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CN110743544A - Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof - Google Patents

Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof Download PDF

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CN110743544A
CN110743544A CN201911080016.7A CN201911080016A CN110743544A CN 110743544 A CN110743544 A CN 110743544A CN 201911080016 A CN201911080016 A CN 201911080016A CN 110743544 A CN110743544 A CN 110743544A
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palladium
preparing
carrier
acetophenone
catalyst
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CN110743544B (en
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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
    • B01J23/38—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
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • B01J23/894—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 rare earths or actinides
    • 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
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • C07C29/143—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 ketones
    • C07C29/145—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 ketones with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/18—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part
    • C07C33/20—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part monocyclic
    • C07C33/22—Benzylalcohol; phenethyl alcohol

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Abstract

The invention discloses a palladium-carbon catalyst for preparing α -phenethyl alcohol by selective hydrogenation of acetophenone, which consists of a carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary agent, the auxiliary agent is at least one of lanthanum, copper, cerium, neodymium and nickel, the carrier is activated carbon, and the content of each component is 1-5% of palladium, 0.1-0.5% of the auxiliary agent and the balance of the carrier according to 100% by weight.

Description

Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof
Technical Field
The invention belongs to the technical field of noble metal catalysts, and particularly relates to a palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone, and a preparation method and application thereof.
Background
α -phenethyl alcohol is an important chemical product and widely used in the pharmaceutical and flavor industries, α -phenethyl alcohol is widely applied in the pharmaceutical and flavor industries, α -phenethyl alcohol synthesis method comprises a microbial fermentation method and an organic synthesis method, the microbial fermentation method generally takes phenylalanine and fluorophenylalanine as raw materials, α -phenethyl alcohol is prepared by microbial fermentation and conversion, the raw materials adopted by the method are expensive, the production cost is high, and the industrial production is not realized4, NaBH4) The homogeneous catalytic reduction technology has higher hydrogenation activity and selectivity, but the catalyst is difficult to recover and the like to influence the industrial application of the homogeneous catalytic reduction technology, and the preparation of α -phenethyl alcohol by using acetophenone hydrogenation has a good application prospect, when the precious metal catalyst is used for acetophenone hydrogenation reaction, the selectivity of α -phenethyl alcohol is often lower, or higher acetophenone conversion rate and the selectivity of α -phenethyl alcohol cannot be obtained at the same time.
At present, the supported noble metal catalyst for acetophenone hydrogenation is mainly a nano palladium and lanthanum metal catalyst supported by activated carbon, and the ubiquitous problem of the catalysts is how to further improve the activity and selectivity of the catalyst on the basis of the existing level, and the most important point is how to improve the service life of the catalyst in consideration of the high cost of the noble metal.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone, and a preparation method and application thereof.
A palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary agent, the auxiliary agent is at least one of lanthanum, copper, cerium, neodymium and nickel, the carrier is activated carbon, and the palladium-carbon catalyst comprises 1-5 wt% of palladium, 0.1-0.5 wt% of the auxiliary agent and the balance of the carrier, wherein the auxiliary agent is at least one of lanthanum, copper, cerium, neodymium and nickel.
Preferably, the particle size of the carrier is 200-800 meshes, and the specific surface area is 800-1500 m2/g。
Preferably, the palladium has an average particle size of 10 to 30 nm.
Preferably, the content of the palladium is 5%, the content of the auxiliary agent is 0.5%, and the balance is the carrier.
The preparation method of the palladium-carbon catalyst for preparing α -phenethyl alcohol by selective hydrogenation of acetophenone comprises the following steps:
(1) adding the carrier into 5-10mol/L nitric acid water solution, boiling for 0.5-2h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain a pretreated carrier;
(2) dissolving soluble palladium compound and soluble salt of an auxiliary agent in a solvent, and uniformly stirring to obtain a precursor solution, wherein the solvent is water or alcohol;
(3) carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring and dipping to obtain slurry, adjusting the pH of the slurry to 8-10 by using alkali liquor, continuously stirring for 3-5h and filtering to obtain a filter cake, washing the filter cake by using deionized water until the pH of washing liquor is neutral, and reserving the filter cake; correspondingly adding 20mL of precursor solution into each gram of the 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 by using alkali liquor, adding a reducing agent, carrying out reduction treatment at the temperature of 60-100 ℃ for 0.5-6h, and then filtering, washing, drying and drying the slurry.
Preferably, the soluble palladium compound is palladium trichloride.
