JPH0568453B2 - - Google Patents

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention provides an industrially advantageous method for producing ethane dichloride by reacting ethylene and chlorine in a liquid reaction medium containing ethane dichloride as a main component. It is related to.

[Conventional technology]

Ethane dichloride is useful as a monomer for vinyl chloride or as a raw material for ethylenediamine and the like. One of the biggest problems when producing dichloroethane industrially by reacting ethylene and chlorine is that 1,1,2-
Higher chlorinated products such as trichloroethane are produced as by-products. When ethane dichloride is supplied as a raw material for vinyl chloride monomer, etc., a large amount of thermal energy is required in a distillation column for purifying and removing higher chlorinated compounds. Moreover, if there is a large amount of by-products of higher-order chlorides, raw materials will be lost, which is economically undesirable.

There are two methods for producing ethane dichloride by reacting ethylene and chlorine in a liquid reaction medium: a low-temperature method in which the reaction is carried out below the boiling point of ethane dichloride, that is, below 83°C, and a high-temperature method in which the reaction is carried out above 83°C. is known. Among these, the low-temperature method has the advantage of producing fewer higher-order chloride by-products than the high-temperature method.
The reaction is exothermic and generates a huge amount of heat of reaction, approximately 50 Kcal/mol, but the low temperature method not only cannot effectively utilize this heat of reaction, but also removes the heat of reaction. The disadvantage is that it requires special means such as cooling water and a heat exchanger. In addition, in the low-temperature method, it is necessary to separate and take out the product from the liquid reaction medium, and metal chloride catalysts such as ferric chloride flow out with the product, so the catalyst concentration in the reactor must be kept constant. Therefore, there are drawbacks such as the need to add a catalyst.

On the other hand, the high-temperature method is an advantageous method for solving the drawbacks of the above-mentioned low-temperature method, and many proposals have been made. For example, in the method described in US Pat. No. 2,929,852 or British Patent No. 1,231,127, the reaction is carried out with the reaction medium boiling at around 83°C, which is the boiling point of ethane dichloride, and the reaction liquid medium is evaporated. Since the heat of reaction can be removed by heating, there is no need for special cooling means, and the steam generated by the heat of reaction is directly guided to the distillation column to purify ethane dichloride, making effective use of the heat of reaction. are doing. Further, since the product is taken out as vapor, it is easy to separate it from the metal chloride catalyst contained in the reaction medium, and there are advantages such as no need to add a catalyst. The biggest problem with the high temperature method is that higher chlorinated products such as 1,1,2-trichloroethane are produced as by-products, and as a result, the amount of hydrochloric acid generated increases. If there are many by-products of higher chlorides, not only will there be a loss due to a decrease in the yield of ethane dichloride, but also a large amount of alkali will be consumed to neutralize the hydrochloric acid generated at the same time.

