EP1891032A2

EP1891032A2 - Method for making an epoxy starting from a chlorhydrine

Info

Publication number: EP1891032A2
Application number: EP06763200A
Authority: EP
Inventors: Philippe Krafft; Dominique Balthasart; Valentine Smets; Patrick Gilbeau
Original assignee: Solvay SA
Current assignee: Solvay SA
Priority date: 2005-05-20
Filing date: 2006-05-19
Publication date: 2008-02-27
Also published as: US20080200701A1; WO2006100312A3; WO2006100314A1; MX2007014523A; CA2608961C; US20090131631A1; CA2608816A1; CN102603474A; EP2284162A2; CN101052606B; US8106245B2; CN101098843A; US8389777B2; US7906691B2; WO2006100315A3; WO2006100315A2; BRPI0610745A2; TW200700361A; TW200700401A; EP2284162A3

Abstract

The invention concerns a method for making an epoxy including at least one step of purifying the formed epoxy, the epoxy being at least partly made by a method for dehydrochlorinating chlorhydrine, the latter being at least partly made from a method for chlorinating a polyhydroxylated aliphatic hydrocarbon, a polyhydroxylated aliphatic hydrocarbon ester, or a mixture thereof.

Description

Process for producing an epoxide from a chlorohydrin

The present patent application claims the benefit of the patent application FR 05.05120 and the patent application EP 05104321.4, filed on May 20, 2005 and the provisional US patent applications 60/734659, 60/734627, 60/734657, 60 / 734658, 60/734635, 60/734634, 60/734637 and 60/734636, filed November 8, 2005, the contents of which are hereby incorporated by reference.

The present invention relates to an epoxide manufacturing process. Epoxides are important raw materials for the production of other compounds. Ethylene oxide is used for example for the production of ethylene glycol, di and polyethylene glycols, mono-, di- and triethanolamines, etc. (See K. Weissermel and H. J. Arpe in Industrial Organic Chemistry, Third Completely Revised Edition, VCH Editor, 1997, page 149). Propylene oxide is an important intermediate in the manufacture of 1,2-propylene glycol, dipropylene glycol, propylene glycol ethers, isopropylamines, and the like. (See K. Weissermel and H.-J. Arpe in Industrial Organic Chemistry, Third Completely Revised Edition, VCH Editor, 1997, page 275). Epichlorohydrin is an important raw material for the production of glycerol, epoxy resins, synthetic elastomers, glycidyl ethers, polyamide resins, etc. (see Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition, Vol A9, p.539).

In the industrial production of propylene oxide, the most widely used technology comprises the following steps: hypochlorination of propylene to monochloropropanol and dehydrochlorination of monochloropropanol to propylene oxide by an aqueous alkaline solution.

In the industrial production of epichlorohydrin, the most widely used technology comprises the following steps: high temperature radical substitutive chlorination of propylene to allyl chloride, hypochlorination of allyl chloride thus synthesized in dichloropropanol and dehydrochlorination of dichloropropanol to epichlorohydrin by an aqueous alkaline solution. Another technology used on a smaller scale includes the following steps: catalytic acetoxylation of propylene to allyl acetate, hydrolysis of acetate allyl to allyl alcohol, catalytic chlorination of allyl alcohol to dichloropropanol and alkaline dehydrochlorination of dichloropropanol to epichlorohydrin. Other technologies that have not yet been industrially applied can be envisaged, including direct catalytic oxidation of allyl chloride to epichlorohydrin by means of hydrogen peroxide or hydrochlorination of glycerol to dichloropropanol followed by an alkaline dehydrochlorination of the dichloropropanol thus formed in epichlorohydrin.

The application WO 2005/054167 of SOLVAY SA describes a process for the manufacture of dichloropropanol by reaction between glycerol and hydrogen chloride in the presence of an organic acid as catalyst. In this process, the dichloropropanol is separated from the other reaction products, hydrogen chloride and organic acid and the dichloropropanol is subjected to a dehydrochlorination reaction to obtain reaction products containing epichlorohydrin. The dehydrochlorination can be carried out in the presence of a basic agent and in particular an aqueous solution of a basic agent. The epichlorohydrin formed can be used in the manufacture of polyglycerols or epoxy resins. The presence of impurities such as chlorinated ketones or aldehydes in the epichlorohydrin obtained may, however, be detrimental to the applications mentioned. According to the invention, it has been found that the presence of impurities in the epoxide can for example be the cause of color problems of the organic products obtained or the source of undesirable chemical contaminations of these products by halogens for example.

The object of the present invention is to provide a method of manufacturing an epoxide, which does not have these disadvantages.

The invention therefore relates to a process for the production of an epoxide comprising at least one stage of purification of the epoxide formed, the epoxide being at least partially manufactured by a process for the dehydrochlorination of a chlorohydrin, the latter being at least partly manufactured by a process for chlorinating a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them. The term "epoxide" is used herein to describe a compound having at least one oxygen bridged on a carbon-carbon bond. Generally the carbon atoms of the carbon-carbon bond are adjacent and the compound may contain other atoms than carbon and oxygen atoms, such as hydrogen atoms and halogens. Epoxies Preferred are ethylene oxide, propylene oxide, glycidol, epichlorohydrin and mixtures of at least two of them.

The term "olefin" is used herein to describe a compound having at least one carbon-carbon double bond. Generally the compound may contain other atoms than carbon atoms, such as hydrogen atoms and halogens. The preferred olefins are ethylene, propylene, allyl chloride and mixtures of at least two of them.

The term "polyhydroxylated aliphatic hydrocarbon" refers to a hydrocarbon that contains at least two hydroxyl groups attached to two different saturated carbon atoms. The polyhydroxylated aliphatic hydrocarbon may contain, but is not limited to, from 2 to 60 carbon atoms.

Each of the carbons of a polyhydroxylated aliphatic hydrocarbon bearing the functional hydroxyl (OH) group can not have more than one OH group, and must be of sp3 hybridization. The carbon atom carrying the OH group may be primary, secondary or tertiary. The polyhydroxylated aliphatic hydrocarbon used in the present invention must contain at least two sp3 hybridization carbon atoms carrying an OH group. The polyhydroxylated aliphatic hydrocarbon includes any hydrocarbon containing a vicinal diol (1,2-diol) or a vicinal triol (1,2,3-triol) including higher orders of these repeating units, vicinal or contiguous . The definition of the polyhydroxylated aliphatic hydrocarbon also includes, for example, one or more 1,3-, 1,4-, 1,5- and 1,6-diol functional groups. The polyhydroxylated aliphatic hydrocarbon may also be a polymer such as polyvinyl alcohol. Geminated diols, for example, are excluded from this class of polyhydroxylated aliphatic hydrocarbons.

