JP2021013885A - Catalyst and production method therefor - Google Patents
Catalyst and production method therefor Download PDFInfo
- Publication number
- JP2021013885A JP2021013885A JP2019129047A JP2019129047A JP2021013885A JP 2021013885 A JP2021013885 A JP 2021013885A JP 2019129047 A JP2019129047 A JP 2019129047A JP 2019129047 A JP2019129047 A JP 2019129047A JP 2021013885 A JP2021013885 A JP 2021013885A
- Authority
- JP
- Japan
- Prior art keywords
- carbon material
- porous carbon
- catalyst
- polysilane compound
- transition metal
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 103
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 229920000548 poly(silane) polymer Polymers 0.000 claims abstract description 56
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 34
- 150000003624 transition metals Chemical class 0.000 claims abstract description 34
- 239000002923 metal particle Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 45
- 241000196324 Embryophyta Species 0.000 claims description 30
- 229910052763 palladium Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 235000007164 Oryza sativa Nutrition 0.000 claims description 18
- 235000009566 rice Nutrition 0.000 claims description 18
- 239000010903 husk Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- 244000058871 Echinochloa crus-galli Species 0.000 claims description 4
- 235000008247 Echinochloa frumentacea Nutrition 0.000 claims description 4
- 240000005979 Hordeum vulgare Species 0.000 claims description 4
- 235000007340 Hordeum vulgare Nutrition 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- -1 sawdust Substances 0.000 claims description 4
- 241000209056 Secale Species 0.000 claims description 3
- 235000007238 Secale cereale Nutrition 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 241000209140 Triticum Species 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 2
- 235000005043 Oryza sativa Japonica Group Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 230000006866 deterioration Effects 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 36
- 239000011148 porous material Substances 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 18
- 241000209094 Oryza Species 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000001994 activation Methods 0.000 description 13
- 238000011282 treatment Methods 0.000 description 13
- 230000004913 activation Effects 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000003763 carbonization Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 5
- 239000000787 lecithin Substances 0.000 description 5
- 229940067606 lecithin Drugs 0.000 description 5
- 235000010445 lecithin Nutrition 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010902 straw Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 244000236458 Panicum colonum Species 0.000 description 1
- 235000015225 Panicum colonum Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000219492 Quercus Species 0.000 description 1
- 235000016976 Quercus macrolepis Nutrition 0.000 description 1
- 240000005498 Setaria italica Species 0.000 description 1
- 244000062793 Sorghum vulgare Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 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
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 235000019713 millet Nutrition 0.000 description 1
- 235000002252 panizo Nutrition 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
Abstract
Description
本発明は、触媒、及び触媒の製造方法に関する。 The present invention relates to a catalyst and a method for producing the catalyst.
不均一触媒を使用する水素化反応、カップリング反応等の合成系において、ハロゲン又はその化合物、燐又はその化合物、硫黄又はその化合物などは触媒毒とされ、触媒の活性を低下させることが知られている。 In synthetic systems such as hydrogenation reactions and coupling reactions using heterogeneous catalysts, halogen or its compounds, phosphorus or its compounds, sulfur or its compounds, etc. are known to be catalytic poisons and reduce the activity of the catalyst. ing.
このような触媒毒になる元素や、その化合物を含む原料を反応基質とした場合、例えば、レシチンの水素化反応では、反応基質であるレシチンに含まれる燐が触媒の被毒を引き起こし、触媒の活性を低下させてしまう。このため、触媒は一度しか使用できず、生産コストが高くなってしまうという課題がある。 When such an element that becomes a catalyst poison or a raw material containing the compound is used as a reaction substrate, for example, in a hydrogenation reaction of lecithin, phosphorus contained in lecithin, which is a reaction substrate, causes poisoning of the catalyst, and the catalyst It reduces the activity. Therefore, the catalyst can be used only once, and there is a problem that the production cost becomes high.
一方、ポリシラン化合物を使用した不均一触媒としては、例えば、ポリシラン化合物としてポリジメチルシランを用い、担体として金属酸化物を用いた固定化パラジウム触媒が提案されている（例えば、特許文献１参照）。 On the other hand, as a heterogeneous catalyst using a polysilane compound, for example, an immobilized palladium catalyst using polydimethylsilane as a polysilane compound and a metal oxide as a carrier has been proposed (see, for example, Patent Document 1).
しかしながら、特許文献１には、被毒性の向上については記載がなく、担体として植物由来の多孔質炭素材料を用いておらず、ポリジメチルシロキサンは常温で固体であり、溶剤に不溶であるため、多孔質炭素材料のメソ孔内部にまでポリジメチルシロキサンを導入し、付着させることができず、担体として多孔質炭素材料を用いることによる効果が得られないという課題がある。 However, Patent Document 1 does not describe the improvement of toxicity, does not use a plant-derived porous carbon material as a carrier, and polydimethylsiloxane is solid at room temperature and is insoluble in a solvent. There is a problem that polydimethylsiloxane cannot be introduced and adhered to the inside of the mesopores of the porous carbon material, and the effect of using the porous carbon material as a carrier cannot be obtained.
本発明は、従来における前記諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、触媒の活性低下を抑制でき、再利用が可能な触媒及び触媒の製造方法を提供することを目的とする。 An object of the present invention is to solve the above-mentioned problems in the past and to achieve the following object. That is, an object of the present invention is to provide a catalyst and a method for producing the catalyst, which can suppress a decrease in the activity of the catalyst and can be reused.
前記課題を解決するための手段としては、以下の通りである。即ち、
＜１＞ ポリシラン化合物を含有する植物由来の多孔質炭素材料と、遷移金属粒子とを含むことを特徴とする触媒である。
＜２＞ 前記遷移金属粒子は、ポリシラン化合物を含有する植物由来の多孔質炭素材料に担持されている前記＜１＞に記載の触媒である。
＜３＞ 前記ポリシラン化合物が常温で液体である前記＜１＞から＜２＞のいずれかに記載の触媒である。
＜４＞ 前記ポリシラン化合物がポリメチルフェニルシランである前記＜１＞から＜３＞のいずれかに記載の触媒である。
＜５＞ 前記ポリシラン化合物の含有量が１質量％以上３０質量％以下である前記＜１＞から＜４＞のいずれかに記載の触媒である。
＜６＞ 前記多孔質炭素材料のメソ孔容積が０．１５ｃｍ３／ｇ以上である前記＜１＞から＜５＞のいずれかに記載の触媒である。
＜７＞ 前記多孔質炭素材料の原材料が、米、大麦、小麦、ライ麦、稗、もしくは粟のもみ殻、おが屑、又は木片である前記＜１＞から＜６＞のいずれかに記載の触媒である。
＜８＞ 前記遷移金属粒子がパラジウム粒子である前記＜１＞から＜７＞のいずれかに記載の触媒である。
＜９＞ 不均一遷移金属触媒である前記＜１＞から＜８＞のいずれかに記載の触媒である。
＜１０＞ 植物由来の多孔質炭素材料にポリシラン化合物を導入し、ポリシラン化合物含有多孔質炭素材料を作製する工程と、
遷移金属を含む溶剤中に前記ポリシラン化合物含有多孔質炭素材料を添加し、混合及び含浸する工程と、
を含むことを特徴とする触媒の製造方法である。
＜１１＞ 前記遷移金属が前記ポリシラン化合物により還元されて遷移金属粒子となる前記＜１０＞に記載の触媒の製造方法である。
The means for solving the above-mentioned problems are as follows. That is,
<1> A catalyst characterized by containing a plant-derived porous carbon material containing a polysilane compound and transition metal particles.
<2> The transition metal particles are the catalyst according to <1>, which is supported on a plant-derived porous carbon material containing a polysilane compound.
<3> The catalyst according to any one of <1> to <2>, wherein the polysilane compound is liquid at room temperature.
