CN113578390A - Preparation method of low-noble metal catalyst for acetylene hydrochlorination - Google Patents

Preparation method of low-noble metal catalyst for acetylene hydrochlorination Download PDF

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CN113578390A
CN113578390A CN202110900481.1A CN202110900481A CN113578390A CN 113578390 A CN113578390 A CN 113578390A CN 202110900481 A CN202110900481 A CN 202110900481A CN 113578390 A CN113578390 A CN 113578390A
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noble metal
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metal catalyst
catalyst
reaction
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CN113578390B (en
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高子豪
王富民
张旭斌
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HEBEI MEIBANG ENGINEERING TECHNOLOGY CO LTD
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HEBEI MEIBANG ENGINEERING TECHNOLOGY CO LTD
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Abstract

The invention belongs to the technical field of catalysts for acetylene hydrochlorination and preparation technologies and reaction processes thereof, and particularly relates to a preparation method of a low-noble metal catalyst for acetylene hydrochlorination; according to the preparation method of the low-noble-metal catalyst for hydrochlorination of acetylene, through the composite action of the fluoroalkyl methyl dichlorosilane, the imidazolyl group, the pyrrolyl group and the like, and the complex formed by the fluoroalkyl methyl dichlorosilane, the imidazolyl group, the pyrrolyl group and the like and the metal ions, the thermal stability of the catalyst can be improved, the effect of effectively activating products can be achieved, and meanwhile, the service life of the catalyst is greatly prolonged.

Description

Preparation method of low-noble metal catalyst for acetylene hydrochlorination
Technical Field
The invention belongs to the technical field of catalysts for acetylene hydrochlorination and preparation technologies and reaction processes thereof, and particularly relates to a preparation method of a low-noble metal catalyst for acetylene hydrochlorination.
Background
Vinyl chloride also known as vinyl chloride (C)2H3Cl), is an important chemical raw material for synthesizing polyvinyl chloride. The common preparation methods mainly comprise a calcium carbide acetylene method, an ethane method and an ethylene oxychlorination method, wherein the ethylene oxychlorination method is the most main method for producing vinyl chloride in the world at present; meanwhile, vinyl chloride is a monomer for preparing polyvinyl chloride and copolymers thereof, also commonly referred to as vinyl chloride monomer, and is one of the most important chemical products in parallel with ethylene, sodium hydroxide and the like worldwide.
With the development of social economy, the yield of polyvinyl chloride plastics is continuously increased, and the consumption of the catalyst is also continuously increased. Mercury is a toxic substance and causes serious environmental pollution. Therefore, the reaction process for synthesizing chloroethylene from acetylene has double pressure of mercury resource and environmental protection. Aiming at the current industrial situation of preparing chloroethylene by a calcium carbide method in China, in order to realize green sustainable development of the polyethylene industry, research and development of mercury-free catalysts are imperative.
Application number CN200910000950.3 discloses a mercury-free catalyst for hydrochlorination of acetylene and a preparation method and application thereof. The catalyst contains bismuth element and phosphorus element, and the balance is promoter metal element and carrier. The bismuth element exists in the form of bismuth oxide, bismuth inorganic salt or bismuth organic salt; the phosphorus element exists in the mixture of one or more of inorganic acid containing phosphorus, inorganic salt and oxide containing phosphorus. The preparation method comprises the process steps of preparing impregnation mother liquor, adding a catalyst carrier, impregnating in equal volume, drying, roasting and the like, and can be used for acetylene hydrochlorination reaction in the production of polyvinyl chloride by a calcium carbide method.
Application number CN202110079145.5 discloses a catalyst for acetylene hydrochlorination and a preparation method thereof. The catalyst comprises a carrier and a metal chloride active component loaded on the carrier; the carrier is silicon carbide, and the specific surface area of the silicon carbide is not less than 20 square meters per gram; the metal chloride active components comprise noble metal chlorides and common metal chlorides; the noble metal chloride is selected from any one of AuCl3, RuCl3, PtCl4 or PdCl 2; the common metal chloride is selected from any one of SnCl4, CsCl, CuCl2 or CeCl 3. Preparation: (1) dissolving a noble metal chloride to obtain a solution A; (2) adding common metal chloride into the solution A to obtain a solution B; (3) adding a solvent into the solution B to obtain a solution C; (4) adding silicon carbide into the solution C, performing ultrasonic treatment, and removing the solvent to obtain a pre-product; (4) and drying the pre-product to obtain the catalyst for the hydrochlorination of acetylene.
