KR100843606B1 - Preparation method of vinyl chloride from methane - Google Patents

Abstract

The present invention relates to a method for producing vinyl chloride from methane, and more particularly, methane, which is a main component of natural gas, is subjected to an oxychlorination reaction and pyrolysis reaction in the presence of a reaction catalyst to produce an olefin including ethylene. In addition, there is provided a method for producing vinyl chloride consisting of a process of producing vinyl chloride by oxycyclorelation and pyrolysis reaction of ethylene separated from the olefin.

In the method for producing vinyl chloride according to the present invention, the conversion and selectivity can be increased by using a catalyst whose activity is further improved as a catalyst for the oxcyclorelation reaction and pyrolysis reaction, and the oxcyclorelation reaction of methane and ethylene Can be carried out using one reactor or two different reactors using the same catalyst, thereby simplifying the reaction and reducing the production cost.

Natural gas, methane, methyl chloride, ethylene, 1,2-dichloroethane, oxcyclolination, pyrolysis reaction, vinyl chloride, fluidized bed reaction, fixed bed reaction

Description

Preparation method of vinyl chloride from methane

1 is a process chart showing a process for preparing ethylene from methane which is a part of the vinyl chloride manufacturing process according to the present invention.

Figure 2 is a process chart showing a process for producing vinyl chloride from ethylene which is part of the vinyl chloride manufacturing process according to the present invention.

Figure 3 shows that the chlorocyclochlorination reaction of methane and the chlorocyclochlorination reaction of ethylene are carried out in one reactor and the first pyrolysis reaction and the second pyrolysis reaction are carried out in one reactor according to an embodiment of the present invention. It is a process chart which shows the process to be manufactured.

4 is a flowchart illustrating a process in which vinyl chloride is prepared by performing an oxcyclolination reaction of methane and an oxcyclolination reaction of ethylene according to one embodiment of the present invention.

The present invention relates to a method for producing vinyl chloride from methane, and more particularly, to a method for preparing vinyl chloride from methane, which is a main component of natural gas, by using an oxcyclolination reaction and a pyrolysis reaction.

Vinyl chloride is widely used as a monomer for producing vinyl chloride resin (PVC) and various vinyl chloride-containing copolymers. These and manufacturing method of the vinyl chloride is now well known, and is described with respect to the production method of the polyvinyl chloride in various literature (K. Weissermel and H, -J Arpe, Industrial Organic Chemistry, 2 ^nd Edition;. VCH mbH Verlagsgesellshaft , Weinheim, Germany, 1993, Chapter 9, pp.213-233).

In addition, research on the production of the vinyl chloride from natural gas having a low price and abundant reserves is ongoing as a result of rising oil prices. In particular, a method for producing the vinyl chloride from methane, which is a main component of natural gas, has been studied. There is a lot of research going on. Among them, US Pat. No. 4,199,533, US Pat. No. 4,804,797, US Pat. No. 4,714,796, US Pat. No. 4,983,783, and the like are used as methods for using a chlorine compound to activate methane, which is an inactive substance. The method of activating methane by pyrolyzing methane and chlorine compounds at high temperature is used. WO 84/03277, US Pat. No. 4,769,504, US Pat. No. 5,087,786, and the like describe a method of activating methane by oxidizing methane using an air and a chlorine compound. In particular, the oxcyclorelation patents have been reported for the production of methyl chloride by the reaction of methane, air and chlorine gas on a supported catalyst based on copper or iron. In addition, J. Am. Chem. Soc., 107 (1985), 7097; Appl. Catal., 46 (1989), 251 and Chem. Eng. Sci., 49 (1994), 4617, et al., Described the method of adjusting the reaction pressure and the method of adding copper as the base catalyst to improve the stability of the oxcyclolination catalyst and the selectivity of methyl chloride. I'm reporting on how to do that. In addition, methyl chloride produced by the activation of methane can be condensed again in the presence of a catalyst to convert to olefins including ethylene, in particular US Pat. No. 4,795,843, US Pat. No. 6,797,845 and US Patent Publication No. 2005/0027084. Et al. Disclose a method for producing olefins from methyl chloride using an aluminosilicate catalyst and a method for producing vinyl chloride by dehydrochlorination. The method used in this patent consists of two processes of activating methane by oxcyclolination followed by conversion to olefins. In addition to Appl. Catal., 75 (1991), 133 and Catal. Today, 101 (2005), et al. Report on catalyst preparation and catalysis associated with the conversion of methyl chloride to olefins on a zeolite carrier catalyst of the ZSM structure code.

However, in the production of vinyl chloride from methane, the conventional methods have a problem that the conversion and selectivity are not high, and the manufacturing process is too complicated.

The present invention is to solve the problems of the prior art, the technical problem to be solved by the present invention is to produce an oxcyclorelation reaction and pyrolysis reaction using a reaction catalyst with improved activity in the production of vinyl chloride from methane. It is to provide a method for producing vinyl chloride that can further increase the conversion and selectivity of the reaction, and simplify the manufacturing process.

The above and other objects of the present invention can be achieved by the present invention described below.

The present invention to achieve the above technical problem

(a) oxidizing the first reactant comprising methane, air and chlorine compounds in the presence of a reaction catalyst to produce a first reaction product comprising methyl chloride;

(b) pyrolysing the first reaction product in the presence of a reaction catalyst to produce a second reaction product comprising ethylene;

(c) separating the ethylene from the second reaction product, and then reacting the second reaction product in which the ethylene is mixed with air and a chlorine compound in the presence of a reaction catalyst to oxcyclorelation to include 1,2-dichloroethane. Generating a reaction product;

(d) pyrolysing the third reaction product in the presence of a reaction catalyst to produce a fourth reaction product comprising vinyl chloride; And

(e) providing a method for producing vinyl chloride comprising separating vinyl chloride from the fourth reaction product.

In accordance with the present invention, the use of a catalyst having further enhanced activity in the oxcyclorelation reaction and a catalyst having higher activity in the pyrolysis reaction increase the conversion and selectivity of the reaction, thereby making it possible to produce vinyl chloride as a final product. May be increased by one process as the oxcyclorelation reaction of methane and oxcyclorelation reaction of ethylene may be carried out simultaneously in one reactor or separately in two different reactors. This simplifies the process and reduces manufacturing costs.

Hereinafter, the present invention will be described in detail.

