JP4964717B2 - Method and apparatus for producing 1,1,2-trichloroethane - Google Patents

Description

  The present invention relates to a method for producing 1,1,2-trichloroethane capable of continuously producing 1,1,2-trichloroethane with high production capacity and high yield by reacting vinyl chloride and chlorine, and It relates to the device.

  Conventionally, a vinylidene chloride monomer used as a production raw material for producing a polyvinylidene chloride resin having excellent gas barrier properties generally produces 1,1,2-trichloroethane by adding chlorine to vinyl chloride. It is known to be produced by bringing 1,1,2-trichloroethane into contact with slaked lime emulsion to dehydrochlorinate 1,1,2-trichloroethane (edited by the Practical Plastics Encyclopedia Editorial Committee, Inc.) Issued by the Encyclopedia Publishing Center, “Practical Plastics Encyclopedia Materials”, pages 81-94).

As a general method for producing conventional 1,1,2-trichloroethane, a steel tank reactor (chlorination reactor) having a stirrer and a cooling jacket is preliminarily charged with 1,1,2-trichloroethane. In this, vinyl chloride and chlorine gas are slightly rich (for example, 1 / 1.05: molar ratio) and simultaneously blown into it, and chlorine is added to vinyl chloride to obtain 1,1,2-trichloroethane. . This reaction proceeds with iron chloride produced by the reaction of iron and chlorine on the wall of the reactor as a catalyst.
However, in the conventional general production method described above, since the reaction is performed at a constant temperature using a tank reactor, (i) when the reaction is performed at a high temperature in order to improve the reaction rate, high chlorine The amount of chemical by-products generated is increased. On the other hand, in order to improve the purity of 1,1,2-trichloroethane while suppressing the amount of by-products generated, the residence time must be increased at low temperatures, so the production capacity of 1,1,2-trichloroethane is low. There was a problem of lowering.

In addition, the addition reaction of chlorine to vinyl chloride is a reaction with a large exotherm, so cooling is necessary. However, because the cooling efficiency of the cooling jacket for cooling the tank reactor is small, (ii) the production equipment is large. (Iii) There is a problem that energy cannot be effectively used.
Furthermore, in the conventional general production method, iron chloride produced by the reaction of iron and chlorine on the reactor wall is used as a catalyst. (Iv) The amount of catalyst is difficult to control and the reactor is corroded. There was also a problem that happened.
Edited by Practical Plastics Encyclopedia Editorial Committee Published by Center for Industrial Research Co., Ltd. “Practical Plastics Encyclopedia Materials” pages 81-94

The present invention aims to solve these problems, suppresses the formation of by-products, can increase the reaction rate of (i) vinyl chloride and chlorine, and (ii) It is an object of the present invention to provide a method and an apparatus for producing 1,1,2-trichloroethane that can reduce the volume and (iii) can effectively use energy.
Furthermore, it is an object of the present invention to provide (iv) a method and an apparatus for producing 1,1,2-trichloroethane in which the catalyst concentration is easily controlled and there is no problem of corrosion of the reaction vessel.

  As a result of intensive studies in view of the above problems, the present inventor can (i) increase the reaction rate by using a circulation reactor comprising an addition reaction zone, a cooling zone, and a circulator. The present invention has been completed based on the knowledge that (ii) production equipment can be reduced in volume, and (iii) energy can be effectively utilized.

That is, the method for producing 1,1,2-trichloroethane according to the present invention is a method for producing 1,1,2-trichloroethane by reacting vinyl chloride and chlorine, wherein the reaction is carried out as follows: A circulating liquid mainly composed of 1,2-trichloroethane is circulated between the reaction tower and the cooler, and vinyl chloride and chlorine are circulated in the circulating liquid flowing upward from below the reaction section of the reaction tower. To produce 1,1,2-trichloroethane by reacting vinyl chloride and chlorine, and removing the heat of reaction generated by the reaction of vinyl chloride and chlorine with the cooler, 1,1,2-trichloroethane produced by extracting a part of the product is separated and recovered.