Conventionally, methods to advantageously produce dichloroethane by suppressing the by-product of higher chlorides while utilizing the advantages of a high-temperature method have included adding additives, the shape of an appropriate reactor, and the like. Methods of selecting reaction operating conditions are known. As a method of adding additives, there is a method of adding oxygen described in British Patent No. 1186742, but it is not recommended for safety reasons because the oxygen concentration in the gas discharged from the reactor increases and there is a risk of an explosive composition. requires special handling. In addition, Japanese Patent Publication No. 58-50203 proposes a method of adding benzene, and Japanese Patent Publication No. 56-40620 proposes that a method of adding cresol is effective for suppressing byproducts, but these methods do not require continuous or Disadvantages include the need for intermittent supply of additives and the inclusion of these substances in the product. Next, among the methods of suppressing the by-product ratio by changing the shape of the reactor and operating conditions,
The method of 57906 uses a two-stage method, in which about 17% of the reaction is carried out using a high-temperature method and the rest is carried out using a low-temperature method, which has the disadvantages that the amount of reaction heat that can be used effectively is small and that the reaction equipment becomes very complex. . Also, JP-A-48
-405 describes the idea that a side reaction occurs in the bubbles formed by the vapors of the raw materials ethylene, chlorine, and dichloroethane.
Based on this idea, we have proposed a method in which a liquid reaction medium is circulated by connecting it to an external circuit equipped with a heat exchanger, and dispersed into small bubbles. Japanese Patent Publication No. 58-46489 also describes a method of suppressing the bubbles of dichloride ethane vapor in the reaction section by using a liquid circulation type reactor to circulate the liquid based on the principle of air lift. Furthermore, Japanese Patent Publication No. 46-3363 proposes a method in which a filler is charged in order to disperse and dissolve gas bubbles in the raw material gas. Looking at these examples of high-temperature methods, all of them target the reaction temperature at the boiling point of ethane dichloride at normal pressure, that is, around 83°C, and even at high temperatures, the temperature is up to 110°C. From the standpoint of saving energy by effectively utilizing the reaction heat, the higher the reaction temperature, the more effective heat utilization becomes. Heat can be utilized more advantageously by recovering heat through a heat exchanger, without being limited to the method used as energy for refining ethane dichloride. However, in the above conventional method, increasing the reaction temperature increases by-products such as 1,1,2-trichloroethane, which is economically disadvantageous.

[Problem that the invention seeks to solve]

The present inventors solved the problems of the conventional method as described above, suppressed by-products at reaction temperatures of 110°C or higher, and produced dichloroethane with a higher reaction yield than the conventional method even at 110°C or lower. As a result of intensive studies aimed at perfecting the method, we found that lowering the concentration of chlorine dissolved in the reaction liquid medium has a great effect in suppressing the by-product of higher chlorides. Heading The invention has been completed.

In the conventional method, chlorine and ethylene are introduced from the bottom of the reactor containing the reaction liquid medium, and the chlorine rapidly dissolves in the reaction liquid medium, causing ethylene bubbles to rise due to buoyancy. However, a state is formed in which the mixture gradually dissolves and reacts. Therefore, the concentration of dissolved chlorine in the vicinity of where chlorine is supplied becomes significantly high. If the reaction is carried out in a state where the concentration of dissolved chlorine is high, the production of ethane dichloride will be accelerated, and at the same time, the higher order chlorination reaction will be further promoted, resulting in an increase in the proportion of by-products. In the conventional low temperature method, the maximum dissolved chlorine concentration is 1000~
The reaction was carried out at 10000wt ppm, but
In the high-temperature method, the rate of production of higher-order chlorides increases, so it is preferable that the dissolved chlorine concentration is 1000 wt ppm or less. Among the conventional methods, JP-A-48-405
Alternatively, if you use a liquid circulation type reactor such as that used in Japanese Patent Publication No. 58-46489, dissolved chlorine can be diluted by the liquid circulation and the concentration can be lowered. In order to lower the dissolved chlorine concentration, it is necessary to increase the circulation flow rate of the liquid. However, when the circulation flow rate of the liquid increases, it is disadvantageous because the amount of unreacted ethylene and chlorine discharged from the reactor increases. In addition, in the method of Japanese Patent Publication No. 46-3363, the bubbles are broken down into small pieces and dissolved quickly by using a packing material, but since the packing material prevents mixing of liquids, it is not possible to reduce the concentration of dissolved chlorine. .

The point of view of the present invention is that by dividing the supply of chlorine into multiple stages, the dissolved chlorine concentration can be lowered compared to the conventional case of supplying from one place. The present invention provides a method that can significantly lower the dissolved chlorine concentration compared to conventional methods and thereby suppress by-products, and the by-product ratio remains low even when the reaction is carried out at a high temperature of 110°C or higher. It is possible to achieve the remarkable effect of reducing

[Means for solving problems]

That is, the present invention provides a method for producing ethane dichloride by reacting ethylene and chlorine in a reaction liquid medium containing ethane dichloride as a main component. This method of producing ethane dichloride is characterized in that at least two or more locations are provided and chlorine is dividedly supplied to each location. The details will be explained below.

