Nozzle reactor for production of 1.2-dichloroethane

FIELD: chemical industry; designs of the bubble-type reactors for production of 1.2-dichloroethane.

SUBSTANCE: the invention is pertaining to the design of the bubble-type reactors for production of 1.2-dichloroethane by the method of the liquid-phase chlorination of ethylene with the reaction heat removal at boiling of the working medium. As the contact device the reactor uses two layers of the metallic nozzle. The liquid 1.2-dichloroethane is fed from above to the nozzle, into the space between the layers of the nozzle feed the gaseous chlorine with nitrogen, and under the lower layer of the nozzle feed the gaseous ethylene with nitrogen, that allows to reduce the diameter of the reactor in 1.5-2 times due to the increased effectiveness of stirring and formation of the developed contact surface of the phases. At that the heat of the reaction is removed by evaporation of 1.2-dichloroethane in nitrogen. At that the temperature of the liquid is maintained below the boiling temperature. The technical result of the invention is the increased selectivity of the process, reduction of the outlet of the by-products (the highest ethane chlorides) and the decreased overall dimensions of the reactor.

EFFECT: the invention ensures the increased selectivity of the process, reduction of the outlet of the by-products (the highest ethane chlorides) and the decreased overall dimensions of the reactor.

1 ex, 4 dwg

 

The technical field

The invention relates to a reactor for producing 1,2-dichloroethane by means of liquid-phase chlorination of ethylene to remove the heat of reaction at boiling of the working environment.

The level of technology

Most similar designs of reactors for producing 1,2-dichloroethane are high-temperature and low-temperature reactors liquid-phase chlorination of ethylene [1].

In the high temperature reactor, the process is conducted at a temperature equal to the boiling temperature of the working environment (83,5-110°depending on the pressure). Reactor high-temperature process is a bubbling gas-lift column 1 with internal circulation tube 4 (Fig 1). The working environment is liquid 1,2-dichloroethane. The catalyst is FeCl3, which is located in the reactor in dissolved form. To obtain a solution of chlorine gas through the distributor 2 is fed in the lower part of the annular space. The reaction is carried out upstream when entering into the reactor in gaseous ethylene through the distributor 3. Due to the difference of density in the circulation pipe and the annular space occurs the liquid circulation. In the upper part of the reactor are perforated plates 6, designed to intensify the agitation. The heat removal is carried out by evaporation of 1,2-dichloroethane at boiling. The upper part of the reactor plays the role of a separator for separating liquid droplets from the steam. The reaction products are discharged in the form of vapor to the stage rectification through the nozzle in the lid of the reactor. Due to the low volatility of the catalyst remains in the reactor. To maintain the liquid level in the lower part of the reactor is introduced 1,2-dichloroethane.

An important advantage of the high-temperature reactor in comparison with the low temperature is efficiency: heat is consumed for evaporation and distillation products, waste no water, the catalyst consumption is minimal.

The disadvantage of the high-temperature reactor is a low selectivity (98,0-98,7%), associated with an increased rate of adverse reactions with increasing temperature. By-products - trichloroethane, trichlorethylene and other higher chlorinated ethane is formed in the reactor as a result of substitution reactions of chlorination. The rate of adverse reactions decreases with decreasing temperature [2]. In the formation of 1 mol of 1,2-dichloroethane is allocated an amount of heat sufficient to evaporate 6 moles of 1,2-dichloroethane.

Low-temperature reactor (figure 2) is bubbling column 1, connected at the top and bottom with an external shell and tube heat exchanger 5. The working environment in the reactor is the reaction product -1,2-dichloroethane in water the state. Chlorine is introduced into the lower part of the column through the dispenser 2. Earlier in the resulting chlorine solution through the dispenser 3 is introduced ethylene. Due to the difference of density in the refrigerator and column raises the circulation of the working environment with upward flow in the column. The temperature in the reactor is 65°C. the Removal of the synthesized product by gravity flow through the overflow. The separation of product from catalyst is carried out at the stage of purification. The catalyst after the cleanup phase and not subject to regeneration. The products of the process from the stage of purification act of rectification.

The advantage of the low temperature reactor is a high selectivity (99,6%), owing to the slowdown of adverse reactions substitution chlorination at lower temperature. The disadvantages of the low-temperature reactor are large wastewater flow at the stage of purification of the product from the catalyst, significant consumption of catalyst per unit of production, high energy costs for cooling the reaction mass and irrational use of the heat of reaction.