<4> The catalyst according to any one of <1> to <3>, wherein the polysilane compound is polymethylphenylsilane.
<5> The catalyst according to any one of <1> to <4>, wherein the content of the polysilane compound is 1% by mass or more and 30% by mass or less.
<6> The catalyst according to any one of <1> to <5>, wherein the porous carbon material has a mesopore volume of 0.15 cm 3 / g or more.
<7> The catalyst according to any one of <1> to <6>, wherein the raw material of the porous carbon material is rice, barley, wheat, rye, Japanese millet, or millet rice husk, sawdust, or wood chips. is there.
<8> The catalyst according to any one of <1> to <7>, wherein the transition metal particles are palladium particles.
<9> The catalyst according to any one of <1> to <8>, which is a heterogeneous transition metal catalyst.
<10> A step of introducing a polysilane compound into a plant-derived porous carbon material to prepare a polysilane compound-containing porous carbon material, and
A step of adding, mixing and impregnating the polysilane compound-containing porous carbon material in a solvent containing a transition metal, and
It is a method for producing a catalyst, which comprises.
<11> The method for producing a catalyst according to <10>, wherein the transition metal is reduced by the polysilane compound to form transition metal particles.
本発明によると、従来における前記諸問題を解決し、前記目的を達成することができ、触媒の活性低下を抑制でき、再利用が可能な触媒及び触媒の製造方法を提供することができる。 According to the present invention, it is possible to provide a catalyst and a method for producing a catalyst, which can solve the above-mentioned problems in the past, achieve the above object, suppress a decrease in the activity of the catalyst, and can be reused.
（触媒）
本発明の触媒は、ポリシラン化合物を含有する植物由来の多孔質炭素材料と、遷移金属粒子とを含み、更に必要に応じてその他の成分を含む。
前記遷移金属粒子は、ポリシラン化合物を含有する植物由来の多孔質炭素材料に担持されていることが、触媒活性を生じさせる点から好ましい。
前記触媒は、不均一遷移金属触媒として好適に用いられる。不均一遷移金属触媒では、遷移金属触媒が反応基質や気体と接触し、植物由来の多孔質炭素材料の表面で反応が行われる。
(catalyst)
The catalyst of the present invention contains a plant-derived porous carbon material containing a polysilane compound, transition metal particles, and if necessary, other components.
It is preferable that the transition metal particles are supported on a plant-derived porous carbon material containing a polysilane compound from the viewpoint of causing catalytic activity.
The catalyst is preferably used as a heterogeneous transition metal catalyst. In a heterogeneous transition metal catalyst, the transition metal catalyst comes into contact with a reaction substrate or gas, and the reaction takes place on the surface of a plant-derived porous carbon material.
＜遷移金属粒子＞
遷移金属粒子としては、周期律表における３族から１２族の遷移金属が用いられ、例えば、パラジウム（Ｐｄ）、白金（Ｐｔ）、金（Ａｕ）などが挙げられる。これらの遷移金属は、水素化反応、カップリング反応などに高い活性を有しているので好適に用いることができる。
還元金属は、ポリシラン化合物を含有する植物由来の多孔質炭素材料におけるポリシラン化合物により還元されて粒子化し、遷移金属粒子がポリシラン化合物に付着し、多孔質炭素材料に担持される。
<Transition metal particles>
As the transition metal particles, transition metals of groups 3 to 12 in the periodic table are used, and examples thereof include palladium (Pd), platinum (Pt), and gold (Au). Since these transition metals have high activity in hydrogenation reaction, coupling reaction and the like, they can be preferably used.
The reduced metal is reduced to particles by the polysilane compound in the plant-derived porous carbon material containing the polysilane compound, and the transition metal particles adhere to the polysilane compound and are supported on the porous carbon material.
＜ポリシラン化合物＞
前記ポリシラン化合物は、ケイ素（Ｓｉ）−ケイ素（Ｓｉ）結合を有する化合物の総称であり、還元性を有し、常温（２５℃）で液体であることが、ポリシラン化合物を溶剤に溶解させたポリシラン化合物溶液に多孔質炭素材料を浸漬することにより、多孔質炭素材料のメソ孔内部にまで浸透し、ポリシラン化合物をメソ孔内部にまで付着できる点から好ましい。なお、ポリシラン化合物としては、ポリジメチルシランが知られているが、ポリジメチルシランは常温で固体であり、溶剤に不溶であるため、多孔質炭素材料との混合になってしまい、ポリジメチルシランを多孔質炭素材料のメソ孔内部にまで付着させることができず、本発明の効果が得られない。
前記ポリシラン化合物としては、常温で液体であるポリメチルフェニルシランを用いることが好ましい。
ポリメチルフェニルシランとしては、市販品を用いることができ、該市販品としては、例えば、大阪ガスケミカル株式会社製のＯＧＳＯＬ ＳＩ−１０−２０、ＯＧＳＯＬ ＳＩ−１０−１０などが挙げられる。
前記ポリシラン化合物の含有量は、多孔質炭素材料の全量に対して、１質量％以上３０質量％以下が好ましく、１０質量％以上３０質量％以下がより好ましい。ポリシラン化合物の含有量が１質量％以上３０質量％以下であると、触媒の活性低下を抑制でき、再利用が可能な触媒が得られる。
<Polysilane compound>
The polysilane compound is a general term for compounds having a silicon (Si) -silicon (Si) bond, and the fact that it has reducing properties and is liquid at room temperature (25 ° C.) means that the polysilane compound is dissolved in a solvent. By immersing the porous carbon material in the compound solution, it is preferable because it can penetrate into the mesopores of the porous carbon material and the polysilane compound can be adhered to the inside of the mesopores. As a polysilane compound, polydimethylsilane is known, but since polydimethylsilane is solid at room temperature and is insoluble in a solvent, it is mixed with a porous carbon material, and polydimethylsilane is used. The effect of the present invention cannot be obtained because it cannot be adhered to the inside of the mesopores of the porous carbon material.
As the polysilane compound, it is preferable to use polymethylphenylsilane which is a liquid at room temperature.
As the polymethylphenylsilane, a commercially available product can be used, and examples of the commercially available product include OGSOL SI-10-20 and OGSOL SI-10-10 manufactured by Osaka Gas Chemical Co., Ltd.
The content of the polysilane compound is preferably 1% by mass or more and 30% by mass or less, and more preferably 10% by mass or more and 30% by mass or less with respect to the total amount of the porous carbon material. When the content of the polysilane compound is 1% by mass or more and 30% by mass or less, a decrease in the activity of the catalyst can be suppressed, and a reusable catalyst can be obtained.
＜多孔質炭素材料＞
多孔質炭素材料としては、植物由来であり、前記多孔質炭素材料のメソ孔容積は、０．１５ｃｍ３／ｇ以上が好ましく、０．１５ｃｍ３／ｇ以上０．５ｃｍ３／ｇ以下がより好ましい。前記メソ孔容積が、０．１５ｃｍ３／ｇ以上であると、メソ孔が発達しており、反応基質の反応場として利用でき、遷移金属粒子が微分散するエリアが確保できるので、触媒活性を高くすることができる。
<Porous medium>
The porous carbon material is derived from a plant, mesopore volume of the porous carbon material is preferably 0.15 cm 3 / g or more, more preferably at most 0.15 cm 3 / g or more 0.5 cm 3 / g .. When the mesopore volume is 0.15 cm 3 / g or more, the mesopores are developed and can be used as a reaction field of the reaction substrate, and an area in which the transition metal particles are finely dispersed can be secured. Can be high.
