CN106140260B - It is a kind of using silica modified ZSM-5 molecular sieve as catalyst of carrier and its preparation method and application - Google Patents
It is a kind of using silica modified ZSM-5 molecular sieve as catalyst of carrier and its preparation method and application Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 239000003054 catalyst Substances 0.000 title claims abstract description 135
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 88
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 71
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 77
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 77
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 76
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 70
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000011787 zinc oxide Substances 0.000 claims abstract description 30
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- -1 silica modified Hydrogen Chemical class 0.000 claims abstract description 19
- 230000031709 bromination Effects 0.000 claims abstract description 15
- 238000005893 bromination reaction Methods 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 238000012545 processing Methods 0.000 claims abstract description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract 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 abstract description 7
- 239000010457 zeolite Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 229940102001 zinc bromide Drugs 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 94
- 239000007789 gas Substances 0.000 claims description 85
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 74
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 72
- 239000002253 acid Substances 0.000 claims description 43
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910052736 halogen Inorganic materials 0.000 claims description 27
- 150000002367 halogens Chemical class 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 23
- 239000012298 atmosphere Substances 0.000 claims description 21
- 150000004820 halides Chemical class 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052794 bromium Inorganic materials 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000008246 gaseous mixture Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 2
- 235000005979 Citrus limon Nutrition 0.000 claims 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims 1
- 239000012300 argon atmosphere Substances 0.000 claims 1
- GZUXJHMPEANEGY-BJUDXGSMSA-N bromomethane Chemical group Br[11CH3] GZUXJHMPEANEGY-BJUDXGSMSA-N 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 238000001802 infusion Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- VSGLNOKIDSFELP-UHFFFAOYSA-N bromomethane 2-methylprop-1-ene Chemical compound C=C(C)C.CBr VSGLNOKIDSFELP-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 82
- 229910052757 nitrogen Inorganic materials 0.000 description 41
- 239000008367 deionised water Substances 0.000 description 26
- 229910021641 deionized water Inorganic materials 0.000 description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- 238000005253 cladding Methods 0.000 description 18
- 229960003511 macrogol Drugs 0.000 description 18
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 18
- 230000032683 aging Effects 0.000 description 12
- 241000790917 Dioxys <bee> Species 0.000 description 11
- 229910003978 SiClx Inorganic materials 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 11
- 238000011068 loading method Methods 0.000 description 11
- 238000005070 sampling Methods 0.000 description 11
- 238000011084 recovery Methods 0.000 description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229950005228 bromoform Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910001509 metal bromide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- AGYKGLGUMGTNHK-UHFFFAOYSA-N C.[Br] Chemical compound C.[Br] AGYKGLGUMGTNHK-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XDYHDLLKHFVVSE-UHFFFAOYSA-N hydrate;dihydrobromide Chemical compound O.Br.Br XDYHDLLKHFVVSE-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry 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
- 239000010936 titanium Substances 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of using modified zsm-5 zeolite as catalyst of carrier and its preparation method and application.It is a kind of using modified zsm-5 zeolite as the catalyst of carrier, the catalyst contains zinc oxide, zinc bromide and silica modified Hydrogen ZSM-5 molecular sieve.The preparation method of the catalyst, comprises the following processes: (1) using coated with silica Hydrogen ZSM-5 molecular sieve carrier, obtain silica modified Hydrogen ZSM-5 molecular sieve carrier；(2) by zinc oxide and/or auxiliary agent oxide be introduced to it is silica modified after Hydrogen ZSM-5 molecular sieve carrier in；(3) bromination processing is carried out to the silica modified Hydrogen ZSM-5 molecular sieve carrier after introducing zinc oxide.The catalyst is for that can significantly improve the selectivity of isobutene during isobutene bromomethane.
Description
Technical field
It as catalyst of carrier and preparation method thereof and is answered the present invention relates to a kind of using silica modified ZSM-5 molecular sieve
With.
Background technique
Isobutene is a kind of important basic organic chemical industry raw material, and derived product is numerous, and vertical industry chain is complicated, is disappeared
Take structure in diversified trend.A variety of high value-added products can be prepared by raw material of isobutene, such as: butyl rubber, gather it is different
A variety of Organic Chemicals such as butylene, methyl tertiary butyl ether(MTBE), isoprene and organic glass and fine chemistry product.Due to isobutyl
The market scale of alkene downstream product constantly expands, and imbalance between supply and demand will be protruded gradually, especially increasingly depleted in petroleum resources
Under background, the yield of isobutene has become the critical bottleneck for restricting downstream industry development.Therefore, the isobutyl of Non oil-based route is developed
Alkene preparation route is extremely urgent.
Methane is the main component of natural gas, therefore methane trans-utilization important grinding of just becoming in gas chemical industry's technology
Study carefully content.Especially in recent years, under the overall background of shale gas development and utilization, if it is possible to realize from methane and produce isobutyl
Alkene will provide a new approach to obtain isobutene.But methane property is stablized, and it is not easily-activated, become methane chemical industry benefit
Bottleneck.Domestic and international many researchers carry out methane activation, Study on Transformation one after another, and among these, methane is through halogen functional groupization
The technology converted again afterwards is expected to become an important breakthrough mouth for solving methane transformation technology problem.
Many chemical products can be prepared from halide.Chinese patent CN 101041609A, CN
101284232A disclose it is a kind of by methane in oxygen and HBr/H2Bromomethane is converted under the action of O, then bromomethane
The further method that reaction generates C3 ~ C13 mixing high-carbon hydrocarbon, the hydrocarbon selective of C5 or more are 70%.Wherein, HBr is at first
It is used for methane bromination in reactor, is then discharged in second reactor, is used further in back reaction, realizes after recovered
The recycling of HBr.(CN 102527427A, Jieli He, Ting Xu, the Zhihui Wang, et.al. such as Wang Ye
Angew. Chem. Int. Ed. 2012,51,2438-2442) disclose a kind of modified molecules of halide propylene
Sieve catalyst and preparation method thereof.By using fluorochemical moditied processing molecular sieve, obtains one kind and contain appropriate microporous knot
The catalyst of structure and acidity, the catalyst can effectively be catalyzed the reaction that halide is converted into propylene.Prepared catalysis
Agent one way bromomethane conversion ratio in the preparing propylene transformed reaction of bromomethane is 35 ~ 99%, and the selectivity of propylene is 27 ~ 70%；?
