KR102773697B1 - Al-Ti Mixed Oxide Catalysts for Dechlorination of Chloromethanes and the Method for Manufacturing Dechlorinated Chloromethanes Using the Catalysts - Google Patents

Abstract

The present invention relates to a catalyst for methane dechlorination reaction and a method for producing dechlorinated methane chloromethane using the same, and provides a catalyst comprising titanium aluminate mixed oxide as the catalyst for methane dechlorination reaction. In addition, the present invention provides a method for producing dechlorinated methane chloromethane having a methane chloromethane conversion rate and a dechlorinated methane yield superior to those of a commercial metal catalyst using the catalyst.

Description

Titanium-aluminate mixed oxide catalyst for dechlorination of chloromethanes and the method for manufacturing dechlorinated chloromethanes using the catalysts

The present invention relates to a titanium-aluminate mixed oxide catalyst for a methane dechlorination reaction and a method for producing dechlorinated methane using the same, and more particularly, to a reaction catalyst that mediates the dechlorination reaction of methane containing two or more chlorines using a mixed oxide, and a method for producing dechlorinated methane using the same.

Recently, due to problems such as global climate change and supply and price instability due to international situations, attempts are being made to produce light olefins, which are raw materials for the chemical industry, from non-petroleum resources. As part of the above attempts, there is a method of using shale gas, which is attracting attention as an alternative resource for petroleum. The shale gas contains a lot of methane, so it can produce monochloromethane, a type of chlorinated hydrocarbon, through a chlorination method, and this is a method of producing light olefins through substitution reactions of monochloromethane, etc.

However, many attempts have been made to improve the conversion rate of methane and the selectivity and yield of monochloromethane by involving a reaction catalyst including a solid acid, zeolite, as in Korean Patent Publication No. 10-2019-0024122 (2019.03.08.) and Non-patent Documents 1 and 2, for producing monochloromethane through chlorination of the above methane. On the other hand, there have not been many attempts to convert monochloromethane, etc. by removing one or more chlorine from methane chloride substituted with two or more chlorine atoms, such as dichloromethane.

With respect to the reaction of removing one or more chlorines from the above-mentioned chloromethane substituted with one or more chlorines, Non-Patent Document 3 proposes a reaction pathway in which monochloromethane is generated through a disproportionation reaction of dichloromethane in the presence of γ-alumina. Since the disproportionation reaction is consumed by the reaction between the hydroxyl groups of alumina and dichloromethane under dry air, the activity thereof rapidly decreases, and therefore it is preferable to perform the reaction under air containing moisture in order to recover the activity through replenishment of the hydroxyl groups. As shown in FIG. 1 and Equation 1 showing the reaction pathway of monochloromethane proposed in Non-Patent Document 3, the hydrated alumina undergoes a dechlorination reaction with dichloromethane to form chloromethoxy, thereby ultimately generating monochloromethane.

(Formula 1)

2CH ₂ Cl ₂ + H ₂ O → CO + CH ₃ Cl + 3HCl

Inspired by this, the applicant of the present invention began to develop a titanium-aluminate mixed oxide catalyst for chloromethane dechlorination reaction, and completed the reaction catalyst of the present invention having chloromethane conversion rate, dechlorinated chloromethane selectivity, and yield better than commercial metal catalysts.

Korean Patent Publication No. 10-2019-0024122 (Published on March 8, 2019)

Catalysis Letters, 1992, 16, 27-38 (1992.06.22.) Solid State Sciences, 2018, 77, 74-80 (2018.01.31.) Journal of Catalysis, 2012, 291, 104-109 (2012.05.25.)

The present invention provides a catalyst including a titanium aluminate mixed oxide as a catalyst for a methane dechlorination reaction, and aims to provide a method for producing dechlorinated methane using the catalyst having a methane conversion rate and a selectivity and yield of dechlorinated methane superior to those of a commercial metal catalyst.

In order to solve the above problem, the titanium-aluminate mixed oxide catalyst for dechlorination of methane chloride substituted with two or more chlorines of the present invention has a composition represented by the following chemical formula 1, and is characterized by dechlorinating methane chloride substituted with two or more chlorines in the presence of air containing moisture, thereby converting it into methane chloride with a reduced number of chlorines.

[Chemical Formula 1]

Al _1-n Ti _n O _x

(In the above chemical formula 1, n is 0.2 to 0.8 and x is 1.5 to 2.0.)

