EP1441850A1 - Supported catalyst for hydrogenation of nitroaromatics - Google Patents
Supported catalyst for hydrogenation of nitroaromaticsInfo
- Publication number
- EP1441850A1 EP1441850A1 EP02779300A EP02779300A EP1441850A1 EP 1441850 A1 EP1441850 A1 EP 1441850A1 EP 02779300 A EP02779300 A EP 02779300A EP 02779300 A EP02779300 A EP 02779300A EP 1441850 A1 EP1441850 A1 EP 1441850A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- precious metal
- metal component
- primary
- hydrogenation
- catalyst
- 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.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 20
- 239000010970 precious metal Substances 0.000 claims abstract description 90
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 29
- 239000000725 suspension Substances 0.000 claims description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 150000004998 toluenediamines Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910052703 rhodium Inorganic materials 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- VMMLSJNPNVTYMN-UHFFFAOYSA-N dinitromethylbenzene Chemical class [O-][N+](=O)C([N+]([O-])=O)C1=CC=CC=C1 VMMLSJNPNVTYMN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 150000002828 nitro derivatives Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 229910052697 platinum Inorganic materials 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 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
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 5
- 239000011269 tar Substances 0.000 description 5
- 229910019891 RuCl3 Inorganic materials 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 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
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- 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
- 229910003603 H2PdCl4 Inorganic materials 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910021065 Pd—Fe Inorganic materials 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
- 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
- 239000011541 reaction mixture Substances 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 class 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
- 238000005620 Bechamp reaction Methods 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 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 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 230000014759 maintenance of location Effects 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
- 230000002459 sustained effect Effects 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Definitions
- the invention relates to a supported hydrogenating catalyst in powder form, a process for its production and its use in the catalytic hydrogenation of nitroaromatics.
- TDA toluenediamines
- a number of catalysts are known for the catalytic hydrogenation of nitroaromatics, in particular of dinitrotoluene, in the suspension phase.
- US 2,823,235 discloses palladium, platinum and palladium- platinum catalysts on black, which are doped with iron. Very similar catalysts, which contain blacks as supports, are disclosed in US 3,127,356.
- US 4,256,671 discloses, in addition to Pd and Pt, also Ni, Ru and Rh as a precious metal component for catalysts used in the catalytic hydrogenation of dinitrotoluenes to toluenediamines .
- US 6,096,924 discloses, as a catalytically active component, Rh, Ru, Ir, Pt, Pd, Ni and Co. These metals are applied to powder-form supports. V is used as a doping metal.
- the former printed publication shows that platinum may be present only in a smaller molar quantity than palladium.
- the optimum is ca. 20 mol% Pt in relation to Pd. If a larger quantity of Pt is used, lower activity is determined.
- the object of the present invention is to improve the selectivity and activity of the catalytic hydrogenation of nitroaromatics to aminoaromatics, i.e. to reduce the formation of by-products and to increase the yield of the desired product, through the selection and production of a hydrogenating catalyst.
- the invention provides a supported hydrogenating catalyst in powder form, which contains, as catalytically active components, a mixture of a primary precious metal component, a secondary precious metal domponent and one or more non-precious metal components, wherein either Pt is used as the primary precious metal component with Pd, Ru, Rh as the secondary precious metal component and V, Fe, Mn, Ce and/or Cr as the non-precious metal component, or Pd is used as the primary precious metal component with Ru, Rh as the secondary precious metal component and V, Fe, Mn, Ce and/or Cr as the non-precious metal component or Pd is used as the primary precious metal component with Pt as the secondary precious metal component and Ce and/or Cr as the non-precious metal component.
- the hydrogenating catalyst according to the ' invention can contain, per 100 g dry hydrogenating catalyst, 10 to 50 mmol of the primary precious metal component.
- the proportion of the secondary precious metal component can be 1 to 60 mol% in relation to the primary precious metal component, preferably 8 to 12 mol% in relation to the primary precious metal component and that of the non- precious metal component 1-700 mol%, preferably 100-600 mol% in relation to the primary precious metal component.
- doping metals for the combination Pd as primary precious metal component and Ru Rh as secondary precious metal component, V, Fe, Mn, Ce and/or Cr are particularly suitable as the non-precious metal component.
- the secondary precious metal component is responsible for the high activity of the catalyst, the non- precious metal component is decisive for selectivity.