One way methyl chloride conversion rate is 30 ~ 99% in the preparing propylene transformed reaction of chloromethanes, and the selectivity of propylene is 15 ~ 70%.Ivan M.
Lorkovic et al. (Ivan M. Lorkovic, Aysen Yilmaz, Gurkan A. Yilmaz, et al.
Catalysis Today, 2004,98,317-322) it is also proposed that bromo-hydrocarbons is generated with the alkane reaction in bromine and natural gas,
Then dimethyl ether, methanol and metal bromide, metal bromide oxygen are converted by bromo-hydrocarbons on metal oxide catalyst
Metal oxide is obtained after gas regeneration and releases simple substance bromine, completes the circulation of bromine.
Currently, being mainly methanol, dimethyl ether, acetic acid, high-carbon about purpose product in the existing literature of halide conversion
Hydro carbons, ethylene and propylene etc..In the technology using the low-carbon alkene compared with high added value as target product, single selectivity of product
It is not high, not yet find the relevant report of bromomethane high selectivity isobutene.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provide it is a kind of using modified zsm-5 zeolite as the catalyst of carrier and its
Preparation method and application.
It is a kind of using modified zsm-5 zeolite as the catalyst of carrier, the catalyst is by zinc oxide, zinc bromide and titanium dioxide
The Hydrogen ZSM-5 molecular sieve carrier of Si modification forms, and based on the weight content of catalyst, zinc oxide content 0.5%-20% is excellent
It is selected as 1%-15%, further preferably 1%-9%, bromination Zn content is 10%-50%, preferably 15%-45%, further preferably
18%-39%, silica modified Hydrogen ZSM-5 molecular sieve vector contg be 40%-90%, preferably 50%-85%, further it is excellent
It is selected as 55%-80%, in the silica modified Hydrogen ZSM-5 molecular sieve carrier, the weight of silica in the carrier contains
Amount is 5%-20%, and preferably 10%-15%, Hydrogen ZSM-5 molecular sieve silica alumina ratio is 20 ~ 200, preferably 20 ~ 150.
In catalyst of the present invention, suitable auxiliary agent can also be contained, the auxiliary agent be selected from one of Ti, Zr, Ce, La or
Several, preferred zirconium, the weight content of auxiliary agent based on the element in the catalyst is 0.1%-10%, preferably 0.5%-5%, more preferably
0.5%-3%。
In catalyst of the present invention, 450 DEG C or less total acid content (NH3- TPD) it is 0.5mmol/g-1.3mmol/g, preferably
0.6mmol/g-1.2mmol/g, further preferred 0.7mmol-1.1mmol/g, 250 DEG C -350 DEG C of acid content account for 450 DEG C with
The 20%-90% of lower total acid content, preferably 30%-80%, further preferred 40%-80%.
It is a kind of using modified zsm-5 zeolite as the preparation method of the catalyst of carrier, comprise the following processes: (1) using dioxy
SiClx coats Hydrogen ZSM-5 molecular sieve carrier, obtains silica modified Hydrogen ZSM-5 molecular sieve carrier；(2) by zinc oxide
And/or auxiliary agent oxide be introduced to it is silica modified after Hydrogen ZSM-5 molecular sieve carrier in；(3) after to zinc oxide is introduced
Silica modified Hydrogen ZSM-5 molecular sieve carrier carry out bromination processing.
In above-mentioned preparation method step (1), the Hydrogen ZSM-5 molecular sieve carrier can be existing commercial product,
It can be prepared by those skilled in the art's well-known process.Carrier can be made or choose according to the needs of use suitable granulated
State, such as bar shaped, piece shape, cylindricality, spherical shape is made, forming can be carried out by this field general knowledge.
In above-mentioned preparation method step (1), using coated with silica Hydrogen ZSM-5 molecular sieve carrier, specific method is such as
Under: organic acid, dispersion aids are mixed with water and are made into mixed solution, silicon source is added in mixed solution, after mixing, is added
Enter Hydrogen ZSM-5 molecular sieve carrier, 2h-6h is stirred at 40 DEG C -90 DEG C, then stirs at 50 DEG C -90 DEG C at gel, room
Warm aging 5h-12h obtains coated with silica in 300 DEG C of -600 DEG C of roasting 2h-6h in 90 DEG C -120 DEG C dry 5h-12h
Hydrogen ZSM-5 molecular sieve carrier；The organic acid is one of citric acid, tartaric acid and malic acid or a variety of, organic acid
It is 0.05-0.25 with molar ratio of the silicon source in terms of silica；Dispersion aids is that molecular weight is in the polyethylene glycol of 200-2000
It is one or more, the molar ratio of polyethylene glycol and silicon source in terms of silica is 0.05-0.20；Institute's silicon source is positive silicic acid second
One of ester, silica solution are a variety of.
In above-mentioned preparation method step (2), the zinc oxide and/or auxiliary agent oxide are introduced to modified Hydrogen ZSM-5
The method of carrier is method well known to those skilled in the art, can such as be introduced using impregnation method.The specific method is as follows: using
Hydrogen ZSM-5 molecular sieve carrier after zinc salt, promoter metal salt solution impregnation are silica modified, obtains after drying, roasting
Bromomethane preparing isobutene catalyst precarsor.The drying condition is -150 DEG C of temperature 60 C, preferably 80 DEG C -120 DEG C；Time
For 1h-24h, preferably 4h-8h；It can be vacuum drying when dry, or it is dry under the conditions of inert gas shielding, may be used also
To dry in air atmosphere.The roasting condition is 200 DEG C -800 DEG C of temperature, preferably 400 DEG C -600 DEG C；Time is 1h-
For 24 hours, preferably 4h-8h；It can also be roasted in air atmosphere to be roasted under the conditions of inert gas shielding when roasting.On
It states in method, zinc salt can be inorganic salts, or organic salt, preferably nitrate, hydrochloride, acetate, citrate
One or more of.
In above-mentioned preparation method step (3), the bromination processing refers to using gas phase bromine-containing compound to load zinc oxide
Sample handled.Bromine-containing compound refers to one or more of bromomethane, methylene bromide, bromoform, preferably bromine
Methane.Bromination processing can also be carried out using the mixed gas of gas phase bromine-containing compound and inert gas, using mixed gas bromine
When changing processing, bromomethane volumetric concentration is not less than 20%, preferably not less than 30%.Specific bromination process is as follows: will load oxygen
The sample for changing zinc is placed in continuous fixed bed reactor, is warming up to 150 DEG C -400 DEG C under inert atmosphere, preferably 180 DEG C -
350 DEG C, more preferably 200 DEG C -300 DEG C are passed through gas phase bromine-containing compound gas, gas space velocity 50h-1-1000 h-1, preferably
For 100h-1-500h-1；It can carry out, can also carry out under a certain pressure, system pressure 0.1MPa- in normal pressure when processing
0.5MPa(absolute pressure), preferably 0.1MPa-0.3MPa(absolute pressure), the processing time is 0.5h-8h, preferably 1h-4h.
