JP5991553B2 - 炭素担持コバルト及びモリブデン触媒 - Google Patents
炭素担持コバルト及びモリブデン触媒 Download PDFInfo
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- JP5991553B2 JP5991553B2 JP2014505538A JP2014505538A JP5991553B2 JP 5991553 B2 JP5991553 B2 JP 5991553B2 JP 2014505538 A JP2014505538 A JP 2014505538A JP 2014505538 A JP2014505538 A JP 2014505538A JP 5991553 B2 JP5991553 B2 JP 5991553B2
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- 239000003054 catalyst Substances 0.000 title claims description 140
- 229910052750 molybdenum Inorganic materials 0.000 title claims description 36
- 229910017052 cobalt Inorganic materials 0.000 title claims description 14
- 239000010941 cobalt Substances 0.000 title claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims description 13
- 239000011733 molybdenum Substances 0.000 title claims description 13
- 239000000203 mixture Substances 0.000 claims description 107
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 56
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 55
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 51
- 150000003839 salts Chemical class 0.000 claims description 40
- 230000015572 biosynthetic process Effects 0.000 claims description 35
- 239000012018 catalyst precursor Substances 0.000 claims description 32
- 238000003786 synthesis reaction Methods 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 100
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 238000001556 precipitation Methods 0.000 description 24
- 239000012153 distilled water Substances 0.000 description 23
- 239000002244 precipitate Substances 0.000 description 22
- 239000003153 chemical reaction reagent Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 11
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 11
- 235000013162 Cocos nucifera Nutrition 0.000 description 10
- 244000060011 Cocos nucifera Species 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 9
- 229940011182 cobalt acetate Drugs 0.000 description 9
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 9
- 238000005086 pumping Methods 0.000 description 9
- 239000012266 salt solution Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 150000001298 alcohols Chemical class 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- JSRLCNHTWASAJT-UHFFFAOYSA-N helium;molecular nitrogen Chemical compound [He].N#N JSRLCNHTWASAJT-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000011900 installation process Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910019614 (NH4)6 Mo7 O24.4H2 O Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical group O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000010514 hydrogenated cottonseed oil Substances 0.000 description 1
