Method for producing vinyl chloride through continuous photocatalytic acetylene hydrochlorination at normal temperature

Abstract

The invention provides a method for producing vinyl chloride through continuous photocatalytic acetylene hydrochlorination at normal temperature, and belongs to the technical field of organic synthesis. Comprising the following steps: adding an organic solvent into a device with a sealing cover, adding a photocatalyst, a chlorine source and a hydrogen source into the organic solvent, introducing inert gas before reaction to remove impurity gases in the device and the solvent, then introducing acetylene raw materials into the organic solvent, and performing illumination by using a light source under continuous stirring to obtain acetylene. The gas product from the device is vinyl chloride. The hydrochloric acid is used as a hydrogen source and a chlorine source to realize production of vinyl chloride by photocatalytic acetylene high-selectivity hydrochlorination at normal temperature and pressure, the reaction energy consumption is low, the use of a mercury-containing catalyst, HCl gas and an extra heat source is avoided, the reaction system is simple, the reaction condition is mild, the process is simple, the activity selectivity is high, the green chemical development requirement is met, and the method has great application value.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for producing vinyl chloride by continuous photocatalytic acetylene hydrochlorination at room temperature. Background Art

[0002] Vinyl chloride monomer (VCM) is an important chemical commodity, with an estimated annual production capacity of 60 million tons in 2030. It is an important monomer for the production of polyvinyl chloride (PVC), one of the five major general-purpose plastics. PVC has a wide range of uses, especially in the construction industry, due to its strong resistance to light and chemical degradation. The current methods for producing VCM are: acetylene method, ethylene method and ethane method. The ethylene method has a complex process, a large investment scale for the device, and hydrogen chloride by-product gas is produced; while the ethane method has a simple process flow, but the reaction temperature is high, and more by-products are generated during the reaction. These problems limit their practical applications.

[0003] According to the characteristics of my country's energy structure, the acetylene method will become the main method of vinyl chloride in my country through coal production. At present, the industry mainly uses mercuric chloride (HgCl2) as the main active component and activated carbon as the carrier catalyst for the acetylene hydrochlorination reaction. However, due to the volatility and toxicity of mercuric chloride, the catalyst is unstable and easily deactivated, causing serious environmental problems and endangering human health. In order to achieve the goals of the Minamata Convention on Mercury, the search for green catalysts to replace toxic mercuric chloride has attracted widespread attention from researchers. Although the research on environmentally friendly mercury-free catalysts has made surprising progress, it is mainly based on expensive and limited reserves of precious metal elements such as Au and Pd as catalysts. Even if some non-metallic catalysts (for example, silicon-carbon derived carbon nanocomposites, nitrogen-doped carbon derived from ZIF-8, etc.) are studied and applied to the acetylene hydrochlorination reaction, they still react at a high temperature of about 200°C, which is a great test for the catalyst. Therefore, it is still very desirable to develop a new process technology that is green, economical and efficient.

[0004] Photocatalysis can directly convert solar energy into chemical energy, which has attracted the attention of a large number of researchers in recent years. And photoredox catalysis has become a powerful synthetic platform. For example, complete water splitting, activation of CH and CC bonds, etc. Similarly, the hydrochlorination of acetylene requires simultaneous oxidation and reduction reactions to add a chlorine atom and a hydrogen atom to the acetylene molecule. Acetylene hydrochlorination through photoredox reaction is a sustainable green synthetic strategy, but it faces two major challenges, namely the extremely low solubility of acetylene in water and the poor photocatalytic hydrochlorination activity of gaseous acetylene. Recently, researchers reported a sequencing batch photocatalytic strategy to achieve acetylene production of vinyl chloride in aqueous solution containing chloride ions using g-C3N4 / BiOCl catalyst, but due to mass transfer limitations and low reaction activity, the yield was very low (47.26μmolVCM produced in 8 hours), so it was difficult to achieve the goal of practical application. Summary of the invention

[0005] The purpose of the present invention is to provide a method for producing vinyl chloride by continuous photocatalytic acetylene hydrochlorination at room temperature, which uses hydrochloric acid as a hydrogen source and a chlorine source to realize high-selective photocatalytic acetylene hydrochlorination to produce vinyl chloride at room temperature and pressure. The reaction energy consumption is low and the use of mercury-containing catalysts, HCl gas and additional heat sources is avoided. The reaction system is simple, the reaction conditions are mild, the process is simple, the activity selectivity is high, the requirements for the development of green chemical industry are met, and the application value is great.