In above-mentioned preparation method step (3), related inert gas is nitrogen, argon gas, helium etc. involved by the present invention
The gas not chemically reacted under the conditions of and, preferably nitrogen.
The above-mentioned application using modified zsm-5 zeolite as the catalyst of carrier in preparing isobutene, including to catalyst into
The activation of row hydrogen reducing makes the content of halogen in catalyst restore the 20%-90% of total halogen content in procatalyst, then makes
Catalyst after halide is activated with above-mentioned hydrogen reducing contacts, to prepare isobutene.
In above-mentioned application, the condition of the hydrogen reducing activation is urged before the content of halogen in catalyst is preferably restored
The 30%-80% of total halogen content in agent, further preferred 40%-80%.
In above-mentioned application, the mode of hydrogen reducing activation include under an inert atmosphere by catalyzer temperature-elevating to 300 DEG C-
600℃；Then passing to air speed is 200h-1-2000h-1Hydrogen or hydrogen and inert gas mixed gas, in 0.1MPa-
0.5MPa keeps 2h-16h, and hydrogen volume percentage composition is 10%-95% in mixed gas；Preferably, it is warming up to 350 DEG C -550
℃；Then passing to air speed is 500h-1-1000h-1Hydrogen or hydrogen and inert gas mixed gas, in 0.1MPa-
0.3MPa keeps 4h-8h, and hydrogen volume percentage composition is 30%-90% in the mixed gas.
In above-mentioned application, the halide can be one of a halide, methylene halide, three halides
Or a variety of, preferably one of bromomethane, methylene bromide, bromoform or a variety of.
In above-mentioned application, the condition of the contact includes that reaction temperature is 150 DEG C -350 DEG C；Reaction pressure is 0.1MPa-
5MPa；Air speed is 50h-1-1000h-1；It is highly preferred that reaction temperature is 180 DEG C -300 DEG C more preferably 200-270 DEG C；Reaction
Pressure is 0.1MPa-3MPa；Air speed is 200h-1-500h-1。
By catalyzer temperature-elevating to 300 DEG C -600 DEG C under one of above-mentioned application specific embodiment, including inert atmosphere,
Preferably 350 DEG C -550 DEG C；Then passing to air speed is 200h-1-2000h-1, preferably 500h-1-1000h-1Hydrogen or hydrogen
With the mixed gas of inert gas, in 0.1MPa-0.5MPa(absolute pressure), preferably 0.1MPa-0.3MPa(absolute pressure) processing 2h-
After 16h, preferably 4h-8h, it is down to reaction temperature and is passed through halide and reacted.Hydrogen volume percentage contains in the gaseous mixture
Amount is 10%-95%, preferably 30%-90%, more preferably 50%-90%.
In above-mentioned application, raw material may be the mixed gas of halide and inert gas, halogenated first in mixed gas
The volumetric concentration of alkane is 10%-90%, preferably 30%-80%.
Inert gas involved in above-mentioned application is that nitrogen, argon gas, helium etc. are not sent out under the conditions of involved in the present invention
The gas of biochemical reaction, preferably nitrogen.
In above-mentioned application, the reaction of halide preparing isobutene can carry out in existing any form reactor, such as fixed
Bed, fluidized bed, fixed fluidized bed, moving bed, the reactor of the forms such as slurry bed system or ebullated bed, preferably fixed bed, fluidized bed
Reactor.
Compared with prior art, catalyst prepared by the present invention can by bromomethane it is highly selective be converted into isobutene.
By the method for the present invention carry out bromomethane conversion preparing isobutene reaction, 85% or more bromomethane conversion ratio, selective isobutene 70% with
On.The present invention relates to bromomethane conversion preparing isobutene method for preparing catalyst it is simple, be easy to industrialize.Bromomethane conversion of the present invention
Preparing isobutene method has many advantages, such as that reaction condition is mild, selectivity of product is high, industrialization easy to accomplish, and application prospect is very wide
It is wealthy.
Specific embodiment
Technology contents and effect of the invention are further illustrated below with reference to embodiment, but are not so limited the present invention.
Acidimetric estimation uses NH in following embodiment and comparative example3- TPD method, the instrument model used is the U.S.
2920 chemical adsorption instrument of MICROMERITICS company AutoChem, specific continuous mode are as follows: by sample at 450 DEG C with helium
Purging was cooled to 150 DEG C after 1 hour, introduced the mixed gas of ammonia and helium, ammonia volume content 10%, reached for Pulse adsorption five times
Balance；Helium purge 2 hours, ammonia is then carried out with 10 DEG C/min of heating rate temperature programming and is desorbed to 450 DEG C；After desorption
Ammonia using TCD detector detect, quantitatively calculate catalyst surface acid amount.
Embodiment 1
Appropriate citric acid and polyethylene glycol 200 are add to deionized water, mixed solution is made into, is then added in right amount just
Silester is added in appropriate Hydrogen ZSM-5 molecular sieve (silica alumina ratio 50) after mixing evenly, 2h is stirred at 50 DEG C, then
Stirring is at gel at 80 DEG C, and aging 8h, then obtains titanium dioxide in 550 DEG C of roasting 3h in 110 DEG C of dry 8h at room temperature
The ZSM-5 molecular sieve of silicon cladding, wherein silica accounts for the 10% of vehicle weight, and the molar ratio of citric acid and silica is 0.1, gathers
The molar ratio of ethylene glycol 200 and silica is 0.1.
