TW201117880A - Process for the preparation of chlorine by gas phase oxidation on nanostructured supported ruthenium catalysts - Google Patents
Process for the preparation of chlorine by gas phase oxidation on nanostructured supported ruthenium catalysts Download PDFInfo
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- TW201117880A TW201117880A TW099124240A TW99124240A TW201117880A TW 201117880 A TW201117880 A TW 201117880A TW 099124240 A TW099124240 A TW 099124240A TW 99124240 A TW99124240 A TW 99124240A TW 201117880 A TW201117880 A TW 201117880A
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- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000000460 chlorine Substances 0.000 title claims abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 11
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 11
- 230000008569 process Effects 0.000 title claims abstract description 8
- 230000003647 oxidation Effects 0.000 title abstract description 11
- 238000007254 oxidation reaction Methods 0.000 title abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 39
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000002309 gasification Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 241000894007 species Species 0.000 claims description 5
- -1 barium oxygen oxychloride Chemical compound 0.000 claims description 4
- 150000001785 cerium compounds Chemical class 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 2
- 239000010931 gold Substances 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000013590 bulk material Substances 0.000 claims 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 210000004709 eyebrow Anatomy 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 claims 1
- 238000011105 stabilization Methods 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 229910001631 strontium chloride Inorganic materials 0.000 claims 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 1
- 150000003568 thioethers Chemical class 0.000 claims 1
