EP1885706A2

EP1885706A2 - Method for making an epoxide starting with a polyhydroxylated aliphatic hydrocarbon and a chlorinating agent

Info

Publication number: EP1885706A2
Application number: EP06755271A
Authority: EP
Inventors: Philippe Krafft; Patrick Gilbeau; Dominique Balthasart; Valentine Smets
Original assignee: Solvay SA
Current assignee: Solvay SA
Priority date: 2005-05-20
Filing date: 2006-05-19
Publication date: 2008-02-13
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 epoxide which consists in subjecting in a reaction medium resulting from the reaction between a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof, 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 any intermediate treatment.

Description

Process for producing an epoxide from a polyhydroxylated aliphatic hydrocarbon and a chlorinating agent

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 a method of manufacturing an epoxide. 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, isopropyl amines 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 allyl acetate to allyl alcohol, catalytic chlorination of allyl alcohol to dichloropropanol and alkaline dehydrochlorination of dichloropropanol to epichlorohydrin. Other technologies that have not yet received industrial application can be envisaged, including direct catalytic oxidation of allyl chloride to epichlorohydrin by means of hydrogen peroxide or chlorination of glycerol to dichloropropanol followed by 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 separation of the organic acid is delicate if it forms an azeotrope with water or its relative volatility is significant in the ternary water-dichloropropanol-hydrogen chloride mixture and in this case the dichloropropanol is also contaminated by the esters that it forms with the organic acid.

The object of the present invention is to provide a process for preparing an epoxide which does not have these disadvantages.

The invention therefore relates to 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.

The subsequent chemical reaction is preferably a dehydrochlorination reaction.

The dehydrochlorination reaction is preferably carried out by adding a basic compound to the reaction medium.

More specifically, the invention relates to a process for producing an epoxide comprising the steps of: (a) reacting a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof, with a chlorinating agent and an organic acid to form chlorohydrin and chlorohydrin esters in a reaction medium containing polyhydroxylated aliphatic hydrocarbon, polyhydroxylated aliphatic hydrocarbon ester, water, 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 with the chlorohydrin, the chlorohydrin esters, the chlorinating agent and the organic acid to form epoxide and salts. It has now been found that separation of the organic acid and its derivatives is not essential because by subjecting a mixture containing chlorohydrin, the chlorinating agent and an organic acid to a reaction with a basic compound, one can produce an epoxy with excellent performance. Surprisingly, the formation of salts resulting from the neutralization of the chlorinating agent and the organic acid by the basic compound and the hydrolysis of the esters formed between the chlorohydrin and the organic acid do not disturb the manufacturing process. epoxide, even when substantial amounts of organic acid are present in reaction step (c) with the basic compound. A significant advantage of the process is that it is not necessary to separate the chlorinating agent and the organic acid used in the chlorohydrin manufacturing step.

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. Preferred epoxides are ethylene oxide, propylene oxide, glycidol and 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 - AT -

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. Preferably, 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 of at 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 "chorhydrin" 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-chloropropan-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, and the mixtures of them, and the chlorohydrin, in the process according to the invention can be obtained starting from fossil raw materials or starting from materials. renewable raw materials, preferably from renewable raw materials.

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 chlorohydrin is dichloropropanol, or chloropropanediol, allyl chloride, allyl alcohol and "synthetic" glycerol are particularly preferred. By "Synthetic" glycerol means a glycerol generally obtained from petrochemical resources. When chlorohydrin is chloroethanol, ethylene and "synthetic" ethylene glycol are particularly preferred. By "synthetic" ethylene glycol is meant an ethylene glycol generally obtained from petrochemical resources. When the chlorohydrin is monochloropropanol, 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 sugar conversion via thermochemical processes, which 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. By "natural glycerol" or "glycerol obtained from renewable raw materials" is meant in particular glycerol obtained during the manufacture of biodiesel or glycerol obtained during transformations of fats or oils of vegetable origin or animal in general such as saponification, transesterification or hydrolysis reactions.

