The way to obtain cis - and trans-1,2-dichlorethylene

 

(57) Abstract:

The invention relates to organic synthesis, in particular, to methods for CIS - and TRANS-1,2-dichlorethylene that are used in the process of synthesis of polymeric materials, adhesives and resins. The invention consists in dehydrochlorinating 1,1,2-dichloroethane in the presence of a heterogeneous catalyst based on FeCl3and-Al2O3and the process is conducted at atmospheric pressure, the concentration of 1,1,2-trichloro-ethane in nitrogen 0,510-3- 310-3mol/l, flow rate 70-700 h-1the temperature of 200-280oC. Yield CIS-1,2-delaration is 33,0 is 65.5 mol. %, and TRANS-1,2-dichlorethylene 19,3-32,4 mol.%. 5 table.

The invention relates to organic synthesis, in particular, to a catalytic process for the production of CIS - and TRANS-1,2-dichlorethylene used in the synthesis of polymers.

The known method (U.S. patent N 4816609 ΜM C 07 C 17/14 Appl. 26.05.1987, N 53925. Publ. 28.03.1989) obtain CIS - and TRANS-1,2-dichlorethylene by dehydrohalogenating 1,1,2-trichloroethane, which consists in the fact that the catalyst composition CsMgCl36H2O at a temperature of 325oC serves the reaction mixture containing 101,43 ml of methyl alcohol and 211,17 ml of 1,1,2 - trichloro is loratidine equal to 11.5% and TRANS-1,2-dichlorethylene 10,2% ie the yield of CIS-1,2-dichlorethylene is 10.2% and TRANS-1,2-dichlorethylene 9%

The disadvantages of this method include the low yield of CIS - and TRANS-1,2-dichlorethylene, high reaction temperature, and the process of methanol.

The closest in technical essence to the claimed method is to obtain CIS - and TRANS-1,2-dichlorethylene according to the method described in Japan patent [Japan patent N 58.172.329 (83.172.329) MCI C 07 C 21/08. Appl. 01.04.1982, N 82/52376. Publ. 11.10.1983] and chosen as a prototype.

The essence of this method is that the catalyst composition of 10 parts of a mixture (1:1) of tetraphenylporphyrin and CsCl, applied to 90 parts of colloidal silica gel, 300oC and flow rate of 500 h-1let the reaction mixture is about 10. 1,1,2-trichloroethane in nitrogen. The degree of conversion of 1,1,2-trichloroethane is 12.0 percent selectivity for CIS-1,2-dichlorethylene equal to 6.8% and TRANS-1,2-dichlorethylene 6,7% i.e. the output for CIS-1,2-dichlorethylene is 0.8% and TRANS-1,2-dichlorethylene 0,8%

The disadvantages of this process is the low yield of CIS - and TRANS-1,2-dichlorethylene.

The basis of the invention is to increase the yield of CIS-1,2-dichlorethylene and Tran is I process parameters.

The invention consists in carrying out the reaction dehydrochlorinating 1,1,2-trichloroethane in the presence of a catalyst containing 1-20 wt. FeCl3media Al2O3the reaction is conducted at atmospheric pressure, the concentration of 1,1,2-trichloroethane in nitrogen 0.5 to 10-33 10-3mol/l, flow rate 70 700 h-1, a temperature of 200 to 280oC.

Example 1. The catalyst containing 1 wt. FeCl3on the media g-Al2O3(catalyst K-1), is prepared as follows.

1,67 g of iron chloride (III) FeCl36H2O dissolved in 100 ml of distilled water and the resulting solution was added 100 g of the carrier of g-Al2O3with a grain size of 1-2 mm, the mixture is evaporated to dryness, get the catalyst To-1.

The process is carried out as follows.

In the reactor of stainless steel load the catalyst and set the temperature of the reactor 255oC, passed through him, the reaction mixture consisting of 1,54 10-3mol 1,1,2-trichloroethane/l of nitrogen at flow rate of 170 h-1. The products leaving the reactor, collected and then separated by rectification, selecting sequentially fraction with temperature distillation 31,7oC (fraction 1), 47,9oC (chloride, in the second TRANS-1,2-dichlorethylene and in the third CIS-1,2-dichlorethylene.

