阅读说明：本技术 1,2,3,4-四氯丁烷的制造方法和制造装置 (Method and apparatus for producing 1,2,3, 4-tetrachlorobutane ) 是由 三神克己 福地阳介 小黑慎也 小林浩 于 2019-03-01 设计创作，主要内容包括：提供难以发生作为原料的3,4-二氯-1-丁烯和作为生成物的1,2,3,4-四氯丁烷的损失、并且能够稳定且经济地制造1,2,3,4-四氯丁烷的1,2,3,4-四氯丁烷的制造方法和制造装置。将含有3,4-二氯-1-丁烯的反应液(1)收纳于反应容器(11)之后,向反应容器(11)内的气相部分(2)供给氯气,使3,4-二氯-1-丁烯与氯气反应,制造1,2,3,4-四氯丁烷。(Provided are a method and an apparatus for producing 1,2,3, 4-tetrachlorobutane, whereby loss of 3, 4-dichloro-1-butene as a raw material and 1,2,3, 4-tetrachlorobutane as a product is less likely to occur, and 1,2,3, 4-tetrachlorobutane can be produced stably and economically. A reaction liquid (1) containing 3, 4-dichloro-1-butene is stored in a reaction vessel (11), and then 3, 4-dichloro-1-butene is reacted with chlorine gas by supplying chlorine gas to a gas phase portion (2) in the reaction vessel (11), thereby producing 1,2,3, 4-tetrachlorobutane.)

1. A method for producing 1,2,3, 4-tetrachlorobutane, comprising: after a reaction solution containing 3, 4-dichloro-1-butene was stored in a reaction vessel, chlorine gas was supplied to a gas phase portion in the reaction vessel, and the 3, 4-dichloro-1-butene was reacted with the chlorine gas.

2. The process for producing 1,2,3, 4-tetrachlorobutane according to claim 1, wherein the amount of chlorine gas supplied is 5.0 mol/h/cm per unit area of the liquid surface of the reaction solution in the reaction vessel²The following.

3. The method for producing 1,2,3, 4-tetrachlorobutane according to claim 1 or 2, wherein the pressure in the reaction vessel is 0.01 to 1.0 MPa.

4. The method for producing 1,2,3, 4-tetrachlorobutane according to any one of claims 1 to 3, wherein a part of the reaction solution is extracted and returned to the gas phase portion in the reaction vessel in the reaction of the 3, 4-dichloro-1-butene with the chlorine gas.

5. The method for producing 1,2,3, 4-tetrachlorobutane according to claim 4, wherein when a part of the reaction liquid is returned to the gas phase portion in the reaction vessel, a part of the reaction liquid is sprayed to the gas phase portion in the reaction vessel.

6. An apparatus for producing 1,2,3, 4-tetrachlorobutane, which is used for producing 1,2,3, 4-tetrachlorobutane by the method for producing 1,2,3, 4-tetrachlorobutane according to any one of claims 1 to 5,

the production apparatus comprises a reaction vessel for containing a reaction solution containing 3, 4-dichloro-1-butene, and a chlorine gas introduction pipe for introducing chlorine gas into the reaction vessel,

the chlorine gas introduction pipe is configured to: the chlorine gas ejection port can be provided above the liquid surface of the reaction solution in the reaction vessel.

Technical Field

The present invention relates to a method and an apparatus for producing 1,2,3, 4-tetrachlorobutane.

Background

1,2,3, 4-tetrachlorobutane (hereinafter also referred to as "TCB") is produced by chlorination of 3, 4-dichloro-1-butene, but the chlorination reaction is an exothermic reaction because chlorine is added to a double bond, and the reaction rate is high. Therefore, in order to prevent the reaction solution from flowing backward through the chlorine gas outlet of the chlorine gas inlet pipe for blowing the chlorine gas into the reaction solution, it is necessary to blow the chlorine gas diluted with an inert gas such as nitrogen gas into the reaction solution to reduce the reaction rate. As a result, the inert gas is accumulated in the reaction vessel, and therefore, it is necessary to carry out the reaction while discharging the inert gas from the reaction vessel, but 3, 4-dichloro-1-butene and TCB are also discharged when the inert gas is discharged, and there is a possibility that the loss of the raw material and the product may occur.

