CN114478896B - Preparation method of pour point depressant and pour point depressant - Google Patents
Preparation method of pour point depressant and pour point depressant Download PDFInfo
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- 230000000994 depressogenic effect Effects 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 145
- 239000000178 monomer Substances 0.000 claims abstract description 69
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 239000003999 initiator Substances 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 19
- 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 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000004711 α-olefin Substances 0.000 claims description 8
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- 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 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 239000010779 crude oil Substances 0.000 abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 16
- 238000009833 condensation Methods 0.000 abstract description 7
- 230000005494 condensation Effects 0.000 abstract description 7
- 230000001603 reducing effect Effects 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 description 25
- -1 acrylic alcohol ester Chemical class 0.000 description 17
- 230000000881 depressing effect Effects 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910001873 dinitrogen Inorganic materials 0.000 description 12
- 239000013078 crystal Substances 0.000 description 7
- 125000003944 tolyl group Chemical group 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- FVRPPSYXTLVAKR-UHFFFAOYSA-N ethenyl acetate;prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.CC(=O)OC=C.C=CC1=CC=CC=C1 FVRPPSYXTLVAKR-UHFFFAOYSA-N 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 1
- 235000003320 Adansonia digitata Nutrition 0.000 description 1
- 244000056971 Adansonia gregorii Species 0.000 description 1
- 235000003319 Adansonia gregorii Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
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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
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
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Abstract
The invention discloses a preparation method of a pour point depressant and the pour point depressant, and belongs to the field of petrochemical industry. The preparation method of the pour point depressant comprises the following steps: providing reaction raw materials, wherein the reaction raw materials comprise the following components in percentage by mass: 15% -65% of a first monomer, 15% -65% of a second monomer, 0.35% -0.6% of a chain transfer agent, 0.05% -1% of an initiator and the balance of a solvent; placing a first monomer, a chain transfer agent, an initiator and a solvent in a reaction vessel, and performing a first reaction in a nitrogen atmosphere; and after the first reaction is finished, dropwise adding high-carbon alcohol acrylate into the reactor to perform a second reaction, and after the second reaction is finished, obtaining the pour point depressant. The pour point depressant can obtain better pour point and viscosity reducing effects on crude oil with high wax content and high condensation point.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a preparation method of a pour point depressant and the pour point depressant.
Background
The crude oil pour point depressant is generally prepared from an oil-soluble polymer or condensate and a solvent, and comprises polar groups and nonpolar groups, wherein the polar groups and the nonpolar groups change the structure of wax crystals in the modes of eutectic, adsorption and the like, so that the viscosity and the condensation point of crude oil are reduced, and the low-temperature fluidity of the crude oil is changed, thereby being beneficial to the transportation of the crude oil. It can be seen that it is necessary to provide a pour point depressant.
The related art provides an acrylic alcohol ester pour point depressant which is generally a homopolymer of acrylic alcohol ester or a random copolymer of acrylic alcohol ester and other monomers.
In carrying out the invention, the inventors have found that there are at least the following problems in the prior art:
the pour point depressant has poor pour point depressing and viscosity depressing effects on crude oil with high wax content and high condensation point, can not achieve uniform dispersion and wax crystal adsorption, and hardly achieves ideal pour point depressing and viscosity depressing effects.
Disclosure of Invention
In view of the above, the present invention provides a preparation method of a pour point depressant and a pour point depressant, which can solve the above technical problems.
Specifically, the method comprises the following technical scheme:
in one aspect, the embodiment of the invention provides a preparation method of a pour point depressant, which comprises the following steps: providing reaction raw materials, wherein the reaction raw materials comprise the following components in percentage by mass: 15% -65% of a first monomer, 15% -65% of a second monomer, 0.35% -0.6% of a chain transfer agent, 0.05% -1% of an initiator and the balance of a solvent;
placing the first monomer, the chain transfer agent, the initiator and the solvent in a reaction vessel, and performing a first reaction under a nitrogen atmosphere;
and after the first reaction is finished, dropwise adding the acrylic acid higher alcohol ester into the reactor to perform a second reaction, and after the second reaction is finished, obtaining the pour point depressant.