The above methane chloride is methane containing two or more chlorine atoms, such as dichloromethane, chloroform, and carbon tetrachloride, and is preferably dichloromethane.

In another embodiment of the present invention, n in the chemical formula 1 is preferably 0.4 to 0.6, and more preferably 0.5.

The titanium-aluminate mixed oxide catalyst for dechlorination of methane chloride containing two or more chlorine atoms is characterized in that the chemical formula 1 has a composition of Al _0.5 Ti _0.5 O _x and has an amorphous form.

In one embodiment of the present invention, the titanium-aluminate mixed oxide catalyst for chloromethane dechlorination reaction containing two or more chlorine atoms may have a BET surface area measurement value of 50 to 400 m ² /g.

A method for producing dechlorinated methane chloride using a titanium-aluminate mixed oxide catalyst for methane chloride dechlorination containing two or more chlorine atoms, the method may include a first step of introducing the titanium-aluminate mixed oxide catalyst for methane chloride dechlorination under air containing moisture to dechlorinate a first reactant containing methane chloride containing two or more chlorine atoms to form a first reaction product containing dechlorinated methane chloride; and a second step of separating and recovering the dechlorinated methane chloride from the first reaction product.

In one embodiment of the present invention, the first step is performed in a gas phase, and the dechlorination reaction can be performed under a gas containing 0.1 to 20 v/v % of moisture.

In another embodiment of the present invention, the first stage dechlorination reaction space velocity (GHSV) may be 1,000 to 100,000 mL/g/h, and the methane chloride contained in the first reactant may be 100 to 20,000 ppm.

In another embodiment of the present invention, in the methane chlorine dechlorination reaction including two or more chlorine atoms in the first step, the reaction temperature may be 200 to 350°C and the pressure may be 0.1 to 2 bar when the reaction is carried out in a gas phase, and may be 10 to 30°C and 0.1 to 2 bar when the reaction is carried out in a liquid phase.

In another embodiment of the present invention, the method may further include a step of recycling unreacted compounds after separation of the dechlorinated methane chloride in the second step to the first step.

Meanwhile, a system for producing dechlorinated methane chloride may include a reactor having a titanium-aluminate mixed oxide catalyst for the dechlorination reaction positioned therein, an inlet for introducing a first reactant including methane chloride containing two or more chlorine atoms, and an outlet for flowing out of the reactor after the first reactant comes into contact with the catalyst; and a separator for separating dechlorinated methane chloride from an effluent from the reactor.

In one embodiment of the present invention, the system for producing dechlorinated methane chloride may further include a recirculator for returning the effluent after separation of dechlorinated methane chloride in the separator to the reactor.

In the titanium-aluminate mixed oxide catalyst for methane chlorodechlorination according to the present invention, the catalyst can improve the conversion of methane chlorode and the yield of dechlorinated methane chlorode compared to a commercial alumina catalyst in the dechlorination reaction of methane chlorode containing two or more chlorine atoms in the presence of air containing moisture by adjusting the ratio of aluminum and titanium metals constituting the catalyst and controlling the structure of the catalyst accordingly.

In addition, the method for producing dechlorinated methane chloride using the titanium-aluminate mixed oxide catalyst of the present invention can easily configure the process because the dechlorination reaction is performed by introducing the catalyst in the presence of air containing moisture, and continuously produces dechlorinated methane chloride by including a step of reintroducing an unreacted compound containing methane chloride into the initial reactant flow after the dechlorination reaction.

Figure 1 illustrates the reaction mechanism for producing monochloromethane, a type of dechlorinated methane, from dichloromethane, a type of methane chloro.
Figure 2 is a graph showing (a) the XRD pattern, (b) NH ₃ -TPD, and (c) pyridine FT-IR spectra according to the metal composition ratio of the mixed oxide catalyst.
FIG. 3 is a graph showing the conversion rate of methane and the selectivity and yield of monochloromethane according to the reaction temperature and the metal composition ratio of the mixed oxide catalyst as an example of the present invention.
FIG. 4 is a graph showing the conversion of dichloromethane and the selectivity and yield of monochloromethane of a commercial alumina catalyst and an Al _0.5 Ti _0.5 O _x mixed oxide catalyst according to reaction time as an example of the present invention.
FIG. 5 is a graph showing the production rate of monochloromethane according to the dichloromethane concentration and reaction temperature of an Al _0.5 Ti _0.5 O _x mixed oxide catalyst as an example of the present invention.
FIG. 6 is a graph showing the production rate of monochloromethane according to the concentration of moisture and dichloromethane contained in the air of an Al _0.5 Ti _0.5 O _x mixed oxide catalyst as an example of the present invention.