前記多孔質炭素材料は、細孔（ポア）を多く有している。細孔は、メソ孔、マイクロ孔、マクロ孔に分類される。ここで、メソ孔は孔径が２ｎｍ以上５０ｎｍ以下の細孔をいい、マイクロ孔は孔径が２ｎｍよりも小さい細孔をいい、マクロ孔は孔径が５０ｎｍよりも大きい細孔をいう。 The porous carbon material has many pores. The pores are classified into mesopores, micropores, and macropores. Here, the mesopores refer to pores having a pore diameter of 2 nm or more and 50 nm or less, micropores refer to pores having a pore diameter smaller than 2 nm, and macropores refer to pores having a pore diameter larger than 50 nm.
前記メソ孔容積は、例えば、以下の装置を使用して測定することができる。
マイクロメリテックスジャパン合同会社製の３ＦＬＥＸを使用して、窒素吸着等温線を測定し、ＢＪＨ法で算出することができる。
前記ＢＪＨ法は、細孔分布解析法として広く用いられている方法である。ＢＪＨ法に基づき細孔分布解析をする場合、まず、吸着剤（多孔質炭素材料）に吸着分子として窒素を吸脱着させることにより、脱着等温線を求める。そして、求められた脱着等温線に基づき、細孔が吸着分子（例えば窒素）によって満たされた状態から吸着分子が段階的に着脱する際の吸着層の厚さ、及び、その際に生じた孔の内径（コア半径の２倍）を求め、式（１）に基づき細孔半径ｒｐを算出し、式（２）に基づき細孔容積を算出する。そして、細孔半径及び細孔容積から細孔径（２ｒｐ）に対する細孔容積変化率（ｄＶｐ／ｄｒｐ）をプロットすることにより細孔分布曲線が得られる（日本ベル株式会社製、ＢＥＬＳＯＲＰ−ｍｉｎｉ及びＢＥＬＳＯＲＰ解析ソフトウェアのマニュアル、第８５頁〜第８８頁参照）。
The mesopore volume can be measured using, for example, the following device.
Using 3FLEX manufactured by Micromeritex Japan GK, the nitrogen adsorption isotherm can be measured and calculated by the BJH method.
The BJH method is a method widely used as a pore distribution analysis method. When analyzing the pore distribution based on the BJH method, first, the desorption isotherm is obtained by adsorbing and desorbing nitrogen as an adsorbent molecule on an adsorbent (porous carbon material). Then, based on the obtained desorption isotherm, the thickness of the adsorption layer when the adsorption molecules are gradually attached and detached from the state where the pores are filled with the adsorption molecules (for example, nitrogen), and the pores generated at that time. obtains an inner diameter (twice the core radius) of calculating the pore radius r p based on equation (1), to calculate the pore volume based on the equation (2). The rate of change in pore volume relative to the pore diameter (2r p) from the pore radius and the pore volume (dV p / dr p) pore distribution curve is obtained by plotting the (Nippon Bell Co., BELSORP- Mini and BELSORP analysis software manuals, pp. 85-88).
ここで、
ｒｐ：細孔半径
ｒｋ：細孔半径ｒｐの細孔の内壁にその圧力において厚さｔの吸着層が吸着した場合のコア半径（内径／２）
Ｖｐｎ：窒素の第ｎ回目の着脱が生じたときの細孔容積
ｄＶｎ：そのときの変化量
ｄｔｎ：窒素の第ｎ回目の着脱が生じたときの吸着層の厚さｔｎの変化量
ｒｋｎ：その時のコア半径
ｃ：固定値
ｒｐｎ：窒素の第ｎ回目の着脱が生じたときの細孔半径
である。また、ΣＡｐｊは、ｊ＝１からｊ＝ｎ−１までの細孔の壁面の面積の積算値を表す。
here,
r p: pore radius r k: when the adsorption layer having a thickness of t in the pressure on the inner wall of the pores in the pore radius r p is adsorbed core radius (inside diameter / 2)
V pn : Pore volume when the nth attachment / detachment of nitrogen occurs dV n : Amount of change at that time dt n : Change in thickness t n of the adsorption layer when the nth attachment / detachment of nitrogen occurs Amount r kn : Core radius at that time c: Fixed value r pn : Pore radius when the nth attachment / detachment of nitrogen occurs. Further, ΣA pj represents an integrated value of the wall surface area of the pores from j = 1 to j = n-1.
［具体的な測定方法］
多孔質炭素材料を３０ｍｇ用意し、相対圧（Ｐ／Ｐ０）０．００００００１から０．９９５の範囲を測定する条件に設定した３ＦＬＥＸを使用して、メソ孔容積を測定することができる。
[Specific measurement method]
The mesopore volume can be measured by preparing 30 mg of the porous carbon material and using 3FLEX set under the conditions for measuring the relative pressure (P / P0) in the range of 0.000000001 to 0.995.
＜多孔質炭素材料の原材料＞
前記多孔質炭素材料の原材料は、植物由来の材料であることが好ましい。植物由来の材料であると、メソ孔容積を上記所望の値に調整することが容易となる。また、環境負荷が少ない点でも、植物由来とする利点がある。
<Raw material for porous carbon material>
The raw material of the porous carbon material is preferably a plant-derived material. When the material is derived from a plant, it becomes easy to adjust the mesopore volume to the desired value. In addition, there is an advantage that it is derived from plants in that it has a small environmental load.
前記植物由来の材料としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、米（稲）、大麦、小麦、ライ麦、稗（ヒエ）、粟（アワ）等のもみ殻や藁、あるいは、スギ、マツ、カシ、ナラ等のおが屑や木片などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。これらの中でも、メソ孔容積が大きい点から、米のもみ殻が好ましい。
ヤシガラ活性炭は、メソ孔が発達しておらず、メソ孔容積が小さいので、遷移金属粒子を微分散するエリアが不十分であるため、本発明の効果が得られない。
また、植物由来の材料の形状や形態も特に限定はなく、例えば、もみ殻や藁そのものでもよいし、あるいは乾燥処理品でもよい。更には、ビールや洋酒等の飲食品加工において、発酵処理、焙煎処理、抽出処理等の種々の処理を施されたものを使用することもできる。特に、産業廃棄物の資源化を図るという観点から、脱穀等の加工後の藁やもみ殻を使用することが好ましい。これらの加工後の藁やもみ殻は、例えば、農業協同組合や酒類製造会社、食品会社から、大量、且つ容易に入手することができる。
The plant-derived material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, rice husks such as rice (rice), barley, wheat, rye, Japanese millet (Japanese millet), and millet (foxtail millet). Rice husks, straw, barley, pine, oak, rice husks, etc. These may be used alone or in combination of two or more. Among these, rice husks are preferable because they have a large mesopore volume.
Since the mesopores of the coconut shell activated carbon are not developed and the mesopore volume is small, the area where the transition metal particles are finely dispersed is insufficient, so that the effect of the present invention cannot be obtained.
The shape and form of the plant-derived material are also not particularly limited, and may be, for example, rice husks or straw itself, or a dried product. Further, in the processing of foods and drinks such as beer and Western liquor, those subjected to various treatments such as fermentation treatment, roasting treatment and extraction treatment can also be used. In particular, from the viewpoint of recycling industrial waste, it is preferable to use straw and rice husks after processing such as threshing. These processed straws and rice husks can be easily obtained in large quantities from, for example, agricultural cooperatives, liquor manufacturing companies, and food companies.
前記多孔質炭素材料の製造方法としては、特に制限はなく、目的に応じて適宜選択することができるが、以下に詳細に説明する多孔質炭素材料の製造方法が好ましい。 The method for producing the porous carbon material is not particularly limited and may be appropriately selected depending on the intended purpose, but the method for producing the porous carbon material described in detail below is preferable.
