CN114225935B - Preparation and application of onion-shaped supported carbon-coated platinum catalyst - Google Patents
Preparation and application of onion-shaped supported carbon-coated platinum catalyst Download PDFInfo
- Publication number
- CN114225935B CN114225935B CN202111679232.0A CN202111679232A CN114225935B CN 114225935 B CN114225935 B CN 114225935B CN 202111679232 A CN202111679232 A CN 202111679232A CN 114225935 B CN114225935 B CN 114225935B
- Authority
- CN
- China
- Prior art keywords
- platinum catalyst
- supported
- catalyst
- carbon
- temperature
- 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.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses preparation and application of an onion-shaped supported carbon-coated platinum catalyst. The preparation method of the supported carbon-coated platinum catalyst comprises the following steps: (1) Weighing a supported platinum catalyst, uniformly mixing the supported platinum catalyst with water, adding an aqueous solution of a soluble carbon source compound, uniformly soaking, and removing water; repeating loading the soluble carbon source compound for 2-5 times to obtain a loaded platinum catalyst loaded with the carbon source compound; (2) Roasting a supported platinum catalyst loaded with a carbon source compound at a high temperature of 400-900 ℃ for 2-10 hours in an inert protective atmosphere, a hydrogen atmosphere or a vacuum state to obtain a roasting product; (3) And (3) reducing the temperature to 100-180 ℃, and treating the roasting product for 4-10 hours in an air atmosphere to prepare the supported carbon-coated platinum catalyst. The invention provides an application of the supported carbon-coated platinum catalyst in preparation of alkoxy substituted or phenolic hydroxyl substituted aniline compounds from nitrobenzene compounds, and the supported carbon-coated platinum catalyst has high stability and high target product yield.
Description
Field of the art
The invention relates to an onion-shaped supported carbon-coated platinum catalyst and application thereof in catalytic hydrogenation reaction under an acidic condition, in particular to application in preparation of p-aminophenol by nitrobenzene hydrogenation.
(II) background art
Catalytic hydrogenation is an extremely important chemical reaction in the production process of medical (agricultural) drugs, dyes, organic materials, electronic chemicals and the like. However, the catalytic hydrogenation reaction is carried out in a (strongly) acidic solvent or the like, and the solubility of the active metal component of the catalyst is lost, so that the catalyst is irreversibly deactivated and the metal in the product remains. Even the supported noble metal catalyst with excellent hydrogenation performance and wide application has metal loss and irreversible deactivation in a strong acid reaction environment, which directly causes poor reusability and increased production cost. Therefore, the application of the supported noble metal catalyst in the catalytic hydrogenation reaction of a strongly acidic system is greatly restricted. In addition, the residue of noble metals in products seriously affects the quality of high-end fine chemicals such as medicines, electronic chemicals and the like.
It is known that medicines, dyes, organic materials, electronic chemicals and the like are very harsh on the content of residual metal ions (especially heavy metal ions), and that noble metal loss during the reaction process is one of the main reasons for exceeding the standard of heavy metal ion residues of high-end fine chemicals. Thus, the metal ions remaining in the product must be removed by a process such as resin adsorption separation purification.
Therefore, it is important to invent a supported (noble) metal hydrogenation catalyst with good catalytic performance in (strong) acidic environment. The use of inert materials that are insoluble in acid to encapsulate noble metal particles is one of the effective methods for avoiding noble metal loss. However, how to obtain the catalytic hydrogenation performance required by the target reaction of the coated supported noble metal, especially the regulation and control of the selective hydrogenation performance, is a difficulty in preparing the catalyst, and is why the supported carbon coated noble metal catalyst has not been applied in an acidic environment.
Chinese patent CN201810831980.8 discloses a method for preparing carbon-encapsulated metal nanoparticles with controllable layer number, which comprises converting metal cation salt into layered metal hydroxide, depositing on the surface of silica spheres, heat treating in reducing atmosphere, introducing carbon source, removing silica spheres with hydrofluoric acid solution to obtain target catalyst product, wherein the carbon source is selected from methanol, ethanol, pyridine, pyrrole, acetonitrile, methane, ethane, ethylene, acetylene or propyleneAt least one catalyst prepared by the method can be used as an electrode material for preparing hydrogen by electrocatalytic decomposition of hydrogen sulfide. Chinese patent CN201711330761.3 discloses a carbon-coated nano iron-based fischer-tropsch synthesis catalyst and a preparation method thereof, wherein hydroxyl-rich carbon-containing compounds are used as carbon sources, ferric nitrate and alkali metal salts are used as raw materials, carbon microspheres are used as carriers, and a co-impregnation-in-situ carbonization strategy is adopted to prepare the carbon-coated nano iron-based fischer-tropsch synthesis catalyst, so that the fischer-tropsch reaction performance is improved. Document [ Nature Communications,2017,8:14969]Reported a method for preparing graphene-coated metal catalyst by carbonization of MOFs material, and Ru-substituted Co 3 [Co(CN) 6 ] 2 And carbonizing the precursor at 600 ℃ in nitrogen atmosphere to obtain the N-doped graphene-coated RuCo catalyst RuCo@NC, wherein the catalyst shows excellent performance in electrocatalytic hydrogen evolution reaction. However, there is no report of the use of the encapsulated noble metal catalyst in an acidic environment.
The p-aminophenol is an important chemical product widely used in medicines, dyes, antioxidants, photosensitive materials, pesticides and the like. In the pharmaceutical industry, it is used for synthesizing acetaminophen (analgesic and analgesic drug-paracetamol), avine, nitrone, vitamin B, compound amide and other drugs. In the rubber industry, p-phenylenediamine antioxidants such as 4010, 4010NA, 4020, 4030 and the like can be synthesized; the said process has the features of high efficiency, no toxicity, no pollution, etc. and is one kind of antioxidant for radial tyre. In the dye industry, it is used for synthesizing bulk materials, sulfur dyes, acid dyes, azo dyes, fur dyes, etc. Para-aminophenols are also used in the production of photographic developers, as antioxidants, petroleum product additives, acrylonitrile dimerization catalysts, inhibitors of urea addition reactions, as well as synthetic herbicides, pesticides, and the like.
The traditional production route of the p-aminophenol is that chlorobenzene is nitrified to generate p-nitrochlorobenzene, hydrolyzed to generate p-nitrophenol, and the p-aminophenol is obtained through three chemical reactions of a reduction method (iron powder, sodium sulfide or hydrogen) and a series of separation processes. The method has mature process, but the three wastes are discharged and amplified, and the product purity is low.
Obviously, nitrobenzene is taken as a raw material to generate hydroxyaniline through catalytic hydrogenation in a strong acid medium, and then p-aminophenol is generated in situ through Bamberger rearrangement reaction, so that the method is a green and efficient production route. However, the method has the defects that the yield of the target product p-aminophenol is low, the active component Pt and the like of the noble metal hydrogenation catalyst in the strong acid reaction environment are easy to run off, and the catalyst is seriously and irreversibly deactivated.
