CN107413330B

CN107413330B - Catalyst, preparation method and application thereof

Info

Publication number: CN107413330B
Application number: CN201710207078.4A
Authority: CN
Inventors: 卢春山; 冯振龙; 齐亚妮; 王梦君; 丰枫; 马磊; 张群峰; 李小年
Original assignee: Zhejiang University of Technology ZJUT
Current assignee: Zhejiang University of Technology ZJUT
Priority date: 2017-03-31
Filing date: 2017-03-31
Publication date: 2019-12-24
Anticipated expiration: 2037-03-31
Also published as: CN107413330A

Abstract

The invention discloses a catalyst and a preparation method and application thereof. The catalyst consists of a carrier and composite carbon-metal quantum dots loaded on the carrier, the particle size of the catalyst is 100-1000 nm, and the carrier is mesoporous carbon microspheres; the size of the composite carbon-metal quantum dots is not more than 15nm, and the mass percentage of metal in the composite carbon-metal quantum dots is 10-90%; the metal in the composite carbon-metal quantum dot is one or a combination of more of platinum, palladium, iridium, ruthenium and rhodium, and based on the mass of the carrier, the metal is platinum, palladium, iridium, ruthenium and rhodiumThe loading amounts of the palladium, the platinum and the rhodium are respectively 0-10.0%, 0-10.0% and 0-5.0%, and the loading amounts of the palladium, the platinum and the rhodium are not all 0, and the total loading amount of the metal is 1.0-11.5%. The invention provides the application of the catalyst in the reaction of synthesizing the chloroarylamine compound shown in the formula (II) by selective catalytic hydrogenation of the chloroaromatic nitro compound shown in the formula (I), and the catalyst has the characteristics of high hydrogenation reaction rate, high conversion rate, high catalytic activity and high stability.

Description

Catalyst, preparation method and application thereof

(I) technical field

The invention relates to a mesoporous carbon microsphere supported catalyst, a preparation method and application thereof.

(II) technical background

The process of reducing the chloro-aromatic nitro compound into the chloro-aromatic amine compound is an important basic organic synthesis reaction, and the chloro-aromatic amine compound is an organic chemical intermediate with wide application and occupies a great position in the field of fine chemical industry. The reduction process mainly comprises an iron powder reduction method, an electrochemical reduction method, a sodium sulfide reduction method, a catalytic hydrogenation reduction method and the like. The catalytic hydrogenation process is advanced, low in energy consumption and less in waste emission, and meets the requirements of modern chemical industry on green chemistry and atom economy. However, the method has dechlorination phenomenon, and other organic matters and hydrochloric acid are generated, which bring serious adverse effects on catalytic reaction, product quality and production equipment.

The existing industrial technology generally adopts the addition of dehalogenation inhibitor (the university of inner Mongolia university: science edition, 2001,16(1): 96-100), metal auxiliary agent (petrochemical, 2012,14(5): 515-. In addition, the commonly used catalyst adopts an activated carbon carrier, and the properties of different carbon sources of different manufacturers are greatly different, so that the performance of the catalyst and the catalytic reaction of the catalyst are greatly influenced. Therefore, the developed pore structure of the carbon microspheres is utilized to facilitate the high dispersion of the active components, and the utilization rate of the noble metal is improved; the surface groups of the mesoporous carbon microspheres are single and controllable, the influence of the complex surface groups of the conventional activated carbon carrier on metal dispersion and catalytic reaction is avoided, and the preparation process of the mesoporous carbon microspheres is simple, low in cost and easy to realize industrialization. Recently, quantum dots have unique size and electronic characteristics, show excellent catalytic performance in the field of photocatalysis, and also show good application prospects in other traditional catalytic fields. The composite carbon-metal quantum dots are prepared by adopting a one-step synthesis method and loaded on a porous carbon material, the combination of the two quantum dots exerts a composite effect, and the composite carbon-metal quantum dots have a very good catalytic effect in the reaction of synthesizing the chloroarylamine compound by selective catalytic hydrogenation of the chloroaromatic nitro compound.

Disclosure of the invention

The invention aims to provide a mesoporous carbon microsphere supported catalyst, a preparation method and application thereof, wherein the catalyst can be applied to the reaction of synthesizing chloroarylamine compounds by selective catalytic hydrogenation of chloroaromatic nitro compounds, and has the characteristics of high hydrogenation reaction rate, high conversion rate, high catalytic activity and high stability.

In order to achieve the purpose, the invention adopts the following technical scheme:

the catalyst consists of a carrier and composite carbon-metal quantum dots loaded on the carrier, the particle size of the catalyst is 100-1000 nm, and the carrier is mesoporous carbon microspheres; the size of the composite carbon-metal quantum dots is not more than 15nm, and the mass percentage of metal in the composite carbon-metal quantum dots is 10-90%; the composite carbon-metal quantum dots are characterized in that the metal in the composite carbon-metal quantum dots is one or a combination of more of platinum, palladium, iridium, ruthenium and rhodium, the loading amounts of the platinum, the palladium, the iridium, the ruthenium and the rhodium are respectively 0-10.0%, 0-10.0% and 0-5.0% based on the mass of the carrier, the loading amounts of the palladium, the platinum and the rhodium are not all 0, and the total loading amount of the metal is 1.0-11.5%.

Furthermore, the loading amount of palladium is preferably 1.5-7.5%.

Further, the amount of platinum carried is preferably 1.0 to 6.5%.

Further, the loading amount of rhodium is preferably 1.0 to 4.0%.

Further, the composite carbon-metal quantum dot is prepared by the following method: dissolving metal salt by using ethylenediamine and a citric acid aqueous solution, wherein the molar ratio of the metal salt to citric acid to the ethylenediamine to deionized water used for preparing the citric acid aqueous solution is as follows: 1: 5-50: 50-500: 1500-10000, fully mixing, putting into a hydrothermal reaction kettle, keeping at 100-250 ℃ for 3-24 hours, cooling to room temperature, taking out, and removing the solvent from the obtained aqueous solution containing the composite carbon-metal quantum dots to obtain the composite carbon-metal quantum dots.

Still further, the metal salt may be selected from one or more of the following: palladium nitrate, chloropalladic acid, ethylenediamine palladium chloride, ammonium tetrachloropalladate, sodium chloropalladate, tetraamminepalladium nitrate, tetraamminepalladium dihydrogencarbonate, chloroplatinic acid, platinum nitrate, sodium chloroplatinate, tetraammineplatinum nitrate, dinitrosoplatinum, potassium trichloroammatoplatinate, sodium hexachloroplatinate, rhodium trichloride, rhodium nitrate, rhodium acetate, iridium dichloride, iridium trichloride, ammonium hexachlororuthenate, ruthenium nitrate, ruthenium trichloride, and the like.

