KR20100044390A - Catalyst for synthesizing ethylene dichloride and method for preparing ethylene dichloride - Google Patents

Abstract

PURPOSE: A catalyst for synthesizing ethylene dichloride using the reaction of ethylene and chlorine and a manufacturing method of the ethylene dichloride using thereof are provided to obtain the ethylene dichloride with the excellent yield. CONSTITUTION: A catalyst for synthesizing ethylene dichloride using the reaction of ethylene and chlorine is selected from the group consisting of a selenium tetravalent compound and a phosphorus pentavalent compound. The selenium tetravalent compound is SeCl_4 and the phosphorus pentavalent compound is PCl_5. The concentration of the catalyst for manufacturing the ethylene dichloride is 0.06~1.0%. 0.6~1% of oxygen is injected during the reaction of the ethylene and the chlorine under the presence of a solvent which is the ethylene dichloride.

Description

Catalyst for Synthesizing Ethylene Dichloride And Method For Preparing Ethylene Dichloride

The present invention relates to a catalyst used to prepare ethylene dichloride by direct reaction of ethylene and chlorine and to a process for producing ethylene dichloride prepared using the catalyst.

The process for producing ethylene dichloride can be classified into a direct chlorine method by the reaction of ethylene and chlorine and a chlorine oxide method by the reaction of ethylene, hydrogen chloride and air.

The process for producing ethylene dichloride by the direct chlorine method is mainly the reaction of ethylene and chlorine in a liquid medium. At this time, the lower half of the reactor in the form of a reaction column is filled with a solvent such as ethylene dichloride in advance, and in such a state, ethylene and chlorine are supplied in the form of a mixed gas or separately from the bottom of the reaction column. Ethylene and chlorine fed from the bottom are dissolved in the solvent and react to produce ethylene dichloride.

Although the process of preparing such ethylene dichloride can be performed without a catalyst, it is preferable to use a catalyst to increase the conversion of ethylene and the selectivity of ethylene dichloride, that is, to increase the yield of ethylene dichloride. FeCl ₃ has conventionally been used as such catalyst. When the FeCl ₃ catalyst is used, the yield of ethylene dichloride is improved as compared with the case where no catalyst is used, but the improvement in yield is not sufficiently satisfactory. Therefore, there is a need for a catalyst that can further improve the yield of ethylenedichloride.

Therefore, the present invention is to solve the above problems of the prior art, an object of the present invention is a catalyst used to produce ethylene dichloride by the reaction of ethylene and chlorine, it is possible to greatly improve the yield of ethylene dichloride It is an object to provide a catalyst.

It is also an object of the present invention to provide a method for producing ethylene dichloride in which the yield of ethylene dichloride is greatly improved by using the catalyst of the present invention described above.

It is also an object of the present invention to provide a method for producing ethylene dichloride which can further improve the yield of ethylene dichloride by injecting a small amount of air while using the catalyst of the present invention or the conventional catalyst described above.

The present invention provides a catalyst used to prepare ethylenedichloride by reaction of ethylene and chlorine. The catalyst according to the invention is selected from the group consisting of Se tetravalent compounds and P pentavalent compounds. In particular, the Se tetravalent compound may be SeCl ₄ , The P pentavalent compound may be PCl ₅ .

The present invention also provides a method for producing ethylene dichloride by the reaction of ethylene and chlorine using the catalyst described above. This reaction is carried out in the presence of a solvent, in particular using ethylenedichloride as the solvent. It is preferable that the density | concentration of the said catalyst is 0.06 to 1.0%, and it is preferable to further inject | pour oxygen at the concentration of 0.6-1% in the said reaction.

In another aspect, the present invention is a method for producing ethylene dichloride by the reaction of ethylene and chlorine using a catalyst, characterized in that the reaction is carried out in the presence of oxygen in a concentration of 0.6 ~ 1% To provide.