- 150000003304 ruthenium compounds Chemical class 0.000 abstract description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 229910000420 cerium oxide Inorganic materials 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000011163 secondary particle Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 238000007138 Deacon process reaction Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- GSJBKPNSLRKRNR-UHFFFAOYSA-N $l^{2}-stannanylidenetin Chemical group [Sn].[Sn] GSJBKPNSLRKRNR-UHFFFAOYSA-N 0.000 description 1
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 206010003402 Arthropod sting Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- JHZICVAIDBTSOQ-UHFFFAOYSA-N [O-2].[Na+].[Ar].[Na+] Chemical compound [O-2].[Na+].[Ar].[Na+] JHZICVAIDBTSOQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/04—Preparation of chlorine from hydrogen chloride
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, 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
- 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
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- 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
- B01J23/63—Platinum group metals with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6445—Antimony
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- 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
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6447—Bismuth
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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Description
201117880 、發明說明: 【發明所屬之技術領域】 本發明係關於一種用於經由使用一種以釕為基質之經支 撐的催化劑之氣相氧化而製備氯之方法,其特徵為該催化劑 撐體具有多數的具有>50奈米之孔隙直徑之孔隙及帶有包 含釕及/或釕化合物作為催化活性組分之奈来粒子。 【先前技術】 於一種放熱平衡反應中使用氧之催化氣化氫氧化之方 法,由Deacon於1868年開發,係工業氯化學之開始: 4HC1 + 02 + 2C12 + 2H20。 然而’ Deacon方法係經由氯驗電解而大程度地推至背景 中。實質地所有之氯係經由水性氯化鈉溶液之電解而製造 [Ullmann Encyclopedia of Industrial Chemistry, 7th Edition, 2006]。然而,Deacon方法之吸引力最近已經再度上升,此 由於遍及全世界之氣需求係比對於氩氧化鈉溶液之需求成 長較快速之緣故。用於經由氯化氫之氧化而製備氣之方法, 其與氫氧化鈉溶液之製備不相關’很符合此種發展。此外, 大數量之氣化氫係於,例如於異氰酸酯類之製備中,例如, 光氣化反應中作為一種副產物生成。 氣化氫轉變成氯之氧化係一種平衡反應。當溫度升高時平 衡之位置朝向有利於期望之最終產品方向移動。因此使用具 有盡可能高之活性的催化劑,其容許該反應於較低之溫度進 行,係有利的。 用於氣化氫氧化之第/種催化劑包含氯化銅或氧化銅作 201117880 為活性組分及係早至1868年由Deacon敍述。