CN116237059B - Modified hydrotalcite-loaded platinum ruthenium catalyst and preparation method and application thereof - Google Patents
Modified hydrotalcite-loaded platinum ruthenium catalyst and preparation method and application thereof Download PDFInfo
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- CN116237059B CN116237059B CN202310008136.6A CN202310008136A CN116237059B CN 116237059 B CN116237059 B CN 116237059B CN 202310008136 A CN202310008136 A CN 202310008136A CN 116237059 B CN116237059 B CN 116237059B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 105
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 50
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 27
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 25
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 24
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- 238000011068 loading method Methods 0.000 claims abstract description 22
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 21
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 18
- 238000006722 reduction reaction Methods 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 235000011837 pasties Nutrition 0.000 claims description 10
- QIKYZXDTTPVVAC-UHFFFAOYSA-N 4-Aminobenzamide Chemical compound NC(=O)C1=CC=C(N)C=C1 QIKYZXDTTPVVAC-UHFFFAOYSA-N 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- ZESWUEBPRPGMTP-UHFFFAOYSA-N 4-nitrobenzamide Chemical compound NC(=O)C1=CC=C([N+]([O-])=O)C=C1 ZESWUEBPRPGMTP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 6
- 150000003058 platinum compounds Chemical class 0.000 claims description 4
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000004873 anchoring Methods 0.000 abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 239000002082 metal nanoparticle Substances 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000001976 improved effect Effects 0.000 description 7
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000002923 metal particle Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- 229910002848 Pt–Ru Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910002849 PtRu Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- BIEQEMWVZPRERG-UHFFFAOYSA-N [Ru].[Ce].[Pt] Chemical compound [Ru].[Ce].[Pt] BIEQEMWVZPRERG-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- DMTIXTXDJGWVCO-UHFFFAOYSA-N iron(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Fe++].[Ni++] DMTIXTXDJGWVCO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of noble metal catalysts, and particularly relates to a modified hydrotalcite-loaded platinum ruthenium catalyst, a preparation method thereof and application thereof in nitro hydrogenation reduction reaction. The catalyst (PtRu-XYCe/LDO) is a modified hydrotalcite (XYCe/LDO) carrier and carries platinum ruthenium nano particles; wherein X, Y can be the same or different from metal ions, the loading of the platinum nano particles accounts for 0.1-3% of the mass of the carrier, and the loading of the ruthenium nano particles accounts for 0.05-1% of the mass of the carrier. The invention adopts the steps that cerium solution is doped into hydrotalcite, cerium oxide is formed after calcination, and the cerium oxide is combined with hydrotalcite to obtain a modified hydrotalcite carrier; the cerium oxide makes the carrier have rich oxygen vacancies, and has the advantages of providing ideal anchoring sites for metal nano particles when loading active metal components, promoting the carrier to be combined with the active metal components more effectively, generating metal synergistic effect between the carrier and the active components as well as between the carrier and the bimetallic active components, and improving the reactivity of the catalyst.
Description
Technical Field
The invention belongs to the technical field of noble metal catalysts, and particularly relates to a modified hydrotalcite-loaded platinum ruthenium catalyst, a preparation method thereof and application thereof in nitro hydrogenation reduction reaction.
Background
The para aminobenzamide is an important dye pigment intermediate, and as a chromophore, diazotization is carried out to form azo salt, and the azo salt and different color phenols are coupled to synthesize different types of ice-dyeing dyes, so that the color fastness is higher, the para aminobenzamide is mainly used for printing artificial cotton and fibrilia, dyeing and manufacturing organic pigment, and is used for coloring paint and printing paste, and the demand of the para aminobenzamide in the market is great.
Many methods for synthesizing p-nitrobenzamide exist, but some methods have complex process flows and are unfavorable for actual production operation. At present, most of domestic enterprises utilize catalytic reduction of paranitrobenzamide to prepare paraaminobenzamide, and the process has the advantages of simple operation and low cost. However, in the reduction process, most of the reduction processes adopt iron powder or sodium sulfide, so that a large amount of acid wastewater and metal waste residues are generated after the reaction, or harmful gases are emitted, which is unfavorable for green industrial production. The hydrogenation reduction process has the advantages of green and environmental protection, and is one of better alternative processes for the iron powder reduction method.
