JP4523275B2 - Supported catalysts for the hydrogenation of nitroaromatic compounds. - Google Patents
Supported catalysts for the hydrogenation of nitroaromatic compounds. Download PDFInfo
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- JP4523275B2 JP4523275B2 JP2003541628A JP2003541628A JP4523275B2 JP 4523275 B2 JP4523275 B2 JP 4523275B2 JP 2003541628 A JP2003541628 A JP 2003541628A JP 2003541628 A JP2003541628 A JP 2003541628A JP 4523275 B2 JP4523275 B2 JP 4523275B2
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- 239000003054 catalyst Substances 0.000 title claims description 73
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 34
- 150000001875 compounds Chemical class 0.000 title claims description 11
- 229910000510 noble metal Inorganic materials 0.000 claims description 78
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 15
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 13
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims description 12
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 11
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052703 rhodium Inorganic materials 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000010970 precious metal Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 150000002828 nitro derivatives Chemical class 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012876 carrier material Substances 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229910052763 palladium Inorganic materials 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- -1 aromatic nitro compounds Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRTYPQGPARWINR-UHFFFAOYSA-N palladium platinum Chemical compound [Pd].[Pt] JRTYPQGPARWINR-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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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
- B01J23/54—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
- B01J23/63—Platinum group metals with rare earths or actinides
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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
- B01J23/54—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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6482—Vanadium
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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
- B01J23/54—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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
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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
- B01J23/54—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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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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
- B01J23/70—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
- B01J23/8906—Iron and noble metals
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、粉末の形の担持水素化触媒、その製造法および該担持水素化触媒のニトロ芳香族化合物の接触水素化への使用に関する。 The present invention relates to a supported hydrogenation catalyst in powder form, to a process for its preparation and to the use of this supported hydrogenation catalyst for the catalytic hydrogenation of nitroaromatic compounds.
アミンへの芳香族ニトロ化合物の水素化は、工業化学においてアミンを製造する主要な方法の１つである。現在、芳香族アミンは、微細で特殊な大量生産化学薬品の生産における中心的な成分である。殊に、大量生産化学薬品の分野における例は、アニリンおよびトルエンジアミン（ＴＤＡ）である。アニリンへのニトロベンゼンの接触水素化は、古典的なベシャン還元に代わり、持続的な開発に著しく貢献している。ＴＤＡは、ポリウレタンフォームを製造するための中間体として評価されることができ、この場合には、ホスゲン化反応においてトルエンジイソシアネート（ＴＤＩ）に変換され、このトルエンジイソシアネートは、ポリアルコールと一緒に処理され、ポリウレタンフォームが製造される。 Hydrogenation of aromatic nitro compounds to amines is one of the major methods for producing amines in industrial chemistry. At present, aromatic amines are central components in the production of fine and specialized mass-produced chemicals. In particular, examples in the field of mass-produced chemicals are aniline and toluenediamine (TDA). Catalytic hydrogenation of nitrobenzene to aniline has contributed significantly to sustainable development, replacing the classic Beshan reduction. TDA can be evaluated as an intermediate for producing polyurethane foam, in which case it is converted to toluene diisocyanate (TDI) in a phosgenation reaction, which is treated with a polyalcohol. A polyurethane foam is produced.
種々の方法および触媒は、相応する芳香族ニトロ化合物の水素化によって芳香族アミンを製造するために公知である。気相中でのアニリンへのニトロベンゼンの水素化以外に、数多くの他の方法が存在し、この方法の全ての方法が液相中で作業される。また、担持非貴金属成分触媒および担持ラニー型触媒以外に、貴金属を含有する担持触媒が使用される。 Various processes and catalysts are known for producing aromatic amines by hydrogenation of the corresponding aromatic nitro compounds. There are many other methods besides hydrogenation of nitrobenzene to aniline in the gas phase, and all methods of this method work in the liquid phase. In addition to the supported non-noble metal component catalyst and the supported Raney-type catalyst, a supported catalyst containing a noble metal is used.
懸濁相中でニトロ芳香族化合物、殊にジニトロトルエンを接触水素化するためには、数多くの触媒が公知である。 Numerous catalysts are known for the catalytic hydrogenation of nitroaromatic compounds, in particular dinitrotoluene, in the suspension phase.
米国特許第２８２３２３５号明細書には、鉄でドープされている、カーボンブラック上のパラジウム触媒、白金触媒およびパラジウム−白金触媒が開示されている。 U.S. Pat. No. 2,823,235 discloses palladium, platinum and palladium-platinum catalysts on carbon black which are doped with iron.
カーボンブラックを担体として含む極めて類似した触媒は、米国特許第３１２７３５６号明細書中に開示されている。 A very similar catalyst containing carbon black as a support is disclosed in US Pat. No. 3,127,356.
