CN113499764A - Platinum-loaded catalyst on aminated graphene and preparation method thereof - Google Patents
Platinum-loaded catalyst on aminated graphene and preparation method thereof Download PDFInfo
- Publication number
- CN113499764A CN113499764A CN202110661340.9A CN202110661340A CN113499764A CN 113499764 A CN113499764 A CN 113499764A CN 202110661340 A CN202110661340 A CN 202110661340A CN 113499764 A CN113499764 A CN 113499764A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- platinum
- solution
- graphene
- solid phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 59
- 239000010439 graphite Substances 0.000 claims abstract description 59
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007788 liquid Substances 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 23
- 150000003057 platinum Chemical class 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 10
- 238000005576 amination reaction Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 58
- 239000007790 solid phase Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 238000005406 washing Methods 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000000926 separation method Methods 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 18
- 230000007935 neutral effect Effects 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000012286 potassium permanganate Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- 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
- 238000007598 dipping method Methods 0.000 claims description 4
- 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
- 239000002245 particle Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000009467 reduction Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000009833 condensation Methods 0.000 description 19
- 230000005494 condensation Effects 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 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 14
- OIJHFHYPXWSVPF-UHFFFAOYSA-N para-Nitrosodiphenylamine Chemical compound C1=CC(N=O)=CC=C1NC1=CC=CC=C1 OIJHFHYPXWSVPF-UHFFFAOYSA-N 0.000 description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 8
- 229910000510 noble metal Inorganic materials 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
- 238000006722 reduction reaction Methods 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
- 238000006482 condensation reaction Methods 0.000 description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- QGMGHALXLXKCBD-UHFFFAOYSA-N 4-amino-n-(2-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC1=CC=CC=C1N QGMGHALXLXKCBD-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
- 238000009825 accumulation Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000013078 crystal Substances 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
- 238000005470 impregnation Methods 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
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002994 raw material Substances 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
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 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
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect 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
- 238000009396 hybridization Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 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
- 229920000642 polymer Polymers 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
- 238000011084 recovery Methods 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
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B01J35/393—
-
- 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
-
- 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
Abstract
The invention discloses a preparation method of a platinum catalyst loaded on aminated graphene, which comprises the steps of pretreating natural crystalline flake graphite, oxidizing the pretreated natural crystalline flake graphite to prepare graphite oxide, ultrasonically stripping the graphite oxide to obtain graphene oxide, aminated graphene is obtained by amination of the graphene oxide, and a platinum salt solution is added into the aminated graphene to prepare the platinum catalyst loaded on the aminated graphene. The invention solves the problems that the reduction catalyst in the prior p-aminodiphenylamine production can not remove reaction heat in time, so that the catalyst is locally overheated and is sintered and inactivated, the catalyst loss is large, impurities in a hydrogenation liquid are more, and the production capacity is reduced. The catalyst is used for preparing p-aminodiphenylamine by catalytic nitrobenzene hydrogenation, and has the advantages of high activity, high selectivity, good stability, long service life and good application prospect.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a platinum-loaded catalyst on aminated graphene and a preparation method thereof, which are used for preparing p-aminodiphenylamine by hydrogenation through a catalytic nitrobenzene method.
Background
P-aminodiphenylamine (also known as RT base and 4-aminodiphenylamine) is an important organic intermediate, is widely applied to rubber auxiliaries, dyes, textile, printing, pharmaceutical industry and the like, and is mainly used as an intermediate of p-phenylenediamine rubber antioxidants for preparing the rubber antioxidants 4010NA, 6PPD and the like.
The present technique for industrial production at home and abroad mainly comprises a dianiline method and a nitro method, wherein the dianiline method is used for preparing p-aminodiphenylamine and uses nitrite as raw material in an organic solvent to carry out nitrosation in the presence of inorganic acid to obtain N-nitrosodiphenylamine, then anhydrous hydrogen chloride is used for rearrangement to obtain 4-nitrosodiphenylamine hydrochloride, alkali is used for neutralization to generate 4-nitrosodiphenylamine, and finally reduction is carried out to obtain 4-aminodiphenylamine. The process for preparing p-aminodiphenylamine by nitrobenzene method uses nitrobenzene and phenylamine as raw materials, uses tetramethyl ammonium hydroxide as condensation catalyst to make condensation reaction to produce p-nitrosodiphenylamine (4-nitrosodiphenylamine) and p-nitrodiphenylamine (4-nitrodiphenylamine), after the condensation reaction is completed, the condensation liquid is hydrogenated under the action of hydrogenation catalyst to prepare p-aminodiphenylamine.