The polyhydroxylated aliphatic hydrocarbons may contain aromatic entities or hetero atoms including, for example, hetero atoms of the halogen, sulfur, phosphorus, nitrogen, oxygen, silicon and boron type, and mixtures thereof. Polyhydroxylated aliphatic hydrocarbons for use in the present invention include, for example, 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 1-chloro-2, 3- propanediol (chloropropanediol), 2-chloro-1,3-propanediol (chloropropanediol), 1,4-butanediol, 1,5-pentanediol, cyclohexanediols, 1,2-butanediol, 1,2-butane diol cyclohexanedimethanol, 1,2,3-propanetriol (also known as "glycerol" or "glycerin"), and mixtures thereof. In a way - AT -

preferred, the polyhydroxylated aliphatic hydrocarbon used in the present invention includes, for example, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, chloropropanediol and 1,2,3-propanetriol, and mixtures of at least two of them. More preferably, the polyhydroxylated aliphatic hydrocarbon used in the present invention includes, for example, 1,2-ethanediol, 1,2-propanediol, chloropropanediol and 1,2,3-propanetriol, and mixtures thereof. least two of them. 1,2,3-propanetriol or glycerol is the most preferred.

The esters of the polyhydroxylated aliphatic hydrocarbon may be present in the polyhydroxylated aliphatic hydrocarbon and / or may be produced in the process for the manufacture of chlorohydrin and / or may be manufactured prior to the process for producing the chlorohydrin. Examples of polyhydroxylated aliphatic hydrocarbon esters include ethylene glycol monoacetate, propanediol monoacetates, glycerol monoacetates, glycerol monostearates, glycerol diacetates, and mixtures thereof.

The term "chlorohydrin" is used here to describe a compound containing at least one hydroxyl group and at least one chlorine atom attached to different saturated carbon atoms. A chlorohydrin which contains at least two hydroxyl groups is also a polyhydroxylated aliphatic hydrocarbon. Thus, the starting material and the product of the reaction can each be chlorohydrins. In this case, the "produced" chlorohydrin is more chlorinated than the starting chlorohydrin, that is to say that it has more chlorine atoms and fewer hydroxyl groups than the starting chlorohydrin. Preferred chlorohydrins are chloroethanol, chloropropanol, chloropropanediol, dichloropropanol and mixtures of at least two of them. Dichloropropanol is particularly preferred. More particularly preferred chlorohydrins are 2-chloroethanol, 1-chloropropan-2-ol, 2-chloropropane-1-ol, 1-chloropropane-2,3-diol, 2-chloropropane-1,3-diol. 1,3-dichloropropan-2-ol, 2,3-dichloropropan-1-ol and mixtures of at least two of them.

The polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, in the process according to the invention can be obtained from fossil raw materials or from renewable raw materials. It is preferred that at least one part be obtained from renewable raw materials. It is preferred that at least one part be obtained from fossil raw materials. The polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, can be subjected to a purification treatment so as to reduce the content of salts and / or organic compounds which do not are not the polyhydroxylated aliphatic hydrocarbon, or the polyhydroxylated aliphatic hydrocarbon ester, before the chlorination process.

Fossil raw materials are understood to mean materials from the processing of petrochemical natural resources, for example, petroleum, natural gas, and coal. Of these materials, organic compounds having 2 and 3 carbon atoms are preferred. When the polyhydroxylated aliphatic hydrocarbon is glycerol, allyl chloride, allyl alcohol and "synthetic" glycerol are particularly preferred. By "synthetic" glycerol is meant a glycerol generally obtained from petrochemical resources. When the polyhydroxylated aliphatic hydrocarbon is ethylene glycol, ethylene and "synthetic" ethylene glycol are particularly preferred. By "synthetic" ethylene glycol is meant an ethylene glycol generally obtained from petrochemical resources. When the polyhydroxylated aliphatic hydrocarbon is propylene glycol, propylene and "synthetic" propylene glycol are particularly preferred. By "synthetic" propylene glycol is meant a propylene glycol generally obtained from petrochemical resources.

Renewable raw materials are defined as materials derived from the treatment of renewable natural resources. Among these materials, "natural" ethylene glycol, "natural" propylene glycol and "natural" glycerol are preferred. For example, "natural" ethylene glycol, propylene glycol and glycerol are obtained by conversion of sugars via thermochemical processes, for example, these sugars can be obtained from biomass, as described in "Industrial Bioproducts: Today and Tomorrow". , Energetics, Incorporated for the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Office of the Biomass Program, July 2003, pages 49, 52 to 56 ". One of these processes is, for example, the catalytic hydrogenolysis of sorbitol obtained by thermochemical conversion of glucose. Another method is for example the catalytic hydrogenolysis of xylitol obtained by hydrogenation of xylose. The xylose can for example be obtained by hydrolysis of the hemicellulose contained in the corn fibers. "Glycerol obtained from renewable raw materials" means designate in particular glycerol obtained during the manufacture of biodiesel or glycerol obtained during transformations of fats or oils of plant or animal origin in general such as saponification, transesterification or hydrolysis reactions. Among the oils that can be used in the process of the invention, mention may be made of all common oils, such as palm, palm kernel, coconut, babassu, old or new rapeseed, sunflower, corn, castor oil and cotton, peanut, soybean, flax and crambe oils and all oils derived for example from sunflower or rapeseed plants obtained by genetic modification or hybridization.

You can even use used cooking oils, various animal oils, such as fish oils, tallow, lard and even rendering fats.

Among the oils used, it is also possible to indicate partially modified oils, for example by polymerization or oligomerization, for example the "standolies" of linseed oil, sunflower oil and blown vegetable oils.

A particularly suitable glycerol can be obtained during the processing of animal fats. Another particularly suitable glycerol can be obtained during the manufacture of biodiesel. A third particularly suitable glycerol can be obtained during the transformation of fats or oils, animal or vegetable by trans-esterification in the presence of a heterogeneous catalyst, as described in documents FR 2752242, FR 2869612 and FR More specifically, the heterogeneous catalyst is chosen from mixed oxides of aluminum and zinc, mixed oxides of zinc and titanium, mixed oxides of zinc, titanium and aluminum, and mixed oxides of bismuth and of aluminum, and the heterogeneous catalyst is implemented in the form of a fixed bed. The latter process may be a biodiesel manufacturing process. In the process for manufacturing an epoxide according to the invention, the polyhydroxylated aliphatic hydrocarbon may be as described in the patent application entitled "Process for preparing chlorohydrin by conversion of polyhydroxylated aliphatic hydrocarbons" deposited in the name of SOLVAY SA the same day as the present application, the contents of which are hereby incorporated by reference. Particular mention is made of a process for producing a chlorohydrin in which a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof, of which the total content of expressed metals, is reacted. in the form of elements is greater than or equal to 0.1 μg / kg and less than or equal to 1000 mg / kg, with a chlorinating agent.

