WO2015067133A1 - 一种负载型催化剂及其制备方法和应用及卤代甲烷制异丁烯的方法 - Google Patents
一种负载型催化剂及其制备方法和应用及卤代甲烷制异丁烯的方法 Download PDFInfo
- Publication number
- WO2015067133A1 WO2015067133A1 PCT/CN2014/089683 CN2014089683W WO2015067133A1 WO 2015067133 A1 WO2015067133 A1 WO 2015067133A1 CN 2014089683 W CN2014089683 W CN 2014089683W WO 2015067133 A1 WO2015067133 A1 WO 2015067133A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- content
- zinc
- gas
- carrier
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 223
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 140
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims abstract description 136
- 238000006243 chemical reaction Methods 0.000 claims abstract description 128
- 239000011787 zinc oxide Substances 0.000 claims abstract description 70
- -1 zinc halide Chemical class 0.000 claims abstract description 42
- 239000011701 zinc Substances 0.000 claims abstract description 30
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims description 131
- 239000002253 acid Substances 0.000 claims description 89
- 230000009467 reduction Effects 0.000 claims description 85
- 229910052736 halogen Inorganic materials 0.000 claims description 64
- 150000002367 halogens Chemical class 0.000 claims description 64
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 59
- 239000001257 hydrogen Substances 0.000 claims description 56
- 229910052739 hydrogen Inorganic materials 0.000 claims description 56
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 45
- 239000012298 atmosphere Substances 0.000 claims description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000011261 inert gas Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 9
- 230000026030 halogenation Effects 0.000 claims description 9
- 238000005658 halogenation reaction Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 229940102001 zinc bromide Drugs 0.000 claims description 5
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229950005228 bromoform Drugs 0.000 claims description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 68
- 239000012018 catalyst precursor Substances 0.000 description 51
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 34
- 229940102396 methyl bromide Drugs 0.000 description 33
- 229910052757 nitrogen Inorganic materials 0.000 description 33
- 238000005470 impregnation Methods 0.000 description 25
- 239000002994 raw material Substances 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000011148 porous material Substances 0.000 description 20
- 238000001354 calcination Methods 0.000 description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 17
- 238000001035 drying Methods 0.000 description 14
- 229910052794 bromium Inorganic materials 0.000 description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 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 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 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 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- HHIFKVVLBKXWOC-UHFFFAOYSA-N methane;2-methylprop-1-ene Chemical class C.CC(C)=C HHIFKVVLBKXWOC-UHFFFAOYSA-N 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 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
- 229940050176 methyl chloride Drugs 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 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
- 238000007598 dipping method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
- C07C1/30—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms by splitting-off the elements of hydrogen halide from a single molecule
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/08—Alkenes with four carbon atoms
- C07C11/09—Isobutene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/20—Use of additives, e.g. for stabilisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/138—Compounds comprising a halogen and an alkaline earth metal, magnesium, beryllium, zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
Definitions
- the present invention relates to a supported catalyst, a process for the preparation thereof and an application thereof, and a process for producing isobutylene from a halogenated methane using the supported catalyst.
- Isobutylene is an important basic organic chemical raw material, with many derivative products, complex upstream and downstream industrial chains, and diversified consumption structure. Isobutylene can be used as a raw material to prepare a variety of high value-added products, such as butyl rubber, polyisobutylene, methyl tert-butyl ether, isoprene and organic glass, and other organic chemical raw materials and fine chemical products.
- high value-added products such as butyl rubber, polyisobutylene, methyl tert-butyl ether, isoprene and organic glass, and other organic chemical raw materials and fine chemical products.
- Methane is the main component of natural gas, so methane conversion and utilization has become an important research content in natural gas chemical technology. Especially in recent years, in the context of the development and utilization of shale gas, if the production of isobutylene from methane can be achieved, it will provide a new way to obtain isobutylene. However, methane is stable in nature and difficult to activate, which has become a bottleneck for methane chemical utilization. Many researchers at home and abroad have carried out methane activation and transformation research. Among them, the technology of methane undergoing halogen functionalization and then conversion is expected to become an important breakthrough to solve the problem of methane conversion technology.
- CN101041609A and CN101284232A disclose a method for converting methane into methyl bromide under the action of oxygen and HBr/H 2 O, and then further reacting methyl bromide to form a C3-C13 mixed high-carbon hydrocarbon, and the hydrocarbon selectivity above C5. It is 70%.
- HBr is used for bromination of methane in the first reactor, then released in the second reactor, and recovered and used in the previous step to realize the recycling of HBr.
- a modified molecular sieve catalyst for producing methyl halide from propylene and preparation thereof method.
- the molecular sieve is modified by using a fluorine-containing compound to obtain a catalyst having a suitable microporous structure and acidity, which is effective for catalyzing the conversion of methyl halide to propylene.
- the single-pass methyl bromide conversion rate of the prepared catalyst in the conversion of methyl bromide to propylene is 35 to 99%, the selectivity of propylene is 27 to 70%; and the single-pass methyl chloride conversion rate in the reaction of converting methyl chloride to propylene is 30 to 99. %, the selectivity of propylene is 15 to 70%.
- Ivan M discloses a modified molecular sieve catalyst for producing methyl halide from propylene and preparation thereof method.
- the molecular sieve is modified by using a fluorine-containing compound to obtain a catalyst having a suitable microporous structure and acidity, which is effective for cataly
- Lorkovic et al. (Ivan M. Lorkovic, Aysen Yilmaz, Gurkan A. Yilmaz, et al. Catalysis Today, 2004, 98, 317-322) also proposed the reaction of bromine with alkanes in natural gas to form bromohydrocarbons, and then The brominated hydrocarbon is converted to dimethyl ether, methanol and metal bromide on a metal oxide catalyst, and the metal bromide is regenerated with oxygen to obtain a metal oxide and release elemental bromine, thereby completing the bromine cycle.
- the target products in the prior literature on the conversion of methyl halide are mainly methanol, dimethyl ether, acetic acid, high carbon hydrocarbons, ethylene and propylene, and the like.
- the selectivity of a single product is not high, and there has been no report on the highly selective synthesis of isobutylene by methyl bromide.
- the present invention provides a supported catalyst for highly selective formation of isobutylene by methyl halide, a preparation method and application thereof.
- a supported catalyst characterized in that the catalyst comprises a carrier and a metal active component supported on a carrier, the metal active component comprising zinc oxide and zinc halide, And based on the total amount of the catalyst, the content of zinc oxide is 0.5%-20%, the content of zinc halide is 10%-50%, and the content of the carrier is 40%-88%.
- a method for producing a supported catalyst characterized in that the method comprises the steps of: introducing zinc oxide into a carrier, and then subjecting the carrier after the introduction of zinc oxide to a halogenation treatment.
- the invention provides the use of the above supported catalyst in the manufacture of isobutylene.
- a process for producing isobutylene from a halogenated methane which comprises subjecting the supported catalyst to hydrogen reduction activation such that the halogen content of the catalyst is the total halogen content of the catalyst before reduction. 20% to 90%, and then the methyl halide is contacted with the above hydrogen-reduced activated catalyst to prepare isobutylene.
- the catalyst of the present invention can convert a highly selective conversion of methyl halide to isobutylene as compared to the prior art.
- the conversion of methyl bromide to isobutene is carried out, the conversion of methyl bromide is over 90%, and the selectivity of isobutylene is more than 80%.
- the preparation method of the catalyst is simple and easy to industrialize.
- the method for converting methyl bromide to isobutylene has the advantages of mild reaction conditions and high product selectivity, and is easy to realize industrialization, and has a broad application prospect.
