CN107879885A - A kind of method and apparatus for mixing carbon four and producing raw material for alkylation - Google Patents
A kind of method and apparatus for mixing carbon four and producing raw material for alkylation Download PDFInfo
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- CN107879885A CN107879885A CN201610875568.7A CN201610875568A CN107879885A CN 107879885 A CN107879885 A CN 107879885A CN 201610875568 A CN201610875568 A CN 201610875568A CN 107879885 A CN107879885 A CN 107879885A
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- liquid
- gas
- maleic anhydride
- mixed
- solid
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- 230000029936 alkylation Effects 0.000 title claims abstract description 39
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 39
- 239000002994 raw material Substances 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002156 mixing Methods 0.000 title claims abstract description 22
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000047 product Substances 0.000 claims abstract description 57
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 238000000926 separation method Methods 0.000 claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000008247 solid mixture Substances 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 22
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001273 butane Substances 0.000 claims abstract description 20
- 239000012265 solid product Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 49
- 150000001336 alkenes Chemical group 0.000 claims description 39
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 30
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 24
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 238000005191 phase separation Methods 0.000 claims description 19
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 16
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 14
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 239000001282 iso-butane Substances 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 7
- -1 azo compound Chemical class 0.000 claims description 7
- 238000006053 organic reaction Methods 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 13
- 235000013844 butane Nutrition 0.000 description 19
- 239000000203 mixture Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 208000012839 conversion disease Diseases 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 229940117955 isoamyl acetate Drugs 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XINCECQTMHSORG-UHFFFAOYSA-N Isoamyl isovalerate Chemical compound CC(C)CCOC(=O)CC(C)C XINCECQTMHSORG-UHFFFAOYSA-N 0.000 description 2
- CRZQGDNQQAALAY-UHFFFAOYSA-N Methyl benzeneacetate Chemical compound COC(=O)CC1=CC=CC=C1 CRZQGDNQQAALAY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- RGFNRWTWDWVHDD-UHFFFAOYSA-N isobutyl butyrate Chemical compound CCCC(=O)OCC(C)C RGFNRWTWDWVHDD-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- JLIDRDJNLAWIKT-UHFFFAOYSA-N 1,2-dimethyl-3h-benzo[e]indole Chemical compound C1=CC=CC2=C(C(=C(C)N3)C)C3=CC=C21 JLIDRDJNLAWIKT-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- MLLAPOCBLWUFAP-UHFFFAOYSA-N 3-Methylbutyl benzoate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1 MLLAPOCBLWUFAP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DIQMPQMYFZXDAX-UHFFFAOYSA-N Pentyl formate Chemical compound CCCCCOC=O DIQMPQMYFZXDAX-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- MLHOXUWWKVQEJB-UHFFFAOYSA-N Propyleneglycol diacetate Chemical compound CC(=O)OC(C)COC(C)=O MLHOXUWWKVQEJB-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- DULCUDSUACXJJC-UHFFFAOYSA-N benzeneacetic acid ethyl ester Natural products CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 description 1
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- JSLCOZYBKYHZNL-UHFFFAOYSA-N isobutyric acid butyl ester Natural products CCCCOC(=O)C(C)C JSLCOZYBKYHZNL-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/177—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by selective oligomerisation or polymerisation of at least one compound of the mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to mixing carbon four to produce raw material for alkylation field, discloses a kind of method and apparatus for mixing carbon four and producing raw material for alkylation, including：(1) in the presence of initiator and organic solvent, mixing carbon four is in contact with maleic anhydride, C in the mixing carbon four4Terminal olefine carries out copolyreaction with maleic anhydride；(2) product for obtaining step (1) carries out gas-liquid separation, obtains gas-phase product and liquid-solid mixture；(3) gas-phase product is subjected to the isolated raw material for alkylation containing butane and 2 butylene of gas phase；(4) liquid-solid mixture is separated, obtained solid product is the polymer containing maleic anhydride functional groups；Wherein, the C of the mixing carbon four containing 1~90 weight %4Terminal olefine.Mixing carbon four can be effectively utilized and produce raw material for alkylation, co-production contains the copolymer of maleic anhydride functional groups, can be as the raw material of functional material.
