CN113750995A - 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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- CN113750995A CN113750995A CN202010505421.5A CN202010505421A CN113750995A CN 113750995 A CN113750995 A CN 113750995A CN 202010505421 A CN202010505421 A CN 202010505421A CN 113750995 A CN113750995 A CN 113750995A
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- gallium
- titanium dioxide
- platinum
- indium
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 166
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 89
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 85
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 83
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 80
- 239000007788 liquid Substances 0.000 title claims abstract description 65
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 58
- 239000000956 alloy Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 20
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 14
- 238000006722 reduction reaction Methods 0.000 claims description 14
- 239000002253 acid 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
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 8
- 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
- 238000001914 filtration Methods 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 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
- USLHPQORLCHMOC-UHFFFAOYSA-N triethoxygallane Chemical compound CCO[Ga](OCC)OCC USLHPQORLCHMOC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 150000002739 metals Chemical class 0.000 abstract description 4
- 238000009827 uniform distribution Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 52
- 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 12
- 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
- 230000000694 effects Effects 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000003960 organic solvent 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
- 238000003917 TEM image Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 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
- 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
- 150000002505 iron Chemical class 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004519 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
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical compound NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 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
- 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
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 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
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses 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. The composite catalyst provided by the invention takes platinum-gallium-indium liquid alloy as an active component, increases the dispersion degree of platinum atoms by utilizing indium atoms, forms a liquid stable trimetal structure by the interaction of the three metal atoms, and enables the trimetal structure to uniformly and firmly cover the surface of a titanium dioxide carrier, and charge transfer is generated between the trimetal 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 more active sites, high stability and high catalytic performance in uniform distribution is obtained. When the composite catalyst provided by the invention is used for catalyzing the hydrogenation of the p-nitroaniline to prepare the p-aminostyrene, the conversion rate of the p-nitroaniline is 97.9%, the selectivity of the p-aminostyrene is 99.2%, and water is used as a solvent, so that the environment is protected.
Description
Technical Field
The invention 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
P-aminostyrene is a valuable intermediate for pharmaceuticals, dyes, herbicides and other fine chemicals. The industrial production of p-amino styrene is mainly carried out by selective hydrogenation of p-nitroaniline. At present, the catalysts used for hydrogenation to prepare p-amino styrene are: CoS3、Co3O4、Fe2O3The like, and Au, Ag and other metal catalysts, but the activity of these catalysts is low, the reaction requires high temperature and long time, and the long time reaction can lead to the conversion of the generated p-amino styrene into the byproduct amino styrene by further hydrogenation, which leads to the reduction of selectivity of the p-amino styrene and the accumulation of a plurality of byproducts, thus causing the accumulation of some harmful byproducts.
In the prior art, a second metal is added into a noble metal catalyst for modification, and a promoter of iron salt or quaternary ammonium base is added to increase the selectivity of nitro hydrogenation, but the introduction of the iron salt or the quaternary ammonium base causes difficult separation of products and complicated process flow. In addition, the catalyst has good activity only in organic solvents such as toluene, tetrahydrofuran and the like. Therefore, it is desirable to provide a catalyst for the hydrogenation of p-nitroaniline to produce p-amino-styrene with high selectivity.
Disclosure of Invention
The invention aims to provide a titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst, 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 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 invention 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 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 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, 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 indium source in step (1) comprises one or more of indium chloride, indium acetate, indium nitrate and indium sulphate.
Preferably, the particle size of the titanium dioxide in the step (2) is 20-100 nm.
Preferably, the calcining temperature in the step (3) is 400-800 ℃, 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 the application of the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst or the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst prepared by the preparation method in the preparation of p-amino styrene by hydrogenation of p-nitroaniline.
The invention 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 invention takes platinum-gallium-indium liquid alloy as an active component, increases the dispersion degree of platinum atoms by utilizing indium atoms, meanwhile, through the interaction among three metal atoms, a stable liquid trimetal structure is formed and uniformly and firmly covered on the surface of the titanium dioxide carrier, and charge transfer is generated between the trimetal structure and the carrier titanium dioxide with high electron mobility and high dielectric constant, thereby changing the electronic structure of the three metals, finally obtaining the catalyst with more active sites, uniform distribution, high stability and high catalytic performance, and the metal active components form a liquid film in the catalytic reaction process, the liquid film layer can reduce the adsorption of p-amino styrene, thereby avoiding further hydrogenation of p-amino styrene, reducing the generation of by-products, in addition, the catalyst provided by the application still has higher activity in a reaction system using water as a solvent. The results of the examples show that when the titanium dioxide loaded platinum gallium indium liquid alloy composite 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 97.9%, the selectivity of the p-amino styrene is 99.2%, and water is used as a solvent, so that the environment-friendly effect is achieved.