- a supported catalyst characterized in that the catalyst comprises a carrier and a metal active component supported on a carrier, the metal active component comprising zinc oxide and zinc halide, And based on the total amount of the catalyst, the content of zinc oxide is 0.5%-20%, the content of zinc halide is 10%-50%, and the content of the carrier is 40%-88%.
- the content of zinc oxide is 1%-15%, the content of zinc halide is 15%-45%, and the content of carrier is 50%-84%, based on the total amount of the catalyst.
- the content of zinc oxide is 1% to 9%, the content of zinc halide is 18% to 39%, and the content of the carrier is 55% to 80%.
- the zinc halide may be selected from one or more of zinc fluoride, zinc chloride, zinc bromide, and zinc iodide.
- the support may be one or more of alumina, silica, or ZSM-5 molecular sieves.
- the zinc halide is zinc bromide and the support is alumina.
- the alumina may be one or more of ⁇ -alumina and ⁇ -alumina.
- the catalyst further contains an appropriate amount of an auxiliary agent selected from one or more of Ti, Zr, Ce, and La. Further preferably, the auxiliary agent is zirconium.
- the auxiliary agent is contained in the catalyst in an amount of from 0.1% to 10% by weight, more preferably from 0.5% to 5%, still more preferably from 0.5% to 3%.
- the supported catalyst according to the present invention wherein the NH 3 -TPD method measures a total acid amount of 0.5 mmol/g to 1.3 mmol/g at 450 ° C or less, and an acid content of 250 ° C to 350 ° C as a total acid of 450 ° C or less.
- the total acid amount below 450 ° C in the catalyst is 0.6 mmol / g - 1.2 mmol / g
- the acid content of 250 ° C - 350 ° C accounts for 30% - 80 of the total acid amount below 450 ° C
- the total acid amount of the catalyst below 450 ° C is from 0.7 mmol to 1.1 mmol / g
- the acid content of from 250 ° C to 350 ° C is from 40% to 80% of the total acid amount below 450 ° C.
- the acid corresponding to 150 to 250 ° C measured by the NH 3 -TPD method is a weak acid
- the acid corresponding to 250 to 400 ° C is a medium strong acid
- the acid corresponding to 400 to 500 ° C is a strong acid
- the amount of weak acid, medium strong acid and strong acid is a strong acid
- the method comprises the steps of: introducing zinc oxide into a carrier, and then subjecting the carrier after the introduction of zinc oxide to a halogenation treatment.
- the introduction amount of zinc oxide and the conditions of the halogenation treatment are such that the content of zinc oxide is 0.5% to 20% by weight, and the content of zinc halide is 10% to 50% by weight based on the total amount of the supported catalyst.
- the content is 40%-88%.
- the content of zinc oxide is 1%-15%
- the content of zinc halide is 15%-40%
- the content of the carrier is 50%-84%
- the content of zinc oxide is 1%-9%
- the content of the zinc halide is 18% to 39%
- the content of the carrier is 55% to 80%.
- the carrier after the introduction of zinc oxide can be subjected to a halogenation treatment in various ways as long as the zinc oxide therein is appropriately converted into a zinc halide.
- the halogenation treatment comprises contacting the gas phase halogen-containing compound with a support after introducing the zinc oxide, and the contact conditions are such that the zinc oxide on the support is partially converted into a halogenation. Zinc.
- the gas phase halogen-containing compound may be directly contacted with the carrier after the introduction of the zinc oxide, or the gas phase halogen-containing compound may be contacted with the carrier after the introduction of the zinc oxide in the form of a gas mixture of a halogen-containing compound and an inert gas, and the gas phase in the mixed gas is contained.
- the concentration of the halogen compound is not less than 20% by volume, preferably not less than 30% by volume, more preferably 30 to 90% by volume, still more preferably 50 to 80% by volume.
- the gas phase halogen-containing compound may be a halogen-containing compound which is a gas under contact conditions, preferably a halogenated methane, further preferably one or more of a monohalogenated methane, a dihalogenated methane, and a trihalomethane.
- a halogenated methane preferably one or more of a monohalogenated methane, a dihalogenated methane, and a trihalomethane.
- kind. Preferred is monohalomethane.
- the halogen may be one or more of F, Cl, Br and I, preferably Cl and/or Br.
- the gas phase halogen-containing compound is monobromomethane.
- the manner of contacting preferably comprises placing the support after the introduction of zinc oxide in a continuous flow fixed bed reactor, raising the temperature to 150 ° C to 400 ° C under an inert atmosphere, introducing a halogen-containing compound in the gas phase or containing a halogen in the gas phase.
- a mixed gas of the compound a gas space velocity of 50 h -1 -1000 h -1 ; a contact pressure of 0.1 MPa - 0.5 MPa, and a time of 0.5 h - 8 h; preferably, the temperature is raised to 180 ° C - 350 ° C in an inert atmosphere, more preferably To 200 ° C -300 ° C, the gas space velocity is 100h -1 -500h -1 ; the contact pressure is 0.1MPa-0.3MPa, and the time is 1h-4h.
- the pressure is absolute.
- the airspeed is a volume airspeed.
- the manner of introducing zinc oxide into the carrier can be carried out by various methods in the prior art, for example, by impregnation, or by kneading during molding, and also by a carrier preparation process such as gelation. Introduced during precipitation. It is preferably introduced by means of impregnation, that is, a soluble compound of zinc is prepared as an immersion liquid, and then the carrier is immersed in the immersion liquid, followed by drying and baking.
- the soluble compound of zinc may be a soluble inorganic salt and/or an organic salt of zinc, such as one or more of a chloride salt, a nitrate salt, a sulfate salt, a hydrochloride salt, an acetate salt, and a citrate salt.
- concentration of the impregnation liquid is from 5 g/liter to 300 g/liter, preferably from 20 g/liter to 200 g/liter, further preferably from 40 g/liter to 160 g/liter, based on the zinc element. It can be impregnated with an equal volume or supersaturated.
- the adjuvant can be introduced before, after or simultaneously with the zinc oxide. It may be introduced by impregnation, or may be introduced by kneading during molding, or may be introduced during preparation of a carrier such as gelation or coprecipitation.
- the method is introduced by using a dipping method. The specific method is as follows: the carrier after being impregnated with a zinc salt or a metal salt solution is dried, calcined and then halogenated or the carrier after being impregnated with a zinc salt solution is dried and calcined. After halogenation treatment, finally, the auxiliary metal salt solution is impregnated, and after drying and calcination, a halogenated methane to isobutylene catalyst is obtained.
- the drying temperature may be from 50 ° C to 200 ° C, preferably from 60 ° C to 150 ° C, more preferably from 80 ° C to 120 ° C; Drying time is 1h-24h, preferably 4h-8h; drying can be vacuum drying, drying under inert gas protection conditions, and drying under air atmosphere; baking temperature is 200°C-800°C, preferably 400 °C-600 ° C; calcination time is 1h-24h, preferably 4h-8h; roasting can be calcined under inert gas protection conditions, or can be calcined under air atmosphere.
- the carrier may be an existing commercial product or may be prepared by methods well known to those skilled in the art.
- the carrier may be formed or selected in a suitable particle form, such as in the form of a strip, a sheet, a cylinder, a sphere, or the like, depending on the needs of use. Forming can be carried out according to the general knowledge in the art.
- the invention also provides the use of the above supported catalyst in the manufacture of isobutylene.
- the present invention also provides a method for producing isobutylene from a halogenated methane, the method comprising: performing hydrogen reduction activation on the supported catalyst, wherein the halogen content in the catalyst is 20%-90% of the total halogen content in the catalyst before reduction, and then The methyl halide is contacted with the above hydrogen-reduced activated catalyst to prepare isobutylene.
- the hydrogen reduction activation conditions are such that the halogen content in the catalyst is preferably from 30% to 80%, more preferably from 40% to 80%, based on the total halogen content of the catalyst before reduction.