In some possible implementations, the reactant first monomer includes: styrene, vinyl acetate, alpha-olefins or dicyclopentadiene;
the preparation method of the pour point depressant further comprises the following steps: and after the second reaction is finished, dropwise adding the styrene, the alpha-olefin or the dicyclopentadiene into the reactor to perform a third reaction, and after the third reaction is finished, obtaining the pour point depressant.
In some possible implementations, the first reaction is performed at a reaction temperature of 65 ℃ to 75 ℃ for a reaction time of 70 minutes to 100 minutes.
In some possible implementations, the second reaction is performed at a reaction temperature of 65 ℃ to 75 ℃ for a reaction time of 50 minutes to 100 minutes.
In some possible implementations, the second reaction is performed under stirring conditions, and the stirring rate is 300rpm to 400rpm.
In some possible implementations, the reaction temperature is 65 ℃ to 75 ℃ and the reaction time is 60 minutes to 80 minutes when the third reaction is performed.
In some possible implementations, the second monomer is selected from higher alcohol acrylates, maleic anhydride, or polyfluoroalcohol esters.
In some possible implementations, the chain transfer agent is 2-cyano-2-propylbenzodisulfide or butyl-2-methyl-2- [ (dodecylsulfanylthiocarbonyl) ] sulfanyl (CTA-ester).
In some possible implementations, the initiator is selected from at least one of azobisisobutyronitrile, benzoyl peroxide, dimethyl azobisisobutyrate.
On the other hand, the embodiment of the invention also provides a pour point depressant, which is prepared by adopting any one of the preparation methods.
The technical scheme provided by the embodiment of the invention has the beneficial effects that at least:
according to the preparation method of the pour point depressant, provided by the embodiment of the invention, the homopolymer of the first monomer is obtained by carrying out the first reaction of the first monomer, the chain transfer agent, the initiator and the solvent in the nitrogen atmosphere. By subjecting the first monomer to the second reaction, an-AB-AB-type polymer (wherein A represents a reactive radical formed by the first monomer and B represents a reactive radical formed by the second monomer) can be obtained as an active ingredient of the pour point depressant desired in the examples of the present invention. According to the preparation method provided by the embodiment of the invention, due to the existence of the chain transfer agent, reversible addition-fragmentation chain transfer reaction can occur, and due to the influence of parameters such as interaction force, steric hindrance, polymerization ratio and the like of groups, two monomers are alternately polymerized, so that the sequence regulation and control of the molecular structure of the-AB-AB-type polymer are realized, and the polar group-containing part and the alkyl side chain-containing part of the-AB-AB-type polymer are directionally distributed, so that wax crystals can be more uniformly dispersed and adsorbed by the-AB-type polymer, and the pour point depressant prepared by the embodiment of the invention can obtain better pour point depressing and viscosity reducing effects on crude oil with high wax content and high condensation point.
Detailed Description
In order to make the technical scheme and advantages of the present invention more apparent, the following detailed description of the embodiments of the present invention will be provided.
Along with the change of crude oil physical properties, more and more crude oil with high wax content and high congealing point is provided, at present, the pour point depressing and viscosity depressing effects of the acrylic acid ester pour point depressing agent provided by the prior art on the crude oil with high wax content and high congealing point are poor, even dispersion and wax crystal absorption cannot be achieved, and ideal pour point depressing and viscosity depressing effects are difficult to achieve.
The embodiment of the invention provides a preparation method of a pour point depressant, which comprises the following steps: providing reaction raw materials, wherein the reaction raw materials comprise the following components in percentage by mass: 15% -65% of a first monomer, 15% -65% of a second monomer, 0.35% -0.6% of a chain transfer agent, 0.05% -1% of an initiator and the balance of a solvent. That is, the amount of solvent is such that the total mass percent of the first monomer, second monomer, chain transfer agent, initiator, and solvent is up to 100%.
The first monomer, chain transfer agent, initiator and solvent are placed in a reaction vessel and the first reaction is carried out under nitrogen atmosphere.
And after the first reaction is finished, dropwise adding high-carbon alcohol acrylate into the reactor to perform a second reaction, and after the second reaction is finished, obtaining the pour point depressant.
