JP7098862B2 - 水素化プロセスのための金属粉末状触媒 - Google Patents
水素化プロセスのための金属粉末状触媒 Download PDFInfo
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- JP7098862B2 JP7098862B2 JP2019554920A JP2019554920A JP7098862B2 JP 7098862 B2 JP7098862 B2 JP 7098862B2 JP 2019554920 A JP2019554920 A JP 2019554920A JP 2019554920 A JP2019554920 A JP 2019554920A JP 7098862 B2 JP7098862 B2 JP 7098862B2
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- 239000003054 catalyst Substances 0.000 title claims description 87
- 229910052751 metal Inorganic materials 0.000 title claims description 13
- 239000002184 metal Substances 0.000 title claims description 13
- 239000000843 powder Substances 0.000 title description 14
- 238000005984 hydrogenation reaction Methods 0.000 title description 8
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 59
- 229910044991 metal oxide Inorganic materials 0.000 claims description 31
- 150000004706 metal oxides Chemical class 0.000 claims description 31
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000007858 starting material Substances 0.000 claims description 8
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 238000000034 method Methods 0.000 description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- 239000011651 chromium Substances 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000527 sonication Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910000684 Cobalt-chrome Inorganic materials 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000010952 cobalt-chrome Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910000599 Cr alloy Inorganic materials 0.000 description 2
- 229910000823 Megallium Inorganic materials 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004675 formic acid derivatives Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- BZAZNULYLRVMSW-UHFFFAOYSA-N 2-Methyl-2-buten-3-ol Natural products CC(C)=C(C)O BZAZNULYLRVMSW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 229910003244 Na2PdCl4 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- -1 for example Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011981 lindlar catalyst Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013580 millipore water Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
Classifications
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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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J23/89—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