The 1,1,2-trichloroethane production apparatus of another invention of the present invention is characterized by comprising the following (A) to (D).
(A): A supply port provided at the lower part of the reactor of the circulating liquid mainly composed of 1,1,2-trichloroethane, an exhaust port provided at the upper part of the reactor, a supply part of vinyl chloride, and chlorine A reaction tower (B) for producing 1,1,2-trichloroethane, a cooler (C) for cooling the circulating liquid: cooling the circulating liquid to the reaction tower (A) Circulator (D) for circulating between chambers (B): Circulating fluid extraction part for extracting part of the circulating fluid

  Such a 1,1,2-trichloroethane production method and apparatus according to the present invention includes a circulating reactor having a catalyst preparation tank and a cooler for removing reaction heat, and thus has a high production capacity. Since it is possible to produce continuously in a high yield, it is an industrially extremely useful production method and apparatus.

[I] Raw materials
(1) Vinyl chloride As the vinyl chloride used in the method for producing 1,1,2-trichloroethane of the present invention, one produced by dehydrochlorination reaction by thermal decomposition of 1,2-dichloroethane (EDC) is used. It is normal.
(2) Chlorine Chlorine used in the method for producing 1,1,2-trichloroethane of the present invention is ordinary chlorine gas, and industrially electrolyzes a saline solution by a diaphragm method or an ion exchange membrane method. Usually, the chlorine gas obtained in this way is used.

(3) Catalyst As a catalyst used in the method for producing 1,1,2-trichloroethane of the present invention, iron chloride (FeCl ₃ ), aluminum chloride (AlCl ₃ ), antimony chloride (SbCl ₃ ) and the like are used.

[II] 1,1,2-Trichloroethane production equipment (circulation reactor)
(1) Reaction tower (A)
As shown in FIG. 1, the reaction tower (A) in the circulation reactor 1a of the 1,1,2-trichloroethane production apparatus 1 of the present invention is a vertical hollow cylindrical body, and a catalyst is provided in the lower part. A circulating fluid supply port (a1) for supplying the circulating fluid containing 1,1,2-trichloroethane as a main component is provided, and the circulating fluid outlet (a2) for discharging the circulating fluid to the upper part. ), A vinyl chloride supply part (a3) is provided above the circulating liquid supply port part (a1), and chlorine supply is also provided above the circulating liquid supply port part (a1). A reaction part (a5) for providing 1,1,2-trichloroethane by reacting vinyl chloride and chlorine on the vinyl chloride supply part (a3) and the chlorine supply part (a4). A space is formed.

In order to produce 1,1,2-trichloroethane using this reaction tower (A), 1,1 containing catalyst from the circulating liquid supply port (a1) provided at the lower part of the reaction tower (A). , 2-trichloroethane as a main component, a circulating liquid is supplied using a circulator such as a pump.
Then, vinyl chloride and chlorine are supplied from the vinyl chloride supply part (a3) and the chlorine supply part (a4), respectively, into the circulating liquid containing 1,1,2-trichloroethane as a main component, and the reaction part (a5 ) To produce 1,1,2-trichloroethane by reacting vinyl chloride with chlorine.
The 1,1,2-trichloroethane produced here is, together with 1,1,2-trichloroethane supplied as a circulating liquid from below the reaction tower (A), a circulating liquid outlet (a2) at the upper part of the reaction tower (A). )
By using such a reaction tower (A), the reaction rate of chlorination can be increased.

When supplying vinyl chloride and chlorine in the form of gas, the vinyl chloride supply unit (a3) and the chlorine supply unit (a4) are composed of 1,1,2-trichloroethane as the main component. For example, pipes having a large number of fine pores are installed and connected to a vinyl chloride gas supply line and a chlorine gas supply line, respectively, so that the bubbles can be uniformly supplied into the circulating liquid.
In the reaction tower (A), the circulating liquid mainly composed of 1,1,2-trichloroethane in which vinyl chloride and chlorine are dissolved flows from the lower part to the upper part of the reaction part (a5). Therefore, in the reaction part (a5), the concentrations of unreacted vinyl chloride and chlorine are gradually decreased from the bottom to the top.
Therefore, in the reaction tower (A) in the 1,1,2-trichloroethane production apparatus of the present invention, it is preferable that the reaction part (a5) has a temperature gradient in which the temperature increases from the lower part toward the upper part. . By providing such a temperature gradient, the reaction temperature increases in the upper region of the reaction tower where the concentration of vinyl chloride and chlorine in the reaction raw material decreases, and the reaction rate between vinyl chloride and chlorine can be further increased. It becomes.

