CN100335473C - Method for preparing gamma-butyrolactone and cyclohexanone by couple process - Google Patents
Method for preparing gamma-butyrolactone and cyclohexanone by couple process Download PDFInfo
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- CN100335473C CN100335473C CNB2005100481905A CN200510048190A CN100335473C CN 100335473 C CN100335473 C CN 100335473C CN B2005100481905 A CNB2005100481905 A CN B2005100481905A CN 200510048190 A CN200510048190 A CN 200510048190A CN 100335473 C CN100335473 C CN 100335473C
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- China
- Prior art keywords
- pimelinketone
- butyrolactone
- preparation
- gamma
- cis
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 title claims abstract description 96
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 45
- 230000008569 process Effects 0.000 title abstract description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 55
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000001257 hydrogen Substances 0.000 claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 39
- 239000007789 gas Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 20
- 238000010168 coupling process Methods 0.000 claims abstract description 16
- 230000008878 coupling Effects 0.000 claims abstract description 15
- 238000005859 coupling reaction Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000012159 carrier gas Substances 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 229960001866 silicon dioxide Drugs 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims 8
- 229960004643 cupric oxide Drugs 0.000 claims 4
- MUCRYNWJQNHDJH-OADIDDRXSA-N Ursonic acid Chemical compound C1CC(=O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CC[C@@H](C)[C@H](C)[C@H]5C4=CC[C@@H]3[C@]21C MUCRYNWJQNHDJH-OADIDDRXSA-N 0.000 claims 2
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims 1
- 239000000391 magnesium silicate Substances 0.000 claims 1
- 235000019792 magnesium silicate Nutrition 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 description 30
- 239000007788 liquid Substances 0.000 description 18
- 239000002994 raw material Substances 0.000 description 18
- 239000012071 phase Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 230000003213 activating effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- -1 pyrrolidine ketone Chemical class 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- 238000010977 unit operation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- OMQHDIHZSDEIFH-UHFFFAOYSA-N 3-Acetyldihydro-2(3H)-furanone Chemical compound CC(=O)C1CCOC1=O OMQHDIHZSDEIFH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing gamma-butyrolactone and cyclohexanone in a coupling mode. In the method, the mixture of cyclohexanol and maleic anhydride is treated with integral reaction by using hydrogenation catalysts at an optimal temperature under the conditions of gas phases and attach hydrogenation or no-attach hydrogenation. Compared with the prior art, in the integral process of hydrogenation and dehydrogenation, energy required by the reaction is little without hydrogenation or hydrogen recovery, and the present invention has the advantages of low production cost, high selectivity, yield, simple preparing process and easy operation.
Description
Affiliated field
The invention belongs to a kind of method for preparing gamma-butyrolactone and pimelinketone, relating in particular to a kind of is the method for feedstock production gamma-butyrolactone and pimelinketone with cis-butenedioic anhydride and hexalin.
Background technology
Gamma-butyrolactone is a kind of important organic chemical industry's product; widespread use petrochemical complex, medicine, dyestuff, agricultural chemicals and fine chemistry industry aspect, in recent years especially in synthesis of pyrrolidine ketone, N-Methyl pyrrolidone, vinyl pyrrolidone, α-staple products such as ethanoyl butyrolactone application quantity bigger.Gamma-butyrolactone or high boiling solvent in addition, solvency power is strong, and electroconductibility and good stability use and Administrative Security makes things convenient for.
Mainly contain two kinds of raw material routes at present in the world and produce gamma-butyrolactones, promptly 1,4-butanediol dehydrogenation method and maleic anhydride hydrogenation method.Wherein the maleic anhydride hydrogenation method is because raw material cis-butenedioic anhydride source is sufficient, low price and being widely adopted.
