The method of obtaining vinylidenechloride
(57) Abstract:The invention relates to a method for vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane by the action of aqueous NaOH in the presence of a catalyst. Water-alkaline dehydrochlorination subjected 1,1,2-trichloroethane contained in the clarified waste production of vinyl chloride, the obtained gas-phase dehydrochlorination of 1,2-dichloroethane, without separating it from the waste mixture containing (wt.%) 1,1,2-trichloroethane 50-70, dichloroethane 10-15, perchloroethylene 15-20, tetrachlorethane 2-3. The process is carried out at a temperature of 15-20°C in the presence of diethylether--chloropropylamine chloride or di-oxicillin--chloropropylamine chloride with the addition of alcohol of the formula ROH, where R is alkyls2-C4with further addition of water to dissolve the precipitated NaCl, separation of the organic phase and the division into individual products: vinylidenechloride, 1,2-dichloroethane and perchlorethylene, when the molar ratio of alcohol to catalyst - 1-3:1. As a result of waste vinyl chloride receive vinylidenechloride. The invention relates to organic synthesis, in particular, to a method for vinylidenechloride, prima is vinylidenechloride the dehydrochlorination 1,1,2-trichloroethane 6-24% aqueous solution of hydroxide of an alkali metal at a temperature of 90oC in the presence of the catalyst alkylbenzene chloride of the formula (R1R1R2C6H5CH2N)Cl, where R1- CH3or HOCH2-CH2-, R2- C10-C18. Vinylidenechloride formed with the yield up to 85% (Japan patent N 164416, 1961 ).Expensive raw materials limits the possibility of using this method.The closest technical solution to the same destination on the totality of symptoms is the way to get vinylidenechloride with odnowionym the dehydrochlorination 1,1,2-trichloroethane action 33-40% aqueous NaOH solution in the presence of 0.3-1% of the catalyst to 1,1,2-trichloroethane ( Savanov S. C., Tolstikov, A. and others "On the liquid-phase catalysis dehydrochlorinating 1,1,2-trichloroethane". ZH N 1, 1987, S. 150-1530).For reasons that impede the achievement of specified following technical result when using the known method include:
- expensive raw materials;
- inaccessibility of the used catalysts.The task of the invention is to develop a method of obtaining vinylidenechloride from waste products of vinyl chloride, the resulting gas-phase dehydrochlorination of dichloroethane.During implementation of the invention can be obtained the following technical result:
- the problem of waste disposal production of vinyl chloride, the resulting gas-phase dehydrochlorination of dichloroethane;
- mark dichloromethane and perchloroethylene from waste products of vinyl chloride;
- obtaining relatively inexpensive vinylidenechloride.This technical result in the implementation of the invention is achieved in that in the known method of obtaining vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane by the action of NaOH in the presence of a catalyst, is h the production of vinyl chloride, the obtained gas-phase dehydrochlorination of 1,2-dichloroethane, without separating it from the waste mixture containing (wt.%) 1,1,2-trichloroethane - 50-70, dichloroethane - 10-15, perchlorethylene - 15-20 at a temperature of 5-10oC in the presence of diethylether--chloropropylamine chloride or di-oxicillin--chloropropylamine chloride with the addition of alcohol of the formula ROH, where R is alkyl (C2-C4, HOCH2-CH=CHCl, when the molar ratio of alcohol to catalyst equal 1-3 : 1, with the further addition of water to dissolve the precipitated NaCl, separation of the organic phase and the division into individual products: vinylidenechloride, dichloromethane and perchloroethylene.The method consists in the following.Waste of vinyl chloride after their clarification is subjected to selective (1,1,2-trichloroethane) dehydrochlorination aqueous NaOH at a temperature of 5-10oC in the presence of 0.8-1% 1,1,2-trichloroethane catalyst diethylether--chloropropylamine chloride or di-oxicillin--- chloropropylamine chloride with the addition of alcohol of the formula ROH, where R is alkyl (C2-C4, HOCH2-CH=CHCl, at a molar ratio to the catalyst, is 1-3:1. The addition of water provides the dissolution of precipitated salt NaC is ATM.In a reactor equipped with a stirrer, thermometer, reflux condenser, separating funnel, and a thermostatic device, put the estimated amount of the clarified waste of vinyl chloride, containing (wt. %) 1,1,2-trichloroethane - 50-70, dichloroethane - 10-15, perchlorethylene - 15-20, tetrachlorethane - 2-3. To this mixture are added 1% to 1,1,2-trichloroethane catalyst in the form of a 50% aqueous solution of 1-3 mol to Quaternary ammonium salt of the