- B01J23/8993—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 chromium, molybdenum or tungsten
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0242—Coating followed by impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
- 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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/283—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/8878—Chromium
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- Materials Engineering (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
(i)金属合金担体の総重量に基づいて55重量%(wt%)~80wt%のCoと、
(ii)金属合金担体の総重量に基づいて20wt%~40wt%のCrと、
(iii)金属合金担体の総重量に基づいて2wt%~10wt%のMoと、
を含む金属合金担体を含む粉末状触媒系(I)に関し、この場合に、前記金属合金担体は、金属酸化物層で被覆されPdナノ粒子で含浸され、金属酸化物層はCeO2を含むことを特徴とする。
(i)金属合金担体の総重量に基づいて55重量%(wt%)~80wt%のCoと、
(ii)金属合金担体の総重量に基づいて20wt%~40wt%のCrと、
(iii)金属合金担体の総重量に基づいて2wt%~10wt%のMoと、
からなる金属合金担体からなる粉末状触媒系(I’)に関し、この場合に、前記金属合金担体は、金属酸化物層で被覆されPdナノ粒子で含浸され、金属酸化物層は、CeO2を含むことを特徴する。
〇触媒は反応後のリサイクル(及び除去)が容易である。これは、例えば、ろ過によって行うことができる。
〇触媒は複数回使用することができる(再利用可能)。
〇触媒は簡単に製造できる。
〇触媒の取り扱いは簡単である。
〇水素化は溶媒の有無にかかわらず実行できる。
〇触媒は鉛を含まない。
〇触媒は水素化反応で高い選択性及び活性を示す。
(i)金属合金の総重量に基づいて55wt%~70wt%のCoと、
(ii)金属合金の総重量に基づいて20wt%~35wt%のCrと、
(iii)金属合金の総重量に基づいて4wt%~10wt%のMoと、
を含む。
(i)金属合金の総重量に基づいて55wt%~70wt%のCoと、
(ii)金属合金の総重量に基づいて20wt%~35wt%のCrと、
(iii)金属合金の総重量に基づいて4wt%~10wt%のMoと、
からなる。
(i)金属合金担体の総重量に基づいて55wt%~70wt%のCoと、
(ii)金属合金担体の総重量に基づいて20wt%~35wt%のCrと、
(iii)金属合金担体の総重量に基づいて4wt%~10wt%のMoと、
を含む。
(i)金属合金担体の総重量に基づいて55wt%~70wt%のCoと、
(ii)金属合金担体の総重量に基づいて20wt%~35wt%のCrと、
(iii)金属合金担体の総重量に基づいて4wt%~10wt%のMoと、
からなる。
(a)ポリエチレングリコールを任意選択的に加えるPd塩の水溶液を調製する工程、
(b)工程(a)の溶液を加熱し、溶液を音波処理にかける工程、
(c)還元剤、好ましくはギ酸塩溶液をPd溶液に加える工程、
(d)金属酸化物粉末を加える工程、
(e)工程(d)で得られた懸濁液をろ過し乾燥する工程。
Pd塩を水(又は水性溶媒、これは水が少なくとも1つの他の溶媒と混合されることを意味する)に溶解する。任意の一般的に知られ使用されているPd塩を使用できる。適切な塩は、PdCl2又はNa2PdCl4である。1つのPd塩並びに2つ以上のPd塩の混合物であり得る。更に、少なくとも1つの界面活性剤を溶液に加えることが有利である。適切なものは、例えば、ポリエチレングリコール(PEG)、ポリビニルピロリドン(PVP)又はグルコサミドである。
工程の溶液は通常、高温まで加熱される。通常、溶媒(又は使用される溶媒混合物)の沸点ほど高い温度までではない。
通常、30~80℃の温度まで加熱される。
音波処理は、通常、30~50kHzの周波数で実行される。
音波処理工程の期間は、通常、少なくとも10分で、20を超えることが好ましい(適切で好ましい範囲は30~120分)。音波処理工程の期間の最大長さは重要ではない。
音波処理工程は、超音波浴又は浸漬プローブを使用して実行できる。又は更には、両方の方法の組み合わせが可能である。
工程(b)の溶液に還元剤を加える。通常、これはギ酸ナトリウム溶液である。しかし又、他のギ酸塩(又はギ酸塩の混合物)を使用できる。任意選択的に(代わりに又は更に)又、H2ガス、L-アスコルビン酸、及び/又はギ酸を加えることができる。
工程(c)の溶液に、金属酸化物粉末(又は金属酸化物粉末の混合物)が加えられる。通常、反応混合物は攪拌される。
