CN113499764B - Platinum catalyst loaded on aminated graphene and preparation method thereof - Google Patents
Platinum catalyst loaded on aminated graphene and preparation method thereof Download PDFInfo
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- CN113499764B CN113499764B CN202110661340.9A CN202110661340A CN113499764B CN 113499764 B CN113499764 B CN 113499764B CN 202110661340 A CN202110661340 A CN 202110661340A CN 113499764 B CN113499764 B CN 113499764B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 140
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 54
- 239000010439 graphite Substances 0.000 claims abstract description 54
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims abstract description 40
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 30
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 22
- 150000003057 platinum Chemical class 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000007790 solid phase Substances 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 17
- 230000007935 neutral effect Effects 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 37
- 230000009467 reduction Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005576 amination reaction Methods 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract 1
- 238000007781 pre-processing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 33
- 230000008569 process Effects 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- OIJHFHYPXWSVPF-UHFFFAOYSA-N para-Nitrosodiphenylamine Chemical compound C1=CC(N=O)=CC=C1NC1=CC=CC=C1 OIJHFHYPXWSVPF-UHFFFAOYSA-N 0.000 description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- 238000009833 condensation Methods 0.000 description 11
- 230000005494 condensation Effects 0.000 description 11
- 229910000510 noble metal Inorganic materials 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 11
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- XXYMSQQCBUKFHE-UHFFFAOYSA-N 4-nitro-n-phenylaniline Chemical compound C1=CC([N+](=O)[O-])=CC=C1NC1=CC=CC=C1 XXYMSQQCBUKFHE-UHFFFAOYSA-N 0.000 description 8
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 8
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 8
- RUKISNQKOIKZGT-UHFFFAOYSA-N 2-nitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC=CC=C1NC1=CC=CC=C1 RUKISNQKOIKZGT-UHFFFAOYSA-N 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 3
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000009935 nitrosation Effects 0.000 description 1
- 238000007034 nitrosation reaction Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
- B01J31/0238—Amines with a primary amino group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- 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
- 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
- C07C209/38—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 nitroso groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a platinum catalyst loaded on aminated graphene, which comprises the steps of preprocessing natural crystalline flake graphite, preparing graphite oxide from the preprocessed natural crystalline flake graphite through oxidization, obtaining graphene oxide through ultrasonic stripping of the graphite oxide, obtaining the aminated graphene by amination of the graphene oxide, and adding a platinum salt solution into the aminated graphene to prepare the platinum catalyst loaded on the aminated graphene. The invention solves the problems of high catalyst loss, high impurity content in hydrogenation liquid and reduced production capacity caused by the fact that the reduction catalyst cannot timely remove reaction heat in the conventional production of para-aminodiphenylamine, and the catalyst is locally overheated and sintered and deactivated. The catalyst provided by the invention is used for preparing p-aminodiphenylamine by catalyzing nitrobenzene hydrogenation, has high activity, high selectivity, good stability and long service life, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a platinum catalyst loaded on aminated graphene and a preparation method thereof, which are used for preparing p-aminodiphenylamine by catalyzing nitrobenzene hydrogenation.
Background
Para-aminodiphenylamine (also called RT pessary, 4-aminodiphenylamine) is an important organic intermediate, is widely applied to rubber additives, dyes, textile, printing, pharmaceutical industry and the like, and is mainly used as an intermediate of para-phenylenediamine rubber antioxidants for preparing rubber antioxidants 4010NA, 6PPD and the like.
The synthesis method of p-aminodiphenylamine includes more than ten kinds of processes of aniline process, formanilide process, carbanilide process, diphenylamine process and nitro process, etc., at present, the industrial production process mainly includes diphenylamine process and nitro process, the diphenylamine process is used for preparing p-aminodiphenylamine, using diphenylamine as raw material, in the presence of inorganic acid, using nitrite to make nitrosation in organic solvent to obtain N-nitrosodiphenylamine, using anhydrous hydrogen chloride to make rearrangement into 4-nitrosodiphenylamine hydrochloride, using alkali to make neutralization and then producing 4-nitrosodiphenylamine, and finally reducing to obtain 4-aminodiphenylamine. The process for preparing p-aminodiphenylamine by nitrobenzene method uses nitrobenzene and aniline as raw materials, and uses tetramethyl ammonium hydroxide as condensation catalyst to make condensation so as to produce p-nitrosodiphenylamine (4-nitrosodiphenylamine) and p-nitrodiphenylamine (4-nitrodiphenylamine).