Description
Technical Field
The invention relates to the field of producing alkylation raw materials by mixing C4, in particular to a method and a device for producing alkylation raw materials by mixing C4. In particular, an alkylation feed containing butane and 2-butene is produced.
Background
Alkylation is carried out by combining low molecular weight olefin (mainly comprising propylene or butylene) with isobutane in the presence of a catalyst (sulfonic acid or hydrofluoric acid) to form an alkylate (mainly comprising higher octane and side-chain alkane).
Common mixed carbon four resources are available from ethylene plants, and refinery units, such as reforming, catalytic cracking, coking, thermal cracking, hydrocracking, etc. The mixed carbon four fraction obtained from the refinery is mainly butanes (n-butane and isobutane). The alkane content in the mixed C4 obtained by the ethylene device is very low, and the alkane content is increased after the mixed C4 is extracted or etherified by butadiene.
The utilization of carbon four resources mainly includes the following ways. Isobutene is converted into methyl tert-butyl ether (MTBE) through an etherification process of the reaction of methanol and isobutene, and the MTBE is added into gasoline as an additive to adjust the octane number of the gasoline. The four-carbon hydrocarbon can also be alkylated and aromatized to prepare aromatic substances or high-octane gasoline. The C-tetrahydrocarbon can also be cracked to prepare chemical basic raw materials such as ethylene, propylene and the like. The pure carbon four resource can be used as a chemical basic raw material to produce related industrial products. Butadiene can be used for synthesizing butadiene styrene rubber, butadiene rubber, nitrile rubber and other rubber products. The n-butene can be used for oligomerization production of C eight and C dodecene, poly-1-butene, methyl ethyl ketone, n-butyl acetate, maleic anhydride and other chemical products. Isobutylene can be used to produce MTBE, synthetic resins, and synthetic rubbers. The n-butane can be used for producing methyl ethyl ketone, acetic acid, maleic anhydride and the like, and can also be directly used as a foaming agent and the like. In various processes for producing chemical products, the purity of certain carbon tetraolefin is required to be higher, so that the separation of related components in mixed carbon four resources is very important.
Industrially, the separation of the hydrocarbon substances can be carried out by adopting a rectification mode according to the difference of the boiling points of the carbon-four hydrocarbon substances. However, the boiling point of some hydrocarbons is low, and the volatility of the carbon four components is very close, which makes the distillation separation of the hydrocarbons difficult and the operation cost is high. Although it is possible to extract and separate hydrocarbons by selecting an appropriate solvent according to the solubility of the hydrocarbon material, it is difficult to select a solvent having a high selectivity, a high solubility, a stable property, a low toxicity, a low corrosion, a low boiling point, and the like, for a mixture of hydrocarbons having a complicated content.
Therefore, to improve the effective utilization of the mixed carbon four resource, it is important to select a resource utilization method which is simple and easy to operate, convenient to operate and low in cost.
CN101781387A discloses a method for copolymerization of maleic anhydride/conjugated diene.
CN102212166B discloses a copolymerization reaction method of dicyclopentadiene and maleic anhydride, which has the advantages of simple reaction system, easy product separation, clean surface of the prepared polymer microsphere, uniform particle size, controllable morphology and good dispersibility under the condition of not increasing a stabilizer and a co-stabilizer.
CN102690393A discloses a copolymer containing functional groups, which is prepared from C5 mixed-maleic anhydride. The C5 mixture and maleic anhydride are copolymerized alternately to prepare the highly crosslinked copolymer containing functional groups in one step, thereby fully utilizing the olefin and the diene in the C5 mixture, and not concerning the condition of the low-carbon olefin below C5.
Disclosure of Invention
The invention aims to solve the problem of how to produce mixed C4 into alkylation raw materials, and provides a method and a device for producing the alkylation raw materials by using the mixed C4. In particular, the production of an alkylation feedstock containing butane and 2-butene from mixed C4 is achieved, and by copolymerizing mixed C4 with maleic anhydride in this process, the separation of terminal olefins in mixed C4 can be achieved and polymerized to produce polymers containing maleic anhydride functionality, providing a feedstock useful as a production functional material.
