CN112321768B - Preparation method of composite thick oil viscosity reducer - Google Patents
Preparation method of composite thick oil viscosity reducer Download PDFInfo
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- CN112321768B CN112321768B CN202110006409.4A CN202110006409A CN112321768B CN 112321768 B CN112321768 B CN 112321768B CN 202110006409 A CN202110006409 A CN 202110006409A CN 112321768 B CN112321768 B CN 112321768B
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000654 additive Substances 0.000 claims abstract description 27
- 230000000996 additive effect Effects 0.000 claims abstract description 27
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 15
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 101
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 86
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 239000008367 deionised water Substances 0.000 claims description 46
- 229910021641 deionized water Inorganic materials 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 35
- 238000010992 reflux Methods 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 28
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 24
- 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 description 23
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 23
- 239000000706 filtrate Substances 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 18
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 16
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000741 silica gel Substances 0.000 claims description 15
- 229910002027 silica gel Inorganic materials 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 12
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 11
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 11
- 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 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 claims description 9
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical group BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- ZJHSRWNUEOUFAZ-UHFFFAOYSA-N BrC1C(=O)NC(C1)=O.[N] Chemical compound BrC1C(=O)NC(C1)=O.[N] ZJHSRWNUEOUFAZ-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000011698 potassium fluoride Substances 0.000 claims description 8
- 235000003270 potassium fluoride Nutrition 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 abstract description 10
- 239000000084 colloidal system Substances 0.000 abstract description 6
- 238000009833 condensation Methods 0.000 abstract description 5
- 230000005494 condensation Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 47
- 230000001603 reducing effect Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000295 fuel oil Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F212/00—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 aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/30—Sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
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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
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
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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
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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
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- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention belongs to the field of petroleum development, and particularly discloses a preparation method of a composite thick oil viscosity reducer, the intermediate 8 and oxalic acid are condensed under the action of 1-hydroxybenzotriazole, and then react with the composite carrier, so that the residual carboxyl of the oxalic acid and the active hydroxyl on the composite carrier are subjected to dehydration condensation to prepare the viscosity-reducing additive, the side chain of the additive contains a large amount of long-chain alkyl, and the long-chain alkyl is a nonpolar chain segment, so that the hydrogen bond strength between colloid and asphaltene molecules in the thickened oil can be reduced, the external environment of the asphaltene aggregate is converted into nonpolar, thereby leading the colloid and the asphaltene not to be aggregated, leading the side chain to contain rigid structures such as benzene rings and the like and a large amount of conjugated pi bonds, the viscous oil viscosity reducer is easier to count in a stacking structure of colloid and asphaltene, and a good effect can be achieved by using a small amount of viscous oil viscosity reducer.
Description
Technical Field
The invention relates to the technical field of petroleum exploitation, in particular to a preparation method of a composite thick oil viscosity reducer.
Background
In the global petroleum resources, a large part of the petroleum resources belong to unconventional petroleum resources, and have the characteristics of high condensation point, high viscosity and the like. Most of petroleum resources belong to 'three-high' thickened oil with high condensation point, high viscosity and high wax content. While the reserves of conventional petroleum resources are gradually reduced, the development and utilization of unconventional petroleum resources become increasingly important, but the unconventional petroleum brings great difficulty to the exploitation and transportation process due to the characteristics of high condensation point, high viscosity and the like. The heavy oil has high content of asphaltene and wax, and the heavy oil can be solidified due to the loss of fluidity caused by the precipitation of the wax and the asphaltene at normal temperature, so that the pipeline is blocked, and serious production accidents are caused. With the decreasing of the easy-to-recover reserves of petroleum, the pour point depression and viscosity reduction of the thick oil have important significance on the exploitation and production of the thick oil.
When the viscosity of high-viscosity thick oil is reduced by the conventional thick oil viscosity reducer, the viscosity reduction rate of the thick oil is not high, the performance of the thick oil viscosity reducer is obviously reduced in a high-temperature environment, and a large amount of thick oil viscosity reducer is required to be added to achieve the viscosity reduction effect of the conventional viscosity reducer, so that the viscosity reduction cost is increased.
Disclosure of Invention
The invention aims to provide a preparation method of a composite thick oil viscosity reducer.