- the hydrogen reduction methods include activation of the catalyst was heated to 300 °C -600 °C under an inert atmosphere; then purged with hydrogen gas or hydrogen gas space velocity is 200h -1 -2000h -1 in an inert
- the mixed gas of gas is maintained at 0.1 MPa-0.5 MPa for 2 h-16 h, and the volume percentage of hydrogen in the mixed gas is 10%-95%; preferably, the temperature is raised to 350 ° C - 550 ° C; then the space velocity is 500 h - 1 - 1000 h -1 of hydrogen or a mixed gas of hydrogen and an inert gas is maintained at 0.1 MPa - 0.3 MPa for 4 h - 8 h, and the volume percentage of hydrogen in the mixed gas is 30% - 90%.
- the methyl halide may be one or more of monohalomethane, dihalomethane, and trihalomethane, preferably one or more of monobromomethane, dibromomethane, and tribromomethane. .
- the conditions of the contacting include a reaction temperature of 150 ° C to 350 ° C; a reaction pressure of 0.1 MPa to 5 MPa; a space velocity of 50 h -1 to 1000 h -1 ; more preferably, the reaction temperature is 180 ° C to 300 ° C. Preferably, it is 200-270 ° C; the reaction pressure is 0.1 MPa - 3 MPa; and the space velocity is 200 h -1 - 500 h -1 .
- the method for producing isobutylene from a halogenated methane comprises heating the catalyst to 300 ° C to 600 ° C, preferably 350 ° C to 550 ° C under an inert atmosphere; and then introducing a space velocity of 200 h - 1 -2000h -1 , preferably 500h -1 -1000h -1 of hydrogen or a mixed gas of hydrogen and an inert gas, treated at 0.1MPa-0.5MPa (absolute pressure), preferably 0.1MPa-0.3MPa (absolute pressure) for 2h After 16h, preferably 4h-8h, the reaction is carried out by introducing a methyl halide to the reaction temperature.
- the volume percentage of hydrogen in the mixed gas is from 10% to 95%, preferably from 30% to 90%, more preferably from 50% to 90%.
- the raw material may also be a mixed gas of a halogenated methane and an inert gas, and the volume concentration of the methyl halide in the mixed gas is from 10% to 90%, preferably from 30% to 80%.
- the inert gas involved in the above application is a gas which does not undergo a chemical reaction under the conditions of the present invention, such as nitrogen gas, argon gas or helium gas, and is preferably nitrogen gas.
- reaction of methyl halide to isobutylene can be carried out in any existing reactor, such as a fixed bed, a fluidized bed, a fixed fluidized bed, a moving bed, a slurry bed or a fluidized bed. It is a fixed bed, fluidized bed reactor.
- the acid amount was measured by the NH 3 -TPD method, and the instrument model used was the American MICROMERITICS AutoChem 2920 chemical adsorption instrument.
- the specific measurement process was as follows: the sample was cooled at 450 ° C with helium gas for 1 hour and then cooled. To 150 ° C, a mixture of ammonia and helium gas was introduced, the volume content of ammonia was 10%, and the pulse was adsorbed five times to reach equilibrium; the helium gas was purged for 2 hours, and then the temperature was ramped at 10 ° C / min to carry out ammonia desorption to 450. °C; The desorbed ammonia was detected by TCD detector to quantitatively calculate the acidity of the catalyst surface.
- the contents of Br element and Zn element were measured by XRF (X-ray fluorescence spectrometry) method, and the instrument model was a ZSX X fluorescence spectrometer of Rigaku Corporation of Japan.
- the ZnBr 2 content was calculated from the Br element content, and the ZnO content was calculated by subtracting the Zn content in the ZnBr 2 from the total Zn content.
- the catalyst precursor ZnO/Al 2 O 3 was prepared by calcination at 600 ° C for 4 h. 5g of the catalyst precursor was placed in a continuous flow fixed bed reactor, and the catalyst precursor was treated with methyl bromide. The treatment conditions were 250 ° C, 0.2 MPa (absolute pressure), 100 h -1 , time 2 h to obtain isobutylene of methyl halide.
- Catalyst denoted as C-1.
- the weight composition of the catalyst is 27% by weight of ZnBr 2 , 6% by weight of ZnO, the total acid amount of the catalyst below 450 ° C is 0.92 mmol / g, and the acid content of 250 ° C - 350 ° C is 55.1 of the total acid amount below 450 ° C. %.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst loading is 5g
- the raw material gas is a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane is 50%, the reaction temperature is 230 ° C, the reaction pressure is 1 MPa (absolute pressure), the space velocity is 500 h -1 , and the feed gas is introduced.
- the procatalyst was activated under a hydrogen atmosphere with a reduction condition of 400 ° C, 0.2 MPa (absolute pressure), 1000 h -1 , and a reduction time of 4 h.
- the halogen content in the catalyst after reduction was 67.51% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- the catalyst precursor ZnO/Al 2 O 3 was prepared by calcination at 500 ° C for 8 h. 5 g of the catalyst precursor was placed in a continuous flow fixed bed reactor, and the catalyst precursor was treated with a mixed gas of monobromomethane and nitrogen. The volume concentration of monobromomethane was 80%, and the treatment conditions were 250 ° C, 0.3 MPa (absolute pressure), 300 h.
- a halogenated methane to isobutylene catalyst denoted as C-2.
- the weight composition of the catalyst is ZnBr 2
- the weight content of the bromine is 30%
- the weight content of ZnO is 4% by weight of the oxide
- the total acid amount of the catalyst below 450 ° C is 0.93 mmol / g
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was loaded in an amount of 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 70%, the reaction temperature was 230 ° C, the reaction pressure was 2 MPa (absolute pressure), and the space velocity was 200 h -1 .
- the catalyst is activated under a mixed atmosphere containing hydrogen.
- the volume of hydrogen in the mixed gas is 80%, the reduction conditions are 450 ° C, 0.3 MPa (absolute pressure), 800 h -1 , reduction time 4 h, catalyst after reduction.
- the halogen content in the catalyst is 53.47% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- the volume concentration of monobromomethane was 30%, and the treatment conditions were 300 ° C, 0.1 MPa (absolute pressure), 500 h. -1 , 4h, to obtain a halogenated methane to isobutylene catalyst, denoted as C-3.
- the weight composition of the catalyst is ZnBr 2 , the weight content of the bromine is 33%, the weight content of ZnO is 2% by weight of the oxide, the total acid amount of the catalyst below 450 ° C is 0.95 mmol / g, and the acid content of 250 ° C - 350 ° C. It accounts for 75.5% of the total acid amount below 450 °C.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was loaded in an amount of 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 80%, the reaction temperature was 200 ° C, the reaction pressure was 3 MPa (absolute pressure), and the space velocity was 350 h -1 .
- the catalyst is activated in a mixed atmosphere containing hydrogen.
- the volume of hydrogen in the mixed gas is 50%, the reduction conditions are 500 ° C, 0.1 MPa (absolute pressure), 500 h -1 , reduction time 4 h, catalyst after reduction.
- the halogen content in the catalyst was 47.22% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- the catalyst precursor ZnO/Al 2 O 3 was prepared by calcination at 500 ° C for 8 h. 5 g of the catalyst precursor was placed in a continuous flow fixed bed reactor, and the catalyst precursor was treated with methyl bromide at a treatment condition of 200 ° C, 0.3 MPa (absolute pressure), 300 h -1 , and 1 h to obtain an isobutylene of methyl halide.
- Catalyst denoted as C-4.