In the lower part of the reactor containing the reaction liquid medium,
First, the first chlorine is introduced. The first amount of chlorine can range from 1 to 99% of the total amount of chlorine supplied, preferably from 20 to 50%. The second chlorine is introduced above the first chlorine introduction position at a position where most of the first chlorine reacts and the dissolved chlorine concentration is low.
The second chlorine introduction position can be determined appropriately by measuring the concentration of dissolved chlorine, but usually the first
~20cm after the first introduced chlorine starts the reaction
Preferably above 200cm. Chlorine supply 3
If more than one division is required, they are introduced one after another in the same manner at positions above the second introduction position. Preferably, it can be divided into 2 to 5 parts. The ratio of dividing chlorine can be approximately equally divided, but it can also be determined appropriately by measuring the dissolved chlorine concentration.

Ethylene is fed in its entirety at the bottom of the reactor, below the second chlorine introduction point. 1st
It is preferable that the position is above the second chlorine introduction position and below the second chlorine introduction position,
It can also be supplied below the first chlorine introduction position. It is also possible to supply a portion of the ethylene from another location.

The chlorine divided into each position can be introduced using a porous pipe type blowing port, but in this case, it is introduced by branching into multiple blowing pipes in the radial direction of the reactor column. You can also do that.

By such a method of dividing chlorine supply according to the present invention, the concentration of dissolved chlorine in the liquid reaction medium can be lowered, and the by-product of higher chlorinated products can be significantly suppressed.

In the present invention, the amounts of ethylene and chlorine supplied to the reactor can be in the range of 1 to 1000 Ncm ³ /cm ² /sec per unit cross-sectional area of the reactor. The total amount of ethylene and total amount of chlorine supplied to the reactor can be in excess of either one, but
Excess components are discharged unreacted and result in a loss of raw materials, or equipment is required to recover unreacted components, so the ethylene/chlorine molar ratio is preferably in the range of 0.9 to 1.2, more preferably 1.00 to 1.01. It can be done.

In the present invention, the reaction can be carried out in a temperature range from room temperature to 180°C. As the reaction temperature increases, the saturated vapor pressure of the reaction liquid medium increases and the operating pressure of the reactor increases;
A temperature range below 0.degree. C. is preferred. In the low temperature range of 83°C or lower, the reaction can be carried out while removing the reaction heat by installing a heat exchanger in the reactor, but when the reaction is carried out at 83°C or higher, the reaction liquid medium may evaporate. The heat of reaction can be removed by the method and many of the advantages of the high temperature method described above can be exploited. The pressure inside the reactor is the pressure at which the upper liquid level of the reaction liquid medium boils or higher, and is in the range of normal pressure to 10 kg/cm ² G.

In the present invention, known metal chlorides can be used as catalysts for this reaction, typically ferric chloride. The concentration of ferric chloride present in the reaction liquid medium can range from 1 to 5000 wt ppm, but in the low temperature process it may range from 10 to 100 wt ppm.
ppm, preferably in the range of 20 to 700 wt ppm in the high temperature method. If the ferric chloride concentration is too low, the rate of by-product of 1,1,2-trichloroethane will increase.

In the present invention, oxygen can be added together with the feedstock in order to suppress the by-product rate of higher chlorides. The amount of oxygen is relative to the amount of chlorine supplied.
It can be in the range of 0.1-5%. In order to increase the effect of suppressing byproducts, it is desirable to increase the amount of oxygen added, but as the oxygen concentration in the gas discharged from the reactor increases, special safety measures must be taken. for the amount
It is preferable to add about 0.5 to 2.0% oxygen.