The research results are summarized in table. 1.

Example 2. The catalyst containing 5 wt. FeCl3on the media g-Al2O3(catalyst K-2) prepared as described in example 1, except that the take of 6.8 g of iron chloride (III).

The process is conducted as described in example 1.

The research results are summarized in table. 1.

Example 3. The catalyst containing 10 wt. FeCl3on the media g-Al2O3(catalyst K-3), prepared as described in example 1, except that the take of 16.7 g of iron chloride (III).

The process is conducted as described in example 1.

The research results are summarized in table. 1.

Example 4. The catalyst containing 15 wt. FeCl3on the media g-Al2O3(catalyst K-4), prepared as described in example 1, except that take 25,05 g of iron chloride (III).

The process is conducted as described in example 1.

The research results are summarized in table. 1.

Example 5. The catalyst containing 20 wt. FeCl3on the media g-Al2O3(catalyst K-5), prepared as is, as described in example 1.

The research results are summarized in table. 1.

From table. 1 shows that the maximum yield of CIS-1,2 - and TRANS-1,2-dichlorethylene (respectively, 62,5 and 31.1 mol.) observed when using in the process of catalyst K-3, which corresponds to 10 wt. FeCl3on the media g Al2O3.

Examples 6-10. The effect of reactor temperature on the process of dehydrochlorinating 1,1,2-trichloroethane.

The process is conducted as described in example 1 with the difference that we bring the catalyst To 3 and change the temperature of the reactor from 200 to 275oC and maintain the volumetric rate of 170 h-1.

The results are presented in table. 2.

From table. 2 shows that with increasing reaction temperature the yield of CIS - and TRANS-1,2-dichlorethylene increases and reaches the maximum value, respectively, at 62.5 and 31.1% at a temperature of 250oC, and then falls.

Examples 11-15. The influence of the flow rate of the reaction mixture in the process of dehydrochlorinating 1,1,2-trichloroethane.

The process of dehydrochlorinating 1,1,2-trichloroethane are as described in example 1 with the difference that changing the volumetric rate of the reaction mixture from 70 to 700 h-1and support tenebrioides in table. 3.

From table. 3 shows that the optimal output of CIS - and TRANS-1,2-dichlorethylene is the interval velocity 170-500 h-1moreover , the maximum yield of CIS - and TRANS-1,2-dichlorethylene per missed 1,1,2-trichloroethane in the above reaction conditions are, respectively 65,2 and 32.4 mol. when flow rate 250 h-1.

Examples 16-20. The effect of the concentration of 1,1,2-trichloroethane in the reaction mixture in the process of dehydrochlorinating.

The process of dehydrochlorinating 1,1,2-trichloroethane are as described in example 1 with the difference that changing the concentration of 1,1,2-trichloroethane in nitrogen from 0.5 to 10-3up to 3 of 10-3mol/l and maintain the temperature of the reactor 265oC and a space velocity of 250 h-1.

The results are presented in table. 4.

From table. 4 shows that the optimal solution is the interval of concentration of 1,1,2-trichloroethane 0.5 to 10-32 10-3mol/l, and the maximum yield of CIS - and TRANS-1,2-dichlorethylene per missed 1,1,2-trichloroethane in the above reaction conditions, respectively 65,2 and 32.4 mol. when the concentration in the nitrogen 1.5 to 10-3mol/L.

Comparative characteristic of this method with the known method. Thus, in the present method, the yield of CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene more than 30 times higher in comparison with the known method.

The way to obtain CIS - and TRANS-1,2-dichlorethylene transmission diluted with nitrogen 1,1,2-trichloroethane when the concentration in the nitrogen 0.5 to 10-33 10-3mol/l, flow rate 70 - 700 h-1at elevated temperature and atmospheric pressure over a heterogeneous catalyst on a carrier, characterized in that the use of catalyst containing FeCl3on the media-Al2O3when their ratio, wt.

FeCl31 20

-Al2O3The rest is up to 100

and the process is conducted at a temperature of 200 to 280oC.

 

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