In a first aspect of the process according to the invention, at least a fraction of the chlorohydrin can be manufactured by a process of hypochlorination of an olefin. The olefin may be selected from ethylene, propylene, allyl chloride and mixtures thereof.

In a second aspect of the process according to the invention, at least a fraction of the chlorhdyrine can be manufactured by a process for the chlorination of an unsaturated aliphatic alcohol. The term "unsaturated aliphatic alcohol" refers to a hydrocarbon that contains at least one hydroxyl group and a carbon-carbon double bond. The unsaturated aliphatic alcohol may contain, but is not limited to, from 2 to 60 carbon atoms. Allyl alcohol is an example of unsaturated alcohol.

In a third aspect of the process according to the invention, at least a part of the epoxide can be manufactured by a process for the epoxidation of an olefin. Epoxidation can be carried out using any peroxide. Of the inorganic peroxides, perborates, percarbonates and hydrogen peroxide are preferred, with hydrogen peroxide being particularly preferred. Organic peroxides, organic hydroperoxides and urea hydrogen peroxide adduct may also be used. The different aspects of the process according to the invention can be combined with one another.

In the process for producing an epoxide according to the invention, the use of the chlorohydrin obtained from the polyhydroxylated aliphatic hydrocarbon, from the ester of the polyhydroxylated aliphatic hydrocarbon, or from the mixture of they, by reaction with a chlorinating agent, can be carried out for example according to the process described in application WO 2005/054167 of SOLVAY SA, the content of which is hereby incorporated by reference.

In the process for producing an epoxide according to the invention, the polyhydroxylated aliphatic hydrocarbon, the ester of the polyhydroxylated aliphatic hydrocarbon, or the mixture of them can be a crude product or a product. purified as described in SOLVAY SA application WO 2005/054167, page 2, line 8, to page 4, line 2.

In the process for manufacturing an epoxide according to the invention, the polyhydroxylated aliphatic hydrocarbon, the ester of the polyhydroxylated aliphatic hydrocarbon, or the mixture of them, may have an alkali metal and / or alkaline content. -terreux is less than or equal to 5 g / kg as described in the application entitled "Process for producing a chlorohydrin by chlorination of a polyhydroxylated aliphatic hydrocarbon" deposited in the name of SOLVAY SA the same day as the present application, whose content is hereby incorporated by reference.

In the process according to the invention, the content of alkali and / or alkaline-earth metals of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, is less than or equal to at 5 g / kg, often less than or equal to 1 g / kg, more particularly less than or equal to 0.5 g / kg and in some cases less than or equal to 0.01 g / kg. The content of alkaline and / or alkaline-earth metals of glycerol is generally greater than or equal to 0.1 μg / kg.

In the process according to the invention, the alkali metals are generally lithium, sodium, potassium and cesium, often sodium and potassium, and frequently sodium.

In the process for producing a chlorohydrin according to the invention, the lithium content of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, is generally less than or equal to at 1 g / kg, often less than or equal to 0.1 g / kg and more particularly less than or equal to 2 mg / kg. This content is generally greater than or equal to 0.1 μg / kg.

In the process according to the invention, the sodium content of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, is generally less than or equal to 1 g / kg, often less than or equal to 0.1 g / kg and more particularly less than or equal to 2 mg / kg. This content is generally greater than or equal to 0.1 μg / kg.

In the process according to the invention, the potassium content of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, is generally less than or equal to 1 g / kg, often less than or equal to 0.1 g / kg and more particularly less than or equal to 2 mg / kg. This content is generally greater than or equal to 0.1 μg / kg.

In the process according to the invention, the rubidium content of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, is generally less than or equal to 1 g / kg, often less than or equal to 0.1 g / kg and more particularly less than or equal to 2 mg / kg. This content is generally greater than or equal to 0.1 μg / kg.

In the process according to the invention, the cesium content of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, is generally less than or equal to 1 g / kg, often less than or equal to 0.1 g / kg and more particularly less than or equal to 2 mg / kg. This content is generally greater than or equal to 0.1 μg / kg. In the process according to the invention, the alkaline-earth elements are generally magnesium, calcium, strontium and barium, often magnesium and calcium and frequently calcium.

In the process according to the invention, the magnesium content of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, is generally less than or equal to 1 g / kg, often less than or equal to 0.1 g / kg and more particularly less than or equal to 2 mg / kg. This content is generally greater than or equal to 0.1 μg / kg.

In the process according to the invention, the calcium content of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, is generally less than or equal to 1 g / kg, often less than or equal to 0.1 g / kg and more particularly less than or equal to 2 mg / kg. This content is generally greater than or equal to 0.1 μg / kg. In the process according to the invention, the strontium content of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, is generally less than or equal to 1 g / kg, often less than or equal to 0.1 g / kg and more particularly less than or equal to 2 mg / kg. This content is generally greater than or equal to 0.1 μg / kg. In the process according to the invention, the barium content of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, is generally less than or equal to 1 g / kg, often less than or equal to 0.1 g / kg and more particularly less than or equal to 2 mg / kg. This content is generally greater than or equal to 0.1 μg / kg.

In the process according to the invention, the alkali and / or alkaline earth metals are generally present in the form of salts, frequently in the form of chlorides, sulphates and mixtures thereof. Sodium chloride is most often encountered.

In the process for producing organic products according to the invention, the chlorinating agent of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, may be the hydrogen and / or hydrochloric acid as described in SOLVAY SA application WO 2005/054167, page 4, line 30, to page 6, line 2.

Particular mention is made of a chlorinating agent which may be aqueous hydrochloric acid or preferably anhydrous hydrogen chloride. Hydrogen chloride may be derived from a process for pyrolysis of chlorinated organic compounds such as vinyl chloride production, a process for the manufacture of 4,4-methylenediphenyl diisocyanate (MDI) or toluene diisocyanate ( TDI), metal stripping processes or a reaction between an inorganic acid such as sulfuric or phosphoric acid and a metal chloride such as sodium chloride, potassium chloride or calcium chloride.

In an advantageous embodiment of the process for producing an epoxide according to the invention, the chlorinating agent is gaseous hydrogen chloride or an aqueous solution of hydrogen chloride or a combination of both.

In the process for producing an epoxide according to the invention, the chlorinating agent of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, may be aqueous hydrochloric acid or preferably anhydrous hydrogen chloride, resulting from a process for producing allyl chloride and / or chloromethanes and / or chlorinolysis and / or high temperature oxidation of chlorinated compounds such as described in the application entitled "Process for producing a chlorohydrin by reaction between a polyhydroxylated aliphatic hydrocarbon and a chlorinating agent" deposited in the name of SOLVAY SA on the same day as the present application, the contents of which are hereby incorporated by reference. The hydrogen chloride may be gaseous hydrogen chloride and / or an aqueous solution of hydrogen chloride.

