The method of obtaining vinylidenechloride
(57) Abstract:The invention relates to a method for vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane in the presence of a catalyst and an alcohol additive. The process is carried out at 15-20°C in the presence as catalyst diethylether--chloropropylamine chloride or di-oxicillin--chloropropylamine chloride and an alcohol additive of the formula ROH, where R is alkyl (C2-C4, SSN=CH-CH2HE. The molar ratio of the catalyst to the alcohol additive is 1:3-1. Water-alkaline dehydrochlorination subjected 1,1,2-trichloroethane in a mixture of clarified waste of perchlorovinyl with a further allocation of vinylidenechloride, trichloroethylene and 1,1,1,2-tetrachlorethane from the organic phase. The result is vinylidenechloride of waste production perchlorovinyl. The invention relates to organic synthesis, in particular, to a method for vinylidenechloride waste disposal production of chlorinated polyvinyl chloride (perchlorovinyl).A method of obtaining vinylidenechloride the dehydrochlorination individually 1,1,2-trichloroethane 6-24% aqueous solution of hydroxide of alkali metal at Thames6H5CH2N+/-Cl, where R1-CH3or HOCH2-CH2, R2-C10-C18vinylidenechloride formed with the yield up to 85% /Japan patent N 164416, 1961/.The disadvantage of this method is to conduct the reaction at a high temperature and a low yield of the target product.Closest to the claimed invention, the technical solution according to the totality of symptoms is the way to get vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane in the presence of a catalyst and an alcohol additive /Savenow C. S. and others "On the liquid-phase catalysis dehydrochlorinating 1,1,2-trichloroethane". Russian journal of applied chemistry, No. 1, 1987, 150-153 C./.Water-alkaline dehydrochlorination 1,1,2-trichloroethane carry out the action of 40% NaOH at its molar ratio to the trichloroethane 1:1,3 at a temperature of 25oC in the presence of catalysts, such as alkoxides of triethylenediamine or catalytic system triethylmethylammonium chloride: benzyl alcohol.The authors have shown that the highest catalytic activity possesses benzilate of triethylenediamine or system triethylmethylammonium chloride: benzyl alcohol.Nedocenene to obtain catalysts hard triethylamine, benzyl alcohol and benzylchloride.The objective of the invention is to develop a method of obtaining vinylidenechloride waste from the production of chlorinated polyvinyl chloride.When the chlorination of polyvinyl chloride in 1,2-dichloroethane formed a significant amount of 1,1,2-trichloroethane. After rectification distillation residues (waste of perchlorovinyl) can be used to obtain a carbon tetrachloride /Oshin L. A. "Industrial organochlorine products. M.: Chemistry, 1978, S. 577/.However, according to the Montreal agreement on the protection of asenavage layer of soil carbon tetrachloride is not recommended for commercial use.Disposal and recycling of organochlorine products is one of the most urgent problems of the chemical industry.When using the invention may be obtained from the technical result:
- waste production perchlorovinyl;
- the possibility of obtaining relatively expensive vinylidenechloride;
- allows separation of the remaining components of organochlorine waste of perchlorovinyl and return them in the process for manufacturing the catalyst.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 in the presence of a catalyst and an alcohol additive, the peculiarity lies in the fact that the water is alkaline dehydrochlorination at a temperature of 15-20oC in the presence of a catalyst, which is used as diethylether--chloropropylamine chloride or di-oxicillin--chloropropylamine chloride and an alcohol additive of the formula ROH, where R is alkyl (C2-C4, ClCH=CH-CH2OH when the molar ratio of the catalyst to the alcohol additive is 1: 3-1, is exposed to 1,1,2-trichloroethane in a mixture of clarified waste of perchlorovinyl with a further allocation of vinylidenechloride, trichloroethylene and 1,1,1,2-tetrachlorethane from the organic phase.The method is as follows.In a reactor equipped with a heating device, a reflux condenser, a stirrer, a thermometer and a separating funnel, put the estimated number of bleached rectification distillation, containing (wt.