- the weight composition of the catalyst is ZnBr 2 , the weight content of the bromine is 18% by weight, the weight content of ZnO is 2% by weight of the oxide, the total acid amount of the catalyst below 450 ° C is 0.72 mmol / g, and the acid content of 250 ° C - 350 ° C. It accounts for 66.8% of the total acid amount below 450 °C.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was loaded in an amount of 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 30%, the reaction temperature was 270 ° C, the reaction pressure was 2 MPa (absolute pressure), and the space velocity was 350 h -1 .
- the catalyst is activated under a mixed atmosphere containing hydrogen.
- the volume of hydrogen in the mixed gas is 70%, the reduction conditions are 350 ° C, 0.3 MPa (absolute pressure), 800 h -1 , reduction time 6 h, catalyst after reduction.
- the halogen content in the catalyst was 57.81% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- the catalyst precursor ZnO/Al 2 O 3 was prepared by calcination at 500 ° C for 6 h under nitrogen atmosphere. 5 g of the catalyst precursor was placed in a continuous flow fixed bed reactor, and the catalyst precursor was treated with a mixed gas of monobromomethane and nitrogen. The volume concentration of monobromomethane was 70%, and the treatment conditions were 200 ° C, 0.3 MPa (absolute pressure), 300 h.
- a catalyst for the formation of isobutylene from methyl halide was recorded as C-5.
- the weight composition of the catalyst is ZnBr 2
- the weight content of the bromine is 39% by weight
- the weight content of ZnO is 6% by weight of the oxide
- the total acid amount of the catalyst below 450 ° C is 0.98 mmol / g
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was charged in 5 g, the raw material gas was monobromomethane, the reaction temperature was 270 ° C, the reaction pressure was 2 MPa (absolute pressure), and the space velocity was 350 h -1 .
- the catalyst is activated under a mixed atmosphere containing hydrogen, the volume content of hydrogen in the mixed gas is 60%, the reduction condition is 550 ° C, 0.3 MPa (absolute pressure), 800 h -1 , reduction time 8 h, catalyst after reduction
- the halogen content in the catalyst is 41.37% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- the catalyst precursor ZnO/Al 2 O 3 was prepared by drying in an atmosphere for 4 h and calcination at 500 ° C for 4 h in a nitrogen atmosphere.
- the catalyst precursor was placed in a continuous flow fixed bed reactor, and the catalyst precursor was treated with methyl bromide at a treatment condition of 250 ° C, 0.2 MPa (absolute pressure), 100 h -1 , and 1 h, denoted as C-6.
- the weight composition of the catalyst is ZnBr 2 , the weight content of the bromine is 35%, the weight content of ZnO is 9% by weight of the oxide, the total acid amount of the catalyst below 450 ° C is 0.94 mmol / g, and the acid content of 250 ° C - 350 ° C. It accounts for 57.3% of the total acid amount below 450 °C.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was charged in 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 50%, the reaction temperature was 230 ° C, the reaction pressure was 0.1 MPa (absolute pressure), and the space velocity was 500 h -1 .
- the catalyst is activated under a mixed atmosphere containing hydrogen.
- the volume of hydrogen in the mixed gas is 80%, the reduction condition is 450 ° C, 0.2 MPa (absolute pressure), 1000 h -1 , reduction time 4 h, catalyst after reduction
- the halogen content in the catalyst is 58.39% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- the catalyst precursor ZnO/Al 2 O 3 was prepared by calcination at 500 ° C for 4 h. 5 g of the catalyst precursor was placed in a continuous flow fixed bed reactor, and the catalyst precursor was treated with a mixed gas of monobromomethane and nitrogen. The volume concentration of monobromomethane was 90%, and the treatment conditions were 300 ° C, 0.1 MPa (absolute pressure), 500 h.
- a halogenated methane to isobutylene catalyst denoted as C-7.
- the weight composition of the catalyst is ZnBr 2 , the weight content of the bromine is 20% by weight, the weight content of ZnO is 1% by weight of the oxide, the total acid amount of the catalyst below 450 ° C is 0.79 mmol / g, and the acid content of 250 ° C - 350 ° C. It accounts for 74.9% of the total acid amount below 450 °C.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was loaded in an amount of 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 80%, the reaction temperature was 200 ° C, the reaction pressure was 3 MPa (absolute pressure), and the space velocity was 350 h -1 .
- the catalyst is activated under a mixed atmosphere containing hydrogen.
- the volume of hydrogen in the mixed gas is 90%, the reduction conditions are 500 ° C, 0.1 MPa (absolute pressure), 500 h -1 , reduction time 6 h, catalyst after reduction.
- the halogen content in the catalyst was 51.94% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- the catalyst precursor ZnO-Zr/Al 2 O 3 was prepared by drying at 120 ° C for 4 h and calcination at 500 ° C for 4 h. 5 g of the catalyst precursor was placed in a continuous flow fixed bed reactor, and the catalyst precursor was treated with a mixed gas of monobromomethane and nitrogen.
- the volume concentration of monobromomethane was 80%, and the treatment conditions were 250 ° C, 0.3 MPa (absolute pressure), 300 h. -1 , time 2h, to obtain a halogenated methane to isobutylene catalyst, denoted as C-8.
- the weight composition of the catalyst is ZnBr 2 in terms of bromide, the weight content is 30%, the ZnO is 4% by weight of the oxide, the Zr is 2% by weight of the element, and the total acid amount of the catalyst below 450 ° C is 0.97 mmol / g, the acid content of 250 ° C - 350 ° C accounted for 69.7% of the total acid amount below 450 ° C.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was loaded in an amount of 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 70%, the reaction temperature was 230 ° C, the reaction pressure was 2 MPa (absolute pressure), and the space velocity was 200 h -1 .
- the catalyst is activated under a mixed atmosphere containing hydrogen.
- the volume of hydrogen in the mixed gas is 80%, the reduction conditions are 450 ° C, 0.3 MPa (absolute pressure), 800 h -1 , reduction time 4 h, catalyst after reduction.
- the halogen content in the catalyst was 39.14% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- the catalyst precursor ZnO-Ce/Al 2 O 3 was prepared by drying at 120 ° C for 4 h and calcination at 500 ° C for 4 h. 5 g of the catalyst precursor was placed in a continuous flow fixed bed reactor, and the catalyst precursor was treated with a mixed gas of monobromomethane and nitrogen.
- the volume concentration of monobromomethane was 80%, and the treatment conditions were 250 ° C, 0.3 MPa (absolute pressure), 300 h. -1 , time 2h, to obtain a halogenated methane isobutene catalyst, denoted as C-9.
- the weight composition of the catalyst is ZnBr 2 in terms of bromide, the weight content is 30%, the ZnO is 4% by weight based on the oxide, the Ce content is 1% by weight, and the total acid amount in the catalyst below 450 ° C is 0.91 mmol / g, the acid content of 250 ° C - 350 ° C accounted for 68.9% of the total acid amount below 450 ° C.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was loaded in an amount of 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 70%, the reaction temperature was 230 ° C, the reaction pressure was 2 MPa (absolute pressure), and the space velocity was 200 h -1 .
- the catalyst is activated under a mixed atmosphere containing hydrogen.
- the volume of hydrogen in the mixed gas is 80%, the reduction conditions are 450 ° C, 0.3 MPa (absolute pressure), 800 h -1 , reduction time 4 h, catalyst after reduction.
- the halogen content in the catalyst is 63.73% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed.
- the reaction results are shown in Table 1.
- the catalyst precursor ZnO-La/Al 2 O 3 was prepared by drying at 120 ° C for 4 h and calcination at 500 ° C for 4 h. 5 g of the catalyst precursor was placed in a continuous flow fixed bed reactor, and the catalyst precursor was treated with a mixed gas of monobromomethane and nitrogen.