To achieve the above object, the present invention provides a method for producing an alkylation feedstock by mixing carbon four, the method comprising: (1) contacting mixed C4 with maleic anhydride in the presence of an initiator and an organic solvent, wherein C is4Partially or totally copolymerizing the terminal olefin with maleic anhydride; (2) carrying out gas-liquid separation on the product obtained in the step (1) to obtain a gas-phase product and a liquid-solid mixture; c in the gas-phase product based on the total weight of the gas-phase product4The content of terminal olefin is 1 wt% or less; (3) carrying out the gas-phase product obtained in the step (2)Gas phase separation to obtain an alkylation raw material containing butane and 2-butene; (4) separating the liquid-solid mixture obtained in the step (2) to obtain a solid product and a liquid, wherein the solid product is a polymer containing a maleic anhydride functional group, and the liquid is returned to the organic solvent in the step (1); wherein the mixed C4 contains 1-90 wt% of C4A terminal olefin.
The invention also provides a device for producing alkylation raw materials by mixing C4, comprising: polymerization equipment, a gas-liquid separator, gas-phase separation equipment and a liquid-solid separator; wherein,
the polymerization equipment is used for mixing carbon four and maleic anhydride to carry out copolymerization reaction; the gas-liquid separator is communicated with the polymerization equipment and is used for performing gas-liquid separation on a product discharged by the polymerization equipment to obtain a gas-phase product and a liquid-solid mixture;
the gas phase separation equipment is communicated with the gas-liquid separator and is used for separating the gas phase product to obtain an alkylation raw material containing butane and 2-butene;
the liquid-solid separator is communicated with the gas-liquid separator and is used for separating the liquid-solid mixture to obtain a polymer containing maleic anhydride functional groups; the liquid-solid separator is in communication with the polymerization apparatus to return separated liquid.
According to the technical scheme, the mixed C4 is subjected to copolymerization reaction, gas-liquid separation, gas-phase separation and liquid-solid separation in sequence, so that the alkylated raw material containing butane and 2-butene can be obtained by producing the mixed C4, and the yield can reach 0.1-99%; meanwhile, the copolymerization reaction can realize the copolymerization reaction of the terminal olefin in the mixed C4 and the maleic anhydride, the reaction conversion rate of the copolymerization reaction reaches 85-90%, and the obtained copolymer can be used as a raw material for producing functional materials and is utilized.
In the present invention, on the one hand, the production of an alkylation raw material from mixed C4 can be realized, and on the other hand, a copolymer containing a maleic anhydride structure can be obtained and can be further used as a raw material for producing a functional material.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic process flow diagram for producing an alkylation feedstock from mixed C4's provided by the present invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for producing alkylation raw materials by mixing C4, which comprises the following steps: (1) contacting mixed C4 with maleic anhydride in the presence of an initiator and an organic solvent, wherein C is4Partially or totally copolymerizing the terminal olefin with maleic anhydride; (2) carrying out gas-liquid separation on the product obtained in the step (1) to obtain a gas-phase product and a liquid-solid mixture; so thatBased on the total weight of the gas-phase product, C in the gas-phase product4The content of terminal olefin is 1 wt% or less; (3) carrying out gas phase separation on the gas phase product obtained in the step (2) to obtain an alkylation raw material containing butane and 2-butene; (4) separating the liquid-solid mixture obtained in the step (2) to obtain a solid product and a liquid, wherein the solid product is a polymer containing a maleic anhydride functional group, and the liquid is returned to the organic solvent in the step (1); wherein the mixed C4 contains 1-90 wt% of C4A terminal olefin.
According to the invention, the mixed carbon four can come from various petroleum processing and refining processes, and can be liquefied fuel produced in the petroleum refining process, pyrolysis gas produced by naphtha cracking, gas produced by methanol-to-olefin and the like. Preferably, the mixed carbon four may further contain at least one of isobutane, n-butane and 2-butene. The composition of the mixed C.sub.D can be analyzed by gas chromatography using Agilent's 7890A Gas Chromatograph (GC).
Because the mixed carbon four comes from a plurality of different petroleum processing and refining processes, the actual composition and content difference is large, preferably, the mixed carbon four contains 0.1-50 wt% of isobutane, 1-50 wt% of normal butane and 1-50 wt% of 2-butene based on the total amount of the mixed carbon four.
In a preferred embodiment of the present invention, the content of the mixed C4 may be 10-15 wt% of 1-butene, 8-15 wt% of 2-butene, 45-55 wt% of 1, 3-butadiene, 18-25 wt% of isobutene, 1-5 wt% of n-butane, and 0.5-2 wt% of isobutane.
