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CN113578390B - Preparation method of low noble metal catalyst for hydrochlorination of acetylene - Google Patents

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

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CN113578390B
CN113578390B CN202110900481.1A CN202110900481A CN113578390B CN 113578390 B CN113578390 B CN 113578390B CN 202110900481 A CN202110900481 A CN 202110900481A CN 113578390 B CN113578390 B CN 113578390B
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noble metal
acetylene
catalyst
hydrochlorination
metal catalyst
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CN113578390A (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 hydrochlorination of acetylene and preparation technology and reaction technology thereof, and particularly relates to a preparation method of a low-noble metal catalyst for hydrochlorination of acetylene; according to the preparation method of the low-noble metal catalyst for acetylene hydrochlorination, complex formed by the fluorocarbon methyl dichlorosilane, imidazolyl, pyrrolyl and the like and metal ions can play a role in improving the thermal stability of the catalyst and effectively activating a product, and meanwhile, the service life of the catalyst is greatly prolonged.

Description

Preparation method of low noble metal catalyst for hydrochlorination of acetylene
Technical Field
The invention belongs to the technical field of catalysts for hydrochlorination of acetylene and preparation technology and reaction technology thereof, and particularly relates to a preparation method of a low-noble metal catalyst for hydrochlorination of acetylene.
Background
Vinyl chloride, also known as vinyl chloride (C2H 3 Cl), 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 chloroethylene in the world at present; meanwhile, vinyl chloride is a monomer for preparing polyvinyl chloride and its copolymer, 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 in the world.
With the development of social economy, the yield of polyvinyl chloride plastics is continuously increased, and the consumption of catalysts is also continuously increased. Mercury is a toxic substance and has serious environmental pollution. The reaction process for synthesizing vinyl chloride from acetylene is thus under double pressure of mercury resources and environmental protection. Aiming at the current industrial situation of preparing vinyl chloride by using calcium carbide in China, in order to realize green sustainable development in 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, a preparation method and application thereof. The catalyst contains bismuth element and phosphorus element, and the balance of auxiliary catalytic metal element and carrier. The bismuth element exists in the form of bismuth oxide, bismuth inorganic salt or bismuth organic salt; the phosphorus element is present as a mixture of one or more of a phosphorus-containing inorganic acid, an inorganic salt and a phosphorus-containing oxide. The preparation method comprises the process steps of preparing impregnation mother liquor, adding catalyst carrier for isovolumetric impregnation, drying, roasting and the like, and can be used for hydrochlorination of acetylene for producing polyvinyl chloride by a calcium carbide method.
Application number CN202110079145.5 discloses a catalyst for hydrochlorination of acetylene 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 component comprises noble metal chloride and common metal chloride; the noble metal chloride is selected from AuCl 3 、RuCl 3 、PtCl 4 Or PdCl 2 Any one of them; the common metal chloride is selected from SnCl 4 、CsCl、CuCl 2 Or CeCl 3 Any one of them. Preparation: (1) dissolving noble metal chloride to obtain 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-productThe method comprises the steps of carrying out a first treatment on the surface of the (4) The pre-product is dried and used as a catalyst for hydrochlorination of acetylene.
However, the mercury-free catalyst systems reported in the current literature and patent are mainly characterized in that the catalyst disperses metal in an ionic liquid layer in a metal-based catalyst system loaded with ionic liquid, the metal is agglomerated, the metal is anchored on the surface of a carbon carrier, and then the metal dispersion and mass transfer caused by the ionic liquid layer are influenced, so that the catalyst life in the metal-based catalyst system loaded with ionic liquid is poor.
Disclosure of Invention
The invention discloses a preparation method of a low noble metal catalyst for acetylene hydrochlorination, which aims at overcoming the defects in the prior art, and belongs to the technical fields of catalysts for acetylene hydrochlorination, preparation technology and reaction technology.
A preparation method of a low noble metal catalyst for hydrochlorination of acetylene, which comprises the following steps:
the preparation method comprises the steps of 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 with fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the organic ligand with the common metal halide and the noble metal salt to obtain the 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:
according to the weight portions, 5 to 10 portions of (R) -4-mercapto-2-pyrrolidone, 2.6 to 4.2 portions of 1-allyl-3-vinyl imidazole nitrate and 100 to 150 portions of ethanol are added into a closed high-pressure reaction kettle, 2.2 to 5.14 portions of sodium methoxide are added, the temperature is raised and stirred to 48 to 68 ℃ for reacting for 100 to 200 minutes, and the ethanol is removed by evaporation, thus obtaining the intermediate 1.