The hydrogenation of p-aminodiphenylamine prepared by the nitrobenzene method is generally adopted as a nickel catalyst and a noble metal catalyst, and the noble metal catalyst mainly comprises a palladium/carbon catalyst and a platinum/carbon catalyst.
The condensation liquid is hydrogenated by a nickel catalyst, and the solvent is methanol generally; the method comprises the steps of hydrogenating a condensation liquid by using a noble metal catalyst, generally using water as a solvent, separating a solid catalyst from a hydrogenation reaction liquid after hydrogenation is finished, treating the hydrogenation reaction liquid to obtain a water phase and an organic phase, concentrating the water phase of the noble metal hydrogenation liquid to recover tetramethyl ammonium hydroxide, treating the water phase of a nickel catalyst hydrogenation liquid to recover tetramethyl ammonium hydroxide and methanol, recycling the tetramethyl ammonium hydroxide for condensation reaction, recycling the methanol for hydrogenation reaction, rectifying the organic phase in a rectifying process to obtain p-aminodiphenylamine, and recycling aniline for condensation reaction.
The patent CN103420849A adopts Ni catalyst, the mass content of 4-nitrodiphenylamine in the reaction liquid is 5-20%, the mass content of 4-aminodiphenylamine is 20-30%, the reaction temperature is 100-250 ℃, the reaction pressure is 2.0-4.0 MPa, and the liquid phase space velocity is 6.0 h-1~16.0h-1And the volume ratio of the hydrogen to the 4-nitrodiphenylamine is 200-600: 1, and the 4-aminodiphenylamine is continuously synthesized, wherein the yield reaches 92%.
Patent CN102344376A describes that 4-nitrodiphenylamine and 4-nitrosodiphenylamine are hydrogenated in the presence of a Pd/C catalyst to prepare p-aminodiphenylamine, rare earth metal elements are added into active components of the catalyst, namely palladium, and the content of substances except aniline and p-aminodiphenylamine in a hydrogenation product is 18.40-22.68%.
Patent CN106179332A describes a method for preparing a palladium/carbon catalyst for hydrogenation preparation of 4-aminodiphenylamine. The preparation method is characterized in that active carbon is taken as a carrier, palladium is taken as an active component, and the preparation process comprises the following steps: the prepared catalyst is used for catalytic hydrogenation for preparing 4-aminodiphenylamine by a nitrobenzene method, the selectivity of the 4-aminodiphenylamine is 95.5-99.7%, but the catalyst is not used indiscriminately.
The Anhui Tongling Xinda company develops and constructs a 3kt/a nitrobenzene method p-aminodiphenylamine production device, the trial run is successful in 2001 within 4 months, a precious metal catalyst Pt/C is adopted for hydrogenation reduction, and the RT base production cost is high and the production is stopped because the precious metal catalyst is low in activity and few in cycle times when being applied mechanically.
The p-nitrosodiphenylamine in the condensation liquid in the production of p-aminodiphenylamine by the nitrobenzene method and the p-aminodiphenylamine reduced by the p-nitrodiphenylamine are in a strong exothermic reaction, so that catalyst metal accumulation and high-temperature sintering are easily caused, and the activity is reduced.
The nickel catalyst is low in price, but the using amount is large, 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 the soft water and the RT reducing solution; the noble metal catalyst is easy to inactivate and has few application times, so that the noble metal catalyst for preparing p-aminodiphenylamine by hydrogenation reduction has high activity, high selectivity, good stability, more application times and long service life and 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 p-aminodiphenylamine by hydrogenation through a catalytic nitrobenzene method and aims to solve the problems of metal accumulation and high-temperature sintering caused by incapability of timely removing reaction heat by a reduction catalyst in the existing p-aminodiphenylamine production so as to reduce activity.
Graphene is a polymer made of carbon atoms in sp2The novel inorganic nano material with the honeycomb crystal structure formed by hybridization has high strength and high heat conductivity coefficient, benefits from the unique structure of the novel inorganic nano material, weak van der Waals force exists between graphene, so that the graphene is not uniformly dispersed, and is easy to agglomerate, so that the application is not good.