然而,彼等於 較低之溫度(<400°C )顯示僅輕微之活性。雖然該活性可 係經由提高反應溫度而增加,但是此具有活性組分於較高溫 度之揮發性導致於催化活性中之快速降低及活性組分自反 應器之排出之缺點。 EP 0184413敍述氣化氫使用以鉻氧化物為基質之催化劑 之氧化。然而,其中進行之方法需要大量之催化劑負荷,此 由於不適合的催化活性及高的反應溫度之緣故。 用於氣化氫氧化具有釕作為催化活性組分之第一種催化 劑係早至1965年於DE 1567788中敍述;於此案例中自ruC13 開始,例如支撐於二氧化石夕或氧化銘之上者。然而,此等 RuCL/SiO2催化劑之活性係很低的。於de_a 19748299中已 主張其他包含氧化釕或經釕混合的氧化物作為活性組分及 =氧化物作為撑體材料(諸如’例如,二氧化鈦、二氧 3 = 為基質之催化劑。氧化釕催化财 至至2G重量%及氧灿之平均粒子直徑係 支撐於三氧化鈦或二氧化錯上之另外 之釕催化劑係自DE-A 19734412而為吾人所卜 及之氣化釘及氧化釕催化劑(其等包含二氧化鈦= 中提 之至少-種化合物)之製備,已提及多種之-氧化錯 =例如,韻錯合物類、有機=物’ 或釕-乙醯丙_錯合物類。於一種較 了錯“勿類、 呈金紅石形式之Ti〇2作為撐體。 貫施例中,使用 4 201117880 DE 102007020154A1 及 DE 102006024543A1 敍述―種用 於催化氯化氫氧化之方法,其中催化劑包含二氧化錫(作為 撐體)’較佳地呈錫石結構之二氧化錫,及至少一種含函素 之釕化合物(DE 102007020154A1)或至少一種含氧之訂化 合物(DE 102006024543A1)。 迄今對於Deacon方法開發之不含釕之催化劑係太不活性 或太不穩定。雖然迄今已敍述之經支撐之釕催化劑理論上係 適合於Deacon方法中之使用,但是由於被主張為較佳者之 撐體金紅石-二氧化鈦及錫石·二氧化錫之結晶結構,因此彼 等具有僅低之表面積,其對於彼等作為於HC1氧化中之撐體 之用途係缺點。 【發明内容】 於是,本發明之目的係提供一種用於氣化氫氧化之催化 系統’其提供比自先前技藝所知之催化劑較高之特異(以釕 含量計)活性。 令人驚訝地’已發現,特異(即以釕為基礎)活性及(高 μ度)穩定性可係藉由經奈米結構化的催化劑之有目的的製 備而值彳于注意地提高。 本發明係關於一種用於自氣化氫與含氧之氣體熱催化製 備氯之催化劑材料,其根據一種以釕為基質之經支撐的催化 劑’其特徵為該催化劑撐體具有多數的具有>50奈米之孔隙 直控之孔隙、及帶有包含釕及/或釕化合物作為催化活性組分 之奈米粒子。為了簡略,自氯化氫與含氧之氣體熱催化製備 氣通常係於後文中如Deacon方法提及。 201117880 較佳地至少50%,特別較佳地至少8〇%之根據本發明之 催化劑材料的孔隙體積係以其直徑係歸於大孔性之範圍(即 >50奈米)之孔隙存在。此種大孔隙性容許催化劑撐體均勻 地以奈米粒子負荷,避免孔隙經由奈米粒子之黏聚作用而變 成堵塞,及於Deacon反應之期間導致降低之孔隙擴散限制。 為了測定孔隙體積及孔隙直徑,於本發明之範圍内使用水 銀孔隙度測定法。該測量係根據13〇度之水銀接觸角及48〇 達因/厘米2之表面張力。 該催化劑材料較佳地包含一或多種來自下列群組之化合 物作為撐體材料:鋁化合物類、矽化合物類、鈦化合物類、 鍅化合物類或錫化合物類,特別較佳地鋁化合物類及/或矽化 合物類’及最特職佳地下晴組之—❹齡屬之氧化物 類、氧化物混合物類或經混合的氧化物類:銘、石夕、欽、錯 或錫。鋁與矽之經混合的氧化物類係特別較佳的。於一種^ 能之應用形式中,將黏合劑類(例如μ-Α1203)加入,其主 要功能不是用於活性組分之稽體。 夕於催化劑材料上存在之含纟了之奈米粒子較佳地包含一或 f種來自下列群組之化合物作為催化活性組分:釕氧化物 經釕混合的氧化物類、#氧化物混合物類、釕氧基i化 ^員、封自化物類或金狀釕。氣化釕、氧氣化釕或氧化釘 /、氟化釕之混合物類係特別較佳的。 較佳地至)5G%之存在於催化劑上之含釕之奈米粒子具 ,不超過50奈米之直徑,特別較佳地至少5〇%具有自$奈 ' 〇 ’τ'米之直控,更特別較佳地至少80%具有自5奈米 6 201117880 至50奈米之直徑。存在於催化劑上之含釕之奈米粒子之爭 均直徑最特別較佳地係自10至30奈米。令人驚#地,尋找 釘之最大之分散(即盡可能小之釕的一次粒子(primary particles),例如小於5奈米),不是有利的。 較佳地’以催化劑之總重量計,催化劑之釕含量係至多2〇 重量%,較佳地自〇.丨至2〇重量%,特別較佳地自〇.5至5 重量% °太高之負荷可能導致奈米粒子之黏聚作用,其係不 利的。 具有—種另外的活性組分或促進劑之功能之額外的奈米 粒子較佳地係存在於催化劑材料上,特別較佳地一或多種之 元素 Ag、Au、Bi、Ce、Co、Cr、Cu、Ni、Sb、Sn、Ti、W、