[0006] The technical solution of the present invention is achieved in this way: The present invention provides a method for producing vinyl chloride by continuous photocatalytic acetylene hydrochlorination at room temperature. The principle is as follows: in an organic solvent containing a chlorine source and a hydrogen source, under the action of light and a photocatalyst, continuous photocatalytic acetylene hydrochlorination is carried out to produce vinyl chloride at room temperature and pressure, comprising the following steps: An organic solvent is added into a device with a sealed cover, a photocatalyst, a chlorine source and a hydrogen source are added into the organic solvent, an inert gas is introduced into the device and impurity gases in the solvent are removed before the reaction, and then the acetylene raw material is exposed into the organic solvent and illuminated with a light source under continuous stirring. The gaseous product coming out of the device is vinyl chloride.

[0007] As a further improvement of the present invention, the organic solvent is selected from one or more organic solvents of N,N-dimethylformamide, acetone, N-methylpyrrolidone, dimethyl sulfoxide, formic acid, acetic acid, ethyl acetate, glycerol, ethylene glycol, methanol, and isopropanol.

[0008] As a further improvement of the present invention, the photocatalyst is a semiconductor photocatalyst loaded with one or more metals or metal oxides.

[0009] As a further improvement of the present invention, the photocatalyst is an A / B type catalyst, the active component A is selected from one or a multi-element alloy of ruthenium, palladium, gold, platinum, silver, rhodium, iridium, copper, nickel, cobalt, iron and manganese or one or more metal oxides thereof; the semiconductor carrier B is selected from at least one of titanium dioxide, sodium tantalate, tungsten trioxide, niobium pentoxide, bismuth vanadate, cuprous oxide, cadmium sulfide, molybdenum disulfide, indium phosphide, graphite phase carbon nitride or a combination thereof to form a heterojunction composite material.

[0010] As a further improvement of the present invention, the loading amount of the active component A is 0.1-8.0 wt.% by mass, and the remainder is the semiconductor carrier B.

[0011] As a further improvement of the present invention, the hydrogen source is selected from any one of water, ethanol, methanol, tert-butyl alcohol, isopropanol, hydrochloric acid, hydrogen chloride gas, hypochlorous acid, perchloric acid, chloroacetyl, nitric acid, nitrous acid, sulfuric acid, sulfurous acid, phosphoric acid, boric acid, hydroiodic acid, hydrofluoric acid, hydrobromic acid, formic acid, acetic acid, ascorbic acid, citric acid, oxalic acid, and lactic acid, or a mixture of more than one of them.

[0012] As a further improvement of the present invention, the chlorine source includes any one of lithium chloride, hydrochloric acid, hydrogen chloride gas, cobalt chloride hexahydrate, cupric chloride dihydrate, ferric chloride trihydrate, ferrous chloride tetrahydrate, manganese dichloride tetrahydrate, chromium trichloride hexahydrate, cerium trichloride heptahydrate, magnesium dichloride hexahydrate, hypochlorous acid, tert-butyl hypochlorite, chloroacetyl, N-chlorosuccinimide, trichloroisocyanuric acid, dichlorohydantoin, and chloramine-T, or a mixture of multiple thereof.

[0013] As a further improvement of the present invention, the acetylene raw material is selected from at least one of pure acetylene or mixed acetylene gas balanced with inert gas or other acetylenic compounds; the light source is selected from at least one of real sunlight, xenon lamp, mercury lamp and LED lamp.

[0014] As a further improvement of the present invention, the device with the sealing cover is a single chamber or multiple chambers connected in series.

