KR101049588B1 - Device of preparing 1,2-dichloroethane using dual fluidized bed reactor and method of preparing the same - Google Patents

Abstract

The present invention relates to an apparatus for producing 1,2-dichloroethane and a method for producing the same. More specifically, the catalyst is continuously circulated while the oxidation reaction using oxygen and hydrogen chloride and the cloning reaction of ethylene proceed independently. It relates to a method for producing 1,2-dichloroethane by a two-stage oxcyclolination reactor having a structure.

When producing 1,2-dichloroethane in accordance with the present invention, a separate unit process for purification is not required, thereby simplifying the operation, reducing the investment cost and reducing the energy consumption.

1,2-dichloroethane, two stage reactor, oxcyclolination reaction, fluidized bed reactor

Description

DEVICE OF PREPARING 1,2-DICHLOROETHANE USING DUAL FLUIDIZED BED REACTOR AND METHOD OF PREPARING THE SAME}

The present invention relates to an apparatus for producing 1,2-dichloroethane and a method for producing the same. More specifically, the catalyst is continuously circulated while the oxidation reaction using oxygen and hydrogen chloride and the cloning reaction of ethylene proceed independently. It relates to a method for producing 1,2-dichloroethane by a two-stage oxcyclolination reactor having a structure.

In the conventionally known oxcyclorelation process of ethylene, a process of converting ethylene into 1,2-dichloroethane in the presence of oxygen and hydrogen chloride using a solid catalyst is commercialized by two methods, a fixed bed and a fluidized bed. In these two methods, a mixed gas of ethylene, hydrogen chloride and oxygen is injected into the reactor and the reaction proceeds as shown in the following equation (1).

C ₂ H ₄ + 2HCl + 1 / 2O ₂ → CH ₂ Cl-CH ₂ Cl + H ₂ O Δ H ^o ₂₉₈ = -295 kJ / mol (1)

As the catalyst used in the oxcyclorelation process, a copper catalyst supported mainly on alumina is used, and the catalytic reaction thereof is shown in the following formula (2).

C ₂ H ₄ + 2CuCl ₂ (catalyst) → CH ₂ Cl-CH ₂ Cl + Cu ₂ Cl ₂ (catalyst) (2)

Cu ₂ Cl ₂ (catalyst) + 1 / 2O ₂ → Cu ₂ OCl ₂ (catalyst)

Cu ₂ OCl ₂ (catalyst) + 2HCl → 2CuCl ₂ (catalyst) + H ₂ O

The conventional oxcyclolination method has the following limitations and problems.

First, in order to perform a safe reaction, the mixing ratio of ethylene and oxygen must be out of the explosion risk range. Thus, by injecting excess ethylene gas, it can be kept out of the explosion risk range. In this case excess ethylene must be separated after the reaction and re-injected back into the reactor as a reactant.

Second, the product through oxcyclorelation of ethylene is chloride containing water and 1,2-dichloroethane and unreacted hydrogen chloride is discharged together. In particular, water and hydrogen chloride produced during the reaction lead to reactor corrosion and shorten reactor life.

Third, CO or CO ₂ is generated due to the combustion reaction of ethylene and oxygen because a mixed gas of ethylene, oxygen and hydrogen chloride is injected. The combustion reaction consumes oxygen in the injection gas, which inhibits the oxcyclorelation reaction and the generation of CO and CO2 reduces the selectivity of 1,2-dichloroethane.

As mentioned above, the conventional oxcyclorelation method of injecting a mixture of ethylene, hydrogen chloride and oxygen has problems of oxygen utilization, explosion risk, reactor corrosion, CO or CO ₂ generation, and ethylene and oxygen Because of the excessive use of ethylene in the mixed gas to avoid the explosive mixing ratio of, unreacted ethylene will be excessively mixed into the product, resulting in low ethylene conversion.

In order to solve the problems of the prior art as described above, the present invention provides an apparatus for producing 1,2-dichloroethane using a two-stage oxcyclolination reactor in which the cloning reaction and the oxidation reaction are independently and continuously performed. For the purpose of

It is also an object of the present invention to provide a method for producing 1,2-dichloroethane using a two-stage oxcyclolination reactor according to the present invention.