Hereinafter, the composition of the invention including preferred embodiments that can be easily carried out by a person having ordinary skill in the art to which the present invention belongs will be described in detail. In explaining the principles of preferred embodiments of the present invention in detail, if it is judged that a specific description of related known functions or configurations may unnecessarily obscure the gist of the present invention, such detailed descriptions will be omitted.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout this specification, whenever a part is said to “include” a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

The present invention relates to a catalyst for methane dechlorination, and the catalyst is characterized in that the conversion of methane and the yield of dechlorinated methane are superior to those of a commercial alumina catalyst in the dechlorination reaction of methane containing two or more chlorine atoms in the presence of air containing moisture by controlling the ratio of aluminum and titanium metals constituting the catalyst and thus controlling the structure of the catalyst.

The mixed oxide catalyst of the present invention mediates a dechlorination reaction resulting from a disproportionation reaction in the presence of air containing moisture, and can produce dechlorinated methane as a result of the reaction.

The mixed oxide catalyst mediating the dechlorination reaction is characterized by including a titanium-aluminate mixed oxide having a composition represented by the following chemical formula 1.

[Chemical Formula 1]

Al _1-n Ti _n O _x

(In the above chemical formula 1, n is 0.2 to 0.8 and x is 1.5 to 2.0)

The reactant in the dechlorination reaction mediated by the mixed oxide catalyst of the present invention is methane chloride, and dichloromethane, chloroform, carbon tetrachloride, etc. can be used.

The mixed oxide catalyst of the present invention can be manufactured in the form of a complex in which alumina (Al ₂ O ₃ ) and titania (TiO ₂ ) precursors are simultaneously oxidized and co-precipitated, or in the form of an alloy in which aluminum, titanium, and oxygen are irregularly or regularly arranged, in order to improve the catalytic activity compared to a catalyst containing only a metal oxide. In addition, it is preferable to manufacture the mixed oxide catalyst in the form of a complex having a porous structure that provides a wide reaction area from the viewpoint of a dechlorination reaction catalyst.

The method for producing a mixed oxide catalyst using the above alumina and titania precursors can use a known method for producing a multi-component mixed oxide, such as a sol-gel method or a co-precipitation method, and preferably, the sol-gel method can be used.

In the chemical formula 1 above, n is the number of moles of titanium included in the catalyst structure of the present invention, expressed as a composition ratio, and the value of n is in the range of 0.2 to 0.8, preferably in the range of 0.4 to 0.6, and more preferably has a value of 0.5. When n is less than 0.2 or more than 0.8, the conversion rate of methane chloride in the dechlorination reaction may decrease.

The composition of aluminum and titanium affects the structure, surface area, acid sites, and strength of acid sites of the mixed oxide catalyst, and is directly related to the conversion of reactants, selectivity of reaction products, and yield in the dechlorination reaction of methane chlorination by the catalyst. Therefore, it is most important to identify the composition with optimal characteristics in the mixed oxide catalyst.

The above mixed oxide catalyst is amorphous and/or crystalline, preferably has an amorphous form, and has a BET surface area measurement value of 50 to 400 m ² /g.

In addition, the present invention can provide a method for producing dechlorinated methane chloride through a dechlorination reaction using the titanium-aluminate mixed oxide catalyst for the methane chloride dechlorination reaction.

A method for producing dechlorinated methane chloride using the mixed oxide catalyst of the present invention is characterized by including a first step of contacting a first reactant including methane chloride with the catalyst in a liquid or gaseous state in the presence of moisture to perform a dechlorination reaction, thereby forming a first reaction product including dechlorinated methane chloride; and a second step of separating and recovering the dechlorinated methane chloride from the first reaction product. After the second step, a step of recycling an unreacted compound from which the dechlorinated methane chloride is separated to the first step may be further included.

The dechlorination reaction of the first step is carried out in a reactor constituting a reaction system, and the reactor is not particularly limited in its form or type, and for example, a fluidized bed reactor or a fixed bed reactor capable of continuously introducing reactants or transporting reaction products to another location may be used. In addition, the reaction may be carried out in a liquid phase or a gas phase, and preferably, it may be carried out in a gas phase.