The present invention makes it possible to obtain ethylene dichloride in excellent yields by using Se tetravalent compounds, in particular SeCl ₄ or P pentavalent compounds, in particular PCl ₅ , as catalysts for producing ethylene dichloride by the reaction of ethylene and chlorine. In addition, the present invention can be obtained by using the catalyst of the present invention described above or by using a conventional catalyst by additionally adding a specific concentration of oxygen to perform the above-described reaction to obtain ethylene dichloride in an improved yield.

The present invention provides Se tetravalent compounds, in particular SeCl ₄ or P pentavalent compounds, in particular PCl ₅ , as catalysts for the preparation of ethylenedichloride by the reaction of ethylene and chlorine.

The Se tetravalent compound as the catalyst of the present invention is not particularly limited as long as it is a tetravalent compound of Se, but inorganic materials are preferred. Examples of such Se tetravalent compounds include SeO ₂ , SeCl ₄ , SeBr ₄ , Se (CO ₃ ) ₄ , and the like, with SeCl ₄ being preferred.

The P pentavalent compound, which is the catalyst of the present invention, is not particularly limited as long as it is a pentavalent compound of P number, but an inorganic substance is preferable. Examples of such P pentavalent compounds include PCl ₅ , P ₂ O ₅ , P (CO ₃ ) ₅ , and the like, with PCl ₅ being preferred.

The present invention also provides a process for the preparation of ethylene dichloride using the catalyst described above.

The process of the invention is preferably a reaction of ethylene and chlorine in a liquid medium. At this time, the lower half of the reactor in the form of a reaction column is filled with a solvent such as ethylene dichloride in advance, and in such a state, ethylene and chlorine are supplied in the form of a mixed gas or separately from the bottom of the reaction column. Ethylene and chlorine fed from the bottom are dissolved in the solvent and react to produce ethylenedichloride.

In such a reaction of the present invention, the concentration of the catalyst is preferably 0.06 to 1.0%. The catalyst acts in a dissolved or suspended state in the liquid medium, and when the concentration of the catalyst is too low, it is difficult to substantially expect the catalytic activity, and when it is too high, the degree of improvement of the catalyst activity due to the concentration increase becomes small. Therefore, the above range can be said that the catalyst can be substantially active and can be used economically.

It is preferred that the above liquid medium or solvent is ethylenedichloride. At this time, the ethylene dichloride produced by the reaction may be continuously or intermittently recovered from the reactor in which the reaction occurs, so that the production of ethylene dichloride may be continuously performed while maintaining almost constant reaction conditions. At this time, when the concentration of the catalyst is lowered due to the production of ethylene dichloride, the addition of additional catalyst can be made continuously or intermittently.

The reaction is preferably carried out at a temperature of 100 ~ 140 ℃, especially about 120 ℃ and at a pressure of 1 to 10 atm, especially about 3 atm.

On the other hand, the reaction is preferably carried out in the presence of oxygen of 0.6 ~ 1% concentration. This addition of oxygen serves to further improve the yield of ethylenedichloride. Thus, this additional input of oxygen can be applied not only to the method using the catalyst of the present invention but also to the method using the conventional catalyst. If the concentration of oxygen introduced is too low, the practical effect is insignificant, and in too many cases, the effect saturation occurs and the degree of further improvement is insignificant.

Hereinafter, the specific Example which concerns on this invention is illustrated below. Since these embodiments are merely illustrative of the present invention, it is obvious that the scope of the present invention should not be understood as being limited by these embodiments.

Example

Example 1

Ethylene and chlorine were injected into a reactor 50 ml high pressure reactor to analyze the conversion of ethylene and the selectivity of the resulting ethylene dichloride (EDC).

The screen test of the catalyst showed that SeCl ₄ showed the highest conversion and selectivity, and the concentration of SeCl ₄ was 0.06 ~ 0.1%.

Table 1. Activity by catalyst

catalyst Ethylene Conversion (%) Ethylenedichloride Selectivity (%) Ethylenedichloride Yield (%) Tetrachloroethlylene 63 91 57.33 Hexachloro-1,3-butadien 64 91 58.24 POCl ₃ 63 88 55.44 PCl ₃ 66 86 56.76 PCl ₅ 67 94 62.98 Benzene 64 90 57.6 SeCl ₄ 72 95 68.4

Comparative Example 1

The conventionally used catalyst FeCl ₃ was used in the same manner as in Example 1 to measure the conversion and selectivity, which was compared with that of SeCl ₄ .