Since the addition reaction of chlorine to vinyl chloride is an exothermic reaction, it is possible to provide a temperature gradient in the reaction tower (A) so that the temperature increases from the lower part to the upper part using this reaction heat. Become.
Such a temperature gradient of the reaction tower (A) is such that the temperature of the circulating liquid mainly composed of 1,1,2-trichloroethane containing the catalyst supplied to the reaction tower (A), and the region of the reaction tower (A). It can be set to an optimum state by cooling, keeping warm, or actively heating.

The reaction tower (A) is preferably made of a material whose inner wall hardly reacts with chlorine from the viewpoint of control of the catalyst amount and corrosion. The materials include austenitic stainless steel (JIS standard SUS304, SUS304L, SUS316, SUS316L), ferritic stainless steel (JIS standard SUS430), martensitic stainless steel (JIS standard SUS410), duplex stainless steel (JIS standard). SUS329J1, SUS329J3L, and SUS329J4L), and SUS304, SUS304L, and SUS329J1 are preferably used.
The catalyst acts as a catalyst for the addition reaction of chlorine to vinyl chloride, and iron chloride (FeCl ₃ ), aluminum chloride (AlCl ₃ ), antimony chloride (SbCl ₃ ) and the like are used. Iron chloride (FeCl ₃ ) can be preferably used.

(2) Cooler (B)
The cooler (B) in the circulation reactor 1a of the 1,1,2-trichloroethane production apparatus 1 according to the present invention comprises vinyl chloride and chlorine produced when passing through the reaction tower (A) as shown in FIG. Cooling the circulating liquid mainly composed of 1,1,2-trichloroethane containing the heat of addition reaction, shell-tube type, spiral type, plate type, etc. with large heat transfer area Is preferred.
As the cooling medium, water, liquid calcium chloride, liquid such as vinyl chloride, ammonia, ethylene glycol, and gas are used.
Cooling can be performed in multiple stages, and different cooling media may be used in each cooler part. For example, a part of the cooler (B) can be cooled with liquid vinyl chloride, and can also serve as a vaporizer for producing vinyl chloride gas to be supplied to the reaction tower (A).
By adopting such a configuration, it is not necessary to separately install a liquid vinyl chloride vaporizer, and the apparatus can be made compact and energy-saving.

(3) Circulator (C)
The circulator (C) in the circulation reactor 1a of the 1,1,2-trichloroethane production apparatus 1 of the present invention is mainly composed of 1,1,2-trichloroethane cooled by the cooler (B). The circulating liquid is supplied to the circulating liquid supply port (a1) below the reaction tower (A), and the circulating liquid is circulated from the cooler (B) to the reaction tower (A).
As the circulator (C), various pumps such as a turbo pump, a reciprocating pump, and a rotary pump are employed. Among these, an axial pump belonging to the turbo pump is preferably used.

(4) Circulating fluid extraction part (D)
The circulating liquid extraction part (D) in the 1,1,2-trichloroethane production apparatus of the present invention is for separating and recovering the generated 1,1,2-trichloroethane by extracting a part of the circulating liquid. Therefore, in order to extract a part of the circulating fluid in the 1,1,2-trichloroethane manufacturing apparatus 1, a circulating liquid extraction port may be formed at an appropriate part of the manufacturing apparatus. good.

1,1,2-Trichloroethane recovery device In addition to the circulating fluid extraction port, the circulating fluid extraction unit (D) can be used for various types of recovery, such as an apparatus utilizing overflow and an apparatus utilizing liquid level. It is also possible to form a 1,1,2-trichloroethane recovery device provided with the device.
For example, as a device using the above liquid level, a cushion tank is provided at a position where the circulating fluid becomes the highest, and the circulating fluid level of the cushion tank is linked with the extraction pump so that the liquid level in the cushion tank is constant. An apparatus that adjusts the amount of extraction so that
In the aspect of the apparatus provided with the cushion tank, for example, a part of the piping or a catalyst self-manufacturing tank described later can be used as the cushion tank.
By this 1,1,2-trichloroethane recovery device, 1,1,2-trichloroethane having the same amount as 1,1,2-trichloroethane produced by the reaction of vinyl chloride and chlorine in the reaction tower (A). Is extracted from the circulating fluid.