The hydrogenation of p-aminodiphenylamine prepared by nitrobenzene method is generally adopted as nickel catalyst and noble metal catalyst, and the noble metal catalyst is mainly palladium/carbon catalyst and platinum/carbon catalyst.
Hydrogenating the condensate liquid by using a nickel catalyst, wherein the solvent is generally methanol; the noble metal catalyst is used for hydrogenating the condensation liquid, a solvent is generally water, the solid catalyst and the hydrogenation reaction liquid are separated after the hydrogenation is finished, the hydrogenation reaction liquid is treated to obtain a water phase and an organic phase, the noble metal hydrogenation liquid is concentrated in the water phase to recover tetramethyl ammonium hydroxide, the nickel catalyst hydrogenation liquid is treated in the water phase to recover tetramethyl ammonium hydroxide and methanol, a tetramethyl ammonium hydroxide sleeve is recovered for the condensation reaction, a methanol sleeve is recovered for the hydrogenation reaction, the organic phase is rectified in a rectification process to obtain p-aminodiphenylamine, and an aniline recovery sleeve is used for the condensation reaction.
The patent CN103420849A adopts Ni-based catalyst, the mass content of 4-nitrodiphenylamine in the reaction solution is 5% -20%, the mass content of 4-aminodiphenylamine is 20% -30%, the reaction temperature is 100 ℃ -250 ℃, the reaction pressure is 2.0 MPa-4.0 MPa, the liquid phase airspeed is 6.0 h -1~16.0h-1, the volume ratio of hydrogen to 4-nitrodiphenylamine is 200-600:1, and the yield reaches 92%.
Patent CN102344376A describes that 4-nitrodiphenylamine and 4-nitrosodiphenylamine are hydrogenated in the presence of Pd/C catalyst to obtain para-aminodiphenylamine, the active component palladium of the catalyst is added with rare earth metal element, and the content of other substances except aniline and para-aminodiphenylamine in hydrogenation product is 18.40% -22.68%.
Patent CN106179332a describes a process for the preparation of palladium on carbon catalysts for the hydrogenation of 4-aminodiphenylamine. The preparation method is characterized by taking active carbon as a carrier and palladium as an active component, and comprises the following preparation processes: the preparation method comprises the steps of pretreatment of activated carbon, dipping, reduction, washing, drying and the like, the prepared catalyst is used for catalytic hydrogenation of 4-aminodiphenylamine prepared by a nitrobenzene method, the selectivity of 4-aminodiphenylamine is 95.5% -99.7%, and the catalyst is not used.
The device for producing the p-aminodiphenylamine by using the nitrobenzene method is developed and built by the company of the Xinda of the Anhui, and the trial run is successful in 4 th 2001, and the noble metal catalyst Pt/C is adopted for hydrogenation reduction, so that the activity is low when the noble metal catalyst is used mechanically, the cycle times are low, and the production cost of RT pessaries is high and the production is stopped.
In the process of preparing p-aminodiphenylamine by nitrobenzene method, p-nitrosodiphenylamine and p-nitrodiphenylamine in the condensed liquid are reduced to form strong exothermic reaction, so that the catalyst metal is easy to accumulate and high-temperature sintering is easy to cause activity reduction.
The nickel catalyst is low in price, but the using amount is more, methanol is used as a solvent, the methanol is mutually soluble with water and can dissolve aniline, and the existence of the methanol in the reducing solution influences the separation effect of soft water and RT reducing solution; the noble metal catalyst is easy to deactivate and has less application times, so that the noble metal catalyst which has high activity, high selectivity, good stability, more application times and long service life for preparing the p-aminodiphenylamine by hydrogenation reduction is developed, and the noble metal catalyst has good application prospect.
Disclosure of Invention
The invention aims to provide a preparation method of a platinum catalyst loaded on aminated graphene, which is used for preparing para-aminodiphenylamine by catalyzing nitrobenzene hydrogenation, and aims to solve the problem that the activity is reduced due to metal accumulation and high-temperature sintering caused by the fact that a reduction catalyst cannot timely remove reaction heat in the existing production of para-aminodiphenylamine.