These and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object,

An oxidation reactor (2) in which a CuCl ₂ catalyst and water are produced by an oxidation reaction of a CuCl catalyst carried out in the presence of hydrogen chloride and oxygen supplied through an oxidation reactor inlet (1);

A chlorination reactor catalyst injection tube (3) for transferring the CuCl ₂ catalyst produced in the oxidation reactor (2);

1,2-dichloroethane and CuCl catalyst are formed by a cloning reaction between the CuCl ₂ catalyst transferred through the clolation reactor catalyst injection pipe 3 and the ethylene supplied through the clone reactor reactor 4. The resulting clomination reactor (5);

Oxidation reactor catalyst injection pipe (6) for transferring the CuCl catalyst produced in the cloning reactor (5); And

CuCl catalyst passing through the oxidation reactor catalyst injection tube (6) comprises a catalyst transfer tube (7) which is conveyed to be re-introduced into the oxidation reactor (2),

The oxidation reactor (2), the chlorination reactor catalyst injection pipe (3), the chlorination reactor (5), the oxidation reactor catalyst injection pipe (6), and the catalyst transfer pipe (7) are sequentially connected to each other It is characterized in that the structure, wherein the oxidation reactor (2) provides an apparatus for producing 1,2-dichloroethane, characterized in that located higher than the chloride reactor (5).

Also,

Supplying hydrogen chloride and oxygen to the oxidation reactor 2 through the oxidation reactor inlet 1;

Oxidizing the CuCl catalyst in the presence of the supplied hydrogen chloride and oxygen in the oxidation reactor (2) to produce a CuCl ₂ catalyst and water;

Transferring the generated CuCl ₂ catalyst to a cloning reactor (5) via a cloning reactor catalyst injection tube (3);

A step of producing a 1,2-dichloroethane and a CuCl catalyst by performing a clolation reaction of the transferred CuCl ₂ catalyst and the ethylene supplied through the clolation reactor inlet 4 in the cloning reactor 5 ; And

Re-injecting the generated CuCl catalyst into the oxidation reactor (2) located higher than the clolation reactor (5) via an oxidation reactor catalyst injection tube (6) and a catalyst transfer tube (7); ,

Each step provides a method for producing 1,2-dichloroethane, which is circulated sequentially.

The process of purifying 1,2-dichloroethane prepared according to the present invention may be omitted, thereby simplifying the operation, reducing the investment cost and reducing the energy consumption.

Further, according to the present invention, the conversion rate of ethylene, the yield and purity of 1,2-dichloroethane are high, and unreacted hydrogen chloride can be reduced, thereby extending the life of the reactor.

In addition, there is no risk of explosion as oxygen and ethylene are separated, and no separate device for separating CO or CO ₂ is required.

Hereinafter, the present invention will be described in detail.

The present invention divides the oxcyclolination reaction into two stages, that is, the oxidation reaction of the catalyst using oxygen and hydrogen chloride and the chlorination reaction injecting ethylene are sequentially performed.

The oxcyclolination reaction of ethylene can be divided into two stage reactions as shown in the following formulas (3) and (4).

Oxidation reaction: 2CuCl + 1 / 2O ₂ + 2HCl → 2CuCl ₂ + H ₂ O (3)

Chloride reaction: C ₂ H ₄ + 2CuCl ₂ → CH ₂ Cl-CH ₂ Cl + 2CuCl (4)

The inventors have found that this object can be achieved by achieving high conversion and selectivity in the preparation of 1,2-dichloroethane and by applying fluidization or fluidized bed techniques as a method for smooth catalyst circulation. The fluidization technique or the fluidized bed technique is a technique that changes the solid particles to a fluid-like property by flowing a medium such as a gas or a liquid to the solid particles, which is widely used in the process of processing solid particles.

1 is a schematic configuration diagram of an apparatus for producing 1,2-dichloroethane according to the present invention.

As shown in FIG. 1, the apparatus for preparing 1,2-dichloroethane according to the present invention has a structure of a two-stage oxcyclolination reactor in which a chlorination reaction and an oxidation reaction are independently and continuously performed.

In addition, in the case of the oxychlorination reaction using a fluidized bed, in order to secure sufficient reaction time and particle retention time, a two-stage fluidized bed reactor in which both reactions are performed in a bubble fluidized bed region should be used. Is shown.