Furthermore, the aqueous solution containing the composite carbon-metal quantum dots can be subjected to low-temperature vacuum drying to obtain composite carbon-metal quantum dot powder, wherein the low-temperature vacuum drying conditions are as follows: the relative vacuum degree is-0.099 to-0.05 MPa, the temperature is 20 to 50 ℃, and the time is 24 to 36 hours.

Furthermore, the aqueous solution containing the composite carbon-metal quantum dots can also be subjected to freeze drying to obtain composite carbon-metal quantum dot solid powder, wherein the freeze drying conditions are as follows: the relative vacuum degree is-0.099 to-0.05 MPa, the temperature is-10 to 0 ℃, and the time is 10 to 24 hours.

The invention also provides a preparation method of the catalyst, which comprises the following steps:

1) taking an ammonia water solution with the mass concentration of 25-28%, ethanol and deionized water, fully mixing, then adding resorcinol, slowly dropwise adding a formaldehyde solution with the mass concentration of 37-40%, stirring at 10-50 ℃ for 12-48 hours, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 50-200 ℃ for 12-36 hours, and then carrying out centrifugal washing to obtain reddish brown polymer solid powder; wherein the molar ratio of the resorcinol to the formaldehyde is as follows: 1: 1-4, wherein the volume ratio of the ammonia water solution to the formaldehyde solution to the ethanol to the deionized water is 1: 1.4-5.6: 60-120: 150-300;

2) dispersing the polymer solid powder obtained in the step 1) and the composite carbon-metal quantum dots in an alcohol aqueous solution, wherein the volume ratio of alcohol to water in the alcohol aqueous solution is 5-100: 1, the feeding proportion of the alcohol aqueous solution, the composite carbon-metal quantum dots and the polymer solid powder is 3-18 ml: 15-125 mg: 1g, loading carbon-metal quantum dots on a polymer solid by a hydrothermal synthesis method or an isometric impregnation method, and then drying in vacuum to obtain a sample;

3) roasting the sample obtained in the step 2) in a mixed atmosphere of hydrogen and inert gas, wherein the volume concentration of the hydrogen in the mixed atmosphere is 5-50%, and the roasting process is temperature programmed control: keeping the temperature constant for 1-4 hours from room temperature to 200-300 ℃, wherein the heating rate is 0.5-5 ℃/min; the temperature rise rate is 5-8.5 ℃/min from 200-300 ℃ to 400-600 ℃, and the temperature is kept constant for 3-6 hours; the temperature rise rate is 8.5-15 ℃/min between 400 ℃ and 600 ℃ and 700-800 ℃, and the catalyst can be obtained after constant temperature is kept for 4-6 hours.

Further, in the step 2), the alcohol is preferably ethanol, methanol or ethylene glycol in the aqueous solution of the alcohol.

Further, in the step 2), the hydrothermal synthesis method is to keep the temperature of 50-250 ℃ for 3-12 hours, and obtain a solid after centrifugal washing.

Further, in the step 2), in the isometric impregnation method, the impregnation temperature is 20-50 ℃, and the impregnation time is 5-24 hours.

Further, in step 2), the vacuum drying conditions are as follows: drying for 6-24 hours at the temperature of 40-150 ℃ under the relative vacuum degree of-0.099-0.05 MPa.

Further, in step 3), the inert gas in the mixed atmosphere may be one or more selected from argon, helium and nitrogen.

Further, in the step 3), in the roasting process, the airspeed is not less than 30h^-1。

The invention further provides the application of the catalyst in the reaction of synthesizing the chloroarylamine compound shown in the formula (II) by selective catalytic hydrogenation of the chloroaromatic nitro compound shown in the formula (I);

in the formula (I) or (II), R₁、R₂、R₃、R₄、R₅At least one of which is Cl and the others are each independently H, CH₃、CH₂CH₃、NO₂、NH₂、OCH₃、OCH₂CH₃、C₆H₅COOH or COOCH₃。

Specifically, the application method of the catalyst comprises the following steps:

putting a catalyst and an aromatic chloronitro compound shown as a formula (I) into a high-pressure hydrogenation reaction kettle, sealing the reaction kettle, replacing air with nitrogen, replacing nitrogen with hydrogen, heating to 20-150 ℃, ensuring that materials in the kettle are in a molten or solution state, filling hydrogen until the pressure in the kettle is 0.1-3.5 MPa (preferably 0.2-2.5 MPa), starting stirring to start reaction, continuing stirring at constant temperature and constant pressure for a period of time (such as 30 minutes) when the pressure in the kettle does not drop, stopping stirring, cooling to room temperature, opening the kettle, taking out a hydrogenation liquid, and separating and treating the hydrogenation liquid to obtain the chloroarylamine compound shown as a formula (II).

Furthermore, the chloroarylamine compound (namely the product) shown in the formula (II) and/or the solvent can be added into the high-pressure hydrogenation reaction kettle together with the catalyst and the chloroaromatic nitro compound shown in the formula (I). That is, in the application method of the present invention, the reaction can be carried out in the absence of a solvent, in the chloroarylamine compound (i.e., product) represented by the formula (II), or in a mixture of the chloroarylamine compound represented by the formula (II) and the solvent in any ratio. The applicable solvent is one or a mixed solvent of more than two of methanol, ethanol, water, n-propanol and isopropanol in any proportion. Generally, the volume usage of the chloroarylamine compound (i.e. product) represented by formula (II) and/or the solvent is 0.5-15 mL/g, preferably 1-10 mL/g, based on the mass of the reactant [ the compound represented by formula (I) ].

Further, the charging mass ratio of the chloro-aromatic nitro compound shown in the formula (I) to the catalyst is 100: 0.1 to 3.0, preferably 100: 0.2 to 1.5.

Further, the method for separating and post-treating the hydrogenation liquid comprises the following steps: filtering the hydrogenation liquid to separate out the catalyst, and carrying out vacuum rectification on the filtrate to obtain a product; in the post-treatment process, a catalyst filter cake obtained by filtering the hydrogenation liquid can be returned to the reaction kettle for catalyst reuse.

Compared with the prior art, the invention has the beneficial effects that:

1) the mesoporous carbon microspheres are used as carriers of active components, the surface groups are single and controllable, the influence of the complex surface groups of the conventional active carbon carriers on metal dispersion and catalytic reaction is avoided,

2) the mesoporous carbon microsphere has simple synthesis method and lower cost, and is beneficial to industrial application.

3) The quantum dot is a novel nano material with carbon or metal as a framework structure and good dispersibility, is a dispersed spherical-like nano particle with small size, has strong electron transfer capacity, modulates the electron distribution characteristic of the outer layer of active component particles, and improves the dechlorination inhibiting effect. The composite carbon-metal quantum dot synthesized in situ by one step is an organic combination of two kinds of quantum dots, and exerts dual effects of size and electrons. The catalyst has high catalytic activity and selectivity, high hydrogenation reaction rate, obvious dechlorination inhibiting effect and high chloro-arylamine compound selectivity up to 99.9%.