In another preferred embodiment of the present invention, the content of the mixed C4 may be 10-15 wt% of 1-butene, 20-30 wt% of 2-butene, 0.1-0.3 wt% of 1, 3-butadiene, 15-25 wt% of isobutene, 8-15 wt% of n-butane, and 25-35 wt% of isobutane.
The process flow diagram of the method provided by the invention is shown in figure 1.
Copolymerization reaction
According to the invention, step (1) is carried out for mixing C of C44The terminal olefin component and maleic anhydride are subjected to copolymerization reaction, so that on one hand, a copolymer can be obtained, and further the copolymer can be used as a raw material of a functional material; on the other hand, C in the mixed C4 can be consumed4The terminal olefin component, leaving unreacted alkane and internal olefin components, can be used as alkylation feedstock. The copolymerization reaction can also serve to separate C from the mixed C4Terminal olefins and other components. Wherein in particular the terminal olefins in the mixed C.sub.D may include 1-butene, isobutene and 1, 3-butadiene. The alkylation feedstock may contain butanes and 2-butenes (trans-2-butene and cis-2-butene). Preferably, the weight ratio of the mixed C4 to the maleic anhydride is 0.3: 1 or more, preferably the weight ratio is (0.3-5): 1.
preferably, C in the mixed C44The weight ratio of terminal olefin to maleic anhydride is 1: 1 or less, preferably in a weight ratio of 1: (1-5).
In order to achieve more efficient copolymerization according to the present invention, it is preferable that the initiator is used in an amount of 0.01 to 30% by weight based on maleic anhydride.
According to the present invention, it is preferable that the initiator copolymerizes the mixed C.sub.four medium-terminal olefin more efficiently with maleic anhydride, it is preferable that the initiator is a thermal decomposition type initiator, it is preferable that the initiator is an azo compound or an organic peroxide, it is more preferable that the initiator is at least one selected from the group consisting of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, and azobisisoheptonitrile. Particularly preferably, the initiator is azobisisobutyronitrile and/or dibenzoyl peroxide.
According to the present invention, the organic solvent may be added in an amount sufficient to dissolve the initiator and maleic anhydride, preferably, maleic anhydride is used in an amount of 30 wt% or less of the organic solvent, preferably, maleic anhydride is used in an amount of 5 wt% to 25 wt%, more preferably, 10 wt% to 20 wt% of the organic solvent.
According to the invention, the organic solvent may be used to dissolve the initiator and maleic anhydride, preferably the organic solvent is selected from alkanes, aromatic hydrocarbons and compounds of formula R1-COO-R2At least one of organic acid alkyl esters of (1), wherein R1And R2Is C1～C5Alkyl group of (1).
In the present invention, the organic acid alkyl ester is selected from at least one of but not limited to methyl formate, ethyl formate, methyl propyl ester, methyl butyl ester, methyl isobutyl ester, amyl formate, methyl acetate, ethyl ester, propylene acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate and ethyl phenylacetate. More preferably, the organic acid alkyl ester is isoamyl acetate.
In the present invention, the alkane is selected from, but not limited to, at least one of propane, n-butane, isobutane, pentane, isopentane, n-hexane, isohexane, cyclohexane, n-heptane, n-octane, and isooctane.
In the present invention, the aromatic hydrocarbon is selected from at least one of, but not limited to, benzene, toluene, xylene, chlorobenzene, and bromobenzene.
According to the invention, the copolymerization enables the selective mixing of C in C44The terminal olefin is copolymerized with maleic anhydride to obtain a raw material which can be further used as a functional material. Separation of the mixture in order to effect the copolymerizationAnd (3) finally obtaining an alkylation raw material under the action of the components in the C4, wherein the copolymerization reaction temperature is 50-90 ℃, the copolymerization reaction pressure is 0-0.25 MPa, and the copolymerization reaction time is 0.5-12 h under the optimal condition. The copolymerization pressure is preferably 0.1 to 0.2MPa, and more preferably 0.12 to 0.15 MPa. The preferable copolymerization reaction time is 4-12 h.
