CN104710560A - A kind of dicyclopentadiene and acrylate higher carbon alcohol ester polymer crude oil pour point depressant - Google Patents
A kind of dicyclopentadiene and acrylate higher carbon alcohol ester polymer crude oil pour point depressant Download PDFInfo
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- acrylate
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- 239000010779 crude oil Substances 0.000 title claims abstract description 61
- 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 title claims abstract description 50
- 230000000994 depressogenic effect Effects 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 27
- -1 carbon alcohol ester Chemical class 0.000 title claims description 22
- 229920000642 polymer Polymers 0.000 title claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 21
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims abstract description 19
- KHAYCTOSKLIHEP-UHFFFAOYSA-N docosyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C=C KHAYCTOSKLIHEP-UHFFFAOYSA-N 0.000 claims abstract description 12
- NGYRYRBDIPYKTL-UHFFFAOYSA-N icosyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCOC(=O)C=C NGYRYRBDIPYKTL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 5
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- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000003921 oil Substances 0.000 claims description 13
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- 230000008859 change Effects 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 239000000047 product Substances 0.000 claims description 9
- 238000001308 synthesis method Methods 0.000 claims description 8
- 229960000735 docosanol Drugs 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
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- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
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- 238000010189 synthetic method Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
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- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical group FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000881 depressing effect Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000000034 method Methods 0.000 description 2
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- 239000008096 xylene Substances 0.000 description 2
- APWFVHHGZWXBPA-ODZAUARKSA-N (z)-but-2-enedioic acid;furan-2,5-dione Chemical compound O=C1OC(=O)C=C1.OC(=O)\C=C/C(O)=O APWFVHHGZWXBPA-ODZAUARKSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000009671 shengli Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920006029 tetra-polymer Polymers 0.000 description 1
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- Liquid Carbonaceous Fuels (AREA)
- Lubricants (AREA)
Abstract
本发明涉及一种双环戊二烯与丙烯酸高碳醇酯聚合物原油降凝剂；该降凝剂由双环戊二烯与丙烯酸高碳醇酯聚合物和有机溶剂组成，按总重量100%计，各组分的比例为：双环戊二烯与丙烯酸高碳醇酯聚合物原油降凝剂3～25%、有机溶剂75～97%；双环戊二烯与丙烯酸高碳醇酯聚合物是由双环戊二烯与丙烯酸十八酯、丙烯酸二十酯、丙烯酸二十二酯的单酯或混合酯，用偶氮二异丁腈为引发剂进行自由基聚合，双环戊二烯与丙烯酸酯的摩尔比为1:10、3:10、1:2和1:1；本降凝剂在原油中加剂量100ppm降凝剂固体，处理温度为80℃和静态条件下，可将混合原油凝点由30℃降低到19℃，在29℃处的降粘率为93.9～95.1%。The invention relates to a dicyclopentadiene and high-carbon alcohol acrylate polymer crude oil pour point depressant; the pour point depressant is composed of dicyclopentadiene and high-carbon alcohol acrylate polymer and an organic solvent, calculated by 100% of the total weight , the proportion of each component is: dicyclopentadiene and higher alcohol acrylate polymer crude oil pour point depressant 3-25%, organic solvent 75-97%; dicyclopentadiene and higher alcohol acrylate polymer is composed of Dicyclopentadiene and octadecyl acrylate, eicosyl acrylate, behenyl acrylate monoester or mixed ester, using azobisisobutyronitrile as the initiator for free radical polymerization, dicyclopentadiene and acrylate The molar ratios are 1:10, 3:10, 1:2 and 1:1; this pour point depressant is added to the crude oil with a dose of 100ppm solid pour point depressant, and the treatment temperature is 80°C and under static conditions, the pour point depressant of the mixed crude oil can be reduced to From 30°C to 19°C, the viscosity reduction rate at 29°C is 93.9-95.1%.
Description
技术领域technical field
本发明是一种双环戊二烯与丙烯酸高碳醇酯聚合物原油降凝剂。涉及一般化学方法、高分子聚合物的制备和原油管道输送技术领域。The invention is a dicyclopentadiene and high-carbon alcohol acrylate polymer crude oil pour point depressant. It involves the technical fields of general chemical methods, high molecular polymer preparation and crude oil pipeline transportation.
