CN113750995B - Titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst and preparation method and application thereof - Google Patents
Titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst and preparation method and application thereof Download PDFInfo
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- CN113750995B CN113750995B CN202010505421.5A CN202010505421A CN113750995B CN 113750995 B CN113750995 B CN 113750995B CN 202010505421 A CN202010505421 A CN 202010505421A CN 113750995 B CN113750995 B CN 113750995B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 77
- 239000007788 liquid Substances 0.000 title claims abstract description 58
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 53
- 239000000956 alloy Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 99
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 52
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 47
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000006722 reduction reaction Methods 0.000 claims description 13
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 11
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 7
- 238000001035 drying 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 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
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 3
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 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
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 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
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 3
- USLHPQORLCHMOC-UHFFFAOYSA-N triethoxygallane Chemical compound CCO[Ga](OCC)OCC USLHPQORLCHMOC-UHFFFAOYSA-N 0.000 claims description 3
- YFZHODLXYNDBSM-UHFFFAOYSA-N 1-ethenyl-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(C=C)C=C1 YFZHODLXYNDBSM-UHFFFAOYSA-N 0.000 abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 238000005984 hydrogenation 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 8
- 150000002739 metals Chemical class 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 49
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000007259 addition reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical group 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
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 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
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical compound NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001514 detection method 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
- 239000000975 dye Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- B01J35/40—
-
- 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
-
- 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
-
- 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
Abstract
The application relates to a titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst and a preparation method and application thereof, belonging to the field of catalytic materials. According to the composite catalyst provided by the application, the platinum-gallium-indium liquid alloy is used as an active component, the dispersion degree of platinum atoms is increased by utilizing indium atoms, meanwhile, a liquid stable trimetallic structure is formed through interaction among three metal atoms, the trimetallic structure is uniformly and firmly covered on the surface of a titanium dioxide carrier, and charge transfer occurs between the trimetallic structure and the carrier titanium dioxide with high electron mobility and high dielectric constant, so that the electronic structure of the three metals is changed, and finally, the catalyst with multiple active sites, high uniformly distributed stability and high catalytic performance is obtained. When the composite catalyst provided by the application is used for catalyzing the hydrogenation of the p-nitrostyrene to prepare the p-aminostyrene, the conversion rate of the p-nitrostyrene is 97.9%, the selectivity of the p-aminostyrene is 99.2%, and the environment is friendly by adopting water as a solvent.
Description
Technical Field
The application relates to the field of catalytic materials, in particular to a titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst, and a preparation method and application thereof.
Background
Para-aminostyrenes are high value intermediates for pharmaceuticals, dyes, herbicides and other fine chemicals. Industrially, the method is thatPara-aminostyrene is produced primarily by selective hydrogenation of para-nitrostyrene. Currently, catalysts for the hydrogenation of para-aminostyrene are: coS (CoS) 3 、Co 3 O 4 、Fe 2 O 3 And the like, and metal catalysts such as Au, ag and the like, but the catalysts have lower activity, require higher temperature and longer time for reaction, and can lead to further hydrogenation and conversion of the generated para-aminostyrene into byproduct aminostyrene after long-term reaction, so that the selectivity of the para-aminostyrene is reduced, and more byproducts are generated, thereby causing accumulation of some harmful byproducts.
In the prior art, the selectivity of nitro hydrogenation is increased by adding a second metal modification to a noble metal catalyst and adding a promoter ferric salt or a quaternary amine base, etc., but the introduction of the ferric salt or the quaternary amine base can cause difficult separation of products and complicating the process flow. The catalyst needs to have good activity in organic solvents such as toluene, tetrahydrofuran and the like. Therefore, it is desirable to provide a catalyst for the hydrogenation of p-nitrostyrene to para-aminostyrene with high selectivity.
Disclosure of Invention
The application aims to provide a titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst, a preparation method and application thereof.
In order to achieve the above object, the present application provides the following technical solutions:
the application provides a titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst, which comprises a carrier and an active component loaded on the carrier, wherein the carrier is titanium dioxide, and the active component is platinum-gallium-indium liquid alloy.
Preferably, the mass ratio of the platinum element, the gallium element, the indium element and the titanium dioxide in the titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst is (0.1-0.6): 0.3-4): 1-5): 100.
