positive and negative charges; the invention can reduce the particle size of asphaltene micelle, improve the dispersity and further reduce the viscosity of the thickened oil by preparing the assistant containing the amphiprotic high polymer and adding the assistant into the thickened oil.
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.
In the following examples, the starting materials were selected from the conventional commercial products, and the initiator was selected from the azodiisopropylimidazoline hydrochloride, unless otherwise specified.
Example 1
The high-temperature-resistant thick oil viscosity reducer comprises the following raw materials in parts by weight: 15 parts of a main agent, 10 parts of an auxiliary agent, 55 parts of a solvent and 5 parts of an ethylene-vinyl acetate copolymer;
the high-temperature resistant thick oil viscosity reducer is prepared by the following method:
adding ethylene-vinyl acetate copolymer into a solvent, stirring at a constant speed at 45 ℃ until the ethylene-vinyl acetate copolymer is completely dissolved, then sequentially adding a main agent and an auxiliary agent, heating to 60 ℃, stirring at a constant speed at the temperature, and ultrasonically dispersing for 4 +/-0.5 h, wherein the ultrasonic power is controlled to be 60W, so as to prepare the high-temperature resistant thick oil viscosity reducer.
The solvent is composed of petroleum fractions at 200 ℃ and is 200# solvent oil.
The main agent is prepared by the following method:
step S1, adding maleic anhydride into a three-neck flask, adding deionized water according to the weight ratio of 1: 10, heating to 60 ℃, introducing nitrogen into water, stirring at a constant speed of 150r/min until the solution is uniform and transparent, respectively dropwise adding a 10 mass percent aqueous solution of 2-acrylamide-2-methylpropanesulfonic acid and a 15 mass percent aqueous solution of ammonium persulfate, controlling the dropwise adding time to be 30 +/-5 min, preserving heat, stirring at a constant speed at the temperature, reacting for 4h to obtain an intermediate crude product, dropwise adding a 10 mass percent aqueous solution of sodium hydroxide into the intermediate crude product to adjust the pH value until the pH value is =8, then distilling under reduced pressure, evaporating deionized water at 60 ℃ to obtain a concentrate, washing the concentrate with acetone and ethanol for three times, then drying under vacuum at 80 ℃ for 20h to obtain a product A, controlling maleic anhydride, adding deionized water into the mixture, and performing vacuum drying at 80 ℃ for 20h, The weight ratio of the 2-acrylamide-2-methylpropanesulfonic acid to the ammonium persulfate is 1.5: 1: 0.05;
step S2, adding the mixed solution a into a three-neck flask, adding ethylenediamine, stirring at a constant speed for 35min, placing the mixture into an ice water bath, dropwise adding carbon disulfide into the three-neck flask, heating to 30 ℃ after dropwise adding, stirring at a constant speed of 100r/min at the temperature, reacting for 2h, performing suction filtration on a reaction product, washing for 2 times with absolute ethyl alcohol, performing vacuum drying at 40 ℃ to constant weight to obtain a product B, compounding the product A and the product B according to a weight ratio of 5: 1 to obtain a main agent, and controlling the weight ratio of the ethylenediamine to the carbon disulfide to be 1: 2.
The mixed liquid a is formed by mixing ethanol and water according to the weight ratio of 1: 2.
The auxiliary agent is prepared by the following method:
step S11, adding dimethyl diallyl ammonium chloride into deionized water, and stirring at a constant speed to prepare a solution b with the mass fraction of 40%; adding acrylamide into deionized water, and stirring at a constant speed to prepare a solution c with the mass fraction of 15%; adding the solution b and a half of the solution C into a three-neck flask, introducing nitrogen to discharge oxygen, heating to 45 ℃, uniformly stirring and adding an initiator, uniformly stirring and dropwise adding the rest solution C, controlling the dropwise adding time to be 15min, uniformly stirring and reacting for 4h, adding a reaction product into anhydrous acetone after the reaction is finished for precipitation to prepare a copolymer C, and controlling the weight ratio of dimethyl diallyl ammonium chloride, acrylamide and the initiator to be 10: 0.5: 0.05;
step S12, adding the copolymer C into deionized water, stirring at a constant speed to prepare a solution D with the mass fraction of 10%, then dropwise adding a sodium hydroxide solution with the mass fraction of 15% to adjust the pH until the pH is =10, then adding formaldehyde, heating to 40 ℃, stirring at a constant speed and reacting for 1h, adding triethylene tetramine after the reaction is finished, stirring at a constant speed and reacting for 2h to prepare a copolymer D, and controlling the weight ratio of the copolymer C to the formaldehyde to the triethylene tetramine to be 10: 0.1;
and S13, cooling the copolymer D prepared in the step S12 to 30 ℃, adding sodium hydroxide, dropwise adding carbon disulfide after uniformly stirring for 30min, controlling the dropwise adding time to be 30min, after the dropwise adding is finished, uniformly stirring at the rotating speed of 100r/min and reacting for 4h, then heating to 50 ℃, uniformly stirring at the rotating speed of 200r/min and reacting for 2h, after the reaction is finished, adding a product into acetone for precipitation, filtering, washing, and drying in vacuum at 40 ℃ for 4h to prepare the auxiliary agent, wherein the weight ratio of triethylene tetramine to sodium hydroxide to carbon disulfide is controlled to be 1.2: 1: 3.5.