背景技术Background technique
原油流降凝剂在近几十年的发展中，其种类不断增加，但都以分子量在几千到3～5万的高分子聚合物为主，以烯烃、丙烯酸酯、乙烯醋酸乙烯酯、苯乙烯、马来酸酐（顺丁烯二酸）、丙烯酰胺、丙烯腈等单体进行聚合反应。主要有：中科院兰化所的油溶性降凝剂，主要由聚异丁烯、氢化聚异戊二烯、乙烯丙烯嵌段共聚物等高聚物组成。天津师范大学的一种用丙烯酸高碳醇酯和其他共聚物合成的原油降凝剂。中国石油管道科技研究中心为苏丹油田管输原油研制的降凝剂含丙烯酸高碳醇酯和乙烯等。天津师大与大港油田联合研制的对大港原油有高效降凝作用的降凝剂是以丙烯酸高碳醇酯和顺丁烯二酸酐等组成。中国石油天然气公司的一项降凝剂专利系由乙烯共聚物和丙烯酸高碳醇酯等复配的特种溶剂配制而成。中石油西气东输上海分部与中石油管道科研中心的一种特殊支链聚丙烯酸高碳醇酯的合成及降凝性能研究。天津师大用合成的丙烯酸高碳醇酯与顺丁烯二酸酐、苯乙烯进行了三元共聚的降凝剂研究实验。中国石油大学重质油国家重点实验室与胜利油田对原油降凝剂乙烯-丙烯酸甲酯共聚物的制备研究。天津科技大学通过调节高碳醇的链长可使降凝剂能更好地适于不同组成原油的研究。上海工程大学通过对丙烯酸高碳酯与醋酸乙烯酯等共聚后进行不同系列胺解得到一系列新型高蜡原油降凝剂的研究。辽宁师范大学以甲基丙烯酸高碳酯苯乙烯、顺丁烯二酸酐等为原料的高凝点原油降凝剂的研制。湖北大学与仙桃市九院联合研制的一种由单体丙烯酸高碳醇酯等四元共聚物的原油降凝剂。吉林化工学院研制的以高活性聚异丁烯为主要原料的原油降凝剂。中国石油管道科技研究中心关于国内外原油降凝剂降凝作用的机理研究。德国德士古公司的一种热裂解的非晶乙烯-丙烯-非共轭二烯三元共聚物降凝剂的专利技术。德士古公司申请包含乙烯-丙烯-二烯三元共聚物的降凝添加剂作为矿物油降凝剂的专利。德国赫斯特公司的一种用高烷基（甲基）丙烯酸酯和乙烯基单体-乙醚，二酯，嘧啶或氨基Gp.的共聚物作为原油降凝剂。法国石油与天然气公司的一种聚丙烯型降凝剂在原油中的效果研究。巴西石油公司研究中心和里约热内卢大学研制的采用乙烯-醋酸乙烯共聚物（EVA）作为巴西原油的蜡抑制剂。法国碳化和石油活性炭公司研发的一种用于降低原油凝点和抑制石蜡沉积的稳定乳液，乳液中的成分以烯烃共聚物/聚丙烯为基础。印度普纳市化学工程与自然科学实验室在氢化双环戊二烯存在下，进行的关于聚丙烯的相溶性、形态、结晶、和动态力学性能的研究。美国亚什兰石油公司的一种采用四氢双环戊二烯和低碳烃降低闪点的高密度液态烃燃料等。上面提到的双环戊二烯不是应用在原油降凝剂中。In the development of crude oil flow point depressants in recent decades, the types of them have been increasing, but they are mainly polymers with a molecular weight of several thousand to 30,000 to 50,000, such as olefins, acrylates, ethylene vinyl acetate, Styrene, maleic anhydride (maleic acid), acrylamide, acrylonitrile and other monomers are polymerized. The main ones are: the oil-soluble pour point depressant of the Lanhua Institute of Chinese Academy of Sciences, which is mainly composed of high polymers such as polyisobutylene, hydrogenated polyisoprene, and ethylene-propylene block copolymer. A kind of crude oil pour point depressant synthesized with high carbon alcohol ester of acrylate and other copolymers from Tianjin Normal University. The pour point depressant developed by China Petroleum Pipeline Science and Technology Research Center for crude oil pipeline transportation in Sudan Oilfield contains higher carbon alcohol ester of acrylate and ethylene. The pour point depressant for Dagang crude oil jointly developed by Tianjin Normal University and Dagang Oilfield is composed of higher alcohol acrylate and maleic anhydride. A pour point depressant patent of China National Petroleum Corporation is formulated from special solvents such as ethylene copolymer and high-carbon alcohol ester of acrylate. Synthesis and pour point depressing performance of a special branched chain polyacrylic acid high carbon alcohol ester produced by CNPC West-East Gas Pipeline Shanghai Branch and PetroChina Pipeline Research Center. Tianjin Normal University used the synthesized high-carbon alcohol ester of acrylate, maleic anhydride and styrene to carry out the research experiment of ternary copolymerization of pour point depressant. Research on preparation of crude oil pour point depressant ethylene-methyl acrylate copolymer by State Key Laboratory of Heavy Oil, China University of Petroleum and Shengli Oilfield. By adjusting the chain length of higher alcohols, Tianjin University of Science and Technology can make pour point depressants more suitable for the research of crude oils with different compositions. Shanghai Engineering