JP2015505799A - 中温で作用する水性ガスシフト触媒およびその調製のための方法 - Google Patents
中温で作用する水性ガスシフト触媒およびその調製のための方法 Download PDFInfo
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- JP2015505799A JP2015505799A JP2014543829A JP2014543829A JP2015505799A JP 2015505799 A JP2015505799 A JP 2015505799A JP 2014543829 A JP2014543829 A JP 2014543829A JP 2014543829 A JP2014543829 A JP 2014543829A JP 2015505799 A JP2015505799 A JP 2015505799A
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- Prior art keywords
- hydrotalcite
- formula
- catalyst
- type compound
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- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 37
- 238000000034 method Methods 0.000 title claims description 24
- 230000008569 process Effects 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 17
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 13
- -1 carbonate anion Chemical class 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims description 68
- 238000006243 chemical reaction Methods 0.000 claims description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 239000011701 zinc Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229960001545 hydrotalcite Drugs 0.000 claims description 8
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 claims description 2
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 10
- 238000010189 synthetic method Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 40
- 229910052799 carbon Inorganic materials 0.000 description 40
- 239000002243 precursor Substances 0.000 description 34
- 230000000694 effects Effects 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000007787 solid Substances 0.000 description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 12
- 238000003760 magnetic stirring Methods 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- ZJQPLBFKBQYYIO-UHFFFAOYSA-N dodecasodium;trisilicate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] ZJQPLBFKBQYYIO-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions 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
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
- B01J27/236—Hydroxy carbonates
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- B01J23/007—Mixed salts
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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
- B01J23/76—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
- B01J23/80—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 zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B01J35/391—Physical properties of the active metal ingredient
- B01J35/392—Metal surface area
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J35/393—Metal or metal oxide crystallite size
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/006—Compounds containing, besides zinc, two ore more other elements, with the exception of oxygen or hydrogen
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- 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
- C07C29/154—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 copper, silver, gold, or compounds thereof
