JP6232672B2 - Fe合金を含む金属粉末状触媒 - Google Patents
Fe合金を含む金属粉末状触媒 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims description 88
- 229910052751 metal Inorganic materials 0.000 title claims description 9
- 239000002184 metal Substances 0.000 title claims description 9
- 239000000843 powder Substances 0.000 title description 12
- 229910000640 Fe alloy Inorganic materials 0.000 title description 2
- 239000010935 stainless steel Substances 0.000 claims description 29
- 229910001220 stainless steel Inorganic materials 0.000 claims description 29
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims description 22
- 150000004706 metal oxides Chemical class 0.000 claims description 22
- 229910052804 chromium Inorganic materials 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000002105 nanoparticle Substances 0.000 claims description 9
- 239000007858 starting material Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910007541 Zn O Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 239000011651 chromium Substances 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910000734 martensite Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000001371 (5E)-3,5-dimethylocta-1,5,7-trien-3-ol Substances 0.000 description 3
- 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 3
- JNVHVDDAOGRVDT-UHFFFAOYSA-N 3,7-dimethyloct-6-en-1-yn-3-yl acetate Chemical compound CC(C)=CCCC(C)(C#C)OC(C)=O JNVHVDDAOGRVDT-UHFFFAOYSA-N 0.000 description 3
- ZJIQIJIQBTVTDY-SREVYHEPSA-N dehydrolinalool Chemical compound CC(=C)\C=C/CC(C)(O)C=C ZJIQIJIQBTVTDY-SREVYHEPSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000007725 thermal activation Methods 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- -1 for example Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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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
- 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
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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
- B01J37/0225—Coating of metal substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/44—Palladium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- 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
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
(i)金属合金の総重量に基づいて60重量%〜80重量%のFeと、
(ii)金属合金の総重量に基づいて1重量%〜30重量%のCrと、
(iii)金属合金の総重量に基づいて0.5重量%〜10重量%のNiと、
を含む金属合金担体を含み、この場合に、前記金属合金は、金属酸化物層によって被覆され、且つ、Pdで含浸される、粉末状触媒系(I)に関する。
・触媒は、反応の後、容易に再利用(及び除去)される。これは、例えば濾過によって行われることができる。
・触媒は、2回以上使用可能である(再利用可能)。
・触媒は、そのままで、非常に安定な系である。例えば、酸、並びに、水に対して安定である。
・触媒は、容易に生成される。
・触媒は、容易に処理される。
・水素化は、いかなる溶媒をも用いることなく実行可能である。
・触媒は、鉛を含まない。
・触媒は、水素化反応において高い選択性を示す。
