Metal halide acid radical ion liquid for catalyzing acetylene hydrochlorination as well as application method thereof

Abstract

The invention relates to metal halide acid radical ion liquid for catalyzing acetylene hydrochlorination as well as an application method thereof. The metal halide acid radical ion liquid takes one ofalkyl-containing amine hydrogen halide, alkyl monosubstituted pyrrolidone hydrogen halide and pyridine hydrogen halide as a cationic source material and takes one of halide of zinc, copper, iron andtin as an anionic source material, wherein the molar ratio of the cationic source material to the anionic source material is 1:(0.3-3.0). In a bubbling reactor, the metal halide acid radical ion liquid serves as a catalyst, the reaction raw material gas acetylene and hydrogen chloride are mixed, the mixture is introduced into the metal halide acid radical ion liquid to perform reaction, the reaction temperature is 120 to 200 DEG C, the volume velocity ratio of the acetylene to the hydrogen chloride is 1:(1.0-1.6), the volumetric space velocity of the acetylene is 10 to 100 h<-1>, and under thecondition of not using noble metal, the highest conversion rate of the acetylene can reach to above 90 percent and the selectivity of chloroethylene is still more than 99 percent.

Description

technical field

[0001] The invention belongs to the technical field of preparing vinyl chloride by hydrochlorination of acetylene, and furthermore, relates to a metal halide ion liquid for catalyzing hydrochlorination of acetylene and an application method thereof. Background technique

[0002] Vinyl chloride is a colorless, easily liquefied, insoluble gas at room temperature, and is an important chemical raw material for the synthesis of polyvinyl chloride. As one of the five most widely used general-purpose plastics, polyvinyl chloride is closely related to our lives. Therefore, the industrial production of vinyl chloride is of great significance. my country is the main consumer and producer of polyvinyl chloride. According to the domestic energy pattern of "poor oil, rich coal, and little gas", the acetylene method with coal as the basic raw material is the main method of vinyl chloride production in my country. At present, mercury catalysts have been used in the indust...

Examples

Embodiment 1

[0029] (1) Slowly add 0.25 moles (24.75 grams) of CuCl to 0.25 moles (23.89 grams) of trimethylamine hydrochloride, under nitrogen protection, stir at 100°C for 12 hours to complete the reaction to obtain trimethylammonium chloride Cuprite ionic liquid [Me 3 NH]Cl / CuCl.

[0030] (2) get 18 milliliters of synthetic trimethylammonium cuprous chloride ionic liquid [Me 3 NH]Cl / CuCl, put it into the reaction tube for acetylene hydrochlorination reaction, the conversion rate of acetylene was 58.46% after reaction at 140°C for 12 hours, the selectivity of vinyl chloride was 99.69%, and the reaction continued for 24 hours There was no significant decrease in activity. The change curve of acetylene conversion rate with reaction time is shown in figure 1 .

Embodiment 2

[0032] (1) Slowly add 0.25 moles (24.75 grams) of CuCl to 0.25 moles (34.41 grams) of triethylamine hydrochloride, under nitrogen protection, stir at 100°C for 12 hours to complete the reaction to obtain triethylammonium chloride Cuprousite ionic liquid [Et 3 NH]Cl / CuCl.

[0033] (2) get 18 milliliters of synthetic triethylammonium cuprous chloride ionic liquid [Et 3 NH]Cl / CuCl, put it into the reaction tube for acetylene hydrochlorination reaction, the conversion rate of acetylene was 75.87% after reaction at 140°C for 12 hours, the selectivity of vinyl chloride was 99.78%, and the reaction continued for 24 hours There was no significant decrease in activity. The change curve of acetylene conversion rate with reaction time is shown in figure 1 .

Embodiment 3

[0035] (1) Slowly add 0.25 moles (24.75 grams) of CuCl to 0.25 moles (28.89 grams) of pyridine hydrochloride, under nitrogen protection, and stir at 100°C for 12 hours to complete the reaction to obtain pyridine cuprous chloride Ionic liquid [PyH]Cl / CuCl.