Zn、Zr及鉑金屬,最特別較佳地屬於元素Bi、Sb、% 及Ti之另外的金屬類、金屬化合物類及經混合的化合物類。 』外:也?ί於催化劑上之此等奈米粒子較佳地包含氧化物 、,此5的氧化物類、氧化物混合物類、氧基函化物類、 自化物類、經還原之金屬類或其等之合金類。 、 =催化劑之總重量計’存在於催化劑材料上之額外的太 旦=之含量較佳地係至多20重量%,特別較佳地至多^重 =。『太高之負荷可能導致奈米粒子之聚作用,其係不利 2地至少寒之存在於催化劑上之額外的奈卡粒子里 ^超過5〇奈米之直徑,特職佳地至少卿具有自^ ^ srT/米之直徑,最制較佳地至少啊具有自3夺^ 示米之直徑。存在於催化劑上之額外的奈米粒子之^ 201117880 均直徑最特別較佳地係自5至30奈米。 於一種可能之較佳具體實施例中,存在於催化劑上之奈米 粒子包含至少釕及至少一種另外之金屬作為促進劑,較佳地
Ag、Au、Bi、Ce、Co、Cr、C\i、Ni、Sb、Sn、Ti、W、Y、
Zn 、Zr 白 H , :¾ 对寺另幸交4圭 & Bi 、Sb、 Sn & Ti ,即 H 可係如雙金屬或多金屬提及。如此描述之奈米粒子包含氧化 物類、經混合的氧化物類、氧化物混合物類、氧基齒化物類、 鹵化物類、金屬類及合金類。 較佳地至少50%之存在於催化劑上之雙金屬或多金屬之 奈米粒子具有不超過50奈米之直徑,特別較佳地至少5〇% 具有自5奈米至50奈米之直徑,最特別較佳地至少8〇%具 有自5奈米至50奈米之直徑。存在於催化劑上之雙金屬或 多金屬之奈米粒子之平均直徑最特別較佳地係自1〇至3〇奈 米。 以催化劑之總重量計,存在於催化劑上之雙金屬或多金屬 之奈米粒子之含量較佳地係至多3〇重量%,特別較佳地至 多20重量%。太高之負荷導致奈米粒子之黏聚作用,其係 不利的。 該等奈米粒子較佳地係經由火焰熱解作用而製備。一種較 佳之製備方法係如下: 將至少一種前驅物以粉末之形式置於一種容器中。倘若製 備雙金屬或多金屬之奈米粒子,則較佳地將不同之粉狀之前 驅物集合一起及徹底地混合。該等粉末係進料至一種電漿室 或明火中及係於其中立即地汽化。如此製造之氣體金屬化合 8 201117880 物係自該電漿排出及於一種冷卻器區域中冷 確之尺寸分布之奈米粒子。該等奈米粒子心由^具有明 及清潔劑之添加而於-種乳液中穩定化。較佳地使::: 種有機溶劑,以製備該乳液。然後使用該乳液,7或 兩種以上乳液之混合物(其等包含該活性组>、另兩種或 組分及/或促進劑)以浸漬一種催化劑撐體,較佳 ^活, 業文獻中如、、初期之_,,習用地提及之—種方法^此^ 方法中,包含該活性組分之浸潰溶液係以剛好能W 樓體吸收之數量置於-種容器中,因此確保該等活 由撐體完全地吸收。可能的另外形式係,例如,於專利二 案 US 20080277270-Α1 中找到。 為了自催化劑表面移出任何破裂有機化合物、及黏合及穩 定化於催化劑上之奈米粒子,.隨後於提高之溫度锻燒該催化 劑。锻燒較佳地躲-種包含氧之大氣巾進行,制較佳地 於工氣或一種惰性氣體/氧混合物中。溫度係至高8〇〇。〇,較 佳地自25〇°C至600°C。有利地選擇煅燒時間,較佳地係自i 小時至50小時。以乳液浸潰之催化劑較佳地係於煅燒之前 乾燥,較佳地於降低之壓力下及有利地歷時自1小時至50 小時。 適合作為另外之促進劑者係具有鹼性作用之金屬的化合 物類(例如鹼、鹼土及稀土金屬鹽類);鹼金屬(特別是1^ 及Cs)、及鹼土金屬之化合物類係較佳的;鹼土金屬(特別 是Sr及Ba)之化合物類係特別較佳的。於一種較佳具體實 施例中,該等具有鹼性作用之金屬係以氧化物類、氫氧化物 201117880 類、氣化物類、氧基氯化物類或硝酸鹽類之形式使用。於一 種較佳具體實施例中,此種類型之促進劑係經二浸潰或化學 蒸鍍(CVD)方法而塗敷至催化劑。 根據本發明使用之撐體較佳地係市售的(例如來自saim Gobain Norpro) 〇 根據本發賴於氯化氫氧化之催化劑係以彼等顯示高活 性然而同時於高溫度下具有高穩定性為特徵。 催化之氣化氫氧化難地可絲熱地轉溫地或近似等 溫地’不連續地(但較佳地連續地)如—種频化或固定床 方法(較佳地如-翻定床方法)崎,特職佳地於管式 反應器中於不均之催化劑上於自⑽至财c(較佳地自細 至4〇〇°C,特別較佳地自25〇至Wc)之反應器溫度及 自1至25巴(自1,_至25,_百帕)(較佳地自12至如 巴,特別較佳地自1.5至17巴及特別地自2 〇至15巴 壓力下i隹;?千。 於絕熱、等溫或近似等溫程序之案例 具有中間冷卻之多個(即自2至H)個,較佳地自2至=接 特別較佳地自2至5個,特別地自2至3個)反應器 能的。氣化氫可係與氧—起於第—反應器之上游完全加入