However, the mercury-free catalyst system reported in the literature and the patent at present is mainly characterized in that the catalyst disperses metal in an ionic liquid layer in a metal-based catalyst system loaded with the ionic liquid, the metal caused by the metal agglomeration anchors the metal on the surface of a carbon carrier, and the influence of metal dispersion and mass transfer caused by loading the ionic liquid layer again causes poor catalytic life in the metal-based catalyst system loaded with the ionic liquid.
Disclosure of Invention
The invention aims at the defects in the prior art, discloses a preparation method of a low-noble metal catalyst for acetylene hydrochlorination, and belongs to the technical field of catalysts for acetylene hydrochlorination, preparation technologies and reaction processes thereof.
A preparation method of a low noble metal catalyst for acetylene hydrochlorination reaction comprises the following steps:
carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluoro-alkyl methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1: 1-4.0.
Further, the preparation method of the intermediate 1 comprises the following steps:
adding 5-10 parts by weight of (R) -4-mercapto-2-pyrrolidone, 2.6-4.2 parts by weight of 1-allyl-3-vinyl imidazole nitrate and 100 parts by weight of ethanol into a closed high-pressure reaction kettle, adding 2.2-5.14 parts by weight of sodium methoxide, heating and stirring to 48-68 ℃, reacting for 100-200min, and evaporating to remove the ethanol to obtain an intermediate 1.
The fluorocarbon methyl dichlorosilane is one of (1H,1H,2H, 2H-perfluorohexyl) methyl dichlorosilane, (1H,1H,2H, 2H-perfluorooctyl) methyl dichlorosilane and (1H,1H,2H, 2H-perfluorodecyl) methyl dichlorosilane.
Further, the preparation method of the organic ligand comprises the following steps:
adding 12-18 parts by mass of intermediate 1, 18-23 parts by mass of fluoro-alkyl methyl dichlorosilane, 0.01-0.3 part by mass of N-propenyl imidazole and 100-120 parts by mass of N, N-dimethylformamide into a reaction kettle, dropwise adding 0.5-1.2 parts by mass of a chloroplatinic acid isopropanol solution with the mass percent of 3-7% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature to be 60-70 ℃, stirring for 1-3h, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
Furthermore, the metal halide is lanthanide halide.
Furthermore, the lanthanide is one or more of lanthanum, cerium, praseodymium, neodymium and the like.
Further, the mass content of the noble metal may be 0.001 to 0.1% by mass of the low noble metal catalyst.
Further, the mass content of the noble metal may be 0.005 to 0.01% of the mass of the low noble metal catalyst.
Further, the noble metal compound may be a soluble salt thereof, preferably a chloride, sulfate, phosphate, nitrate, etc., more preferably a chloride.
Further, the noble metal is selected from gold, palladium, ruthenium, platinum and iridium.
Further, the preparation method of the low noble metal catalyst comprises the following steps:
according to the weight portion, 20-30 portions of organic ligand and 15-22 portions of metal halide are stirred for 12-24 hours at 35-45 ℃ by taking alkane as a solvent at 60-120 ℃, and the alkane is evaporated after the reaction is finished, so that the low-noble metal catalyst is prepared.
Further, the organic solvent is selected from one of methanol, ethanol, diethyl ether, acetone, ethyl acetate, benzene, toluene, chloroform or carbon tetrachloride.
Furthermore, the molar ratio of the organic ligand to the metal halide is optimized to be 1: 1-2.0.
Further: the preparation of the low noble metal catalyst is utilized to catalyze the hydrochlorination of acetylene to prepare chloroethylene, the low noble metal catalyst is used as the catalyst in a bubble reactor, the reaction temperature is 120-: the volume ratio of hydrogen chloride/acetylene is 0.5-1.5, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 70-120h-1。
Furthermore, the volume ratio of the hydrogen chloride/acetylene is 0.8-1.2, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 90-100h-1。
The reaction mechanism is as follows:
(R) -4-mercapto-2-pyrrolidone, 2.6-4.2 parts of 1-allyl-3-vinyl imidazole nitrate are subjected to Michael addition reaction to obtain an intermediate product 1 with double bonds, and then the intermediate product 1 is subjected to hydrosilylation reaction with fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, and the organic ligand and metal halide are stirred and mixed to obtain the fluorine-containing catalyst for acetylene hydrochlorination.