Maleic anhydride hydrogenation legal system gamma-butyrolactone equation is as follows:
The maleic anhydride hydrogenation process is divided into two kinds of raw material routes of liquid and gas hydrogenation.In the cis-butenedioic anhydride liquid-phase hydrogenatin process, be solvent, mix with recycle hydrogen through preheating, at 6-12Mpa, under 160-280 ℃, by the reactor hydrogenation of catalyzer is housed with the gamma-butyrolactone; This liquid phase cracking process is favourable to strong exothermal reaction, but needs solvent, carry out in the mesohigh condition, and the process complexity, investment is high.
Cis-butenedioic anhydride gas phase hydrogenation process is fairly simple, and the cis-butenedioic anhydride of gasification and hydrogen mix, under normal pressure, 200-300 ℃, by the fixed bed hydrogenation catalyst hydrogenation.This gas phase process operational condition is gentle, less investment.
Chinese patent " cis-anhydride normal pressure gas phase synthetic gamma butyrolactone " (CN1058400A) disclosed catalyzer by Cu, ZnO, Al
2O
3Reach at least a the mixing in Ni, Ru, four kinds of elements of Ce, Zr.Catalyzer consists of Cu 25% (wt%), ZnO 30%, Al
2O
340%, Ni 4%, Ce+Zr1%, catalyst grain size 20-40 order is at internal diameter 16mm, react hydrogen and cis-butenedioic anhydride mol ratio 40,290 ℃ of temperature of reaction on the stainless steel fixed-bed reactor of long 75mm, cis-butenedioic anhydride transformation efficiency 99.6%, gamma-butyrolactone selectivity 84.5%.
U.S. Pat 5,122,495 introduce the Cu-Zn-Al catalyzer uses in the cis-butenedioic anhydride hydrogenation preparing gama-butalactone.Catalyzer consists of: CuO 55%, and ZnO 23%, Al
2O
318%, with the 400g catalyzer fixed-bed reactor of packing into, 250-280 ℃, under the hydrogen acid anhydride mol ratio 230-280 condition, cis-butenedioic anhydride transformation efficiency 100%, the gamma-butyrolactone selectivity is average 90%, and catalyzer uses 100-500hr continuously, promptly need under 400-450 ℃ of high temperature, to regenerate, thereby increased the difficulty of industrial application.
It is strong exothermal reaction that the cis-butenedioic anhydride ordinary-pressure gas-phase hydrogenation prepares gamma-butyrolactone, because focus is obvious, cause gamma-butyrolactone reaction decarburization to generate propyl alcohol, system's foreign gases such as propionic acid and carbon monoxide are cumulative, need continuous emptying just can keep the reaction hydrogen content, the hydrogen consumption is significantly increased.In a word, this hydrogenation process yield is low, and the hydrogen consumption is high, makes gamma-butyrolactone lose market price competition power.
Pimelinketone is a kind of colourless oil liquid, and water-soluble, pure, ether and common solvent have earth fragrance.Pimelinketone is the raw material of nylon intermediates such as preparation hexanolactam, hexanodioic acid as a kind of important chemical material.Pimelinketone also is a kind of good middle high boiling organic solvent, has fabulous solvability and low volatility.It can dissolve that poly-acetic acid second is rare, urethane, polymethylmethacrylate and ABS resin etc., also solubilized polystyrene, Synolac, acrylic resin, natural resin, natural rubber, synthetic rubber, chlorinated rubber etc.When pimelinketone is used as paint solvent, have good spraying and brushing function, can improve coating gloss.It can also be used as the silk-screen ink solvent, the sensitive materials coating is used thinner with the rumbling compound in solvent, the process hides shoe industry and leather grease-removing agent, covering with paint, is used for pesticide industry preparation aerosol bomb etc. in addition.Along with making rapid progress of science and technology, the applicating and exploitation of pimelinketone is just towards field development widely.
Mainly contain oxidation style and two kinds of technologies of dehydriding by the hexalin preparing cyclohexanone.Wherein the side reaction of dehydriding technological process is few, processing ease, and the yield height, and compare safety, therefore, larger pimelinketone industrial production generally adopts the dehydriding of hexalin.Industrial, the hexalin catalytic dehydrogenation is to pass through heating dehydrogenation tube furnace with pure hexalin gasification and with hydrogen, carries out continuous vapor catalytic dehydrogenation reaction.Reaction mixture is cooled off by condenser, and thick product is removed less water and tetrahydrobenzene from cat head after distillation is purified, carry out underpressure distillation again under the pressure of high-efficient spiral-screen column at about 4kPa, makes that cyclohexanone content reaches 98%-99% in the product.