應器中。個別反應器之此種系列連接亦可係於 一個裝置中達成。 W 201117880 適合於該方法之裝置之—種另外 使用一種經結構化之催化劑床組成,於哕/由収貫施例係由 流動之方向中增加。催化劑床之此種結構俜 者=型:ir:'具::何:〜形狀之成型體,較佳 t或星形狀之㈣物係特別較佳乏;狀車=二二 :之情況t之直徑)較佳地係於自。2至==】二於 特別較佳地自G.5至7毫米。 主心水之犯圍内, 體亦種:=(成型之)催化劑體之-種替代方案,撐 向地互相。’其具有平行之通道,料通道不是徑 内具广丄一種替代之較佳具體 實施例係於撐體實體之 以ί匕6物之發泡體、海棉狀物或其類似物,亦單塊 1具有父叉的流動通道之擇體實體。 構。:::::::自蜂冓或開放或封閉之交 較佳孔隙密度,特別ϋG至9GG孔隙每平方叶(㈣)之 於本發明之範圍内t地自D 200至600孔隙每平方忖。 種單塊係,例如,於、'Monoliths in 201117880 multiphase catalytic processes - aspects and prospects" by F. Kapteijn,J.J. Heiszwolf,T.A. Nijhuis 及 j A M〇ulijn,以攸化 3,1999, p. 24 中揭示。 於單次通過中之氣化氫轉化率係於自15至1〇〇%之範圍 内,及較佳地可係限制至自15至9〇%,較佳地自4〇至9〇 =,特別較佳地自60至90%。所有或部分之未反應的氣化 氫’ ^分離出之後,可係進料返回至催化之氣化氮氧化。於 反應器入口之氣化氫對於氧之體積比較佳地係自1:1至 2〇 : 1,特別較佳地自2 : 1至8 :卜最特別較佳地自2 : i 至 6 : 1。 、可有利地使祕化之氣化氫氧化之反應熱,以製造高壓蒸 /飞。可使用此rij壓蒸汽以操作—種光氣化反應器及/或蒸鶴 塔’特別是異氰酸酯蒸潑塔。 於Deacon彳法之最後步驟中,已生成之氯係分離出。該 分離步驟通常包含多個階段,即催化之氯化氫氧化之產物氣 體流的未反應氣化氫之分離及視情況循環、實f地包含氣與 氧之生成流之乾燥、及來自已經乾燥之流的氣之分離。 未反應之氣化ft與生成之流的分離可係經由以冷卻冷凝 來自氣化氫氧化之絲氣體流的水性氫氣酸而進行。氣化氣 亦可係吸收於稀氫氯酸或水中。 下列之實例舉例說明本發明。 【實施方式】 實例 貫例1 (比較實例):$是根據本發明之催化劑之製備 12 201117880 以氣化釕η-水合物於水中之溶液浸潰100克之Ti02顆粒 (圓柱形,直徑約2毫米,長度2至10毫米,Saint-Gobain ), 致使Ru含量係3重量%。如此獲得之濕顆粒係於60°C乾燥 過夜及以乾燥狀態引進,同時以氮沖洗,入NaOH與25%之 肼水合物溶液於水中之溶液中,及該混合物係留下靜置歷時 1小時。然後蒸發出過量之水。該等濕顆粒係於60°C乾燥歷 時2小時然後每次以300克之水洗滌4次。如此獲得之濕顆 粒係於一種蒙孚(muffle)爐(空氣)中於120°C乾燥歷時20 分中然後於35(TC烺燒歷時3小時。 實例2 :根據本發明藉由實例選擇之催化劑之製備 將元素之穩定的氧化物Ru(Ru02)、Sn(Sn02)、Ni(NiO)、 Sb (Sb203)、Zr-Y (90 重量%之 Zr02,10 重量%之 Y203)、 Ti (Ti02)、Bi (Bi205)以微米尺度粉末之形式置於一種容器 中。該等粉末係個別地(以2a-b、2e-i表示之樣本一>單金屬 之奈米粒子)或以預混合之形式(以2c-d表示之樣本—雙金 屬之奈米粒子)進料至電漿室及係於其中立即汽化(於高於 20,000凱氏溫標之溫度)。如此生成之氣體金屬化合物係自 該電漿排出及於冷卻器區域(低於500°C之溫度)中冷凝, 生成具有明確尺寸分布之奈米粒子。該等奈米粒子係於一種 水性乳液中經由一種以胺為基質之非離子的梳形聚合物(製 造商:SDC Materials)之添加而穩定化,達成於7.5重量% 之奈米粒子的含量。於該乳液中,達成釕奈米粒子對於催化 劑上之額外的奈米粒子之所欲比率,及催化劑撐體係因此藉 由一種於專業之文獻中以、、初期之潤濕〃習用地提及之方法 13 201117880 而重複地浸潰,直到所欲的總負荷係已經塗敷至催化劑撐體 為止。於此種方法中,包含活性組分之浸潰溶液係以剛好可 由受浸潰之撐體吸收之數量置於一種容器中,因此確保該等 活性組分係由撐體完全地吸收。撐體之性質,如由 Saint-Gobain描述,係如下: >平均孔隙直徑:1.2微米,BET表面積:30米2/克 >孔隙體積:0.55厘米3/克,水吸收容量:60重量% >組成:82重量%之α/轉移A1203,18重量%之Si02 > 尺寸:d=3-4毫米,1=6-8毫米(2a-d、2h-i); d=3-4毫米,1=3-4毫米(2e-g) 濕催化劑樣本係於浸潰步驟之間及最後於110°C乾燥歷時 2 · 5小時及係於空氣中於5 5 0 °C煅燒歷時2小時。奈米粒子之 金屬含量於催化劑之總重量中之比例係於表1中找到(藉由 XRF測定)。 