[0036] (2) Get 18 milliliters of synthetic pyridine cuprous chloride ionic liquid [PyH]Cl / CuCl, put it into the reaction tube and carry out the acetylene hydrochlorination reaction, and the acetylene conversion rate is 63.53%, the selectivity of vinyl chloride is 99.73%, and there is no obvious decrease in activity during the 24-hour continuous reaction. The change curve of acetylene conversion rate with reaction time is shown in figure 1 .

technical field

[0001] The invention belongs to the technical field of preparing vinyl chloride by hydrochlorination of acetylene, and furthermore, relates to a metal halide ion liquid for catalyzing hydrochlorination of acetylene and an application method thereof. Background technique

[0002] Vinyl chloride is a colorless, easily liquefied, insoluble gas at room temperature, and is an important chemical raw material for the synthesis of polyvinyl chloride. As one of the five most widely used general-purpose plastics, polyvinyl chloride is closely related to our lives. Therefore, the industrial production of vinyl chloride is of great significance. my country is the main consumer and producer of polyvinyl chloride. According to the domestic energy pattern of "poor oil, rich coal, and little gas", the acetylene method with coal as the basic raw material is the main method of vinyl chloride production in my country. At present, mercury catalysts have been used in the indust...

Examples

Embodiment 1

[0029] (1) Slowly add 0.25 moles (24.75 grams) of CuCl to 0.25 moles (23.89 grams) of trimethylamine hydrochloride, under nitrogen protection, stir at 100°C for 12 hours to complete the reaction to obtain trimethylammonium chloride Cuprite ionic liquid [Me 3 NH]Cl / CuCl.

[0030] (2) get 18 milliliters of synthetic trimethylammonium cuprous chloride ionic liquid [Me 3 NH]Cl / CuCl, put it into the reaction tube for acetylene hydrochlorination reaction, the conversion rate of acetylene was 58.46% after reaction at 140°C for 12 hours, the selectivity of vinyl chloride was 99.69%, and the reaction continued for 24 hours There was no significant decrease in activity. The change curve of acetylene conversion rate with reaction time is shown in figure 1 .

Embodiment 2

[0032] (1) Slowly add 0.25 moles (24.75 grams) of CuCl to 0.25 moles (34.41 grams) of triethylamine hydrochloride, under nitrogen protection, stir at 100°C for 12 hours to complete the reaction to obtain triethylammonium chloride Cuprousite ionic liquid [Et 3 NH]Cl / CuCl.

[0033] (2) get 18 milliliters of synthetic triethylammonium cuprous chloride ionic liquid [Et 3 NH]Cl / CuCl, put it into the reaction tube for acetylene hydrochlorination reaction, the conversion rate of acetylene was 75.87% after reaction at 140°C for 12 hours, the selectivity of vinyl chloride was 99.78%, and the reaction continued for 24 hours There was no significant decrease in activity. The change curve of acetylene conversion rate with reaction time is shown in figure 1 .

Embodiment 3

[0035] (1) Slowly add 0.25 moles (24.75 grams) of CuCl to 0.25 moles (28.89 grams) of pyridine hydrochloride, under nitrogen protection, and stir at 100°C for 12 hours to complete the reaction to obtain pyridine cuprous chloride Ionic liquid [PyH]Cl / CuCl.

[0036] (2) Get 18 milliliters of synthetic pyridine cuprous chloride ionic liquid [PyH]Cl / CuCl, put it into the reaction tube and carry out the acetylene hydrochlorination reaction, and the acetylene conversion rate is 63.53%, the selectivity of vinyl chloride is 99.73%, and there is no obvious decrease in activity during the 24-hour continuous reaction. The change curve of acetylene conversion rate with reaction time is shown in figure 1 .

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