As the shape of the reactor used in the present invention, a conventional bubble column reactor or a liquid circulation type reactor using an air lift effect can be used. In the case of a liquid circulation type, an external circulation type loop reactor or double tube type reactor can be used, and in this case, the liquid circulation flow rate is 10 to 400 cm/sec, preferably 50 to 150 cm/sec.
It can be in the range of sec. The faster the liquid circulation flow rate, the lower the dissolved chlorine concentration can be.
If the flow rate is too high, a large amount of unreacted components will be discharged from the reactor, which is disadvantageous. When a loop reactor is used, a flow rate regulator such as a butterfly valve may be provided in the liquid circulation channel to adjust the flow rate to a preferable value. When using a liquid circulation type reactor, either increase the diameter of the upper column of the reactor and reduce the flow rate in that part, or make it so that only the lower part of the reactor is of the circulation type. This makes it possible to increase the reaction rate and reduce the amount of unreacted components discharged. In a liquid circulation reactor,
Although the rising side of the liquid is used as a reactor, the chlorine that is supplied first among the chlorine that is dividedly supplied in the method of the present invention can be introduced into the falling side of the liquid. When introducing chlorine into the upper part of the liquid downcomer, the pressure at the chlorine injection part can be lower by the height of the liquid column than at the bottom of the column.

In order to advantageously recover the heat of reaction in the present invention, it is desirable to conduct the reaction at as high a temperature as possible.
At this time, it is necessary to increase the pressure inside the reactor according to the boiling temperature of the reaction liquid medium. In order to introduce chlorine into the reactor under such pressure conditions, energy is usually required to increase the pressure of chlorine, so it is advantageous to lower the pressure at the chlorine introduction part as much as possible.

In the present invention, as a method for preferably adjusting the amounts of ethylene and chlorine supplied to the reactor, a method can be used in which the respective supply flow rates are detected and the ratio of the values is controlled so as to be preferable. If a normal orifice flow meter is used as the flow rate detector at this time, it can be controlled with an accuracy of about ±2%, but there is no conventional method for adjusting the ratio of ethylene and chlorine with higher accuracy. The method used was to detect the concentration of chlorine dissolved in the reaction liquid medium and finely adjust the amount of ethylene or chlorine supplied to bring this value to a predetermined value. In the present invention, when adjusting the ratio of ethylene to chlorine with an accuracy of ±2% or more, the conventional method using the chlorine concentration as a detected value does not allow easy adjustment because the concentration changes depending on the division of chlorine. In the method of the present invention, the amount of unreacted ethylene discharged from the reactor is detected, and the flow rate of ethylene or chlorine is adjusted to maintain this value at a preferable level, thereby achieving an advantageous method with less loss of unreacted components. Control can be performed with high precision. It is desirable that the amount of unreacted ethylene discharged be excessive to the extent that unreacted chlorine is not discharged, but it should be 0.5% or less, preferably 0.1%, based on the amount of ethylene supplied to keep the loss of unreacted components to a low level.
It can be done as below. By controlling the supply ratio of ethylene and chlorine in this manner, it is possible to prevent an increase in the concentration of dissolved chlorine in the liquid reaction medium due to excessive supply of chlorine. The effects of this method can be achieved even better.

To detect the amount of unreacted ethylene discharged, after cooling the gas discharged from the top of the reactor and condensing the dichloride ethane, dilute the non-condensed gas with a constant flow of nitrogen gas, etc. The concentration of ethylene contained can be measured by gas chromatography, infrared absorption spectrometry, or the like. An example of a system in which the amount of unreacted ethylene discharged from the reactor is detected and monitored while controlling the ratio between the total amount of ethylene supplied and the total amount of chlorine supplied is shown in Figure 3. ing.