The method for producing vinyl chloride from methane according to the present invention consists of the following procedure. In other words,

 (A) the first reactant containing methane, air and chlorine compounds in the presence of the reaction catalyst to the oxcyclorelation reaction to produce a first reaction product containing methyl chloride (first oxcyclorelation reaction step) ;

(b) pyrolysing the first reaction product in the presence of a reaction catalyst to produce a second reaction product comprising ethylene (first pyrolysis reaction step);

(c) separating the ethylene from the second reaction product, and then reacting the second reaction product in which the ethylene is mixed with air and a chlorine compound in the presence of a reaction catalyst to oxcyclorelation to include 1,2-dichloroethane. Generating a reaction product (second octacyclolation reaction step);

(d) pyrolysing the third reaction product in the presence of a reaction catalyst to produce a fourth reaction product including vinyl chloride (second pyrolysis reaction step); And

(e) separating the vinyl chloride from the fourth reaction product (vinyl chloride separation step).

Hereinafter, the production method of vinyl chloride from methane according to the present invention will be described in more detail by dividing each step.

(a) first Oxcyclolination  Reaction step

This step is to prepare a first reaction product containing methyl chloride by oxidizing the first reactant containing methane, air and chlorine compounds in the presence of a reaction catalyst.

In this step, the chlorine compound includes chlorine gas or hydrogen chloride.

The content of the chlorine compound to the methane which is a reactant in this step is preferably used in 0.1 to 5 molar ratio, more preferably 1 to 3 molar ratio. If the content of the chlorine compound to methane is less than 0.1 molar ratio or more than 5 molar ratio, the reaction efficiency is lowered and the cost of the separation process due to unreacted material may be excessively increased. In addition, in this step, the air may be injected at an equivalence ratio of the methane and chlorine compounds within a range not exceeding the explosion range.

In the present step, the reaction catalyst is characterized in that copper is a first component, and the second component includes Zn or a lanthanide metal on the periodic table. In addition, in this step, the reaction catalyst may further include a Group 2A metal or metal salt on the periodic table as a third component in addition to the first component and the second component. In the present invention, the content of each member of the reaction catalyst is not particularly limited, but 5 to 20 parts by weight of the first component copper and 0.1 to 10 parts by weight of the second component; It is preferable that 5-20 weight part of copper which is a 1st component, 0.1-10 weight part of said 2nd components, and 0.1-10 weight part of said 3rd components . In the case of using the catalyst having the composition, since the dispersion of the active ingredient may be increased or the oxidation and reduction reactions of the active ingredient may be easily performed, the conversion of methane and the selectivity of methyl chloride may be increased.

In this step, in order to effectively increase the active site, the catalysts preferably use a carrier catalyst calcined by supporting each component on at least one carrier selected from the group consisting of zeolite, alumina, titania and silica. In the present invention, each component of the catalyst may be simultaneously or sequentially supported on the carrier. The firing method may be fired using any method known in the art to which the present invention pertains, and the method does not limit the present invention.

In this step, the octacyclolation reaction of the methane may be performed using a fixed bed reactor or a fluidized bed reactor.

The method using the fixed bed reactor refers to a method in which a carrier carrying the catalyst is charged in the reactor and the reactants are reacted while passing the carrier catalyst under suitable reaction conditions. In the present invention, the first oxcyclorelation reaction by the fixed bed reaction is preferably carried out at a reaction temperature of 100 to 600 ℃, more preferably 200 to 500 ℃. If the reaction temperature is less than 100 ℃ is a problem that the conversion rate of the methane is insignificant to increase the cost of separating the product and if it exceeds 600 ℃ it is not preferable because the problem of catalyst deactivation by the sublimation of the active ingredient according to the progress of the reaction. Further, in the present invention, the first oxcyclorelation reaction by the fixed bed reaction is preferably carried out at a reaction pressure of 1 to 20 atm, more preferably 1 to 10 atm. If the reaction pressure is less than 1 atm, the volume of the reactor is increased, not only the investment cost is increased, but also the cost of the separation process is excessively increased, and if it exceeds 20 atm, the loss of reactants due to the decrease in selectivity is increased. It is not desirable to have. In addition, in the present invention, the first oxcyclolation reaction by the fixed bed reaction is preferably carried out under the condition that the weight hourly space velocity (WHSP) of the reactants is 200 to 10,000 L / kgcat / hr, and more. Preferably it is 1,000-5,000 L / kgcat / hr. When the space passing rate of the reactants is less than 200 L / kgcat / hr, the size of the reactor is too large compared to the throughput of the reactor, which causes a problem of lowering efficiency. When it exceeds 10,000 L / kgcat / hr, the deactivation of the catalyst rapidly increases. It is not preferable because there is a problem.

In addition, the method using the fluidized bed reactor may be used as a method for preventing catalyst deactivation due to hot spot generation, as the reaction is performed while the reactants and the catalyst are suspended by the hot gas. The method using the fluidized bed reactor in the present invention is not particularly limited, and any method known in the art to which the present invention pertains may be used.

In this step, the first reaction product generated by the first oxcyclorelation reaction may include methyl chloride, hydrogen chloride, methylene chloride, unreacted methane, high boiling chlorine compounds and water as a byproduct.

The first reaction product prepared in this step is transferred to the first pyrolysis reaction step after the by-product water and unreacted hydrogen chloride are removed.

(b) first pyrolysis reaction step

In this step, the first reaction product is pyrolyzed by using a reaction catalyst to generate a second reaction product including ethylene.

In this step, the reaction catalyst is preferably a zeolite-based carrier including ZSM, X, Y, SAPO or β-zeolite. In this step, the catalyst is preferably a catalyst having a structure in which the Group 2A metal or metal salt (second component) on the periodic table is supported, ion exchanged, or substituted on the zeolite skeleton in the zeolite carrier (first component). Do. Since the catalyst having the composition has a shape selectivity, only the first reaction product having an appropriate pore size improves the selectivity to olefins, and in the case of too large pores, a high boiling point compound having 4 or more carbon atoms is produced. Group 2A metal (second component) on the periodic table in the present invention; The supporting method, ion exchange method, and substitution bonding method of the phosphine-based compound or transition metal (third component) on the zeolite-based carrier (first component) are not particularly limited and any known in the art to which the present invention pertains. Method can be used. In the present invention, the ZSM, X, Y, SAPO and β-zeolite means a carrier having a zeolite structure, the carrier having a zeolite structure means a catalyst consisting of silicon and aluminum metal. Specific examples of the zeolitic carrier that can be used in the present invention include ZSM5 or SAPO34. In the case of the ZSM5, the molar ratio of Si / Al is preferably 10 to 1,000, and more particularly, the ZSM5 carrier catalyst having a molar ratio of Si / Al is in the range of 20 to 500. In addition, in the case of SAPO34, the molar ratio of Si / Al is preferably 0.01 to 2, and more preferably, the molar ratio of Si / Al is 0.1 to 1. In the present invention, the transition metal included in the catalyst is preferably Ni, Co, Cr, Mn, Ti or Mo.