（多孔質炭素材料の製造方法）
本発明の多孔質炭素材料の製造方法は、成型物作製工程と、炭化物作製工程と、賦活工程とを含み、好ましくは脱灰分工程を含み、更に必要に応じて、その他の工程を含む。
前記多孔質炭素材料の製造方法は、本発明の前記多孔質炭素材料を製造する方法である。
(Manufacturing method of porous carbon material)
The method for producing a porous carbon material of the present invention includes a molded product manufacturing step, a carbide manufacturing step, and an activation step, preferably including a decalcification step, and further includes other steps, if necessary.
The method for producing the porous carbon material is the method for producing the porous carbon material of the present invention.
＜成型物作製工程＞
前記成型物作製工程としては、植物由来の材料を加圧成型し、成型物を得る工程であれば、特に制限はなく、目的に応じて適宜選択することができる。
<Molding process>
The molded product manufacturing step is not particularly limited as long as it is a step of pressure molding a plant-derived material to obtain a molded product, and can be appropriately selected depending on the intended purpose.
前記植物由来の材料としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、前記多孔質炭素材料の説明で例示した前記植物由来の材料が挙げられる。これらの中でも、メソ孔が発達しており、所望の多孔質炭素材料を製造しやすい点で、もみ殻が好ましい。 The plant-derived material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the plant-derived material exemplified in the description of the porous carbon material. Among these, rice husks are preferable because the mesopores are developed and it is easy to produce a desired porous carbon material.
前記成型物の形状としては、特に制限はなく、目的に応じて適宜選択することができる。 The shape of the molded product is not particularly limited and may be appropriately selected depending on the intended purpose.
前記加圧成型においては、例えば、バイオマスの成型に一般的に使われているペレタイザーを用いて行い、すり潰したもみ殻を３質量％以上３０質量％以下、好ましくは５質量％以上２０質量％以下の含水率になるよう水分を加え成型する。この時の圧力は成型機を通過する際の金型ともみ殻の摩擦抵抗によって決まるため、成型物の大きさによって水分量を調整することが望ましい。
また、前記加圧成型において、摩擦により熱が発生することがあるが、更に加熱装置により熱を加えてもよい。
水分と圧力と熱とを適度に調整することにより、前記植物由来の材料中に含まれる水溶性成分が抽出され、これが粉体同士を接着し、成型物ができると推測される。
In the pressure molding, for example, a pelletizer generally used for molding biomass is used to grind rice husks in an amount of 3% by mass or more and 30% by mass or less, preferably 5% by mass or more and 20% by mass or less. Add water so that the water content is as high as. Since the pressure at this time is determined by the frictional resistance of the mold and the rice husk when passing through the molding machine, it is desirable to adjust the water content according to the size of the molded product.
Further, in the pressure molding, heat may be generated by friction, but heat may be further applied by a heating device.
It is presumed that by appropriately adjusting the water content, pressure, and heat, the water-soluble component contained in the plant-derived material is extracted, and the powders adhere to each other to form a molded product.
前記植物由来の材料を加圧成型することにより、加圧成型しない場合に比べて、メソ孔が発達しつつも、嵩比重が大きい多孔質炭素材料が得られる。 By pressure-molding the plant-derived material, a porous carbon material having a large bulk specific gravity can be obtained while developing mesopores as compared with the case where pressure molding is not performed.
＜炭化物作製工程＞
前記炭化物作製工程としては、前記成型物を炭化（炭素化）し、炭化物（炭素質物質）を得る工程であれば、特に制限はなく、目的に応じて適宜選択することができる。
前記炭化（炭素化）とは、一般に、有機物質（本発明においては、植物由来の材料）を熱処理して炭素質物質に変換することを意味する（例えば、ＪＩＳ Ｍ０１０４−１９８４参照）。なお、炭素化のための雰囲気として、酸素を遮断した雰囲気を挙げることができ、具体的には、真空雰囲気、窒素ガスやアルゴンガスといった不活性ガス雰囲気、前記成型物を一種の蒸し焼き状態とする雰囲気などが挙げられる。炭素化温度に至るまでの昇温速度として、前記雰囲気下、１℃／分以上、好ましくは３℃／分以上、より好ましくは５℃／分以上が挙げられる。また、炭素化時間の上限として、１０時間、好ましくは７時間、より好ましくは５時間が挙げられるが、これに限定するものではない。炭素化時間の下限は、前記成型物が確実に炭素化される時間とすればよい。
<Ccarbide production process>
The carbide manufacturing step is not particularly limited as long as it is a step of carbonizing (carbonizing) the molded product to obtain a carbide (carbonic substance), and can be appropriately selected depending on the intended purpose.
The carbonization generally means that an organic substance (in the present invention, a plant-derived material) is heat-treated to be converted into a carbonaceous substance (see, for example, JIS M0104-1984). As an atmosphere for carbonization, an atmosphere in which oxygen is blocked can be mentioned. Specifically, a vacuum atmosphere, an inert gas atmosphere such as nitrogen gas or argon gas, and the molded product are put into a kind of steamed state. The atmosphere is mentioned. Examples of the rate of temperature rise to reach the carbonization temperature include 1 ° C./min or higher, preferably 3 ° C./min or higher, and more preferably 5 ° C./min or higher under the above atmosphere. Further, the upper limit of the carbonization time is 10 hours, preferably 7 hours, more preferably 5 hours, but the present invention is not limited to this. The lower limit of the carbonization time may be the time during which the molded product is surely carbonized.
前記熱処理の温度としては、例えば、３００℃〜１，０００℃などが挙げられる。 Examples of the temperature of the heat treatment include 300 ° C. to 1,000 ° C. and the like.
＜賦活工程＞
前記賦活工程としては、前記炭化物を賦活する工程であれば、特に制限はなく、目的に応じて適宜選択することができ、例えば、ガス賦活法、薬品賦活法などが挙げられる。
ここで、賦活とは、炭素材料の細孔構造を発達させ、細孔を付加することをいう。
<Activation process>
The activation step is not particularly limited as long as it is a step of activating the carbide, and can be appropriately selected depending on the intended purpose. Examples thereof include a gas activation method and a chemical activation method.
Here, activation means developing the pore structure of the carbon material and adding pores.
前記ガス賦活法とは、賦活剤として酸素や水蒸気、炭酸ガス、空気等を用い、係るガス雰囲気下、例えば、７００℃〜１，０００℃にて、数十分〜数時間、前記炭化物を加熱することにより、前記炭化物中の揮発成分や炭素分子により微細構造を発達させる方法である。なお、加熱温度は、植物由来の材料の種類、ガスの種類や濃度等に基づき、適宜、選択すればよいが、好ましくは、８００℃〜９５０℃である。
前記薬品賦活法とは、ガス賦活法で用いられる酸素や水蒸気の替わりに、塩化亜鉛、塩化鉄、リン酸カルシウム、水酸化カルシウム、炭酸マグネシウム、炭酸カリウム、硫酸等を用いて賦活させ、塩酸で洗浄、アルカリ性水溶液でｐＨを調整し、乾燥させる方法である。
In the gas activation method, oxygen, water vapor, carbon dioxide, air, or the like is used as an activator, and the carbide is heated in a gas atmosphere, for example, at 700 ° C. to 1,000 ° C. for several tens of minutes to several hours. This is a method of developing a fine structure by means of volatile components and carbon molecules in the carbide. The heating temperature may be appropriately selected based on the type of plant-derived material, the type and concentration of gas, and the like, but is preferably 800 ° C. to 950 ° C.
In the chemical activation method, instead of oxygen and water vapor used in the gas activation method, zinc chloride, iron chloride, calcium phosphate, calcium hydroxide, magnesium carbonate, potassium carbonate, sulfuric acid, etc. are used for activation, and the mixture is washed with hydrochloric acid. This is a method of adjusting the pH with an alkaline aqueous solution and drying.