Chinese patent CN1169417A and CN1381434A, report such as Japanese Patent JP2000288395 adopts the operational path of preparing cyclohexanone by cyclohexanol dehydrogenation.
The preparing cyclohexanone by cyclohexanol dehydrogenation equation is as follows:
It is the reversible thermo-negative reaction on thermodynamics that pimelinketone is produced in cyclohexanol dehydrogenation, because reaction is inhaled
Heat, being subjected in the actual production process to conduct heat influences, its high liquid air can not be given full play of, be subjected to the characteristics of thermodynamics equilibrium limit simultaneously, make the preparing cyclohexanone by cyclohexanol dehydrogenation transformation efficiency not high, the hydrogen emptying of reaction generation then causes waste in addition, if through a series of unit operations recovery then having increased production costs.The cyclohexanol dehydrogenation reaction also generates tetrahydrobenzene, phenol, cyclonene, hexanaphthene, benzene and cyclohexyl ring hexanone etc. because of side reaction except that the principal product pimelinketone.
Summary of the invention
The purpose of this invention is to provide a kind ofly need not sources of hydrogen, be the preparation of coupling gamma-butyrolactone of raw material and the method for pimelinketone with cyclohexanol dehydrogenation and maleic anhydride hydrogenation cheaply.
The object of the present invention is achieved like this: traditional technological line, and adopt cyclohexanol dehydrogenation to produce the direct emptying of pimelinketone by-product hydrogen, or reclaim through multiple unit operation, increase production cost.In addition, maleic anhydride hydrogenation is produced gamma-butyrolactone, and sources of hydrogen needs to buy from other places or build hydrogen producer, has increased cost, so two processes unite two into one, can make full use of sources of hydrogen, has reduced production cost, improves the market competitiveness, sees formula (3).
From top hydrogenation dehydrogenation coupled wave equation Shi Kede, hexalin and cis-butenedioic anhydride mol ratio are to get final product at 3: 1, consider system's gas leakage in the actual procedure, and rare gas element accumulative total needs emptying, factors such as hexalin can not transform fully generally take hexalin and cis-butenedioic anhydride mol ratio greater than 3.
Preparation method of the present invention is as follows:
The mixture of these two kinds of materials of cis-butenedioic anhydride and hexalin in gas phase, additional hydrogen is arranged or do not have under the additional hydrogen condition, in optimal temperature, carries out integrated reacting on the hydrogenation catalyst.
Because the used catalyzer of the present invention uses as hydrogenation (being hydrogenation) catalyzer industrial usually, although these catalyzer have dehydrogenation within the scope of the present invention, continues to be called " hydrogenation catalyst " in the method that the present invention narrated.
In the method for the present invention, the mixture of these two kinds of compounds of hexalin and cis-butenedioic anhydride is under gas phase condition, on the hydrogenation catalyst, the mol ratio of circulating hydrogen/hexalin and cis-butenedioic anhydride mixture is 1-60, is preferably 5-50, hexalin/cis-butenedioic anhydride mol ratio 3-10, be preferably 4-7, reaction pressure is a normal pressure, temperature of reaction 220-350 ℃, be preferably and carry out dehydrogenation hydrogenation integrated reacting under the 250-300 ℃ of condition, generate gamma-butyrolactone and pimelinketone.
As the heterogeneous catalyst in present method, not only can use the sedimentation type catalyzer, and the immersion type carried catalyst can be used also.Catalyzer prepares by the following method: at first with catalytic active component from their salts solution, especially from their nitrate and/or the solution of acetate, by adding basic metal and/or alkaline earth metal hydroxides solution and/or carbonate solution, for example as the oxyhydroxide of indissoluble, oxide hydrate, basic salt or carbonate deposition come out, and the throw out that obtains filters subsequently, washing and dry, and calcining.