Example 2
The high-temperature-resistant thick oil viscosity reducer comprises the following raw materials in parts by weight: 20 parts of a main agent, 12 parts of an auxiliary agent, 65 parts of a solvent and 6 parts of an ethylene-vinyl acetate copolymer;
the high-temperature resistant thick oil viscosity reducer is prepared by the following method:
adding ethylene-vinyl acetate copolymer into a solvent, stirring at a constant speed at 45 ℃ until the ethylene-vinyl acetate copolymer is completely dissolved, then sequentially adding a main agent and an auxiliary agent, heating to 60 ℃, stirring at a constant speed at the temperature, and ultrasonically dispersing for 4 +/-0.5 h, wherein the ultrasonic power is controlled to be 60W, so as to prepare the high-temperature resistant thick oil viscosity reducer.
The solvent is composed of petroleum fractions at 200 ℃ and is 200# solvent oil.
The main agent is prepared by the following method:
step S1, adding maleic anhydride into a three-neck flask, adding deionized water according to the weight ratio of 1: 10, heating to 60 ℃, introducing nitrogen into water, stirring at a constant speed of 150r/min until the solution is uniform and transparent, respectively dropwise adding a 10 mass percent aqueous solution of 2-acrylamide-2-methylpropanesulfonic acid and a 15 mass percent aqueous solution of ammonium persulfate, controlling the dropwise adding time to be 30min, preserving heat, stirring at a constant speed at the temperature, reacting for 4h to obtain an intermediate crude product, dropwise adding a 10 mass percent aqueous solution of sodium hydroxide into the intermediate crude product to adjust the pH value until the pH value is =8, then distilling under reduced pressure, evaporating deionized water at 60 ℃ to obtain a concentrate, washing the concentrate with acetone and ethanol for three times, then drying in vacuum at 80 ℃ for 20h to obtain a product A, and controlling the weight ratio of maleic anhydride, 2-acrylamide-2-methylpropanesulfonic acid and ammonium persulfate to be 1.5: 1 0.05: of;
step S2, adding the mixed solution a into a three-neck flask, adding ethylenediamine, stirring at a constant speed for 35min, placing the mixture into an ice water bath, dropwise adding carbon disulfide into the three-neck flask, heating to 30 ℃ after dropwise adding, stirring at a constant speed of 100r/min at the temperature, reacting for 2h, performing suction filtration on a reaction product, washing for 2 times with absolute ethyl alcohol, performing vacuum drying at 40 ℃ to constant weight to obtain a product B, compounding the product A and the product B according to a weight ratio of 5: 1 to obtain a main agent, and controlling the weight ratio of the ethylenediamine to the carbon disulfide to be 1: 2.
The mixed liquid a is formed by mixing ethanol and water according to the weight ratio of 1: 2.
The auxiliary agent is prepared by the following method:
step S11, adding dimethyl diallyl ammonium chloride into deionized water, and stirring at a constant speed to prepare a solution b with the mass fraction of 40%; adding acrylamide into deionized water, and stirring at a constant speed to prepare a solution c with the mass fraction of 15%; adding the solution b and a half of the solution C into a three-neck flask, introducing nitrogen to discharge oxygen, heating to 45 ℃, uniformly stirring and adding an initiator, uniformly stirring and dropwise adding the rest solution C, controlling the dropwise adding time to be 15min, uniformly stirring and reacting for 4h, adding a reaction product into anhydrous acetone after the reaction is finished for precipitation to prepare a copolymer C, and controlling the weight ratio of dimethyl diallyl ammonium chloride, acrylamide and the initiator to be 10: 0.5: 0.05;
step S12, adding the copolymer C into deionized water, stirring at a constant speed to prepare a solution D with the mass fraction of 10%, then dropwise adding a sodium hydroxide solution with the mass fraction of 15% to adjust the pH until the pH is =10, then adding formaldehyde, heating to 40 ℃, stirring at a constant speed and reacting for 1h, adding triethylene tetramine after the reaction is finished, stirring at a constant speed and reacting for 2h to prepare a copolymer D, and controlling the weight ratio of the copolymer C to the formaldehyde to the triethylene tetramine to be 10: 0.1;
and S13, cooling the copolymer D prepared in the step S12 to 30 ℃, adding sodium hydroxide, dropwise adding carbon disulfide after uniformly stirring for 30min, controlling the dropwise adding time to be 30min, after the dropwise adding is finished, uniformly stirring at the rotating speed of 100r/min and reacting for 4h, then heating to 50 ℃, uniformly stirring at the rotating speed of 200r/min and reacting for 2h, after the reaction is finished, adding a product into acetone for precipitation, filtering, washing, and drying in vacuum at 40 ℃ for 4h to prepare the auxiliary agent, wherein the weight ratio of triethylene tetramine to sodium hydroxide to carbon disulfide is controlled to be 1.2: 1: 3.5.