According to the preparation method of the pour point depressant, provided by the embodiment of the invention, the homopolymer of the first monomer is obtained by carrying out the first reaction of the first monomer, the chain transfer agent, the initiator and the solvent in the nitrogen atmosphere. By subjecting the first monomer to the second reaction, an-AB-AB-type polymer (wherein A represents a reactive radical formed by the first monomer and B represents a reactive radical formed by the second monomer) can be obtained as an active ingredient of the pour point depressant desired in the examples of the present invention. According to the preparation method provided by the embodiment of the invention, due to the existence of the chain transfer agent, reversible addition-fragmentation chain transfer reaction can occur, and due to the influence of parameters such as interaction force, steric hindrance, polymerization ratio and the like of groups, two monomers are alternately polymerized, so that the sequence regulation and control of the molecular structure of the-AB-AB-type polymer are realized, and the polar group-containing part and the alkyl side chain-containing part of the-AB-AB-type polymer are directionally distributed, so that wax crystals can be more uniformly dispersed and adsorbed by the-AB-type polymer, and the pour point depressant prepared by the embodiment of the invention can obtain better pour point depressing and viscosity reducing effects on crude oil with high wax content and high condensation point.
In some possible implementations, the first monomer provided in the embodiments of the present invention includes: styrene, vinyl acetate, alpha-olefins or dicyclopentadiene, the second monomer comprising: maleic anhydride, higher alcohol acrylate or polyfluoroalcohol ester). That is, the reaction raw materials comprise the following components in percentage by mass: 15% -65% of a first monomer, 15% -65% of a second monomer, 0.35% -0.6% of a chain transfer agent, 0.05% -1% of an initiator and the balance of a solvent. So that the total mass percent of the first monomer, the second monomer, the chain transfer agent, the initiator and the solvent reaches 100 percent.
In this case, the preparation method of the pour point depressant provided by the embodiment of the invention further comprises the following steps: and after the second reaction is finished, dropwise adding styrene, alpha-olefin or dicyclopentadiene into the reactor to perform a third reaction, and obtaining the pour point depressant after the third reaction is finished.
In the third reaction, styrene, alpha-olefin or dicyclopentadiene is further polymerized with the AB-AB-type polymer to form an ABC-ABC-type polymer (wherein C represents a styrene group, an alpha-olefin group or a dicyclopentadienyl group), and the polar group-containing part and the alkyl side chain-containing part of the ABC-ABC-type polymer are directionally distributed, so that wax crystals can be more uniformly dispersed and adsorbed in the same principle as the AB-AB-type polymer, and the pour point depressant prepared by the embodiment of the invention can obtain better pour point and viscosity reducing effects on crude oil with high wax content and high condensation point.
The following further describes each step involved in the preparation method of the pour point depressant provided by the embodiment of the present invention:
for the reaction raw material, higher alcohol acrylate, in some possible examples, higher alcohol acrylate is produced by esterification of a higher alcohol having 16 to 26 carbon atoms, also called higher fatty alcohol, with acrylic acid.
In an embodiment of the invention, the second monomer is selected from higher alcohol acrylate, maleic anhydride or polyfluoroalcohol ester. In some possible implementations, the first monomer is vinyl acetate, and thus, the-AB-AB-type polymer is a higher alcohol acrylate-vinyl acetate copolymer. Further, styrene is used for the third reaction, and the ABC-ABC-type polymer formed at this time is the acrylic acid high-carbon alcohol ester-vinyl acetate-styrene terpolymer.
In embodiments of the present invention, the chain transfer agent can control the chain length of the polymer, i.e., control the degree of polymerization of the polymer, or the viscosity of the polymer. The more chain transfer agent is added, the shorter the chain of the polymer, and the lower the viscosity. In some possible implementations, the chain transfer agent is 2-cyano-2-propylbenzodisulfide or butyl-2-methyl-2- [ (dodecylsulfanylthiocarbonyl) ] sulfanyl (CTA-ester).
In some possible implementation manners, the initiator is at least one of azodiisobutyronitrile, benzoyl peroxide and dimethyl azodiisobutyrate, so that a better initiation effect can be obtained.
In some possible implementations, the organic solvent is selected from at least one of alkanes (e.g., gasoline, diesel, etc.), isobutanol, t-butanol, toluene, xylenes, heavy aromatics.
In the embodiment of the invention, a first monomer, a chain transfer agent, an initiator and a solvent are placed in a reaction vessel, and a first reaction is performed under a nitrogen atmosphere.