The first pyrolysis reaction according to this step may be performed using a fixed bed reactor or a fluidized bed reactor. The method using a fixed bed reactor refers to charging the carrier catalyst in the reactor and then reacting the first reaction product as a reactant while passing the carrier catalyst under suitable reaction conditions. In the present invention, the pyrolysis reaction of methyl chloride by the fixed bed reaction is preferably performed at a reaction temperature of 200 to 700 ° C, more preferably 300 to 600 ° C. If the reaction temperature is less than 200 ℃, the conversion rate is low, there is a problem that the separation cost of the unreacted material is excessively increased, and if it exceeds 700 ℃, the amount of conversion of the reactant to coke is increased is not preferred to reduce the yield. In the present invention, the pyrolysis reaction of methyl chloride by the fixed bed reaction is a reaction pressure of 1 It is preferably carried out at from 20 atmospheres, more preferably from 1 to 10 atmospheres. If the reaction pressure is less than 1 atm, the volume of the reactor is increased, not only the investment cost is increased, but also the separation cost is excessively increased, and if it exceeds 20 atm, there is a problem that the amount of coke is excessively increased, which is not preferable. In the present invention, the pyrolysis reaction of methyl chloride by the fixed bed reaction is preferably carried out under the conditions of the space passing rate (WHSP) of the reaction 200 to 10,000 L / kgcat / hr, more preferably 1,000 to 5,000 L / kgcat / hr Do. When the space passing rate of the reactants is less than 200 L / kgcat / hr, there is a problem that the size of the reactor is excessively increased compared to the throughput of the reactants, and when the amount exceeds 10,000 L / kgcat / hr, the deactivation of the catalyst is rapidly progressed. It is not desirable.

In the present invention, the first pyrolysis reaction may use a fluidized bed reactor to easily remove coke generated as a by-product. In the present invention, the reaction conditions of the pyrolysis reaction of methyl chloride using the fluidized bed reactor are not particularly limited, and any method known in the art to which the present invention pertains may be used.

In this step, the reaction product (second reaction product) produced by the first pyrolysis reaction includes ethylene, hydrogen chloride, methylene chloride, unreacted products including unreacted methane, BTX, and high boiling point chlorine compounds.

The second reaction product prepared in this step is then continuously transferred to a separation reactor after the removal of hydrogen chloride and the like.

The process of the first oxcyclorelation of step (a) and the first pyrolysis reaction step of step (b) according to the present invention is well illustrated in FIG. 1. 1 is a process chart showing a process for preparing ethylene from methane which is a part of the vinyl chloride manufacturing process according to the present invention.

Referring to FIG. 1, methane (101), air (102), and chlorine compound (123) are reacted with oxcycloreaction in the presence of a reaction catalyst in an oxcyclorelation reactor to form a first reaction product containing methyl chloride. Create The first reaction product is then transferred to the condenser 1 and the by-product water 105 is removed. Subsequently, after the first reaction product 104 is transferred to the separation reactor A, the hydrogen chloride and the high boiling point chlorine compound 107 are separated using the boiling point difference. The high boiling point chlorine compound is then removed from the hydrogen chloride regeneration reactor as carbon oxide (COx) is separated and removed as the combustion gas 121, and then introduced into the hydrogen chloride stripper as hydrogen chloride 122a without carbon oxides. The hydrogen chloride 122 introduced into the hydrogen chloride stripper is mixed with the chlorine compound 123b which is separated and added as anhydrous hydrogen chloride 123a, and is recycled and supplied to the oxcyclorelation reaction of methane in step (a). On the other hand, the first reaction product containing the methyl chloride and the by-products methylene chloride, unreacted methane and the like as the main product of the octacyclolation reaction of the methane is continuously transferred to the pyrolysis reactor.

The first reaction product 111 transferred to the pyrolysis reactor is pyrolyzed in the pyrolysis reactor in the presence of a reaction catalyst to produce a second reaction product 112. The second reaction product includes ethylene and olefins such as propylene and butene, hydrogen chloride, methylene chloride, unreacted methane and unreacted methane and methyl chloride, BTX and by-product water.

The generated second reaction product 112 is a condenser (2) to remove the reaction by-product water and the hydrogen chloride and chlorine compounds (113, 114) are separated through a scrubber (scrubber). The hydrogen chloride 113 is directly transferred to the hydrogen chloride stripper, or is transferred to the hydrogen chloride stripper as hydrogen chloride 122a from which the carbon oxide 121 is removed through the hydrogen chloride regeneration reactor. The hydrogen chloride 122 introduced into the hydrogen chloride stripper is mixed with the chlorine compound 123b which is separated as anhydrous chlorine gas 123a and additionally added, and is recycled and supplied to the first oxcyclorelation reaction of step (a). .

On the other hand, the second reaction product 115 from which the hydrogen chloride is separated is transferred to the separation reactor (B) and then olefins containing ethylene (118), BTX (119), and unreacted methane (117), using the boiling point difference. Reaction methyl chloride (116) or the like, the unreacted methane (117) is recycled to the first oxcyclorelation reaction step of step (a) and supplied, and the unreacted methyl chloride (116) (b) It is recycled and fed to the first pyrolysis reaction stage of the stage. Of the olefins 118, ethylene is fed to the second oxcyclolination reaction step of step (c) described below to be used for the synthesis of 1,2-dichloroethane or through an additional olefin separation process, followed by ethylene, propylene and After separation into butenes and the like, it can be transferred to a subsequent downstream process for use.

(c) the second Oxcyclolination  Reaction step

This step is to prepare a third reaction product containing 1,2-dichloroethane by oxcyclorelation reaction of the second reactant including ethylene, air and chlorine compounds in the presence of the reaction catalyst. In this step, a third reaction product including 1,2-dichloroethane is prepared by oxcycloling only one component of ethylene using a copper-based catalyst known in the art, or a reaction catalyst described below. The third reaction product containing 1,2-dichloroethane may be prepared by performing an oxcyclolination reaction of methane and ethylene.

In this step, the chlorine compound includes chlorine gas or hydrogen chloride.

In this step, the content of the chlorine compound to the reactant ethylene is preferably used in 0.1 to 5 molar ratio, more preferably 1 to 3 molar ratio. If the content of the chlorine compound to the ethylene is less than 0.1 molar ratio or more than 5 molar ratio, the reaction efficiency is lowered and the cost of the separation process due to unreacted material may be excessively increased. In addition, in this step, the air may be injected at an equivalence ratio of the ethylene and the chlorine compound within a range that does not depart from the explosion range.