Supported catalyst preparation: can adopt carrier direct impregnation active constituent, perhaps from relevant salts solution, be precipitated out then more favourable simultaneously with carrier active ingredient.Used carrier substance is generally aluminium and titanyl compound, and the oxide compound of zinc, zirconium dioxide, silicon-dioxide, diatomite, silica gel, shale soil if you would take off stone, silicate such as magnesium or aluminosilicate, zeolite such as ZSM-5 or ZSM-10 zeolite and gac.Preferred carrier is aluminum oxide, titanium dioxide, zinc oxide, zirconium dioxide, gac and silicon-dioxide.Certainly if need, the mixture of various carriers also can be used as the carrier of the catalyzer that uses in the present invention.
Particularly preferred catalyzer comprises a kind of metal in the copper metal at least.The precipitated catalyst that contains copper contains the 25-80%wt that accounts for total catalyst weight usually, preferably contains the copper of 45-70%wt, calculates with CuO.By the dipping of solid support material or the copper containing carrier catalyzer of coating preparation, the CuO weight content is 1-30%, and preferred content is 3-25%wt.
Catalyzer is handled at 100-300 ℃ usually by with hydrogen or hydrogenous gas, is reduced into corresponding metal and/or than the oxide compound of suboxide valency, and changes into the form of their real catalytic activity.Can select other suitable reductive agent for this reason, as: formaldehyde, hydrazine to replace hydrogen, have economic worth or hydrogen most certainly.Usually under certain reductive condition, be reacted to and do not consume hydrogen, or beds import and export hydrogen richness is constant, and the generation water yield does not become principle.
Method of the present invention is preferably carried out continuously.At this, can adopt tubular reactor, preferably dispose at this kind catalyst reactor with the fixed bed form.
Raw material hexalin and cis-butenedioic anhydride before they are passed through catalyzer, can be vaporized in vaporizer.Raw material is preferably in the carrier gas stream and is vaporized, can be for example adopted as carrier gas at this: rare gas, nitrogen or C
1-C
4Hydrocarbon, preferably methane and most preferably be hydrogen.
Carrier gas stream used during feed vaporization is preferably formed as the loop, that is to say, when breaking away from catalyst bed, in carrier gas stream, contain product, in a gas-liquid separator or after separated going out in the condenser, can be reused for the gasification of raw material, serve as carrier gas stream.
Gaseous phase crude product from reactor comes out after cooling and condensation, becomes the liquid crude product, gets final product sampling analysis, obtains its crude product and constitutes, and grasps the activity and the selectivity of catalyzed reaction.Crude product can be handled by traditional mode, by fractional distillation, removes by product, obtains qualified product.
The present invention compared with prior art has following advantage:
(1) is that two reactions of carrying out are respectively lumped together, avoided the hydrogen compressed of dehydrogenation gained in another reactor, to carry out hydrogenation again.
(2) dehydrogenation is thermo-negative reaction, and hydrogenation is thermopositive reaction, and the two coupling can be alleviated the heat effect in the reaction process.Coupling will be a process efficiently.
(3) hydrogenation dehydrogenation integrated process can be saved hydrogen producer.
(4) the present invention reacts required little energy, need not hydrogenation or reclaims hydrogen.