Example 3
The high-temperature-resistant thick oil viscosity reducer comprises the following raw materials in parts by weight: 30 parts of a main agent, 14 parts of an auxiliary agent, 70 parts of a solvent and 8 parts of an ethylene-vinyl acetate copolymer;
the high-temperature resistant thick oil viscosity reducer is prepared by the following method:
adding ethylene-vinyl acetate copolymer into a solvent, stirring at a constant speed at 45 ℃ until the ethylene-vinyl acetate copolymer is completely dissolved, then sequentially adding a main agent and an auxiliary agent, heating to 60 ℃, stirring at a constant speed at the temperature, and ultrasonically dispersing for 4 +/-0.5 h, wherein the ultrasonic power is controlled to be 60W, so as to prepare the high-temperature resistant thick oil viscosity reducer.
The solvent is composed of petroleum fractions at 200 ℃ and is 200# solvent oil.
The main agent is prepared by the following method:
step S1, adding maleic anhydride into a three-neck flask, adding deionized water according to the weight ratio of 1: 10, heating to 60 ℃, introducing nitrogen into water, stirring at a constant speed of 150r/min until the solution is uniform and transparent, respectively dropwise adding a 10 mass percent aqueous solution of 2-acrylamide-2-methylpropanesulfonic acid and a 15 mass percent aqueous solution of ammonium persulfate, controlling the dropwise adding time to be 30min, preserving heat, stirring at a constant speed at the temperature, reacting for 4h to obtain an intermediate crude product, dropwise adding a 10 mass percent aqueous solution of sodium hydroxide into the intermediate crude product to adjust the pH value until the pH value is =8, then distilling under reduced pressure, evaporating deionized water at 60 ℃ to obtain a concentrate, washing the concentrate with acetone and ethanol for three times, then drying in vacuum at 80 ℃ for 20h to obtain a product A, and controlling the weight ratio of maleic anhydride, 2-acrylamide-2-methylpropanesulfonic acid and ammonium persulfate to be 1.5: 1 0.05: of;
step S2, adding the mixed solution a into a three-neck flask, adding ethylenediamine, stirring at a constant speed for 35min, placing the mixture into an ice water bath, dropwise adding carbon disulfide into the three-neck flask, heating to 30 ℃ after dropwise adding, stirring at a constant speed of 100r/min at the temperature, reacting for 2h, performing suction filtration on a reaction product, washing for 2 times with absolute ethyl alcohol, performing vacuum drying at 40 ℃ to constant weight to obtain a product B, compounding the product A and the product B according to a weight ratio of 5: 1 to obtain a main agent, and controlling the weight ratio of the ethylenediamine to the carbon disulfide to be 1: 2.
The mixed liquid a is formed by mixing ethanol and water according to the weight ratio of 1: 2.
The auxiliary agent is prepared by the following method:
step S11, adding dimethyl diallyl ammonium chloride into deionized water, and stirring at a constant speed to prepare a solution b with the mass fraction of 40%; adding acrylamide into deionized water, and stirring at a constant speed to prepare a solution c with the mass fraction of 15%; adding the solution b and a half of the solution C into a three-neck flask, introducing nitrogen to discharge oxygen, heating to 45 ℃, uniformly stirring and adding an initiator, uniformly stirring and dropwise adding the rest solution C, controlling the dropwise adding time to be 15min, uniformly stirring and reacting for 4h, adding a reaction product into anhydrous acetone after the reaction is finished for precipitation to prepare a copolymer C, and controlling the weight ratio of dimethyl diallyl ammonium chloride, acrylamide and the initiator to be 10: 0.5: 0.05;
step S12, adding the copolymer C into deionized water, stirring at a constant speed to prepare a solution D with the mass fraction of 10%, then dropwise adding a sodium hydroxide solution with the mass fraction of 15% to adjust the pH until the pH is =10, then adding formaldehyde, heating to 40 ℃, stirring at a constant speed and reacting for 1h, adding triethylene tetramine after the reaction is finished, stirring at a constant speed and reacting for 2h to prepare a copolymer D, and controlling the weight ratio of the copolymer C to the formaldehyde to the triethylene tetramine to be 10: 0.1;
and S13, cooling the copolymer D prepared in the step S12 to 30 ℃, adding sodium hydroxide, dropwise adding carbon disulfide after uniformly stirring for 30min, controlling the dropwise adding time to be 30min, after the dropwise adding is finished, uniformly stirring at the rotating speed of 100r/min and reacting for 4h, then heating to 50 ℃, uniformly stirring at the rotating speed of 200r/min and reacting for 2h, after the reaction is finished, adding a product into acetone for precipitation, filtering, washing, and drying in vacuum at 40 ℃ for 4h to prepare the auxiliary agent, wherein the weight ratio of triethylene tetramine to sodium hydroxide to carbon disulfide is controlled to be 1.2: 1: 3.5.