- the hydrogenating catalyst according to the invention can contain, per 100 g dry hydrogenating catalyst, 15 to 20 mmol of the primary precious metal component, 8 to 12 mol%, in relation to the primary precious metal component, of the secondary precious metal component, and 1 to 600 mol%, in relation to the primary precious metal component, of cerium.
- Supports in powder form are used as supports, and these powder supports may be physically activated carbons, chemically activated carbons, blacks, aluminium oxides or silicon oxides, preferably physically activated carbons, chemically activated carbons or blacks.
- the invention further provides a process for the production of the hydrogenating catalyst according to the invention, which is characterised in that an aqueous solution containing the primary and secondary precious metal • components and the non-precious metal component in dissolved form is added to a suspension of a powder-form support material in water, the primary and secondary precious metal components and the non-precious metal component are deposited on the powder-form support using a base and reduction is optionally carried out using a reducing agent such as for example formaldehyde, hydrazine, hydrogen, sodium tetrahydroborate, formic acid or sodium formate.
- a reducing agent such as for example formaldehyde, hydrazine, hydrogen, sodium tetrahydroborate, formic acid or sodium formate.
- Reduction can be carried out at a temperature of 0 to 100°C.
- the order in which the support material, water, metal salt solutions and reducing agents are added can also be varied.
- reduction can take place with hydrogen on the dried catalyst.
- the use of a reducing agent is optional, i.e. the catalyst according to the invention can be separated out from the reaction mixture by filtration, without the addition of a reducing agent, after the primary and secondary precious metal and non-precious metal components have been deposited on the support.
- the catalyst according to the invention can be used for the hydrogenation of nitroaromatics.
- the catalyst according to the invention can be used in particular for the hydrogenation of nitrobenzene to aniline and for the hydrogenation of dinitrot ⁇ luenes to toluenediamines .
- the catalytic hydrogenation of the nitro-compound can be carried out in the liquid phase as a continuously or discontinuously operated process at pressures of 1 to 100 bar and temperatures of 0 to 250 °C in the presence of the catalyst according to the invention.
- the catalytic hydrogenation of the nitro-compound in the liquid phase can be carried out as a continuously or discontinuously operated process at pressures of 1 to 100 bar and temperatures of 0°C to 200°C in the presence of the catalyst according to the invention.
- the catalytic hydrogenation of nitrobenzene or dinitrotoluenes in the presence of the catalyst according to the invention can be carried out in a continuously or discontinuously operated agitated reactor or in a continuously operated circulating reactor in the presence of a solvent, such as for example methanol or toluene.
- the solvent can also be a mixture of aniline and water, for the hydrogenation of nitrobenzene, or a mixture of dinitrotoluenes in water, for the hydrogenation of dinitrotoluenes .
- the hydrogenation of dinitrotoluenes to toluenediamines can be carried out at temperatures of 70 to 200 °C, preferably 90 to 150°C, and pressures of 1 to 100 bar, preferably 10 to 40 bar. If hydrogenation is carried out continuously, the quantity of converted dinitrotoluenes must be replaced by topping up and the product-water mixture must be removed from the reactor.
- Rh or Ru as a secondary precious metal component would have been expected to have a negative effect as it is known (see for example P. N. Rylander, Catalytic Hydrogenation in Organic Syntheses, Academic Press, 1979, New York, page 175 ff) , that Rh and Ru are highly suitable for hydrogenating aromatic rings and would thus be likely to have poor selectivity (i.e. undesirable secondary reactions) . Surprisingly, this is not observed. Examples
- Catalysts according to the invention and reference catalysts are produced and their catalytic properties in the hydrogenation of nitroaromatics are compared.
- Pd-Pt-Fe/SB trimetallic catalyst (1.6% Pd + 0.2% Pt + 4.0% Fe) with Pd as the primary precious metal component, Pt as the secondary precious metal component and a non-precious metal component according to the prior art.
- the Pd-Pt-Fe/SB (1.6% Pd, 0.2% Pt, 4.0% Fe) catalyst is produced as disclosed in US 3,127,356, Example VII.
- a solution of 2 g tetrachloropalladic (II) acid (20%), 0.2 g hexachloroplatinic (IV) acid (25%) and 6.98 g cerium (III) chloride heptahydrate in 200 ml deionised water is added to this suspension. After heating to 80°C the pH is set at 6.4 using sodium carbonate solution, and the suspension is stirred and filtered.