In the following embodiments, the transformation efficiency, the selectivity that provide are measured with vapor-phase chromatography.Because the integrated back of cyclohexanol dehydrogenation and maleic anhydride hydrogenation purpose product is pimelinketone and gamma-butyrolactone, so the selectivity of pimelinketone and gamma-butyrolactone is calculated by the following method:
Pimelinketone selectivity=100%* (mole number of pimelinketone in the product)/(mole number of the hexalin that has transformed)
Gamma-butyrolactone selectivity=100%* (mole number of gamma-butyrolactone in the product)/(mole number of the cis-butenedioic anhydride that has transformed)
Embodiment
Comparative Examples 1 preparing gamma-butyrolactone from cis-aldehyde by ordinary-pressure gas-phase hydrogenation
(1) catalyst preparation process: take by weighing needed cupric nitrate and zinc nitrate, being neutralized to the pH value with sodium carbonate solution is 7-8, throw out after filtration, washing, dry, 400 ℃ of calcinings, add 1% Graphite Powder 99 compression molding at last, obtain required catalyst sample.Each constituent mass percentage composition of this example catalyst system therefor is: CuO 60%, and ZnO 40%
(2) reactivity worth:
Catalyst activity evaluation and stability test are all carried out on fixed bed evaluating apparatus (being commonly called as small testing device).Wherein reactor is made by the stainless steel tube of internal diameter 12mm, long 500mm, and there is 4mm Thermal couple casing pipe at the center, and metal sleeve is arranged outward, is tied with electric stove wire on it.Temperature of reaction is measured by the 1mm armoured thermocouple that inserts center sleeve, and controls with temperature controller (passing through solid state relay).Each catalyzer (20-40 order) 5 grams of packing into, about 4.5 milliliters estimated.The about 50mm of catalyst bed layer height is positioned at the reaction tubes constant temperature zone.The activity rating procatalyst need be used hydrogen reducing, reducing gas air speed＞500h
-1The reduction process bed heats up gradually, ℃ approximately needs 30 hours by room temperature to 270.Reduction finishes, and can feed intake.
Normal pressure, hydrogen acid anhydride than 35, liquid air speed 0.06hr
-1Condition under, when temperature of reaction was 260 ℃, the cis-butenedioic anhydride transformation efficiency was 97.6%, gamma-butyrolactone selectivity 85.5%.When temperature of reaction was 280 ℃, the cis-butenedioic anhydride transformation efficiency was 98.2%, gamma-butyrolactone selectivity 85.3%.In the reaction operation process, need continuous hydrogen make-up.
Comparative Examples 2 hexalin normal pressure preparing cyclohexanone by dehydrogenating
Catalyst loading is in the gas phase fixed-bed reactor, at normal pressure, hydrogen alcohol ratio 9, liquid air speed 0.3hr
-1Condition under, when temperature of reaction was 260 ℃, the hexalin transformation efficiency was 52.8%, pimelinketone selectivity 85.9%.When temperature of reaction was 280 ℃, the hexalin transformation efficiency was 65.0%, pimelinketone selectivity 80.5%.In the normal reaction process, need constantly toward the outer emptying hydrogen of the recycle system.All the other are with Comparative Examples 1.
Embodiment 1
In the gas phase fixed-bed reactor (the catalyzer composition and activating and reducing and structure of reactor adorned with comparison example 1), Qi Hua hexalin, cis-butenedioic anhydride enter reactor after mixing by 6.3: 1 mol ratios and circulating hydrogen respectively.In normal pressure, the total air speed of liquid is 0.4hr
-1, circulating hydrogen and mixing raw material mole ratio be that when temperature was 260 ℃, the hexalin transformation efficiency was 53.3%, cis-butenedioic anhydride transformation efficiency 99.0%, pimelinketone selectivity 92.6%, gamma-butyrolactone selectivity 89.5% under 7: 1 the condition; When temperature of reaction was 280 ℃, the hexalin transformation efficiency was 66.1%, cis-butenedioic anhydride transformation efficiency 99.5%, pimelinketone selectivity 91.3%, gamma-butyrolactone selectivity 87.8%; Run well after the reaction, need not extraneous hydrogen supply gas.
Embodiment 2
In the gas phase fixed-bed reactor (the catalyzer composition and activating and reducing and structure of reactor adorned with Comparative Examples 1), 270 ℃ of reaction pressure normal pressure, temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 6: 1 mol ratios respectively, the mole ratio of circulating hydrogen and mixing raw material is 15: 1, and the total air speed of liquid is about 0.4hr
-1Condition, hexalin transformation efficiency 58.1%, cis-butenedioic anhydride transformation efficiency 99.3%, pimelinketone selectivity 92.0%, gamma-butyrolactone selectivity 88.2%.