Illustratively, the vinyl acetate, 2-cyano-2-propylbenzodisulfide, and azobisisobutyronitrile are first reacted in toluene with a first monomer being vinyl acetate, a chain transfer agent being 2-cyano-2-propylbenzodisulfide, an initiator being azobisisobutyronitrile, and a solvent being toluene, for example. The first reaction is essentially a homo-polymerization of vinyl acetate.
In order to improve the reaction efficiency and reduce the generation of reaction byproducts, in the embodiment of the invention, the reaction temperature is 65-75 ℃ and the reaction time is 70-100 minutes when the first reaction is carried out.
For example, the above reaction temperatures include, but are not limited to: 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, and the like.
Reaction times include, but are not limited to: 70 minutes, 75 minutes, 80 minutes, 85 minutes, 90 minutes, 95 minutes, 100 minutes, etc.
And after the first reaction is finished, dripping acrylic acid high-carbon alcohol ester into the reactor for a second reaction, and obtaining the pour point depressant after the second reaction is finished.
Wherein, the high-carbon alcohol acrylate can be dripped by a syringe or a dropper, and the reaction vessel can be a three-neck flask.
The first monomer is vinyl acetate, the chain transfer agent is 2-cyano-2-propyl benzodisulfide, the initiator is azodiisobutyronitrile, and the solvent is toluene, for example, after the first reaction is finished, the high-carbon alcohol acrylate and the homopolymer of vinyl acetate are subjected to a second reaction to achieve the aim of reversible addition-fragmentation chain transfer polymerization, short RAFT polymerization. That is, the second reaction is essentially a RAFT polymerization of higher alcohol acrylates with vinyl acetate.
In order to improve the reaction efficiency and reduce the generation of reaction byproducts, in the embodiment of the invention, the reaction temperature is 65-75 ℃ and the reaction time is 50-100 minutes when the second reaction is carried out.
For example, the above reaction temperatures include, but are not limited to: 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, and the like.
Reaction times include, but are not limited to: 50 minutes, 60 minutes, 70 minutes, 75 minutes, 80 minutes, 85 minutes, 90 minutes, 95 minutes, 100 minutes, etc.
In order to allow the second reaction to proceed sufficiently thoroughly, the second reaction is carried out under stirring conditions, and the stirring rate is 300rpm to 400rpm, for example, 300rpm, 320rpm, 350rpm, 370rpm, 390rpm, 400rpm, etc.
In order to improve the reaction efficiency and reduce the generation of reaction byproducts, in the embodiment of the invention, the reaction temperature is 65-75 ℃ and the reaction time is 60-80 minutes when the third reaction is carried out.
For example, the above reaction temperatures include, but are not limited to: 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, and the like.
Reaction times include, but are not limited to: 60 minutes, 65 minutes, 67 minutes, 70 minutes, 73 minutes, 75 minutes, 80 minutes, etc.
In one possible implementation mode (1), the first monomer is vinyl acetate, the chain transfer agent is 2-cyano-2-propylbenzodisulfide, the initiator is azobisisobutyronitrile, and the solvent is toluene, and the preparation method of the pour point depressant provided by the embodiment of the invention comprises the following steps:
the first monomer, the chain transfer agent and the solvent were placed in a three-necked flask, and then nitrogen gas was introduced into the three-necked flask to remove air in the three-necked flask, and the nitrogen gas introduction time was 30 minutes. Then, an initiator was added to the three-necked flask, and a first reaction was performed under a nitrogen atmosphere for 70 minutes to 100 minutes, wherein the reaction temperature of the first reaction was 65℃to 75 ℃.
After the first reaction is finished, high-carbon alcohol acrylate is dripped into the three-neck flask by adopting an injector, and the second reaction is carried out for 50 minutes to 100 minutes at the temperature of 65 ℃ to 75 ℃. The second reaction is carried out under stirring and the stirring rate is 300rpm to 400rpm. And after the second reaction is finished, obtaining the pour point depressant.
It can be seen that, for this implementation manner, the prepared pour point depressant not only includes acrylic acid higher alcohol ester-vinyl acetate binary copolymer, but also includes low content of other side reaction monomers, solvents and other organic matters, such as higher alcohol, acrylic acid oligomer, acrylic acid higher alcohol ester oligomer, vinyl acetate and the like.
