CN117358152A - Olefin radical polymerization apparatus and method for radical polymerization of olefin - Google Patents
Olefin radical polymerization apparatus and method for radical polymerization of olefin Download PDFInfo
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- CN117358152A CN117358152A CN202210774665.2A CN202210774665A CN117358152A CN 117358152 A CN117358152 A CN 117358152A CN 202210774665 A CN202210774665 A CN 202210774665A CN 117358152 A CN117358152 A CN 117358152A
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- pressure polymerization
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- tubular reactor
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 82
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000010526 radical polymerization reaction Methods 0.000 title claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 242
- 239000000178 monomer Substances 0.000 claims abstract description 122
- 238000006243 chemical reaction Methods 0.000 claims abstract description 109
- 239000003999 initiator Substances 0.000 claims abstract description 67
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 34
- 230000003797 telogen phase Effects 0.000 claims description 70
- 239000007870 radical polymerization initiator Substances 0.000 claims description 54
- 230000006835 compression Effects 0.000 claims description 49
- 238000007906 compression Methods 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 36
- 238000000926 separation method Methods 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- -1 aliphatic alcohols Chemical class 0.000 claims description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 150000001993 dienes Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 150000001451 organic peroxides Chemical class 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000005673 monoalkenes Chemical class 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 56
- 238000009826 distribution Methods 0.000 description 41
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 22
- 239000005977 Ethylene Substances 0.000 description 18
- 229920001684 low density polyethylene Polymers 0.000 description 17
- 239000004702 low-density polyethylene Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- 210000003918 fraction a Anatomy 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 210000002196 fr. b Anatomy 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- 239000004815 dispersion polymer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 125000005603 azodicarboxylic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- RQHGZNBWBKINOY-PLNGDYQASA-N (z)-4-tert-butylperoxy-4-oxobut-2-enoic acid Chemical compound CC(C)(C)OOC(=O)\C=C/C(O)=O RQHGZNBWBKINOY-PLNGDYQASA-N 0.000 description 1
- GOAHRBQLKIZLKG-UHFFFAOYSA-N 1-tert-butylperoxybutane Chemical compound CCCCOOC(C)(C)C GOAHRBQLKIZLKG-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 description 1
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 1
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 description 1
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 description 1
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 1
- NGCFVIRRWORSML-UHFFFAOYSA-N 3-phenylbutan-2-ylbenzene Chemical class C=1C=CC=CC=1C(C)C(C)C1=CC=CC=C1 NGCFVIRRWORSML-UHFFFAOYSA-N 0.000 description 1
- ZPQAKYPOZRXKFA-UHFFFAOYSA-N 6-Undecanone Chemical compound CCCCCC(=O)CCCCC ZPQAKYPOZRXKFA-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- RFAZFSACZIVZDV-UHFFFAOYSA-N butan-2-one Chemical compound CCC(C)=O.CCC(C)=O RFAZFSACZIVZDV-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QFOJTGAPBXCVOK-UHFFFAOYSA-N hexyl 2-ethylhexaneperoxoate Chemical compound CCCCCCOOC(=O)C(CC)CCCC QFOJTGAPBXCVOK-UHFFFAOYSA-N 0.000 description 1
- AQIRXGQDSUUKQA-UHFFFAOYSA-N hydrogen peroxide;4-methylpentan-2-one Chemical compound OO.CC(C)CC(C)=O AQIRXGQDSUUKQA-UHFFFAOYSA-N 0.000 description 1
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KXYJPVZMZBJJBZ-UHFFFAOYSA-N tert-butyl 2-ethylbutaneperoxoate Chemical compound CCC(CC)C(=O)OOC(C)(C)C KXYJPVZMZBJJBZ-UHFFFAOYSA-N 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- ZUSDEBDNDIJDMZ-UHFFFAOYSA-N tert-butyl 7-methyloctaneperoxoate Chemical compound CC(C)CCCCCC(=O)OOC(C)(C)C ZUSDEBDNDIJDMZ-UHFFFAOYSA-N 0.000 description 1
- GSECCTDWEGTEBD-UHFFFAOYSA-N tert-butylperoxycyclohexane Chemical compound CC(C)(C)OOC1CCCCC1 GSECCTDWEGTEBD-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/04—Pressure vessels, e.g. autoclaves
- B01J3/042—Pressure vessels, e.g. autoclaves in the form of a tube
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/02—Feed or outlet devices therefor
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to the field of high-pressure polymerization, and discloses an olefin free radical polymerization device and an olefin free radical polymerization method. The device comprises: a first stage high pressure polymerization unit and a multistage high pressure polymerization unit; wherein the primary high-pressure polymerization unit is connected in series with the upstream of the multistage high-pressure polymerization unit and comprises at least two parallel tubular reactors for carrying out primary high-pressure polymerization on at least two reaction monomer streams containing olefin sources respectively; the multistage high-pressure polymerization unit comprises one or more tubular reactors which are sequentially connected in series and is used for carrying out multistage high-pressure polymerization on the product from the first-stage high-pressure polymerization unit; and an initiator feed inlet is arranged on at least one tubular reactor in the first-stage high-pressure polymerization unit and/or the multistage high-pressure polymerization unit. The device provided by the invention can produce various olefin homo-polymerization and copolymerization products, improves the utilization rate and applicability of the device, and has better economic benefit.
Description
Technical Field
The invention relates to the field of high-pressure olefin polymerization, in particular to an olefin free radical polymerization device and an olefin free radical polymerization method.
Background
Low density polyethylene is produced by a high pressure free radical polymerization process, which is a step by step dominant because of the relatively easy scale-up and economic justification of the tubular reactor during the polymerization process.
The existing high-pressure pipe type process flow compresses the reaction materials to more than 200MPa, and the reaction materials are introduced into a preheater to be heated to 170 ℃ and then enter into a reactor to initiate reaction. The tubular reactor outlet material is separated by a high pressure separator and a low pressure separator, wherein ethylene, telogen, part of the oligomers enter a high circulation loop and a low circulation loop, and LDPE dissolving a small amount of ethylene enters an extruder for pelletization. However, the LDPE polymer produced by the high-pressure tubular reactor generally has narrower Molecular Weight Distribution (MWD) and lower long chain branching degree (LCB), and different downstream products have different requirements on the Molecular Weight Distribution (MWD) and higher long chain branching degree (LCB), for example, medical grade/food grade LDPE resins need narrower Molecular Weight Distribution (MWD), while products with excellent mechanical properties such as heavy packaging bags, floor heating pipes and the like need wide Molecular Weight Distribution (MWD), so that the realization of the production of products with different molecular chain structures on one device has better economic benefit.
Currently, the current art methods of adjusting the Molecular Weight Distribution (MWD) and Long Chain Branching (LCB) of LDPE polymer products are to vary the feed location of the polymerization agent, including secondary inlet, secondary interstage, secondary outlet, preheater, reactor, upstream of the reactor side feed point, etc. However, injection of telogen into the compression system can lead to premature polymerization, scaling in the compression system, and a reduction in production load. Injecting a telogen into the reactor or reactor side feed can result in the telogen mixing with the initiator, reducing initiator initiation efficiency, and the mixing action of the additional stream of telogen with the main stream can create cold spots, reducing heat transfer.
Disclosure of Invention
The invention aims to overcome the defects that in the existing high-pressure olefin polymerization process, production of products with different molecular chain structures cannot be realized on the same device, a telogen is injected into a reactor or side line feeding of the reactor to cause mixing of the telogen and an initiator, initiator initiation efficiency is reduced, cold spots can be generated due to mixing behaviors of an additional flow of the telogen and a main flow, and heat transfer is reduced, and provides an olefin free radical polymerization device and an olefin free radical polymerization method.
In order to achieve the above object, a first aspect of the present invention provides an olefin radical polymerization apparatus comprising:
a first stage high pressure polymerization unit and a multistage high pressure polymerization unit; wherein,
the first-stage high-pressure polymerization unit is connected in series at the upstream of the multi-stage high-pressure polymerization unit;
the primary high-pressure polymerization unit comprises at least two parallel tubular reactors for carrying out primary high-pressure polymerization on at least two reaction monomer streams containing olefin sources respectively;
the multistage high-pressure polymerization unit comprises one or more tubular reactors which are sequentially connected in series and is used for carrying out multistage high-pressure polymerization on the product from the first-stage high-pressure polymerization unit;
at least one tubular reactor in the primary high-pressure polymerization unit and/or the multistage high-pressure polymerization unit is provided with an initiator feed inlet.
