The method of simultaneous receipt of chloroform and formic acid salt

 

(57) Abstract:

The invention relates to chemical technology and is designed to produce chloroform, used as raw material in the production of perchloromethane (Halocarbon 22 halon 21), and to obtain sodium formate used as a preservative roughage (silage, wet hay) in agriculture. The method consists in processing technical Chlorella aqueous solution of sodium hydroxide in the presence of active chlorine. As a last take an aqueous solution of sodium hydroxide, treated with chlorine at 20 - 40oC, or an aqueous solution of sodium hypochlorite. Excess chlorine 9 - 51% from stoichiometry to dichloroacetamide found in organic raw materials necessary for the conversion of dichloroacetamide along with Harlem in the target products. Upholding separate the lower layer of chloroform. From the upper water layer, by evaporation and drying at 100 - 160oC allocate commodity sodium formate. 5 C.p. f-crystals.

The invention relates to the chemical industry, namely the production of chloroform, used to obtain perchloromethane (Halocarbon 22 halon 21), and to the production of sodium formate used in selecionou receipt of chloroform and calcium formate processing lime milk products of interaction of ethanol with gaseous chlorine (technical Chlorella), when the treatment is carried out in a saturated solution of calcium formate using chlorinated products (technical chloral) with a specific gravity not lower than the 1.6 [ed.St. USSR N 125245, class C 07 C 19/04, publ. 1960]

The relatively low solubility of calcium hydroxide in water and the formation of a sufficiently stable suspension leads to the necessity of Stripping the resulting chloroform from the resulting slurry of calcium hydroxide in aqueous saturated solution of calcium formate. And this in turn requires high temperature (up to 100oC), which leads to partial hydrolysis of chloroform and thus to reduce its output. Present technical chorale admixture dichloroacetamide or alcohol-containing compound in terms of processing lime milk hydrolyzed.

The technical problem of this invention to increase the yield of chloroform by reducing hydrolysis and utilization of impurities.

The problem is solved in that in the method of simultaneous receipt of chloroform and salts of formic acid by treating technical Chlorella alkaline reagent, followed by separation of the target product treatment is carried out with an aqueous solution of sodium hydroxide in the presence of active 20 40oC gaseous chlorine aqueous solution of sodium hydroxide. Active chlorine charge excess 9 of 15% from stoichiometry to dichloroacetamide found in the technical chorale. The selection of target products is carried out by settling, followed by separation of the lower layer of chloroform and the top aqueous solution of sodium formiate. This solution is subjected to Parke and drying at 100 160oC C obtain a commercial product.

Example 1. In a glass flask equipped with stirrer, reflux condenser and feed system reagents simultaneously filed technical chloral, an aqueous solution of sodium hydroxide and an aqueous solution of sodium hypochlorite with such speed that the temperature of the reaction mixture did not rise above 40oC. During the experience consumed 300 g technical Chlorella containing 177,45 g (0,203 mol) of trichloroacetaldehyde, 19.32 g (0,171 mol) of dichloroacetamide, 2.5 g (0,054 mol) alcohol-containing compounds in the calculation of the ethanol. Also spent 105 ml of 40% aqueous sodium hydroxide solution (1.50 mol) and 150 ml of sodium hypochlorite solution containing 93 g/l of active chlorine (0,197 mol). Excess chlorine from stoichiometry in relation to dichloroacetamide is (0,197 0,171):0,171100 15% Duration of chloroform:

on trichloroacetaldehyde 1,27:1,203100 105,6%

the amount of aldehydes 1,27:(1,203 + 0,171) 92,4%

The aqueous layer was evaporated on a water bath (100oC) c, followed by drying the precipitate at 160oC. Received 108 grams of technical sodium formate containing 80% of the main product (86,4 g).

Example 2. Into a flask equipped as in example 1, were simultaneously applied technical chloral and an aqueous solution of sodium hydroxide, treated at a temperature of 20 40oC gaseous chlorine. The reagents were filed with speed, providing the temperature of the reaction mass in the range of 30 50oC. duration of the experiment 1 o'clock During the experience consumed 300 g technical Chlorella containing 177,45 g (1,203 mol) of trichloroacetaldehyde, 19.32 g (0,171 mol) of dichloroacetamide, 21,5 g (0,054 mol) alcohol-containing compounds in the calculation of the ethanol. Also spent 200 ml of an aqueous solution of sodium hydroxide, treated with chlorine containing 67,6 g (0,187 mol) of active chlorine (9% in excess of stoichiometry on dichloroacetamide). At the end of the experience the mixture was separated by sedimentation. Received 155 g (1,297 mol) of chloroform. The output of chloroform:

on trichloroacetaldehyde 1,297:1,203100 107,8%

the amount of aldehydes 1,297:(1,203+0,171)100 94,4%

The aqueous layer was processed CLASS="ptx2">

Example 3 (control, without active chlorine).

For an experience similar to examples 1 and 2 technical chloral in the same amount, and 125 ml of 40% aqueous sodium hydroxide solution (1.77 mol) without active chlorine. Received 142.3 g (1,191 mol) of chloroform with access 1,191:1,203100 99,0% trichloroacetaldehyde. After parki and drying of an aqueous solution obtained 115,6 g painted in dark brown color precipitate containing 70% of sodium formiate (80,9 g).

Similar to the output of chloroform obtained on the prototype when used as the alkaline reagent lime milk.

The examples demonstrate the industrial applicability and the effectiveness of the proposed method.

1. The method of simultaneous receipt of chloroform and salts of formic acid by treating technical Chlorella alkaline reagent, followed by separation of the target product, wherein the treatment is carried out with an aqueous solution of sodium hydroxide in the presence of active chlorine.

2. The method according to p. 1, characterized in that the use of active chlorine, obtained from an aqueous solution of sodium hypochlorite.

3. The method according to p. 1, characterized in that the use of active chlorine obtained from the

4. The method according to PP. 1, 2 or 3, characterized in that the active chlorine charge excess 9 of 15% from stoichiometry in relation to dichloroacetamide found in the technical chorale.

5. The method according to PP. 1, 2, 3 or 4, characterized in that the selection of target products is carried out by settling, followed by the separation of the lower layer of chloroform and the top aqueous solution of sodium formiate.

6. The method according to p. 5, characterized in that an aqueous solution of sodium formiate are oparka and drying at a temperature of 100 160oWith obtaining a marketable product.

 

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