The preparation method of the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst 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-nitrostyrene and the selectivity of p-aminostyrene in the preparation of p-aminostyrene by using the catalysts prepared in examples 1 to 3, comparative example 1 and comparative example 2 according to the present invention;
fig. 2 is a TEM image of the titania-supported platinum gallium indium liquid alloy composite catalyst prepared in example 1 of the present invention.
Detailed Description
The invention 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 invention comprises a carrier, wherein the carrier is titanium dioxide. In the invention, the titanium dioxide has good stability, high electron mobility, higher dielectric constant and strong binding capacity with active components, and charge transfer is generated 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 invention comprises an active component loaded on the carrier, wherein the active component is platinum gallium indium liquid alloy. The active component platinum gallium indium of the catalyst provided by the invention exists in the form of alloy, and platinum atoms, gallium atoms and indium atoms are mutually combined in the form of metallic bonds, so that the stability of the catalyst is improved; the alloy exists in a liquid state, so that the alloy can not be aggregated, active sites are uniformly distributed on the surface of the carrier, indium atoms increase the dispersion degree of platinum atoms, and electronic structures among the platinum atoms, gallium atoms and indium atoms are influenced mutually, so that the selectivity of the p-amino styrene is finally improved.
In the invention, 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 further preferably 0.40:2.00:2.01: 100. The invention 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 within the range, can be beneficial to the interaction among three metal atoms, forms a liquid stable structure, and enables the liquid stable structure to uniformly and firmly cover the surface of a titanium dioxide carrier, thereby obtaining the catalyst with more active sites, high stability and high catalytic performance in uniform distribution.
The invention 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 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 titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst.
The invention mixes platinum source, gallium source, indium source 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 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 indium source preferably includes one or more of indium chloride, indium acetate, indium nitrate, and indium sulfate; in the embodiment of the present invention, indium chloride is specifically used. The source of the indium 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 titanium dioxide is preferably 20 to 100nm, more preferably 40 to 80nm, and further preferably 50 nm. The source of the titanium dioxide 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 titanium dioxide within the range, and can be beneficial to uniformly and firmly covering the active component on the surface of the titanium dioxide carrier.
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 indium source is preferably (17-23) mL (0.5-8) mg, and more preferably (18-22) mL (1.5-6) mg.
In the present invention, 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 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 invention preferably mixes the platinum source, the gallium source, the indium source and part of the solvent respectively to prepare the platinum precursor solution, the gallium precursor solution and the indium precursor solution. In the present invention, the preparation methods of the platinum precursor solution, the gallium precursor solution, and the indium precursor solution are preferably: 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 invention, the mass concentrations of the platinum precursor solution, the gallium precursor solution and the indium precursor solution are preferably 5 to 15mg/mL independently, and more preferably 8 to 12mg/mL independently.
After obtaining the platinum precursor solution, the gallium precursor solution and the indium precursor solution, the invention preferably mixes the platinum precursor solution, the gallium precursor solution and the indium precursor solution with the rest of the solvent to obtain a mixed solution. In the present invention, 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 20-120 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 titanium dioxide are mixed, filtered and dried to obtain the precursor. In the present invention, the mixing of the mixed solution and titanium dioxide 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. 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 70-100 ℃, and more preferably 80-90 ℃; the drying time is preferably 6-12 hours, and more preferably 7-10 hours.
After the precursor is obtained, the precursor is calcined and then subjected to reduction reaction in a reducing gas atmosphere to obtain the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst. In the present invention, during the calcination process, the platinum precursor, the gallium precursor, and the indium precursor are pyrolyzed to form corresponding platinum oxide, gallium oxide, and indium oxide, respectively, and are firmly supported on the surface of the titanium dioxide. In the invention, the calcining temperature is preferably 400-800 ℃, 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, can further ensure that the precursor is fully calcined and completely converted into the corresponding metal oxide. In the present invention, the calcination is preferably carried out in an air atmosphere.
In the invention, in the reduction reaction process, the platinum oxide, the gallium oxide and the indium oxide are respectively reduced into platinum, gallium and indium, and the platinum, the gallium and the indium are interacted to form a stable liquid trimetal structure which 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 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 150-300 ℃; 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 formed by calcination is fully reduced, and finally prepares the titanium dioxide loaded platinum-gallium-indium liquid alloy catalyst with proper particle size and regular morphology.
The preparation method of the titanium dioxide loaded platinum-gallium-indium liquid alloy catalyst provided by the invention is simple to operate, mild in reaction conditions 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 is low in production cost.
The invention also provides a titanium dioxide supported platinum gallium indium liquid alloy composite catalyst prepared by the preparation method in the technical scheme, which comprises titanium dioxide and platinum-gallium-indium ternary alloy supported on the surface of the titanium dioxide.