米国特許第４２５６６７１号明細書には、トルエンジアミンへのジニトロトルエンの接触水素化に使用される触媒のための貴金属成分として、ＰｄおよびＰｔ以外にＮｉ、ＲｕおよびＲｈも開示されている。 U.S. Pat. No. 4,256,671 also discloses Ni, Ru and Rh in addition to Pd and Pt as noble metal components for the catalyst used in the catalytic hydrogenation of dinitrotoluene to toluenediamine.
米国特許第６０９６９２４号明細書には、触媒活性成分としてＲｈ、Ｒｕ、Ｉｒ、Ｐｔ、Ｐｄ、ＮｉおよびＣｏが開示されている。これらの金属は、粉末の形の担体に塗布されている。Ｖは、ドーピング金属として使用される。 US Pat. No. 6,096,924 discloses Rh, Ru, Ir, Pt, Pd, Ni and Co as catalytic active components. These metals are applied to a carrier in the form of a powder. V is used as a doping metal.
ドイツ連邦共和国特許出願公開第１９９１１８６５号明細書Ａ１には、貴金属としてのＩｒおよびドーピング金属としてのＶを有する同様の系が開示されている。 German Offenlegungsschrift DE 1911865 A1 discloses a similar system with Ir as the noble metal and V as the doping metal.
前記の刊行物には、Ｐｄ触媒、Ｉｒ触媒またはＰｄ−Ｐｔ触媒が開示されており、一方で、米国特許第４２１２８２４号明細書には、Ｆｅでドープされている、カーボンブラック上のＰｔ触媒が開示されている。ＦｅおよびＶは、断然に最も頻繁にドーピングに使用される非貴金属成分である。 Said publication discloses a Pd catalyst, an Ir catalyst or a Pd-Pt catalyst, while US Pat. No. 4,212,824 discloses a Pt catalyst on carbon black doped with Fe. It is disclosed. Fe and V are by far the most precious metal components used for doping.
また、担持パラジウム触媒への数モル％の白金（例えば、１５モル％）の添加により、活性に対してプラスの相乗効果が生じることも公知である。これは、Pol. Chem. Stosow. 1981, 25 (1), 53-68またはChin. Chem. Lett. 1996, 7(7), 663-664に開示されている。 It is also known that the addition of a few mole percent platinum (eg, 15 mole percent) to the supported palladium catalyst produces a positive synergistic effect on activity. This is disclosed in Pol. Chem. Stosow. 1981, 25 (1), 53-68 or Chin. Chem. Lett. 1996, 7 (7), 663-664.
前者の刊行物は、白金がパラジウムよりも少ないモル量でのみ存在しうることを示す。最適値は、Ｐｄに対してＰｔ約２０モル％である。大量のＰｔが使用される場合には、より低い活性が測定される。 The former publication shows that platinum can only be present in lower molar amounts than palladium. The optimum value is about 20 mol% Pt relative to Pd. Lower amounts of activity are measured when large amounts of Pt are used.
本発明の目的は、水素化触媒の選択および生産によって、アミノ芳香族化合物へのニトロ芳香族化合物の接触水素化の選択性および活性を改善すること、即ち副生成物の形成を減少させること、および望ましい生成物の収量を増加させることである。 The object of the present invention is to improve the selectivity and activity of the catalytic hydrogenation of nitroaromatic compounds to aminoaromatic compounds by the selection and production of hydrogenation catalysts, i.e. to reduce the formation of by-products, And increasing the yield of the desired product.
本発明は、触媒活性成分として一次貴金属成分、二次貴金属成分および１つ以上の非貴金属成分の混合物を含有する、粉末の形の担持水素化触媒を提供し、この場合には、Ｐｔが一次貴金属成分として、二次貴金属成分としてのＰｄ、Ｒｕ、Ｒｈおよび非貴金属成分としてのＶ、Ｆｅ、Ｍｎ、Ｃｅおよび／またはＣｒと一緒に使用されていてもよいか、またはＰｄが一次貴金属成分として、二次貴金属成分としてのＲｕ、Ｒｈおよび非貴金属成分としてのＶ、Ｆｅ、Ｍｎ、Ｃｅおよび／またはＣｒと一緒に使用されていてもよいか、またはＰｄが一次貴金属成分として、二次貴金属成分としてのＰｔおよび非貴金属成分としてのＣｅおよび／またはＣｒと一緒に使用されていてもよい。 The present invention provides a supported hydrogenation catalyst in the form of a powder containing a mixture of a primary noble metal component, a secondary noble metal component and one or more non-noble metal components as a catalytically active component, wherein Pt is the primary As a noble metal component, it may be used together with Pd, Ru, Rh as secondary noble metal components and V, Fe, Mn, Ce and / or Cr as non-noble metal components, or Pd as a primary noble metal component May be used together with Ru, Rh as secondary noble metal components and V, Fe, Mn, Ce and / or Cr as non-noble metal components, or Pd as secondary noble metal component, secondary noble metal component May be used together with Pt as a non-noble metal component and Ce and / or Cr.
