JP6447940B2 - 新規な触媒システム - Google Patents
新規な触媒システム Download PDFInfo
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- JP6447940B2 JP6447940B2 JP2017202007A JP2017202007A JP6447940B2 JP 6447940 B2 JP6447940 B2 JP 6447940B2 JP 2017202007 A JP2017202007 A JP 2017202007A JP 2017202007 A JP2017202007 A JP 2017202007A JP 6447940 B2 JP6447940 B2 JP 6447940B2
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- nanoparticles
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- metal oxide
- smf
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- 239000003054 catalyst Substances 0.000 title claims description 68
- 239000002105 nanoparticle Substances 0.000 claims description 55
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 50
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims description 20
- 150000004706 metal oxides Chemical class 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000000835 fiber Substances 0.000 claims description 16
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 53
- 239000011787 zinc oxide Substances 0.000 description 24
- 229910052763 palladium Inorganic materials 0.000 description 22
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 229910052709 silver Inorganic materials 0.000 description 15
- 239000002245 particle Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 229910001038 basic metal oxide Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- MULUCORRSAVKOA-UHFFFAOYSA-N 3,7,11,15-tetramethylhexadec-1-yn-3-ol Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)C#C MULUCORRSAVKOA-UHFFFAOYSA-N 0.000 description 7
- JQZGUQIEPRIDMR-UHFFFAOYSA-N 3-methylbut-1-yn-1-ol Chemical compound CC(C)C#CO JQZGUQIEPRIDMR-UHFFFAOYSA-N 0.000 description 7
- KEVYVLWNCKMXJX-ZCNNSNEGSA-N Isophytol Natural products CC(C)CCC[C@H](C)CCC[C@@H](C)CCC[C@@](C)(O)C=C KEVYVLWNCKMXJX-ZCNNSNEGSA-N 0.000 description 6
- 239000001371 (5E)-3,5-dimethylocta-1,5,7-trien-3-ol Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- ZJIQIJIQBTVTDY-SREVYHEPSA-N dehydrolinalool Chemical compound CC(=C)\C=C/CC(C)(O)C=C ZJIQIJIQBTVTDY-SREVYHEPSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZERULLAPCVRMCO-UHFFFAOYSA-N Dipropyl sulfide Chemical compound CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 239000000356 contaminant Substances 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
- 239000006185 dispersion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 239000005417 food ingredient Substances 0.000 description 1
- -1 for example Chemical class 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GFAZHVHNLUBROE-UHFFFAOYSA-N hydroxymethyl propionaldehyde Natural products CCC(=O)CO GFAZHVHNLUBROE-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 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
- 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
- B01J23/66—Silver or gold
-
- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J23/89—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
- B01J23/8953—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 zinc, cadmium or mercury
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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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
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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
- B01J37/0217—Pretreatment of the substrate before coating
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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
- 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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- 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
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
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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
- B01J37/08—Heat treatment
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
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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
- 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
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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
- C07C29/17—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
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
- C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
- C07C33/03—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond in beta-position, e.g. allyl alcohol, methallyl alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/66—Silver or gold
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- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Crystallography & Structural Chemistry (AREA)
Description
(式中、R1が、直鎖状または分岐状C5〜C35アルキルまたは直鎖状または分岐状C5〜C35アルケニル部位であり、そのC鎖が置換されていてもよく、
R2が、直鎖状または分岐状C1〜C4アルキルであり、そのC鎖が置換されていてもよい)
を水素と反応させるプロセス(P)であって、Pd:Agナノ粒子の比が1:1〜10:1であることを特徴とする、プロセスにも関する。
の、リナロオール(LL)
への選択的接触水素化も特に好ましい。これらの反応のどちらに関しても、構造化触媒のすべての選択が適用される。好ましくはSC、さらに好ましくはSC’、またさらに好ましくはSC’’、および最も好ましくはSC’’’がこれらのプロセスで使用される。
[触媒の製造]
[実施例1:0.2%Pd(Ag)/5%ZnO/SMF(Pd:Agモル比=3.5)]
[材料]
焼結金属繊維(SMFFecral)、Fecralloy、40FP3は、Southwest Screen & Filters SA(now Bekaert SA,Belgium)から入手可能である。使用されるすべての化学物質(>99%)はアルドリッチ社(Aldrich)から購入し、受け取った状態のまま使用した。すべての気体(>99.5%)はカーバガス社(Carbagas)によって供給された。
混入物を除去するために、沸騰トルエン中でSMFFecralパネル(10×10cm,m=6〜7g)を0.5時間処理し、空気乾燥させた。次いで、SMFFecralを空気中で600℃にて3時間酸化した。室温まで冷却した後、処理したSMFFecralを乾燥雰囲気中で保管した。
工程1に記載のようにクリーニングされたSMFFecralパネルを、酸化亜鉛層によって浸漬コーティングした。ZnO前駆溶液を以下のように調製した:モノエタノールアミン18.3g、およびアセトイン12.8gをイソプロパノール0.75Lに溶解する。次いで、Zn(CH3COO)2・2H2O65.8gを混合物に添加し、攪拌下にて溶解した。ZnO層の付着は、ZnO前駆溶液にSMFFecralパネルを浸し、続いて空気中で室温(0.5時間)にて乾燥させ、600℃(0.5時間)でか焼することによって行われた。浸し塗り−乾燥−か焼のサイクルを6回繰り返して行い、ZnO約5重量%を付着させた。次いで、被覆されたSMFFecralパネルを900℃にて15分間、ポストアニーリングした。製造された5%ZnO/SMFFecralを乾燥雰囲気中で保管した。