Preferably, the soluble salt of the auxiliary agent is chloride of the auxiliary agent or nitrate of the auxiliary agent.
Preferably, the reducing agent is any one of sodium hypophosphite, sodium borohydride, potassium borohydride, hydrazine hydrate, formic acid or sodium formate; the molar weight of the reducing agent is 3-10 times of the molar weight of the palladium.
Preferably, the drying temperature is 60-100 ℃ and the drying time is 5-12 h.
A method for preparing α -phenethyl alcohol by selectively hydrogenating acetophenone by using the catalyst comprises the steps of adding acetophenone, the 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 0.5-2 MPa to obtain a product α -phenethyl alcohol, wherein the addition amount of the catalyst is 0.5-5% of the mass of the acetophenone, and the solvent is absolute ethyl alcohol or methanol.
Preferably, the acetophenone, 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 3 hours under the pressure of 1 MPa and at the temperature of 80 ℃ to obtain a product α -phenethyl alcohol, wherein the addition amount of the catalyst is 1 percent of the mass of the acetophenone.
The invention has the advantages that:
1. according to the catalyst provided by the invention, after the carrier activated carbon is subjected to boiling pretreatment in a nitric acid aqueous solution, metal components are uniformly dispersed on the carrier, the particle size of palladium metal ions in the catalyst is 10-30nm, and the catalyst has good catalytic activity and selectivity;
2. the metal components are uniformly dispersed on the carrier by ultrasonic atomization treatment, so that the dispersibility and the activity of the catalyst are improved;
3. the preparation method of the catalyst provided by the invention is easy to operate, the raw materials are easy to obtain, large-scale industrial production is easy to realize, the prepared catalyst is convenient to recover after being used, the production-recovery-reproduction of noble metals can be realized, the loss in the recovery process is less, and the production cost of the catalyst is greatly reduced;
4. when the catalyst provided by the invention is used for preparing α -phenethyl alcohol by selective catalytic hydrogenation of acetophenone, the steps are simple, the conditions are mild, the product yield exceeds 90%, the selectivity is more than 94%, the product yield is greatly improved, the production cost is greatly reduced, the catalyst belongs to a high-efficiency green environment-friendly technology, 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. A palladium-carbon catalyst for preparing α -phenethyl alcohol by selective hydrogenation of acetophenone is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary agent, the auxiliary agent is neodymium, and the carrier is activated carbon, wherein the palladium content, the auxiliary agent and the carrier are respectively 5% of palladium, 0.5% of auxiliary agent and the balance of carrier, and the auxiliary agent is 100% of neodymium;
wherein the particle size of the carrier is 200-800 meshes, and the specific surface area is 1200 m2(ii)/g; the average particle size of the palladium is 10-30 nm.
2. The preparation method of the palladium-carbon catalyst for preparing α -phenethyl alcohol by selective hydrogenation of acetophenone comprises the following steps:
(1) adding 10g of carrier into 6mol/L nitric acid water 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 palladium trichloride and neodymium chloride in water, and uniformly stirring to obtain a precursor solution;
(3) carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, then soaking 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, then filtering to obtain a filter cake, washing the filter cake with deionized water until the pH of a washing liquid is neutral, and keeping the filter cake for later use; correspondingly adding 20mL of precursor solution into each gram of the pretreated carrier;
(4) adding the filter cake washed in the step (3) into pure water with the mass of 20 times, pulping to obtain slurry, adjusting the pH of the slurry to 9 by using a sodium hydroxide solution with the mass concentration of 1%, adding sodium borohydride, carrying out reduction treatment for 3 hours at 80 ℃, then filtering, washing, drying for 5 hours at 100 ℃ to obtain the filter cake; the molar weight of the sodium borohydride is 3 times of that of the palladium.
Example 2
1. A palladium-carbon catalyst for preparing α -phenethyl alcohol by selective hydrogenation of acetophenone is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary agent, the auxiliary agent is lanthanum, and the carrier is activated carbon, wherein the palladium content, the auxiliary agent and the carrier are respectively 5% of palladium, 0.5% of auxiliary agent and the balance of carrier, and the auxiliary agent is 100% of lanthanum;
wherein the particle size of the carrier is 200-800 meshes, and the specific surface area is 1200 m2(ii)/g; the average particle size of the palladium is 10-30 nm.