- 100 g dry catalyst contains 1.6% Pd, 0.2% Pt and 10.5% Ce .
- the catalyst is abbreviated to Pd-Pt-Ce/SB (1.6, 0.2, 10.5).
- the catalyst Pd-Pt/SB (1.6% Pd, 0.2% Pt) is produced as described in example 1, but instead of the quantities given there, 24.69 g Shawinigan Black is used and no cerium salt. 100 g dry catalyst contains 1.6% Pd and 0.2% Pt .
- Activated carbon is suspended in 500 ml de-ionised water and the suspension is set at a pH of 10 using sodium carbonate solution. 8 g tetrachloropalladic (II) acid (20%), a solution of the secondary precious metal component and a salt of the non-precious metal component, dissolved in 200 ml de-ionised water are added to this suspension. After heating to 80 °C the pH is set at 6.4 using sodium carbonate solution and the suspension is stirred, reduced with formaldehyde and filtered. The quantities are given in Table 1.
- Activated carbon is suspended in 500 ml de-ionised water and the suspension is set at a pH of 10 using sodium carbonate solution. 11.6 g hexachloroplatinic (IV) acid (25%) , a solution of the secondary precious metal component and a salt of the non-precious metal component, each dissolved in 200 ml de-ionised water, are added to this suspension. After heating to 80°C, the pH is set at 6.4 with sodium carbonate solution, and the suspension is stirred, reduced with formaldehyde and filtered. The quantities are given in Table 2.
- the catalysts according to the examples are used in the discontinuous hydrogenation of dinitrotoluene to toluene- diamine and the activity and selectivity of the catalysts are determined.
- the reaction is carried out in a 0.5 1 Hastelloy autoclave.
- 40 g 2, 4-Dinitrotoluene, 101 g 2, 4-toluenediamine, 59 g water and 1.2 g catalyst (in relation to the solids) are fed into the autoclave.
- the gas space is flushed first with nitrogen and then with hydrogen and finally a hydrogen pressure of 10 bar is established.
- the reaction After heating to 120°C, the reaction is started by switching on the stirring mechanism.
- the end point of the reaction can be determined precisely by the rapid reduction in hydrogen absorption.
- toluidines diaminobenzenes (called low-boilers)
- tars tars describes all compounds which have a longer retention time than the primary product TDA.
Abstract
Supported, hydrogenating catalyst in powder form containing, as a catalytically active component, a primary precious metal component, a secondary precious metal component and one or more non-precious metal components. It is used for the hydrogenation of nitroaromatics, in particular nitrobenzene and DNT.
Description
SUPPORTED CATALYST FOR HYDROGENATION OF NITROAROMATICS
The invention relates to a supported hydrogenating catalyst in powder form, a process for its production and its use in the catalytic hydrogenation of nitroaromatics.
The hydrogenation of aromatic nitro-compounds to amines is one of the major ways of producing amines in industrial chemistry. Today, aromatic amines are central components in the prodution of fine, speciality and even bulk chemicals. Examples in the field of bulk chemicals, in particular, are aniline and toluenediamines (TDA) . The catalytic hydrogenation of nitrobenzene to aniline replaced the old Bechamps reduction method, making an important contribution to sustained development. TDA can be regarded as an intermediate for the production of polyurethane foams, being converted in a phosgenation reaction to toluene diisocyanate (TDI) , which is processed together with polyalcohols to produce polyurethane foams.
Various processes and catalysts are known for the production of aromatic amines by hydrogenation of the corresponding aromatic nitro-compounds.
In addition to the hydrogenation of nitrobenzene to aniline in the gas phase, there are a number of other processes, all of which work in the liquid phase. In addition to supported non-precious metal catalysts and Raney-type catalysts, supported catalysts containing precious metals are also used.
A number of catalysts are known for the catalytic hydrogenation of nitroaromatics, in particular of dinitrotoluene, in the suspension phase.
US 2,823,235 discloses palladium, platinum and palladium- platinum catalysts on black, which are doped with iron.
Very similar catalysts, which contain blacks as supports, are disclosed in US 3,127,356.
US 4,256,671 discloses, in addition to Pd and Pt, also Ni, Ru and Rh as a precious metal component for catalysts used in the catalytic hydrogenation of dinitrotoluenes to toluenediamines .
