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.
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a new mixture of perfluoro-, α-chloroperfluoro- and α,ω-dichloroperfluoroalkanes of the formula: X(CF2)nY (wherein X = Y means F, Cl; X means F; Y means Cl; n = 12, 14, 16) used as powder-accelerators for plastic ski, and to a method for preparing these mixtures. Method for preparing mixtures of perfluoro-, α-chloroperfluoro- and α,ω-dichloroperfluoroalkanes involves interaction of perfluoro- and ω-chloroperfluorocarboxylic acids with potassium alkali at temperature below 60°C and then with potassium persulfate at 90-95°C. As the parent acid method involves using mixtures of perfluoroenanthic acid and ω-chloroperfluoroenanthic acid, perfluoroenanthic acid and ω-chloroperfluoropelargonic acid, perfluoropelargonic acid and ω-chloroperfluoroenanthic, perfluoropelargonic, ω-chloroperfluoropelargonic, ω-chloroperfluoroenanthic and ω-chloroperfluoropelargonic acids taken in the mole ratio = 1:1. Process is carried out in the mole ratio of acids mixture and potassium persulfate = 1:0.6. The developed method provides preparing new mixtures of powder-accelerators for plastic ski based on domestic raw.
EFFECT: improved preparing method, valuable properties of mixtures.
4 cl, 4 tbl, 9 ex
FIELD: chemical industry; methods of production of the diene compounds.
SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of production of the diene compound of the formula CR1R2=CR3CFR4CR5R6OCR7=CR8R9 (1), which includes the initiation of the reaction of Claisen rearrangement for the compound of the formula CFR1R2CR3=CR4CR5R6OCR7=CR8R9 (2) in the mixture containing the diene compound of the formula (1) and compound of the formula (2), with production the product containing the reaction product of Claisen rearrangement of the formula CR5R6=CR4CR3 (CFR1R2) CR8R9CR7=O (3) and the diene compound of the formula (1), and separation of the diene compound of the formula (1) from the reaction product of Claisen rearrangement. At that R1-R9 in the above-stated formulas may be similar or different, and represent the atom of halogen, the atom of hydrogen, the trifluoromethyl group or the trifluoromethoxy group. The method allows to produce the diene compound of the formula (1) with the high degree of purity.
EFFECT: the invention ensures production of the diene compound of the formula (1) with the high degree of purity.
8 cl, 9 ex
FIELD: chemical technology.
SUBSTANCE: invention relates to a method for synthesis of chloroform. Method involves hydrolysis or hexachloroacetone with water at increased temperature in the presence of inorganic silicon compound of natural or synthetic origin or mixture of such compounds as a catalyst followed by isolation of chloroform from the reaction mixture by the known methods. Talc, wollastonite, xonotlite, diatomite, silica gel, aerosil, silica filler, silicates and/or hydrosilicates of metals, such as sodium, potassium, magnesium, calcium, aluminum, copper, titanium, lead, manganese, iron and nickel are used as silicon compounds indicated above. Catalyst is used preferably in the amount 1-25% of the reaction mixture mass. Invention provides the significant simplifying technology in synthesis of chloroform based on elimination the catalyst regeneration step and expanding the raw base of substances used in the catalytic process.
EFFECT: improved method of synthesis.
3 cl, 6 ex
SUBSTANCE: present invention relates to a method of producing benzyl alcohol, used in primary organic synthesis, textile, paint-and-varnish and medical industry. The method involves alkaline hydrolysis of benzyl chloride, which is obtained by treating dibenzyl ether with hydrochloric acid in two steps, at the first step at temperature 85-90°C with 30-40% hydrochloric acid with weight ratio of dibenzyl ether to hydrochloric acid equal to 1:3-4, at the second step at temperature 100-108°C with 30-40% hydrochloric acid with weight ratio of dibenzyl ether to hydrochloric acid equal to 1:2-3, with recycling of the obtained crude benzyl chloride to the hydrolysis step.
EFFECT: improved and simple method of producing benzyl alcohol by recycling wastes of said production, which improves cost-performance ratio of the disclosed method.
FIELD: chemistry, in particular utilization of chlorine-containing waste.
SUBSTANCE: claimed method includes passing of organochlorine compound vapors blended with oxygen-containing reaction gaseous mixture through catalyst layer providing oxidation of starting organochlorine compounds. Said catalyst represents geometrically structured system from microfibers with length of 5-20 mum. Catalyst has active centers which are characterized by presence of absorption band in absorbed ammonia IR-spectrum with wave number ν = 1410-1440 cm-1; contains platinum group metal as active ingredient; and glass fiber carrier. Said carrier in NMR29Si-spectrum has lines with chemical shifts of -100±3 ppm (Q3-line) and -110±3 ppm (Q4-line) in integral intensity ratio of Q3/Q4 = 0.7-1.2; in IR-spectrum it has hydroxyl absorption band with wave number ν = 3620-1440 cm-1 and half-width of 65-75 cm-1; has specific surface, measured by BET using argon thermal absorption: SAr = 0.5-30 m2/g; surface area, measured by alkali titration: SNa = 10-250 m2/g, wherein SNa/SAr = 5-30.
