JP2008540114A - 触媒の製造方法 - Google Patents
触媒の製造方法 Download PDFInfo
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- JP2008540114A JP2008540114A JP2008511799A JP2008511799A JP2008540114A JP 2008540114 A JP2008540114 A JP 2008540114A JP 2008511799 A JP2008511799 A JP 2008511799A JP 2008511799 A JP2008511799 A JP 2008511799A JP 2008540114 A JP2008540114 A JP 2008540114A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000010941 cobalt Substances 0.000 claims abstract description 52
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 34
- 239000007789 gas Substances 0.000 claims abstract description 27
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 21
- 239000011261 inert gas Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 description 19
- 238000006722 reduction reaction Methods 0.000 description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 150000001869 cobalt compounds Chemical class 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- -1 diatomaceous earth) Chemical compound 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000003921 particle size analysis Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000011787 zinc oxide Substances 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
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
-
- 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8896—Rhenium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
炭化水素の水素添加反応またはフィッシャー−トロプシュ合成に適した、担持されたコバルト触媒は、一般的に、可溶性コバルト化合物の「予備形成された」酸化支持体材料への含浸、または、支持体粉末または押出し物の存在下での溶液からのコバルト化合物の沈殿、それに続く空気中での加熱工程、続いて、使用前の、触媒前駆体中の得られたコバルト化合物を、典型的には水素を含むガスストリームを用いて元素または「ゼロ価」の形態に還元することによる触媒の活性化によって製造される。空気中で加熱することによって、少なくともいくらかのコバルト化合物が酸化コバルト(Co3O4)に変換される。それに続く水素での還元によって、Co3O4は一酸化コバルト(CoO)に変換され、触媒活性のコバルト金属が得られる。
従って、本発明は、触媒の支持体を硝酸コバルトに含浸させることによって形成されたコバルト触媒前駆体中の硝酸塩含量を低くする方法を提供し、本方法は、含浸させた支持体を空気中で焼成し、部分的に脱窒させること、その後、不活性ガス中に0.1〜10体積%の水素を含むガス混合物の存在下で、焼成された含浸させた支持体を250℃未満の温度に加熱することを含む。
含浸させた支持体に存在する硝酸塩の量は、実際に含浸させた硝酸コバルトの量に依存し、すなわち含浸させた支持体のコバルト含量に比例する。焼成工程は、含浸させた支持体から、元々存在する硝酸塩の好ましくは50%より多く、より好ましくは75%より多く、最も好ましくは90%より多くを除去する。例えば、焼成された含浸させた支持体のコバルト含量が、約20重量%である場合、我々は、水素を含むガスで処理する前の焼成された含浸させた支持体の残留した硝酸塩含量(NO3の重量として示される)は1重量%より多く、焼成条件に応じて3〜7重量%の場合もあることを見出した。(還元した触媒中に20重量%のCoが存在する場合、焼成工程前の含浸させた支持体は、約30重量%のNO3を含むようになると予想される)。本発明において、焼成は、触媒前駆体に好ましくは1〜10%の範囲、より好ましくは1〜5%の範囲の硝酸塩レベルが含まれるように行われる。残留した硝酸塩レベルが1重量%より多いことは、それに続く還元段階中に、具体的には、還元が水素添加反応器中に、または、フィッシャー−トロプシュ反応器中の系内で行われる場合、顕著な問題となる。
焼成された含浸させた支持体の水素を含むガスでの処理によってさらに、硝酸塩含量が、好ましくは50%より多く、より好ましくは75%より多く減少する。例えば、1重量%より多い硝酸塩含量を有する焼成された含浸させた支持体は、好ましくは、0.1〜10体積%の水素を含むガスで処理した後、0.5重量%未満、好ましくは0.25重量%未満、最も好ましくは0.1重量%未満の残留した硝酸塩含量を有する。
