CN113952977B - Nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst, and preparation method and application thereof - Google Patents
Nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 165
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 69
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 55
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 39
- 239000007791 liquid phase Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000002253 acid Substances 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000009467 reduction Effects 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 21
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005470 impregnation Methods 0.000 claims abstract description 17
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- JTZLIGVBEAGAFZ-UHFFFAOYSA-N 5-chloro-4-methyl-2-nitrobenzenesulfonic acid Chemical compound CC1=CC([N+]([O-])=O)=C(S(O)(=O)=O)C=C1Cl JTZLIGVBEAGAFZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- SPXOTSHWBDUUMT-UHFFFAOYSA-N 138-42-1 Chemical compound OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 SPXOTSHWBDUUMT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 229950000244 sulfanilic acid Drugs 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 83
- 239000002002 slurry Substances 0.000 claims description 59
- 229910052757 nitrogen Inorganic materials 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 38
- 238000001816 cooling Methods 0.000 claims description 37
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 35
- 229910052717 sulfur Inorganic materials 0.000 claims description 35
- 239000011593 sulfur Substances 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 239000011261 inert gas Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000009210 therapy by ultrasound Methods 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000012535 impurity Substances 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 17
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 17
- 239000002023 wood Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 13
- 238000007598 dipping method Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 238000004108 freeze drying Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 239000004570 mortar (masonry) Substances 0.000 claims description 12
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- 238000007873 sieving Methods 0.000 claims description 12
- 229920001661 Chitosan Polymers 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 238000007710 freezing Methods 0.000 claims description 9
- 230000008014 freezing Effects 0.000 claims description 9
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- VYZCFAPUHSSYCC-UHFFFAOYSA-N 2-amino-5-chloro-4-methylbenzenesulfonic acid Chemical compound CC1=CC(N)=C(S(O)(=O)=O)C=C1Cl VYZCFAPUHSSYCC-UHFFFAOYSA-N 0.000 claims description 6
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 6
- 244000060011 Cocos nucifera Species 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 35
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 27
- 238000006722 reduction reaction Methods 0.000 description 25
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 17
- 229910052697 platinum Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- 230000002829 reductive effect Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910052737 gold Inorganic materials 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- GUWKQWHKSFBVAC-UHFFFAOYSA-N [C].[Au] Chemical compound [C].[Au] GUWKQWHKSFBVAC-UHFFFAOYSA-N 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000607 poisoning effect Effects 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 5
- 229940083342 drysol Drugs 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 231100000572 poisoning Toxicity 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000012696 Pd precursors Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
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- 238000002347 injection Methods 0.000 description 3
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- 238000010606 normalization Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- AKAXCFAQCKRJOT-UHFFFAOYSA-N 1-nitro-3-(3-nitrophenyl)sulfonylbenzene Chemical compound [O-][N+](=O)C1=CC=CC(S(=O)(=O)C=2C=C(C=CC=2)[N+]([O-])=O)=C1 AKAXCFAQCKRJOT-UHFFFAOYSA-N 0.000 description 2
- KSYSOIGKYYSWBD-UHFFFAOYSA-N 2,3-dinitrothiophene Chemical compound [O-][N+](=O)C=1C=CSC=1[N+]([O-])=O KSYSOIGKYYSWBD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000012847 fine chemical Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 125000001477 organic nitrogen group Chemical group 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- ODPYDILFQYARBK-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2SC2=C1 ODPYDILFQYARBK-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
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Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
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Abstract
The invention discloses a nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst, and a preparation method and application thereof. The preparation method is implemented according to the following steps: (1) acid washing the activated carbon material; (2) Adding an activated carbon material into a solution of a pre-prepared noble metal precursor for impregnation treatment; (3) reducing the hydrogen to obtain a noble metal catalyst; (4) Coating the noble metal catalyst obtained in the step (3) with carbon; (5) Roasting in inert atmosphere to obtain the nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst. The invention provides application of the nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst in synthesizing aniline from nitrobenzene, synthesizing CLT acid from 2-nitro-4-methyl-5-chlorobenzenesulfonic acid by reduction, and synthesizing sulfanilic acid from p-nitrobenzenesulfonic acid by reduction, and the catalyst has high conversion rate, high selectivity and high stability.
Description
Field of the art
The invention relates to the technical field of catalysts, in particular to a nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst with good sulfur resistance, a preparation method and application thereof.
(II) background art
The noble metal catalyst can realize hydrogenation in chemical reaction and is widely applied to the fields of fine chemical industry, energy chemical industry, environmental protection and the like. However, the noble metal catalyst has higher requirements on the reaction environment, and the existence of trace sulfur impurities in the raw materials easily causes poisoning of the noble metal catalyst, so that the activity of the catalyst is reduced or even deactivated, the reaction is prolonged or even impossible to carry out, and the production is irreparably influenced. The removal of trace sulfur impurities from the feedstock requires significant effort and little effort. Therefore, research and development of a noble metal catalyst having good sulfur resistance has become a more practical problem.
In industrial production, sulfur impurities mainly exist in the form of organic sulfur and inorganic sulfur, and in liquid phase hydrogenation, the sulfur impurities are usually mainly in the form of organic sulfur, wherein low-valence sulfides such as disulfide, mercaptan and derivatives thereof have the strongest poisoning effect on the noble metal catalyst, and the activity in the noble metal catalyst is reduced or even deactivated due to the concentration of ppm level.
In the current production application, the catalyst activity caused by sulfur impurities is low, even complete inactivation and the difficulty in recovering the catalyst activity are serious barriers for restricting numerous catalytic processes to realize industrialization. Because sulfur-containing compounds can be chemisorbed on the active metal, covering the active sites (or dissociative adsorption occurs on the metal, strong bonding action occurs between the reduced sulfur and the noble metal), resulting in deactivation of the catalyst; under more severe conditions, sulfur atoms even gradually enter the active metal phase, forming a crystalline phase such as a sulfide salt, which forms to some extent a further decrease in the activity of the catalyst.
In order to avoid this, it is necessary to effectively suppress the process of occupying the active site of the noble metal by the sulfur component by letting the noble metal hydrogenation catalyst under the premise of ensuring the hydrogenation activity. The structure of the noble metal hydrogenation catalyst needs to be studied specifically, the interaction between the active component of the noble metal and the sulfur component is weakened, and the effect of reducing the adsorption capacity of the sulfur component on the noble metal is exerted, so that the active site of the noble metal is protected, the activity of the hydrogenation group is kept, the noble metal hydrogenation catalyst has stronger sulfur resistance, and the service life of the noble metal hydrogenation catalyst is prolonged. The noble metal hydrogenation catalyst with good sulfur resistance has extremely broad market prospect in the liquid phase catalytic hydrogenation process with higher sulfur content in the fields of coping with energy chemical industry, fine chemical industry, environmental protection and the like.
