JP5574387B2 - 炭化水素の脱水素化用触媒 - Google Patents
炭化水素の脱水素化用触媒 Download PDFInfo
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- JP5574387B2 JP5574387B2 JP2011518829A JP2011518829A JP5574387B2 JP 5574387 B2 JP5574387 B2 JP 5574387B2 JP 2011518829 A JP2011518829 A JP 2011518829A JP 2011518829 A JP2011518829 A JP 2011518829A JP 5574387 B2 JP5574387 B2 JP 5574387B2
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- catalyst
- oxide
- weight
- chromium
- dehydrogenation
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- 239000003054 catalyst Substances 0.000 title claims description 210
- 238000006356 dehydrogenation reaction Methods 0.000 title claims description 80
- 229930195733 hydrocarbon Natural products 0.000 title description 9
- 150000002430 hydrocarbons Chemical class 0.000 title description 9
- 239000004215 Carbon black (E152) Substances 0.000 title description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 60
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 46
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 41
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 39
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 39
- 230000008569 process Effects 0.000 claims description 37
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 31
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 23
- 150000001845 chromium compounds Chemical class 0.000 claims description 9
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 8
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 150000002681 magnesium compounds Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 150000003112 potassium compounds Chemical class 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 2
- 150000003388 sodium compounds Chemical class 0.000 claims 2
- 239000011651 chromium Substances 0.000 description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 26
- 239000008188 pellet Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 22
- 229910052804 chromium Inorganic materials 0.000 description 22
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 15
- 239000011734 sodium Substances 0.000 description 14
- 229910052783 alkali metal Inorganic materials 0.000 description 13
- 150000001340 alkali metals Chemical class 0.000 description 13
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 13
- 229910052697 platinum Inorganic materials 0.000 description 13