(i)ステンレス鋼担体の総重量に基づいて60重量%〜80重量%のFeと、
(ii)ステンレス鋼担体の総重量に基づいて10重量%〜30重量%のCrと、
(iii)ステンレス鋼担体の総重量に基づいて0.5重量%〜10重量%のNiと、
を含むステンレス鋼であり、且つ、ステンレス鋼は、金属酸化物層によって被覆されPdで含浸される、粉末状触媒系(II)に関する。
(i)ステンレス鋼担体の総重量に基づいて60重量%〜80重量%のFeと、
(ii)ステンレス鋼担体の総重量に基づいて12重量%〜25重量%のCrと、
(iii)ステンレス鋼の総重量に基づいて1重量%〜8重量%のNiと、
(iv)ステンレス鋼担体の総重量に基づいて1重量%〜8重量%のCuと、
を含むステンレス鋼であり、且つ、ステンレス鋼は、金属酸化物層によって被覆されPdで含浸される、粉末状触媒系(III)に関する。
(式中、R1は、直鎖型又は分岐型のC5〜C35アルキル、又は、直鎖型又は分岐型のC5〜C35アルケニル部位であり、炭素鎖は置換されることができ、且つ、R2は、直鎖型又は分岐型のC1〜C4アルキルであり、炭素鎖は置換されることができる)の化合物を、触媒(I)、(II)、(III)、(IV)、(IV’)、(V)、(V’)、(VI)、(VII)、(VII’)、(VIII)、及び/又は(IX)の存在下にて、水素と反応させる方法に関する。
[実施例1触媒の合成(Al2O3/ZnO及びPdの沈積によって被覆されたステンレス鋼)]
[ステップ1:熱による前処理]
ステンレス鋼の粉末(EOS GmbH、独国より市販のEOS StainlessSteel GP1(登録商標))に対して、450℃で3時間、熱による前処理を実施した。
100mlフラスコに、Al(NO3)39H2O20.0g(53.3ミリモル)及び水70mlを加えた。Al(NO3)3・9H2Oが完全に溶解するまで、混合物を撹拌した。溶液を95℃まで加熱した。次いで、ZnOの粉末4.34g(53.3ミリモル)を反応溶液にゆっくりと加えた。ZnOが完全に溶解するまで、加熱及び撹拌を維持した。次いで、溶液を室温まで冷却し、メンブランフィルターを通して濾過した。
モリブデン酸ナトリウム二水和物318mg(1.31ミリモル)と無水パラジウム(II)塩化物212mg(1.20ミリモル)を、加熱下にて(約95℃)、脱イオン水60mlに加えた。混合物を撹拌した。水が完全に蒸発するまで、加熱及び撹拌を継続した(固体の残渣が形成した)。その後、脱イオン水60mlを、攪拌下にて残渣に加えた。蒸発−溶解のサイクルは、PdCl2を完全に溶解させるために、2回繰り返した。最後に、熱水100mlを、固体の残渣に加えた。濃い茶色の溶液を室温まで冷却し、濾紙を通して濾過した。前駆体溶液の最終的な量が120mLになるまで、フィルターを水で洗浄した。
ステップ3から得られた粉末触媒に対して、H2−Ar気流下にて、300℃で4時間、温度処理を実施した。次いで、同じH2−Ar気流下にて、室温まで冷却した。
実施例2aと同一の反応条件を使用した。反応の終わりにおいては(約13〜19時間後)、反応混合物を不活性雰囲気下にて冷却し、反応溶液を新たなMBY(再度285g)で交換し、再度、水素化を開始した。
Claims (16)
- 金属合金担体を含む粉末状選択的接触水素化用触媒であって、前記金属合金担体は、
(i)前記金属合金の総重量に基づいて60重量%〜80重量%のFeと、
(ii)前記金属合金の総重量に基づいて1重量%〜30重量%のCrと、
(iii)前記金属合金の総重量に基づいて0.5重量%〜10重量%のNiと、
を含み、前記金属合金は、金属酸化物層によって被覆され、且つ、Pdで含浸される、
粉末状接触水素化用触媒。 - 前記金属合金はステンレス鋼である、請求項1に記載の触媒。
- 前記金属合金は更なる金属を含む、請求項1又は2に記載の触媒。
- 前記金属合金は炭素を含む、請求項1〜3のいずれか一項に記載の触媒。
- 前記金属合金はステンレス鋼であって、前記ステンレス鋼は、
(i)前記ステンレス鋼の総重量に基づいて60重量%〜80重量%のFeと、
(ii)前記ステンレス鋼の総重量に基づいて12重量%〜25重量%のCrと、
(iii)前記ステンレス鋼の総重量に基づいて1重量%〜8重量%のNiと、
(iv)前記ステンレス鋼の総重量に基づいて1重量%〜8重量%のCuと、
を含み、前記金属合金は、金属酸化物層によって被覆され、且つ、Pdで含浸される、
請求項1〜4のいずれか一項に記載の触媒。 - 前記金属酸化物層は、塩基性又は両性である、請求項1〜5のいずれか一項に記載の触媒。
- 前記金属酸化物層は、Zn、Cr、Mn、Cu、及び/又はAlを含む、請求項1〜6のいずれか一項に記載の触媒。
- 前記酸化物層は、ZnOを含む、請求項1〜7のいずれか一項に記載の触媒。
- 前記酸化物層は、ZnOと、Cr、Mn、Mg、Cu、及びAlからなる群から選択される少なくとも1つの更なる金属酸化物とを含む、請求項1〜8のいずれか一項に記載の触媒。
- 前記酸化物層は、ZnO及びAl2O3を含む、請求項1〜9のいずれか一項に記載の触媒。
- 前記触媒の総重量に基づいて0.1重量%〜50重量%の前記ZnOを含む、請求項8〜10のいずれか一項に記載の触媒。
- 前記金属酸化物は、2:1〜1:2のモル比におけるZnOとAl2O3の混合物である、請求項1〜11のいずれか一項に記載の触媒。
- 前記Pd−ナノ粒子は、0.5〜20nmの平均粒径を有する、請求項1〜12のいずれか一項に記載の触媒。
- 前記触媒は、前記触媒の総重量に基づいて0.001重量%〜5重量%の前記Pd−ナノ粒子を含む、請求項1〜13のいずれか一項に記載の触媒。
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PCT/EP2013/053513 WO2013124393A1 (en) | 2012-02-24 | 2013-02-22 | Metal powderdous catalyst comprising a fe-alloy |
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