In another possible implementation manner (2), the first monomer is vinyl acetate, the chain transfer agent is 2-cyano-2-propylbenzodisulfide, the initiator is azobisisobutyronitrile, and the solvent is toluene, and the preparation method of the pour point depressant provided by the embodiment of the invention comprises the following steps:
the first monomer, the chain transfer agent and the solvent were placed in a three-necked flask, and then nitrogen gas was introduced into the three-necked flask to remove air in the three-necked flask, and the nitrogen gas introduction time was 30 minutes. Then, an initiator was added to the three-necked flask, and a first reaction was performed under a nitrogen atmosphere for 70 minutes to 100 minutes, wherein the reaction temperature of the first reaction was 65℃to 75 ℃.
After the first reaction is finished, high-carbon alcohol acrylate is dripped into the three-neck flask by adopting an injector, and the second reaction is carried out for 50 minutes to 100 minutes at the temperature of 65 ℃ to 75 ℃. The second reaction is carried out under stirring and the stirring rate is 300rpm to 400rpm. And after the second reaction is finished, obtaining the pour point depressant.
After the second reaction is finished, styrene is dripped into the three-neck flask by adopting an injector, and the third reaction is carried out for 60 minutes to 80 minutes at the temperature of 65 ℃ to 75 ℃. The third reaction is carried out under stirring and the stirring rate is 300rpm to 400rpm. And after the third reaction is finished, obtaining the pour point depressant.
It can be seen that, for this implementation, the pour point depressant prepared includes not only the higher alcohol acrylate-vinyl acetate-styrene terpolymer, but also low content of other side reaction monomers and organic matters such as solvents, for example, higher alcohol acrylate oligomers, vinyl acetate, etc.
On the other hand, the embodiment of the invention also provides a pour point depressant, which is prepared by adopting any one of the preparation methods.
According to the pour point depressant provided by the embodiment of the invention, the-AB-AB-type polymer or the-ABC-ABC-type polymer is used as an active component, and the polar groups and the alkyl side chains of the polymer are distributed in a directional manner, so that wax crystals can be dispersed and adsorbed more uniformly, and the pour point depressant prepared by the embodiment of the invention can obtain better pour point depressant and viscosity-reducing effects on crude oil with high wax content and high condensation point.
For polymers of the-AB-AB-type or of the-ABC-ABC-type, the number average molecular weight of this type is 5X 10 3 -2×10 4 So as to ensure good pour point depressing and viscosity depressing effects.
In some possible implementations, the polymers of the above type may be treated with water or a high flash point alcohol, such as ethylene glycol, to form an emulsion or stable suspension that can address the problem of low flash point of the acrylate pour point depressants.
In practical applications, the addition amount of the pour point depressant to crude oil is determined according to the content of the above polymer, such as higher alcohol acrylate-vinyl acetate copolymer or higher alcohol acrylate-vinyl acetate-styrene terpolymer, to ensure that a sufficient pour point depressant and viscosity reducing effect is obtained.
The invention will be further described by means of specific examples:
example 1
This example 1 provides a pour point depressant prepared by the process of:
providing reaction raw materials, wherein the reaction raw materials comprise the following components in percentage by mass: 28% of a first monomer, 20% of a second monomer, 0.5% of a chain transfer agent, 0.7% of an initiator and the balance of a solvent.
The first monomer is vinyl acetate, the second monomer is acrylic acid higher alcohol ester, the acrylic acid higher alcohol ester is prepared by esterification reaction of higher alcohol with 20 carbon atoms and acrylic acid, the chain transfer agent is 2-cyano-2-propyl benzodisulfide, the initiator is azodiisobutyronitrile, and the solvent is toluene.
The first monomer, the chain transfer agent and the solvent were placed in a three-necked flask according to the above mass percentages of the respective components, and then nitrogen gas was introduced into the three-necked flask to remove air in the three-necked flask, and the nitrogen gas introduction time was 30 minutes. Then, an initiator was added to the three-necked flask, and a first reaction was performed under a nitrogen atmosphere for 90 minutes, wherein the reaction temperature of the first reaction was 70 ℃.
After the completion of the first reaction, a syringe was used to drop a high-carbon alcohol acrylate into the three-necked flask, and the second reaction was carried out at a temperature of 70℃for 50 minutes. The second reaction is carried out under stirring, the stirring speed is 350rpm, and the pour point depressant is obtained after the second reaction is finished.