2. The preparation method of the palladium-carbon catalyst for preparing α -phenethyl alcohol by selective hydrogenation of acetophenone comprises the following steps:
(1) adding 10g of carrier into 6mol/L nitric acid water 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 palladium trichloride and lanthanum chloride in water, and uniformly stirring to obtain a precursor solution;
(3) carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, dipping for 6 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 5 hours, filtering to obtain a filter cake, washing the filter cake with deionized water until the pH of a washing liquid is neutral, and reserving the filter cake; correspondingly adding 20mL of precursor solution into each gram of the pretreated carrier;
(4) adding the filter cake washed in the step (3) into pure water with the mass of 20 times, pulping to obtain slurry, adjusting the pH of the slurry to 8 by using a sodium hydroxide solution with the mass concentration of 1%, adding potassium borohydride, carrying out reduction treatment at 100 ℃ for 2h, then filtering, washing, and drying at 90 ℃ for 4h to obtain the filter cake; the molar weight of the potassium borohydride is 3 times of that of the palladium.
Example 3
1. A palladium-carbon catalyst for preparing α -phenethyl alcohol by selective hydrogenation of acetophenone is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary agent, the auxiliary agent comprises lanthanum, neodymium and nickel, the carrier is active carbon, and the palladium-carbon catalyst comprises, by weight percent 100%, 5% of palladium, 0.5% of the auxiliary agent, and the lanthanum, neodymium and nickel have the same content, and the balance is the carrier;
wherein the particle size of the carrier is 200-800 meshes, and the specific surface area is 1200 m2(ii)/g; the average particle size of the palladium is 10-30 nm.
2. The preparation method of the palladium-carbon catalyst for preparing α -phenethyl alcohol by selective hydrogenation of acetophenone comprises the following steps:
(1) adding 10g of carrier into 10mol/L nitric acid water 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 palladium trichloride, lanthanum chloride, neodymium nitrate and nickel nitrate in water, and uniformly stirring to obtain a precursor solution;
(3) carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, dipping for 3h 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 5h, filtering to obtain a filter cake, washing the filter cake with deionized water until the pH of a washing liquid is neutral, and reserving the filter cake; correspondingly adding 20mL of precursor solution into each gram of the pretreated carrier;
(4) adding the filter cake washed in the step (3) into pure water with the mass of 20 times, pulping to obtain slurry, adjusting the pH of the slurry to 6 by using a sodium hydroxide solution with the mass concentration of 1%, adding sodium hypophosphite, carrying out reduction treatment for 3h at 90 ℃, filtering, washing, and drying for 12h at 60 ℃ to obtain the filter cake; the molar weight of the sodium hypophosphite is 3 times of that of the palladium.
Example 4
1. A palladium-carbon catalyst for preparing α -phenethyl alcohol by selective hydrogenation of acetophenone is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary agent, the auxiliary agent comprises copper and cerium, the carrier is active carbon, the contents of the components are as follows according to 100% by weight, the contents of the palladium are 5%, the auxiliary agent is 0.5%, the contents of the copper and the cerium are equal, and the balance is the carrier;
wherein the particle size of the carrier is 200-800 meshes, and the specific surface area is 1200 m2(ii)/g; the average particle size of the palladium is 10-30 nm.
2. The preparation method of the palladium-carbon catalyst for preparing α -phenethyl alcohol by selective hydrogenation of acetophenone comprises the following steps:
(1) adding 10g of carrier into 5mol/L nitric acid water 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 palladium trichloride, copper nitrate and cerous nitrate in water, and uniformly stirring to obtain a precursor solution;
(3) carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, dipping for 4 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, washing the filter cake with deionized water until the pH of a washing liquid is neutral, and reserving the filter cake; correspondingly adding 20mL of precursor solution into each gram of the pretreated carrier;
(4) adding the filter cake washed in the step (3) into pure water with the mass 30 times that of the filter cake, pulping to obtain slurry, adjusting the pH of the slurry to 9 by using a sodium hydroxide solution with the mass concentration of 1%, adding formic acid, carrying out reduction treatment at 60 ℃ for 6 hours, then filtering, washing, drying at 100 ℃ for 5 hours, and thus obtaining the filter cake; the molar amount of formic acid is 5 times of the molar amount of palladium.
Example 5
1. A palladium-carbon catalyst for preparing α -phenethyl alcohol by selective hydrogenation of acetophenone is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary agent, the auxiliary agent comprises lanthanum, copper, cerium, neodymium and nickel, the carrier is activated carbon, the contents of the components are as follows according to 100% by weight, 1% of palladium and 0.2% of auxiliary agent, the lanthanum, copper, cerium, neodymium and nickel are equal in mass, and the balance is the carrier;
wherein the particle size of the carrier is 200-800 meshes, and the specific surface area is 1500 m2(ii)/g; the average particle size of the palladium is 10-30 nm.