Particular mention is made of a process for producing a chlorohydrin from a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, and a chlorinating agent, the latter containing at least one of the following compounds: nitrogen, oxygen, hydrogen, chlorine, an organic hydrocarbon compound, a halogenated organic compound, an oxygenated organic compound and a metal. Particular mention is made of an organic hydrocarbon compound which is selected from aromatic hydrocarbons, saturated or unsaturated aliphatic and mixtures thereof.

Particular mention is made of an unsaturated aliphatic hydrocarbon which is selected from acetylene, ethylene, propylene, butene, propadiene, methylacetylene, and mixtures thereof, of a saturated aliphatic hydrocarbon which is selected from methane , ethane, propane, butane, and mixtures thereof, and an aromatic hydrocarbon which is benzene.

Particular mention is made of a halogenated organic compound which is a chlorinated organic compound chosen from chloromethanes, chloroethanes, chloropropanes, chlorobutanes, vinyl chloride, vinylidene chloride, monochloropropenes, perchlorethylene, trichlorethylene, chlorobutadiene, chlorobenzenes and mixtures thereof.

Particular mention is made of a halogenated organic compound which is a fluorinated organic compound selected from fluoromethanes, fluoroethanes, vinyl fluoride, vinylidene fluoride, and mixtures thereof.

Particular mention is made of an oxygenated organic compound which is chosen from alcohols, chloroalcohols, chloroethers and their mixtures

Particular mention is made of a metal selected from alkali metals, alkaline earth metals, iron, nickel, copper, lead, arsenic, cobalt, titanium, cadmium, antimony, mercury, zinc, selenium, aluminum, bismuth, and mixtures thereof.

Particular mention is made of a process in which the chlorinating agent is derived at least partially from a process for producing allyl chloride and / or a process for producing chloromethanes and / or a process chlorinolysis and / or a process for the oxidation of chlorinated compounds at a temperature greater than or equal to 800 ° C. In an advantageous embodiment of the process for manufacturing the epoxide according to the invention, the chlorinating agent for the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or a mixture of them , does not contain gaseous hydrogen chloride. In the process for producing an epoxide according to the invention, the chlorination reaction of the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or a mixture of them can be carried out in a reactor as described in the application WO 2005/054167 SOLVAY SA, on page 6, lines 3 to 23. Mention is particularly laite an installation made of or covered with resistant materials under the conditions of the reaction to agents chlorination, in particular with hydrogen chloride. Mention is more particularly made of an installation made of enamelled steel or tantalum. In the process for producing an epoxide according to the invention, the chlorination reaction of the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or a mixture of them can be carried out in equipment, made of or covered with chlorine-resistant materials, as described in the application "Process for producing a chlorohydrin in corrosion-resistant equipment" filed in the name of SOLVAY SA on the same day as the present application , the contents of which are hereby incorporated by reference.

Particular mention is made of a process for the manufacture of a chlorohydrin comprising a step in which a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon or a mixture thereof is subjected to a reaction with a chlorinating agent containing hydrogen chloride and at least one other step performed in equipment, made of or coated with chlorinating agent resistant materials, under the conditions of carrying out this step. Mention is more particularly made of metallic materials such as enamelled steel, gold and tantalum and non-metallic materials such as high density polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene , perfluoroalkoxyalkanes and poly (perfluoropropylvinylether), polysulfones and polysulfides, graphite and impregnated graphite.

In the process for producing an epoxide according to the invention, the chlorination reaction of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, may be performed in a reaction medium, as described in the application entitled "Continuous process for the manufacture of chlorohydrins" filed in the name of SOLVAY SA on the same day as the present application, the contents of which are hereby incorporated by reference. Particular mention is made of a continuous process for the production of chlorohydrin in which a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon or a mixture of them is reacted with a chlorinating agent and an organic acid. in a liquid reaction medium whose composition in the stationary state comprises polyhydroxylated aliphatic hydrocarbon and esters of the polyhydroxylated aliphatic hydrocarbon whose sum of the contents expressed in moles of polyhydroxylated aliphatic hydrocarbon is greater than 1, 1 mol% and less than or equal to 30 mol%, the percentage being related to the organic part of the liquid reaction medium. In the process for producing an epoxide according to the invention, the chlorination reaction of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, can be carried out in the presence a catalyst as described in the application WO 2005/054167 SOLVAY SA, page 6, line 28, on page 8, line 5. Mention is made particularly of a catalyst based on a carboxylic acid or on a carboxylic acid derivative having an atmospheric boiling point greater than or equal to 200 ° C, in particular adipic acid and adipic acid derivatives.

In the process for producing an epoxide according to the invention, the chlorination reaction of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, can be carried out at a temperature of catalyst concentration, a temperature, a pressure and for residence times as described in SOLVAY SA application WO 2005/054167, page 8, line 6 to page 10, line 10. Mention is particularly made of a temperature of at least 20 ° C and at most 160 ° C, a pressure of at least 0.3 bar and a maximum of 100 bar, and a residence time of from less than 1 hour and not more than 50 hours.

In the process for producing an epoxide according to the invention, the chlorination reaction of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, may be carried out in the presence of a solvent as described in the application WO 2005/054167 of SOLVAY SA, on page 11, lines 12 to 36.

Particular mention is made of an organic solvent such as a chlorinated organic solvent, an alcohol, a ketone, an ester or an ether, a non-aqueous solvent miscible with the polyhydroxylated aliphatic hydrocarbon such as chloroethanol, chloropropanol and chloropropanediol. , dichloropropanol, dioxane, phenol, cresol, and mixtures of chloropropanediol and dichloropropanol, or heavy products of the reaction such as oligomers of at least partially chlorinated and / or esterified polyhydroxylated aliphatic hydrocarbon.

In the process for producing an epoxide according to the invention, the chlorination reaction of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, can be carried out in the presence a liquid phase comprising heavy compounds other than the polyhydroxylated aliphatic hydrocarbon, as described in the application entitled "Process for producing a chlorohydrin in a liquid phase" deposited in the name of SOLVAY SA on the same day as the present application , the contents of which are hereby incorporated by reference.

Particular mention is made of a process for producing a chlorohydrin, wherein a polyhydroxylated aliphatic hydrocarbon, a polyhydroxylated aliphatic hydrocarbon ester, or a mixture thereof is subjected to a reaction with a chlorinating agent. in the presence of a liquid phase comprising heavy compounds other than the polyhydroxylated aliphatic hydrocarbon and whose boiling point at a pressure of 1 bar absolute is at least 15 ° C higher than the boiling point of chlorohydrin under a pressure of 1 bar absolute.