According to the invention, it is particularly preferred that the copolymerization is a free radical polymerization. The 1, 3-butadiene in the mixed C4 can be polymerized mainly in a 1,2 mode, and the side chain of the polymer chain segment can contain double bonds (double bonds at positions 3 and 4) and can further react to form a crosslinking structure.
In a preferred embodiment, the copolymerization is carried out in a process comprising: and mixing the organic solvent, maleic anhydride and the initiator to form an organic reaction solution, and then adding the mixed C4 into the organic reaction solution to carry out copolymerization reaction.
In the present invention, the polymerization reactor for carrying out the copolymerization reaction may be a pressure-resistant reaction vessel with a stirrer and a jacket or a tubular reactor. The medium in the jacket is used for removing reaction heat and controlling the reaction temperature.
Separation of
In the present invention, after the copolymerization reaction is completed, the copolymerization reaction product needs to be separated to obtain the alkylation raw material and the polymer product. Two-stage separation can be adopted: the first stage is gas-liquid separation to obtain gas phase product and liquid-solid mixture; the second stage comprises two processes, wherein one process is to carry out gas-phase separation on the gas-phase product to obtain an alkylation raw material; another process is that the liquid-solid mixture is separated into liquid containing organic solvent and polymer containing maleic anhydride functional group by liquid-solid separation.
First, gas-liquid separation
According to the present invention, the step (2) is for gas-liquid separating the product of the copolymerization reaction of the step (1).
In the inventionThe gas-liquid separation method may be flash separation. Preferably, the flash separation conditions are: reducing the pressure of a product subjected to the copolymerization reaction to be less than 0MPa at the temperature of more than 20 ℃, preferably 20-40 ℃, wherein C in the product4The following hydrocarbon compounds were discharged to obtain the gas phase product.
In the present invention, C is contained in the gas-phase product4The terminal olefin content can be determined by gas chromatography using an agilent 7890A Gas Chromatograph (GC). Wherein, C4The content of terminal olefin is 1 wt% or less.
In the invention, the flash separator can be a simple container with a jacket for controlling temperature, various internal components which are commonly known in the field and used for fully increasing the surface area of materials can be provided, and hot special material flow can be introduced from the bottom of the device to fully increase the heat exchange quantity.
Second, gas phase separation and liquid-solid separation
1. Gas phase separation
According to the invention, step (3) is used to subject the gaseous product to a gas-phase separation from which an alkylation feed containing butane and 2-butene is separated.
In the present invention, the gas phase separation can be further separated and purified by feeding the gas phase product to a condenser apparatus for cooling, obtaining a mixture containing butane and 2-butene. The cooling temperature may be conditions conventional in the art, for example, the gas phase product is cooled to around 40 ℃. The detailed description may be well known to those skilled in the art and will not be described herein.
2. Liquid-solid separation
And carrying out liquid-solid separation on the liquid-solid mixture to obtain a polymer product.
The liquid-solid separation may be performed by centrifugation. The centrifugal separation conditions are as follows: under the condition that the centrifugal rotating speed is more than 4000rpm, the centrifugal separation time is more than 5min, for example, the centrifugal rotating speed is 4000-16000 rpm, and the centrifugal separation time is 5-20 min.
In the present invention, the centrifugal separator may be of any type, horizontal or vertical.
According to the invention, through liquid-solid separation, the liquid-solid mixed liquid is separated into a supernatant and a lower solid product; the clear solution is an organic solvent and can be removed and returned for the copolymerization reaction; the solid product is a polymer containing maleic anhydride functional groups. Preferably, the polymer is C in the mixed C44Copolymers of terminal olefins with maleic anhydride; preferably, the content of the maleic anhydride structural unit in the polymer is 45-52 mol%. Preferably, the maleic anhydride structural unit contained in the polymer can be in a main chain, a side chain or a terminal group. The content of the maleic anhydride structural unit can be determined by1H and13c nuclear magnetic measurement.
Preferably, the polymer also contains a structural unit formed by at least one of 1-butene, 1, 3-butadiene and isobutene. The content of the above-mentioned structural units in the polymer may be determined by1H and13c nuclear magnetic measurement. For example, the content of the structural unit in the polymer may be 48 to 55 mol%.
Preferably, the polymer is a powder solid substance after being dried, and the average diameter of particles can be 0.2-250 μm. The average diameter of the polymer particles can be measured by scanning electron microscopy.