Graphene is a novel inorganic nano material with a honeycomb crystal structure and formed by hybridization of carbon atoms in sp 2, the high strength and the high heat conductivity coefficient benefit from the unique structure of the novel inorganic nano material, weak van der Waals force exists between the graphene, so that the graphene is unevenly dispersed and easy to generate an agglomeration phenomenon, poor application is caused, amino groups are introduced into the surface or edge of the graphene by adopting a graphene modification method, the hydrophilicity and polarity of the surface of the graphene can be improved, and the distance between graphene layers can be increased by the existence of the amino groups, so that the graphene is not easy to agglomerate.
According to the preparation method, the aminated graphene is used as a carrier, the platinum salt solution is used as a platinum precursor, and the preparation of the catalyst is completed through the steps of carrier pretreatment, oxidization, stripping, amination, impregnation, washing, drying and the like, and in the preparation process, the noble metal platinum is dispersed more uniformly on the aminated graphene through the control of the pretreatment, oxidization, stripping, amination and impregnation processes of the carrier, and the size of the platinum grain size is regulated and controlled, so that the noble metal catalyst with high activity, high selectivity, good stability, multiple application times and long service life is obtained.
The invention is realized in the following way: the platinum catalyst is characterized by comprising a carrier and an active component, wherein the carrier is the aminated graphene, the active component is platinum, and the mass content of the platinum in the catalyst is 0.1% -3.0%.
Generally, the size of the aminated graphene is 2-9 mu m, the thickness of the aminated graphene is 0.8-3.6 nm, and the ammoniation rate is 3.8-4.5%.
The total number of platinum grains with the grain diameter smaller than 10nm in the catalyst is more than or equal to 85 percent.
The invention also provides a preparation method of the platinum catalyst loaded on the aminated graphene, which comprises the following preparation steps: (1) Soaking natural crystalline flake graphite in an inorganic acid solution, boiling and refluxing, then carrying out solid-liquid separation, and washing a solid phase by water to obtain a solid phase which is the pretreated natural crystalline flake graphite; (2) Adding the pretreated natural crystalline flake graphite into concentrated sulfuric acid, fully stirring and mixing, adding potassium permanganate into the mixed solution for reaction, adding deionized water for reaction, and then adding hydrogen peroxide solution for reaction to obtain graphite oxide solution; (3) Ultrasonic stripping and filtering the graphite oxide solution, washing a solid phase with deionized water until the filtrate is neutral, and drying the solid phase to obtain graphene oxide; (4) Ultrasonically dispersing graphene oxide in ethylene glycol and ethylenediamine solution to react to obtain aminated graphene; (5) And adding the platinum salt solution into the aminated graphene for impregnation, reduction, washing and drying to obtain the platinum catalyst loaded on the aminated graphene.
An exemplary preparation step of the invention comprises: (1) Soaking natural crystalline flake graphite in an inorganic acid solution with the mass fraction of 3% -20%, boiling and refluxing for 1.5-12 hours, then carrying out solid-liquid separation, and washing a solid phase by water to obtain a solid phase which is the pretreated natural crystalline flake graphite; (2) Adding the pretreated natural crystalline flake graphite into concentrated sulfuric acid, fully stirring and mixing, adding potassium permanganate into the mixed solution to react for 2.0-3.5 hours, adding deionized water to react for 0.5-1.5 hours, and adding hydrogen peroxide solution to react for 0.5-1.5 hours to obtain a graphite oxide solution; (3) Ultrasonically stripping the graphite oxide solution for 0.5-1.0 h, filtering, washing the solid phase with deionized water until the filtrate is neutral, and drying the solid phase to obtain graphene oxide; (4) Ultrasonically dispersing graphene oxide in a glycol and ethylenediamine solution to react for 8-18 hours to obtain aminated graphene; (5) And adding the platinum salt solution into the aminated graphene for impregnation, reduction, washing and drying to obtain the platinum catalyst loaded on the aminated graphene.
The inorganic acid is one or more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
The platinum salt solution is one or more of platinum chloride, platinum acetate, platinum nitrate or chloroplatinic acid.
The mass concentration of the platinum salt solution is 5% -32%.