Chinese patent CN1869003A adopts Raney nickel as a catalyst in the hydrogenation process of paranitrobenzamide, and the process has the characteristics of environmental protection and high product yield, but has higher pressure required by hydrogenation, higher requirement on pressure-resistant conditions of production equipment, and higher catalyst consumption, and has potential safety hazard. Chinese patent CN108456147A adopts a titanium dioxide supported Ni-Co catalyst, and has the advantages of good selectivity and high yield of paraaminobenzamide, but adopts non-noble metal as the catalyst, so that the problem of low catalytic activity exists. The use of noble metal catalysts, although affected by cost problems, has a high catalytic activity for the hydrogenation of nitro groups. The primary purpose of improving the dispersity, catalytic activity and selectivity of the active metal in the carrier is to consider the cost problem of the noble metal catalyst, and the used catalyst has better stability and longer service life, thereby increasing the use times and reducing the cost. Therefore, the development of a high-efficiency, safe and stable catalyst for catalyzing the hydrogenation of the p-nitrobenzamide has great significance.
Disclosure of Invention
The invention provides a modified hydrotalcite-loaded platinum ruthenium catalyst, a preparation method thereof and application thereof in nitro hydrogenation reduction reaction.
In order to achieve the above purpose, the invention adopts the technical scheme that:
a modified hydrotalcite-loaded platinum ruthenium catalyst (PtRu-XYCe/LDO) is a modified hydrotalcite (XYCe/LDO) carrier and carries platinum ruthenium nano particles; wherein X, Y can be respectively selected from metal ions in the same or different modes, the loading of platinum nano particles accounts for 0.1-3 percent (preferably 0.5-2 percent) of the carrier mass, the loading of ruthenium nano particles accounts for 0.05-1 percent (preferably 0.1-0.5 percent) of the carrier mass, the hydrotalcite accounts for 95.475-99.675 percent of the modified hydrotalcite carrier mass, the doping amount of cerium oxide accounts for 0.175-0.525 percent of the modified hydrotalcite carrier mass, the molar ratio of X to Y is (2-5): 1, and the molar ratio of X to Ce ions is (600-900): 1.
The metal ions are divalent metal cations or trivalent metal cations; the divalent metal cation is at least one of Mg 2+、Zn2+、Ni2+, and the trivalent metal cation is Fe 3+ and/or A1 3+.
The preparation method of the modified hydrotalcite supported platinum ruthenium catalyst comprises the steps of taking hydrotalcite (XY/LDH) as a base material, adding cerium solution into a muffle furnace for calcination to prepare a modified hydrotalcite (XYCe/LDO) carrier, and then supporting platinum ruthenium nano particles on the modified hydrotalcite carrier by adopting an excessive impregnation method to prepare the platinum ruthenium supported modified hydrotalcite catalyst (PtRu-XYCe/LDO).
The mode of mixing the cerium solution and hydrotalcite (XY/LDH) is that an ultrasonic sprayer is adopted to spray the cerium solution on the hydrotalcite; calcining in a muffle furnace to obtain a modified hydrotalcite (XYCe/LDO) carrier; wherein the temperature rise rate of the muffle furnace is 8-12 ℃/min, the calcining temperature of the muffle furnace is 400-600 ℃, and the calcining time of the muffle furnace is 2-7h.
Adding a platinum ruthenium precursor solution into the XYCe/LDO carrier, uniformly stirring, performing ultrasonic treatment to obtain a pasty mixture, and drying the pasty mixture to obtain a hydrotalcite precursor containing platinum ruthenium;
and (3) calcining the hydrotalcite precursor in a tube furnace, introducing hydrogen-nitrogen mixed gas, and carrying out reduction reaction to obtain the platinum-ruthenium supported modified hydrotalcite catalyst (PtRu-XYCe/LDO).
The platinum ruthenium precursor solution is a mixed aqueous solution of a platinum compound and a ruthenium compound, and the mass ratio of platinum to ruthenium is 3-9:1; wherein the platinum compound is one or more of platinum nitrate, platinum chloride and chloroplatinic acid, and the ruthenium compound is one or more of ruthenium nitrate and ruthenium chloride.
The calcining temperature rise rate in the tube furnace is 5-8 ℃/min, the calcining temperature in the tube furnace is 150-300 ℃, and the calcining time is 2-4h.