University researched a series of new high-wax crude oil pour point depressants through different series of aminolysis after copolymerization of high-carbon esters of acrylate and vinyl acetate. Liaoning Normal University developed a high pour point crude oil pour point depressant using high carbon methacrylate styrene, maleic anhydride, etc. as raw materials. A crude oil pour point depressant made of tetrapolymers such as monomeric high-carbon alcohol esters jointly developed by Hubei University and Xiantao No. 9 Academy. A crude oil pour point depressant developed by Jilin Institute of Chemical Technology with high activity polyisobutene as the main raw material. China Petroleum Pipeline Science and Technology Research Center's research on the mechanism of pour point depressant for crude oil at home and abroad. A patented technology of thermal cracking amorphous ethylene-propylene-non-conjugated diene terpolymer pour point depressant from Germany Texaco. Texaco applied for a patent for a pour point depressant additive containing ethylene-propylene-diene terpolymer as a mineral oil pour point depressant. A copolymer of high alkyl (meth)acrylate and vinyl monomer-ether, diester, pyrimidine or amino Gp. is used as a crude oil pour point depressant by Hearst Company of Germany. Research on the effect of a polypropylene type pour point depressant of French oil and gas company in crude oil. Developed by the Petrobras Research Center and the University of Rio de Janeiro using ethylene-vinyl acetate copolymer (EVA) as a wax inhibitor for Brazilian crude oil. A stable emulsion developed by French Carbonation and Petroleum Activated Carbon Company to lower the freezing point of crude oil and inhibit paraffin deposition. The ingredients in the emulsion are based on olefin copolymer/polypropylene. Research on the compatibility, morphology, crystallization, and dynamic mechanical properties of polypropylene in the presence of hydrogenated dicyclopentadiene, Chemical Engineering and Natural Science Laboratory, Pune, India. A high-density liquid hydrocarbon fuel that uses tetrahydrodicyclopentadiene and low-carbon hydrocarbons to reduce the flash point of the Ashland Petroleum Company of the United States. The dicyclopentadiene mentioned above is not used in crude oil pour point depressant.
上述降凝剂的主链是烷烃，不能与原油中含有特殊的芳香烃和其他环状化学物有效作用。本专利通过研究反引发剂、催化剂和反应温度对聚合物的影响，合成双环戊二烯与丙烯酸高碳醇酯聚合物。通过反应量热器研究反应过程中的放热速率和转化率，实现产品的中试和工业化生产。通过现场试验，将本专利研发的产品应用到乍得的原油管道输送，实现乍得原油管道常温、高效和安全的输送。The main chain of the above-mentioned pour point depressants is alkanes, which cannot effectively interact with special aromatic hydrocarbons and other cyclic chemicals contained in crude oil. This patent synthesizes dicyclopentadiene and high-carbon alcohol acrylate polymers by studying the influence of anti-initiators, catalysts and reaction temperature on polymers. The heat release rate and conversion rate in the reaction process are studied by the reaction calorimeter, and the pilot test and industrial production of the product are realized. Through the field test, the product developed by this patent is applied to the crude oil pipeline transportation in Chad to realize the normal temperature, efficient and safe transportation of the crude oil pipeline in Chad.