When the above reaction proceeds in the gas phase, the first step is a dechlorination reaction under a gas containing 0.1 to 20 v/v% of moisture, and preferably, the dechlorination reaction is performed under a gas containing 2 to 6.5 v/v% of moisture. When the moisture content is less than 0.1 v/v%, the dechlorination reaction may not occur sufficiently, and when it exceeds 10 v/v%, the production rate of the dechlorinated methane chloride, which is a reaction product, may decrease.

In the first-stage dechlorination reaction, the space velocity (GHSV) is 1,000 to 100,000 mL/g/h, and the amount of methane chloride substituted with two or more chlorines contained in the first reactant is 100 to 20,000 ppm, preferably, the space velocity is 5,000 to 50,000 mL/g/h, and the amount of methane chloride substituted with two or more chlorines is 1,000 to 15,000 ppm. When the amount of methane chloride as the first reactant is less than 100 ppm, the dechlorination reaction does not sufficiently occur, and when it exceeds 20,000 ppm, the efficiency of the dechlorination reaction may decrease.

In the above-mentioned gas-phase reaction, when the first step of the methane chlorine dechlorination reaction proceeds in the gas phase, the reaction temperature is 200 to 350°C. When the reaction temperature is less than 200°C, the dechlorination reaction of the present invention hardly proceeds, resulting in a very low yield. When the temperature exceeds 350°C, the selectivity and yield of the dechlorinated methane chlorine may actually decrease compared to commercial alumina. When the dechlorination reaction proceeds in the liquid phase, the reaction temperature may proceed in the range of 10 to 30°C.

The second step is a step of separating dechlorinated methane chloride produced from the dechlorination reaction of methane chloride substituted with two or more chlorines in the first step.

The separation of the above dechlorinated methane chloride is performed by a separator, and the separator is not limited to the separation process method or the number of detailed processes as long as separation of components of the first reaction product is performed.

The unreacted methane chloride separated in the above separator can be recycled to the first stage, and a known gas flow conveying process can be used as the recycling method.

In addition, the present invention provides a system for producing dechlorinated methane chloride from methane chloride, characterized in that it comprises a reactor in which the titanium-aluminate mixed oxide catalyst for methane chloride dechlorination of the present invention is positioned in an internal space, and which includes an inlet for introducing a reactant including methane chloride substituted with two or more chlorines, and an outlet for flowing the reactant out of the reactor after contacting the catalyst; and a separator for separating dechlorinated methane chloride from an effluent from the reactor. The system may further include a recirculator for returning an effluent of the separated dechlorinated methane chloride to the reactor.

The above reactor may be a fixed bed or fluidized bed reactor, and the separator may use one or more of the separators known to date in the technical field to which the present invention belongs.

Hereinafter, the details of the process of the present invention will be explained through examples, comparative examples, and experimental examples. These are representative examples related to the present invention, and the scope of application of the present invention is not limited thereby.

<Example 1>

15.4 g of aluminum-tri-sec-butoxide (97%, sigma-aldrich), an alumina precursor, is added to 118.1 mL of a mixture of propan-2-ol (99.5%, sigma-aldrich) and acetylacetone (>99%, sigma-aldrich) at room temperature so that the composition ratio (mole ratio) of alumina to the total metal in the mixed oxide catalyst becomes 0.5, and then 18.0 g of titanium(IV) isopropoxide (97%, sigma-aldrich), a titania precursor, is added to the mixture to prepare a sol-state mixed oxide aqueous solution. A 0.5 M HNO ₃ aqueous solution is gradually added to gel the sol-state mixed oxide aqueous solution. The above gelled mixed oxide aqueous solution is dried at room temperature for 2 days and then pulverized to obtain a mixed oxide powder. The powder is calcined at 600°C for 5 hours to obtain a titanium-aluminate mixed oxide catalyst (Al _0.5 Ti _0.5 O _x ) for methane chlorination dechlorination having an alumina composition ratio of 0.5.

<Comparative examples 1 to 4>

In the above Example 1, alumina and titania precursors are added so that the composition ratio (mole ratio) of alumina to the total metal in the mixed oxide catalyst becomes 0.0, 0.2, 0.8, or 1.0, respectively, to obtain a titanium-aluminate mixed oxide catalyst for methane dechlorination (Al _0.0 Ti _1.0 O _x , Al _0.2 Ti _0.8 O _x , Al _0.8 Ti _0.2 O _{x ,} Al _1.0 Ti _0.0 O _x ).

