CN113751021A - Catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline ethylene and preparation method and application thereof - Google Patents
Catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline ethylene and preparation method and application thereof Download PDFInfo
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- CN113751021A CN113751021A CN202010506415.1A CN202010506415A CN113751021A CN 113751021 A CN113751021 A CN 113751021A CN 202010506415 A CN202010506415 A CN 202010506415A CN 113751021 A CN113751021 A CN 113751021A
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- nitroaniline
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- ZFBKNBCQWGCZQM-UHFFFAOYSA-N C=C.[N+](=O)([O-])C1=CC=C(N)C=C1 Chemical group C=C.[N+](=O)([O-])C1=CC=C(N)C=C1 ZFBKNBCQWGCZQM-UHFFFAOYSA-N 0.000 title claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 82
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 80
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 72
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims abstract description 50
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 48
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 41
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 40
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 36
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 238000006722 reduction reaction Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims description 49
- 238000002156 mixing Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 6
- ZVYYAYJIGYODSD-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]gallanyloxypent-3-en-2-one Chemical compound [Ga+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZVYYAYJIGYODSD-LNTINUHCSA-K 0.000 claims description 3
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- DAPUDVOJPZKTSI-UHFFFAOYSA-L ammonium nickel sulfate Chemical compound [NH4+].[NH4+].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DAPUDVOJPZKTSI-UHFFFAOYSA-L 0.000 claims description 3
- ZBFQOIBWJITQRI-UHFFFAOYSA-H disodium;hexachloroplatinum(2-);hexahydrate Chemical compound O.O.O.O.O.O.[Na+].[Na+].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] ZBFQOIBWJITQRI-UHFFFAOYSA-H 0.000 claims description 3
- 229940044658 gallium nitrate Drugs 0.000 claims description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 3
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- ZLQBNKOPBDZKDP-UHFFFAOYSA-L nickel(2+);diperchlorate Chemical compound [Ni+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZLQBNKOPBDZKDP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 3
- 229910002058 ternary alloy Inorganic materials 0.000 claims description 3
- USLHPQORLCHMOC-UHFFFAOYSA-N triethoxygallane Chemical compound CCO[Ga](OCC)OCC USLHPQORLCHMOC-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 57
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- YFZHODLXYNDBSM-UHFFFAOYSA-N 1-ethenyl-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(C=C)C=C1 YFZHODLXYNDBSM-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000007259 addition reaction Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- -1 arylamine compounds Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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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
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/896—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- 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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Abstract
The invention provides a catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline and a preparation method and application thereof, belonging to the field of catalytic materials. The preparation method provided by the invention takes a platinum source, a gallium source, a nickel source and silicon dioxide as raw materials, and utilizes calcination and reduction reactions to enable three generated metal atoms to interact to form a liquid stable tri-metal structure, so that three metal active components are uniformly and firmly distributed on the surface of carrier silicon dioxide with high stability and a three-dimensional net structure, and the catalyst with more active sites, high stability and high catalytic performance is obtained. When the catalyst provided by the invention is used for catalyzing the hydrogenation of p-nitroaniline to prepare p-amino styrene, the conversion rate of the p-nitroaniline is 99.5%, the selectivity of the p-amino styrene is 99.4%, and water is used as a solvent, so that the catalyst is environment-friendly.
Description
Technical Field
The invention relates to the field of catalytic materials, in particular to a catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline and a preparation method and application thereof.
Background
Para-amino-styrene is one of arylamine compounds and is an intermediate for producing important chemical products such as medicines, stabilizers, bactericides, insecticides, herbicides and the like. Catalytic hydrogenation of p-nitroaniline is an effective method for preparing p-amino styrene. However, in the p-nitroaniline molecule, both the nitro group and the ethylene group are easy to be reduced by hydrogenation, so that the research and development of the catalyst with higher activity for the hydrogenation of the nitro group and lower activity for the hydrogenation of the ethylene group is the key for improving the yield of the p-aminophenylene.