＜脱灰分工程＞
前記脱灰分工程としては、前記炭化物中の灰分（例えば、ケイ素化合物など）を除去する工程であれば、特に制限はなく、目的に応じて適宜選択することができ、例えば、酸性水溶液又はアルカリ性水溶液に前記炭化物を浸漬する方法などが挙げられる。
前記脱灰分工程の前は、前記炭化物を粉砕して、前記炭化物を酸性水溶液又はアルカリ性水溶液が浸透し易い大きさにすることが好ましい。
<Decalcification process>
The decalcification step is not particularly limited as long as it is a step of removing ash (for example, a silicon compound) in the carbide, and can be appropriately selected depending on the intended purpose. For example, an acidic aqueous solution or an alkaline aqueous solution. Examples thereof include a method of immersing the carbide.
Before the decalcification step, it is preferable to pulverize the carbide to a size that allows the acidic aqueous solution or the alkaline aqueous solution to easily permeate the carbide.
前記多孔質炭素材料の製造方法の一例を以下に示す。
もみ殻を加圧成型したものを、窒素気流中において５００℃、５時間、加熱することにより炭化させ炭化物を得る。その後、この炭化物の１０ｇをアルミナ製の坩堝に入れ、窒素気流中（１０リットル／分）において５℃／分の昇温速度で１，０００℃まで昇温させる。そして、１，０００℃で５時間、炭素化して、炭素質物質（多孔質炭素材料前駆体）に変換した後、室温まで冷却する。なお、炭素化及び冷却中、窒素ガスを流し続ける。次に、炭素質物質をアルカリ処理がしやすい１ｃｍ以下の大きさに粗粉砕し、１ｍｏｌ％の水酸化ナトリウム水溶液で材料内の灰分を除去する。その後、材料を洗浄し材料表面のアルカリを除去し、更に洗浄する。その後、材料を水蒸気雰囲気下で９５０℃の熱処理をして、メソ孔が発達した植物由来の多孔質炭素材料を得る。
An example of the method for producing the porous carbon material is shown below.
The rice husks are pressure-molded and heated in a nitrogen stream at 500 ° C. for 5 hours to carbonize them to obtain carbides. Then, 10 g of this carbide is placed in an alumina crucible, and the temperature is raised to 1,000 ° C. at a heating rate of 5 ° C./min in a nitrogen stream (10 liters / minute). Then, it is carbonized at 1,000 ° C. for 5 hours to be converted into a carbonaceous substance (porous carbon material precursor), and then cooled to room temperature. During carbonization and cooling, nitrogen gas continues to flow. Next, the carbonaceous substance is roughly pulverized to a size of 1 cm or less, which is easily treated with alkali, and the ash content in the material is removed with a 1 mol% sodium hydroxide aqueous solution. Then, the material is washed to remove the alkali on the surface of the material, and further washed. Then, the material is heat-treated at 950 ° C. in a water vapor atmosphere to obtain a plant-derived porous carbon material having developed mesopores.
（触媒の製造方法）
本発明の触媒の製造方法は、植物由来の多孔質炭素材料にポリシラン化合物を導入し、ポリシラン化合物含有多孔質炭素材料を作製する工程（「ポリシラン化合物含有多孔質炭素材料作製工程」という）と、遷移金属を含む溶剤中に前記ポリシラン化合物含有多孔質炭素材料を添加し、混合及び含浸する工程（「混合含浸工程」という）と、を含み、更に必要に応じてその他の工程を含む。
(Catalyst manufacturing method)
The method for producing a catalyst of the present invention includes a step of introducing a polysilane compound into a plant-derived porous carbon material to prepare a polysilane compound-containing porous carbon material (referred to as "polysilane compound-containing porous carbon material preparation step"). It includes a step of adding the polysilane compound-containing porous carbon material to a solvent containing a transition metal, mixing and impregnating the material (referred to as “mixing impregnation step”), and further includes other steps as necessary.
＜ポリシラン化合物含有多孔質炭素材料作製工程＞
ポリシラン化合物含有多孔質炭素材料作製工程は、植物由来の多孔質炭素材料にポリシラン化合物を導入し、ポリシラン化合物含有多孔質炭素材料を作製する工程である。
ポリシラン化合物の植物由来の多孔質炭素材料への導入方法としては、例えば、ポリフェニルメチルシランを溶剤に溶解させたポリフェニルメチルシラン溶液を、多孔質炭素材料に対し、所定量添加し、撹拌する方法などが挙げられる。ポリシラン化合物を溶剤に溶解させたポリシラン化合物溶液中に多孔質炭素材料を浸漬することにより、多孔質炭素材料のメソ孔内部に浸透し、メソ孔内部にまでポリシラン化合物を付着させることができる。
ポリシラン化合物を溶解する溶剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、テトラヒドロフラン（ＴＨＦ）、ベンゼン、トルエン、キシレン等の芳香族炭化水素、クロロホルム、塩化メチレン、ジクロロエタン等のハロゲン化炭化水素などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
なお、ポリシラン化合物が多孔質炭素材料のメソ孔内部にまで付着していることは、多孔質炭素材料の断面のＴＥＭ／ＥＤＸでメソ孔内のケイ素を分析することにより確認することができる。
<Process for producing porous carbon material containing polysilane compound>
The polysilane compound-containing porous carbon material preparation step is a step of introducing a polysilane compound into a plant-derived porous carbon material to prepare a polysilane compound-containing porous carbon material.
As a method for introducing the polysilane compound into the plant-derived porous carbon material, for example, a predetermined amount of a polyphenylmethylsilane solution in which polyphenylmethylsilane is dissolved in a solvent is added to the porous carbon material in a predetermined amount, and the mixture is stirred. The method etc. can be mentioned. By immersing the porous carbon material in the polysilane compound solution in which the polysilane compound is dissolved in a solvent, the porous carbon material can penetrate into the mesopores of the porous carbon material, and the polysilane compound can be adhered to the inside of the mesopores.
The solvent for dissolving the polysilane compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, aromatic hydrocarbons such as tetrahydrofuran (THF), benzene, toluene and xylene, chloroform, methylene chloride and dichloroethane. Such as halogenated hydrocarbons and the like. These may be used alone or in combination of two or more.
The fact that the polysilane compound adheres to the inside of the mesopores of the porous carbon material can be confirmed by analyzing the silicon in the mesopores with TEM / EDX of the cross section of the porous carbon material.
＜混合含浸工程＞
混合含浸工程は、遷移金属を含む溶剤中に前記ポリシラン化合物含有多孔質炭素材料を添加し、混合及び含浸する工程である。
前記混合含浸工程において、遷移金属がポリシラン化合物により還元されて粒子化し、遷移金属粒子となり、多孔質炭素材料のメソ孔内のポリシラン化合物に付着する。これにより、多孔質炭素材料のメソ孔内部にまで遷移金属粒子を担持させることができる。
<Mixing impregnation process>
The mixed impregnation step is a step of adding the polysilane compound-containing porous carbon material to a solvent containing a transition metal, mixing and impregnating the material.
In the mixing impregnation step, the transition metal is reduced by the polysilane compound to form particles, which become transition metal particles and adhere to the polysilane compound in the mesopores of the porous carbon material. As a result, the transition metal particles can be supported even inside the mesopores of the porous carbon material.
前記その他の工程としては、溶剤除去工程、水素化処理工程などが挙げられる。 Examples of the other steps include a solvent removing step and a hydrogenation treatment step.