- the volume concentration of monobromomethane was 80%, and the treatment conditions were 250 ° C, 0.3 MPa (absolute pressure), 300 h. -1 , time 2h, to obtain a halogenated methane to isobutylene catalyst, denoted as C-10.
- the weight composition of the catalyst is ZnBr 2 in terms of bromide, the weight content is 30%, the ZnO is 4% by weight of the oxide, the La content is 0.5% by weight, and the total acid amount in the catalyst below 450 ° C is 0.87 mmol / g, the acid content of 250 ° C - 350 ° C accounted for 65.3% of the total acid amount below 450 ° C.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was loaded in an amount of 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 70%, the reaction temperature was 230 ° C, the reaction pressure was 2 MPa (absolute pressure), and the space velocity was 200 h -1 .
- the catalyst is activated under a mixed atmosphere containing hydrogen.
- the volume of hydrogen in the mixed gas is 80%, the reduction conditions are 450 ° C, 0.3 MPa (absolute pressure), 800 h -1 , reduction time 4 h, catalyst after reduction.
- the halogen content in the catalyst is 62.72% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- the catalyst precursor ZnO-Ti/Al 2 O 3 was prepared by drying at 120 ° C for 4 h and calcination at 500 ° C for 4 h. 5 g of the catalyst precursor was placed in a continuous flow fixed bed reactor, and the catalyst precursor was treated with a mixed gas of monobromomethane and nitrogen.
- the volume concentration of monobromomethane was 80%, and the treatment conditions were 250 ° C, 0.3 MPa (absolute pressure), 300 h. -1 , time 2h, to obtain a halogenated methane isobutene catalyst, denoted as C-11.
- the weight composition of the catalyst is ZnBr 2 in terms of bromide, the weight content is 30%, the ZnO is 4% by weight of the oxide, the Ti content is 3% by weight, and the total acid amount of the catalyst below 450 ° C is 0.96 mmol / g, the acid content of 250 ° C - 350 ° C accounted for 63.4% of the total acid amount below 450 ° C.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was loaded in an amount of 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 70%, the reaction temperature was 230 ° C, the reaction pressure was 2 MPa (absolute pressure), and the space velocity was 200 h -1 .
- the catalyst is activated under a mixed atmosphere containing hydrogen.
- the volume of hydrogen in the mixed gas is 80%, the reduction conditions are 450 ° C, 0.3 MPa (absolute pressure), 800 h -1 , reduction time 4 h, catalyst after reduction.
- the halogen content in the catalyst was 53.62% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- the catalyst precursor ZnO/Al 2 O 3 was prepared by drying for 4 h and calcination at 500 ° C for 4 h. 5 g of the catalyst precursor was placed in a continuous flow fixed bed reactor, and the catalyst precursor was treated with a mixed gas of monobromomethane and nitrogen. The volume concentration of monobromomethane was 80%, and the treatment conditions were 250 ° C, 0.3 MPa (absolute pressure), 300 h.
- a halogenated methane to isobutylene catalyst denoted as C-12.
- the weight composition of the catalyst is ZnBr 2 , the weight content of the bromine is 30%, the weight content of ZnO is 4% by weight of the oxide, the total acid amount of the catalyst below 450 ° C is 0.87 mmol / g, and the acid content of 250 ° C - 350 ° C. It accounts for 65.7% of the total acid amount below 450 °C.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was loaded in an amount of 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 70%, the reaction temperature was 230 ° C, the reaction pressure was 2 MPa (absolute pressure), and the space velocity was 200 h -1 .
- the catalyst is activated under a mixed atmosphere containing hydrogen.
- the volume of hydrogen in the mixed gas is 80%, the reduction conditions are 450 ° C, 0.3 MPa (absolute pressure), 800 h -1 , reduction time 4 h, catalyst after reduction.
- the halogen content in the catalyst is 47.89% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- the catalyst precursor ZnO/SiO 2 was prepared by calcination at 500 ° C for 4 h. 5 g of the catalyst precursor was placed in a continuous flow fixed bed reactor, and the catalyst precursor was treated with a mixed gas of monobromomethane and nitrogen. The volume concentration of monobromomethane was 80%, and the treatment conditions were 250 ° C, 0.3 MPa (absolute pressure), 300 h.
- a halogenated methane to isobutylene catalyst denoted as C-13.
- the weight composition of the catalyst is ZnBr 2 , the weight content of the bromine is 30%, the weight content of ZnO is 4% by weight of the oxide, the total acid amount of the catalyst below 450 ° C is 1.08 mmol / g, and the acid content of 250 ° C - 350 ° C. It accounts for 49.7% of the total acid amount below 450 °C.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was loaded in an amount of 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 70%, the reaction temperature was 230 ° C, the reaction pressure was 2 MPa (absolute pressure), and the space velocity was 200 h -1 .
- the catalyst is activated under a mixed atmosphere containing hydrogen.
- the volume of hydrogen in the mixed gas is 80%, the reduction condition is 400 ° C, 0.3 MPa (absolute pressure), 800 h -1 , reduction time 4 h, catalyst after reduction
- the halogen content in the catalyst is 31.28% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- the volume concentration of monobromomethane was 80%, and the treatment conditions were 250 ° C, 0.3 MPa (absolute pressure), 300 h. -1 , time 2h, to obtain a halogenated methane to isobutylene catalyst, denoted as C-14.
- the weight composition of the catalyst is ZnBr 2 , the weight content of the bromine is 30%, the weight content of ZnO is 4% by weight of the oxide, the total acid amount of the catalyst below 450 ° C is 0.74 mmol / g, and the acid content of 250 ° C - 350 ° C. It accounts for 48.7% of the total acid amount below 450 °C.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was loaded in an amount of 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 70%, the reaction temperature was 230 ° C, the reaction pressure was 2 MPa (absolute pressure), and the space velocity was 200 h -1 .
- the catalyst is activated under a mixed atmosphere containing hydrogen.
- the volume of hydrogen in the mixed gas is 80%, the reduction condition is 400 ° C, 0.3 MPa (absolute pressure), 800 h -1 , reduction time 4 h, catalyst after reduction
- the halogen content in the catalyst is 79.73% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- the catalyst precursor ZnO/Al 2 O 3 was prepared by calcination at 500 ° C for 4 h. 5 g of the catalyst precursor was placed in a continuous flow fixed bed reactor, and the catalyst precursor was treated with a mixed gas of monobromomethane and nitrogen. The volume concentration of monobromomethane was 80%, and the treatment conditions were 250 ° C, 0.3 MPa (absolute pressure), 300 h.
- the weight composition of the catalyst is ZnBr 2 in terms of bromide, the weight content is 30%, the ZnO is 4% by weight of the oxide, the Zr is 1% by weight of the element, and the total acid amount of the catalyst below 450 ° C is 0.72 mmol / g, the acid content of 250 ° C - 350 ° C accounted for 71.4% of the total acid amount below 450 ° C.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was loaded in an amount of 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 70%, the reaction temperature was 230 ° C, the reaction pressure was 2 MPa (absolute pressure), and the space velocity was 200 h -1 .
- the catalyst is activated under a mixed atmosphere containing hydrogen.
- the volume of hydrogen in the mixed gas is 80%, the reduction conditions are 450 ° C, 0.3 MPa (absolute pressure), 800 h -1 , reduction time 4 h, catalyst after reduction.
- the halogen content in the catalyst is 42.57% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- the catalyst precursor ZnO/Al 2 O 3 was prepared by calcination at 500 ° C for 4 h. 5 g of the catalyst precursor was placed in a continuous flow fixed bed reactor, and the catalyst precursor was treated with a mixed gas of monobromomethane and nitrogen. The volume concentration of monobromomethane was 80%, and the treatment conditions were 250 ° C, 0.3 MPa (absolute pressure), 300 h.