发明内容Contents of the invention
本发明的目的是提供一种对原油降凝和降粘更好的双环戊二烯与丙烯酸高碳醇酯聚合物原油降凝剂。该高分子聚合物在主链中含有5元环，可以充分地与原油中的胶质中芳香环和其它环状化学物作用，提高含胶质对原油蜡晶的改性效果。The object of the present invention is to provide a kind of dicyclopentadiene and high carbon alcohol acrylate polymer crude oil point depressant which is better for crude oil point depressing and viscosity reducing. The high-molecular polymer contains 5-membered rings in the main chain, which can fully interact with aromatic rings and other cyclic chemicals in colloids in crude oil, and improve the modification effect of colloids on crude oil wax crystals.
本发明是由双环戊二烯与丙烯酸高碳醇酯聚合物和有机溶剂组成，在总重量为100%中各组分的比例为：双环戊二烯与丙烯酸高碳醇酯聚合物型原油降凝剂3%～25%、有机溶剂75%～97%。The present invention is made up of dicyclopentadiene and acrylate higher carbon alcohol ester polymer and organic solvent, and the ratio of each component in total weight is 100% is: dicyclopentadiene and acrylate higher carbon alcohol ester polymer type crude oil drop Coagulant 3% ~ 25%, organic solvent 75% ~ 97%.
其中：双环戊二烯与丙烯酸高碳醇酯聚合物是由双环戊二烯与丙烯酸十八酯、丙烯酸二十酯和丙烯酸二十二酯的单酯或混合酯，用偶氮二异丁腈(AIBN)为引发剂进行自由基聚合，双环戊二烯与丙烯酸酯的摩尔比为1:10、3:10、1:2和1:1。丙烯酸酯为单醇（C18醇、C20醇、C22醇）或混合醇，混合醇比为C18醇：C20醇：C22醇摩尔比为1:1:1；1:2:1、2:2:1、3:2:1。聚合物的重均分子量Mw为1*104～80*104。Among them: the polymer of dicyclopentadiene and high-carbon alcohol acrylate is a monoester or mixed ester of dicyclopentadiene and octadecyl acrylate, eicosyl acrylate and behenyl acrylate, and azobisisobutyronitrile (AIBN) was used as the initiator for radical polymerization, and the molar ratios of dicyclopentadiene and acrylate were 1:10, 3:10, 1:2 and 1:1. Acrylate is monoalcohol (C18 alcohol, C20 alcohol, C22 alcohol) or mixed alcohol, the ratio of mixed alcohol is C18 alcohol: C20 alcohol: C22 alcohol molar ratio is 1:1:1; 1:2:1, 2:2: 1. 3:2:1. The weight average molecular weight Mw of the polymer is 1*10 4 to 80*10 4 .
首先制备丙烯酸高碳醇酯：First prepare higher carbon alcohol ester of acrylate:
往250mL的三口瓶中加入25mL丙烯酸、81.17g十八醇、0.9829g对甲苯磺酸（催化剂）、0.6881g对苯二酚（阻聚剂）和50mL环己烷，放入磁子，装上回流冷凝管和分水器。将反应装置放入125℃的油浴中，搅拌，反应6小时。反应结束后，通过减压蒸馏的方法将反应产物中的环己烷和未反应的丙烯酸抽出。上述产物为丙烯酸十八酯。丙烯酸二十酯的合成需将上述合成中添加的醇改为89.57g二十醇。丙烯酸二十二酯的合成需将上述合成中添加的醇改为97.98g二十二醇。Add 25mL of acrylic acid, 81.17g of stearyl alcohol, 0.9829g of p-toluenesulfonic acid (catalyst), 0.6881g of hydroquinone (inhibitor) and 50mL of cyclohexane into a 250mL three-necked bottle, put in the magnet, and install Reflux condenser and water separator. Put the reaction device into an oil bath at 125°C, stir, and react for 6 hours. After the reaction, cyclohexane and unreacted acrylic acid in the reaction product were extracted by vacuum distillation. The above product is stearyl acrylate. The synthesis of eicosyl acrylate needs to change the alcohol added in the above synthesis into 89.57g eicosanol. The synthesis of behenyl acrylate needs to change the alcohol added in the above synthesis into 97.98g behenyl alcohol.