Example 4
The high-temperature-resistant thick oil viscosity reducer comprises the following raw materials in parts by weight: 35 parts of main agent, 15 parts of auxiliary agent, 80 parts of solvent and 10 parts of ethylene-vinyl acetate copolymer;
the high-temperature resistant thick oil viscosity reducer is prepared by the following method:
adding ethylene-vinyl acetate copolymer into a solvent, stirring at a constant speed at 45 ℃ until the ethylene-vinyl acetate copolymer is completely dissolved, then sequentially adding a main agent and an auxiliary agent, heating to 60 ℃, stirring at a constant speed at the temperature, and ultrasonically dispersing for 4 +/-0.5 h, wherein the ultrasonic power is controlled to be 60W, so as to prepare the high-temperature resistant thick oil viscosity reducer.
The solvent is composed of petroleum fractions at 200 ℃ and is 200# solvent oil.
The main agent is prepared by the following method:
step S1, adding maleic anhydride into a three-neck flask, adding deionized water according to the weight ratio of 1: 10, heating to 60 ℃, introducing nitrogen into water, stirring at a constant speed of 150r/min until the solution is uniform and transparent, respectively dropwise adding a 10 mass percent aqueous solution of 2-acrylamide-2-methylpropanesulfonic acid and a 15 mass percent aqueous solution of ammonium persulfate, controlling the dropwise adding time to be 30min, preserving heat, stirring at a constant speed at the temperature, reacting for 4h to obtain an intermediate crude product, dropwise adding a 10 mass percent aqueous solution of sodium hydroxide into the intermediate crude product to adjust the pH value until the pH value is =8, then distilling under reduced pressure, evaporating deionized water at 60 ℃ to obtain a concentrate, washing the concentrate with acetone and ethanol for three times, then drying in vacuum at 80 ℃ for 20h to obtain a product A, and controlling the weight ratio of maleic anhydride, 2-acrylamide-2-methylpropanesulfonic acid and ammonium persulfate to be 1.5: 1 0.05: of;
step S2, adding the mixed solution a into a three-neck flask, adding ethylenediamine, stirring at a constant speed for 35min, placing the mixture into an ice water bath, dropwise adding carbon disulfide into the three-neck flask, heating to 30 ℃ after dropwise adding, stirring at a constant speed of 100r/min at the temperature, reacting for 2h, performing suction filtration on a reaction product, washing for 2 times with absolute ethyl alcohol, performing vacuum drying at 40 ℃ to constant weight to obtain a product B, compounding the product A and the product B according to a weight ratio of 5: 1 to obtain a main agent, and controlling the weight ratio of the ethylenediamine to the carbon disulfide to be 1: 2.
The mixed liquid a is formed by mixing ethanol and water according to the weight ratio of 1: 2.
The auxiliary agent is prepared by the following method:
step S11, adding dimethyl diallyl ammonium chloride into deionized water, and stirring at a constant speed to prepare a solution b with the mass fraction of 40%; adding acrylamide into deionized water, and stirring at a constant speed to prepare a solution c with the mass fraction of 15%; adding the solution b and a half of the solution C into a three-neck flask, introducing nitrogen to discharge oxygen, heating to 45 ℃, uniformly stirring and adding an initiator, uniformly stirring and dropwise adding the rest solution C, controlling the dropwise adding time to be 15min, uniformly stirring and reacting for 4h, adding a reaction product into anhydrous acetone after the reaction is finished for precipitation to prepare a copolymer C, and controlling the weight ratio of dimethyl diallyl ammonium chloride, acrylamide and the initiator to be 10: 0.5: 0.05;
step S12, adding the copolymer C into deionized water, stirring at a constant speed to prepare a solution D with the mass fraction of 10%, then dropwise adding a sodium hydroxide solution with the mass fraction of 15% to adjust the pH until the pH is =10, then adding formaldehyde, heating to 40 ℃, stirring at a constant speed and reacting for 1h, adding triethylene tetramine after the reaction is finished, stirring at a constant speed and reacting for 2h to prepare a copolymer D, and controlling the weight ratio of the copolymer C to the formaldehyde to the triethylene tetramine to be 10: 0.1;
and S13, cooling the copolymer D prepared in the step S12 to 30 ℃, adding sodium hydroxide, dropwise adding carbon disulfide after uniformly stirring for 30min, controlling the dropwise adding time to be 30min, after the dropwise adding is finished, uniformly stirring at the rotating speed of 100r/min and reacting for 4h, then heating to 50 ℃, uniformly stirring at the rotating speed of 200r/min and reacting for 2h, after the reaction is finished, adding a product into acetone for precipitation, filtering, washing, and drying in vacuum at 40 ℃ for 4h to prepare the auxiliary agent, wherein the weight ratio of triethylene tetramine to sodium hydroxide to carbon disulfide is controlled to be 1.2: 1: 3.5.