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 230000032683 aging Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 150000001844 chromium Chemical class 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 239000001282 iso-butane Substances 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- -1 lower paraffins Chemical class 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 150000003755 zirconium compounds Chemical class 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000013020 final formulation Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 235000004035 Cryptotaenia japonica Nutrition 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 102000007641 Trefoil Factors Human genes 0.000 description 2
- 235000015724 Trifolium pratense Nutrition 0.000 description 2
- 229910001680 bayerite Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 229910021480 group 4 element Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001682 nordstrandite Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 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
- DJFTXJLLHZRHKO-UHFFFAOYSA-N dipotassium oxygen(2-) hydrate Chemical compound O.[O--].[K+].[K+] DJFTXJLLHZRHKO-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite 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
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
- C07C2523/04—Alkali metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/26—Chromium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
触媒は、例えばC2−C6の脱水素可能な炭化水素をオレフィン及び/又はジオレフィンに変換する静止床及び/又は流動床脱水素反応プロセスに使用するためのものである。脱水素反応は、通常、最適収率を上げる最も高い実用スループットで行われる。収率は、触媒の変換率と選択性に依存する。これらの特性は、プロセスの効率を決定する。触媒の選択性は、例えば、生成したプロピレン、イソブチレン、あるいは分子量がより高いオレフィンなどの所望の製品のモル数を変換したパラフィンのモル数の比として規定される。活性あるいは変換率は、所望の生成物と副産物に変換される原料部分を意味する。プロセスの効率を上げるためには、新しい触媒を用いたときの高い初期収率と、触媒が古くなったときの触媒の高い活性と選択性の双方があることが重要である。この開示の目的のためには、触媒がストリーム上で7−8ヶ月間使用した後、「老化した」と考えられる。代替的に、触媒は、後述する態様で「人工的に老化させた」後、「老化した」と考えられる。これらの両基準(初期収率及び「老化した」後の収率)を用いて、触媒全体の効率を決定する。
このような触媒製造プロセスの一つにおいて、バイヤライト、ギブサイト、ノルドストランドダイト、又はこれらの混合物などの水酸化アルミニウム、あるいはその他のアルミナ水和物と含水硝酸から、アルミナペレットを作成する。か焼アルミナ担体は、ガンマ−アルミナ、シータ−アルミナ、あるいはイータ−アルミナ、及びこれに類するもの、あるいはこれらの混合物の形であっても良い。また、一の実施例では、この材料が混合時間の間に予め混合され、アルミナと酸化窒素の反応が完了している。次いで、この混合物を適宜の形態で中間前駆物質に形成し、所望の形に成形する。例えば、この混合物をダイプレートを通して押し出して、ひも状にし、切断してペレットにするようにしても良い。代替的に、アルミナを、限定するものではないが、球形、タブレット形、筒形、星形、三つ葉形、これらの類似する形を含むその他の形状にすることもできる。
この触媒は、静止床及び流動床脱水素化プロセスに使用することを意図している。この触媒は、脱水素化触媒として有効であり、特に、プロパン、イソブタン、n−ブタン、及びイソペンタンの脱水素化を促進して、関連するオレフィンまたはジオレフィンを生成するのに有効である。この触媒の組成物と処理条件は、本発明の様々な実施例の範囲を超えることなく、変更することができる。
以下の例は、本発明の様々な実施例を説明するものであるが、いかなる関連においても、実施例を限定するものと解するべきではない。部分及びパーセントは、特に記載がない限り、重量による。
19.7重量%のCr2O3と0.65重量%のNa2Oの組成物であり、残余部分がアルミナを含む脱水素化触媒を以下の通り調整する。
例1のプロセスによって、硬質アルミナペレットから触媒を作成する。硬質アルミナペレットを、42重量%の酸化クロム溶液、0.4重量%の酸化ナトリウム、及び1.1重量%の酸化カリウムに、含浸させ、以下に挙げた成分の重量パーセントとする。含浸させたアルミナペレットを、121℃で10時間乾燥させ、例1のプロセスに従って、760℃でか焼する。この触媒の最終処方は、19.7重量%のCr2O3と0.21重量%のNa2Oと0.52重量%のK2Oの組成であり、残余部分がAl2O3を含む。