双环戊二烯与丙烯酸高碳醇酯聚合物的合成方法：The synthetic method of dicyclopentadiene and acrylate higher carbon alcohol ester polymer:
双环戊二烯与丙烯酸高碳醇酯聚合物制备方法：用于双环戊二烯与丙烯酸高碳醇酯聚合物合成的丙烯酸酯为单醇（C18醇、C20醇、C22醇），或混合醇（C18醇：C20醇：C24醇摩尔比为1:1:1；1:2:1、2:2:1、3:2:1）等。双环戊二烯与丙烯酸高碳醇酯的摩尔比例为1:10；3:10；1:2和1:1。Preparation method of dicyclopentadiene and high-carbon alcohol acrylate polymer: the acrylate used for the synthesis of dicyclopentadiene and high-carbon alcohol acrylate polymer is monoalcohol (C18 alcohol, C20 alcohol, C22 alcohol), or mixed alcohol (C18 alcohol: C20 alcohol: C24 alcohol molar ratio is 1:1:1; 1:2:1, 2:2:1, 3:2:1), etc. The molar ratio of dicyclopentadiene to higher alcohol acrylate is 1:10; 3:10; 1:2 and 1:1.
双环戊二烯与丙烯酸十八酯聚合物的合成：Synthesis of Dicyclopentadiene and Octadecyl Acrylate Polymer:
双环戊二烯与丙烯酸十八酯摩尔比为1:10时的合成方法：往250mL的三口烧瓶中，加入25.000g丙烯酸十八酯、100mg偶氮二异丁腈（AIBN）、1.018g双环戊二烯，磁子，抽真空-充氮气三次，加入回流过的甲苯25mL，油浴65℃，聚合10小时。The synthesis method when the molar ratio of dicyclopentadiene to octadecyl acrylate is 1:10: Into a 250mL three-necked flask, add 25.000g of octadecyl acrylate, 100mg of azobisisobutyronitrile (AIBN), 1.018g of dicyclopentadiene Diene, magneton, vacuum-filled three times with nitrogen, add refluxed toluene 25mL, oil bath 65°C, polymerize for 10 hours.
双环戊二烯与丙烯酸十八酯摩尔比为3:10时的合成方法：往250mL的三口烧瓶中，加入25.000g丙烯酸十八酯、120mg偶氮二异丁腈（AIBN）、3.055g双环戊二烯，磁子，抽真空-充氮气三次，加入回流过的甲苯25mL，油浴65℃，聚合10小时。The synthesis method when the molar ratio of dicyclopentadiene to octadecyl acrylate is 3:10: Into a 250mL three-necked flask, add 25.000g of octadecyl acrylate, 120mg of azobisisobutyronitrile (AIBN), 3.055g of dicyclopentadiene Diene, magneton, vacuum-filled three times with nitrogen, add refluxed toluene 25mL, oil bath 65°C, polymerize for 10 hours.
双环戊二烯与丙烯酸十八酯摩尔比为1:2时的合成方法：往250mL的三口烧瓶中，加入25.000g丙烯酸十八酯、150mg偶氮二异丁腈（AIBN）、5.092g双环戊二烯，磁子，抽真空-充氮气三次，加入回流过的甲苯25mL，油浴65℃，聚合10小时。The synthesis method when the molar ratio of dicyclopentadiene to octadecyl acrylate is 1:2: Into a 250mL three-necked flask, add 25.000g of octadecyl acrylate, 150mg of azobisisobutyronitrile (AIBN), 5.092g of dicyclopentadiene Diene, magneton, vacuum-filled three times with nitrogen, add refluxed toluene 25mL, oil bath 65°C, polymerize for 10 hours.
双环戊二烯与丙烯酸十八酯摩尔比为1:1时的合成方法：往250mL的三口烧瓶中，加入25.000g丙烯酸十八酯、200mg偶氮二异丁腈（AIBN）、10.185g双环戊二烯，磁子，抽真空-充氮气三次，加入回流过的甲苯25mL，油浴65℃，聚合10小时。The synthesis method when the molar ratio of dicyclopentadiene to octadecyl acrylate is 1:1: Into a 250mL three-necked flask, add 25.000g of octadecyl acrylate, 200mg of azobisisobutyronitrile (AIBN), 10.185g of dicyclopentadiene Diene, magneton, vacuum-filled three times with nitrogen, add refluxed toluene 25mL, oil bath 65°C, polymerize for 10 hours.