That is, an oxidation reactor (2) in which a CuCl ₂ catalyst and water are produced by an oxidation reaction of a CuCl catalyst carried out in the presence of hydrogen chloride and oxygen supplied through the oxidation reactor inlet (1);

A chlorination reactor catalyst injection tube (3) for transferring the CuCl ₂ catalyst produced in the oxidation reactor (2);

1,2-dichloroethane and CuCl catalyst are formed by a cloning reaction between the CuCl ₂ catalyst transferred through the clolation reactor catalyst injection pipe 3 and the ethylene supplied through the clone reactor reactor 4. The resulting clomination reactor (5);

Oxidation reactor catalyst injection pipe (6) for transferring the CuCl catalyst produced in the cloning reactor (5); And

CuCl catalyst passing through the oxidation reactor catalyst injection tube (6) comprises a catalyst transfer tube (7) which is conveyed to be re-introduced into the oxidation reactor (2),

The oxidation reactor (2), the chlorination reactor catalyst injection pipe (3), the chlorination reactor (5), the oxidation reactor catalyst injection pipe (6), and the catalyst transfer pipe (7) are sequentially connected to each other It is characterized by a mold structure. In addition, the oxidation reactor (2) is characterized in that it is located higher than the chloride reactor (5).

In the two-stage fluidized bed reactor as shown in FIG. Through (7) the movement of the particles is achieved. The arrangement of the reactor is such that one reactor is set at a higher position than the other reactor so that particles can be naturally transported by gravity, and the particles discharged from the reactor located below are transferred to the catalyst transfer pipe 7. The gas in charge of transporting the solid in the catalyst transfer pipe 7 is efficient to use an inert material such as N ₂ that does not participate in the reaction, and in addition to transporting the solid, it includes the role of blocking the reaction gas and the generated gas of the two reactors. The gas supplied to the catalyst transfer pipe 7 flows directly into the reactor located at a high place, so when the two reaction products are compared, an oxidation reactor in which H ₂ O is generated is easily generated. It is preferable to set. In particular, in such a reactor, the reaction heat generated in the oxidation reactor may enter the chlorination reactor with the CuCl ₂ particles generated by the reaction as it is, and thus may assist the endothermic amount required in the chlorination reaction proceeding at a higher temperature. It is expected that the heat loss experienced by the particles exiting the chlorination reactor through the catalyst feed tube 7 is reduced to the reaction temperature of the oxidation reaction proceeding at a lower temperature.

The oxidation reactor (2) and the cloning reactor (5) is preferably a tubular reactor in the form of a pipe, the cross section of the reactor any shape consisting of obtuse angle, such as circular, triangular, square, pentagonal, hexagonal. Can be.

Method for preparing 1,2-dichloroethane through a two-stage oxcyclorelation reactor according to the present invention is as follows.

That is, hydrogen chloride and oxygen are supplied to the oxidation reactor (2) through the oxidation reactor inlet (1), the oxidation reaction of the CuCl catalyst occurs in the presence of the hydrogen chloride and oxygen to produce a CuCl ₂ catalyst and water.

The oxidation reaction proceeds at a reaction temperature of 100 ° C. to 400 ° C. and a reaction pressure of 1 to 20 atm in the reactor, and preferably at a reaction temperature of 200 to 300 ° C. and a reaction pressure of 1 to 10 atm.

In addition, the residence time of the reactants can be carried out in the range of 1 to 100 seconds, preferably in the range of 1 to 30 seconds.

On the other hand, the two-stage oxychlorination reaction can expect the maximum production yield of 1,2-dichloroethane when finally operated in a continuous process, in the case of the reaction system of the present invention should ensure a smooth fluidity of the catalyst, this fluidity There should be no interparticle adhesion. However, CuCl ₂ catalyst using alumina support increases the adhesion of the catalyst with the molar ratio of HCl to ethylene, resulting in the collapse of the catalyst bed and the dead zone in extreme cases, resulting in smooth catalyst circulation and reaction. This will not happen. Therefore, the molar ratio of the reactant oxygen and hydrogen chloride gas is preferably from 0.1 to 5, more preferably from 0.2 to 2. When the molar ratio is less than 0.1, the catalyst agglomeration occurs due to excess hydrogen chloride, causing problems in the catalyst transfer, and when it is 5 or more, it is not preferable because an excessive amount of air must be used.

The CuCl ₂ catalyst produced in the oxidation reactor (2) is transferred to the chloride reactor (5) via the chloride reactor catalyst inlet tube (3), and is supplied through the clone reactor (4) The 1,2-dichloroethane and CuCl catalyst are produced by the cloning reaction with ethylene.

The cloning reaction proceeds at a reaction temperature of 100 ° C. to 500 ° C. and a reaction pressure of 1 atm to 20 atm in the reactor, and preferably at a reaction temperature of 200 ° C. to 350 ° C. and a reaction pressure of 1 atm to 10 atm. .

In addition, the residence time of the reactants can be carried out in the range of 0.1 to 100 seconds, more preferably in the range of 1 to 30 seconds.

In addition, the reactant ethylene can be injected by diluting with nitrogen gas, and it is also possible to inject only ethylene without nitrogen.