Embodiment 3
In the gas phase fixed-bed reactor (the catalyzer composition and activating and reducing and structure of reactor adorned with comparison example 1), under the normal pressure, 290 ℃ of temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 4.5: 1 mol ratios respectively, circulating hydrogen and mixing raw material mole ratio are 10: 1, and the total air speed of liquid is about 0.5hr
-1Condition, hexalin transformation efficiency 75.8%, cis-butenedioic anhydride transformation efficiency 98.8%, pimelinketone selectivity 89.0%, gamma-butyrolactone selectivity 86.8%.
Embodiment 4
In the gas phase fixed-bed reactor (the catalyzer composition and activating and reducing and structure of reactor adorned with comparison example 1), under the normal pressure, 270 ℃ of temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 6: 1 mol ratios respectively, circulating hydrogen and mixing raw material mole ratio are 49: 1, and the total air speed of liquid is about 0.4hr
-1Condition, hexalin transformation efficiency 57.0%, cis-butenedioic anhydride transformation efficiency 99.5%, pimelinketone selectivity 92.2%, gamma-butyrolactone selectivity 88.8%.
Embodiment 5
(each constituent mass percentage composition of this example catalyst system therefor is: CuO 57%, and ZnO 43% in the gas phase fixed-bed reactor.Method for preparing catalyst, activating and reducing and structure of reactor are with comparison example 1), under the normal pressure, 270 ℃ of temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 6.1: 1 mol ratios respectively, circulating hydrogen and mixing raw material mole ratio are 50: 1, and the total air speed of liquid is about 0.4hr
-1Condition, hexalin transformation efficiency 56.8%, cis-butenedioic anhydride transformation efficiency 99.0%, pimelinketone selectivity 91.2%, gamma-butyrolactone selectivity 87.8%.
Embodiment 6
(each constituent mass percentage composition of this example catalyst system therefor is: CuO 47%, and ZnO 53% in the gas phase fixed-bed reactor.Method for preparing catalyst, activating and reducing and structure of reactor are with comparison example 1), under the normal pressure, 270 ℃ of temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 5.8: 1 mol ratios respectively, circulating hydrogen and mixing raw material mole ratio are 10: 1, and the total air speed of liquid is about 0.4hr
-1Condition, hexalin transformation efficiency 59.3%, cis-butenedioic anhydride transformation efficiency 99.6%, pimelinketone selectivity 92.0%, gamma-butyrolactone selectivity 86.9%.
Embodiment 7
The composition of this example catalyst system therefor; Copper is with the CuO restatement, and CuO 51%, and Cr is with Cr
2O
3Meter 49%, caking agent about 1%.The catalyzer method for making: copper nitrate solution and chromic acid solution neutralize, and regulate acid-basicity with ammoniacal liquor simultaneously, obtain that precipitation is washed, drying, and 350 ℃ of roastings add caking agent and carry out moulding.Catalyst activation reduction and structure of reactor are with comparison example 1.Under the normal pressure, 260 ℃ of temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 5.8: 1 mol ratios respectively, and circulating hydrogen and mixing raw material mole ratio are 5: 1, and the total air speed of liquid is about 0.4hr
-1Condition, hexalin transformation efficiency 56.3%, cis-butenedioic anhydride transformation efficiency 99.2%, pimelinketone selectivity 94.0%, gamma-butyrolactone selectivity 90.0%.
