CN1280116A - 从合成气中制备含两个碳原子的一氧合物的方法和催化剂 - Google Patents
从合成气中制备含两个碳原子的一氧合物的方法和催化剂 Download PDFInfo
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- CN1280116A CN1280116A CN00122220A CN00122220A CN1280116A CN 1280116 A CN1280116 A CN 1280116A CN 00122220 A CN00122220 A CN 00122220A CN 00122220 A CN00122220 A CN 00122220A CN 1280116 A CN1280116 A CN 1280116A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 title 1
- 239000010948 rhodium Substances 0.000 claims abstract description 21
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 18
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 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 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011591 potassium Substances 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 239000011575 calcium Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 5
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 229910052728 basic metal Inorganic materials 0.000 claims description 7
- 150000003818 basic metals Chemical class 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 238000006424 Flood reaction Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910006655 Li—K Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- -1 and if desired Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
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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
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- B01J23/6525—Molybdenum
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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
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
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- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
- C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
- C07C29/158—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof containing rhodium or compounds thereof
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Abstract
一种在载体上的含铑催化剂存在下,通过CO和H2的反应制备C2-氧合物的方法,其中该催化剂包括以总重量为基准计,在惰性载体上的:0.01~10%(按重量计算)的铑,0.001~10%(按重量计算)的锆,0.01~5%(按重量计算)的铱,0.01~10%(按重量计算)的选自铜、钴、镍、锰、铁、钌、和钼中的至少一种金属,0.01~10%(按重量计算)的选自锂、钠、钾、铷、镁和钙中的至少一种碱金属或碱土金属。
Description
本发明涉及一种从合成气,即CO/H2气体混合物制备C2氧合物的方法和催化剂。
自从二十年代以来,已经知道将合成气经多相催化作用转化为烃(费-托合成法)或转化为甲醇。直到1975年才发现了铑催化剂能够将合成气直接地转化为C2氧合物。