In this step, the catalyst is a copper as a first component, it is characterized in that it contains Zn or a lanthanum metal of the periodic table as a second component. In addition, in the present step, the catalyst may further include a Group 2A metal or metal salt on the periodic table as a third component in addition to the first component and the second component. In the present invention, the content of each component of the catalyst is not particularly limited, but 5 to 20 parts by weight of the first component copper and 0.1 to 10 parts by weight of the second component; It is preferable that 5-20 weight part of copper which is a 1st component is 0.1-10 weight part of said 2nd components, and 0.1-10 weight part of said 3rd components.

In this step, in order to effectively increase the active site, the catalysts preferably use a carrier catalyst calcined by supporting each component on at least one carrier selected from the group consisting of zeolite, alumina, titania and silica. In the present invention, each component of the catalyst may be simultaneously or sequentially supported on the carrier. The firing method may be fired using any method known in the art to which the present invention pertains, which does not limit the present invention.

In this step, the second oxcyclolination reaction may be performed using a fixed bed reactor or a fluidized bed reactor. In the present invention, the second oxcyclorelation reaction by the fixed bed reaction is preferably carried out at a reaction temperature of 100 to 600 ℃, more preferably 200 to 500 ℃. If the reaction temperature is less than 100 ℃ is not preferable because the conversion rate is insignificant to increase the separation cost excessively exceeds 600 ℃ because of the problem of catalyst deactivation by the sublimation of the active ingredient according to the progress of the reaction. Further, in the present invention, the second oxcyclolation reaction by the fixed bed reaction is preferably performed at a reaction pressure of 1 to 20 atm, more preferably 1 to 10 atm. If the reaction pressure is less than 1 atm, the reactor volume is required to be large, the efficiency is lowered, and the separation process is complicated, and if it exceeds 20 atm, there is a problem that the loss of reactants due to the decrease in selectivity increases. . Further, in the present invention, the second oxcyclolation reaction by the fixed bed reaction is preferably performed under the condition that the weight hourly space velocity (WHSP) of the reactants is 200 to 10,000 L / kgcat / hr, and more. Preferably it is 1,000-5,000 L / kgcat / hr. When the space passing rate of the reactants is less than 200 L / kgcat / hr, there is a problem that the size of the reactor is excessively increased compared to the throughput of the reactants, and when the amount exceeds 10,000 L / kgcat / hr, the deactivation of the catalyst is rapidly progressed. It is not desirable.

In this step, the third reaction product produced by the second oxcyclolination reaction may include 1,2-dichloroethane, hydrogen chloride, chloroethane and unreacted ethylene.

The third reaction product prepared in this step is transferred to the second pyrolysis step after the reaction by-product water and unreacted hydrogen chloride are removed.

(d) second pyrolysis step

In this step, the third reaction product is thermally decomposed using a reaction catalyst to prepare a fourth reaction product including vinyl chloride.

In this step, the reaction catalyst is preferably a zeolite-based carrier including ZSM, X, Y, SAPO or β-zeolite. In this step, the catalyst is preferably a catalyst having a structure in which the Group 2A metal or metal salt (second component) on the periodic table is supported, ion exchanged, or substituted on the zeolite skeleton in the zeolite carrier (first component). Do. In the present invention, the transition metal included in the catalyst is preferably Ni, Co, Cr, Mn, Ti or Mo. Group 2A metal or metal salt (second component) on the periodic table in the present invention; The method of supporting the phosphine-based compound or transition metal on the zeolite carrier (first component), the ion exchange method, and the substitution-bonding method are not particularly limited, and any method known in the art to which the present invention pertains may be used. . In the present invention, the ZSM, X, Y, SAPO and β-zeolite means a carrier having a zeolite structure, the carrier having a zeolite structure means a catalyst consisting of silicon and aluminum metal. Specific examples of the zeolitic carrier that can be used in the present invention include ZSM5 or SAPO34. In the case of the ZSM5, the molar ratio of Si / Al is preferably 10 to 1,000, and more particularly, the ZSM5 carrier catalyst having a molar ratio of Si / Al is in the range of 20 to 500. In addition, in the case of SAPO34, the molar ratio of Si / Al is preferably 0.01 to 2, and more preferably, the molar ratio of Si / Al is 0.1 to 1.

In this step, the second pyrolysis reaction may be performed in a fixed bed reactor or a fluidized bed reactor. In the present invention, the second pyrolysis reaction by the fixed bed reaction is preferably carried out at a reaction temperature of 200 to 700 ℃, more preferably 300 to 600 ℃. If the reaction temperature is less than 200 ℃ has a problem that the conversion rate is low, the separation cost of the unreacted material is excessively increased, and if the reaction temperature is higher than 700 ℃, the amount of conversion of the reactant to coke is increased to reduce the yield is not preferable. Further, in the present invention, the second pyrolysis reaction by the fixed bed reaction is preferably performed at a reaction pressure of 1 to 20 atm, and more preferably 1 to 10 atm. If the reaction pressure is less than 1 atm, the volume of the reactor is increased not only to increase the investment cost but also to increase the separation process cost, and if the reaction pressure is more than 20 atm, there is a problem that the amount of coke is excessively increased. not.

In the present invention, the second pyrolysis reaction by the fixed bed reaction is preferably carried out under the conditions of the space passing rate (WHSP) of 200 to 10,000 L / kgcat / hr, more preferably 1,000 to 5,000 L / kgcat / hr to be. When the space passing rate of the reactants is less than 200 L / kgcat / hr, there is a problem that the size of the reactor is excessively increased compared to the throughput of the reactants, and when the amount exceeds 10,000 L / kgcat / hr, the deactivation of the catalyst is rapidly progressed. It is not desirable.

In the present invention, the second pyrolysis reaction may use a fluidized bed reactor to easily remove coke produced as a by-product. In the present invention, the reaction conditions of the second pyrolysis reaction using the fluidized bed reactor are not particularly limited, and any method known in the art may be used.

In this step, the reaction product (fourth reaction product) produced by the second pyrolysis reaction includes vinyl chloride, hydrogen chloride, 1,2-dichloroethane, chloroethane, unreacted material including ethylene, BTX, and the like.

The fourth reaction product prepared in this step is subsequently transferred to a separation reactor after the water and chlorine gas, which are byproducts of the reaction, are removed.

(e) vinyl chloride separation step

This step is a step of separating the fourth reaction product into an olefin including vinyl chloride, hydrogen chloride, BTX, ethylene, methane, propylene, unreacted 1,2-dichloroethane and the like by using a boiling point difference in a separation reactor. The method of separating the compounds in this step may use any method known in the art to which the present invention pertains, and the method does not limit the present invention.