In the process for producing an epoxide according to the invention, the chlorination reaction of the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or a mixture of them can be carried out in the batch or in continuous mode. Continuous mode is particularly preferred.

In the process for producing an epoxide according to the invention, the chlorination reaction of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, is preferably carried out in a liquid reaction medium. The liquid reaction medium may be mono- or multiphasic. The liquid reaction medium consists of all the dissolved or dispersed solid compounds, dissolved or dispersed liquids and gaseous dissolved or dispersed, at the reaction temperature.

The reaction medium comprises the reactants, the catalyst, the solvent, the impurities present in the reagents, in the solvent and in the catalyst, the reaction intermediates, the products and the by-products of the reaction.

By reagents is meant the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester and the chlorinating agent.

Among the impurities present in the polyhydroxylated aliphatic hydrocarbon, mention may be made of carboxylic acids, carboxylic acid salts, fatty acid esters with polyhydroxylated aliphatic hydrocarbon, esters of fatty acids with the alcohols used. during the trans-esterification, inorganic salts such as chlorides and sulphates alkali or alkaline earth.

When the polyhydroxylated aliphatic hydrocarbon is glycerol, mention may be made, among the impurities of glycerol, of carboxylic acids, carboxylic acid salts, fatty acid esters such as mono-, di- and triglycerides, esters of fatty acids with the alcohols used in transesterification; inorganic salts such as alkali or alkaline earth chlorides and sulphates. Among the reaction intermediates, mention may be made of the monochlorohydrins of the polyhydroxylated aliphatic hydrocarbon and their esters and / or polyesters, the esters and / or polyesters of the polyhydroxylated aliphatic hydrocarbon and the polychlorohydrin esters.

When the chlorohydrin is dichloropropanol, mention may be made, among the reaction intermediates, of glycerol monochlorohydrin and its esters and / or polyesters, esters and / or polyesters of glycerol and esters of dichloropropanol.

The polyhydroxylated aliphatic hydrocarbon ester may therefore be, depending on the case, a reagent, an impurity of the polyhydroxylated aliphatic hydrocarbon or a reaction intermediate.

By products of the reaction is meant chlorohydrin and water. The water may be the water formed in the chlorination reaction and / or the water introduced into the process, for example via the polyhydroxylated aliphatic hydrocarbon and / or the chlorinating agent, as described in the application WO 2005/054167 of SOLVAY SA, on page 2, lines 22 to 28, on page 3, lines 20 to 25, on page 5, lines 7 to 31 and on page 12, lines 14 to 19. Among the by-products include, for example, partially chlorinated and / or esterified polyhydroxylated aliphatic hydrocarbon oligomers. When the polyhydroxylated aliphatic hydrocarbon is glycerol, among the by-products, mention may be made, for example, of partially chlorinated and / or esterified glycerol oligomers.

The reaction intermediates and by-products may be formed in the various process steps such as, for example, during the chlorohydrin manufacturing step and during the chlorohydrin separation steps. The liquid reaction medium may thus contain the polyhydroxylated aliphatic hydrocarbon, the dissolved or dispersed chlorination agent in the form of bubbles, the catalyst, the solvent, the impurities present in the reactants, the solvent and the catalyst, such as dissolved salts. or solids for example, reaction intermediates, products and by-products of the reaction. In the manufacturing method according to the invention, the reaction between the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, and the chlorinating agent can be carried out in the presence an organic acid. The organic acid may be a product from the process for producing the polyhydroxylated aliphatic hydrocarbon or a product not from this process. In the latter case, it may be an organic acid used to catalyze the reaction between the polyhydroxylated aliphatic hydrocarbon and the hydrogen chloride and / or an acid generated in the process for producing the chlorohydrin. For example, acids derived from aldehydes present in the polyhydroxylated aliphatic hydrocarbon or formed during the manufacture of the chlorohydrin are considered. The organic acid may also be an organic acid mixture derived from the process for producing the polyhydroxylated aliphatic hydrocarbon and an organic acid not derived from the process for producing the polyhydroxylated aliphatic hydrocarbon. In the process according to the invention, the esters of the polyhydroxylated aliphatic hydrocarbon can come from the reaction between the polyhydroxylated aliphatic hydrocarbon and the organic acid before, during or in the steps which follow the reaction with the chlorinating agent. .

In the process according to the invention, the separation of the chlorohydrin and the other compounds from the reaction medium can be carried out according to the modes as described in the application WO 2005/054167 of SOLVAY SA, of page 12, line 1, page 16, line 35 and page 18, lines 6 to 13. These other compounds are those mentioned above and include the reagents not consumed, the impurities present in the reagents, the catalyst, the solvent, reaction intermediates, water and by-products of the reaction. Particular mention is made of separation by azeotropic distillation of a water / chlorohydrin / chlorinating agent mixture under conditions which minimize losses of chlorinating agent followed by separation of the chlorohydrin by decantation.

In the process according to the invention, the separation of the chlorohydrin and the other compounds from the reaction medium can be carried out according to the methods described in the patent application EP 05104321.4 filed in the name of SOLVAY SA on 20/05/2005 with the content is here incorporated by reference. A separation mode comprising at least one separation operation for removing salt from the liquid phase is particularly preferred. Particular mention is made of a process for producing a chlorohydrin by reaction between a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, and a chlorinating agent in which the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them used contains at least one solid or dissolved metal salt, the process comprising a separation operation for removing a portion of the metal salt. Mention is more particularly made of a process for producing a chlorohydrin by reaction between a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, and a chlorinating agent in which the polyhydroxylated aliphatic hydrocarbon used contains at least one sodium and / or potassium chloride and / or sulfate and wherein the separation operation for removing a portion of the metal salt is a filtration operation. Particular mention is also made of a process for producing a chlorohydrin in which (a) a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof is subjected to a reaction with a chlorinating agent in a reaction medium, (b) a fraction of the reaction medium containing at least water and the chlorohydrin is withdrawn continuously or periodically, (c) at least part of the fraction obtained in step ( b) is introduced into a distillation step and (d) the reflux ratio of the distillation step is controlled by supplying water at said step of distillation. Particular mention is made of a process for producing a chlorohydrin in which (a) a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon or a mixture thereof is subjected to a reaction with hydrogen chloride in a reaction medium, (b) a fraction of the reaction medium containing at least water and the chlorohydrin is withdrawn continuously or periodically, (c) at least a part of the fraction obtained in the step (b) is introduced into a distillation step, wherein the ratio between the hydrogen chloride concentration and the water concentration in the fraction introduced into the distillation step is smaller than the hydrogen chloride concentration ratio / water in the azeotropic hydrogen chloride / water binary composition at distillation temperature and pressure.