US 6,096,924 discloses, as a catalytically active component, Rh, Ru, Ir, Pt, Pd, Ni and Co. These metals are applied to powder-form supports. V is used as a doping metal.
DE 199 11 865 Al discloses a similar system with Ir as the precious metal and V as the doping metal.
Whilst the stated printed publications disclose Pd-, Ir- or Pd-Pt-catalysts, US 4212824 discloses a Pt-catalyst on black, which is doped with Fe. Fe and V are the non- precious metals used by far the most frequently for doping.
It is also known that the addition of a few mol-percent of platinum (for example 15 mol%) to supported palladium catalysts produces a positive synergetic effect on activity. This is disclosed in Pol . Chem . Stosow. 1981,
25 (1 ) , 53-68 or in Chin . Chem . Lett . 1996, 7(7 , 663-664.
The former printed publication shows that platinum may be present only in a smaller molar quantity than palladium. The optimum is ca. 20 mol% Pt in relation to Pd. If a larger quantity of Pt is used, lower activity is determined.
The object of the present invention is to improve the selectivity and activity of the catalytic hydrogenation of nitroaromatics to aminoaromatics, i.e. to reduce the formation of by-products and to increase the yield of the desired product, through the selection and production of a hydrogenating catalyst.
The invention provides a supported hydrogenating catalyst in powder form, which contains, as catalytically active components, a mixture of a primary precious metal component, a secondary precious metal domponent and one or more non-precious metal components, wherein either Pt is used as the primary precious metal component with Pd, Ru, Rh as the secondary precious metal component and V, Fe, Mn, Ce and/or Cr as the non-precious metal component, or Pd is used as the primary precious metal component with Ru, Rh as the secondary precious metal component and V, Fe, Mn, Ce and/or Cr as the non-precious metal component or Pd is used as the primary precious metal component with Pt as the secondary precious metal component and Ce and/or Cr as the non-precious metal component.
The hydrogenating catalyst according to the' invention can contain, per 100 g dry hydrogenating catalyst, 10 to 50 mmol of the primary precious metal component. The proportion of the secondary precious metal component can be 1 to 60 mol% in relation to the primary precious metal component, preferably 8 to 12 mol% in relation to the primary precious metal component and that of the non- precious metal component 1-700 mol%, preferably 100-600 mol% in relation to the primary precious metal component.
The formation of by-products is influenced only slightly by the ratio of primary to secondary precious metal components which, however has a strong influence on the activity of the catalyst.
As doping metals for the combination Pt as primary precious metal component and Pd, Ru, Rh as secondary precious metal component, V, Fe, Mn, Ce and/or Cr are particularly suitable as the non-precious metal component.
As doping metals for the combination Pd as primary precious metal component and Ru, Rh as secondary precious metal component, V, Fe, Mn, Ce and/or Cr are particularly suitable as the non-precious metal component.
As a doping metal for the combination Pd as primary precious metal component and Pt as secondary precious metal component, Ce and/or Cr are particularly suitable as the non-precious metal component.
Whilst the secondary precious metal component is responsible for the high activity of the catalyst, the non- precious metal component is decisive for selectivity.
The hydrogenating catalyst according to the invention can contain, per 100 g dry hydrogenating catalyst, 15 to 20 mmol of the primary precious metal component, 8 to 12 mol%, in relation to the primary precious metal component, of the secondary precious metal component, and 1 to 600 mol%, in relation to the primary precious metal component, of cerium.
Supports in powder form are used as supports, and these powder supports may be physically activated carbons, chemically activated carbons, blacks, aluminium oxides or silicon oxides, preferably physically activated carbons, chemically activated carbons or blacks.
The invention further provides a process for the production of the hydrogenating catalyst according to the invention, which is characterised in that an aqueous solution containing the primary and secondary precious metal • components and the non-precious metal component in dissolved form is added to a suspension of a powder-form support material in water, the primary and secondary precious metal components and the non-precious metal component are deposited on the powder-form support using a base and reduction is optionally carried out using a reducing agent such as for example formaldehyde, hydrazine, hydrogen, sodium tetrahydroborate, formic acid or sodium formate.
Reduction can be carried out at a temperature of 0 to 100°C.