Weigh appropriate zinc nitrate, zirconium nitrate is dissolved in deionized water, above-mentioned titanium dioxide is carried on using equi-volume impregnating
ZSM-5 molecular sieve (the Kong Rongwei 0.43ml/g, specific surface area 417m of silicon cladding2/ g, bar shaped, equivalent diameter 1.5mm), 80 DEG C
Dry 8h, 600 DEG C of roasting 4h, are made catalyst precarsor ZnO-Zr/ZSM-5.5g catalyst precarsor is placed in continuous flowing to fix
In bed reactor, catalyst precarsor is handled using bromomethane, treatment conditions are 250 DEG C, 0.2MPa(absolute pressure), 100h-1, the time
2h is made bromomethane preparing isobutene catalyst, is denoted as C-1.Catalyst weight group becomes ZnBr2Weight content is 27%, ZnO weight
Measuring content be that weight content is 1% to 6%, Zr based on the element, and 450 DEG C or less total acid contents are 0.82mmol/g in catalyst, 250 DEG C-
350 DEG C of acid content accounts for the 68.3% of 450 DEG C or less total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 50%, and reaction temperature is 230 DEG C, reaction pressure
For 1MPa(absolute pressure), air speed 500h-1, it being passed through unstripped gas procatalyst and activates in a hydrogen atmosphere, reducing condition is 400 DEG C,
0.2MPa(absolute pressure), 1000h-1, recovery time 4h, restoring the content of halogen in rear catalyst is that halogen is total in reduction procatalyst
The 69.86% of content.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.
Embodiment 2
Appropriate citric acid and Macrogol 600 are add to deionized water, mixed solution is made into, is then added in right amount just
Silester is added in appropriate Hydrogen ZSM-5 molecular sieve (silica alumina ratio 100) after mixing evenly, 2h is stirred at 50 DEG C, so
Stirring is at gel at 80 DEG C afterwards, and aging 8h, then obtains dioxy in 550 DEG C of roasting 3h in 110 DEG C of dry 8h at room temperature
The ZSM-5 molecular sieve of SiClx cladding, wherein silica accounts for the 12% of vehicle weight, and the molar ratio of citric acid and silica is 0.15,
The molar ratio of Macrogol 600 and silica is 0.15.
Weigh appropriate zinc nitrate, zirconium nitrate is dissolved in deionized water, above-mentioned titanium dioxide is carried on using equi-volume impregnating
ZSM-5 molecular sieve (the Kong Rongwei 0.55ml/g, specific surface area 428m of silicon cladding2/ g, bar shaped, equivalent diameter 1.5mm), 120
DEG C dry 4h, 500 DEG C of roasting 8h, obtained catalyst precarsor ZnO-Zr/ZSM-5.It is solid that 5g catalyst precarsor is placed in continuous flowing
In fixed bed reactor, catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is 80%, place
Manage bar part is 250 DEG C, 0.3MPa(absolute pressure), 300h-1, time 2h, be made bromomethane preparing isobutene catalyst, be denoted as C-2.It obtains
Catalyst weight group becomes ZnBr2It is 4%, Zr with member that weight content, which is 30%, ZnO weight content in terms of oxide, in terms of bromide
Element meter weight content is 1%, and 450 DEG C or less total acid contents are 0.87mmol/g in catalyst, and 250 DEG C -350 DEG C of acid content accounts for 450
DEG C or less total acid content 75.5%.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure
For 2MPa(absolute pressure), air speed 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen and nitrogen, mixing
Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 4h, after reduction
Content of halogen in catalyst is restore total halogen content in procatalyst 55.87%.After stable reaction one hour, sampling point
Analysis.Reaction result is shown in Table 1.
Embodiment 3
Appropriate citric acid and polyethylene glycol 400 are add to deionized water, mixed solution is made into, is then added in right amount just
Silester is added in appropriate Hydrogen ZSM-5 molecular sieve (silica alumina ratio 100) after mixing evenly, 2h is stirred at 50 DEG C, so
Stirring is at gel at 80 DEG C afterwards, and aging 8h, then obtains dioxy in 550 DEG C of roasting 3h in 110 DEG C of dry 8h at room temperature
The ZSM-5 molecular sieve of SiClx cladding, wherein silica accounts for the 15% of vehicle weight, and the molar ratio of citric acid and silica is 0.2,
Polyethylene glycol 400 and the molar ratio of silica are 0.18.
Weigh appropriate zinc nitrate, zirconium nitrate is dissolved in deionized water, above-mentioned titanium dioxide is carried on using equi-volume impregnating
ZSM-5 molecular sieve (the Kong Rongwei 0.59ml/g, specific surface area 443m of silicon cladding2/ g, bar shaped, equivalent diameter 1.5mm), 100
DEG C vacuum drying 8h, 400 DEG C of roasting 8h, obtained catalyst precarsor ZnO-Zr/ZSM-5.5g catalyst precarsor is placed in continuous flow
In dynamic fixed bed reactors, catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is
30%, treatment conditions are 300 DEG C, 0.1MPa(absolute pressure), 500h-1, time 4h, be made bromomethane preparing isobutene catalyst, be denoted as C-
3.Catalyst weight group is obtained as ZnBr2It is 2% that weight content, which is 33%, ZnO weight content in terms of oxide, in terms of bromide,
Weight content is 1% to Zr based on the element, and 450 DEG C or less total acid contents are 0.89mmol/g in catalyst, and 250 DEG C -350 DEG C of acid contains
Amount accounts for the 72.2% of 450 DEG C or less total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 80%, and reaction temperature is 200 DEG C, reaction pressure
For 3MPa(absolute pressure), air speed 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen and nitrogen, mixing
Hydrogen volume content is 50% in gas, and reducing condition is 500 DEG C, 0.1MPa(absolute pressure), 500h-1, recovery time 4h, after reduction
Content of halogen in catalyst is restore total halogen content in procatalyst 50.23%.After stable reaction one hour, sampling point
Analysis.Reaction result is shown in Table 1.
Embodiment 4
Appropriate citric acid and Macrogol 600 are add to deionized water, mixed solution is made into, is then added in right amount just
Silester is added in appropriate Hydrogen ZSM-5 molecular sieve (silica alumina ratio 100) after mixing evenly, 2h is stirred at 50 DEG C, so
Stirring is at gel at 80 DEG C afterwards, and aging 8h, then obtains dioxy in 550 DEG C of roasting 3h in 110 DEG C of dry 8h at room temperature
The ZSM-5 molecular sieve of SiClx cladding, wherein silica accounts for the 12% of vehicle weight, and the molar ratio of citric acid and silica is 0.15,
The molar ratio of Macrogol 600 and silica is 0.15.