[0015] As a further improvement of the present invention, the added amount of the photocatalyst is 0.01-10 g / L.

[0016] The present invention has the following beneficial effects: When transporting acetylene gas and removing acetylene impurities from ethylene streams in industry, organic solvents are usually used to dissolve acetylene for transportation or selectively remove acetylene through solubility differences. Since the solubility of acetylene in organic solvents (such as N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) and acetone) is almost two orders of magnitude higher than that in water, this is conducive to the diffusion of acetylene to the photocatalyst, thus providing a possibility to solve the mass transport limitation, that is, to transform the classic gas phase reaction of acetylene hydrochlorination into a liquid phase reaction. A large number of studies have shown that the photocatalytic reaction is crystal face dependent. Through crystal face engineering to regulate the ratio of {101} and {001} crystal faces of anatase TiO2, the photogenerated electrons / holes are promoted to migrate to {101} and {001} crystal faces respectively to undergo reduction and oxidation reactions to add hydrogen atoms and chlorine atoms to acetylene molecules. In addition, TiO2 has a suitable redox potential to simultaneously oxidize chloride ions and reduce hydrogen ions. Loading a co-catalyst on the TiO2 photocatalyst can further promote the separation of photogenerated carriers and catalytic activity. Based on this, under mild conditions, the A / B type catalyst is used in an organic solution containing an organic or inorganic hydrogen and chlorine source to achieve photocatalytic acetylene hydrochlorination, and the performance in organic solvents is much better than in water. Among them, the best photocatalytic performance is shown in DMF solvent, with the highest acetylene conversion efficiency and vinyl chloride selectivity.

[0017] In the present invention, a continuous photocatalytic acetylene hydrochlorination method is proposed, which combines the advantages of acetylene solvent absorption and in-situ photocatalytic hydrochlorination, and can achieve efficient and highly selective conversion of acetylene to vinyl chloride under mild conditions. This method can overcome the key challenges encountered in traditional catalytic processes (using mercury-containing catalysts, high energy consumption and carbon emissions, and requiring HCl corrosive gas as a hydrogen and chlorine source), and has broad application prospects in the coal chemical vinyl chloride production industry.

[0018] The vinyl chloride synthesis method of the present invention is a green, safe, low-energy, and efficient photocatalytic synthesis method. Compared with the traditional thermal catalytic technology, light energy (or sunlight) is used to replace the heat source, which greatly reduces the energy consumption of the acetylene hydrochlorination reaction process; at the same time, hydrochloric acid can be used as a hydrogen source and a chlorine source to replace the corrosive HCl gas, effectively solving the safety problems caused by the use of HCl gas and meeting the needs of green chemical industry. Through the screening, design and regulation of the photocatalyst, the selectivity of vinyl chloride close to 100% can be obtained.

[0019] In addition, in the method of the present invention, the catalyst preparation process is simple, and it can be reused and recycled (collected by centrifugation or suction filtration). After a 48-hour durability test, the acetylene conversion rate and vinyl chloride selectivity are maintained at more than 80% and 99%, respectively. The catalyst has good universality and is suitable for photocatalytic hydrochlorination reactions of various alkynes. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0021] Figure 1 This is a comparison chart of catalytic performances of different catalyst loadings in Example 1; Figure 2 This is a comparison chart of catalytic performance at different catalyst dosages in Example 2; Figure 3 This is the performance diagram of producing vinyl chloride by real sunlight-catalyzed acetylene hydrochlorination in Example 3; Figure 4 This is a qualitative analysis diagram of the production of vinyl chloride by continuous photocatalytic acetylene hydrochlorination in a small chamber in Example 4; Figure 5 This is a graph showing the effect of different gas flow rates on the production of vinyl chloride by continuous photocatalytic acetylene hydrochlorination in a small chamber in Example 5; Figure 6 This is a graph showing the effect of different gas flow rates on the production of vinyl chloride by continuous photocatalytic hydrochlorination of acetylene in a two-chamber series system in Example 6; Figure 7 This is a diagram showing the durability evaluation results of the continuous photocatalytic hydrochlorination of acetylene to produce vinyl chloride under dual-chamber series connection. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] [Example 1] Catalytic performance of different loading amounts of active component A (1) Preparation of catalyst Preparation of TiO2 nanosheets (TNS). 25 mL of tetrabutyl titanate and 5 mL of HF solution (concentration of 40 wt.%) were mixed under stirring for 30 min, and then the solution was transferred to a 50 mL Teflon-lined stainless steel autoclave and kept at 180 ° C for 24 h. After cooling to room temperature, the white precipitate was separated, collected by high-speed centrifugation, and washed with ultrapure water and ethanol at least 10 times, respectively, to remove residual organic matter and fluoride ions. Finally, the sample was dried in an oven at 80 ° C for 12 h and then ground to obtain TNS.