The reaction conversion rate of the copolymerization reaction can be determined by weighing the weight of the polymer obtained after the reaction.
The invention selectively converts the terminal olefin in the mixed C4 and maleic anhydride into a polymer containing maleic anhydride functional groups through free radical copolymerization, and the polymer can be used as a raw material of a functional material and further can be prepared into other high molecular materials.
In the present invention, the pressure refers to gauge pressure.
Fig. 1 is a schematic diagram of a preferred embodiment of the present invention, and the working process can be briefly described as follows:
continuously introducing the mixed C4 into a polymerization reactor added with maleic anhydride, an initiator and an organic solvent, carrying out copolymerization reaction at a certain temperature, pressure and retention time, introducing the obtained product into a gas-liquid separator for gas-liquid separation, and introducing the obtained gas-phase product into gas-phase separation equipment for gas-phase separation to obtain an alkylation raw material containing butane and 2-butene; and (3) sending the liquid-solid mixture obtained by gas-liquid separation into a liquid-solid separator for liquid-solid separation to obtain a solid product, namely a polymer, and obtaining liquid, namely an organic solvent, for recycling the copolymerization reaction.
The invention also provides a device for producing alkylation raw materials by mixing C4, comprising: polymerization equipment, a gas-liquid separator, gas-phase separation equipment and a liquid-solid separator; wherein,
the polymerization equipment is used for mixing carbon four and maleic anhydride to carry out copolymerization reaction; the gas-liquid separator is communicated with the polymerization equipment and is used for performing gas-liquid separation on a product discharged by the polymerization equipment to obtain a gas-phase product and a liquid-solid mixture;
the gas phase separation equipment is communicated with the gas-liquid separator and is used for separating the gas phase product to obtain an alkylation raw material containing butane and 2-butene;
the liquid-solid separator is communicated with the gas-liquid separator and is used for separating the liquid-solid mixture to obtain a polymer containing maleic anhydride functional groups; the liquid-solid separator is in communication with the polymerization apparatus to return separated liquid.
In the device provided by the invention, the polymerization equipment can be a pressure-resistant reaction kettle or a tubular reactor with a stirring sleeve and is used for carrying out copolymerization reaction on mixed C4 and maleic anhydride in the presence of an initiator and an organic solvent to form C4Copolymers of terminal olefins with maleic anhydride,can be used as raw material of functional material.
In the device provided by the invention, the gas-liquid separator can be a flash separator. For separating the product of the polymerization reaction to obtain a gas phase product and a liquid-solid mixture.
In the apparatus provided by the present invention, the gas phase separation device may be a condenser apparatus.
The device provided by the invention is characterized in that the liquid-solid separator is a centrifugal separator which can be in any horizontal or vertical form and is used for separating the liquid-solid mixture to obtain a solid copolymer product in the liquid-solid mixture.
The present invention will be described in detail below by way of examples.
In the following examples, the composition of the mixed carbon four raw material is shown in table 1. Mixed carbon four component analysis was performed by gas chromatography using agilent 7890A Gas Chromatograph (GC);
the terminal olefin content in the gas product was determined by gas chromatography using agilent 7890A Gas Chromatograph (GC);
the content of maleic anhydride structural units in the polymer obtained is determined by1H and13c, nuclear magnetism measurement;
the average diameter of the obtained polymer particles was measured by scanning electron microscopy;
the reaction conversion of the copolymerization reaction was determined by weighing the polymer after the reaction by calculating from the following formula:
reaction conversion (%) of copolymerization reaction [ (% C in C4)4Weight-polymerization of terminal olefins C in gas phase product4Weight of terminal olefin)/C in Mixed carbon four4Weight of terminal olefin]×100％。
The total yield of butane and 2-butene was calculated by the following formula:
total yield (%) of butane and 2-butene ═ weight of butane and 2-butene in the final product ÷ total weight of mixed carbon four in the starting material) × 100%.
Example 1
This example illustrates the process of the present invention for producing an alkylation feedstock from mixed C4's.