When the method of the present invention is carried out at a high temperature of 83°C or higher, the reaction medium vapor evaporated by the heat of reaction is directly guided to the distillation column, thereby making it possible to carry out the process according to the US Patent No.
Ethane dichloride can be purified using the same method as in No. 2,929,852, US Pat. No. 1,231,127, or Japanese Patent Publication No. 58-46489. In the present invention, by reacting at an even higher temperature of 110 to 180°C,
The reaction heat can be utilized much more advantageously than conventional methods. That is, the reaction medium vapor evaporated by the reaction heat is guided to the heat exchanger, and the heat of condensation of the vapor is taken out through the heat exchanger, thereby making it possible to perform more preferable heat utilization. One of the more preferable heat utilization methods is when refining ethane dichloride as a raw material for producing vinyl chloride monomer.
This method uses the distillation method described in JP-A-55-39591 and uses the reaction medium vapor generated from the reactor according to the present invention as a heat source for the reboiler of the distillation column. When using this method, the amount of thermal energy consumed for purifying ethane dichloride is small, and ethane dichloride containing carbon tetrachloride, which is preferable as a raw material for producing vinyl chloride monomer, can be obtained. You get all the benefits that come with it. In order to make such advantageous use of heat, the reaction temperature needs to be as high as 110 to 180°C, but conventional high-temperature methods produce by-products of higher chlorides at such high temperatures. In contrast to the disadvantageous increase in the proportion of by-products, according to the present invention, the proportion of by-products can be reduced even at such high temperatures, making it possible to utilize heat advantageously. For example, when the reaction was carried out at 135°C using the conventional method, 0.6% or more of 1,1,2-trichloroethane was produced as a by-product, but in the present invention, 1,1,2-trichloroethane was produced under the same conditions.
The amount of 1,2-trichloroethane as a by-product is 0.33% or less.

An example of a specific embodiment of the present invention will be described based on the drawings. In Figure 1, a tower-type reactor A is filled with ethane dichloride liquid, ethylene is supplied from a blowing pipe 5 at the bottom of the tower, and chlorine is dividedly supplied to four places, blowing pipes 1, 2, 3, and 4. . Ethane dichloride vapor generated by the heat of reaction is liquefied in heat exchanger B through conduit 6 and enters receiver C, where it is refluxed to the reactor and a portion is taken out as a product. In FIG. 2, a liquid circulation reactor A is used, and ethylene is supplied from a blowing pipe 5 at the bottom of the column. For chlorine, blow pipe 1,
Divide and supply to 3 locations, 2 and 3. The reaction medium vapor generated by the reaction heat passes through the conduit 6, and a part of it is led to the heat exchanger B where it is liquefied. At the same time, hot water is created by heat exchange and heat is utilized, and part of the reaction medium vapor is The fraction is led to the reboiler E where it is liquefied, and at the same time it gives heat to the rectification column D to effectively utilize the heat. The liquefied reaction medium is refluxed from receiver C to reactor A, and at the same time, a portion is taken out as a product.

〔Effect of the invention〕

As described above, when chlorine is supplied in parts according to the present invention, the chlorine concentration in the reactor is kept low to suppress by-products of higher chlorinated products, and as a result, the yield based on ethylene can be increased. High-temperature reactions that tend to produce by-products (especially reactions over 110℃)
However, since the method of the present invention allows operation at high temperatures while suppressing by-products, the heat of reaction produced can be used not only for direct distillation of dichloroethane but also for a variety of purposes, making it extremely effective in terms of energy utilization. It is.

〔Example〕

EXAMPLES Below, Examples and Comparative Examples of the present invention will be given and explained in more detail.

Example 1 In a cylindrical reactor with a diameter of 20 cm and a height of 7 m, ethane dichloride was charged as a liquid reaction medium up to a liquid level of 6 m, and chlorine was added to the bottom of the column at a rate of 25 Ncm ³ /Hr, 20 cm higher than that.
Ethylene was introduced at the upper position at a rate of 50 Ncm ³ /Hr, and chlorine was introduced at a position 50 cm above at a rate of 25 Ncm ³ /Hr. At this time, the ethylene/chlorine ratio was controlled by detecting the amount of unreacted ethylene discharged into the reactor exhaust gas. The chlorine feed contained 1.5% oxygen. Approximately 500 wt ppm of ferric chloride was present as a catalyst in the reaction liquid medium. The reaction temperature rises due to the reaction heat, and the upper liquid level reaches 135℃.
The pressure at the top of the column was kept constant to maintain a constant boiling temperature. The pressure at the top of the tower at this time is approximately 3.0Kg/
It was cm ² G. The reaction medium vapor evaporated by the reaction heat is condensed into a liquid in a heat exchanger, and is continuously refluxed to the reactor so that the liquid level in the reactor is maintained at 6 m, and the remainder is used as a product. It was taken out continuously.