The technical problems to be solved by the invention are as follows:
when the viscosity of high-viscosity thick oil is reduced by the conventional thick oil viscosity reducer, the viscosity reduction rate of the thick oil is not high, the performance of the thick oil viscosity reducer is obviously reduced in a high-temperature environment, and a large amount of thick oil viscosity reducer is required to be added to achieve the viscosity reduction effect of the conventional viscosity reducer, so that the viscosity reduction cost is increased.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of the composite thick oil viscosity reducer specifically comprises the following steps:
step S1: adding acrylamide, sodium p-styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid and deionized water into a reaction kettle, and stirring at the rotation speed of 150-;
step S2: dispersing the viscosity-reducing additive in ethanol, stirring and adding the mixed solution and azodiisobutyronitrile under the condition that the rotation speed is 200-300r/min, reacting for 8-10h under the condition that the temperature is 70-80 ℃, and distilling to remove distillate under the condition that the temperature is 110-120 ℃ to prepare the composite thick oil viscosity reducer;
the viscosity-reducing additive is prepared by the following steps:
step A1: adding concentrated sulfuric acid and deionized water into a reaction kettle, stirring for 10-15min under the condition that the rotating speed is 500-800r/min, adding montmorillonite, stirring for 2-4h under the condition that the temperature is 85-90 ℃, washing with deionized water to be neutral, filtering to remove filtrate to obtain primary modified montmorillonite, dispersing the primary modified montmorillonite in ethanol, adding N- (4-alkenyl butyl) phthalimide and acrylamide, keeping the temperature for 15-20min under the condition of nitrogen protection at the temperature of 80-90 ℃, adding azobisisobutyronitrile for reacting for 4-6h, and centrifuging to obtain secondary modified montmorillonite;
step A2: adding tetraethoxysilane, ethanol and deionized water into a reaction kettle, stirring and adjusting the pH value of reaction liquid to 3-4 under the conditions that the rotating speed is 200 plus or minus 300r/min and the temperature is 60-65 ℃, adjusting the pH value of the reaction liquid to 8-9 after reacting for 30-40min to prepare nano silica gel, adding secondary modified montmorillonite into the silica gel, carrying out ultrasonic treatment for 2-3h under the condition that the frequency is 5-8MHz, filtering to remove filtrate, and roasting a filter cake for 2-3h under the condition that the temperature is 200 +/-5 ℃ to prepare a composite carrier;
step A3: adding pyromellitic dianhydride, sulfolane and thionyl chloride into a reaction kettle, stirring for 1-1.5h at the rotation speed of 200-85 ℃ and the temperature of 80-85 ℃, adding potassium fluoride, reacting for 3-4h at the temperature of 210-220 ℃ to obtain an intermediate 1, adding the intermediate 1, a sodium hydroxide solution and copper powder into the reaction kettle, reacting for 5-8h at the pressure of 28-30MPa and the temperature of 280-300 ℃ to obtain an intermediate 2, adding the intermediate 2, octadecanol and toluene into the reaction kettle, introducing nitrogen for protection, stirring and adding p-toluenesulfonic acid at the rotation speed of 150-200r/min, performing reflux reaction for 3-5h at the temperature of 120-130 ℃, to prepare an intermediate 3;
the reaction process is as follows:
step A4: adding toluene and mixed acid into a reaction kettle, reacting for 2-3h at the rotation speed of 150-, refluxing for 4-6h, distilling to remove the solvent, adding hydrochloric acid until the pH value is 7 +/-0.5 to obtain an intermediate 6, adding the intermediate 6, the intermediate 3, dibromoethane, acetone and sodium bicarbonate into a reaction kettle, performing reflux reaction for 1-2h at the temperature of 60-65 ℃, adding 3-bromopropylene, and performing reflux reaction for 6-8h to obtain an intermediate 7;
the reaction process is as follows:
step A5: adding the intermediate 7, iron powder and ethanol into a reaction kettle, performing reflux reaction for 3-5h at the temperature of 80-85 ℃, adding a hydrochloric acid solution for 20min, continuing to react for 5-8h, adjusting the pH value of a reaction solution to 7-8 to obtain an intermediate 8, adding the intermediate 8 and oxalic acid into the reaction kettle, adding 1-hydroxybenzotriazole at the temperature of 50-60 ℃ to perform reaction for 5-6h to obtain an intermediate 9, dispersing a composite carrier into deionized water, adding the intermediate 9 and concentrated sulfuric acid, performing reflux reaction for 5-8h at the temperature of 110-120 ℃, removing the deionized water, and thus obtaining the viscosity-reducing additive.
The reaction process is as follows:
further, the dosage ratio of the acrylamide, the sodium p-styrenesulfonate, the 2-acrylamido-2-methylpropanesulfonic acid, and the deionized water in the step S1 is 0.2mol:0.2mol:0.1mol:200mL, the dosage ratio of the viscosity-reducing additive and the mixed solution in the step S2 is 3g:40mL, and the dosage of the azobisisobutyronitrile is 1.2-1.5% of the dosage of the viscosity-reducing additive.
Further, the mass ratio of the concentrated sulfuric acid to the deionized water to the montmorillonite in the step A1 is 1:1:6, the mass fraction of the concentrated sulfuric acid is 98%, the mass ratio of the primary modified montmorillonite to the N- (4-alkenyl butyl) phthalimide to the acrylamide is 5:1:1.2, and the mass ratio of the azodiisobutyronitrile to the N- (4-alkenyl butyl) phthalimide to the acrylamide is 1-1.5 ‰.
Further, the using amount molar ratio of the ethyl orthosilicate, the ethanol and the deionized water in the step A2 is 1:1.2:6.5, and the using amount ratio of the secondary modified montmorillonite and the silica gel is 1g:5 mL.
Further, the using amount mass ratio of the pyromellitic dianhydride, the sulfolane, the thionyl chloride and the potassium fluoride in the step A3 is 2.5:5:2:1.1, the using amount ratio of the intermediate 1, the sodium hydroxide solution and the copper powder is 1g:10mL:0.3g, the mass fraction of the sodium hydroxide solution is 15%, the using amount molar ratio of the intermediate 2 to the octadecanol is 1:2.1, and the using amount of the p-toluenesulfonic acid is 0.8-1% of the mass sum of the intermediate 2 and the octadecanol.