The ethylene separated in this step is recycled and supplied to the second oxcyclolation reaction step of step (c), and the methane is recycled and supplied to the first oxcyclorelation reaction step of step (a) The unreacted 1,2-dichloroethane is recycled to the second pyrolysis step of step (d) and supplied.

In addition, the vinyl chloride separated in this step may be transferred to the PVC polymerization process, olefins, propylene, including propylene may be transferred to the downstream process (downstream) to be used.

The process of the second oxcyclorelation of step (c), the second pyrolysis step of step (d) and the separation of vinyl chloride of step (e) according to the present invention are well illustrated in FIG. 2. Figure 2 is a process chart showing a process for producing vinyl chloride from ethylene which is part of the vinyl chloride manufacturing process according to the present invention.

Referring to FIG. 2, a third reactant including ethylene 201, air 202, and a chlorine compound 223 may be subjected to oxcycloreaction in the presence of a reaction catalyst to include 1,2-dichloroethane. Produce a reaction product. In the third reaction product, water 205, which is a byproduct of the condenser 1, is separated. The third reaction product 204 from which the water is removed is transferred to the separation reactor A, and the hydrogen chloride and chlorine compounds 207 are separated from the third reaction product using the boiling point difference. The separated hydrogen chloride and chlorine compound 207 is then introduced into the hydrogen chloride stripper as carbon oxide (COx) without hydrogen oxide 222a after the carbon oxide (COx) is separated as the combustion gas 221 in the hydrogen chloride regeneration reactor. Hydrogen chloride 222 introduced into the hydrogen chloride stripper is mixed with the chlorine compound 223b which is separated and added as anhydrous chlorine gas 223a and is recycled to the second oxcyclorelation reaction step of step (c). do.

Meanwhile, the third reaction product 211 including 1,2-dichloroethane as a main product of the second oxcyclolation reaction and chloroethane and unreacted ethylene as a by-product is continuously transferred to the pyrolysis reactor.

The third reaction product 211 transferred to the pyrolysis reactor is pyrolyzed in the pyrolysis reactor in the presence of a reaction catalyst to produce a fourth reaction product 212. The fourth reaction product includes vinyl chloride, hydrogen chloride, methyl chloride, unreacted ethylene, unreacted 1,2-dichloroethane, chloroethane and the like.

The fourth reaction product 212 is then passed through the condenser 2 to remove the reaction by-product water, and the hydrogen chloride and chlorine compounds 213 and 214 are separated from the fourth reaction product through a scrubber. The separated hydrogen chloride and chlorine compounds 213 are directly transferred to the hydrogen chloride stripper, or are transferred to the hydrogen chloride stripper as hydrogen chloride 222a from which the carbon oxide 221 is removed through a hydrogen chloride regeneration reactor. Hydrogen chloride 222 introduced to the hydrogen chloride stripper is mixed with an additional chlorine compound 223b which is separated and added as anhydrous hydrogen chloride 223a, and is recycled and supplied to the second oxcyclolation reaction step of step (c). .

Meanwhile, the fourth reaction product 215 in which the hydrogen chloride is separated is transferred to the separation reactor (B), and then vinyl chloride (218), unreacted ethylene (217), unreacted 1,2-dichloroethane using a boiling point difference. 216 and other materials including chloroethane and the like, and the unreacted ethylene 217 is recycled and supplied to the second oxcyclolination reaction step of step (c), and unreacted 1 The, 2-dichloroethane 216 is recycled and supplied to the second pyrolysis step of step (d).

The present invention includes simultaneously performing the first oxcyclorelation reaction of step (a) and the second oxcyclorelation reaction of step (c) in one reactor, and the first of step (b) Simultaneously carrying out the pyrolysis reaction and the second pyrolysis reaction of step (d) in one reactor.

In the present invention, the method of simultaneously reacting the oxidized methane and ethylene in one reactor includes the step of recycling the ethylene produced in the step (c) to the step (a), thereby not supplying separate ethylene. Vinyl chloride can be produced from methane in one process. In addition, in the present invention, since the methyl chloride and 1,2-dichloroethane are simultaneously reacted in one pyrolysis reactor, vinyl chloride may be prepared without a separate pyrolysis reactor of 1,2-dichloroethane.

The process for producing vinyl chloride by simultaneously oxidizing the methane and ethylene followed by pyrolysis reaction is shown in FIG. 3. FIG. 3 illustrates that a first oxcyclorelation reaction and a second oxcyclorelation reaction are performed in one reactor, and a first pyrolysis reaction and a second pyrolysis reaction are carried out in one reactor, according to an embodiment of the present invention. It is a process chart which shows the process in which vinyl is manufactured.

Referring to FIG. 3, the reactants introduced into the oxcyclolination reactor are methane 301, air 302, ethylene 317 and chlorine compound 323 recycled after the reaction. The water in the first reaction product 303 is first removed 305 from the condenser 1 and then the remaining components 304 are introduced into the separation reactor A. In the separation reactor (A), the hydrogen chloride and the high boiling point chlorine compound 307 are separated and introduced into the hydrogen chloride regeneration reactor, and the hydrogen chloride is a hydrogen chloride stripper 323a without carbon oxide after the carbon oxide is burned and removed 321. The chlorine compound (323b), which is separated into anhydrous hydrogen chloride (323a), and then additionally added thereto, is introduced into the oxcyclolination reactor. The reaction product 311 in which the hydrogen chloride is separated from the separation reactor A includes methyl chloride, 1,2-dichloroethane, methylene chloride, unreacted methane, and the like, and is continuously transferred to the pyrolysis reactor. The pyrolysis reaction using a catalyst in the pyrolysis reactor produces a reaction product 312 including ethylene, propylene, butene, vinyl chloride, unreacted methane, and the like. The reaction product 312 is transferred to the condenser 2 and the scrubber. After the water is removed, the hydrogen chloride and high boiling point chlorine compounds (313, 314) are introduced directly to the hydrogen chloride stripper (322) or the chloride gas (322a) containing no carbon oxide after the carbon oxide 321 is removed from the hydrogen chloride regeneration reactor Is introduced into the hydrogen chloride stripper. Meanwhile, the hydrogen chloride-removed reaction product 315 is continuously transferred to the separation reactor (B), and then vinyl chloride 318 is separated from the separation reactor (B), and propylene, butene, BTX, and the like (319) Separated, unreacted 1,2-dichloroethane 216 is recycled and introduced into the pyrolysis reactor, and unreacted methane and ethylene 317 are separated and fed back to the oxcyclolination reactor.

The process allows the oxcyclorelation reaction of methane and ethylene to be carried out in one reactor, so that ethylene, the reaction product of methane, is fed back to the oxcyclolination reaction while simultaneously adding methyl chloride and 1,2-dichloroethane. The pyrolysis reaction can be performed in the reactor of to simplify the process and further improve the yield of the final product, vinyl chloride.