The application also provides a preparation method of the titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst, which comprises the following steps:
(1) Mixing a platinum source, a gallium source, an indium source and a solvent to obtain a mixed solution;
(2) Mixing the mixed solution obtained in the step (1) with titanium dioxide, and sequentially filtering and drying to obtain a precursor;
(3) Calcining the precursor obtained in the step (2), and then carrying out reduction reaction in a reducing gas atmosphere to obtain the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst.
Preferably, the platinum source in step (1) comprises one or more of chloroplatinic acid, platinum nitrate, potassium chloroplatinate, potassium chloroplatinite, sodium hexachloroplatinate hexahydrate, and platinum chloride.
Preferably, the gallium source in the step (1) includes one or more of gallium nitrate, gallium chloride, gallium ethoxide, gallium isopropoxide, gallium acetylacetonate and gallium triethyl.
Preferably, the indium source in step (1) comprises one or more of indium chloride, indium acetate, indium nitrate and indium sulfate.
Preferably, the particle size of the titanium dioxide in the step (2) is 20 to 100nm.
Preferably, the calcination temperature in the step (3) is 400-800 ℃ and the calcination 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 application also provides an application of the titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst prepared by the scheme or the preparation method in preparing para-aminostyrene by hydrogenating para-nitrostyrene.
The application provides a titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst, which comprises a carrier and an active component loaded on the carrier, wherein the carrier is titanium dioxide, and the active component is platinum-gallium-indium liquid alloy. According to the application, platinum-gallium-indium liquid alloy is used as an active component, the dispersity of platinum atoms is increased by utilizing indium atoms, meanwhile, a liquid stable trimetallic structure is formed through interaction among three metal atoms, the trimetallic structure is uniformly and firmly covered on the surface of a titanium dioxide carrier, and charge transfer occurs between the trimetallic structure and the carrier titanium dioxide with high electron mobility and higher dielectric constant, so that the electronic structure of the three metals is changed, a catalyst which has multiple active sites and high uniformly distributed stability and high catalytic performance is finally obtained, a liquid film is formed by the metal active component in the catalytic reaction process, and the adsorption effect of para-aminostyrene can be reduced by the liquid film layer, so that further hydrogenation of para-aminostyrene is avoided, and the generation of byproducts is reduced. The example results show that when the titanium dioxide supported platinum gallium indium liquid alloy composite catalyst provided by the application is used for catalyzing the hydrogenation of p-nitrostyrene to prepare the p-aminostyrene, the conversion rate of the p-nitrostyrene is 97.9%, the selectivity of the p-aminostyrene is 99.2%, and the environment is friendly by adopting water as a solvent.
The preparation method of the titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst provided by the application is simple to operate, mild in reaction condition and suitable for large-scale production.
Drawings
FIG. 1 is a graph showing the conversion rate of p-nitrostyrene and the selectivity of p-aminostyrene in the preparation of p-aminostyrene by hydrogenation of p-nitrostyrene using the catalysts prepared in examples 1 to 3, comparative example 1 and comparative example 2 according to the present application;
fig. 2 is a TEM image of a titanium dioxide-supported platinum-gallium-indium liquid alloy composite catalyst prepared in example 1 of the present application.
Detailed Description
The application provides a titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst, which comprises a carrier and an active component loaded on the carrier, wherein the carrier is titanium dioxide, and the active component is platinum-gallium-indium liquid alloy.
The titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst provided by the application comprises a carrier, wherein the carrier is titanium dioxide. In the application, the titanium dioxide has good stability, high electron mobility and higher dielectric constant, and strong binding capacity with active components, and charge transfer occurs between the active components and the carrier titanium dioxide, so that the electronic structures of three metals are changed, and the catalytic performance of the catalyst is improved.
The titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst provided by the application comprises an active component loaded on the carrier, wherein the active component is platinum-gallium-indium liquid alloy. The platinum-gallium-indium catalyst active component provided by the application exists in an alloy form, and platinum atoms, gallium atoms and indium atoms are combined with each other in a metal bond form, so that the stability of the catalyst is improved; the alloy exists in a liquid state, so that the alloy cannot be agglomerated, active sites are uniformly distributed on the surface of the carrier, the dispersion degree of platinum atoms is increased by indium atoms, the electronic structures among the platinum atoms, gallium atoms and indium atoms are mutually influenced, and finally the selectivity of the para-aminostyrene is improved.