The technical effects are as follows:
(1) the thioether functional group of the organic ligand can improve the interaction between the organic ligand and the metal halide and stabilize the valence state of the metal, and the pyridine functional group can play a certain role in catalysis and plays an auxiliary role in the main active component.
(2) The complex formed by the fluorocarbon alkyl methyl dichlorosilane, the imidazolyl group, the pyrrolyl group and the like and metal ions has stronger thermal stability, is beneficial to acetylene hydrochlorination, and can effectively activate products, thereby achieving better reaction conversion rate and selectivity. The service life of the catalyst is long.
Drawings
FIG. 1: a is the conversion of the acetylene of example 5; b is the selectivity of vinyl chloride.
Detailed Description
Catalyst preparation example 1
A preparation method of a low noble metal catalyst for acetylene hydrochlorination reaction comprises the following steps:
carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1:1.
The preparation method of the intermediate 1 comprises the following steps:
adding 5g of (R) -4-mercapto-2-pyrrolidone, 2.6g of 1-allyl-3-vinyl imidazole nitrate and 100g of ethanol into a sealed high-pressure reaction kettle, adding 2.2g of sodium methoxide, heating and stirring to 48 ℃, reacting for 100min, and evaporating to remove ethanol to obtain an intermediate 1.
The fluorine alkyl methyl dichlorosilane is (1H,1H,2H, 2H-perfluorohexyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
adding 12g of intermediate 1, 18g of fluoro-alkyl methyl dichlorosilane, 0.01g of N-propenyl imidazole, 100g N, N-dimethylformamide into a reaction kettle, dropwise adding 0.5g of chloroplatinic acid isopropanol solution with the mass percent content of 3% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature at 60 ℃, stirring for 1h, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
The metal halide is lanthanum chloride.
The mass content of the noble metal is 0.001% of the mass of the low noble metal catalyst.
The noble metal compound is palladium chloride.
The preparation method of the low-noble metal catalyst comprises the following steps:
20g of organic ligand and 15g of metal halide are stirred at 35 ℃ for 12 hours at 60 ℃ by using alkane as a solvent, and the alkane is evaporated after the reaction is finished to prepare the low-noble metal catalyst.
The organic solvent is methanol.
The catalyst was evaluated by reaction example 1.
Catalyst preparation example 2
A preparation method of a low noble metal catalyst for acetylene hydrochlorination reaction comprises the following steps:
carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1: 1.5.
The preparation method of the intermediate 1 comprises the following steps:
adding 6g of (R) -4-mercapto-2-pyrrolidone, 3g of 1-allyl-3-vinyl imidazole nitrate and 110g of ethanol into a sealed high-pressure reaction kettle, adding 2.6g of sodium methoxide, heating and stirring to 50 ℃, reacting for 120min, and evaporating to remove ethanol to obtain an intermediate 1.
The fluorine alkyl methyl dichlorosilane is (1H,1H,2H, 2H-perfluorohexyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
14g of intermediate 1, 19g of fluoro-alkyl methyl dichlorosilane, 0.015g of N-propenyl imidazole, 100g N, N-dimethylformamide are added into a reaction kettle, 0.6g of chloroplatinic acid isopropanol solution with the mass percent content of 4% is dropwise added into the reaction kettle under the protection of high-purity nitrogen, the temperature is controlled at 60 ℃, stirring is carried out for 1h, and the N, N-dimethylformamide is evaporated to obtain the organic ligand.
The metal halide is cerium chloride.
The mass content of the noble metal is 0.005% of the mass of the low noble metal catalyst.
The noble metal compound is palladium chloride.
Further, the preparation method of the low noble metal catalyst comprises the following steps:
under 80 ℃, 22g of organic ligand and 16g of metal halide are stirred for 14 hours at 40 ℃ by using alkane as a solvent, and the alkane is evaporated after the reaction is finished, so that the low-noble metal catalyst is prepared.
The organic solvent is methanol.
The catalyst was evaluated by reaction example 2.
Catalyst preparation example 3
A preparation method of a low noble metal catalyst for acetylene hydrochlorination reaction comprises the following steps:
carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1:2.