The order in which the support material, water, metal salt solutions and reducing agents are added can also be varied. Optionally, reduction can take place with hydrogen on the dried catalyst. The use of a reducing agent is optional, i.e. the catalyst according to the invention can be separated out from the reaction mixture by filtration, without the addition of a reducing agent, after the primary and secondary precious metal and non-precious metal components have been deposited on the support.
The catalyst according to the invention can be used for the hydrogenation of nitroaromatics. The catalyst according to the invention can be used in particular for the hydrogenation of nitrobenzene to aniline and for the hydrogenation of dinitrotσluenes to toluenediamines .
The catalytic hydrogenation of the nitro-compound can be carried out in the liquid phase as a continuously or discontinuously operated process at pressures of 1 to 100 bar and temperatures of 0 to 250 °C in the presence of the catalyst according to the invention.
The catalytic hydrogenation of the nitro-compound in the liquid phase can be carried out as a continuously or discontinuously operated process at pressures of 1 to 100 bar and temperatures of 0°C to 200°C in the presence of the catalyst according to the invention.
The catalytic hydrogenation of nitrobenzene or dinitrotoluenes in the presence of the catalyst according to the invention can be carried out in a continuously or discontinuously operated agitated reactor or in a continuously operated circulating reactor in the presence of a solvent, such as for example methanol or toluene. The solvent can also be a mixture of aniline and water, for the hydrogenation of nitrobenzene, or a mixture of dinitrotoluenes in water, for the hydrogenation of dinitrotoluenes .
The hydrogenation of dinitrotoluenes to toluenediamines can be carried out at temperatures of 70 to 200 °C, preferably 90 to 150°C, and pressures of 1 to 100 bar, preferably 10 to 40 bar. If hydrogenation is carried out continuously, the quantity of converted dinitrotoluenes must be replaced by topping up and the product-water mixture must be removed from the reactor.
When using the catalyst according to the invention, a synergetic effect is observed i.e. the addition of the secondary precious metal component increases the activity of the catalyst significantly in comparison with the corresponding catalyst containing no second precious metal.
This could not be expected from the prior art according to the printed publications Pol . Chem . Stosow. 1981, 25 (1 ) , 53-68 or Chin . Chem . Lett . 1996, 7(7;, 663-664, as they disclose that the activity of the Pd falls if the proportion of Pt is increased.
Consequently, it is surprising that Pd as a secondary precious metal component has a similar synergetic effect when Pt is used as the primary precious metal component.
There is no reference at all in the literature to particularly high activity of the other metal combinations in the hydrogenation of nitro groups. On the contrary, the use of Rh or Ru as a secondary precious metal component would have been expected to have a negative effect as it is known (see for example P. N. Rylander, Catalytic Hydrogenation in Organic Syntheses, Academic Press, 1979, New York, page 175 ff) , that Rh and Ru are highly suitable for hydrogenating aromatic rings and would thus be likely to have poor selectivity (i.e. undesirable secondary reactions) . Surprisingly, this is not observed.
Examples
Catalysts according to the invention and reference catalysts are produced and their catalytic properties in the hydrogenation of nitroaromatics are compared.
Reference example 1: Pd-containing trimetallic catalyst on black
Production of a Pd-Pt-Fe/SB trimetallic catalyst (1.6% Pd + 0.2% Pt + 4.0% Fe) with Pd as the primary precious metal component, Pt as the secondary precious metal component and a non-precious metal component according to the prior art. The product Shawinigan Black from Chevron (abbreviated in the catalyst to SB = Shawinigan Black) is used as the black support. The Pd-Pt-Fe/SB (1.6% Pd, 0.2% Pt, 4.0% Fe) catalyst is produced as disclosed in US 3,127,356, Example VII.
Example 1 : Trimetallic catalyst on black
22.06 g Shawinigan Black (commercial product of Chevron, abbreviated in the catalyst to SB = Shawinigan Black) are suspended in 2000 ml de-ionised water and the suspension is set at a pH of 10 using sodium carbonate solution. A solution of 2 g tetrachloropalladic (II) acid (20%), 0.2 g hexachloroplatinic (IV) acid (25%) and 6.98 g cerium (III) chloride heptahydrate in 200 ml deionised water is added to this suspension. After heating to 80°C the pH is set at 6.4 using sodium carbonate solution, and the suspension is stirred and filtered. 100 g dry catalyst contains 1.6% Pd, 0.2% Pt and 10.5% Ce . The catalyst is abbreviated to Pd-Pt-Ce/SB (1.6, 0.2, 10.5).