Copolymerization:
according to the mixed carbon four: maleic anhydride: initiator: the feeding weight ratio of the organic solvent is 1: 1: 0.05: 5, obtaining the mixed C-IV-1 (C)485.6 percent of terminal olefin content), maleic anhydride, azobisisobutyronitrile and isoamyl acetate (wherein, C4Terminal olefin: the weight ratio of maleic anhydride is 1: 1.17), carrying out copolymerization reaction for 6h at 70 ℃ and 0.2 MPa;
gas-liquid separation:
introducing the copolymerization reaction product into a flash separator for gas-liquid separation at 25 ℃ and 0.1MPa to obtain a gas-phase product and a liquid-solid mixture;
subjecting the resulting gas phase product to gas chromatography, wherein C4The content of terminal olefins is less than 1% by weight.
Gas phase separation:
and (3) sending the gas-phase product into a condenser device to be cooled to 40 ℃, and separating to obtain a mixture containing butane and 2-butene, namely the alkylation raw material. The total yield of butane and 2-butene was 13.4%. The composition of the alkylation feed obtained is shown in table 1.
Liquid-solid separation:
the resulting liquid-solid mixture was placed in a centrifugal separator (model TG18G, Ware scientific instruments, Beijing) and centrifuged at 4000rpm for 20min to obtain solid copolymer particles.
The maleic anhydride structure content of the solid copolymer particles was determined to be 45 mol%, and the average diameter of the particles was 0.2. mu.m.
The reaction conversion in the copolymerization reaction was 100%.
Example 2
Copolymerization:
according to the mixed carbon four: maleic anhydride: initiator: the feeding weight ratio of the organic solvent is 1: 0.5: 0.05: 5, obtaining the mixed C-2 (C)431.5 percent of terminal olefin content), maleic anhydride, azobisisobutyronitrile and methyl acetate (wherein, C4Terminal olefin: the weight ratio of maleic anhydride is 1: 1.59) and carrying out copolymerization reaction for 8h at 50 ℃ and 0.15 MPa;
gas-liquid separation:
introducing the copolymerization reaction product into a flash separator for gas-liquid separation at 30 ℃ and 0.1MPa to obtain a gas-phase product and a liquid-solid mixture;
subjecting the resulting gas phase product to gas chromatography, wherein C4The content of terminal olefins is less than 1% by weight.
And (3) sending the gas-phase product into a condenser device to be cooled to 40 ℃, and separating to obtain a mixture containing butane and 2-butene, namely the alkylation raw material. The total yield of butane and 2-butene was 68.5%. The composition of the alkylation feed obtained is shown in table 1.
Liquid-solid separation:
the resulting liquid-solid mixture was placed in a centrifugal separator, and subjected to centrifugal separation at 4000rpm for 20min for liquid-solid separation to obtain solid copolymer particles.
The maleic anhydride structure content of the solid copolymer particles was determined to be 52 mol%, and the average particle diameter was 200. mu.m.
The reaction conversion in the copolymerization reaction was 100%.
TABLE 1
From the above results, it can be seen that the method of the present invention can give an alkylated material and a copolymer containing a maleic anhydride structure, which is useful as a raw material for a functional material. Thereby solving the problems of low utilization rate and economic added value of the existing mixed carbon four.
Claims (10)
1. A method for producing an alkylation feedstock from mixed carbon four, the method comprising:
(1) contacting mixed C4 with maleic anhydride in the presence of an initiator and an organic solvent, wherein C is4Partially or totally copolymerizing the terminal olefin with maleic anhydride;
(2) carrying out gas-liquid separation on the product obtained in the step (1) to obtain a gas-phase product and a liquid-solid mixture; c in the gas-phase product based on the total weight of the gas-phase product4The content of terminal olefin is 1 wt% or less;
(3) carrying out gas phase separation on the gas phase product obtained in the step (2) to obtain an alkylation raw material containing butane and 2-butene;
(4) carrying out liquid-solid separation on the liquid-solid mixture obtained in the step (2) to obtain a solid product and liquid, wherein the solid product is a polymer containing a maleic anhydride functional group, and the liquid is returned to the organic solvent in the step (1);
wherein the mixed C4 contains 1-90 wt% of C4A terminal olefin.
2. The method according to claim 1, wherein the mixed C4 comprises 0.1-50 wt% of isobutane, 1-50 wt% of n-butane, and 1-50 wt% of 2-butene.
3. The method of claim 1 or 2, wherein the weight ratio of mixed C4 and maleic anhydride is 0.3: 1 or more, preferably the weight ratio is (0.3-5): 1.