4) The carbon quantum dot material in the catalyst can be removed through oxidation treatment, so that the noble metal is easy to recover and recycle, and the use cost of the catalyst in the production process is effectively reduced.

5) The catalyst has the advantages of mild condition, good stability, low catalyst consumption, multiple application times and long service life in the recycling process.

(IV) description of the drawings

FIGS. 1(a), 1(b) and 1(c) are EDX elemental analyses of the catalyst prepared in example 1, in which the line segments indicated in FIG. 1(a) are subjected to EDX line scan analysis, and the test points in FIG. 1(b) are bright spots similar to those in FIG. 1(a), showing palladium and carbon elements; the line scanning path is along the direction of the marked line segment in fig. 1(a), the line scanning result is shown in fig. 1(c), the curve 1 marked in fig. 1(c) is the distribution of palladium element, and the curve 2 is the distribution of carbon element.

Fig. 2 is a transmission electron micrograph of the catalyst prepared in example 1, and it can be seen that the lattice spacing of the palladium (111) crystal planes of the metal in fig. 2 is 0.225nm and the lattice spacing of the graphite (102) crystal planes of the quantum dots is 0.208nm, and that carbon and metal constitute one quantum dot of about 10 nm.

FIG. 3 is a scanning electron micrograph of the catalyst prepared in example 1. The sphere in the figure is the carbon microsphere of the catalyst.

(V) detailed description of the preferred embodiments

The technical solutions of the present invention are further described below with specific examples, but the scope of the present invention is not limited thereto.

Example 1

Weighing 0.8mL of 25-28% ammonia water by mass concentration, 64mL of ethanol and 160mL of deionized water, fully stirring the three, adding 1.6g of resorcinol, stirring until the resorcinol is completely dissolved, slowly dropwise adding 2.24mL of formaldehyde water by mass concentration of 37-40%, stirring at 20 ℃ for 12 hours, transferring to a hydrothermal reaction kettle, keeping at 80 ℃ for 12 hours, and then centrifugally washing to obtain reddish brown polymer solid powder.

Dissolving 2g of citric acid in 30ml of deionized water, adding 0.2942g of sodium chloropalladate and 6.67ml of ethylenediamine, mixing and stirring uniformly, transferring the mixed solution into a reaction kettle, keeping the temperature at 100 ℃ for 5 hours, and freeze-drying for 10 hours at the relative vacuum degree of-0.05 MPa and the temperature of-10 ℃ to obtain the composite noble metal carbon quantum dot solid powder. The ICP analysis result of the composite carbon-metal quantum dots shows that the mass percentage of the metal is 50%.

300mg of composite noble metal carbon quantum dot powder, 4g of polymer solid powder and 40ml of methanol aqueous solution (the volume ratio of alcohol to water is 5:1) are uniformly mixed and stirred, then the mixture is transferred into a reaction kettle and kept at 50 ℃ for 8 hours, and then the mixture is centrifugally washed and dried for 12 hours at 50 ℃ under the relative vacuum degree of-0.099 MPa.

Then, the solid obtained above is roasted by using hydrogen-argon mixed gas (the volume fraction of hydrogen is 10%), and the process is as follows: the temperature is 1 ℃/minute from room temperature to 200 ℃, and the temperature is kept for 2 hours at 200 ℃; keeping the temperature at 200-600 ℃ for 3 hours at 5 ℃/min and 600 ℃; the temperature of 600 ℃ to 800 ℃ is 10 ℃/min, and the temperature is kept for 4 hours at 800 ℃. Space velocity of 50h^-1. Thus obtaining the catalyst with the grain diameter of 700 nm.

Example 2

Weighing 0.8mL of 25-28% ammonia water by mass concentration, 48mL of ethanol and 180mL of deionized water, fully stirring the three, adding 1.6g of resorcinol, stirring until the resorcinol is completely dissolved, slowly dropwise adding 1.6mL of formaldehyde water by mass concentration of 37-40%, stirring at 25 ℃ for 20 hours, transferring to a hydrothermal reaction kettle, keeping the temperature at 100 ℃ for 15 hours, and then centrifugally washing to obtain reddish brown polymer solid powder.

Dissolving 1.19g of citric acid in 165ml of deionized water, adding 0.5618g of sodium chloroplatinate and 6.67ml of ethylenediamine, mixing and stirring uniformly, transferring the mixed solution into a reaction kettle, keeping the temperature at 100 ℃ for 24 hours, and freeze-drying the mixed solution at the relative vacuum degree of-0.05 MPa and the temperature of-10 ℃ for 10 hours to obtain quantum dot solid powder. Wherein the mass percentage of the metal in the composite carbon-metal quantum dots is 10%.

200mg of composite noble metal carbon quantum dot powder, 4g of polymer solid powder and 40ml of methanol aqueous solution (the volume ratio of alcohol to water is 5:1) are uniformly mixed and stirred, transferred into a reaction kettle and kept at 50 ℃ for 8 hours, then centrifuged and washed, and dried for 12 hours at 50 ℃ under the relative vacuum degree of-0.05 MPa.

Then, the prepared solid is roasted by hydrogen-helium mixed gas (the volume fraction of hydrogen is 10 percent), and the process comprises the following steps: the temperature is 5 ℃/min from room temperature to 200 ℃, and the temperature is kept for 2 hours at 200 ℃; keeping the temperature at 200-600 ℃ for 3 hours at 5 ℃/min and 600 ℃; the temperature of 600 ℃ to 800 ℃ is 10 ℃/min, and the temperature is kept for 4 hours at 800 ℃. Space velocity of 30h^-1. Thus obtaining a catalyst with a particle size of-500 nm.

Example 3

Weighing 0.8mL of 25-28% ammonia water by mass concentration, 96mL of ethanol and 240mL of deionized water, fully stirring the three, adding 1.65g of resorcinol, stirring until the resorcinol is completely dissolved, slowly dropwise adding 4.48mL of formaldehyde water by mass concentration of 37-40%, stirring at 10 ℃ for 30 hours, transferring to a hydrothermal reaction kettle, keeping at 120 ℃ for 12 hours, and then centrifugally washing to obtain reddish brown polymer solid powder.

Dissolving 3g of citric acid in 60ml of deionized water, adding 0.2842g of ammonium tetrachloropalladate and 10ml of ethylenediamine, mixing and stirring uniformly, transferring the mixed solution into a reaction kettle, keeping the temperature at 100 ℃ for 20 hours, and freeze-drying at the relative vacuum degree of-0.099 MPa and the temperature of-10 ℃ for 10 hours to obtain the quantum dot solid powder. Wherein the mass percentage of the metal in the composite carbon-metal quantum dots is 90%.