The application of the modified hydrotalcite-loaded platinum ruthenium catalyst in the hydrogenation reaction of paranitrobenzamide.
A method for preparing paraaminobenzamide, which takes paranitrobenzamide as a raw material and is prepared by catalytic hydrogenation reaction by the catalyst of claim 1; wherein the addition amount of the catalyst is 0.5% -1.0% of the mass of the raw materials.
The catalyst after the catalytic reaction is filtered and washed, and can be continuously applied to the hydrogenation reaction of the paranitrobenzamide.
Compared with the prior art, the invention has the beneficial effects that:
The invention adopts the steps that cerium solution is doped into hydrotalcite, cerium oxide is formed after calcination, and the cerium oxide is combined with hydrotalcite to obtain a modified hydrotalcite carrier; the cerium oxide has rich oxygen vacancies of the carrier, and has the advantages of providing ideal anchoring sites for metal nano particles when loading active metal components, promoting the carrier to be combined with the active metal components more effectively, generating metal synergistic effect between the carrier, the active components and the bimetallic active components, and improving the reactivity of the catalyst; the method for forming the complex metal oxide by uniformly spraying the trace cerium solution on the prepared hydrotalcite by using the ultrasonic sprayer in the preparation process of the modified hydrotalcite carrier, wherein the fine mist of the micron-sized liquid drops enables the hydrotalcite to more uniformly and effectively adsorb the cerium solution, and the method for forming the complex metal oxide after high-temperature calcination has the advantages of not affecting the excellent pore channel structure of the hydrotalcite carrier, enabling the cerium oxide to be more uniformly distributed on the carrier, being beneficial to anchoring of active metal on the carrier, improving the dispersity of the active component, avoiding agglomeration of metal particles in the reaction process, improving the stability of the catalyst and prolonging the service life of the catalyst. In addition, the invention further determines that the cerium doping amount in the preparation process of the modified hydrotalcite carrier accounts for 0.35 percent of the mass of the modified hydrotalcite carrier, when the calcination temperature of a muffle furnace is 500 ℃ and the ratio of metal platinum to ruthenium is 5:1, the prepared modified hydrotalcite-loaded platinum-ruthenium catalyst has higher catalytic activity and selectivity when being applied to the hydrogenation reaction of paranitrobenzamide, can be continuously used for 20 times, and has longer service life.
Detailed Description
The invention is described in detail below with reference to the drawings and the specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods used in the present invention are all conventional methods, and all experimental equipment, materials, reagents, etc. used can be obtained from commercial sources.
The invention takes modified hydrotalcite as a carrier to load metal platinum and ruthenium, thereby preparing a noble metal catalyst loaded by the modified hydrotalcite, and the catalyst is applied to the hydrogenation reaction of paranitrobenzamide. The invention adopts an ultrasonic sprayer to spray the aqueous solution of cerium onto hydrotalcite with high specific surface area and rich pore canal structure, then carries out ultrasonic treatment, forms complex metal oxide after high-temperature calcination of a muffle furnace, and then loads platinum and ruthenium bimetallic to prepare the modified hydrotalcite-loaded platinum ruthenium catalyst. The catalyst has the advantages that cerium oxide is doped, the excellent pore channel structure of the hydrotalcite carrier is not influenced, the carrier can have rich oxygen vacancies, the carrier and the active metal component are more effectively combined when the active metal component is loaded, the metal synergistic effect is generated between the carrier and the active component as well as between the carrier and the bimetallic active component, the reaction activity of the catalyst is improved, the anchoring of the active metal is facilitated, the dispersity of the active component is improved, the agglomeration of metal particles in the reaction process is avoided, the stability of the catalyst is improved, and the service life of the catalyst is prolonged. In the hydrogenation reaction of the paranitrobenzamide, the catalyst has high catalytic activity and high selectivity, and simultaneously has excellent cycle performance, thereby effectively saving the cost.
Drawings
FIG. 1 is a scanning electron microscope image of a PtRu-NiFeCe/LDO catalyst provided by an embodiment of the invention.