原则上,在铑催化剂下合成气的直接反应能够产生宽范围的产物。因此,在自发的Rh/SiO2催化剂作用下,形成甲烷和高级烃以及氧合物例如甲醇、乙醇、高级醇、二醇、乙醛和乙酸。通过用其他元素掺杂或适当选择载体可以大大改变铑催化剂的选择性和活性。例如,用锂或钾掺杂可抑制甲烷的形成,用锰掺杂大大增加其活性,而不会显著影响选择性,而使用CeO2代替SiO2作为载体会显著增加形成乙醇的选择性。而且,产物分布取决于例如压力、温度、转化率和CO/H2比这样的反应参数。
EP-A-0010295描述了一种从合成气制备乙醇的方法,其中在包括一种或多种元素锆、铪、镧、铂、铬和汞作为助催化剂、载体铑作为催化剂下进行反应。
EP-A-0079132涉及一种在包括铑、银、锆和钼作为活性组份的载体上的催化剂下通过合成气的催化反应制备氧化的烃的方法,且如果需要,铁、锰、铼、钨、钌、铬、钍和钾也作为活性组份。优先的载体材料是二氧化硅。
J59078130-A涉及一种在包括锰、锆和至少一种碱金属作为促进剂的铑催化剂作用下,通过合成气的反应制备乙酸、乙醛和乙醇的方法。
特别在1980到1986年,在作为日本的C1项目部分“从一氧化碳和化学药品生产基础工业的化学制品的新技术研究和开发计划”中,已经广泛地研究了在铑催化剂作用下,从合成气直接、多相催化的气相合成乙酸。在合成乙酸的工作过程中,有组织地检验大约60种作为促进剂的元素对不同的铑催化剂的活性和选择性的影响。人们发现促进剂例如Mg、Sc、Ti、V、Cr、Mn、Mo或La增加了催化活性,而促进剂例如Li、K、Zr或Ir会增加乙酸形成的选择性。在该项目的最后,在344g/l*h的时空产率时,最佳的Rh-Mn-Ir-Li-K/SiO2催化剂能使乙酸选择性达到71%。也开发出另一种催化剂,该催化剂没有更详细地描述,但是在时空产率为480g/l*h时使乙酸+乙醛的总的选择性达到90%。
日本的C1项目的结果已经编译在“C1化学在日本的发展”(Elsevier,1989)一书上,特别是在第6章(第287-330页)描述了从合成气制备乙酸的过程。在对催化剂优化的筛选试验中,不仅阐明了不同的促进剂对催化剂性能的影响,而且也试验了许多其它的参数例如试验条件(P、T、SV、CO/H2比)、部分硫中毒、载体组成和孔径结构、Rh粒子大小和该催化剂干燥和还原的条件。另外,试验了Rh-Mn-Ir-Li-K/SiO2催化剂的反应历程和Rh-Mn-Ir-Li/SiO2催化剂的时效行为。
本发明的目的是提供制备C2氧合物的方法和催化剂,其使所希望的产物在高催化剂活性和使用年限方面具有高转化和高选择性。
我们已经发现在含铑载体上的催化剂存在下,通过CO和H2的反应制备C2氧合物的方法可以达到此目的,其中该催化剂包括以总重量为基准计,在惰性载体上的:
0.01~10%(按重量计算)的铑,
0.001~10%(按重量计算)的锆,
0.01~5%(按重量计算)的铱,
0.01~10%(按重量计算)的选自铜、钴、镍、锰、铁、钌、和钼中的至少一种金属,
0.01~10%(按重量计算)的选自锂、钠、钾、铷、镁和钙中的至少一种碱金属或碱土金属,
根据本发明已经发现,上述催化剂在合成气转化为C2氧合物方面表现出很好的特征光谱。即使当铑含量非常低时,该催化剂也表现出高的活性和选择性。
该催化剂载体优选SiO2、Al2O3、TiO2、沸石、活性碳、硅藻土和它们的混合物。
碱金属或碱土金属或金属优选锂、钾和镁。
金属优选铜、锰、铁、钌和钼。
优先的催化剂包括载于隋性载体上的:
0.1~5%(按重量计算),特别是0.5~3.5%(按重量计算)的铑,
0.05~5%(按重量计算),特别是0.08~4.5%(按重量计算)的锆,
0.1~3.5%(按重量计算),特别是0.2~2.5%(按重量计算)的铱,
0.1~5%(按重量计算),特别是0.2~1.5%(按重量计算)的选自铜、钴、镍、锰、铁、钌和钼中的至少一种金属,
0.05~5%(按重量计算),特别是0.1~1.2%(按重量计算)的选自锂、钠、钾、铷、镁和钙中的至少一种碱金属或碱土金属。
通过用溶于水或有机溶剂的催化剂金属化合物,特别是催化剂金属盐浸渍该隋性载体,干燥和煅烧该浸渍的载体,随后还原它可以获得本发明的催化剂。可以以任何希望的方式,例如浸渍或喷雾进行浸透。优选使用溶解在水或有机溶剂例如乙醇中的催化剂金属盐。可以自由地选择用催化剂金属间化合物浸渍该载体的顺序。可以连续或同时浸透所有组分。
根据本发明,该催化剂用于合成气的反应,特别是产生C2氧合物例如乙醇、乙醛和乙酸的反应。
该反应优选在1~100巴的压力和200~400℃的温度下进行。
H2与CO的摩尔比优选为10-0.05∶1。
通过下面的实施例来说明本发明。
实施例1
将RhCl3、ZrO(NO3)2、H2IrCl6、Cu(NO3)2和KNO3按照相应于在载体上所要求的浓度比的量溶于水中。然后将该载体(SiO2、20-40μm)在该溶液中浸泡1到2小时。在从该溶液移出并让过剩的溶液滴完后,将该载体在50~600℃下干燥24小时,随后在110℃下煅烧6小时。获得的催化剂包含1.5%(按重量计算)的Rh、0.1%(按重量计算)的Zr、0.3%(按重量计算)的Ir、0.8%(按重量计算)的Cu和0.2%(按重量计算)的K。
在与合成气反应之前,在300℃下用氢气还原该催化剂3小时。然后在300℃下使合成气反应。CO和H2的总压力为3.0MPa,H2/CO的摩尔比是2。空间速度为15000h-1。
CO转化率为4.5%,C2-氧合物的空间-时间产率为312.6g/kg h。CO的选择性是70.1%。
实施例2