Therefore, the invention is a stable and efficient catalyst suitable for strongly acidic reaction medium, especially suitable for the high-selectivity preparation of p-aminophenol by the selective hydrogenation of nitrobenzene, and has great significance.
(III) summary of the invention
The invention aims at providing a preparation method of an onion-shaped supported carbon-coated platinum catalyst, wherein the prepared catalyst has good acid resistance, and the active metal component platinum of the catalyst does not have solubility loss in a strong acid reaction medium and has stable catalytic performance.
The second purpose of the invention is to provide the application of the supported carbon-coated platinum catalyst in the preparation of alkoxy substituted or phenolic hydroxyl substituted aniline compounds from nitrobenzene compounds, and the supported carbon-coated platinum catalyst has high stability and high target product yield.
In order to solve the above-mentioned purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a supported carbon-coated platinum catalyst, the method comprising:
(1) Weighing a supported platinum catalyst, wherein the supported platinum catalyst comprises a carrier and a metal active component supported on the carrier, the metal active component is platinum metal, uniformly mixing the platinum metal with water, adding an aqueous solution of a soluble carbon source compound, uniformly soaking, and removing water; repeating loading the soluble carbon source compound for 2-5 times to obtain a loaded platinum catalyst loaded with the carbon source compound; the soluble carbon source compound is at least one of glucose, sucrose, fructose, maltose, lactose and polyethylene glycol; the ratio of the total mass usage of the soluble carbon source compounds (namely the sum of the mass of the soluble carbon source compounds used for 2-5 times of repeated loading) to the mass usage of the supported platinum catalyst is 0.4-1.5: 1, a step of;
(2) Then, the supported platinum catalyst loaded with the carbon source compound is roasted for 2 to 10 hours at a high temperature of 400 to 900 ℃ in an inert protective atmosphere, a hydrogen atmosphere or a vacuum state to obtain a roasting product;
(3) Then, the temperature is reduced to 100-180 ℃, and the roasting product is treated for 4-10 hours in the air atmosphere, so as to prepare the supported carbon-coated platinum catalyst.
Preferably, the carrier of the supported platinum catalyst is activated carbon or TiO 2 Or diatomaceous earth.
Preferably, the supported platinum catalyst has a platinum loading (relative to the carrier) of 0.5 to 5wt%.
Preferably, in the step (1), the feeding mass ratio of the supported platinum catalyst to water is 1:1-5.
Preferably, the concentration of the aqueous solution of the soluble carbon source compound in the step (1) is 10 to 50wt%.
Preferably, in the step (1), the impregnation is performed at room temperature for 30 to 300 minutes each.
Preferably, in the step (1), the method of removing water is vacuum drying, the vacuum drying temperature is 20-80 ℃, and the vacuum drying time is 4-40 hours.
Preferably, the inert protective atmosphere is one or more of nitrogen, argon and helium.
The supported platinum catalyst of the present invention may be prepared by itself using commercially available products or according to methods reported in the literature. The supported carbon-coated platinum catalyst prepared by the method forms an onion-shaped structure, namely, a carbon layer with proper thickness and structure coats metal platinum, so that the platinum can be protected, the platinum is not easy to run off in an acidic environment, and the catalytic performance of the platinum can be maintained through quantum tunneling effect. Therefore, the supported carbon-coated platinum catalyst has good catalytic hydrogenation performance in an acidic solution.
In a second aspect, the invention provides the supported carbon-coated platinum catalyst shown in the formula (I)The application of nitrobenzene compounds in preparing alkoxy substituted or phenolic hydroxyl substituted aniline compounds shown in formula (II), (III) or (IV) is that nitrobenzene compounds and solvent R are contained 6 Introducing hydrogen into a reaction container of OH and strong acid, and carrying out hydrogenation and Bamberger rearrangement reaction under the stirring condition to obtain an alkoxy substituted or phenolic hydroxyl substituted aniline compound; the strong acid is sulfuric acid with the concentration of more than 98 percent, hydrochloric acid with the concentration of more than 35 percent or phosphoric acid with the concentration of more than 75 percent;
in the formula (I) or the formula (II), (III), (IV), -R 1 、-R 2 、-R 3 、-R 4 、-R 5 Independently selected from one of the following groups: -H, -CH 3 、-CH 2 CH 3 、-OH、-NH 2 、-OCH 3 、-COOCH 3 、-NHCH 2 CH 3 、-N(CH 3 ) 2 -F, -Cl, -Br, and-R 1 、-R 3 、-R 5 At least one of them is-H; -R 6 Selected from one of the following groups: -H, -CH 3 、-CH 2 CH 3 。
In general, the para-position R of the nitro group 3 When H is H, obtaining a product II; when the para-position of the nitro group is other than H, the product III or IV is obtained.
Preferably, the solvent R 6 The mass ratio of the OH, the strong acid, the nitrobenzene compounds and the supported carbon-coated platinum catalyst is 300-500: 50-100: 60-200: 1.
as a further preference, the R 6 OH is water, and surfactant is added into the reaction system, wherein the surfactant is dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride and hexadecylOne of trimethyl ammonium bromide and hexadecyl trimethyl ammonium chloride, wherein the mass ratio of the surfactant to the nitrobenzene compound shown in the formula (I) is 0.005-0.04: 1.
preferably, the temperature of the reaction is 50-120 ℃ and the hydrogen pressure is 0.3-3.0 MPa.
The supported carbon-coated platinum catalyst is particularly suitable for preparing p-aminophenol by selectively hydrogenating nitrobenzene. The application method of the supported carbon-coated platinum catalyst in preparing the p-aminophenol by nitrobenzene hydrogenation comprises the following steps: distilled water, 98wt% concentrated sulfuric acid, nitrobenzene, surfactant and supported carbon-coated platinum catalyst are added into an acid-resistant high-pressure reaction kettle, and the mass ratio of the catalyst is 300-500: 50-100: 60-200: 0.4 to 1: and 1, introducing hydrogen to perform hydrogenation rearrangement reaction under stirring to obtain the target product p-aminophenol.
Preferably, the surfactant is cetyltrimethylammonium chloride.
Preferably, the temperature of the reaction is 60-90 ℃ and the hydrogen pressure is 0.6-2.0 MPa.