In the application, the mass ratio of the platinum element, the gallium element, the indium element and the titanium dioxide in the titanium dioxide supported platinum-gallium-indium liquid alloy composite catalyst is preferably (0.1-0.6): (0.3-4): (1-5): 100, more preferably (0.3-0.5): (1-3): 100, and even more preferably 0.40:2.00:2.01:100. The application controls the mass ratio of the platinum element, the gallium element, the indium element and the titanium dioxide in the titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst in the above range, can be favorable for the interaction among three metal atoms to form a liquid stable structure, and ensures that the three metal atoms are uniformly and firmly covered on the surface of a titanium dioxide carrier to obtain the catalyst with multiple active sites, uniform distribution, high stability and high catalytic performance.
The application also provides a preparation method of the titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst, which comprises the following steps:
(1) Mixing a platinum source, a gallium source, an indium source and a solvent to obtain a mixed solution;
(2) Mixing the mixed solution obtained in the step (1) with titanium dioxide, and sequentially filtering and drying to obtain a precursor;
(3) Calcining the precursor obtained in the step (2), and then carrying out reduction reaction in a reducing gas atmosphere to obtain the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst.
The application mixes the platinum source, the gallium source, the indium source and the solvent to obtain the mixed solution. In the present application, the platinum source preferably includes one or more of chloroplatinic acid, platinum nitrate, potassium chloroplatinate, potassium chloroplatinic acid, sodium hexachloroplatinate hexahydrate, and platinum chloride; in the examples of the present application, chloroplatinic acid is specifically used. The source of the platinum source is not particularly limited in the present application, and commercially available products known to those skilled in the art may be used.
In the present application, the gallium source preferably includes one or more of gallium nitrate, gallium chloride, gallium ethoxide, gallium isopropoxide, gallium acetylacetonate, and gallium triethylide; in embodiments of the present application, gallium chloride is particularly employed. The source of the gallium source is not particularly limited in the present application, and commercially available products known to those skilled in the art may be used.
In the present application, the indium source preferably includes one or more of indium chloride, indium acetate, indium nitrate, and indium sulfate; in embodiments of the present application, indium chloride is particularly used. The source of the indium source is not particularly limited in the present application, and commercially available products known to those skilled in the art may be used.
In the present application, the particle diameter of the titanium dioxide is preferably 20 to 100nm, more preferably 40 to 80nm, and even more preferably 50nm. The source of the titanium dioxide is not particularly limited in the present application, and commercially available products known to those skilled in the art may be used. The application controls the grain diameter of the titanium dioxide in the range, and is beneficial to uniformly and firmly covering the surface of the titanium dioxide carrier with the active component.
In the present application, the solvent is preferably deionized water, and the source of the solvent is not particularly limited, and commercially available products known to those skilled in the art may be used. In the present application, the ratio of the volume of the solvent to the total mass of the platinum source, the gallium source and the indium source is preferably (17 to 23) mL (0.5 to 8) mg, more preferably (18 to 22) mL (1.5 to 6) mg.
In the present application, the mixing of the platinum source, the gallium source, the indium source and the solvent preferably includes: respectively mixing a platinum source, a gallium source, an indium source and a part of solvent to prepare a platinum precursor solution, a gallium precursor solution and an indium precursor solution; and mixing the platinum precursor solution, the gallium precursor solution and the indium precursor solution with the rest of the solvent to obtain a mixed solution.
The present application preferably mixes the platinum source, the gallium source, the indium source, and a portion of the solvent, respectively, to prepare a platinum precursor solution, a gallium precursor solution, and an indium precursor solution. In the present application, the preparation methods of the platinum precursor solution, the gallium precursor solution and the indium precursor solution are preferably as follows: and respectively dissolving a platinum source, a gallium source and an indium 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 an indium precursor solution. In the present application, the mass concentrations of the platinum precursor solution, the gallium precursor solution, and the indium precursor solution are preferably independently 5 to 15mg/mL, more preferably independently 8 to 12mg/mL.
After the platinum precursor solution, the gallium precursor solution and the indium precursor solution are obtained, the platinum precursor solution, the gallium precursor solution, the indium precursor solution and the rest of the solvent are preferably mixed to obtain a mixed solution. In the present application, the mixing of the platinum precursor solution, the gallium precursor solution, the indium precursor solution, and the remaining part of the solvent is preferably performed under stirring conditions; the stirring time is preferably 20 to 120 minutes, more preferably 30 to 60 minutes. The stirring rate is not particularly limited in the application, and conventional stirring rate is sufficient.