Disclosure of inventions

The objective of the invention is to increase the selectivity of the process through the development of a new type of reactor Packed reactor liquid-phase chlorination of ethylene (figure 4). As a nozzle, you can use any reinforcement of the private modern type of nozzle: ring process, PAL, regular types of nozzles. The material for the nozzle selected carbon steel. This promotes uniform temperature distribution in the liquid film. The flow of liquid dichloroethane with the dissolved catalyst is served on the top of the packing layer, the liquid film is distributed over the surface of the nozzle. In the reactor are two layers of the nozzle. The top layer of the nozzle is designed for absorption of chlorine stream of 1,2-dichloroethane, and the bottom layer of the nozzle - to chemisorption of ethylene with chlorine solution. In the space between the layers of the nozzle is served gaseous mixture of chlorine and nitrogen. The resulting chlorine solution flow to the bottom layer of the nozzle, the bottom of which a gaseous mixture of ethylene and nitrogen. Heat of reaction is given by evaporation of 1,2-dichloroethane in a stream of nitrogen, the temperature of the liquid is maintained below the boiling point.

The invention can be obtained the following results:

1. Reducing the diameter of the reactor compared to the prototypes. For carrying out process in the bubbling regime with an average volumetric gas content environment 20-30% requires a large amount of liquid 1,2-dichloroethane. This explains the large diameter bubble reactor. In a Packed reactor process is carried out by contact with the film of liquid chlorine, ethylene and nitrogen. In this case, not trebuet the large number of 1,2-dichloroethane. 1,2-dichloroethane in a Packed reactor is fed in an amount necessary for removal of reaction by evaporation. Industrial bubble reactor with a load on chlorine 3000 m3/h has a diameter of 3600 mm Calculations show that the Packed reactor with the same load has a diameter of 2000 mm

2. The increase in selectivity. In a Packed reactor is served chlorine in the mixture with nitrogen. As a result, the concentration of chlorine in the gas phase is lower than in the bubble reactor. This will lead to lower equilibrium concentration of chlorine in the liquid phase according to Henry's law [3].

By reducing the concentration of chloride in 1,2-dichloroethane will decrease the rate of adverse reactions. It follows from the work [4], which shows that increasing the concentration of dissolved chlorine in the reaction mass leads to an increase in the rate of formation of by-products, in accordance with the equation for the rate of formation of by-products.

In addition, due to evaporative cooling of 1,2-dichloroethane in nitrogen the temperature in the reactor is below the boiling point of 1,2-dichloroethane (figure 3). The graph of figure 3. based on the material, the heat balance of the Packed reactor for the next regime: chlorine consumption 300 nm3per hour, the consumption of ethylene 315 nm3per hour, nitrogen flow of 300 nm3per hour, the initial concentration of chlorine in the liquid 0.1 KMOL the/m 3a final concentration of chlorine in the liquid 0,005 KMOL/m3the specific surface of the nozzle 400 m2/m3, the volume flow of the fluid 134 m3/h, the inner diameter of the reactor 1,36 m Of figure 3. you can see that as you move down the working fluid is first heated by the released heat of reaction, and then begins to cool in nitrogen, moving from the bottom up. The average temperature of the working fluid is 77°C. Thus, the temperature in the Packed reactor is less than the boiling temperature in the bubble reactor. It is known [2]that with decrease in temperature decreases the rate of adverse reactions that will increase the selectivity of the process carried out in a Packed reactor. Thus, in the nozzle reactor selectivity is higher than in the high-temperature bubbling reactor in which the temperature of the working environment is 83,5-110°and the selectivity of the process 98,0-98,7% [5].

Thus, in the nozzle reactor liquid-phase chlorination of ethylene create more favorable conditions for the process than in the reactor with bubbling typing reagents.

Brief description of drawings

List of figures:

figure 1. Bubbling gas-lift reactor high-temperature liquid-phase chlorination of ethylene;

figure 2. Bubble reactor low-chlorinated what I ethylene;

figure 3. The temperature distribution of the liquid along the height of the Packed reactor;

figure 4. The Packed reactor for producing 1,2-dichloroethane.

In figure 1 and figure 2 describes analogs of the invention. Figure 3 shows the dependence to determine the temperature of the working fluid in any section of the reactor. Figure 4 describes the structure and principle of operation of the reactor, which can be implemented in the invention.

The implementation of the invention

The Packed reactor (figure 4) to get 1,2-dichloroethane works in the following mode: chlorine consumption 300 nm3per hour, the consumption of ethylene 315 nm3per hour, nitrogen flow of 300 nm3per hour, the initial concentration of chlorine in the liquid of 0.1 KMOL/m3a final concentration of chlorine in the liquid 0,005 KMOL/m3the coefficient of mass transfer coefficients in the liquid 0.4 m/h, the specific surface of the nozzle 400 m2/m3, the volume flow of the fluid 134 m3/h, the inner diameter of the reactor 1,36 m Height layer of the nozzles in these conditions was 3,12 m as a nozzle rings are used process. The material for the nozzle selected carbon steel, it will promote uniform temperature distribution in the liquid film. The nozzle is placed in two layers.