The invention provides a preparation method of a supported carbon-coated platinum catalyst and a preparation method of a nitrobenzene compound in a solvent R 6 The application of the alkoxy substituted or phenolic hydroxyl substituted aniline compound is prepared by hydrogenation and Bamberger rearrangement reaction in OH and strong acid. It is known that in the actual production of high-end fine chemicals such as medicines and electronic chemicals, when the catalytic hydrogenation reaction is required in a strongly acidic solvent, the active metal component of the catalyst is liable to dissolve and lose, resulting in deactivation of the catalyst. The invention adopts the protective layer which is insoluble in acid, namely the carbon layer to wrap the active metal, thereby realizing the effect of protecting the active metal during the catalytic reaction in the strong acid solution medium. However, the pure carbon layer does not have catalytic hydrogenation activity, and the catalytic performance of the active metal must be transferred to the outermost carbon layer through the intermediate carbon layer. The outer layer d orbit of the platinum atom can be hybridized with the carbon layer p orbit tightly wrapped by the platinum metal, so that the electron cloud density and the Fermi energy level of the electrons of the carbon layer are enhanced, the adsorption free energy of hydrogen molecules and the like on the surface of the carbon layer is reduced, and further the carbon layer is promotedThe ability of the carbon layer to adsorb the activating reactant molecules; and p-orbit electrons of graphitized carbon form delocalized pi electrons, which can be freely transmitted in a graphite lattice layer, thereby being beneficial to forming catalytic active sites with uniform performance on the surface of the carbon layer. However, in a perfect graphite lattice, the p-electrons of carbon are difficult to traverse the graphite layer, and electron transport channels traversing the carbon layer can only be obtained by defects or doped heteroatoms in the graphite layer. In order to be able to transport the catalytic hydrogenation properties of platinum to the outermost layer, it is necessary to make defects or incorporate heteroatoms in the carbon layer. In addition, the adsorption capacity of the complete graphite layer to hydrogen and nitrobenzene is weak, and if the outermost carbon layer is grafted with an oxygen-containing functional group rich in electrons, the adsorption activation capacity to hydrogen can be obviously enhanced. Meanwhile, the acidic oxygen-containing functional group can be helpful for further Bamberger rearrangement reaction of the reaction intermediate phenylhydroxylamine, so that the reaction speed and the selectivity of target products are improved.
Thus, controlling the thickness, degree of densification, electron transport capacity, incorporation of heteroatoms, and the type and number of functional groups on the outer carbon layer are key to determining the performance of the catalyst. According to the preparation method, the carbon source compound, the carbonization temperature, the treatment atmosphere and the carbonization time are controlled, so that the carbon layer with proper thickness and carbon layer structure is prepared, the quantum tunneling effect is conveniently exerted, and the catalyst with excellent performance under the acidic condition is obtained.
Compared with the prior art, the invention has the following advantages:
1) Since the platinum catalyst is covered by the carbon layer, the metal platinum is not lost when it is in an acidic hydrogenation environment. Therefore, the catalyst has good stability in hydrogenation reaction in a strong acid environment, and the catalyst is continuously used for 10 times without obvious deactivation. And the carbon layer has proper structure and thickness, and can maintain the catalytic performance through quantum tunneling effect.
2) In the preparation process of the catalyst, oxygen atoms can be introduced into the carbon layer and the surface of the carbon layer by treating the catalyst in the air atmosphere at a proper temperature to form acidic oxygen-containing functional groups, which is beneficial to improving the catalytic activity and the selectivity of target products.
3) The catalyst adopted by the invention does not contain other metal elements except the active component of the metal platinum, and the difficulty of recycling the noble metal catalyst is not increased.
4) The catalyst prepared by the invention is used for preparing alkoxy substituted or phenolic hydroxyl substituted aniline compounds by hydrogenation rearrangement of nitrobenzene compounds, and has better stability and higher target product selectivity compared with catalysts without carbon coating. .
(IV) description of the drawings
FIG. 1 is a transmission electron micrograph of an onion-shaped supported carbon-coated platinum catalyst prepared in example one.
(fifth) detailed description of the invention
The following specific embodiments are used to illustrate the technical solution of the present invention, but the scope of the present invention is not limited thereto:
the commercially available catalysts used in the examples of the present invention were all purchased from Deqing county chemical Co., ltd.
Example 1
Weighing 10g of commercial 3wt% Pt/C, adding the Pt/C into 15ml of water, uniformly mixing, adding 10g of aqueous solution of lactose with concentration of 20wt%, soaking for 60min at room temperature, and then drying at 40 ℃ in vacuum for 20h to remove water; adding the obtained catalyst into 15ml of water, uniformly mixing, adding 10g of aqueous solution of lactose with concentration of 20wt%, soaking for 60min at room temperature, and vacuum drying at 40 ℃ for 20h to remove water; then roasting the mixture at 400 ℃ for 20 hours under nitrogen; then the temperature is reduced to 100 ℃, and the mixture is treated for 10 hours in an air atmosphere to prepare the supported carbon-coated platinum catalyst.
Example two
10g of commercially available 5wt% Pt/TiO were weighed out 2 Adding the mixture into 15ml of water, uniformly mixing, adding 10g of a glucose aqueous solution with the concentration of 50wt%, soaking for 60 minutes at room temperature, and then drying in vacuum at 80 ℃ for 10 hours to remove water; adding the obtained catalyst into 15ml of water, uniformly mixing, adding 10g of a glucose aqueous solution with the concentration of 50wt%, soaking for 60 minutes at room temperature, and then drying for 10 hours at 80 ℃ in vacuum to remove water; the loading is thus repeated once more (three times in total) under the same conditions; then roasting the mixture at 900 ℃ for 2 hours under hydrogen; then the temperature is reducedAnd (3) the mixture is treated for 4 hours in an air atmosphere at 180 ℃ to prepare the supported carbon-coated platinum catalyst.
Example III
Weighing 10g of commercially available 0.5wt% Pt/diatomite, adding the mixture into 15ml of water, uniformly mixing, adding 10g of aqueous solution of 10wt% sucrose, soaking at room temperature for 60min, and then drying at 20 ℃ in vacuum for 40h to remove water; adding the obtained catalyst into 15ml of water, uniformly mixing, adding 10g of aqueous solution of sucrose with the concentration of 10wt%, soaking for 60min at room temperature, and vacuum drying at 20 ℃ for 40h to remove water; the load was thus repeated twice (four times in total) under the same conditions; then roasting the mixture at 600 ℃ for 4 hours under vacuum; then the temperature is reduced to 160 ℃, and the mixture is treated for 6 hours in an air atmosphere to prepare the supported carbon-coated platinum catalyst.
Example IV
Weighing 10g of commercial 2wt% Pt/C, adding the Pt/C into 15ml of water, uniformly mixing, adding 5g of 30wt% fructose aqueous solution, soaking at room temperature for 60min, and then drying at 50 ℃ in vacuum for 10h to remove water; adding the catalyst obtained above into 15ml of water, uniformly mixing, adding 5g of 30wt% fructose aqueous solution, soaking for 60min at room temperature, and vacuum drying at 50 ℃ for 10h to remove water; the loading was repeated three more times (five times in total) under the same conditions; then roasting the mixture at a high temperature of 500 ℃ for 10 hours under helium; then the temperature is reduced to 150 ℃ and the mixture is treated for 5 hours in the air atmosphere to prepare the supported carbon-coated platinum catalyst.
Example five
Weighing 10g of commercial 4wt% Pt/C, adding the Pt/C into 15ml of water, uniformly mixing, adding 10g of 20wt% maltose aqueous solution, soaking at room temperature for 60min, and then vacuum drying at 60 ℃ for 4h to remove water; adding the obtained catalyst into 15ml of water, uniformly mixing, adding 10g of a 20wt% maltose aqueous solution, soaking for 60min at room temperature, and vacuum drying at 60 ℃ for 4h to remove water; then roasting the mixture at a high temperature of 800 ℃ for 5 hours under argon; then the temperature is reduced to 140 ℃, and the mixture is treated for 8 hours in an air atmosphere to prepare the supported carbon-coated platinum catalyst.