- the weight composition of the catalyst is ZnBr 2 in terms of bromide, the weight content is 30%, the ZnO is 4% by weight based on the oxide, the Ce content is 0.5% by weight, and the total acid amount in the catalyst below 450 ° C is 0.81 mmol / g, the acid content of 250 ° C - 350 ° C accounted for 69.3% of the total acid amount below 450 ° C.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was loaded in an amount of 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 70%, the reaction temperature was 230 ° C, the reaction pressure was 2 MPa (absolute pressure), and the space velocity was 200 h -1 .
- the catalyst is activated under a mixed atmosphere containing hydrogen.
- the volume of hydrogen in the mixed gas is 80%, the reduction conditions are 450 ° C, 0.3 MPa (absolute pressure), 500 h -1 , reduction time 6 h, catalyst after reduction.
- the halogen content in the catalyst is 65.49% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- a supported catalyst was prepared according to the method of Example 16 and a reaction of methyl bromide to isobutylene was carried out, except that alumina having a pore volume of 0.51 ml/g, a specific surface area of 162.4 m 2 /g, a strip shape and an equivalent diameter of 1 mm was used.
- the carrier was used to prepare an isobutylene catalyst made of methyl halide, which was designated as C-17.
- the total acid amount of the catalyst obtained at 450 ° C or lower was 0.72 mmol / g, and the acid content at 250 ° C - 350 ° C accounted for 70.5% of the total acid amount below 450 ° C.
- the halogen content in the catalyst after reduction activation is 72.57% of the total halogen content in the catalyst before reduction.
- the catalyst properties and reaction results are shown in Table 1.
- the supported catalyst was prepared in the same manner as in Example 16 except that methyl bromide was replaced with methylene chloride in the same molar amount of dichloromethane.
- the conversion of methylene chloride was 97.4%, and the selectivity of isobutylene. It is 67.9%.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was loaded in an amount of 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 30%, the reaction temperature was 270 ° C, the reaction pressure was 2 MPa (absolute pressure), and the space velocity was 350 h -1 .
- the catalyst is activated under a mixed atmosphere containing hydrogen.
- the volume of oxygen in the mixed gas is 70%, the reduction conditions are 350 ° C, 0.3 MPa (absolute pressure), 800 h -1 , and the reduction time is 6 h.
- the sample was analyzed. The reaction results are shown in Table 1.
- the catalyst precursor ZnO/Al 2 O 3 was prepared by calcination at 500 ° C for 8 h. 5 g of the catalyst precursor was placed in a continuous flow fixed bed reactor, and the catalyst precursor was treated with a mixed gas of monobromomethane and nitrogen. The volume concentration of monobromomethane was 80%, and the treatment conditions were 250 ° C, 0.3 MPa (absolute pressure), 300 h.
- a halogenated methane to isobutylene catalyst denoted as D-2.
- the weight composition of the catalyst is ZnBr 2 , the weight content of the bromine is 30%, the weight content of ZnO is 4% by weight of the oxide, the total acid amount of the catalyst below 450 ° C is 0.93 mmol / g, and the acid content of 250 ° C - 350 ° C. It accounts for 63.2% of the total acid amount below 450 °C.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was loaded in an amount of 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 70%, the reaction temperature was 230 ° C, the reaction pressure was 2 MPa (absolute pressure), and the space velocity was 200 h -1 . After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- the weight composition of the catalyst was obtained as ZnBr 2 in an amount of 30% by weight based on the bromide, the total acid amount in the catalyst below 450 ° C was 1.01 mmol/g, and the acid content in the range of 250 ° C to 350 ° C was 74.3% of the total acid amount below 450 ° C.
- the conversion of methyl bromide to isobutene is carried out in a continuous flow micro fixed bed reactor.
- the catalyst was loaded in an amount of 5 g, and the raw material gas was a mixed gas of monobromomethane and nitrogen, wherein the volume of monobromomethane was 70%, the reaction temperature was 230 ° C, the reaction pressure was 2 MPa (absolute pressure), and the space velocity was 200 h -1 .
- the catalyst is activated under a mixed atmosphere containing hydrogen.
- the volume of hydrogen in the mixed gas is 80%, the reduction conditions are 450 ° C, 0.3 MPa (absolute pressure), 800 h -1 , reduction time 4 h, catalyst after reduction.
- the halogen content in the catalyst is 91.27% of the total halogen content in the catalyst before reduction. After the reaction was stable for one hour, the sample was analyzed. The reaction results are shown in Table 1.
- the catalyst of the present invention has significantly higher methyl bromide conversion and isobutane selectivity.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims (19)
- 一种负载型催化剂,其特征在于:该催化剂含有载体和负载在载体上的金属活性组分,所述金属活性组分含有氧化锌和卤化锌,且以催化剂的总量为基准,按重量含量计,氧化锌的含量为0.5%-20%,卤化锌的含量为10%-50%,载体的含量为40%-88%。