According to the invention, aminated graphene is used as a carrier, a platinum salt solution is used as a platinum precursor, the preparation of the catalyst is completed through the steps of carrier pretreatment, oxidation, stripping, amination, impregnation, washing, drying and the like, and the noble metal platinum is dispersed on the aminated graphene more uniformly by controlling the carrier pretreatment, oxidation, stripping, amination and impregnation processes in the preparation process, and the grain size of the platinum is regulated, so that the noble metal catalyst with high activity, high selectivity, good stability, multiple times of application and long service life is obtained.
The invention is realized by the following steps: the catalyst is characterized by comprising a carrier and an active component, wherein the carrier is aminated graphene, the active component is platinum, and the mass content of platinum in the catalyst is 0.1% -3.0%.
Generally, the size of the aminated graphene is 2-9 μm, 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 the platinum crystal grains with the grain diameter less than 10nm in the catalyst is more than or equal to 85 percent.
The invention also provides a preparation method of the platinum-loaded catalyst on the aminated graphene, which comprises the following preparation steps: (1) soaking natural crystalline flake graphite in an inorganic acid solution, boiling, refluxing, performing solid-liquid separation, and washing a solid phase to obtain a pretreated natural crystalline flake graphite solid phase; (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 adding a hydrogen peroxide solution for reaction to obtain a graphite oxide solution; (3) ultrasonically stripping and filtering the graphite oxide solution, washing a solid phase with deionized water until filtrate is neutral, and drying the solid phase to obtain graphene oxide; (4) ultrasonically dispersing graphene oxide in a solution of ethylene glycol and ethylenediamine to react to obtain aminated graphene; (5) and adding a platinum salt solution into the aminated graphene, dipping, reducing, washing and drying to obtain the platinum catalyst loaded on the aminated graphene.
One typical preparation step of the present 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 h, then carrying out solid-liquid separation, washing a solid phase with water, and obtaining the 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, reacting for 2.0-3.5 hours, adding deionized water, reacting for 0.5-1.5 hours, adding a hydrogen peroxide solution, and reacting 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 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 a solution of ethylene glycol and ethylenediamine, and reacting for 8-18 h to obtain aminated graphene; (5) and adding a platinum salt solution into the aminated graphene, dipping, reducing, 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 invention is carried out in a 0.45L high-pressure reaction kettle. 200g of condensation liquid (wherein the mass content of the p-nitrodiphenylamine is about 4 percent, the mass content of the p-nitrosodiphenylamine is about 23 percent, and the balance is aniline, azobenzene, water, tetramethylammonium hydroxide and the like), 80g of distilled water and 0.4g of catalyst are added into a reaction kettle, the hydrogenation reduction reaction temperature is 78 ℃, the hydrogen pressure is 1.8MPa, the stirring speed is 1200r/min, and a 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 the potential safety hazard caused by catalyst agglomeration;
2. the catalyst can avoid the sintering inactivation caused by local overheating of the catalyst, reduce the loss of the catalyst and improve the selectivity of the hydrogenation reduction reaction;
3. the catalyst is used for preparing p-aminodiphenylamine by hydrogenation reduction, water is used as a solvent, other organic solvents are not required to be added in the reaction process, and the solvent consumption and the recovery cost are reduced;
4. the catalyst of the invention is used for preparing p-aminodiphenylamine by catalytic nitrobenzene hydrogenation, and has the advantages of high activity, high selectivity, good stability and long service life.
Detailed Description
The present invention will be described in detail with reference to examples (the percentages in the following comparative examples and examples are by mass).
Example 1
Soaking natural crystalline flake graphite in a sulfuric acid solution with the content of 10%, boiling and refluxing for 8.0h, then carrying out solid-liquid separation, and washing a 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, reacting for 3.0 hours, adding deionized water, reacting for 1.0 hour, adding a hydrogen peroxide solution, and reacting for 1.0 hour 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 solution of ethylene glycol and ethylenediamine, and reacting for 15h to obtain aminated graphene; adding chloroplatinic acid solution with the content of 10% into aminated graphene, soaking for 10h, reducing for 4h by hydrazine hydrate solution with the content of 20%, filtering, washing to be neutral, performing solid-liquid separation to remove water, and drying for 10h at 90 ℃ to obtain the platinum catalyst loaded on the aminated graphene.