Further, the dosage ratio of the toluene and the mixed acid in the step A4 is 3mL:8mL, the mixed acid is formed by mixing nitric acid with the mass fraction of 68% and sulfuric acid with the mass fraction of 95% in a volume ratio of 3:1, the dosage ratio of the intermediate 4, the nitrogen-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride is 0.03mol:0.03mol:0.1g:60mL, the dosage ratio of the acetic acid, the sodium carbonate and the intermediate 5 is 15mL:1.08g:5g, the dosage ratio of the substrate, the ethanol, the deionized water and the sodium hydroxide is 5g:20mL:20mL:2.6g, and the dosage molar ratio of the intermediate 6, the intermediate 3, the dibromoethane, the 3-bromopropylene and the sodium bicarbonate is 1:1: 1:0.5:1: 1.
Further, the dosage ratio of the intermediate 7, the iron powder, the ethanol and the hydrochloric acid solution in the step A5 is 3.2g:5g:80mL:10mL, the volume fraction of the ethanol is 90%, the hydrochloric acid solution is formed by mixing concentrated hydrochloric acid with the mass fraction of 36% and ethanol with the volume fraction of 95% in a volume ratio of 1:9, the dosage molar ratio of the intermediate 8 and the oxalic acid is 1:1, the dosage of the 1-hydroxybenzotriazole is 10-15% of the mass sum of the intermediate 8 and the oxalic acid, the dosage ratio of the composite carrier, the intermediate 9 and the concentrated sulfuric acid is 10g:5g:1.3mL, and the mass fraction of the concentrated sulfuric acid is 98%.
The invention has the beneficial effects that: the invention prepares a viscosity reduction additive in the process of preparing a composite thick oil viscosity reducer, the viscosity reduction additive takes montmorillonite as a raw material, the montmorillonite is treated by concentrated sulfuric acid to prepare primary modified montmorillonite, the primary modified montmorillonite is subjected to intercalation polymerization by N- (4-alkene butyl) phthalimide and acrylamide to prepare secondary modified montmorillonite, a large amount of imide structures are arranged on the secondary modified montmorillonite, so that the thick oil viscosity reducer still has good viscosity reduction effect in high temperature environment, tetraethoxysilane is hydrolyzed to prepare silica gel, the secondary modified montmorillonite is added into the silica gel to be subjected to ultrasonic treatment, so that nano silica is inserted into the secondary modified montmorillonite, pyromellitic dianhydride is treated by thionyl chloride to prepare an intermediate 1, the intermediate 1 is treated, preparing an intermediate 2, reacting the intermediate 2 with octadecanol to prepare an intermediate 3, treating toluene with mixed acid to prepare an intermediate 4, reacting the intermediate 4 with nitrogen-bromosuccinimide to prepare an intermediate 5, treating the intermediate 5 to prepare an intermediate 6, reacting the intermediate 6, the intermediate 3 and dibromoethane, then reacting with 3-bromopropylene to prepare an intermediate 7, reducing the intermediate 7 to convert nitro into amino to prepare an intermediate 8, condensing the intermediate 8 and oxalic acid under the action of 1-hydroxybenzotriazole, then reacting with a composite carrier to ensure that residual carboxyl of oxalic acid and active hydroxyl on the composite carrier are subjected to dehydration condensation to prepare the viscosity reduction additive, wherein the side chain of the additive contains a large amount of long-chain alkyl which is a nonpolar chain segment and can reduce the hydrogen bond strength between colloid and asphaltene molecules in the thick oil, the external environment of the asphaltene aggregate is changed into non-polarity, so that the colloid and the asphaltene cannot be aggregated, and the side chain contains rigid structures such as benzene rings and the like and contains a large number of conjugated pi bonds, so that the viscous oil viscosity reducer is easier to count in the stacking structure of the colloid and the asphaltene, and the viscous oil viscosity reducer can achieve a good effect with less dosage.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Unless otherwise stated, each component in each example is a conventional commercially available product, and is not described in detail. The amounts and concentrations of the components in the various examples were selected as follows:
the dosage ratio of the acrylamide, the sodium p-styrenesulfonate, the 2-acrylamido-2-methylpropanesulfonic acid and the deionized water in the step S1 is 0.2mol:0.2mol:0.1mol:200mL, the dosage ratio of the viscosity-reducing additive and the mixed solution in the step S2 is 3g:40mL, and the dosage of the azobisisobutyronitrile is 1.2-1.5% of the dosage of the viscosity-reducing additive.
The mass ratio of the concentrated sulfuric acid to the deionized water to the montmorillonite in the step A1 is 1:1:6, the mass fraction of the concentrated sulfuric acid is 98%, the mass ratio of the primary modified montmorillonite to the N- (4-alkenyl butyl) phthalimide to the acrylamide is 5:1:1.2, and the mass ratio of the azodiisobutyronitrile to the N- (4-alkenyl butyl) phthalimide to the acrylamide is 1-1.5 per mill.
The using amount molar ratio of the ethyl orthosilicate, the ethanol and the deionized water in the step A2 is 1:1.2:6.5, and the using amount ratio of the secondary modified montmorillonite to the silica gel is 1g:5 mL.
The using amount mass ratio of the pyromellitic dianhydride, the sulfolane, the thionyl chloride and the potassium fluoride in the step A3 is 2.5:5:2:1.1, the using amount ratio of the intermediate 1, the sodium hydroxide solution and the copper powder is 1g:10mL:0.3g, the mass fraction of the sodium hydroxide solution is 15%, the using amount molar ratio of the intermediate 2 to the octadecanol is 1:2.1, and the using amount of the p-toluenesulfonic acid is 0.8-1% of the mass sum of the intermediate 2 and the octadecanol.