In addition, the present invention includes that the first oxcyclorelation reaction of step (a) and the second oxcyclorelation reaction of step (c) are each performed separately in two different reactors.

In the present invention, the method of separately reacting the methane and ethylene in two different reactors in the OCcyclolination reaction includes the step of recycling the ethylene produced in step (b) to step (c), thereby supplying a separate ethylene. Vinyl chloride can be produced in one process from methane without

Process for preparing ethylene and vinyl chloride by oxidizing the methane and ethylene in two different reactors and then pyrolyzing the reaction products of the oxcyclolination, such as methyl chloride and 1,2-dichloroethane. Is shown in the accompanying FIG. 4. 4 is a flowchart illustrating a process in which vinyl chloride is prepared by performing an oxcyclolination reaction of methane and an oxcyclolination reaction of ethylene according to one embodiment of the present invention.

Referring to FIG. 4, first, the reactants supplied to the oxcyclorelation reactor of methane are methane (401), air (402), methane (426) and chlorine compound (433), which are recycled after the reaction, and octacycloethylene of ethylene. The reactants fed to the reaction reactor are air 411, chlorine compound 412 to be replenished, anhydrous hydrogen chloride 433c to be recycled and ethylene 427 to be recycled. The product 403 of the oxcyclorelation reaction of methane and the product 413 of the oxcyclorelation reaction of ethylene are transferred to the condenser 1, mixed, and then condensed to remove the by-product water 407. The remaining reaction product 404 from which water is removed is introduced into the separation reactor (A). In the separation reactor (A), the hydrogen chloride and the high boiling point chlorine compound 406 are separated and introduced into a hydrogen chloride regeneration reactor, and the hydrogen chloride is a hydrogen chloride stripper as hydrogen chloride 431 without carbon oxide after the carbon oxide 432 is burned and removed. It is introduced into an anhydrous hydrogen chloride (433a), and then mixed with hydrogen chloride (433b) which is additionally added, and then introduced into an oxcyclolination reactor of methane and an oxcyclolination reactor of ethylene. The reaction product 405 in which hydrogen chloride is separated from the separation reactor (A) includes methyl chloride, 1,2-dichloroethane, methylene chloride, unreacted methane, and the like, and is continuously transferred to a pyrolysis reactor. The pyrolysis reaction using the catalyst in the pyrolysis reactor produces a reaction product 421 including ethylene, propylene, butene, vinyl chloride, unreacted methane, and the like. The reaction product 421 is transferred to the condenser 2 and the scrubber. After the water is removed, the hydrogen chloride and high boiling point chlorine compounds (423, 424) are introduced directly into the hydrogen chloride stripper (423) or after the removal of the carbon oxide (42) in the hydrogen chloride regenerator, hydrogen chloride (431) containing no carbon oxides As a hydrogen chloride stripper. The hydrogen chloride-removed reaction product 422 is continuously transferred to the separation reactor (B), and then vinyl chloride (429) is separated from the separation reactor (B), and propylene, butene, BTX, and the like (428) are separated. , Unreacted 1,2-dichloroethane (425) is fed back to the pyrolysis reactor, ethylene (427) is separated and recycled to the ethylene cyclocyclization reactor, and unreacted methane (426) is fed to the methane It is fed back to the renation reactor.

The process allows the oxcyclorelation reaction of methane and ethylene to be carried out in two different reactors, while the reaction product of methane is fed to the oxcyclorelation reaction of ethylene with 1,2- and methyl chloride. The pyrolysis reaction of dichloroethane in the same reactor can simplify the process and improve the yield of the final product, vinyl chloride.

In the above, the production method of vinyl chloride from methane according to the present invention has been described by dividing each step.

When using the preparation method according to the present invention it is possible to increase the selectivity of vinyl chloride by using an oxidized reaction catalyst and pyrolysis reaction catalyst with improved catalytic activity. In addition, the oxcyclorelation of methane and the oxcyclorelation of ethylene can be carried out in one reactor or two different reactors and the final separated ethylene can be recycled and fed to the oxcyclorelation of ethylene. It can simplify and improve the selectivity of vinyl chloride.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Example

Example  One

First Oxcyclolination  reaction

An oxcyclorelation reactor, a 60-cm-high 1-inch diameter reactor (Inconel reactor) was charged with 5 g of a catalyst and had a reaction temperature of 350 ° C., a reaction pressure of 1 atmosphere, and a space passing rate (WHSV) of 2,250 L / kgcat / hr. Oxychlorination was carried out in a fixed bed reactor. As a catalyst, 5 parts by weight of Cu and 1.01 parts by weight of lanthanum metal were supported on a zeolite-based ZSM5 carrier, and a carrier catalyst calcined with nitrogen at 300 ° C. was used. The reactant was injected at a molar ratio of methane: chlorine gas: air fixed at 1.5: 1: 0.5, diluted with nitrogen, and fixed at 50%. From the contents of methyl chloride, methylene chloride, carbon oxide and unreacted methane produced as a result of the reaction, conversion of methane and selectivity of methyl chloride were obtained from the following equation.

% Conversion of methane = [(moles of methane initially added-moles of unreacted methane) / (moles of methane initially added)] × 100

% Selectivity of methyl chloride = [(moles of produced methyl chloride) / (moles of reacted methane)] × 100

The conversion rate of methane by the first oxcyclorelation reaction was 21.5%, and the selectivity of methyl chloride was 95.5%. The selectivity of methylene chloride as an impurity was 3.2% and that of other carbon oxides was 0.4%.

First pyrolysis reaction

5 g of catalyst was placed in a pyrolysis reactor (Inconel reactor) having a height of 60 cm and an outer diameter using methyl chloride, and the reaction temperature was 400 ° C., the reaction pressure was 1 atm, and the space passing rate (WHSV) was 2,500 L / kgcat / hr. The pyrolysis reaction was carried out in a fixed bed reactor under the conditions. As a catalyst, 1.5 parts by weight of MgCl ₂ was supported on a ZSM5 (Si / Al = 0.3) carrier, and then calcined at 500 ° C. From the contents of ethylene and unreacted methyl chloride produced as a result of the reaction, conversion of methyl chloride and selectivity of ethylene were determined from the following equation.

% Conversion of methyl chloride = [(moles of initially added methyl chloride-moles of unreacted methyl chloride) / (moles of initially added methyl chloride)] × 100

% Selectivity of ethylene = [(moles of ethylene produced) / (moles of methyl chloride reacted x 2)] × 100

The conversion rate of methyl chloride by the first pyrolysis reaction was 97.2%, the selectivity of ethylene was 58.6%, and the selectivity of propylene was 18.7%.

2nd Oxcyclolination  reaction

The oxcyclorelation reactor was filled with 5 g of catalyst in a 60-inch-high 1-inch-diameter reactor (Inconel reactor), and the reaction temperature was 300 ° C., the reaction pressure was 1 atm, and the space passing rate (WHSV) 2250 L / kgcat / hr Oxychlorination was carried out in a fixed bed reactor. As a catalyst, 5 parts by weight of Cu, 1.0 parts by weight of lanthanum metal and 1.0 parts by weight of Ba metal salt were supported on an alumina carrier and calcined with nitrogen at 300 ° C. The reactants were injected with a fixed molar ratio of ethylene: chlorine gas: air of 1: 2: 0.5, diluted with nitrogen, and fixed at 50%. From the contents of 1,2-dichloroethane, carbon oxide and unreacted ethylene produced as a result of the reaction, conversion of ethylene and selectivity of 1,2-dichloroethane were obtained from the following equation.

% Conversion of ethylene = [(moles of ethylene initially charged-moles of unreacted ethylene) / (moles of ethylene initially charged)] × 100

% Selectivity of 1,2-dichloroethane = [(moles of generated 1,2-dichloroethane) / (moles of ethylene reacted)] × 100

The conversion rate of ethylene by the second oxcyclorelation reaction was 88.6%, and the selectivity of 1,2-dichloroethane was 85.3%.

Second pyrolysis reaction

5 g of catalyst was charged into a pyrolysis reactor (Inconel reactor) having a height of 60 cm and an outer diameter of 1 inch using 1,2-dichloroethane, reaction temperature of 450 ° C., reaction pressure of 1 atmosphere, and space passing rate (WHSV) of 2,500 L / Pyrolysis was carried out in a fixed bed reactor under the conditions of kgcat / hr. As a catalyst, 1.5 parts by weight of MgCl ₂ was supported on a ZSM5 (Si / Al = 23) carrier, and then calcined at 500 ° C. From the contents of vinyl chloride and unreacted 1,2-dichloroethane produced as a result of the reaction, the conversion rate of 1,2-dichloroethane and the selectivity of vinyl chloride were determined from the following equation.

% Conversion of 1,2-dichloroethane = [(moles of first-injected 1,2-dichloroethane-moles of unreacted 1,2-dichloroethane) / (moles of first-injected 1,2-dichloroethane)] × 100

Selectivity of vinyl chloride (%) = [(moles of generated vinyl chloride) / (moles of reacted 1,2-dichloroethane)] × 100

The conversion of 1,2-dichloroethane by the second pyrolysis reaction was 71.7%, the selectivity of vinyl chloride was 82.5%, and the selectivity of ethylene was 15.5%.

Example  2

First Oxyclination  Reaction and second Oxcyclolination  reaction

Methane and ethylene, which are reactants of the first and second oxcyclorelations, were charged into a 1-inch-diameter reactor (Pyrex glass reactor) having a height of 100 cm as an octacyclolation reactor, and a reaction temperature was charged. Oxychlorination was carried out in a fluidized bed reactor under the conditions of 350 ° C., a reaction pressure of 1 atmosphere and a space passing rate (WHSV) of 600 L / kgcat / hr. As a catalyst, a carrier catalyst in which 5 parts by weight of Cu and 1.0 parts by weight of lanthanum metal was supported on a zeolite-based ZSM5 (Sl / Al = 80) carrier and pretreated with nitrogen at 300 ° C. was used. The reactant was injected with a molar ratio of methane: ethylene: hydrogen chloride: oxygen fixed at 1: 1: 3: 0.5, diluted with nitrogen, and fixed at 50%. Methyl chloride, methylene chloride, 1,2-dichloroethane, carbon oxide and high boiling point chlorine compound produced as a result of the reaction were produced.

As a result of the reaction of the first and second oxcyclorelation, the conversion rate of methane was 15.3%, the conversion rate of ethylene was 99.5%, and the selectivity of methyl chloride by the first oxcyclorelation in the product was 89.8%. , Methylene chloride, the selectivity was 1.3%, 1,2-dichloroethane selectivity by the second octacyclolation was 85.8%, trichloroethane selectivity was 11.7%.

First pyrolysis reaction and second pyrolysis reaction

5 g of a catalyst was charged in a pyrolysis reactor (Inconel reactor) having a height of 60 cm and an outer diameter of 1 cm using methyl chloride and 1,2-dichloroethane as the first pyrolysis reaction and the second pyrolysis reaction as a reactor, and a reaction temperature of 400 ° C., Pyrolysis was carried out in a fixed bed reactor under a reaction pressure of 1 atmosphere and a space passing rate (WHSV) of 2,500 L / kgcat / hr. As a catalyst, 1.5 parts by weight of MgCl ₂ was supported on a ZSM5 (Si / Al = 23) carrier, and then calcined at 500 ° C. The reactant was injected at a molar ratio of methyl chloride: 1,2-dichloroethane at 1: 0.5, diluted with nitrogen, and fixed at 50%. The reaction result was 98% conversion of methyl chloride and 99% conversion of 1,2-dichloroethane, 19.7% selectivity of ethylene by 1st pyrolysis reaction, 10.5% selectivity of propylene, and 2nd pyrolysis reaction. Vinyl chloride showed 86.6%.

Example  3

An oxcyclolination reaction was carried out under the same reaction conditions as those of the first and second oxcyclolination reactions of Example 2, and the pyrolysis reaction was carried out on the following catalyst.

First pyrolysis reaction and second pyrolysis reaction

5 g of a catalyst was charged in a pyrolysis reactor (Inconel reactor) having a height of 60 cm and an outer diameter of 1 cm using methyl chloride and 1,2-dichloroethane as the first pyrolysis reaction and the second pyrolysis reaction as a reactor, and a reaction temperature of 400 ° C., Pyrolysis was carried out in a fixed bed reactor under a reaction pressure of 1 atmosphere and a space passing rate (WHSV) of 2,500 L / kgcat / hr. As a catalyst, 1.5 parts by weight of MgCl ₂ was supported on an SAPO 34 (Si / Al = 0.3) carrier, and then calcined at 500 ° C. The reactant was injected after fixing the molar ratio of methyl chloride: 1,2-dichloroethane to 1: 1 and diluting with nitrogen to 50%. As a result of the reaction, the conversion rate of methyl chloride and 1,2-dichloroethane was more than 99%. The selectivity of ethylene by the first pyrolysis reaction was 53.7%, the selectivity of propylene by 9.4% and the vinyl chloride by the second pyrolysis reaction. Showed a selectivity of 81.3%.

Comparative example  One

As the reaction catalyst of the first oxcyclorelation reaction, 5 parts by weight of copper / Al ₂ O ₃ catalyst was used in the same manner as in Example 1 except that 5 g of a supported catalyst supported by CuCl ₂ copper precursor and Aldrich's alumina was used. The reaction was carried out. As a result of the reaction, the conversion rate of methane was 6.8%, the selectivity of methyl chloride was 81.2%, the selectivity of methylene chloride was 6.2%, and the selectivity of carbon oxide (COx) was 0.5%.

The results of Examples 1 to 4 and Comparative Example 1 are summarized in Table 1.

division Example 1 Example 2 Example 3 Comparative Example 1 1st occyclolination Methane conversion 21.5 15.3 15.3 6.8 Selectivity of methyl chloride 95.5 89.8 89.8 81.2 First pyrolysis reaction Conversion of methyl chloride 97.2 98 99 - Selectivity of ethylene 58.6 19.7 53.7 - Second octacyclolation Conversion of ethylene 88.6 99.5 99.5 - Selectivity of EDC 85.3 85.8 85.8 - 2nd pyrolysis reaction EDC Conversion Rate 71.7 99 99 - Selectivity of vinyl chloride 82.5 86.6 81.3 -

EDC = 1,2-dichloroethane unit =%

From the results of Table 1, the conversion rate of methane as a result of the first oxcyclorelation reaction according to the present invention is 15% or more, and the selectivity of methyl chloride formed therefrom is 89% or more, compared with the case of Comparative Example 1 It can be seen that is a good level and the selectivity is very high. In addition, as a result of the first pyrolysis reaction after the first oxcyclorelation reaction, the conversion rate of methyl chloride was greater than 97% in Examples 1 to 3, and the selectivity of ethylene was obtained by obtaining about 19% to 58%. It can be seen that this is very high and the selectivity is good. In addition, the conversion rate after the first pyrolysis reaction and the second oxcyclorelation reaction was 88% or more. By indicating that the reaction was found to be very efficient. It can be seen that the selectivity of 1,2-dichloroethane in the second oxcyclolination reaction is very high as 85% or more. The second pyrolysis reaction followed by the second pyrolysis reaction resulted in a conversion rate of 70% or more. In particular, in Examples 2 and 3, which were performed together with the first pyrolysis reaction, the conversion rate was 99% or more. It was found to be very efficient. The selectivity of vinyl chloride in the second pyrolysis reaction was at least 81%, indicating a good level.

In each of the above embodiments of the present invention, it was found that the conversion rate and product selectivity of each reaction were generally high, so that the reaction was efficient. However, in Comparative Example 1, the reaction rate was low because the conversion rate and selectivity of the first oxcyclorelation reaction were low. It can be seen that it is not as efficient as Examples 1 to 3 according to the present invention.

When using the preparation method according to the present invention, when the ethylene is prepared from the methane by the oxcyclorelation reaction and pyrolysis reaction using the catalyst with improved activity, it is possible to improve the conversion of methane and selectivity of ethylene, Even when vinyl chloride is prepared from ethylene by an oxcyclolination reaction and a pyrolysis reaction, the conversion of ethylene and the selectivity of vinyl chloride can be improved. In the present invention, the oxcyclorelation of methane, the oxcyclorelation of ethylene, the pyrolysis of methyl chloride and the pyrolysis of 1,2-dichloroethane are carried out in one reactor or in two different reactors. Since the process can be carried out in one process, the reaction can be simplified to reduce the production cost of vinyl chloride.

Although the present invention has been described above through specific embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope of the technical idea of the present invention, and such modifications and modifications belong to the appended claims.

Claims (15)

(a) oxidizing the first reactant comprising methane, air and chlorine compounds in the presence of the first reaction catalyst to produce a first reaction product comprising methyl chloride; (b) pyrolysing the first reaction product in the presence of a second reaction catalyst to produce a second reaction product comprising ethylene; (c) separating ethylene from the second reaction product, and then reacting the second reaction product in which the ethylene is mixed with air and a chlorine compound in the presence of a third reaction catalyst to contain 1,2-dichloroethane. Generating a third reaction product; (d) pyrolysing the third reaction product in the presence of a fourth reaction catalyst to produce a fourth reaction product comprising vinyl chloride; And (e) separating the vinyl chloride from the fourth reaction product; The chlorine compound of step (a) and (c) is chlorine gas or hydrogen chloride, The reaction catalyst of step (a) and step (c) is copper (first component); And Zn or lanthanum metal (second component), The reaction catalyst of step (b) and step (d) is a production method of vinyl chloride, characterized in that the zeolite carrier containing ZSM, X, Y, SAPO or β-zeolite. delete delete The method of claim 1, The reaction catalyst of steps (a) and (c) further comprises a Group 2A metal or metal salt (third component) on the periodic table. The method of claim 1, The reaction catalyst of step (a) and (c) is a method for producing vinyl chloride, characterized in that supported on a carrier which is zeolite, alumina, titania, silica or a combination thereof. The method of claim 1, The method of producing vinyl chloride, characterized in that the oxcyclorelation reaction of steps (a) and (c) is carried out by a fixed bed reaction or a fluidized bed reaction. The method of claim 6, The fixed bed reaction is a method of producing a vinyl chloride, characterized in that the reaction temperature is carried out under the conditions of 100 to 600 ℃, reaction pressure 1 to 20 atm, the reaction room space passing rate (WHSV) 200 to 10,000 L / kgcat / hr. delete The method of claim 1, And the reaction catalyst is supported on the zeolite-based carrier by a group 2A metal or metal salt on the periodic table, ion-exchanged, or substituted and bonded to the zeolite skeleton. delete The method of claim 1, The pyrolysis reaction of steps (b) and (d) is carried out by a fixed bed reaction or a fluidized bed reaction. The method of claim 11, The fixed bed reaction is a method for producing vinyl chloride, characterized in that the reaction temperature is carried out under the conditions of 200 to 700 ℃, reaction pressure 1 to 20 atm, reactant space passing rate (WHSV) of 200 to 10,000 L / kgcat / hr. The method of claim 1, The method of producing vinyl chloride, characterized in that the oxcyclorelation reaction of step (a) and the oxcyclorelation reaction of step (c) are carried out in one reactor. The method of claim 1, The method of producing vinyl chloride, characterized in that the oxcyclorelation reaction of step (a) and the oxcyclorelation reaction of step (c) are carried out in two different reactors. The method of claim 1, The pyrolysis reaction of step (b) and the pyrolysis reaction of step (d) are carried out in one reactor.

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