The fluorocarbon methyl dichlorosilane is (1H, 2H-perfluorohexyl) methyl dichlorosilane.
Further, the preparation method of the organic ligand comprises the following steps:
according to the parts by weight, adding 12-18 parts of intermediate 1, 18-23 parts of fluorocarbon methyl dichlorosilane, 0.01-0.3 part of N-propenyl imidazole and 100-120 parts of N, N-dimethylformamide into a reaction kettle, using high-purity nitrogen to protect, dripping 0.5-1.2 parts of chloroplatinic acid isopropanol solution with the mass percent content of 3-7% into the reaction kettle, controlling the temperature to be 60-70 ℃, stirring for 1-3h, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
Further, the metal halide is a lanthanide halide.
Further, the lanthanoid is one or more of lanthanum, cerium, praseodymium, neodymium and other elements.
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 used as a soluble salt thereof, preferably chloride, sulfate, phosphate, nitrate, or the like, more preferably 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 parts by weight, at 60-120 ℃, 20-30 parts of organic ligand, 15-22 parts of metal halide and noble metal salt are stirred for 12-24 hours by taking alkane as a solvent, and the alkane is distilled off 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.
Further, 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 vinyl chloride, the low noble metal catalyst is used as a catalyst in a bubbling reactor, the reaction temperature is 120-220 ℃, and the reaction raw material gases of hydrogen chloride and acetylene are introduced.
The ratio of the reaction raw material gases is as follows: volume ratio of hydrogen chloride/acetylene=0.5-1.5, volume ratio of reaction raw material gas flow rate to catalyst=70-120 h -1 。
Further, the volume ratio of hydrogen chloride/acetylene=0.8-1.2, the volume ratio of the reaction raw material gas flow rate to the catalyst=90-100 h -1 。
The reaction mechanism is as follows:
2.6-4.2 parts of 1-allyl-3-vinyl imidazole nitrate undergo Michael addition reaction to obtain an intermediate product 1 with double bonds, then undergo hydrosilylation reaction with fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, and the organic ligand, metal halide and noble metal salt are stirred and mixed to obtain the fluorine-containing catalyst for hydrochlorination of acetylene.
The technical effects are as follows:
the complex of fluorocarbon methyl dichlorosilane, imidazolyl, pyrrolyl and the like and metal ions have stronger thermal stability, are favorable for hydrochlorination of acetylene, can effectively activate products, and can achieve better reaction conversion rate and selectivity. The catalyst has long service life.
Detailed Description
Catalyst preparation example 1
A preparation method of a low noble metal catalyst for hydrochlorination of acetylene, which comprises the following steps:
the preparation method comprises the steps of 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 with fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the organic ligand with the common metal halide and the noble metal salt to obtain the 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:
5g (R) -4-mercapto-2-pyrrolidone, 2.6g 1-allyl-3-vinylimidazole nitrate and 100g ethanol are added into a closed high-pressure reaction kettle, 2.2g sodium methoxide is added, the temperature is raised and stirred to 48 ℃, the reaction is carried out for 100min, and the ethanol is removed by evaporation, thus obtaining the intermediate 1.
The fluorocarbon methyl dichlorosilane is (1H, 2H-perfluorohexyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
12g of intermediate 1, 18g of fluorocarbon methyl dichlorosilane, 0.01g of N-propenyl imidazole and 100g of N, N-dimethylformamide are added into a reaction kettle, high-purity nitrogen is used for protection, 0.5g of chloroplatinic acid isopropanol solution with the mass percent content of 3% is dripped into the reaction kettle, the temperature is controlled at 60 ℃, stirring is carried out for 1h, and the N, N-dimethylformamide is removed by evaporation, so that the organic ligand can be obtained.
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:
at 60 ℃, 20g of organic ligand, 15g of metal halide and noble metal salt are stirred for 12 hours at 35 ℃ by taking alkane as a solvent, and alkane is distilled off 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 1.
Catalyst preparation example 2
A preparation method of a low noble metal catalyst for hydrochlorination of acetylene, which comprises the following steps:
the preparation method comprises the steps of 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 with fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the organic ligand with the common metal halide and the noble metal salt to obtain the 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:
6g (R) -4-mercapto-2-pyrrolidone, 3g 1-allyl-3-vinylimidazole nitrate, 110g ethanol and 2.6g sodium methoxide are added into a closed high-pressure reaction kettle, the temperature is raised and stirred to 50 ℃, the reaction is carried out for 120min, and the ethanol is removed by evaporation, thus obtaining the intermediate 1.