The resulting CuCl catalyst is reintroduced into the oxidation reactor 2 located higher than the cloning reactor 5 via an oxidation reactor catalyst injection tube 6 and a catalyst transfer tube 7.

The CuCl catalyst is circulated by rejoining the oxidation reaction.

The yield of 1,2-dichloroethane prepared according to the present invention is at least 97%, purity of at least 99.0% can be obtained.

According to the present invention, the following advantages can be expected.

First, since chlorination of ethylene proceeds after sufficient oxidation of the catalyst, conversion of ethylene is increased. In fact, you can get a conversion rate of 99.5% or more.

Second, there is no need to consider the explosion hazard, because oxygen and ethylene separate and react with the catalyst at different stages.

Third, unreacted hydrogen chloride can be reduced by injecting a mixed gas of oxygen and hydrogen chloride during the oxidation reaction in consideration of the stoichiometric ratio.

Fourth, since no oxygen is present in the reaction conditions of ethylene, CO or CO ₂ due to the combustion reaction is not generated. Therefore, no device for separating CO _X in the off-gas is required.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

[Example]

Example  One

For the chlorination reaction of ethylene, the residence time of ethylene was adjusted to 5 seconds while raising the temperature of the chlorination reactor (5) to 250 ° C. The reaction was carried out by mixing with the catalyst particles injected from the oxidation reactor (2). Was performed. As a catalyst, a catalyst in which 10 wt% of Cu was supported on alumina was used. The catalyst particles of 1,2-dichloroethane and fine powder generated in the upper part of the chlorination reactor (5) were separated through the catalyst particle separator (8), and the reaction products and unreacted substances separated in the process were transferred to the outside. The product was discharged to obtain pure 1,2-dichloroethane through cooling and separation. The catalyst particles in the CuCl state by the chlorination reaction were reinjected into the oxidation reactor 2 via the catalyst transfer device 7. At this time, nitrogen was introduced into the catalyst transfer device 7 so as not to enter the oxidization reactor 2 generated gas generated in the cloning reactor (5). The catalyst transferred from the chlorination reactor 5 to the oxidation reactor 2 was subjected to the oxidation reaction in a fluidized bed while maintaining the temperature at 250 ° C. Oxidation reaction was carried out by adjusting the residence time of the mixed gas to 15 seconds by fixing the O ₂ : HCl molar ratio to 0.5 at 250 ℃. CuCl ₂ by oxidation reaction The catalyst particles regenerated in the state were re-injected into the chloride reactor 5 while injecting nitrogen into the catalyst injection tube 3 and the above process was repeated.

Example  2

Except for adjusting the O ₂ : HCl molar ratio of 0.25 in the oxidation reaction in Example 1 was carried out under the same conditions as in Example 1.

Comparative example  One

The oxcyclolination reaction of ethylene was carried out in a single fluid bed reactor according to known methods. In other words, a solid catalyst was used to convert ethylene into 1,2-dichloroethane in the presence of oxygen and hydrogen chloride in a single fluidized bed reactor. 180 g of the catalyst was put in a vertical tubular INCOLLOY reactor having a length of 1 m and an inner diameter of 1 inch, and the catalytic reaction was performed in a fluidized bed. As the catalyst, the same catalyst as in Example 1 in which 10 wt% of Cu was supported on alumina was used. The oxcyclorelation reaction was carried out by fixing the C ₂ H ₄ : HCl: O ₂ molar ratio of 1: 2: 0.5 at 250 ° C. and fixing the residence time of the mixed gas to 20 seconds.

Table 1 shows the results of Examples 1 and 2 and Comparative Example 1.

TABLE 1

Process conditions Example 1 Example 2 Comparative Example 1 Chloride reactor temperature ( ^o C)
Gas residence time (seconds) in the chloride reactor
Oxidation Reactor Temperature ( ^o C)
Gas residence time in oxidation reactor (seconds)
O ₂ / HCl molar ratio 250
5

250
15

0.5 250
5

250
15

0.25 250
20




0.25 Analysis Example 1 Example 2 Comparative Example 1 Ethylene conversion [%]
COx [%]
1,2-dichloroethane purity [%]
Yield [%] 99.8
0
99.2
99.0 99.5
0
99.3
98.8 99.4
2.2
98.9
96.3

Through Table 1, Examples 1 and 2 prepared through a two-stage fluidized bed reactor according to the present invention is a conversion rate of ethylene, 1,2-dichloroethane compared to Comparative Example 1 prepared through a conventional single fluidized bed reactor It was confirmed that the purity and yield are higher.