(III) summary of the invention
The invention aims to overcome and supplement the defects existing in the prior art, and provides a noble metal liquid-phase hydrogenation catalyst with good sulfur resistance, a preparation method and application thereof, and the hydrogenation performance and the sulfur poisoning resistance of the catalyst are improved.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the preparation method of the nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst is implemented according to the following steps:
(1) Acid washing: adding the activated carbon material into a nitric acid aqueous solution, heating to 60-100 ℃ and maintaining for 4-6 hours, cooling, washing with deionized water for 3-5 times, and drying in a blast oven at 80-120 ℃ for 2-6 hours;
(2) Dipping: adding the acid-washed active carbon material into a solution of a pre-prepared noble metal precursor by adopting an impregnation method (preferably an isovolumetric impregnation method), stirring for 15-60 min, impregnating for 12-36h at room temperature, and drying the impregnated catalyst in a vacuum oven for 4-12h at 80-120 ℃;
(3) And (3) reduction: placing the catalyst dried in the vacuum in the step (2) in a tube furnace, roasting and reducing a noble metal precursor in a hydrogen atmosphere, fully cooling, and aging in a drying oven at room temperature for 12-24 hours to obtain a noble metal catalyst;
(4) Carbon coating: adding the noble metal catalyst obtained in the step (3) into a pre-prepared organic carbon nitrogen material solution, stirring the formed slurry at room temperature for 10-60 min, carrying out ultrasonic treatment for 15-60 min, transferring the slurry into a reaction kettle, introducing nitrogen for protection, heating to 50-100 ℃ at a stirring rate of 500-1000 rpm, keeping the temperature for 2-6 h, cooling, keeping the temperature at room temperature for 6-12h, carrying out ultrasonic treatment for 15-60 min, placing the cooled slurry on a copper ingot placed in liquid nitrogen, freezing the slurry from bottom to top for 6-18h, and placing the frozen slurry in a freeze dryer for freeze drying treatment for 24-48h; the organic nitrogen-containing carbon material is one or more of urea formaldehyde resin, polyethylene diamine, polyvinylpyrrolidone (PVP), polyacrylonitrile and chitosan, and the mass ratio of the organic nitrogen-containing carbon material to the noble metal catalyst obtained in the step (3) is 20-100%;
(5) Roasting: and (3) fully grinding the slurry obtained in the step (4) in a mortar, sieving, placing in a tube furnace, roasting in an inert gas atmosphere by adopting a temperature programming method, and cooling to obtain the nitrogen-doped carbon-coated noble metal catalyst.
In the step (1), the activated carbon is one of coconut shell activated carbon, wood activated carbon and coal activated carbon, the activated carbon is powdery microporous activated carbon, and the parameters of the activated carbon are as follows: specific surface area of 800-1400m 2 Per g, pore volume of 0.6-1.0cm 3 And/g, average pore size of 1.9-2.3nm.
In the step (1), the mass fraction of nitric acid in the aqueous nitric acid solution is preferably 5 to 20%.
In the step (2), the noble metal precursor is one of palladium chloride, chloroplatinic acid and chloroauric acid, the noble metal precursor is fed according to the mass fraction of noble metal in the catalyst of 1-10%, and the mass fraction of noble metal in the catalyst is calculated according to the following formula: mass fraction of noble metal in the catalyst = mass of noble metal in noble metal precursor/(mass of noble metal in noble metal precursor + mass of activated carbon) ×100%.
In the step (3), the roasting temperature of the tube furnace is preferably 150-300 ℃, the roasting temperature is maintained at the temperature for 0.5-1 h, the temperature is continuously raised to 300-600 ℃, the roasting temperature is maintained at the temperature for 2-3 h, wherein the heating rate is 5-10 ℃/min, and the hydrogen flow rate is 40-100mL/min.
In the step (4), the solvent of the organic carbon-nitrogen material solution is preferably capable of dissolving the organic nitrogen-carbon material, and specifically deionized water, aqueous nitric acid (10 wt%) and aqueous acetic acid (1 wt%) may be selected. The concentration of the organic carbon-nitrogen material in the organic carbon-nitrogen material solution may be determined according to the dissolution condition in the solvent and the impregnation method (e.g., equal volume impregnation).
In the step (5), the roasting temperature of the tube furnace is preferably 300-800 ℃, the temperature is maintained for 2-4 hours, the heating rate is 2-10 ℃/min, the inert gas atmosphere is one of nitrogen, argon and helium, and the flow rate of the inert gas is 50-300mL/min.
In a second aspect, the present invention provides a nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst prepared according to the above-described preparation method.
According to the preparation method of the nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst, the nitrogen-doped carbon coating layer can be formed on the surface of the noble metal particles, the noble metal can be basically coated by the coating layer, the thickness range of the coating layer is 0.6-1.0nm, and the catalyst is mainly of a non-porous structure.
In a third aspect, the invention provides an application of the nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst in synthesizing aniline through nitrobenzene hydrogenation reduction.
Further, the nitrobenzene contains sulfur impurities, and the sulfur impurities are dinitrothiophene. Further, the sulfur impurity is present in the reaction solution in the range of 500 to 1000ppm.
Further, the application is specifically: adding nitrobenzene solution into a reaction kettle, wherein the solvent of the nitrobenzene solution is absolute ethyl alcohol, the mass fraction of nitrobenzene is 20-40 wt% and sulfur impurities are contained, and reacting for 0.5-1.5 h in the batch reaction kettle at the reaction temperature of 60-90 ℃ and the hydrogen pressure of 0.6-1.4 MPa and the rotating speed of 600-1200 rpm to generate aniline.
After the nitrobenzene hydrogenation reduction reaction is finished, the product can be obtained and the catalyst can be recovered through a conventional post-treatment process.
In a fourth aspect, the invention provides an application of the nitrogen-doped carbon-coated noble metal liquid phase hydrogenation catalyst in 2-amino-4-methyl-5-chlorobenzenesulfonic acid hydrogenation reduction synthesis of 2-amino-4-methyl-5-chlorobenzenesulfonic acid (CLT acid).
Further, the 2-nitro-4-methyl-5-chlorobenzenesulfonic acid contains sulfur impurities, wherein the sulfur impurities are 2-nitro-4-methyl-5-chlorophenyl sulfone. Further, the sulfur impurity is in the range of 200 to 500ppm in the reaction liquid.
Further, the application is specifically: adding 2-nitro-4-methyl-5-chlorobenzenesulfonic acid aqueous solution into a reaction kettle, wherein the pH range of the 2-nitro-4-methyl-5-chlorobenzenesulfonic acid aqueous solution is 4.5-7.5, and the 2-nitro-4-methyl-5-chlorobenzenesulfonic acid mass fraction of 20-40 wt% reacts for 1.5-3 hours in the batch reaction kettle under the conditions that the reaction temperature is 70-100 ℃, the hydrogen pressure is 0.8-1.6 MPa and the rotating speed is 600-1200 rpm, so as to generate 2-amino-4-methyl-5-chlorobenzenesulfonic acid (CLT acid).
After the hydrogenation reduction reaction of the 2-nitro-4-methyl-5-chlorobenzenesulfonic acid is finished, a product can be obtained and a catalyst can be recovered through a conventional post-treatment process.
In a fifth aspect, the invention provides an application of the nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst in synthesizing p-amino benzenesulfonic acid by hydrogenation reduction of p-nitro benzenesulfonic acid.