2. The preparation method of the palladium-carbon catalyst for preparing α -phenethyl alcohol by selective hydrogenation of acetophenone comprises the following steps:
(1) adding 10g of carrier into 6mol/L nitric acid water 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 palladium trichloride, lanthanum chloride, copper nitrate, cerium nitrate, neodymium chloride and nickel nitrate in water, and uniformly stirring to obtain a precursor solution;
(3) carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, introducing the atomized dropping liquid 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 3 hours, filtering to obtain a filter cake, washing the filter cake with deionized water until the pH of a washing liquid is neutral, and reserving the filter cake; correspondingly adding 20mL of precursor solution into each gram of the pretreated carrier;
(4) adding the filter cake washed in the step (3) into pure water with the mass 30 times that of the filter cake, pulping to obtain slurry, adjusting the pH of the slurry to 8 by using a sodium hydroxide solution with the mass concentration of 1%, adding sodium formate, carrying out reduction treatment at 100 ℃ for 0.5h, then filtering, washing, and drying at 100 ℃ for 5h to obtain the filter cake; the molar weight of the sodium formate is 4 times of that of the palladium.
Example 6
1. A palladium-carbon catalyst for preparing α -phenethyl alcohol by selective hydrogenation of acetophenone is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary agent, the auxiliary agent comprises copper, cerium, neodymium and nickel, the carrier is activated carbon, the contents of the components are as follows according to 100% by weight, the contents of the palladium are 3%, the auxiliary agent is 0.1%, the mass of the copper, the cerium, the neodymium and the nickel are equal, and the balance is the carrier;
wherein the particle diameter of the carrier is 200-800 meshes, and the specific surface area is 800 m2(ii)/g; the average particle size of the palladium is 10-30 nm.
2. The preparation method of the palladium-carbon catalyst for preparing α -phenethyl alcohol by selective hydrogenation of acetophenone comprises the following steps:
(1) adding 10g of carrier into 10mol/L nitric acid water solution, boiling for 0.5h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain the pretreated carrier;
(2) dissolving palladium trichloride, copper nitrate, cerium nitrate, neodymium chloride and nickel nitrate in water, and uniformly stirring to obtain a precursor solution;
(3) carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, then soaking for 2 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, then filtering to obtain a filter cake, washing the filter cake with deionized water until the pH of a washing liquid is neutral, and keeping the filter cake for later use; correspondingly adding 20mL of precursor solution into each gram of the pretreated carrier;
(4) adding the filter cake washed in the step (3) into pure water with the mass 30 times that of the filter cake, pulping to obtain slurry, adjusting the pH of the slurry to 9 by using a sodium hydroxide solution with the mass concentration of 1%, adding hydrazine hydrate, carrying out reduction treatment for 1h at 90 ℃, then filtering, washing, drying for 5h at 100 ℃ to obtain the finished product; the molar amount of hydrazine hydrate is 5 times of the molar amount of palladium.
Example 7
The assistant is neodymium, the palladium content is 1%, the corresponding soluble salt in the preparation method is neodymium chloride, and the rest is the same as the example 1.
Example 8
The assistant is neodymium, the corresponding soluble salt in the preparation method with 3 percent of palladium content is neodymium chloride, and the rest is the same as the example 1.
Example 9
The auxiliary agent is cerium, the corresponding soluble salt in the preparation method is cerium nitrate, and the rest is the same as example 1.
Example 10
The auxiliaries are copper, cerium and nickel, the corresponding soluble salts in the preparation method are copper nitrate, cerium nitrate and nickel nitrate, and the rest is the same as in example 3.
Comparative example 1
The palladium/active carbon catalyst obtained by a market purchase method is used as a comparative example 1, the mass percentage of palladium in the catalyst is 5 percent, the active carbon carrier is 95 percent, the particle size of the carrier is 200-800 meshes, and the specific surface area is 1200 m2The particle diameter of the palladium metal is 10-30 nm.
Example 11
A method for preparing α -phenethyl alcohol by selectively hydrogenating acetophenone by using the catalyst comprises the steps of adding acetophenone, the 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 0.5-2 MPa to obtain a product α -phenethyl alcohol, wherein the adding amount of the catalyst is 0.5-5% of the mass of the acetophenone, and the solvent is absolute ethyl alcohol or methanol.