例1のプロセスによって、硬質アルミナペレットから触媒を作成する。硬質アルミナペレットを、42重量%の酸化クロム、1.8重量%の酸化カリウムの溶液に含浸させ、以下に挙げた成分の重量パーセントとする。含浸させたアルミナペレットを、121℃で数時間乾燥させ、例1のプロセスに従って、760℃でか焼する。この触媒の最終組成は、19.7重量%のCr2O3と0.93重量%のK2Oであり、残余部分がAl2O3を含む。
例1のプロセスによって、硬質アルミナペレットから触媒を作成する。硬質アルミナペレットを、42重量%の酸化クロム、0.95重量%の酸化ナトリウム、及び0.55重量%の酸化リチウムの溶液に含浸させ、以下に挙げた成分の重量パーセントとする。含浸させたアルミナペレットを、121℃で乾燥させ、例1のプロセスに従って、760℃でか焼する。この触媒の最終処方は、19.5重量%のCr2O3と0.5重量%のNa2Oと0.3重量%のLi2Oであり、残余部分がAl2O3を含む。
例1のプロセスによって、硬質アルミナペレットから触媒を作成する。硬質アルミナペレットを、42重量%の酸化クロム、0.75重量%の酸化ナトリウム、及び0.25重量%の酸化リチウム、及び0.44%の酸化カリウムの溶液に含浸させ、以下に挙げた成分の重量%とする。含浸させたアルミナペレットを、121℃で乾燥させ、例1のプロセスに従って、760℃でか焼する。この触媒の最終処方は、19.8重量%のCr2O3と0.45重量%のNa2Oと0.21重量%のK2Oと、0.11重量%のLi2Oの組成であり、残余部分がAl2O3を含む。
Claims (10)
- 脱水素化プロセスに使用する触媒において:
担体としてのアルミナと;
触媒総重量につき10重量%乃至30重量%の酸化クロム濃度の酸化クロムと;
触媒総重量につき0.1重量%乃至2重量%の酸化ナトリウム濃度の促進剤としての酸化ナトリウムと;
触媒総重量につき0.1重量%乃至5重量%の酸化カリウム濃度の促進剤としての酸化カリウムと;
を含み、前記酸化カリウムと前記酸化ナトリウムとの比が、重量ベースで0.1:1乃至10:1であり、前記触媒が酸化リチウムを含まないことを特徴とする触媒。 - 脱水素化プロセスに使用する触媒において:
担体としてのアルミナと;
触媒総重量につき10重量%乃至30重量%の酸化クロム濃度の酸化クロムと;
触媒総重量につき0.1重量%乃至2重量%の酸化ナトリウム濃度の促進剤としての酸化ナトリウムと;
触媒総重量につき0.1重量%乃至5重量%の酸化カリウム濃度の促進剤としての酸化カリウムと;
を含み、前記酸化カリウムと前記酸化ナトリウムとの比が、重量ベースで0.1:1乃至3:1であり、前記触媒が酸化リチウムを含まないことを特徴とする触媒。 - 請求項1又は2に記載の触媒において、前記酸化クロムが、触媒総重量につき15重量%乃至28重量%の濃度で存在することを特徴とする触媒。
- 請求項1又は2に記載の触媒において、前記酸化ナトリウムが、触媒総重量につき0.1重量%乃至1重量%の濃度で存在することを特徴とする触媒。
- 請求項1又は2に記載の触媒において、前記酸化ナトリウムが、触媒総重量につき0.1重量%乃至0.3重量%の濃度で存在することを特徴とする触媒。
- 請求項1又は2に記載の触媒において、前記酸化カリウムが、触媒総重量につき0.1重量%乃至2重量%の濃度で存在することを特徴とする触媒。
- 請求項1又は2に記載の触媒が更に、ジルコニウムとマグネシウムの化合物及びこれらの混合物からなる群から選択された少なくとも一の追加の促進剤を含むことを特徴とする触媒。
- 酸化リチウムを含まない脱水素化反応触媒を製造するプロセスにおいて:
42重量%のクロム化合物と、0.4重量%のナトリウム化合物と、1.1重量%のカリウム化合物を準備するステップと;
アルミナを、前記クロム化合物と、前記ナトリウム化合物及び前記カリウム化合物からなるアルカリ金属化合物とを含む化合物と混合して、前駆体材料を形成するステップと;
当該前駆体材料を熱処理して、前記脱水素化触媒を形成するステップと;
を具えることを特徴とするプロセス。 - 請求項8に記載のプロセスにおいて、前記クロム化合物が、前記アルミナの担体の上に含浸させたCrO3溶液の形で追加されることを特徴とするプロセス。
- 請求項1又は2に記載の触媒において、前記酸化ナトリウム及び前記酸化カリウムの促進剤が、前記担体上に、前記酸化クロムと、共含浸されていることを特徴とする触媒。
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2008
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JP2011527941A (ja) | 2011-11-10 |
SA109300460B1 (ar) | 2013-11-17 |
US8101541B2 (en) | 2012-01-24 |
DK2300157T3 (da) | 2021-03-01 |
CN102123790A (zh) | 2011-07-13 |
ES2856774T3 (es) | 2021-09-28 |
EP2300157A4 (en) | 2012-10-10 |
EP2300157B1 (en) | 2021-02-17 |
US20100010280A1 (en) | 2010-01-14 |
PL2300157T3 (pl) | 2021-09-06 |
WO2010009076A2 (en) | 2010-01-21 |
EA017327B1 (ru) | 2012-11-30 |
EP2300157A2 (en) | 2011-03-30 |
WO2010009076A3 (en) | 2010-05-06 |
CN102123790B (zh) | 2014-01-08 |
EA201100109A1 (ru) | 2011-10-31 |
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