The dosage ratio of the toluene and the mixed acid in the step A4 is 3mL:8mL, the mixed acid is formed by mixing nitric acid with the mass fraction of 68% and sulfuric acid with the mass fraction of 95% according to the volume ratio of 3:1, the dosage ratio of the intermediate 4, the nitrogen-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride is 0.03mol:0.03mol:0.1g:60mL, the dosage ratio of the acetic acid, the sodium carbonate and the intermediate 5 is 15mL:1.08g:5g, the dosage ratio of the substrate, the ethanol, the deionized water and the sodium hydroxide is 5g:20mL:20mL:2.6g, and the dosage molar ratio of the intermediate 6, the intermediate 3, the dibromoethane, the 3-bromopropylene and the sodium bicarbonate is 1:1: 1:0.5:1: 1.
The dosage ratio of the intermediate 7, the iron powder, the ethanol and the hydrochloric acid solution in the step A5 is 3.2g:5g:80mL:10mL, the volume fraction of the ethanol is 90%, the hydrochloric acid solution is formed by mixing concentrated hydrochloric acid with the mass fraction of 36% and ethanol with the volume fraction of 95% in a volume ratio of 1:9, the dosage molar ratio of the intermediate 8 and the oxalic acid is 1:1, the dosage of the 1-hydroxybenzotriazole is 10-15% of the mass sum of the intermediate 8 and the oxalic acid, the dosage ratio of the composite carrier, the intermediate 9 and the concentrated sulfuric acid is 10g:5g:1.3mL, and the mass fraction of the concentrated sulfuric acid is 98%.
Example 1
A preparation method of the composite thick oil viscosity reducer specifically comprises the following steps:
step S1: adding acrylamide, sodium p-styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid and deionized water into a reaction kettle, and stirring at the rotation speed of 150r/min until the acrylamide, the sodium p-styrenesulfonate and the 2-acrylamido-2-methylpropanesulfonic acid are completely dissolved to prepare a mixed solution;
step S2: dispersing the viscosity-reducing additive in ethanol, stirring and adding the mixed solution and azobisisobutyronitrile at the rotation speed of 200r/min, reacting for 8 hours at the temperature of 70 ℃, and distilling to remove distillate at the temperature of 110 ℃ to obtain the composite thick oil viscosity reducer.
The viscosity-reducing additive is prepared by the following steps:
step A1: adding concentrated sulfuric acid and deionized water into a reaction kettle, stirring for 10min at the rotation speed of 500r/min, adding montmorillonite, stirring for 2h at the temperature of 85 ℃, washing with deionized water to be neutral, filtering to remove filtrate to obtain primary modified montmorillonite, dispersing the primary modified montmorillonite in ethanol, adding N- (4-alkenyl butyl) phthalimide and acrylamide, keeping the temperature for 15min under the protection of nitrogen at the temperature of 80 ℃, adding azodiisobutyronitrile, reacting for 4h, and centrifuging to obtain secondary modified montmorillonite;
step A2: adding tetraethoxysilane, ethanol and deionized water into a reaction kettle, stirring and adjusting the pH value of reaction liquid to 3 under the conditions of the rotating speed of 200r/min and the temperature of 60 ℃, reacting for 30min, adjusting the pH value of the reaction liquid to 8 to prepare nano silica gel, adding secondary modified montmorillonite into the silica gel, carrying out ultrasonic treatment for 2h under the condition of the frequency of 5MHz, filtering to remove filtrate, and roasting a filter cake for 2h under the condition of the temperature of 200 ℃ to prepare a composite carrier;
step A3: adding pyromellitic dianhydride, sulfolane and thionyl chloride into a reaction kettle, stirring for 1h at the rotation speed of 200r/min and the temperature of 80 ℃, adding potassium fluoride, reacting for 3h at the temperature of 210 ℃ to obtain an intermediate 1, adding the intermediate 1, a sodium hydroxide solution and copper powder into the reaction kettle, reacting for 5h at the pressure of 28MPa and the temperature of 280 ℃ to obtain an intermediate 2, adding the intermediate 2, octadecanol and toluene into the reaction kettle, introducing nitrogen for protection, stirring and adding p-toluenesulfonic acid at the rotation speed of 150r/min, and performing reflux reaction for 3h at the temperature of 120 ℃ to obtain an intermediate 3;
step A4: adding toluene and mixed acid into a reaction kettle, reacting for 2h at the rotation speed of 150r/min and the temperature of 50 ℃ to obtain an intermediate 4, adding the intermediate 4, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 8h at the temperature of 80 ℃ to obtain an intermediate 5, adding acetic acid, sodium carbonate and the intermediate 5 into the reaction kettle, performing reflux reaction for 5h at the temperature of 120 ℃, filtering to remove filtrate, washing a filter cake with ethanol, filtering to remove filtrate, mixing the filtrate and ethyl acetate, distilling, mixing a substrate, ethanol, deionized water and sodium hydroxide, adjusting the pH value of the mixed solution to 10, performing reflux for 4h at the temperature of 110 ℃, distilling to remove a solvent, adding hydrochloric acid until the pH value is 7, preparing an intermediate 6, adding the intermediate 6, the intermediate 3, dibromoethane, acetone and sodium bicarbonate into a reaction kettle, performing reflux reaction for 1h at the temperature of 60 ℃, adding 3-bromopropylene, and performing reflux reaction for 6h to prepare an intermediate 7;
step A5: adding the intermediate 7, iron powder and ethanol into a reaction kettle, performing reflux reaction for 3 hours at the temperature of 80 ℃, adding a hydrochloric acid solution, adding for 20 minutes, continuing to react for 5 hours, adjusting the pH value of a reaction solution to 7 to prepare an intermediate 8, adding the intermediate 8 and oxalic acid into the reaction kettle, adding 1-hydroxybenzotriazole into the reaction kettle at the temperature of 50 ℃ to perform reaction for 5 hours to prepare an intermediate 9, dispersing a composite carrier into deionized water, adding the intermediate 9 and concentrated sulfuric acid, performing reflux reaction for 5-8 hours at the temperature of 110 ℃, removing the deionized water, and preparing the viscosity-reducing additive.