After the mixed solution is obtained, the mixed solution and titanium dioxide are mixed, filtered and dried to obtain the precursor. In the present application, the mixing of the mixed liquid and titanium dioxide is preferably performed under stirring conditions; the stirring time is preferably 2 to 12 hours, more preferably 4 to 10 hours, and still more preferably 6 hours. The stirring rate is not particularly limited in the application, and conventional stirring rate is sufficient. The filtering mode is not particularly limited, and modes well known to those skilled in the art can be adopted. In the present application, the drying temperature is preferably 70 to 100 ℃, more preferably 80 to 90 ℃; the drying time is preferably 6 to 12 hours, more preferably 7 to 10 hours.
After the precursor is obtained, the precursor is calcined, and then the reduction reaction is carried out in the atmosphere of reducing gas, so that the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst is obtained. In the application, in the calcination process, the platinum precursor, the gallium precursor and the indium precursor are respectively pyrolyzed to form corresponding platinum oxide, gallium oxide and indium oxide, and are firmly loaded on the surface of titanium dioxide. In the present application, the temperature of the calcination is preferably 400 to 800 ℃, more preferably 450 to 600 ℃; the calcination time is 1 to 7 hours, more preferably 2 to 5 hours. The application controls the calcination temperature and time within the above range, and can further ensure that the precursor is fully calcined and completely converted into the corresponding metal oxide. In the present application, the calcination is preferably performed in an air atmosphere.
In the application, in the reduction reaction process, platinum oxide, gallium oxide and indium oxide are respectively reduced into platinum, gallium and indium, and the three are interacted to form a liquid stable trimetallic structure, and the liquid stable trimetallic structure is uniformly and firmly covered on the surface of a titanium dioxide carrier, so that three metal active components are uniformly and firmly distributed on the surface of the carrier, and the catalyst with multiple active sites, uniform distribution, high stability and high catalytic performance is obtained. In the present application, 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 application.
In the present application, the temperature of the reduction reaction is preferably 100 to 600 ℃, more preferably 150 to 300 ℃; the time of the reduction reaction is preferably 1 to 5 hours, more preferably 2 to 4 hours. The temperature and time of the reduction reaction are controlled within the range, so that the metal oxide formed by calcination can be further ensured to be fully reduced, and the titanium dioxide supported platinum-gallium-indium liquid alloy catalyst with proper particle size and regular morphology is finally prepared.
The preparation method of the titanium dioxide loaded platinum-gallium-indium liquid alloy catalyst provided by the application is simple to operate, mild in reaction condition and suitable for large-scale production; the prepared titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst takes three metals as active components, has low noble metal content, high conversion rate, high selectivity and high stability, and low production cost.
The application also provides the titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst prepared by the preparation method, which comprises titanium dioxide and platinum-gallium-indium ternary alloy loaded on the surface of the titanium dioxide.
The application also provides an application of the titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst prepared by the scheme or the preparation method in preparing para-aminostyrene by hydrogenating para-nitrostyrene.
In the application, the application of the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst in preparing para-aminostyrene by hydrogenation of para-nitrostyrene preferably comprises the following steps:
mixing titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst, p-nitrostyrene and water, introducing hydrogen, and performing addition reaction to obtain the p-aminostyrene.
The application preferably mixes the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst, the paranitrostyrene and the water, and then introduces hydrogen for addition reaction to obtain the paraaminostyrene. The apparatus for the addition reaction is not particularly limited, and a reactor well known to those skilled in the art may be used. In the present application, the apparatus for the addition reaction is preferably an autoclave.
The mixing mode of the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst, the p-nitrostyrene and the water is not specially specified, and the conventional mixing mode of the person skilled in the art is adopted. In the embodiment of the application, the mixing mode is preferably that the titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst is firstly filled on the high-pressure reaction kettle, and then the p-nitrostyrene and the water are sequentially added.
In the application, the mass ratio of the titanium dioxide supported platinum gallium indium liquid alloy composite catalyst to the p-nitrostyrene is preferably 1 (1-40), more preferably 1 (1-20), and even more preferably 1:5.
In the present application, the ratio of the amount of the substance of p-nitrostyrene to water is preferably (0.1 to 0.5) mmol (2 to 6) mL, more preferably (0.4 to 1) mmol (3 to 5) mL, and still more preferably 0.3 mmol/4 mL.