The preparation method of the intermediate 1 comprises the following steps:
adding 8g of (R) -4-mercapto-2-pyrrolidone, 3.2g of 1-allyl-3-vinyl imidazole nitrate and 125g of ethanol into a sealed high-pressure reaction kettle, adding 2.8g of sodium methoxide, heating and stirring to 55 ℃, reacting for 160min, and evaporating to remove ethanol to obtain an intermediate 1.
The fluorine alkyl methyl dichlorosilane is (1H,1H,2H, 2H-perfluorooctyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
adding 15g of intermediate 1,20g of fluoro-alkyl methyl dichlorosilane, 0.2g of N-propenyl imidazole, 110g N, N-dimethylformamide into a reaction kettle, dropwise adding 0.8g of chloroplatinic acid isopropanol solution with the mass percent of 5% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature to be 65 ℃, stirring for 2 hours, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
The metal halide is praseodymium chloride.
The mass content of the noble metal is 0.008 percent of the mass of the low noble metal catalyst.
The noble metal compound is iridium chloride.
The preparation method of the low-noble metal catalyst comprises the following steps:
at 90 ℃, 24g of organic ligand and 18g of metal halide are stirred for 16 hours at 40 ℃ by taking alkane as a solvent, and the alkane is evaporated after the reaction is finished, so that the low-noble metal catalyst is prepared.
The organic solvent is ethanol.
The catalyst was evaluated by reaction example 3.
Catalyst preparation example 4
A preparation method of a low noble metal catalyst for acetylene hydrochlorination reaction comprises the following steps:
carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1: 3.
The preparation method of the intermediate 1 comprises the following steps:
adding 8g of (R) -4-mercapto-2-pyrrolidone, 3.6g of 1-allyl-3-vinyl imidazole nitrate and 135g of ethanol into a sealed high-pressure reaction kettle, adding 3.5g of sodium methoxide, heating and stirring to 65 ℃, reacting for 180min, and evaporating to remove ethanol to obtain an intermediate 1.
The fluorine alkyl methyl dichlorosilane is (1H,1H,2H, 2H-perfluorooctyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
adding 16g of intermediate 1,21g of fluoro-alkyl methyl dichlorosilane, 0.25g of N-propenyl imidazole, 120g N, N-dimethylformamide into a reaction kettle according to the mass parts, dropwise adding 0.8g of chloroplatinic acid isopropanol solution with the mass percent content of 5% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature to be 70 ℃, stirring for 3 hours, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
The metal halide is neodymium chloride.
The mass content of the noble metal is 0.001% of the mass of the low noble metal catalyst.
The noble metal compound is ruthenium chloride.
The preparation method of the low-noble metal catalyst comprises the following steps:
at 100 ℃, 28g of organic ligand and 20g of metal halide are stirred for 20 hours at 40 ℃ by using alkane as a solvent, and the alkane is evaporated after the reaction is finished to prepare the low-noble metal catalyst.
The organic solvent is ethyl acetate.
The catalyst was evaluated by reaction example 4.
Catalyst preparation example 5
A preparation method of a low noble metal catalyst for acetylene hydrochlorination reaction comprises the following steps:
carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1: 4.
The preparation method of the intermediate 1 comprises the following steps:
adding 10g of (R) -4-mercapto-2-pyrrolidone, 4.2g of 1-allyl-3-vinyl imidazole nitrate and 150g of ethanol into a sealed high-pressure reaction kettle, adding 5.14g of sodium methoxide, heating and stirring to 68 ℃, reacting for 200min, and evaporating to remove ethanol to obtain an intermediate 1.
The fluorine alkyl methyl dichlorosilane is (1H,1H,2H, 2H-perfluorodecyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
adding 18g of intermediate 1, 23g of fluoro-alkyl methyl dichlorosilane, 0.3g of N-propenyl imidazole, 120g N, N-dimethylformamide into a reaction kettle, dropwise adding 1.2g of chloroplatinic acid isopropanol solution with the mass percent of 7% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature to be 70 ℃, stirring for 3 hours, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
The metal halide is neodymium chloride.
The mass content of the noble metal is 0.1 percent of the mass of the low noble metal catalyst.
The noble metal compound is gold chloride.