本発明による水素化触媒は、水素化触媒１００ｇ当たり一次貴金属成分１０〜５０ｍｍｏｌを含有する。二次貴金属成分の割合は、一次貴金属成分に対して１〜６０モル％、好ましくは一次貴金属成分に対して８〜１２モル％であることができ、非貴金属成分の割合は、一次貴金属成分に対して１〜７００モル％、好ましくは１００〜６００モル％であることができる。 The hydrogenation catalyst according to the invention contains 10 to 50 mmol of primary noble metal component per 100 g of hydrogenation catalyst. The proportion of the secondary noble metal component can be 1 to 60 mol% with respect to the primary noble metal component, preferably 8 to 12 mol% with respect to the primary noble metal component, and the proportion of the non-noble metal component can be It can be 1 to 700 mol%, preferably 100 to 600 mol%.
副生成物の形成は、一次貴金属成分と二次貴金属成分との比によって僅かにのみ影響を及ぼされるが、しかし、この比は、触媒の活性に強い影響を及ぼす。 By-product formation is affected only slightly by the ratio of primary and secondary noble metal components, but this ratio has a strong effect on the activity of the catalyst.
一次貴金属成分としてのＰｔと二次貴金属成分としてのＰｄ、Ｒｕ、Ｒｈとの組合せ物のためのドーピング金属として、非貴金属成分としてのＶ、Ｆｅ、Ｍｎ、Ｃｅおよび／またはＣｒは、特に好適である。 As doping metals for the combination of Pt as primary noble metal component and Pd, Ru, Rh as secondary noble metal components, V, Fe, Mn, Ce and / or Cr as non-noble metal components are particularly suitable. is there.
一次貴金属成分としてのＰｄと二次貴金属成分としてのＲｕ、Ｒｈとの組合せ物のためのドーピング金属として、非貴金属成分としてのＶ、Ｆｅ、Ｍｎ、Ｃｅおよび／またはＣｒは、特に好適である。 As doping metals for the combination of Pd as primary noble metal component and Ru, Rh as secondary noble metal components, V, Fe, Mn, Ce and / or Cr as non-noble metal components are particularly suitable.
一次貴金属成分としてのＰｄと二次貴金属成分としてのＰｔとの組合せ物のためのドーピング金属として、非貴金属成分としてのＣｅおよび／またはＣｒは、特に好適である。 As doping metal for the combination of Pd as primary noble metal component and Pt as secondary noble metal component, Ce and / or Cr as non-noble metal components are particularly suitable.
二次貴金属成分は、触媒の高い活性にとって重要であり、一方で、非貴金属成分は、選択性にとって重要である。 Secondary noble metal components are important for high activity of the catalyst, while non-noble metal components are important for selectivity.
本発明による水素化触媒は、無水水素化触媒１００ｇ当たり一次貴金属成分１５〜２０ｍｍｏｌ、一次貴金属成分に対して８〜１２モル％の二次貴金属成分および一次貴金属成分に対して１〜６００モル％のセリウムを含有する。 The hydrogenation catalyst according to the present invention comprises 15 to 20 mmol of primary noble metal component per 100 g of anhydrous hydrogenation catalyst, 8 to 12 mol% of secondary noble metal component with respect to primary noble metal component and 1 to 600 mol% with respect to primary noble metal component. Contains cerium.
粉末の形の担体は、担体として使用され、この粉末状担体は、物理的に活性化された炭素、化学的に活性化された炭素、カーボンブラック、酸化アルミニウムまたは酸化珪素、好ましくは物理的に活性化された炭素、化学的に活性化された炭素またはカーボンブラックであることができる。 A carrier in the form of a powder is used as the carrier, which is a physically activated carbon, chemically activated carbon, carbon black, aluminum oxide or silicon oxide, preferably physically. It can be activated carbon, chemically activated carbon or carbon black.