corresponding alcohol. Under stirring at a temperature of 5-10oC add 1.3 to 1.5 mole to 1,1,2-trichloroethane NaOH, taken in the form of 33-35% aqueous solution. Before the addition of NaOH mixture chlorohydrocarbons blown off with nitrogen. Upon completion of addition of NaOH (10-15 min) the reaction mixture is stirred for another 0.5-1 h and add demineralized water to dissolve the precipitated NaCl. The organic layer is separated, rinsed with nitrogen and distilled under reflux at a temperature in the cube is not above 65oC, selecting the fraction with boiling point 32oC.Get vinylidenechloride purity not less than 99%, the conversion of 1,1,2-trichloroethane is 98-99%. VAT residue containing mainly 1,2-dichloroethane and perchlorethylene, is distilled in a distillation column.The method is illustrated Satnam refrigerator, a separating funnel and thermostatic device is placed 204 g of clarified waste of vinyl chloride, containing (wt. %) 1,1,2-trichloroethane - 65, 1,2-dichloroethane - 15,6, perchlorethylene - 18,4, tetrachlorethane - 1. To this mixture was added 1.3 g (1% trichloroethane) diethylether--chloropropylamine chloride in the form of a 50% aqueous solution and 1.4 g (2 mol of a catalyst) - chloropropanediol alcohol. With vigorous stirring and at a temperature of 5-10oC added 52 g of NaOH (molar ratio trichloroethane : NaOH is 1:3), taken in the form of a 35% aqueous solution for 10-15 minutes After which the reaction mixture is stirred at the same temperature for another 0.5-1 hours After that, the reactor add demineralized water to dissolve the precipitated salt is NaCl. The reaction mass is placed in a separating funnel. The mixture defend 0.5 h and separated the organic layer, is placed in an alembic, equipped with a reflux condenser and a fridge, blown off with nitrogen and the temperature, first 55-65oC, distilled vinylidenechloride selected fraction, boiling at a temperature of 32oC (yield 97%), then distilled dichloromethane (yield 92%) at the corresponding temperature and then perchlorethylene (yield of 92.5%).Example 2. In the conditions of example 1 as the catalysis of the hours get 94 g vinylidenechloride (yield 96%), 29 g of 1,2-dichloroethane (yield 92%), 36 g of perchloroethylene (yield of 91.5%).Example 3. In the conditions of example 1 as alcohol Supplement take 3 mol of ethanol. The output vinylidenechloride was 92%, dichloroethane 92 percent, of perchloroethylene - 91%.The advantages of the proposed method of obtaining vinylidenechloride expressed in the following:
- in opportunities from waste products of vinyl chloride valuable individual products - vinylidenechloride, dichloroethane, perchloroethylene, each of which has its own practical application;
- to obtain relatively inexpensive vinylidenechloride. The method of obtaining vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane by the action of aqueous NaOH in the presence of a catalyst, characterized in that the aqueous-alkaline dehydrochlorination subjected 1,1,2-trichloroethane contained in the clarified waste production of vinyl chloride, the obtained gas-phase dehydrochlorination of 1,2-dichloroethane, without separating it from the mixture of waste containing, wt.%: 1,1,2-trichloroethane 50-70, dichloroethane 10-15, perchloroethylene 15-20, tetrachlorethane 2-3, at a temperature of 15-20oC in the presence of diethylether--chloropropylamine chloride (/(S2nilamani chloride (/(NON2-CH2)2-CH2-CH= CH2, -CH2CH=Cl-N+/Cl-) add alcohol of the formula ROH, where R is alkyls2-C4NON2CH=HCl, when the molar ratio of alcohol to catalyst equal 1-3:1, with the further addition of water to dissolve the precipitated NaCl, separation of the organic phase and the division into individual products: vinylidenechloride, 1,2-dichloroethane and perchlorethylene.
FIELD: organic synthesis catalysts.
SUBSTANCE: catalyst is prepared from allyl chloride production wastes comprising 30-50% 1,3-dichloropropenes, 30-60% 1,2-dichloropropane, and 3-5% 1,2,3-trichloropropane, which are treated at 5-10°C with 30-50% dimethylamine aqueous solution in such amount as to ensure stoichiometric ratio of dimethylamine with respect to 1,3-dichloropropenes. Resulting mixture is held at 20-25°C for 0.5-1.0 h and then 40-44 sodium hydroxide solution is added in stoichiometric amount regarding dimethylamine, after which clarified waste is added to dimethylamine at 60-70°C and stirring in amount ensuring stoichiometric ratio of dimethylamine to 1,3-dichloropropenes contained in clarified waste. Mixture is aged for 2-3 h, organic phase is separated, and remaining interaction phase is supplemented by C1-C4-alcohol or benzyl alcohol at alcohol-to-dimethylamine molar ratio 1:(1-3).
EFFECT: reduced expenses on starting materials.
