The way to obtain 1-chloro-1,3-butadiene
(57) Abstract:Describes how to obtain 1-chloro-1,3-butadiene by dehydrochlorination of dichlorobutenes selected from 3,4-dichlorobutene-1, 1,4-dichlorobutene-2 or mixtures thereof, and the process is conducted in the gas phase in the presence of a catalyst selected from lanthanum phosphate or phosphate of lanthanum, additive comprising an alkaline or alkaline-earth metal, or mixtures of these phosphates. The proposed method is simpler and cheaper than known. 2 C.p. f-crystals, 2 tab. The present invention relates to a method for producing 1-chloro-3,4-butadiene by the dehydrochlorination of 3,4-dichlorobutene-1, 1,4-dichlorobutene-2 or mixtures thereof.It is known that 1-chloro-1,3-butadiene, also called "alpha chloroprene, you can polimerizuet or copolymerizate preferably, chloroprene 2-chloro-1,3-butadiene.A method of obtaining 1-chloro-1,3-butadiene degidrirovanie 1,4-dichlorobutene-2 by the action of sodium amide in liquid paraffin - see Methods elementool. chemistry, Ed. by A. N. PL, M: Nauka, 1973, S. 460.Alpha chloroprene usually obtained as a by-product in most of the reactions that receive a 2-chlorobutadiene. In fact, a small amount of al is ropren stands, the quantity which can vary from the conditions of reaction formed during the chlorination reactions of butadiene, or isomerization of 1,4-chloro-2-butene to obtain 3,4-sodium dichloro-1-butene, or also dehydrochlorinating 3,4-sodium dichloro-1-butene.High level output alpha chloroprene can be obtained by dehydrochlorination of 1,4-sodium dichloro-2 butene, obtained in turn from butandiol with amidon of sodium in mineral oil. This method is very expensive, as it requires at least stoichiometric quantities of sodium amide.The purpose of the present invention is an improved way to obtain 1-chloro-1,3-butadiona, which is free from the above disadvantages.In accordance with the foregoing, the present invention relates to a method for producing 1-chloro-1,3-butadiene, wherein dichlorobutene is selected from 3,4-sodium dichloro-1-butene, 1,4-di-sodium dichloro-2-butene and mixtures thereof, and dehydrochlorinated in the gas phase in the presence of a catalyst selected from lanthanum phosphate, lanthanum phosphate with an additive of at least one alkali or alkaline earth metal, and mixtures of these phosphates.The catalyst preferably is selected from phosphate and lanthanum phosphate landata La" refers to the connection, which is defined in EP-A-440555, i.e. a compound with the General formula on the basis of dry material/: LaPO4/Imp/p/1/.In connection with the General formula /1/ "Imp" refers to the primary treatment composition, which comprises a metal selected from alkali metal or alkaline earth metal, preferably alkaline earth metals, and these metals are associated with the counter-ion as to ensure the neutrality of the compounds of General formula /1/. In the above formula, /1/, the ratio "R" is in the range from 10-2up to 1/3 , preferably from 0.05 to 0.2.The phosphate landata can be well-known technology, for example, by reaction of phosphoric acid and salts of lanthanum, for example, lanthanum carbonate.Receiving lanthanum phosphate with an additive of alkaline metal or alkaline earth metal is disclosed in EP-A-440555.Before using the catalyst in the method degidro-chlorination according to the present invention, the catalyst is subjected to conventional procedures calcination, preferably at temperatures in the range from 420 to 480oC.The catalyst can be used in the method of the present invention as such, or as lump is particularly suitable oxides such as alumina, silica, titanium oxide, magnesium oxide, zirconium dioxide, taken separately or combined with each other.The catalyst and binder can be mixed in a weight ratio of 30: 70, preferably in a ratio of from 50:50 to 70:30. The mixture can be shaped in a desired form, for example, extruded bodies or granules.The reaction dihydrochloride, which is based on the method of the present invention, is as follows:
the isomerization of 3,4-sodium dichloro-1-butene /3,4-DCB/, obtaining 1,4-sodium dichloro-1-butene /1,4-DCB/;
the dehydrochlorination of 1,4-DCB to obtain 1-chloro-1,3-butadiene /1-SW/.It follows from the above that the method according to the present invention is equally effective as of 3,4-DCB and 1,4-DCB as starting compounds.The method of the present invention provides a process in which 3,4-DCB or 1,4-DCB or mixtures thereof are skipped over a specified catalyst.In accordance with a variant of the invention it is possible to use a carrier gas, which consists of one or more inert gases, preferably is nitrogen.The contact time is in the range of 5 to 0.5 seconds, better than 2 to 1 second.The method of the invention mainly provoditj examples to further illustrate the invention.Example 1. Getting LaPO4< / BR>57 g of H3PO4/85% Prolabo/, and 150 ml of deionized water are loaded into the reactor. The resulting mixture was stirred at a speed of 500 to 700 rpm In a cold state with strong stirring is added 166.6 g of La2/CO3/312H2O. the Reaction medium is heated for 60 minutes and then cooled with bringing to room temperature for 30 minutes. The suspension is filtered on a filter with a porous glass plate N 3 until then, until you leave the mother liquor.The pressed residue is immersed in 1000 ml of water with strong stirring and maintained in suspension for 30 minutes while stirring. Stage washing is repeated twice. The product is filtered, then dried at 110oC.Example 2. Getting LaPO4with the cesium additive.4,7 ml 6M CsOH is added to 14.12 ml 1M H3PO4. The addition of water, the volume of the mixture is brought to 50 ml.ofTo 50 g LaPO4prepared in accordance with the previous example, is added dropwise 20 ml of the indicated solution.The product is brewed for 60 minutes, dried overnight at 110oC, and then fired at 500oC for 120 minutes.
the calcination: 120 minutes at 400oC;
- air conditioning heat: 120 minutes at 250oC.The resulting reaction products were separated by trap /being isolated in three traps set by the cascade/ p separation was performed within 1 hour after a period beginning 45 minutes.Experimental conditions:
- N2: 2.8 l/h
the feed rate of 3,4-dichlorobutene /reduction States "3,4 -, or 1,4-di-sodium dichloro-2 butene: g/h;
- temperature: 250oC.The results are shown in Table 1, where: RRICBoutput 1-chloroprene,
RR1,4- yield of 1,4-di-sodium dichloro-2-butene,
TT3,4- conversion of 3,4-sodium dichloro-1-butene,
TT1,4- conversion of 1,4-di-sodium dichloro-2-butene.Example 4.In this example, /TableA in the presence of CS2NRA4LaPO4obtained as disclosed in example 2 above. Was also calculated yield of chloroprene /RRCP.The data in table 2 show that the best results in the transformation and exit out at a temperature of approximately 200oC, albeit with 250oC data is also satisfactory. 1. The way to obtain 1-chloro-1,3-butadiene by dehydrochlorination of dichlorobutene in the presence of a catalyst, characterized in that use dichlorobutene selected from 3,4-dichlorobutene-1, 1,4-dichlorobutene-2 or mixtures thereof, and the process is conducted in the gas phase at a temperature of 190 - 280oC, and as a catalyst using a catalyst selected from lanthanum phosphate or phosphate of lanthanum, additive comprising an alkaline or alkaline-earth metal, or mixtures of these phosphates.2. The method according to p. 1, wherein the used catalyst is selected from phosphate and lanthanum phosphate, lanthanum, including cesium additive.3. The method according to p. 1, wherein the process is conducted at 200 to 250oC.
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