- 239000008173 hydrogenated soybean oil Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 oxygen hydrocarbons Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Images
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
- B01J23/70—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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B01J35/19—
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/618—
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- 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
- C07C29/153—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
- 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
-
- B01J35/30—
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
CoaMobMcC
で表され、
式中、
Mは、アルカリ金属及びアルカリ土類金属から成る群から選択される一つ以上の元素であり、
aは1E−3〜0.3であり;
bは1E−3〜0.9であり;
cは0〜1E−2であり;且つ、
前記Co及びMoはそれらの金属形態であり、前記触媒組成物は、少なくとも320m2/gのBET表面積を有する。
(a)700〜1500m2/gのBET表面積を有する活性化した炭素担持粒子と、可溶性のCo含有塩及びMo含有塩を含む溶液とを含む混合物を調製する工程、
(b)可溶性Co及びMo含有塩を不溶性Co及びMo含有塩へ変換することによりCo及びMoを沈殿させ、任意に、その後、Mを含む溶液を混合する工程、
(c)液体から固体を分離して、触媒前駆体を得る工程、及び、
(d)300〜550℃の温度で、触媒前駆体を還元剤と接触させる工程
を含む。
(d1)不活性雰囲気中で触媒前駆体を焼成して、焼成された触媒前駆体を得る工程、及び
(d2)焼成した触媒前駆体を還元剤と接触させる工程
を含む。
(a)700〜1500m2/gのBET表面積を有する活性化した炭素担持粒子と、可溶性Co含有塩及びMo含有塩を含む溶液とを含む混合物を調製する工程;
(b)可溶性Co含有塩及びMo含有塩を、不溶性Co含有塩及びMo含有塩へ変換することによりCo及びMoを沈殿させ、必要に応じてその後にMを含む溶液を混合する工程;
(c)液体から固体を分離して、触媒前駆体を得る工程;及び、
(d)300〜550℃の温度で、触媒前駆体を還元剤と接触させる工程
を含む方法により、得ることができる触媒組成物に関する。
(a)700〜1500m2/gのBET表面積を有する活性化された炭素担持粒子と、可溶性Co含有塩及びMo含有塩を含む溶液とを含む混合物を調製する工程、
(b)可溶性Co含有塩及びMo含有塩を不溶性Co含有塩及びMo含有塩へ変換することによりCo及びMoを沈殿させ、必要に応じてその後にMを含む溶液を混合する工程、
(c)液体から固体を分離して、触媒前駆体を得る工程、及び、
(d)300〜550℃の温度で、触媒前駆体を還元剤と接触させる工程
を含む。
本発明を、以下の非限定的な実施例によって、より完全に説明する。
CoMoS2
Co0.159Mo0.079C
Co0.159Mo0.079C
Co0.126Mo0.766C
Co0.177Mo0.547C
触媒金属(0.5g)を反応器中に入れ、数時間350〜400℃でH2を用いて還元した。圧力を75barに上げた。全ての触媒を、同じ反応条件(T=250℃、p=75bar、及び、WHSV=1225時間-1)下で試験した。供給流の組成物は、CO:H2:N2=47.5:47.5:5であった。従って、供給流は、1のCO:H2モル比を有する合成ガスを含んでいた。
変換率:
触媒の活性の指標は、一酸化炭素の変換率の程度により、又は、より活性な触媒について、試薬ガスの体積減少の程度により、測定する(内部標準として窒素を使用する)。使用された基本的な式は以下であった:
変換率%=COinのモル数−COoutのモル数/COinのモル数*100/1
まず、各生成物成分に対する検出器の様々な反応を、オンライン校正係数でそれらを乗算することにより、%体積/体積に変換した。次に、これらを、内部標準の流出、供給物のモル数及び時間を考慮することにより、モル数へ変換した。それぞれの生成物のモル数はモル%へ変換し、選択性%は、炭素数を考慮に入れることにより測定した。
Co0.126Mo0.255C
Co0.126Mo0.255C
Co0.126Mo0.255C
Co0.126Mo0.255C
Co0.126Mo0.255C
比較触媒を、本発明による触媒と同じ反応条件下(T=250℃、p=75bar、及び、WHSV=1225時間-1)で試験した。供給流の組成物は、CO:H2:N2=47.5:47.5:5であった。従って、供給流は、1のCO:H2モル比を有する合成ガスを含んでいた。
本発明のまた別の態様は、以下のとおりであってもよい。
〔1〕活性化した炭素担体(C)上に、コバルト(Co)及びモリブデン(Mo)を含む触媒組成物であって、前記組成物中に含まれる元素の相対モル比が、以下の式:
Co a Mo b M c C
によって表され、
式中、
Mは、アルカリ金属及びアルカリ土類金属から成る群から選択される一つ以上の元素であり、
