Method for producing 1,2-dichloroethane

 

(57) Abstract:

Usage: raw material of large monomer is vinyl chloride, 1-2-dichloroethane is a solvent with a wide range of properties and raw material for production of other chlorinated solvents (trichloroethylene, perchloroethylene and other ). The inventive process is conducted by the chlorination of ethylene with chlorine in the liquid 1,2-dichloroethane at a temperature of 20 deg. C to the boiling temperature of the reaction mass (84 deg C and above) in the presence of a complex catalyst in an amount of 0.1-2.0 wt.%. As catalysts for use ternary catalyst system comprising complexes of halides of metals such FeCl2, FeCl3, SnCl4, SbCl5with nitrogen donors such as hexamethylphosphorotriamide, pyridine and inhibitors of radical reactions of 2,6-di-tert-butyl-4 methyl phenol, n-NITROPHENOL, 2,2-di(n oksifenil)propane. table 2.

The invention relates to a method for producing 1,2-dichloroethane (EDC), used as raw material for one of the most important large-capacity monomer is vinyl chloride, used for the production of polymers and copolymers, EDC is also a solvent with a wide range of properties and raw material for production of other chlorinated m ethylene in the environment EDC at temperatures 20 64oC in the presence of ferric chloride as a catalyst (patent Germany N 2540291, publ. 1977; N 31448450, publ. 1983; U.S. patent N 4072728, publ. 1978).

The selectivity for EDC in these conditions is 98 to 99% of the Main disadvantages of these methods are:

the need for cleaning EDC raw from the catalyst and related wastewater;

significant loss of ethylene from the exhaust gases, since the process is conducted at a ratio of chlorine:1 ethylene:1,1 1,2.

Known methods for producing EDC chlorination of ethylene with chlorine in the environment of boiling EDC in the presence of 0.06 to 0.60% anhydrous ferric chloride (U.S. patent N 2929852, publ. 1960, N 4172099, publ. 1979; application Germany N 3137513, publ. 1975). The selectivity for EDC in these methods, chlorination is 97%

The main disadvantages of these methods of obtaining the EDC are:

rapid accumulation of high compounds and oligomers (Asmolov) in the reaction mass, which causes deactivation of the catalyst and the waste of raw materials;

the need for private update of the reaction mass in the reactor chlorination due to the accumulation in it of the catalyst, Asmolov and high products.

Known methods closest to the proposed us ablatherm pressure or under a pressure of 1.3 - 1.5 ATA in the presence of a catalyst anhydrous tetrachloroferrate alkaline or alkaline-earth metal, or ammonium, or a mixture of iron chloride (III) and salts of alkaline or alkaline-earth metal, or ammonium, and the inhibitor - oxygen (patent USSR N 1277887).

The present invention aims to increase the duration of operation of catalytic systems with a high selectivity of the process of chlorination of ethylene to 1,2-dichloroethane.

As a catalyst propose to use an integrated system that includes halides of metals FeCl2, FeCl3, SnCl4, SbCl5and nitrogen-containing electron-donating compounds: hexamethylphosphorotriamide (GMPP), pyridine (PY), as well as compounds that inhibit radical reactions: 2,2-di-(n oksifenil)-propane (Suite); 2,6-ditretbutyl-4-methyl-phenol (BHT), n-NITROPHENOL.

About the effectiveness of the used complex catalytic systems when receiving EDC chlorination of ethylene judged on the following parameters:

content (wt.) the target product and the products of the side chlorination in coming out of the reactor EDC raw without pre-treatment;

validity of the catalyst;

the flow of catalyst to edit the system drying chlorine, supplied from a cylinder, the chlorination reactor and system for capturing gases.

To prevent possible accumulation and the catalytic effect of ferric chloride, is easily generated in the presence of chlorine steel reactor experiments were used reactors chlorination of lead and glass.

Chlorination of ethylene was carried out at the boiling point of EDC (84,5oC) and temperatures of 20, 45oC an EDC. For chlorination of ethylene at the boiling temperature of EDC was used bubbling reactor type, made of lead (N=800 mm, d=70 mm), equipped with a condenser and a jacket for heating. The reactor was loaded fresh EDC containing not less than 99.9% and a complex catalytic system of 0.1 to 2.0 wt. Then EDC was heated to 60oC and submitted chlorine 12,0 l/h and ethylene 12.5 l/h due to the heat of the reaction temperature in the reactor rises to the boiling point of EDC. Pair EDC from the reactor is cooled and condensed in the condenser, from which part of the EDC is returned to the reactor, and a portion is withdrawn continuously at this rate, to ensure a constant level of the liquid phase in the reactor. The content of EDC and impurities in selected product and the reaction mass was determined by GC-analysis of the TB reactor through the bubblers were filed ethylene and chlorine, with a cost of 7.5 and 7.0 l/h, respectively. Received EDC raw continuously withdrawn in the receiver. After the EDC distillation bottoms distillation residue containing the catalytic system is returned to the synthesis reactor EDC to maintain the initial concentration of the catalyst. As a result of experiments revealed that the catalytic system is stable and does not lose activity upon recycling (more than 10 times).

Further examples of chlorination of ethylene in the presence of the proposed catalytic systems.

Example 1. Chlorination of ethylene in the presence of catalytic systems (iron dichloride, gmpt, Suite 2 Mac. at a temperature of 84oC.

Charged to the reactor 1000 g EDC (99,9%), 4.5 g of iron dichloride, 5,85 g gmpt and 10.0 g Suite. Chlorine and ethylene are served with a cost of 12.0 and 12.5 l/h, respectively. The duration of the opt 450 hours During this time received 23770 g of the product with the content of EDC 99,9% (trichloroethane 0,10%). At the end of the experiment the content of EDC in selected product made of 99.85 wt. (trichloroethane - 0,15%).

Similarly conduct the process of chlorination of ethylene in the examples 2 to 23. Conditions and results of experiments are shown in table. 1.

Example 24. In a glass reactor (V=1000 ml) equipped with a stirrer, bubblers chlorine and ethylene, load 800 g of EDC (99,9%) and 3.8 g whom is responsible. The temperature in the reactor support 45oC. EDC Formed through the side outlet in the reactor is poured into the receiver. Received the product in a quantity of 500 ml is subjected to rectification, with the cube of the evaporating device containing the catalyst returned to the chlorination reactor. During the experience (400 hours) accumulated 12370 g of the product with the content of EDC at 99.95% (trichloroethane 0,05%).

Similarly, lead the process of chlorination of ethylene in examples 25 to 35. Conditions and results of experiments are shown in table. 2.

Method for producing 1,2-dichloroethane by chlorination of ethylene with chlorine in the liquid 1,2-dichloroethane at a temperature of 20oC to the boiling temperature of the reaction mass in the presence of a metal complex catalyst in an amount of 0.1 to 2.0 wt. and inhibitor of radical reactions, characterized in that the catalyst used complex halide of a metal selected from the group FeCl2, FeCl3, SnCl4, SbCl5with the nitrogen-containing compound selected from the group hexamethylphosphorotriamide, pyridine, and as an inhibitor of radical reactions using 2,2-di-(n oksifenil)-propane, 2,6-di-tertbutyl-4-METHYLPHENOL, n-NITROPHENOL.

 

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