Pdナノ粒子溶液を以下のように調製した:ポリ(N−ビニル−2−ピロリドン)(K30,M約50000)0.277gおよびアスコルビン酸0.156gを熱水(95〜98℃)15mlに溶解した(溶液1)。他のビーカー内で、PdCl20.088gおよびNaCl 0.058gを熱水10ml中に溶解した(溶液2)。攪拌しながら、溶液2を溶液1に迅速に添加した。溶液の色が即座に、茶色から黒色に変化し、Pdナノ粒子の形成が示された。得られたコロイド溶液を攪拌および加熱下にて3時間維持した。次いで、溶液を冷却し、アセトン75mlで希釈した。攪拌することなく、混合物を一晩静置した。無色の液相を廃棄した。黒色の粘性残留物を水12.5mlに溶解し、安定なPd溶液が得られた。合成されたPdナノ粒子をAgによって修飾するために(Pd:Agモル比=3.5:1)、溶液3を以下のように調製した:KAg(CN)20.026gを水1mlに溶解し、20%N2H4水溶液0.03gを添加した。攪拌下にて、調製されたPd溶液に溶液3を迅速に添加した。攪拌下にて最終溶液を2時間維持した。調製されたPd/Ag(3.5:1)溶液は数ヶ月間安定であった。調製されたPd/Ag(3.5:1)溶液で、ZnO被覆SMFFeCrAlパネル(2枚,10×10cm,約14g)を含浸し、空気中で室温にて乾燥させた。Pd0.2重量%のローディングを達成するために、含浸−乾燥のサイクルを2回繰り返した。
0.2%Pd(Ag)/5%ZnO/SMFFeCrAlパネルを空気中で600℃(2時間)にてか焼し、次いで300℃(2時間)にて10%H2+90%Arフロー(流量−450ml/分)中で還元した。時に、触媒性能を改善するために、酸化−還元サイクルを数回繰り返した。
KAg(CN)2の代わりに、等モル量のKAu(CN)2を使用したことを除いて、この触媒は実施例1の触媒と同様に製造した。
[実施例1の触媒を用いた、デヒドロイソフィトール(DIP)のイソフィトール(IP)への水素化]
攪拌機、温度および圧力制御を備えた500mlステンレス鋼オートクレーブ内で、実施例1の触媒約0.8gおよびDIP70gを添加した。水素圧力下にて反応器を95℃および4バール(絶対圧力)に加熱し、反応混合物を攪拌した(2000rpm)。反応の最後(x=99%)ならびに反応中に(x=50%およびx=95%)、粗製反応生成物を回収し、分析した。
x=95%で測定されたこの水素化の選択率は96.0%であった。
x=99%で測定されたこの水素化の選択率は94.4%であった。
攪拌機、温度および圧力制御を備えた500mlステンレス鋼オートクレーブ内で、実施例2の触媒約0.8gおよびDIP70gを添加した。水素圧力下にて反応器を95℃および4バール(絶対圧力)に加熱し、反応混合物を攪拌した(2000rpm)。反応の最後(x=99%)ならびに反応中に(x=50%およびx=95%)、粗製反応生成物を回収し、分析した。
x=95%で測定されたこの水素化の選択率は86.4%であった。
x=99%で測定されたこの水素化の選択率は76.0%であった。
攪拌機、温度および圧力制御を備えた500mlステンレス鋼オートクレーブ内で、実施例1の触媒約1.5gおよびMBY285gを添加した。水素圧力下にて反応器を65℃および4バール(絶対圧力)に加熱し、反応混合物を攪拌した(1050rpm)。反応の最後(x=99%)ならびに反応中に、粗製反応生成物を回収し、分析した。
MBY(46.6g)およびMBE(187g)を500mL反応器に添加した(転化率80%で反応を開始するために、この混合物を使用した)。ガス吸込みインペラーに取り付けられた金属格子バスケット内に、全重量1.77gを有するSMF触媒片6個(0.2%Pd(Ag)/5%ZnO/SMFFecraloy)を入れた。続いて、反応器を水素4バールで3回加圧した。圧力を開放した後、攪拌(500rpm)反応混合物を65℃に加熱した。続いて、混合物を1700rpmで攪拌することによって、反応を開始した。水素化の過程中に反応器の重量が一定に維持され、かつ転化率が約80%となるように、MBYの供給および生成物のフローを調整した。試料を採取し、GCで分析して、反応をモニターした。
転化率:82%
選択率:93%
反応時間300時間:
DLL(285g,1.87モル)を500mL反応器に添加した。ガス吸込みインペラーに取り付けられた金属格子バスケット内に、全重量1.49gを有するSMF触媒片6個(0.2%Pd(Ag)/5%ZnO/SMFFecraloy)を入れた。次いで、反応器を閉め、窒素4バールで3回加圧した。圧力を開放した後、攪拌(400rpm)反応混合物を65℃に加熱した。65℃に達したら、攪拌機を止め、反応器を水素4バールで4回加圧した。続いて、混合物を1050rpmで攪拌することによって、反応を開始した。試料を120分および1678分で採取し、GCで分析して、反応をモニターした。
Claims (9)
- Agナノ粒子で修飾されているPdナノ粒子が付着している非酸性金属酸化物層によって被覆された焼結金属繊維(SMF)をベースとする、下記式(I)の化合物の選択的接触水素化のための構造化触媒であって、
Pd:Agナノ粒子のモル比が1:1〜10:1であり、
前記非酸性金属酸化物層が、ZnO、および任意選択的に少なくとも1種類の更なる金属酸化物を含み、当該金属酸化物における金属が、Cr、Mn、Mg、CuおよびAlからなる群から選択される、構造化触媒。
(式中、R1は、直鎖状若しくは分岐状C5〜C35アルキルまたは直鎖状若しくは分岐状C5〜C35アルケニル部位であり、そのC鎖が置換されていてもよく、かつ
R2は、直鎖状または分岐状C1〜C4アルキルであり、そのC鎖が置換されていてもよい) - 前記SMFが、Alを含有しない合金からなる、請求項1に記載の構造化触媒。
- 前記合金がステンレス鋼である、請求項2に記載の構造化触媒。
- 前記SMFがFeCrAl合金からなる、請求項1に記載の構造化触媒。
- 前記触媒の全重量に対して、ZnOを0.01〜20重量%含む、請求項1〜4のいずれか一項に記載の構造化触媒。
- 前記Pd:Agナノ粒子のモル比が1.5:1〜8:1である、請求項1〜5のいずれか一項に記載の構造化触媒。
- 触媒の全重量に対して、前記Agナノ粒子で修飾されているPdナノ粒子を0.001〜5重量%含む、請求項1〜6のいずれか一項に記載の構造化触媒。
- 前記水素化が、絶対圧力0.1〜6MPaおよび温度250K〜500Kで行われる、請求項8に記載の水素化方法。
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