Example 5
The high-temperature-resistant thick oil viscosity reducer comprises the following raw materials in parts by weight: 15 parts of a main agent, 10 parts of an auxiliary agent, 55 parts of a solvent and 5 parts of an ethylene-vinyl acetate copolymer;
the high-temperature resistant thick oil viscosity reducer is prepared by the following method:
adding ethylene-vinyl acetate copolymer into a solvent, stirring at a constant speed at 55 ℃ until the ethylene-vinyl acetate copolymer is completely dissolved, then sequentially adding a main agent and an auxiliary agent, heating to 65 ℃, stirring at a constant speed at the temperature, and ultrasonically dispersing for 3.5 hours, wherein the ultrasonic power is controlled to be 80W, so as to prepare the high-temperature resistant thick oil viscosity reducer.
The solvent is composed of petroleum fractions at 200 ℃ and is 200# solvent oil.
The main agent is prepared by the following method:
step S1, adding maleic anhydride into a three-neck flask, adding deionized water according to the weight ratio of 1: 9, heating to 75 ℃, introducing nitrogen into water, stirring at a constant speed of 200r/min until the solution is uniform and transparent, respectively dropwise adding a 9 mass percent aqueous solution of 2-acrylamide-2-methylpropanesulfonic acid and a 14 mass percent aqueous solution of ammonium persulfate, controlling the dropwise adding time to be 25min, keeping the temperature, stirring at a constant speed at the temperature, reacting for 3.5h to obtain an intermediate crude product, dropwise adding a 9 mass percent aqueous solution of sodium hydroxide into the intermediate crude product to adjust the pH value until the pH value is =7, then distilling under reduced pressure, evaporating the deionized water at the temperature of 60 +/-2 ℃ to obtain a concentrate, washing the concentrate with acetone and ethanol for three times, then drying in vacuum at the temperature of 80 +/-2 ℃ for 18h to obtain a product A, controlling the maleic anhydride, and controlling the weight ratio of the deionized, The weight ratio of the 2-acrylamide-2-methylpropanesulfonic acid to the ammonium persulfate is 1.4: 1: 0.04;
step S2, adding the mixed solution a into a three-neck flask, adding ethylenediamine, stirring at a constant speed for 45min, placing the mixture into an ice water bath, dropwise adding carbon disulfide into the three-neck flask, heating to 28 ℃ after dropwise adding, stirring at a constant speed of 200r/min at the temperature, reacting for 1.5h, performing suction filtration on a reaction product, washing for 2 times with absolute ethyl alcohol, performing vacuum drying at 38 ℃ to constant weight to obtain a product B, and compounding the product A and the product B according to a weight ratio of 4: 1 to obtain a main agent, wherein the weight ratio of the ethylenediamine to the carbon disulfide is controlled to be 1: 1.8.
The mixed liquid a is formed by mixing ethanol and water according to the weight ratio of 1: 1.8.
The auxiliary agent is prepared by the following method:
step S11, adding dimethyldiallylammonium chloride into deionized water, and stirring at a constant speed to prepare a solution b with the mass fraction of 38%; adding acrylamide into deionized water, and stirring at a constant speed to prepare a solution c with the mass fraction of 14%; adding the solution b and a half of the solution C into a three-neck flask, introducing nitrogen to discharge oxygen, heating to 65 ℃, uniformly stirring and adding an initiator, uniformly stirring and dropwise adding the rest solution C, controlling the dropwise adding time to be 13min, uniformly stirring and reacting for 3.5h, adding a reaction product into anhydrous acetone after the reaction is finished for precipitation to prepare a copolymer C, and controlling the weight ratio of the dimethyl diallyl ammonium chloride to the acrylamide to the initiator to be 9: 0.45: 0.04;
step S12, adding the copolymer C into deionized water, stirring at a constant speed to prepare a solution D with the mass fraction of 9%, then dropwise adding a sodium hydroxide solution with the mass fraction of 14% to adjust the pH until the pH is =9.5, then adding formaldehyde, heating to 60 ℃, stirring at a constant speed to react for 0.5h, adding triethylene tetramine after the reaction is finished, stirring at a constant speed to react for 1.5h to prepare a copolymer D, and controlling the weight ratio of the copolymer C to the formaldehyde to the triethylene tetramine to be 9: 0.09: 0.1;
and S13, cooling the copolymer D prepared in the step S12 to 28 ℃, adding sodium hydroxide, dropwise adding carbon disulfide after uniformly stirring for 25min, controlling the dropwise adding time to be 25min, uniformly stirring and reacting at the temperature for 3.5h at the rotating speed of 150r/min after dropwise adding, heating to 60 ℃, uniformly stirring and reacting at the rotating speed of 300r/min for 1.5h, adding a product after the reaction is finished into acetone for precipitation, filtering, washing, and vacuum drying at 60 ℃ for 3.5h to prepare the auxiliary agent, wherein the weight ratio of triethylene tetramine, sodium hydroxide and carbon disulfide is controlled to be 1.15: 1: 3.