Example 2
A preparation method of the composite thick oil viscosity reducer specifically comprises the following steps:
step S1: adding acrylamide, sodium p-styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid and deionized water into a reaction kettle, and stirring at the rotation speed of 150r/min until the acrylamide, the sodium p-styrenesulfonate and the 2-acrylamido-2-methylpropanesulfonic acid are completely dissolved to prepare a mixed solution;
step S2: dispersing the viscosity-reducing additive in ethanol, stirring and adding the mixed solution and azobisisobutyronitrile at the rotation speed of 300r/min, reacting for 10 hours at the temperature of 70 ℃, and distilling to remove distillate at the temperature of 110 ℃ to obtain the composite thick oil viscosity reducer.
The viscosity-reducing additive is prepared by the following steps:
step A1: adding concentrated sulfuric acid and deionized water into a reaction kettle, stirring for 10min at the rotation speed of 800r/min, adding montmorillonite, stirring for 2h at the temperature of 90 ℃, washing with deionized water to be neutral, filtering to remove filtrate to obtain primary modified montmorillonite, dispersing the primary modified montmorillonite in ethanol, adding N- (4-alkenyl butyl) phthalimide and acrylamide, keeping the temperature for 15min under the protection of nitrogen at the temperature of 90 ℃, adding azodiisobutyronitrile, reacting for 6h, and centrifuging to obtain secondary modified montmorillonite;
step A2: adding tetraethoxysilane, ethanol and deionized water into a reaction kettle, stirring and adjusting the pH value of reaction liquid to 3 under the conditions of the rotating speed of 200r/min and the temperature of 65 ℃, reacting for 40min, adjusting the pH value of the reaction liquid to 8 to prepare nano silica gel, adding secondary modified montmorillonite into the silica gel, carrying out ultrasonic treatment for 2h under the condition of the frequency of 8MHz, filtering to remove filtrate, and roasting a filter cake for 3h under the condition of the temperature of 200 ℃ to prepare a composite carrier;
step A3: adding pyromellitic dianhydride, sulfolane and thionyl chloride into a reaction kettle, stirring for 1h at the rotation speed of 200r/min and the temperature of 85 ℃, adding potassium fluoride, reacting for 3h at the temperature of 220 ℃ to obtain an intermediate 1, adding the intermediate 1, a sodium hydroxide solution and copper powder into the reaction kettle, reacting for 8h at the pressure of 30MPa and the temperature of 280 ℃ to obtain an intermediate 2, adding the intermediate 2, octadecanol and toluene into the reaction kettle, introducing nitrogen for protection, stirring and adding p-toluenesulfonic acid at the rotation speed of 150r/min, and performing reflux reaction for 3h at the temperature of 130 ℃ to obtain an intermediate 3;
step A4: adding toluene and mixed acid into a reaction kettle, reacting for 3h at the rotation speed of 200r/min and the temperature of 50 ℃ to obtain an intermediate 4, adding the intermediate 4, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 10h at the temperature of 80 ℃ to obtain an intermediate 5, adding acetic acid, sodium carbonate and the intermediate 5 into the reaction kettle, performing reflux reaction for 6h at the temperature of 120 ℃, filtering to remove filtrate, washing a filter cake with ethanol, filtering to remove filtrate, mixing the filtrate and ethyl acetate, distilling, mixing a substrate, ethanol, deionized water and sodium hydroxide, adjusting the pH value of the mixed solution to 10, performing reflux for 6h at the temperature of 110 ℃, distilling to remove a solvent, adding hydrochloric acid until the pH value is 7, preparing an intermediate 6, adding the intermediate 6, the intermediate 3, dibromoethane, acetone and sodium bicarbonate into a reaction kettle, performing reflux reaction for 2 hours at the temperature of 60 ℃, adding 3-bromopropylene, and performing reflux reaction for 6 hours to prepare an intermediate 7;
step A5: adding the intermediate 7, iron powder and ethanol into a reaction kettle, performing reflux reaction for 3 hours at the temperature of 85 ℃, adding a hydrochloric acid solution, adding for 20 minutes, continuing to react for 8 hours, adjusting the pH value of a reaction solution to 7 to prepare an intermediate 8, adding the intermediate 8 and oxalic acid into the reaction kettle, adding 1-hydroxybenzotriazole into the reaction kettle at the temperature of 60 ℃ to perform reaction for 5 hours to prepare an intermediate 9, dispersing a composite carrier into deionized water, adding the intermediate 9 and concentrated sulfuric acid, performing reflux reaction for 5 hours at the temperature of 120 ℃, removing the deionized water, and preparing the viscosity-reducing additive.
