The method of obtaining vinylidenechloride

 

(57) Abstract:

The invention relates to organic synthesis, in particular, to a catalytic process for the production of vinylidenechloride, which is the raw material for plastics, composite materials, paints, adhesives and other valuable products. The invention consists in the dehydrochlorination 1,1,2-trichloroethane in the presence of a catalyst containing the oxides of copper, chromium, zinc and aluminum in a ratio of components, wt.%: CuO 3,2-6,4; Cr2O33,3 - 7,5; ZnO 1,3 - 7,1; media-Al2O3else, and the reaction is conducted at atmospheric pressure, the concentration of 1,1,2-trichloroethane in nitrogen 0,510-3- 510-3mol/l, obymnu speed 90 - 500 h-1, temperature of 110 - 190oC. the Maximum yield of vinylidenechloride per missed 1,1,2-trichloroethane is 99,8 mol.%. 5 table.

The invention relates to organic synthesis, in particular, to a catalytic process for the production of vinylidenechloride, which is the raw material for plastics, composite materials, paints, adhesives and other valuable products.

The known method [U.S. patent N 4816609, MKI C 07 C 17/14, Appl. 26.05.1987, N 53925, publ. 28.03.1989] get vinylidenechloride by dehydrogenator 325oC serves the reaction mixture containing 101,43 ml of methyl alcohol and 211,17 ml of 1,1,2-trichloroethane, at a rate of 10 ml/min Degree of conversion of 1,1,2-trichloroethane is 88.6% selectivity for vinylidenechloride equal to 80.1% i.e. the output of vinylidenechloride is 71%

The disadvantage of this method is the low output vinylidenechloride, high reaction temperature, and the process of methanol.

The known method [Japan patent N7731005, MKI C 07 C 21/06, Appl. 09.03.1977, N 75/104896, publ. 01.09.1979] get vinylidenechloride by dehydrohalogenating 1,1,2-trichloroethane, which consists in the fact that the catalyst containing salt CuCl20.05 mol, PdCl20,005 mol and CsCl 0.02 mol printed on 100 ml of the carrier-Al2O3at a temperature of 229oC serves the reaction mixture containing 0.5 mol of hydrogen and 0.6 mol 1,1,2-trichloroethane. The degree of conversion of 1,1,2-trichloroethane is 58% selectivity for vinylidenechloride equal 94,6% i.e. the output of vinylidenechloride is 54,91%

The disadvantages of this method are the low yield of vinylidenechloride, high reaction temperature, and the process of hydrogen and of a catalyst containing precious metal.

Nebolsina in the Japan patent [Japan patent N 58162537 (83162537), MCI C 07 C 21/08 declared 23.03.1982, N 85/44497 published 27.09.1983] and chosen as a prototype.

The essence of this method is that the mixture is about 5. 1,1,2-trichloroethane and about 95. nitrogen is passed at a temperature of 280oC at 150 h-1over the catalyst, which is obtained by impregnating silica gel with 3% solution of polyacrylonitrile in dimethylformamide, followed by drying and calcining at 600oC. the Degree of conversion of 1,1,2-trichloroethane is 25% selectivity for vinylidenechloride equal to 83% i.e. the output of vinylidenechloride is 20,75%

The disadvantages of this method include low output vinylidenechloride and high temperature process.

The basis of the invention is to increase the output of vinylidenechloride and reduce the temperature of the process through the use of catalyst a composition with increased activity.

The invention consists in dehydrochlorinating 1,1,2-trichloroethane in the presence of a catalyst containing the oxides of copper, chromium, zinc and aluminum in a ratio of components, wt.

CuO 3,2 6,4

Cr2O33,3 7,5

ZnO 1,3 7,1

Media g-Al2O3Else

and hamnoy speed 90 - 500 h-1, temperature of 110 190oC.

Example 1. A catalyst consisting of active mass and the media is prepared as follows.

7.0 g of copper carbonate basic CuCO3Cu(OH)2, 2,63 chromic anhydride CrO3and 1.5 g of zinc nitrate Zn(NO)33H2O dissolved in 200 ml of distilled water under heating, and then the solution was added 34 g (60 ml) of the carrier of g-Al2O3(grains 1-2 mm) and the resulting mixture is evaporated with stirring to dryness, the solid residue is calcined at 600oC air flow 4 o'clock Obtain a catalyst containing about 6.4 wt. CuO, 5.1 wt. Cr2O31.3 wt. ZnO and media g-Al2O3- the rest (catalyst A), and load it into the reactor.