[0024] Synthesis of RuO2 / TNS. 0.5 g of TNS powder was dispersed in 50 mL of 0.05 M NaIO3 solution, and 1.88 mL of 0.01 M RuCl3·3H2O solution was added. After ultrasonic treatment for 15 min, the solution was placed under a 300 W xenon lamp (PLS-SXE300 / 300UV, 300 <λ <780 nm) and stirred for 2 h. The powdered catalyst was collected by rinsing with ultrapure water and filtered, and dried in a vacuum oven at 60 ° C for 12 h, then ground and collected to obtain RuO2 / TNS, in which the theoretical loading of RuO2 was 0.5 wt.%. For 1.0 wt.%, 2.0 wt.%, 4.0 wt.% and 8.0 wt.% RuO2 catalyst loadings, the volume of 0.01 M RuCl3·3H2O solution was increased proportionally, and other synthetic conditions were the same. Unless otherwise specified, the catalyst with a RuO2 mass loading of 4.0 wt.% is generally used herein, named RuO2 / TNS.

[0025] (2) Experiment on producing vinyl chloride by photocatalytic acetylene hydrochlorination Add 10mL of DMF solvent to a 20mL screw-capped quartz glass headspace sample bottle equipped with a magnetic stirrer, add 40mg of RuO2 / TNS (RuO2 mass loadings are: 0.0wt.%, 0.5wt.%, 1.0wt.%, 2.0wt.%, 4.0wt.% and 8.0wt.%) to the DMF solvent, then add 100μL of concentrated hydrochloric acid (36.0-38.0%) to the DMF solvent, and then purge with argon for at least 30min to remove gas impurities in the bottle. Then, screw on the headspace sample bottle cap to make the bottle airtight. Then use a syringe to inject 1mL of acetylene gas (35.0vol.% + Ar balance gas) into the DMF mixture, turn on the magnetic stirrer, stir for 30min to reach gas-liquid equilibrium, turn on a 300W xenon lamp (PLS-SXE300 / 300UV, 300<λ<780nm) and react for 1h. During this period, 100 μL of gas was taken from the headspace of the reaction bottle at intervals of 20 minutes and entered into the gas chromatograph for analysis.

[0026] The conversion of acetylene and the selectivity of vinyl chloride are calculated as follows: ; ; in, is the concentration of acetylene in the feed, , and is the concentration of acetylene, ethylene and ethane in the outlet.

[0027] Test results such as Figure 1 As shown: It can be seen that RuO2 plays a key role in the generation of vinyl chloride. As the loading amount increases from 0.0wt.% to 4.0wt.%, the conversion rate of acetylene gradually increases, but when it further increases to 8.0wt.%, the conversion rate of acetylene decreases. This may be because more RuO2 causes photogenerated carrier recombination, thereby resulting in a decrease in catalytic activity. Here 4.0wt.% is the optimal loading amount.