Example 3
A preparation method of the composite thick oil viscosity reducer specifically comprises the following steps:
step S1: adding acrylamide, sodium p-styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid and deionized water into a reaction kettle, and stirring at the rotation speed of 200r/min until the acrylamide, the sodium p-styrenesulfonate and the 2-acrylamido-2-methylpropanesulfonic acid are completely dissolved to prepare a mixed solution;
step S2: dispersing the viscosity-reducing additive in ethanol, stirring and adding the mixed solution and azodiisobutyronitrile under the condition that the rotation speed is 300r/min, reacting for 10 hours at the temperature of 80 ℃, and distilling to remove distillate under the temperature of 120 ℃ to prepare the composite thick oil viscosity reducer.
The viscosity-reducing additive is prepared by the following steps:
step A1: adding concentrated sulfuric acid and deionized water into a reaction kettle, stirring for 15min at the rotation speed of 800r/min, adding montmorillonite, stirring for 4h at the temperature of 90 ℃, washing with deionized water to be neutral, filtering to remove filtrate to obtain primary modified montmorillonite, dispersing the primary modified montmorillonite in ethanol, adding N- (4-alkenyl butyl) phthalimide and acrylamide, keeping the temperature for 20min under the protection of nitrogen at the temperature of 90 ℃, adding azodiisobutyronitrile, reacting for 6h, and centrifuging to obtain secondary modified montmorillonite;
step A2: adding tetraethoxysilane, ethanol and deionized water into a reaction kettle, stirring and adjusting the pH value of reaction liquid to be 4 under the conditions of the rotating speed of 300r/min and the temperature of 65 ℃, reacting for 40min, adjusting the pH value of the reaction liquid to be 9 to prepare nano silica gel, adding secondary modified montmorillonite into the silica gel, carrying out ultrasonic treatment for 3h under the condition of the frequency of 8MHz, filtering to remove filtrate, and roasting a filter cake for 3h under the condition of the temperature of 200 ℃ to prepare a composite carrier;
step A3: adding pyromellitic dianhydride, sulfolane and thionyl chloride into a reaction kettle, stirring for 1.5 hours at the rotation speed of 300r/min and at the temperature of 85 ℃, adding potassium fluoride, reacting for 4 hours at the temperature of 220 ℃ to obtain an intermediate 1, adding the intermediate 1, a sodium hydroxide solution and copper powder into the reaction kettle, reacting for 8 hours at the pressure of 30MPa and the temperature of 300 ℃ to obtain an intermediate 2, adding the intermediate 2, octadecanol and toluene into the reaction kettle, introducing nitrogen for protection, stirring and adding p-toluenesulfonic acid at the rotation speed of 200r/min, and performing reflux reaction for 5 hours at the temperature of 130 ℃ to obtain an intermediate 3;
step A4: adding toluene and mixed acid into a reaction kettle, reacting for 3h at the rotation speed of 200r/min and the temperature of 60 ℃ to obtain an intermediate 4, adding the intermediate 4, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 10h at the temperature of 90 ℃ to obtain an intermediate 5, adding acetic acid, sodium carbonate and the intermediate 5 into the reaction kettle, performing reflux reaction for 6h at the temperature of 130 ℃, filtering to remove filtrate, washing a filter cake with ethanol, filtering to remove filtrate, mixing the filtrate and ethyl acetate, distilling, mixing a substrate, ethanol, deionized water and sodium hydroxide, adjusting the pH value of the mixed solution to 10, performing reflux for 6h at the temperature of 120 ℃, distilling to remove a solvent, adding hydrochloric acid until the pH value is 7, preparing an intermediate 6, adding the intermediate 6, the intermediate 3, dibromoethane, acetone and sodium bicarbonate into a reaction kettle, performing reflux reaction for 2 hours at the temperature of 65 ℃, adding 3-bromopropylene, and performing reflux reaction for 8 hours to prepare an intermediate 7;
step A5: adding the intermediate 7, iron powder and ethanol into a reaction kettle, performing reflux reaction for 5 hours at the temperature of 85 ℃, adding a hydrochloric acid solution, adding for 20 minutes, continuing to react for 8 hours, adjusting the pH value of a reaction solution to 8 to prepare an intermediate 8, adding the intermediate 8 and oxalic acid into the reaction kettle, adding 1-hydroxybenzotriazole into the reaction kettle at the temperature of 60 ℃ to perform reaction for 6 hours to prepare an intermediate 9, dispersing a composite carrier into deionized water, adding the intermediate 9 and concentrated sulfuric acid, performing reflux reaction for 8 hours at the temperature of 120 ℃, removing the deionized water, and preparing the viscosity-reducing additive.
Comparative example
This comparative example is an LDPS heavy oil viscosity reducer.
Comparative example 2
The comparative example is a thick oil emulsifying viscosity reducer XDD-XP 9000.