In the prior art, a noble metal-ionic liquid composite catalyst is adopted for preparing p-aminostyrene by hydrogenation of p-nitrostyrene so as to improve the selectivity of the p-aminostyrene. However, the ionic liquid is easy to absorb moisture in the air to react, so that the ionic liquid is gradually degraded, and the stability of the noble metal-organic ligand (ionic liquid) composite catalyst is poor. Therefore, it is desirable to provide a catalyst for hydrogenation of p-nitroaniline to prepare p-aminostyrene, which has high selectivity and high stability.
Disclosure of Invention
The invention aims to provide a catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline, which comprises the following steps:
(1) mixing a platinum source, a gallium source, a nickel source and a solvent to obtain a mixed solution;
(2) mixing the mixed solution obtained in the step (1) with silicon dioxide, and then sequentially filtering and drying to obtain a precursor;
(3) and (3) calcining the precursor obtained in the step (2), and then carrying out reduction reaction in a reducing gas atmosphere to obtain the catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline.
Preferably, the platinum source in the step (1) comprises one or more of chloroplatinic acid, platinum nitrate, potassium chloroplatinate, sodium hexachloroplatinate hexahydrate and platinum chloride.
Preferably, the gallium source in step (1) comprises one or more of gallium nitrate, gallium chloride, gallium ethoxide, gallium isopropoxide, gallium acetylacetonate and gallium triethylate.
Preferably, the nickel source in step (1) comprises one or more of nickel chloride hexahydrate, nickel formate, nickel carbonate, nickel ammonium sulfate, nickel perchlorate, nickel acetylacetonate and nickel nitrate hexahydrate.
Preferably, the particle size of the silicon dioxide in the step (2) is 20-60 nm.
Preferably, in the step (1), the mass ratio of the platinum element in the platinum source, the gallium element in the gallium source, the nickel element in the nickel source and the silicon dioxide is (0.1-0.6): (0.3-4): 3-10): 100.
Preferably, the calcining temperature in the step (3) is 400-1200 ℃, and the calcining time is 1-7 h.
Preferably, the temperature of the reduction reaction in the step (3) is 100-600 ℃, and the time of the reduction reaction is 1-5 h.
The invention also provides a catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline ethylene, which is prepared by the preparation method in the technical scheme and comprises silicon dioxide and platinum-gallium-nickel ternary alloy loaded on the surface of the silicon dioxide.
The invention also provides the application of the catalyst in the technical scheme in the preparation of p-amino styrene by hydrogenation of p-nitroaniline.
The invention provides a preparation method of a catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline, which comprises the following steps: mixing a palladium source, a nickel source, a gallium source, silicon dioxide and a solvent, sequentially filtering and drying to obtain a precursor, sequentially calcining, and carrying out reduction reaction in a reducing gas atmosphere to obtain the catalyst for preparing p-aminostyrene by hydrogenation of p-nitroaniline. The preparation method provided by the invention takes a palladium source, a nickel source, a gallium source and silicon dioxide as raw materials, and utilizes calcination and reduction reactions to enable electronic structures of three generated metal atoms to interact to form a liquid stable tri-metal structure, and the liquid stable tri-metal structure is uniformly and firmly covered on the surface of a silicon dioxide carrier with high stability and a three-dimensional net structure, so that three metal active components are uniformly and firmly distributed on the surface of the carrier, a catalyst with a plurality of active sites, high stability and high catalytic performance is obtained, the metal active components are partially oxidized in the catalytic reaction process to form a self-protection oxide layer, and the oxide layer can inhibit hydrogenation reaction of p-amino styrene on the surface of the catalyst, and the generation of p-amino styrene by over-hydrogenation of the p-amino styrene is avoided. The results of the examples show that the selectivity of the catalyst provided by the invention for catalyzing the hydrogenation of p-nitroaniline to p-amino styrene can reach 99.4%, the conversion rate of p-nitroaniline can reach 99.5%, and water is used as a solvent, thereby avoiding environmental pollution caused by the adoption of an organic solvent.