(5) Catalyst supply tank (E)
As the catalyst supply tank (E) in the 1,1,2-trichloroethane production apparatus of the present invention, the 1,1,2-trichloroethane is extracted for separation / recovery or lost after being deactivated 1 , 1,2-trichloroethane as a main component is replenished with a dissolved or dispersed catalyst.
The catalyst supplied from the catalyst supply tank (E) acts as a catalyst for producing 1,1,2-trichloroethane by adding chlorine to vinyl chloride, for example, iron chloride (FeCl ₃ ), aluminum chloride (AlCl ₃ ) antimony chloride and the like.
Therefore, the catalyst supply tank (E) is a tank for preparing or injecting the catalyst for producing 1,1,2-trichloroethane in the circulating liquid mainly composed of 1,1,2-trichloroethane. .
The catalyst supply tank (E) may contain the catalyst in the circulating liquid mainly composed of 1,1,2-trichloroethane before being circulated to the reaction tower (A). Although it can be formed as incidental equipment for injection, it is preferably incorporated in a cycle in which the circulating fluid circulates in order to omit the production of the catalyst by a separate apparatus, and is particularly installed upstream of the cooler (C). It is preferable.

Catalyst self- manufacturing device In the catalyst supply tank (E), in order to omit the production of the catalyst by another device, as shown in FIG. 1, during the circulation cycle of the circulating liquid in the 1,1,2-trichloroethane production device 1 It is preferable to incorporate a catalyst preparation tank (F) capable of producing the catalyst into the tank, since the volume reduction and energy efficiency of the 1,1,2-trichloroethane production apparatus can be improved.
As shown in FIG. 1, the catalyst preparation tank (F) is disposed between the reaction tower (A) and the cooler (B) at a position higher than the reactor (A) and the cooler (B). The structure is mainly composed of a housing part (f) containing a metal material (f1) serving as a catalyst raw material and the 1,1,2-trichloroethane located below the uppermost part of the metal housing part. It has an inflow part (f2) and an outflow part (f3) for circulating fluid as components.

Inside the catalyst preparation tank (F), the metal material that is the raw material of the catalyst and the circulating fluid come into contact with each other, and the chlorine and the metal material that are present in the circulating fluid react to produce a metal chloride catalyst. can do.
In the catalyst preparation tank (F), the contact area between iron, aluminum, antimony, etc., which are the raw material materials of the catalyst accommodated in the inside, and the circulating liquid whose main component is 1,1,2-trichloroethane is arbitrary. The structure is adjustable.
An example of a catalyst supply tank (E) provided with such a catalyst preparation tank (F) is described below.
The catalyst preparation tank (F) is a hollow cylinder, installed at the upper part of the reaction tower (A) and the cooler (B), so that the metal pipe as the catalyst raw material is almost horizontal inside It has an accommodating part (f) loaded in parallel with the body.

FIG. 2 shows a KK cross section of the catalyst preparation tank (F) in FIG.
The downstream side of the reaction tower (A) and the circulating liquid inlet (f2) of the catalyst preparation tank (F) are connected, and the circulating liquid outlet (f3) of the catalyst preparation tank (F) and the cooler (B ) And the circulating fluid flows in the catalyst preparation tank (F) in contact with the metal pipe.
Since the level of the circulating fluid level in the catalyst preparation tank (F) can be changed by the amount of the circulating fluid extracted from the circulating fluid, the contact area between the metal pipe and the circulating fluid can be adjusted.
By adopting such a structure, a configuration in which the catalyst supply tank and the 1,1,2-trichloroethane recovery device are combined can be obtained.
The elution rate of the catalyst that is self-made in the catalyst preparation tank (F) and elutes into the circulating liquid is the contact area between the circulating liquid and the metal pipe, the chlorine concentration and water content in the circulating liquid, the temperature of the catalyst preparation tank (F) The concentration of the catalyst in the circulating fluid can be changed by changing the contact area between the circulating fluid and the metal pipe by making the chlorine concentration and water content in the circulating fluid, the temperature of the catalyst preparation tank (F), etc. almost constant. Is preferably controlled.

  Equipment and devices constituting the circulation reactor 1a of the 1,1,2-trichloroethane production apparatus 1 of the present invention, for example, a reaction tower (A), a cooler (B), a circulator (C), and a circulating liquid extraction In the part (D), catalyst preparation tank (F), piping, etc., it is preferable that the device member that contacts the circulating liquid is made of a material that is not easily corroded by chlorine. SUS316L), ferritic stainless steel (JIS standard SUS430), martensitic stainless steel (JIS standard SUS410), duplex stainless steel (JIS standard SUS329J1, SUS329J3L, SUS329J4L), and SUS304, SUS304L, SUS329J1 should be used. Is preferred.