The process is carried out as follows.

Set the temperature of the reactor 140oC and passed through him, the reaction mixture consisting of 2,210-3mol 1,1,2-trichloroethane and other environment friendly/l in nitrogen at flow rate of 130 h-1. The products leaving the reactor, analyzed by gas chromatography. The main product of the reaction is vinylidenechloride.

The research results are summarized in table.1.

Example 2. The catalyst containing 3.2 wt. CuO, 7.5 wt. Cr2Oexcept that take 3,55 g of copper carbonate basic CuCO3Cu(OH)2, 3,94 chromic anhydride CrO3and the 4.29 g of zinc nitrate Zn(NO)33H2O.

The process is conducted as described in example 1.

The research results are summarized in table. 1.

Example 3. The catalyst containing 3.3 wt. CuO, 3.4 wt. Cr2O3, 3.7 wt. ZnO and media g-Al2O3- the rest (the catalyst), prepared as described in example 1, except that take 3,55 g of copper carbonate basic CuCO3Cu(OH)2, 1.7 g of chromic anhydride CrO3and the 4.29 g of zinc nitrate Zn(NO)33H2O.

The process is conducted as described in example 1.

The research results are summarized in table. 1.

Example 4. The catalyst containing 3.3 wt. CuO, 3.3 wt. Cr2O3, 5.2 wt. ZnO and media g-Al2O3- the rest (catalyst G), prepared as described in example 1, except that take 3,55 g of copper carbonate basic CuCO3Cu(OH)2, 1.7 g of chromic anhydride CrO3and 6.0 g of zinc nitrate Zn(NO)33H2O.

The process is conducted as described in example 1.

The research results are summarized in table. 1.

Example 5. Ka is Aligator D), prepared as described in example 1, except that take 3,55 g of copper carbonate basic CuCO3Cu(OH)2, 1.7 g of chromic anhydride CrO3and 8.4 g of zinc nitrate Zn(NO)33H2O.

The research results are summarized in table. 1.

From table. 1 shows that the highest yield of vinylidenechloride (and 99.8 mol.) observed when using the process of the catalyst of the following composition: 3.3 wt. CuO, 3.4 wt. Cr2O3, 3.7 wt. ZnO and media g-Al2O3the rest of it.

Examples 6 to 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 taking the catalyst, changing the reactor temperature from 110 to 190oC and maintain the volumetric rate of 130 h-1.

The results are presented in table. 2.

From table. 2 shows that with increasing reaction temperature output vinylidenechloride increases and reaches the maximum value at a temperature of 140oC, and then falls.

Examples 11 to 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 lead, cmaci from 90 to 500 h-1and keep the temperature of the reactor 140oC and the concentration of 1,1,2-trichloroethane in nitrogen 2,210-3mol/L.

The results are shown in table. 3.

From table. 3 shows that the optimal output vinylidenechloride is the velocity range of 110 to 200 h-1and a maximum output vinylidenechloride per missed 1,1,2-trichloroethane under these conditions the reaction is 99,8 mol. when flow rate 130 h-1.

Examples 16 to 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 the use of catalyst, changing the concentration of 1,1,2-trichloroethane in nitrogen from 0,510-3up to 510-3mol/l, the temperature of the reactor support 140oC, and the volumetric rate of 130 h-1.

The results are presented in table. 4.

From table. 4 shows that the optimal output vinylidenechloride is the interval of concentrations of 1,1,2-trichloroethane 110-3- 4,110-3mol/l, and the maximum output vinylidenechloride per missed 1,1,2-trichloroethane in these conditions, the reaction composition is his way with prototype presented in table. 5.

As can be seen from the table. 5, the described method differs from the known. So, in this way the output vinylidenechloride more than 3 times higher in comparison with the known method, and the process is conducted at lower temperatures, indicating a higher activity of the used catalyst.

The method of obtaining vinylidenechloride transmission diluted with nitrogen 1,1,2-trichloroethane when the concentration in the nitrogen 0.5 to 10-3- 5 10-3mol/l with a bulk velocity 90 500 h-1at elevated temperature and atmospheric pressure over a heterogeneous catalyst on a carrier, characterized in that the use of a catalyst containing the oxides of copper, chromium and zinc on the media-Al2O3, in the following ratio, wt.

CuO 3,2 6,4

Cr2O33,3 7,5

ZnO 1,3 7,1

Media-Al2O3The rest is up to 100

and the process is conducted at a temperature of 110 190oC.

 

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