In addition, depending on the reaction conditions, the TCB formed may solidify in the reaction solution and block the chlorine gas introduction pipe, and therefore the chlorination reaction may not be able to produce TCB stably and economically. That is, TCB contains d, l and meso isomers as optical isomers, the melting point of dl is 0 ℃ or lower and is liquid at room temperature, and the melting point of meso is about 73 ℃ and is solid at room temperature. Therefore, the temperature at which the TCB is cured varies depending on the ratio of meso body to dl body, and for example, when the ratio of meso body is large, a part of the TCB is cured at room temperature.

For example, patent document 1 describes that curing of TCB adversely affects the industrial production of the compound, and discloses that the ratio of TCB mesogen is preferably 60 mass% or less in the reaction of TCB with fluorine. If the ratio of the mesogen is 60% by mass or less, the TCB can be prevented from being solidified, and therefore, the temperature at which the TCB is dissolved in the reaction solvent and the reaction temperature can be set to be low.

Iron chloride and the like are mixed in the reaction solution, and one of the reasons why many meso-compounds are produced depends on the reaction conditions. Patent document 2 discloses that in the reaction of 3, 4-dichloro-1-butene with chlorine, the ratio of TCB formation of meso form is increased by placing a catalyst in which 0.1 to 20 mass% of ferric chloride is supported on silica gel in the reaction field. Therefore, in order to suppress the ratio of meso-form and prevent TCB from solidifying, it is necessary to avoid the use of a metal such as iron as a material of a reaction vessel for carrying out the reaction in the reaction of 3, 4-dichloro-1-butene with chlorine.

Prior art documents

Patent document 1: japanese patent application laid-open No. 5528334

Patent document 2: british patent application publication No. 1019150 specification

Disclosure of Invention

The reaction vessel for carrying out the reaction of 3, 4-dichloro-1-butene with chlorine is generally a metal reaction vessel lined with a fluororesin or a glass reaction vessel. However, if it is considered that the reaction vessel is easily damaged by swelling of the fluororesin or breaking of the glass, the use of these reaction vessels is not considered to be industrially advantageous.

The invention provides a method and an apparatus for producing 1,2,3, 4-tetrachlorobutane, wherein loss of 3, 4-dichloro-1-butene as a raw material and loss of 1,2,3, 4-tetrachlorobutane as a product are less likely to occur, and 1,2,3, 4-tetrachlorobutane can be produced stably and economically.

To solve the above problems, one aspect of the present invention is as described in the following [1] to [6 ].

[1] A method for producing 1,2,3, 4-tetrachlorobutane, comprising: after a reaction solution containing 3, 4-dichloro-1-butene was stored in a reaction vessel, chlorine gas was supplied to a gas phase portion in the reaction vessel, and the 3, 4-dichloro-1-butene was reacted with the chlorine gas.

[2]According to [1]The process for producing 1,2,3, 4-tetrachlorobutane, wherein the amount of the chlorine gas supplied is 5.0 mol/h/cm per unit area of the liquid surface of the reaction solution in the reaction vessel ²The following.

[3] The process for producing 1,2,3, 4-tetrachlorobutane according to [1] or [2], wherein the pressure in the reaction vessel is 0.01MPa or more and 1.0MPa or less.

[4] The process for producing 1,2,3, 4-tetrachlorobutane according to any one of [1] to [3], wherein a part of the reaction solution is extracted and returned to the gas phase in the reaction vessel in the reaction of the 3, 4-dichloro-1-butene with the chlorine gas.

[5] The process for producing 1,2,3, 4-tetrachlorobutane according to [4], wherein when a part of the reaction liquid is returned to the gas phase portion in the reaction vessel, a part of the reaction liquid is sprayed to the gas phase portion in the reaction vessel.

[6] An apparatus for producing 1,2,3, 4-tetrachlorobutane, which is used for producing 1,2,3, 4-tetrachlorobutane by the process for producing 1,2,3, 4-tetrachlorobutane according to any one of [1] to [5],

the production apparatus comprises a reaction vessel for containing a reaction solution containing 3, 4-dichloro-1-butene, and a chlorine gas introduction pipe for introducing chlorine gas into the reaction vessel,

the chlorine gas introduction pipe is configured to: the chlorine gas ejection port can be provided above the liquid surface of the reaction solution in the reaction vessel.