Example six
Weighing 10g of commercial 1wt% Pt/C, adding the Pt/C into 15ml of water, uniformly mixing, adding 10g of aqueous solution of polyethylene glycol with concentration of 20wt%, soaking at room temperature for 60min, and then drying at 50 ℃ in vacuum for 8h to remove water; adding the obtained catalyst into 15ml of water, uniformly mixing, adding 10g of aqueous solution of polyethylene glycol with concentration of 20wt%, soaking for 60min at room temperature, and drying at 50 ℃ in vacuum for 8h to remove water; the loading is thus repeated once more (three times in total) under the same conditions; then roasting the mixture at 700 ℃ for 6 hours under nitrogen; then the temperature is reduced to 120 ℃, and the mixture is treated for 7 hours in an air atmosphere to prepare the supported carbon-coated platinum catalyst.
Example seven
300g of distilled water, 60g of 98wt% concentrated sulfuric acid, 100g of nitrobenzene, 0.5g of hexadecyl trimethyl ammonium chloride and 1g of the supported carbon-coated platinum catalyst prepared in the first embodiment are added into an acid-resistant high-pressure reaction kettle, the reaction kettle is closed, air in the reaction kettle is replaced by nitrogen for three times, and hydrogen is replaced for three times; raising the temperature to 60 ℃ and the hydrogen pressure to 1MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction solution after the temperature is reduced to room temperature, filtering to remove the catalyst, analyzing the filtrate by liquid chromatography, wherein the nitrobenzene conversion rate is 100wt% and the paracetamol selectivity is 81.2wt%.
Example eight
Adding 500g of distilled water, 100g of 98wt% concentrated sulfuric acid, 200g of nitrobenzene, 1g of hexadecyl trimethyl ammonium chloride and 1g of the supported carbon-coated platinum catalyst prepared in the second embodiment into an acid-resistant high-pressure reaction kettle, closing the reaction kettle, replacing air in the reaction kettle for three times by nitrogen, and replacing the air with hydrogen for three times; raising the temperature to 90 ℃ and the hydrogen pressure to 2MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction solution after the temperature is reduced to room temperature, filtering to remove the catalyst, analyzing the filtrate by liquid chromatography, wherein the nitrobenzene conversion rate is 100wt% and the paracetamol selectivity is 80.4wt%. The recovered catalyst is continuously subjected to a mechanically applied experiment, the reaction conditions are the same as above, and after 10 times of mechanically applied, the nitrobenzene conversion rate is 100wt% and the paracetamol selectivity is 80.9wt%.
Example nine
400g of distilled water, 50g of 98wt% concentrated sulfuric acid, 70g of nitrobenzene, 0.6g of hexadecyl trimethyl ammonium chloride and 1g of the supported carbon-coated platinum catalyst prepared in the third embodiment are added into an acid-resistant high-pressure reaction kettle, the reaction kettle is closed, air in the reaction kettle is replaced by nitrogen for three times, and hydrogen is replaced for three times; raising the temperature to 80 ℃ and the hydrogen pressure to 0.6MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction solution after the temperature is reduced to room temperature, filtering to remove the catalyst, analyzing the filtrate by liquid chromatography, wherein the nitrobenzene conversion rate is 100wt% and the paracetamol selectivity is 82.4wt%. The recovered catalyst is continuously subjected to a mechanically applied experiment, the reaction conditions are the same as above, and after 10 times of mechanically applied, the nitrobenzene conversion rate is 100wt% and the paracetamol selectivity is 81.5wt%.
Examples ten
450g of distilled water, 65g of 98wt% concentrated sulfuric acid, 170g of nitrobenzene, 0.7g of hexadecyl trimethyl ammonium chloride and 1g of the supported carbon-coated platinum catalyst prepared in the fourth embodiment are added into an acid-resistant high-pressure reaction kettle, the reaction kettle is closed, air in the reaction kettle is replaced by nitrogen for three times, and hydrogen is replaced for three times; raising the temperature to 80 ℃ and the hydrogen pressure to 1.6MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction solution after the temperature is reduced to room temperature, filtering to remove the catalyst, analyzing the filtrate by liquid chromatography, wherein the nitrobenzene conversion rate is 100wt% and the paracetamol selectivity is 81.7wt%.
Example eleven
550g of distilled water, 75g of 98wt% concentrated sulfuric acid, 110g of nitrobenzene, 0.75g of hexadecyl trimethyl ammonium chloride and 1g of the supported carbon-coated platinum catalyst prepared in the fifth embodiment are added into an acid-resistant high-pressure reaction kettle, the reaction kettle is closed, air in the reaction kettle is replaced by nitrogen for three times, and hydrogen is replaced for three times; raising the temperature to 75 ℃, and reacting for 3 hours at the stirring speed of 900r/min with the hydrogen pressure of 1.2 MPa; stopping the reaction, taking out the reaction solution after the temperature is reduced to room temperature, filtering to remove the catalyst, analyzing the filtrate by liquid chromatography, wherein the nitrobenzene conversion rate is 100wt% and the paracetamol selectivity is 81.1wt%.
Example twelve
Adding 500g of distilled water, 90g of 98wt% concentrated sulfuric acid, 100g of nitrobenzene, 0.5g of hexadecyl trimethyl ammonium chloride and 1g of the supported carbon-coated platinum catalyst prepared in the sixth embodiment into an acid-resistant high-pressure reaction kettle, closing the reaction kettle, replacing air in the reaction kettle for three times by nitrogen, and replacing the air with hydrogen for three times; raising the temperature to 75 ℃ and the hydrogen pressure to 1.5MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction solution after the temperature is reduced to room temperature, filtering to remove the catalyst, analyzing the filtrate by liquid chromatography, wherein the nitrobenzene conversion rate is 100wt% and the paracetamol selectivity is 80.7wt%.
Examples thirteen to seventeen
Adding a solvent, acid, nitrobenzene compounds and 1g of the supported carbon-coated platinum catalyst prepared in the first embodiment into an acid-resistant high-pressure reaction kettle, closing the reaction kettle, replacing air in the reaction kettle with nitrogen for three times, and replacing the air with hydrogen for three times; raising the temperature to the reaction temperature, taking the hydrogen pressure as the reaction pressure, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction liquid after the temperature is reduced to room temperature, filtering to remove the catalyst, and analyzing the filtrate by liquid chromatography. The results are shown in Table 1.
