CN110756198A - Ruthenium-aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane and preparation method and application thereof - Google Patents
Ruthenium-aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane and preparation method and application thereof Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
- C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2601/14—The ring being saturated
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- 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
Abstract
The invention discloses a ruthenium-alumina catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane, which consists of a carrier and metal components loaded on the carrier, wherein the metal components comprise ruthenium, barium and an auxiliary agent, the auxiliary agent is at least one of platinum, palladium, rhodium and nickel, and the carrier is activated alumina; the content of each component is as follows according to the weight percentage of 100 percent: 1-10% of ruthenium, 0.1-0.5% of barium, 0.1-1% of auxiliary agent and the balance of carrier; meanwhile, the invention also discloses a preparation method of the catalyst and a method for applying the catalyst to catalytic hydrogenation of 4, 4' -diaminodiphenylmethane. The catalyst provided by the invention contains barium, the catalytic activity, selectivity and stability of the catalyst are improved, when the catalyst is used for catalytic hydrogenation of 4, 4' -diaminodiphenylmethane, the conversion rate of raw materials is more than 95%, the product yield is high, the catalyst can be recycled, the service life is long, repeated application can be realized, and the catalyst is green and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of noble metal catalysts, and particularly relates to a ruthenium aluminum oxide catalyst for hydrogenation of 4, 4' -diaminodiphenylmethane, and a preparation method and application thereof.
Background
4, 4' -diaminodicyclohexylmethane (H)12MDA or PACM) is an important raw material for preparing a new generation of saturated polyurethane ' dicyclohexyl methane diisocyanate (HMDI) ' with excellent performance, and the H is prepared by taking 4,4 ' -diamino diphenylmethane (MDA) as a raw material and carrying out high-pressure hydrogenation under the action of a catalyst12MDA, then H12And carrying out phosgenation on the MDA to obtain the HMDI. The isocyanate has the characteristics of stable performance, strong oxidation resistance, wide application field and the like, is widely used for preparing light polyurethane coatings, paints, foamed plastics, various elastomers, adhesives, fibers, synthetic leather, paving materials and the like, and the application field relates to important departments of national economy such as spaceflight, aviation, electromechanics, ships, vehicles, civil construction, light industry, textile and the like. In recent years, market demand at home and abroad has been increasing year by year. The catalytic systems reported so far include the following: a rhodium-based catalyst; ruthenium-based catalysts and ruthenium-rhodium bimetallic catalyst systems. How to prepare and apply a proper high-efficiency catalyst and a catalyst system in a specific reaction system is always a key technology of MDA hydrogenation at present.
The polyurethane industry in China has rapidly developed in recent years, wherein the yield and the quality of monomer MDA jump the top of the world, and various phosgenation technologies are mature day by day. In order to further manufacture HMDI and meet the increasingly strong demand of high-performance and high-quality polyurethane products in China, the development of an MDA high-efficiency hydrogenation technology is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a ruthenium aluminum oxide catalyst for hydrogenation of 4, 4' -diaminodiphenylmethane, and a preparation method and application thereof.
A ruthenium-alumina catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane is composed of a carrier and a metal component loaded on the carrier, wherein the metal component is ruthenium, barium and an auxiliary agent, the auxiliary agent is at least one of platinum, palladium, rhodium and nickel, and the carrier is activated alumina; the content of each component is as follows according to the weight percentage of 100 percent: 1 to 10 percent of ruthenium, 0.1 to 0.5 percent of barium, 0.1 to 1 percent of auxiliary agent and the balance of carrier.
Preferably, the particle size of the carrier is 300-800 meshes, and the specific surface area is 100-800m2/g。
Preferably, the average particle size of the ruthenium is 30 to 50 nm.
Preferably, the content of the ruthenium is 5%, and the content of the auxiliary agent is 0.5%.
The preparation method of the ruthenium aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane comprises the following steps:
(1) adding the carrier into a 10-15mol/L sodium hydroxide aqueous solution, boiling for 1-2h, naturally cooling, washing with deionized water until the pH value of a washing solution is neutral, and filtering to obtain a pretreated carrier;
(2) dissolving a soluble ruthenium compound, soluble salt of barium and soluble salt of an auxiliary agent in a solvent, then adjusting the pH of the system to 2-7, and uniformly stirring to obtain a precursor solution; the solvent is water or alcohol;
(3) carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, then introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, dipping to obtain slurry, continuously stirring for 10-20h, filtering to obtain a filter cake, and drying the filter cake; in the slurry, 5mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) and (4) placing the product obtained in the step (3) in a tubular furnace, purging with nitrogen for 0.5h, and reacting for 4-8h at the temperature of 200-400 ℃ in a hydrogen atmosphere.
Preferably, the pH of the system is adjusted in step (2) with a sodium or potassium carbonate solution.
Preferably, the soluble ruthenium compound is ruthenium trichloride or/and ruthenium nitrate.
Preferably, the soluble salt of barium and the soluble salt of the auxiliary agent are both corresponding chloride salt or nitrate salt.
Preferably, the drying temperature in the step (3) is 80-120 ℃ and the time is 12-24 h.
A method for carrying out catalytic hydrogenation on 4, 4' -diaminodiphenylmethane by using the catalyst comprises the following steps: adding 4, 4' -diaminodiphenylmethane, a catalyst and a solvent into a high-pressure reaction kettle, introducing hydrogen into the high-pressure reaction kettle, and carrying out catalytic hydrogenation reaction for 3-5h at 90-120 ℃ under 8-10MPa to obtain a hydrogenated product; wherein the mass ratio of the catalyst to the 4, 4' -diaminodiphenylmethane is (5-10): 100, respectively; the solvent is deionized water or methanol.
Preferably, the 4, 4' -diaminodiphenylmethane, the catalyst and the solvent are added into a high-pressure reaction kettle, hydrogen is introduced into the high-pressure reaction kettle, and the catalytic hydrogenation reaction is carried out for 5 hours at the temperature of 100 ℃ and under the pressure of 9MPa, so as to obtain a hydrogenated product; wherein the mass ratio of the catalyst to the 4, 4' -diaminodiphenylmethane is 10: 100.
the invention has the advantages that:
1. the catalyst provided by the invention contains barium, so that the catalytic activity, selectivity and stability of the catalyst are improved;
2. the carrier is pretreated, and the precursor solution of the metal component is uniformly dispersed on the carrier through ultrasonic atomization, so that the dispersibility and the activity of the catalyst are improved;
3. the preparation method of the invention is easy to operate, the raw materials are easy to obtain, and the large-scale industrial production is easy to realize. The prepared catalyst is convenient to recover after use, can realize the production-recovery-reproduction of noble metals, has less loss in the recovery process, and greatly reduces the production cost of the catalyst;
4. when the catalyst provided by the invention is used for catalytic hydrogenation of 4, 4' -diaminodiphenylmethane, the conversion rate of raw materials is more than 95%, the product yield is high, the cost is reduced, the catalytic hydrogenation reaction condition is mild, the steps are simple, the catalyst can be recycled, the catalyst is green and environment-friendly, and favorable conditions are provided for large-scale application of the catalyst.
5. The catalyst provided by the invention has good stability and long service life, can be reused for many times, reduces the cost problem of using the catalyst for one time, and is easy to realize industrialization.
Detailed Description
Example 1
1. A ruthenium-alumina catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise ruthenium, barium and an auxiliary agent, the auxiliary agent comprises platinum, palladium, rhodium and nickel, and the carrier is active alumina; the content of each component is as follows according to the weight percentage of 100 percent: 5% of ruthenium, 0.1% of barium and 0.5% of auxiliary agent, wherein the contents of platinum, palladium, rhodium and nickel are equal, and the balance is carrier;
the particle size of the carrier is 300-800 meshes, and the specific surface area is 300m2/g；
The average grain diameter of the ruthenium is 30-50 nm.
2. The preparation method of the ruthenium aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane comprises the following steps:
(1) adding 10g of carrier into a 12mol/L sodium hydroxide aqueous solution, boiling for 2h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain a pretreated carrier;
(2) dissolving ruthenium trichloride, barium chloride, platinum chloride, palladium nitrate, rhodium trichloride and nickel nitrate in water, adjusting the pH of the system to 2 by using a sodium carbonate solution, and uniformly stirring to obtain a precursor solution;
(3) carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, then introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, dipping for 2 hours to obtain slurry, continuously stirring for 15 hours, filtering to obtain a filter cake, and drying the filter cake for 24 hours at 80 ℃; in the slurry, 5mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) and (4) placing the product obtained in the step (3) in a tubular furnace, purging with nitrogen for 0.5h, and reacting at 400 ℃ for 5h in a hydrogen atmosphere.
Example 2
1. A ruthenium-alumina catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise ruthenium, barium and an auxiliary agent, the auxiliary agent is platinum, and the carrier is activated alumina; the content of each component is as follows according to the weight percentage of 100 percent: 5% of ruthenium, 0.3% of barium, 0.5% of auxiliary agent and the balance of carrier;
the particle size of the carrier is 300-800 meshes, and the specific surface area is 300m2/g；
The average grain diameter of the ruthenium is 30-50 nm.
2. The preparation method of the ruthenium aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane comprises the following steps:
(1) adding 10g of carrier into a 15mol/L sodium hydroxide aqueous solution, boiling for 1h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain a pretreated carrier;
(2) dissolving ruthenium trichloride, barium chloride and platinum chloride in water, adjusting the pH of a system to 7 by using a potassium carbonate solution, and uniformly stirring to obtain a precursor solution;
(3) carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, then introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, dipping for 6 hours to obtain slurry, continuously stirring for 20 hours, filtering to obtain a filter cake, and drying the filter cake for 12 hours at 120 ℃; in the slurry, 5mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) and (4) placing the product obtained in the step (3) in a tubular furnace, purging with nitrogen for 0.5h, and reacting at 400 ℃ for 5h in a hydrogen atmosphere.
Example 3
1. A ruthenium-alumina catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise ruthenium, barium and an auxiliary agent, the auxiliary agent is palladium, and the carrier is activated alumina; the content of each component is as follows according to the weight percentage of 100 percent: 5% of ruthenium, 0.2% of barium, 0.1% of auxiliary agent and the balance of carrier;
the particle size of the carrier is 300-800 meshes, and the specific surface area is 800m2/g；
The average grain diameter of the ruthenium is 30-50 nm.
2. The preparation method of the ruthenium aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane comprises the following steps:
(1) adding 10g of carrier into 10mol/L sodium hydroxide aqueous solution, boiling for 2h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain the pretreated carrier;
(2) dissolving ruthenium trichloride, barium chloride and palladium nitrate in water, adjusting the pH of a system to 6 by using a sodium carbonate solution, and uniformly stirring to obtain a precursor solution;
(3) carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, then introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, dipping for 3 hours to obtain slurry, continuously stirring for 10 hours, filtering to obtain a filter cake, and drying the filter cake for 18 hours at the temperature of 100 ℃; in the slurry, 5mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) and (4) placing the product obtained in the step (3) in a tube furnace, purging with nitrogen for 0.5h, and reacting at 200 ℃ for 8h in a hydrogen atmosphere.
Example 4
1. A ruthenium-alumina catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise ruthenium, barium and an auxiliary agent, the auxiliary agent comprises palladium, rhodium and nickel, and the carrier is activated alumina; the content of each component is as follows according to the weight percentage of 100 percent: 5% of ruthenium, 0.5% of barium and 1% of assistant, wherein the contents of palladium, rhodium and nickel are the same, and the balance is a carrier;
the particle size of the carrier is 300-800 meshes, and the specific surface area is 100m2/g；
The average grain diameter of the ruthenium is 30-50 nm.
2. The preparation method of the ruthenium aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane comprises the following steps:
(1) adding 10g of carrier into a 15mol/L sodium hydroxide aqueous solution, boiling for 1.5h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain a pretreated carrier;
(2) dissolving ruthenium trichloride, ruthenium nitrate, barium chloride, palladium chloride, rhodium trichloride and nickel nitrate in water, adjusting the pH of the system to 7 by using a sodium carbonate solution, and uniformly stirring to obtain a precursor solution;
(3) carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, then introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, dipping for 3 hours to obtain slurry, continuously stirring for 15 hours, filtering to obtain a filter cake, and drying the filter cake for 20 hours at the temperature of 90 ℃; in the slurry, 5mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) and (4) placing the product obtained in the step (3) in a tube furnace, purging with nitrogen for 0.5h, and reacting at 400 ℃ for 4h in a hydrogen atmosphere.
Example 5
1. A ruthenium-alumina catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise ruthenium, barium and an auxiliary agent, the auxiliary agent comprises platinum and nickel, and the carrier is activated alumina; the content of each component is as follows according to the weight percentage of 100 percent: 5% of ruthenium, 0.1% of barium and 0.3% of auxiliary agent, wherein the contents of platinum and nickel are the same, and the balance is carrier;
the particle size of the carrier is 300-800 meshes, and the specific surface area is 300m2/g；
The average grain diameter of the ruthenium is 30-50 nm.
2. The preparation method of the ruthenium aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane comprises the following steps:
(1) adding 10g of carrier into 10mol/L sodium hydroxide aqueous solution, boiling for 2h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain the pretreated carrier;
(2) dissolving ruthenium trichloride, ruthenium nitrate, barium chloride, platinum chloride and nickel nitrate in water, adjusting the pH of the system to 6 by using a sodium carbonate solution, and uniformly stirring to obtain a precursor solution;
(3) carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, then introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, dipping for 3 hours to obtain slurry, continuously stirring for 20 hours, filtering to obtain a filter cake, and drying the filter cake for 20 hours at the temperature of 100 ℃; in the slurry, 5mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) and (4) placing the product obtained in the step (3) in a tube furnace, purging with nitrogen for 0.5h, and reacting at 300 ℃ for 6h in a hydrogen atmosphere.
Example 6
The addition agent is rhodium, the ruthenium content is 1%, the soluble salt added correspondingly in the preparation method is rhodium nitrate, and the rest is the same as the example 2.
Example 7
The addition agent is rhodium, the ruthenium content is 10%, the soluble salt added correspondingly in the preparation method is rhodium nitrate, and the rest is the same as that in example 2.
Example 8
The assistant is palladium and nickel, the soluble salt added in the preparation method is palladium nitrate and nickel nitrate, and the rest is the same as the example 5.
Comparative examples 1 to 5
The metal component contained no barium, and the examples 1 to 5 were the same as the examples.
Example 9
A method for catalytically hydrogenating 4, 4' -diaminodiphenylmethane (MDA) using the catalyst, the method comprising: adding 4, 4' -diaminodiphenylmethane, a catalyst and a solvent into a high-pressure reaction kettle, introducing hydrogen into the high-pressure reaction kettle, and carrying out catalytic hydrogenation reaction for 3-5h at 90-120 ℃ under 8-10MPa to obtain a hydrogenated product; wherein the mass ratio of the catalyst to the 4, 4' -diaminodiphenylmethane is (5-10): 100, respectively; the solvent is water or methanol.
Example 10
The catalysts of examples 1-5, comparative examples 1-5 and comparative examples are used to implement the examples, and the details are as follows:
a method for catalytically hydrogenating 4, 4' -diaminodiphenylmethane (MDA) using the catalyst, the method comprising: adding 4, 4' -diaminodiphenylmethane, a catalyst and a solvent into a high-pressure reaction kettle, introducing hydrogen into the high-pressure reaction kettle, and carrying out catalytic hydrogenation reaction for 5 hours at the temperature of 100 ℃ under 9MPa to obtain a hydrogenated product; wherein the mass ratio of the catalyst to the 4, 4' -diaminodiphenylmethane is 10: 100, respectively; the solvent is methanol, and the hydrogenation product is 4, 4' -diaminodicyclohexylmethane.
1.5 mL of the reaction solution of example 10 was collected, filtered, diluted with methanol to 50mL, and analyzed by Shimadzu liquid chromatography, the analysis results of which are shown in Table 1.
TABLE 1 conversion results (%) -for the catalytic hydrogenation of 4, 4' -diaminodiphenylmethane over different catalysts
As is apparent from Table 1, the catalyst prepared by the invention for the catalytic hydrogenation of 4, 4' -diaminodiphenylmethane has a raw material conversion rate of over 95%.
2. Catalyst stability Performance test
The catalyst was recovered and tested for stability by catalytic hydrogenation repeatability as described in example 10, with the results shown in Table 2.
TABLE 2 conversion results (%)
As is apparent from Table 2, the catalyst provided by the present invention has stable performance and good reproducibility.
Claims (10)
1. A ruthenium aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane is characterized in that: the catalyst consists of a carrier and a metal component loaded on the carrier, wherein the metal component comprises ruthenium, barium and an auxiliary agent, the auxiliary agent is at least one of platinum, palladium, rhodium and nickel, and the carrier is activated alumina; the content of each component is as follows according to the weight percentage of 100 percent: 1 to 10 percent of ruthenium, 0.1 to 0.5 percent of barium, 0.1 to 1 percent of auxiliary agent and the balance of carrier.
2. A ruthenium alumina catalyst for the selective hydrogenation of 4, 4' -diaminodiphenylmethane according to claim 1, characterised in that: the particle diameter of the carrier is 300-800 meshes, and the specific surface area is 100-800m2/g。
3. A ruthenium alumina catalyst for the selective hydrogenation of 4, 4' -diaminodiphenylmethane according to claim 1, characterised in that: the average grain diameter of the ruthenium is 30-50 nm.
4. Ruthenium alumina catalyst for the selective hydrogenation of 4, 4' -diaminodiphenylmethane according to any one of claims 1 to 3, characterized in that: the content of the ruthenium is 5 percent, and the content of the auxiliary agent is 0.5 percent.
5. A process for the preparation of a ruthenium alumina catalyst for the selective hydrogenation of 4, 4' -diaminodiphenylmethane according to any one of claims 1 to 3, characterised in that: the method comprises the following steps:
(1) adding the carrier into a 10-15mol/L sodium hydroxide aqueous solution, boiling for 1-2h, naturally cooling, washing with deionized water until the pH value of a washing solution is neutral, and filtering to obtain a pretreated carrier;
(2) dissolving a soluble ruthenium compound, soluble salt of barium and soluble salt of an auxiliary agent in a solvent, then adjusting the pH of the system to 2-7, and uniformly stirring to obtain a precursor solution; the solvent is water or alcohol;
(3) carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, then introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, dipping to obtain slurry, continuously stirring for 10-20h, filtering to obtain a filter cake, and drying the filter cake; in the slurry, 5mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) and (4) placing the product obtained in the step (3) in a tubular furnace, purging with nitrogen for 0.5h, and reacting for 4-8h at the temperature of 200-400 ℃ in a hydrogen atmosphere.
6. The process for preparing ruthenium alumina catalysts for the selective hydrogenation of 4, 4' -diaminodiphenylmethane according to claim 5, characterized in that: and (3) adjusting the pH value of the system by using a sodium carbonate or potassium carbonate solution in the step (2).
7. The process for preparing ruthenium alumina catalysts for the selective hydrogenation of 4, 4' -diaminodiphenylmethane according to claim 5, characterized in that: the soluble ruthenium compound is ruthenium trichloride or/and ruthenium nitrate.
8. The process for preparing ruthenium alumina catalysts for the selective hydrogenation of 4, 4' -diaminodiphenylmethane according to claim 5, characterized in that: the soluble salt of barium and the soluble salt of the auxiliary agent are respectively corresponding chloride or nitrate.
9. The process for preparing ruthenium alumina catalysts for the selective hydrogenation of 4, 4' -diaminodiphenylmethane according to claim 5, characterized in that: the drying temperature in the step (3) is 80-120 ℃, and the drying time is 12-24 h.
10. A process for the catalytic hydrogenation of 4, 4' -diaminodiphenylmethane using a catalyst as claimed in any one of claims 1 to 3, characterised in that: the method comprises the following steps: adding 4, 4' -diaminodiphenylmethane, a catalyst and a solvent into a high-pressure reaction kettle, introducing hydrogen into the high-pressure reaction kettle, and carrying out catalytic hydrogenation reaction for 3-5h at 90-120 ℃ under 8-10MPa to obtain a hydrogenated product; wherein the mass ratio of the catalyst to the 4, 4' -diaminodiphenylmethane is (5-10): 100, respectively; the solvent is deionized water or methanol.
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| CN114192159A (en) * | 2021-12-31 | 2022-03-18 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide and preparation method and application thereof |
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