The fluorocarbon methyl dichlorosilane is (1H, 2H-perfluorohexyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
14g of intermediate 1, 19g of fluorocarbon methyl dichlorosilane, 0.015g of N-propenyl imidazole and 100g of N, N-dimethylformamide are added into a reaction kettle, high-purity nitrogen is used for protection, 0.6g of chloroplatinic acid isopropanol solution with the mass percent of 4% is dripped into the reaction kettle, the temperature is controlled at 60 ℃, stirring is carried out for 1h, and the N, N-dimethylformamide is removed by evaporation, so that the organic ligand can be obtained.
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:
at 80 ℃, 22g of organic ligand, 16g of metal halide and noble metal salt are stirred for 14 hours at 40 ℃ by taking alkane as a solvent, and alkane is distilled off 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 comparative example 1
The preparation method comprises the steps of 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 with N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the organic ligand with the N-propenyl imidazole to obtain the 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:
according to the weight parts, 5g (R) -4-mercapto-2-pyrrolidone, 2.6g 1-allyl-3-vinylimidazole nitrate and 100g ethanol are added into a closed high-pressure reaction kettle, 2.2g sodium methoxide is added, the temperature is raised and stirred to 48 ℃, the reaction is carried out for 100min, and the ethanol is removed by evaporation, thus obtaining the intermediate 1.
The preparation method of the organic ligand comprises the following steps:
adding 12g of intermediate 1, 0.01g of N-propenyl imidazole and 100g of N, N-dimethylformamide into a reaction kettle, using high-purity nitrogen to protect, dripping 0.5g of chloroplatinic acid isopropanol solution with the mass percent content of 3% into the reaction kettle, controlling the temperature to be 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 for 12 hours at the temperature of 60 ℃ by taking alkane as a solvent, and alkane is distilled off after the reaction is finished, so that the low-noble metal catalyst is prepared.
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 hydrochlorination of acetylene, which comprises the following steps:
the preparation method comprises the steps of 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 with fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding noble metal salt, and reacting the organic ligand with the fluorocarbon methyl dichlorosilane and the N-propenyl imidazole to obtain the 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:
8g (R) -4-mercapto-2-pyrrolidone, 3.5g 1-allyl-3-vinylimidazole nitrate and 120g ethanol are added into a closed high-pressure reaction kettle, 4g sodium methoxide is added, the temperature is raised and stirred to 55 ℃, the reaction is carried out for 150min, and the ethanol is removed by evaporation, thus obtaining an intermediate 1;
the fluorocarbon methyl dichlorosilane is (1H, 2H-perfluorohexyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
15g of intermediate 1, 20g of fluorocarbon methyl dichlorosilane, 0.15g of N-propenyl imidazole and 110g of N, N-dimethylformamide are added into a reaction kettle, high-purity nitrogen is used for protection, 0.8g of chloroplatinic acid isopropanol solution with the mass percent content of 5% is dripped into the reaction kettle, the temperature is controlled to 65 ℃, stirring is carried out for 2 hours, and the N, N-dimethylformamide is removed by evaporation, so that the organic ligand can be obtained.
The mass content of the noble metal is 0.01% 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:
25g of organic ligand and noble metal salt are stirred for 18 hours at the temperature of 90 ℃ by taking alkane as a solvent, and alkane is distilled off after the reaction is finished, so that the low noble metal catalyst is prepared.
The organic solvent is acetone.
The catalyst was evaluated by comparative reaction example 2.
Reaction example 1:
preparation of catalyst the low noble metal catalyst of example 1, 10ml, was used to catalyze the hydrochlorination of acetylene to prepare vinyl chloride, and in a bubbling reactor, the reaction temperature was 120 ℃, and the reactant gases hydrogen chloride and acetylene were fed in the ratio of reactant gases: volume ratio of hydrogen chloride/acetylene=0.5, volume ratio of reaction raw material gas flow rate to catalyst=70 h -1 。
The analysis result of the reaction product by gas chromatography is as follows: the conversion rate of acetylene is 80.47 percent and the selectivity of vinyl chloride is 99.10 percent. After 96 hours of reaction, the activity and selectivity of the catalyst are unchanged.