The above operations were continued until the composition in the system reached a steady state. After 40 hours, the product was collected and analyzed for composition, and the following results were obtained.

1,1,2-trichloroethane 0.328wt% 1,1,2,2-tetrachloroethane 0.010 〃 Ethyl chloride 0.011 〃 Other by-products 0.02 〃 Ethane dichloride Residue The reaction rate of ethylene is 99.9% or more, and ethylene The selectivity to standard ethane dichloride was 99.63%. The by-product rate of 1,1,2-trichloroethane is
It was low at 0.328%.

Comparative Example 1 In the same reactor as Example 1, chlorine was added to the bottom of the column.
50Nm ³ /hr, 50Ncm ³ /hr of ethylene was introduced at a position 20cm above that, and other conditions were as follows.
The product composition when the reaction was carried out in the same manner as in Example 1 was as follows.

1,1,2-trichloroethane 0.659wt% 1,1,2,2-tetrachloroethane 0.015 〃 Ethyl chloride 0.014 〃 Other by-products 0.03 〃 Ethane dichloride Residue The reaction rate of ethylene is 99.9% or more, Selectivity to ethane chloride was 99.28%. 1, 1,
The by-product rate of 2-trichloroethane was 0.659%, which was higher than in Example 1.

Example 2 Ethane dichloride solution was put into a loop-type reactor made of a circular tube with a diameter of 20 cm to a height of 6 m, and chlorine was added at a rate of 50 Nm ³ / 80 cm higher than the bottom of the column on the downcomer side.
Hr, 50N of ethylene is added to the bottom of the tower on the liquid riser side.
m ³ /Hr, chlorine is placed 70 cm higher than the ethylene.
It was introduced so that the flow rate was 25m ³ /Hr. The amount of oxygen in the chlorine feed was approximately 1%. Using a butterfly valve installed at the connection between the liquid down pipe and the liquid rise pipe at the bottom of the reactor, the flow rate of the liquid was adjusted to about 100 cm/sec. The reaction temperature was 130℃, and the top pressure was 2.65.
Kg/cm ² G and other conditions were the same as in Example 1. When the reaction was carried out, the product composition was as follows.

1,1,2-trichloroethane 0.210wt% 1,1,2,2-tetrachloroethane 0.003 〃 Ethyl chloride 0.010 〃 Other by-products 0.02 〃 Ethane dichloride Residue The reaction rate of ethylene is 99.9% or more, Selectivity to ethane chloride was 99.75%.

Example 3 In the same reactor as in Example 2, 18Nm ³ /Hr of chlorine was placed at a position 80cm higher than the bottom on the liquid downcomer side, and 50Nm ³ /Hr of ethylene was placed at a position 80cm higher than the bottom on the liquid riser side, 50cm higher than the ethylene. 17m ³ /Hr of chlorine in a high position,
Furthermore, 15Nm ³ / chlorine was applied at a position 50cm higher than that.
It was introduced to become Hr. The reaction was carried out under the same conditions as in Example 2, and the product composition was as follows.

1,1,2-trichloroethane 0.145wt% 1,1,2,2-tetrachloroethane 0.002 〃 Ethyl chloride 0.010 〃 Other by-products 0.02 〃 Ethane dichloride Residue The reaction rate of ethylene is 99.9% or more, The selectivity to ethane chloride was 99.82%.

Comparative Example 2 In the same reactor as in Examples 2 and 3, chlorine was added at a rate of 50 Nm ³ /Hr at a position 80 cm higher than the bottom of the column on the descending side of the liquid.
Add 50Nm ³ /Hr of ethylene to the bottom of the tower on the liquid riser side.
When the reaction was carried out under the same conditions as in Examples 2 and 3, the product composition was as follows.