Further, the p-nitro benzenesulfonic acid contains sulfur impurities, wherein the sulfur impurities are 3, 3-dinitrodiphenyl sulfone. Further, the sulfur impurity is in the range of 200 to 500ppm in the reaction liquid.
Further, the application is specifically: adding p-nitrobenzenesulfonic acid aqueous solution into a reaction kettle, wherein the p-nitrobenzenesulfonic acid aqueous solution contains sulfur impurities, the mass fraction of the p-nitrobenzenesulfonic acid is 20-40 wt%, and the pH range is 4.5-7.5; reacting for 1.5-2.5 hours in a batch reactor under the conditions that the reaction temperature is 60-100 ℃, the hydrogen pressure is 0.6-1.2 MPa and the rotating speed is 600-1200 rpm, so as to generate the p-amino benzenesulfonic acid.
After the p-nitro benzenesulfonic acid hydrogenation reduction reaction is finished, the product can be obtained and the catalyst can be recovered through a conventional post-treatment process.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation process is simple, and the catalyst is stable and reliable, thereby being beneficial to industrial production.
(2) The nitrogen-doped carbon coating layer obtained by the preparation method disclosed by the invention has good hydrophilicity and higher isoelectric point, so that the contact and adsorption of sulfur impurities in reaction liquid and noble metal precursors are isolated, and the agglomeration and falling-off of noble metals can be prevented to a certain extent. Therefore, on the premise of ensuring the activity of the catalyst, the sulfur poisoning resistance of the noble metal catalyst is obviously improved under the combined action of the nitrogen doped carbon coating layer and the particle size of the smaller noble metal, so that the service life of the catalyst is greatly prolonged.
(3) The nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst prepared by the method is suitable for the processes of synthesizing aniline from nitrobenzene, reducing and synthesizing CLT acid, preparing sulfanilic acid from p-nitrobenzenesulfonic acid by reduction, and the like, and shows high conversion rate, high selectivity and high stability.
(IV) description of the drawings
FIG. 1 is a graph showing the results of 10 applications of the catalysts of example 3 and comparative example 1 to nitrobenzene hydrogenation;
FIG. 2 is the results of the catalysts of example 3 and comparative example 1 for 10 applications of reduction synthesis of CLT acid;
FIG. 3 is the result of the catalyst of example 3 and comparative example 1 for 10 applications in the reductive synthesis of sulfanilic acid;
fig. 4 is a TEM image of the catalyst of example 3.
(fifth) detailed description of the invention
The technical scheme of the present invention is further described below with reference to the specific embodiments, but the scope of the present invention is not limited thereto.
The activated carbon used in the examples of the present invention was produced by the company of the division of the carbon industry, xinsen, fujian, and the parameters of the activated carbon are shown in the following table:
sources of the noble metal precursors used in the examples are: palladium chloride is produced by Macklin company, the Pd content is 59-60%, the product number is P815731-5g, and the palladium chloride is dissolved in concentrated hydrochloric acid to prepare a palladium chloride acid solution; chloroplatinic acid is produced by Alfa corporation, hexachloroplatinic (iv) acid hexahydrate, 99.9%metals basis, under the designation 01051-5 g; chloroauric acid is produced by Macklin corporation, 48-50% Au basic, cat# C805628-5g.
Example 1
Step 1, acid washing: 2g of coal-based activated carbon is added into 50mL of 5wt% nitric acid aqueous solution, heated to 80 ℃ and maintained for 4 hours, cooled, washed 3-5 times with deionized water and dried in a forced air oven at 110 ℃ for 3 hours.
Step 2, dipping: adding the coal activated carbon dried in the step 1 into a pre-prepared chloropalladite solution (the palladium concentration is 0.010 g/mL) by adopting an isovolumetric impregnation method, stirring for 0.5h, impregnating for 24h at room temperature, and drying the impregnated catalyst in a vacuum oven at 100 ℃ for 6h; wherein the mass fraction of palladium in the catalyst is 2%.
And 3, reduction: placing the catalyst dried in the step 2 in vacuum in a tube furnace, roasting and reducing a palladium precursor in a hydrogen atmosphere, fully cooling to obtain a palladium-carbon catalyst, and aging in a drying oven for 10 hours at room temperature; wherein, the roasting temperature of the tube furnace is 200 ℃, the temperature is maintained for 1h, the temperature is continuously raised to 350 ℃, the temperature is maintained for 2h, the heating rates are 10 ℃/min, and the hydrogen flow rate is 80mL/min.
Step 4: adding quantitative chitosan into acetic acid aqueous solution (1 wt%) to make chitosan concentration be 0.065g/mL, adding palladium-carbon catalyst reduced in step 3 into chitosan solution, stirring formed slurry at room temperature for 30min, making ultrasonic treatment for 60min, transferring the slurry into reaction kettle, introducing nitrogen gas to make protection, heating to 80 deg.C at stirring speed of 1000rpm, holding at this temperature for 4 hr, cooling, holding at room temperature for 8 hr, making ultrasonic slurry on copper ingot placed in liquid nitrogen so as to make the slurry be frozen from bottom to top, freezing for 12 hr, and placing the fully frozen slurry into freeze-drying machine to make freeze-drying treatment for about 36 hr. Wherein the mass ratio of the chitosan to the catalyst after roasting and reducing in the step 3 is 65%.
Step 5: fully grinding the dried slurry in the step 4 in a mortar, sieving, placing in a tube furnace, roasting in an inert gas atmosphere by adopting a temperature programming method, and fully cooling to obtain the nitrogen-doped carbon-coated palladium-carbon catalyst; wherein the roasting temperature of the tube furnace is 650 ℃, the temperature is maintained for 2 hours, the heating rate is 4 ℃/min, the inert gas atmosphere is nitrogen, and the nitrogen flow rate is 150mL/min.
Example 2
Step 1, acid washing: 2g of coconut shell activated carbon is added into 50mL of 10wt% nitric acid aqueous solution, heated to 80 ℃ and maintained for 6h, cooled, washed 3-5 times with deionized water and dried in a forced air oven at 100 ℃ for 3h.
Step 2, dipping: adding the coconut shell activated carbon dried in the step 1 into a solution of pre-prepared chloroauric acid (the gold concentration is 0.015 g/mL) by adopting an isovolumetric impregnation method, stirring for 0.5h, impregnating for 24h at room temperature, and drying the impregnated catalyst in a vacuum oven at 120 ℃ for 6h; wherein the mass fraction of gold in the catalyst is 3%.
And 3, reduction: placing the catalyst dried in the step 2 in vacuum in a tube furnace, roasting and reducing a gold precursor in a hydrogen atmosphere, fully cooling to obtain a gold-carbon catalyst, and aging in a drying oven for 10 hours at room temperature; wherein, the roasting temperature of the tube furnace is 250 ℃, the temperature is maintained for 0.5h, the temperature is continuously raised to 400 ℃, the temperature is maintained for 3h, the heating rate is 10 ℃/min, and the hydrogen flow rate is 60mL/min.