Reference example 2: Bimetallic catalyst on black
The catalyst Pd-Pt/SB (1.6% Pd, 0.2% Pt) is produced as described in example 1, but instead of the quantities given there, 24.69 g Shawinigan Black is used and no cerium salt. 100 g dry catalyst contains 1.6% Pd and 0.2% Pt .
Reference example 3: Pd-containing trimetallic catalyst on activated carbon
98.21 g activated carbon are suspended in 500 ml de-ionised water and the suspension is set at a pH of 10 using sodium carbonate solution. 8 g tetrachloropalladic (II ) acid (20%), 0.8 g hexachloroplatinic(IV) acid (25%) and 30.39 g iron (III) nitrate-nonahydrate, dissolved in 200 ml deionised water are added to this suspension. After heating to 80°C, the pH is set at 6.4 using sodium carbonate solution and the suspension is stirred, reduced with formaldehyde and filtered. 100 g dry catalyst contains 1.6% Pd, 0.2% Pt and 4.2% Fe. The catalyst is abbreviated to Pd- Pt-Fe/AC (1.6, 0.2, 4.2).
Example 2 : Pd-containing trimetallic catalysts on activated carbon
Activated carbon is suspended in 500 ml de-ionised water and the suspension is set at a pH of 10 using sodium carbonate solution. 8 g tetrachloropalladic (II) acid (20%), a solution of the secondary precious metal component and a salt of the non-precious metal component, dissolved in 200 ml de-ionised water are added to this suspension. After heating to 80 °C the pH is set at 6.4 using sodium carbonate solution and the suspension is stirred, reduced with formaldehyde and filtered. The quantities are given in Table 1.
Example 3 : Pt-containing trimetallic catalysts on activated carbon
Activated carbon is suspended in 500 ml de-ionised water and the suspension is set at a pH of 10 using sodium carbonate solution. 11.6 g hexachloroplatinic (IV) acid (25%) , a solution of the secondary precious metal component and a salt of the non-precious metal component, each dissolved in 200 ml de-ionised water, are added to this suspension. After heating to 80°C, the pH is set at 6.4 with sodium carbonate solution, and the suspension is stirred, reduced with formaldehyde and filtered. The quantities are given in Table 2.
Table 1. Data for Example 2
Catalyst Composition Quantity Solution of secondary Salt of non-precious metal of precious metal component component activated carbon
Pd-Ru-Fe/AC 1.6, 0.1, 4.2 98.31 g RuCl3 (20%) 0.49 g Fe(N03)3(H20)9 30.39 g
Pd-Rh-Fe/AC 1.6, 0.1, 4.2 98.31 g RhCl3ι (20%) 0.5 g Fe(N03)3(H20)9 30.39 g
Pd-Pt-Ce/AC 1.6, 0.2, 10.5 91.63 g H2PtCl6 (25%) 0.8 g CeCl3(H20)7 27.93 g
Pd-Ru-Ce/AC 1.6, 0.1, 10.5 91.98 g RuCl3 (20%) 0.49 g CeCl3(H20)727.93 g
Pd-Rh-Ce/AC 1.6, 0.1, 10.5 91.98 g RhCl3 (20%) 0.5 g CeCl3(H20)727.93 g
Table 2 . Data for Example 3 ,
Catalyst Composition Quantity Solution of secondary Salt of non-precious metal of precious metal component component activated carbon
Pt-Ru-Fe/AC 2.9, 0.1, 4.2 96.95 g RuCl3 (20%) 0.49 g Fe(N03)3(H20)9 30.39 g
Pt-Rh-Fe/AC 2.9 0.1, 4.2 96.95 g RhCl3 (20%) 0.5 g Fe(N03)3(H20)9 30.39 g
Pt-Pd-Fe/AC 2.9 0.1, 4.2 96.95 g H2PdCl4 (20%) 0.5 g Fe(N03)3(H20)9 30.39 g
Pt-Ru-Ce/AC 2.9 0.1, 10.5 90.62 g RuCl3 (20%) 0.49 g CeCl3(H20)727.93 g
Pt-Rh-Ce/AC 2.9 0.1, 10.5 90.62 g RhCl3 (20%) 0.5 g CeCl3(H20)727.93 g
Pt-Pd-Ce/AC 2.9 0.2, 10.5 90.62 g H2PdCl4 (20%) 0.5 g CeCl3(H20)7 27.93 g
The catalysts according to the examples are used in the discontinuous hydrogenation of dinitrotoluene to toluene- diamine and the activity and selectivity of the catalysts are determined.