The invention also provides the application of the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst or the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst prepared by the preparation method in the preparation of p-amino styrene by hydrogenation of p-nitroaniline.
In the invention, the application of the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst in the preparation of p-amino styrene by hydrogenation of p-nitroaniline preferably comprises the following steps:
mixing the titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst, p-nitrostyrene and water, introducing hydrogen, and carrying out addition reaction to obtain p-amino styrene.
The invention preferably mixes the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst, p-nitrostyrene and water, then introduces hydrogen, and carries out addition reaction to obtain 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 regulation on the mixing mode of the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst, the p-nitrostyrene and the water, and the conventional mixing mode of the technical personnel in the field can be adopted. In the embodiment of the invention, the mixing mode is preferably that the titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst is filled on the high-pressure reaction kettle, and then the p-nitrostyrene and the water are sequentially added.
In the invention, the mass ratio of the titanium dioxide supported platinum gallium indium liquid alloy composite catalyst to the p-nitroanisole is preferably 1 (1-40), more preferably 1 (1-20), and further preferably 1: 5.
In the present invention, the mass-to-volume ratio of the p-nitroarene to water is preferably (0.1-0.5) mmol, (2-6) mL, more preferably (0.4-1) mmol, (3-5) mL, and still more preferably 0.3mmol:4 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 0.1 to 3MPa of hydrogen pressure, more preferably 0.15 to 1MPa of hydrogen pressure, and even more preferably 0.2MPa 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 titanium dioxide loaded platinum-gallium-indium liquid alloy composite 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 protected, 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 indium 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 indium chloride, dissolving the indium chloride in deionized water, transferring the solution into a 100mL volumetric flask, and adding the deionized water to corresponding scales to prepare an indium 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 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, 5.05mL of gallium chloride solution and 10.23mL of deionized water which are prepared by the preparation method by using a 1mL liquid transfer gun, and then stirring for 0.5h to obtain mixed liquid;
(2) mixing the mixed solution obtained in the step (1) with 1g of titanium dioxide with the particle size of 50nm, stirring for 6 hours, filtering, and drying in vacuum at 80 ℃ for 8 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 titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst, wherein the mass ratio of platinum element, gallium element, indium element and 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 it can be seen from fig. 2 that 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-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 0.2MPa hydrogen to obtain p-aminostyrene, wherein 10mg of the catalyst prepared in example 1, 50mg of p-nitrostyrene, and the mass-to-volume ratio of p-nitrostyrene to water was 0.3mmol:4mL, 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 the embodiment 1, the 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, 1.94mL of indium chloride solution and 14.7mL of deionized water are mixed, 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 the embodiment 1, the 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, 5.82mL of indium chloride solution and 5.78mL of deionized water are mixed, 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 p-aminostyrene preparation 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 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 preparation of p-aminostyrene by the hydrogenation of p-nitroaniline according to the method of application example 1, and the specific experimental results are shown in table 1.
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 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 preparation of p-aminostyrene by the 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 97.9%, 92.4% and 87.6%, respectively, the selectivity of p-aminostyrene is 99.2%, 90.4% and 89.7%, respectively, the conversion rates of p-nitrostyrene of the catalysts prepared in comparative example 1 and comparative example 2 are 70.4% and 62.3%, respectively, and the selectivity of p-aminostyrene is 81.3% and 75.4%, 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 99.2%, and the conversion rate of p-nitroaniline is as high as 97.9%, 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. The titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst 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 titanium dioxide-loaded platinum gallium indium liquid alloy composite catalyst as claimed in claim 1, wherein the mass ratio of platinum element, gallium element, indium element and 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.
3. The preparation method of the titanium dioxide supported platinum gallium indium liquid alloy composite catalyst according to any one of claims 1 to 2, comprising 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 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 titanium dioxide loaded platinum gallium indium liquid alloy composite catalyst.
4. 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.
5. 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.
6. The method according to claim 1, wherein the indium source in the step (1) includes one or more of indium chloride, indium acetate, indium nitrate, and indium sulfate.
7. The method according to claim 1, wherein the titanium dioxide in the step (2) has a particle size of 20 to 100 nm.
8. The preparation method according to claim 1, wherein the calcining temperature in the step (3) is 400-800 ℃, and the calcining time is 1-7 h.
9. The preparation method according to claim 1, 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.
10. The application of the titanium dioxide supported platinum gallium indium liquid alloy composite catalyst according to any one of claims 1 to 2 or the titanium dioxide supported platinum gallium indium liquid alloy composite catalyst prepared by the preparation method according to any one of claims 3 to 9 in the preparation of p-amino styrene by hydrogenation of p-nitroaniline.
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