It weighs appropriate zinc nitrate to be dissolved in deionized water, above-mentioned coated with silica is carried on using equi-volume impregnating
ZSM-5 molecular sieve (Kong Rongwei 0.54ml/g, specific surface area 428m2/ g, bar shaped, equivalent diameter 1.5mm), 120 DEG C of dry 4h,
Catalyst precarsor ZnO/ZSM-5 is made in 500 DEG C of roasting 8h.5g catalyst precarsor is placed in continuous fixed bed reactor,
Catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is 80%, and treatment conditions are 250 DEG C,
0.3MPa(absolute pressure), 300h-1, time 2h.It weighs appropriate zirconium nitrate to be dissolved in deionized water, bromine is impregnated using equi-volume impregnating
Sample after change, dry 4h under 120 DEG C of nitrogen atmospheres roast 4h under 500 DEG C of nitrogen atmospheres, the catalysis of bromomethane preparing isobutene are made
Agent is denoted as C-4.Catalyst weight group is obtained as ZnBr2Weight content is 30%, ZnO with oxide weight calculation amount in terms of bromide
Content is that weight content is 1% to 4%, Zr based on the element, and 450 DEG C or less total acid contents are 0.83mmol/g in catalyst, 250 DEG C -350
DEG C acid content account for the 71.12% of 450 DEG C or less total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure
For 2MPa(absolute pressure), air speed 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen and nitrogen, mixing
Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 4h, after reduction
Content of halogen in catalyst is restore total halogen content in procatalyst 53.31%.After stable reaction one hour, sampling point
Analysis.Reaction result is shown in Table 1.
Embodiment 5
Appropriate citric acid and Macrogol 600 are add to deionized water, mixed solution is made into, is then added in right amount just
Silester is added in appropriate Hydrogen ZSM-5 molecular sieve (silica alumina ratio 100) after mixing evenly, 2h is stirred at 50 DEG C, so
Stirring is at gel at 80 DEG C afterwards, and aging 8h, then obtains dioxy in 550 DEG C of roasting 3h in 110 DEG C of dry 8h at room temperature
The ZSM-5 molecular sieve of SiClx cladding, wherein silica accounts for the 12% of vehicle weight, and the molar ratio of citric acid and silica is 0.15,
The molar ratio of Macrogol 600 and silica is 0.15.
Weigh appropriate zinc nitrate, lanthanum nitrate is dissolved in deionized water, above-mentioned titanium dioxide is carried on using equi-volume impregnating
ZSM-5 molecular sieve (the Kong Rongwei 0.54ml/g, specific surface area 428m of silicon cladding2/ g, bar shaped, equivalent diameter 1.5mm), 120
DEG C dry 4h, 500 DEG C of roasting 8h, obtained catalyst precarsor ZnO-La/ZSM-5.It is solid that 5g catalyst precarsor is placed in continuous flowing
In fixed bed reactor, catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is 80%, place
Manage bar part is 250 DEG C, 0.3MPa(absolute pressure), 300h-1, time 2h, be made bromomethane preparing isobutene catalyst, be denoted as C-5.It obtains
Catalyst weight group becomes ZnBr2It is 4%, La with member that weight content, which is 30%, ZnO weight content in terms of oxide, in terms of bromide
Element meter weight content is 1%, and 450 DEG C or less total acid contents are 0.85mmol/g in catalyst, and 250 DEG C -350 DEG C of acid content accounts for 450
DEG C or less total acid content 72.37%.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure
For 2MPa(absolute pressure), air speed 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen and nitrogen, mixing
Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 4h, after reduction
Content of halogen in catalyst is restore total halogen content in procatalyst 51.62%.After stable reaction one hour, sampling point
Analysis.Reaction result is shown in Table 1.
Embodiment 6
Appropriate citric acid and Macrogol 600 are add to deionized water, mixed solution is made into, is then added in right amount just
Silester is added in appropriate Hydrogen ZSM-5 molecular sieve (silica alumina ratio 100) after mixing evenly, 2h is stirred at 50 DEG C, so
Stirring is at gel at 80 DEG C afterwards, and aging 8h, then obtains dioxy in 550 DEG C of roasting 3h in 110 DEG C of dry 8h at room temperature
The ZSM-5 molecular sieve of SiClx cladding, wherein silica accounts for the 12% of vehicle weight, and the molar ratio of citric acid and silica is 0.15,
The molar ratio of Macrogol 600 and silica is 0.15.
Weigh appropriate zinc nitrate, cerous nitrate is dissolved in deionized water, above-mentioned titanium dioxide is carried on using equi-volume impregnating
ZSM-5 molecular sieve (the Kong Rongwei 0.54ml/g, specific surface area 428m of silicon cladding2/ g, bar shaped, equivalent diameter 1.5mm), 120
DEG C dry 4h, 500 DEG C of roasting 8h, obtained catalyst precarsor ZnO-Ce/ZSM-5.It is solid that 5g catalyst precarsor is placed in continuous flowing
In fixed bed reactor, catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is 80%, place
Manage bar part is 250 DEG C, 0.3MPa(absolute pressure), 300h-1, time 2h, be made bromomethane preparing isobutene catalyst, be denoted as C-6.It obtains
Catalyst weight group becomes ZnBr2It is 4%, Ce with member that weight content, which is 30%, ZnO weight content in terms of oxide, in terms of bromide
Element meter weight content is 1%, and 450 DEG C or less total acid contents are 0.83mmol/g in catalyst, and 250 DEG C -350 DEG C of acid content accounts for 450
DEG C or less total acid content 70.49%.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure
For 2MPa(absolute pressure), air speed 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen and nitrogen, mixing
Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 4h, after reduction
Content of halogen in catalyst is restore total halogen content in procatalyst 58.29%.After stable reaction one hour, sampling point
Analysis.Reaction result is shown in Table 1.
Embodiment 7
Appropriate citric acid and Macrogol 600 are add to deionized water, mixed solution is made into, is then added in right amount just
Silester is added in appropriate Hydrogen ZSM-5 molecular sieve (silica alumina ratio 100) after mixing evenly, 2h is stirred at 50 DEG C, so
Stirring is at gel at 80 DEG C afterwards, and aging 8h, then obtains dioxy in 550 DEG C of roasting 3h in 110 DEG C of dry 8h at room temperature
The ZSM-5 molecular sieve of SiClx cladding, wherein silica accounts for the 12% of vehicle weight, and the molar ratio of citric acid and silica is 0.15,
The molar ratio of Macrogol 600 and silica is 0.15.