- 根据权利要求1所述的负载型催化剂,其中,以催化剂的总量为基准,按重量含量计,氧化锌的含量为1%-15%,卤化锌的含量为15%-40%,载体的含量为50%-84%,优选地,氧化锌的含量为1%-9%,卤化锌的含量为18%-39%,载体的含量为55%-80%。
- 根据权利要求1或2所述的负载型催化剂,其中,所述卤化锌选自氟化锌、氯化锌、溴化锌、碘化锌中的一种或几种,所述载体为氧化铝、氧化硅、ZSM-5分子筛中的一种或几种;优选地,所述卤化锌为溴化锌,所述载体为氧化铝。
- 根据权利要求1-3中任意一项所述的负载型催化剂,其中,该催化剂还含有助剂,所述助剂选自Ti、Zr、Ce、La中的一种或几种,助剂以元素计在催化剂中的重量含量为0.1%-10%。
- 根据权利要求4所述的负载型催化剂,其中,所述助剂为锆,助剂以元素计在催化剂中的重量含量为0.5%-5%。
- 根据权利要求1-5中任意一项所述的负载型催化剂,其中,NH3-TPD方法测得催化剂中450℃以下总酸量为0.5mmol/g-1.3mmol/g,250℃-350℃的酸含量占450℃以下总酸量的20%-90%;优选地,催化剂中450℃以下总酸量为0.6mmol/g-1.2mmol/g,250℃-350℃的酸含量占450℃以下总酸量的30%-80%;进一步优选地,催化剂中450℃以下总酸量为0.7mmol-1.1mmol/g,250℃-350℃的酸含量占450℃以下总酸量的40%-80%。
- 一种负载型催化剂的制备方法,其特征在于:该方法包括如下步骤:将氧化锌引入至载体,然后对引入氧化锌后的载体进行卤化处理。
- 根据权利要求7所述的方法,其中,所述卤化处理的方式包括将气相含卤素化合物与引入氧化锌后的载体接触,接触的条件使得载体上的氧化锌部分地转化为卤化锌。
- 根据权利要求7或8所述的方法,其中,氧化锌的用量使得以所得负载型催化剂的总量为基准,按重量含量计,载体的含量为40%-88%,接触的条件使得载体上的氧化锌的含量为0.5%-20%,卤化锌的含量为10%-50%。
- 根据权利要求9所述的方法,其中,以气相含卤素化合物与惰性气体的混合气 体的形式使气相含卤素化合物与引入氧化锌后的载体接触,混合气体中气相含卤素化合物浓度不小于20体积%。
- 根据权利要求10所述的方法,其中,所述气相含卤素化合物为一卤代甲烷、二卤代甲烷、三卤代甲烷中的一种或多种。
- 根据权利要求10或11所述的方法,其中,所述接触的方式包括将引入氧化锌后的载体置于连续流动固定床反应器中,惰性气氛下升温至150℃-400℃,通入气相含卤素化合物或者含有气相含卤素化合物的混合气体,气体空速为50h-1-1000h-1;接触的压力为0.1MPa-0.5MPa,时间为0.5h-8h;优选地,惰性气氛下升温至180℃-350℃,气体空速为100h-1-500h-1;接触的压力为0.1MPa-0.3MPa,时间为1h-4h。
- 权利要求1-6中任意一项所述的负载型催化剂在制异丁烯中的应用。
- 一种卤代甲烷制异丁烯的方法,该方法包括对权利要求1-6中任意一项所述的负载型催化剂进行氢气还原活化,使催化剂中的卤素含量为还原前催化剂中卤素总含量的20%-90%,然后使卤代甲烷与上述氢气还原活化后的催化剂接触,以制备异丁烯。
- 根据权利要求14所述的方法,其中,所述接触的条件包括反应温度为150℃-350℃;反应压力为0.1MPa-5MPa;空速为50h-1-1000h-1;优选地,反应温度为180℃-300℃;反应压力为0.1MPa-3MPa;空速为200h-1-500h-1。
- 根据权利要求14所述的方法,其中,氢气还原活化的条件使得催化剂中的卤素含量为还原前催化剂中卤素总含量的30%-80%。
- 根据权利要求14-16中任意一项所述的方法,其中,所述氢气还原活化的方式包括在惰性气氛下将催化剂升温至300℃-600℃;然后通入空速为200h-1-2000h-1的氢气或氢气与惰性气体的混合气体,在0.1MPa-0.5MPa保持2h-16h,混合气体中氢气体积百分含量为10%-95%;优选地,升温至350℃-550℃;然后通入空速为500h-1-1000h-1的氢气或氢气与惰性气体的混合气体,在0.1MPa-0.3MPa保持4h-8h,所述混合气体中氢气体积百分含量为30%-90%。
- 根据权利要求14-17中任意一项所述的方法,其中,卤代甲烷为一卤代甲烷、二卤代甲烷、三卤代甲烷中的一种或多种,优选为一溴甲烷、二溴甲烷、三溴甲烷中的一种或多种。
- 根据权利要求14-18中任意一项所述的方法,其中,所述接触在固定床、流化床、固定流化床、移动床、浆态床或沸腾床反应器中进行。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP14859617.4A EP3056269B1 (en) | 2013-11-07 | 2014-10-28 | Supported catalyst, preparation method therefor and use thereof, and method for preparation of isobutylene from halomethane |
KR1020167014981A KR101840772B1 (ko) | 2013-11-07 | 2014-10-28 | 담지 촉매, 이의 제조 방법 및 용도, 및 할로메탄으로부터 이소부틸렌의 제조 방법 |
DK14859617.4T DK3056269T3 (da) | 2013-11-07 | 2014-10-28 | Båret katalysator, fremgangsmåde til fremstilling og anvendelse deraf, og fremgangsmåde til fremstilling af isobutylen fra halogeneret methan |
JP2016552658A JP6268305B2 (ja) | 2013-11-07 | 2014-10-28 | 担持触媒、その製造方法およびその使用、ならびにハロメタンからイソブチレンの製造方法 |
US15/034,913 US10087122B2 (en) | 2013-11-07 | 2014-10-28 | Supported catalyst, preparation method therefor and use thereof, and method for preparation of isobutylene from halomethane |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310546339 | 2013-11-07 | ||
CN201310546339.7 | 2013-11-07 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2015067133A1 true WO2015067133A1 (zh) | 2015-05-14 |
WO2015067133A8 WO2015067133A8 (zh) | 2016-06-16 |
Family
ID=53040890
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2014/089683 WO2015067133A1 (zh) | 2013-11-07 | 2014-10-28 | 一种负载型催化剂及其制备方法和应用及卤代甲烷制异丁烯的方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US10087122B2 (zh) |
EP (1) | EP3056269B1 (zh) |
JP (1) | JP6268305B2 (zh) |
KR (1) | KR101840772B1 (zh) |
CN (1) | CN104624210B (zh) |
DK (1) | DK3056269T3 (zh) |
WO (1) | WO2015067133A1 (zh) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108067263B (zh) * | 2016-11-11 | 2020-09-11 | 中国石油化工股份有限公司抚顺石油化工研究院 | 一种具有壳核结构的催化剂及其制备方法和应用 |
CN108067286B (zh) * | 2016-11-11 | 2020-09-11 | 中国石油化工股份有限公司抚顺石油化工研究院 | 一种甲烷卤氧化催化剂及其制备方法和应用 |
CN108067262B (zh) * | 2016-11-11 | 2020-09-11 | 中国石油化工股份有限公司抚顺石油化工研究院 | 一种高选择性甲烷卤氧化催化剂的制备方法 |
CN108067298B (zh) * | 2016-11-11 | 2020-06-09 | 中国石油化工股份有限公司抚顺石油化工研究院 | 一种制备卤代甲烷催化剂及其制备方法和应用 |
CN108067264B (zh) * | 2016-11-11 | 2020-09-11 | 中国石油化工股份有限公司抚顺石油化工研究院 | 一种甲烷转化催化剂及其制备方法和应用 |
CN108067260B (zh) * | 2016-11-11 | 2020-08-11 | 中国石油化工股份有限公司抚顺石油化工研究院 | 一种用于甲烷卤氧化的核壳型催化剂的制备方法 |
CN108067258B (zh) * | 2016-11-11 | 2020-08-11 | 中国石油化工股份有限公司抚顺石油化工研究院 | 一种甲烷卤氧化催化剂的制备方法 |
CN108067259B (zh) * | 2016-11-11 | 2020-06-09 | 中国石油化工股份有限公司抚顺石油化工研究院 | 一种高活性甲烷卤氧化催化剂的制备方法 |
CN108067265B (zh) * | 2016-11-11 | 2020-09-11 | 中国石油化工股份有限公司抚顺石油化工研究院 | 一种甲烷转化催化剂的制备方法 |
CN108067266B (zh) * | 2016-11-11 | 2020-09-11 | 中国石油化工股份有限公司抚顺石油化工研究院 | 一种核壳型催化剂及其制备方法和应用 |
US11865515B2 (en) * | 2021-12-06 | 2024-01-09 | ExxonMobil Technology and Engineering Company | Catalyst for olefins generation |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4154969A (en) * | 1977-03-24 | 1979-05-15 | Monsanto Company | Production of dihydroxydiphenyl alkanes |
CN86107833A (zh) * | 1986-11-17 | 1988-07-20 | 吉林省化学纤维技术研究所 | 合成醋酸乙烯用氧化锌催化剂 |
CN1502411A (zh) * | 2002-11-20 | 2004-06-09 | ��Խ��ѧ��ҵ��ʽ���� | 载氯化锌支持物及其生产方法 |
CN101041609A (zh) | 2006-03-20 | 2007-09-26 | 微宏科技(湖州)有限公司 | 从甲烷经过非合成气方法合成碳三至碳十三高碳烃的流程 |
CN101284232A (zh) | 2007-04-13 | 2008-10-15 | 微宏科技(湖州)有限公司 | 甲烷溴氧化制溴甲烷及其转化制碳氢化合物的催化剂 |