更に、本発明は、本発明による水素化触媒の製造法を提供し、この方法は、一次貴金属成分および二次貴金属成分ならびに非貴金属成分を溶解された形で含有する水溶液を、水中の粉末の形の担体材料の懸濁液に添加し、一次貴金属成分および二次貴金属成分ならびに非貴金属成分を塩基を用いて粉末の形の担体上に付着させ、場合によっては還元剤、例えばホルムアルデヒド、ヒドラジン、水素、テトラヒドロホウ酸ナトリウム、蟻酸または蟻酸ナトリウムを用いて還元を実施することによって特徴付けられている。 Furthermore, the present invention provides a method for producing a hydrogenation catalyst according to the present invention, which comprises an aqueous solution containing primary and secondary noble metal components and non-noble metal components in dissolved form as a powder in water. Added to the suspension of the carrier material in the form, and the primary and secondary noble metal components and the non-noble metal component are deposited on the carrier in powder form using a base, optionally reducing agents such as formaldehyde, hydrazine, Characterized by carrying out the reduction with hydrogen, sodium tetrahydroborate, formic acid or sodium formate.
還元は、０〜１００℃の温度で実施されることができる。 The reduction can be carried out at a temperature of 0-100 ° C.
担体材料、水、金属塩溶液および還元剤が添加される順序は、変動されてもよい。場合によっては、還元は、水素で無水触媒上で行なわれてもよい。還元剤の使用は、場合によるものであり、即ち本発明による触媒は、還元剤の添加なしに一次貴金属成分および二次貴金属成分ならびに非貴金属成分が担体上に付着された後に濾過によって反応混合物から分離されることができる。 The order in which the support material, water, metal salt solution and reducing agent are added may vary. In some cases, the reduction may be performed over anhydrous catalysts with hydrogen. The use of the reducing agent is optional, ie the catalyst according to the invention is removed from the reaction mixture by filtration after the primary and secondary noble metal components and non-noble metal components have been deposited on the support without the addition of a reducing agent. Can be separated.
本発明による触媒は、ニトロ芳香族化合物の水素化に使用されることができる。本発明による触媒は、殊にアニリンへのニトロベンゼンの水素化およびトルエンジアミンへのジニトロトルエンの水素化に使用されることができる。 The catalyst according to the invention can be used for the hydrogenation of nitroaromatic compounds. The catalyst according to the invention can be used in particular for the hydrogenation of nitrobenzene to aniline and of dinitrotoluene to toluenediamine.
ニトロ化合物の接触水素化は、液相中で連続的または非連続的に操作される方法として１〜１００バールの圧力および０℃〜２００℃の温度で本発明による触媒の存在で実施されることができる。 The catalytic hydrogenation of nitro compounds is carried out in the presence of the catalyst according to the invention at a pressure of 1 to 100 bar and a temperature of 0 ° C. to 200 ° C. as a process operated continuously or discontinuously in the liquid phase. Can do.
液相中でのニトロ化合物の接触水素化は、連続的または非連続的に操作される方法として１〜１００バールの圧力および０℃〜２００℃の温度で本発明による触媒の存在で実施されることができる。 Catalytic hydrogenation of nitro compounds in the liquid phase is carried out in the presence of the catalyst according to the invention at a pressure of 1 to 100 bar and a temperature of 0 ° C. to 200 ° C. as a process operated continuously or discontinuously. be able to.
本発明による触媒の存在でのニトロベンゼンまたはジニトロトルエンの接触水素化は、連続的または非連続的に操作される攪拌された反応器中で溶剤、例えばアニリンおよび水の存在で実施されることができる。また、溶剤は、ニトロベンゼンの水素化のためにアニリンと水との混合物であってもよいし、ジニトロトルエンの水素化のために水中でのジニトロトルエンの混合物であってもよい。 Catalytic hydrogenation of nitrobenzene or dinitrotoluene in the presence of a catalyst according to the invention can be carried out in the presence of solvents such as aniline and water in a stirred reactor operated continuously or discontinuously. . The solvent may be a mixture of aniline and water for hydrogenation of nitrobenzene, or a mixture of dinitrotoluene in water for hydrogenation of dinitrotoluene.
トルエンジアミンへのジニトロトルエンの水素化は、７０〜２００℃、好ましくは９０〜１５０℃の温度および１〜１００バール、好ましくは１０〜４０バールの圧力で実施されることができる。水素化を連続的に実施する場合には、変換されたジニトロトルエンの量は、常圧蒸留（topping up）によって代替されなければならず、生成物−水混合物は、反応器から除去されなければならない。 Hydrogenation of dinitrotoluene to toluenediamine can be carried out at a temperature of 70 to 200 ° C., preferably 90 to 150 ° C. and a pressure of 1 to 100 bar, preferably 10 to 40 bar. If the hydrogenation is carried out continuously, the amount of dinitrotoluene converted must be replaced by topping up and the product-water mixture must be removed from the reactor. Don't be.
本発明による触媒を使用する場合には、相乗効果が観察され、即ち二次貴金属成分の添加により、二次貴金属成分を含有していない相応する触媒と比較して触媒の活性は、十分に増加する。 When using the catalyst according to the invention, a synergistic effect is observed, ie the addition of the secondary noble metal component increases the activity of the catalyst sufficiently compared to the corresponding catalyst not containing the secondary noble metal component. To do.
