The method of producing vinyl chloride
(57) Abstract:Usage: as a monomer in the production of the most important polymeric materials. The inventive dehydrochlorination of 1,2-dichloroethane in the vapor phase at 280-400oC, preferably at 325-350oC, in the presence of hydrogen addition at a molar ratio to ethylene dichloride, 0,02-0,25:1, Treherne catalyst containing Pt or Pd - Al2O3. Significantly reduced process temperature, decreases the quantity of generated by-products, as well as tar and soot, and energy consumption. table 2. The invention relates to a method for producing vinyl chloride heavy chlorine-containing monomer used in the production of the most important polymeric materials and products based on them.In industry the vinyl chloride basically get thermal dehydrochlorination of 1,2-dichloroethane in the hollow tubular reactors. To achieve an acceptable practice for conversion dichloroethane ( 50%), the reaction is carried out at high temperatures (500-550oC) 
The disadvantages of this process include: high temperature reactions leading to the formation of by-products, as well as tar and soot, and relatively miscellenous to introduce additives, accelerating the process of dehydrochlorinating (chlorine [2,3] oxygen ). Thus, the use of the most effective according to  initiator of chlorine reduces the temperature of the pyrolysis of dichloroethane to 400-420oC and increase its conversion to 70% According to the calculations  reducing the temperature to 420oAt the speed of transformation of dichloroethane to reduce the number of the resulting resinous products 10 times. Thereby the reduction of fuel consumption in pyrolysis furnaces by 25% and water consumption for quenching the products of the process approximately 55%
Technological design of this process is difficult and not achieve a high conversion of dichloroethane at considerable expense to add chlorine.There are also known methods for producing vinyl chloride by dehydrochlorination of 1,2-dichloroethane in the presence of catalysts. Thus, in  as the catalyst recommend deposited on fluorinated alumina Nickel metal for enhancing the conversion of 1,2-dichloroethane up to 98% at relatively low temperatures (350 to 400oC) and contact times (()) to about 30 C. In [6,7] described methods for producing vinyl chloride in the presence of catalysts based on magnesium chloride and kobany in  and provide 98-100% conversion and selectivity 97-98% at lower contact times ( 10-11). In  recommend the catalytic dehydrochlorination carried out with the addition of oxygen, although as described in , it has virtually no effect on the performance of the catalytic process.The closest in technical essence and the achieved effect is the way (prototype), described in  where the catalyst using platinum coated on fluorinated alumina. The process is carried out in the presence of an inert diluent, such as nitrogen, in the range of 350-450oC. under optimal conditions (400oC, the molar dilution with nitrogen of 1:1, t 1.6 (C) conversion of 1,2-dichloroethane and the selectivity to vinyl chloride are 97-98 and 97-99%, respectively.The main disadvantage of such a method of producing vinyl chloride is the need for a temperature high enough to achieve high process performance.The purpose of the invention, the activation of the catalyst, lowering the process temperature while maintaining its high performance.This is achieved by carrying out the catalytic dehydrochlorination in the presence of hydrogen at a molar ratio of N2/C2H4Cl2from 0.02 to 0.25 for palladium or Latinoamerica katalizatorov obtain vinyl chloride is illustrated by examples 1, 4, 5, 7-9, 11-15 (table 1) and 16-21 (table 2). In examples 2, 3, 6, 10 are provided for comparing experimental data obtained in the absence of hydrogen, i.e., in terms of the prototype. From a comparison with data obtained with the prototype, it is necessary that the hydrogen intensifies the catalytic process: the reaction rate of dehydrochlorination and conversion of 1,2-dichloroethane significantly increased (examples 3 and 4, 6 and 7, 10 and 11). The addition of hydrogen at a molar ratio of N2/C2H4Cl20.25 initial mixture has no significant effect on the selectivity to vinyl chloride. If more than the specified molar ratio along with the dehydrochlorination start to flow processes hydrodechlorination of 1,2-dichloroethane and the product of its dihydrochloride with the formation of ethylene, ethane, ethylchloride etc. This leads to a noticeable decrease in the selectivity to vinyl chloride.The dehydrochlorination of 1,2-dichloroethane accompany the process of coke formation, which reduces the activity of the catalyst over time. This is illustrated by the examples of 2.3, which presents the experimental results obtained on the first and third hour of the experiment. In the presence of hydrogen significantly retard the deactivation of the catalyst that bring the oC increase associated processes that may adversely affect the catalyst activity and selectivity to vinyl chloride. At temperatures below 325oC achieving high performance leads to poor performance of the reactor.The preferred palladium catalyst in comparison with platinum in relation to the selectivity of the process is illustrated by examples 14 and 15.Examples. The process is carried out in cellopane flow-circulation (table 1) or flow (table 2) installations. In eraksoy reactor of 30 cm3download the catalyst (the grain size of 0.25 to 0.5 mm) in the amount shown in the tables. As the palladium catalyst used (examples 1-13, 16-22) or platinum (examples 14, 15) supported on activated alumina in amounts of 0.5 wt. metal by weight of the catalyst. Supply of vaporous 1,2-dichloroethane in the reactor is performed by the saturation of nitrogen. In examples 1-20 feed rate dichloroethane vapor in the reactor is 1,24 nl/h, in examples 21, 22 0,62 nl/h In examples 6-9, 14, 15 in the reaction gas mixture to dilute it further to add nitrogen in the amount of 4.5 nl/hAnalysis of the reaction mixture is performed with chromatographic and litty experiments are shown in tables. The method of producing vinyl chloride by dehydrochlorination of 1,2-dichloroethane in the vapor phase at elevated temperature in the presence of a catalyst containing platinum on alumina, wherein the process is conducted in the presence of additives of hydrogen at a molar ratio with dichloroethane 0,02 - 0,25 1 and use tragerdy catalyst containing Pt or Pd deposited on gamma-Al2O3and the process is conducted at 280 400oWith, preferably 325 350oC.
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