EFFECT: selective oxidation of starting organochlorine compounds to safe and easily utilizing substances without toxic by-product formation.
3 cl, 4 ex
FIELD: conversion processes of chlorohydrocarbons; catalysts for joint production of chloroform and alkane chlorides.
SUBSTANCE: proposed catalyst is just product of interaction of ferrous chloride with nitrogen-containing organic derivative - amino alcohols of common formula R2NR1OH, where R=H or alkyl C1-C2, R1=C2-C5 alkyl applied on silica gel at content of FeCl2 of 0.7-1.5 mass-% of mass of silica gel at mass ratio of FeCl2/amino alcohol 1 : (5-20). Proposed catalyst makes it possible to increase life of heterogeneous catalyst, thus excluding stage of cleaning the products of process of joint production of chloroform and alkane chlorides and decreasing the cost of process due to replacement of copper chloride by ferrous chloride in the amount lesser by at least three times.
EFFECT: enhanced efficiency.
1 tbl, 12 ex
FIELD: petrochemical and industrial organic synthesis.
SUBSTANCE: process comprises separating gaseous pyrolysis products to recover ethylene-containing fraction with 54-65% ethylene content and C3-C5-hydrocarbon fraction. Ethylene-containing fraction is subjected to liquid-phase catalytic chlorination. Gas phase of chlorination product is purified via adsorption and fed into furnace as fuel. C3-C5-Hydrocarbon fraction is subjected to exhaustive hydrogenation, hydrogenation product is combined with fresh raw material at weight ratio (0.05ч1):1 and sent to pyrolysis plant.
EFFECT: achieved integration of process, increased reliability thereof, and reduced expenses.
1 dwg, 1 tbl, 15 ex
FIELD: industrial organic synthesis.
SUBSTANCE: invention is dealing with catalysts showing high catalytic stability in production of chloroform from carbon tetrachloride via catalytic dehydrochlorination reaction. Catalyst containing γ-alumina-supported platinum is characterized by that platinum in the form of particles 1 to 12 nm in size is distributed throughout the bulk of microspheric γ-alumina particles having median diameter 30 to 70 μm and pore volume 0.3 -0.6 cm3/g. Preparation of catalyst involves impregnation step accomplished via spraying γ-alumina with aqueous platinum compound solution used in amount equal to or less than alumina pore volume followed by platinum compound reduction step, wherein this compound is deposited onto γ-alumina with aqueous solution of formic acid or alkali metal formate.
EFFECT: achieved retention of high catalyst activity and selectivity over a long time period without being preliminarily activated.
9 cl, 2 tbl, 4 cl
FIELD: chemical technology.
SUBSTANCE: invention relates to a method for preparing 1,2-dichloroethane. Method involves the oxychlorination reaction of ethylene with hydrogen chloride and oxygen-containing gas and alkaline treatment of dichloroethane also. Before alkaline treatment of 1,2-dichloroethane carbon dioxide is removed that is carried out by decrease of the reaction mixture pressure comprising 1,2-dichloroethane, or by addition of inert gas wherein nitrogen is used, or by heating. Before separation of carbon dioxide the product of the 1,2-dichloroethane-containing the oxychlorination reaction is quenched, cooled and/or condensed. After separation of carbon dioxide the 1,2-dichloethane-containing reaction mixture is treated with an aqueous alkaline solution followed by its separation. The prepared 1,2-dichloroethane-containing reaction mixture is characterized by the content of chloral and/or chloral hydrate less 0.02 wt.-% but preferable less 0.005 wt.-%, and especially preferably, less 0.002 wt.-%. Invention provides reducing consumption of an alkaline solution, prevention of formation of by-side products of chloral and chloral hydrate, and preparing the pure 1,2-dichloroethane with respect to such by-side products.
EFFECT: improved preparing method.
16 cl, 3 dwg, 3 ex
FIELD: organic synthesis catalysts.
SUBSTANCE: catalyst includes Cu and Mg compounds deposited on alumina as carrier and has copper compounds, expressed as Cu, from 2 to 8%, Mg/Cu atomic ratio ranging from 1.2 to 2.5, wherein concentration of copper atoms is higher in the interior of catalyst particle than on the surface (layer 20-30 Å thick) thereof and concentration of magnesium atoms prevails on the surface of catalyst particle, while specific surface of catalyst ranged from 30 to 130 m2/g. Oxychlorination of ethylene is carried out under fluidized bed conditions using air and/or oxygen as oxidants in presence of above-defined catalyst. Catalyst is prepared by impregnating alumina with aqueous Cu and Mg solutions acidified with hydrochloric acid solution or other strong acids using volume of solution equal or lesser than porosity of alumina.
EFFECT: increased activity of catalyst at high temperatures and avoided adhesion of catalyst particles and loss of active components.
8 cl, 2 tbl, 5 ex