The way to obtain cis - and trans-1,2-dichlorethylene
(57) Abstract:The invention relates to organic synthesis, in particular, to methods for CIS - and TRANS-1,2-dichlorethylene that are used in the process of synthesis of polymeric materials, adhesives and resins. The invention consists in dehydrochlorinating 1,1,2-dichloroethane in the presence of a heterogeneous catalyst based on FeCl3and-Al2O3and the process is conducted at atmospheric pressure, the concentration of 1,1,2-trichloro-ethane in nitrogen 0,510-3- 310-3mol/l, flow rate 70-700 h-1the temperature of 200-280oC. Yield CIS-1,2-delaration is 33,0 is 65.5 mol. %, and TRANS-1,2-dichlorethylene 19,3-32,4 mol.%. 5 table. The invention relates to organic synthesis, in particular, to a catalytic process for the production of CIS - and TRANS-1,2-dichlorethylene used in the synthesis of polymers.The known method (U.S. patent N 4816609 ΜM C 07 C 17/14 Appl. 26.05.1987, N 53925. Publ. 28.03.1989) obtain CIS - and TRANS-1,2-dichlorethylene by dehydrohalogenating 1,1,2-trichloroethane, which consists in the fact that the catalyst composition CsMgCl36H2O at a temperature of 325oC serves the reaction mixture containing 101,43 ml of methyl alcohol and 211,17 ml of 1,1,2 - trichloro is loratidine equal to 11.5% and TRANS-1,2-dichlorethylene 10,2% ie the yield of CIS-1,2-dichlorethylene is 10.2% and TRANS-1,2-dichlorethylene 9%
The disadvantages of this method include the low yield of CIS - and TRANS-1,2-dichlorethylene, high reaction temperature, and the process of methanol.The closest in technical essence to the claimed method is to obtain CIS - and TRANS-1,2-dichlorethylene according to the method described in Japan patent [Japan patent N 58.172.329 (83.172.329) MCI C 07 C 21/08. Appl. 01.04.1982, N 82/52376. Publ. 11.10.1983] and chosen as a prototype.The essence of this method is that the catalyst composition of 10 parts of a mixture (1:1) of tetraphenylporphyrin and CsCl, applied to 90 parts of colloidal silica gel, 300oC and flow rate of 500 h-1let the reaction mixture is about 10. 1,1,2-trichloroethane in nitrogen. The degree of conversion of 1,1,2-trichloroethane is 12.0 percent selectivity for CIS-1,2-dichlorethylene equal to 6.8% and TRANS-1,2-dichlorethylene 6,7% i.e. the output for CIS-1,2-dichlorethylene is 0.8% and TRANS-1,2-dichlorethylene 0,8%
The disadvantages of this process is the low yield of CIS - and TRANS-1,2-dichlorethylene.The basis of the invention is to increase the yield of CIS-1,2-dichlorethylene and Tran is I process parameters.The invention consists in carrying out the reaction dehydrochlorinating 1,1,2-trichloroethane in the presence of a catalyst containing 1-20 wt. FeCl3media Al2O3the reaction is conducted at atmospheric pressure, the concentration of 1,1,2-trichloroethane in nitrogen 0.5 to 10-33 10-3mol/l, flow rate 70 700 h-1, a temperature of 200 to 280oC.Example 1. The catalyst containing 1 wt. FeCl3on the media g-Al2O3(catalyst K-1), is prepared as follows.1,67 g of iron chloride (III) FeCl36H2O dissolved in 100 ml of distilled water and the resulting solution was added 100 g of the carrier of g-Al2O3with a grain size of 1-2 mm, the mixture is evaporated to dryness, get the catalyst To-1.The process is carried out as follows.In the reactor of stainless steel load the catalyst and set the temperature of the reactor 255oC, passed through him, the reaction mixture consisting of 1,54 10-3mol 1,1,2-trichloroethane/l of nitrogen at flow rate of 170 h-1. The products leaving the reactor, collected and then separated by rectification, selecting sequentially fraction with temperature distillation 31,7oC (fraction 1), 47,9oC (chloride, in the second TRANS-1,2-dichlorethylene and in the third CIS-1,2-dichlorethylene.The research results are summarized in table. 1.Example 2. The catalyst containing 5 wt. FeCl3on the media g-Al2O3(catalyst K-2) prepared as described in example 1, except that the take of 6.8 g of iron chloride (III).The process is conducted as described in example 1.The research results are summarized in table. 1.Example 3. The catalyst containing 10 wt. FeCl3on the media g-Al2O3(catalyst K-3), prepared as described in example 1, except that the take of 16.7 g of iron chloride (III).The process is conducted as described in example 1.The research results are summarized in table. 