還元は、水素、合成ガス、または、水素と窒素またはその他の不活性ガスとの混合物などの水素を含むガスを、高温で酸化組成物の上を通過させることによって行ってもよく、例えば、水素を含むガスを、300〜600℃の範囲の温度で、1〜16時間、好ましくは1〜8時間で触媒前駆体の上を通過させることによって行ってもよい。好ましくは、還元ガスは、25体積%より多く、より好ましくは50体積%より多く、最も好ましくは75%より多く、特に90体積%より多くの水素を含む。還元は、雰囲気圧で行ってもよいし、または、高い圧力で行ってもよく、すなわち、還元ガスの圧力は、適切には1〜50、好ましくは1〜20、より好ましくは1〜10絶対barであり得る。還元が系内で行われる場合、それより高い、10絶対barを超える圧力がより適切な場合もある。
Co表面領域=(6.023×1023×V×SF×A)/22414
上記式中、Vは、H2の取り込み量(ml/g)であり、
SFは化学量論の係数(CoへのH2の化学吸着の場合は2と考えられる)であり、
Aは1個のコバルト原子が占有する領域(0.0662nm2と考えられる)である。
典型的な水素添加反応は、アルデヒドおよびニトリルに水素添加して、それぞれアルコールおよびアミンにすること、および、環状芳香族化合物または不飽和炭化水素に水素添加することを含む。本発明の触媒は、具体的には、不飽和有機化合物の水素添加に適しており、具体的には油、脂肪、脂肪酸、およびニトリルのような脂肪酸誘導体の水素添加に適している。このような水素添加反応は、典型的には、上記化合物を、オートクレーブ中での加圧下で、周囲温度または高温で、コバルト触媒の存在下で水素を含むガスを用いて水素化することによって処理することによって、連続的に、またはバッチ式で行われ、例えば、水素添加は、80〜250℃、0.1〜5.0×106Paの範囲の圧力の水素で行うことができる。
それぞれの実施例において、含浸させた支持体を以下のように製造した;ガンマアルミナ支持体(サソール・コンデア(Sasol Condea)製のプラロックス(Puralox)20/190)を、支持体100gあたり125.91gのCo(NO3)2・6H2O、0.91gのNH4ReO4、および、29.4gの脱塩水を含む溶液を用いて含浸させ、湿潤したケークを形成した。これを、トレイ上で、オーブン中で110℃で4時間、床厚さ(bed depth)25mmで乾燥させた。
還元した触媒のコバルト含量はいずれも、20重量%であった。
乾燥させた材料を、空気中で150mmの床厚さで焼成した。焼成中の粉末の温度を、2時間かけて370℃に高め、続いて1.5時間かけて400℃に高め、その後、1.5時間かけて270℃に下げた。
従って、焼成単独では低いコバルト表面領域の触媒が生じ、前駆体の硝酸塩含量は、それでもなお約1重量%であった。
乾燥させた材料を、空気中で50mmの床厚さで焼成した。焼成中の粉末の温度を、18分間かけて180℃に高め、続いて10分間かけて200℃に高め、続いて200℃で10分間保持し、その後、20分間かけて130℃に下げた。
乾燥させた材料を50mmの床厚さで焼成した。焼成中の粉末の温度を、18分間かけて180℃に高め、続いて10分間かけて200℃に高め、続いて200℃で10分間保持し、その後20分間かけて130℃に下げた。
Claims (10)
- 触媒の支持体を硝酸コバルトに含浸させることによって形成されるコバルト触媒前駆体中の硝酸塩含量を低くする方法であって、該含浸させた支持体を空気中で焼成し、部分的に脱窒させること、その後、不活性ガス中に0.1〜10体積%の水素を含むガス混合物の存在下で、焼成された含浸させた支持体を250℃未満の温度に加熱すること、を含む、前記方法。
- 前記焼成が、130〜500℃の範囲の温度で行われる、請求項1に記載の方法。
- 最大の焼成温度が、400℃以下である、請求項2に記載の方法。
- 前記焼成された含浸させた支持体が、50℃より高い温度に加熱される、請求項1〜3のいずれか一項に記載の方法。
- 前記不活性ガスが窒素である、請求項1〜4のいずれか一項に記載の方法。
- 前記不活性ガス中の水素濃度が、1〜5体積%である、請求項1〜5のいずれか一項に記載の方法。
- 前記水素を含むガス混合物の圧力が、1〜50絶対barである、請求項1〜6のいずれか一項に記載の方法。
- 前記焼成された含浸させた支持体のコバルト含量が、5〜40重量%である、請求項1〜7のいずれか一項に記載の方法。
- 前記触媒前駆体が、コバルトに加えて、水素添加反応、および/または、フィッシャー−トロプシュ触媒反応において有用な、1種またはそれより多くの適切な添加剤または促進剤をさらに含む、請求項1〜8のいずれか一項に記載の方法。
- (i)請求項1〜9のいずれか一項に記載の方法に従って触媒前駆体を製造する工程、および、
(ii)水素を含むガスのストリーム中、300〜600℃で、該触媒前駆体を還元する工程、
を含む、コバルト触媒の製造方法。
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JP2009011938A (ja) * | 2007-07-04 | 2009-01-22 | Muneyoshi Yamada | 一酸化炭素還元用触媒、その製造方法および炭化水素の製造方法 |
WO2011105118A1 (ja) * | 2010-02-26 | 2011-09-01 | Jx日鉱日石エネルギー株式会社 | 活性化フィッシャー・トロプシュ合成触媒の製造方法及び炭化水素の製造方法 |
JP2011528983A (ja) * | 2008-07-25 | 2011-12-01 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | 高分散されたコバルト触媒の製造、およびフィッシャー−トロプシュ反応におけるその使用 |
JP2014518757A (ja) * | 2011-05-06 | 2014-08-07 | サゾル テクノロジー(プロプライアタリー)リミティド | コバルト含有炭化水素合成触媒前駆体を調製する方法 |
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