In the present application, the temperature of the addition reaction is preferably 30 to 180 ℃, more preferably 50 to 100 ℃, still more preferably 80 ℃; the pressure of the addition reaction is preferably a hydrogen pressure of 0.1 to 3MPa, more preferably a hydrogen pressure of 0.15 to 1MPa, and still more preferably a hydrogen pressure of 0.2 MPa.
In the application, the detection instrument for the reaction of preparing the para-aminostyrene by hydrogenating the para-nitrostyrene is preferably a flame ionization detector, and in the embodiment of the application, the flame ionization detector is preferably a gas chromatograph.
When the titanium dioxide supported platinum-gallium-indium liquid alloy composite catalyst provided by the application is used for preparing the para-aminostyrene by hydrogenating the para-nitrostyrene, the selectivity of the para-aminostyrene product is high, meanwhile, the conversion rate of the para-nitrostyrene raw material is high, water is used as a solvent, the environmental pollution caused by using an organic solvent is avoided, the environment is friendly, the noble metal content in the catalyst is low, and the production cost is greatly reduced.
The technical solutions of the present application will be clearly and completely described in the following in connection with the embodiments of the present application. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
1. Preparing chloroplatinic acid solution, gallium chloride solution and indium chloride solution
a. 1g of chloroplatinic acid is weighed and dissolved in concentrated hydrochloric acid, transferred to a 100mL volumetric flask, deionized water is added to corresponding scales, and a chloroplatinic acid solution with the mass concentration of 10mg/mL is prepared.
b. 1g of indium chloride is weighed and dissolved in deionized water, the solution is transferred to a 100mL volumetric flask, deionized water is added to corresponding scales, and an indium chloride solution with the mass concentration of 10mg/mL is prepared.
c. 1g of gallium chloride is weighed and dissolved in 2mL of concentrated hydrochloric acid, transferred to a 100mL volumetric flask, deionized water is added to corresponding scales, and a gallium chloride solution with the mass concentration of 10mg/mL is prepared.
2. Preparation of titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst
(1) Respectively transferring 0.84mL of chloroplatinic acid solution, 3.88mL of indium chloride solution and 5.05mL of gallium chloride solution prepared by the preparation method by using a 1mL pipette, mixing with 10.23mL of deionized water, and stirring for 0.5h to obtain a mixed solution;
(2) Mixing the mixed solution obtained in the step (1) with 1g of titanium dioxide with the particle size of 50nm, stirring for 6h, filtering, and drying in vacuum at 80 ℃ for 8h to obtain a precursor;
(3) And (3) calcining the precursor obtained in the step (2) for 4 hours at 500 ℃, and then performing reduction reaction for 2 hours in a hydrogen atmosphere at 300 ℃ to obtain the titanium dioxide-supported platinum-gallium-indium liquid alloy composite catalyst, wherein the mass ratio of the platinum element, the gallium element, the indium element and the titanium dioxide in the prepared composite catalyst is 0.40:2.00:2.01:100.
Fig. 2 is a TEM image of the catalyst prepared in example 1, and as can be seen from fig. 2, the alloy particles on the surface of the catalyst prepared in example 1 are small and the particles are uniformly distributed.
Application example 1
The catalyst prepared in example 1 was applied to the hydrogenation of p-nitrostyrene to prepare p-aminostyrene:
filling the catalyst prepared in the example 1 into a high-pressure reaction kettle, adding p-nitrostyrene and water into the high-pressure reaction kettle to obtain the p-aminostyrene through an addition reaction at the temperature of 80 ℃ and the reaction pressure of 0.2MPa hydrogen, wherein the catalyst prepared in the example 1 is 10mg, the p-nitrostyrene is 50mg, the mass-volume ratio of the p-nitrostyrene to the water is 0.3 mmol/4 mL, and analyzing the mixture by using a gas chromatograph of a FID detector. The specific experimental results are shown in table 1.
Example 2
According to the method of example 1, a titanium dioxide supported platinum-gallium-indium liquid alloy composite catalyst is prepared, wherein 0.84mL of chloroplatinic acid solution, 2.52mL of gallium chloride solution and 1.94mL of indium chloride solution are mixed with 14.7mL of deionized water, and the mass ratio of platinum element, gallium element, indium element and titanium dioxide in the prepared composite catalyst is 0.40:1.00:1.01:100.