1,1,2-trichloroethane 0.440wt% 1,1,2,2-tetrachloroethane 0.020 〃 Ethyl chloride 0.021 〃 Other by-products 0.03 〃 Ethane dichloride Residue The reaction rate of ethylene is 99.9% or more, The selectivity to ethane chloride was 99.49%. 1, 1,
The by-product rate of 2-trichloroethane was 0.44%, which was higher than in Examples 2 and 3.

Example 4 Using the same reactor as in Example 2, chlorine was introduced in two portions as in Example 2, with the ferric chloride concentration in the dichloroethane solution being 100 wt ppm.
The flow rate of the liquid was adjusted to about 200 cm/sec. A cooling water jacket was provided outside the liquid downcomer pipe, and the reaction temperature was maintained at about 60° C. by adjusting the flow rate of the cooling water. The pressure at the top of the reactor was 1 Kg/cm ² G. Ethane dichloride produced by the reaction overflowed from the top of the reactor and was taken out as a product.
A dichloride ethane solution containing 3000 wt ppm of ferric chloride dissolved therein was supplied to the reactor using a metering pump to keep the ferric chloride concentration in the reactor constant. The results of analyzing the composition of the product after the reaction had been carried out for over 30 hours to reach a steady state are as follows.

1,1,2-trichloroethane 0.032wt% Ethyl chloride 0.010 Other by-products 0.04 Ethane dichloride Residue The selectivity to ethane dichloride at this time is 99.92%.

Comparative example 3 50Nm ³ / on the liquid downcomer side without dividing chlorine
When Hr was introduced and the reaction was carried out in the same manner as in Example 4 with respect to other conditions, the product composition was as follows.

1,1,2-Trichloroethane 0.058wt% Ethyl chloride 0.012wt% Other by-products 0.04 Ethane dichloride Residue The selectivity to ethane dichloride at this time is 99.89%.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of an apparatus for producing ethane dichloride for explaining one embodiment of the present invention, and FIGS. 2 and 3 are schematic diagrams of other embodiments of the present invention. A...Reactor, B...Heat exchanger, C...Receiver,
D... Rectification column, E... Reboiler, 1 to 4... Chlorine introduction pipe, 5... Ethylene introduction pipe, 6 to 9... Piping.

Claims (1)

[Claims] 1. In a method for producing ethane dichloride by reacting ethylene and chlorine in a liquid reaction medium mainly composed of chlorinated hydrocarbons, the position at which chlorine is introduced is set in the reaction vessel. A method for producing ethane dichloride, which comprises providing at least two or more locations in the height direction and supplying chlorine to each location in a divided manner. 2. The method according to claim 1, wherein the reaction temperature is maintained in the range of 83° C. to 160° C. and the liquid reaction medium is maintained at a boiling state or a pressure level higher than that. 3. The method of claim 1, comprising ferric chloride in the liquid reaction medium. 4. The method according to claim 1, in which oxygen is added to the supplied chlorine. 5. A patent that removes the reaction heat by evaporating the reaction liquid medium and directs the generated reaction medium vapor directly to a distillation column for distillation, or indirectly through a heat exchanger to recover and utilize the latent heat of the vapor. Claim 2
The method described in section. 6. The method according to claim 1, wherein the ratio between the total amount of ethylene supplied and the total amount of chlorine supplied is controlled while detecting and monitoring the amount of unreacted ethylene discharged from the reactor. 7. The method according to claim 1 or 6, in which the flow rate of the liquid is adjusted in the range of 10 to 400 cm/sec using a valve for adjusting the circulation rate of the liquid in a liquid circulation type reactor. 8. The method according to claim 1, wherein ethylene and chlorine are supplied at the second position from the bottom so that the ethylene and chlorine are supplied in the order of chlorine, ethylene, and chlorine from the bottom of the reactor. 9. The method according to claim 1, which uses a reactor in which the diameter of the column in the upper part is larger than that in the lower part.