The preparation method of the catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline provided by the invention is simple to operate, mild in reaction conditions and suitable for large-scale production.
Drawings
FIG. 1 is a graph showing the relationship between the conversion rate of p-nitroaniline and the selectivity of p-aminostyrene in the catalysts of examples 1-5;
FIG. 2 is a TEM image of the catalyst for hydrogenation of p-nitroaniline to prepare p-aminostyrene, prepared by the example 1 of the present invention;
FIG. 3 is a TEM image of the catalyst for hydrogenation of p-nitroaniline to prepare p-amino styrene prepared in example 2 of the present invention.
Detailed Description
The invention provides a preparation method of a catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline, which comprises the following steps:
(1) mixing a platinum source, a gallium source, a nickel source and a solvent to obtain a mixed solution;
(2) mixing the mixed solution obtained in the step (1) with silicon dioxide, and then sequentially filtering and drying to obtain a precursor;
(3) and (3) calcining the precursor obtained in the step (2), and then carrying out reduction reaction in a reducing gas atmosphere to obtain the catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline.
The invention mixes platinum source, gallium source, nickel source, silicon dioxide and solvent to obtain mixed liquid. In the present invention, the platinum source preferably includes one or more of chloroplatinic acid, platinum nitrate, potassium chloroplatinate, sodium hexachloroplatinate hexahydrate, and platinum chloride; in the embodiment of the invention, chloroplatinic acid is specifically used. The source of the platinum source is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the gallium source preferably comprises a gallium source including one or more of gallium nitrate, gallium chloride, gallium ethoxide, gallium isopropoxide, gallium acetylacetonate and gallium triethylate; in the examples of the present invention, gallium chloride is specifically used. The source of the gallium source is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the nickel source preferably includes one or more of nickel chloride hexahydrate, nickel formate, nickel carbonate, nickel ammonium sulfate, nickel perchlorate, nickel acetylacetonate, and nickel nitrate hexahydrate; in the examples of the present invention, nickel chloride is specifically used. The source of the nickel source is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the particle size of the silica is preferably 20 to 60nm, more preferably 30 to 50nm, and further preferably 40 nm. The source of the silica is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. The invention controls the particle size of the silicon dioxide within the range, and can be beneficial to more uniformly and firmly covering the trimetallic active component on the surface of the silicon dioxide carrier with high stability and a three-dimensional net structure.
In the present invention, the solvent is preferably deionized water, and the source of the solvent is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used. In the invention, the volume ratio of the solvent to the total mass of the platinum source, the gallium source and the nickel source is preferably (7-13) mL, (1.5-5) mg, and more preferably (8-12) mL, (2-4) mg.
In the present invention, the mixing of the platinum source, the gallium source, the nickel source, and the solvent preferably includes: respectively mixing a platinum source, a gallium source, a nickel source and a part of solvent to prepare a platinum precursor solution, a gallium precursor solution and a nickel precursor solution; and mixing the platinum precursor solution, the gallium precursor solution and the nickel precursor solution with the rest of the solvent to obtain a mixed solution.
According to the invention, a platinum source, a gallium source, a nickel source and a part of solvent are preferably mixed respectively to prepare a platinum precursor solution, a gallium precursor solution and a nickel precursor solution. The preparation methods of the platinum precursor solution, the gallium precursor solution and the nickel precursor solution are not particularly limited, and the platinum precursor solution, the gallium precursor solution and the nickel precursor solution can be prepared by methods well known by persons skilled in the art. In the present invention, the preparation methods of the platinum precursor solution, the gallium precursor solution, and the nickel precursor solution are preferably: respectively dissolving a platinum source, a gallium source and a nickel source in a small amount of solvent, and then adding the solvent for dilution to obtain a platinum precursor solution, a gallium precursor solution and a nickel precursor solution. In the invention, the mass concentrations of the platinum precursor solution, the gallium precursor solution and the nickel precursor solution are preferably 5-15 mg/mL independently, and more preferably 8-12 mg/mL independently.