Embodiment 8
This example catalyst system therefor, its composition (weight percent) CuO 49%, CaO 2%, Cr
2O
348%, caking agent 1%, its method for making is with embodiment 7.Catalyst activation reduction and structure of reactor are with comparison example 1.Under the normal pressure, 265 ℃ of temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 6: 1 mol ratios respectively, and circulating hydrogen and mixing raw material mole ratio are 7: 1, and the total air speed of liquid is about 0.4hr
-1Condition, hexalin transformation efficiency 57.0%, cis-butenedioic anhydride transformation efficiency 99.3%, pimelinketone selectivity 94.2%, gamma-butyrolactone selectivity 90.5%.。
Embodiment 9
This example catalyst system therefor, its composition (weight percent) is CuO 20%, SiO
280%; The preparation method: with the copper carbonate solution impregnating carrier of dropping ammonia, the carrier of dipping is at 110 ℃, 450 ℃ of roastings.Catalyst activation reduction and structure of reactor are with comparison example 1.Under the normal pressure, 275 ℃ of temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 5.2: 1 mol ratios respectively, and circulating hydrogen and mixing raw material mole ratio are 7: 1, and the total air speed of liquid is about 0.3hr
-1Condition, hexalin transformation efficiency 64.0%, cis-butenedioic anhydride transformation efficiency 99.6%, pimelinketone selectivity 92.2%, gamma-butyrolactone selectivity 87.5%.
Embodiment 10
This example catalyst system therefor, its composition (mass percent) is 22% for CuO, gac 78%; The preparation method: with the copper liquid impregnated carrier that drips sal volatile, the carrier of dipping is 110 ℃ of dryings, 400 ℃ of roastings (protecting in the oxide gas).Catalyst activation reduction and structure of reactor are with comparison example 1.Under the normal pressure, 287 ℃ of temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 5: 1 mol ratios respectively, and circulating hydrogen and mixing raw material mole ratio are 20: 1, and the total air speed of liquid is about 0.5hr
-1Condition, hexalin transformation efficiency 69.9%, cis-butenedioic anhydride transformation efficiency 99.8%, pimelinketone selectivity 89.8%, gamma-butyrolactone selectivity 87.0%.
Claims (11)
1, the method for a kind of preparation of coupling gamma-butyrolactone and pimelinketone, the mixture that it is characterized in that these two kinds of compounds of hexalin and cis-butenedioic anhydride is under gas phase condition, on the hydrogenation catalyst, the mol ratio of circulating hydrogen/hexalin and cis-butenedioic anhydride mixture is 5-60, hexalin/cis-butenedioic anhydride mol ratio 3-10, reaction pressure is a normal pressure, carries out dehydrogenation hydrogenation integrated reacting under the temperature of reaction 220-350 ℃ of condition, generates gamma-butyrolactone and pimelinketone.
2, the method for a kind of according to claim 1 preparation of coupling gamma-butyrolactone and pimelinketone, the mol ratio that it is characterized in that circulating hydrogen/hexalin and cis-butenedioic anhydride mixture is 5-50, and hexalin/cis-butenedioic anhydride mol ratio is 4-7, and temperature of reaction is 250-300 ℃.
3. the method for a kind of preparation of coupling gamma-butyrolactone according to claim 1 and 2 and pimelinketone is characterized in that described catalyzer is the copper containing carrier catalyzer of cupric precipitation hydrogenation catalyst or dipping that passes through solid support material or coating preparation.
4. the method for a kind of preparation of coupling gamma-butyrolactone according to claim 3 and pimelinketone is characterized in that the cupric oxide content of described cupric precipitation hydrogenation catalyst accounts for the 25-80%wt of total catalyst weight.
5. the method for a kind of preparation of coupling gamma-butyrolactone according to claim 4 and pimelinketone is characterized in that the cupric oxide content of described cupric precipitation hydrogenation catalyst accounts for the 45-70%wt of total catalyst weight.
6. the method for a kind of preparation of coupling gamma-butyrolactone according to claim 3 and pimelinketone is characterized in that the cupric oxide content of the copper containing carrier hydrogenation catalyst of described dipping preparation by solid support material accounts for the 1-30% of total catalyst weight.
7. the method for a kind of preparation of coupling gamma-butyrolactone according to claim 6 and pimelinketone is characterized in that the cupric oxide content of the copper containing carrier hydrogenation catalyst of described dipping preparation by solid support material accounts for the 3-25% of total catalyst weight.