<Experimental Example 1>

XRD crystal structure analysis was performed on the titanium-aluminate mixed oxide catalysts of Example 1 and Comparative Examples 1 to 4, and the results are shown in Fig. 2(a).

<Experimental Example 2>

NH ₃ -TPD analysis was performed on the titanium-aluminate mixed oxide catalysts of Example 1 and Comparative Examples 1 to 4, and the results are shown in Fig. 2(b).

<Experimental Example 3>

Pyridine FT-IR analysis was performed on the titanium-aluminate mixed oxide catalysts of Example 1 and Comparative Examples 1 to 4, and the results are shown in Fig. 2(c).

<Experimental Example 4>

A gas containing 35.1 g/m ³ of moisture (He 90 to 99 v/v%) corresponding to 5 v/v% and 5,000 ppm of dichloromethane, a type of methane chloride, was supplied to a reactor charged with 600 mg of the titanium-aluminate mixed oxide catalysts of Example 1 and Comparative Examples 1 to 4 at a gas space velocity (GHSV) of 10,000 mL/g/h, and then the dechlorination reaction was performed in the gas phase at 200 to 400°C. The conversion of dichloromethane, the selectivity and the yield of monochloromethane, a dechlorination reaction product, depending on the reaction temperature and the metal composition ratio of the mixed oxide catalyst from the dechlorination reaction are shown in FIG. 3.

The conversion of dichloromethane, selectivity and yield of monochloromethane were calculated according to Equation 2 below.

(Formula 2)

<Experimental Example 5>

Example 1 (Al _0.5 Ti _0.5 O _x ) and Comparative Example 3 (Al ₂ O ₃ ) were charged with 600 mg of titanium-aluminate mixed oxide catalysts for chloromethane dechlorination, and a gas containing 35.1 g/m ³ of moisture (He 90 to 99 v/v%) corresponding to 5 v/v% and 5,000 ppm of dichloromethane, a type of methane chlorochloride, were supplied at a gas space velocity (GHSV) of 10,000 mL/g/h, and then a dechlorination reaction was performed with the mixed oxide catalyst at 340°C for 250 minutes. The conversion of dichloromethane, and the selectivity and yield of monochloromethane according to the reaction time from the dechlorination reaction are shown in FIG. 4.

<Experimental Example 6>

Example 1 (Al _0.5 Ti _0.5 O _x ) Dechlorination of Monochloromethane A titanium-aluminate mixed oxide catalyst was charged to a reactor, and a gas containing 35.1 g/m ³ of moisture (He 90 to 99 v/v%) corresponding to 5 v/v% and 2,500 to 10,000 ppm of dichloromethane, a type of methane chloromethane, were supplied at a gas space velocity (GHSV) of 60,000 mL/g/h, and then the dechlorination reaction was performed at 280, 290, 300, 310, or 320°C with the mixed oxide catalyst, respectively. The production rate of monochloromethane depending on the dichloromethane concentration and reaction temperature is shown in FIG. 5.

<Experimental Example 7>

Example 1 (Al _0.5 Ti _0.5 O _x ) and Comparative Example 3 (Al ₂ O ₃ ) were charged with 100 mg of titanium-aluminate mixed oxide catalysts for chloromethane dechlorination, and a gas containing 14.0 to 45.6 g/m ³ of moisture (He 90 to 99 v/v%) corresponding to 2, 3.5, 5, or 6.5 v/v%, respectively, and 2,500, 5,000, 7,500, or 10,000 ppm of dichloromethane, a type of methane chlorohydrate, was supplied at a gas space velocity (GHSV) of 10,000 mL/g/h, and then a dechlorination reaction was performed with the mixed oxide catalyst at 300°C. The production rate of monochloromethane according to the moisture concentration and dichloromethane concentration contained in the air is shown in FIG. 6.

<Analysis>

Referring to FIG. 3, Example 1 (Al _0.5 Ti _0.5 O _x ) has the highest conversion rate of dichloromethane over the entire reaction rate compared to other examples and comparative examples, and the yield of monochloromethane of Example 1 is also the highest in the relatively low temperature range of 340° C. or lower for the reaction rate.