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Abstract
Description
[CuxZnyAlw(OH)2](2x+2y+3w-2)+(A2-)(2x+2y+3w-2)/2、kH2O (I)
式中:
− (A2-)は炭酸塩アニオンまたはケイ酸塩アニオンのいずれかを表し、
− x>0、
− y>0、
− w>0、
− (x+y)=(1−w)、
− 1<[(x+y)/w]<5、および
− 1/99≦x/y≦1/1。
[Cu0.075Zn0.675Al0.25(OH)2]0.25+(CO3 2-)0.125 kH2O、
[Cu0.150Zn0.600Al0.25(OH)2]0.25+(CO3 2-)0.125 kH2O、
[Cu0.066Zn0.600Al0.333(OH)2]0.25+(CO3 2-)0.125 kH2O、
[Cu0.134Zn0.532Al0.333(OH)2]0.31+(CO3 2-)0.155 kH2O。
− 硝酸アルミニウム、硝酸亜鉛および硝酸銅をともに含有する水溶液を、前記硝酸塩を望ましいモル比で水と混合することによって調製する工程A;
− 工程Aで得られた前記溶液を、炭酸ナトリウムの水溶液と混合し、pHを8〜10、好ましくはおよそ9に維持して、沈殿物を生成する工程B;
− 工程Bで得られた前記沈殿物を、濾過により単離し、洗浄し、次いで乾燥させて、所期の前記式(I)のハイドロタルサイト型化合物を形成する工程C。
− 工程Cで得られた、上で定義した前記式(I)の前記ハイドロタルサイト型化合物をすり潰して、前記式(I)の前記ハイドロタルサイト型化合物の粒子の粉末を形成する工程Dをさらに含む。
− 上で定義した式(I)のハイドロタルサイト型化合物の粉末をか焼する工程F;
− 工程Fで得られたか焼粉末を、230℃未満の温度で水素を用いて還元させる工程G。
例1:触媒ZAC1cの調製
この例は、10wt.%の銅を含有し、原子比率(Cu+Zn)/Al=3を有し、ハイドロタルサイト型前駆体における層間アニオンとして炭酸塩を使用する、20グラムの触媒の調製方法を説明する。
[Cu0.117Zn0.629Al0.254(OH)2]0.25+(CO3 2-)0.125 kH2O、
次いで、この生じた固体を多量の温水(60℃、400cm3/g試料)を用いて洗浄し、70℃で一晩乾燥させる。得られた前駆体をすり潰した後、粉末をマッフル炉において550℃(10℃/分)で6時間か焼し、次いで形成し、30から40メッシュのサイズでふるい分ける。
Cu含有量(wt.%)が例1(ZAC1c)の2倍多いことを除いて、例1と同様に調製方法を使う。
[Cu0.234Zn0.514Al0.252(OH)2]0.25+(CO3 2-)0.125 kH2O、
この生じた固体を、多量の温水(60℃、400cm3/g試料)を用いて洗浄し、70℃で一晩乾燥させる。得られた前駆体をすり潰した後、粉末をマッフル炉において550℃(10℃/分)で6時間か焼し、次いで形成し、30から40メッシュのサイズでふるい分ける。
Cu含有量(wt.%)が例1(ZAC1c)の3倍多いことを除いて、例1と同様に調製方法を使う。
[Cu0.349Zn0.399Al0.251(OH)2]0.25+(CO3 2-)0.125 kH2O、
生じた固体を、多量の温水(60℃、400cm3/g試料)を用いて洗浄し、70℃で一晩乾燥させる。得られた前駆体をすり潰した後、粉末をマッフル炉において550℃(10℃/分)で6時間か焼し、次いで形成し、30から40メッシュのサイズでふるい分ける。
Na2CO3溶液をケイ酸ナトリウム(Na2SiO3)溶液で置きかえることを除いて、例1と同様に調製方法を使う。
[Cu0.117Zn0.629Al0.254(OH)2]0.25+(SiO3 2-)0.125 kH2O、
この生じた固体を、多量の温水(60℃、400cm3/g試料)を用いて洗浄し、70℃で一晩乾燥させる。得られた前駆体をすり潰した後、粉末をマッフル炉において550℃(10℃/分)で6時間か焼し、次いで形成し、30から40メッシュのサイズでふるい分ける。
炭酸塩溶液をケイ酸塩溶液で置きかえることを除いて、例2の方法に従う。
[Cu0.234Zn0.514Al0.252(OH)2]0.25+(SiO3 2-)0.125 kH2O、
この生じた固体を、多量の温水(60℃、400cm3/g試料)を用いて洗浄し、70℃で一晩乾燥させる。得られた前駆体をすり潰した後、粉末をマッフル炉において550℃(10℃/分)で6時間か焼し、次いで形成し、30から40メッシュのサイズでふるい分ける。
例1と同様に調製方法を使う;しかし、か焼後に、炭酸カリウム(2wt.%のK)(K2CO3)溶液を使用して、初期湿式含浸(Incipient Wetness Impregnation)(IWI)方法により触媒をドープする。
比較例は、市販のCu系触媒であり、低温および/または中温で水性ガスシフト反応を行うように最適化されている。
図1は、触媒ZAC1c、ZAC2c、ZAC3c、ZAC1sおよびZAC2sのそれぞれのハイドロタルサイト型前駆体(HT−ZAC1c、HT−ZAC2c、HT−ZAC3c、HT−ZAC1sおよびHT−ZAC2sとして識別する)のXRD分析から得られたグラフを示す。
− 1)反応器において、窒素(N2)をパージすることにより酸素(O2)を除去し、その後175℃(50℃/h)に触媒を加熱する;
− 2)温度が175℃に達し、一定に維持されると、0.8v/v%の水素(H2)の流れを加える;
− 3)この段階で、18時間にわたって、1.2v/v%のH2/N2を超えることなく、0.2v/v%ずつ、H2の濃度を徐々に増加させる;
− 4)N2中で1.5v/v%のH2を超えることを避けながら、入口温度を220℃(15℃/h)まで上昇させる;
− 5)N2中のH2濃度を、0.5v/v%ずつ、4v/v%まで徐々に上昇させて、温度が220℃に達し、安定したら、触媒のホットスポット温度が230℃を超えないことを確認する。触媒のホットスポットが250℃を超えると、プロトコルを中断しなければならない(H2/N2注入の停止、反応器の減圧および新しいN2によるスイープ)。
本発明の触媒を、参照触媒(ZA3K)とともに、30〜40メッシュのサイズをもつペレットに成形し、栓流反応器において試験する。
ZAC触媒の活性および選択性を、MeOH合成ならびにMTSおよびLTS反応に使用される市販の材料のものと比較した。以下の表は、選択性および生産性に関して、280〜320℃の温度条件下で、炭酸塩含有前駆体のか焼により得られたEx−ハイドロタルサイト Cu系触媒の最良の性能を明らかに示している。
触媒について可能な不活化を、最も有利な接触時間(1.0秒)を使用するが、S/DG値(0.25v/v)に関しては厳しい条件で、300℃で100時間にわたり調べた。調製した触媒はすべて、特に炭酸塩HT前駆体のか焼により得られた触媒は、時間の経過(tos)とともに最適な安定性を示している。安定性に関して、調査したすべての試料(例1から6)について同一の挙動が観察されている。より穏和な条件において平衡値に達するので、これらの結果は中温シフト操作条件における触媒の良好な性能を示唆している。