According to the present invention, 3, 4-dichloro-1-butene as a raw material and 1,2,3, 4-tetrachlorobutane as a product are less likely to be lost, and 1,2,3, 4-tetrachlorobutane can be produced stably and economically.

Drawings

Fig. 1 is a diagram for explaining an embodiment of the method for producing 1,2,3, 4-tetrachlorobutane according to the present invention, and is a schematic diagram for explaining the structure of an apparatus for producing 1,2,3, 4-tetrachlorobutane.

Fig. 2 is a schematic diagram for explaining the structure of a conventional apparatus for producing 1,2,3, 4-tetrachlorobutane.

Detailed Description

Hereinafter, an embodiment of the present invention will be described with reference to the drawings. The present embodiment is an example of the present invention, and the present invention is not limited to the present embodiment. Various modifications and improvements may be added to the present embodiment, and embodiments to which such modifications and improvements are added are also included in the present invention.

According to the studies of the present inventors, it was found that in the reaction of synthesizing TCB by reacting 3, 4-dichloro-1-butene with chlorine gas, if a solid component containing ferric chloride or the like is present in the reaction system, the amount of TCB produced is more dominant as solid meso form than as liquid d form and liquid l form. The solid TCB meso form is a factor causing problems such as clogging of a chlorine gas outlet of a chlorine gas introduction pipe for introducing chlorine gas into the reaction vessel and clogging of a pipe for transporting the reaction solution after the reaction is completed.

Therefore, conventionally, it has been necessary to apply a fluororesin liner or a glass liner to the inner surface of a metal reaction vessel, to prevent the metal from contacting the reaction solution in the reaction vessel, and to use a shell-and-tube member made of teflon (registered trademark) for a heat exchanger for cooling the reaction solution. However, if the heat exchanger is used for a long period of time, there may be a problem that the tube-making expansion of the heat exchanger is open due to the 3, 4-dichloro-1-butene.

In addition, since chlorine gas has been conventionally diluted with nitrogen gas and introduced into the reaction solution, there has been a problem that nitrogen gas flows out of the reaction vessel together with 3, 4-dichloro-1-butene as a raw material and TCB as a product, causing a loss.

The present inventors have earnestly studied to solve the above problems. As a result, they have found that the loss of 3, 4-dichloro-1-butene as a raw material and TCB as a product due to nitrogen gas can be suppressed and the production of TCB as a meso-form can be suppressed by introducing chlorine gas into a gas phase portion existing above the liquid surface of the reaction liquid in the reaction vessel, and have completed the present invention.

That is, the method for producing 1,2,3, 4-tetrachlorobutane according to the present embodiment includes: after the reaction solution 1 containing 3, 4-dichloro-1-butene was stored in the reaction vessel 11, chlorine gas was supplied to the gas phase portion 2 in the reaction vessel 11, and 3, 4-dichloro-1-butene was reacted with chlorine gas to produce 1,2,3, 4-tetrachlorobutane (see fig. 1).

The reaction field can be limited to a gas-liquid interface by the method for producing 1,2,3, 4-tetrachlorobutane according to the present embodiment. Even if a solid component such as iron chloride, which increases the production of the meso form, is present in the reaction solution, it does not cause the increase of the meso form unless it is present at the gas-liquid interface which is the reaction field. Therefore, conventionally, it has been necessary to apply a fluororesin liner, a glass liner, or the like to a metal reaction vessel, but in the present embodiment, the metal reaction vessel 11 can be used for the reaction as it is without applying a fluororesin liner or a glass liner.

As described above, the production method of 1,2,3, 4-tetrachlorobutane according to the present embodiment is difficult to produce TCB as a meso form, and therefore clogging of the chlorine gas ejection port of the chlorine gas introduction pipe 23, clogging of the piping for transporting the reaction solution 1 after the completion of the reaction, and the like are difficult to occur. Thus, 1,2,3, 4-tetrachlorobutane can be produced stably and economically. 1,2,3, 4-tetrachlorobutane can be used as a raw material for synthesizing hexafluoro-1, 3-butadiene via 1,2,3, 4-tetrachloro-1, 1,2,3,4, 4-hexafluorobutane. Hexafluoro-1, 3-butadiene is used in a large amount as an etching gas in a semiconductor production process, and therefore, a method for stably and economically producing TCB is very useful.