これは、刊行物Pol. Chem. Stosow. 1981, 25(1), 53-68またはChin. Chem. Lett. 1996, 7(7), 663-664の記載の公知技術水準からは、Ｐｔの割合が増加した場合にＰｄの活性は減少することが開示されているので、予想することができなかった。 From the known state of the art described in the publication Pol. Chem. Stosow. 1981, 25 (1), 53-68 or Chin. Chem. Lett. 1996, 7 (7), 663-664, Since it has been disclosed that the activity of Pd decreases when the increase is increased, it could not be expected.
従って、Ｐｔを一次貴金属成分として使用した場合に二次貴金属成分としてのＰｄが同様に相乗効果を有することは、意外なことである。 Therefore, it is surprising that Pd as the secondary noble metal component similarly has a synergistic effect when Pt is used as the primary noble metal component.
ニトロ基の水素化において他の金属の組合せ物の活性が特に高いことについては、刊行物には何も引用されていない。むしろ、二次貴金属成分としてのＲｈまたはＲｕの使用は、ＲｈおよびＲｕが芳香環の水素化にとって著しく好適であったので、少ない選択性（即ち、望ましくない二次反応）を有するものと思われていたという公知の不利な効果を有することが予想されていた（例えば、P. N. Rylander, Catalytic Hydrogenation in Organic Syntheses, Academic Press, 1979, New York, 第175頁以降参照）。意外なことに、この事実は、観察されていない。 Nothing is cited in the publication about the particularly high activity of other metal combinations in the nitro group hydrogenation. Rather, the use of Rh or Ru as the secondary noble metal component appears to have low selectivity (ie, undesirable secondary reactions) since Rh and Ru were remarkably suitable for aromatic hydrogenation. It was expected to have a known disadvantageous effect (see, for example, PN Rylander, Catalytic Hydrogenation in Organic Syntheses, Academic Press, 1979, New York, p. 175 et seq.). Surprisingly, this fact has not been observed.
実施例
本発明による触媒および基準触媒が製造され、ニトロ芳香族化合物の水素化における前記触媒の触媒特性が比較される。
Examples A catalyst according to the invention and a reference catalyst are prepared and their catalytic properties in the hydrogenation of nitroaromatic compounds are compared.
参考例１：カーボンブラック上のＰｄ含有３金属原子性触媒（Pd-containing trimetallic catalyst）
一次貴金属成分としてのＰｄ、二次貴金属成分としてのＰｔおよび刊行物に記載の非貴金属成分を有するＰｄ−Ｐｔ−Ｆｅ／ＳＢ３金属原子性触媒（trimetallic catalyst）（Ｐｄ１．６％＋Ｐｔ０．２％＋Ｆｅ４．０％）の製造。Chevron社の製品Shawinigan Black（この触媒Shawinigan BlackをＳＢと略記した）をカーボンブラック担体として使用する。米国特許第３１２７３５６号明細書、実施例ＶＩＩに開示されたようなＰｄ−Ｐｔ−Ｆｅ／ＳＢ（Ｐｄ１．６％＋Ｐｔ０．２％＋Ｆｅ４．０％）触媒を製造する。
Reference Example 1: Pd-containing trimetallic catalyst on carbon black
Pd-Pt-Fe / SB3 trimetallic catalyst with Pd as primary noble metal component, Pt as secondary noble metal component and non-noble metal components as described in the publication (Pd 1.6% + Pt 0.2% + Fe 4 0.0%). Chevron product Shawinigan Black (this catalyst Shawinigan Black is abbreviated as SB) is used as a carbon black support. A Pd—Pt—Fe / SB (Pd 1.6% + Pt 0.2% + Fe 4.0%) catalyst as disclosed in US Pat. No. 3,127,356, Example VII is prepared.