Step 4 nitrogen doped carbon coating: adding quantitative polyacrylonitrile into a 10wt% nitric acid solution to enable the concentration of the polyacrylonitrile to be 0.035g/mL, adding the gold-carbon catalyst reduced in the step 3 into the polyacrylonitrile solution, stirring the formed slurry at room temperature for 15min, carrying out ultrasonic treatment for 30min, transferring the slurry into a reaction kettle, introducing nitrogen for protection, heating to 60 ℃ at a stirring speed of 1000rpm, keeping the temperature for 6h, cooling, keeping the temperature at room temperature for 8h, carrying out ultrasonic treatment for 30min, placing the ultrasonic slurry on a copper ingot placed in liquid nitrogen, freezing for 8h, enabling the slurry to be frozen from bottom to top, and placing the fully frozen slurry into a freeze dryer for freeze drying treatment for about 24h. Wherein the mass ratio of the polyacrylonitrile to the catalyst after roasting and reducing in the step 3 is 35%.
Step 5: fully grinding the dried slurry in the step 4 in a mortar, sieving, placing in a tube furnace, roasting in an inert gas atmosphere by adopting a temperature programming method, and fully cooling to obtain the nitrogen-doped carbon-coated gold-carbon catalyst; wherein the roasting temperature of the tube furnace is 600 ℃, and the tube furnace is maintained at the roasting temperature for 3 hours, wherein the heating rate is 6 ℃/min. The inert gas atmosphere was argon, and the argon flow rate was 100mL/min.
Example 3
Step 1, acid washing: 2g of wood-based activated carbon is added into 50mL of 15wt% nitric acid aqueous solution, heated to 60 ℃ and maintained for 6 hours, cooled, washed 3-5 times with deionized water and dried in a forced air oven at 90 ℃ for 3 hours.
Step 2, dipping: adding the wood activated carbon dried in the step 1 into a solution of pre-prepared chloroplatinic acid (the platinum concentration is 0.023 g/mL) by adopting an isovolumetric impregnation method, stirring for 0.5h, impregnating for 24h at room temperature, and drying the impregnated catalyst in a vacuum oven at 110 ℃ for 6h; wherein the mass fraction of platinum in the catalyst is 5%.
And 3, reduction: placing the catalyst dried in the step 2 in vacuum in a tube furnace, roasting and reducing a platinum precursor in a hydrogen atmosphere, fully cooling to obtain a platinum-carbon catalyst, and aging in a drying oven for 10 hours at room temperature; wherein, the roasting temperature of the tube furnace is 250 ℃, the temperature is maintained for 0.5h, the temperature is continuously raised to 500 ℃, the temperature is maintained for 2h, the heating rates are 8 ℃/min, and the hydrogen flow rate is 100mL/min.
Step 4 nitrogen doped carbon coating: adding quantitative urea-formaldehyde resin into deionized water to enable the concentration of the urea-formaldehyde resin to be 0.050g/mL, adding the reduced platinum carbon catalyst in the step 3 into the pre-prepared urea-formaldehyde resin solution, stirring the formed slurry at room temperature for 40min, performing ultrasonic treatment for 20min, transferring the slurry into a reaction kettle, introducing nitrogen for protection, heating to 50 ℃ at the stirring speed of 600rpm, keeping the temperature for 8h, cooling, keeping the temperature for 8h at room temperature, performing ultrasonic treatment for 20min, placing the ultrasonic slurry on a copper ingot placed in liquid nitrogen, freezing the slurry from bottom to top for 12h, and placing the fully frozen slurry into a freeze dryer for freeze drying treatment for about 24h. Wherein the mass ratio of the urea-formaldehyde resin to the catalyst after roasting and reducing in the step 3 is 50%.
Step 5: fully grinding the dry sol obtained in the step 4 in a mortar, sieving, placing in a tube furnace, roasting in an inert gas atmosphere by adopting a temperature programming method, and fully cooling to obtain the nitrogen-doped carbon-coated platinum-carbon catalyst; wherein the roasting temperature of the tube furnace is 750 ℃, and the tube furnace is maintained at the roasting temperature for 4 hours, wherein the heating rate is 8 ℃/min. The inert gas atmosphere was nitrogen and the argon flow rate was 50mL/min.
The TEM image of the catalyst of example 3 is shown in fig. 4, and it can be seen from fig. 4 that the Pt nanoparticles of the nitrogen-doped carbon-coated catalyst of example 3 are completely coated with a carbon layer, and the carbon layer is uniformly dense, and the average thickness of the carbon layer is about 0.7nm.
Example 4
Step 1, acid washing: 2g of wood-based activated carbon is added into 50mL of 8wt% nitric acid aqueous solution, heated to 80 ℃ and maintained for 4 hours, cooled, washed 3-5 times with deionized water and dried in a forced air oven at 120 ℃ for 3 hours.
Step 2, dipping: adding the wood activated carbon dried in the step 1 into a solution of pre-prepared chloroplatinic acid (the platinum concentration is 0.014 g/mL) by adopting an isovolumetric impregnation method, stirring for 0.5h, impregnating for 24h at room temperature, and drying the impregnated catalyst in a vacuum oven at 100 ℃ for 8h; wherein the mass fraction of platinum in the catalyst is 3%.
And 3, reduction: placing the catalyst dried in the step 2 in vacuum in a tube furnace, roasting and reducing a platinum precursor in a hydrogen atmosphere, fully cooling to obtain a platinum-carbon catalyst, and aging in a drying oven for 10 hours at room temperature; wherein, the roasting temperature of the tube furnace is 200 ℃, the temperature is maintained for 1h, the temperature is continuously raised to 400 ℃, the temperature is maintained for 2h, the heating rates are 8 ℃/min, and the hydrogen flow rate is 50mL/min.
Step 4: adding quantitative polyethylene diamine into deionized water to enable the concentration of the polyethylene diamine to be 0.060g/mL, adding the platinum carbon catalyst reduced in the step 3 into the polyethylene diamine solution, stirring the formed slurry at room temperature for 30min, performing ultrasonic treatment for 40min, transferring the slurry into a reaction kettle, introducing nitrogen for protection, heating to 80 ℃ at the stirring speed of 1000rpm, keeping the temperature for 3h, cooling, keeping the temperature at room temperature for 8h, performing ultrasonic treatment for 40min, placing the ultrasonic slurry on a copper ingot placed in liquid nitrogen, freezing for 8h, enabling the slurry to be frozen from bottom to top, and placing the fully frozen slurry into a freeze dryer for freeze drying treatment for about 36h. Wherein the mass ratio of the polyethylene diamine to the catalyst after roasting and reducing in the step 3 is 60 percent.
Step 5: fully grinding the dried slurry in the step 4 in a mortar, sieving, placing in a tube furnace, roasting in an inert gas atmosphere by adopting a temperature programming method, and fully cooling to obtain the nitrogen-doped carbon-coated palladium-carbon catalyst; wherein the roasting temperature of the tube furnace is 650 ℃, the temperature is maintained for 2 hours, the heating rate is 10 ℃/min, the inert gas atmosphere is nitrogen, and the nitrogen flow rate is 120mL/min.
Example 5
Step 1, acid washing: 2g of coconut charcoal is added into 50mL of 10wt% nitric acid aqueous solution, heated to 70 ℃ and maintained for 5h, cooled, washed 3-5 times with deionized water and dried in a forced air oven at 120 ℃ for 3h.