The concentration of the chlorine gas used in the reaction is not particularly limited, and it is not necessary to use a chlorine gas diluted with an inert gas such as nitrogen, and therefore, if a chlorine gas which is not diluted at all is used, the off-gas discharged from the gas phase portion 2 of the reaction vessel 11 can be eliminated. Therefore, it is difficult to cause loss of 3, 4-dichloro-1-butene as a raw material and 1,2,3, 4-tetrachlorobutane as a product, and an apparatus for removing the chlorine gas flowing out is not required.

An exhaust pipe (not shown) for discharging the gas phase portion 2 of the reaction vessel 11 to the outside of the reaction vessel 11 and a nitrogen gas supply pipe (not shown) for introducing nitrogen gas into the reaction vessel 11 are not essential in the reaction, but may be provided for maintenance of the reaction vessel 11 or for preventing negative pressure at the time of discharging the reaction solution 1. If the reaction amount of the chlorine gas decreases during the reaction, the pressure (reaction pressure) in the reaction vessel 11 increases, and the amount of the chlorine gas dissolved in the reaction solution increases due to the increase in the reaction pressure, and as a result, the reaction amount increases, and the increase in the reaction pressure is stopped, which is not problematic.

When chlorine gas is used for the reaction without being diluted with an inert gas such as nitrogen, the supplied chlorine gas is consumed rapidly by the reaction, and therefore the reaction is performed while maintaining a pressure adjusted in advance with an inert gas such as nitrogen. The reaction pressure can be arbitrarily set. The reaction pressure is preferably 0.01MPa or more and 1.0MPa (absolute pressure) or less, and if it is 1.0MPa (absolute pressure) or less, it is necessary to provide a pressure resistance of the 1,2,3, 4-tetrachlorobutane production facility to more than necessary.

The amount of chlorine gas supplied is preferably 0.01 mol/h/cm per unit area of the liquid surface 1a of the reaction solution 1 in the reaction vessel 11²Above and 5.0 mol/h/cm²Hereinafter, more preferably 0.01 mol/h/cm²Above and 2.5 mol/h/cm²The following. If the amount of chlorine gas supplied is 5.0 mol/h/cm²Hereinafter, since the reaction pressure does not rise faster than the reaction rate and does not become very high, the production facility of 1,2,3, 4-tetrachlorobutane does not need to have high pressure resistance and is economical.

In the method for producing 1,2,3, 4-tetrachlorobutane according to the present embodiment, the reaction solution 1 may be stirred or not stirred during the reaction. That is, the apparatus for producing 1,2,3, 4-tetrachlorobutane according to the present embodiment is an apparatus for producing 1,2,3, 4-tetrachlorobutane by the method for producing 1,2,3, 4-tetrachlorobutane according to the present embodiment, and includes a reaction vessel 11 for containing a reaction solution 1 containing 3, 4-dichloro-1-butene, and a chlorine gas introduction pipe 23 for introducing chlorine gas into the reaction vessel 11, and may or may not include a stirrer for stirring the reaction solution 1.

The apparatus for producing 1,2,3, 4-tetrachlorobutane according to the present embodiment may not include a stirrer for stirring the reaction solution 1 if it includes a circulation device for extracting a part of the reaction solution 1 in the reaction vessel 11 during the reaction to the outside of the reaction vessel 11 and returning the extracted part to the reaction vessel 11. For example, if an operation of extracting a part of the reaction solution 1 to the outside of the reaction vessel 11, cooling the extracted part by the heat exchanger 19, and returning the cooled part to the reaction vessel 11 is performed in order to remove the reaction heat, it is not necessary to stir the reaction solution 1 by a stirrer.