Example 6
The high-temperature-resistant thick oil viscosity reducer comprises the following raw materials in parts by weight: 20 parts of a main agent, 12 parts of an auxiliary agent, 65 parts of a solvent and 6 parts of an ethylene-vinyl acetate copolymer;
the high-temperature resistant thick oil viscosity reducer is prepared by the following method:
adding ethylene-vinyl acetate copolymer into a solvent, stirring at a constant speed at 50 ℃ until the ethylene-vinyl acetate copolymer is completely dissolved, then sequentially adding a main agent and an auxiliary agent, heating to 60 ℃, stirring at a constant speed at the temperature, and ultrasonically dispersing for 4.5 hours, wherein the ultrasonic power is controlled to be 70W, thus obtaining the high-temperature resistant thick oil viscosity reducer.
The solvent is composed of petroleum fractions at 200 ℃ and is 200# solvent oil.
The main agent is prepared by the following method:
step S1, adding maleic anhydride into a three-neck flask, adding deionized water according to the weight ratio of 1: 11, heating to 70 ℃, introducing nitrogen into water, stirring at a constant speed of 150r/min until the solution is uniform and transparent, respectively dropwise adding 11 mass percent of 2-acrylamide-2-methylpropanesulfonic acid aqueous solution and 16 mass percent of ammonium persulfate aqueous solution into the solution, controlling the dropwise adding time to be 35min, preserving the temperature, stirring at a constant speed at the temperature, reacting for 4.5h to obtain an intermediate crude product, dropwise adding 11 mass percent of sodium hydroxide aqueous solution into the intermediate crude product to adjust the pH value until the pH value is =7.5, then distilling under reduced pressure, evaporating the deionized water at 62 ℃ to obtain a concentrate, washing the concentrate with acetone and ethanol for three times, then drying under vacuum at 82 ℃ for 22h to obtain a product A, and controlling the weight ratio of the maleic anhydride, the 2-acrylamide-2-methylpropanesulfonic acid and the ammonium persulfate to be 1.5: 1 0.06 of the mixture;
step S2, adding the mixed solution a into a three-neck flask, adding ethylenediamine, stirring at a constant speed for 40min, placing the mixture into an ice water bath, dropwise adding carbon disulfide into the three-neck flask, heating to 32 ℃ after dropwise adding, stirring at a constant speed of 150r/min at the temperature, reacting for 2.5h, performing suction filtration on a reaction product, washing for 2 times with absolute ethyl alcohol, performing vacuum drying at 42 ℃ to constant weight to obtain a product B, compounding the product A and the product B according to a weight ratio of 6: 1 to obtain a main agent, and controlling the weight ratio of the ethylenediamine to the carbon disulfide to be 1: 2.2.
The mixed liquid a is formed by mixing ethanol and water according to the weight ratio of 1: 2.2.
The auxiliary agent is prepared by the following method:
step S11, adding dimethyldiallylammonium chloride into deionized water, and stirring at a constant speed to prepare a solution b with the mass fraction of 42%; adding acrylamide into deionized water, and stirring at a constant speed to prepare a solution c with the mass fraction of 16%; adding the solution b and a half of the solution C into a three-neck flask, introducing nitrogen to discharge oxygen, heating to 55 ℃, uniformly stirring and adding an initiator, uniformly stirring and dropwise adding the rest solution C, controlling the dropwise adding time to be 17min, uniformly stirring and reacting for 4.5h, adding a reaction product into anhydrous acetone after the reaction is finished for precipitation to prepare a copolymer C, and controlling the weight ratio of dimethyl diallyl ammonium chloride to acrylamide to the initiator to be 11: 0.55: 0.06;
step S12, adding the copolymer C into deionized water, stirring at a constant speed to prepare a solution D with the mass fraction of 11%, then dropwise adding a sodium hydroxide solution with the mass fraction of 16% to adjust the pH until the pH is =10.5, then adding formaldehyde, heating to 42 ℃, stirring at a constant speed to react for 1.5h, adding triethylene tetramine after the reaction is finished, stirring at a constant speed to react for 2.5h to prepare a copolymer D, and controlling the weight ratio of the copolymer C to the formaldehyde to the triethylene tetramine to be 11: 0.11;
and S13, cooling the copolymer D prepared in the step S12 to 32 ℃, adding sodium hydroxide, dropwise adding carbon disulfide after uniformly stirring for 35min, controlling the dropwise adding time to be 35min, uniformly stirring and reacting at the temperature for 4.5h at the rotating speed of 100r/min after dropwise adding, heating to 55 ℃, uniformly stirring and reacting at the rotating speed of 250r/min for 2.5h, adding a product after the reaction is finished into acetone for precipitation, filtering, washing, and vacuum drying at 50 ℃ for 4.5h to prepare the auxiliary agent, wherein the weight ratio of triethylene tetramine, sodium hydroxide and carbon disulfide is controlled to be 1.25: 1: 4.
Comparative example 1
In comparison with example 1, no main agent was added in this comparative example.
Comparative example 2
In comparison with example 1, no auxiliary was added in this comparative example.
Comparative example 3
The comparative example is a viscosity reducer of Juxin Da JXD-5 in the market.