In the production apparatus used in the method for producing 1,1,2-trichloroethane of the present invention, the reaction rate can be increased by using the reaction tower (A), and the reaction section (a5) of the reaction tower (A) can be increased. ) Has a temperature gradient in which the temperature increases from the lower part toward the upper part, the reaction temperature increases in the upper region of the reaction tower where the concentration of vinyl chloride and chlorine in the reaction material decreases, and vinyl chloride and chlorine The reaction rate can be further increased.
In addition, by separating the reaction tower (A) for performing the reaction and the cooler (B) for performing the cooling, it is possible to employ a cooler having a large heat transfer area, and to provide a device having a large cooling capacity. The reaction heat can be easily removed by the reaction between vinyl chloride and chlorine, and the reaction apparatus can be made compact.

As another embodiment of the 1,1,2-trichloroethane production apparatus 1 of the present invention, a second reaction column 1b is further added to the circulation reactor 1a of the 1,1,2-trichloroethane production apparatus 1. Embodiments can be mentioned.
In the apparatus for producing 1,1,2-trichloroethane, since the reaction is generally performed under the condition of excess chlorine, unreacted chlorine exists in the produced 1,1,2-trichloroethane.
Accordingly, vinyl chloride is further added to the 1,1,2-trichloroethane extracted through the 1,1,2-trichloroethane recovery device and supplied to the second reaction column 1b to react the vinyl chloride and chlorine again. Thus, the amount of residual chlorine in 1,1,2-trichloroethane can be reduced and the reaction rate can be improved.

[III] Production of 1,1,2-trichloroethane The 1,1,2-trichloroethane production method of the present invention includes a 1,1,2-trichloroethane production apparatus 1 equipped with the above-described circulation reactor 1a. And 1,1,2-trichloroethane is produced by reacting vinyl chloride and chlorine.
In the method for producing 1,1,2-trichloroethane of the present invention, the catalyst is generally added in an amount of 10 to 1000 mg / liter, preferably 50 to 1, in the reaction tower (A) of the 1,1,2-trichloroethane production apparatus 1. The circulating liquid mainly composed of 1,1,2-trichloroethane contained at a concentration of 500 mg / liter is supplied so that the residence time in the reaction tower (A) is 10 to 50 seconds.
When the amount of catalyst is too small or when the residence time is short, the reaction rate between vinyl chloride and chlorine tends to be small. Moreover, when there is too much catalyst amount or when residence time is long, there exists a tendency for the production | generation of by-products, such as a highly chlorinated thing, to increase.

In the circulating liquid mainly composed of 1,1,2-trichloroethane supplied to the reaction tower (A), vinyl chloride and chlorine are supplied, and the vinyl chloride and chlorine react to produce 1,1,2-trichloroethane. Is generated.
Due to the heat of reaction between vinyl chloride and chlorine generated by this reaction, the temperature in the reaction tower (A) becomes a temperature gradient that gradually increases from the lower part toward the upper part.
The maximum temperature in the upper part of the reaction tower (A) is preferably controlled at a temperature of 30 to 70 ° C, preferably 40 to 60 ° C.

The circulating liquid mainly composed of 1,1,2-trichloroethane containing the catalyst supplied to the reaction tower (A) is set so that the maximum temperature in the upper part of the reaction tower (A) becomes a predetermined set value. Then, it is supplied after being cooled by the cooler (B).
If the reaction temperature of the reaction tower (A) is too high, by-products such as highly chlorinated substances increase, and if the reaction temperature is too low, the reaction rate between vinyl chloride and chlorine decreases.
The vinyl chloride gas and the chlorine gas supplied to the reaction tower (A) are preferably in a molar ratio of vinyl chloride / chlorine of 1 / 1.005 to 1 / 1.10. If the molar ratio of vinyl chloride / chlorine is too large, the amount of unreacted vinyl chloride will increase, and the chlorine concentration in the circulating fluid will be low when the process is carried out using a production apparatus having a catalyst preparation tank for producing the catalyst. This is not preferable because the preparation rate of the catalyst becomes too small. On the other hand, if the vinyl chloride / chlorine molar ratio is too small, the production of by-products such as highly chlorinated products increases, and the amount of unreacted chlorine increases.