aは1E−3〜0.3であり、
bは1E−3〜0.9であり、
cは0〜1E−2であり、且つ、
前記Co及びMoはそれらの金属形態であり、前記触媒組成物は、少なくとも320m 2 /gのBET表面積を有する、触媒組成物。
〔2〕前記Mが、カリウム(K)、ナトリウム(Na)、カルシウム(Ca)及びマグネシウム(Mg)から成る群から選択される、前記〔1〕に記載の触媒組成物。
〔3〕式中、
aは1E−2〜0.3であり;且つ
bは5E−3〜0.9である、
前記〔1〕又は〔2〕に記載の触媒組成物。
〔4〕前記触媒組成物は、350〜1200m 2 /gのBET表面積を有する、前記〔1〕〜〔3〕のいずれか一項に記載の触媒組成物。
〔5〕前記Co及び/又はMoは、硫化物形態でない、前記〔1〕〜〔4〕のいずれか一項に記載の触媒組成物。
〔6〕前記触媒組成物が、不活性結合剤を更に含む、前記〔1〕〜〔5〕のいずれか一項に記載の触媒組成物。
〔7〕以下の工程:
(a)700〜1500m 2 /gのBET表面積を有する活性化した炭素担持粒子と、可溶性Co含有塩及びMo含有塩を含む溶液とを含む混合物を調製する工程;
(b)前記可溶性Co含有塩及びMo含有塩を不溶性Co含有塩及びMo含有塩へ変換することによりCo及びMoを沈殿させ、任意に、その後、Mを含む溶液を混合する工程;
(c)液体から固体を分離して、触媒前駆体を得る工程;及び、
(d)300〜550℃の温度で、前記触媒前駆体を還元剤と接触させる工程
を含む、前記〔1〕〜〔6〕のいずれか一項に記載の触媒組成物を調製するための方法。
〔8〕前記工程(d)が、以下の:
(d1)不活性雰囲気中で前記触媒前駆体を焼成して、焼成した触媒前駆体を得る工程;及び、
(d2)前記焼成した触媒前駆体を還元剤と接触させる工程
を含む、前記〔7〕に記載の方法。
〔9〕焼成前に、前記分離された触媒前駆体を洗浄及び乾燥させる工程を更に含む、前記〔7〕又は〔8〕に記載の方法。
〔10〕前記〔1〕〜〔6〕のいずれか一項に記載の前記触媒組成物を、合成ガス混合物と接触させることを含む、アルコール含有生成物流を生成するための方法。
〔11〕前記触媒組成物が、固定床反応器又は流動床反応器中に含まれる、前記〔10〕に記載の方法。
〔12〕前記合成ガス混合物が、0.5〜5の、一酸化炭素(CO)に対する水素(H 2 )モル比を有する、前記〔10〕又は〔11〕に記載の方法。
〔13〕前記方法を、150〜450℃の反応温度、400〜5000時間 -1 の空間速度、大気圧〜20MPaの圧力で行う、前記〔10〕〜〔12〕のいずれか一項に記載の方法。
Claims (13)
- 水素及び一酸化炭素を含む合成ガス混合物からアルコールを生成するための触媒組成物であって、前記触媒組成物が、活性炭担体(C)上に、コバルト(Co)及びモリブデン(Mo)を含み、前記組成物中に含まれる元素の相対モル比が、以下の式:
CoaMobMcC
によって表され、
式中、
Mは、アルカリ金属及びアルカリ土類金属から成る群から選択される一つ以上の元素であり、
aは1E−3〜0.3であり、
bは1E−3〜0.9であり、
cは0〜1E−2であり、且つ、
前記Co及びMoはそれらの金属形態であり、前記触媒組成物は、少なくとも320m2/gのBET表面積を有する、触媒組成物。 - 前記Mが、カリウム(K)、ナトリウム(Na)、カルシウム(Ca)及びマグネシウム(Mg)から成る群から選択される、請求項1に記載の触媒組成物。
- 式中、
aは1E−2〜0.3であり;且つ
bは5E−3〜0.9である、
請求項1又は2に記載の触媒組成物。 - 前記触媒組成物は、350〜1200m2/gのBET表面積を有する、請求項1〜3のいずれか一項に記載の触媒組成物。
- 前記Co及び/又はMoは、硫化物形態でない、請求項1〜4のいずれか一項に記載の触媒組成物。
- 前記触媒組成物が、不活性結合剤を更に含む、請求項1〜5のいずれか一項に記載の触媒組成物。
- 以下の工程:
(a)700〜1500m2/gのBET表面積を有する活性炭担体粒子と、可溶性Co含有塩及びMo含有塩を含む溶液とを含む混合物を調製する工程;
(b)前記可溶性Co含有塩及びMo含有塩を不溶性Co含有塩及びMo含有塩へ変換することによりCo及びMoを沈殿させ、任意に、その後、Mを含む溶液を混合する工程;
(c)液体から固体を分離して、触媒前駆体を得る工程;及び、
(d)300〜550℃の温度で、前記触媒前駆体を還元剤と接触させる工程
を含む、請求項1〜6のいずれか一項に記載の触媒組成物を調製するための方法。 - 前記工程(d)が、以下の:
(d1)不活性雰囲気中で前記触媒前駆体を焼成して、焼成した触媒前駆体を得る工程;及び、
(d2)前記焼成した触媒前駆体を還元剤と接触させる工程
を含む、請求項7に記載の方法。 - 焼成前に、前記分離された触媒前駆体を洗浄及び乾燥させる工程を更に含む、請求項7又は8に記載の方法。
- 請求項1〜6のいずれか一項に記載の前記触媒組成物を、合成ガス混合物と接触させることを含む、アルコール含有生成物流を生成するための方法。
- 前記触媒組成物が、固定床反応器又は流動床反応器中に含まれる、請求項10に記載の方法。
- 前記合成ガス混合物が、0.5〜5の、一酸化炭素(CO)に対する水素(H2)モル比を有する、請求項10又は11に記載の方法。
- 前記方法を、150〜450℃の反応温度、400〜5000時間-1の空間速度、大気圧〜20MPaの圧力で行う、請求項10〜12のいずれか一項に記載の方法。
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US10745624B2 (en) | 2015-05-08 | 2020-08-18 | Sabic Global Technologies B.V. | Systems and methods related to syngas to olefin production |
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