Step 2, dipping: adding the wood charcoal dried in the step 1 into a solution of pre-prepared chloropalladate (the palladium concentration is 0.010 g/mL) by adopting an isovolumetric impregnation method, stirring for 0.5h, impregnating for 24h at room temperature, and drying the impregnated catalyst in a vacuum oven at 100 ℃ for 6h; wherein the mass fraction of palladium in the catalyst is 2%.
And 3, reduction: placing the catalyst dried in the step 2 in vacuum in a tube furnace, roasting and reducing a palladium precursor in a hydrogen atmosphere, fully cooling to obtain a palladium-carbon catalyst, and aging in a drying oven for 10 hours at room temperature; wherein, the roasting temperature of the tube furnace is 250 ℃, the temperature is maintained for 0.5h, the temperature is continuously raised to 350 ℃, the temperature is maintained for 3h, the heating rates are 10 ℃/min, and the hydrogen flow rate is 40mL/min.
Step 4 nitrogen doped carbon coating: adding quantitative chitosan into acetic acid aqueous solution (1 wt%) to make chitosan concentration be 0.060g/mL, adding the reduced palladium-carbon catalyst in the step 3 into the pre-prepared chitosan solution, stirring the formed slurry at room temperature for 50min, conducting ultrasonic treatment for 30min, transferring the slurry into a reaction kettle, introducing nitrogen for protection, heating to 70 ℃ at a stirring rate of 800rpm, keeping at the temperature for 8h, cooling, keeping at room temperature for 8h, conducting ultrasonic treatment for 30min, placing the ultrasonic slurry on a copper ingot placed in liquid nitrogen to freeze the slurry from bottom to top for 12h, and placing the fully frozen slurry in a freeze dryer for freeze drying treatment for about 24h. Wherein the mass ratio of the chitosan to the reduced palladium-carbon catalyst in the step 3 is 60%.
And 5, roasting: fully grinding the dry sol obtained in the step 4 in a mortar, sieving, placing in a tube furnace, roasting in an inert gas atmosphere by adopting a temperature programming method, and fully cooling to obtain the nitrogen-doped carbon-coated palladium-carbon catalyst; wherein the roasting temperature of the tube furnace is 400 ℃, and the tube furnace is maintained at the roasting temperature for 2 hours, wherein the heating rate is 8 ℃/min. The inert gas atmosphere was nitrogen, and the nitrogen flow rate was 100mL/min.
Example 6
Step 1, acid washing: 2g of coconut shell activated carbon is added into 50mL of 8wt% nitric acid aqueous solution, heated to 90 ℃ and maintained for 5h, cooled, washed 3-5 times with deionized water and dried in a forced air oven at 120 ℃ for 3h.
Step 2, dipping: adding the coconut shell activated carbon dried in the step 1 into a solution of pre-prepared chloroplatinic acid (the platinum concentration is 0.019 g/mL) by adopting an isovolumetric impregnation method, stirring for 0.5h, impregnating for 24h at room temperature, and drying the impregnated catalyst in a vacuum oven at 110 ℃ for 5h; wherein the mass fraction of palladium in the catalyst is 4%.
And 3, reduction: placing the catalyst dried in the step 2 in vacuum in a tube furnace, roasting and reducing a platinum precursor in a hydrogen atmosphere, fully cooling to obtain a platinum-carbon catalyst, and aging in a drying oven for 10 hours at room temperature; wherein, the roasting temperature of the tube furnace is 200 ℃, the temperature is maintained for 0.5h, the temperature is continuously raised to 440 ℃, the temperature is maintained for 3h, the heating rates are 10 ℃/min, and the hydrogen flow rate is 50mL/min.
Step 4 nitrogen doped carbon coating: adding quantitative polyvinylpyrrolidone (PVP) into deionized water to enable PVP concentration to be 0.070g/mL, adding the reduced platinum carbon catalyst in the step 3 into a pre-prepared polyvinylpyrrolidone solution, stirring the formed slurry for 20min at room temperature, carrying out ultrasonic treatment for 30min, transferring the slurry into a reaction kettle, introducing nitrogen for protection, heating to 70 ℃ at a stirring rate of 800rpm, keeping the temperature at the temperature for 8h, cooling, keeping the temperature at the room temperature for 8h, carrying out ultrasonic treatment for 30min, placing the ultrasonic slurry on a copper ingot placed in liquid nitrogen, freezing the slurry from bottom to top for 8h, and placing the fully frozen slurry into a freeze dryer for freeze drying treatment for about 24h. Wherein the mass ratio of the polyvinylpyrrolidone to the reduced platinum-carbon catalyst is 70%.
And 5, roasting: fully grinding the dry sol obtained in the step 4 in a mortar, sieving, placing in a tube furnace, roasting in an inert gas atmosphere by adopting a temperature programming method, and fully cooling to obtain the nitrogen-doped carbon-coated platinum-carbon catalyst; wherein the roasting temperature of the tube furnace is 500 ℃, and the tube furnace is maintained at the roasting temperature for 2 hours, wherein the heating rate is 10 ℃/min. The inert gas atmosphere was nitrogen, and the nitrogen flow rate was 100mL/min.
Example 7
Step 1, acid washing: 2g of wood-based activated carbon is added into 50mL of 12wt% acid aqueous solution, heated to 100 ℃ and maintained for 4 hours, cooled, washed 3-5 times with deionized water and dried in a forced air oven at 100 ℃ for 3 hours.
Step 2, dipping: adding the wood activated carbon dried in the step 1 into a solution of pre-prepared chloroauric acid (the gold concentration is 0.022 g/mL) by adopting an isovolumetric impregnation method, stirring for 0.5h, impregnating for 24h at room temperature, and drying the impregnated catalyst in a vacuum oven at 100 ℃ for 6h; wherein the mass fraction of gold in the catalyst is 5%.
And 3, reduction: placing the catalyst dried in the step 2 in vacuum in a tube furnace, roasting and reducing a gold precursor in a hydrogen atmosphere, fully cooling to obtain a gold-carbon catalyst, and aging in a drying oven for 10 hours at room temperature; wherein, the roasting temperature of the tube furnace is 300 ℃, the temperature is maintained for 0.5h, the temperature is continuously raised to 350 ℃, the temperature is maintained for 3h, the heating rate is 5 ℃/min, and the hydrogen flow rate is 60mL/min.
Step 4 nitrogen doped carbon coating: adding quantitative urea-formaldehyde resin into deionized water to enable the concentration of the urea-formaldehyde resin to be 0.040g/mL, adding the gold-carbon catalyst reduced in the step 3 into the urea-formaldehyde resin mixed solution, stirring the formed slurry at room temperature for 60min, carrying out ultrasonic treatment for 30min, transferring the slurry into a reaction kettle, introducing nitrogen for protection, heating to 80 ℃ at the stirring speed of 800rpm, keeping the temperature for 6h, cooling, keeping the temperature for 8h at room temperature, carrying out ultrasonic treatment for 30min, placing the ultrasonic slurry on a copper ingot placed in liquid nitrogen, freezing the slurry from bottom to top, and placing the fully frozen slurry in a freeze dryer for freeze drying treatment for about 24h. Wherein, the mass ratio of the urea-formaldehyde resin to the catalyst after roasting and reducing in the step 3 is 40 percent.