The preparation method of the low-noble metal catalyst comprises the following steps:
at 120 ℃, 30g of organic ligand and 22g of metal halide are stirred for 24 hours at 45 ℃ by using alkane as a solvent, and the alkane is evaporated after the reaction is finished, so that the low-noble metal catalyst is prepared.
The organic solvent is carbon tetrachloride.
The catalyst was evaluated by reaction example 5.
Catalyst preparation comparative example 1
Carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1:1.
The preparation method of the intermediate 1 comprises the following steps:
adding 5g of (R) -4-mercapto-2-pyrrolidone, 2.6g of 1-allyl-3-vinyl imidazole nitrate and 100g of ethanol into a closed high-pressure reaction kettle in parts by weight, adding 2.2g of sodium methoxide, heating and stirring to 48 ℃, reacting for 100min, and evaporating to remove ethanol to obtain an intermediate 1.
The preparation method of the organic ligand comprises the following steps:
adding 12g of intermediate 1, 18g of fluoro-alkyl methyl dichlorosilane, 0.01g of N-propenyl imidazole, 100g N, N-dimethylformamide into a reaction kettle, dropwise adding 0.5g of chloroplatinic acid isopropanol solution with the mass percent content of 3% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature at 60 ℃, stirring for 1h, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
The metal halide is lanthanum chloride.
The mass content of the noble metal is 0.001% of the mass of the low noble metal catalyst.
The noble metal compound is gold chloride.
The preparation method of the low-noble metal catalyst comprises the following steps:
20g of organic ligand and 15g of metal halide are stirred at 35 ℃ for 12 hours at 60 ℃ by using alkane as a solvent, and the alkane is evaporated after the reaction is finished to prepare the low-noble metal catalyst.
The organic solvent is methanol.
The catalyst was evaluated by comparative reaction example 1.
Catalyst preparation comparative example 2
A preparation method of a low noble metal catalyst for acetylene hydrochlorination reaction comprises the following steps:
carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding noble metal salt, and reacting the organic ligand and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1: 2.5.
The preparation method of the intermediate 1 comprises the following steps:
adding 8g of (R) -4-mercapto-2-pyrrolidone, 3.5g of 1-allyl-3-vinyl imidazole nitrate and 120g of ethanol into a sealed high-pressure reaction kettle, adding 4g of sodium methoxide, heating and stirring to 55 ℃, reacting for 150min, and evaporating to remove ethanol to obtain an intermediate 1.
The fluorine alkyl methyl dichlorosilane is (1H,1H,2H, 2H-perfluorohexyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
adding 15g of intermediate 1,20g of fluoro-alkyl methyl dichlorosilane, 0.15g of N-propenyl imidazole, 110g N, N-dimethylformamide into a reaction kettle, dropwise adding 0.8g of chloroplatinic acid isopropanol solution with the mass percent of 5% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature to be 65 ℃, stirring for 2 hours, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
The mass content of the noble metal is 0.01 percent of the mass of the low noble metal catalyst.
The noble metal compound is palladium chloride.
The preparation method of the low-noble metal catalyst comprises the following steps:
at 90 ℃, stirring 25g of organic ligand and noble metal salt at 40 ℃ for 18 hours by using alkane as a solvent, and evaporating the alkane after the reaction is finished to prepare the low-noble metal catalyst.
The organic solvent is acetone.
The catalyst was evaluated by comparative reaction example 2.
Catalyst preparation comparative example 3
Carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1: 4.
The preparation method of the intermediate 1 comprises the following steps:
adding 10g of (R) -4-mercapto-2-pyrrolidone, 4.2g of 1-allyl-3-vinyl imidazole nitrate and 150g of ethanol into a sealed high-pressure reaction kettle, adding 5.14g of sodium methoxide, heating and stirring to 68 ℃, reacting for 200min, and evaporating to remove ethanol to obtain an intermediate 1.
The fluorine alkyl methyl dichlorosilane is (1H,1H,2H, 2H-perfluorohexyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
adding 12-18 parts of intermediate 1, 0.3g of N-propenyl imidazole and 100 parts of N, N-dimethylformamide into a reaction kettle, dropwise adding 1.2g of chloroplatinic acid isopropanol solution with the mass percentage content of 7% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature at 70 ℃, stirring for 3 hours, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
The metal halide is praseodymium chloride.
The mass content of the noble metal is 0.1 percent of the mass of the low noble metal catalyst.