Table 2. Comparison of Catalytic Activity of SeCl ₄ and FeCl ₃

catalyst Ethylene Conversion (%) Ethylenedichloride Selectivity (%) Ethylenedichloride Yield (%) SeCl ₄ 72 95 68.4 FeCl ₃ 67 92 61.64

 Comparative Example 2

The conversion and selectivity were measured in the same manner as in Example 1 except that no catalyst was used, which was compared with that of SeCl ₄ .

Table 3. SeCl ₄ vs. Noncatalytic Activity

catalyst Ethylene Conversion (%) Ethylenedichloride Selectivity (%) Ethylenedichloride Yield (%) No catalyst 65 91 59.15 SeCl ₄ 72 95 68.4

When the catalyst is injected with 0.6 ~ 1% oxygen, the conversion and selectivity increase.

[Example 2]

The conversion and selectivity were measured in the same manner as in Example 1, except that oxygen of 0.6-1% concentration was additionally added. This is shown in the table below.

Example 3

The conversion and selectivity were measured in the same manner as in Example 1, except that an additional amount of oxygen of 0.6-1% and FeCl ₃ used as a catalyst were used. This is shown in the table below.

Table 4. Activity comparison with additional input of oxygen

catalyst Ethylene Conversion (%) Ethylenedichloride Selectivity (%) Ethylenedichloride Yield (%) O ₂ / SeCl ₄ 75 93 69.7 O ₂ / FeCl ₃ 70 93 65.1 FeCl ₃ 67 92 61.64

From the above results, it was confirmed that SeCl ₄ and PCl ₅ catalyst according to the present invention improved the ethylene dichloride yield than other catalysts, especially FeCl ₃ catalyst used in the prior art, and also the catalyst according to the present invention or the conventional catalyst In addition to the use of additionally, it was confirmed that the ethylene dichloride yield was further improved when oxygen was added to the reaction medium (solvent) at a specific concentration.

Claims (10)

A catalyst for synthesizing ethylenedichloride by the reaction of ethylene and chlorine, characterized in that it is selected from the group consisting of Se tetravalent compound and P pentavalent compound. The method of claim 1, Wherein said Se tetravalent compound is SeCl ₄ and said P pentavalent compound is PCl ₅ . In the method for producing ethylene dichloride by the reaction of ethylene and chlorine, Method for producing ethylene dichloride, characterized in that the catalyst selected from the group consisting of Se tetravalent compound and P pentavalent compound as the catalyst for the reaction. The method of claim 3, The Se tetravalent compound is SeCl ₄ , The P pentavalent compound is a method of producing ethylene dichloride, characterized in that the PCl ₅ . The method of claim 3, Method for producing ethylene dichloride, characterized in that the concentration of the catalyst is 0.06 ~ 1.0%. The method of claim 3, Method for producing ethylene dichloride, characterized in that further injecting oxygen at a concentration of 0.6 ~ 1% in the reaction. The method of claim 3, Process for producing ethylene dichloride, characterized in that the reaction is carried out in the presence of a solvent. The method of claim 7, wherein The solvent is ethylene dichloride, and the production of ethylene dichloride is continuously carried out by continuously or intermittently removing the resulting ethylene dichloride from the reactor in which the reaction takes place. The method of claim 8, The reaction is carried out at a temperature of 100 ~ 140 ℃ and a pressure of 1 ~ 10 atm, ethylene and chlorine in the reactor is injected from the bottom of the reactor, respectively, dissolved in the solvent to proceed with the ethylene di Method for preparing chloride. In the process for producing ethylene dichloride by reaction of ethylene and chlorine in the presence of a catalyst, The reaction is a method for producing ethylene dichloride, characterized in that carried out in the presence of 0.6 ~ 1% oxygen.