1.Example 4. The catalyst containing 15 wt. FeCl3on the media g-Al2O3(catalyst K-4), prepared as described in example 1, except that take 25,05 g of iron chloride (III).The process is conducted as described in example 1.The research results are summarized in table. 1.Example 5. The catalyst containing 20 wt. FeCl3on the media g-Al2O3(catalyst K-5), prepared as is, as described in example 1.The research results are summarized in table. 1.From table. 1 shows that the maximum yield of CIS-1,2 - and TRANS-1,2-dichlorethylene (respectively, 62,5 and 31.1 mol.) observed when using in the process of catalyst K-3, which corresponds to 10 wt. FeCl3on the media g Al2O3.Examples 6-10. The effect of reactor temperature on the process of dehydrochlorinating 1,1,2-trichloroethane.The process is conducted as described in example 1 with the difference that we bring the catalyst To 3 and change the temperature of the reactor from 200 to 275oC and maintain the volumetric rate of 170 h-1.The results are presented in table. 2.From table. 2 shows that with increasing reaction temperature the yield of CIS - and TRANS-1,2-dichlorethylene increases and reaches the maximum value, respectively, at 62.5 and 31.1% at a temperature of 250oC, and then falls.Examples 11-15. The influence of the flow rate of the reaction mixture in the process of dehydrochlorinating 1,1,2-trichloroethane.The process of dehydrochlorinating 1,1,2-trichloroethane are as described in example 1 with the difference that changing the volumetric rate of the reaction mixture from 70 to 700 h-1and support tenebrioides in table. 3.From table. 3 shows that the optimal output of CIS - and TRANS-1,2-dichlorethylene is the interval velocity 170-500 h-1moreover , the maximum yield of CIS - and TRANS-1,2-dichlorethylene per missed 1,1,2-trichloroethane in the above reaction conditions are, respectively 65,2 and 32.4 mol. when flow rate 250 h-1.Examples 16-20. The effect of the concentration of 1,1,2-trichloroethane in the reaction mixture in the process of dehydrochlorinating.The process of dehydrochlorinating 1,1,2-trichloroethane are as described in example 1 with the difference that changing the concentration of 1,1,2-trichloroethane in nitrogen from 0.5 to 10-3up to 3 of 10-3mol/l and maintain the temperature of the reactor 265oC and a space velocity of 250 h-1.The results are presented in table. 4.From table. 4 shows that the optimal solution is the interval of concentration of 1,1,2-trichloroethane 0.5 to 10-32 10-3mol/l, and the maximum yield of CIS - and TRANS-1,2-dichlorethylene per missed 1,1,2-trichloroethane in the above reaction conditions, respectively 65,2 and 32.4 mol. when the concentration in the nitrogen 1.5 to 10-3mol/L.Comparative characteristic of this method with the known method. Thus, in the present method, the yield of CIS-1,2-dichloroethylene and TRANS-1,2-dichlorethylene more than 30 times higher in comparison with the known method. The way to obtain CIS - and TRANS-1,2-dichlorethylene transmission diluted with nitrogen 1,1,2-trichloroethane when the concentration in the nitrogen 0.5 to 10-33 10-3mol/l, flow rate 70 - 700 h-1at elevated temperature and atmospheric pressure over a heterogeneous catalyst on a carrier, characterized in that the use of catalyst containing FeCl3on the media-Al2O3when their ratio, wt.FeCl31 20
-Al2O3The rest is up to 100
and the process is conducted at a temperature of 200 to 280oC.
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
SUBSTANCE: invention relates to nonflammable compositions which contain a fluorinated compound which is 1,1,1,3,3-pentafluorobutane, 1,2-dichloroethylene, and effective amount of a stabiliser for the fluorinated compound or 1,2-dichloroethylene, where the amount of the stabiliser is less than 0.5 wt % of the composition. These nonflammable compositions can be used as solvents for cleaning and removing fluxing material from components of electronic devices and for degreasing metals. The compositions can also contain a propellant, e.g., 1,1,1,2-tetrafluoroethane.
EFFECT: obtaining compositions which can be suitable as cleaning agents.
16 cl, 9 ex, 2 tbl