2 cl, 3 ex
FIELD: chemical industry, in particular method for production of value monomer such as vinylchloride.
SUBSTANCE: claimed method includes passing of reaction mixture containing dichloroethane vapor trough catalytic layer providing dehydrochlorination of dichloroethane to vinylchloride. Catalyst has active centers having in IR-spectra of adsorbed ammonia absorption band with wave numbers in region of ν = 1410-1440 cm-1, and contains one platinum group metal as active component, and glass-fiber carrier. Carrier has in NMR29Si-specrum lines with chemical shifts of -100±3 ppm (Q3-line) and -110±3 ppm (Q4-line) in integral intensity ratio Q3/Q4 from 0.7 to 1.2; in IR-specrum it has absorption band of hydroxyls with wave number of ν = 3620-3650 cm-1 and half-width of 65-75 cm-1, and has density, measured by BET-method using argon thermal desorption, SAr = 0.5-30 m2/g, and specific surface, measured by alkali titration, SNa = 10-250 m2/g in ratio of SAr/SNa = 5-30.
EFFECT: method with high conversion ratio and selectivity.
3 cl, 2 ex
FIELD: industrial organic synthesis.
SUBSTANCE: gas-phase thermal dehydrochlorination of 1,2-dichloroethane is conducted in presence of hydrogen chloride as promoter dissolved in feed in concentration between 50 and 10000 ppm.
EFFECT: increased conversion of raw material and reduced yield of by-products.
4 cl, 1 tbl, 8 ex
FIELD: chemistry of organochlorine compounds, chemical technology.
SUBSTANCE: method involves treatment of 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane with solid calcium hydroxide or a mixture of solid calcium hydroxide and solid sodium hydroxide with the content of sodium hydroxide in mixture 30%, not above, in the molar ratio 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane to alkali = 1:(1.5-1.75) at heating in the presence of catalyst. As catalysts method involves benzyltrialkyl ammonium halides, preferably, benzyltriethyl ammonium chloride or benzyltrimethyl ammonium bromide, tetraalkyl ammonium halides, preferably, tetrabutyl ammonium bromide taken in the amount 0.0005-0.005 mole. Invention provides the development of a new method for preparing 1,1-dichloro-2,2-bis-(4-chlorophenyl)-ethylene allowing to enhance ecological safety of technological process and to improve quality of the end product.
EFFECT: improved method preparing.
2 cl, 15 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for preparing vinyl chloride monomer and to a catalyst sued in catalytic preparing vinyl chloride monomer from flows comprising ethylene. Method for preparing vinyl chloride from ethylene is carried out by the oxidehydrochlorination reaction. Method involves combining reagents including ethylene, the source of oxygen and chlorine in the catalyst-containing reactor at temperature 350-500°C and under pressure from atmosphere to 3.5 MPa, i. e. under conditions providing preparing the product flow comprising vinyl chloride and ethylene. Catalyst comprises one or some rare-earth elements under condition that the atomic ratio between rare-earth metal and oxidative-reductive metal (iron and copper) is above 10 in the catalyst and under the following condition: when cerium presents then the catalyst comprises additionally at least one rare-earth element distinctive from cerium. Ethylene is recirculated from the product flow inversely for using at stage for combining reagents. Invention proposes a variant for a method for preparing vinyl chloride. Also, invention proposes variants of a method for catalytic dehydrochlorination of raw comprising one or some components taken among ethyl chloride, 1,2-dichloroethane and 1,1,2-trichloroethane in the presence of catalyst. Catalyst represents the composition of the formula MOCl or MCl3 wherein M represents a rare-earth element or mixture of rare-earth elements taken among lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium. The catalytic composition has the surface area BET value from 12 m2/g to 200 m2/g. Invention provides simplifying technology and enhanced selectivity of the method.
EFFECT: improved conversion method.
61 cl, 8 tbl, 32 ex
FIELD: industrial organic synthesis.
SUBSTANCE: invention relates to perfluoroolefins production technology, notably to heaxafluorobutadiene CF2=CF-CF=CF2. Process comprises reaction of 1,2,3,4-tetrachlorohexafluorobutane with zinc in aqueous medium at 30 to 90°C. Reaction is carried out by metering 1,2,3,4-tetrachlorohexafluorobutane into reaction vessel containing zinc and water, while simultaneously desired product formed is recovered. Advantageously, process is conducted in presence of promoter selected from acids such as sulfuric acid and hydrochloric acid, soluble weak base salts such as zinc and ammonium halides, interphase transfer catalysts such as quaternary ammonium salts, quaternary phosphonium salts, tetrakis(dialkylamino)phosphonium salts, and N,N',N"-hexaalkyl-substituted guanidinium salts, or mixtures of indicated substances.