The reaction is carried out in a 0.5 1 Hastelloy autoclave. First, 40 g 2, 4-Dinitrotoluene, 101 g 2, 4-toluenediamine, 59 g water and 1.2 g catalyst (in relation to the solids) are fed into the autoclave. Then, after locking the autoclave, the gas space is flushed first with nitrogen and then with hydrogen and finally a hydrogen pressure of 10 bar is established.
After heating to 120°C, the reaction is started by switching on the stirring mechanism. The end point of the reaction can be determined precisely by the rapid reduction in hydrogen absorption.
Hydrogen absorption is recorded during the reaction. Once the reaction has ended and the reaction mixture has cooled, it is taken up in methanol, filtered and analysed by gas chromatography. This allows the yield of TDA, the conversion of DNT and the quantity of by-products to be determined.
The following can be obtained as by-products: toluidines, diaminobenzenes (called low-boilers) and tars. The term tars describes all compounds which have a longer retention time than the primary product TDA.
Activity is calculated from the absorption of hydrogen during the reaction time in relation to the catalyst mass and is given as ml H2/ (min g catalyst). The results are summarised in Table 3, Table 4 and Table 5.
Tables of results
Table 3. Pd-containing catalysts on black
Catalyst Charge Activity Low boilers TDA yield Tars [%] [%] [%] [ml H2/min g]
Reference Pd-Pt-Fe/SB 1.6, 0.2, 4.2 1000 0.01 97.92 2.07 example 1
Reference Pd-Pt/SB 1.6, 0.2 1050 0.28 98.85 0.87 example 2
Example 1 Pd-Pt-Ce/SB 1.6, 0.2, 10.5 1200 0.0 99.47 0.53
Table 4. Pd-containing trimetallic catalysts on activated carbon
Catalyst Charge Activity Low-boilers TDA yield Tars [%] [%] [%] [ml H2/min g]
Reference Pd-Pt-Fe/AC 1.6, 0.2, 4.2 917 0.01 97.98 2.01 example 3
Example 2 Pd-Ru-Fe/AC 1.6, 0.1, 4.2 913 0.01 97.8 2.19
Example 2 Pd-Rh-Fe/AC 1.6, 0.1, 4.2 901 0.01 98.28 1.71
Example 2 Pd-Pt-Ce/AC 1.6, 0.2, 10.5 866 0.01 99.58 0.41
Example 2 Pd-Ru-Ce/AC 1.6, 0.1, 10.5 777 0.01 99.64 0.35
Example 2 Pd-Rh-Ce/AC 1.6, 0.1, 10.5 800 0.02 99.64 0.34
Table 5. Pt-containing trimetallic catalysts on activated carbon
Catalyst Charge Activity Low-boilers TDA yield Tars [%] [%] [%] [ml H2/min g]
Reference Pd-Pt-Fe/AC 1.6, 0.2, 4.2 917 0.01 97.98 2.01 example 3
Example 3 Pt-Ru-Fe/AC 2.9, 0.1, 4.2 923 0.01 99.38 0.61
Example 3 Pt-Rh-Fe/AC 2.9, 0.1, 4.2 920 0.00 99.13 0.87
Example 3 Pt-Pd-Fe/AC 2.9, 0.1, 4.2 950 0.01 99.2 0.79
Example 3 Pt-Ru-Ce/AC 2.9, 0.1, 10.5 895 0.05 99.61 0.39
Example 3 Pt-Rh-Ce/AC 2.9, 0.1, 10.5
Example 3 Pt-Pd-Ce/AC 2.9, 0.2, 10.5 892 0.08 99.35 0.57
Claims
1. Supported hydrogenating catalyst in powder form containing, as catalytically active components, a mixture of a primary precious metal component, a secondary precious metal component and one or more non- precious metal components, wherein either Pt can be used as the primary precious metal component with Pd, Ru, Rh as the secondary precious metal component and V, Fe, Mn, Ce and/or Cr as the non-precious metal component, or Pd can be used as the primary precious metal component with Ru, Rh as the secondary precious metal component and V, Fe, Mn, Ce and/or Cr as the non- precious metal component or Pd can be used as the primary precious metal component with Pt as the secondary precious metal component and Ce and/or Cr as the non-precious metal component.