表1 :奈米粒子之金屬含量於催化劑之總重量中之比例(藉 由XRF)_ 催化劑 Ru Sn Ni Sb Zr/Y Ti Bi (%) (%) (%) (%) (%) (%)(%) 2a 1.9 2b 1.6 4.5 2c 1.5 29 2d 2.1 11 2e 1.7 2f 1.9 14 201117880 2g 1.6 5.2 2h 2.2 2i 2.4 實例3 (比較實例广不是根據本發明之催化劑(來自實例1} 之試驗 5.9 8.9 1克之以1表示之成型催化劑體係以惰性之Spheriglass球稀 釋及置於一種石英反應管(内徑10毫米)中。將此批量經歷 相同於實例4中之測量程序。於STYRuf之改變及自其獲得之 特性數據係於表2中找到。 一一種不是根據本發明之催化劑之於STYRu中之改變 開始 於19 於37 於103 於121 催化 之 小時 小時 小時 小時 a* b* 劑 STYRu 後[克/ 後[克/ 後[克/ 後[克/ [克/克 克小 克小 克小 克小 小時】 時] 時】 時】 時] 1 27.0 23.0 21.7 20.3 n.d. 26.9 0.061 *對於參數a及b之定義’見實例4 ; k.d.:未測定。 貝例4 ·根據本發明之催化劑(來自實例2)之試驗 於每種案例中’ 1克之以2a-i表示之成型之催化劑體係以惰 性之Spheriglass球稀釋及置於一種石英反應管(内徑1〇毫米) 中。在氮氣之固定流下加熱之後,將由丨公升/小時之氯化氫、 4公升/小時之氧及5公升/小時之氮組成之氣體混合物(1〇公 升/小時)於380 C流動通過每種的該等批量歷時約π小時。 然後降低溫度至330。(:及測定空間_時間產率(開始STY )。然 15 201117880 後提高溫度至430°C。為了測量去活化作用,溫度係以間隔 之方式降低至330Ϊ (於X小時後之STY)。空間-時間產率係 經由將每個反應器之產物氣體流流動通過一種20%之硬化 卸溶液歷時約15分鐘,然後以〇.1 N之硫代硫酸鹽測量溶液滴 定該生成之碘化物而測定(重複之測定)。特殊之(以釘含 量計)空間-時間產率(STY)然後係自如此測定之氯化物之 數量’根據下列式測定(表3a/b): STYRu=克(氣)*克-1 (於所使用之催化劑上的釕重量)* 小時_1 (時間) 於STYRu中之改變係使用一種乘方方法(power approach ) 而模擬: STYRu= a rb (t係於43(TC以小時TOS表示), 其中a代表開始之活性及表去活化作用之速率。此等兩種 參數亦係已經包括於表3a/b中。 _色3a :根據本發明之催化劑之於STYtt,,中之改變 開始之 於109 於123 於198 催化STYru小時後小時後小時後 a b 劑[克/克[克/克[克/克[克/克 _小時] 小時】 小時] 小時】 2a 18,4 17.9 17 4 16.3 18.5 0.016 2b 33.8 30*° 29·4 28.8 33.8 0.029 2c 27.3 20 7 19.3 18.0 27.5 0.072 —————__ 17·6 17·! 16.7 25.2 0.079 201117880 表3b :根據本發明之催化劑之於STYP..中之改變 開始 於19 於37 於103 A iRu 1 - 於121 催化 之 小時 小時 小時 小時 a b 劑 STYru 後[克/ 後[克/ 後[克/ 後[克/ [克/克 克小 克小 克小 克小 小時] 時] 時】 時] 時】 2e 19.4 21.2 22.4 21.8 21.2 n.d.1 n.d.1 2f 33.7 26.3 25.3 22.1 22.6 33.8 0.086 2g 20.0 18.8 18:8 17.5 18.1 20.1 0.024 2h 23.6 22.3 21.4 20.9 20.5 23.8 0.029 2i 30.7 29.0 28.5 26.9 n.d.1 30.9 0.026 1 n.d.:未測定 以實例(2a、2b、2g、2h、2i)提及之根據本發明之某些 催化劑的穩定性(模擬之去活化作用參數_b)於某些案例中 顯然地係比不是根據本發明之先前技藝之催化劑顯著地較 高。以實例(2b、2f、2i)提及之根據本發明之某些催化劑 之特異開始活性於某些案例中顯然地係比不是根據本發明 之先刖技藝之催化劑值得注意地較高。催化劑樣本2&及2()甚 至具有比根據先前技藝之催化劑顯著地較高(高溫度)穩定 性及值得注意地較高之開始活性。 實例5 :於催化劑上之奈米粒子之尺寸分布 數種10克之以實例提及,以2a、2b、2(;及2(1表示之根據本 發明之催化劑係於一種研鉢中精細地研磨及懸浮於乙酵 中,及所生成之懸浮液係逐滴地塗敷至用於TEM測量之一種 17 201117880 樣本載體(Tecnai20, Megaview ΠΙ)。兩種樣本之不同區域係 以ΤΕΜ研究。