前記触媒の製造方法の一例を以下に示す。
ポリフェニルメチルシランのテトラヒドロフラン（ＴＨＦ）の１０質量％溶液を作製し、このポリフェニルメチルシラン溶液を、植物由来の多孔質炭素材料に対し、所定のポリシラン導入量になるように計量して、投入し、１時間撹拌して、ポリフェニルメチルシラン含有多孔質炭素材料の分散液を作製する。次に、酢酸パラジウムを、パラジウムが所定の濃度になるようにテトラヒドロフラン（ＴＨＦ）に溶解し、遷移金属としてのパラジウム溶解液を作製し、作製したパラジウム溶解液を、ポリフェニルメチルシラン含有多孔質炭素材料の分散液に、１０Ｌ／ｈの速さで滴定し、混合含浸する。次に、全てのＴＨＦを、減圧蒸留にて揮発させる。その後、水素を２．５Ｌ／ｍｉｎを流通させながら、４００℃雰囲気で３時間、水素処理を行うことにより、触媒を得る。
An example of the method for producing the catalyst is shown below.
A 10% by mass solution of polyphenylmethylsilane in tetrahydrofuran (THF) was prepared, and this polyphenylmethylsilane solution was weighed and added to a plant-derived porous carbon material so as to have a predetermined amount of polysilane introduced. Then, the mixture is stirred for 1 hour to prepare a dispersion of a porous carbon material containing polyphenylmethylsilane. Next, palladium acetate was dissolved in tetrahydrofuran (THF) so that palladium had a predetermined concentration to prepare a palladium solution as a transition metal, and the prepared palladium solution was used as a polyphenylmethylsilane-containing porous carbon. The material dispersion is titrated at a rate of 10 L / h and mixed and impregnated. Next, all THF is volatilized by vacuum distillation. Then, a catalyst is obtained by performing hydrogen treatment in an atmosphere of 400 ° C. for 3 hours while circulating 2.5 L / min of hydrogen.
以下、本発明の実施例を説明するが、本発明は、これらの実施例に何ら限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
（多孔質炭素材料の製造例１）
＜多孔質炭素材料１の作製＞
原材料として、宮城県産のもみ殻を使用した。
まず、もみ殻に含有されているケイ素成分を除去するための処理は、もみ殻を水酸化ナトリウム５．３質量％水溶液９０℃に１４時間浸漬することで、ケイ素成分除去処理を行った。
次に、温度：６００℃、雰囲気：Ｎ２＝３０Ｌ／ｍｉｎの条件下で、３時間炭化処理を行った。
次に、ロータリーキルンを使用し、水蒸気により９５０℃で０．５時間、賦活処理を行った。
次に、雰囲気：Ｎ２＝１０Ｌ／ｍｉｎでバブリングしながら賦活処理を行った。
以上により、多孔質炭素材料１を作製した。
得られた多孔質炭素材料１について、前述の方法でメソ孔容積を測定したところ、０．２７ｃｍ３／ｇであった。
(Production Example 1 of Porous Carbon Material)
<Preparation of Porous Carbon Material 1>
Rice husks from Miyagi prefecture were used as raw materials.
First, in the treatment for removing the silicon component contained in the rice husk, the silicon component was removed by immersing the rice husk in a 5.3 mass% sodium hydroxide aqueous solution at 90 ° C. for 14 hours.
Next, carbonization treatment was carried out for 3 hours under the conditions of temperature: 600 ° C. and atmosphere: N 2 = 30 L / min.
Next, using a rotary kiln, activation treatment was performed at 950 ° C. for 0.5 hours with steam.
Next, the activation treatment was performed while bubbling at an atmosphere: N 2 = 10 L / min.
From the above, the porous carbon material 1 was prepared.
When the mesopore volume of the obtained porous carbon material 1 was measured by the above-mentioned method, it was 0.27 cm 3 / g.
（多孔質炭素材料の製造例２）
＜多孔質炭素材料２の作製＞
多孔質炭素材料の製造例１において、ロータリーキルンを使用し、水蒸気により９５０℃で３時間、賦活処理を行った以外は、多孔質炭素材料の製造例１と同様にして、多孔質炭素材料２を作製した。
得られた多孔質炭素材料２について、前述の方法でメソ孔容積を測定したところ、０．４４ｃｍ３／ｇであった。
(Production Example 2 of Porous Carbon Material)
<Preparation of Porous Carbon Material 2>
In the production example 1 of the porous carbon material, the porous carbon material 2 was prepared in the same manner as in the production example 1 of the porous carbon material except that the rotary kiln was used and the activation treatment was performed at 950 ° C. for 3 hours with steam. Made.
When the mesopore volume of the obtained porous carbon material 2 was measured by the above-mentioned method, it was 0.44 cm 3 / g.
（比較例１）
＜触媒の作製＞
（１）上記多孔質炭素材料１ １ｇを、テトラヒドロフラン（ＴＨＦ）２０ｍＬに添加し、混合させて、分散液を調製した。
（２）酢酸パラジウムを、パラジウムが０．５質量％になるようにテトラヒドロフラン（ＴＨＦ）に溶解し、パラジウム溶解液を作製した。
（３）（２）で作製したパラジウム溶解液を、上記多孔質炭素材料１の分散液に、１０ｍＬ／ｈの速さで滴定混合した。
（４）全てのＴＨＦを、減圧蒸留にて揮発させた。
（５）その後、水素を２．５Ｌ／ｍｉｎを流通させながら、４００℃雰囲気で３時間、水素処理を行った。
以上により、パラジウムを５質量％含有する比較例１の触媒を作製した。
(Comparative Example 1)
<Catalyst preparation>
(1) 11 g of the above porous carbon material was added to 20 mL of tetrahydrofuran (THF) and mixed to prepare a dispersion.
(2) Palladium acetate was dissolved in tetrahydrofuran (THF) so that the amount of palladium was 0.5% by mass to prepare a palladium solution.
(3) The palladium solution prepared in (2) was titrated and mixed with the dispersion of the porous carbon material 1 at a rate of 10 mL / h.
(4) All THF was volatilized by vacuum distillation.
(5) After that, hydrogen treatment was carried out in an atmosphere of 400 ° C. for 3 hours while circulating 2.5 L / min of hydrogen.
From the above, the catalyst of Comparative Example 1 containing 5% by mass of palladium was prepared.
（比較例２）
比較例１において、多孔質炭素材料１を多孔質炭素材料２に代えた以外は、比較例１と同様にして、パラジウムを５質量％含有する比較例２の触媒を作製した。
(Comparative Example 2)
In Comparative Example 1, the catalyst of Comparative Example 2 containing 5% by mass of palladium was produced in the same manner as in Comparative Example 1 except that the porous carbon material 1 was replaced with the porous carbon material 2.
（実施例１）
＜触媒の作製＞
（１）ポリフェニルメチルシラン（商品名：ＯＧＳＯＬ ＳＩ−１０−２０、大阪ガスケミカル株式会社製）のテトラヒドロフラン（ＴＨＦ）の１０質量％溶液を作製した。
（２）（１）のポリフェニルメチルシラン溶液を、上記多孔質炭素材料２ １ｇに対し、ポリシラン導入量が１０質量％になるように計量し、それに、多孔質炭素材料２を投入し、１時間撹拌して、ポリフェニルメチルシラン含有多孔質炭素材料２の分散液を作製した。
（３）酢酸パラジウムを、パラジウムが０．５質量％になるようにテトラヒドロフラン（ＴＨＦ）に溶解し、パラジウム溶解液を作製した。
（４）（３）で作製したパラジウム溶解液を、上記ポリフェニルメチルシラン含有多孔質炭素材料２の分散液に、１０ｍＬ／ｈの速さで滴定混合した。
（５）全てのＴＨＦを、減圧蒸留にて揮発させた。
（６）その後、水素を２．５Ｌ／ｍｉｎを流通させながら、４００℃雰囲気で３時間、水素処理を行った。
以上により、パラジウムを５質量％含有する実施例１の触媒を作製した。
(Example 1)
<Catalyst preparation>
(1) A 10% by mass solution of tetrahydrofuran (THF) of polyphenylmethylsilane (trade name: OGSOL SI-10-20, manufactured by Osaka Gas Chemical Co., Ltd.) was prepared.