2. Supported hydrogenating catalyst in powder form according to claim 1, characterised in that physically activated carbons, chemically activated carbons, blacks, aluminium oxides or silicon oxides are used as the powder-form support.
3. Hydrogenating catalyst according to claim 1, characterised in that 100 g dry hydrogenation catalyst contains 10-50 mmol of the primary precious metal component, 1-60 mol%, in relation to the primary precious metal component, of the secondary precious metal component, and 1-700 mol%, in relation to the primary precious metal component, of the non-precious metal component .
4. Hydrogenating catalyst according to claim 1, characterised in that 100 g dry hydrogenating catalyst contains 15-20 mmol of the primary precious metal component, 8-12 mol%, in relation to the primary precious metal component, of the secondary precious metal component and 1-600 mol%, in relation to the primary precious metal component, of cerium.
5. Process for the production of a hydrogenating catalyst according to claims 1-4, characterised in that an aqueous solution containing the primary precious metal component, the secondary precious metal component and the non-precious metal component in dissolved form is added to a suspension of a powder-form support in water, the primary and secondary precious metal components and the non-precious metal component are deposited on the powder-form support material using a base and reduction is optionally carried out using a reducing agent.
6. Use of the catalyst according to claims 1-4 for the hydrogenation of nitroaromatics to aminoaromatics .
7. Use of the catalyst according to claims 1-4 for the hydrogenation of nitrobenzene to aniline.
8. Use of the catalyst according to claims 1-4 for the hydrogenation of dinitrotoluenes to toluenediamines.
9. Process for the production of aniline, characterised in that the catalytic hydrogenation of the corresponding nitro-compound is carried out in the liquid phase as a continuously or discontinuously operated process at pressures of 1 to 100 bar and temperatures of 0°C to 200 °C in the presence of the catalyst according to claims 1-4.
10. Process for the production of toluenediamines, characterised in that the catalytic hydrogenation of the corresponding nitro-compounds is carried out in the liquid phase as a continuously or discontinuously operated process at pressures of 1 to 100 bar and temperatures of 0°C to 200°C in the presence of the catalyst according to claims 1-4.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
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| DE10154811 | 2001-11-08 | ||
| DE10154811 | 2001-11-08 | ||
| US33315301P | 2001-11-27 | 2001-11-27 | |
| US333153P | 2001-11-27 | ||
| DE10216108 | 2002-04-12 | ||
| 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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| ES2294075T3 (en) * | 2001-12-07 | 2008-04-01 | Basf Se | PROCEDURE FOR OBTAINING RUTENIUM / IRON CATALYSTS ON CARBON SUPPORTS. |
| DE10349095A1 (en) | 2003-10-17 | 2005-05-19 | Basf Ag | Process for the preparation of amines |
| WO2005061479A1 (en) * | 2003-12-19 | 2005-07-07 | Ube Industries, Ltd. | 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 cut fraction section 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 |
| JPWO2017163680A1 (en) * | 2016-03-23 | 2019-01-31 | エヌ・イーケムキャット株式会社 | Reaction composition and reaction system using the same |
| US10322992B2 (en) | 2016-12-13 | 2019-06-18 | King Abdulaziz University | Methods of making cerium oxide polyaniline composite nanospheres and methods of use |
| 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 |
| GB2112414B (en) * | 1981-12-23 | 1985-07-03 | Metallurg Im A A Baikova Akade | Palladium-based alloy |
| JP2801381B2 (en) * | 1990-09-18 | 1998-09-21 | 三井化学株式会社 | Production method of high purity aniline |
| GB9226434D0 (en) * | 1992-12-18 | 1993-02-10 | Johnson Matthey Plc | Catalyst |
| DE19641688A1 (en) * | 1996-10-10 | 1998-04-16 | Bayer Ag | Catalysts and processes for the preparation of cycloaliphatic amines |
| DE19848032A1 (en) * | 1998-10-17 | 2000-04-20 | Degussa | Pt / Rh / Fe alloy catalyst for fuel cells and process for its manufacture |
| DE19909168A1 (en) * | 1999-03-03 | 2000-09-07 | Basf Ag | Process for the production of amines |
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