After obtaining the platinum precursor solution, the gallium precursor solution and the nickel precursor solution, the invention preferably mixes the platinum precursor solution, the gallium precursor solution, the nickel precursor solution and the rest of the solvent to obtain a mixed solution. In the invention, the mixing of the platinum precursor solution, the gallium precursor solution, the nickel precursor solution and the rest of the solvent is preferably carried out under stirring conditions; the stirring time is preferably 20-120 min, and more preferably 30-60 min. The stirring speed is not particularly limited in the present invention, and a conventional stirring speed is sufficient.
After the mixed solution is obtained, the mixed solution and silicon dioxide are mixed to obtain a suspension. In the present invention, the mixing of the mixed solution and silica is preferably performed under stirring conditions; the stirring time is preferably 2-12 h, more preferably 4-10 h, and further preferably 6 h. The stirring speed is not particularly limited in the present invention, and a conventional stirring speed is sufficient.
In the invention, the mass ratio of the platinum element in the platinum source, the gallium element in the gallium source and the nickel element in the nickel source to the silicon dioxide is preferably (0.1-0.6): (0.3-4): 3.0-10.0): 100, more preferably (0.2-0.5): 1-3): 4.0-6.0): 100, and further preferably 0.40:2.00:5.04: 100. The invention controls the mass ratio of the platinum element in the platinum source, the gallium element in the gallium source, the nickel element in the nickel source and the silicon dioxide within the range, can be beneficial to the interaction among three metal atoms generated in the subsequent reduction reaction, forms a liquid stable three-metal structure, and enables the three-metal structure to uniformly and firmly cover the surface of the silicon dioxide carrier, so as to finally prepare the catalyst with more active sites, uniform distribution, high stability and high catalytic performance.
After the suspension is obtained, the suspension is filtered and dried to obtain a precursor. The filtration method is not particularly limited in the present invention, and may be a method known to those skilled in the art. In the invention, the drying temperature is preferably 40-100 ℃, and more preferably 60-80 ℃; the drying time is preferably 3-16 h, and more preferably 8-12 h.
After the precursor is obtained, the precursor is calcined and then subjected to reduction reaction in a reducing gas atmosphere to obtain the catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline. In the invention, in the calcination process, the platinum precursor, the gallium precursor and the nickel precursor are pyrolyzed to form corresponding platinum oxide, gallium oxide and nickel oxide respectively, and are firmly loaded on the surface of silicon dioxide.
In the invention, the calcining temperature is preferably 400-1200 ℃, and more preferably 450-600 ℃; the calcining time is 1-7 h, and more preferably 2-5 h. The invention controls the calcining temperature and time within the range, and can further ensure that the precursor is fully calcined and converted into the metal oxide. In the present invention, the calcination is preferably carried out in an air atmosphere.
In the invention, in the reduction reaction process, platinum oxide, gallium oxide and nickel oxide are respectively reduced into platinum, gallium and nickel, and the three interact to form a stable liquid tri-metal structure which is uniformly and firmly covered on the surface of a silicon dioxide carrier, so that three metal active components are uniformly and firmly distributed on the surface of the carrier, and the catalyst with more active sites, uniform distribution, high stability and high catalytic performance is obtained. In the present invention, the reducing gas preferably includes one or more of hydrogen, methane, hydrogen sulfide, and ammonia. When the reducing gas includes two or more components, the volume ratio of the two or more components is not particularly limited in the present invention.
In the invention, the temperature of the reduction reaction is preferably 100-600 ℃, and more preferably 200-400 ℃; the time of the reduction reaction is preferably 1-5 h, and more preferably 2-4 h. The invention controls the temperature and time of the reduction reaction within the range, can further ensure that the metal oxide obtained after calcination is fully reduced, and finally prepares the catalyst with proper particle size and regular shape for preparing the p-amino-styrene by the hydrogenation of the p-nitroaniline.
The preparation method of the catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline provided by the invention is simple to operate, mild in reaction conditions and suitable for large-scale production; the prepared catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline ethylene takes three metals as active components, has low content of noble metal, and has high conversion rate, high selectivity and high stability.
The invention also provides a catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline ethylene, which is prepared by the preparation method in the technical scheme and comprises silicon dioxide and platinum-gallium-nickel ternary alloy loaded on the surface of the silicon dioxide.
The invention also provides the application of the catalyst in the technical scheme in the preparation of p-amino styrene by hydrogenation of p-nitroaniline.
In the present invention, the application of the catalyst in the preparation of p-amino styrene by hydrogenation of p-nitroaniline preferably comprises the following steps:
mixing a catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline, p-nitroaniline and water, introducing hydrogen, and carrying out addition reaction to obtain the p-amino styrene.
The invention preferably mixes the catalyst for preparing the p-amino styrene by the hydrogenation of the p-nitroaniline, the p-nitroaniline and water, then introduces hydrogen and carries out addition reaction to obtain the p-amino styrene. The apparatus for the addition reaction of the present invention is not particularly limited, and a reactor known to those skilled in the art may be used. In the present invention, the apparatus for the addition reaction is preferably a high-pressure reaction vessel.
The invention has no special provisions on the mixing mode of the catalyst for preparing the p-amino styrene by the hydrogenation of the p-nitroaniline, the p-nitroaniline and the water, and the conventional mixing mode of a person skilled in the art can be adopted. In the embodiment of the present invention, the mixing manner is preferably that the catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline is firstly loaded on the high-pressure reaction kettle, and then the p-nitroaniline and water are sequentially added.
In the invention, the mass ratio of the catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline to p-nitroaniline is preferably 1 (1-40), more preferably 1 (1-30), and even more preferably 1: 8.
In the present invention, the mass-to-volume ratio of the p-nitroarene to water is preferably (0.3-1.5) mmol, (4-20) mL, more preferably (0.4-1) mmol, (4.5-10) mL, and still more preferably 0.5mmol:5 mL.
In the invention, the temperature of the addition reaction is preferably 30-180 ℃, more preferably 50-100 ℃, and further preferably 80 ℃; the pressure of the addition reaction is preferably 0.2 to 3MPa of hydrogen pressure, more preferably 0.3 to 1MPa of hydrogen pressure, and even more preferably 0.5MPa of hydrogen pressure.
In the present invention, the detecting apparatus for the reaction of preparing p-aminostyrene by hydrogenating p-nitroaniline is preferably a flame ionization detector, and in the embodiment of the present invention, the flame ionization detector is preferably a gas chromatograph.
When the catalyst provided by the invention is used for preparing p-amino styrene by hydrogenation of p-nitroaniline, the selectivity of a product p-amino styrene is high, the conversion rate of the raw material p-nitroaniline is high, water is used as a solvent, the environmental pollution caused by the use of an organic solvent is avoided, the environment is friendly, the content of noble metal in the catalyst is low, and the production cost is greatly reduced.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Firstly, preparing chloroplatinic acid solution, gallium chloride solution and nickel chloride solution
a. Weighing 1g of chloroplatinic acid, dissolving the chloroplatinic acid in concentrated hydrochloric acid, transferring the solution to a 100mL volumetric flask, and adding deionized water to corresponding scales to prepare a chloroplatinic acid solution with the mass concentration of 10 mg/mL.
b. Weighing 1g of nickel chloride, dissolving the nickel chloride in deionized water, transferring the nickel chloride into a 100mL volumetric flask, and adding the deionized water to corresponding scales to prepare a nickel chloride solution with the mass concentration of 10 mg/mL.
c. Weighing 1g of gallium chloride, dissolving the gallium chloride in 2mL of concentrated hydrochloric acid, transferring the solution to a 100mL volumetric flask, and adding deionized water to corresponding scales to prepare a gallium chloride solution with the mass concentration of 10 mg/mL.
Secondly, preparing the catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline ethylene
(1) Respectively transferring 0.84mL of chloroplatinic acid solution, 11.12mL of nickel chloride solution, 5.05mL of gallium chloride solution and 22.99mL of deionized water prepared by the preparation method by using a 1mL liquid transfer gun, and then stirring for 0.5h to obtain mixed solution;
(2) mixing the mixed solution obtained in the step (1) with 1g of silicon dioxide with the particle size of 40nm, stirring for 6 hours, filtering, and drying in vacuum at 80 ℃ for 12 hours to obtain a precursor;
(3) and (3) calcining the precursor obtained in the step (2) at 500 ℃ for 4h in air, and then carrying out reduction reaction at 300 ℃ for 2h in hydrogen atmosphere to obtain the catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline, wherein the mass ratio of platinum element, gallium element, nickel element and silicon dioxide in the prepared catalyst is 0.40:2.00:5.04: 100.
Fig. 2 is a TEM image of the catalyst prepared in example 1, and it can be seen from fig. 2 that the catalyst prepared in example 1 has a uniform particle distribution and uniform particle size.
Application example 1
The catalyst prepared in example 1 was applied to the hydrogenation of p-nitroaniline to prepare p-aminostyrene:
the catalyst prepared in example 1 was filled in a high pressure reactor, p-nitrostyrene and water were added as a solution, and an addition reaction was performed at a temperature of 80 ℃ and a reaction pressure of 0.5MPa hydrogen to obtain p-aminostyrene, wherein 10mg of the catalyst prepared in example 1, 80mg of p-nitrostyrene, and the mass-to-volume ratio of p-nitrostyrene to water was 0.5mmol:5mL, and the analysis was performed by a gas chromatograph using a FID detector. The specific experimental results are shown in table 1.
Example 2
According to the method of example 1, a catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline is prepared, wherein 0.84mL of chloroplatinic acid solution, 2.52mL of gallium chloride solution and 8.90mL of nickel chloride solution are mixed with 27.74mL of deionized water, and the mass ratio of platinum element, gallium element, nickel element and silicon dioxide in the prepared catalyst is 0.40:1.00:4.03: 100.
Fig. 3 is a TEM image of the catalyst for hydrogenation of p-nitroaniline to produce p-aminostyrene prepared in example 2, and it can be seen from fig. 3 that the catalyst prepared in example 2 has a relatively uniform particle distribution and a larger particle size than the catalyst prepared in example 1.
Example 3
According to the method of example 1, a catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline is prepared, wherein 0.84mL of chloroplatinic acid solution, 7.56mL of gallium chloride solution and 13.34mL of nickel chloride solution are mixed with 18.26mL of deionized water, and the mass ratio of platinum element, gallium element, nickel element and silicon dioxide in the prepared catalyst is 0.40:3.00:6.04: 100.
Application examples 2 and 3
The catalysts prepared in examples 2 and 3 were applied to the preparation of p-aminostyrene by hydrogenation of p-nitroaniline according to the method of application example 1, and the specific experimental results are shown in table 1.
Comparative example 1
A catalyst was prepared according to the method of example 1, wherein 0.84mL of chloroplatinic acid solution and 11.12mL of nickel chloride solution were mixed with 28.04mL of deionized water, and the mass ratio of platinum element, nickel element and silica in the prepared catalyst was 0.40:5.04: 100.
Comparative example 2
The catalyst was prepared according to the method of example 1, wherein 0.84mL of chloroplatinic acid solution and 5.05mL of gallium chloride solution were mixed with 34.11mL of deionized water, and the mass ratio of platinum element, gallium element and silica in the prepared catalyst was 0.40:2.00: 100.
Application examples 4 and 5
The catalysts prepared in comparative examples 1 and 2 were applied to the preparation of p-aminostyrene by hydrogenation of p-nitroaniline according to the method of application example 1, and the specific experimental results are shown in table 1.
Fig. 1 is a graph showing the relationship between the conversion rate of p-nitrostyrene and the selectivity of p-aminostyrene in the preparation of p-aminostyrene by hydrogenating p-nitrostyrene according to examples 1 to 3, comparative example 1 and comparative example 2 of the present invention, and it can be seen from fig. 1 that the conversion rates of p-nitrostyrene of the catalysts prepared in examples 1 to 3 are 99.5%, 93.4% and 89.6%, respectively, the selectivity of p-aminostyrene is 99.4%, 94.2% and 90.2%, the conversion rates of p-nitrostyrene of the catalysts prepared in comparative example 1 and comparative example 2 are 72.4% and 60.3%, respectively, and the selectivity of p-aminostyrene is 80.3% and 72.4%, respectively.
TABLE 1 catalytic Properties of different catalysts
As can be seen from table 1, the catalyst provided by the present invention is used to catalyze the hydrogenation of p-nitroaniline to prepare p-amino styrene with a selectivity as high as 99.4%, and the conversion rate of p-nitroaniline is as high as 99.5%, so that the catalyst has a high conversion rate and a high selectivity, the technical effect achieved is far higher than that of the comparative example and the prior art, and water is used as a solvent, so that the environmental pollution caused by the use of an organic solvent is avoided, and the catalyst is environment-friendly.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline ethylene comprises the following steps:
(1) mixing a platinum source, a gallium source, a nickel source and a solvent to obtain a mixed solution;
(2) mixing the mixed solution obtained in the step (1) with silicon dioxide, and then sequentially filtering and drying to obtain a precursor;
(3) and (3) calcining the precursor obtained in the step (2), and then carrying out reduction reaction in a reducing gas atmosphere to obtain the catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline.
2. The method according to claim 1, wherein the platinum source in the step (1) includes one or more of chloroplatinic acid, platinum nitrate, potassium chloroplatinate, sodium hexachloroplatinate hexahydrate, and platinum chloride.
3. The method according to claim 1, wherein the gallium source in step (1) comprises one or more of gallium nitrate, gallium chloride, gallium ethoxide, gallium isopropoxide, gallium acetylacetonate, and gallium triethylate.
4. The method according to claim 1, wherein the nickel source in step (1) comprises one or more of nickel chloride hexahydrate, nickel formate, nickel carbonate, nickel ammonium sulfate, nickel perchlorate, nickel acetylacetonate, and nickel nitrate hexahydrate.
5. The method according to claim 1, wherein the silica in the step (2) has a particle size of 20 to 60 nm.
6. The production method according to any one of claims 1 to 4, wherein the mass ratio of the platinum element in the platinum source, the gallium element in the gallium source, the nickel element in the nickel source and the silicon dioxide in the step (1) is (0.1-0.6): (0.3-4): (3-10): 100.
7. The preparation method according to claim 1, wherein the calcining temperature in the step (3) is 400-1200 ℃, and the calcining time is 1-7 h.
8. The preparation method according to claim 1 or 7, wherein the temperature of the reduction reaction in the step (3) is 100 to 600 ℃, and the time of the reduction reaction is 1 to 5 hours.
9. The catalyst for preparing p-amino styrene by hydrogenation of p-nitroaniline ethylene prepared by the preparation method of any one of claims 1-8, which comprises silicon dioxide and a platinum-gallium-nickel ternary alloy loaded on the surface of the silicon dioxide.
10. Use of the catalyst of claim 9 for the hydrogenation of p-nitroaniline to p-amino-styrene.
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