実施例１：カーボンブラック上の３金属原子性触媒（trimetallic catalyst）
Shawinigan Black２２．０６ｇ（Chevron社の市販製品、この触媒Shawinigan BlackをＳＢと略記した）を脱イオン水２０００ｍｌ中に懸濁させ、この懸濁液を炭酸ナトリウム溶液を用いて１０のｐＨに設定する。テトラクロロパラジウム（ＩＩ）酸２ｇ（２０％）、ヘキサクロロ白金（ＩＶ）酸０．２ｇ（２５％）および脱イオン水２００ｍｌ中の塩化セリウム（ＩＩＩ）七水和物の溶液を、前記懸濁液に添加する。８０℃への加熱後、炭酸ナトリウム溶液を用いてｐＨを６．４に設定し、懸濁液を攪拌し、濾過する。無水触媒１００ｇは、Ｐｄ１．６％、Ｐｔ０．２％およびＣｅ１０．５％を含有する。この触媒は、Ｐｄ−Ｐｔ−Ｃｅ／ＳＢ（１．６、０．２、１０．５）と略記される。
Example 1: Trimetallic catalyst on carbon black
22.06 g of Shawinigan Black (a commercial product of Chevron, this catalyst Shawinigan Black is abbreviated as SB) is suspended in 2000 ml of deionized water and the suspension is set to a pH of 10 using sodium carbonate solution. A solution of cerium (III) chloride heptahydrate in 2 g (20%) tetrachloropalladium (II) acid, 0.2 g (25%) hexachloroplatinic (IV) acid and 200 ml deionized water is added to the suspension. Add to. After heating to 80 ° C., the pH is set to 6.4 using sodium carbonate solution, the suspension is stirred and filtered. 100 g of anhydrous catalyst contains 1.6% Pd, 0.2% Pt and 10.5% Ce. This catalyst is abbreviated as Pd—Pt—Ce / SB (1.6, 0.2, 10.5).
参考例２：カーボンブラック上の２金属原子性触媒（Bimetallic catalyst）
触媒Ｐｄ−Ｐｔ／ＳＢ（Ｐｄ１．６％、Ｐｔ０．２％）を実施例１の記載と同様に製造するが、しかし、実施例１に記載の量の代わりに、Shawinigan Black２４．６９ｇを使用し、セリウム塩は使用しない。無水触媒１００ｇは、Ｐｄ１．６％およびＰｔ０．２％を含有する。
Reference Example 2: Bimetallic catalyst on carbon black
The catalyst Pd-Pt / SB (Pd 1.6%, Pt 0.2%) is prepared as described in Example 1, but using 24.69 g of Shawinigan Black instead of the amount described in Example 1. Do not use cerium salts. 100 g of anhydrous catalyst contains 1.6% Pd and 0.2% Pt.
参考例３：活性炭上のＰｄ含有３金属原子性触媒
活性炭９８．２１ｇを脱イオン水５００ｍｌ中に懸濁させ、この懸濁液を炭酸ナトリウム溶液を用いて１０のｐＨに設定する。テトラクロロパラジウム（ＩＩ）酸８ｇ（２０％）、ヘキサクロロ白金（ＩＶ）酸０．８ｇ（２５％）および脱イオン水２００ｍｌ中の硝酸鉄（ＩＩＩ）九水和物の溶液を、前記懸濁液に添加する。８０℃への加熱後、炭酸ナトリウム溶液を用いてｐＨを６．４に設定し、懸濁液を攪拌し、ホルムアルデヒドで還元し、濾過する。無水触媒１００ｇは、Ｐｄ１．６％、Ｐｔ０．２％およびＦｅ４．２％を含有する。この触媒は、Ｐｄ−Ｐｔ−Ｆｅ／ＡＣ（１．６、０．２、４．２）と略記される。
Reference Example 3: Pd-containing trimetallic atomic catalyst on activated carbon 98.21 g of activated carbon is suspended in 500 ml of deionized water, and this suspension is set to a pH of 10 using sodium carbonate solution. A solution of iron (III) nitrate nonahydrate in 8 g (20%) tetrachloropalladium (II) acid, 0.8 g (25%) hexachloroplatinic (IV) acid and 200 ml deionized water is added to the suspension. Add to. After heating to 80 ° C., the pH is set to 6.4 with sodium carbonate solution, the suspension is stirred, reduced with formaldehyde and filtered. 100 g of anhydrous catalyst contains 1.6% Pd, 0.2% Pt and 4.2% Fe. This catalyst is abbreviated as Pd—Pt—Fe / AC (1.6, 0.2, 4.2).
実施例２：活性炭上のＰｄ含有３金属原子性触媒
活性炭を脱イオン水５００ｍｌ中に懸濁させ、この懸濁液を炭酸ナトリウム溶液を用いて１０のｐＨに設定する。テトラクロロパラジウム（ＩＩ）酸８ｇ（２０％）、二次貴金属成分および脱イオン水２００ｍｌ中の非貴金属成分の塩の溶液を、前記懸濁液に添加する。８０℃への加熱後、炭酸ナトリウム溶液を用いてｐＨを６．４に設定し、懸濁液を攪拌し、ホルムアルデヒドで還元し、濾過する。量は、第１表中に記載されている。
Example 2: Pd-containing trimetallic atomic catalyst on activated carbon Activated carbon is suspended in 500 ml of deionized water and this suspension is set to a pH of 10 using sodium carbonate solution. A solution of a salt of the non-noble metal component in 8 g (20%) tetrachloropalladium (II) acid, the secondary noble metal component and 200 ml of deionized water is added to the suspension. After heating to 80 ° C., the pH is set to 6.4 using sodium carbonate solution, the suspension is stirred, reduced with formaldehyde and filtered. The amounts are listed in Table 1.