TABLE 1 catalytic hydrogenation rearrangement of different feedstocks
Example eighteen
Adding 500g of distilled water, 90g of 98wt% concentrated sulfuric acid, 100g of nitrobenzene, 0.5g of hexadecyl trimethyl ammonium chloride and 1g of the supported carbon-coated platinum catalyst prepared in the sixth embodiment into an acid-resistant high-pressure reaction kettle, closing the reaction kettle, replacing air in the reaction kettle for three times by nitrogen, and replacing the air with hydrogen for three times; raising the temperature to 75 ℃ and the hydrogen pressure to 1.5MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction liquid after the temperature is reduced to room temperature, filtering to remove the catalyst, and analyzing the filtrate by liquid chromatography. The recovered catalyst was further subjected to the experiment, the reaction conditions were the same as above, and the results are shown in Table 2.
Table 2 results of the application of the catalyst prepared in example one
| Number of times of application | Catalyst make-up/g | Nitrobenzene conversion/% | Para-aminophenol selectivity/% |
| 1 | 1.0 | 100 | 81.2 |
| 2 | 0 | 100 | 81.6 |
| 3 | 0 | 100 | 80.8 |
| 4 | 0.05 | 100 | 82.4 |
| 5 | 0 | 100 | 80.5 |
| 6 | 0 | 100 | 81.7 |
| 7 | 0.05 | 100 | 81.1 |
| 8 | 0 | 100 | 82.6 |
| 9 | 0 | 100 | 80.9 |
| 10 | 0.05 | 100 | 81.4 |
Comparative example one
Comparative example one examined the performance of supported carbon-coated platinum catalysts prepared from different carbon sources.
Weighing 10g of commercial 3wt% Pt/C, adding the Pt/C into 15ml of water, uniformly mixing, adding 10g of water solution of starch with concentration of 20wt%, soaking for 60min at room temperature, and vacuum drying at 40 ℃ for 20h to remove water; adding the obtained catalyst into 15ml of water, uniformly mixing, adding 10g of water solution of starch with concentration of 20wt%, soaking for 60min at room temperature, and vacuum drying at 40 ℃ for 20h to remove water; then roasting the mixture at 400 ℃ for 20 hours under nitrogen; then the temperature is reduced to 100 ℃, and the mixture is treated for 10 hours in an air atmosphere to prepare the supported carbon-coated platinum catalyst.
Adding 300g of distilled water, 60g of 98wt% concentrated sulfuric acid, 100g of nitrobenzene, 0.5g of hexadecyl trimethyl ammonium chloride and 1g of the prepared supported carbon-coated platinum catalyst into an acid-resistant high-pressure reaction kettle, closing the reaction kettle, replacing air in the reaction kettle for three times by nitrogen, and replacing the air with hydrogen for three times; raising the temperature to 60 ℃ and the hydrogen pressure to 1MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction solution after the temperature is reduced to room temperature, filtering to remove the catalyst, analyzing the filtrate by liquid chromatography, wherein the nitrobenzene conversion rate is 100wt% and the p-aminophenol selectivity is 45.5wt%.
Comparative example two
Comparative example two examined the performance of a supported carbon-coated platinum catalyst prepared at a lower carbonization temperature.
Weighing 10g of commercial 3wt% Pt/C, adding the Pt/C into 15ml of water, uniformly mixing, adding 10g of aqueous solution of lactose with concentration of 20wt%, soaking for 60min at room temperature, and then drying at 40 ℃ in vacuum for 20h to remove water; adding the obtained catalyst into 15ml of water, uniformly mixing, adding 10g of aqueous solution of lactose with concentration of 20wt%, soaking for 60min at room temperature, and vacuum drying at 40 ℃ for 20h to remove water; then roasting the mixture at 300 ℃ for 20 hours under nitrogen; then the temperature is reduced to 100 ℃, and the mixture is treated for 10 hours in an air atmosphere to prepare the supported carbon-coated platinum catalyst.
Adding 300g of distilled water, 60g of 98wt% concentrated sulfuric acid, 100g of nitrobenzene, 0.5g of hexadecyl trimethyl ammonium chloride and 1g of the prepared supported carbon-coated platinum catalyst into an acid-resistant high-pressure reaction kettle, closing the reaction kettle, replacing air in the reaction kettle for three times by nitrogen, and replacing the air with hydrogen for three times; raising the temperature to 60 ℃ and the hydrogen pressure to 1MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction solution after the temperature is reduced to room temperature, filtering to remove the catalyst, analyzing the filtrate by liquid chromatography, wherein the nitrobenzene conversion rate is 100wt% and the paracetamol selectivity is 48.7wt%.
Comparative example three
Comparative example three examined the performance of a supported carbon-coated platinum catalyst prepared at a higher carbonization temperature.
Weighing 10g of commercial 3wt% Pt/C, adding the Pt/C into 15ml of water, uniformly mixing, adding 10g of aqueous solution of lactose with concentration of 20wt%, soaking for 60min at room temperature, and then drying at 40 ℃ in vacuum for 20h to remove water; adding the obtained catalyst into 15ml of water, uniformly mixing, adding 10g of aqueous solution of lactose with concentration of 20wt%, soaking for 60min at room temperature, and vacuum drying at 40 ℃ for 20h to remove water; then roasting the mixture at 1200 ℃ for 20 hours under nitrogen; then the temperature is reduced to 100 ℃, and the mixture is treated for 10 hours in an air atmosphere to prepare the supported carbon-coated platinum catalyst.
Adding 300g of distilled water, 60g of 98wt% concentrated sulfuric acid, 100g of nitrobenzene, 0.5g of hexadecyl trimethyl ammonium chloride and 1g of the prepared supported carbon-coated platinum catalyst into an acid-resistant high-pressure reaction kettle, closing the reaction kettle, replacing air in the reaction kettle for three times by nitrogen, and replacing the air with hydrogen for three times; raising the temperature to 60 ℃ and the hydrogen pressure to 1MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction solution after the temperature is reduced to room temperature, filtering to remove the catalyst, and analyzing the filtrate by liquid chromatography, wherein the nitrobenzene conversion rate is 76.8wt% and the para-aminophenol selectivity is 66.2wt%.
Comparative example four
Comparative example four examined the performance of a supported carbon-coated platinum catalyst prepared with a smaller carbon source.
Weighing 10g of commercial 3wt% Pt/C, adding the Pt/C into 15ml of water, uniformly mixing, adding 5g of aqueous solution of lactose with the concentration of 10wt%, soaking for 60min at room temperature, and then drying for 20h at 40 ℃ in vacuum to remove water; adding the obtained catalyst into 15ml of water, uniformly mixing, adding 5g of lactose aqueous solution with the concentration of 10wt%, soaking for 60min at room temperature, and vacuum drying at 40 ℃ for 20h to remove water; then roasting the mixture at 400 ℃ for 20 hours under nitrogen; then the temperature is reduced to 100 ℃, and the mixture is treated for 10 hours in an air atmosphere to prepare the supported carbon-coated platinum catalyst.