Example 3
According to the method of example 1, a titanium dioxide supported platinum-gallium-indium liquid alloy composite catalyst is prepared, wherein 0.84mL of chloroplatinic acid solution, 7.56mL of gallium chloride solution and 5.82mL of indium chloride solution are mixed with 5.78mL of deionized water, and the mass ratio of platinum element, gallium element, indium element and titanium dioxide in the prepared composite catalyst is 0.40:2.99:3.02:100.
Application examples 2 and 3
The catalysts prepared in examples 2 and 3 were applied to the preparation of para-aminostyrene by hydrogenation of para-nitrostyrene 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 3.88mL of indium chloride solution were mixed with 15.28mL of deionized water, and the mass ratio of platinum element, indium element and titanium dioxide in the prepared catalyst was 0.40:2.01:100. The prepared catalyst is applied to the hydrogenation of p-nitrostyrene to prepare p-aminostyrene according to the method of application example 1, and the specific experimental results are shown in table 1.
Comparative example 2
A 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 14.11mL of deionized water, and the mass ratio of platinum element, gallium element and titanium dioxide in the prepared catalyst was 0.40:2.00:100. The prepared catalyst is applied to the hydrogenation of p-nitrostyrene to prepare p-aminostyrene 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 conversion of p-nitrostyrene and the selectivity of p-aminostyrene in the preparation of p-aminostyrene by hydrogenation of p-nitrostyrene using the samples prepared in examples 1 to 3, comparative example 1 and comparative example 2 according to the present application, and as can be seen from FIG. 1, the conversion of p-nitrostyrene in the catalysts prepared in examples 1 to 3 was 97.9%, 92.4% and 87.6%, the selectivity of p-aminostyrene was 99.2%, 90.4% and 89.7%, respectively, and the conversion of p-nitrostyrene in the catalysts prepared in comparative example 1 and comparative example 2 was 70.4% and 62.3%, respectively, and the selectivity of p-aminostyrene was 81.3% and 75.4%, respectively.
TABLE 1 catalytic Properties of different catalysts
As can be seen from Table 1, the selectivity of the p-aminostyrene prepared by catalyzing the hydrogenation of the p-nitrostyrene is up to 99.2%, the conversion rate of the p-nitrostyrene is up to 97.9%, the p-aminostyrene has high conversion rate and high selectivity, the technical effect is far higher than that of the comparative example and the prior art, water is adopted as a solvent, environmental pollution caused by using an organic solvent is avoided, and the catalyst provided by the application is environment-friendly, three metals are adopted as active components, the noble metal content is low, and the production cost is greatly reduced.
The foregoing is merely a preferred embodiment of the present application and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present application, which are intended to be comprehended within the scope of the present application.
Claims (9)
1. The application of the titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst in preparing para-aminostyrene by hydrogenating para-nitrostyrene comprises a carrier and an active component loaded on the carrier, wherein the carrier is titanium dioxide, and the active component is platinum-gallium-indium liquid alloy.
2. The use according to claim 1, wherein the mass ratio of the platinum element, the gallium element, the indium element and the titanium dioxide in the titanium dioxide supported platinum gallium indium liquid alloy composite catalyst is (0.1-0.6): 0.3-4): 1-5): 100.
3. The use according to any one of claims 1-2, characterized in that the preparation method of the titanium dioxide supported platinum-gallium-indium liquid alloy composite catalyst comprises the following steps:
(1) Mixing a platinum source, a gallium source, an indium source and a solvent to obtain a mixed solution;
(2) Mixing the mixed solution obtained in the step (1) with titanium dioxide, and sequentially filtering and drying to obtain a precursor;
(3) Calcining the precursor obtained in the step (2), and then carrying out reduction reaction in a reducing gas atmosphere to obtain the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst.
4. The use according to claim 3, wherein the platinum source in step (1) comprises one or more of chloroplatinic acid, platinum nitrate, potassium chloroplatinate, sodium hexachloroplatinate hexahydrate, and platinum chloride.
5. The use according to claim 3, wherein the gallium source in step (1) comprises one or more of gallium nitrate, gallium chloride, gallium ethoxide, gallium isopropoxide, gallium acetylacetonate and gallium triethylide.
6. The use according to claim 3, wherein the source of indium in step (1) comprises one or more of indium chloride, indium acetate, indium nitrate and indium sulphate.
7. The use according to claim 3, wherein the particle size of the titanium dioxide in step (2) is 20 to 100nm.
8. The method according to claim 3, wherein the calcination in step (3) is carried out at a temperature of 400 to 800 ℃ for a time of 1 to 7 hours.
9. The method according to claim 3, 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.
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