Step 5: fully grinding the dried slurry in the step 4 in a mortar, sieving, placing in a tube furnace, roasting in an inert gas atmosphere by adopting a temperature programming method, and fully cooling to obtain the nitrogen-doped carbon-coated gold-carbon catalyst; wherein the roasting temperature of the tube furnace is 700 ℃, and the tube furnace is maintained at the roasting temperature for 3 hours, wherein the heating rate is 5 ℃/min. The inert gas atmosphere was nitrogen, and the nitrogen flow rate was 100mL/min.
Example 8
Step 1, acid washing: 2g of coal activated carbon is added into 50mL of 10wt% nitric acid aqueous solution, heated to 100 ℃ and maintained for 4 hours, cooled, washed 3-5 times by deionized water, and dried in a blast oven at 100 ℃ for 3 hours.
Step 2, dipping: adding the coal activated carbon dried in the step 1 into a solution of pre-prepared chloropalladate (the palladium concentration is 0.015 g/mL) by adopting an isovolumetric impregnation method, stirring for 0.5h, impregnating for 24h at room temperature, and drying the impregnated catalyst in a vacuum oven at 110 ℃ for 8h; wherein the mass fraction of palladium in the catalyst is 3%.
And 3, reduction: placing the catalyst dried in the step 2 in vacuum in a tube furnace, roasting and reducing a palladium precursor in a hydrogen atmosphere, fully cooling to obtain a palladium-carbon catalyst, and aging in a drying oven for 10 hours at room temperature; wherein, the roasting temperature of the tube furnace is 200 ℃, the temperature is maintained for 1h, the temperature is continuously raised to 400 ℃, the temperature is maintained for 2h, the heating rates are 8 ℃/min, and the hydrogen flow rate is 50mL/min.
Step 4: adding quantitative polyethylene diamine into deionized water to enable the concentration of the polyethylene diamine to be 0.050g/mL, adding the palladium-carbon catalyst reduced in the step 3 into the polyethylene diamine solution, stirring the formed slurry at room temperature for 10min, performing ultrasonic treatment for 60min, transferring the slurry into a reaction kettle, introducing nitrogen for protection, heating to 70 ℃ at a stirring rate of 1000rpm, keeping the temperature for 3h, cooling, keeping the temperature at room temperature for 8h, performing ultrasonic treatment for 40min, placing the ultrasonic slurry on a copper ingot placed in liquid nitrogen, freezing the slurry from bottom to top for 12h, and placing the fully frozen slurry into a freeze dryer for freeze drying treatment for about 36h. Wherein the mass ratio of the mass consumption of the polyethylene diamine to the mass ratio of the catalyst after roasting and reducing in the third step is 50%.
Step 5: fully grinding the dried slurry in the step 4 in a mortar, sieving, placing in a tube furnace, roasting in an inert gas atmosphere by adopting a temperature programming method, and fully cooling to obtain the nitrogen-doped carbon-coated palladium-carbon catalyst; wherein the roasting temperature of the tube furnace is 600 ℃, the temperature is maintained for 2 hours, the heating rate is 8 ℃/min, the inert gas atmosphere is helium, and the helium flow rate is 120mL/min.
Comparative example 1: (comparison with example 3)
Step 1, acid washing: 2g of wood-based activated carbon is added into 50mL of 15wt% nitric acid aqueous solution, heated to 60 ℃ and maintained for 6 hours, cooled, washed 3-5 times with deionized water and dried in a forced air oven at 90 ℃ for 3 hours.
Step 2, dipping: adding the wood activated carbon dried in the step 1 into a solution of pre-prepared chloroplatinic acid (the platinum concentration is 0.023 g/mL) by adopting an isovolumetric impregnation method, stirring for 0.5h, impregnating for 24h at room temperature, and drying the impregnated catalyst in a vacuum oven at 110 ℃ for 6h; wherein the mass fraction of platinum in the catalyst is 5%.
And 3, reduction: placing the catalyst dried in the step 2 in vacuum in a tube furnace, roasting and reducing a platinum precursor in a hydrogen atmosphere, fully cooling to obtain a platinum-carbon catalyst, and aging in a drying oven for 10 hours at room temperature; wherein, the roasting temperature of the tube furnace is 250 ℃, the temperature is maintained for 0.5h, the temperature is continuously raised to 500 ℃, the temperature is maintained for 2h, the heating rates are 8 ℃/min, and the hydrogen flow rate is 100mL/min.
Comparative example 2: (comparison with example 3)
Step 1, acid washing: 2g of wood-based activated carbon is added into 50mL of 15wt% nitric acid aqueous solution, heated to 60 ℃ and maintained for 6 hours, cooled, washed 3-5 times with deionized water and dried in a forced air oven at 90 ℃ for 3 hours.
Step 2, dipping: adding the wood activated carbon dried in the step 1 into a solution of pre-prepared chloroplatinic acid (the platinum concentration is 0.023 g/mL) by adopting an isovolumetric impregnation method, stirring for 0.5h, impregnating for 24h at room temperature, and drying the impregnated catalyst in a vacuum oven at 110 ℃ for 6h; wherein the mass fraction of platinum in the catalyst is 5%.
Step 3 nitrogen doped carbon coating: adding quantitative urea-formaldehyde resin into deionized water to enable the concentration of the urea-formaldehyde resin to be 0.050g/mL, adding the platinum carbon catalyst in the step 2 into the pre-prepared urea-formaldehyde resin solution, stirring the formed slurry for 12 hours at room temperature, performing ultrasonic treatment for 30 minutes every 2 hours, performing ultrasonic treatment for 5 times, heating to 80 ℃ at a stirring speed of 1000rpm until stirring is finished, and drying in an oven for about 12 hours. Wherein the mass ratio of the urea-formaldehyde resin to the catalyst after roasting and reducing in the step 3 is 50%.
Step 4: fully grinding the dry sol in the step 3 in a mortar, sieving, placing in a tube furnace, roasting in an inert gas atmosphere by adopting a temperature programming method, and fully cooling; wherein the roasting temperature of the tube furnace is 750 ℃, and the tube furnace is maintained at the roasting temperature for 4 hours, wherein the heating rate is 8 ℃/min. The inert gas atmosphere was nitrogen and the argon flow rate was 50mL/min.
And 5, reduction: placing the catalyst dried in the step 3 into a tube furnace, roasting and reducing a platinum precursor in a hydrogen atmosphere, fully cooling to obtain a nitrogen-doped carbon-coated platinum-carbon catalyst, and aging in a drying oven for 10 hours at room temperature; wherein, the roasting temperature of the tube furnace is 250 ℃, the temperature is maintained for 0.5h, the temperature is continuously raised to 500 ℃, the temperature is maintained for 2h, the heating rates are 8 ℃/min, and the hydrogen flow rate is 100mL/min.