In a second aspect, the present invention provides a process for the free radical polymerisation of olefins, the process being carried out in an olefin free radical polymerisation apparatus as described above, the process comprising: respectively introducing at least two reaction monomer streams containing olefin sources into at least two parallel tubular reactors in a primary high-pressure polymerization unit included in the device, respectively performing primary high-pressure polymerization, and then flowing the obtained primary high-pressure polymerization product into the tubular reactors in a multistage high-pressure polymerization unit included in the device for multistage high-pressure polymerization; wherein at least one free radical polymerization initiator is introduced into each of the initiator feed ports included in the apparatus to participate in one-stage high pressure polymerization and/or multistage high pressure polymerization, and the pressure of the reactive monomer stream is greater than 100MPa.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The first-stage high-pressure polymerization unit provided by the invention comprises at least two parallel tubular reactors, wherein the parallel structure can better control parameters such as the feeding temperature, the feeding pressure and the like of the tubular reactors, so that the regulation and control of products are realized on the premise of ensuring the conversion rate;
(2) According to the invention, on the basis of a parallel structure, different regulator feed inlets such as an initiator feed inlet are arranged, so that the concentration distribution of the regulator such as the initiator in the tubular reactor can be better controlled under the condition of not increasing the scale formation of a compression unit and not changing the temperature of a reaction section of the tubular reactor, the regulation of molecular chain structures such as the number average molecular weight, the Molecular Weight Distribution (MWD) and the like of a product is realized, and the device can be utilized to produce downstream products matched with different fields;
(3) The device provided by the invention is not only suitable for the homopolymerization of olefin initiated by a free radical polymerization initiator, but also suitable for the copolymerization of olefin and other olefinic monomers, thereby producing and obtaining various olefin homo-and copolymerization products, improving the utilization rate and applicability of the device, and having better economic benefit.
Drawings
FIG. 1 is an olefin free radical polymerization apparatus in accordance with a preferred embodiment of the present invention;
FIG. 2 is an olefin free radical polymerization apparatus in accordance with another preferred embodiment of the present invention.
Description of the reference numerals
1. Circulating material compressor 2 and primary compressor
3. Two-stage compressor 4/4a/4b, preheater
5a/5b/5c/6a/6b/6c, tubular reactor 7, high pressure relief valve
8. Cooler 9, high pressure separator
10. High circulation circuit 11 and low pressure separator
12. Low circulation loop
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Unless otherwise indicated, terms of orientation such as "upstream" and "downstream" are used with respect to the direction of flow of material in the device.
As shown in fig. 1-2, a first aspect of the present invention provides an olefin radical polymerization apparatus comprising: a first stage high pressure polymerization unit and a multistage high pressure polymerization unit; wherein the primary high-pressure polymerization unit is connected in series upstream of the multi-stage high-pressure polymerization unit; the primary high-pressure polymerization unit comprises at least two parallel tubular reactors for carrying out primary high-pressure polymerization on at least two reaction monomer streams containing olefin sources respectively; the multistage high-pressure polymerization unit comprises one or more tubular reactors which are sequentially connected in series and is used for carrying out multistage high-pressure polymerization on the product from the first-stage high-pressure polymerization unit; and an initiator feed inlet is arranged on at least one tubular reactor in the first-stage high-pressure polymerization unit and/or the multistage high-pressure polymerization unit.
In the device, by arranging the first-stage high-pressure polymerization unit comprising at least two parallel tubular reactors and the multistage high-pressure polymerization unit comprising one or more tubular reactors connected in series in sequence, compared with the prior art for producing polyolefin by using the tubular reactors, polyolefin products with wider molecular distribution and higher Polymer Dispersion Index (PDI) can be produced when the device is used for producing polyolefin, and the inventor speculates that the arrangement of the first-stage high-pressure polymerization unit comprising at least two parallel tubular reactors can better control the reaction time at high and low temperatures during polymerization, thereby increasing the Polymer Dispersion Index (PDI); meanwhile, the temperature, pressure and other parameters of the feed inlet of the tubular reactor can be better controlled when the device is used, and then the conversion rate of the reaction monomer flow containing olefin sources is ensured and the regulation and control of products are realized on the premise of not increasing the scaling of the device by arranging the initiator feed inlets at different positions.
In the apparatus of the present invention, the position of the initiator feed port is not limited, and may be selected as desired, and in some embodiments, the initiator feed port is provided at the reactive monomer flow feed port end of at least one tubular reactor in the primary high pressure polymerization unit; in some embodiments, at least one initiator feed port (e.g., 1, 2, 3, 4, etc.) is provided in at least one tubular reactor of the primary high pressure polymerization unit along its length, preferably 1 to 3 (referring to 1 to 3 initiator feed ports each provided in any one or more tubular reactors of the primary high pressure polymerization unit along its length); in some embodiments, at least one initiator feed port (e.g., 1, 2, 3, 4, etc.) is disposed on at least one tubular reactor in the multistage high pressure polymerization unit, wherein "on the tubular reactor" includes the material feed port end of the tubular reactor and any location along its length on the tubular reactor, and "material feed port end" of the tubular reactor in the multistage high pressure polymerization unit refers to the inlet port for receiving material from a first stage high pressure polymerization unit and the inlet port for receiving material from an adjacent tubular reactor), preferably 1 to 5 (referring to 2 to 5 initiator feed ports each disposed on any one or more tubular reactors in the multistage high pressure polymerization unit). By adopting the embodiment, the device can better realize the adjustment of molecular chain structures such as Molecular Weight Distribution (MWD) and long chain branching quantity (LCB) of the product, and can be used for producing downstream products matched with different fields.
Wherein the "reaction monomer flow feed port end" refers to a reaction monomer flow feed port at one end of a tubular reactor in a first-stage high-pressure polymerization unit, and it should be understood by those skilled in the art that the other end of the tubular reactor is a discharge port; the inlet end of a tubular reactor in a multistage high pressure polymerization unit refers to the end of the product flowing into a first tubular reactor in a multistage high pressure polymerization unit.
In the apparatus according to the present invention, there is no limitation on the number of parallel tubular reactors in the primary high-pressure polymerization unit as long as the object of the present invention can be achieved, and in some preferred embodiments, the primary high-pressure polymerization unit includes 2 to 4 parallel tubular reactors, and the molecular chain structure such as the Molecular Weight Distribution (MWD) and the long chain branching amount (LCB) can be adjusted using the foregoing preferred embodiments.
In the apparatus of the present invention, in order to provide each of the olefin-source containing reactant monomer streams with an inlet pressure to the primary high pressure polymerization unit, in some embodiments, the apparatus further comprises at least one compression unit located upstream of the primary high pressure polymerization unit.
In the apparatus of the present invention, in order to provide each of the olefin-source containing reactant monomer streams with an inlet temperature into the primary high pressure polymerization unit, in some embodiments, the apparatus further comprises at least one preheater located upstream of the primary high pressure polymerization unit; preferably, the preheater is located between the compression unit and the primary high pressure polymerisation unit. By adopting the embodiment, the first-stage high-pressure polymerization can be more smoothly carried out.
In the device according to the invention, the compression unit comprises one (or more compressors connected in series, for example 2 compressors connected in series, 3 compressors connected in series, 4 compressors connected in series, 5 compressors connected in series), preferably the compression unit comprises 2-4 compressors connected in series. In some embodiments, the compression unit comprises 2 compressors in series, in turn, a primary compressor 2 and a secondary compressor 3; in other embodiments, the compression unit comprises 3 compressors in series, in turn, a primary compressor 2, a secondary compressor 3, and a tertiary compressor. With the foregoing embodiments, each reactive monomer stream can be brought to the inlet pressure of a primary high pressure polymerization unit.
In the apparatus according to the present invention, the number of compression units is not limited as long as each olefin-source-containing reaction monomer stream can be provided with an inlet pressure into the primary high-pressure polymerization unit, respectively, and in some preferred embodiments, at least one compression unit is disposed in series upstream of the cascade of at least two parallel tubular reactors in the primary high-pressure polymerization unit; in some embodiments, at least one compression unit is disposed in series upstream of each respective tubular reactor in the first stage high pressure polymerization unit.
In the apparatus of the present invention, the number of said preheaters is not limited as long as each olefin-source-containing reaction monomer stream is capable of having an inlet temperature into said primary high pressure polymerization unit, and in some preferred embodiments at least one preheater is disposed in series upstream of the cascade of at least two parallel tubular reactors in the primary high pressure polymerization unit; in some embodiments, at least one preheater is disposed in series upstream of each respective tubular reactor in the first stage high pressure polymerization unit.
In the apparatus of the present invention, preferably, the apparatus further comprises at least one telogen feed (e.g., 1, 2, 3, 4, 5, 6, etc.). The telogen feed port can be used for introducing the telogen into the device to participate in the primary high-pressure polymerization and/or the multistage high-pressure polymerization, so that the molecular weight of the product can be better regulated.
In the apparatus of the present invention, the number and the positions of the telogen feed inlets are not limited, and may be selected according to the needs, and in some preferred embodiments, the telogen feed inlets are disposed at any position upstream of the outlet of the multistage high-pressure polymerization unit, i.e., the telogen feed inlet is disposed at any position upstream of the outlet of the last tubular reactor in the multistage high-pressure polymerization unit according to the needs of the product.