[0028] [Example 2] Catalytic performance of different catalyst dosages Add 10 mL of N,N-dimethylformamide (DMF) solvent to a 20 mL screw-capped quartz glass headspace sample bottle equipped with a magnetic stirrer, add different masses of RuO2 / TNS (respectively: 10 mg, 20 mg, 30 mg, 40 mg and 50 mg) to the DMF solvent, then add 100 μL of concentrated hydrochloric acid (36.0-38.0%) to the DMF solvent, and then purge with argon for at least 30 minutes to remove gas impurities in the bottle. Then, screw on the headspace sample bottle cap to make the bottle airtight. Then, inject 1 mL of acetylene gas (35.0 vol.% + Ar balance gas) into the DMF mixture with a syringe, turn on the magnetic stirrer, stir for 30 minutes to reach gas-liquid equilibrium, and turn on a 300 W xenon lamp (PLS-SXE300 / 300UV, 300 <λ <780nm) to react for 1 hour. During this period, 100 μL of gas was taken from the headspace of the reaction bottle at intervals of 20 minutes and entered into the gas chromatograph for analysis.

[0029] Test results such as Figure 2 As shown: It can be seen from the figure that as the catalyst dosage increases from 10 mg to 40 mg, the conversion rate of acetylene gradually increases, but when it increases to 50 mg, the conversion rate does not increase much, and the selectivity for vinyl chloride decreases. The possible reason is that the increase in catalyst dosage affects the transmittance of the catalyst and the absorption of light by the catalyst, thereby reducing the catalytic activity. Here, 40 mg is selected as the optimal dosage.

[0030] [Example 3] Performance of Real Sunlight Photocatalytic Acetylene Hydrochlorination to Produce Vinyl Chloride Add 150mL of N,N-dimethylformamide (DMF) solvent to a 250mL quartz glass reaction chamber equipped with a magnetic stirrer, add 150mgRuO2 / TNS and 1.5mL of concentrated hydrochloric acid (36.0-38.0%) to the DMF solvent, cover the quartz device lid, expose the DMF mixture with Ar for 30 minutes, then close the ball valve knob on the lid to make the reaction chamber airtight. Then use a syringe to inject 15mL of acetylene gas (35.0vol.% acetylene + Ar balance gas) into the DMF mixture from the sampling port, turn on the magnetic stirrer, stir for 30 minutes, and place the device under real sunlight for 6 hours. During this period, take 100μL of gas from the headspace of the reaction chamber every 1 hour and enter the gas chromatograph for analysis. Real photocatalytic acetylene hydrochlorination experiments were conducted under solar radiation in Changsha, China (location: 28.184141°N, 112.950264°E, date: 07 / 21-23 / 2024, temperature: 29-39°C, average light power: 79.45 mWcm -2 , illumination: 103697.29±15003.12LUX).

[0031] Test results such as Figure 3 As shown: It can be seen from the figure that the conversion rate of acetylene gradually increases with time, and there is a higher selectivity for vinyl chloride, indicating that it is feasible to use real sunlight for photocatalytic acetylene hydrochlorination.

[0032] Example 4-7 Production of vinyl chloride by photocatalytic acetylene hydrochlorination under continuous conditions.

[0033] [Example 4] Qualitative analysis of continuous photocatalytic acetylene hydrochlorination to produce vinyl chloride in a small chamber A continuous flow photocatalytic acetylene hydrochlorination reaction was carried out in a 40 mL quartz glass reactor. First, 30 mL of DMF, concentrated hydrochloric acid (36.8-38.0%, 500 μL) and 30 mg of RuO2 / TNS photocatalyst were added to the reactor; then, Ar was purged for at least 30 min to remove impurity gases in the photocatalytic cell. Then, under stirring conditions, acetylene feedstock (1.0 vol.% acetylene + Ar balance; 2 sccm) was introduced into the DMF solvent using a mass flow controller (AST10 series, ASERT Instruments (Beijing) Co., Ltd.) to control the flow rate. A 300 W xenon lamp (PLS-SXE300 / 300UV, 300 <λ <780 nm) was turned on. The photocatalytic acetylene hydrochlorination reaction was carried out for 0.5 h. The outlet gas sample was injected into a gas chromatograph-mass spectrometer for product analysis.