双环戊二烯与丙烯酸二十酯聚合物的合成方法是将上述合成中添加的醇改为27.157g二十醇。双环戊二烯与丙烯酸二十二酯聚合物的合成方法是将上述合成中添加的醇改为27.157g二十二醇。The synthetic method of dicyclopentadiene and eicosyl acrylate polymer is to change the alcohol added in the above synthesis into 27.157g eicosyl alcohol. The synthetic method of dicyclopentadiene and behenyl acrylate polymer is to change the alcohol added in the above synthesis into 27.157g behenyl alcohol.
双环戊二烯与不同比例的丙烯酸混合酯聚合物制备方法：将上述合成中添加的醇按下表中的添加量Dicyclopentadiene and different proportions of acrylic acid mixed ester polymer preparation method: the alcohol added in the above synthesis is added in the following table
有机溶剂为：有汽油、柴油，或芳香烃溶剂如：二甲苯、重芳烃、C9芳烃、C10芳烃。Organic solvents are: gasoline, diesel oil, or aromatic solvents such as xylene, heavy aromatics, C9 aromatics, and C10 aromatics.
本发明是由上述高分子聚合物和有机溶剂的混合物，有机聚合物中含有羧酸，可与原油中胶质、沥青质的有机胺进行反应。本发明对原油凝点和粘度有改进明显。The invention is a mixture of the above-mentioned high molecular polymer and organic solvent, and the organic polymer contains carboxylic acid, which can react with organic amines of colloid and asphaltenes in crude oil. The invention can significantly improve the freezing point and viscosity of crude oil.
具体实施方式Detailed ways
实施例1.Example 1.
(1)首先丙烯酸高碳醇酯：(1) First, high carbon alcohol ester of acrylate:
往250mL的三口瓶中加入25mL丙烯酸、81.17g十八醇、0.9829g对甲苯磺酸（催化剂）、0.6881g对苯二酚（阻聚剂）和50mL环己烷，放入磁子，装上回流冷凝管和分水器。将反应装置放入125℃的油浴中，搅拌，反应6小时。反应结束后，通过减压蒸馏的方法将反应产物中的环己烷和未反应的丙烯酸抽出。上述产物为丙烯酸十八酯。丙烯酸二十酯的合成需将上述合成中添加的醇改为89.57g二十醇。丙烯酸二十二酯的合成需将上述合成中添加的醇改为97.98g二十二醇。Add 25mL of acrylic acid, 81.17g of stearyl alcohol, 0.9829g of p-toluenesulfonic acid (catalyst), 0.6881g of hydroquinone (inhibitor) and 50mL of cyclohexane into a 250mL three-necked bottle, put in the magnet, and install Reflux condenser and water separator. Put the reaction device into an oil bath at 125°C, stir, and react for 6 hours. After the reaction, cyclohexane and unreacted acrylic acid in the reaction product were extracted by vacuum distillation. The above product is stearyl acrylate. The synthesis of eicosyl acrylate needs to change the alcohol added in the above synthesis into 89.57g eicosanol. The synthesis of behenyl acrylate needs to change the alcohol added in the above synthesis into 97.98g behenyl alcohol.
(2)双环戊二烯与丙烯酸高碳醇酯聚合物的合成方法：(2) The synthetic method of dicyclopentadiene and higher alcohol acrylate polymer:
双环戊二烯与丙烯酸十八酯摩尔比为3:10时的合成方法：往250mL的三口烧瓶中，加入8.329g丙烯酸十八酯、9.048g丙烯酸二十酯、9.766g丙烯酸二十二酯、120mg偶氮二异丁腈（AIBN）、3.055g双环戊二烯，磁子，抽真空-充氮气三次，加入回流过的甲苯25mL，油浴65℃，聚合10小时。The synthesis method when the molar ratio of dicyclopentadiene to octadecyl acrylate is 3:10: Into a 250mL three-necked flask, add 8.329g of octadecyl acrylate, 9.048g of eicosyl acrylate, 9.766g of behenyl acrylate, 120mg of azobisisobutyronitrile (AIBN), 3.055g of dicyclopentadiene, magneton, vacuum-filled three times with nitrogen, add 25mL of refluxed toluene, oil bath at 65°C, polymerize for 10 hours.