The performance of the catalyst in this example: the platinum content in the catalyst is 1.0 percent, the total number of platinum grains with the grain diameter less than 10nm in the catalyst is 88 percent, the condensation liquid in the process of preparing p-aminodiphenylamine by the catalytic hydrogenation nitrobenzene method, and the conversion rate and the selectivity of p-nitrosodiphenylamine and p-nitrodiphenylamine in the condensation liquid are shown in the following table.
| Number of times of application | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| P- (sub) nitrodiphenylamine conversion percentage% | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| P-aminodiphenylamine selectivity,% | 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 1.5h, then carrying out solid-liquid separation, washing a solid phase with water, and obtaining the 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, reacting for 2.5 hours, adding deionized water, reacting for 1.5 hours, adding a hydrogen peroxide solution, and reacting for 0.5 hour 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 solution of ethylene glycol and ethylenediamine, and reacting for 8 hours to obtain aminated graphene; adding a chloroplatinic acid solution with the content of 15% into aminated graphene, soaking for 10h, reducing for 6h by adopting a hydrazine hydrate solution with the content of 10%, filtering, washing to be neutral, carrying out solid-liquid separation, removing water, and drying for 9h at 95 ℃ to obtain the platinum catalyst loaded on the aminated graphene.
The performance of the catalyst in this example: the platinum content in the catalyst is 0.8%, the total number of platinum grains with the grain diameter less than 10nm in the catalyst is 90%, and the conversion rate and the selectivity of p-nitroso diphenylamine and p-nitrodiphenylamine in the condensation liquid are shown in the following table in the process of preparing p-aminodiphenylamine by a catalytic hydrogenation nitrobenzene method.
| Number of times of application | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| P- (sub) nitrodiphenylamine conversion percentage% | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| P-aminodiphenylamine selectivity,% | 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, performing solid-liquid separation, and washing the solid phase with water to obtain a solid phase which is 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, reacting for 3.5 hours, adding deionized water, reacting for 0.5 hour, adding a hydrogen peroxide solution, and reacting 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 solution of ethylene glycol and ethylenediamine, and reacting for 12h to obtain aminated graphene; adding a chloroplatinic acid solution with the content of 32% into aminated graphene, soaking for 10h, reducing for 3h by adopting a hydrazine hydrate solution with the content of 30%, filtering, washing to be neutral, carrying out solid-liquid separation, removing water, and drying for 8h at 100 ℃ to obtain the platinum catalyst loaded on the aminated graphene.
The performance of the catalyst in this example: the platinum content in the catalyst is 0.5 percent, the total number of platinum grains with the grain diameter less than 10nm in the catalyst is 91 percent, the condensation liquid in the process of preparing p-aminodiphenylamine by the catalytic hydrogenation nitrobenzene method, and the conversion rate and the selectivity of p-nitrosodiphenylamine and p-nitrodiphenylamine in the condensation liquid are shown in the following table.
| Number of times of application | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| P- (sub) nitrodiphenylamine conversion percentage% | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| P-aminodiphenylamine selectivity,% | 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, performing solid-liquid separation, and washing the solid phase to obtain a solid phase which is 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, reacting for 3.0 hours, adding deionized water, reacting for 0.5 hours, adding a hydrogen peroxide solution, and reacting for 1.5 hours 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 solution of ethylene glycol and ethylenediamine, and reacting for 15h to obtain aminated graphene; adding a chloroplatinic acid solution with the content of 5% into aminated graphene, soaking for 8h, reducing for 5h by adopting a hydrazine hydrate solution with the content of 15%, filtering, washing to be neutral, carrying out solid-liquid separation, removing water, and drying for 10h at 85 ℃ to obtain the platinum catalyst loaded on the aminated graphene.
The performance of the catalyst in this example: the platinum content in the catalyst is 1.5 percent, the total number of platinum grains with the grain diameter less than 10nm in the catalyst is 88 percent, the condensation liquid in the process of preparing p-aminodiphenylamine by the catalytic hydrogenation nitrobenzene method, and the conversion rate and the selectivity of p-nitrosodiphenylamine and p-nitrodiphenylamine in the condensation liquid are shown in the following table.
| Number of times of application | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| P- (sub) nitrodiphenylamine conversion percentage% | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| P-aminodiphenylamine selectivity,% | 99.3 | 99.3 | 99.4 | 99.4 | 99.3 | 99.4 | 99.3 | 99.4 |
Example 5
Soaking natural crystalline flake graphite in a sulfuric acid solution with the content of 3%, boiling and refluxing for 10.0h, then carrying out solid-liquid separation, and washing a 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, reacting for 3.5 hours, adding deionized water, reacting for 1.5 hours, adding a hydrogen peroxide solution, and reacting for 0.5 hour 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 solution of ethylene glycol and ethylenediamine, and reacting for 18h to obtain aminated graphene; adding a platinum chloride solution with the content of 15% into aminated graphene, soaking for 6h, reducing for 4h by using a formaldehyde solution with the content of 18%, filtering, washing to be neutral, carrying out solid-liquid separation, removing water, and drying for 12h at 80 ℃ to obtain the platinum catalyst loaded on the aminated graphene.