Adding 300g of distilled water, 60g of 98wt% concentrated sulfuric acid, 100g of nitrobenzene, 0.5g of hexadecyl trimethyl ammonium chloride and 1g of the prepared supported carbon-coated platinum catalyst into an acid-resistant high-pressure reaction kettle, closing the reaction kettle, replacing air in the reaction kettle for three times by nitrogen, and replacing the air with hydrogen for three times; raising the temperature to 60 ℃ and the hydrogen pressure to 1MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction solution after the temperature is reduced to room temperature, filtering to remove the catalyst, analyzing the filtrate by liquid chromatography, wherein the nitrobenzene conversion rate is 100wt% and the paracetamol selectivity is 59.3wt%.
Comparative example five
Comparative example five examined the performance of a supported carbon-coated platinum catalyst prepared from a greater number of carbon sources.
Weighing 10g of commercial 3wt% Pt/C, adding the Pt/C into 15ml of water, uniformly mixing, adding 25g of aqueous solution of lactose with the concentration of 50wt%, soaking at room temperature for 60min, and then drying at 40 ℃ in vacuum for 20h to remove water; adding the obtained catalyst into 15ml of water, uniformly mixing, adding 25g of lactose aqueous solution with the concentration of 50wt%, soaking for 60min at room temperature, and vacuum drying at 40 ℃ for 20h to remove water; then roasting the mixture at 400 ℃ for 20 hours under nitrogen; then the temperature is reduced to 100 ℃ and the mixture is treated for 10 hours in an air atmosphere to prepare the supported carbon-coated platinum catalyst.
Adding 300g of distilled water, 60g of 98wt% concentrated sulfuric acid, 100g of nitrobenzene, 0.5g of hexadecyl trimethyl ammonium chloride and 1g of the prepared supported carbon-coated platinum catalyst into an acid-resistant high-pressure reaction kettle, closing the reaction kettle, replacing air in the reaction kettle for three times by nitrogen, and replacing the air with hydrogen for three times; raising the temperature to 60 ℃ and the hydrogen pressure to 1MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction solution after the temperature is reduced to room temperature, filtering to remove the catalyst, and analyzing the filtrate by liquid chromatography, wherein the nitrobenzene conversion rate is 75.3wt% and the para-aminophenol selectivity is 63.1wt%.
Comparative example six
Comparative example six examined the performance of a supported carbon-coated platinum catalyst that was not air atmosphere retreated.
Weighing 10g of commercial 3wt% Pt/C, adding the Pt/C into 15ml of water, uniformly mixing, adding 10g of aqueous solution of lactose with concentration of 20wt%, soaking for 60min at room temperature, and then drying at 40 ℃ in vacuum for 20h to remove water; adding 15ml of water, mixing uniformly, adding 10g of lactose aqueous solution with concentration of 20wt%, soaking at room temperature for 60min, and vacuum drying at 40 ℃ for 20h to remove water; and then roasting the catalyst at 400 ℃ for 20 hours under nitrogen to prepare the supported carbon-coated platinum catalyst.
Adding 300g of distilled water, 60g of 98wt% concentrated sulfuric acid, 100g of nitrobenzene, 0.5g of hexadecyl trimethyl ammonium chloride and 1g of the prepared supported carbon-coated platinum catalyst into an acid-resistant high-pressure reaction kettle, closing the reaction kettle, replacing air in the reaction kettle for three times by nitrogen, and replacing the air with hydrogen for three times; raising the temperature to 60 ℃ and the hydrogen pressure to 1MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; after the reaction was stopped and the temperature was lowered to room temperature, the reaction solution was taken out, the catalyst was removed by filtration, and the filtrate was analyzed by liquid chromatography, so that the conversion of nitrobenzene was 89.8wt% and the selectivity for paracetamol was 58.4wt%.
Comparative example seven
Comparative example seven examined the performance of a supported carbon-coated platinum catalyst obtained without multiple loading of carbon source compounds.
Weighing 10g of commercial 3wt% Pt/C, adding the Pt/C into 15ml of water, uniformly mixing, adding 20g of aqueous solution of lactose with concentration of 20wt%, soaking for 60min at room temperature, and then drying at 40 ℃ in vacuum for 20h to remove water; then roasting the mixture at 400 ℃ for 20 hours under nitrogen; then the temperature is reduced to 100 ℃ and the mixture is treated for 10 hours in an air atmosphere to prepare the supported carbon-coated platinum catalyst.
Adding 300g of distilled water, 60g of 98wt% concentrated sulfuric acid, 100g of nitrobenzene, 0.5g of hexadecyl trimethyl ammonium chloride and 1g of the prepared supported carbon-coated platinum catalyst into an acid-resistant high-pressure reaction kettle, closing the reaction kettle, replacing air in the reaction kettle for three times by nitrogen, and replacing the air with hydrogen for three times; raising the temperature to 60 ℃ and the hydrogen pressure to 1MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; after the reaction was stopped and the temperature was lowered to room temperature, the reaction solution was taken out, the catalyst was removed by filtration, and the filtrate was analyzed by liquid chromatography to give 94.8wt% nitrobenzene conversion and 69.9wt% p-aminophenol selectivity.
Comparative example eight
Comparative example eight examined the performance of a supported carbon-coated platinum catalyst obtained at an air heat treatment temperature of 60 ℃.
Weighing 10g of commercial 3wt% Pt/C, adding the Pt/C into 15ml of water, uniformly mixing, adding 10g of aqueous solution of lactose with concentration of 20wt%, soaking for 60min at room temperature, and then drying at 40 ℃ in vacuum for 20h to remove water; adding the obtained catalyst into 15ml of water, uniformly mixing, adding 10g of aqueous solution of lactose with concentration of 20wt%, soaking for 60min at room temperature, and vacuum drying at 40 ℃ for 20h to remove water; then roasting the mixture at 400 ℃ for 20 hours under nitrogen; then the temperature is reduced to 60 ℃ and the mixture is treated for 10 hours in the air atmosphere to prepare the supported carbon-coated platinum catalyst.
Adding 300g of distilled water, 60g of 98wt% concentrated sulfuric acid, 100g of nitrobenzene, 0.5g of hexadecyl trimethyl ammonium chloride and 1g of the prepared supported carbon-coated platinum catalyst into an acid-resistant high-pressure reaction kettle, closing the reaction kettle, replacing air in the reaction kettle for three times by nitrogen, and replacing the air with hydrogen for three times; raising the temperature to 60 ℃ and the hydrogen pressure to 1MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction solution after the temperature is reduced to room temperature, filtering to remove the catalyst, and analyzing the filtrate by liquid chromatography, wherein the nitrobenzene conversion rate is 85.1wt% and the para-aminophenol selectivity is 63.2wt%.
Comparative example nine
Comparative example nine the performance of a supported carbon-coated platinum catalyst was examined at an air atmosphere heat treatment temperature of 250 c.
Weighing 10g of commercial 3wt% Pt/C, adding the Pt/C into 15ml of water, uniformly mixing, adding 10g of aqueous solution of lactose with concentration of 20wt%, soaking for 60min at room temperature, and then drying at 40 ℃ in vacuum for 20h to remove water; adding the obtained catalyst into 15ml of water, uniformly mixing, adding 10g of aqueous solution of lactose with concentration of 20wt%, soaking for 60min at room temperature, and vacuum drying at 40 ℃ for 20h to remove water; then roasting the mixture at 400 ℃ for 20 hours under nitrogen; then the temperature is reduced to 250 ℃ and the mixture is treated for 10 hours in an air atmosphere to prepare the supported carbon-coated platinum catalyst.
Adding 300g of distilled water, 60g of 98wt% concentrated sulfuric acid, 100g of nitrobenzene, 0.5g of hexadecyl trimethyl ammonium chloride and 1g of the prepared supported carbon-coated platinum catalyst into an acid-resistant high-pressure reaction kettle, closing the reaction kettle, replacing air in the reaction kettle for three times by nitrogen, and replacing the air with hydrogen for three times; raising the temperature to 60 ℃ and the hydrogen pressure to 1MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction solution after the temperature is reduced to room temperature, filtering to remove the catalyst, analyzing the filtrate by liquid chromatography, wherein the nitrobenzene conversion rate is 100wt% and the selectivity to the paracetamol is 50.8wt%.
Comparative example ten
Comparative example ten the performance of a supported platinum catalyst without carbon inclusion was examined.
300g of distilled water, 60g of 98wt% concentrated sulfuric acid, 100g of nitrobenzene, 0.5g of hexadecyl trimethyl ammonium chloride and 1g of commercial 3wt% Pt/C catalyst are added into an acid-resistant high-pressure reaction kettle, the reaction kettle is closed, the air in the reaction kettle is replaced by nitrogen for three times, and then the reaction kettle is replaced by hydrogen for three times; raising the temperature to 60 ℃ and the hydrogen pressure to 1MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction liquid after the temperature is reduced to room temperature, filtering to remove the catalyst, and analyzing the filtrate by liquid chromatography. The recovered catalyst was further subjected to the experiment, the reaction conditions were the same as above, and the results are shown in Table 3.
TABLE 3 results of application of ordinary Pt/C catalysts
| Number of times of application | Catalyst make-up/g | Nitrobenzene conversion/% | Para-aminophenol selectivity/% |
| 1 | 1.0 | 100 | 43.6 |
| 2 | 0 | 91.3 | 44.8 |
| 3 | 0 | 84.7 | 42.5 |
| 4 | 0.05 | 70.8 | 43.0 |
| 5 | 0 | 58.1 | 40.4 |
300g of distilled water, 60g of 98wt% concentrated sulfuric acid, 100g of nitrobenzene, 0.5g of hexadecyl trimethyl ammonium chloride and 1g of commercial 5wt% Pt/TiO are added into an acid-resistant high-pressure reaction kettle 2 Closing the reaction kettle, replacing air in the reaction kettle with nitrogen for three times, and replacing the air with hydrogen for three times; raising the temperature to 60 ℃ and the hydrogen pressure to 1MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction liquid after the temperature is reduced to room temperature, filtering to remove the catalyst, and analyzing the filtrate by liquid chromatography. The recovered catalyst is continuously subjected to the application experiment, and the reaction conditions are the same as the aboveThe results are shown in Table 4.
TABLE 4 ordinary Pt/TiO 2 Results of catalyst application
| Number of times of application | Catalyst make-up/g | Nitrobenzene conversion/% | Para-aminophenol selectivity/% |
| 1 | 1.0 | 100 | 44.1 |
| 2 | 0 | 90.4 | 43.9 |
| 3 | 0 | 87.0 | 43.1 |
| 4 | 0.05 | 81.8 | 43.3 |
| 5 | 0 | 72.2 | 43.0 |
300g of distilled water, 60g of 98wt% concentrated sulfuric acid, 100g of nitrobenzene, 0.5g of hexadecyl trimethyl ammonium chloride and 1g of commercial 0.5wt% Pt/diatomite catalyst are added into an acid-resistant high-pressure reaction kettle, the reaction kettle is closed, the air in the reaction kettle is replaced by nitrogen for three times, and the air is replaced by hydrogen for three times; raising the temperature to 60 ℃ and the hydrogen pressure to 1MPa, starting stirring, and reacting for 3 hours at the stirring speed of 900 r/min; stopping the reaction, taking out the reaction liquid after the temperature is reduced to room temperature, filtering to remove the catalyst, and analyzing the filtrate by liquid chromatography. The recovered catalyst was further subjected to the experiment, the reaction conditions were the same as above, and the results are shown in Table 5.
TABLE 5 results of application of ordinary Pt/diatomaceous earth catalyst
| Number of times of application | Catalyst make-up/g | Nitrobenzene conversion/% | Para-aminophenol selectivity/% |
| 1 | 1.0 | 100 | 43.2 |
| 2 | 0 | 90.1 | 43.0 |
| 3 | 0 | 81.3 | 42.7 |
| 4 | 0.05 | 72.5 | 41.8 |
| 5 | 0 | 60.9 | 40.5 |
Claims (10)
1. A method for preparing a supported carbon-coated platinum catalyst, which comprises the following steps:
(1) Weighing a supported platinum catalyst, wherein the supported platinum catalyst comprises a carrier and a metal active component supported on the carrier, the metal active component is platinum metal, uniformly mixing the platinum metal with water, adding an aqueous solution of a soluble carbon source compound, uniformly soaking, and removing water; repeating loading the soluble carbon source compound for 2-5 times to obtain a loaded platinum catalyst loaded with the carbon source compound; the soluble carbon source compound is at least one of glucose, sucrose, fructose, maltose, lactose and polyethylene glycol; the ratio of the total mass consumption of the soluble carbon source compound to the mass consumption of the supported platinum catalyst is 0.4-1.5: 1, a step of;
(2) Then, the supported platinum catalyst loaded with the carbon source compound is roasted for 2 to 10 hours at a high temperature of 400 to 900 ℃ in an inert protective atmosphere, a hydrogen atmosphere or a vacuum state to obtain a roasting product;
(3) Then, the temperature is reduced to 100-180 ℃, and the roasting product is treated for 4-10 hours in the air atmosphere, so as to prepare the supported carbon-coated platinum catalyst.
2. The method of manufacturing according to claim 1, wherein: the carrier of the supported platinum catalyst is active carbon and TiO 2 Or diatomaceous earth.
3. The preparation method according to claim 1 or 2, characterized in that: the loading amount of platinum in the supported platinum catalyst is 0.5-5 wt%.
4. The method of manufacturing according to claim 1, wherein: in the step (1), the feeding mass ratio of the supported platinum catalyst to water is 1:1-5, and the concentration of the aqueous solution of the soluble carbon source compound is 10-50wt%.
5. The method of manufacturing according to claim 1, wherein: in the step (1), the soaking is carried out at room temperature, and the soaking time is 30-300 min each time.
6. The method of manufacturing according to claim 1, wherein: in the step (1), the moisture removing method is vacuum drying, the vacuum drying temperature is 20-80 ℃, and the vacuum drying time is 4-40 hours.
7. The method of claim 1, wherein the supported carbon-coated platinum catalyst is used in the preparation of an alkoxy-substituted or phenolic hydroxyl-substituted aniline compound of formula (II), (III) or (IV) from a nitrobenzene compound of formula (I), wherein the nitrobenzene compound and the solvent R are contained 6 Introducing hydrogen into a reaction container of OH and strong acid, and carrying out hydrogenation and Bamberger rearrangement reaction under the stirring condition to obtain an alkoxy substituted or phenolic hydroxyl substituted aniline compound; the strong acid is sulfuric acid with the concentration of more than 98 percent, hydrochloric acid with the concentration of more than 35 percent or phosphoric acid with the concentration of more than 75 percent;
in the formula (I) or the formula (II), (III), (IV), -R 1 、-R 2 、-R 3 、-R 4 、-R 5 Independently selected from one of the following groups: -H, -CH 3 、-CH 2 CH 3 、-OH、-NH 2 、-OCH 3 、-COOCH 3 、-NHCH 2 CH 3 、-N(CH 3 ) 2 -F, -Cl, -Br, and-R 1 、-R 3 、-R 5 At least one of them is-H; -R 6 Selected from one of the following groups: -H, -CH 3 、-CH 2 CH 3 。
8. The use according to claim 7, wherein: the solvent R 6 The mass ratio of the OH, the strong acid, the nitrobenzene compounds and the supported carbon-coated platinum catalyst is 300-500: 50-100: 60-200: 1.
9. the use according to claim 8, wherein: the R is 6 OH is water, a surfactant is also added into the reaction system, the surfactant is one of dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide and hexadecyl trimethyl ammonium chloride, and the mass ratio of the added surfactant to nitrobenzene compounds shown in the formula (I) is 0.005-0.04: 1.
10. use according to one of claims 7 to 9, characterized in that: the temperature of the reaction is 50-120 ℃, and the hydrogen pressure is 0.3-3.0 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111679232.0A CN114225935B (en) | 2021-12-31 | 2021-12-31 | Preparation and application of onion-shaped supported carbon-coated platinum catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111679232.0A CN114225935B (en) | 2021-12-31 | 2021-12-31 | Preparation and application of onion-shaped supported carbon-coated platinum catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114225935A CN114225935A (en) | 2022-03-25 |
| CN114225935B true CN114225935B (en) | 2023-09-05 |
Family
ID=80745414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111679232.0A Active CN114225935B (en) | 2021-12-31 | 2021-12-31 | Preparation and application of onion-shaped supported carbon-coated platinum catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114225935B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108970608A (en) * | 2018-07-18 | 2018-12-11 | 南京大学 | Loaded noble metal catalyst with clad structure and preparation method thereof and the application in Cu (II) liquid phase catalytic reduction |
| CN110252407A (en) * | 2019-07-09 | 2019-09-20 | 福州大学 | A kind of method that Carboxyl-functional Ionic Liquid prepares core-shell structure catalyst |
| CN112774710A (en) * | 2020-12-18 | 2021-05-11 | 南京大学 | Method for reducing selenite through liquid-phase catalytic hydrogenation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019513078A (en) * | 2016-03-09 | 2019-05-23 | ビーエーエスエフ コーポレーション | Core / shell hydrocarbon trap catalyst and method of making |
| CN109309214B (en) * | 2017-07-28 | 2023-04-11 | 中国石油化工股份有限公司 | Preparation method of carbon-coated nickel nano composite material |
-
2021
- 2021-12-31 CN CN202111679232.0A patent/CN114225935B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108970608A (en) * | 2018-07-18 | 2018-12-11 | 南京大学 | Loaded noble metal catalyst with clad structure and preparation method thereof and the application in Cu (II) liquid phase catalytic reduction |
| CN110252407A (en) * | 2019-07-09 | 2019-09-20 | 福州大学 | A kind of method that Carboxyl-functional Ionic Liquid prepares core-shell structure catalyst |
| CN112774710A (en) * | 2020-12-18 | 2021-05-11 | 南京大学 | Method for reducing selenite through liquid-phase catalytic hydrogenation |
Non-Patent Citations (1)
| Title |
|---|
| Highly Stable Porous-Carbon-Coated Ni Catalysts for the Reductive Amination of Levulinic Acid via an Unconventional Pathway;Guang Gao 等;《ACS Catalyst》(第7期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114225935A (en) | 2022-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107413330B (en) | Catalyst, preparation method and application thereof | |
| WO2022012098A1 (en) | Hydrogenation catalyst, preparation method therefor and use thereof | |
| CN110302769B (en) | Catalyst carrier, supported catalyst, preparation method and application thereof | |
| CN112916033A (en) | Carbon-nitrogen-doped silicon dioxide-loaded Co catalyst and preparation method and application thereof | |
| JPS5916816B2 (en) | Ammonia production method | |
| CN114308027A (en) | Supported carbon-coated bimetallic catalyst and application thereof | |
| CN114054061B (en) | Nitrogen-doped carbon-supported palladium catalyst and preparation method and application thereof | |
| CN114308024B (en) | Preparation method and application of carbon-doped coated platinum catalyst | |
| CN115301275A (en) | Cheap metal catalyst and preparation method and application thereof | |
| CN113797952B (en) | Catalyst for synthesizing alicyclic amine through selective hydrogenation saturation of benzene ring containing benzene ring amine compounds and preparation method thereof | |
| CN111151283B (en) | Nitrogen-cobalt co-doped porous carbon loaded sulfur-zinc-cobalt catalytic material and preparation method and application thereof | |
| CN113351214A (en) | Carbon-doped silicon dioxide-loaded nickel-copper alloy and preparation method and application thereof | |
| CN109928898B (en) | Green preparation method of azoxy compound by taking MOFs derived magnetic nanoparticles as recyclable catalyst | |
| CN108080025A (en) | A kind of preparation method of palladium base polyaniline package carbon nanotube catalyst and its application in Heck reactions | |
| CN114225935B (en) | Preparation and application of onion-shaped supported carbon-coated platinum catalyst | |
| CN111185214A (en) | Alumina biomass charcoal composite material, preparation method and application thereof | |
| KR100928871B1 (en) | Palladium Catalyst Supported on Activated Carbon and Manufacturing Method Thereof | |
| CN114345341B (en) | Graphene coated solid acid catalyst and preparation method thereof | |
| Nouri et al. | Selenium-doped porous-C3N4 decorated with Cu NPs, as an operative heterogenous catalyst for the nitroarenes reduction reaction | |
| CN112295569B (en) | Catalyst for preparing aniline by one-step ammoniation of benzene and preparation method thereof | |
| CN112275311B (en) | Heavy aromatic hydrocarbon light catalyst based on VIII metal element, and preparation method and application thereof | |
| CN109012737B (en) | Catalytic synthesis method of antidepressant drug intermediate | |
| CN111068729A (en) | Phosphorus-doped or nitrogen-doped multiwalled carbon nanotube catalyst and preparation method and application thereof | |
| CN114367282A (en) | Catalyst and preparation method and application thereof | |
| CN112604685A (en) | Supported catalyst and preparation method and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |