JP5436851B2 - 触媒 - Google Patents
触媒 Download PDFInfo
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- JP5436851B2 JP5436851B2 JP2008504852A JP2008504852A JP5436851B2 JP 5436851 B2 JP5436851 B2 JP 5436851B2 JP 2008504852 A JP2008504852 A JP 2008504852A JP 2008504852 A JP2008504852 A JP 2008504852A JP 5436851 B2 JP5436851 B2 JP 5436851B2
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- catalyst
- chromium
- chromia
- temperature
- amorphous
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- 239000003054 catalyst Substances 0.000 title claims description 183
- 238000000034 method Methods 0.000 claims description 43
- 238000004519 manufacturing process Methods 0.000 claims description 32
- 238000003682 fluorination reaction Methods 0.000 claims description 31
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 29
- 229910052725 zinc Inorganic materials 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 20
- 239000012018 catalyst precursor Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 11
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 5
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 150000008282 halocarbons Chemical class 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 229910052751 metal Inorganic materials 0.000 description 33
- 239000002184 metal Substances 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 29
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 22
- 229950011008 tetrachloroethylene Drugs 0.000 description 22
- 239000011651 chromium Substances 0.000 description 21
- 229910052804 chromium Inorganic materials 0.000 description 20
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 239000006227 byproduct Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000001354 calcination Methods 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 9
- 229910000423 chromium oxide Inorganic materials 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000007259 addition reaction Methods 0.000 description 7
- 239000000908 ammonium hydroxide Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 7
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 7
- 229940007718 zinc hydroxide Drugs 0.000 description 7
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical group FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 description 3
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- -1 chromium (VI) compound Chemical class 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RFCAUADVODFSLZ-UHFFFAOYSA-N 1-Chloro-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Cl RFCAUADVODFSLZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 235000019406 chloropentafluoroethane Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010421 standard material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SLGOCMATMKJJCE-UHFFFAOYSA-N 1,1,1,2-tetrachloro-2,2-difluoroethane Chemical compound FC(F)(Cl)C(Cl)(Cl)Cl SLGOCMATMKJJCE-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- UGCSPKPEHQEOSR-UHFFFAOYSA-N 1,1,2,2-tetrachloro-1,2-difluoroethane Chemical compound FC(Cl)(Cl)C(F)(Cl)Cl UGCSPKPEHQEOSR-UHFFFAOYSA-N 0.000 description 1
- HTHNTJCVPNKCPZ-UHFFFAOYSA-N 2-chloro-1,1-difluoroethene Chemical group FC(F)=CCl HTHNTJCVPNKCPZ-UHFFFAOYSA-N 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004340 Chloropentafluoroethane Substances 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001804 chlorine Chemical group 0.000 description 1
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
水酸化アンモニウムの添加で硝酸亜鉛およびクロムの溶液からの共沈により得られる、水酸化亜鉛と水酸化クロムとの混合物のか焼により、触媒を製造した。
圧縮および造粒された水酸化物の6gバッチを1/2″径か焼管へ入れ、60mL/minの窒素でパージした。次いで、触媒を300℃で4時間加熱することによりか焼し、最後に窒素下で室温に冷却させて、性能試験用に最終触媒を得た。