8,, it is characterized in that described solid support material is oxide compound, the titanyl compound of aluminium, oxide compound, zirconium dioxide, silicon-dioxide, diatomite, silica gel, shale soil, magnesium silicate, aluminosilicate, ZSM-5 zeolite, ZSM-10 zeolite or the gac of zinc according to the method for claim 6 or 7 described a kind of preparation of coupling gamma-butyrolactone and pimelinketone.
9, the method for a kind of preparation of coupling gamma-butyrolactone according to claim 8 and pimelinketone is characterized in that described solid support material is aluminum oxide, titanium dioxide, zinc oxide, zirconium dioxide, gac or silicon-dioxide.
10, the method for a kind of preparation of coupling gamma-butyrolactone according to claim 1 and 2 and pimelinketone, the mixture that it is characterized in that these two kinds of compounds of described hexalin and cis-butenedioic anhydride is to be vaporized in the carrier gas stream at gas phase condition, and carrier gas is: rare gas, nitrogen, C1-C4 hydrocarbon or hydrogen.
11, the method for a kind of preparation of coupling gamma-butyrolactone according to claim 10 and pimelinketone is characterized in that described carrier gas is methane or hydrogen.
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| CN110898841B (en) * | 2018-09-18 | 2022-09-13 | 中国石油化工股份有限公司 | Cyclohexanone light oil hydrogenation catalyst and application thereof |
| CN112517013B (en) * | 2020-12-23 | 2023-07-28 | 中科合成油技术股份有限公司 | Cu-based catalyst and method for preparing gamma-valerolactone and delta-cyclopentalactone by using same |
| CN113620784B (en) * | 2021-07-26 | 2022-09-27 | 武汉工程大学 | Alkane dehydrogenation and lignin-based ether hydrogenation reaction coupling process |
| CN113578238A (en) * | 2021-08-11 | 2021-11-02 | 安徽晟捷新能源科技有限公司 | Tower reactor for synthesizing NMP |
| CN117816224A (en) * | 2021-08-27 | 2024-04-05 | 中国石油化工股份有限公司 | Preparation method and application of maleic anhydride selective hydrogenation catalyst |
| CN113731480B (en) * | 2021-09-07 | 2022-10-18 | 中国科学院大连化学物理研究所 | Reaction catalyst for preparing gamma-butyrolactone by maleic anhydride hydrogenation and its preparation and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021490A (en) * | 1975-10-14 | 1977-05-03 | Phillips Petroleum Company | Process for production of phenol and cyclohexanone |
| CN1035819A (en) * | 1988-03-07 | 1989-09-27 | 三井石油化学工业株式会社 | The production method of phenol and/or pimelinketone |
| CN1053442C (en) * | 1993-08-10 | 2000-06-14 | 阿克佐诺贝尔公司 | Process for producing gamma-butyrolactone |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021490A (en) * | 1975-10-14 | 1977-05-03 | Phillips Petroleum Company | Process for production of phenol and cyclohexanone |
| CN1035819A (en) * | 1988-03-07 | 1989-09-27 | 三井石油化学工业株式会社 | The production method of phenol and/or pimelinketone |
| CN1053442C (en) * | 1993-08-10 | 2000-06-14 | 阿克佐诺贝尔公司 | Process for producing gamma-butyrolactone |
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| CP02 | Change in the address of a patent holder |
Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee after: Synefuels China Inc. Address before: 100195, Haidian District Zhongguancun East Road, No. 1, building 3, Tsinghua Science and Technology Park, pioneering building, 609, Beijing Patentee before: Synefuels China Inc. |
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| C56 | Change in the name or address of the patentee |
Owner name: SYNEFUELS CHINA CO., LTD. Free format text: FORMER NAME: SYNEFUELS CHINA INC. |
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| CP01 | Change in the name or title of a patent holder |
Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee after: SYNFUELS CHINA Address before: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee before: Synefuels China Inc. |
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| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone Park south two Street No. 1 Patentee after: SYNEFUELS CHINA Inc. Address before: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee before: SYNFUELS CHINA |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070905 Termination date: 20211214 |