Comparative example 1
(1) Preparation of hydrotalcite: dissolving Ni (NO 3)2·6H2O、Fe(NO3)3·9H2 O) with a molar ratio of 3:1 into 300ml of deionized water to prepare a mixed salt solution, preparing a mixed alkali solution from a NaOH solution with a mol/L and a Na 2CO3 solution with a mol/L of 0.5:1 according to a volume ratio of 8:1, simultaneously dripping the mixed salt solution and the mixed alkali solution into a beaker filled with deionized water to prepare a mixed solution, continuously stirring, keeping the pH of the mixed solution to be about 10.0, transferring the mixed solution into a stainless steel high-pressure reaction kettle after the dripping is completed, continuously stirring at a high temperature for 1h, continuously preserving heat and crystallizing for 20h after stopping stirring, centrifuging and washing to be neutral after the temperature is reduced to room temperature, drying, and grinding to obtain powdered nickel-iron hydrotalcite NiFe/LDH.
(2) Preparation of platinum ruthenium catalyst: a certain amount of chloroplatinic acid (platinum content: 37.5 wt%) and ruthenium chloride (ruthenium content: 37 wt%) were weighed and mixed with deionized water to obtain a platinum ruthenium precursor solution having a concentration of 3.3g/L, wherein the mass ratio of metal platinum to ruthenium was 5:1. Adding a platinum ruthenium precursor solution into the NiFe/LDH obtained by the preparation, uniformly stirring, carrying out ultrasonic treatment for 30min to obtain a pasty mixture, then putting the pasty mixture into a baking oven for drying to obtain a hydrotalcite precursor containing platinum ruthenium, putting the hydrotalcite precursor into a tubular furnace, introducing hydrogen-nitrogen mixed gas at 250 ℃, calcining for 2h to obtain a platinum ruthenium-loaded nickel-iron hydrotalcite catalyst (PtRu-NiFe/LDH), and marking as C-0; wherein, the loading of the platinum nano particles is 1% of the carrier mass, and the loading of the ruthenium nano particles is 0.2% of the carrier mass.
The obtained catalyst has an irregular block structure, is non-uniform in size and 300-500nm in size, is calcined in a tubular furnace at 250 ℃, and the hydrotalcite carrier in a hydroxide state cannot be converted into metal oxide, so that the prepared carrier is thick and is not beneficial to the high dispersion of metal particles. In addition, cerium oxide is not added into the carrier, so that the catalyst has a loose overall structure, poor mechanical strength and poor service life.
Comparative example 2
(1) The hydrotalcite was prepared in the same manner as in comparative example 1.
(2) Preparation of modified platinum ruthenium catalyst: a certain amount of chloroplatinic acid (the platinum content is 37.5 wt%) and ruthenium chloride (the ruthenium content is 37 wt%) are weighed and mixed with deionized water to prepare a platinum ruthenium precursor solution with the concentration of 3.3g/L, wherein the mass ratio of metal platinum to ruthenium is 5:1. Weighing a certain amount of cerium nitrate solution (Ce (NO 3)3·6H2 O), wherein the mass ratio of metal platinum to cerium is 3.5:1, adding NiFe/LDH into the cerium nitrate solution, stirring uniformly, adding a platinum ruthenium precursor solution into the NiFe/LDH containing cerium, performing ultrasonic treatment for 30min to obtain a pasty mixture, drying the pasty mixture in an oven to obtain a modified hydrotalcite precursor containing platinum ruthenium cerium, placing the modified hydrotalcite precursor into a tubular furnace, introducing hydrogen-nitrogen mixed gas at 250 ℃, calcining for 2h to obtain a platinum ruthenium loaded modified nickel iron hydrotalcite catalyst (PtRu-NiFeCe/LDH), and marking as C-1, wherein the loading amount of platinum nano particles is 1% of the carrier mass, and the loading amount of ruthenium nano particles is 0.2% of the carrier mass.