The Packed reactor liquid-phase chlorination of ethylene (figure 4) is as follows. Above served 1,2-dichloroethane in the quantity of no is required for the reaction and cooling of the reaction mixture in the result of evaporative cooling. 1,2-dichloroethane film flows over the surface of the nozzle. In the reactor are two layers of the nozzle. The top layer of the nozzle is designed for absorption of chlorine stream of 1,2-dichloroethane, and the bottom layer of the nozzle - to chemisorption of ethylene with chlorine solution. In the space between the layers of the nozzle through the valve 2 is supplied gaseous mixture of chlorine and nitrogen. The resulting chlorine solution from the upper layer of the nozzle onto the bottom layer of the nozzle. Under the bottom layer of the nozzle through the valve 3 is fed gaseous mixture of ethylene and nitrogen. The gas and liquid phases move countercurrent. The upper part of the reactor plays the role of a separator for separating liquid droplets from the steam. This also contributes to the drop entrainment 8. As the nozzle 7 decided to use a metal cap for a more uniform temperature distribution in the liquid film. Nitrogen and excess ethylene from the top of the reactor after condensation of the vapors in the condenser 5 is separated from the liquid 1,2-dichloroethane in a gas-liquid separator 10 and returned to the compressor 9 in the reactor. The condensate after the gas-liquid separator 10 is fed to a distribution node 11, a portion of the condensate pump 12 is returned to the reactor, and the remainder in the form of the finished product is discharged into collection vessels. Heat of reaction is given by evaporation of 1,2-dichloroethane in nitrogen. Method of removal of heat when Sporitelna cooling effective. In this nozzle reactor due to evaporative cooling of 1,2-dichloroethane in nitrogen the temperature in the reactor is below the boiling point of 1,2-dichloroethane, which is reflected in figure 3. The graph of figure 3. based on the material, the heat balance of the Packed reactor. As evidence that the selectivity in the nozzle reactor is higher than in the prototype (bubbling high temperature reactor), you can use the readings from the graph (figure 3). In accordance with these data, the average temperature of the working environment in the reactor is equal to 77°C. As is known from [2], reducing the temperature in the reactor will reduce the rate of adverse reactions, the selectivity of the process will be higher than in the high-temperature bubbling reactor (figure 1). In bubbling high temperature reactor operating temperature is 83,5-110°and the heat of reaction is given by boiling of the working environment. Thus the selectivity of the process in the high temperature reactor is 98,0-98,7% [5].

Nozzle reactor can be controlled by regulating the flow rate of the working fluid flow of nitrogen and the initial temperature of the working fluid. The lower the initial temperature of the working fluid will increase the selectivity of the process, but this will require increasing the flow of nitrogen and, as a consequence, HC is the increase of the layer height of the nozzle. Increasing the flow rate of the working fluid will reduce the average temperature in the layer of the nozzle, but it will also result in the need to increase the height of the nozzle layer. Due to the increase in consumption of nitrogen can reduce the temperature of the working fluid, but due to the decrease of the concentration of ethylene and driving force of mass transfer will be increased to the desired height of the layer of the nozzle.

Literature

1. Lebedev N.N. Chemistry and technology of basic organic and petrochemical synthesis. Ed. 2nd Per. M., "Chemistry", 1975 - 736 S.

2. Avetyan MG, Sonin EV, zeidman O.A. and others Research process direct chlorination of ethylene in an industrial environment. // Chemical engineering, 1991, No. 12, s-713.

3. Ramm, V.M. gas Absorption. M., High school, 1975.

4. Rozhkov V., zeidman O.A., Sonin EV, krištáľ NF, Avetyan MG, Traeger Y.A., V. Kharitonov, Passes A.F., Mubarak RG Patterns of liquid-phase chlorination of ethylene. // Chem. prom. 1991. No. 7. S.

5. Mubarak R., Hydraulics and mass transfer in bubble reactor chlorination of ethylene. - Diss. for the degree of Kida. technology. Sciences. Angarsk, 1998. 132 C.

The bubbling reactor type for producing 1,2-dichloroethane by means of liquid-phase chlorination of ethylene to remove the heat of reaction at boiling working medium, characterized in that the reactor is placed two layers of metal density and, on top of the nozzle serves liquid 1,2-dichloroethane, in the space between the layers of the nozzle serves gaseous chlorine with nitrogen, and under the bottom layer of the nozzle serves gaseous ethylene with nitrogen, and the heat of reaction away due to the evaporation of 1,2-dichloroethane in nitrogen and the temperature of the liquid support below the boiling point.



 

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