本原油降凝剂对乍得原油混合原油在加剂量100ppm降凝剂（固体）、处理温度为80℃和静态实验条件下，可将原油混合原油凝点由30℃降低到19℃，在29℃处的降粘率为93.9%。This crude oil pour point depressant can reduce the freezing point of crude oil blended crude oil from 30°C to 19°C under the conditions of adding 100ppm pour point depressant (solid) to Chad crude oil blended crude oil, the treatment temperature is 80°C, and at 29°C The viscosity reduction rate at the place is 93.9%.
实施例2.Example 2.
(1)首先丙烯酸高碳醇酯：(1) First, high carbon alcohol ester of acrylate:
往250mL的三口瓶中加入25mL丙烯酸、81.17g十八醇、0.9829g对甲苯磺酸（催化剂）、0.6881g对苯二酚（阻聚剂）和50mL环己烷，放入磁子，装上回流冷凝管和分水器。将反应装置放入125℃的油浴中，搅拌，反应6小时。反应结束后，通过减压蒸馏的方法将反应产物中的环己烷和未反应的丙烯酸抽出。上述产物为丙烯酸十八酯。丙烯酸二十酯的合成需将上述合成中添加的醇改为89.57g二十醇。丙烯酸二十二酯的合成需将上述合成中添加的醇改为97.98g二十二醇。Add 25mL of acrylic acid, 81.17g of stearyl alcohol, 0.9829g of p-toluenesulfonic acid (catalyst), 0.6881g of hydroquinone (inhibitor) and 50mL of cyclohexane into a 250mL three-necked bottle, put in the magnet, and install Reflux condenser and water separator. Put the reaction device into an oil bath at 125°C, stir, and react for 6 hours. After the reaction, cyclohexane and unreacted acrylic acid in the reaction product were extracted by vacuum distillation. The above product is stearyl acrylate. The synthesis of eicosyl acrylate needs to change the alcohol added in the above synthesis into 89.57g eicosanol. The synthesis of behenyl acrylate needs to change the alcohol added in the above synthesis into 97.98g behenyl alcohol.
(2)双环戊二烯与丙烯酸高碳醇酯聚合物的合成方法：(2) The synthetic method of dicyclopentadiene and higher alcohol acrylate polymer:
双环戊二烯与丙烯酸十八酯摩尔比为1:2时的合成方法：往250mL的三口烧瓶中，加入6.247g丙烯酸十八酯、13.572g丙烯酸二十酯、7.325丙烯酸二十二酯、150mg偶氮二异丁腈（AIBN）、5.092g双环戊二烯，磁子，抽真空-充氮气三次，加入回流过的甲苯25mL，油浴65℃，聚合10小时。The synthesis method when the molar ratio of dicyclopentadiene to octadecyl acrylate is 1:2: Into a 250mL three-necked flask, add 6.247g octadecyl acrylate, 13.572g eicosyl acrylate, 7.325 behenyl acrylate, 150mg Azobisisobutyronitrile (AIBN), 5.092g of dicyclopentadiene, magneton, vacuum-filled three times with nitrogen, add 25mL of refluxed toluene, oil bath at 65°C, polymerize for 10 hours.
本原油降凝剂对乍得原油混合原油在加剂量100ppm降凝剂（固体）、处理温度为80℃和静态实验条件下，可将原油混合原油凝点由30℃降低到19℃，在29℃处的降粘率为95.1%。This crude oil pour point depressant can reduce the freezing point of crude oil blended crude oil from 30°C to 19°C under the conditions of adding 100ppm pour point depressant (solid) to Chad crude oil blended crude oil, the treatment temperature is 80°C, and at 29°C The viscosity reduction rate is 95.1%.
实施例3.Example 3.