更なる試験に向けた結晶性のレベルを得るために、圧縮された水酸化物の6gバッチを用いて、上記で製造された触媒をある範囲の温度で更に熱処理した。この方法論を用いて、処理温度を高めながら、か焼された触媒の結晶構造を初期XRD非晶質構造から次第に高結晶性の組成物へと調整した。
4%w/wZnのZn含有率を有する混合酸化物配合ZnO.Cr2O3の結晶を製造するために、上記方法に従った。基準触媒は300℃の温度で1回のか焼を経て、こうして完全に非晶質の基本ケースの触媒を生じた。次いで520、540、および560℃の処理温度を用いて、次第に高含有率の結晶酸化クロムを含有した3種の触媒サンプルを製造した。
ペルクロロエチレンのフッ素化を触媒する際における所期活性および選択性を測定するために触媒を試験し、次いで高温HFへ曝された場合の相対的安定性について試験した。試験方法論は次の通りであった:
0.5〜1.4mmの粒径範囲を有する装入量2gの触媒粒子をinconel反応器へ入れ、120mL/minの流量で窒素でパージした。次いで触媒を250℃で30分間加熱することにより窒素流中で乾燥させた。次いで、最初に15mL/minの流量でHFを希釈窒素へ加え、250℃で90分間かけて触媒を調整することにより、触媒を調整した。次いで希釈窒素の流量を2.5mL/minに減らし、触媒を40℃/hrの速度で380℃まで加熱した。これらのHFの流量の条件下380℃で更に16時間にわたり触媒をフッ素化させた。次いでHF安定化触媒を350℃に冷却し、5mL/minの流量の窒素中1mL/minの流量のペルクロロエチレンを供給材料へ加えて、1:15:7.5mL/minのPer:HF:N2の反応器供給比とした。
上記の触媒製造方法を用いて得られた、4質量%亜鉛を含有する、水酸化亜鉛と水酸化クロムとの混合物を、窒素中520℃で4時間加熱することにより、更に熱処理した。結果として得られた物質は1.0%w/w結晶酸化クロムを含有していた。
上記の触媒製造方法を用いて得られた、4質量%亜鉛を含有する、水酸化亜鉛と水酸化クロムとの混合物を、窒素中540℃で4時間にわたり更に熱処理した。結果として得られた物質は2.6%w/w結晶酸化クロムを含有していた。
上記の触媒製造方法を用いて得られた、4質量%亜鉛を含有する、水酸化亜鉛と水酸化クロムとの混合物を、窒素中560℃で4時間にわたり更に処理した。処理された触媒は11.5%w/w結晶酸化クロムを含有していた。上記の方法論を用いたところ、この触媒は例1および2の触媒より低い活性および低い選択性を呈したが、非晶質の基本ケースの触媒より優れていた。
上記の触媒製造方法を用いて得られた、6質量%亜鉛を含有する、水酸化亜鉛と水酸化クロムとの混合物を用いて、例1〜3で用いられた上記の方法論を繰り返し、窒素中520、540、560、580、および600℃で4時間加熱することにより熱処理した。
上記の触媒製造方法を用いて得られた、8質量%亜鉛を含有する、水酸化亜鉛と水酸化クロムとの混合物を用いて、例1〜3で用いられた上記の方法論を繰り返し、窒素中540、560、580、600、および620℃で4時間加熱することにより熱処理した。
上記の触媒製造方法を用いて得られた、10質量%亜鉛を含有する、水酸化亜鉛と水酸化クロムとの混合物を用いて、例1〜3で用いられた上記の方法論を繰り返し、窒素中600℃で4時間加熱することにより熱処理した。
6%Znを含んでなる非晶質触媒と、1%の結晶化度を有して6%Znを含有する(例4で記載されたように得られた)触媒とを、約1.3秒間の固定滞留時間でトリクロロエチレンおよびフッ化水素からHFC‐134aを製造するプロセスで用いた。
6%Zn/クロミア触媒の結晶化に際するか焼温度、時間、および雰囲気とそれらの効果との相互作用を研究し、必要とされる様々な結晶性のレベルを導く上でどのようなか焼条件が用いられることができるかを明らかにするために統計的モデリング法を用いた。
Xst(%)=−71.75−11.37*時間+0.2050*温度+0.975*希釈+0.03250*時間*温度+0.08750*時間*希釈−0.008500*温度*希釈−0.0002500*時間*温度*希釈
Claims (10)
- 亜鉛を含んでなるクロミア系フッ素化触媒であって、前記触媒の0.1〜7.5質量%が、クロミアの結晶化合物の形態であることを特徴とする、クロミア系フッ素化触媒。
- 前記触媒の0.1〜5質量%が、クロミアの結晶化合物の形態である、請求項1に記載の触媒。
- 少なくとも50m2/gの表面積を有する、請求項1または2に記載の触媒。
- 70〜250m2/gの表面積を有する、請求項1または2に記載の触媒。
- 10%w/w未満のサルフェート含有率を有する、請求項1〜4のいずれか一項に記載の触媒。
- 窒素の雰囲気、または窒素中0.1〜10%v/vの酸素レベルを有する雰囲気中で1〜12時間にわたり300〜600℃の温度で、非晶質触媒前駆体を熱処理することを含んでなる、請求項1〜5のいずれか一項に記載された触媒の製造方法。
- フッ化水素の存在下において大気圧または過圧下で1〜16時間にわたり250〜500℃の温度で、非晶質触媒前駆体を熱処理することを含んでなる、請求項1に記載された触媒の製造方法。
- 請求項1〜5のいずれか一項に記載された触媒の存在下において、ハロゲン化炭化水素をフッ化水素と反応させることを含んでなる、フッ素化炭化水素の製造方法。
- 気相中、250〜500℃の温度で行われる、請求項8に記載の方法。
- 1,1,1,2‐テトラフルオロエタンまたはペンタフルオロエタンを製造するための、請求項8または9に記載の方法。
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PCT/GB2006/001291 WO2006106353A1 (en) | 2005-04-08 | 2006-04-10 | Chromia based fluorination catalyst |
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-
2005
- 2005-04-08 GB GBGB0507139.4A patent/GB0507139D0/en not_active Ceased
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2006
- 2006-04-10 JP JP2008504852A patent/JP5436851B2/ja active Active
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- 2006-04-10 PL PL06726692T patent/PL1877181T3/pl unknown
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- 2006-04-10 KR KR1020077025902A patent/KR101366051B1/ko active IP Right Grant
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EP1877181B1 (en) | 2015-06-17 |
PL1877181T3 (pl) | 2016-01-29 |
US20090209792A1 (en) | 2009-08-20 |
US10189757B2 (en) | 2019-01-29 |
US9771309B2 (en) | 2017-09-26 |
US20180022671A1 (en) | 2018-01-25 |
ES2544243T3 (es) | 2015-08-28 |
WO2006106353A1 (en) | 2006-10-12 |
KR101366051B1 (ko) | 2014-02-21 |
CN101175564A (zh) | 2008-05-07 |
JP2008534276A (ja) | 2008-08-28 |
ZA200708460B (en) | 2016-04-28 |
CN101175564B (zh) | 2012-09-05 |
GB0507139D0 (en) | 2005-05-18 |
KR20070118303A (ko) | 2007-12-14 |
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