(2) The polyphenylmethylsilane solution of (1) is weighed so that the amount of polysilane introduced is 10% by mass with respect to 21 g of the porous carbon material, and the porous carbon material 2 is added thereto. After stirring for hours, a dispersion of the polyphenylmethylsilane-containing porous carbon material 2 was prepared.
(3) Palladium acetate was dissolved in tetrahydrofuran (THF) so that the amount of palladium was 0.5% by mass to prepare a palladium solution.
(4) The palladium solution prepared in (3) was titrated and mixed with the dispersion of the polyphenylmethylsilane-containing porous carbon material 2 at a rate of 10 mL / h.
(5) All THF was volatilized by vacuum distillation.
(6) After that, hydrogen treatment was carried out in an atmosphere of 400 ° C. for 3 hours while circulating 2.5 L / min of hydrogen.
As described above, the catalyst of Example 1 containing 5% by mass of palladium was prepared.
（実施例２）
実施例１において、ポリフェニルメチルシラン導入量が２０質量％になるように、ポリフェニルメチルシランＴＨＦ溶液を計量し、ポリフェニルメチルシラン含有多孔質炭素材料２の分散液を作製した以外は、実施例１と同様にして、パラジウムを５質量％含有する実施例２の触媒を作製した。
(Example 2)
In Example 1, the polyphenylmethylsilane THF solution was weighed so that the amount of polyphenylmethylsilane introduced was 20% by mass, and a dispersion of the polyphenylmethylsilane-containing porous carbon material 2 was prepared. In the same manner as in Example 1, the catalyst of Example 2 containing 5% by mass of palladium was prepared.
（実施例３）
実施例１において、多孔質炭素材料２を多孔質炭素材料１とし、ポリフェニルメチルシラン導入量が１質量％になるように、ポリフェニルメチルシラン含有多孔質炭素材料１の分散液を作製した以外は、実施例１と同様にして、パラジウムを５質量％含有する実施例３の触媒を作製した。
(Example 3)
In Example 1, the porous carbon material 2 was used as the porous carbon material 1, and a dispersion liquid of the polyphenylmethylsilane-containing porous carbon material 1 was prepared so that the amount of polyphenylmethylsilane introduced was 1% by mass. Made a catalyst of Example 3 containing 5% by mass of palladium in the same manner as in Example 1.
（実施例４）
実施例１において、多孔質炭素材料２を多孔質炭素材料１とし、ポリフェニルメチルシラン導入量が５質量％になるように、ポリフェニルメチルシラン含有多孔質炭素材料１の分散液を作製した以外は、実施例１と同様にして、パラジウムを５質量％含有する実施例４の触媒を作製した。
(Example 4)
In Example 1, the porous carbon material 2 was used as the porous carbon material 1, and a dispersion liquid of the polyphenylmethylsilane-containing porous carbon material 1 was prepared so that the amount of polyphenylmethylsilane introduced was 5% by mass. Made a catalyst of Example 4 containing 5% by mass of palladium in the same manner as in Example 1.
（実施例５）
実施例１において、ポリフェニルメチルシラン導入量が３０質量％になるように、ポリフェニルメチルシラン含有多孔質炭素材料２の分散液を作製した以外は、実施例１と同様にして、パラジウムを５質量％含有する実施例５の触媒を作製した。
(Example 5)
In Example 1, palladium was added in the same manner as in Example 1 except that a dispersion liquid of the polyphenylmethylsilane-containing porous carbon material 2 was prepared so that the amount of polyphenylmethylsilane introduced was 30% by mass. The catalyst of Example 5 containing mass% was prepared.
（実施例６）
実施例１において、ポリフェニルメチルシラン導入量が１質量％になるように、ポリフェニルメチルシラン含有多孔質炭素材料２の分散液を作製した以外は、実施例１と同様にして、パラジウムを５質量％含有する実施例６の触媒を作製した。
(Example 6)
In Example 1, palladium was added in the same manner as in Example 1 except that a dispersion liquid of the polyphenylmethylsilane-containing porous carbon material 2 was prepared so that the amount of polyphenylmethylsilane introduced was 1% by mass. The catalyst of Example 6 containing mass% was prepared.
（実施例７）
実施例１において、ポリフェニルメチルシラン導入量が５質量％になるように、ポリフェニルメチルシラン含有多孔質炭素材料２の分散液を作製した以外は、実施例１と同様にして、パラジウムを５質量％含有する実施例７の触媒を作製した。
(Example 7)
In Example 1, palladium was added in the same manner as in Example 1 except that a dispersion liquid of the polyphenylmethylsilane-containing porous carbon material 2 was prepared so that the amount of polyphenylmethylsilane introduced was 5% by mass. The catalyst of Example 7 containing mass% was prepared.
次に、得られた実施例１〜７及び比較例１〜２の触媒について、以下のようにして、レシチンの水素化反応を行った。結果を表２に示した。 Next, the obtained catalysts of Examples 1 to 7 and Comparative Examples 1 and 2 were subjected to a hydrogenation reaction of lecithin as follows. The results are shown in Table 2.
＜水素化反応＞
原料としては、富士フィルム和光純薬工業株式会社製のレシチンを使用した。
水素化反応に使用した装置は、Ｃｈｅｍｉ Ｃｈｅｍｉ ３００（柴田科学株式会社製）である。
反応組成は、レシチンを５ｇ、作製した各触媒を０．３ｇ、ヘキサン／エタノール＝４／１（体積比）２０ｇで調合し、水素環境下、０．４ＭＰａ、６０℃で８時間反応させた。
２回目の合成については、１００ｍＬのヘキサンでろ過し、各触媒を洗浄し、再利用したもので、前述の水素化反応を行った。
<Hydrogenation reaction>
As a raw material, lecithin manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. was used.
The apparatus used for the hydrogenation reaction is Chemi Chemi 300 (manufactured by Sibata Scientific Technology Co., Ltd.).
As for the reaction composition, 5 g of lecithin, 0.3 g of each prepared catalyst, and 20 g of hexane / ethanol = 4/1 (volume ratio) were prepared, and the reaction was carried out at 0.4 MPa and 60 ° C. for 8 hours in a hydrogen environment.
For the second synthesis, the catalyst was filtered through 100 mL of hexane, each catalyst was washed and reused, and the above-mentioned hydrogenation reaction was carried out.
反応１回目及び２回目の反応性生物を、ＡＴ−７１０（京都電子工業株式会社製）の自動滴定装置を使用し、ヨウ化度測定を行った。得られたヨウ化度を、反応前のヨウ化度で割ることで、反応収率を求めた。
下記の数式から、収率差、及び低下率を求めた。
収率差（％）＝反応収率１回目（％）−反応収率２回目（％）
低下率（％）＝［反応収率１回目（％）−反応収率２回目（％）］／反応収率１回目（％）×１００
The first and second reactive organisms were measured for the degree of iodide using an automatic titrator of AT-710 (manufactured by Kyoto Denshi Kogyo Co., Ltd.). The reaction yield was determined by dividing the obtained degree of iodide by the degree of iodide before the reaction.
The yield difference and the rate of decrease were calculated from the following formulas.
Yield difference (%) = reaction yield 1st (%) -reaction yield 2nd (%)
Decrease rate (%) = [Reaction yield 1st (%) -Reaction yield 2nd (%)] / Reaction yield 1st (%) x 100
表１及び表２の結果から、実施例１〜７は、比較例１及び２に比べて、触媒活性の低下を抑制することができ、２回目の使用でも８０％以上の高収率が得られることがわかった。 From the results of Tables 1 and 2, Examples 1 to 7 can suppress a decrease in catalytic activity as compared with Comparative Examples 1 and 2, and a high yield of 80% or more can be obtained even in the second use. It turned out to be.