EFFECT: increased purity of heaxafluorobutadiene and simplified technology.
4 cl, 7 ex
FIELD: petrochemical processes.
SUBSTANCE: invention relates to oxidative halogenation processes to obtain halogenated products, in particular allyl chloride and optionally propylene. Process comprises interaction of hydrocarbon having between 3 and 10 carbon atoms or halogenated derivative thereof with halogen source and optionally oxygen source in presence of catalyst at temperature above 100°C and below 600°C and pressure above 97 kPa and below 1034 kPa. Resulting olefin containing at least 3 carbon atoms and halogenated hydrocarbon containing at least 3 carbon atoms and larger number of halogen atoms than in reactant. Catalyst contains essentially iron and copper-free rare-earth metal halide or oxyhalide. Atomic ratio of rare-earth metal to iron or copper is superior to 10:1. In case of cerium-containing catalyst, catalyst has at least one more rare-earth element, amount of cerium present being less than 10 atomic % of the total amount of rare-earth elements. Advantageously, process is conducted at volumetric alkane, halogen, and oxygen supply rate above 0.1 and below 1.0 h-1, while diluent selected from group including nitrogen, helium, argon, carbon monoxide or dioxide or mixture thereof is additionally used. Halogenated product is recycled while being converted into supplementary olefin product and olefin product is recycled in order to be converted into halogenated hydrocarbon product. Optionally, allyl chloride and ethylene are obtained via interaction of propane with chlorine source in presence of catalyst.
EFFECT: increased productivity of process and improved economical characteristics.
26 cl, 1 tbl
FIELD: chemical technology.
SUBSTANCE: invention relates to a method for synthesis of chlorinated ethylene derivatives, in particular, vinyl chloride, vinylidene chloride, trichloroethylene by the dehydrochlorination reaction of corresponding chlorinated ethane derivatives. The process is carried out in the presence of sodium hydroxide aqueous solution, catalyst of interphase transfer relating to polyglycols and an extractant-promoter representing mixture of chlorinated hydrocarbons of the general formula: CnH2n +2-xClx wherein n = 10-30; x = 1-7 with molecular mass 250-305 Da and the chlorine content is 24-43% followed by isolation of end substances by the known procedures. As a catalyst of interfase transfer the method uses polyethylene glycols in the amount 0.0001-1% of the mass of the parent chlorinated ethane derivative. Extractant-promoter is used in the amount 1-10% of the mass of the parent ethane derivative. The mole ratio of chlorinated ethane derivative to sodium hydroxide = 1:(1.15-5) at the concentration of sodium hydroxide aqueous solution 5-35 wt.-%. Invention provides the development of the complex method for synthesis of chlorinated ethylene derivatives from chlorinated ethane derivatives, among them, from depleted reagents of the method or waste of corresponding industry, and increasing yield of end products.
EFFECT: improved method of synthesis.
7 cl, 1 tbl, 12 ex
FIELD: chemical industry; methods of production of vinylidene chloride.
SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of production of vinylidene chloride by the dehydrochlorination of 1,1,2- trichloroethane with formation of the target product and the quaternary ammonium salts. As the reactant of the dehydrochlorination they use the water-alcoholic solutions of hydroxides - dimethyl-β or γ- chlorodipropenyl of ammonium gained by the electrolysis of the solutions of dimethyl-β or γ- chlorodipropenyl of ammonium chloride in the water at presence of methyl, ethyl or butyl alcohols in the electrolyzers with the ion-exchange membranes. At that the gained hydroxides are sent to the dehydrochlorination. The technical result of the invention is creation of the waste-free, highly-efficient and pollution-free process of production of vinylidene chloride.
EFFECT: the invention ensures creation of the waste-free, highly-efficient and pollution-free process of production of vinylidene chloride.
3 cl, 3 ex, 1 dwg
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for synthesis of vinyl chloride by the liquid-phase dehydrochlorination process of 1,2-dichloroethane. As reagent for the liquid-phase dehydrochlorination process of 1,2-dichloroethane the method involves using alcoholic solutions of quaternary ammonium salts of the general formula: [R1-R2-R3-R4N]+OR- wherein R1-R2-R3 mean (C1-C4)-alkyl; R3-R4 mean propenyl, β- or γ-chloropropenyl; R means (C1-C4)-alkyl, benzyl synthesized by electrolysis of corresponding quaternary ammonium salts in electrolyzers with ion-exchange membranes. Invention provides the development of wasteless, highly efficient, ecologically pure technology of synthesis of vinyl chloride and simplifying a method for synthesis of vinyl chloride based on decreasing temperature and pressure in carrying out the process.
EFFECT: improved method of synthesis.
2 cl, 1 tbl, 1 dwg, 4 ex