実施例３：活性炭上のＰｔ含有３金属原子性触媒
活性炭を脱イオン水５００ｍｌ中に懸濁させ、この懸濁液を炭酸ナトリウム溶液を用いて１０のｐＨに設定する。ヘキサクロロ白金（ＩＶ）酸１１．６ｇ（２５％）、それぞれ脱イオン水２００ｍｌ中溶解された二次貴金属成分および非貴金属成分の塩の溶液を、前記懸濁液に添加する。８０℃への加熱後、炭酸ナトリウム溶液を用いてｐＨを６．４に設定し、懸濁液を攪拌し、ホルムアルデヒドで還元し、濾過する。量は、第２表中に記載されている。
Example 3: Pt-containing trimetallic atomic catalyst on activated carbon Activated carbon is suspended in 500 ml of deionized water and this suspension is set to a pH of 10 using sodium carbonate solution. A solution of 11.6 g (25%) of hexachloroplatinic acid (25%), each of a salt of the secondary noble metal component and non-noble metal component dissolved in 200 ml of deionized water, is added to the suspension. After heating to 80 ° C., the pH is set to 6.4 using sodium carbonate solution, the suspension is stirred, reduced with formaldehyde and filtered. The amounts are listed in Table 2.
実施例に記載の触媒をトルエンジアミンへのジニトロトルエンの非連続的水素化に使用し、触媒の活性および選択性を測定する。 The catalyst described in the examples is used for the discontinuous hydrogenation of dinitrotoluene to toluenediamine to determine the activity and selectivity of the catalyst.
反応を０．５ ｌのハステロイ（Hastelloy）オートクレーブ中で実施する。最初に、２，４−ジニトロトルエン４０ｇ、２，４−トルエンジアミン１０１ｇ、水５９ｇおよび触媒１．２ｇ（固体に対して）をオートクレーブ中に供給する。次に、オートクレーブを閉鎖した後、ガス空間を最初に窒素でフラッシし、次に水素でフラッシし、最後に１０バールの水素圧力を確立させる。 The reaction is carried out in a 0.5 l Hastelloy autoclave. First, 40 g of 2,4-dinitrotoluene, 101 g of 2,4-toluenediamine, 59 g of water and 1.2 g of catalyst (based on the solid) are fed into the autoclave. Then, after closing the autoclave, the gas space is first flushed with nitrogen, then flushed with hydrogen and finally a hydrogen pressure of 10 bar is established.
１２０℃への加熱後、攪拌機構のスイッチを入れることによって、反応を開始させる。反応の終結点は、水素吸収における急速な還元によって正確に測定することができる。 After heating to 120 ° C., the reaction is started by switching on the stirring mechanism. The end point of the reaction can be accurately measured by rapid reduction in hydrogen absorption.
水素吸収量を反応の間に記録する。反応が終結し、反応混合物が冷却されたら直ちに、この反応混合物をメタノール中に入れ、濾過し、ガスクロマトグラフィーによって分析する。これは、ＴＤＡの収率、ＤＮＴの変換率および測定することができる副生成物の量の分析を可能にする。 The amount of hydrogen absorbed is recorded during the reaction. As soon as the reaction is complete and the reaction mixture has cooled, the reaction mixture is taken up in methanol, filtered and analyzed by gas chromatography. This allows analysis of TDA yield, DNT conversion and the amount of by-products that can be measured.
次のものは、副生成物として取得されうる：トルイジン、ジアミノベンゼン（低沸点物と呼ばれる）およびタール。タールの用語は、一次生成物ＴＤＡよりも長い滞留時間を有する全ての化合物を表わす。 The following can be obtained as by-products: toluidine, diaminobenzene (called low boilers) and tar. The term tar represents all compounds with a residence time longer than the primary product TDA.
活性は、触媒質量に対する反応時間の間の水素の吸収量から計算され、Ｈ2 ｍｌ／（ｍｉｎ 触媒ｇ）として記載される。結果は、第３表、第４表および第５表に記載されている。 The activity is calculated from the amount of hydrogen absorbed during the reaction time relative to the catalyst mass and is described as H2 ml / (min catalyst g). The results are listed in Tables 3, 4 and 5.