使用与实施例1相同的催化剂,在它的制备中首先将该载体浸泡在ZrO(NO3)2溶液中,随后干燥,然后浸泡在由RhCl3、H2IrCl6、Cu(NO3)2和KNO3组成的溶液中。然后干燥该催化剂。
CO的转化率为4.3%,C-氧合物的时空产率为351.2g/kg h。CO的选择性为73.5%。
实施例3-11
按照在实施例1描述的那样进行该反应,但是使用在下列表中表示的催化剂。结果显示在下列表中。
实施例 | 催化剂 | CO转化率% | C2-氧合物的时空产率 | C2-氧合物选择性%(C) |
3 | 3.5Rh-0.2Zr-0.2Ir-0.7Cu-0.1Li/SiO2 | 8.7 | 726.8 | 75.8 |
4 | 1Rh-0.08Zr-0.5Ir-0.5Mn-0.8K-0.1Li/SiO2 | 3.4 | 273.5 | 69.2 |
5 | 1.5Rh-0.1Zr-0.5Ir-0.2Fe-0.1Ru-0.2K/SiO2 | 4.8 | 414.9 | 77.8 |
6 | 2.0Rh-0.1Zr-1.0Ir-0.2Ru-0.5Li/SiO2 | 5.4 | 440.2 | 73.2 |
7 | 0.5Rh-0.3Zr-0.8Ir-0.9Ru-0.3Mo-0.2Mg/ZSM-5 | 2.1 | 148.6 | 63.7 |
8 | 1.0Rh-2.8Zr-0.2Ir-1.0Mn-0.5Mo-1.2Li/SiO2 | 4.2 | 336.5 | 72.1 |
9 | 1.0Rh-4.5Zr-0.5Ir-0.5Mn-0.5Cu-0.8K/SiO2 | 3.9 | 340.2 | 78.5 |
10 | 1.0Rh-0.3Zr-2.5Ir-0.5Mn-0.2K/SiO2 | 4.2 | 363.5 | 77.9 |
11 | 1.0Rh-0.3Zr-2.5Ir-0.5Mn-0.2K/Al2O3 | 5.9 | 362.1 | 55.7 |
C1 | 1.0Rh-0.5Mn-0.2K/SiO2 | 1.2 | 96.7 | 65.3 |
C2 | 1.0Rh-2.5Ir-5Mn-2K/SiO2 | 3.9 | 289.4 | 66.8 |
Claims (9)
1.一种在载体上的含铑催化剂存在下,通过CO和H2的反应制备C2-氧合物的方法,其中该催化剂包括以总重量为基准计,在惰性载体上的:
0.01~10%(按重量计算)的铑,
0.001~10%(按重量计算)的锆,
0.01~5%(按重量计算)的铱,
0.01~10%(按重量计算)的选自铜、钴、镍、锰、铁、钌、和钼中的至少一种金属,和
0.01~10%(按重量计算)的选自锂、钠、钾、铷、镁和钙中的至少一种碱金属或碱土金属。
2.根据权利要求1所述的方法,其中催化剂载体选自SiO2、Al2O3、TiO2、沸石、活性碳和硅藻土。
3.根据权利要求1或2的方法,其中碱金属或碱土金属或金属选自锂、钾和镁。
4.根据权利要求1-3任何一个所述的方法,其中金属是选自铜、锰、铁、钌和钼。
5.根据权利要求1-4的任何一个所述的方法,其中在1~100巴的压力和在200~400℃的温度下进行该反应。
6.根据权利要求1-5的任何一个所述的方法,其中H2与CO的摩尔比为10-0.05∶1。
7.一种在载体上的含铑催化剂,包括以总重量为基准计,在惰性载体上的:
0.01~10%(按重量计算)的铑,
0.001~10%(按重量计算)的锆,
0.01~5%(按重量计算)的铱,
0.01~10%(按重量计算)的选自铜、钴、镍、锰、铁、钌、和钼中的至少一种金属,
0.01~10%(按重量计算)的选自锂、钠、钾、铷、镁和钙中的至少一种碱金属或碱土金属。
8.一种制备权利要求7所述的催化剂的方法,包括用溶于含水溶剂或有机溶剂中的催化剂金属化合物浸渍该惰性载体,干燥和煅烧该浸渍的载体,随后还原它。
9.权利要求7所述的催化剂在合成气的反应中的应用。
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CN113145132A (zh) * | 2021-04-26 | 2021-07-23 | 中国科学院上海高等研究院 | 一种钌基催化剂及其制备方法和用途 |
CN115591556A (zh) * | 2021-06-28 | 2023-01-13 | 中石化南京化工研究院有限公司(Cn) | 用于合成气一步法制甲醛的催化剂及其制备方法、合成气一步法制甲醛的方法 |
CN115591556B (zh) * | 2021-06-28 | 2024-03-01 | 中石化南京化工研究院有限公司 | 用于合成气一步法制甲醛的催化剂及其制备方法、合成气一步法制甲醛的方法 |
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US20020037938A1 (en) | 2002-03-28 |
EP1064997A3 (de) | 2004-02-25 |
US6346555B1 (en) | 2002-02-12 |
EP1064997A2 (de) | 2001-01-03 |
DE19929281A1 (de) | 2000-12-28 |
US6500781B2 (en) | 2002-12-31 |
CN1219733C (zh) | 2005-09-21 |
JP2001031602A (ja) | 2001-02-06 |
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