Example 12
The catalyst of the embodiment 1-6 and the comparative example 1 is used for selectively hydrogenating acetophenone to prepare α -phenethyl alcohol, and the specific method comprises the steps of adding acetophenone, the catalyst and a solvent into a high-pressure reaction kettle, introducing hydrogen into the high-pressure reaction kettle, and carrying out catalytic hydrogenation reaction at 1 MPa and 80 ℃ for 3 hours to obtain a product α -phenethyl alcohol, wherein the adding amount of the catalyst is 1 percent of the mass of the acetophenone, and the solvent is absolute ethyl alcohol;
1. 5mL of the reaction product of example 12 was 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 results of the selective hydrogenation of acetophenone by different catalysts
Figure DEST_PATH_IMAGE001
As can be seen from Table 1, the catalyst provided by the invention has high raw material conversion rate and high product yield when used for catalyzing acetophenone to prepare α -phenethyl alcohol.
2. Stability testing of the catalyst
The catalyst was recovered and recycled as described in example 12, with the test results shown in Table 2.
TABLE 2 recycle of different catalysts
Figure 495510DEST_PATH_IMAGE002
As can be seen from Table 2, the catalyst provided by the invention has stable catalytic performance, high repeated use frequency and recycling property.

Claims (10)

1. A palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone is characterized in that the catalyst consists of a carrier and metal components loaded on the carrier, the metal components comprise palladium and an auxiliary agent, the auxiliary agent is at least one of lanthanum, copper, cerium, neodymium and nickel, the carrier is activated carbon, and the palladium-carbon catalyst comprises 1-5 wt% of palladium, 0.1-0.5 wt% of the auxiliary agent and the balance of the carrier, wherein the auxiliary agent is at least one of lanthanum, copper, cerium, neodymium and nickel.
2. The method for preparing α -phenethyl alcohol by selective hydrogenation of acetophenone according to claim 1,the method is characterized in that: the particle size of the carrier is 200-800 meshes, and the specific surface area is 800-1500 m2/g。
3. The palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone as claimed in claim 1, wherein the average particle size of the palladium is 10-30 nm.
4. The palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone according to any one of claims 1-3, characterized in that the palladium content is 5%, the adjuvant content is 0.5%, and the rest is carrier.
5. The method for preparing the palladium-carbon catalyst for preparing α -phenethyl alcohol by selectively hydrogenating acetophenone as claimed in any one of claims 1 to 3 is characterized by comprising the following steps:
(1) adding the carrier into 5-10mol/L nitric acid water solution, boiling for 0.5-2h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain a pretreated carrier;
(2) dissolving soluble palladium compound and soluble salt of an auxiliary agent in a solvent, and uniformly stirring to obtain a precursor solution, wherein the solvent is water or alcohol;
(3) carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring and dipping to obtain slurry, adjusting the pH of the slurry to 8-10 by using alkali liquor, continuously stirring for 3-5h and filtering to obtain a filter cake, washing the filter cake by using deionized water until the pH of washing liquor is neutral, and reserving the filter cake; correspondingly adding 20mL of precursor solution into each gram of the 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 by using alkali liquor, adding a reducing agent, carrying out reduction treatment at the temperature of 60-100 ℃ for 0.5-6h, and then filtering, washing, drying and drying the slurry.
6. The method for preparing the palladium-carbon catalyst for preparing α -phenylethyl alcohol by selectively hydrogenating acetophenone according to claim 5, wherein the soluble palladium compound is palladium trichloride.
7. The method for preparing the palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone according to claim 5, wherein the soluble salt of the auxiliary is an auxiliary chloride or an auxiliary nitrate.
8. The method for preparing the palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone according to claim 5, wherein the reducing agent is any one of sodium hypophosphite, sodium borohydride, potassium borohydride, hydrazine hydrate, formic acid or sodium formate, and the molar weight of the reducing agent is 3-10 times that of palladium.
9. The method for preparing the palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone according to claim 5, wherein the drying temperature is 60-100 ℃ and the drying time is 5-12 h.
10. A method for preparing α -phenylethyl alcohol by selectively hydrogenating acetophenone by using the catalyst of any one of claims 1 to 3 is characterized in that acetophenone, the catalyst and a 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 1 to 5 hours at the temperature of between 60 and 100 ℃ under the pressure of between 0.5 and 2 MPa to obtain α -phenylethyl alcohol, wherein the adding amount of the catalyst is 0.5 to 5 percent of the mass of the acetophenone, and the solvent is absolute ethyl alcohol or methanol.
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