Also, referring to FIG. 4, it can be confirmed that the selectivity of monochloromethane in Example 1 is at a level equal to or lower than that of commercial alumina in Example 3, but the conversion rate of dichloromethane is about twice as high, so the yield is also nearly twice as high.

The mixed oxide catalyst of the present invention is expected to have a higher conversion rate of reactants, yield of reaction products, etc., when added to a methane chlorodechlorination reaction, compared to a commercial metal oxide catalyst, and in particular, it is thought that the utility of the catalyst will be maximized when the composition ratio of aluminum constituting the catalyst is 0.5.

While the specific parts of the present invention have been described in detail above, it will be apparent to those skilled in the art that such specific descriptions are merely preferred embodiments and that the scope of the present invention is not limited thereby. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (12)

A titanium-aluminate mixed oxide catalyst for dechlorination of methane chlorine substituted with two or more chlorines, characterized in that it converts methane chlorine substituted with two or more chlorines into dechlorinated methane chlorine in the presence of air containing moisture, and has a composition represented by the following chemical formula 1.
[Chemical Formula 1]
Al _1-n Ti _n O _x
(In the above chemical formula 1, n is 0.2 to 0.8 and x is 1.5 to 2.0.)
In the first paragraph,
A titanium-aluminate mixed oxide catalyst for methane chlorination reaction, characterized in that the methane chloride is dichloromethane.
In the first paragraph,
A titanium-aluminate mixed oxide catalyst for methane dechlorination reaction, characterized in that in the above chemical formula 1, n is 0.4 to 0.6.
In the first paragraph,
The titanium-aluminate mixed oxide catalyst for the above-mentioned methane dechlorination reaction is a titanium-aluminate mixed oxide catalyst for the above-mentioned methane dechlorination reaction, characterized in that the chemical formula 1 has a composition of Al _0.5 Ti _0.5 O _x and has an amorphous form.
In the first paragraph,
The titanium-aluminate mixed oxide catalyst for the above-mentioned methane dechlorination reaction is a titanium-aluminate mixed oxide catalyst for the methane dechlorination reaction, characterized in that the BET surface area measurement value is 50 to 400 m ² /g.
A method for producing dechlorinated methane chloride using a titanium-aluminate mixed oxide catalyst for methane chloride dechlorination according to any one of claims 1 to 5,
A first step of contacting a titanium-aluminate mixed oxide catalyst for the methane chlorodechlorination reaction with a first reactant including methane chlorodeoxygenated by two or more chlorines in a liquid or gaseous state in which moisture is present, thereby performing the methane chlorodechlorination reaction and forming a first reaction product including dechlorinated methane chlorodeoxygenated; and
A second step of separating and recovering dechlorinated methane chloride from the first reaction product;
A method for producing dechlorinated methane chloride, characterized by comprising:
In Article 6,
A method for producing dechlorinated methane chloride, characterized in that the first step is carried out in the gas phase and the dechlorination reaction is performed under a gas containing 0.1 to 20 v/v% of moisture.
In Article 6,
A method for producing dechlorinated methane chloride, characterized in that in the first-stage dechlorination reaction, the space velocity (GHSV) is 1,000 to 100,000 mL/g/h, and the amount of methane chloride substituted with two or more chlorines included in the first reactant is 100 to 20,000 ppm.
In Article 6,
A method for producing dechlorinated methane chloride, characterized in that in the first step of the methane chloride dechlorination reaction, the reaction temperature in the gas phase is 200 to 350°C, and the reaction temperature in the liquid phase is 10 to 30°C.
In Article 6,
A method for producing dechlorinated methane chloride, characterized in that it further comprises a step of recycling an unreacted compound containing methane chloride to the first step after separating the dechlorinated methane chloride in the second step.
A reactor comprising a titanium-aluminate mixed oxide catalyst for methane chlorination according to any one of claims 1 to 5, an inlet for introducing a first reactant including methane chlorine substituted with two or more chlorines, and an outlet for flowing out of the reactor after the first reactant comes into contact with the catalyst;
A system for producing dechlorinated methane chloride, characterized by comprising a separator for separating dechlorinated methane chloride from the effluent from the reactor.
In Article 11,
A system for producing dechlorinated methane chloride, characterized in that it further includes a recirculator for returning the effluent after separation of dechlorinated methane chloride in the separator to the reactor.