Comparative example 3
(1) Preparation of modified hydrotalcite carrier: dissolving Ni (NO 3)2·6H2O、Fe(NO3)3·9H2 O) with a molar ratio of 3:1 into 300mL of deionized water, adding a certain amount of cerium nitrate solution (Ce (NO 3)3·6H2 O) to prepare a mixed salt solution, wherein Ni (NO 3)2·6H2 O and Ce (NO 3)3·6H2 O) with a molar ratio of 850:1 are prepared into a mixed alkali solution according to a volume ratio of 8:1 by 1mol/L NaOH solution and 0.5mol/L Na 2CO3 solution, simultaneously dripping the mixed salt solution and the mixed alkali solution into a beaker filled with deionized water to prepare cerium doped mixed solution, continuously stirring, keeping the pH of the mixed solution to be about 10.0, transferring the mixed solution into a stainless steel high-pressure reaction kettle after the dripping is completed, continuously stirring at a high temperature for 1h, continuously preserving heat and crystallizing for 20h after stopping stirring, centrifugally washing to be neutral after the temperature is reduced to room temperature, and drying and grinding to obtain powdery modified nickel-iron hydrotalcite NiFeCe/LDH.
(2) Preparation of modified platinum ruthenium catalyst: a certain amount of chloroplatinic acid (the platinum content is 37.5 wt%) and ruthenium chloride (the ruthenium content is 37 wt%) are weighed and mixed with deionized water to prepare a platinum ruthenium precursor solution with the concentration of 3.3g/L, wherein the mass ratio of metal platinum to ruthenium is 5:1. Adding a platinum ruthenium precursor solution into NiFeCe/LDH carrier, stirring uniformly, carrying out ultrasonic treatment for 30min to obtain a pasty mixture, then putting the pasty mixture into an oven for drying to obtain a modified hydrotalcite precursor containing platinum ruthenium, putting the modified hydrotalcite precursor into a tube furnace, introducing hydrogen-nitrogen mixed gas at 250 ℃, calcining for 2h, and obtaining a platinum ruthenium loaded modified ferronickel hydrotalcite-like catalyst (PtRu-NiFeCe/LDH) which is marked as C-2. Wherein, the loading of the platinum nano particles is 1% of the carrier mass, and the loading of the ruthenium nano particles is 0.2% of the carrier mass.
Example 1
(1) The hydrotalcite was prepared in the same manner as in comparative example 1.
(2) Preparation of modified hydrotalcite carrier: preparing 0.02mol/L Ce (NO 3)3·6H2 O solution), uniformly spraying 2mLCe (NO 3)3·6H2 O solution onto 2g of the obtained NiFe/LDH under stirring by using a metering pump through an ultrasonic sprayer, carrying out ultrasonic treatment for 30min, transferring the carrier with the cerium solution into a crucible, and calcining in a muffle furnace at a temperature rising rate of 400 ℃ for 5h to obtain the cerium oxide-doped nickel iron oxide carrier (NiFeCe/LDO), wherein the doping amount of cerium oxide accounts for 0.35% of the mass of the modified hydrotalcite carrier.
(3) Preparation of modified platinum ruthenium catalyst: the amounts of chloroplatinic acid (platinum content: 37.5 wt%) and ruthenium chloride (ruthenium content: 37 wt%) were weighed and mixed with deionized water. A platinum ruthenium precursor solution with a concentration of 3.3g/L was prepared, wherein the mass ratio of metallic platinum to ruthenium was 5:1. Adding the platinum ruthenium precursor solution into NiFeCe/LDO carrier, stirring uniformly, and ultrasonic treating for 30min to obtain slurry mixture. And then the slurry mixture is put into a baking oven for drying to obtain a modified hydrotalcite precursor containing platinum and ruthenium, the modified hydrotalcite precursor is put into a tube furnace, hydrogen and nitrogen mixed gas is introduced at 250 ℃ and calcined for 2 hours, and the platinum and ruthenium loaded modified nickel-iron hydrotalcite catalyst (PtRu-NiFeCe/LDO) is obtained and is marked as C-3. Wherein, the loading of the platinum nano particles is 1% of the carrier mass, and the loading of the ruthenium nano particles is 0.2% of the carrier mass.
Example 2
(1) The hydrotalcite was prepared in the same manner as in comparative example 1.
(2) The procedure for the preparation of the modified hydrotalcite support was different from example 3 in that the muffle furnace calcination temperature was 500℃and the other conditions were the same as in example 3.
(3) The procedure for preparing the modified platinum ruthenium catalyst was the same as in example 3 to prepare a cerium oxide doped nickel iron hydrotalcite supported platinum ruthenium metal catalyst (PtRu-NiFeCe/LDO), designated C-4 (see FIG. 1).