Comparative example 3: (comparison with example 3)
Step 1, acid washing: 2g of wood-based activated carbon is added into 50mL of 15wt% nitric acid aqueous solution, heated to 60 ℃ and maintained for 6 hours, cooled, washed 3-5 times with deionized water and dried in a forced air oven at 90 ℃ for 3 hours.
Step 2, dipping: adding the wood activated carbon dried in the step 1 into a pre-prepared mixed solution of chloroplatinic acid and urea-formaldehyde resin (the concentration of platinum and urea-formaldehyde resin is 0.0046g/mL and 0.023g/mL respectively) by adopting a co-impregnation method, stirring the formed slurry for 12 hours at room temperature, carrying out ultrasonic treatment for 30 minutes every 2 hours, carrying out ultrasonic treatment for 5 times, heating to 80 ℃ at a stirring speed of 1000rpm until stirring is carried out, and drying in an oven for about 12 hours. Drying the impregnated catalyst in a vacuum oven at 110 ℃ for 6 hours; wherein, the mass ratio of platinum to active carbon is 5.0 percent, and the mass ratio of urea-formaldehyde resin to active carbon is 50 percent.
Step 3: fully grinding the dry sol in the step 2 in a mortar, sieving, placing in a tube furnace, roasting in an inert gas atmosphere by adopting a temperature programming method, and fully cooling; wherein the roasting temperature of the tube furnace is 750 ℃, and the tube furnace is maintained at the roasting temperature for 4 hours, wherein the heating rate is 8 ℃/min. The inert gas atmosphere was nitrogen and the argon flow rate was 50mL/min.
And 4, reduction: placing the catalyst dried in the step 3 into a tube furnace, roasting and reducing a platinum precursor in a hydrogen atmosphere, fully cooling to obtain a nitrogen-doped carbon-coated platinum-carbon catalyst, and aging in a drying oven for 10 hours at room temperature; wherein, the roasting temperature of the tube furnace is 250 ℃, the temperature is maintained for 0.5h, the temperature is continuously raised to 500 ℃, the temperature is maintained for 2h, the heating rates are 8 ℃/min, and the hydrogen flow rate is 100mL/min.
Application example 1
The catalysts obtained in example 3 and comparative example 1 were used for the reduction of nitrobenzene to aniline under the same conditions: 100mL of nitrobenzene solution (nitrobenzene is an industrial raw material, the reaction solution contains about 500ppm of dinitrothiophene, the mass fraction of nitrobenzene is 20wt percent, and the solvent is absolute ethyl alcohol) is added into a batch reaction kettle, and the reaction temperature in the reaction kettle is controlled to be 80 ℃, the hydrogen pressure is controlled to be 1MPa, the rotating speed is 1000rpm, and the reaction time is controlled to be 1.0h, so that aniline is produced. After the reaction is finished, filtering to obtain a reaction solution and a catalyst, diluting the reaction solution with a proper amount of acetonitrile, and detecting and analyzing the diluted reaction solution by using an HPLC-1100 high performance liquid chromatograph of Agilent company. The detection conditions are as follows: the wavelength was 254nm, the flow rate was 1mL/min, the mobile phase was a mixture of acetonitrile and water (V acetonitrile and V water=2:3), the sample injection amount was 5. Mu.L, the chromatographic column was a C18 column, and the composition of the product was analyzed by peak area normalization. Fresh catalyst was added 5wt% each time during the catalyst sleeve. The results are shown in FIG. 1.
Application example 2
The catalysts obtained in example 3 and comparative example 1 were used under the same conditions for the reduction synthesis of 2-amino-4-methyl-5-chlorobenzenesulfonic acid, CLT acid, from 2-nitro-4-methyl-5-chlorobenzenesulfonic acid, under the following reaction conditions: 100mL of 2-nitro-4-methyl-5-chlorobenzenesulfonic acid aqueous solution (2-nitro-4-methyl-5-chlorobenzenesulfonic acid is an industrial raw material purchased from Zhejiang Qin Yan technology Co., ltd., contains about 280ppm of 2-nitro-4-methyl-5-chlorophenyl sulfone, the mass fraction of 2-nitro-4-methyl-5-chlorobenzenesulfonic acid in the aqueous solution is 30wt%, the pH value is about 5.0), the reaction temperature is controlled to 90 ℃, the hydrogen pressure is controlled to 1MPa, the rotating speed is 1000rpm, and the reaction time is 2.5h, so that CLT acid is produced. After the reaction is finished, filtering to obtain a reaction solution and a catalyst, diluting the reaction solution with a proper amount of acetonitrile, and detecting and analyzing the diluted reaction solution by using an HPLC-1100 high performance liquid chromatograph of Agilent company. The detection conditions are as follows: the wavelength is 234nm, the flow rate is 0.8mL/min, the mobile phase is a mixture of acetonitrile and water (V acetonitrile and V water=1:4), the sample injection amount is 5 mu L, the chromatographic column is C18 column, and the composition of the product is analyzed by adopting a peak area normalization method. Fresh catalyst was added 5wt% each time during the catalyst sleeve. The reaction results are shown in FIG. 2.
Application example 3
The catalysts obtained in example 3 and comparative example 1 were used in the reductive synthesis of sulfanilic acid under the same conditions: 100mL of p-nitrobenzenesulfonic acid aqueous solution (p-nitrobenzenesulfonic acid is an industrial raw material purchased from Qinyan, zhejiang, technology Co., ltd., contains about 200ppm of 3,3' -dinitrodiphenyl sulfone aqueous solution and has the mass fraction of 20wt% and the pH of about 6.0) is added into a batch reaction kettle, and the reaction temperature is controlled to be 80 ℃, the hydrogen pressure is controlled to be 0.8MPa, the rotating speed is controlled to be 800rpm, and the reaction time is controlled to be 2.0 hours, so that the p-aminobenzenesulfonic acid is produced. After the reaction is finished, filtering to obtain a reaction solution and a catalyst, diluting the reaction solution with a proper amount of acetonitrile, and detecting and analyzing the diluted reaction solution by using an HPLC-1100 high performance liquid chromatograph of Agilent company. The detection conditions are as follows: the wavelength is 234nm, the flow rate is 1.0mL/min, the mobile phase is a mixture of acetonitrile and water (V acetonitrile and V water=1:4), the sample injection amount is 5 mu L, the chromatographic column is C18 column, and the composition of the product is analyzed by adopting a peak area normalization method. Fresh catalyst was added 5wt% each time during the catalyst sleeve. The reaction results are shown in FIG. 3.