The thick oil viscosity reducers prepared in examples 1 to 3 and comparative examples 1 to 2 were subjected to performance tests, and the test results are shown in the following table 1;
taking 5 parts of thickened oil with the viscosity of 50000 mPas and the asphaltene content of 18.25%, respectively adding the thickened oil viscosity reducer prepared in the examples 1-3 and the thickened oil viscosity reducer prepared in the comparative examples 1-2 with the total mass of 0.5wt% into the thickened oil, measuring the viscosity of the thickened oil after viscosity reduction at normal temperature, and calculating the viscosity reduction rate;
taking 15 parts of thickened oil with the viscosity of 50000 mPas and the asphaltene content of 18.25%, respectively adding three parts of the thickened oil viscosity reducers prepared in the examples 1-3 and the comparative examples 1-2 with the total mass of 0.5wt% into the thickened oil, respectively measuring the viscosity of the thickened oil after viscosity reduction at the temperature of 60, 80 and 100 ℃, and calculating the viscosity reduction rate;
TABLE 1
From table 1 above, it can be seen that the viscosity reducing agent for thick oil prepared in examples 1 to 3 has a viscosity reducing rate of 62.8 to 64.0% after being applied to thick oil at room temperature, a viscosity reducing rate of 63.0 to 63.8% at 60 ℃, a viscosity reducing rate of 63.4 to 63.8% at 80 ℃, a viscosity reducing rate of 60.4 to 61.6% at 100 ℃, the viscosity reducing agent for thick oil prepared in comparative example 1 has a viscosity reducing rate of 58.0% after being applied to thick oil at room temperature, a viscosity reducing rate of 48.8% at 60 ℃, a viscosity reducing rate of 38.0% at 80 ℃, a viscosity reducing rate of 22.0% at 100 ℃, the viscosity reducing agent for thick oil prepared in comparative example 2 has a viscosity reducing rate of 55.0% after being applied to thick oil at room temperature, a viscosity reducing rate of 50.4% at 60 ℃, a viscosity reducing rate of 35.0% at 80 ℃, a viscosity reducing rate of 23.0% at 100 ℃, the viscosity reducer has good viscosity reducing effect on high-viscosity thick oil, does not reduce viscosity reducing efficiency in a high-temperature environment, and is less in addition amount compared with the existing viscosity reducer.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (6)
1. A preparation method of the composite thick oil viscosity reducer is characterized by comprising the following steps: the method specifically comprises the following steps:
step S1: adding acrylamide, sodium p-styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid and deionized water into a reaction kettle, and stirring at the rotation speed of 150-;
step S2: dispersing the viscosity-reducing additive in ethanol, stirring and adding the mixed solution and azodiisobutyronitrile under the condition that the rotation speed is 200-300r/min, reacting for 8-10h under the condition that the temperature is 70-80 ℃, and distilling to remove distillate under the condition that the temperature is 110-120 ℃ to prepare the composite thick oil viscosity reducer;
the viscosity-reducing additive is prepared by the following steps:
step A1: adding concentrated sulfuric acid and deionized water into a reaction kettle, stirring for 10-15min under the condition that the rotating speed is 500-800r/min, adding montmorillonite, stirring for 2-4h under the condition that the temperature is 85-90 ℃, washing with deionized water to be neutral, filtering to remove filtrate to obtain primary modified montmorillonite, dispersing the primary modified montmorillonite in ethanol, adding N- (4-alkenyl butyl) phthalimide and acrylamide, keeping the temperature for 15-20min under the condition of nitrogen protection at the temperature of 80-90 ℃, adding azobisisobutyronitrile for reacting for 4-6h, and centrifuging to obtain secondary modified montmorillonite;
step A2: adding tetraethoxysilane, ethanol and deionized water into a reaction kettle, stirring and adjusting the pH value of reaction liquid to 3-4 under the conditions that the rotating speed is 200 plus or minus 300r/min and the temperature is 60-65 ℃, adjusting the pH value of the reaction liquid to 8-9 after reacting for 30-40min to prepare nano silica gel, adding secondary modified montmorillonite into the silica gel, carrying out ultrasonic treatment for 2-3h under the condition that the frequency is 5-8MHz, filtering to remove filtrate, and roasting a filter cake for 2-3h under the condition that the temperature is 200 +/-5 ℃ to prepare a composite carrier;
step A3: adding pyromellitic dianhydride, sulfolane and thionyl chloride into a reaction kettle, stirring at the rotation speed of 200-85 ℃ for 1-1.5h, adding potassium fluoride, and reacting at the temperature of 210-220 ℃ for 3-4h to obtain an intermediate 1, wherein the structural formula is shown in the specification
Adding the intermediate 1, sodium hydroxide solution and copper powder into a reaction kettle, and reacting for 5-8h under the conditions that the pressure is 28-30MPa and the temperature is 280-300 ℃ to obtain an intermediate 2, wherein the structural formula is shown in the specification
Adding the intermediate 2, octadecanol and toluene into a reaction kettle, introducing nitrogen for protection, stirring and adding p-toluenesulfonic acid under the condition of the rotating speed of 150-
；
Step A4: toluene and mixed acid are added into a reaction kettle and react for 2 to 3 hours under the conditions that the rotating speed is 150-200r/min and the temperature is 50 to 60 ℃ to prepare an intermediate 4, the structural formula of which is shown in the specification
Adding the intermediate 4, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, and reacting for 8-10h at 80-90 ℃ to obtain an intermediate 5 with a structural formula