4. the method of claim 3, wherein C4Terminal olefins include 1-butene, isobutylene and 1, 3-butadiene; c in the mixed C44The weight ratio of terminal olefin to maleic anhydride is 1: 1 or less, preferably in a weight ratio of 1: (1-5).
5. The process according to any one of claims 1 to 4, wherein in the step (1), the copolymerization reaction temperature is 50 to 90 ℃, the copolymerization reaction pressure is 0 to 0.25MPa, and the copolymerization reaction time is 0.5 to 12 hours.
6. The method of claim 1, wherein the initiator is used in an amount of 0.01 to 30 wt% of maleic anhydride; preferably, the initiator is an azo compound or an organic peroxide, and preferably the initiator is selected from at least one of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, and azobisisoheptonitrile.
7. The method according to claim 1, wherein maleic anhydride is used in an amount of 30% by weight or less of the organic solvent; preferably, the maleic anhydride is used in an amount of 5 to 25 wt%, more preferably 10 to 20 wt% of the organic solvent; preferably, the organic solvent is selected from alkanes, aromatics and compounds of formula R1-COO-R2At least one of organic acid alkyl esters of (1), wherein R1And R2Is C1～C5Alkyl group of (1).
8. The process of any one of claims 1-7, wherein the copolymerization is a free radical polymerization; preferably, the copolymerization reaction is carried out by a method comprising: and mixing the organic solvent, maleic anhydride and the initiator to form an organic reaction solution, and then adding the mixed C4 into the organic reaction solution to carry out copolymerization reaction.
9. The method of any one of claims 1-8, wherein the polymer is C of the mixed C44Copolymers of terminal olefins with maleic anhydride; the content of the maleic anhydride structural unit in the polymer is 45-52 mol%.
10. An apparatus for mixing C4 to produce an alkylation feedstock, comprising: polymerization equipment, a gas-liquid separator, gas-phase separation equipment and a liquid-solid separator; wherein,
the polymerization equipment is used for mixing carbon four and maleic anhydride to carry out copolymerization reaction;
the gas-liquid separator is communicated with the polymerization equipment and is used for performing gas-liquid separation on a product discharged by the polymerization equipment to obtain a gas-phase product and a liquid-solid mixture;
the gas phase separation equipment is communicated with the gas-liquid separator and is used for separating the gas phase product to obtain an alkylation raw material containing butane and 2-butene;
the liquid-solid separator is communicated with the gas-liquid separator and is used for separating the liquid-solid mixture to obtain a polymer containing maleic anhydride functional groups; the liquid-solid separator is in communication with the polymerization apparatus to return separated liquid.
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| CN107879882A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of method and apparatus for mixing carbon four and producing normal butane, iso-butane and 2 butylene |
| CN110499187A (en) * | 2019-08-07 | 2019-11-26 | 北京化工大学 | The reduction method of olefin(e) centent in raw gasoline |
| CN111269092A (en) * | 2020-02-19 | 2020-06-12 | 江苏迈达新材料股份有限公司 | Method for synthesizing antioxidant BHT (butylated hydroxytoluene) by replacing raffinose with tetrakis |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949388A (en) * | 2016-05-23 | 2016-09-21 | 北京化工大学 | Functional copolymer directly prepared from higher olefin mixture and preparation method |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949388A (en) * | 2016-05-23 | 2016-09-21 | 北京化工大学 | Functional copolymer directly prepared from higher olefin mixture and preparation method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107879882A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of method and apparatus for mixing carbon four and producing normal butane, iso-butane and 2 butylene |
| CN107879882B (en) * | 2016-09-30 | 2020-09-15 | 中国石油化工股份有限公司 | Method and device for producing normal butane, isobutane and 2-butene by mixing C4 |
| CN110499187A (en) * | 2019-08-07 | 2019-11-26 | 北京化工大学 | The reduction method of olefin(e) centent in raw gasoline |
| CN111269092A (en) * | 2020-02-19 | 2020-06-12 | 江苏迈达新材料股份有限公司 | Method for synthesizing antioxidant BHT (butylated hydroxytoluene) by replacing raffinose with tetrakis |
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| Publication number | Publication date |
|---|---|
| CN107879885B (en) | 2019-11-12 |
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