Second Reaction Tower A case where 1,1,2-trichloroethane is produced using a 1,1,2-trichloroethane production apparatus in which the second reaction tower 1b is added to the circulation reactor of the present invention will be described.
In the 1,1,2-trichloroethane production method using the 1,1,2-trichloroethane production apparatus not provided with the second reaction tower 1b described above, the reaction is generally performed in an excess of chlorine. A relatively large amount of unreacted chlorine remains in the 1,1,2-trichloroethane produced.
Therefore, as shown in FIG. 1, the circulating liquid mainly composed of 1,1,2-trichloroethane extracted through the liquid level control type 1,1,2-trichloroethane recovery device (D1) Further, after adding vinyl chloride, it is supplied to the vertical second reaction column 1b to react vinyl chloride and chlorine, thereby reducing the amount of residual chlorine in 1,1,2-trichloroethane and improving the reaction rate. be able to.
The amount of newly added vinyl chloride is such that the total amount of newly added vinyl chloride and initially supplied vinyl chloride is approximately 1/1 in molar ratio with the initially supplied chlorine amount. It is preferable to do.

The reaction between vinyl chloride and chlorine in the second reaction tower 1b is generally carried out at a reaction temperature of 40 to 80 ° C., preferably 50 to 70 ° C. and a residence time of generally 1 to 10 minutes, preferably 2 to 6 minutes. preferable.
A catalyst may be supplied to the second reaction column 1b. However, since the catalyst already exists in 1,1,2-trichloroethane extracted through the 1,1,2-trichloroethane recovery device, the catalyst The reaction of vinyl chloride and chlorine can be made to proceed sufficiently even without newly supplying.

The present invention will be described more specifically with reference to the following examples and comparative examples.
Example 1
As shown in FIG. 1, a catalyst supply using a reaction tower (A), a cooling tower (B), a circulator (C), and a 1,1,2-trichloroethane recovery device and a catalyst preparation tank (F) having the following specifications. 1,1,2-Trichloroethane was produced by reacting vinyl chloride and chlorine under the following reaction conditions using an apparatus for producing 1,1,2-trichloroethane composed of the tank (E).

(1) 1,1,2-trichloroethane production equipment
Reaction tower (A)
A cylindrical body of SUS304 having an inner wall having a vinyl chloride supply part (a3) and a chlorine supply part (a4) made of a pipe having many drill holes in the lower part.
Cooler (B)
Shell-tube type heat exchanger made of duplex stainless steel SUS329J1 in contact with the circulating fluid.
Circulator (C)
An axial flow pump with a discharge flow rate of 400 to 800 m ³ / hour and a lift of 8 m.
Catalyst preparation tank (F)
A hollow cylinder of an inner wall SUS304 in which a large number of iron pipes are stacked and accommodated.
The approximate device volume obtained by adding the volumes of the above devices is about 22 m ³ .

(2) Reaction conditions Circulator (C) -circulatory liquid mainly composed of 1,1,2-trichloroethane is circulated (C) -reaction tower (A) -catalyst preparation tank (F) -cooler ( B)-circulated through the path of the circulator (C).
Vinyl chloride gas was supplied from the vinyl chloride supply part (a3) at 600 m ³ / hour (standard condition conversion), and chlorine gas was supplied from the chlorine supply part (a4) at 605 m ³ / hour (standard condition conversion).
The temperature at the top of the reaction tower (A) was 50 ° C., and the circulating liquid was cooled by a cooler (B) using water as a cooling medium so as to maintain this temperature.
The catalyst concentration was changed by adjusting the amount of 1,1,2-trichloroethane extracted from the circulating liquid in the catalyst preparation tank (F). Extraction of 1,1,2-trichloroethane from the circulating liquid was performed at a flow rate of 2,600 liters / hour from the circulating liquid extraction part (D) provided at the lower part of the catalyst preparation tank (F).
When the extracted 1,1,2-trichloroethane was analyzed by gas chromatography, it contained 1,1,2-trichloroethane having the value (purity) shown in Table 1.