In the apparatus of the present invention, the arrangement of each of the telogen feed ports may be in various ways. Preferably, each telogen feed port is respectively provided at: an inlet of the compression unit; and/or an outlet of the compression unit; and/or the connecting pipelines of any two adjacent compressors in the compression unit; and/or, the reaction monomer of at least one tubular reactor in the primary high-pressure polymerization unit flows to the feed port side (refer to at the connecting pipe of at least one tubular reactor in the primary high-pressure polymerization unit and its corresponding upstream compression unit); and/or at least one tubular reactor in the primary high pressure polymerization unit (including the reactive monomer flow feed end of the tubular reactor and any position along its length on the tubular reactor); and/or at the connecting pipe of the primary high pressure polymerization unit and the multistage high pressure polymerization unit; and/or at least one tubular reactor in the multistage high pressure polymerization unit (including the feed inlet end of the tubular reactor and any position along its length on the tubular reactor). With the various embodiments described above, it is possible to achieve production of polyolefins of different molecular weight widths as desired.
In the apparatus of the present invention, preferably, the apparatus further comprises at least one comonomer feed (e.g., 1, 2, 3, 4, 5, 6, etc.). The comonomer feed can be configured to introduce comonomer into the apparatus to participate in the first stage high pressure polymerization and/or the multistage high pressure polymerization to produce the polyolefin copolymer using the apparatus.
In the apparatus according to the present invention, the number and position of the comonomer feed ports are not limited, and may be selected according to the need, and in some preferred embodiments, the comonomer feed ports are disposed at any position upstream of the outlet of the first stage high pressure polymerization unit, i.e., may be selected according to the need of the product, and the comonomer feed ports are disposed at any position upstream of the outlet of at least one tubular reactor of the outlet of the first stage high pressure polymerization unit.
In the apparatus of the present invention, each of the comonomer feed inlets may be provided in a variety of ways. Preferably, each comonomer feed inlet is provided with: an inlet of the compression unit; and/or the connecting pipelines of any two adjacent compressors in the compression unit; and/or, a reaction monomer flow feed port side with at least one tubular reactor in the first stage high pressure polymerization unit; and/or the connection pipeline of the preheater and the compression unit.
In the apparatus according to the present invention, preferably, the apparatus further comprises a separation circulation unit downstream of the multistage high-pressure polymerization unit for separating the materials obtained by the multistage high-pressure polymerization to obtain a polymerized product and unreacted monomers. With the foregoing embodiments, not only a polymerization product can be obtained, but also unreacted monomers can be recycled to the first-stage high-pressure polymerization and the multistage high-pressure polymerization.
In the apparatus of the present invention, the structure of the separation and circulation unit is not limited as long as the object of the present invention can be achieved, and in some preferred embodiments, the separation and circulation unit includes a separator for separating the product from the multistage high-pressure polymerization unit and a circulation circuit for circulating the unreacted monomer to the upstream of the first-stage high-pressure polymerization unit; further preferably, the separator comprises a high pressure separator 9 and a low pressure separator 11 connected in series in sequence, the circulation circuit comprises a high circulation circuit 10 connected with the high pressure separator 9 and a low circulation circuit 12 connected with the low pressure separator 11, more preferably, one end of the high circulation circuit 10 is connected with the high pressure separator 9, and the other end is connected with the suction side of the secondary compressor 3; one end of the low pressure separator 11 is connected with the low pressure separator 11, and the other end is connected with the suction side of the primary compressor 2.
In the apparatus according to the present invention, preferably, the separation and circulation unit further comprises a high pressure relief valve 7 and a cooler 8 between the second stage reactor and the low pressure separator 11 for depressurizing and cooling the material from the multistage high pressure polymerization unit and then feeding the material into the separation and circulation unit for separation and circulation. In the apparatus according to the invention, the high-circulation circuit 10 preferably also comprises a cooler and a separator for removing some components (e.g. oligomers) other than unreacted monomers from the gaseous fraction coming from the high-pressure separator 9. In the apparatus according to the invention, it is preferred that the low-pressure separator 11 further comprises a cooler and a separator for removing some components (e.g., oligomers) other than unreacted monomers from the gaseous fraction in the low-pressure separator 12; further preferably, the low-circulation circuit 12 further includes at least one circulation compressor 1 (e.g., 1 circulation compressor 1, 2 circulation compressors 1, 3 circulation compressors 1, etc.), and still further preferably, the circulation compressor 1 is provided downstream of the cooler and separator in the low-circulation circuit 12. By adopting the embodiment, not only the polymer product can be obtained, but also the recycling of the unreacted monomers can be better realized, and the economic effect is better.
In the device of the present invention, the specific structures of the compressor, the tubular reactor, the high-pressure relief valve 7, the cooler, the high-pressure separator 9, the low-pressure separator 11 and the separator are not particularly limited, and may be various compressors, tubular reactors, high-pressure relief valves 7, coolers, high-pressure separators and low-pressure separators 11 commonly used in the art, which are all well known to those skilled in the art, and are not described herein, meanwhile, each material inlet or material outlet in the present invention may be cross-connected, and each device is connected through a pipeline, and a valve and other component is also provided in the device to realize material circulation, and the tubular reactor selects a cooling jacket structure to realize heat exchange.
In a second aspect, the present invention provides a process for the free radical polymerisation of olefins, the process being carried out in an olefin free radical polymerisation apparatus as described above, the process comprising: respectively introducing at least two reaction monomer streams containing olefin sources into at least two parallel tubular reactors in a primary high-pressure polymerization unit included in the device, respectively performing primary high-pressure polymerization, and then flowing the obtained primary high-pressure polymerization product into the tubular reactors in a multistage high-pressure polymerization unit included in the device for multistage high-pressure polymerization; wherein at least one free radical polymerization initiator is introduced into each of the initiator feed ports included in the apparatus to participate in one-stage high pressure polymerization and/or multistage high pressure polymerization, and the pressure of the reactive monomer stream is greater than 100MPa.
In the present invention, preferably, at least one olefin-containing source material is passed through the same compression unit; and/or at least two olefin source containing feeds are separately fed to different compression units to compress the olefin source containing feed to a reactive monomer stream having a pressure of greater than 100 MPa.
Wherein the temperature of the olefin-containing source is not limited and may be selected as desired.
In the present invention, the number of strands of the olefin-containing source material is not limited, and the number of strands of the olefin-containing source material corresponds to the number of compression units, and the number of strands of the olefin-containing source material is equal to or less than the number of strands of the reaction monomer stream, and when the number of strands of the olefin-containing source material is less than the number of strands of the reaction monomer stream, it may be compressed by the compression units and then subdivided into the desired number of strands of the olefin-containing source reaction monomer stream. For example, after compressing an olefin-containing feed to a pressure of greater than 100MPa in a compression unit, it is split into two olefin-containing reactant monomer streams.
In the present invention, the high-pressure polymerization conditions in the first-stage high-pressure polymerization and the second-stage high-pressure polymerization are such that the reaction monomer stream can be polymerized under high pressure, preferably the pressure of the reaction monomer stream is 110 to 400MPa (e.g., 110MPa, 130MPa, 150MPa, 170MPa, 200MPa, 250MPa, 300MPa, 330MPa, 350MPa, and a range of any of the above-mentioned values); further preferably 170 to 330MPa. It should be understood that the pressure of each reactant monomer stream may or may not be the same.
In the present invention, it will be understood by those skilled in the art that the pressure of the reactive monomer stream is the inlet pressure of the reactive monomer stream into the first stage high pressure polymerization unit at which the first stage high pressure polymerization is carried out.
In the method of the present invention, the number of the first-stage high-pressure polymerizations is not limited as long as the object of the present invention can be achieved, and in some preferred embodiments, the number of the first-stage high-pressure polymerizations is 2 to 4. The larger the number of the first-stage high-pressure polymerizations under a flow rate of the reaction monomer, the smaller the inner diameter of the reactor to be subjected to the first-stage high-pressure polymerization, and thus the more severe the requirements on equipment, and the above-mentioned preferred embodiment can be used, not only the adjustment of molecular chain structures such as the Molecular Weight Distribution (MWD) and the amount of Long Chain Branching (LCB) of the product, but also the less severe the requirements on the reaction equipment, but it does not mean that more than 4 first-stage high-pressure polymerizations are not suitable for the present invention, and according to the inventive concept of the present invention, the object of the present invention can be achieved as long as the first-stage high-pressure polymerization is two or more.
In the present invention, the order of each stage of the multistage high-pressure polymerization is not limited as long as the object of the present invention can be achieved, and it may be carried out simultaneously or not, as long as the stage of the high-pressure polymerization product flows into a tubular reactor in a multistage high-pressure polymerization unit included in the apparatus as a raw material to carry out the multistage high-pressure polymerization. In some preferred embodiments, each stage of high pressure polymerization is performed simultaneously. With the above preferred embodiments, the molecular chain structure such as the Molecular Weight Distribution (MWD) and the long chain branching amount (LCB) of the product can be adjusted while ensuring the conversion.