In the process for the production of the epoxide according to the invention, the separation of the chlorohydrin and the other compounds from the reaction medium of chlorination of the polyhydroxylated aliphatic hydrocarbon can be carried out according to the modes as described in the application entitled "Process of manufacture of a chlorohydrin "deposited in the name of SOLVAY SA, the same day as the present application, and the contents of which are hereby incorporated by reference.

Particular mention is made of a process for producing a chlorohydrin comprising the following steps: (a) reacting a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof, with a chlorination and an organic acid to obtain a mixture containing chlorohydrin and chlorohydrin esters, (b) subjecting at least a portion of the mixture obtained in step (a) to one or more treatments in subsequent steps in step (a) and (c) polyhydroxylated aliphatic hydrocarbon is added to at least one of the steps subsequent to step (a), so that it reacts at a temperature greater than or equal to 20 ° C, with the chlorohydrin esters so as to at least partially form esters of the polyhydroxylated aliphatic hydrocarbon. Particular mention is made of a process in which the polyhydroxylated aliphatic hydrocarbon is glycerol and the chlorohydrin is dichloropropanol.

In the process for the production of the epoxide according to the invention, the separation of the chlorohydrin and the other compounds from the reaction medium of chlorination of the polyhydroxylated aliphatic hydrocarbon can be carried out according to the modes as described in the application entitled "Process of manufacture of a chlorhydrin starting from a polyhydroxylated aliphatic hydrocarbon deposited in the name of SOLVAY SA the same day as the present application, and the contents of which are hereby incorporated by reference.

Particular mention is made of a process for producing chlorohydrin by reaction between a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, and a chlorinating agent in a reactor which is fed with one or more liquid streams containing less than 50% by weight of the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, based on the weight of all the liquid streams introduced into the polyhydroxylated aliphatic hydrocarbon, the reactor.

Particular mention is made of a method comprising the following steps:

(a) A polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon or a mixture thereof is reacted with a chlorinating agent so as to obtain at least one medium containing chlorohydrin, water and chlorinating agent, (b) at least a fraction of the medium formed in step (a) and (c) is taken off in a distillation operation. and / or stripping in which polyhydroxylated aliphatic hydrocarbon is added so as to separate from the fraction taken in step (b) a mixture containing water and chlorohydrin having a reduced content of chlorinating agent compared to that of the fraction taken in step (b).

In the process for the production of the epoxide according to the invention, the separation of the chlorohydrin and the other compounds from the reaction medium of chlorination of the polyhydroxylated aliphatic hydrocarbon can be carried out according to the modes as described in the application entitled "Process of conversion of polyhydroxylated aliphatic hydrocarbons to chlorhydrins "deposited in the name of SOLVAY SA on the same day as the present application and the contents of which are hereby incorporated by reference. Particular mention is made of a process for preparing a chlorohydrin comprising the following steps: (a) reacting a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, with an agent to obtain a mixture containing chlorohydrin, chlorohydrin esters and water

(b) at least a fraction of the mixture obtained in step (a) is subjected to a distillation and / or stripping treatment so as to obtain a concentrated portion of water, chlorohydrin and chlorohydrin esters. (c) at least a fraction of the part obtained in step (b) is subjected to a separation operation in the presence of at least one additive so as to obtain a concentrated portion of chlorohydrin and of chlorohydrin esters and which contains less than 40% by weight of water. The separation operation is more particularly a settling.

In the process according to the invention, the separation and the treatment of the other compounds of the reaction medium can be carried out according to modes as described in the application entitled "Process for the production of a chlorohydrin by chlorination of a polyhydroxylated aliphatic hydrocarbon" filed on behalf of SOLVAY SA on the same day as this application. A preferred treatment is to subject a fraction of the by-products of the reaction to high temperature oxidation.

Particular mention is made of a process for producing a chlorohydrin comprising the following steps: (a) reacting a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, the alkali and / or alkaline-earth metal content is less than or equal to 5 g / kg, an oxidizing agent and an organic acid so as to obtain a mixture containing at least chlorohydrin and by-products, (b) subject to at least a portion of the mixture obtained in step (a) to one or more treatments in steps subsequent to step (a) and (c) at least one of the steps subsequent to step (a) consists of oxidation at a temperature greater than or equal to 800 ° C. More particular mention is made of a process in which in the subsequent step, a part of the mixture obtained in step (a) is taken and this part is subjected to oxidation at a temperature greater than or equal to 800 ° C. during the sampling. Particular mention is also made of a process in which the treatment of step (b) is a separation operation chosen from among the operations of decantation, filtration, centrifugation, extraction, washing, evaporation, stripping, distillation, adsorption or combinations of at least two of them. In the process according to the invention, when the chlorohydrin is chloropropanol, it is generally used in the form of a mixture of compounds comprising the isomers of 1-chloropropan-2-ol and 2-chloropropane-1. ol. This mixture generally contains more than 1% by weight of the two isomers, preferably more than 5% by weight and more particularly more than 50%. The mixture usually contains less than 99.9% by weight of the two isomers, preferably less than 95% by weight and most particularly less than 90% by weight. The other constituents of the mixture may be compounds derived from chloropropanol production processes, such as residual reagents, reaction by-products, solvents and in particular water. The weight ratio between the 1-chloropropan-2-ol and 2-chloropropan-1-ol isomers is usually greater than or equal to 0.01, preferably greater than or equal to 0.4. This ratio is usually less than or equal to 99 and preferably less than or equal to 25.

In the process according to the invention, when the chlorohydrin is chloroethanol, it is generally used in the form of a mixture of compounds comprising the 2-chloroethanol isomer. This mixture generally contains more than 1% by weight of the isomer, preferably more than 5% by weight and especially more than 50%. The mixture usually contains less than 99.9% by weight of the isomer, preferably less than 95% by weight and most preferably less than 90% by weight. The other constituents of the mixture may be compounds derived from chloroethanol production processes, such as residual reagents, reaction by-products, solvents and in particular water. In the process according to the invention, when the chlorohydrin is dichloropropanol, it is generally used in the form of a mixture of compounds comprising the isomers of 1,3-dichloropropan-2-ol and 2,3-dichloropropan-2-ol. -dichloropropane-l-ol. This mixture generally contains more than 1% by weight of the two isomers, preferably more than 5% by weight and more particularly more than 50%. The mixture usually contains less than 99.9% by weight of the two isomers, preferably less than 95% by weight and most preferably less than 90% by weight. The other constituents of the mixture may be compounds from dichloropropanol production processes, such as residual reagents, reaction by-products, solvents and in particular water.

The weight ratio between the 1,3-dichloropropan-2-ol and 2,3-dichloropropan-1-ol isomers is usually greater than or equal to 0.01, often greater than or equal to 0.4, frequently greater than or equal to 1 , 5, preferably greater than or equal to 3.0, more preferably greater than or equal to 7.0 and most preferably greater than or equal to 20.0. This ratio is usually less than or equal to 99 and preferably less than or equal to 25. In the process according to the invention, when the chlorohydrin is dichloropropanol and the latter is obtained in a process starting from allyl chloride, the mixture of isomers has a weight ratio of 1,3-dichloropropan-2-ol: 2,3-dichloropropan-1-ol which is often 0.3 to 0.6, typically about 0 5. When the dichloropropanol is obtained in a process starting from synthetic and / or natural glycerol, the weight ratio 1,3-dichloropropan-2-ol: 2,3-dichloropropan-1-ol is usually greater than or equal to 1.5, preferably greater than or equal to 3.0 and most preferably greater than or equal to 7.0. When the dichloropropanol is obtained from allyl alcohol, the weight ratio 1,3-dichloropropan-2-ol: 2,3-dichloropropan-1-ol is often of the order of 0.1. In the process according to the invention, the step of purifying the epoxide may be preceded by at least one step of chemical treatment of the epoxide. This chemical treatment may be a washing of the epoxide with an aqueous solution of a metal salt.

In the process according to the invention, the step of purifying the epoxide may comprise at least one distillation step.

In the process for producing an organic product according to the invention, the process for chlorinating the polyhydroxylated aliphatic hydrocarbon generally comprises several steps and preferably (a) at least one reaction step between a polyhydroxylated aliphatic hydrocarbon, a polyhydroxylated aliphatic hydrocarbon ester, or a mixture thereof, and the chlorinating agent, optionally in the presence of an organic acid as a catalyst, to obtain a mixture containing chlorohydrin and water and (b) ) at least one stripping step and / or distillation of at least a first fraction of the mixture obtained in step (a) so as to obtain a first concentrated mixture of chlorohydrin and water. In a particularly preferred manner, the process for chlorinating the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, comprises (I) at least one step of decanting the concentrated mixture obtained. in step (b) so as to obtain at least a first aqueous phase concentrated in water and a first organic phase concentrated in chlorohydrin.

In the process for producing an organic product according to the invention, the process for chlorinating the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, may comprise (c) ) at least one additional step of stripping and / or distillation of a second fraction of the mixture obtained in step (a) so as to obtain at least a second concentrated mixture of chlorohydrin and water. Of particularly preferably, the process for chlorinating the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or a mixture of them, comprises (II) at least one step of decanting the concentrated mixture obtained at step (c) so as to obtain at least a second aqueous phase concentrated in water and a second organic phase concentrated in chlorohydrin.

In the process for producing an organic product according to the invention, the process for chlorinating the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or a mixture of them may comprise (d) at least one additional hydrolysis treatment step of a third fraction of the mixture obtained in step (a) so as to regenerate the acid catalyst.

In the process for producing an organic product according to the invention, the process for chlorinating the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or a mixture of them may comprise (e) at least one additional step of oxidation treatment at a temperature greater than or equal to 800 ° C of a fourth fraction of the mixture obtained in step (a) so as to obtain a gaseous mixture containing the chlorinating agent. The chlorohydrin obtained in the process according to the invention may contain a high content of halogenated ketones, in particular chloroacetone, as described in the patent application FR 05.05120 of 20/05/2005 filed in the name of the Applicant, and whose content is hereby incorporated by reference. The content of halogenated ketone can be reduced by subjecting the chlorohydrin obtained in the process according to the invention to azeotropic distillation in the presence of water or by subjecting the chlorohydrin to a dehydrochlorination treatment as described in this application, on page 4, line 1, on page 6, line 35.

Particular mention is made of a process for producing an epoxide in which halogenated ketones are formed as by-products and which comprises at least one treatment for removing at least a portion of the halogenated ketones formed. Mention is more particularly made of a process for producing an epoxide by dehydrochlorination of a chlorohydrin of which at least one fraction is produced by chlorination of a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, a dehydrochlorination treatment and azeotropic distillation treatment of a water-ketone mixture halogenated compounds for removing at least a portion of the halogenated ketones formed and a process for producing epichlorohydrin in which the halogenated ketone formed is chloroacetone.

The method of manufacturing an organic product according to the invention optionally comprises (f) a step of treating the chlorohydrin so as to reduce the halogenated ketone content of the chlorohydrin.

The chlorohydrin obtained in the process according to the invention can be subjected to a dehydrochlorination reaction to produce an epoxide as described in the patent applications WO 2005/054167 and FR 05.05120 filed in the name of SOLVAY SA

The dehydrochlorination of the chlorohydrin can be carried out as described in the application entitled "Process for producing an epoxide from a polyhydroxylated aliphatic hydrocarbon and a chlorinating agent" deposited in the name of SOLVAY SA on the same day as the present application, and the content of which is hereby incorporated by reference.

Particular mention is made of a process for producing an epoxide in which a reaction medium resulting from the reaction between a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, is subjected to and a chlorinating agent, the reaction medium containing at least 10 g of chlorohydrin per kg of reaction medium, to a subsequent chemical reaction without intermediate treatment.

Mention is also made of manufacturing an epoxide comprising the following steps:

(a) A polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon or a mixture thereof is reacted with a chlorinating agent and an organic acid to form chlorohydrin and chlorohydrin in a reaction medium containing polyhydroxylated aliphatic hydrocarbon, polyhydroxylated aliphatic hydrocarbon ester, water, the chlorinating agent and the organic acid, the reaction medium containing at least 10 g of chlorohydrin per kg of reaction medium

(b) at least one fraction of the reaction medium obtained in step (a), which fraction having the same composition as the reaction medium obtained in step (a), is subjected to one or more treatments in stages subsequent to step (a) (c) A basic compound is added to at least one of the steps subsequent to step (a) to react at least partially with the chlorohydrin, the chlorohydrin esters, the chlorinating agent and the organic acid of to form epoxide and salts. The process for producing organic products according to the invention comprises at least one method for purifying aqueous and / or organic liquid effluents resulting from the constituent processes. These purification processes can be physical, for example, filtration, decantation, adsorption, stripping, distillation, ion-exchange, and chemical processes, such as, for example, oxidation, reduction, precipitation, complexation, acidic or basic treatment or biological. For the treatment of aqueous liquid effluents, chemical and biological processes are preferred. A chemical treatment by chlorination in a basic medium, preferably at a pH of between 7 and 12, at a temperature of between 100 and 150 ° C. and for periods of 0.5 to 7 hours, is particularly preferred.

The process for producing organic products according to the invention comprises at least one process for purifying the gaseous effluents from the constituent processes. These purification processes may be physical, such as, for example, washing, condensation, adsorption or chemical processes such as, for example, oxidation, reduction, precipitation, complexation, and acidic or basic treatments. Treatment of gaseous effluents by high temperature oxidation in a stream of air or oxygen is preferred.

In the process according to the invention, the olefin is preferably allyl chloride, the polyhydroxylated aliphatic hydrocarbon is preferably glycerol and the chlorohydrin is preferably dichloropropanol and the epoxide is preferably epichlorohydrin.

The process according to the invention can be followed by a process for the manufacture of products derived from ethylene oxide, such as ethylene glycol, di and polyethylene glycols, mono-, di- and triethanolamines, derivatives of propylene oxide such as 1,2-propylene glycol, dipropylene glycol, propylene glycol ethers and isopropylamines and products derived from epichlorohydrin such as glycerol, epoxy resins, synthetic elastomers, glycidyl ethers and polyamide resins.

Claims

A method for producing an epoxide comprising at least one step of purifying the epoxide formed, the epoxide being at least partly manufactured by a dehydrochlorination process of a chlorohydrin, the latter being at least partly manufactured by a process for chlorinating a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them.

2. Method according to claim 1 wherein the step of purifying the epoxide formed is preceded by at least one step of chemical treatment of the epoxide.

3. The method of claim 2 wherein the chemical treatment is a wash with an aqueous solution of a metal salt.

The process according to any one of claims 1 to 3, wherein the step of purifying the epoxide comprises at least one distillation step.

5. Process according to any one of claims 1 to 4 wherein at least a fraction of the chlorohydrin is manufactured by a chlorination process of an unsaturated alcohol.

The process of any one of claims 1 to 5 wherein at least a portion of the chlorohydrin is made by a process of hypochlorinating an olefin.

The process of any one of claims 1 to 6 wherein at least a portion of the epoxide is made by a process for epoxidizing an olefin.

The method of any one of claims 1 to 7 wherein the process for chlorinating the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or a mixture of them comprises (a) at least one reaction step between the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or mixture thereof, and the chlorinating agent, optionally in the presence of an organic acid as a catalyst, for get a mixture containing the chlorhydrin and water, (b) at least one step of stripping and / or distillation of at least a first fraction of the mixture obtained in step (a) so as to obtain a first concentrated mixture of chlorohydrin and water.

The process according to claim 8 wherein the process for chlorinating the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or a mixture of them comprises (I) at least one decantation step. of the first concentrated mixture obtained in step (b) so as to obtain at least a first aqueous phase concentrated in water and a first organic phase concentrated in chlorohydrin.

The process according to claim 8 or 9 wherein the process for chlorinating the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them comprises (c) at least one additional step stripping and / or distillation of a second fraction of the mixture obtained in step (a) so as to obtain at least a second concentrated mixture of chlorohydrin and water.

The process according to claim 10 wherein the process for chlorinating the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them comprises (II) at least one decantation step. the second concentrated mixture obtained in step (c) so as to obtain at least a second aqueous phase concentrated in water and a second organic phase concentrated in chlorohydrin.

The process according to any one of claims 8 to 11 wherein the process for chlorinating the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or a mixture of them comprises (d) at least one additional hydrolysis treatment step of a third fraction of the mixture obtained in step (a) so as to regenerate the acid catalyst.

The process according to any one of claims 8 to 12 wherein the process for chlorinating the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them comprises (e) at least one additional oxidation treatment step at a temperature greater than or equal to 800 ° C of a fourth fraction of mixture obtained in step (a) so as to obtain a gaseous mixture containing the chlorinating agent.

The process of any one of claims 1 to 13 wherein halogenated ketones are formed in the process for producing chlorohydrin and optionally comprising (f) a step of treating the chlorohydrin to reduce the content of halogenated ketones. chlorohydrin.

15. The process as claimed in claim 1, in which at least one part of the polyhydroxylated aliphatic hydrocarbon or of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, is obtained initially. renewable raw materials.

16. The process as claimed in claim 1, in which at least one part of the polyhydroxylated aliphatic hydrocarbon or of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, is obtained initially. of fossil raw materials.

17. Process according to any one of claims 6 to 16 wherein the olefin is selected from ethylene, propylene, allyl chloride and mixtures of at least two of them.

18. Process according to any one of claims 1 to 17 wherein the polyhydroxylated aliphatic hydrocarbon is chosen from ethylene glycol, propylene glycol, chloropropanediol, glycerol and mixtures of at least two of them. .

19. A process according to any one of claims 1 to 18 wherein the chlorohydrin is selected from chloroethanol, chloropropanol, chloropropanediol, dichloropropanol and mixtures of at least two of them.

20. Process according to any one of claims 1 to 19 wherein the epoxide is selected from ethylene oxide, propylene oxide, glycidol, epichlorohydrin and mixtures of at least two of between them.

21. A process according to any one of claims 6 to 20 wherein the olefin is allyl chloride, the polyhydroxylated aliphatic hydrocarbon is the glycerol and chlorohydrin is dichloropropanol and the epoxide is epichlorohydrin.

22. A process according to any one of claims 1 to 21 wherein the chlorination of the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or mixture thereof, is carried out with a chlorination containing hydrogen chloride.

23. The method of claim 22 wherein at least a portion of the hydrogen chloride is derived from a process for the manufacture of allyl chloride, a process for producing chloromethanes, a chlorinolysis process and / or a method of oxidizing chlorinated compounds at a temperature above 850 ° C.

24. The method of claim 22 or 23 wherein the hydrogen chloride is a combination of gaseous hydrogen chloride and an aqueous solution of hydrogen chloride, or an aqueous solution of hydrogen chloride.

25. A process according to any one of claims 1 to 24 wherein the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture thereof, is subjected to a purification treatment in a controlled manner. to reduce the content of water, salts and / or organic compounds which are not the polyhydroxylated aliphatic hydrocarbon, prior to the chlorination process.

26. Process according to any one of claims 1 to 25 comprising at least one method for purifying aqueous and / or organic liquid effluents.

27. The method of claim 26 wherein the treatment treatment of aqueous liquid effluents comprises at least a chemical treatment by chlorination or biological treatment.

28. Process according to any one of Claims 1 to 27, comprising at least one process for purifying gaseous effluents.

29. The method of claim 28 wherein the treatment treatment comprises at least one oxidation treatment at a temperature greater than or equal to 800 ° C in the presence of air.

30. A method according to any one of claims 1 to 29 followed by a manufacture of ethylene glycol, di and polyethylene glycols, mono-, di- and triethanolamines, 1,2-propylene glycol, dipropylene glycol , propylene glycol ethers, isopropylamines, glycerol, polyglycerols, epoxy resins, synthetic elastomers, glycidyl ethers and polyamide resins.