The noble metal compound is iridium chloride.
The preparation method of the low-noble metal catalyst comprises the following steps:
at 120 ℃, 30g of organic ligand and 22g of metal halide are stirred for 24 hours at 45 ℃ by using alkane as a solvent, and the alkane is evaporated after the reaction is finished, so that the low-noble metal catalyst is prepared.
The organic solvent is trichloromethane.
The catalyst was evaluated by comparative reaction example 3.
Reaction example 1:
using 10ml of the low noble metal catalyst in catalyst preparation example 1 to catalyze the hydrochlorination of acetylene to prepare vinyl chloride, introducing reaction raw material gases, namely hydrogen chloride and acetylene, into a bubble reactor at the reaction temperature of 120 ℃, wherein the reaction raw material gases comprise the following components in percentage by weight: the volume ratio of hydrogen chloride/acetylene is 0.5, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 70h-1。
The analysis result of the product after the reaction by gas chromatography is as follows: the acetylene conversion is 80.47%, and the vinyl chloride selectivity is 99.10%. After 96 hours of reaction, the activity and selectivity of the catalyst are unchanged.
Reaction example 2:
using 10ml of the low noble metal catalyst in catalyst preparation example 2 to catalyze the hydrochlorination of acetylene to prepare vinyl chloride, introducing reaction raw material gases, namely hydrogen chloride and acetylene, into a bubble reactor at the reaction temperature of 140 ℃, wherein the reaction raw material gases comprise the following components in percentage by weight: the volume ratio of hydrogen chloride/acetylene is 0.8, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 80h-1。
The analysis result of the product after the reaction by gas chromatography is as follows: the acetylene conversion was 85.41%, and the vinyl chloride selectivity was 99.55%. After 96 hours of reaction, the activity and selectivity of the catalyst are unchanged.
Reaction example 3:
the catalyst was used to prepare 10ml of the low noble metal catalyst of example 3, and reaction raw material gases, hydrogen chloride and acetylene, were introduced into a bubble reactor at a reaction temperature of 160 ℃ in the following proportions: the volume ratio of the hydrogen chloride to the acetylene is 1, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 90h-1。
The analysis result of the product after the reaction by gas chromatography is as follows: the acetylene conversion rate is 83.71 percent, and the vinyl chloride selectivity is 99.42 percent. After 96 hours of reaction, the activity and selectivity of the catalyst are unchanged.
Reaction example 4:
the catalyst was used to prepare 10ml of the low noble metal catalyst of example 4, and the reaction raw material gases, hydrogen chloride and acetylene, were fed into a bubble reactor at a reaction temperature of 200 ℃ in the following proportions: the volume ratio of hydrogen chloride/acetylene is 1.2, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 110h-1。
The analysis result of the product after the reaction by gas chromatography is as follows: the acetylene conversion rate is 89.14 percent, and the vinyl chloride selectivity is 99.87 percent. After 96 hours of reaction, the activity and selectivity of the catalyst are unchanged.
Reaction example 5:
the catalyst was used to prepare 10ml of the low noble metal catalyst of example 5, and the reaction raw material gases, hydrogen chloride and acetylene, were introduced into a bubble reactor at a reaction temperature of 220 ℃ in the following proportions: the volume ratio of hydrogen chloride/acetylene is 1.5, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 120h-1。
The analysis result of the product after the reaction by gas chromatography is as follows: the acetylene conversion rate was 91.78% and the vinyl chloride selectivity was 99.93%. After 96 hours of reaction, the activity and selectivity of the catalyst are unchanged.
Comparative reaction example 1:
10ml of the low noble metal catalyst in comparative example 1 was prepared using a catalyst, and in a bubble reactor, reaction temperature was 120 ℃ and reaction raw material gases of hydrogen chloride and acetylene were introduced in the following proportions: the volume ratio of hydrogen chloride/acetylene is 0.5, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 70h-1。
The analysis result of the product after the reaction by gas chromatography is as follows: the acetylene conversion was 54.89% and the vinyl chloride selectivity was 74.41%. After 96 hours of reaction, the activity and selectivity of the catalyst are reduced.