It weighs appropriate zinc nitrate to be dissolved in deionized water, above-mentioned coated with silica is carried on using equi-volume impregnating
ZSM-5 molecular sieve (Kong Rongwei 0.54ml/g, specific surface area 428m2/ g, bar shaped, equivalent diameter 1.5mm), 120 DEG C of dry 4h,
Catalyst precarsor ZnO/ZSM-5 is made in 500 DEG C of roasting 4h.5g catalyst precarsor is placed in continuous fixed bed reactor,
Catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is 80%, and treatment conditions are 250 DEG C,
0.3MPa(absolute pressure), 300h-1, time 2h.It weighs appropriate zirconium nitrate to be dissolved in deionized water, bromine is impregnated using equi-volume impregnating
Sample after change, dry 4h under 120 DEG C of nitrogen atmospheres roast 4h under 500 DEG C of nitrogen atmospheres, the catalysis of bromomethane preparing isobutene are made
Agent is denoted as C-7.Catalyst weight group is obtained as ZnBr2Weight content is 39%, ZnO with oxide weight calculation amount in terms of bromide
Content is that weight content is 5% to 6%, Zr based on the element, and 450 DEG C or less total acid contents are 0.9mmol/g in catalyst, 250 DEG C -350
DEG C acid content account for the 80.76% of 450 DEG C or less total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure
For 2MPa(absolute pressure), air speed 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen and nitrogen, mixing
Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 4h, after reduction
Content of halogen in catalyst is restore total halogen content in procatalyst 60.42%.After stable reaction one hour, sampling point
Analysis.Reaction result is shown in Table 1.
Embodiment 8
Appropriate citric acid and Macrogol 600 are add to deionized water, mixed solution is made into, is then added in right amount just
Silester is added in appropriate Hydrogen ZSM-5 molecular sieve (silica alumina ratio 100) after mixing evenly, 2h is stirred at 50 DEG C, so
Stirring is at gel at 80 DEG C afterwards, and aging 8h, then obtains dioxy in 550 DEG C of roasting 3h in 110 DEG C of dry 8h at room temperature
The ZSM-5 molecular sieve of SiClx cladding, wherein silica accounts for the 12% of vehicle weight, and the molar ratio of citric acid and silica is 0.15,
The molar ratio of Macrogol 600 and silica is 0.15.
It weighs appropriate zinc nitrate to be dissolved in deionized water, above-mentioned coated with silica is carried on using equi-volume impregnating
ZSM-5 molecular sieve (Kong Rongwei 0.54ml/g, specific surface area 428m2/ g, bar shaped, equivalent diameter 1.5mm), 120 DEG C of dry 4h,
Catalyst precarsor ZnO/ZSM-5 is made in 500 DEG C of roasting 4h.5g catalyst precarsor is placed in continuous fixed bed reactor,
Catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is 80%, and treatment conditions are 250 DEG C,
0.3MPa(absolute pressure), 300h-1, time 2h.It weighs appropriate zirconium nitrate to be dissolved in deionized water, bromine is impregnated using equi-volume impregnating
Sample after change, dry 4h under 120 DEG C of nitrogen atmospheres roast 4h under 500 DEG C of nitrogen atmospheres, the catalysis of bromomethane preparing isobutene are made
Agent is denoted as C-8.Catalyst weight group is obtained as ZnBr2Weight content is 18%, ZnO with oxide weight calculation amount in terms of bromide
Content is that weight content is 0.5% to 2%, Zr based on the element, and 450 DEG C or less total acid contents are 0.81mmol/g in catalyst, 250 DEG C-
350 DEG C of acid content accounts for the 66.89% of 450 DEG C or less total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure
For 2MPa(absolute pressure), air speed 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen and nitrogen, mixing
Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 4h, after reduction
Content of halogen in catalyst is restore total halogen content in procatalyst 48.73%.After stable reaction one hour, sampling point
Analysis.Reaction result is shown in Table 1.
Comparative example 1
Appropriate citric acid and Macrogol 600 are add to deionized water, mixed solution is made into, is then added in right amount just
Silester is added in appropriate Hydrogen ZSM-5 molecular sieve (silica alumina ratio 100) after mixing evenly, 2h is stirred at 50 DEG C, so
Stirring is at gel at 80 DEG C afterwards, and aging 8h, then obtains dioxy in 550 DEG C of roasting 3h in 110 DEG C of dry 8h at room temperature
The ZSM-5 molecular sieve of SiClx cladding, wherein silica accounts for the 12% of vehicle weight, and the molar ratio of citric acid and silica is 0.15,
The molar ratio of Macrogol 600 and silica is 0.15.
It weighs appropriate zinc nitrate to be dissolved in deionized water, above-mentioned coated with silica is carried on using equi-volume impregnating
ZSM-5 molecular sieve (Kong Rongwei 0.54ml/g, specific surface area 428m2/ g, bar shaped, equivalent diameter 1.5mm), 120 DEG C of dry 4h,
Catalyst precarsor ZnO/ZSM-5 is made in 500 DEG C of roasting 4h.5g catalyst precarsor is placed in continuous fixed bed reactor,
Catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is 80%, and treatment conditions are 250 DEG C,
0.3MPa(absolute pressure), 300h-1, time 2h.It weighs appropriate zirconium nitrate to be dissolved in deionized water, bromine is impregnated using equi-volume impregnating
Sample after change, dry 4h under 120 DEG C of nitrogen atmospheres roast 4h under 500 DEG C of nitrogen atmospheres, the catalysis of bromomethane preparing isobutene are made
Agent is denoted as D-1.Catalyst weight group is obtained as ZnBr2Weight content is 30%, ZnO with oxide weight calculation amount in terms of bromide
Content is that weight content is 1% to 4%, Zr based on the element, and 450 DEG C or less total acid contents are 0.83mmol/g in catalyst, 250 DEG C -350
DEG C acid content account for the 71.12% of 450 DEG C or less total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure
For 2MPa(absolute pressure), air speed 200h-1.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.
Comparative example 2
Appropriate citric acid and Macrogol 600 are add to deionized water, mixed solution is made into, is then added in right amount just
Silester is added in appropriate Hydrogen ZSM-5 molecular sieve (silica alumina ratio 100) after mixing evenly, 2h is stirred at 50 DEG C, so
Stirring is at gel at 80 DEG C afterwards, and aging 8h, then obtains dioxy in 550 DEG C of roasting 3h in 110 DEG C of dry 8h at room temperature
The ZSM-5 molecular sieve of SiClx cladding, wherein silica accounts for the 12% of vehicle weight, and the molar ratio of citric acid and silica is 0.15,
The molar ratio of Macrogol 600 and silica is 0.15.