CN101342494A (zh) * | 2008-08-28 | 2009-01-14 | 复旦大学 | 一种二氧化碳气氛下丙烷脱氢制丙烯催化剂的制备方法及其应用 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2865845A (en) * | 1953-06-15 | 1958-12-23 | Exxon Research Engineering Co | Hydroforming catalyst promoted by the addition of a zinc halide |
US4091038A (en) * | 1977-03-24 | 1978-05-23 | Monsanto Company | Production of dihydroxydiphenyl alkanes |
JPS60115536A (ja) * | 1983-11-29 | 1985-06-22 | Showa Denko Kk | フルオロメタンの製造方法 |
JPH0819012B2 (ja) * | 1986-07-14 | 1996-02-28 | 旭化成工業株式会社 | シクロオレフインの製造方法 |
JPH07106991B2 (ja) * | 1986-07-14 | 1995-11-15 | 旭化成工業株式会社 | 部分水素化方法 |
JPH0816073B2 (ja) * | 1986-10-02 | 1996-02-21 | 旭化成工業株式会社 | シクロオレフインを製造する方法 |
GB9212410D0 (en) * | 1992-06-11 | 1992-07-22 | Ici Plc | Production of difluoromethane |
US5811365A (en) * | 1992-12-04 | 1998-09-22 | The British Petroleum Company, P.L.C. | Zinc oxide composition for use in catalysts |
WO1999006342A1 (en) * | 1997-07-31 | 1999-02-11 | Imperial Chemical Industries Plc | Vapour phase preparation of 1,1,1,2,3,3,3-heptafluoropropane |
JPH11188703A (ja) * | 1997-12-26 | 1999-07-13 | Showa Denko Kk | 多孔質物品処理物及びその製造方法 |
WO2001015805A1 (fr) * | 1999-08-30 | 2001-03-08 | Cosmo Oil Co., Ltd. | Catalyseur destine a l'hydrotraitement du gas-oil, et procede d'hydrotraitement du gas-oil |
EP1551785A4 (en) * | 2002-10-16 | 2006-04-05 | Conocophillips Co | STABILIZED MOUNTAIN ALUMINUM OXIDE CATALYST CARRIERS AS BOEHMIT AND CATALYSTS MANUFACTURED THEREOF |
US20090163749A1 (en) * | 2006-03-20 | 2009-06-25 | Microvast Technologies, Ltd. | Conversion of methane into c3˜c13 hydrocarbons |
-
2014
- 2014-10-28 JP JP2016552658A patent/JP6268305B2/ja active Active
- 2014-10-28 EP EP14859617.4A patent/EP3056269B1/en active Active
- 2014-10-28 WO PCT/CN2014/089683 patent/WO2015067133A1/zh active Application Filing
- 2014-10-28 KR KR1020167014981A patent/KR101840772B1/ko active IP Right Grant
- 2014-10-28 DK DK14859617.4T patent/DK3056269T3/da active
- 2014-10-28 CN CN201410581306.0A patent/CN104624210B/zh active Active
- 2014-10-28 US US15/034,913 patent/US10087122B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4154969A (en) * | 1977-03-24 | 1979-05-15 | Monsanto Company | Production of dihydroxydiphenyl alkanes |
CN86107833A (zh) * | 1986-11-17 | 1988-07-20 | 吉林省化学纤维技术研究所 | 合成醋酸乙烯用氧化锌催化剂 |
CN1502411A (zh) * | 2002-11-20 | 2004-06-09 | ��Խ��ѧ��ҵ��ʽ���� | 载氯化锌支持物及其生产方法 |
CN101041609A (zh) | 2006-03-20 | 2007-09-26 | 微宏科技(湖州)有限公司 | 从甲烷经过非合成气方法合成碳三至碳十三高碳烃的流程 |
CN101284232A (zh) | 2007-04-13 | 2008-10-15 | 微宏科技(湖州)有限公司 | 甲烷溴氧化制溴甲烷及其转化制碳氢化合物的催化剂 |
CN101342494A (zh) * | 2008-08-28 | 2009-01-14 | 复旦大学 | 一种二氧化碳气氛下丙烷脱氢制丙烯催化剂的制备方法及其应用 |
Non-Patent Citations (3)
Title |
---|
IVAN M. LORKOVIC; AYSEN YILMAZ; GURKAN A. YILMAZ ET AL., CATALYSIS TODAY, vol. 98, 2004, pages 317 - 322 |
JIELI HE; TING XU; ZHIHUI WANG, ANGEW. CHEM. INT. ED., vol. 51, 2012, pages 2438 - 2442 |
See also references of EP3056269A4 |
Also Published As
Publication number | Publication date |
---|---|
JP2016538131A (ja) | 2016-12-08 |
JP6268305B2 (ja) | 2018-01-24 |
EP3056269A1 (en) | 2016-08-17 |
DK3056269T3 (da) | 2019-07-22 |
WO2015067133A8 (zh) | 2016-06-16 |
US20160272555A1 (en) | 2016-09-22 |
EP3056269B1 (en) | 2019-04-24 |
US10087122B2 (en) | 2018-10-02 |
KR20160083925A (ko) | 2016-07-12 |
KR101840772B1 (ko) | 2018-03-21 |
CN104624210A (zh) | 2015-05-20 |
CN104624210B (zh) | 2017-07-28 |
EP3056269A4 (en) | 2017-07-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2015067133A1 (zh) | 一种负载型催化剂及其制备方法和应用及卤代甲烷制异丁烯的方法 | |
CN106140262A (zh) | 一种负载型催化剂及其制备方法和应用 | |
CN106140264A (zh) | 一种以镧改性zsm-5分子筛为载体的催化剂及其制备方法和应用 | |
CN106140218A (zh) | 一种具有介孔结构的负载型催化剂及其制备方法和应用 | |
CN106140263A (zh) | 一种以改性zsm-5为载体的溴甲烷制异丁烯催化剂及其制备方法 | |
CN106140260B (zh) | 一种以二氧化硅改性zsm-5分子筛为载体的催化剂及其制备方法和应用 | |
CN106140259A (zh) | 一种以改性zsm-5分子筛为载体的负载型催化剂及其制备方法和应用 | |
CN109908930B (zh) | 一种费托合成催化剂及其制备方法 | |
CN106140225A (zh) | 一种以二氧化硅为载体的催化剂及其制备方法和应用 | |
CN106140227A (zh) | 一种以改性氧化铝为载体的催化剂及其制备方法和应用 | |
CN106140292B (zh) | 一种以复合分子筛为载体的催化剂及其制备方法和应用 | |
CN106140274B (zh) | 一种溴甲烷高选择性制异丁烯的催化剂及其制备方法 | |
CN106140232A (zh) | 一种以二氧化钛为载体铈为助剂的溴甲烷制异丁烯催化剂及其制备方法与应用 | |
CN106140215B (zh) | 一种卤代甲烷制异丁烯催化剂及其制备方法和应用 | |
WO2024083048A1 (zh) | 用于由二甲醚和/或甲醇羰基化制备乙酸甲酯的催化剂及其用途 | |
CN106140265A (zh) | 一种以磷改性zsm-5分子筛为载体的催化剂及其制备方法和应用 | |
CN106140211B (zh) | 一种稀土元素改性的卤代甲烷制异丁烯催化剂及其制备方法 | |
CN106140231A (zh) | 一种碱土金属改性的负载型催化剂及其制备方法和应用 | |
CN106140233A (zh) | 一种钛修饰二氧化硅为载体的溴甲烷制异丁烯催化剂及其制备方法与应用 | |
CN106146240B (zh) | 一种溴甲烷制异丁烯的方法 | |
CN106140228A (zh) | 一种共结晶制备的溴甲烷制异丁烯催化剂及其制备方法和应用 | |
CN106140214B (zh) | 一种制异丁烯的催化剂及其制备方法和应用 | |
CN106140213B (zh) | 一种助剂改性的卤代甲烷制异丁烯催化剂及其制备方法和应用 | |
CN106140223A (zh) | 一种溴甲烷制异丁烯催化剂及其制备方法和应用 | |
CN106146237A (zh) | 一种制异丁烯的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14859617 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016552658 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15034913 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2014859617 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014859617 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20167014981 Country of ref document: KR Kind code of ref document: A |