Comparative reaction example 2:
the catalyst was used to prepare 10ml of the low noble metal catalyst of comparative example 2, and the reaction was carried out in a bubble reactor at a reaction temperature of 180 ℃ by introducing a reaction raw material gas for chlorinationHydrogen and acetylene, wherein the reaction raw material gas ratio is as follows: the volume ratio of the hydrogen chloride/acetylene is 1, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 90h-1。
The analysis result of the product after the reaction by gas chromatography is as follows: the acetylene conversion rate is 70.12 percent, and the vinyl chloride selectivity is 80.09 percent. After 96 hours of reaction, the activity and selectivity of the catalyst are reduced.
Comparative reaction example 3:
10ml of the low noble metal catalyst in comparative example 3 was prepared using a catalyst, and in a bubble reactor, reaction temperature was 220 ℃ and reaction raw material gases of hydrogen chloride and acetylene were introduced in the following proportions: the volume ratio of hydrogen chloride/acetylene is 1.5, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 120h-1。
The analysis result of the product after the reaction by gas chromatography is as follows: the acetylene conversion is 74.87%, and the vinyl chloride selectivity is 86.41%. After 96 hours of reaction, the activity and selectivity of the catalyst are slightly reduced.

Claims (15)

1. A preparation method of a low noble metal catalyst for acetylene hydrochlorination reaction comprises the following steps:
carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluoro-alkyl methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1: 1-4.0.
2. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the preparation method of the intermediate 1 comprises the following steps:
adding 5-10 parts by weight of (R) -4-mercapto-2-pyrrolidone, 2.6-4.2 parts by weight of 1-allyl-3-vinyl imidazole nitrate and 100 parts by weight of ethanol into a closed high-pressure reaction kettle, adding 2.2-5.14 parts by weight of sodium methoxide, heating and stirring to 48-68 ℃, reacting for 100-200min, and evaporating to remove the ethanol to obtain an intermediate 1.
3. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the fluorocarbon methyl dichlorosilane is one of (1H,1H,2H, 2H-perfluorohexyl) methyl dichlorosilane, (1H,1H,2H, 2H-perfluorooctyl) methyl dichlorosilane and (1H,1H,2H, 2H-perfluorodecyl) methyl dichlorosilane.
4. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the preparation method of the organic ligand comprises the following steps:
adding 12-18 parts by mass of intermediate 1, 18-23 parts by mass of fluoro-alkyl methyl dichlorosilane, 0.01-0.3 part by mass of N-propenyl imidazole and 100-120 parts by mass of N, N-dimethylformamide into a reaction kettle, dropwise adding 0.5-1.2 parts by mass of a chloroplatinic acid isopropanol solution with the mass percent of 3-7% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature to be 60-70 ℃, stirring for 1-3h, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
5. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the metal halide is lanthanide halide.
6. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 5, wherein: the lanthanide is one or more of lanthanum, cerium, praseodymium, neodymium and the like.
7. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the mass content of the noble metal may be 0.001 to 0.1% by mass of the low noble metal catalyst.
8. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the mass content of the noble metal can be optimized to be 0.005-0.01% of the mass of the low noble metal catalyst.
9. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the noble metal compound may be a soluble salt thereof, preferably a chloride, sulfate, phosphate, nitrate, etc., more preferably a chloride.
10. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the noble metal is selected from gold, palladium, ruthenium, platinum and iridium.
11. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the preparation method of the low-noble metal catalyst comprises the following steps:
according to the weight portion, 20-30 portions of organic ligand and 15-22 portions of metal halide are stirred for 12-24 hours at 35-45 ℃ by taking alkane as a solvent at 60-120 ℃, and the alkane is evaporated after the reaction is finished, so that the low-noble metal catalyst is prepared.
12. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 11, wherein: the organic solvent is selected from one of methanol, ethanol, diethyl ether, acetone, ethyl acetate, benzene, toluene, trichloromethane or carbon tetrachloride.
13. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 12, wherein: the molar ratio of the organic ligand to the metal halide is optimized to be 1: 1-2.0.