In the present invention, the reaction monomer stream is preheated to the desired temperature by a preheater included in the apparatus. Preferably, the temperature of each of the reactive monomer streams is in the range of from 100 to 200 ℃ (e.g., 100 ℃, 120 ℃, 150 ℃, 170 ℃, 200 ℃, and any of the values recited above), preferably 150 to 200 ℃. With the above preferred embodiment, not only the reaction fluid can be heated to a temperature at which polymerization can be initiated, but also the adjustment of molecular chain structure such as Molecular Weight Distribution (MWD) and long chain branching degree (LCB) of the product can be better achieved by controlling the conditions such as preheating.
In the present invention, the temperature of the first-stage high-pressure polymerization and each of the multistage high-pressure polymerization may be selected as desired, and in some preferred embodiments, the respective temperatures of each of the first-stage high-pressure polymerization and each of the multistage high-pressure polymerization are in the range of 100 to 350 ℃ (e.g., 100 ℃, 120 ℃, 125 ℃, 135 ℃, 150 ℃, 164 ℃, 170 ℃, 176 ℃, 180 ℃, 190 ℃, 192 ℃, 203 ℃, 211 ℃, 224 ℃, 225 ℃, 295 ℃, 300 ℃, 320 ℃, 350 ℃, and any of the numerical ranges described above). By adopting the preferred embodiment, the molecular weight distribution, branched chain distribution and other molecular structure regulation and control of the product can be realized on the premise of ensuring the conversion rate.
In the present invention, the free radical polymerization is mainly used, and the reaction temperature is changed in the first-stage high-pressure polymerization and the multistage high-pressure polymerization in the reaction process, but the temperature change is in the range of 100-350 ℃. The addition of the free radical polymerization initiator affects the temperature of the polymerization and, in some embodiments of the invention, the temperature of the reactor contents where the free radical polymerization initiator is injected through the initiator feed port is recorded as the "inlet temperature"; while the peak temperature in the tube reactor into which the radical polymerization initiator was introduced was recorded, it is further understood that when no radical polymerization initiator was introduced into the tube reactor in the tube reactor, no radical polymerization reaction occurred, and the temperature of the stream introduced into the tube reactor was not greatly changed, and the corresponding "inlet temperature" and "peak temperature" were not required to be recorded during the experiment. For example, the inlet ends of the tube reactors 6a, 6b, 6c are not provided with initiator inlets, i.e., no radical polymerization initiator is introduced into the tube reactors 6a, 6b, 6c, i.e., no corresponding "inlet temperature" and "peak temperature" in the tube reactors 6a, 6b, 6c need be recorded.
In the present invention, the feed amount of each olefin-containing reactive monomer stream is not limited, and may be selected as desired, and in some preferred embodiments, the ratio of the maximum feed amount to the minimum feed amount of each olefin-containing reactive monomer stream is (20-1): 1, e.g., 20:1, 15:1, 10:1, 5:1, 3:1, 1:1, and ranges of any of the above values; preferably (5-1): 1. by adopting the preferable technical scheme, different tubular reactors for the first-stage high-pressure polymerization can be used for producing polymers with different molecular structural characteristics, so that the molecular structure of a final product is regulated and controlled. At the same time, the difficulty in designing the equipment of the tubular reactor for the first-stage high-pressure polymerization can be reduced.
In the present invention, the feed amount of each of the olefin-source-containing reactive monomer streams means the feed amount of each of the reactive monomer streams flowing into the tubular reactor in the first-stage high-pressure polymerization unit.
In the present invention, the radical polymerization initiator is introduced into the polymerization reactor through the initiator feed port included in the apparatus to participate in the one-stage high pressure polymerization and/or the multistage high pressure polymerization, respectively, by means of batch or continuous injection.
In the present invention, the amount of the radical polymerization initiator to be fed to each strand may be selected as required as long as the object of the present invention is achieved, and the present invention is not particularly limited.
In the present invention, the molecular weight of the product produced may be varied by the addition of a telogen, and in some embodiments the process further comprises feeding at least one strand of telogen each from a telogen feed included in the apparatus to participate in the first stage high pressure polymerization and the multistage high pressure polymerization. In the device of the invention, the concentration distribution of the regulator along the tubular reactor can be better controlled under the condition of not increasing the scale formation of a compressor system and not changing the temperature of a reaction section of the tubular reactor, thereby realizing the regulation of molecular chain structures such as Molecular Weight Distribution (MWD) and Long Chain Branch (LCB) of the product, and the downstream products matched with different fields can be obtained in the same device by utilizing the method.
In the present invention, the amount of the telogen to be fed to each strand may be selected as required, so long as the object of the present invention is achieved, and the present invention is not particularly limited.
In the present invention, the olefin copolymer may be prepared by adding a comonomer, and in some embodiments, the method further comprises feeding at least one comonomer each from a comonomer feed included in the apparatus to participate in the first stage high pressure polymerization and the multistage high pressure polymerization. The method is not only suitable for the free radical polymerization initiator to initiate olefin homopolymerization, but also suitable for the copolymerization of olefin and comonomer, thereby producing and obtaining various olefin homopolymerization and copolymerization products, improving the utilization rate and applicability of the device and having better economic effect.
In the present invention, in order to obtain a polymer product, in some embodiments, the method further comprises subjecting the product obtained by the multistage high-pressure polymerization to reduced pressure cooling, and separating the unreacted monomer and the polymer product by a separation circulation unit included in the apparatus.
In the present invention, preferably, the product obtained by the multistage high-pressure polymerization sequentially passes through a high-pressure release valve 7 and a cooler in the separation and circulation unit and then flows into a high-pressure separator in the separation and circulation unit to be separated into a gaseous fraction A and a liquid fraction A, and the liquid fraction A flows into a low-pressure separator 11 in the separation and circulation unit to be separated into a gaseous fraction B and a polymer product; further preferably, the gaseous fraction a is cooled and separated by a cooler and a separator on the high circulation loop 10 to obtain unreacted monomers, and the unreacted monomers flow into the suction side of the secondary compressor 3; and/or the gaseous fraction B is cooled and separated by a cooler and a separator on the low-circulation loop 12, and unreacted monomers obtained by separation are compressed by a compressor on the low-circulation loop 12 and then flow into the suction side of the primary compressor 2; and/or the polymer is sent to pelletization to obtain the corresponding product.
In the present invention, the cooling separation conditions of the coolers and separators on the high-pressure separator, the low-pressure separator 11, the high-circulation circuit 10 and the low-circulation circuit 12 are not limited as long as the object of the present invention can be achieved, and those skilled in the art can select them as required.
In the present invention, the olefins in the olefin source include R 2 C＝CR 2 One or more of mono-olefins, conjugated dienes, non-conjugated dienes, wherein each R is H, an alkane, or a halogen.
In the present invention, preferably, when the olefin source is ethylene and no comonomer is present, the product produced by the process of the present invention is a linear low density polyethylene.
In the present invention, the kind of the comonomer may be selected according to the need, and it is understood that the comonomer is different from the kind of the olefin source, and the comonomer capable of radical copolymerization with the olefin source under high pressure is applicable to the system of the present invention. In some embodiments, when the olefin source is ethylene, examples of the comonomer are α, β -unsaturated C 3 -C 8 Carboxylic acids, in particular acrylic acid, methacrylic acid, maleic acid and fumaric acid; and/or alpha, beta unsaturated C 3 -C 8 Derivatives of carboxylic acids, e.g. alpha, beta-unsaturated C 3 -C 5 Carboxylic esters or alpha, beta-unsaturated C 3 -C 5 Carboxylic anhydrides, in particular methyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, methacrylic anhydride and maleic anhydride; and/or 1-olefins, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene; preferably one or more of vinyl acetate, propylene, 1-hexene, acrylic acid, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, vinyl acetate or vinyl acrylate is a comonomer.
In the present invention, in the case of preparing the olefin copolymer, the ratio of the olefin monomer to the comonomer is not limited, and may be specifically selected according to actual needs.