Comparative Example 1
As the reaction apparatus, a tank reactor having an inner volume of 37 m ³ made of inner wall steel and equipped with a jacket and a stirrer was used.
After 1,2,2-trichloroethane (purity 96%) was put into a tank reactor 27 m ³ (overflow 30 m ³ ), at normal pressure, vinyl chloride gas 200 m ³ / hour (standard condition conversion), chlorine gas Each was supplied at a flow rate of 202 m ³ / hour (standard state conversion).
1,1,2-trichloroethane was continuously produced by reacting vinyl chloride and chlorine while maintaining the temperature at 30 ° C. while stirring and mixing at a rotation speed of 90 rpm.
The 1,1,2-trichloroethane produced overflowed from the tank reactor at a flow rate of 850 liters / hour.
The concentration of ferric chloride in the reaction mixture during the reaction was 20 ppm.
When the obtained 1,1,2-trichloroethane was analyzed by gas chromatography, it contained 1,1,2-trichloroethane having the value (purity) shown in Table 1.

  As shown in Table 1, when the purity of 1,1,2-trichloroethane produced is kept at the same level, 1,1,2-trichloroethane produced by the method and apparatus for producing 1,1,2-trichloroethane of the present invention is used. It can be seen that the amount of 1,1,2-trichloroethane produced per unit volume is extremely large as compared with the amount of 1,1,2-trichloroethane produced by a method using a conventional tank reactor.

Advantageous Effects of Invention Such a 1,1,2-trichloroethane production method and apparatus according to the present invention includes a circulation reactor having a catalyst preparation tank and a cooler for removing reaction heat. Since the production capacity is high and the continuous production is possible, it is an industrially extremely useful production method and apparatus.

FIG. 1 is a schematic view of an apparatus for producing 1,1,2-trichloroethane according to the present invention. FIG. 2 is a cross-sectional view taken along the line KK of the catalyst self-manufacturing tank of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 1,1,2- Trichloroethane production apparatus 1a Circulating reactor 1b Second reaction tower (A) Reaction tower (a1) Supply port for supplying the circulating liquid (a2) Drain for discharging the circulating liquid Outlet part (a3) Vinyl chloride supply part (a4) Chlorine supply part (a5) Reaction part (B) Cooler (C) Circulator (D) Circulating fluid extraction part (E) Catalyst supply tank (F) Catalyst preparation tank ( f) Storage part containing metal (f1) Metal material (f2) Circulating fluid inflow part (f3) Circulating fluid outflow part

Claims (18)