The platinum catalyst loaded on the aminated graphene can be used for preparing p-aminodiphenylamine by catalyzing hydrogenation of nitrobenzene.
The activity evaluation of the supported platinum catalyst of the present invention was carried out in a 0.45L autoclave. 200g of condensation solution (wherein the mass content of the p-nitrodiphenylamine is about 4%, the mass content of the p-nitrosodiphenylamine is about 23%, the balance of aniline, azobenzene, water, tetramethylammonium hydroxide and the like), 80g of distilled water, 0.4g of catalyst, the hydrogenation reduction reaction temperature of 78 ℃, the hydrogen pressure of 1.8MPa and the stirring rotation speed of 1200r/min are added into a reaction kettle, and the liquid chromatograph is adopted for analysis after the hydrogenation is finished.
Compared with the prior art, the invention has the following advantages:
1. The carrier used by the catalyst can reduce potential safety hazards caused by catalyst agglomeration;
2. the catalyst can avoid the deactivation of the catalyst caused by local overheating, reduce the catalyst loss and improve the hydrogenation reduction reaction selectivity;
3. the catalyst is used for preparing the p-aminodiphenylamine by hydrogenation reduction, water is used as a solvent, other organic solvents are not needed to be added in the reaction process, and the consumption and recovery cost of the solvents are reduced;
4. the catalyst of the invention is used for preparing p-aminodiphenylamine by hydrogenation of catalytic nitrobenzene method, and has high activity, high selectivity, good stability and long service life.
Detailed Description
The invention will be described in detail with reference to examples (percentages in the following comparative examples and examples are by mass).
Example 1
Soaking natural crystalline flake graphite in 10% sulfuric acid solution, boiling and refluxing for 8.0h, then separating solid from liquid, and washing the solid phase with water to obtain a solid phase which is the pretreated natural crystalline flake graphite; adding the pretreated natural crystalline flake graphite into concentrated sulfuric acid, fully stirring and mixing, adding potassium permanganate into the mixed solution to react for 3.0h, adding deionized water to react for 1.0h, and adding hydrogen peroxide solution to react for 1.0h to obtain a graphite oxide solution; ultrasonically stripping the graphite oxide solution for 0.5h, filtering, washing a solid phase with deionized water until the filtrate is neutral, and vacuum drying the solid phase at 110 ℃ for 2h to obtain graphene oxide; ultrasonically dispersing graphene oxide in a glycol and ethylenediamine solution to react for 15 hours to obtain aminated graphene; adding a chloroplatinic acid solution with the content of 10% into the aminated graphene, soaking for 10 hours, adopting a hydrazine hydrate solution with the content of 20% to reduce for 4 hours, filtering, washing to be neutral, and drying for 10 hours at 90 ℃ after solid-liquid separation and water removal to prepare the aminated graphene loaded platinum catalyst.
The performance of the catalyst in this example: the content of platinum in the catalyst is 1.0%, the total number of platinum grains with the grain diameter smaller than 10nm in the catalyst is 88%, the conversion rate and the selectivity of the p-nitrosodiphenylamine in the condensation liquid in the process of preparing the p-aminodiphenylamine by the catalytic hydrogenation nitrobenzene method are shown in the following table.
| Number of times of application | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Conversion of nitrodiphenylamine% | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Selectivity to para-aminodiphenylamine% | 99.2 | 99.1 | 99.3 | 99.2 | 99.1 | 99.3 | 99.3 | 99.2 |
Example 2
Soaking natural crystalline flake graphite in a nitric acid solution with the content of 10%, boiling and refluxing for 1.5 hours, then carrying out solid-liquid separation, and washing a solid phase by water to obtain a solid phase which is the pretreated natural crystalline flake graphite; adding the pretreated natural crystalline flake graphite into concentrated sulfuric acid, fully stirring and mixing, adding potassium permanganate into the mixed solution for reaction for 2.5 hours, adding deionized water for reaction for 1.5 hours, and adding hydrogen peroxide solution for reaction for 0.5 hour to obtain graphite oxide solution; ultrasonically stripping the graphite oxide solution for 1.0h, filtering, washing a solid phase with deionized water until the filtrate is neutral, and vacuum drying the solid phase at 110 ℃ for 2h to obtain graphene oxide; ultrasonically dispersing graphene oxide in a glycol and ethylenediamine solution to react for 8 hours to obtain aminated graphene; adding a chloroplatinic acid solution with the content of 15% into the aminated graphene, soaking for 10 hours, adopting a hydrazine hydrate solution with the content of 10% to reduce for 6 hours, filtering, washing to be neutral, and drying for 9 hours at the temperature of 95 ℃ after solid-liquid separation and water removal to prepare the aminated graphene loaded platinum catalyst.
The performance of the catalyst in this example: the content of platinum in the catalyst is 0.8%, the total number of platinum grains with the grain diameter smaller than 10nm in the catalyst is 90%, the conversion rate and the selectivity of the p-nitrosodiphenylamine in the condensation liquid in the process of preparing the p-aminodiphenylamine by the catalytic hydrogenation nitrobenzene method are shown in the following table.
| Number of times of application | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Conversion of nitrodiphenylamine% | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Selectivity to para-aminodiphenylamine% | 99.3 | 99.4 | 99.4 | 99.3 | 99.5 | 99.5 | 99.4 | 99.4 |
Example 3
Soaking natural crystalline flake graphite in 10% hydrochloric acid solution, boiling and refluxing for 3.0h, then separating solid from liquid, and washing the solid phase with water to obtain a solid phase which is the pretreated natural crystalline flake graphite; adding the pretreated natural crystalline flake graphite into concentrated sulfuric acid, fully stirring and mixing, adding potassium permanganate into the mixed solution for reaction for 3.5 hours, adding deionized water for reaction for 0.5 hour, and adding hydrogen peroxide solution for reaction for 1.5 hours to obtain a graphite oxide solution; ultrasonically stripping the graphite oxide solution for 1.0h, filtering, washing a solid phase with deionized water until the filtrate is neutral, and vacuum drying the solid phase at 110 ℃ for 2h to obtain graphene oxide; ultrasonically dispersing graphene oxide in a glycol and ethylenediamine solution to react for 12 hours to obtain aminated graphene; adding 32% chloroplatinic acid solution into the aminated graphene for soaking for 10 hours, adopting 30% hydrazine hydrate solution for reduction for 3 hours, filtering, washing to be neutral, and drying at 100 ℃ for 8 hours after solid-liquid separation and water removal to prepare the aminated graphene loaded platinum catalyst.
The performance of the catalyst in this example: the content of platinum in the catalyst is 0.5%, the total number of platinum grains with the grain diameter smaller than 10nm in the catalyst is 91%, the conversion rate and the selectivity of the p-nitrosodiphenylamine and the p-nitrodiphenylamine in the condensation liquid in the process of preparing the p-aminodiphenylamine by the catalytic hydrogenation nitrobenzene method are shown in the following table.
| Number of times of application | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Conversion of nitrodiphenylamine% | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Selectivity to para-aminodiphenylamine% | 99.4 | 99.4 | 99.5 | 99.5 | 99.5 | 99.5 | 99.5 | 99.4 |
Example 4
Soaking natural crystalline flake graphite in 10% phosphoric acid solution, boiling and refluxing for 5.0h, then separating solid from liquid, and washing the solid phase with water to obtain a solid phase which is the pretreated natural crystalline flake graphite; adding the pretreated natural crystalline flake graphite into concentrated sulfuric acid, fully stirring and mixing, adding potassium permanganate into the mixed solution to react for 3.0h, adding deionized water to react for 0.5h, and adding hydrogen peroxide solution to react for 1.5h to obtain a graphite oxide solution; ultrasonically stripping the graphite oxide solution for 0.5h, filtering, washing a solid phase with deionized water until the filtrate is neutral, and vacuum drying the solid phase at 110 ℃ for 2h to obtain graphene oxide; ultrasonically dispersing graphene oxide in a glycol and ethylenediamine solution to react for 15 hours to obtain aminated graphene; and adding a chloroplatinic acid solution with the content of 5% into the aminated graphene, soaking for 8 hours, adopting a hydrazine hydrate solution with the content of 15% to reduce for 5 hours, filtering, washing to be neutral, and drying for 10 hours at the temperature of 85 ℃ after solid-liquid separation and water removal to prepare the aminated graphene loaded platinum catalyst.
The performance of the catalyst in this example: the content of platinum in the catalyst is 1.5%, the total number of platinum grains with the grain diameter smaller than 10nm in the catalyst is 88%, the conversion rate and the selectivity of the p-nitrosodiphenylamine in the condensation liquid in the process of preparing the p-aminodiphenylamine by the catalytic hydrogenation nitrobenzene method are shown in the following table.
| Number of times of application | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Conversion of nitrodiphenylamine% | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Selectivity to para-aminodiphenylamine% | 99.3 | 99.3 | 99.4 | 99.4 | 99.3 | 99.4 | 99.3 | 99.4 |
Example 5
Soaking natural crystalline flake graphite in sulfuric acid solution with the content of 3%, boiling and refluxing for 10.0h, then carrying out solid-liquid separation, and washing the solid phase with water to obtain a solid phase which is the pretreated natural crystalline flake graphite; adding the pretreated natural crystalline flake graphite into concentrated sulfuric acid, fully stirring and mixing, adding potassium permanganate into the mixed solution for reaction for 3.5 hours, adding deionized water for reaction for 1.5 hours, and adding hydrogen peroxide solution for reaction for 0.5 hour to obtain graphite oxide solution; ultrasonically stripping the graphite oxide solution for 1.0h, filtering, washing a solid phase with deionized water until the filtrate is neutral, and vacuum drying the solid phase at 110 ℃ for 2h to obtain graphene oxide; ultrasonically dispersing graphene oxide in a glycol and ethylenediamine solution to react for 18 hours to obtain aminated graphene; adding 15% platinum chloride solution into the aminated graphene, soaking for 6 hours, adopting 18% formaldehyde solution to reduce for 4 hours, filtering, washing to be neutral, and drying at 80 ℃ for 12 hours after solid-liquid separation and water removal to obtain the aminated graphene loaded platinum catalyst.
The performance of the catalyst in this example: the content of platinum in the catalyst is 3.0%, the total number of platinum grains with the grain diameter smaller than 10nm in the catalyst is 86%, the conversion rate and the selectivity of the p-nitrosodiphenylamine in the condensation liquid in the process of preparing the p-aminodiphenylamine by the catalytic hydrogenation nitrobenzene method are shown in the following table.
| Number of times of application | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Conversion of nitrodiphenylamine% | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Selectivity to para-aminodiphenylamine% | 99.5 | 99.5 | 99.4 | 99.5 | 99.5 | 99.5 | 99.4 | 99.4 |
Example 6
Soaking natural crystalline flake graphite in 5% sulfuric acid solution, boiling and refluxing for 12.0h, then separating solid from liquid, and washing the solid phase with water to obtain a solid phase which is the pretreated natural crystalline flake graphite; adding the pretreated natural crystalline flake graphite into concentrated sulfuric acid, fully stirring and mixing, adding potassium permanganate into the mixed solution for reaction for 2.5 hours, adding deionized water for reaction for 1.0 hour, and adding hydrogen peroxide solution for reaction for 1.0 hour to obtain graphite oxide solution; ultrasonically stripping the graphite oxide solution for 1.0h, filtering, washing a solid phase with deionized water until the filtrate is neutral, and vacuum drying the solid phase at 110 ℃ for 2h to obtain graphene oxide; ultrasonically dispersing graphene oxide in a glycol and ethylenediamine solution to react for 16 hours to obtain aminated graphene; adding a platinum acetate solution with the content of 18% into the aminated graphene, soaking for 5 hours, adopting a formaldehyde solution with the content of 25% to reduce for 3 hours, filtering, washing to be neutral, carrying out solid-liquid separation, removing water, and drying at 75 ℃ for 14 hours to prepare the platinum catalyst loaded on the aminated graphene.
The performance of the catalyst in this example: the content of platinum in the catalyst is 2.5%, the total number of platinum grains with the grain diameter smaller than 10nm in the catalyst is 88%, the conversion rate and the selectivity of the p-nitrosodiphenylamine in the condensation liquid in the process of preparing the p-aminodiphenylamine by the catalytic hydrogenation nitrobenzene method are shown in the following table.
| Number of times of application | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Conversion of nitrodiphenylamine% | 100 | 100 | 100 | 100 | 100 | 99.9 | 100 | 100 |
| Selectivity to para-aminodiphenylamine% | 99.4 | 99.4 | 99.4 | 99.5 | 99.5 | 99.5 | 99.5 | 99.4 |
Example 7
Soaking natural crystalline flake graphite in a sulfuric acid solution with the content of 20%, boiling and refluxing for 9.0h, then carrying out solid-liquid separation, and washing a solid phase by water to obtain a solid phase which is the pretreated natural crystalline flake graphite; adding the pretreated natural crystalline flake graphite into concentrated sulfuric acid, fully stirring and mixing, adding potassium permanganate into the mixed solution to react for 3.0h, adding deionized water to react for 1.0h, and adding hydrogen peroxide solution to react for 1.0h to obtain a graphite oxide solution; ultrasonically stripping the graphite oxide solution for 0.5h, filtering, washing a solid phase with deionized water until the filtrate is neutral, and vacuum drying the solid phase at 110 ℃ for 2h to obtain graphene oxide; ultrasonically dispersing graphene oxide in a glycol and ethylenediamine solution to react for 12 hours to obtain aminated graphene; adding 25% platinum nitrate solution into the aminated graphene, soaking for 2 hours, adopting 20% sodium hypophosphite solution to reduce for 4 hours, filtering, washing to be neutral, and drying for 15 hours at 70 ℃ after solid-liquid separation and water removal to obtain the aminated graphene loaded platinum catalyst.
The performance of the catalyst in this example: the content of platinum in the catalyst is 1.8%, the total number of platinum grains with the grain diameter smaller than 10nm in the catalyst is 89%, the conversion rate and the selectivity of the p-nitrosodiphenylamine in the condensation liquid in the process of preparing the p-aminodiphenylamine by the catalytic hydrogenation nitrobenzene method are shown in the following table.
| Number of times of application | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Conversion of nitrodiphenylamine% | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Selectivity to para-aminodiphenylamine% | 99.4 | 99.4 | 99.4 | 99.3 | 99.4 | 99.5 | 99.4 | 99.5 |
The present invention may be summarized in other specific forms without departing from the spirit or essential characteristics thereof. The above-described embodiments of the invention are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (1)
1. The platinum catalyst loaded on the aminated graphene is characterized by comprising a carrier and an active component, wherein the carrier is the aminated graphene, the active component is platinum, the mass content of the platinum in the catalyst is 0.1% -3.0%, and the preparation steps of the catalyst comprise: (1) Soaking natural crystalline flake graphite in an inorganic acid solution with the mass fraction of 3% -20%, boiling and refluxing for 1.5-12 hours, then carrying out solid-liquid separation, and washing a solid phase by water to obtain a solid phase which is the pretreated natural crystalline flake graphite; (2) Adding the pretreated natural crystalline flake graphite into concentrated sulfuric acid, fully stirring and mixing, adding potassium permanganate into the mixed solution to react for 2.0-3.5 hours, adding deionized water to react for 0.5-1.5 hours, and then adding hydrogen peroxide solution to react for 0.5-1.5 hours to obtain a graphite oxide solution; (3) Ultrasonically stripping the graphite oxide solution for 0.5-1.0 h, filtering, washing the solid phase with deionized water until the filtrate is neutral, and drying the solid phase to obtain graphene oxide; (4) Ultrasonically dispersing graphene oxide in a glycol and ethylenediamine solution to react for 8-18 hours to obtain aminated graphene; (5) Adding the platinum salt solution into the aminated graphene for dipping, reducing, washing and drying to obtain a platinum catalyst loaded on the aminated graphene; the inorganic acid in the step (1) is one or more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid; the size of the aminated graphene is 2-9 mu m, the thickness of the aminated graphene is 0.8-3.6 nm, the ammoniation rate of the aminated graphene is 3.8-4.5%, the platinum salt in the step (5) is one or more of platinum chloride, platinum acetate, platinum nitrate or chloroplatinic acid, the total number of platinum grains with the grain diameter smaller than 10nm in the catalyst is more than or equal to 85%, the mass concentration of platinum salt solution is 5-32%, and the prepared aminated graphene is loaded with a platinum catalyst for preparing p-aminodiphenylamine by catalyzing nitrobenzene hydrogenation.
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