When the reaction solution 1 is stirred, it is preferable to stir the reaction solution 1 at a low stirring speed to such an extent that the solid content containing iron chloride or the like mixed in the reaction solution 1 does not come close to the liquid surface 1a of the reaction solution 1. Since the reaction field is the liquid surface 1a of the reaction solution 1, when the reaction solution 1 circulated and cooled as described above is returned to the reaction vessel 11 in order to cool the portion of the reaction solution 1 near the liquid surface, the reaction solution can be sprayed from the nozzle 26, that is, can be sprayed in a spray form to form fine droplets, which are spread on the liquid surface 1a of the reaction solution 1 in the reaction vessel 11. Further, a stirrer for stirring the reaction solution 1 in the reaction vessel 11 may be provided.

The metal forming the inner surface of the reaction vessel 11 is preferably corrosion-resistant to chlorine gas, hydrogen chloride, and hydrochloric acid, and examples thereof include at least one metal selected from the group consisting of iron alloys, nickel alloys, and tantalum. These metals may be used alone in 1 kind, or may be used in combination in 2 or more kinds. Examples of the iron alloy include stainless steel such as SUS316L, and examples of the nickel alloy include hastelloy (registered trademark) and monel (registered trademark).

At least one of a grinding process and an acid washing process may be performed on the inner surface of the reaction vessel 11. The polishing treatment includes, for example, a polishing treatment using a polishing paper containing a polishing material having a particle size of more than P150. Examples of the acid washing treatment include a treatment of washing the surface with an acid such as nitric acid or sulfuric acid. In the apparatus for producing 1,2,3, 4-tetrachlorobutane, at least one of the polishing treatment and the acid washing treatment may be performed on the metal surface other than the inner surface of the reaction vessel 11.

If rust or dirt is present on the inner surface of the reaction vessel 11 or on the other metal surface, the rust or dirt is peeled off and suspended in the reaction solution 1, and the rust or dirt is supplied to a place where the reaction of the introduced chlorine gas mainly occurs. If the rust or scale is, for example, an iron-containing substance, it will react with water and hydrogen chloride to form iron oxide, or with chlorine to form iron chloride. The iron oxide or iron chloride produced exhibits a catalytic action, resulting in an increase in the rate of production of meso-form.

In the apparatus for producing 1,2,3, 4-tetrachlorobutane according to the present embodiment, a reaction liquid extraction pipe 29 for extracting the reaction liquid 1 to the outside of the reaction vessel 11 may be attached to the reaction vessel 11. In addition, general equipment necessary for operating the 1,2,3, 4-tetrachlorobutane production apparatus, such as a temperature measuring device such as a thermocouple for measuring the temperature of the reaction solution 1, a pressure gauge for measuring the pressure at each site such as in the reaction vessel 11, and a flow meter for measuring the flow rate of the liquid flowing through each pipe, may be installed in the 1,2,3, 4-tetrachlorobutane production apparatus.

The shape of the reaction vessel 11 is not particularly limited, but is preferably a cylindrical shape having a large diameter in order to increase the area of the liquid surface 1a of the reaction solution 1 in the reaction vessel 11.

The purity of 3, 4-dichloro-1-butene as a raw material is preferably 90% by mass or more.

The reaction of 3, 4-dichloro-1-butene with chlorine can be carried out in the absence of a solvent or in a solvent. In the case of the solvent-free reaction, 3, 4-dichloro-1-butene is used as the reaction solution 1, and chlorine gas is introduced into the gas phase portion 2 existing above the liquid surface 1a of the reaction solution 1 to carry out the reaction. In the case of the reaction in a solvent, 3, 4-dichloro-1-butene is dissolved in the solvent to obtain a solution as a reaction solution 1, and chlorine gas is introduced into a gas phase portion 2 existing above a liquid surface 1a of the reaction solution 1 to carry out the reaction. The type of the solvent is not particularly limited, and 1,2,3, 4-tetrachloro-1, 1,2,3,4, 4-hexafluorobutane, carbon tetrachloride and the like can be used.

The ratio of the meso form produced in the TCB produced does not change depending on the presence or absence of the solvent, and the temperature at which the meso form solidifies changes depending on the concentration of the meso form in the reaction solution 1, so the amount of the solvent is adjusted depending on the treatment temperature of the reaction solution 1.