In the method for producing 1,1,2-trichloroethane by reacting vinyl chloride and chlorine, the reaction is carried out by using a circulating liquid mainly containing 1,1,2-trichloroethane containing a catalyst, and a reaction tower. between the cooler it is circulated, by supplying the vinyl gas and chlorine gas chloride circulating fluid flowing upward from below the reaction section of the reaction column, by reacting the vinyl chloride and chlorine 1,1,2-trichloroethane was produced, the heat of reaction produced by the reaction between vinyl chloride and chlorine was removed by the cooler, and a part of the circulating liquid was withdrawn to produce 1,1,2- A process for producing 1,1,2-trichloroethane, characterized in that trichloroethane is separated and recovered.   The method for producing 1,1,2-trichloroethane according to claim 1, wherein the reaction is carried out while maintaining the maximum temperature of the circulating liquid in the reaction tower at 30 to 70 ° C.   The 1,1,2-trichloroethane according to claim 1 or 2, wherein a catalyst preparation tank is provided between the reaction tower and the cooler, in which a metal material used as a raw material for the catalyst immersed in the circulating liquid is stored. Manufacturing method. Vinyl chloride gas in the circulating liquid of the reaction tower and the chlorine gas, was supplied with chlorine rich state in the range from one to 1.005 pair 1.10 molar ratio, excess of chlorine in the circulating liquid The process for producing 1,1,2-trichloroethane according to any one of claims 1 to 3, wherein   Control the reaction level by adjusting the contact area between the circulating fluid and the metal material that is the raw material of the catalyst by controlling the height of the circulating fluid level in the catalyst preparation tank, and adjusting the catalyst concentration in the circulating fluid. A process for producing 1,1,2-trichloroethane according to claim 3 or 4.   The method for producing 1,1,2-trichloroethane according to any one of claims 3 to 5, wherein the level of the circulating liquid in the catalyst preparation tank is controlled by the amount of the circulating liquid extracted from the catalyst preparation tank. .   The 1,1,2-trichloroethane according to any one of claims 1 to 6, wherein vinyl chloride is added to the extracted circulating liquid to react chlorine remaining in the extracted circulating liquid with vinyl chloride. Production method. An apparatus for producing 1,1,2-trichloroethane composed of the following (A) to (D).
(A): 1,1,2 supply opening provided in the lower part of the reactor trichloroethane circulating fluid mainly containing and reactor outlet section provided in the upper, supply of the vinyl chloride gas, and, A reaction tower (B) for producing 1,1,2-trichloroethane, which is equipped with a chlorine gas supply unit: a cooler (C) for cooling the circulating liquid: the circulating liquid as a reaction tower (A) Circulator (D) that circulates between the chiller and the cooler (B): Circulating fluid extraction part for extracting part of the circulating fluid   The apparatus for producing 1,1,2-trichloroethane according to claim 8, wherein a catalyst supply tank (E) for preparing and supplying the catalyst in the circulating liquid is provided.   The apparatus for producing 1,1,2-trichloroethane according to claim 8, wherein a catalyst preparation tank (F) for making the catalyst in-house is provided in a cycle in which the circulating liquid circulates.   The 1,1,2-trichloroethane collection | recovery apparatus using the liquid level was provided in the circulating fluid extraction part (D) which extracts a part of circulating fluid, 1,1, in any one of Claims 8-10. 2-Trichloroethane production equipment.   The circulator (C) circulates a circulating liquid mainly composed of 1,1,2-trichloroethane from the lower part to the upper part of the reaction tower (A) and further from the upper part to the lower part of the cooler (B). The apparatus for producing 1,1,2-trichloroethane according to claim 8. Circulating liquid supply port (a1) for the reaction tower (A) for producing 1,1,2-trichloroethane to supply a circulating liquid mainly composed of 1,1,2-trichloroethane containing a catalyst the formed located in the lower part, thereby forming circulating fluid outlet portion for discharging the circulating liquid (a2) is located in the upper part, the circulating liquid supply vinyl chloride gas supply unit (a3) located in the upper part formed by the mouth portion (a1), chlorine gas supply unit (a4) is by forming situated in the upper part of the circulating fluid supply opening portion (a1), a vinyl chloride gas supply unit ( The 1,1,2-trichloroethane according to any one of claims 8 to 12, wherein a reaction part (a5) in which vinyl chloride and chlorine react is formed in an upper part of a3) and a chlorine gas supply part (a4). Manufacturing equipment.   In the catalyst supply tank (E), a metal material (f1) as a raw material of the catalyst is accommodated, and a circulating fluid inflow portion (f2) and an outflow portion (f3) are provided below the uppermost end portion of the metal material. And the catalyst preparation tank (F) is located above the reaction tower (A) and the cooler (B), and the catalyst preparation tank (F) is formed. The inflow part (f2) of the circulating liquid in (F) is connected to the downstream side of the reaction tower (A), and the outflow part (f3) of the circulating liquid is connected to the upstream side of the cooler (B). Forming a production apparatus for circulating 1,1,2-trichloroethane that incorporates the preparation tank (F) into the cycle in which the circulating liquid circulates, and the metal material reacts with chlorine in the circulating liquid to make the catalyst in-house The apparatus for producing 1,1,2-trichloroethane according to any one of claims 8 to 13.   For adding vinyl chloride to the extracted liquid obtained by extracting a part of the circulating liquid and reacting the residual chlorine in the extracted liquid with vinyl chloride to produce 1,1,2-trichloroethane. The apparatus for producing 1,1,2-trichloroethane according to any one of claims 8 to 14, wherein the second reaction column 1b is arranged.   The 1, 1, 2 according to any one of claims 8 to 15, wherein vinyl chloride is used as a cooling medium of the cooler (B), and gasified vinyl chloride generated thereby is supplied to the reaction tower (A). -Trichloroethane production equipment.   In the reaction part (a5) of the reaction tower (A), the concentration of unreacted vinyl chloride and chlorine decreases sequentially from the bottom to the top, 1,1, according to any one of claims 8 to 16. 2-Trichloroethane production equipment.   The reaction part (a5) of the reaction tower (A) has a temperature gradient in which the temperature increases from the lower part toward the upper part, of 1,1,2-trichloroethane according to any one of claims 8 to 17. Manufacturing equipment.

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