The performance of the catalyst in this example: the platinum content in the catalyst is 3.0 percent, the total number of platinum grains with the grain diameter less than 10nm in the catalyst is 86 percent, the condensation liquid in the process of preparing p-aminodiphenylamine by the catalytic hydrogenation nitrobenzene method, and the conversion rate and the selectivity of p-nitrosodiphenylamine and p-nitrodiphenylamine in the condensation liquid are shown in the following table.
| Number of times of application | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| P- (sub) nitrodiphenylamine conversion percentage% | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| P-aminodiphenylamine selectivity,% | 99.5 | 99.5 | 99.4 | 99.5 | 99.5 | 99.5 | 99.4 | 99.4 |
Example 6
Soaking natural crystalline flake graphite in a sulfuric acid solution with the content of 5%, boiling, refluxing for 12.0h, performing solid-liquid separation, and washing a solid phase to obtain a solid phase which is 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, reacting for 2.5 hours, adding deionized water, reacting for 1.0 hour, adding a hydrogen peroxide solution, and reacting for 1.0 hour 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 solution of ethylene glycol and ethylenediamine, and reacting for 16h to obtain aminated graphene; adding a platinum acetate solution with the content of 18% into aminated graphene, soaking for 5h, reducing for 3h by using a formaldehyde solution with the content of 25%, filtering, washing to be neutral, carrying out solid-liquid separation, removing water, and drying for 14h at 75 ℃ to obtain the platinum catalyst loaded on the aminated graphene.
The performance of the catalyst in this example: the platinum content in the catalyst is 2.5 percent, the total number of platinum grains with the grain diameter less than 10nm in the catalyst is 88 percent, the condensation liquid in the process of preparing p-aminodiphenylamine by the catalytic hydrogenation nitrobenzene method, and the conversion rate and the selectivity of p-nitrosodiphenylamine and p-nitrodiphenylamine in the condensation liquid are shown in the following table.
| Number of times of application | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| P- (sub) nitrodiphenylamine conversion percentage% | 100 | 100 | 100 | 100 | 100 | 99.9 | 100 | 100 |
| P-aminodiphenylamine selectivity,% | 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 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, reacting for 3.0 hours, adding deionized water, reacting for 1.0 hour, adding a hydrogen peroxide solution, and reacting for 1.0 hour 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 solution of ethylene glycol and ethylenediamine, and reacting for 12h to obtain aminated graphene; adding a platinum nitrate solution with the content of 25% into aminated graphene, soaking for 2h, reducing for 4h by using a sodium hypophosphite solution with the content of 20%, filtering, washing to be neutral, performing solid-liquid separation to remove water, and drying for 15h at 70 ℃ to obtain the platinum catalyst loaded on the aminated graphene.
The performance of the catalyst in this example: the platinum content in the catalyst is 1.8%, the total number of platinum grains with the grain diameter less than 10nm in the catalyst is 89%, the condensation liquid in the process of preparing p-aminodiphenylamine by the catalytic hydrogenation nitrobenzene method, and the conversion rate and the selectivity of p-nitrosodiphenylamine and p-nitrodiphenylamine in the condensation liquid are shown in the following table.
| Number of times of application | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| P- (sub) nitrodiphenylamine conversion percentage% | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| P-aminodiphenylamine selectivity,% | 99.4 | 99.4 | 99.4 | 99.3 | 99.4 | 99.5 | 99.4 | 99.5 |
The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. 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 not by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (9)
1. The catalyst is characterized by comprising a carrier and an active component, wherein the carrier is aminated graphene, the active component is platinum, and the mass content of platinum in the catalyst is 0.1% -3.0%.
2. The catalyst according to claim 1, wherein the aminated graphene has a size of 2 μm to 9 μm, a thickness of 0.8nm to 3.6nm, and an amination rate of 3.8% to 4.5%.