最後に、工程(d)の懸濁液をろ過し、通常、得られたドープされた金属酸化物粉末を洗浄し乾燥させる。
(式中、
R1は、直鎖型又は分岐型C1~C35アルキル或いは直鎖型又は分岐型C5~C35アルケニル部位であり、C鎖は置換されることができ、
R2は、直鎖型又は分岐型C1~C4アルキルであり、C鎖は置換されることができ、
R3はH又は-C(CO)C1~C4アルキルである)の化合物を、触媒(I)、(I’)(II)、(II’)、(III)、(IV)、(V)、(VI)、(VI’)、(VII)、(VIII)、(VIII’)、(VIII’’)、(IX)、(IX’)又は(IX’’)の存在下で水素と反応させるプロセスに関する。
(式中、
R1は、直鎖型又は分岐型C1~C35アルキル或いは直鎖型又は分岐型C5~C35アルケニル部位であり、C鎖は置換されることができ、
R2は直鎖型又は分岐型C1~C4アルキルであり、C鎖は置換されることができ、
R3はH又は-C(CO)C1~C4アルキルである)の化合物を、触媒(I)、(Ι’)(II)、(ΙΙ’)、(III)、(IV)、(V)、(VI)、(VI’)、(VII)、(VIII)、(VIII’)、(VIII’’)、(IX)、(ΙΧ’)又は(IX’’)の存在下で水素と反応させるプロセス(P)に関する。
[実施例1:金属粉末触媒の調製]
EOS CobaltChrome MP1を、空気中450℃で3時間加熱した。プライマー溶液の調製については、Ce(NO3)3・6H2O(508ミリモル)と700mLの水をビーカーに加えた。塩が完全に溶解するまで混合物を撹拌した。溶液を90℃に加熱し、ZnO(508ミリモル)をゆっくりと溶液に加えた。撹拌を90℃で維持し、全てのZnOが完全に溶解するまで(最終CHNO3=1M)65%の硝酸を滴下した。その後、溶液を室温まで冷却し、0.45μmのメンブレンフィルターでろ過した。ZnO/CeO2の堆積は、熱処理したMP1粉末(10.0g)を25mLの前駆体溶液に加えることで行った。この混合物を室温で15分間撹拌した。その後、懸濁液を0.45μmのメンブレンフィルターでろ過し、40℃で2時間真空乾燥した後、450℃で1時間焼成した。所望の数のプライマー層が堆積されるまで、このプロセスを繰り返した。
[アルキンからアルケンへの選択的半水素化]
40.0gの2-メチル-3-ブチン-2-オール(MBY)及び所望の量の金属粉末触媒を125mLのオートクレーブ反応器に加えた。水素化反応中の等温条件(338K)は、加熱/冷却ジャケットによって維持された。反応器にはガス巻込み攪拌機が装備されていた。純水素を窒素雰囲気下で必要な値で供給した。窒素でパージした後、反応器を水素でパージし、所望の温度に加熱した。実験中、外部リザーバーから水素を供給することにより、反応器内の圧力(3.0バール)を維持した。反応混合物を1000rpmで撹拌した。液体試料(200μL)を、MBYの最小変換率95%から開始して定期的に反応器から回収し、ガスクロマトグラフィー(HP 6890シリーズ、GCシステム)で分析した。選択性は、全ての反応生成物と比較して、所望の半水素化生成物(2-メチル-3-ブテン-2-オール(MBE))の量として報告される。
上記の実施例で説明したプロセスに従って調製された触媒を、調製手順で述べたように熱活性化した。
aの反応条件:500mgの触媒、40.0MBY、1000rpm、3.0バールH2、65℃。
bの反応条件:158mgの触媒、30.0MBY、1000rpm、3.0バールH2、65℃。
a条件:500mgの触媒、40.0MBY、1000rpm、3.0バールH2、65℃。
b条件:158mgの触媒、30.0MBY、1000rpm、3.0バールH2、65℃。
Claims (7)
- 炭素-炭素三重結合を含む有機出発物質の水素による選択的接触水素化における、金属合金担体を含む粉末状触媒系の使用であって、前記金属合金担体は、
(i)前記金属合金担体の総重量に基づいて55重量%(wt%)~70wt%のCoと、
(ii)前記金属合金担体の総重量に基づいて20wt%~35wt%のCrと、
(iii)前記金属合金担体の総重量に基づいて4wt%~10wt%のMoと、
を含み、前記金属合金担体は、金属酸化物層で被覆されPdで含浸され、前記金属酸化物層はCeO2 とZnOとを含み、CeO 2 :ZnOのモル比は2:1~1:2であることを特徴とする金属合金担体を含む粉末状触媒系の使用。 - 水素がH2ガスの形態で使用される、請求項1~3のいずれか一項に記載の使用。
- 前記金属合金担体は、Cu、Fe、Ni、Mn、Si、Ti、Al、及びNbからなる群から選択される少なくとも1つの更なる金属を含む、請求項1~4のいずれか一項に記載の使用。
- 前記金属合金担体は炭素を含む、請求項1~5のいずれか一項に記載の使用。
- 炭素-炭素三重結合を含む有機出発物質の水素による選択的接触水素化用の、金属合金担体を含む粉末状触媒系であって、前記金属合金担体は、
(i)前記金属合金担体の総重量に基づいて55重量%(wt%)~70wt%のCoと、
(ii)前記金属合金担体の総重量に基づいて20wt%~35wt%のCrと、
(iii)前記金属合金担体の総重量に基づいて4wt%~10wt%のMoと、
を含み、前記金属合金担体は、金属酸化物層で被覆されPdで含浸され、前記金属酸化物層はCeO2 とZnOとを含み、CeO 2 :ZnOのモル比は2:1~1:2であることを特徴とする、金属合金担体を含む粉末状触媒系。
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