To a thick oil having a viscosity of 10000 mPas, 0.5wt% of the viscosity reducer for thick oil prepared in examples 1 to 4 and comparative examples 1 to 3 and 1.3mL of toluene were added, respectively, and after stirring for 1 hour, the viscosity A1 was measured at 30 ℃, 100 ℃ and 180 ℃ using a rotary viscometer and the viscosity reduction ratio was calculated, and the results are shown in the following table:
the viscosity reduction rate calculation formula is as follows: (10000-A1)/10000x 100%.
As can be seen from the above table, the viscosity reduction rate at 30 ℃ in examples 1 to 6 is 97.5 to 97.8%, the viscosity reduction rate at 100 ℃ is 95.1 to 95.3%, the viscosity reduction rate at 180 ℃ is 90.6 to 91.2%, the viscosity reduction rate at 30 ℃ in comparative examples 1 to 3 is 75.8 to 81.2%, the viscosity reduction rate at 100 ℃ is 55.3 to 75.1%, and the viscosity reduction rate at 180 ℃ is 23.5 to 71.2%; therefore, the main agent can reduce the viscosity of the heavy oil, can also complex metal in the heavy metal heavy oil, further solves the technical problems that the heavy metal-containing heavy oil has high viscosity and is difficult to reduce the viscosity, and the prepared main agent has excellent heat resistance and endows the prepared viscosity reducer with certain high temperature resistance.
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 (7)
1. The preparation method of the high-temperature-resistant thick oil viscosity reducer is characterized by comprising the following raw materials in parts by weight: 15-35 parts of main agent, 10-15 parts of auxiliary agent, 55-80 parts of solvent and 5-10 parts of ethylene-vinyl acetate copolymer;
the high-temperature resistant thick oil viscosity reducer is prepared by the following method:
adding ethylene-vinyl acetate copolymer into a solvent, stirring at a constant speed at 45-55 ℃ until the ethylene-vinyl acetate copolymer is completely dissolved, then sequentially adding a main agent and an auxiliary agent, heating to 60-65 ℃, stirring at a constant speed at the temperature, and ultrasonically dispersing for 4 +/-0.5 h, wherein the ultrasonic power is controlled to be 60-80W, so as to prepare the high-temperature resistant thick oil viscosity reducer;
the main agent is prepared by the following method:
step S1, adding maleic anhydride into a reaction container, adding deionized water according to the weight ratio of 1: 9-11, heating to 60-75 ℃, introducing nitrogen into the water, stirring at a constant speed of 200r/min at 150-, then vacuum drying is carried out for 20 plus or minus 2 hours at the temperature of 80 plus or minus 2 ℃, and a product A is prepared; controlling the weight ratio of maleic anhydride, 2-acrylamide-2-methylpropanesulfonic acid to ammonium persulfate to be (1.4-1.6) to 1 to (0.04-0.06);
step S2, adding the mixed solution a into a reaction container, adding ethylenediamine, uniformly stirring for 35-45min, placing the mixture into an ice water bath, dropwise adding carbon disulfide into the reaction container, heating to 30 +/-2 ℃ after dropwise adding, uniformly stirring at a speed of 100 plus or minus one minute at 200r/min at the temperature, reacting for 2 +/-0.5 h, carrying out suction filtration on a reaction product, washing for 2-3 times by using absolute ethyl alcohol, carrying out vacuum drying at 40 +/-2 ℃ to constant weight to obtain a product B, compounding the product A and the product B according to the weight ratio of (4-6) to 1 to prepare a main agent, and controlling the weight ratio of the ethylenediamine to the carbon disulfide to be 1 to (1.8-2.2); the mixed solution a is formed by mixing ethanol and water according to the weight ratio of 1: 1.8-2.2;
the auxiliary agent is prepared by the following method:
step S11, adding dimethyldiallylammonium chloride into deionized water, and stirring at a constant speed to prepare a solution b with the mass fraction of 40 +/-2%; adding acrylamide into deionized water, and stirring at a constant speed to prepare a solution c with the mass fraction of 15 +/-1%; adding the solution b and a half of the solution C into a reaction container, introducing nitrogen to discharge oxygen, heating to 45-65 ℃, uniformly stirring and adding an initiator, uniformly stirring and dropwise adding the rest solution C, controlling the dropwise adding time to be 15 +/-2 min, uniformly stirring and reacting for 4 +/-0.5 h, adding a reaction product into anhydrous acetone after the reaction is finished for precipitation to obtain a copolymer C, and controlling the weight ratio of the dimethyldiallylammonium chloride to the initiator to be (9-11) to (0.45-0.55) to (0.04-0.06);
step S12, adding the copolymer C into deionized water, stirring at a constant speed to prepare a solution D with the mass fraction of 10 +/-1%, then dropwise adding a sodium hydroxide solution with the mass fraction of 15 +/-1% to adjust the pH until the pH is =10 +/-0.5, then adding formaldehyde, heating to 40-60 ℃, stirring at a constant speed to react for 1 +/-0.5 h, adding triethylene tetramine after the reaction is finished, stirring at a constant speed to react for 2 +/-0.5 h to prepare a copolymer D, and controlling the weight ratio of the copolymer C to the formaldehyde to the triethylene tetramine to be (9-11) to (0.09-0.11) to (0.1-0.11);
step S13, cooling the copolymer D prepared in the step S12 to 30 +/-2 ℃, then adding sodium hydroxide, dropwise adding carbon disulfide after uniformly stirring for 30 +/-5 min, controlling the dropwise adding time to be 30 +/-5 min, uniformly stirring at the temperature of 100 plus one year and 150r/min after the dropwise adding is finished, reacting for 4 +/-0.5 h, then heating to 50-60 ℃, uniformly stirring at the speed of 200 plus one year and 300r/min, reacting for 2 +/-0.5 h, adding the product into acetone after the reaction is finished, precipitating, filtering, washing, and performing vacuum drying at 40-60 ℃ for 4 +/-0.5 h to prepare the auxiliary agent; the weight ratio of triethylene tetramine to sodium hydroxide to carbon disulfide is controlled to be (1.15-1.25) to (1) to (3-4).