Claims (10)
無水水素化触媒１００ｇあたり、一次貴金属成分１０〜５０ｍｍｏｌ、一次貴金属成分に対して１〜６０モル％の二次貴金属成分および一次貴金属成分に対して１〜７００モル％の非貴金属成分を含有する水素化触媒。A supported hydrogenation catalyst in the form of a powder for the hydrogenation of nitroaromatic compounds , comprising a mixture of a primary noble metal component, a secondary noble metal component and one or more non-noble metal components as a catalytically active component, wherein Pt is the primary noble metal as a component, Pd as a secondary precious metal component, Ru or Rh and Fe and / or Ce and Ru are used together as non-noble metal component, or as Pd primary noble metal component, Ru or Rh as a secondary precious metal component and non-noble metal component as Fe and / or Ce and Ru are used together, or as Pd primary noble metal component, characterized in that that are used together with Ce as Pt and non-noble metal component as a secondary precious metal component A supported hydrogenation catalyst in the form of a powder ,
Hydrogen containing 10-50 mmol of primary noble metal component, 1-60 mol% of secondary noble metal component with respect to primary noble metal component and 1-700 mol% of non-noble metal component with respect to primary noble metal component per 100 g of anhydrous hydrogenation catalyst Catalyst .
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| US33315301P | 2001-11-27 | 2001-11-27 | |
| DE10216108A DE10216108A1 (en) | 2001-11-08 | 2002-04-12 | Supported hydrogenating catalyst for hydrogenation of nitroaromatics to aminoaromatics, e.g. nitrobenzene to aniline, contains mixture of secondary precious metal and non-precious metal(s) |
| PCT/EP2002/009874 WO2003039743A1 (en) | 2001-11-08 | 2002-09-04 | Supported catalyst for hydrogenation of nitroaromatics |
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| DE10349095A1 (en) | 2003-10-17 | 2005-05-19 | Basf Ag | Process for the preparation of amines |
| CN1898229B (en) * | 2003-12-19 | 2012-05-30 | 宇部兴产株式会社 | Processes for producing tetrahydropyran-4-one and pyran-4-one |
| DE102005041532A1 (en) | 2005-08-31 | 2007-03-01 | Basf Ag | Preparation of aromatic amines, preferably tolylenediamine comprises catalytic hydrogenation of nitro compounds, preferably dinitrotoluene in presence of hydrogenation catalyst containing platinum, nickel and substrate with metal |
| CN101429453B (en) * | 2008-03-19 | 2010-05-12 | 中国石油天然气股份有限公司 | Pyrolysis gasoline fraction one-stage selective hydrogenation method |
| CN102000568B (en) * | 2010-11-11 | 2012-08-15 | 厦门大学 | Reduction method for nitroaromatic hydrocarbon |
| CN102952022B (en) * | 2012-09-13 | 2014-04-09 | 赛鼎工程有限公司 | Method for continuously preparing tolylenediamine by utilizing dinitrotoluene, catalyst used in method and preparation method of catalyst |
| CN105080567B (en) * | 2014-04-22 | 2017-09-29 | 中国科学院长春应用化学研究所 | The preparation method of catalyst and aromatic amino compound |
| CN105435808A (en) * | 2014-08-20 | 2016-03-30 | 中国石油化工股份有限公司 | Carbon black noble metal catalyst preparation method |
| CN104971738B (en) * | 2015-07-07 | 2017-06-27 | 淮阴工学院 | The preparation method of magnetic Nano palladium catalyst |
| WO2017163680A1 (en) * | 2016-03-23 | 2017-09-28 | エヌ・イー ケムキャット株式会社 | Reaction composition and reaction system using this |
| CN109225258A (en) * | 2018-10-19 | 2019-01-18 | 郴州高鑫铂业有限公司 | A kind of Pt-Fe/C catalyst and its preparation method and application |
| CN111013561A (en) * | 2019-12-31 | 2020-04-17 | 贵研工业催化剂（云南）有限公司 | Preparation method of catalyst for liquid-phase hydrogenation of nitrobenzene to prepare aniline |
| CN114534733B (en) * | 2020-11-24 | 2024-04-12 | 万华化学集团股份有限公司 | Preparation method of aromatic amine catalyst prepared by nitro compound hydrogenation |
| CN113145112B (en) * | 2021-04-30 | 2023-03-24 | 福州大学 | Preparation method of Pd-Pt/C catalyst for selective hydrogenation of dinitrotoluene |
| CN114289034B (en) * | 2021-12-27 | 2024-02-02 | 万华化学集团股份有限公司 | Noble metal catalyst, preparation method and application thereof in preparation of toluenediamine by catalyzing hydrogenation of dinitrotoluene |
| CN114471544A (en) * | 2022-02-25 | 2022-05-13 | 天脊煤化工集团股份有限公司 | Catalyst and application thereof in aniline preparation |
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| JPS58107437A (en) * | 1981-12-16 | 1983-06-27 | インスチツ−ト・メタルルギ−・イメ−ニ・ア−・ア−・バイコワ・アカデミ−・ナウク・エスエスエスエル | Alloy based on palladium |
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