圖1 (催化劑2a)、圖2 (催化劑2b)、圖3 (催 化劑2c)及圖4 (催化劑2d)顯示,以實例之方式,催化劑 樣本之特性區域。 圖1 (催化劑2a):計數具有自5至34奈米(平均16奈米) 之直徑之34個一次粒子。 圖2 (催化劑2b): —次粒子分布(二氧化釕與二氧化錫) 係相似於2a者。 圖3 (催化劑2c): —次粒子分布(二氧化釕與二氧化錫) 係相似於2a者。 圖4 (催化劑2d): —次粒子分布(二氧化釕與二氧化錫) 係相似於2a者。 不同於根據本發明之催化劑,二氧化釕係明顯地存在於 金紅石-Ti02上(見實例1)’此由於兩種金紅石結構於塗布該 撐體之層的形式中之可比較的晶格間隔之緣故 (、、Development of an improved HC1 oxidation process: structure of the Ru02/rutile Ti〇2 catalyst” by Seki,Kohei; Iwanaga, Kiyoshi; Hibi, Takuo; Issoh, Kohtaro; Mori, Yasuhiko; Abe, Tadashi in Studies in Surface Science and Catalysis (2007), 172 (Science and Technology in Catalysis 2006), 55-60)。於該相同出版物中,該催化劑係與以A1203或Si02 為基質之經支撐的釕催化劑比較,該等催化劑儘管假設地具 有高之分散,但是仍然顯示顯著地較低之活性。於此等撐體 上之高分散,如比較金紅石-Ti02之實際(areal)應用,對於催 201117880 化之性質顯然地係負面的。 根據本發明具有界定之釕一次粒度(ruthenium primary particle sizes)之經奈米結構化支樓之釕催化劑係,然而,甚 至比以金紅石-Ti02為基質之經支撐的釕催化劑明顯地較優 越。 【圖式簡單說明】 圖1 (催化劑2a):計數具有自5至34奈米(平均16奈米)之 直徑之34個一次粒子。 圖2 (催化劑2b): —次粒子分布(二氧化釕與二氧化錫)係 相似於2a者。 圖3 (催化劑2c): —次粒子分布(二氧化釕與二氧化錫)係 相似於2a者。 圖4 (催化劑2d): —次粒子分布(二氧化釕與二氧化錫)係 相似於2a者。 【主要元件符號說明】 無 19
Claims (1)
- 201117880 七、申請專利範園: 1. -種用於自氣化1及含氧之氣體熱催化製備氣之催化劑 ,料其根據一種以釕為基質之經支撐的催化劑,其特 徵為該催化_體具有多數的具有〉5G奈米的孔隙直徑 =二帶有包含釘及/或釘化合物作為催化活性組分 2. 圍第1項之催化劑材料,其特徵為該催化 3. ::::少5〇%,較佳地至少8〇%,之孔隙體積係以 八置仏係大於50奈米之孔隙存在。 催:劑材料,其特徵為該 體材料物類 物作為撐 類__化合物類’較佳地紹化合物類及/或石夕化合物 4. 如申請專利範圍第3項之催化 劑樓體包含1乡種之下 I4/賴為該催化 化物混合物類或經混合的氧化物2之氧化物類、氧 矽.、鈦、鍅或錨,妒負作為撐體材料:鋁、 如申請專利範圍第;"至經混合的氧化物類。 特徵為於該催化劑上存在之 ,之催化劑材料,其 種來自下鱗組之化合物作為錄子包含一或多 物類、經心合的氧化 ^化雜組分··釕氧化 基齒化物類、舒4化物類'全眉了,化物混合物類、釕氧 氧氯化釕或氧切與氯切之混合:類較佳地氯化釕、 20 201117880 201117880 6. 士申5月專利範圍第1至5項中你〜 之,含釕, 徑,特別較佳^ 2奈米至5〇奈米之直 如申請專利範圍第Γ至 特徵為該等含釕之夺、1 員之催化劑材料,其 直裎。 之-未粒子具有自10至30奈米之平均 如申請專利範圍第1至7項中任 * 9. =為以該催化劑材料之'二;==,其 2〇重量%,較佳地自Q 。錄化”丨具有至多 如申請專利範圍第里%之釕含置。 ,該催化劑材料額二二=:料’其 或金屬化合物為基質之或夕種另外之金屬 :或作為-種促進劑,二一或多:種辛, ,金屬,特別較佳地元素Bi、 、,、々及 10 ^或金屬化合物類及經混合的化另外的金 .如申請專利範圍第9 σ物颏 外的奈米粒子包含於卜# 斗,其=徵為該等額 之氧化物類、經混合的乾圍弟9項中提及之金屬 基南化物類,特別=類、氧化物混合 氣化物類、或金屬類!=物類、齒化物類’特別是 如申請專利範圍第〗&金類作為金屬化合物。 特徵為以該催化劑材= 員中Γ項之催化劑材料,其 4之、、心重量計,額外地存在於該催 21 11 201117880 ^韌上之奈米粒子的數量係至多20重量%,較佳地至多 10重量%。 夕 12 士 ό 申4專利範圍第〗至n項中任一項之催化劑材料,其 粒徵為至少50%之額外地存在於該催化劑上之該等奈米 ^ ^具有不超過50奈米之直徑,較佳地至少50%具有自 13 太二米至50奈米之直徑,特別較佳地至少8〇%具有自3 τ'考至50奈米之直徑。 