Although described in detail above with reference to the specific embodiments of the present invention, it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention, and such modifications and modifications belong to the appended claims. It is also natural.

1 is a schematic configuration diagram of an apparatus for producing 1,2-dichloroethane according to the present invention.

* Major Code Explanation *

1: Oxidation reactor inlet

2: oxidation reactor

3: Chloride reactor catalyst injection tube

4: Cloning reactor inlet

5: cloning reactor

6: oxidation reactor catalyst injection tube

7: catalyst transfer pipe

8: catalyst particle separation device

9: hopper

Claims (13)

An oxidation reactor (2) in which a CuCl ₂ catalyst and water are produced by an oxidation reaction of a CuCl catalyst carried out in the presence of hydrogen chloride and oxygen supplied through an oxidation reactor inlet (1); A chlorination reactor catalyst injection tube (3) for transferring the CuCl ₂ catalyst produced in the oxidation reactor (2); 1,2-dichloroethane and CuCl catalyst are formed by a cloning reaction between the CuCl ₂ catalyst transferred through the clolation reactor catalyst injection pipe 3 and the ethylene supplied through the clone reactor reactor 4. The resulting clomination reactor (5); Oxidation reactor catalyst injection pipe (6) for transferring the CuCl catalyst produced in the cloning reactor (5); And CuCl catalyst passing through the oxidation reactor catalyst injection tube (6) comprises a catalyst transfer tube (7) which is conveyed to be re-introduced into the oxidation reactor (2), The oxidation reactor (2), the chlorination reactor catalyst injection pipe (3), the chlorination reactor (5), the oxidation reactor catalyst injection pipe (6), and the catalyst transfer pipe (7) are sequentially connected to each other Mold structure, The oxidation reactor (2) is located higher than the chlorination reactor (5) and the ethylene conversion of at least 99.5%, the yield of 1,2-dichloroethane under a molar ratio of 0.25 to 0.5 of oxygen: hydrogen chloride An apparatus for producing 1,2-dichloroethane, wherein the purity of 97% or more and 1,2-dichloroethane satisfies all of 99.0% or more. The method of claim 1, Apparatus for producing 1,2-dichloroethane, wherein the oxidation reactor (2) and the chloride reactor (5) are fluidized bed reactors. The method of claim 1, Apparatus for producing 1,2-dichloroethane, characterized in that the oxidation reactor (2) and the chloride reactor (5) are tubular reactors. Supplying hydrogen chloride and oxygen to the oxidation reactor (2) through an oxidation reactor inlet (1), wherein the molar ratio of oxygen: hydrogen chloride is 0.25 to 0.5; Oxidizing the CuCl catalyst in the presence of the supplied hydrogen chloride and oxygen in the oxidation reactor (2) to produce a CuCl ₂ catalyst and water; Transferring the generated CuCl ₂ catalyst to a cloning reactor (5) via a cloning reactor catalyst injection tube (3); A step of producing a 1,2-dichloroethane and a CuCl catalyst by performing a clolation reaction of the transferred CuCl ₂ catalyst and the ethylene supplied through the clolation reactor inlet 4 in the cloning reactor 5 ; And Re-injecting the generated CuCl catalyst into the oxidation reactor (2) located higher than the clolation reactor (5) via an oxidation reactor catalyst injection tube (6) and a catalyst transfer tube (7); , Each step is sequentially circulated to satisfy at least 99.5% of ethylene conversion in the reaction, a yield of 1,2-dichloroethane of at least 97%, and a purity of 1,2-dichloroethane of at least 99.0%. Process for the preparation of, 2-dichloroethane. The method of claim 4, wherein The reactor is a method of producing 1,2-dichloroethane, characterized in that the fluidized bed reactor. The method of claim 4, wherein The oxidation reaction is a method for producing 1,2-dichloroethane, characterized in that carried out at a temperature of 100 to 400 ℃ and a pressure of 1 to 20 atm. The method of claim 4, wherein The residence time of the hydrogen chloride, oxygen and CuCl catalyst in the reactor in which the oxidation reaction takes place is 1 to 100 seconds, characterized in that for producing 1,2-dichloroethane. The method of claim 4, wherein The method of producing a 1,2-dichloroethane, characterized in that the cloning reaction is carried out at a temperature of 100 to 500 ℃ and a pressure of 1 to 20 atm. The method of claim 4, wherein The residence time of the CuCl ₂ catalyst and ethylene in the reactor in which the cloning reaction occurs is 0.1 to 100 seconds, characterized in that for producing 1,2-dichloroethane. delete delete delete delete

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