%) 1,1,2-trichloroethane - 80-90, 1,1,1,2-tetrachlorethane - 3-8, 1,1,2,2-tetrachlorethane-10-12. To this mixture was added 0.8-1.0 m) is one chloride and 1 to 3 mol of alcohol additives of the formula ROH, where R is alkyl (C2-C4, ClCH=CH-CH2OH. Under stirring at a temperature of 15-20oC is added to 1.3 mol to 1,1,2-trichloroethane 28-30% aqueous NaOH, after which the mixture is stirred for further 0.5 hour.In the reactor, add demineralized water to dissolve the precipitated Sodium chloride and the reaction mixture was placed in a separating funnel. The organic layer is separated, rinsed with nitrogen and distilled under reflux at a temperature not exceeding 65oC, selected fraction, boiling at a temperature of 32oC. Receive vinylidenechloride purity not less than 99%, the conversion of 1,1,2-trichloroethane 93-95%. VAT residue containing trichloroethylene and 1,1,1,2-tetrachlorethane, is subjected to distillation, separating pure trichloroethylene.The method is illustrated by examples.Example 1. In a reactor equipped with a stirrer, reflux condenser, separating funnel, thermometer and thermostatic device, placed 160 g of waste production perchlorovinyl of the following composition, wt%: 1,1,2-trichloroethane - 80; 1,1,1,2-tetrachlorethane - 12; 1,1,2,2-tetrachlorethane - 8.To this mixture products are added 1 g (0.8 wt.% to 1,1,2-trichloroethane) or diethylether--chloropropylamine chloride in the form of a 50% aqueous solution and 1.6 g of butyl spirtes blown off with nitrogen and add 50 g of NaOH, taken in the form of a 30% aqueous solution (the molar ratio of 1,1,2-trichloroethane : NaOH is 1:1,3).Upon completion of addition of NaOH (15 min), the reaction mass at this temperature, stirred for further 1 hour, add demineralized water to dissolve the precipitated Sodium chloride, the reaction mixture is placed in a separating funnel.The organic layer is separated, rinsed and distilled under reflux, selecting a fraction having a boiling point 32oC.Get 89 g vinylidenechloride (yield 96%), 9 g of trichloroethylene, 18 g of 1,1,1,2-tetrachlorethane.Example 2. In the conditions of example 1, taken 160 g of waste production perchlorovinyl composition, wt. %: 1,1,2-trichloroethane - 90, 1,1,2,2-tetrachlorethane - 7%, 1,1,1,2-tetrachlorethane - 3.To this mixture is added 1.4 g of di-oxicillin--chloropropylamine chloride in the form of a 50% aqueous solution and 0.8 g - chloropropanediol alcohol (molar ratio of catalyst : alcohol is 1:1). The dehydrochlorination spend 28% aqueous NaOH.Get 99 g vinylidenechloride (yield 95%), 8 g of trichloroethylene and 4 g of 1,1,2,2 - tetrachlorethane.The advantages of the proposed method:
- waste production perchlorovinyl;
- receipt not expensive vinylacetate of perchlorovinyl;
- enhanced and safe, as well as the possibility of the formation of explosive dihloratsetilena;
- used catalysts obtained from the available raw material: allyl chloride and diethanolamine. The method of obtaining vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane in the presence of a catalyst and an alcohol additive, characterized in that the aqueous-alkaline dehydrochlorination at a temperature of 15-20oC in the presence as catalyst diethylether--chloropropylamine chloride or di-oxicillin--chloropropylamine chloride and an alcohol additive of the formula ROH, where R is alkyl WITH2-C4, ClCH=CH-CH2OH, when the molar ratio of the catalyst to the alcohol additive is 1:3-1, is exposed to 1,1,2-trichloroethane in a mixture of clarified waste of perchlorovinyl with a further allocation of vinylidenechloride, trichloroethylene and 1,1,1,2-tetrachlorethane from the organic phase.
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