[0034] Test results such as Figure 4As shown in the figure, there are two peaks in the chromatogram, the first one is the peak of acetylene, and the second one is the product of vinyl chloride. And the latter peak is scanned, retrieved and analyzed, and the mass ratio (m / z) of the specific fragment of the standard mass spectrum of vinyl chloride in the database is consistent. This result shows that we have achieved the conversion of acetylene to vinyl chloride under continuous conditions.

[0035] [Example 5] Performance evaluation of continuous photocatalytic acetylene hydrochlorination to produce vinyl chloride in a small chamber Continuous flow photocatalytic acetylene hydrochlorination was carried out in a 40 mL quartz glass reactor. First, 30 mL of DMF, concentrated hydrochloric acid (38.0%, 500 μL), and 30 mg of RuO2 / TNS photocatalyst were added to the reactor; then, Ar was purged for at least 30 min to remove impurity gases in the photocatalytic cell. Then, under stirring conditions, acetylene feedstock (1.0 vol.% acetylene + Ar balance; 2, 5, and 10 sccm) was introduced into the DMF solution using a mass flow controller (AST10 series, ASERT Instruments (Beijing) Co., Ltd.) to control the flow rate. A 300 W xenon lamp (PLS-SXE300 / 300UV, 300 <λ <780 nm) was turned on. When the outlet gas product was stable, the photocatalytic acetylene hydrochlorination reaction was carried out for 3 h. At intervals of 30 min, outlet gas samples were injected into the gas chromatograph for real-time product analysis.

[0036] Test results such as Figure 5 As shown: It can be seen from the figure that as the gas flow rate increases from 2 sccm to 10 sccm, the acetylene conversion rate decreases from an average of 50% to about 28%. This can be achieved by increasing the gas residence time to further increase the acetylene conversion rate at high flow rates, see Example 6.

[0037] [Example 6] Performance evaluation of continuous photocatalytic hydrochlorination of acetylene to produce vinyl chloride under dual-chamber series Continuous flow photocatalytic acetylene hydrochlorination was carried out in a quartz glass reactor with 250 mL and 100 mL connected in series. First, 220 and 90 mL of DMF, concentrated hydrochloric acid (36.8-38.0%, 500 μL each) and 220 and 90 mg of RuO2 / TNS photocatalyst were added to the reactor respectively; then, Ar was purged for at least 30 min to remove impurity gases in the photocatalytic cell. Then, under stirring conditions, acetylene feedstock (1.0 vol.% acetylene + Ar balance; 2, 5, and 10 sccm) was introduced into the DMF solution using a mass flow controller (AST10 series, ASERT Instruments (Beijing) Co., Ltd.) to control the flow rate. A 300 W xenon lamp (PLS-SXE300 / 300UV, 300 <λ <780 nm) was turned on. When the outlet gas product was stable, the photocatalytic acetylene hydrochlorination reaction was carried out for 3 h. At intervals of 30 min, outlet gas samples were injected into the gas chromatograph for real-time product analysis.

[0038] Test results such as Figure 6 As shown: It can be seen from the figure that as the gas flow rate increases from 2 sccm to 10 sccm, the conversion rate of acetylene decreases from an average of 95% to about 52%, but its conversion rate is significantly higher than that of the 40mL chamber, which verifies our speculation in Example 5.

[0039] [Example 7] Durability evaluation of continuous photocatalytic hydrochlorination of acetylene to produce vinyl chloride under dual-chamber series Continuous flow photocatalytic acetylene hydrochlorination was carried out in a quartz glass reactor with 250 mL and 100 mL connected in series. First, 220 and 90 mL of DMF, concentrated hydrochloric acid (38.0%, 500 μL each) and 220 and 90 mg of RuO2 / TNS photocatalyst were added to the reactor respectively; then, Ar was purged for at least 30 min to remove the impurity gas in the photocatalytic cell. Then, under stirring conditions, acetylene raw material (1.0 vol.% acetylene + Ar balance; 2 sccm) was introduced into the DMF solvent using a mass flow controller (AST10 series, ASERT Instruments (Beijing) Co., Ltd.) to control the flow rate. A 300 W xenon lamp (PLS-SXE300 / 300UV, 300 <λ <780 nm) was turned on. When the outlet gas product was stable, the reaction time was taken as the starting time, and the photocatalytic acetylene hydrochlorination reaction was carried out for 48 h. At intervals of 2 h, the outlet gas samples were injected into the gas chromatograph for real-time product analysis.

[0040] Test results such as Figure 7 As shown: It can be seen from the figure that when the durability test was carried out for 48 hours, it was found that a higher acetylene conversion rate and vinyl chloride selectivity could be achieved, indicating that the method of the present invention has good durability and has certain practical industrial application potential.

[0041] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for producing vinyl chloride by continuous photocatalytic acetylene hydrochlorination at room temperature, characterized in that: The following steps are involved: An organic solvent is added into a device with a sealing cover, a photocatalyst, a chlorine source and a hydrogen source are added into the organic solvent, an inert gas is introduced into the device to remove impurity gases in the solvent before the reaction, and then acetylene raw material is exposed into the organic solvent and illuminated by a light source under continuous stirring, and the gas product coming out of the device is vinyl chloride; The photocatalyst is a semiconductor photocatalyst loaded with one or more metals or metal oxides; The photocatalyst is an A / B type catalyst, wherein the active component A is selected from one or a multi-component alloy of ruthenium, palladium, gold, platinum, silver, rhodium, iridium, copper, nickel, cobalt, iron and manganese or one or more metal oxides thereof; and the semiconductor carrier B is selected from at least one of titanium dioxide, sodium tantalate, tungsten trioxide, niobium pentoxide, bismuth vanadate, cuprous oxide, cadmium sulfide, molybdenum disulfide, indium phosphide, graphite phase carbon nitride or a combination thereof to form a heterojunction composite material.

2. The method according to claim 1, characterized in that The organic solvent is selected from one or more organic solvents of N,N-dimethylformamide, acetone, N-methylpyrrolidone, dimethyl sulfoxide, formic acid, acetic acid, ethyl acetate, glycerol, ethylene glycol, methanol, and isopropanol.

3. The method according to claim 1, characterized in that The loading amount of the active component A is 0.1-8.0 wt.% by mass, and the balance is the semiconductor carrier B.

4. The method according to claim 1, characterized in that: The hydrogen source is selected from any one of water, ethanol, methanol, tert-butyl alcohol, isopropanol, hydrochloric acid, hydrogen chloride gas, hypochlorous acid, perchloric acid, chloroacetyl, nitric acid, nitrous acid, sulfuric acid, sulfurous acid, phosphoric acid, boric acid, hydroiodic acid, hydrofluoric acid, hydrobromic acid, formic acid, acetic acid, ascorbic acid, citric acid, oxalic acid, and lactic acid, or a mixture of more than one thereof.

5. The method according to claim 1, characterized in that The chlorine source includes any one of lithium chloride, hydrochloric acid, hydrogen chloride gas, cobalt chloride hexahydrate, cupric chloride dihydrate, ferric chloride trihydrate, ferrous chloride tetrahydrate, manganese dichloride tetrahydrate, chromium trichloride hexahydrate, cerium trichloride heptahydrate, magnesium dichloride hexahydrate, hypochlorous acid, tert-butyl hypochlorite, chloroacetyl, N-chlorosuccinimide, trichloroisocyanuric acid, dichlorohydantoin, and chloramine-T, or a mixture of multiple thereof.

6. The method according to claim 1, characterized in that The acetylene raw material is selected from at least one of pure acetylene or mixed acetylene gas balanced with inert gas or other acetylenic compounds; the light source is selected from at least one of real sunlight, xenon lamp, mercury lamp and LED lamp.

7. The method according to claim 1, characterized in that The device with a sealing cover is a single chamber or multiple chambers connected in series.

8. The method according to claim 1, characterized in that The added amount of the photocatalyst is 0.01-10 g / L.

Images