(1)首先丙烯酸高碳醇酯：(1) First, high carbon alcohol ester of acrylate:
往250mL的三口瓶中加入25mL丙烯酸、81.17g十八醇、0.9829g对甲苯磺酸（催化剂）、0.6881g对苯二酚（阻聚剂）和50mL环己烷，放入磁子，装上回流冷凝管和分水器。将反应装置放入125℃的油浴中，搅拌，反应6小时。反应结束后，通过减压蒸馏的方法将反应产物中的环己烷和未反应的丙烯酸抽出。上述产物为丙烯酸十八酯。丙烯酸二十酯的合成需将上述合成中添加的醇改为89.57g二十醇。丙烯酸二十二酯的合成需将上述合成中添加的醇改为97.98g二十二醇。Add 25mL of acrylic acid, 81.17g of stearyl alcohol, 0.9829g of p-toluenesulfonic acid (catalyst), 0.6881g of hydroquinone (inhibitor) and 50mL of cyclohexane into a 250mL three-necked bottle, put in the magnet, and install Reflux condenser and water separator. Put the reaction device into an oil bath at 125°C, stir, and react for 6 hours. After the reaction, cyclohexane and unreacted acrylic acid in the reaction product were extracted by vacuum distillation. The above product is stearyl acrylate. The synthesis of eicosyl acrylate needs to change the alcohol added in the above synthesis into 89.57g eicosanol. The synthesis of behenyl acrylate needs to change the alcohol added in the above synthesis into 97.98g behenyl alcohol.
(2)双环戊二烯与丙烯酸高碳醇酯聚合物的合成方法：(2) The synthetic method of dicyclopentadiene and higher alcohol acrylate polymer:
双环戊二烯与丙烯酸十八酯摩尔比为1:1时的合成方法：往250mL的三口烧瓶中，加入9.995g丙烯酸十八酯、10.857g丙烯酸二十酯、5.860丙烯酸二十二酯、200mg偶氮二异丁腈（AIBN）、10.185g双环戊二烯，磁子，抽真空-充氮气三次，加入回流过的甲苯25mL，油浴65℃，聚合10小时。The synthesis method when the molar ratio of dicyclopentadiene to octadecyl acrylate is 1:1: Into a 250mL three-necked flask, add 9.995g of octadecyl acrylate, 10.857g of eicosyl acrylate, 5.860 of behenyl acrylate, 200mg Azobisisobutyronitrile (AIBN), 10.185g of dicyclopentadiene, magneton, vacuum-filled three times with nitrogen, add 25mL of refluxed toluene, oil bath at 65°C, polymerize for 10 hours.
本原油降凝剂对乍得原油混合原油在加剂量100ppm降凝剂（固体）、处理温度为80℃和静态实验条件下，可将原油混合原油凝点由30℃降低到19℃，在29℃处的降粘率为94.2%。This crude oil pour point depressant can reduce the freezing point of crude oil blended crude oil from 30°C to 19°C under the conditions of adding 100ppm pour point depressant (solid) to Chad crude oil blended crude oil, the treatment temperature is 80°C, and at 29°C The viscosity reduction rate at the place is 94.2%.
应用条件：含有一定量胶质沥青质高凝原油。由于双环戊二烯与丙烯酸高碳醇酯聚合物型原油降凝剂是在高分子聚合物的主链上引入桥环结构，为双环戊二烯与丙烯酸高碳醇酯共聚型原油降凝剂，在主链中含有5元环，可以充分地与原油中的胶质中芳香环和其他环状化学物作用，提高含胶质对原油蜡晶的改性效果。Application conditions: high pour point crude oil containing a certain amount of colloidal asphaltenes. Since the dicyclopentadiene and higher alcohol acrylate polymer type crude oil point depressant introduces a bridging ring structure on the main chain of the polymer, it is a copolymerization type crude oil point depressant of dicyclopentadiene and higher alcohol acrylate , contains 5-membered rings in the main chain, which can fully interact with aromatic rings and other cyclic chemicals in colloids in crude oil, and improve the modification effect of colloids on crude oil wax crystals.
产品的形式：产品可溶于烷烃如汽油、柴油，或溶于芳香烃如二甲苯、重芳烃、C9芳烃、C10芳烃。Product form: The product can be dissolved in alkanes such as gasoline and diesel oil, or in aromatic hydrocarbons such as xylene, heavy aromatics, C9 aromatics, and C10 aromatics.
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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 crude oil pour point depressant, preparation method and application thereof |
| CN106468396A (en) * | 2016-08-28 | 2017-03-01 | 山东成泰化工有限公司 | A kind of petroleum pour depressant of hexahydro-phthalic acid two high-carbon alcohol ester |
| CN113307546A (en) * | 2021-04-09 | 2021-08-27 | 武汉市市政建设集团有限公司 | Durable ultrathin wearing layer and preparation method thereof |
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