中温で行ったWGS反応における7種のか焼HT触媒の活性および選択性を調べている。以下の図は、250℃〜350℃の典型的な生産条件における活性および選択性に関して、炭酸塩含有前駆体のか焼により得られたCu含有触媒の最良の性能を明らかに示している。
図8に示すように、本発明による触媒の触媒活性は、広く普及した市販の触媒と比較して、炭酸塩含有HT前駆体から得られ、20wt.%より低いCu含有量をもつ最良の触媒についての平衡値に達し、より良好な性能を証明している。これらの触媒は、時間の経過とともに非常に良好な安定性も示す。
Claims (12)
- 式(I)のハイドロタルサイト型化合物。
[CuxZnyAlw(OH)2](2x+2y+3w-2)+(A2-)(2x+2y+3w-2)/2、kH2O (I)
[式中、
− (A2-)は炭酸塩アニオンまたはケイ酸塩アニオンのいずれかを表し、
− x>0、
− y>0、
− w>0、
− (x+y)=(1−w)、
− 1<[(x+y)/w]<5、および
− 1/99≦x/y≦1/1。] - 原子比率x/y≦1/2である、請求項1において上で定義した式(I)のハイドロタルサイト型化合物。
- 原子比率x/y≦1/5である、請求項2において上で定義した式(I)のハイドロタルサイト型化合物。
- 原子比率x/y≧1/10である、請求項1ないし3の1項において上で定義した式(I)のハイドロタルサイト型化合物。
- 原子比率[(x+y)/w]が2以上である、請求項1ないし4の1項において上で定義した式(I)のハイドロタルサイト型化合物。
- 原子比率[(x+y)/w]が3以下である、請求項1ないし4の1項において上で定義した式(I)のハイドロタルサイト型化合物。
- 以下の式のうち1つのハイドロタルサイト型化合物。
[Cu0.075Zn0.675Al0.25(OH)2]0.25+(CO3 2-)0.125 kH2O
[Cu0.150Zn0.600Al0.25(OH)2]0.25+(CO3 2-)0.125 kH2O
[Cu0.066Zn0.600Al0.333(OH)2]0.25+(CO3 2-)0.125 kH2O
[Cu0.134Zn0.532Al0.333(OH)2]0.31+(CO3 2-)0.155 kH2O - 以下の工程を含む、請求項1ないし7の1項において上で定義した式(I)のハイドロタルサイト型化合物の合成方法:
− 硝酸アルミニウム、硝酸亜鉛および硝酸銅をともに含有する水溶液を、前記硝酸塩を適切な比で水と混合することによって調製する工程A;
− 工程Aで得られた前記溶液を、炭酸水素ナトリウム塩の水溶液と混合し、pHを8〜10、好ましくはおよそ9に維持して、沈殿物を生成する工程B;
− 工程Bで得られた前記沈殿物を、濾過により単離し、洗浄し、次いで乾燥させて、所期の前記式(I)のハイドロタルサイト型化合物を形成する工程C。 - − 工程Cで得られた、上で定義した前記式(I)の前記ハイドロタルサイト型化合物をすり潰して、前記式(I)の前記ハイドロタルサイト型化合物の粒子の粉末を形成する工程D
をさらに含む、請求項8に記載の式(I)のハイドロタルサイト型化合物の合成方法。 - 以下の工程を含む方法により得られたことを特徴とする化合物:
− 請求項1ないし7の1項において上で定義した式(I)の前記ハイドロタルサイト型化合物の粉末をか焼する工程F;
− 工程Fで得られた前記か焼粉末を、230℃未満の温度で水素を用いて還元する工程G。 - 請求項10に記載の方法によって得られた前記化合物の、合成ガスの水性ガスシフト反応用触媒としての使用。
- 請求項10に記載の方法によって得られた化合物の、メタノールの合成のための触媒としての使用。
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EP2141118B1 (en) | 2008-07-03 | 2013-08-07 | Haldor Topsoe A/S | Chromium-free water gas shift catalyst |
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2011
- 2011-12-02 PT PT113066047T patent/PT2599541T/pt unknown
- 2011-12-02 ES ES11306604.7T patent/ES2628881T3/es active Active
- 2011-12-02 EP EP11306604.7A patent/EP2599541B1/en not_active Not-in-force
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- 2012-11-14 CA CA2856445A patent/CA2856445A1/en not_active Abandoned
- 2012-11-14 KR KR1020147017598A patent/KR20140098823A/ko not_active Application Discontinuation
- 2012-11-14 CN CN201280068891.3A patent/CN104080528A/zh active Pending
- 2012-11-14 BR BR112014013331A patent/BR112014013331A2/pt not_active Application Discontinuation
- 2012-11-14 US US14/361,804 patent/US20140309102A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
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ES2628881T3 (es) | 2017-08-04 |
JP6165759B2 (ja) | 2017-07-19 |
EP2599541A1 (en) | 2013-06-05 |
KR20140098823A (ko) | 2014-08-08 |
CN104080528A (zh) | 2014-10-01 |
US20140309102A1 (en) | 2014-10-16 |
PT2599541T (pt) | 2017-06-30 |
RU2014126869A (ru) | 2016-02-10 |
EP2599541B1 (en) | 2017-05-03 |
WO2013079323A1 (en) | 2013-06-06 |
CA2856445A1 (en) | 2013-06-06 |
BR112014013331A2 (pt) | 2017-06-13 |
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