Weigh appropriate zinc nitrate, zirconium nitrate is dissolved in deionized water, above-mentioned titanium dioxide is carried on using equi-volume impregnating
ZSM-5 molecular sieve (the Kong Rongwei 0.54ml/g, specific surface area 428m of silicon cladding2/ g, bar shaped, equivalent diameter 1.5mm), 120
DEG C dry 4h, 500 DEG C of roasting 4h, obtained catalyst Z nO-Zr/ZSM-5 are denoted as D-2.Obtain catalyst weight group as ZnO with
Oxide meter weight content is that weight content is 1% to 20%, Zr based on the element, and 450 DEG C or less total acid contents are in catalyst
0.43mmol/g, 250 DEG C -350 DEG C of acid content account for the 40.7% of 450 DEG C or less total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure
For 2MPa(absolute pressure), air speed 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen and nitrogen, mixing
Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 4h.Reaction is steady
After one hour fixed, sampling analysis.Reaction result is shown in Table 1.
Comparative example 3
Appropriate citric acid and Macrogol 600 are add to deionized water, mixed solution is made into, is then added in right amount just
Silester is added in appropriate Hydrogen ZSM-5 molecular sieve (silica alumina ratio 100) after mixing evenly, 2h is stirred at 50 DEG C, so
Stirring is at gel at 80 DEG C afterwards, and aging 8h, then obtains dioxy in 550 DEG C of roasting 3h in 110 DEG C of dry 8h at room temperature
The ZSM-5 molecular sieve of SiClx cladding, wherein silica accounts for the 12% of vehicle weight, and the molar ratio of citric acid and silica is 0.15,
The molar ratio of Macrogol 600 and silica is 0.15.
Weigh appropriate zinc bromide, zirconium nitrate is dissolved in deionized water, above-mentioned titanium dioxide is carried on using equi-volume impregnating
ZSM-5 molecular sieve (the Kong Rongwei 0.54ml/g, specific surface area 428m of silicon cladding2/ g, bar shaped, equivalent diameter 1.5mm), 80 DEG C
Nitrogen atmosphere dries 4h, and 500 DEG C of nitrogen atmospheres roast 4h, catalyst Z nBr is made2- Zr/ZSM-5 is denoted as D-3.It is catalyzed
Agent weight group becomes ZnBr2Weight content is that weight content is 1% to 30%, Zr based on the element in terms of bromide, 450 DEG C in catalyst
Following total acid content is 0.89mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 69.52% of 450 DEG C or less total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure
For 2MPa(absolute pressure), air speed 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen and nitrogen, mixing
Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 4h, after reduction
Content of halogen in catalyst is restore total halogen content in procatalyst 91.76%.After stable reaction one hour, sampling point
Analysis.Reaction result is shown in Table 1.
1 catalyst reaction performance of table
Claims (31)
1. a kind of using modified zsm-5 zeolite as the preparing isobutene catalyst of carrier, it is characterised in that: the catalyst includes oxygen
Change zinc, zinc bromide and silica modified Hydrogen ZSM-5 molecular sieve carrier, based on the weight content of catalyst, zinc oxide contains
Amount is 0.5%-20%, and bromination Zn content is 10%-50%, and silica modified Hydrogen ZSM-5 molecular sieve vector contg is 40%-
85%, in the silica modified Hydrogen ZSM-5 molecular sieve carrier, the weight content of silica in the carrier is 5%-
20%, Hydrogen ZSM-5 molecular sieve silica alumina ratio is 20 ~ 200.
2. catalyst according to claim 1, it is characterised in that: zinc oxide content 1%-15%, bromination Zn content are
10%-45%, silica modified Hydrogen ZSM-5 molecular sieve vector contg are 50%-85%, the silica modified Hydrogen
In ZSM-5 molecular sieve carrier, the weight content of silica in the carrier is 10%-15%, Hydrogen ZSM-5 molecular sieve sial mole
Than being 20 ~ 150.
3. catalyst according to claim 2, it is characterised in that: zinc oxide content 1%-9%, bromination Zn content are 18%-
39%, silica modified Hydrogen ZSM-5 molecular sieve vector contg is 55%-80%.
4. catalyst according to claim 1, it is characterised in that: contain auxiliary agent in catalyst, auxiliary agent be selected from Ti, Zr, Ce,
One or more of La, the weight content of auxiliary agent based on the element in the catalyst are 0.1%-10%.
5. catalyst according to claim 4, it is characterised in that: auxiliary agent is zirconium, and auxiliary agent is based on the element in the catalyst
Weight content is 0.5%-5%.
6. catalyst according to claim 1, it is characterised in that: use NH3450 DEG C or less in the catalyst that-TPD is measured
Total acid content is 0.5mmol/g-1.3mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 20%-90% of 450 DEG C or less total acid contents.
7. catalyst according to claim 6, it is characterised in that: use NH3450 DEG C or less the total acid contents that-TPD is measured are
0.6mmol/g-1.2mmol/g, 250 DEG C -350 DEG C of acid content account for the 30%-80% of 450 DEG C or less total acid contents.
8. catalyst according to claim 7, it is characterised in that: use NH3450 DEG C or less in the catalyst that-TPD is measured
Total acid content is 0.7mmol-1.1mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 40%-80% of 450 DEG C or less total acid contents.
9. the preparation method of catalyst described in claim 1, characterized by the following steps:
(1) coated with silica Hydrogen ZSM-5 molecular sieve is used, silica modified Hydrogen ZSM-5 molecular sieve carrier is obtained；
(2) by zinc oxide and auxiliary agent oxide be introduced to it is silica modified after Hydrogen ZSM-5 molecular sieve carrier in；
(3) bromination processing is carried out to the silica modified Hydrogen ZSM-5 molecular sieve carrier after introducing zinc oxide.
10. preparation method according to claim 9, it is characterised in that: use coated with silica Hydrogen in step (1)
ZSM-5 molecular sieve, the specific method is as follows: organic acid, dispersion aids being mixed with water and are made into mixed solution, silicon source is added to mixed
It closes in solution, after mixing, Hydrogen ZSM-5 molecular sieve carrier is added, 2h-6h is stirred at 40 DEG C -90 DEG C, then 50
To at gel, aged at room temperature 5h-12h is roasted in 90 DEG C -120 DEG C dry 5h-12h at 300 DEG C -600 DEG C for stirring at DEG C -90 DEG C
2h-6h obtains the Hydrogen ZSM-5 molecular sieve carrier of coated with silica.