Example 2
This example 2 provides a pour point depressant prepared by the process of:
providing reaction raw materials, wherein the reaction raw materials comprise the following components in percentage by mass: 28% of a second monomer, 22% of a first monomer, 0.4% of a chain transfer agent, 0.4% of an initiator and the balance of a solvent.
The second monomer is acrylic acid high-carbon alcohol ester, which is prepared by esterification reaction of high-carbon alcohol with 22 carbon atoms and acrylic acid, the first monomer is vinyl acetate, the chain transfer agent is 2-cyano-2-propyl benzodisulfide, the initiator is azodiisobutyronitrile, and the solvent is toluene.
The first monomer, the chain transfer agent and the solvent were placed in a three-necked flask according to the above mass percentages of the respective components, and then nitrogen gas was introduced into the three-necked flask to remove air in the three-necked flask, and the nitrogen gas introduction time was 30 minutes. Then, an initiator was added to the three-necked flask, and a first reaction was performed under a nitrogen atmosphere for 80 minutes, wherein the reaction temperature of the first reaction was 72 ℃.
After the completion of the first reaction, a syringe was used to drop a high-carbon alcohol acrylate into the three-necked flask, and the second reaction was carried out at 72℃for 70 minutes. The second reaction is carried out under stirring, the stirring speed is 330rpm, and the pour point depressant is obtained after the second reaction is finished.
Example 3
This example 3 provides a pour point depressant prepared by the process of:
providing reaction raw materials, wherein the reaction raw materials comprise the following components in percentage by mass: 25% of a second monomer, 28% of a first monomer, 28% of styrene, 0.5% of a chain transfer agent, 0.7% of an initiator and the balance of a solvent.
The second monomer is acrylic acid high-carbon alcohol ester, which is prepared by esterification reaction of high-carbon alcohol with 20 carbon atoms and acrylic acid, the first monomer is vinyl acetate, the chain transfer agent is 2-cyano-2-propyl benzodisulfide, the initiator is azodiisobutyronitrile, and the solvent is toluene.
The first monomer, the chain transfer agent and the solvent were placed in a three-necked flask according to the above mass percentages of the respective components, and then nitrogen gas was introduced into the three-necked flask to remove air in the three-necked flask, and the nitrogen gas introduction time was 30 minutes. Then, an initiator was added to the three-necked flask, and a first reaction was performed under a nitrogen atmosphere for 90 minutes, wherein the reaction temperature of the first reaction was 70 ℃.
After the completion of the first reaction, a syringe was used to drop a high-carbon alcohol acrylate into the three-necked flask, and the second reaction was carried out at a temperature of 70℃for 100 minutes. The second reaction was carried out under stirring and the stirring rate was 350rpm.
After the completion of the second reaction, styrene was added dropwise to the three-necked flask by using an injector, and the third reaction was carried out at a temperature of 70℃for 80 minutes. The third reaction was carried out under stirring and the stirring rate was 350rpm. And after the third reaction is finished, obtaining the pour point depressant.
Example 4
This example 4 provides a pour point depressant prepared by the process of:
providing reaction raw materials, wherein the reaction raw materials comprise the following components in percentage by mass: 28% of a second monomer, 25% of a first monomer, 25% of styrene, 0.5% of a chain transfer agent, 0.7% of an initiator and the balance of a solvent.
The second monomer is acrylic acid higher alcohol ester which is prepared by esterification reaction of higher alcohol with 20 carbon atoms and acrylic acid, the first monomer is vinyl acetate, the chain transfer agent is 2-cyano-2-propyl benzodisulfide, the initiator is azodiisobutyronitrile, and the solvent is toluene.
The first monomer, the chain transfer agent and the solvent were placed in a three-necked flask according to the above mass percentages of the respective components, and then nitrogen gas was introduced into the three-necked flask to remove air in the three-necked flask, and the nitrogen gas introduction time was 30 minutes. Then, an initiator was added to the three-necked flask, and a first reaction was performed under a nitrogen atmosphere for 90 minutes, wherein the reaction temperature of the first reaction was 72 ℃.
After the completion of the first reaction, a syringe was used to drop a high-carbon alcohol acrylate into the three-necked flask, and the second reaction was carried out at 72℃for 90 minutes. The second reaction was carried out under stirring and the stirring rate was 350rpm.