Adding acetic acid, sodium carbonate and an intermediate 5 into a reaction kettle, performing reflux reaction for 5-6h at the temperature of 120-130 ℃, filtering to remove filtrate, washing a filter cake with ethanol, filtering to remove filtrate, mixing the filtrate with ethyl acetate, distilling, mixing a substrate, ethanol, deionized water and sodium hydroxide, adjusting the pH value of the mixed solution to 10, performing reflux for 4-6h at the temperature of 110-120 ℃, distilling to remove a solvent, adding hydrochloric acid until the pH value is 7 +/-0.5, and preparing an intermediate 6, wherein the structural formula is shown in the specification
Adding the intermediate 6, the intermediate 3, dibromoethane, acetone and sodium bicarbonate into a reaction kettle, performing reflux reaction for 1-2h at the temperature of 60-65 ℃, adding 3-bromopropylene, and performing reflux reaction for 6-8h to obtain an intermediate 7, wherein the structural formula is shown in the specification
；
Step A5: adding the intermediate 7, iron powder and ethanol into a reaction kettle, performing reflux reaction at 80-85 deg.C for 3-5h, adding hydrochloric acid solution for 20min, reacting for 5-8h, adjusting pH of the reaction solution to 7-8 to obtain intermediate 8 with structural formula of
Adding the intermediate 8 and oxalic acid into a reaction kettle, adding 1-hydroxybenzotriazole at 50-60 deg.C, and reacting for 5-6h to obtain intermediate 9 with structural formula
Dispersing the composite carrier in deionized water, adding the intermediate 9 and concentrated sulfuric acid, performing reflux reaction for 5-8h at the temperature of 110-120 ℃, and removing the deionized water to prepare the viscosity-reducing additive;
the dosage ratio of the acrylamide, the sodium p-styrenesulfonate, the 2-acrylamido-2-methylpropanesulfonic acid and the deionized water in the step S1 is 0.2mol:0.2mol:0.1mol:200mL, the dosage ratio of the viscosity-reducing additive and the mixed solution in the step S2 is 3g:40mL, and the dosage of the azobisisobutyronitrile is 1.2-1.5% of the dosage of the viscosity-reducing additive.
2. The preparation method of the composite thick oil viscosity reducer according to claim 1, characterized in that: the mass ratio of the concentrated sulfuric acid to the deionized water to the montmorillonite in the step A1 is 1:1:6, the mass fraction of the concentrated sulfuric acid is 98%, the mass ratio of the primary modified montmorillonite to the N- (4-alkenyl butyl) phthalimide to the acrylamide is 5:1:1.2, and the mass ratio of the azodiisobutyronitrile to the N- (4-alkenyl butyl) phthalimide to the acrylamide is 1-1.5 per mill.
3. The preparation method of the composite thick oil viscosity reducer according to claim 1, characterized in that: the using amount molar ratio of the ethyl orthosilicate, the ethanol and the deionized water in the step A2 is 1:1.2:6.5, and the using amount ratio of the secondary modified montmorillonite to the silica gel is 1g:5 mL.
4. The preparation method of the composite thick oil viscosity reducer according to claim 1, characterized in that: the using amount mass ratio of the pyromellitic dianhydride, the sulfolane, the thionyl chloride and the potassium fluoride in the step A3 is 2.5:5:2:1.1, the using amount ratio of the intermediate 1, the sodium hydroxide solution and the copper powder is 1g:10mL:0.3g, the mass fraction of the sodium hydroxide solution is 15%, the using amount molar ratio of the intermediate 2 to the octadecanol is 1:2.1, and the using amount of the p-toluenesulfonic acid is 0.8-1% of the mass sum of the intermediate 2 and the octadecanol.
5. The preparation method of the composite thick oil viscosity reducer according to claim 1, characterized in that: the dosage ratio of the toluene and the mixed acid in the step A4 is 3mL:8mL, the mixed acid is formed by mixing nitric acid with the mass fraction of 68% and sulfuric acid with the mass fraction of 95% according to the volume ratio of 3:1, the dosage ratio of the intermediate 4, the nitrogen-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride is 0.03mol:0.03mol:0.1g:60mL, the dosage ratio of the acetic acid, the sodium carbonate and the intermediate 5 is 15mL:1.08g:5g, the dosage ratio of the substrate, the ethanol, the deionized water and the sodium hydroxide is 5g:20mL:20mL:2.6g, and the dosage molar ratio of the intermediate 6, the intermediate 3, the dibromoethane, the 3-bromopropylene and the sodium bicarbonate is 1:1: 1:0.5:1: 1.
6. The preparation method of the composite thick oil viscosity reducer according to claim 1, characterized in that: the dosage ratio of the intermediate 7, the iron powder, the ethanol and the hydrochloric acid solution in the step A5 is 3.2g:5g:80mL:10mL, the volume fraction of the ethanol is 90%, the hydrochloric acid solution is formed by mixing concentrated hydrochloric acid with the mass fraction of 36% and ethanol with the volume fraction of 95% in a volume ratio of 1:9, the dosage molar ratio of the intermediate 8 to the oxalic acid is 1:1, the dosage of the 1-hydroxybenzotriazole is 10-15% of the mass sum of the intermediate 8 and the oxalic acid, the dosage ratio of the composite carrier, the intermediate 9 and the concentrated sulfuric acid is 10g:5g:1.3mL, and the mass fraction of the concentrated sulfuric acid is 98%.
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| CN106939157A (en) * | 2017-03-16 | 2017-07-11 | 西南石油大学 | A kind of double-strand oil soluble heavy crude thinner and preparation method thereof |
| CN107488248A (en) * | 2017-08-31 | 2017-12-19 | 山东大学 | A kind of nano imvite and polymer composite viscosity reducer and preparation method thereof |
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| CN106939157A (en) * | 2017-03-16 | 2017-07-11 | 西南石油大学 | A kind of double-strand oil soluble heavy crude thinner and preparation method thereof |
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