2. The method for preparing the high temperature resistant viscosity reducer for thick oil according to claim 1, wherein the solvent comprises 140-200 ℃ petroleum fractions.
3. The method for preparing the high-temperature-resistant thick oil viscosity reducer according to claim 2, wherein the solvent is 200# solvent oil.
4. The preparation method of the high-temperature-resistant thick oil viscosity reducer according to claim 1, wherein the main agent is prepared by the following method:
step S1, adding maleic anhydride into a three-neck flask, adding deionized water according to the weight ratio of 1: 10, heating to 60-75 ℃, introducing nitrogen into the water, stirring at a constant speed of 200r/min at 150-, controlling the weight ratio of the maleic anhydride, the 2-acrylamide-2-methylpropanesulfonic acid and the ammonium persulfate to be 1.5: 1: 0.05;
step S2, adding the mixed solution a into a three-neck flask, adding ethylenediamine, stirring at a constant speed for 35-45min, placing in an ice water bath, dropwise adding carbon disulfide into the three-neck flask, heating to 30 ℃ after dropwise adding, stirring at a constant speed of 100 plus one liter of water/min at the temperature, reacting for 2h, performing suction filtration on a reaction product, washing for 2-3 times with absolute ethyl alcohol, performing vacuum drying at 40 ℃ to constant weight to obtain a product B, compounding the product A and the product B according to a weight ratio of 5: 1 to obtain a main agent, and controlling the weight ratio of the ethylenediamine to the carbon disulfide to be 1: 2.
5. The method for preparing the high-temperature-resistant viscosity reducer for thick oil according to claim 1, wherein the mixed solution a is formed by mixing ethanol and water according to a weight ratio of 1: 2.
6. The preparation method of the high-temperature-resistant thick oil viscosity reducer according to claim 1, wherein the auxiliary agent is prepared by the following method:
step S11, adding dimethyl diallyl ammonium chloride into deionized water, and stirring at a constant speed to prepare a solution b with the mass fraction of 40%; adding acrylamide into deionized water, and stirring at a constant speed to prepare a solution c with the mass fraction of 15%; adding the solution b and a half of the solution C into a three-neck flask, introducing nitrogen to discharge oxygen, heating to 45-65 ℃, uniformly stirring and adding an initiator, uniformly stirring and dropwise adding the rest solution C, controlling the dropwise adding time to be 15min, uniformly stirring and reacting for 4h, adding a reaction product into anhydrous acetone after the reaction is finished for precipitation to prepare a copolymer C, and controlling the weight ratio of the dimethyl diallyl ammonium chloride to the acrylamide to the initiator to be 10: 0.5: 0.05;
step S12, adding the copolymer C into deionized water, stirring at a constant speed to prepare a solution D with the mass fraction of 10%, then dropwise adding a sodium hydroxide solution with the mass fraction of 15% to adjust the pH until the pH is =10, then adding formaldehyde, heating to 40-60 ℃, stirring at a constant speed to react for 1h, adding triethylene tetramine after the reaction is finished, stirring at a constant speed to react for 2h to prepare a copolymer D, and controlling the weight ratio of the copolymer C to the formaldehyde to the triethylene tetramine to be 10: 0.1;
and S13, cooling the copolymer D prepared in the step S12 to 30 ℃, adding sodium hydroxide, dropwise adding carbon disulfide after uniformly stirring for 30min, controlling the dropwise adding time to be 30min, stirring at a constant speed of 150r/min and reacting for 4h at the temperature after dropwise adding, heating to 50-60 ℃, stirring at a constant speed of 300r/min and reacting for 2h at a constant speed of 200-.
7. The method for preparing the high-temperature-resistant thick oil viscosity reducer according to claim 1, wherein the initiator is azodiisopropyl imidazoline hydrochloride.
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| CN1521236A (en) * | 2003-01-30 | 2004-08-18 | 中国石油化工股份有限公司 | Method for removing metal from hydrocarbon oil using copolymers or its salts containing acrylic acid and sulfonic acid |
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