11. preparation method according to claim 10, it is characterised in that: organic acid as described in step (1) be citric acid,
One of tartaric acid and malic acid are a variety of, and the molar ratio of organic acid and silicon source in terms of silica is 0.05-0.25；It helps point
Powder is that molecular weight is one of polyethylene glycol of 200-2000 or a variety of, polyethylene glycol and silicon source rubbing in terms of silica
You are than being 0.05-0.20；The silicon source is one of ethyl orthosilicate, silica solution or a variety of.
12. preparation method according to claim 9, it is characterised in that: zinc oxide and/or auxiliary agent oxide in step (2)
Modified Hydrogen ZSM-5 carrier is introduced to using infusion process.
13. preparation method according to claim 12, it is characterised in that: the specific method is as follows for dipping: using zinc salt, auxiliary agent
The modified Hydrogen ZSM-5 molecular sieve carrier of metal salt solution impregnation of silica, and be dried, roast.
14. preparation method according to claim 13, it is characterised in that: drying temperature is 60 DEG C -150 DEG C, time 1h-
For 24 hours, maturing temperature is 200 DEG C -800 DEG C, time 1h-24h.
15. preparation method according to claim 14, it is characterised in that: drying temperature is 80 DEG C -120 DEG C；Time is 4h-
8h, maturing temperature are 400 DEG C -600 DEG C, time 4h-8h.
16. preparation method according to claim 13, it is characterised in that: zinc salt is nitrate, hydrochloride, acetate, lemon
One or more of lemon hydrochlorate.
17. according to the method described in claim 9, it is characterized by: in step (3) bromination processing refer to using gas phase containing bromination
Object is closed to handle the sample of load zinc oxide.
18. according to the method for claim 17, it is characterised in that: bromine-containing compound refers to bromomethane, methylene bromide, tribromo
One or more of methane.
19. according to the method described in claim 9, it is characterized by: the specific bromination process of step (3) is as follows: load is aoxidized
The sample of zinc is placed in continuous fixed bed reactor, and 150 DEG C -400 DEG C are warming up under inert atmosphere, is passed through gas phase containing bromination
Close object gas, gas space velocity 50h-1-1000 h-1, system pressure 0.1MPa-0.5MPa, the processing time is 0.5h-8h.
20. according to the method for claim 19, it is characterised in that: related inert atmosphere is argon atmosphere or helium gas
One or more of atmosphere.
21. application of the catalyst described in claim 1 in preparing isobutene, it is characterised in that: including carrying out hydrogen to catalyst
Reduction activation makes the content of halogen in catalyst restore the 20%-90% of total halogen content in procatalyst, then makes halogenated first
Catalyst after alkane is activated with above-mentioned hydrogen reducing contacts, to prepare isobutene.
22. application according to claim 21, it is characterised in that: the condition of the hydrogen reducing activation makes in catalyst
Content of halogen be restore procatalyst in total halogen content 30%-80%.
23. application according to claim 21, it is characterised in that: the mode of the hydrogen reducing activation is included in indifferent gas
By catalyzer temperature-elevating to 300 DEG C -600 DEG C under atmosphere；Then passing to air speed is 200h-1-2000h-1Hydrogen or hydrogen and indifferent gas
The mixed gas of body keeps 2h-16h in 0.1MPa-0.5MPa, and hydrogen volume percentage composition is 10%-95% in mixed gas.
24. application according to claim 23, it is characterised in that: be warming up to 350 DEG C -550 DEG C；Then passing to air speed is
500h-1-1000h-1Hydrogen or hydrogen and inert gas mixed gas, keep 4h-8h in 0.1MPa-0.3MPa, it is described mixed
Closing hydrogen volume percentage composition in gas is 30%-90%.
25. application according to claim 21, it is characterised in that: the halide is a halide, dihalo first
One or more of alkane, three halides.
26. application according to claim 25, it is characterised in that: the halide is bromomethane, methylene bromide, tribromo
One or more of methane.
27. application according to claim 21, it is characterised in that: the condition of the contact include reaction temperature be 150 DEG C-
350℃；Reaction pressure is 0.1MPa-5MPa；Air speed is 50h-1-1000h-1。
28. application according to claim 27, it is characterised in that: reaction temperature is 180 DEG C -300 DEG C；Reaction pressure is
0.1MPa-3MPa；Air speed is 200h-1-500h-1。
29. application according to claim 21, it is characterised in that: including under inert atmosphere by catalyzer temperature-elevating to 300 DEG C-
600℃；Then passing to air speed is 200h-1-2000h-1Hydrogen or hydrogen and inert gas mixed gas, in 0.1MPa-
0.5MPa after handling 2h-16h, is down to reaction temperature and is passed through halide and reacted, hydrogen volume percentage in the gaseous mixture
Content is 10%-95%.
30. application according to claim 29, it is characterised in that: including under inert atmosphere by catalyzer temperature-elevating to 350 DEG C-
550℃；Then passing to air speed is 500h-1-1000h-1Hydrogen or hydrogen and inert gas mixed gas, in 0.1MPa-
After 0.3MPa handles 4h-8h, it is down to reaction temperature and is passed through halide and reacted, hydrogen volume percentage contains in the gaseous mixture
Amount is 30%-90%.
31. application according to claim 21, it is characterised in that: raw material is the gaseous mixture of halide and inert gas
Body, the volumetric concentration of halide is 10%-90% in mixed gas.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4154969A (en) * | 1977-03-24 | 1979-05-15 | Monsanto Company | Production of dihydroxydiphenyl alkanes |
| CN1502411A (en) * | 2002-11-20 | 2004-06-09 | ��Խ��ѧ��ҵ��ʽ���� | Zinc chloride-loaded support and method for producing the same |
| CN100582064C (en) * | 2006-03-20 | 2010-01-20 | 微宏科技（湖州）有限公司 | Flow process for synthesizing C3 to C13 high hydrocarbons by methane through non-synthetic gas method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4154969A (en) * | 1977-03-24 | 1979-05-15 | Monsanto Company | Production of dihydroxydiphenyl alkanes |
| CN1502411A (en) * | 2002-11-20 | 2004-06-09 | ��Խ��ѧ��ҵ��ʽ���� | Zinc chloride-loaded support and method for producing the same |
| CN100582064C (en) * | 2006-03-20 | 2010-01-20 | 微宏科技（湖州）有限公司 | Flow process for synthesizing C3 to C13 high hydrocarbons by methane through non-synthetic gas method |
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