As can be seen from FIG. 1, the catalyst appearance is composed of a multi-layer round sheet structure with the diameter of 100-150nm, and in the preparation process of the carrier, when the calcining temperature in a muffle furnace is 500 ℃, the prepared sheet structure has uniform size, which is favorable for the distribution of metal particles, so that the catalytic performance is better, and meanwhile, the cerium oxide and hydrotalcite can be better combined at the temperature, the prepared sheet carrier has stable structure, the mechanical strength is enhanced, and the service life of the catalyst is prolonged.
Example 3
(1) The hydrotalcite support was prepared in the same manner as in comparative example 1.
(2) The procedure for the preparation of the modified hydrotalcite support was different from example 3 in that the muffle furnace calcination temperature was 600℃and the other conditions were the same as in example 3.
(3) The procedure of the modified platinum ruthenium catalyst was the same as in example 3 to obtain a cerium oxide doped nickel iron hydrotalcite supported platinum ruthenium metal catalyst (PtRu-NiFeCe/LDO), designated C-5.
Example 4
(1) The hydrotalcite was prepared in the same manner as in the comparative example.
(2) The procedure for preparation of the modified hydrotalcite support was different from example 3 in that Ce (concentration of NO 3)3·6H2 O solution was 0.01 mol/L), and the other conditions were the same as in example 3, except that the doped amount of cerium oxide was 0.175% by mass of the modified hydrotalcite support.
(3) The procedure of the modified platinum ruthenium catalyst was the same as in example 3 to obtain a cerium oxide doped nickel iron hydrotalcite-like supported platinum ruthenium metal catalyst (PtRu-NiFeCe/LDO), designated C-6.
Example 5
(1) The hydrotalcite was prepared in the same manner as in comparative example 1.
(2) The procedure for preparation of the modified hydrotalcite support was different from example 3 in that Ce (concentration of NO 3)3·6H2 O solution was 0.03 mol/L), and the other conditions were the same as in example 3, except that the doped amount of cerium oxide was 0.525% by mass of the modified hydrotalcite support.
(3) The procedure for preparing the modified Pt-Ru catalyst was the same as in example 3, wherein a cerium oxide doped Ni-Fe hydrotalcite-like supported Pt-Ru metal catalyst (PtRu-NiFeCe/LDO) was prepared and designated C-7.
Example 6
(1) The hydrotalcite was prepared in the same manner as in comparative example 1.
(2) The procedure for the preparation of the modified hydrotalcite support was the same as in example 4.
(3) The modified platinum ruthenium catalyst preparation procedure differs from example 3 in that the mass ratio of metallic platinum to ruthenium is about 3:1, with the other conditions being the same as in example 3. The prepared platinum ruthenium loaded modified nickel iron hydrotalcite-like catalyst (PtRu-NiFeCe/LDO) is marked as C-8. The loading of the platinum nanoparticles was 1% of the mass of the support, and the loading of the ruthenium nanoparticles was 0.333% of the mass of the support.
Example 7
(1) The hydrotalcite was prepared in the same manner as in comparative example 1.
(2) The procedure for the preparation of the modified hydrotalcite support was the same as in example 4.
(3) The modified platinum ruthenium catalyst preparation procedure differs from example 3 in that the mass ratio of metallic platinum to ruthenium is about 9:1, with the other conditions being the same as in example 3. The prepared platinum ruthenium loaded modified nickel iron hydrotalcite-like catalyst (PtRu-NiFeCe/LDO) is marked as C-9. The loading of the platinum nanoparticles was 1% of the mass of the support, and the loading of the ruthenium nanoparticles was 0.111% of the mass of the support.
The catalysts prepared in the above comparative examples and examples were used in hydrogenation reactions to prepare p-aminobenzamide using p-nitrobenzamide as a starting material.
The evaluation conditions were as follows: 20g of p-nitrobenzamide and 35g of methanol serving as a solvent are added into a 100mL stainless steel high-pressure reaction kettle, the catalyst of each embodiment is added, the catalyst accounts for 0.8% of the mass of the raw materials, the reaction temperature is 65 ℃, the pressure is 0.65-0.7MPa, and the rotating speed is 1200r/min. And (3) introducing hydrogen when the temperature is raised to the reaction temperature, taking the reaction as the end when the hydrogen consumption is zero, filtering and washing the reacted catalyst, and then adding the catalyst back to the reaction kettle for continuous application.
The reaction results were analyzed by high performance liquid chromatography area normalization method, and the Conversion (Conversion) and Selectivity (SELECTIVITY) were calculated as follows, wherein a is the reactant and B is the product.
The reaction activity is calculated according to the reaction time, the catalyst input amount and the reactant consumption, and the specific calculation formula is as follows, wherein n is the molar amount consumed by the reactant and the unit mmol; t is the reaction time, in s; m is the mass sum of Pt and Ru in the catalyst, and the unit g; r is the reactivity in mmol sub·s-1·gPtRu -1.
The catalyst performance of the catalyst prepared in each comparative example and the application time of the catalyst recovery in the catalytic hydrogenation reaction of the paranitrobenzamide are shown in table 1, the last application performance of part of the catalyst is shown in table 2, and the catalyst is not added in the application process.
TABLE 1 catalytic Performance of p-nitrobenzamide hydrogenation
Note that: the catalytic properties in the table are first reaction data.
TABLE 2 catalytic Properties after the hydrogenation of paranitrobenzamide
Note that: the catalytic performance is calculated from the last reaction data.
From the experimental data in tables 1 and 2, after the platinum ruthenium catalyst prepared by the unmodified hydrotalcite carrier is used, the conversion rate and selectivity of the product are obviously reduced, meanwhile, three groups of experimental data of C-1, C-2 and C-3 show that the modification method of hydrotalcite has a great influence on the performance of the catalyst, cerium is introduced into hydrotalcite by using an ultrasonic sprayer, cerium oxide is formed by calcination, the prepared modified hydrotalcite carrier has a better loading effect on active metal components, the reactivity of the catalyst is obviously improved, and the recycling performance is obviously enhanced, so that the fine mist of micron-sized liquid drops enables the hydrotalcite to absorb cerium solution more uniformly and effectively, the cerium oxide and hydrotalcite can be effectively combined, the excellent pore channel structure of hydrotalcite is not influenced, the anchoring of active metal is facilitated, the metal synergistic effect is generated between the carrier and the active component and the bimetallic active component, the dispersibility of the active metal is improved, the stability of the catalyst is improved, and the service life of the catalyst is prolonged.
Further, in the catalyst evaluation experiment, the performance of each catalyst was evaluated by selecting the catalyst to be 0.5%, 0.6%, 0.7%, 0.9%, and 1.0% of the mass of the raw material, respectively, while keeping other evaluation conditions unchanged. Experiments show that the reaction speed is increased, the conversion rate is gradually increased, and the selectivity is almost unchanged with the increase of the catalyst addition amount. Therefore, the economic cost and the catalyst performance are comprehensively considered, and when the catalyst accounts for 0.8 percent of the mass of the raw material, the catalyst performance is better and the economic cost is the lowest.
Under the condition of keeping the condition of the modified hydrotalcite carrier unchanged, the catalyst performance can be further improved by adjusting the calcination temperature, cerium doping amount and platinum ruthenium metal loading amount and proportion in the carrier preparation process, and more stable metal oxide can be formed when the calcination temperature is 500 ℃ in the hydrotalcite carrier modification preparation process, and the catalyst has larger specific surface area than the hydroxide precursor, wherein the cerium oxide doping amount formed by calcination accounts for 0.35% of the modified hydrotalcite carrier mass, plays the maximum role in carrier anchoring metal, and when the mass ratio of platinum ruthenium metal in the carrier is 5:1, the dispersibility of nano particles in the carrier is better, and the synergistic catalytic effect of bimetal is optimal, so that the catalyst has excellent catalytic performance.
Further, as can be seen from the above, the present invention adopts the incorporation of cerium oxide into hydrotalcite carrier, so that the carrier has rich oxygen vacancies, and has the advantages of providing ideal anchoring sites for metal nanoparticles when active metal components are loaded, promoting the carrier to be more effectively combined with the active metal components, generating metal synergistic effect between the carrier and the active components as well as between the carrier and the bimetallic active components, and improving the reactivity of the catalyst; the method for forming the complex metal oxide by uniformly spraying the trace cerium solution on the prepared hydrotalcite by using the ultrasonic sprayer in the preparation process of the modified hydrotalcite carrier has the advantages of not affecting the excellent pore channel structure of the hydrotalcite, ensuring more uniform distribution of cerium oxide on the carrier, facilitating the anchoring of active metal on the carrier, improving the dispersity of active components, avoiding the agglomeration of metal particles in the reaction process, improving the stability of the catalyst and prolonging the service life of the catalyst.