Among the oils that can be used to make natural glycerol are all common oils, such as palm, palm kernel, copra, babassu, old or new rapeseed, sunflower, maize, castor oil and cotton oils. , 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. Chloroethanol can be obtained from these raw materials by any method. The methods of hypochlorination of ethylene and chlorination of "synthetic" and / or "natural" ethylene glycol are preferred. The chlorination process of "synthetic" and / or "natural" ethylene glycol is particularly preferred. Chloropropanol can be obtained from these raw materials by any method. The processes of hypochlorination of propylene and chlorination of "synthetic" and / or "natural" propylene glycol are preferred. The chlorination process of "synthetic" and / or "natural" propylene glycol is particularly preferred. Chloropropane diol can be obtained from these raw materials by any method. The chlorination process of "synthetic" and / or "natural" glycerol is preferred.

Dichloropropanol can be obtained from these raw materials by any method. The processes of hypochlorination of allyl chloride, chlorination of allyl alcohol and chlorination of "synthetic" glycerol and / or "natural" are preferred. The process of chlorination of "synthetic" and / or "natural" glycerol is particularly preferred.

In the process for producing the epoxide according to the invention, it is preferable that at least a fraction of the chlorohydrin be produced by chlorination of a polyhydroxylated aliphatic hydrocarbon. The polyhydroxylated aliphatic hydrocarbon can be "synthetic" or "natural" in the senses defined above.

In the manufacturing method according to the invention, when the epoxide is epichlorohydrin, glycerol "natural" that is to say obtained during the manufacture of biodiesel, or during transformations of fats or oils, of vegetable or animal origin, the transformations being selected from the saponification, trans-esterification and hydrolysis reactions, is preferred. Glycerol obtained by trans-esterification of fats or oils, of vegetable or animal origin, and in which the trans-esterification is carried out in the presence of a heterogeneous catalyst, is particularly preferred. In the process for producing the 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 content of which is 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 the process for producing the epoxide according to the invention, the use of the chlorohydrin obtained from the polyhydroxylated aliphatic hydrocarbon, from the polyhydroxylated aliphatic hydrocarbon ester, or from a mixture of them , 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 the epoxide according to the invention, the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, and the mixtures of them may be a crude product or a purified product as described in SOLVAY SA application WO 2005/054167, page 2, line 8, on page 4, line 2.

In the process for producing the epoxide according to the invention, the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, and the mixture of them, may have an alkali metal content and / or alkaline earth metal 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 on the same day as the present application , the contents of which are 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 the 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 the chloride of hydrogen and / or hydrochloric acid as described in the application WO 2005/054167 of SOLVAY SA, of page 4, line 30, on page 6, line 2.

Particular mention is made of a chlorinating agent which may be aqueous hydrochloric acid or preferably anhydrous hydrogen chloride. The hydrogen chloride may be derived from a process for the pyrolysis of chlorinated organic compounds such as, for example, 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 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 is gaseous hydrogen chloride or an aqueous solution of hydrogen chloride or a combination of both.

In the process for producing the 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 oxidation at a high temperature of chlorinated compounds 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 content of which is here incorporated by reference.

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.Mention is more particularly made of a process in which the chlorinating agent is derived at least partially from a process for the production of chlorine. allyl and / or a process for the manufacture of chloromethanes and / or a chlorinolysis process and / or a process for the oxidation of chlorinated compounds at a temperature of 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 the 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 a reactor as described in the application WO 2005/054167 SOLVAY SA, on page 6, lines 3 to 23.

Particular mention is made of an installation made of or covered with resistant materials under the conditions of the reaction with the chlorinating agents, in particular with hydrogen chloride. Mention is more particularly made of an installation made of enamelled steel or tantalum.

In the process for producing the epoxide according to the invention, the chlorination reaction of the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, can be carried out in equipment , made of or covered with chlorine-resistant materials, as described in the application entitled "Process for the manufacture of a chlorohydrin in corrosion-resistant equipment" filed on behalf 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 the epoxide according to the invention, the chlorination reaction of the polyhydroxylated aliphatic hydrocarbon can be carried out in a reaction medium, as described in the application entitled "Continuous process for the manufacture of chlorhydrins" deposited on behalf 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.

The organic part of the liquid reaction medium consists of all the organic compounds of the liquid reaction medium, that is to say compounds whose molecule contains at least 1 carbon atom. In the process for producing the 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 the 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. Particular mention is made of a temperature of at least 20 ° C and not more than 160 ° C, a pressure of not less than 0.3 bar and not more than 100 bar, and a time of stay of not less than 1 hour and not more than 50 hours.