100mg of composite noble metal carbon quantum dot powder, 4.5g of polymer solid powder and 80ml of ethanol water solution (the volume ratio of alcohol to water is 100:1) are uniformly stirred, transferred into a reaction kettle and kept at 50 ℃ for 12 hours, then centrifuged and washed, and dried for 24 hours at 40 ℃ under the relative vacuum degree of-0.05 MPa.

Then, the solid obtained above was calcined with a hydrogen-argon mixture (30% by volume of hydrogen) in the following procedure: 0.5 ℃/min between room temperature and 200 ℃, and keeping the temperature at 200 ℃ for 4 hours; 8.5 ℃/min at the temperature of between 200 and 600 ℃, and keeping for 6 hours at the temperature of 600 ℃; 600The temperature is 8.5 ℃/min between 800 ℃ and 8.5 ℃, and the temperature is kept for 4 hours at 800 ℃. Space velocity of 50h^-1. The catalyst was thus obtained, having a particle size of 600 nm.

Example 4

Weighing 0.8mL of 25-28% ammonia water by mass concentration, 48mL of ethanol and 120mL of deionized water, fully stirring the three, adding 1.6g of resorcinol, stirring until the resorcinol is completely dissolved, slowly dropwise adding 2.24mL of formaldehyde water solution by mass concentration of 37-40%, stirring at 50 ℃ for 12 hours, transferring to a hydrothermal reaction kettle, keeping the temperature at 50 ℃ for 36 hours, and then centrifugally washing to obtain reddish brown polymer solid powder.

Dissolving 9.65g of citric acid in 108ml of deionized water, adding 0.2365g of ethylenediamine palladium chloride and 33.53ml of ethylenediamine, mixing and stirring uniformly, transferring the mixed solution into a reaction kettle, keeping the temperature at 250 ℃ for 3 hours, and freeze-drying for 24 hours at the relative vacuum degree of-0.099 MPa and the temperature of-8 ℃ to obtain the quantum dot solid powder. Wherein the mass percentage of the metal in the composite carbon-metal quantum dots is 50%.

Taking 240mg of composite noble metal carbon quantum dot powder, 16g of polymer solid powder and 40ml of ethanol water solution (the volume ratio of alcohol to water is 10:1), uniformly stirring, transferring to a reaction kettle, keeping at 250 ℃ for 3 hours, centrifugally washing, and drying at 150 ℃ for 6 hours under the relative vacuum degree of-0.05 MPa.

Then, the solid obtained above is roasted by using hydrogen-argon mixed gas (the volume fraction of hydrogen is 10%), and the process is as follows: the temperature of the room temperature to 200 ℃ is 5 ℃/min, and the temperature is kept for 1 hour at 200 ℃; 8.5 ℃/min at the temperature of between 200 and 600 ℃, and keeping the temperature at 600 ℃ for 3 hours; the temperature of 600 ℃ to 800 ℃ is 15 ℃/min, and the temperature is kept for 4 hours at 800 ℃. Space velocity of 80h^-1. Thus obtaining a catalyst with a particle size of-100 nm.

Example 5

Weighing 0.8mL of 25-28% ammonia water by mass concentration, 60mL of ethanol and 180mL of deionized water, fully stirring the three, adding 2.0g of resorcinol, stirring until the resorcinol is completely dissolved, slowly dropwise adding 3mL of formaldehyde water solution by mass concentration of 37-40%, stirring at 30 ℃ for 48 hours, transferring to a hydrothermal reaction kettle, keeping the hydrothermal reaction kettle at 200 ℃ for 12 hours, and then centrifugally washing to obtain reddish brown polymer solid powder.

Dissolving 1.92g of citric acid in 185ml of deionized water, adding 0.0561g of rhodium trichloride, 0.2985g of iridium trichloride and 20ml of ethylenediamine, mixing and stirring uniformly, transferring the mixed solution into a reaction kettle, keeping the temperature at 120 ℃ for 5 hours, and freeze-drying for 24 hours at the relative vacuum degree of-0.06 MPa and the temperature of 0 ℃ to obtain quantum dot solid powder. Wherein the mass percentage of the metal in the composite carbon-metal quantum dots is 40%.

Weighing 1000mg of composite noble metal carbon quantum dot solid powder, uniformly mixing the composite noble metal carbon quantum dot solid powder with 100ml of ethanol water solution (the volume ratio of alcohol to water is 20:1), then mixing the composite noble metal carbon quantum dot solid powder with 10g of polymer solid powder, performing equal-volume impregnation, impregnating at 50 ℃ for 5 hours, and drying at 60 ℃ for 15 hours under the relative vacuum degree of-0.08 MPa.

Then, the solid obtained above is roasted with a hydrogen-argon mixture (the volume fraction of hydrogen is 50%), and the process is as follows: the temperature of the room temperature to 200 ℃ is 5 ℃/min, and the temperature is kept for 1 hour at 200 ℃; the temperature of 200 ℃ to 600 ℃ is 7 ℃/min, and the temperature is kept for 3 hours at 600 ℃; the temperature of 600 ℃ to 800 ℃ is 10 ℃/min, and the temperature is kept for 6 hours at 800 ℃. Space velocity of 30h^-1. Thus obtaining the catalyst with the grain diameter of 600 nm.

Example 6

Weighing 0.8mL of 25-28% ammonia water by mass concentration, 48mL of ethanol and 120mL of deionized water, fully stirring the three, adding 1.6g of resorcinol, stirring until the resorcinol is completely dissolved, slowly dropwise adding 3mL of formaldehyde water solution by mass concentration of 37-40%, stirring at 50 ℃ for 12 hours, transferring to a hydrothermal reaction kettle, keeping the temperature at 50 ℃ for 36 hours, and then centrifugally washing to obtain reddish brown polymer solid powder.

6g of citric acid is dissolved in 50ml of deionized water, 0.2889g of rhodium trichloride and 20ml of ethylenediamine are added, the mixture is uniformly mixed and stirred, then the mixed solution is transferred to a reaction kettle and kept at 250 ℃ for 6 hours, and then freeze drying is carried out, wherein the relative vacuum degree is-0.09 MPa, the temperature is-5 ℃, and the freeze drying is carried out for 24 hours, so as to obtain the quantum dot solid powder. Wherein the mass percentage of the metal in the composite carbon-metal quantum dots is 30%.

533mg of composite noble metal carbon quantum dot powder, 8g of polymer solid powder and 40ml of methanol aqueous solution (the volume ratio of alcohol to water is 10:1) are uniformly stirred, transferred into a reaction kettle and kept at 250 ℃ for 3 hours, then centrifuged and washed, and dried for 6 hours at 150 ℃ under the relative vacuum degree of-0.07 MPa.

Then, the solid obtained above is roasted by using hydrogen-argon mixed gas (the volume fraction of hydrogen is 10%), and the process is as follows: 5 ℃/min from room temperature to 300 ℃, and keeping for 3 hours at 300 ℃; 8.5 ℃/min at the temperature of 300-500 ℃, and keeping for 3 hours at 500 ℃; 500 ℃ to 750 ℃ is 10 ℃/min, 750 ℃ for 6 hours. Space velocity of 40h^-1. Thus obtaining a catalyst with a particle size of-100 nm.

Example 7

Weighing 0.8mL of 25-28% ammonia water by mass concentration, 80mL of ethanol and 180mL of deionized water, fully stirring the three, adding 2.5g of resorcinol, stirring until the resorcinol is completely dissolved, slowly dropwise adding 3mL of formaldehyde water solution by mass concentration of 37-40%, stirring at 50 ℃ for 12 hours, transferring to a hydrothermal reaction kettle, keeping the temperature at 50 ℃ for 36 hours, and then centrifugally washing to obtain reddish brown polymer solid powder.

Dissolving 5g of citric acid in 64.55ml of deionized water, then adding 0.2354g of ethylenediamine palladium chloride, 0.2887g of ruthenium trichloride and 20ml of ethylenediamine, mixing and stirring uniformly, then transferring the mixed solution into a reaction kettle, keeping the temperature at 250 ℃ for 10 hours, and then carrying out freeze drying at the relative vacuum degree of-0.07 MPa and the temperature of-8 ℃ for 24 hours to obtain the quantum dot solid powder. Wherein the mass percentage of the metal in the composite carbon-metal quantum dots is 50%.

Uniformly stirring 500mg of composite noble metal carbon quantum dot powder, 8g of polymer solid powder and 50ml of ethanol water solution (the volume ratio of alcohol to water is 10:1), transferring the mixture into a reaction kettle, keeping the temperature at 250 ℃ for 3 hours, centrifugally washing, and drying at 150 ℃ for 6 hours under the relative vacuum degree of-0.09 MPa.

Then, the prepared solid is roasted by using mixed hydrogen-nitrogen gas (the volume fraction of hydrogen is 10 percent), and the process comprises the following steps: the temperature is 1 ℃/minute from room temperature to 200 ℃, and the temperature is kept for 2 hours at 200 ℃; 5.5 ℃/min between 200 ℃ and 600 DEG CKeeping at 600 ℃ for 3 hours; the temperature of 600 ℃ to 800 ℃ is 10 ℃/min, and the temperature is kept for 6 hours at 800 ℃. Space velocity of 100h^-1. Thus obtaining the catalyst with the grain diameter of 1000 nm.

Example 8

Weighing 0.8mL of 25-28% ammonia water by mass concentration, 50mL of ethanol and 200mL of deionized water, fully stirring the three, adding 1.6g of resorcinol, stirring until the resorcinol is completely dissolved, slowly dropwise adding 1.12mL of formaldehyde water solution by mass concentration of 37-40%, stirring at 50 ℃ for 12 hours, transferring to a hydrothermal reaction kettle, keeping the temperature at 50 ℃ for 36 hours, and then centrifugally washing to obtain reddish brown polymer solid powder.

Dissolving 10g of citric acid in 278ml of deionized water, then adding 0.2354g of ethylenediamine palladium chloride, 0.3204g of sodium chloroplatinate and 30ml of ethylenediamine, mixing and stirring uniformly, then transferring the mixed solution into a reaction kettle, keeping the temperature at 200 ℃ for 15 hours, and then carrying out freeze drying at the relative vacuum degree of-0.05 MPa and the temperature of-5 ℃ for 24 hours to obtain the quantum dot solid powder. Wherein the mass percentage of the metal in the composite carbon-metal quantum dots is 60 percent.

Uniformly stirring 420mg of composite noble metal carbon quantum dot powder, 16g of polymer solid powder and 40ml of methanol aqueous solution (the volume ratio of alcohol to water is 10:1), transferring the mixture into a reaction kettle, keeping the temperature at 250 ℃ for 3 hours, centrifugally washing the mixture, and drying the mixture for 6 hours at 150 ℃ under the relative vacuum degree of-0.05 MPa.

Then, the solid obtained above is roasted by using hydrogen-argon mixed gas (the volume fraction of hydrogen is 10%), and the process is as follows: the temperature of the room temperature to 200 ℃ is 5 ℃/min, and the temperature is kept for 1 hour at 200 ℃; 8.5 ℃/min at the temperature of between 200 and 600 ℃, and keeping the temperature at 600 ℃ for 3 hours; the temperature of 600 ℃ to 800 ℃ is 10 ℃/min, and the temperature is kept for 4 hours at 800 ℃. Space velocity of 150h^-1. Thus obtaining the catalyst with the grain diameter of 800 nm.

Example 9

Weighing 0.8mL of 25-28% ammonia water by mass concentration, 90mL of ethanol and 180mL of deionized water, fully stirring the three, adding 1.6g of resorcinol, stirring until the resorcinol is completely dissolved, slowly dropwise adding 3.5mL of formaldehyde water by mass concentration of 37-40%, stirring at 50 ℃ for 12 hours, transferring to a hydrothermal reaction kettle, keeping at 150 ℃ for 30 hours, and then centrifugally washing to obtain reddish brown polymer solid powder.

Dissolving 8g of citric acid in 120ml of deionized water, adding 0.1204g of sodium chloroplatinate, 0.6865g of ruthenium trichloride and 11.92ml of ethylenediamine, mixing and stirring uniformly, transferring the mixed solution into a reaction kettle, keeping the temperature at 250 ℃ for 3 hours, drying the mixed solution at the relative vacuum degree of-0.09 MPa and the temperature of 20 ℃, and keeping the temperature for 36 hours to obtain the quantum dot solid powder. Wherein the mass percent of the metal in the composite carbon-metal quantum dots is 75%.

Taking 600mg of composite noble metal carbon quantum dot powder, 8g of polymer solid powder and 30ml of ethylene glycol aqueous solution (the volume ratio of alcohol to water is 10:1), uniformly stirring, transferring to a reaction kettle, keeping at 200 ℃ for 10 hours, centrifugally washing, and drying at 150 ℃ for 6 hours under the relative vacuum degree of-0.05 MPa.

Then, the solid obtained above is roasted with a hydrogen-argon mixture (the volume fraction of hydrogen is 50%), and the process is as follows: the temperature of the room temperature to 250 ℃ is 5 ℃/min, and the temperature is kept for 1 hour at 250 ℃; 5 ℃/min at the temperature of between 250 and 650 ℃, and keeping the temperature of 650 ℃ for 3 hours; 650 ℃ to 800 ℃ is 10 ℃/min and 800 ℃ is maintained for 6 hours. Space velocity of 100h^-1. Thus obtaining the catalyst with the grain diameter of 600 nm.

Example 10

Weighing 0.8mL of 25-28% ammonia water by mass concentration, 60mL of ethanol and 150mL of deionized water, fully stirring the three, adding 3.0g of resorcinol, stirring until the resorcinol is completely dissolved, slowly dropwise adding 3.5mL of formaldehyde water by mass concentration of 37-40%, stirring at 50 ℃ for 12 hours, transferring to a hydrothermal reaction kettle, keeping at 180 ℃ for 24 hours, and then centrifugally washing to obtain reddish brown polymer solid powder.

Dissolving 15g of citric acid in 200ml of deionized water, adding 0.5618g of sodium chloroplatinate, 0.2985g of iridium trichloride and 20ml of ethylenediamine, mixing and stirring uniformly, transferring the mixed solution into a reaction kettle, keeping the temperature at 150 ℃ for 10 hours, drying the mixed solution at the relative vacuum degree of-0.09 MPa and the temperature of 50 ℃ for 24 hours to obtain quantum dot solid powder. Wherein the mass percentage of the metal in the composite carbon-metal quantum dots is 50%.

Uniformly stirring 420mg of composite noble metal carbon quantum dot powder, 8g of polymer solid powder and 40ml of ethanol water solution (the volume ratio of alcohol to water is 50:1), transferring the mixture into a reaction kettle, keeping the temperature at 250 ℃ for 3 hours, centrifugally washing, and drying at 150 ℃ for 6 hours under the relative vacuum degree of-0.05 MPa.

Then, the solid obtained above was calcined with a hydrogen-argon mixture (hydrogen volume fraction of 20%), the procedure being: the temperature of the room temperature to 200 ℃ is 5 ℃/min, and the temperature is kept for 1 hour at 200 ℃; 8.5 ℃/min at the temperature of between 200 and 400 ℃, and keeping the temperature at 400 ℃ for 3 hours; the temperature of 400 ℃ to 700 ℃ is 10 ℃/min, and the temperature is kept at 700 ℃ for 6 hours. Space velocity of 50h^-1. Thus obtaining the catalyst with the grain diameter of 400 nm.

Example 11

Weighing 0.8mL of 25-28% ammonia water by mass concentration, 80mL of ethanol and 200mL of deionized water, fully stirring the three, adding 1.6g of resorcinol, stirring until the resorcinol is completely dissolved, slowly dropwise adding 3.5mL of formaldehyde water by mass concentration of 37-40%, stirring at 50 ℃ for 12 hours, transferring to a hydrothermal reaction kettle, keeping at 150 ℃ for 24 hours, and then centrifugally washing to obtain reddish brown polymer solid powder.

Dissolving 27g of citric acid in 587.07ml of deionized water, then adding 0.1795g of tetraamminepalladium nitrate, 0.7940 iridium trichloride and 90ml of ethylenediamine, mixing and stirring uniformly, then transferring the mixed solution into a reaction kettle, keeping the temperature at 150 ℃ for 20 hours, and then carrying out freeze drying at the relative vacuum degree of-0.08 MPa and the temperature of-5 ℃ for 15 hours to obtain the quantum dot solid powder. Wherein the mass percent of the metal in the composite carbon-metal quantum dots is 45%.

750mg of composite noble metal carbon quantum dot powder, 6g of polymer solid powder and 40ml of methanol aqueous solution (the volume ratio of alcohol to water is 20:1) are uniformly stirred, transferred into a reaction kettle and kept at 250 ℃ for 3 hours, then centrifuged and washed, and dried for 6 hours at 150 ℃ under the relative vacuum degree of-0.05 MPa.

Then, the solid obtained above was calcined with a hydrogen-argon mixture (hydrogen volume fraction of 5%), the procedure was: 5 ℃/min at the temperature of between room temperature and 200 ℃, and keeping at 200 DEG CHolding for 1 hour; 8.5 ℃/min at the temperature of between 200 and 500 ℃, and keeping the temperature at 500 ℃ for 3 hours; 500 ℃ to 800 ℃ is 10 ℃/min, and 800 ℃ is kept for 6 hours. Space velocity of 30h^-1. Thus obtaining the catalyst with the grain diameter of 600 nm.

Example 12

Weighing 0.8mL of 25-28% ammonia water by mass concentration, 80mL of ethanol and 220mL of deionized water, fully stirring the three, adding 1.6g of resorcinol, stirring until the resorcinol is completely dissolved, slowly dropwise adding 3.5mL of formaldehyde water by mass concentration of 37-40%, stirring at 30 ℃ for 24 hours, transferring to a hydrothermal reaction kettle, keeping the temperature at 100 ℃ for 36 hours, and then centrifugally washing to obtain reddish brown polymer solid powder.

5g of citric acid is dissolved in 50ml of deionized water, 0.3985g of platinum tetraammine nitrate and 20ml of ethylenediamine are added, the mixture is uniformly mixed and stirred, then the mixed solution is transferred into a reaction kettle and kept at 200 ℃ for 10 hours, and then freeze drying is carried out, wherein the relative vacuum degree is-0.07 MPa, the temperature is-3 ℃, and the freeze drying is carried out for 24 hours, so as to obtain the quantum dot solid powder. Wherein the mass percentage of the metal in the composite carbon-metal quantum dots is 60 percent.

542mg of composite noble metal carbon quantum dot powder, 10g of polymer solid powder and 40ml of ethanol water solution (the volume ratio of alcohol to water is 10:1) are uniformly stirred, then equal-volume impregnation is carried out, the impregnation is carried out at 20 ℃ for 24 hours, and then the drying is carried out at 120 ℃ for 10 hours under the relative vacuum degree of-0.08 MPa.

Then, the prepared solid is roasted by using mixed hydrogen-nitrogen gas (the volume fraction of hydrogen is 40 percent), and the process comprises the following steps: the temperature is 5 ℃/min from room temperature to 300 ℃, and the temperature is kept for 1 hour at 300 ℃; the temperature of 300 ℃ to 600 ℃ is 8.5 ℃/min, and the temperature is kept for 3 hours at 600 ℃; the temperature of 600 ℃ to 800 ℃ is 10 ℃/min, and the temperature is kept for 6 hours at 800 ℃. Space velocity of 80h^-1. The catalyst was thus obtained, having a particle size of 600 nm.

Comparative example 1

Weighing 0.8mL of 25% ammonia water with mass concentration, 64mL of ethanol and 160mL of deionized water, fully stirring the three, adding 1.6g of resorcinol, stirring until the resorcinol is completely dissolved, slowly dropwise adding 2.24mL of formaldehyde water with mass concentration of 37-40%, stirring at 20 ℃ for 12 hours, transferring to a hydrothermal reaction kettle, keeping at 80 ℃ for 12 hours, and then centrifugally washing to obtain reddish brown polymer solid powder.

0.2942g of sodium chloropalladate is dissolved in 40ml of ethanol water solution (the volume ratio of alcohol to water is 5:1) and 2g of polymer solid powder are uniformly mixed, transferred into a reaction kettle and kept at 50 ℃ for 8 hours, then centrifuged and washed, and dried for 12 hours at 50 ℃ under the relative vacuum degree of-0.05 MPa.

Then, the solid obtained above is roasted by using hydrogen-argon mixed gas (the volume fraction of hydrogen is 10%), and the process is as follows: the temperature is 1 ℃/minute from room temperature to 200 ℃, and the temperature is kept for 2 hours at 200 ℃; keeping the temperature at 200-600 ℃ for 3 hours at 5 ℃/min and 600 ℃; the temperature of 600 ℃ to 800 ℃ is 10 ℃/min, and the temperature is kept for 4 hours at 800 ℃. Space velocity of 30h^-1. Thereby obtaining the mesoporous carbon microsphere loaded metal catalyst with the grain diameter of 500 nm.

Comparative example 2

Weighing 0.8mL of 25-28% ammonia water by mass concentration, 2.0g of F127, 48mL of ethanol and 180mL of deionized water, fully stirring the three, adding 0.5g of resorcinol, stirring until the resorcinol is completely dissolved, slowly dropwise adding 1.6mL of 37-40% formaldehyde water solution by mass concentration, stirring at 30 ℃ for 20 hours, transferring to a hydrothermal reaction kettle, keeping the hydrothermal reaction kettle at 120 ℃ for 20 hours, and then centrifugally washing to obtain reddish brown polymer solid powder.

Weighing 3g of alanine, dissolving the alanine in 30mL of deionized water, adding 3mL of ethylenediamine, uniformly stirring, transferring the mixed solution into a reaction kettle, keeping the temperature at 150 ℃ for 8 hours, transferring the reaction solution into a dialysis bag with the molecular weight cutoff of 5000, and dialyzing for 24 hours; and then freeze-drying the dialysate at a relative vacuum degree of-0.099 to-0.05 MPa and a temperature of-8 ℃ for 15 hours to obtain the quantum dot solid powder.

30mL of alcohol-water solution of chloroplatinic acid with the concentration of 0.002g/mL (the volume ratio of ethanol to water is 40:1), 10mg of quantum dot powder prepared by the method and 4g of polymer solid powder are uniformly mixed and stirred, transferred into a reaction kettle, kept at 80 ℃ for 8 hours, centrifugally washed and dried at 60 ℃ for 15 hours under the relative vacuum degree of-0.099 to-0.05 MPa.

Then mixing the above-obtainedThe solid is reduced by hydrogen-argon mixed gas (the volume fraction of hydrogen is 50%), and the process is as follows: 0.5 ℃/min between room temperature and 300 ℃, and keeping for 4 hours at 300 ℃; 5.5 ℃/min at the temperature of 300-500 ℃, and keeping for 3 hours at 500 ℃; 0.5 ℃/min at 500 ℃ to 800 ℃ and 4 hours at 800 ℃. Space velocity of 150h^-1. Thereby obtaining the mesoporous carbon microsphere-supported composite catalyst.

Example 13

0.1g of the catalyst of example 1, 50 g of 2-chloro-4-nitrotoluene and 100mL of a methanol solvent were put into a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with nitrogen, and then nitrogen was replaced with hydrogen, and then stirring was started, and hydrogenation was carried out under conditions of a temperature of 60 ℃ and a hydrogen pressure of 1.5 MPa. When the pressure in the kettle does not decrease any more, stirring for 30 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 3-chloro-4-methylaniline is 100 percent, and the reaction time is 20 minutes.

Example 14

0.75g of the catalyst of example 2, 50 g of 2, 5-dichloronitrobenzene and 500mL of ethanol solvent were put into a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with nitrogen, and then nitrogen was replaced with hydrogen, and then hydrogenation was carried out under conditions of a temperature of 40 ℃ and a hydrogen pressure of 1.5 MPa. When the pressure in the kettle does not decrease any more, stirring for 30 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100%, the selectivity of 2, 5-dichloroaniline is 99.9%, and the reaction time is 28 minutes.

Example 15

0.5g of the catalyst of example 5, 50 g of methyl 3-nitro-4-chlorobenzoate, 50mL of methanol and 70mL of ethanol solvent are put into a high-pressure hydrogenation reactor, the reactor is closed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, and hydrogenation reaction is carried out under the conditions that the temperature is controlled at 50 ℃ and the hydrogen pressure is 1.0 MPa. When the pressure in the kettle does not decrease any more, stirring for 30 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 3-amino-4-chlorobenzoic acid methyl ester is 99.98 percent, and the reaction time is 28 minutes.

Example 16

0.5g of the catalyst of example 7, 150 g of 2-chloro-4-nitroaniline and 150mL of an n-propanol solvent were put into a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with nitrogen, nitrogen was replaced with hydrogen, stirring was started, and hydrogenation was carried out at a temperature of 40 ℃ and a hydrogen pressure of 0.1 MPa. When the pressure in the kettle does not decrease any more, stirring for 30 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 2-chloro-p-phenylenediamine is 99.97 percent, and the reaction time is 104 minutes.

Example 17

0.5g of the catalyst of example 10, 250 g of methyl 3-nitro-4-chlorobenzoate, 150mL of n-propanol and 100mL of isopropanol solvent were placed in a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with nitrogen, then nitrogen was replaced with hydrogen, stirring was started, and hydrogenation was carried out under conditions of a temperature of 90 ℃ and a hydrogen pressure of 0.8 MPa. When the pressure in the kettle does not decrease any more, stirring for 30 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 3-amino-4-chlorobenzoic acid methyl ester is 99.95 percent, and the reaction time is 168 minutes.

Example 18

1.0g of the catalyst of example 12, 150 g of 4-chloro-3-nitrobenzoic acid and 200mL of m-chloroaniline (about 230g) were charged into a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with nitrogen, nitrogen was replaced with hydrogen, the temperature was raised to a melting state, stirring was started, and hydrogenation was carried out under conditions of a temperature of 150 ℃ and a hydrogen pressure of 3.0 MPa. When the pressure in the kettle does not decrease any more, stirring for 30 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 4-chloro-3-aminobenzoic acid is 100 percent, and the reaction time is 99 minutes.

Example 19

0.5g of the catalyst of example 8, 50 g of p-chloronitrobenzene, 200mL of p-chloroaniline (about 230g) and 50mL of methanol solvent were placed in a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with nitrogen, then nitrogen was replaced with hydrogen, then stirring was started, and hydrogenation was carried out under conditions of a temperature of 60 ℃ and a hydrogen pressure of 1.0 MPa. When the pressure in the kettle does not decrease any more, stirring for 30 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the p-chloroaniline is 99.95 percent, and the reaction time is 32 minutes.

Example 20

1.0g of the catalyst of example 4, 100 g of 2,4, 6-trichloronitrobenzene and 100ml of water were placed in a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with nitrogen, nitrogen was replaced with hydrogen, stirring was started, and hydrogenation was carried out at 100 ℃ and 1.0 MPa. When the pressure in the kettle does not decrease any more, stirring for 30 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 2,4, 6-trichloroaniline is 99.98 percent, and the reaction time is 62 minutes.

Example 21

0.1g of the catalyst of example 3, 50 g of m-chloronitrobenzene and 100mL of m-chloroaniline were placed in a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with nitrogen, and then nitrogen was replaced with hydrogen, and then stirring was started, and hydrogenation was carried out under conditions of a temperature of 100 ℃ and a hydrogen pressure of 2.0 MPa. When the pressure in the kettle does not decrease any more, stirring for 30 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100 percent, the m-chloroaniline selectivity is 99.94 percent, and the reaction time is 32 minutes.

Example 22

0.15g of the catalyst of example 6 and 100 g of o-chloronitrobenzene were charged into a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with nitrogen, and then hydrogen was replaced with nitrogen, and then stirring was started, and hydrogenation was carried out under conditions of a temperature of 20 ℃ and a hydrogen pressure of 1.0 MPa. When the pressure in the kettle does not decrease any more, stirring for 30 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of o-chloroaniline is 99.92 percent, and the reaction time is 71 minutes.

Example 23

0.2g of the catalyst of example 11, 100 g of p-chloronitrobenzene, 100ml of methanol and 50ml of water were placed in a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with nitrogen, and then nitrogen was replaced with hydrogen, and then stirring was started, and hydrogenation was carried out under conditions of a temperature of 95 ℃ and a hydrogen pressure of 1.0 MPa. When the pressure in the kettle does not decrease any more, stirring for 30 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the p-chloroaniline is 99.95 percent, and the reaction time is 63 minutes.

Example 24

0.2g of the catalyst of example 9 and 100 g of 3, 4-dichloronitrobenzene were charged into a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with nitrogen, and then nitrogen was replaced with hydrogen, and then stirring was started, and hydrogenation was carried out under conditions of a temperature of 85 ℃ and a hydrogen pressure of 1.0 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 65 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the conversion rate is 100 percent, and the selectivity is 99.95 percent.

Examples 25 to 33

The results of the catalytic hydrogenation of m-chloronitrobenzene using the catalysts of comparative examples 1 and 2 under the reaction conditions corresponding to examples 13 to 17 and 18 to 21 are shown in Table 1.

TABLE 1 results of comparative examples 1 and 2 applied under reaction conditions corresponding to examples 13 to 17 and 18 to 21, respectively

Example 34

The results of the experiment for applying the catalyst of example 14. As shown in table 2.

Table 2 results of experiment for applying catalyst of example 14

Number of times of application	Conversion rate%	Selectivity%	Reaction time min
				1	100	99.97	30
2	100	99.98	31
				3	100	99.98	32
4	100	99.96	33
				5	100	99.97	31
6	100	99.98	32
				7	100	99.95	35
8	100	99.97	32
				9	100	99.96	33
10	100	99.98	34
				11	100	99.97	35
12	100	99.97	31
				13	100	99.98	35
14	100	99.97	36
				15	100	99.97	32
16	100	99.98	33
				17	100	99.95	34
18	100	99.98	35
				19	100	99.97	32
20	100	99.98	37

Claims

1. The catalyst consists of a carrier and composite carbon-metal quantum dots loaded on the carrier, the particle size of the catalyst is 100-1000 nm, and the carrier is mesoporous carbon microspheres; the size of the composite carbon-metal quantum dots is not more than 15nm, and the mass percentage of metal in the composite carbon-metal quantum dots is 10-90%; the metal in the composite carbon-metal quantum dot is one or a combination of more of platinum, palladium, iridium, ruthenium and rhodium, the loading amounts of platinum, palladium, iridium, ruthenium and rhodium are respectively 0-10.0%, 0-10.0% and 0-5.0% based on the mass of the carrier, the loading amounts of palladium, platinum and rhodium are not all 0, and the total loading amount of the metal is 1.0-11.5%; the composite carbon-metal quantum dot is prepared by the following method: dissolving metal salt by using ethylenediamine and a citric acid aqueous solution, wherein the molar ratio of the metal salt to citric acid to the ethylenediamine to deionized water used for preparing the citric acid aqueous solution is as follows: 1: 5-50: 50-500: 1500-10000, fully mixing, putting into a hydrothermal reaction kettle, keeping at 100-250 ℃ for 3-24 hours, cooling to room temperature, taking out, and removing the solvent from the obtained aqueous solution containing the composite carbon-metal quantum dots to obtain the composite carbon-metal quantum dots.

2. The catalyst of claim 1, wherein: the loading amount of palladium is 1.5-7.5%.

3. The catalyst of claim 1, wherein: the loading amount of platinum is 1.0-6.5%.

4. The catalyst of claim 1, wherein: the loading amount of rhodium is 1.0-4.0%.

5. A method of preparing the catalyst of claim 1, the method comprising:

6. The method of claim 5, wherein: in the step 2), the alcohol is ethanol, methanol or ethylene glycol.

7. The method of claim 5, wherein: in the step 2), the hydrothermal synthesis method is to keep the temperature at 50-250 ℃ for 3-12 hours, and obtain a solid after centrifugal washing;

in the isometric impregnation method, the impregnation temperature is 20-50 ℃, and the impregnation time is 5-24 hours;

the vacuum drying conditions are as follows: drying for 6-24 hours at the temperature of 40-150 ℃ under the relative vacuum degree of-0.099-0.05 MPa.

8. The use of a catalyst according to claim 1 in the selective catalytic hydrogenation of a chlorinated aromatic nitro compound of formula (I) to form a chlorinated aromatic amine compound of formula (II);

in formula (I) or formula (II), R₁、R₂、R₃、R₄、R₅At least one of which is Cl and the others are each independently H, CH₃、CH₂CH₃、NO₂、NH₂、OCH₃、OCH₂CH₃、C₆H₅COOH or COOCH₃。

9. The use of claim 8, wherein: the application method of the catalyst comprises the following steps:

putting a catalyst and an aromatic chloronitro compound shown as a formula (I) into a high-pressure hydrogenation reaction kettle, sealing the reaction kettle, replacing air with nitrogen, replacing nitrogen with hydrogen, heating to 20-150 ℃, ensuring that materials in the kettle are in a molten or solution state, filling hydrogen until the pressure in the kettle is 0.1-3.5 MPa, starting stirring to start reaction, continuing stirring at constant temperature and constant pressure for a period of time when the pressure in the kettle does not decrease, stopping stirring, cooling to room temperature, opening the kettle, taking out a hydrogenation liquid, and separating and treating the hydrogenation liquid to obtain the chloroarylamine compound shown as a formula (II).