3. The catalyst of claim 1, wherein the total number of platinum grains having a particle size of less than 10nm in the catalyst is not less than 85%.
4. The method for preparing the catalyst according to claim 1, characterized in that the preparing step comprises: (1) soaking natural crystalline flake graphite in an inorganic acid solution, boiling, refluxing, performing solid-liquid separation, and washing a solid phase to obtain a pretreated natural crystalline flake graphite solid phase; (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 adding a hydrogen peroxide solution for reaction to obtain a graphite oxide solution; (3) ultrasonically stripping and filtering the graphite oxide solution, washing a solid phase with deionized water until filtrate is neutral, and drying the solid phase to obtain graphene oxide; (4) ultrasonically dispersing graphene oxide in a solution of ethylene glycol and ethylenediamine to react to obtain aminated graphene; (5) and adding a platinum salt solution into the aminated graphene, dipping, reducing, washing and drying to obtain the platinum catalyst loaded on the aminated graphene.
5. The method for preparing the catalyst according to claim 4, characterized by comprising the steps of: (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 h, then carrying out solid-liquid separation, washing a solid phase with water, and obtaining the 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, reacting for 2.0-3.5 hours, adding deionized water, reacting for 0.5-1.5 hours, adding a hydrogen peroxide solution, and reacting 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 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 a solution of ethylene glycol and ethylenediamine, and reacting for 8-18 h to obtain aminated graphene; (5) and adding a platinum salt solution into the aminated graphene, dipping, reducing, washing and drying to obtain the platinum catalyst loaded on the aminated graphene.
6. The method for preparing the catalyst according to claim 4 or 5, wherein the inorganic acid is one or more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
7. The method for preparing a catalyst according to claim 4 or 5, wherein the platinum salt solution is one or more of platinum chloride, platinum acetate, platinum nitrate or chloroplatinic acid.
8. The preparation method of the catalyst according to claim 4 or 5, wherein the mass concentration of the platinum salt solution is 5-32%.
9. The catalyst of claim 1, wherein the catalyst is used for catalyzing hydrogenation of nitrobenzene to prepare p-aminodiphenylamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110661340.9A CN113499764A (en) | 2021-06-15 | 2021-06-15 | Platinum-loaded catalyst on aminated graphene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110661340.9A CN113499764A (en) | 2021-06-15 | 2021-06-15 | Platinum-loaded catalyst on aminated graphene and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113499764A true CN113499764A (en) | 2021-10-15 |
Family
ID=78009992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110661340.9A Pending CN113499764A (en) | 2021-06-15 | 2021-06-15 | Platinum-loaded catalyst on aminated graphene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113499764A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113842904A (en) * | 2021-10-19 | 2021-12-28 | 天津大学 | Tungsten monatomic catalyst with graphene substrate, and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060714A (en) * | 2010-06-25 | 2011-05-18 | 天津市有机化工一厂 | Method for preparing 4-aminodiphenylamine |
| CN105126829A (en) * | 2015-09-09 | 2015-12-09 | 广西师范大学 | Modified graphene platinized catalyst, preparation method of modified graphene platinized catalyst and application of modified graphene platinized catalyst |
| CN106179332A (en) * | 2015-05-07 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of catalyst preparing 4-ADPA and preparation method |
| CN106946246A (en) * | 2017-04-27 | 2017-07-14 | 山东金城石墨烯科技有限公司 | A kind of preparation method of amination graphene |
| CN108993608A (en) * | 2018-07-27 | 2018-12-14 | 北京化工大学 | A kind of multifunction catalyst and the method for producing hydrogen hydrogenation synthesis hydrogenated nitrile-butadiene rubber |
| CN109261214A (en) * | 2018-10-16 | 2019-01-25 | 衡阳师范学院 | A kind of photochemical catalyzing prepares the preparation method of hydrogen catalyst |
-
2021
- 2021-06-15 CN CN202110661340.9A patent/CN113499764A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060714A (en) * | 2010-06-25 | 2011-05-18 | 天津市有机化工一厂 | Method for preparing 4-aminodiphenylamine |
| CN106179332A (en) * | 2015-05-07 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of catalyst preparing 4-ADPA and preparation method |
| CN105126829A (en) * | 2015-09-09 | 2015-12-09 | 广西师范大学 | Modified graphene platinized catalyst, preparation method of modified graphene platinized catalyst and application of modified graphene platinized catalyst |
| CN106946246A (en) * | 2017-04-27 | 2017-07-14 | 山东金城石墨烯科技有限公司 | A kind of preparation method of amination graphene |
| CN108993608A (en) * | 2018-07-27 | 2018-12-14 | 北京化工大学 | A kind of multifunction catalyst and the method for producing hydrogen hydrogenation synthesis hydrogenated nitrile-butadiene rubber |
| CN109261214A (en) * | 2018-10-16 | 2019-01-25 | 衡阳师范学院 | A kind of photochemical catalyzing prepares the preparation method of hydrogen catalyst |
Non-Patent Citations (3)
| Title |
|---|
| RENFENG NIE ET AL.: "Platinum supported on reduced graphene oxide as a catalyst for hydrogenation of nitroarenes", 《CARBON》, vol. 50, no. 2, pages 142 * |
| SANKARAN MURUGESAN ET AL.: "Can Graphene be the Electrode Support for Pt in Formic acid Electrooxidation?", vol. 19, no. 5, pages 250 * |
| XINXIAN ZHONG ET AL.: "Fabrication of Pt nanoparticles on ethylene diamine functionalized graphene for formic acid electrooxidation", vol. 39, no. 28, pages 15921 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113842904A (en) * | 2021-10-19 | 2021-12-28 | 天津大学 | Tungsten monatomic catalyst with graphene substrate, and preparation method and application thereof |
| CN113842904B (en) * | 2021-10-19 | 2023-07-25 | 天津大学 | Tungsten single-atom catalyst with graphene substrate, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5473901B2 (en) | Method for producing amine | |
| US7468461B2 (en) | Method for the production of amines | |
| CN111151284B (en) | Nitrogen-doped carbon-coated catalyst, and preparation method and application thereof | |
| CN105669464B (en) | A kind of application of no catalytic hydrogenation in being catalyzed nitro benzene and its derivative hydrogenation reaction | |
| CN106944065B (en) | Preparation method and application of graphene-supported nickel hydrogenation catalyst | |
| CN110882697B (en) | Catalyst for preparing ethylamine by ethanol amination and preparation method and application thereof | |
| CN102690204A (en) | Method for preparing cyclohexanediamine | |
| CN105080567A (en) | Catalyst and aromatic amino compound preparation method | |
| CN113499764A (en) | Platinum-loaded catalyst on aminated graphene and preparation method thereof | |
| CN102688757A (en) | Catalyst for preparing cyclohexanediamine by phenylenediamine hydrogenation under ammonia reaction conditions | |
| US4185036A (en) | Hydrogenation of mixed aromatic nitrobodies | |
| CN103357423A (en) | Preparation method of modified palladium-carbon catalyst for aromatic amine preparation, and application of catalyst | |
| CN114054061A (en) | Nitrogen-doped carbon-supported palladium catalyst and preparation method and application thereof | |
| WO2018133196A1 (en) | Phosphor-doped carbon material hydrogenation catalyst, preparation method therefor and use thereof | |
| CN106179332B (en) | A kind of catalyst preparing 4-ADPA and preparation method | |
| CN103285856A (en) | Anti-dehalogenation ruthenium-based catalyst for preparing halogenated phenylamine and preparation method thereof | |
| CN101439285B (en) | Method for preparing catalyst for catalytic hydrogenation of nitro compound and catalyst | |
| CN105749954A (en) | Metal-free hydrogenation catalyst and application of metal-free hydrogenation catalyst in catalyzing 1,5-dinitronaphthalene hydrogenation reaction | |
| CN105753717B (en) | A kind of application of no catalytic hydrogenation in 1- nitronaphthalene hydrogenation reactions are catalyzed | |
| CN111686726B (en) | Preparation method and application of carbon-based noble metal catalyst | |
| CN112604685A (en) | Supported catalyst and preparation method and application thereof | |
| JP3541396B2 (en) | Method for producing 4-aminodiphenylamine | |
| CN112300007B (en) | Catalytic hydrogenation method for 4-nitrodiphenylamine and 4-nitrosodiphenylamine-containing condensate | |
| CN109912429B (en) | Method for preparing arylamine compound by catalytic reduction of arylnitro compound with nano-porous gold catalyst | |
| CN105777577B (en) | A kind of application of no catalytic hydrogenation in nitrocyclohexane hydrogenation reaction is catalyzed |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |