The method of producing epichlorohydrin
(57) Abstract:The invention relates to techniques for the production of oxides of galeolaria the dehydrochlorination haloesters alcohols and can be used in the production of epichlorohydrin. In the method of producing epichlorohydrin by dehydrochlorination of dichlorohydrin glycerin sodium hydroxide using anhydrous dichlorohydrin glycerin, alkali concentration of 25-30%, the process is conducted at a temperature of 55-77oC and a reduced pressure of 0.6-0.7 ATM. The technical result - the reduction of wastewater. 1 Il. The invention relates to techniques for the production of oxides halogen-olefins by dehydrochlorination haloesters alcohols and can be used in the chemical industry in the production of epichlorohydrin and synthetic glycerin.Well-known and widely used in industry in the method of producing epichlorohydrin (EPG) by dehydrochlorination 2-5-percentage aqueous solutions of dichlorohydrin glycerol (GHG) water sustancia calcium hydroxide. The main disadvantage of this method is the large number of wastewater from 50 to 100 tons per tonne EPG contaminated mineral, organic and chlorinated organic impurities, purification of which ve is isdi wastewater such production equals and even exceeds the cost of the equipment itself the production EPG. Great and operational costs of such cleanup.In industry, this method of obtaining EPG goes in two stages: first, from allyl chloride and hypochlorous acid to obtain an aqueous solution DHG, and the second is the resulting aqueous solution is treated with an alkaline agent and received EPG allocate distillation. Thus process water from both stages is summarized and is contaminated by the products of both reactions.There are several patented at different times of the attempts to reduce the amount of wastewater, limited mainly to increasing concentrations of solutions DHG and alkaline agents, which should thus reduce the amount of waste water. However this way met serious obstacles: reduce yields of target products and malaysiensis quantity and composition of the contaminants in the wastewater. For these reasons, these attempts have not been implemented in practice.Closest to the present invention is a method of producing epichlorohydrin, in which 4-5% aqueous solution of dichlorohydrin glycerol is subjected to dehydrochlorination aqueous solutions of calcium hydroxide (lime milk) or sodium hydroxide (caustic soda) with concentrational agent 1,1-1,12 (L. A. Oshin. Production of synthetic glycerin, M.: Chemistry, 1974, page 105).The disadvantage of this method is the large number of sewage.The present invention is to develop a practically closed method of producing epichlorohydrin.The task is solved in that the proposed method of producing epichlorohydrin by dehydrochlorination of dichlorohydrin glycerin sodium hydroxide, which is used anhydrous dichlorohydrin glycerol, the concentration of alkali 25-30%, and the process is conducted at a temperature of 55-77oC and a reduced pressure of 0.6-0.7 ATM.The essence of the proposed method is illustrated by a drawing.In the reactor R-1 do: anhydrous DHG and 25-30% solution of sodium hydroxide. When the temperature 55-77oWith a residual pressure of 0.6-0.7 ATM formed EPG Argonauts with water in the form of azeotropic mixtures, vapours which condense in K-2 and the fluid is stratified. Water containing 7-8% EPG, is returned to the reactor and concentrated EPG containing up to 2% of water and other impurities is supplied to the cleaning method of rectification. From a bottom part of the reactor output water containing 20-22% sodium chloride and small amounts of organic primecap can be used in the production of chlorine and in this case, the production of epichlorohydrin is almost closed.EXAMPLE. 654 g of anhydrous GHG mixed with an aqueous solution of sodium hydroxide, the concentration of 28%, in a molar ratio of 1:1. The time of reaction and distillation, azeotropic mixtures DHG + water - 10 minutes With the resulting 438,5 g EPG, the output of which was 93.5%. VAT residue obtained 1312 g containing sodium chloride and 22.6%, glycerin 0.2% and traces DHG and EPG, and it can be used as raw materials in the electrolysis to obtain chlorine.Thus, in comparison with the prototype, the proposed method has the main advantage that there are no contaminated process waters, requiring expensive clean-up, the yield of the target product of epichlorohydrin is not reduced. The method of producing epichlorohydrin by dehydrochlorination of dichlorohydrin glycerin sodium hydroxide, characterized in that use anhydrous dichlorohydrin glycerol, the concentration of alkali 25-30%, and the process is conducted at a temperature of 55-77oC and a reduced pressure of 0.6-0.7 ATM.
SUBSTANCE: method is described for synthesis of aromatic N-glycidylamines, in accordance with which an amine, which contains at least one hydrogen atom of a aromatic amino group, is heated with 0.7 equivalents of epichlorihydrin in terms of the equivalent of the hydrogen atom of the amino group of the aromatic amine, using a catalyst in form of a nitrate of a divalent or polyvalent metal dissolved in propylene carbonate. The product is then dehydrochlorinated.
EFFECT: method for synthesis of aromatic N-glycidylamines is proposed.
6 cl, 1 tbl, 3 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention proposes a method for synthesis of 1,2-epoxy-3-chloropropane. Method involves reaction between allyl chloride and hydrogen peroxide in the presence of catalyst comprising zeolite and, possibly, at least one solvent in the epoxidation medium comprising at least one liquid phase. The distinctive feature of the proposed method involves control of pH value of liquid phase and its maintaining at value 1.5 or above but less 4.8. Invention provides enhancing selectivity of the epoxidation reaction resulting to decrease formation of unfavorable by-side products of reaction.
EFFECT: improved method of synthesis.
10 cl, 3 tbl, 6 ex
SUBSTANCE: method involves a stage of interaction of one or more α-halogenketones with general formula I , where each of "X" independently represents a halogen atom, except fluorine, a hydrogen atom and "Z" represents a halogen atom, except fluorine; with molecular hydrogen in the presence of heterogeneous catalyst, containing a transition metal, where the catalyst is a metallic salt, which is saturated with the catalyst carrier, where the metal consist of iridium, ruthenium or their mixture. The metal catalyses hydrogenation of all carbonyl groups of α-halogenketons to alcohol groups, at temperature from 1° to 200°C and pressure of at least 14 abs. pound/square inch with formation of one or more α-halogenspirits with general formula II . The invention also relates to the method of obtaining epoxides (alternatives), to the method of obtaining epi-halogenhydrine (alternatives) and to the method of obtaining propylene oxide (alternatives).
EFFECT: improved activity of the catalyst.
3 tbl, 3 ex
SUBSTANCE: invention relates to the method of obtaining 1,2-epoxy-3-chlorinepropane, by the reaction between allyl chloride and hydrogen peroxide in the presence of titanium silicate zeolite catalyst and possible presence of, at least, one solvent in the epoxiding medium, which includes, at least, one liquid phase in which allyl chloride being used contains less than 2000 parts/million mass. 1,5-hexadiene.
EFFECT: reduction in the catalyst deactivation without decrease of its activity and selectivity of the reaction of epoxidation.
10 cl, 3 tbl, 7 ex
SUBSTANCE: invention relates to a method of producing epichlorohydrin. According to the disclosed method, a) at the first step of the reaction, allyl chloride and hydrogen peroxide react in the presence of a titanium-containing zeolite catalyst with molar ratio of allyl chloride to hydrogen peroxide equal to at least 1.5:1, wherein the allyl chloride used is contaminated with 1-chloropropane and/or 2-chloropropane; b) the reaction mixture formed at the first step of the reaction is divided during distillation into a mixture (A), which contains unreacted allyl chloride as well as 1-chloropropane and/or 2-chloropropane, and a mixture (B) which contains epichlorohydrin; c) mixture (A) is divided into a mixture (A1) which is returned to the first reaction step and a mixture (A2); d) mixture (A2) at the second reaction step reacts with hydrogen peroxide in the presence of a titanium-containing zeolite catalyst with molar ratio of allyl chloride to hydrogen peroxide ranging from 0.5:1 to 1.25:1; e) the reaction mixture formed at the second reaction step is divided during distillation into a mixture (C), which contains 1-chloropropane and/or 2-chloropropane, and a mixture (D) which contains epichlorohydrin; and f) mixture (C) is removed from the method.
EFFECT: obtaining epichlorohydrin from allyl chloride containing chloropropanes with high selectivity and improved conversion of the starting allyl chloride.
9 cl, 1 dwg, 3 tbl, 2 ex
SUBSTANCE: invention relates to chemical engineering and specifically to a method of producing hexafluoropropylene oxide (HFPO), which is a semi-product for synthesis of a wide range of compounds. According to the invention, HFPO is obtained via liquid-phase oxidation of hexafluoropropylene with oxygen at high temperature and pressure in a medium of a fluorine-containing solvent - perfluoropolyoxamethylene acetyl fluorides of general formula CF3O(CF2O)nCF2COF, where n=1-4, in the presence of a catalyst of a fluorine-containing organic peroxide compound (FOPC). The FOPC is separated from the hexafluoropropylene oxidation products and used in amount of 0.005-0.05 wt % with respect to "active" oxygen. Perfluoropolyoxamethylene acetyl fluorides are separated from hexafluoropropylene oxidation products by distillation and used in a mixture with polyfluorochloroalkane - freon-328, freon-113, freon-123a with content thereof of 0-30 wt %.
EFFECT: high rate, selectivity and explosion safety of the process of producing HFPO by stabilising concentration of the catalyst used, as well as reducing environmental impact by cutting use of freon-113.
3 cl, 3 tbl, 6 ex
SUBSTANCE: invention relates to a method of producing epichlorohydrin which is used as a solvent for cellulose, resins and dyes, as fumigant and as a structural unit when producing plastic, epoxy resins and phenol resins. The method involves reaction of allyl chloride with an oxidant in the presence of a catalyst which contains a water-soluble manganese complex in an aqueous reaction medium with molar ratio of allyl chloride to the oxidant ranging from 1:0.1 to 1:1.2, followed by removal of the epichlorohydrin product. Normally the catalyst contains a mononuclear manganese complex of general formula (I): [LMnX3]Y (1) or a binuclear manganese complex of general formula (II): [LMn(|µ-X)3MnL]Y2 (II), where Mn is manganese; L or each L independently denotes a polydentate ligand; each X independently denotes coordination compounds and each µ-X independently denotes bridge coordination compounds selected from a group consisting of: RO-, Cl-, Br-, I-, F-, NCS-, N3 -, I3 -, NH3, NR3, RCOO-, RSO3 -, RSO4 -, OH-, O2-, O2 2-, HOO-, H2O, SH-, CN-, OCN-, and S4 2- combinations thereof, where R is a C1-C20 radical selected from a group consisting of alkyl, cycloalkyl, aryl, benzyl and combinations thereof, and Y denotes an oxidation-stable counter-ion.
EFFECT: method enables to carry out the process with high selectivity and number of rotations.
15 cl, 4 ex, 3 tbl
SUBSTANCE: method involves reaction of a terminal olefin with an oxidising agent in the presence of a catalyst in a two-phase system which contains an organic phase and aqueous reaction medium, the catalyst containing a water-soluble manganese complex, the terminal olefin having solubility at 20°C of at least 0.01-100 g per litre of water, and molar ratio of the terminal olefin to the oxidising agent ranging from 1:0.1 to about 1:1.
EFFECT: method enables to obtain an end product with large number of revolutions and high selectivity.
20 cl, 6 ex, 5 tbl
SUBSTANCE: invention relates to industrial technology for production of epichlorohydrin (ECH) by means of liquid-phase allyl chloride epoxidation with hydrogen peroxide in methanol on titanium-containing catalyst, more specifically to step for extracting concentrated ECH from reaction mixture. Proposed method for extracting concentrated ECH from products of allyl chloride epoxidation with hydrogen peroxide on titanium-containing zeolite catalyst in presence of methanol involves separation of allyl chloride and methanol from reaction mixture in primary distillation column, separation of remained bottom residue to aqueous and organic solutions, azeotropic rectification of aqueous and organic solutions, return of azeotropic rectification stripping, containing mixture of water, ECH, and methanol residue, into lower part of primary fractionation column. Return of azeotropic rectification stripping therein is carried out in vapour state into lower part of primary fractionation column.
EFFECT: technical result is simplification of process flow of extraction, and reducing specific consumption of heat energy per 1 kg of ECH.
3 cl, 1 dwg, 5 ex
SUBSTANCE: invention relates to a method of producing epoxide, which includes: feeding components to form a reaction mixture, wherein components comprise: olefin, having maximum solubility in water at 20 °C from 0.01 to 100 g/l; hydrogen peroxide; ions of alkaline-earth metal, containing metal ions formed from salts of alkali-earth metal and acid with pKa level equal to 15 or less; water-soluble manganese complex; buffer component; as well as water; and reaction of olefin with hydrogen peroxide in reaction mixture. Manganese complex includes one or more compounds, selected from a group consisting of: mononuclear complex formula (I): [LMnXm]Y (I), binuclear complex of formula (II): [LMn(μ-X)mMnL]Yn (II) or polynuclear complex of formula (III): [LnMnn(μ-X)m]Yn (III), where Mn denotes a manganese atom; L or each of L independently is a polydentate ligand, each X is independently a coordination particle and each μ-X independently represents a bridge coordination particle, where Y is a non-coordinated counterion, and m assumes values from 1 to 4, and value of n ranges from 1 to 2.
EFFECT: increased number of turns of catalyst (TON) due to higher efficiency of using an oxidising agent.
15 cl, 1 dwg, 5 tbl, 3 ex
SUBSTANCE: epichlorohydrin is prepared by reacting allyl chloride with an oxidizing agent in the presence of a titanium silicalite catalyst. As the oxidizing agent, a solution of hydroperoxide in methanol is used at the mass ratio of hydroperoxide and methanol (0.16-0.53):1, and the weight ratio of allyl chloride to the solution of hydroperoxide in methanol is (0.37-0.91):1. The subsequent separation of the reaction products is also described.
EFFECT: increasing the selectivity of the allyl chloride epoxidation process by completely eliminating water from the composition of the reacting components and removing water from the recycled streams of allyl chloride and methanol.
6 cl, 2 tbl, 14 ex