Application example 4
Referring to application example 1, the nitrogen-doped carbon-coated platinum-carbon catalysts obtained in examples 1 to 8 were used in the process of synthesizing aniline by reduction of nitrobenzene (added with 100ppm of phenylene sulfide) under the same conditions: 100mL of nitrobenzene solution (the mass fraction of nitrobenzene is 20wt percent, the solvent is absolute ethyl alcohol, 0.2g of phenyl sulfide is added) is added into a batch reaction kettle, the reaction temperature is controlled to be 80 ℃, the hydrogen pressure is controlled to be 1MPa, the rotating speed is 1000rpm, the reaction time is controlled to be 1.0h, aniline is generated, 5wt percent of fresh catalyst is added each time in the process of applying the aniline, and the use effect of the catalyst is shown in the table 1:
TABLE 1
Application example 5
Referring to application example 2, the nitrogen-doped carbon-coated platinum carbon catalysts obtained in examples 1 to 8 were used in the process of synthesizing 2-amino-4-methyl-5-chlorobenzenesulfonic acid, CLT acid, by reduction of 2-nitro-4-methyl-5-chlorobenzenesulfonic acid under the same conditions, and the reaction conditions were: 100mL of 2-nitro-4-methyl-5-chlorobenzenesulfonic acid aqueous solution (the mass fraction of the 2-nitro-4-methyl-5-chlorobenzenesulfonic acid is 30wt percent, the pH value is about 5.0) is added into a batch reaction kettle, the reaction temperature is controlled to be 90 ℃, the hydrogen pressure is controlled to be 1MPa, the rotating speed is 1000rpm, and the reaction time is controlled to be 2.5 hours, so that CLT acid is generated. Fresh catalyst was added 5wt% each time during the catalyst sleeve. The reaction results are shown in Table 2:
TABLE 2
Application example 6
Referring to application example 3, the nitrogen-doped carbon-coated platinum-carbon catalysts obtained in examples 1 to 8 were used in the process of synthesizing sulfanilic acid by reduction of sulfanilic acid under the same conditions, and the reaction conditions were as follows: 100mL of p-nitrobenzenesulfonic acid aqueous solution (the mass fraction of p-nitrobenzenesulfonic acid is 20wt%, the pH value is about 6.0) is added into a batch reaction kettle, the reaction temperature is controlled to be 80 ℃, the hydrogen pressure is controlled to be 0.8MPa, the rotating speed is controlled to be 800rpm, and the reaction time is controlled to be 2.0h, so that the p-aminobenzenesulfonic acid is generated. Fresh catalyst was added 5wt% each time during the catalyst sleeve. The reaction results are shown in Table 3:
TABLE 3 Table 3
From fig. 1-3, it can be seen that the catalyst of comparative example 1, which is not coated with carbon doped with nitrogen, has obvious poisoning deactivation phenomenon within 3 times of application, the catalyst of comparative example 3 has higher activity and selectivity after 10 times of reaction, and from table 1-3, examples 1-8 have higher activity and selectivity after 10 times of application and the first time, and from table 1, examples 3, comparative example 2 and comparative example 3, it can be seen that the stability of the catalyst of example 3 is obviously better than that of comparative example 2 and comparative example 3 when different nitrogen-doped carbon coating modes are applied. Comparing the results, the nitrogen-doped carbon coated platinum-carbon catalyst prepared by the invention has good sulfur poisoning resistance effect and long service life.
Claims (7)
1. The preparation method of the nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst is implemented according to the following steps:
(1) Acid washing: adding the activated carbon material into a nitric acid aqueous solution, heating to 60-100 ℃ and maintaining for 4-6 hours, cooling, washing with deionized water for 3-5 times, and drying in a blast oven at 80-120 ℃ for 2-6 hours;
(2) Dipping: adding the catalyst into a solution of a pre-prepared noble metal precursor by adopting an impregnation method, stirring for 15-60 min, impregnating for 12-36h at room temperature, and drying the impregnated catalyst in a vacuum oven for 4-12h at 80-120 ℃; the noble metal precursor is one of palladium chloride, chloroplatinic acid and chloroauric acid, and the noble metal precursor is fed according to the mass fraction of noble metal in the catalyst of 1-10%;
(3) And (3) reduction: placing the catalyst dried in the vacuum in the step (2) in a tube furnace, roasting and reducing the noble metal precursor in a hydrogen atmosphere, keeping the roasting temperature of the tube furnace at 150-300 ℃, keeping the roasting temperature at 0.5-1 h, continuously heating to 300-600 ℃, keeping the temperature for 2-3 h, wherein the heating rate is 5-10 ℃/min, the hydrogen flow rate is 40-100mL/min, and aging in a drying oven for 12-24h at room temperature after full cooling to obtain the noble metal catalyst;
(4) Carbon coating: adding the noble metal catalyst obtained in the step (3) into a pre-prepared organic carbon nitrogen material solution, stirring the formed slurry at room temperature for 10-60 min, carrying out ultrasonic treatment for 15-60 min, transferring the slurry into a reaction kettle, introducing nitrogen for protection, heating to 50-100 ℃ at a stirring rate of 500-1000 rpm, keeping the temperature for 2-6 h, cooling, keeping the temperature at room temperature for 6-12h, carrying out ultrasonic treatment for 15-60 min, placing the cooled slurry on a copper ingot placed in liquid nitrogen, freezing the slurry from bottom to top for 6-18h, and placing the frozen slurry in a freeze dryer for freeze drying treatment for 24-48h; the organic carbon-nitrogen material is one or more of urea formaldehyde resin, polyethylene diamine, polyvinylpyrrolidone, polyacrylonitrile and chitosan, and the mass ratio of the organic carbon-nitrogen material to the noble metal catalyst obtained in the step (3) is 20-100%;
(5) Roasting: and (3) fully grinding the slurry obtained after freeze drying in the step (4) in a mortar, sieving, placing in a tube furnace, roasting in an inert gas atmosphere by adopting a temperature programming method, wherein the roasting temperature of the tube furnace is 300-800 ℃, maintaining the roasting temperature for 2-4 h, wherein the heating rate is 2-10 ℃/min, the inert gas atmosphere is one of nitrogen, argon and helium, the flow rate of the inert gas is 50-300mL/min, and cooling to obtain the nitrogen-doped carbon-coated noble metal catalyst.
2. The method of manufacturing according to claim 1, wherein: in the step (1), the activated carbon is one of coconut shell activated carbon, wood activated carbon and coal activated carbon, the activated carbon is powdery microporous activated carbon, and the parameters of the activated carbon are as follows: specific surface area of 800-1400m 2 Per g, pore volume of 0.6-1.0cm 3 And/g, average pore size of 1.9-2.3nm.
3. The method of manufacturing according to claim 1, wherein: in the step (1), the mass fraction of nitric acid in the nitric acid aqueous solution is 5-20%.
4. A nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst prepared according to the preparation method of claim 1.
5. The use of the nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst according to claim 4 in synthesizing aniline by hydrogenation reduction of nitrobenzene, wherein: the nitrobenzene contains sulfur impurities.
6. The use of the nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst according to claim 4 in the hydrogenation reduction synthesis of 2-amino-4-methyl-5-chlorobenzenesulfonic acid from 2-nitro-4-methyl-5-chlorobenzenesulfonic acid, characterized in that: the 2-nitro-4-methyl-5-chlorobenzenesulfonic acid contains sulfur impurities.
7. The use of the nitrogen-doped carbon-coated noble metal liquid-phase hydrogenation catalyst according to claim 4 for synthesizing p-amino benzenesulfonic acid by hydrogenation reduction of p-nitro benzenesulfonic acid, wherein the method comprises the following steps: the p-nitro benzenesulfonic acid contains sulfur impurities.
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