Claims (9)
1. A modified hydrotalcite-supported platinum ruthenium catalyst is characterized in that: the catalyst PtRu-XYCe/LDO takes hydrotalcite XY/LDH as a base material, cerium solution is doped and then put into a muffle furnace for calcination to prepare a modified hydrotalcite XYCe/LDO carrier, and platinum ruthenium nano particles are loaded on the modified hydrotalcite carrier by adopting an excessive dipping method to prepare a platinum ruthenium loaded modified hydrotalcite catalyst PtRu-XYCe/LDO; wherein X, Y can be the same or different and are selected from metal ions, the loading of platinum nano particles accounts for 0.1-3% of the carrier mass, the loading of ruthenium nano particles accounts for 0.05-1% of the carrier mass, the mass of hydrotalcite XY/LDO accounts for 95.475-99.675% of the modified hydrotalcite carrier mass, the doping amount of cerium oxide accounts for 0.175-0.525% of the modified hydrotalcite carrier mass, the molar ratio of X to Y is 2-5:1, and the molar ratio of X to Ce ions is 600-900:1;
the doping mode of the cerium solution and the hydrotalcite XY/LDH is that an ultrasonic sprayer is adopted to spray the cerium solution on the hydrotalcite.
2. The modified hydrotalcite-supported platinum ruthenium catalyst according to claim 1, wherein: the metal ions are divalent metal cations or trivalent metal cations; the divalent metal cation is at least one of Mg 2+、Zn2+、Ni2+, and the trivalent metal cation is Fe 3+ and/or A1 3+.
3. The process for preparing a modified hydrotalcite-supported platinum ruthenium catalyst according to claim 1, wherein: the temperature rise rate of the muffle furnace is 8-12 ℃/min, the calcining temperature of the muffle furnace is 400-600 ℃, and the calcining time of the muffle furnace is 2-7h.
4. A process for preparing a modified hydrotalcite supported platinum ruthenium catalyst according to claim 3, wherein: adding a platinum ruthenium precursor solution into the XYCe/LDO carrier, uniformly stirring, performing ultrasonic treatment to obtain a pasty mixture, and drying the pasty mixture to obtain a hydrotalcite precursor containing platinum ruthenium;
And (3) calcining the hydrotalcite precursor in a tube furnace, introducing hydrogen-nitrogen mixed gas, and carrying out reduction reaction to obtain the platinum-ruthenium supported modified hydrotalcite catalyst PtRu-XYCe/LDO.
5. The process for preparing a modified hydrotalcite-supported platinum ruthenium catalyst according to claim 4, wherein: the platinum ruthenium precursor solution is a mixed aqueous solution of a platinum compound and a ruthenium compound, and the mass ratio of platinum to ruthenium is 3-9:1; wherein the platinum compound is one or more of platinum nitrate, platinum chloride and chloroplatinic acid, and the ruthenium compound is one or more of ruthenium nitrate and ruthenium chloride.
6. The process for preparing a modified hydrotalcite-supported platinum ruthenium catalyst according to claim 4, wherein: the calcining temperature rise rate in the tube furnace is 5-8 ℃/min, the calcining temperature in the tube furnace is 150-300 ℃, and the calcining time is 2-4h.
7. Use of the modified hydrotalcite-supported platinum ruthenium catalyst according to claim 1, characterized in that: the catalyst is applied to the hydrogenation reaction of the paranitrobenzamide.
8. A process for preparing paraaminobenzamide characterized by: p-nitrobenzamide is used as a raw material, and the catalyst is prepared by catalytic hydrogenation reaction; wherein the addition amount of the catalyst is 0.5% -1.0% of the mass of the raw materials.
9. The method of preparing as claimed in claim 8, wherein: the catalyst after the catalytic reaction is filtered and washed, and can be continuously applied to the hydrogenation reaction of the paranitrobenzamide.
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