After the completion of the second reaction, styrene was added dropwise to the three-necked flask by using an injector, and the third reaction was carried out at a temperature of 70℃for 70 minutes. The third reaction was carried out under stirring and the stirring rate was 350rpm. And after the third reaction is finished, obtaining the pour point depressant.
Experimental example
This experimental example uses the pour point depressants provided in examples 1-4 to perform pour point depressant tests on different types of crude oils, see below for specific test procedures:
the crude oil sample was a nicol golumei block crude oil, baobab block crude oil was obtained at first glance, and the physical properties of these two crude oils are shown in table 1.
The determination of the congealing point of crude oil was carried out according to standard SY/T0541-2009, in order to allow the pour point depressant provided in examples 1-4 to react sufficiently with the colloid, asphaltene in the crude oil, the crude oil and the crude oil after pour point depressant addition were warmed to 80℃and kept for 30 minutes, and then the congealing point test was carried out. The test results are shown in tables 2 and 3, respectively.
Table 1 composition and physical properties of crude oil
TABLE 2 pour point depressant Effect on Nile crude oil
TABLE 3 pour point depressant effect on crude oil at first glance
As can be seen from tables 1 to 3, the pour point depressants provided in examples 1 to 4 of the present invention achieve better pour point depressing effects on high wax and high congealing point crude oils.
The foregoing description is only for the convenience of those skilled in the art to understand the technical solution of the present invention, and is not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The preparation method of the pour point depressant is characterized by comprising the following steps of: providing reaction raw materials, wherein the reaction raw materials comprise the following components in percentage by mass: 15% -65% of a first monomer, 15% -65% of a second monomer, 0.35% -0.6% of a chain transfer agent, 0.05% -1% of an initiator and the balance of a solvent;
placing the first monomer, the chain transfer agent, the initiator and the solvent in a reaction vessel, and performing a first reaction under a nitrogen atmosphere;
after the first reaction is finished, dropwise adding the second monomer into the reactor to perform a second reaction, after the second reaction is finished, dropwise adding styrene, vinyl acetate, alpha-olefin or dicyclopentadiene into the reactor to perform a third reaction, and after the third reaction is finished, obtaining the pour point depressant;
the first monomer includes: styrene, vinyl acetate, alpha-olefins or dicyclopentadiene;
the second monomer is selected from acrylic acid high-carbon alcohol ester, maleic anhydride or polyfluoroalcohol ester, and the acrylic acid high-carbon alcohol ester is prepared by esterification reaction of high-carbon alcohol with 16-26 carbon atoms and acrylic acid;
the chain transfer agent is 2-cyano-2-propylbenzodisulfide or butyl-2-methyl-2- [ (dodecylsulfanylthiocarbonyl) ] sulfanyl (CTA-ester);
the solvent is at least one selected from alkane, isobutanol, tertiary butanol, toluene, xylene and heavy aromatic hydrocarbon.
2. The method for producing a pour point depressant according to claim 1, wherein the reaction temperature is 65 ℃ to 75 ℃ and the reaction time is 70 minutes to 100 minutes when the first reaction is carried out.
3. The method for producing a pour point depressant according to claim 1, wherein the reaction temperature is 65 ℃ to 75 ℃ and the reaction time is 50 minutes to 100 minutes when the second reaction is carried out.
4. The method for producing a pour point depressant according to claim 1, wherein the second reaction is carried out under stirring conditions and the stirring rate is 300rpm to 400rpm.
5. The method for preparing a pour point depressant according to claim 1, wherein the reaction temperature is 65 ℃ to 75 ℃ and the reaction time is 60 minutes to 80 minutes when the third reaction is performed.
6. The method for producing a pour point depressant according to claim 1, wherein the initiator is at least one selected from the group consisting of azobisisobutyronitrile, benzoyl peroxide and dimethyl azobisisobutyrate.
7. A pour point depressant prepared by the method of any one of claims 1 to 6.
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CN107619455A (en) * | 2016-07-15 | 2018-01-23 | 中国石油天然气集团公司 | Comb polymer for pour point depressant for crude oil and preparation method thereof, application |
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CN107619455A (en) * | 2016-07-15 | 2018-01-23 | 中国石油天然气集团公司 | Comb polymer for pour point depressant for crude oil and preparation method thereof, application |
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