本発明の触媒は、触媒活性の低下を抑制することができ、２回目の使用でも８０％以上の高収率が得られるので、例えば、水素化反応、カップリング反応などの合成系等に好適に使用することができる。 The catalyst of the present invention can suppress a decrease in catalytic activity, and a high yield of 80% or more can be obtained even after the second use, and is therefore suitable for a synthetic system such as a hydrogenation reaction or a coupling reaction. Can be used for.
しかしながら、特許文献１には、被毒性の向上については記載がなく、担体として植物由来の多孔質炭素材料を用いておらず、ポリジメチルシランは常温で固体であり、溶剤に不溶であるため、多孔質炭素材料のメソ孔内部にまでポリジメチルシランを導入し、付着させることができず、担体として多孔質炭素材料を用いることによる効果が得られないという課題がある。 However, since Patent Document 1, there is no description about improvement of poisoning, not using the porous carbon material derived from a plant as a carrier, polydimethyl silane is solid at ordinary temperature, which is insoluble in a solvent, porous introduced polydimethyl silane into the interior mesopores of the carbon material, it can not be attached, there is a problem that the effect can not be obtained by the use of porous carbon material as a carrier.
Claims (11)
遷移金属を含む溶剤中に前記ポリシラン化合物含有多孔質炭素材料を添加し、混合及び含浸する工程と、
を含むことを特徴とする触媒の製造方法。 A process of introducing a polysilane compound into a plant-derived porous carbon material to prepare a polysilane compound-containing porous carbon material, and
A step of adding, mixing and impregnating the polysilane compound-containing porous carbon material in a solvent containing a transition metal, and
A method for producing a catalyst, which comprises.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019129047A JP7349836B2 (en) | 2019-07-11 | 2019-07-11 | Heterogeneous transition metal catalyst for lecithin hydrogenation reaction and method for producing the same |
| PCT/JP2020/024521 WO2021006027A1 (en) | 2019-07-11 | 2020-06-23 | Catalyst and production method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019129047A JP7349836B2 (en) | 2019-07-11 | 2019-07-11 | Heterogeneous transition metal catalyst for lecithin hydrogenation reaction and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2021013885A true JP2021013885A (en) | 2021-02-12 |
| JP7349836B2 JP7349836B2 (en) | 2023-09-25 |
Family
ID=74114020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019129047A Active JP7349836B2 (en) | 2019-07-11 | 2019-07-11 | Heterogeneous transition metal catalyst for lecithin hydrogenation reaction and method for producing the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP7349836B2 (en) |
| WO (1) | WO2021006027A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002134123A (en) * | 2000-10-20 | 2002-05-10 | Shin Etsu Chem Co Ltd | Catalyst for fuel cell, its manufacturing method, and electrode for the fuel cell |
| JP2007260659A (en) * | 2006-03-02 | 2007-10-11 | Japan Science & Technology Agency | Polysilane-carrying transition metal catalyst |
| JP2017160158A (en) * | 2016-03-09 | 2017-09-14 | 国立大学法人 東京大学 | Process for producing optically active 4-nitro-butanoic acid ester and pregabalin |
| JP2018052750A (en) * | 2016-09-26 | 2018-04-05 | デクセリアルズ株式会社 | Porous carbon material, its manufacturing method, and synthesis reaction catalyst thereof |
| JP2019118854A (en) * | 2017-12-28 | 2019-07-22 | 国立大学法人 東京大学 | Polysilane-palladium/(calcium phosphate-activated carbon) catalyst |
-
2019
- 2019-07-11 JP JP2019129047A patent/JP7349836B2/en active Active
-
2020
- 2020-06-23 WO PCT/JP2020/024521 patent/WO2021006027A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002134123A (en) * | 2000-10-20 | 2002-05-10 | Shin Etsu Chem Co Ltd | Catalyst for fuel cell, its manufacturing method, and electrode for the fuel cell |
| JP2007260659A (en) * | 2006-03-02 | 2007-10-11 | Japan Science & Technology Agency | Polysilane-carrying transition metal catalyst |
| JP2017160158A (en) * | 2016-03-09 | 2017-09-14 | 国立大学法人 東京大学 | Process for producing optically active 4-nitro-butanoic acid ester and pregabalin |
| JP2018052750A (en) * | 2016-09-26 | 2018-04-05 | デクセリアルズ株式会社 | Porous carbon material, its manufacturing method, and synthesis reaction catalyst thereof |
| JP2019118854A (en) * | 2017-12-28 | 2019-07-22 | 国立大学法人 東京大学 | Polysilane-palladium/(calcium phosphate-activated carbon) catalyst |
Non-Patent Citations (2)
| Title |
|---|
| SAITO,YUKI ,ET AL.: "Catalytic Hydrogenation of Aliphatic Nitro Compounds with Polysilane/Bone Charcoal‐Supported Pallad", ASIAN JOURNAL OF ORGANIC CHEMISTRY, vol. 5, JPN6020031135, 2016, pages 1124 - 1127, ISSN: 0004988324 * |
| 降矢 裕一、他: "新規ポリシラン−活性炭−リン酸カルシウム担持パラジウム、および白金触媒を用いた連続フロー法によるニト", 日本化学会第９９春季年会講演予稿集, JPN6020031134, 1 March 2019 (2019-03-01), pages 1 - 4, ISSN: 0004988323 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2021006027A1 (en) | 2021-01-14 |
| JP7349836B2 (en) | 2023-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0643014B1 (en) | Deodorant comprising metal oxide-carrying activated carbon | |
| US9174205B2 (en) | Production of catalytically active activated carbons | |
| JP6450352B2 (en) | Porous carbon material, method for producing the same, and catalyst for synthesis reaction | |
| JPH09239265A (en) | Mercury adsorbent | |
| TWI774653B (en) | Porous carbon material, method for producing the same, filter, sheet, and carrier for catalyst | |
| MX2013003448A (en) | Mesoporous activated carbon and methods of producing same. | |
| JPH0596167A (en) | Forming catalyst for hardening unsaturated fatty acid and method for its production | |
| CN101658761A (en) | Catalyst polymerization method for removing acetylene from gas selectively | |
| WO2021006027A1 (en) | Catalyst and production method therefor | |
| RU2414961C1 (en) | Carbon-mineral sorbent and method of making said sorbent | |
| JP2010207693A (en) | Adsorbent for volatile organic compound and manufacturing method thereof | |
| CN113372191B (en) | Preparation method of tert-butyl cyclohexanol | |
| CA1100721A (en) | Carbon pellets with controlled porosity | |
| Liu et al. | Mechanisms on formation of hierarchically porous carbon and its adsorption behaviors | |
| Prabhu et al. | Synthesis of porous sulfonated carbon as a potential adsorbent for phenol wastewater | |
| JP2000203823A (en) | Production of activated carbon | |
| JP6646088B2 (en) | Porous carbon material, method for producing the same, and catalyst for synthesis reaction | |
| CN113215818B (en) | Metal interstitial compound/activated carbon fiber composite material and preparation method and application thereof | |
| JP2019118854A (en) | Polysilane-palladium/(calcium phosphate-activated carbon) catalyst | |
| JP6646087B2 (en) | Porous carbon material, method for producing the same, and catalyst for synthesis reaction | |
| WO2017126421A1 (en) | Porous carbon material, method for manufacturing same, filter, sheet, and catalyst carrier | |
| JP2019198543A (en) | Deodorization material and deodorization sheet | |
| TW202319075A (en) | Photocatalyst antibacterial deodorizing material, method for producing same, antibacterial deodorizing material, and antibacterial deodorizing filter | |
| KR20070031305A (en) | Adsorbent and process for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190809 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220131 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20220523 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230214 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230303 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20230627 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230809 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20230817 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20230905 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20230912 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7349836 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |