CN110743567B - Iridium-carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method and application thereof - Google Patents

Iridium-carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method and application thereof Download PDF

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CN110743567B
CN110743567B CN201911080000.6A CN201911080000A CN110743567B CN 110743567 B CN110743567 B CN 110743567B CN 201911080000 A CN201911080000 A CN 201911080000A CN 110743567 B CN110743567 B CN 110743567B
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李小虎
李霖
金晓东
曾利辉
李岳峰
曾永康
张之翔
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Kaili Catalyst New Materials Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses an iridium carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde, which consists of a carrier and metal components loaded on the carrier, wherein the metal components comprise iridium, barium, nickel and an auxiliary agent, and the auxiliary agent is at least one of platinum, palladium, ruthenium or rhodium; the carrier is an activated carbon carrier; the content of each component is as follows according to the weight percentage of 100 percent: 1-5% of iridium, 0.1-0.5% of barium, 0.1-0.5% of nickel, 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 catalytic hydrogenation of alpha, beta-unsaturated aldehyde by using the catalyst. The catalyst prepared by the invention contains barium and nickel, so that the catalytic activity, selectivity and stability of the catalyst are improved; the catalyst is used for the selective catalytic hydrogenation of alpha, beta-unsaturated aldehyde, and the product yield is more than 94 percent; and the catalyst has stable service life, can be reused for many times, reduces the production cost, and belongs to the high-efficiency green environmental protection technology.

Description

Iridium-carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method and application thereof
Technical Field
The invention belongs to the technical field of noble metal catalysts, and particularly relates to an iridium carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde, and a preparation method and application thereof.
Background
The selective catalytic hydrogenation of α, β -unsaturated aldehydes is involved in the synthesis of many fine chemicals and their intermediates. Compared with compounds containing single carbon-carbon double bond, nitro, carbonyl and other groups, the selective hydrogenation reaction of the alpha, beta-unsaturated aldehyde is more difficult, and the requirement on the selectivity of the catalyst is higher. The currently used common catalysts such as palladium carbon and platinum carbon catalysts have poor activity and selectivity of reaction, more byproducts and poor selectivity. The supported iridium catalyst has good activity for selective hydrogenation of alpha, beta-unsaturated aldehyde, and generates fewer byproducts and three wastes, thereby meeting the national green and environmental protection requirements.
At present, supported iridium catalysts for alpha, beta-unsaturated aldehyde hydrogenation are mainly active carbon supported nano palladium, platinum and iridium metal catalysts, and the ubiquitous problem of the catalysts is how to further improve the activity and selectivity of the catalysts on the basis of the existing level.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an iridium carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde, and also provides a preparation method and application of the catalyst, which are suitable for catalytic hydrogenation of alpha, beta-unsaturated aldehyde, and have the advantages of high product yield, high selectivity, stable catalyst performance and reusability.
An iridium carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde consists of a carrier and metal components loaded on the carrier, wherein the metal components comprise iridium, barium, nickel and an auxiliary agent, and the auxiliary agent is at least one of platinum, palladium, ruthenium or rhodium; the carrier is an activated carbon carrier; the content of each component is as follows according to the weight percentage of 100 percent: 1 to 5 percent of iridium, 0.1 to 0.5 percent of barium, 0.1 to 0.5 percent of nickel, 0.1 to 1 percent of auxiliary agent and the balance of carrier.
Preferably, the particle size of the carrier is 200-800 meshes, and the specific surface area is 800-1500 m 2 /g。
Preferably, the iridium has an average particle size of 10 to 30 mesh.
Preferably, the content of the auxiliary agent is 0.4-0.6%.
More preferably, the content of iridium is 5% and the content of auxiliary agent is 0.5%.
The preparation method of the iridium carbon catalyst for the selective hydrogenation of the alpha, beta-unsaturated aldehyde comprises the following steps:
(1) Adding the carrier into 10-15mol/L sodium hydroxide aqueous solution, boiling for 1h to 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 a soluble iridium compound, soluble salt of barium, soluble salt of nickel and soluble salt of an auxiliary agent in a solvent, and uniformly stirring to obtain a precursor solution; the solvent is water or alcohol;
(3) Carrying out ultrasonic atomization treatment on the precursor solution to obtain atomized liquid drops, then introducing the atomized liquid drops into a reactor containing the pretreated carrier, uniformly stirring and impregnating to obtain slurry, then adjusting the pH value of the slurry to 8-10, continuously stirring for 3-5h and filtering to obtain filter cakes, and washing the filter cakes with deionized water until the pH value of a washing solution is neutral; in the slurry, 20mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) And (4) pulping the filter cake washed in the step (3) by using pure water to obtain slurry, adjusting the pH of the slurry to 6-9, adding a reducing agent into the slurry, carrying out reduction treatment for 0.5-6h at the temperature of 30-80 ℃, and then sequentially carrying out filtration, washing and drying treatment.
Preferably, the soluble iridium compound is iridium trichloride or/and iridium nitrate.
Preferably, the soluble salt of barium, the soluble salt of nickel and the soluble salt of the auxiliary agent are all chlorides or nitrates thereof.
Preferably, the reducing agent is sodium hypophosphite, sodium borohydride, potassium borohydride, formaldehyde, sodium formate, formic acid or hydrazine hydrate; the molar weight of the reducing agent is 3-6 times of that of the iridium.
Preferably, the temperature of the drying treatment is 60-100 ℃ and the time is 5-12h.
A method for catalytically hydrogenating α, β -unsaturated aldehydes using the catalyst comprises: adding alpha, beta-unsaturated aldehyde, 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 1-5 hours at the temperature of 60-100 ℃ under the pressure of 1-3MPa to obtain a hydrogenated product; the solvent is deionized water or methanol; the mass ratio of the catalyst to the alpha, beta-unsaturated aldehyde is (0.5-5): 100.
preferably, when the catalyst is used for carrying out catalytic hydrogenation on the alpha, beta-unsaturated aldehyde, carrying out catalytic hydrogenation reaction for 3 hours at the temperature of 70 ℃ under the pressure of 1MPa to obtain a hydrogenated product; more preferably, the mass ratio of the catalyst to the α, β -unsaturated aldehyde is 1:100.
the invention has the advantages that:
1. the catalyst prepared by the invention contains barium and nickel, 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 subjected to ultrasonic atomization to highly disperse the metal component on the activated carbon carrier, so that the dispersion uniformity of the activated carbon carrier is improved, and the activity of the catalyst is 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. the catalyst prepared by the invention is used for the selective catalytic hydrogenation of alpha, beta-unsaturated aldehyde, the product yield is more than 94%, the product yield is improved, the production cost is reduced, and the catalyst belongs to an efficient green environment-friendly technology; the catalytic reaction steps are simple, the conditions are mild, and favorable conditions are provided for large-scale application of the catalyst;
5. the catalyst prepared by the method has stable 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. An iridium carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde comprises a carrier and metal components loaded on the carrier, wherein the metal components comprise iridium, barium, nickel and an auxiliary agent, the auxiliary agent comprises platinum, palladium, ruthenium and rhodium, and the carrier is an activated carbon carrier; the content of each component is as follows according to the weight percentage of 100 percent: 5% of iridium, 0.1% of barium, 0.1% of nickel and 0.5% of auxiliary agent, wherein the contents of platinum, palladium, ruthenium and rhodium are equal, and the balance is carrier;
preferably, the carrier has a particle size of 200-800 mesh and a specific surface area of 1200 m 2 /g；
Preferably, the iridium has an average particle size of 10 to 30 mesh.
2. The preparation method of the iridium carbon catalyst for the selective hydrogenation of the alpha, beta-unsaturated aldehyde comprises the following steps:
(1) Adding 10g of carrier into 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 the pretreated carrier;
(2) Dissolving iridium nitrate, barium nitrate, nickel nitrate, platinum chloride, palladium nitrate, ruthenium trichloride and rhodium nitrate in ethanol, and uniformly stirring to obtain a precursor solution;
(3) Placing the precursor solution in an ultrasonic atomizer for ultrasonic atomization treatment to obtain atomized liquid drops, introducing the atomized liquid drops into a reactor containing the pretreated carrier, uniformly stirring, dipping for 2 hours to obtain slurry, adjusting the pH of the slurry to 10 by using a sodium hydroxide solution with the mass concentration of 1%, continuously stirring for 3 hours, filtering to obtain a filter cake, and washing the filter cake by using deionized water until the pH value of a washing liquid is neutral; in the slurry, 20mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) Pulping the filter cake washed in the step (3) by using pure water of which the mass is 20 times that of the filter cake to obtain slurry, adjusting the pH of the slurry to 9 by using a sodium hydroxide solution of which the mass concentration is 1%, then adding a reducing agent sodium borohydride into the slurry to perform reduction treatment for 3 hours at 80 ℃, then sequentially filtering and washing, and then drying the slurry for 5 hours at 100 ℃ to obtain the filter cake; wherein the molar weight of the sodium borohydride is 3 times of that of the iridium.
Example 2
1. An iridium carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde comprises a carrier and metal components loaded on the carrier, wherein the metal components comprise iridium, barium, nickel and an auxiliary agent, and the auxiliary agent is ruthenium; the carrier is an activated carbon carrier; the content of each component is as follows according to the weight percentage of 100 percent: 5% of iridium, 0.2% of barium, 0.3% of nickel, 0.4% of auxiliary agent and the balance of carrier;
preferably, the particle diameter of the carrier is 200-800 meshes, and the specific surface area is 1500 m 2 /g；
Preferably, the iridium has an average particle size of 10 to 30 mesh.
2. The preparation method of the iridium carbon catalyst for selective hydrogenation of the alpha, beta-unsaturated aldehyde comprises the following steps:
(1) Adding 10g of carrier into 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 the pretreated carrier;
(2) Dissolving iridium trichloride, iridium nitrate, barium chloride, nickel nitrate and ruthenium trichloride in water, and uniformly stirring to obtain a precursor solution;
(3) Placing the precursor solution in an ultrasonic atomizer for ultrasonic atomization treatment to obtain atomized liquid drops, then introducing the atomized liquid drops into a reactor containing the pretreated carrier, uniformly stirring, dipping for 6 hours to obtain slurry, then adjusting the pH of the slurry to 9 by using a sodium hydroxide solution with the mass concentration of 1%, continuously stirring for 5 hours, filtering to obtain filter cakes, and washing the filter cakes by using deionized water until the pH value of a washing solution is neutral; in the slurry, 20mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) Pulping the filter cake washed in the step (3) by using pure water of which the mass is 20 times that of the filter cake to obtain slurry, adjusting the pH of the slurry to 7 by using a sodium hydroxide solution of which the mass concentration is 1%, then adding a reducing agent potassium borohydride into the slurry to perform reduction treatment for 1 hour at 70 ℃, then sequentially filtering and washing the slurry, and then drying the slurry for 5 hours at 100 ℃ to obtain the filter cake; wherein the molar weight of the potassium borohydride is 3 times of that of the iridium.
Example 3
1. An iridium carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde comprises a carrier and metal components loaded on the carrier, wherein the metal components comprise iridium, barium, nickel and an auxiliary agent, and the auxiliary agent is platinum; the carrier is an activated carbon carrier; the contents of the components are as follows according to the weight percentage of 100 percent: 5% of iridium, 0.1% of barium, 0.1% of nickel, 1% of auxiliary agent and the balance of carrier;
preferably, the carrier has a particle size of 200-800 mesh and a specific surface area of 800 m 2 /g；
Preferably, the iridium has an average particle size of 10 to 30 mesh.
2. The preparation method of the iridium carbon catalyst for the selective hydrogenation of the alpha, beta-unsaturated aldehyde comprises the following steps:
(1) Adding 10g of carrier into 10mol/L sodium hydroxide aqueous solution, boiling for 2 hours, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain the pretreated carrier;
(2) Dissolving iridium trichloride, iridium nitrate, barium nitrate, nickel nitrate and platinum chloride in water, and uniformly stirring to obtain a precursor solution;
(3) Placing the precursor solution in an ultrasonic atomizer for ultrasonic atomization treatment to obtain atomized liquid drops, introducing the atomized liquid drops into a reactor containing the pretreated carrier, uniformly stirring, dipping for 3 hours to obtain slurry, adjusting the pH of the slurry to 10 by using a sodium hydroxide solution with the mass concentration of 1%, continuously stirring for 3 hours, filtering to obtain a filter cake, and washing the filter cake by using deionized water until the pH value of a washing liquid is neutral; in the slurry, 20mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) Pulping the filter cake washed in the step (3) by using pure water of which the mass is 20 times that of the filter cake to obtain slurry, adjusting the pH of the slurry to 9 by using a sodium hydroxide solution with the mass concentration of 1%, then adding a reducing agent sodium hypophosphite into the slurry to perform reduction treatment for 6 hours at 30 ℃, then sequentially filtering and washing, and then performing drying treatment for 12 hours at 60 ℃ to obtain the filter cake; wherein the molar weight of the sodium hypophosphite is 4 times of the molar weight of the iridium.
Example 4
1. An iridium carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde comprises a carrier and metal components loaded on the carrier, wherein the metal components comprise iridium, barium, nickel and an auxiliary agent, the auxiliary agent comprises platinum and palladium, and the carrier is an activated carbon carrier; the content of each component is as follows according to the weight percentage of 100 percent: 5% of iridium, 0.5% of barium, 0.5% of nickel and 0.1% of auxiliary agent, wherein the platinum and the palladium have equal content, and the balance is carrier;
preferably, the carrier has a particle size of 200-800 mesh and a specific surface area of 1200 m 2 /g；
Preferably, the iridium has an average particle size of 10 to 30 mesh.
2. The preparation method of the iridium carbon catalyst for the selective hydrogenation of the alpha, beta-unsaturated aldehyde comprises the following steps:
(1) Adding 10g of carrier into 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 the pretreated carrier;
(2) Dissolving iridium trichloride, barium nitrate, nickel nitrate, platinum chloride and palladium nitrate in water, and uniformly stirring to obtain a precursor solution;
(3) Putting the precursor solution into an ultrasonic atomizer for ultrasonic atomization treatment to obtain atomized liquid drops, introducing the atomized liquid drops into a reactor containing the pretreated carrier, uniformly stirring, dipping for 4 hours to obtain slurry, adjusting the pH of the slurry to 8 by using a sodium hydroxide solution with the mass concentration of 1%, continuously stirring for 3 hours, filtering to obtain a filter cake, and washing the filter cake by using deionized water until the pH value of a washing liquid is neutral; in the slurry, 20mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) Pulping the filter cake washed in the step (3) by using pure water of which the mass is 20 times that of the filter cake to obtain slurry, adjusting the pH of the slurry to 6 by using a sodium hydroxide solution of which the mass concentration is 1%, then adding a reducing agent formic acid into the slurry to perform reduction treatment for 0.5h at 80 ℃, then sequentially filtering and washing, and then drying the slurry for 10h at 90 ℃; wherein the molar weight of the formic acid is 4 times of that of the iridium.
Example 5
1. An iridium carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde consists of a carrier and metal components loaded on the carrier, wherein the metal components comprise iridium, barium, nickel and an auxiliary agent, the auxiliary agent comprises platinum, palladium and ruthenium, and the carrier is an activated carbon carrier; the content of each component is as follows according to the weight percentage of 100 percent: 5% of iridium, 0.2% of barium, 0.1% of nickel and 0.7% of auxiliary agent, wherein the contents of platinum, palladium and ruthenium are equal, and the balance is carrier;
preferably, the carrier has a particle size of 200-800 meshes and a specific surface area of 1200 m 2 /g；
Preferably, the iridium has an average particle size of 10 to 30 mesh.
2. The preparation method of the iridium carbon catalyst for the selective hydrogenation of the alpha, beta-unsaturated aldehyde comprises the following steps:
(1) Adding 10g of carrier into 15mol/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 iridium trichloride, barium nitrate, nickel nitrate, platinum chloride, palladium nitrate and ruthenium trichloride in water, and uniformly stirring to obtain a precursor solution;
(3) Placing the precursor solution in an ultrasonic atomizer for ultrasonic atomization treatment to obtain atomized liquid drops, introducing the atomized liquid drops into a reactor containing the pretreated carrier, uniformly stirring, dipping for 4 hours to obtain slurry, adjusting the pH of the slurry to 9 by using a sodium hydroxide solution with the mass concentration of 1%, continuously stirring for 4 hours, filtering to obtain a filter cake, and washing the filter cake with deionized water until the pH value of a washing liquid is neutral; in the slurry, 20mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) Pulping the filter cake washed in the step (3) by using pure water of which the mass is 20 times that of the filter cake to obtain slurry, adjusting the pH of the slurry to 8 by using a sodium hydroxide solution of which the mass concentration is 1%, then adding a reducing agent hydrazine hydrate into the slurry to perform reduction treatment for 3 hours at 60 ℃, then sequentially filtering and washing, and then drying the slurry for 10 hours at 90 ℃ to obtain the filter cake; wherein the molar weight of hydrazine hydrate is 5 times of the molar weight of iridium.
Example 6
The auxiliary agent is rhodium, the iridium content is 3%, the corresponding soluble salt in the preparation method is rhodium nitrate, and the rest is the same as the example 2.
Example 7
The auxiliary agent is rhodium, the content of iridium is 1%, the corresponding soluble salt in the preparation method is rhodium nitrate, and the rest is the same as example 2.
Example 8
The auxiliary agents are platinum and ruthenium, the iridium content is 5%, the corresponding soluble salts in the preparation method are platinum chloride and ruthenium trichloride, and the rest is the same as example 4.
Comparative examples 1 to 5
The examples were the same as examples 1 to 5 except that barium and nickel were not contained.
Example 9
The catalysts of examples 1-5 and comparative examples were used to implement the examples as follows:
a method for catalytically hydrogenating α, β -unsaturated aldehydes using the catalyst, comprising: adding alpha, beta-unsaturated aldehyde, 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 hours at the temperature of 70 ℃ under the pressure of 1MPa to obtain a hydrogenated product; the solvent is methanol; the alpha, beta-unsaturated aldehyde is 2-butenal; the mass ratio of the catalyst to the alpha, beta-unsaturated aldehyde is 1:100, and the hydrogenation product is 2-butenol.
Example 10
The catalysts of examples 1-5 and comparative examples were used to implement the examples as follows:
a method for catalytically hydrogenating α, β -unsaturated aldehydes using the catalyst, comprising: adding alpha, beta-unsaturated aldehyde, 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 80 ℃ under the pressure of 2MPa to obtain a hydrogenated product; the solvent is methanol; the alpha, beta-unsaturated aldehyde is acrolein; the mass ratio of the catalyst to the alpha, beta-unsaturated aldehyde is 5:100, the hydrogenation product is allyl alcohol.
Example 11
The catalysts of examples 1-5 and comparative examples 1-5, respectively, were used to practice the examples as follows:
a method for catalytically hydrogenating α, β -unsaturated aldehydes using the catalyst comprises: adding alpha, beta-unsaturated aldehyde, 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 1h at 100 ℃ under 2MPa to obtain a hydrogenated product; the solvent is methanol; the alpha, beta-unsaturated aldehyde is 3-methyl-butenal; the mass ratio of the catalyst to the alpha, beta-unsaturated aldehyde is 1:100, and the hydrogenation product is 3-methyl-butenol.
Example 12
The catalysts of examples 1-5 and comparative examples 1-5, respectively, were used to practice the examples as follows:
a method for catalytically hydrogenating α, β -unsaturated aldehydes using the catalyst comprises: adding alpha, beta-unsaturated aldehyde, 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 60 ℃ under the pressure of 3MPa to obtain a hydrogenated product; the solvent is methanol; the alpha, beta-unsaturated aldehyde is 2-methyl-pentenal; the mass ratio of the catalyst to the alpha, beta-unsaturated aldehyde is 0.5:100, and the hydrogenation product is 2-methyl-pentenol.
First, 5mL of the samples of examples 9-12 were collected, filtered, diluted to 50mL with methanol, and analyzed by Shimadzu gas chromatography GC-2014, the results of which are shown in Table 1.
TABLE 1 test yield results of selective hydrogenation of alpha, beta-unsaturated aldehydes catalyzed by different catalysts
Figure 104153DEST_PATH_IMAGE001
It is obvious from table 1 that when the catalyst prepared by the method is used for hydrogenation of alpha, beta-unsaturated aldehyde, the yield of the product of the catalytic hydrogenation reaction is greatly improved, and the yield exceeds 94%.
Secondly, stability detection of the catalyst
The stability of the catalyst was tested by conducting catalytic hydrogenation repeatability tests as described in examples 9-12, and the results are shown in Table 2.
TABLE 2 test yield results (%)
Figure 710715DEST_PATH_IMAGE002
As is apparent from Table 2, the catalyst provided by the present invention has stable performance and good reproducibility.

Claims (9)

1. An iridium carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde is characterized in that: the metal component is iridium, barium, nickel and an auxiliary agent, wherein the auxiliary agent is at least one of platinum, palladium, ruthenium or rhodium; the carrier is an activated carbon carrier; the contents of the components are as follows according to the weight percentage of 100 percent: 1-5% of iridium, 0.1-0.5% of barium, 0.1-0.5% of nickel, 0.1-1% of auxiliary agent and the balance of carrier;
the iridium carbon catalyst for the selective hydrogenation of the alpha, beta-unsaturated aldehyde is prepared by the following method:
(1) Adding the carrier into 10-15mol/L sodium hydroxide aqueous solution, boiling for 1h to 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 a soluble iridium compound, soluble salt of barium, soluble salt of nickel and soluble salt of an auxiliary agent in a solvent, and uniformly stirring to obtain a precursor solution; the solvent is water or alcohol;
(3) Carrying out ultrasonic atomization treatment on the precursor solution to obtain atomized liquid drops, then introducing the atomized liquid drops into a reactor containing the pretreated carrier, uniformly stirring and impregnating to obtain slurry, then adjusting the pH value of the slurry to 8-10, continuously stirring for 3-5h and filtering to obtain filter cakes, and washing the filter cakes with deionized water until the pH value of a washing solution is neutral; in the slurry, 20mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) And (4) pulping the filter cake washed in the step (3) by using pure water to obtain slurry, adjusting the pH of the slurry to 6-9, adding a reducing agent into the slurry, carrying out reduction treatment for 0.5-6h at the temperature of 30-80 ℃, and then sequentially carrying out filtration, washing and drying treatment.
2. The iridium carbon catalyst for selective hydrogenation of α, β -unsaturated aldehydes according to claim 1, wherein: the particle size of the carrier is 200-800 meshes, and the specific surface area is 800-1500 m 2 /g。
3. The iridium charcoal catalyst for selective hydrogenation of α, β -unsaturated aldehydes according to any one of claims 1 to 2, characterized in that: the content of the auxiliary agent is 0.4-0.6%.
4. A process for producing an iridium charcoal catalyst for selective hydrogenation of α, β -unsaturated aldehydes as claimed in any one of claims 1 to 2, characterized in that: the method comprises the following steps:
(1) Adding the carrier into a 10-15mol/L sodium hydroxide aqueous solution, boiling for 1h to 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 iridium compound, soluble salt of barium, soluble salt of nickel and soluble salt of an auxiliary agent in a solvent, and uniformly stirring to obtain a precursor solution; the solvent is water or alcohol;
(3) Carrying out ultrasonic atomization treatment on the precursor solution to obtain atomized liquid drops, then introducing the atomized liquid drops into a reactor containing the pretreated carrier, uniformly stirring and impregnating to obtain slurry, then adjusting the pH value of the slurry to 8-10, continuously stirring for 3-5h and filtering to obtain filter cakes, and washing the filter cakes with deionized water until the pH value of a washing solution is neutral; in the slurry, 20mL of precursor solution is correspondingly added into each gram of pretreated carrier;
(4) And (4) pulping the filter cake washed in the step (3) by using pure water to obtain slurry, adjusting the pH of the slurry to 6-9, adding a reducing agent into the slurry, carrying out reduction treatment for 0.5-6h at the temperature of 30-80 ℃, and then sequentially carrying out filtration, washing and drying treatment.
5. The process for producing an iridium charcoal catalyst for selective hydrogenation of α, β -unsaturated aldehydes according to claim 4, wherein: the soluble iridium compound is iridium trichloride or/and iridium nitrate.
6. The process for producing an iridium charcoal catalyst for selective hydrogenation of α, β -unsaturated aldehydes according to claim 4, wherein: the soluble salt of barium, the soluble salt of nickel and the soluble salt of the auxiliary agent are all chlorides or nitrates thereof.
7. The method for preparing an iridium carbon catalyst for selective hydrogenation of α, β -unsaturated aldehydes according to claim 4, wherein: the reducing agent is sodium hypophosphite, sodium borohydride, potassium borohydride, formaldehyde, sodium formate, formic acid or hydrazine hydrate; the molar weight of the reducing agent is 3-6 times of that of the iridium.
8. The method for preparing an iridium carbon catalyst for selective hydrogenation of α, β -unsaturated aldehydes according to claim 4, wherein: the drying treatment temperature is 60-100 deg.C, and the drying treatment time is 5-12h.
9. A process for the catalytic hydrogenation of α, β -unsaturated aldehydes using a catalyst as claimed in any one of claims 1-2, characterized in that: the method comprises the following steps: adding alpha, beta-unsaturated aldehyde, 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 1-5 hours at the temperature of 60-100 ℃ under the pressure of 1-3MPa to obtain a hydrogenated product; the solvent is deionized water or methanol; the mass ratio of the catalyst to the alpha, beta-unsaturated aldehyde is (0.5-5): 100.
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