In the present invention, the kind of the radical polymerization initiator is not limited, and any substance capable of generating radicals in the primary high pressure polymerization and/or the multistage high pressure polymerization may be used as the radical polymerization initiator in the present invention. In some embodiments, the free radical polymerization initiator comprises one or more of oxygen, air, azo compounds, organic peroxides, and hydrocarbons of C-C initiators. Organic peroxides which may be mentioned are peroxy esters, peroxy ketals, peroxy ketones and peroxy carbonates, for example di (2-ethylhexyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate, diacetylperoxydicarbonate, t-butyl peroxyisopropylcarbonate, di-t-butyl peroxide, di-t-amyl peroxide, dicumyl peroxide, 2, 5-dimethyl-2, 5-di-t-butylperoxy hexane, t-butylcumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hex-3-yne, 1, 3-diisopropylmono-or t-butylhydroperoxide, didecanoyl peroxide, 2, 5-dimethyl-2, 5-di (2-ethylhexanoylperoxyhexane, t-amyl peroxy-2-ethylhexanoate, dibenzoylperoxide tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxydiethylisobutyrate, tert-butyl peroxy-3, 5-trimethylhexanoate, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane, 1-bis (tert-butylperoxy) cyclohexane, tert-butyl peroxyacetate, cumyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-butyl peroxyneodecanoate, tert-butyl peroxymaleate, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl peroxybenzoate, methyl isobutyl ketone hydroperoxide, 3,6, 9-triethyl-3, 6, 9-trimethyltriperoxycyclononane, 2-di (t-butylperoxy) butane, and the like; azo compounds which may be mentioned are: azoalkanes (diazenes), azodicarboxylic esters, azodicarboxylic dinitriles, azobisisobutyronitrile, and the like; hydrocarbons of the C-C initiator which may be mentioned are 1, 2-diphenyl-1, 2-dimethylethane derivative and 1, 2-tetramethylethane derivative. The radical polymerization initiator of the present invention may be used alone or as a mixture of a plurality of different kinds of radical polymerization initiators.
In the present invention, the radical polymerization initiator may be introduced into the apparatus in any state, for example, liquid, dissolved state, supercritical state. Preferably, when a gaseous radical polymerization initiator (e.g., oxygen or air) is used, the gaseous radical polymerization initiator is introduced into the apparatus in a supercritical state.
In the present invention, preferably, when the initiator is one or more of azo compound, organic peroxide and hydrocarbon of c—c initiator, the radical polymerization initiator is a dissolved radical polymerization initiator; more preferably, the concentration of the radical polymerization initiator in the dissolved state is 5 to 80% by weight.
In the present invention, the term "dissolved radical polymerization initiator" refers to a mixture of a solvent capable of dissolving the radical polymerization initiator and the corresponding radical polymerization initiator, wherein the kind of solvent is not limited, and solvents capable of dissolving the corresponding radical polymerization initiator are all suitable for the system of the present invention, and examples of suitable solvents are ketones, aliphatic hydrocarbons (e.g., octane, decane, isododecane, etc.) and other saturated C' s 8 -C 25 Hydrocarbons, and the like. By adopting the preferred embodiment, the phenomenon of pyrolysis of the free radical polymerization initiator caused by overheating is avoided, so that the safety of the reaction is higher, the efficiency of the initiator is improved, and the use cost of the initiator is reduced.
In the present invention, as long as the object of the present invention can be achieved, there is no limitation on the kind of the telogen, and a telogen capable of changing the molecular weight of the produced product can be used in the system of the present invention. In some embodiments, the telogen comprises one or more of an aliphatic hydrocarbon, an olefin, a ketone, an aldehyde, an aliphatic alcohol, or hydrogen. Examples of the aliphatic hydrocarbon include propane, butane, pentane, hexane, cyclohexane and the like; olefins which may be mentioned are propylene, 1-pentene or 1-hexene; examples of the ketone include acetone, methyl ethyl ketone (2-butanone), methyl isobutyl ketone, methyl isoamyl ketone, diethyl ketone, and dipentyl ketone; aldehydes which may be mentioned are formaldehyde, acetaldehyde or propionaldehyde; examples of the aliphatic alcohol include methanol, ethanol, propanol, isopropanol, butanol, and the like. Preferably, the telogen is one or more of an aliphatic aldehyde (e.g., propionaldehyde), a 1-ene (e.g., propylene or 1-hexene), and an aliphatic hydrocarbon (e.g., propane).
In the present invention, the pressures involved are absolute pressures.
In the present invention, a person skilled in the art may adjust the method of the present invention according to the changes of the apparatus required for different embodiments of the present invention, which will not be described in detail herein.
The present invention will be described in detail by examples. In the following examples: number average molecular weight M n Weight average molecular weight M w And a polymer dispersion index PDI as measured by high temperature gel permeation chromatography HT-GPC method; long chain branching amount LCB passage 13 C-NMR method.
Example 1
A process for the free radical polymerization of olefins carried out in an apparatus as shown in fig. 1, wherein in the apparatus of fig. 1: the lengths of the two parallel tubular reactors 5a and 5b in the one-stage high-pressure polymerization unit connected in series upstream of the one-stage high-pressure polymerization unit are 560m, and the inner diameters are 0.045m; the lengths of the three tubular reactors 6a, 6b and 6c which are sequentially connected in series in the multistage high-pressure polymerization unit are 400m, and the inner diameters are 0.045m; the reaction monomer flow feed inlet ends of the tubular reactor 5a and the tubular reactor 5b are respectively provided with an initiator feed inlet; the feed inlet ends of the tubular reactor 6a, the tubular reactor 6b and the tubular reactor 6c are respectively provided with an initiator feed inlet; the outlet of the compression unit is provided with a telogen feeding port;
a stream of material containing olefin sources is compressed 3 through a first-stage compressor 2 and a second-stage compressor in a compression unit in sequence, a stream of telogen is fed to an outlet of the compression unit through a telogen feed port and is fully mixed with the compressed material containing olefin sources and then is equally divided into two reaction monomer streams containing olefin sources, the two reaction monomer streams containing olefin sources are respectively introduced into two parallel tubular reactors 5a and 5b in a first-stage high-pressure polymerization unit included in a device after passing through a preheater 4a positioned upstream of the tubular reactor 5a and a preheater 4b positioned upstream of the tubular reactor 5b, the first-stage high-pressure polymerization is respectively carried out, and then the obtained first-stage high-pressure polymerization product flows into three tubular reactors 6a, 6b and 6c in a multi-stage high-pressure polymerization unit included in the device; wherein, five free radical polymerization initiators are respectively introduced into the corresponding primary high-pressure polymerization or multi-stage high-pressure polymerization through an initiator feed inlet included in the device; the multi-stage high-pressure polymerization product sequentially passes through a high-pressure relief valve 7 and a cooler 8 in a separation circulation unit and then flows into a high-pressure separator 9 in the separation circulation unit to be separated into a gaseous fraction A and a liquid fraction A, and the liquid fraction A flows into a low-pressure separator 11 in the separation circulation unit to be separated into a gaseous fraction B and a polymer product; the gaseous fraction A is cooled and separated by a cooler and a separator on the high circulation loop 10 to obtain unreacted monomers, and the unreacted monomers flow into the suction side of the secondary compressor; the gaseous fraction B is cooled and separated by a cooler and a separator on the low-circulation loop 12 to obtain unreacted monomers, and the unreacted monomers are compressed by a circulating material compressor 1 on the low-circulation loop and then flow into the suction side of the primary compressor; the polymer product is sent to pelletization to obtain a low-density polyethylene product; wherein:
The material containing olefin source is ethylene; the inlet pressures of the two reaction monomer streams into the tubular reactor 5a and the tubular reactor 5b are: 220MPa;
the inlet temperatures of the two reaction monomer streams into the tubular reactor 5a and the tubular reactor 5b are respectively: 170 ℃ and 180 ℃;
the telogen is propylene; the feeding amount of the telogen is as follows: 250kg/h;
the inlet temperatures of the preheater 4a and the preheater 4b are both: 92 ℃;
the feed amounts of the reaction monomer streams at the feed inlet ends of the reaction monomer streams of the tubular reactor 5a and the tubular reactor 5b were 2179 kg/h;
along the material flow direction, the compositions of the first strand of free radical polymerization initiator and the second strand of free radical polymerization initiator are respectively as follows: a mixture of di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate and tert-butyl peroxypivalate mixed in a mass ratio of 1:2:2:2; the composition of the third to fifth radical polymerization initiators is: a mixture of di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate and tert-butyl peroxypivalate mixed in a mass ratio of 10:2:1:1;
the feed amounts of the radical polymerization initiator at the initiator feed ports at the feed port ends of the reaction monomer flows of the tubular reactors 5a and 5b are respectively: 6.78kg/h, 6.19kg/h;
The feed amounts of the radical polymerization initiator at the initiator feed ports at the feed port ends of the tubular reactor 6a, the tubular reactor 6b and the tubular reactor 6c were 7.33kg/h, 7.44kg/h and 7.80kg/h, respectively;
the inlet temperatures of the tubular reactors 6a, 6b and 6c were 192℃and 211℃and 225℃respectively;
peak temperatures in tube reactor 5a, tube reactor 5b, and tube reactor 6a, tube reactor 6b, and tube reactor 6c were all 295 ℃;
the separation conditions of the high-pressure separator are as follows: 25MPa,235 ℃;
the separation conditions of the low pressure separator are as follows: 2b ar,220 ℃.
As shown in Table 1, the number average molecular weight M of the low density polyethylene in this example n Weight average molecular weight M w Molecular weight distribution index PDI, long chain distribution LCB, yield and ethylene conversion.
Example 2
The procedure of example 1 was followed, except that:
in the apparatus of fig. 2, a preheater 4 is located upstream of two parallel tubular reactors 5a and 5b in the first-stage high-pressure polymerization unit, a stream of olefin-containing material is compressed 3 by a first-stage compressor 2 and a second-stage compressor in the compression unit in sequence, a telogen is fed to the outlet of the compression unit through a telogen feed port and is fully mixed with the compressed olefin-containing material, and then is equally divided into two olefin-containing reaction monomer streams by the preheater 4, and the two olefin-containing reaction monomer streams are respectively introduced into the two parallel tubular reactors 5a and 5b in the first-stage high-pressure polymerization unit included in the apparatus; wherein:
The inlet temperatures of the two reaction monomer streams into the tubular reactor 5a and the tubular reactor 5b are: 170 ℃;
the telogen is propylene; the feeding amount of the telogen is as follows: 180kg/h;
the inlet temperature of the preheater 4 is: 92 ℃;
the feed amounts of the radical polymerization initiator at the initiator feed ports at the feed port ends of the reaction monomer flows of the tubular reactors 5a and 5b are respectively: 6.80kg/h, 6.80kg/h;
the feed amounts of the radical polymerization initiator at the initiator feed ports at the feed port ends of the tubular reactor 6a, the tubular reactor 6b and the tubular reactor 6c were 7.41kg/h, 7.26kg/h and 7.36kg/h, respectively;
the inlet temperatures of the tubular reactors 6a, 6b and 6c were 192℃and 211℃and 229℃respectively.
As shown in Table 1, the number average molecular weight M of the low density polyethylene in this example n Weight average molecular weight M w Molecular weight distribution index PDI, long chain distribution LCB, yield and ethylene conversion.
Example 3
The procedure of example 1 was followed, except that:
in the device of fig. 1, the feed ports of the tubular reactor 6a, the tubular reactor 6b and the tubular reactor 6c are not provided with initiator feed ports, and two free radical polymerization initiators are respectively introduced into the corresponding primary high-pressure polymerization through the initiator feed ports included in the device; wherein:
The telogen is propylene; the feeding amount of the telogen is as follows: 195kg/h;
the feed amounts of the radical polymerization initiator at the initiator feed ports at the feed port ends of the reaction monomer flows of the tubular reactors 5a and 5b are respectively: 6.47kg/h, 6.22kg/h;
the peak temperatures in the tubular reactor 5a and the tubular reactor 5b are all 295 ℃;
the separation conditions of the high-pressure separator are as follows: 23MPa,200 DEG C
The separation conditions of the low pressure separator are as follows: 2b ar,190 ℃.
As shown in Table 1, the number average molecular weight M of the low density polyethylene in this example n Weight average molecular weight M w Molecular weight distribution index PDI, long chain distribution LCB, yield and ethylene conversion.
Example 4
The procedure of example 1 was followed, except that:
in the device of fig. 1: a telogen feed port is arranged at the side of the reaction monomer flow feed port of the tubular reactor 5a, and no telogen feed port is arranged at other positions; a strand of telogen is fed through a telogen feed port and is mixed with the reaction monomer flow flowing into the tubular reactor 5a, and then is introduced into the tubular reactor 5a for corresponding first-stage high-pressure polymerization; wherein:
the inlet temperatures of the two reaction monomer streams into the tubular reactor 5a and the tubular reactor 5b are respectively: 170 ℃ and 190 ℃;
The telogen is propylene; the feeding amount of the telogen is as follows: 170kg/h;
the feed amounts of the radical polymerization initiator at the initiator feed ports at the feed port ends of the reaction monomer flows of the tubular reactors 5a and 5b are respectively: 6.71kg/h, 6.25kg/h;
the feed amounts of the radical polymerization initiator at the initiator feed ports at the feed port ends of the tubular reactor 6a, the tubular reactor 6b and the tubular reactor 6c were 7.32kg/h, 7.42kg/h and 7.78kg/h, respectively;
the inlet temperatures of the tubular reactors 6a, 6b and 6c were 192℃and 211℃and 224℃respectively.
As shown in Table 1, the number average molecular weight M of the low density polyethylene in this example n Weight average molecular weight M w Molecular weight distribution index PDI, long chain distribution LCB, yield and ethylene conversion.
Example 5
The procedure of example 4 was followed, except that:
in the device of fig. 1: the sides of the reaction monomer flow feed inlets of the tubular reactor 5a and the tubular reactor 5b are respectively provided with a telogen feed inlet, and other positions of the device are not provided with telogen feed inlets; the two polymerization regulators are respectively fed to the side of the reaction monomer flow feed inlet of the tubular reactor 5a and the side of the reaction monomer flow feed inlet of the tubular reactor 5b through polymerization regulator feed inlets, are respectively fully mixed with the two reaction monomer flows, and then flow into the tubular reactor 5a and the tubular reactor 5b for single-stage high-pressure polymerization; wherein:
The telogen is propylene; the feed amounts of the two telogens are: 97.5kg/h;
the feed amounts of the radical polymerization initiator at the initiator feed inlet at the end of the reaction monomer flow feed inlet of the tubular reactor 5a and the tubular reactor 5b are respectively: 6.78kg/h, 6.19kg/h;
the inlet temperatures of the tubular reactors 6a, 6b and 6c were 192℃and 211℃and 225℃respectively.
As shown in Table 1, the number average molecular weight M of the low density polyethylene in this example n Weight average molecular weight M w Molecular weight distribution index PDI, long chain distribution LCB, yield and ethylene conversion.
Example 6
The procedure of example 4 was followed, except that:
in the device of fig. 1: a telogen feeding port is arranged at the connecting pipeline of the first-stage high-pressure polymerization unit and the multistage high-pressure polymerization unit, a telogen feeding port is not arranged at other positions of the device, and a strand of telogen is fed to the connecting pipeline of the first-stage high-pressure polymerization unit and the multistage high-pressure polymerization unit through the telogen feeding port, fully mixed with a first-stage high-pressure polymerization product and then flows into the multistage high-pressure polymerization unit; wherein:
the inlet temperatures of the two reaction monomer streams into the tubular reactor 5a and the tubular reactor 5b are: 170 ℃ and 150 ℃;
The telogen is propylene; the feeding amount of the telogen is as follows: 195kg/h;
the feed amounts of the radical polymerization initiator at the initiator feed ports at the feed port ends of the reaction monomer flows of the tubular reactors 5a and 5b are respectively: 6.72kg/h, 2.40kg/h;
the feed amounts of the radical polymerization initiator at the initiator feed ports at the feed port ends of the tubular reactor 6a, the tubular reactor 6b and the tubular reactor 6c were 7.35kg/h, 7.42kg/h and 7.81kg/h, respectively;
the inlet temperatures of the tubular reactors 6a, 6b and 6c were 192℃and 211℃and 224℃respectively;
the temperature peak of the tube reactor 5b was 250℃and the temperature peaks of the other tube reactors were 295 ℃.
As shown in Table 1, the number average molecular weight M of the low density polyethylene in this example n Weight average molecular weight M w Molecular weight distribution index PDI, long chain distribution LCB, yield and ethylene conversion.
Comparative example 1
The procedure of example 1 was followed, except that:
in the apparatus of FIG. 1, the one-stage high-pressure polymerization unit connected in series upstream of the multi-stage high-pressure polymerization unit is a tubular reactor 5a (the tubular reactor 5a has a length of 560m and an inner diameter of 0.045m, respectively), and there are no tubular reactor 5b and a preheater 4b in the apparatus; four initiator feed inlets are arranged in the device and are respectively arranged at the feed inlet ends of the reaction monomer flows of the tubular reactor 5a, the tubular reactor 6b and the tubular reactor 6 c; the other positions of the device are not provided with initiator feed inlets;
A strand of material containing an olefin source is sequentially compressed 3 by a primary compressor 2 and a secondary compressor in a compression unit, a strand of telogen is fed to an outlet of the compression unit through a telogen feeding port and is mixed with the material containing the olefin source after compression, and then a reaction monomer flow containing the olefin source is obtained through a preheater 4a, and four strands of free radical polymerization initiators are respectively introduced into the polymerization reactor through an initiator feeding port included in the device to participate in corresponding primary high-pressure polymerization or multistage high-pressure polymerization; wherein:
the inlet pressure of the reaction monomer stream into the tubular reactor 5a is: 220MPa
The inlet temperature of the reaction monomer stream into the tubular reactor 5a is: 175 ℃;
the feed rate of the reaction monomer stream at the feed inlet end of the monomer stream of the tubular reactor 5a was 43500kg/h;
the feed amounts of the radical polymerization initiator at the initiator feed ports at the feed port ends of the tubular reactor 5a, the tubular reactor 6b, and the tubular reactor 6c are respectively: 13.37kg/h, 6.56kg/h, 7.71kg/h and 7.39kg/h;
the inlet temperatures of the tubular reactors 6a, 6b and 6c were respectively: 206 ℃, 207 ℃, 228 ℃;
the peak temperatures in the tube reactor 5a, the tube reactor 6b and the tube reactor 6c were 295 ℃.
As shown in Table 1, the number average molecular weight M of the low density polyethylene of this comparative example n Weight average molecular weight M w Molecular weight distribution index PDI, long chain distribution LCB, yield and ethylene conversion.
Comparative example 2
The procedure of example 2 was followed, except that,
in the apparatus of FIG. 2, the one-stage high-pressure polymerization unit connected in series upstream of the multi-stage high-pressure polymerization unit is a tubular reactor 5a (the tubular reactor 5a has a length of 560m and an inner diameter of 0.045m, respectively), and the apparatus has no tubular reactor 5b; four initiator feed inlets are arranged in the device and are respectively arranged at the feed inlet ends of the reaction monomer flows of the tubular reactor 5a, the tubular reactor 6b and the tubular reactor 6 c; the other positions of the device are not provided with initiator feed inlets;
a strand of material containing an olefin source is sequentially compressed 3 by a primary compressor 2 and a secondary compressor in a compression unit, a strand of telogen is fed to an outlet of the compression unit through a telogen feeding port and is mixed with the material containing the olefin source after compression, and then a reaction monomer flow containing the olefin source is obtained through a preheater 4a, and four strands of free radical polymerization initiators are respectively introduced into the polymerization reactor through an initiator feeding port included in the device to participate in corresponding primary high-pressure polymerization or multistage high-pressure polymerization; wherein:
The inlet pressure of the reaction monomer stream into the tubular reactor 5a is: 220MPa;
the inlet temperature of the reaction monomer stream into the tubular reactor 5a is: 175 ℃;
the feed rate of the reaction monomer stream at the feed inlet end of the monomer stream of the tubular reactor 5a was 43500kg/h;
the feed amounts of the radical polymerization initiator at the initiator feed ports at the feed port ends of the tubular reactor 5a, the tubular reactor 6b, and the tubular reactor 6c are respectively: 13.34kg/h, 6.54kg/h, 7.36kg/h and 6.82kg/h;
the inlet temperatures of the tubular reactors 6a, 6b and 6c were 206 ℃, 207 ℃, 232 ℃ respectively;
the peak temperatures in the tube reactor 5a, the tube reactor 6b and the tube reactor 6c were 295 ℃.
As shown in Table 1, the number average molecular weight M of the low density polyethylene of this comparative example n Weight average molecular weight M w Molecular weight distribution index PDI, long chain distribution LCB, yield and ethylene conversion.
Comparative example 3
The procedure of example 3 was followed, except that:
in the apparatus of FIG. 1, the one-stage high-pressure polymerization unit connected in series upstream of the multi-stage high-pressure polymerization unit is a tubular reactor 5a (the tubular reactor 5a has a length of 560m and an inner diameter of 0.045m, respectively), and there are no tubular reactor 5b and a preheater 4b in the apparatus; the device is provided with an initiator feed port which is arranged at the reaction monomer flow feed port end of the tubular reactor 5 a; the other positions of the device are not provided with initiator feed inlets;
A stream of material containing olefin sources sequentially passes through a primary compressor 2 and a secondary compressor 3 in a compression unit, a stream of telogen is fed to an outlet of the compression unit through a telogen feed port and is mixed with the compressed material containing olefin sources, and then a stream of reaction monomer flow containing olefin sources is obtained through a preheater 4a, and a stream of free radical polymerization initiator is respectively introduced into the polymerization reactor through an initiator feed port included in the device to participate in corresponding primary high-pressure polymerization; wherein:
the inlet pressure of the reaction monomer stream into the tubular reactor 5a is: 220MPa;
the inlet temperature of the reaction monomer stream into the tubular reactor 5a is: 175 ℃;
the feed amount of the reaction monomer stream at the feed inlet end of the reaction monomer stream of the tubular reactor 5a was 43500kg/h;
the feed amount of the radical polymerization initiator at the initiator feed port at the feed port end of the reaction monomer flow of the tubular reactor 5a is: 12.70kg/h;
the peak temperature of the tubular reactor 5a was 295 ℃.
As shown in Table 1, the number average molecular weight M of the low density polyethylene of this comparative example n Weight average molecular weight M w Molecular weight distribution index PDI, long chain distribution LCB, yield and ethylene conversion.
Comparative example 4
The procedure of example 2 was followed, except that:
In the apparatus of FIG. 2, a full length 1760m, a tube reactor with an inner diameter of 0.045m was used instead of the primary high pressure polymerization unit and the multistage high pressure polymerization unit, and the reaction monomer flow inlet end of the tube reactor, and 560m, 960m, 1360m of the tube reactor along the length direction thereof were respectively provided with an initiator feed inlet; introducing a reaction monomer stream containing an olefin source into a tubular reactor for high-pressure polymerization, and continuously feeding a free radical polymerization initiator into the device through an initiator feed port to participate in the high-pressure polymerization (the product obtained by the high-pressure polymerization corresponds to the product obtained by multistage high-pressure polymerization in the example 1);
the inlet pressure of the reaction monomer stream into the tubular reactor was all: 220MPa;
the inlet temperatures of the reaction monomer streams into the tubular reactor were all: 175 ℃;
the telogen is propylene; the feeding amount of the telogen is as follows: 170kg/h;
the feed amount of the reaction monomer stream at the feed inlet end of the reaction monomer stream of the tubular reactor is as follows: 43500kg/h;
the feeding amount of the free radical polymerization initiator at the feeding port end of the reaction monomer flowing in the tubular reactor and at the four initiator feeding ports of the tubular reactor along the length directions 560m, 960m and 1260m is 14.29kg/h, 7.40kg/h, 7.27kg/h and 7.32kg/h respectively;
The inlet temperatures at 560m, 960m and 1260m of the tubular reactor along the length direction of the tubular reactor at the inlet end of the reaction monomer flow of the tubular reactor are 193 ℃, 211 ℃ and 229 ℃ respectively;
the peak temperatures of the four zones at the inlet end of the tubular reactor, at which the reaction monomers flow, and at the tubular reactor are divided in the length directions 560m, 960m, 1260m are 295 ℃.
As shown in Table 1, the number average molecular weight M of the low density polyethylene of this comparative example n Weight average molecular weight M w Molecular weight distribution index PDI, long chain distribution LCB, yield and ethylene conversion.
Comparative example 5
The procedure of example 6 was followed, except that:
in the apparatus of FIG. 1, the one-stage high-pressure polymerization unit connected in series upstream of the multi-stage high-pressure polymerization unit is a tubular reactor 5a (the tubular reactor 5a has a length of 560m and an inner diameter of 0.045m, respectively), and there are no tubular reactor 5b and a preheater 4b in the apparatus; four initiator feed inlets are arranged in the device and are respectively arranged at the feed inlet ends of the reaction monomer flows of the tubular reactor 5a, the tubular reactor 6b and the tubular reactor 6 c; the other positions of the device are not provided with initiator feed inlets; a telogen feed inlet is arranged at the connecting pipeline of the tubular reactor 5a and the multistage high-pressure polymerization unit, and the telogen feed inlet is not arranged at other positions of the device; a strand of telogen is fed into a tubular reactor 5a in the primary high-pressure polymerization unit through a telogen feed port, is fully mixed with the primary high-pressure polymerization product at a connecting pipeline of the multistage high-pressure polymerization unit, and flows into the multistage high-pressure polymerization unit; wherein:
The inlet pressure of the reaction monomer stream into the tubular reactor 5a is: 220MPa;
the inlet temperature of the reaction monomer stream into the tubular reactor 5a is: 175 ℃;
the feed rate of the reaction monomer stream at the feed inlet end of the monomer stream of the tubular reactor 5a was 43500kg/h;
the feed amounts of the radical polymerization initiator at the initiator feed ports at the feed port ends of the tubular reactor 5a, the tubular reactor 6b, and the tubular reactor 6c are respectively: 13.19kg/h, 6.58kg/h, 7.68kg/h and 7.38kg/h;
the inlet temperatures of the tubular reactors 6a, 6b and 6c were 205 ℃, 208 ℃ and 228 ℃, respectively;
the peak temperatures in the tube reactor 5a, the tube reactor 6b and the tube reactor 6c were 295 ℃.
As shown in Table 1, the number average molecular weight M of the low density polyethylene of this comparative example n Weight average molecular weight M w Molecular weight distribution index PDI, long chain distribution LCB, yield and ethylene conversion.
TABLE 1
| Numbering device | M n [g/mol] | M w [g/mol] | PDI | Yield [ kg/h ]] | Ethylene conversion [%] |
| Example 1 | 13692 | 82355 | 6.01 | 15298 | 35.17 |
| Example 2 | 15838 | 109537 | 6.91 | 15327 | 35.23 |
| Example 3 | 18708 | 61614 | 3.29 | 4452 | 10.23 |
| Example 4 | 16113 | 129673 | 8.04 | 15291 | 35.15 |
| Example 5 | 15251 | 97854 | 6.42 | 15296 | 35.16 |
| Example 6 | 16966 | 163550 | 9.64 | 15480 | 35.59 |
| Comparative example 1 | 13633 | 80966 | 5.94 | 14968 | 34.41 |
| Comparative example 2 | 15680 | 99586 | 6.35 | 14682 | 33.75 |
| Comparative example 3 | 18678 | 61335 | 3.28 | 4448 | 10.23 |
| Comparative example 4 | 16110 | 109045 | 6.77 | 14948 | 34.36 |
| Comparative example 5 | 16598 | 134610 | 8.11 | 14957 | 34.38 |
As can be seen from the results in Table 1, the apparatus in examples 1 to 6 of the present invention can control the inlet temperature and reactor temperature peak of at least two parallel tubular reactors in a primary high pressure polymerization unit, the feeding position of a telogen, and other parameters according to the requirements of the downstream product performance, thereby controlling the Molecular Weight Distribution (MWD) and the Long Chain Branching (LCB) of the product under the condition of ensuring a certain conversion rate; and, at the same peak temperature, through the comparison of examples 1-6 and comparative examples 1-5, the device can be used for producing products with wider molecular weight distribution, the defect that the tubular method cannot produce kettle-type products is overcome, and on the other hand, the ethylene conversion rate of the device is higher. In addition, the method and the device have the effects of convenient control, easy operation and wide product coverage range.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. An olefin free radical polymerization apparatus, comprising:
a first stage high pressure polymerization unit and a multistage high pressure polymerization unit; wherein,
the first-stage high-pressure polymerization unit is connected in series at the upstream of the multi-stage high-pressure polymerization unit;
the primary high-pressure polymerization unit comprises at least two parallel tubular reactors for carrying out primary high-pressure polymerization on at least two reaction monomer streams containing olefin sources respectively;
the multistage high-pressure polymerization unit comprises one or more tubular reactors which are sequentially connected in series and is used for carrying out multistage high-pressure polymerization on the product from the first-stage high-pressure polymerization unit;
and an initiator feed inlet is arranged on at least one tubular reactor in the first-stage high-pressure polymerization unit and/or the multistage high-pressure polymerization unit.
2. The apparatus of claim 1, wherein,
an initiator feed inlet is formed at the feed inlet end of the reaction monomer flow of at least one tubular reactor in the primary high-pressure polymerization unit; and/or
The primary high-pressure polymerization unit comprises 2-4 parallel tubular reactors; and/or
At least one initiator feed inlet, preferably 1-3 initiator feed inlets, are arranged on at least one tubular reactor in the primary high-pressure polymerization unit along the length direction of the tubular reactor; and/or
At least one initiator feed inlet, preferably 2 to 5, is provided on at least one tubular reactor in the multistage high pressure polymerization unit.
3. The device according to claim 1 or 2, wherein,
the apparatus further comprises at least one compression unit upstream of the primary high pressure polymerization unit for providing each of the olefin-containing source of reacted monomer streams with an inlet pressure into the primary high pressure polymerization unit; and/or
The apparatus further comprises at least one preheater located upstream of the primary high pressure polymerization unit for providing each of the olefin-containing source of reaction monomer streams with an inlet temperature into the primary high pressure polymerization unit; and/or
The preheater is located between the compression unit and the primary high pressure polymerization unit.
4. The apparatus of claim 3, wherein,
the compression unit comprises one or more compressors connected in series in turn, preferably the compression unit comprises 2-4 compressors connected in series in turn; and/or
At least one compression unit is arranged in series upstream of the at least two parallel tubular reactors in the first-stage high-pressure polymerization unit; and/or
At least one compression unit is arranged in series at the upstream of each corresponding tubular reactor in the first-stage high-pressure polymerization unit; and/or
At least one preheater is arranged in series upstream of the at least two parallel tubular reactors in the first stage high pressure polymerization unit; and/or
At least one preheater is disposed in series upstream of each respective tubular reactor in the first stage high pressure polymerization unit.
5. The apparatus of any one of claims 1-4, wherein,
the apparatus further comprises at least one telogen feed port and/or at least one comonomer feed port.
6. The apparatus of claim 5, wherein,
the telogen feed inlet is arranged at any position upstream of the outlet of the multistage high-pressure polymerization unit;
preferably, each telogen feed port is respectively provided at:
An inlet of the compression unit; and/or
An outlet of the compression unit; and/or
Connecting pipelines of any two adjacent compressors in the compression unit; and/or
The reaction monomer of at least one tubular reactor in the primary high-pressure polymerization unit flows to the feed port side; and/or
At least one tubular reactor in a first stage high pressure polymerization unit; and/or
A first-stage high-pressure polymerization unit and a connecting pipeline of the multi-stage high-pressure polymerization unit; and/or
At least one tubular reactor in the multistage high pressure polymerization unit; and/or
The comonomer feed inlet is provided at any position upstream of the outlet of the first stage high pressure polymerization unit, preferably,
each comonomer feed inlet is respectively arranged at:
an inlet of the compression unit; and/or
Connecting pipelines of any two adjacent compressors in the compression unit; and/or
The reaction monomer of at least one tubular reactor in the primary high-pressure polymerization unit flows to the feed port side; and/or
And the connecting pipeline of the preheater and the compression unit.
7. The apparatus of any one of claims 1-6, wherein,
the apparatus further comprises a separation circulation unit located downstream of the multistage high pressure polymerization unit for separating the materials obtained by the multistage high pressure polymerization to obtain a polymerized product and unreacted monomers.
8. A process for the free radical polymerization of olefins, characterized in that it is carried out in a device according to any of claims 1 to 7;
the method comprises the following steps: respectively introducing at least two reaction monomer streams containing olefin sources into at least two parallel tubular reactors in a primary high-pressure polymerization unit included in the device, respectively performing primary high-pressure polymerization, and then flowing the obtained primary high-pressure polymerization product into the tubular reactors in a multistage high-pressure polymerization unit included in the device for multistage high-pressure polymerization;
wherein at least one free radical polymerization initiator is introduced into each of the initiator feed ports included in the apparatus to participate in one-stage high pressure polymerization and/or multistage high pressure polymerization, and the pressure of the reactive monomer stream is greater than 100MPa.
9. The method of claim 8, wherein,
the pressure of the reaction monomer stream is 110-400MPa; and/or
The number of the primary high-pressure polymerization is 2-4; and/or
The temperature of each reaction monomer stream is 100-200 ℃; and/or
The respective temperature of each primary high-pressure polymerization and each multistage high-pressure polymerization is 100-350 ℃; and/or
The ratio of the maximum to minimum feed of each olefin-source containing reactive monomer stream was (20-1): 1, preferably (5-1): 1, a step of; and/or
Each strand of free radical polymerization initiator is injected intermittently or continuously.
10. The method according to claim 8 or 9, wherein,
the method further comprises feeding at least one strand of telogen each from a telogen feed port included in the apparatus to participate in the first-stage high-pressure polymerization and the multi-stage high-pressure polymerization; and/or
The method further comprises feeding at least one stream of comonomer from a comonomer feed included in the apparatus to each participate in the first stage high pressure polymerization and the multistage high pressure polymerization; and/or
The method also comprises the step of carrying out reduced pressure cooling on the material obtained by the multistage high-pressure polymerization, and separating the material by a separation circulation unit included in the device to obtain unreacted monomers and polymer products.
11. The method according to any one of claims 8-10, wherein,
the olefins in the olefin source include R 2 C＝CR 2 One or more of mono-olefins, conjugated dienes, non-conjugated dienes, wherein R is selected from H, alkanes or halogens; and/or
The free radical polymerization initiator comprises one or more of oxygen, air, azo compounds, organic peroxides and hydrocarbons of a C-C initiator; and/or
The telogen comprises one or more of aliphatic hydrocarbons, olefins, ketones, aldehydes, aliphatic alcohols, and hydrogen.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210774665.2A CN117358152A (en) | 2022-07-01 | 2022-07-01 | Olefin radical polymerization apparatus and method for radical polymerization of olefin |
| PCT/CN2023/115693 WO2024002393A1 (en) | 2022-07-01 | 2023-08-30 | Olefin free radical polymerization method and olefin free radical polymerization apparatus |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210774665.2A CN117358152A (en) | 2022-07-01 | 2022-07-01 | Olefin radical polymerization apparatus and method for radical polymerization of olefin |
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