Reaction example 2:
preparation of catalyst the low noble metal catalyst of example 2, 10ml, was used to catalyze the hydrochlorination of acetylene to prepare vinyl chloride, and in a bubbling reactor, the reaction temperature was 140 ℃, and the reactant gases hydrogen chloride and acetylene were introduced in the following proportions: volume ratio of hydrogen chloride/acetylene=0.8, volume ratio of reaction raw material gas flow rate to catalyst=80 h -1 。
The analysis result of the reaction product by gas chromatography is as follows: the conversion rate of acetylene is 85.41 percent, and the selectivity of vinyl chloride is 99.55 percent. After 96 hours of reaction, the activity and selectivity of the catalyst are unchanged.
Comparative reaction example 1: preparation of low noble metal catalyst in comparative example 1 using catalyst 10ml, in a bubbling reactor, reaction raw material gases of hydrogen chloride and acetylene were introduced at a reaction temperature of 120 ℃, the ratio of the reaction raw material gases being: volume ratio of hydrogen chloride/acetylene=0.5, volume ratio of reaction raw material gas flow rate to catalyst=70 h 1 。
The analysis result of the reaction product by gas chromatography is as follows: the conversion of acetylene was 54.89% and the selectivity of vinyl chloride was 74.41%. After 96 hours of reaction, the catalyst activity and selectivity decreased.
Comparative reaction example 2:
preparation of low noble metal catalyst in comparative example 2 using catalyst 10ml, in a bubbling reactor, reaction raw material gases of hydrogen chloride and acetylene were introduced at a reaction temperature of 180 ℃, the ratio of the reaction raw material gases being: volume ratio of hydrogen chloride/acetylene=1, volume ratio of reaction raw material gas flow rate to catalyst=90 h 1 。
The analysis result of the reaction product by gas chromatography is as follows: the conversion of acetylene was 70.12% and the selectivity to vinyl chloride was 80.09%. After 96 hours of reaction, the catalyst activity and selectivity decreased.

Claims (9)

1. A preparation method of a low noble metal catalyst for hydrochlorination of acetylene, which 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 with fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding metal halide and noble metal salt, and reacting the organic ligand with the metal halide to obtain a low noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1:1-4.0;
the preparation method of the organic ligand comprises the following steps:
according to the parts by weight, adding 12-18 parts of intermediate 1, 18-23 parts of fluorocarbon methyl dichlorosilane, 0.01-0.3 part of N-propenyl imidazole and 100-120 parts of N, N-dimethylformamide into a reaction kettle, using high-purity nitrogen to protect, dripping 0.5-1.2 parts of chloroplatinic acid isopropanol solution with the mass percent content of 3-7% into the reaction kettle, controlling the temperature to be 60-70 ℃, stirring for 1-3 hours, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand;
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-vinylimidazole nitrate and 100-150 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 ethanol to obtain an intermediate 1;
the metal halide is lanthanide halide;
the fluorocarbon methyl dichlorosilane is (1H, 2H-perfluorohexyl) methyl dichlorosilane.
2. The method for preparing the low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein the method comprises the following steps: the lanthanoid is one or more of lanthanum, cerium, praseodymium and neodymium.
3. The method for preparing the low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein the method comprises the following steps: the mass content of the noble metal is 0.001-0.1% of the mass of the low noble metal catalyst.
4. The method for preparing the low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein the method comprises the following steps: the mass content of the noble metal is 0.005-0.01% of the mass of the low noble metal catalyst.
5. The method for preparing the low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein the method comprises the following steps: the noble metal compound adopts its soluble salt, and is selected from chloride, sulfate, phosphate and nitrate.
6. The method for preparing the low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein the method comprises the following steps: the noble metal is selected from gold, palladium, ruthenium, platinum and iridium.
7. The method for preparing the low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein the method comprises the following steps: the molar ratio of the organic ligand to the metal halide is 1:1-2.0.
8. The method for preparing the low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein the method comprises the following steps: the preparation of the low noble metal catalyst is utilized to catalyze the hydrochlorination of acetylene to prepare vinyl chloride, the low noble metal catalyst is used as a catalyst in a bubbling reactor, the reaction temperature is 120-220 ℃, the reaction raw material gases of hydrogen chloride and acetylene are introduced, and the ratio of the reaction raw material gases is as follows: volume ratio of hydrogen chloride/acetylene=0.5-1.5, volume ratio of reaction raw material gas flow rate to catalyst=70-120 h -1 。
9. The method for preparing the low noble metal catalyst for hydrochlorination of acetylene according to claim 8, wherein the method comprises the following steps: volume ratio of hydrogen chloride/acetylene=0.8-1.2, volume ratio of reaction raw material gas flow rate to catalyst=90-100 h -1 。
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