特:Ϊ專利範圍第1至12項中任一項之催化劑材料,其 徑:為該等額外的奈米粒子具有自5至3()奈米之平均直 14. =用於製備如申請專利範圍第丄至⑴員中任一項之催 材料之方法,其特徵為該催化劑係經由至 方法步驟而製備:. J a)包含針及/或釕化合物之奈米粒子經由火焰熱 之合成, W 含釕及/或釕化合物之奈米粒子於—種乳液中 之穩定化作用, 15. 〜)該經浸潰之催化劑於提高之溫度下炮燒。 政^化ί及含氧之氣體熱催化製備氣之方法, 二特被為使用如中請專利範圍第1至13項中任一項之催 化劑材料作為催化劑。 貞1Μ項之催 如申請專利範圍第15項 係絕熱地或等溫地或近似等溫二===氯= 22 16. 201117880 是連續地,如一種流體化或固定床方法,較佳地如一種 固定床方法,於自180至500°C,較佳地自200至400°C, 特別較佳地自250至380°C之反應器溫度、及自1至25 巴(自1,000至25,000百帕),較佳地自1.2至20巴(自 1,200至20,000百帕),特別較佳地自1.5至17巴(自1,500 至17,000百帕)及特別是自2.0至15巴(自2,000至15,000 百帕)之壓力下進行。 23
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JP6316194B2 (ja) * | 2011-10-24 | 2018-04-25 | バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングBayer Intellectual Property GmbH | 気相酸化により塩素を製造するための触媒および方法 |
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2009
- 2009-07-25 DE DE102009034773A patent/DE102009034773A1/de not_active Withdrawn
-
2010
- 2010-07-14 IN IN739DEN2012 patent/IN2012DN00739A/en unknown
- 2010-07-14 KR KR1020127001664A patent/KR20120040701A/ko not_active Application Discontinuation
- 2010-07-14 EP EP10732315A patent/EP2459312A2/de not_active Withdrawn
- 2010-07-14 US US13/384,792 patent/US20120148478A1/en not_active Abandoned
- 2010-07-14 JP JP2012520932A patent/JP2013500145A/ja active Pending
- 2010-07-14 WO PCT/EP2010/004287 patent/WO2011012226A2/de active Application Filing
- 2010-07-14 CN CN2010800325889A patent/CN102711986A/zh active Pending
- 2010-07-23 TW TW099124240A patent/TW201117880A/zh unknown
Cited By (1)
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TWI782080B (zh) * | 2017-09-01 | 2022-11-01 | 日商恩億凱嘉股份有限公司 | 核氫化反應用觸媒的用途 |
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JP2013500145A (ja) | 2013-01-07 |
EP2459312A2 (de) | 2012-06-06 |
DE102009034773A1 (de) | 2011-01-27 |
US20120148478A1 (en) | 2012-06-14 |
KR20120040701A (ko) | 2012-04-27 |
WO2011012226A3 (de) | 2012-03-01 |
CN102711986A (zh) | 2012-10-03 |
WO2011012226A2 (de) | 2011-02-03 |
IN2012DN00739A (zh) | 2015-06-19 |
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