14. A process for the preparation of acetylene, hydrochlorocarbon, according to claim 1The preparation method of the low-noble metal catalyst for the chemical reaction is characterized by comprising the following steps: the preparation of the low noble metal catalyst is utilized to catalyze the hydrochlorination of acetylene to prepare chloroethylene, the low noble metal catalyst is used as the catalyst in a bubble reactor, the reaction temperature is 120-: the volume ratio of hydrogen chloride/acetylene is 0.5-1.5, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 70-120h-1。
15. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 14, wherein: the volume ratio of hydrogen chloride/acetylene is 0.8-1.2, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 90-100h-1。
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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101716528A (en) * 2009-10-30 2010-06-02 于志勇 Catalyst system of chloroethylene prepared by hydrochlorinating acetylene and preparation method and application thereof
CN101879464A (en) * 2010-05-28 2010-11-10 于志勇 Catalyst system for preparing vinyl chloride by hydrochlorinating acetylene and preparation and application thereof
CN103894208A (en) * 2012-12-25 2014-07-02 中国科学院大连化学物理研究所 Low noble metal mercury-free catalyst for acetylene hydrochlorination reaction, preparation method and application thereof
US20140228602A1 (en) * 2011-07-11 2014-08-14 Johnson Matthey Public Limited Company Catalyst and method for its preparation
CN107715914A (en) * 2017-09-29 2018-02-23 浙江工业大学 The ruthenium catalyst and its application in unsaturated hydrocarbons hydrogenates halogenation that a kind of supported sulfided ionic liquid promotes
WO2018049820A1 (en) * 2016-09-18 2018-03-22 天津大学 Use of catalyst supporting quaternary phosphonium salt and metal chloride for acetylene hydrochlorination
CN109158126A (en) * 2018-07-12 2019-01-08 天津大学 A kind of metal halo acid ion liquid and its application method for catalyzing acetylene hydrochlorination
CN110963883A (en) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 Method for hydrochlorinating acetylene
CN111203278A (en) * 2020-03-05 2020-05-29 石河子大学 Metal complex catalyst for catalyzing hydrochlorination of acetylene and preparation method and application thereof
CN112237945A (en) * 2019-07-18 2021-01-19 中国科学院大连化学物理研究所 Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination
CN112892568A (en) * 2021-01-21 2021-06-04 常州永蓁材料科技有限公司 Catalyst for acetylene hydrochlorination and preparation method thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101716528A (en) * 2009-10-30 2010-06-02 于志勇 Catalyst system of chloroethylene prepared by hydrochlorinating acetylene and preparation method and application thereof
CN101879464A (en) * 2010-05-28 2010-11-10 于志勇 Catalyst system for preparing vinyl chloride by hydrochlorinating acetylene and preparation and application thereof
US20140228602A1 (en) * 2011-07-11 2014-08-14 Johnson Matthey Public Limited Company Catalyst and method for its preparation
CN103894208A (en) * 2012-12-25 2014-07-02 中国科学院大连化学物理研究所 Low noble metal mercury-free catalyst for acetylene hydrochlorination reaction, preparation method and application thereof
WO2018049820A1 (en) * 2016-09-18 2018-03-22 天津大学 Use of catalyst supporting quaternary phosphonium salt and metal chloride for acetylene hydrochlorination
CN107715914A (en) * 2017-09-29 2018-02-23 浙江工业大学 The ruthenium catalyst and its application in unsaturated hydrocarbons hydrogenates halogenation that a kind of supported sulfided ionic liquid promotes
CN109158126A (en) * 2018-07-12 2019-01-08 天津大学 A kind of metal halo acid ion liquid and its application method for catalyzing acetylene hydrochlorination
CN110963883A (en) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 Method for hydrochlorinating acetylene
CN112237945A (en) * 2019-07-18 2021-01-19 中国科学院大连化学物理研究所 Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination
CN111203278A (en) * 2020-03-05 2020-05-29 石河子大学 Metal complex catalyst for catalyzing hydrochlorination of acetylene and preparation method and application thereof
CN112892568A (en) * 2021-01-21 2021-06-04 常州永蓁材料科技有限公司 Catalyst for acetylene hydrochlorination and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JIA ZHAO等: "Supported ionic liquid-palladium catalyst for the highly effective hydrochlorination of acetylene", 《CHEMICAL ENGINEERING JOURNAL》 *
JIN ZUOHONG等: "Design and control of n-butyl acetate synthetic process", 《HEHEI JOURNAL OF INDUSTRIAL SCIENCE & THECHNOLOGY》 *
王小龙: "钌炭催化剂的调控合成及乙炔氢氯化性能研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 *
王录等: "乙炔氯氧化反应无汞催化剂的研究进展", 《化工进展》 *

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