In the process for producing the 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 solvent as described in the application WO 2005/054167 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 the 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 the 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 esters of the polychlorohydrins.

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 be water introduced into the process, for example via the polyhydroxylated aliphatic hydrocarbon and / or the chlorinating agent, as described in US Pat. request 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. 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.

Reaction intermediates and by-products may be formed in the various process steps such as, for example, during step (a) and during subsequent processing steps in step (b).

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.

Steps (a), (b) and (c) of the epoxide manufacturing process according to the invention can be carried out independently in batch mode or in continuous mode. Continuous mode is preferred. The continuous mode for the 3 steps is particularly preferred. In the manufacturing method according to the invention, the organic acid may be a product derived from the process for producing the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or a mixture of them, or a product not coming 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 chlorinating agent. 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. It is preferred to use an organic acid which is not obtained during the manufacture of the polyhydroxylated aliphatic hydrocarbon, which acid is used as a catalyst for the reaction between the polyhydroxylated aliphatic hydrocarbon and the chlorinating agent. It is particularly preferred to use acetic acid or adipic acid.

In the process according to the invention, the esters of the polyhydroxylated aliphatic hydrocarbon can come from the reaction between the aliphatic hydrocarbon polyhydroxy and the organic acid, before, during or in the steps following 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, to on page 16, line 35 and on page 18, lines 6 to 13. These other compounds are those mentioned above and comprise the reagents not consumed, the impurities present in the reagents, the catalyst and the solvent, the solvent, the catalysts, 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 for producing 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, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of between them, can be carried out according to modes as described in the patent application EP 05104321.4 filed in the name of SOLVAY SA on May 20, 2005, the content of which is hereby incorporated by reference. A separation mode comprising at least one separation operation for removing the salt from the liquid phase is particularly expedient.

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 hydrocarbon Polyhydroxylated aliphatic acid, an ester of a polyhydroxylated aliphatic hydrocarbon or a mixture thereof, used contains at least one solid or dissolved metal salt, the process comprising a separation process 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 polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon or mixture thereof, used contains at least one chloride and / or sodium and / or potassium sulfate and wherein the separation operation intended to remove 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 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 to said distillation step. 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 part of the fraction obtained in 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 ratio of hydrogen chloride concentrations / water in the azeotropic hydrogen chloride / water binary composition at the distillation temperature and pressure.

In the process for producing 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, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of between them, can be carried out according to the modes as described in the PCT application entitled "Process for the manufacture of a chlorohydrin" deposited in the name of SOLVAY SA, the same day as the present application, and the contents of which are here 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 at step (a) and (c) adding polyhydroxylated aliphatic hydrocarbon 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. Mention is more particularly made of a process in which the polyhydroxylated aliphatic hydrocarbon is glycerol and the chlorohydrin is dichloropropanol.

In the process for producing 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, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of between them, can be carried out according to the modes as described in the application entitled "Process for the manufacture of a chlorohydrin starting from a polyhydroxylated aliphatic hydrocarbon" deposited in the name of SOLVAY SA the same day as the present application, and whose content is 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 in one or more liquid streams containing less than 50% by weight of the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or a mixture thereof, based on the weight of all the liquid streams introduced into the reactor. More particular mention is made of a process comprising the following steps: (a) reacting a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, with a chlorination agent of to obtain at least one medium containing chlorohydrin, water and chlorinating agent, (b) removing at least a fraction of the medium formed in step (a) and (c) submitting the fraction taken in step (b) from a distillation and / or stripping operation 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 producing 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, of the aliphatic hydrocarbon ester polyhydroxylated, or a mixture of them, may be carried out according to the modes as described in the application entitled "Process for converting polyhydroxylated aliphatic hydrocarbons to chlorhydrins" deposited in the name of SOLVAY SA the same day as the present application and whose contents are here 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 chlorination process so as to obtain a mixture containing chlorohydrin, chlorohydrin esters and water, (b) subjecting at least a fraction of the mixture obtained in step (a) to a distillation treatment and / or stripping so as to obtain a concentrated portion of water, chlorohydrin and chlorohydrin esters and (c) subjecting at least a fraction of the portion obtained in step (b) to a separation operation in the presence of minus an additive so as to obtain a concentrated portion of chlorohydrin and chlorohydrin esters and which contains less than 40% by weight of water.

The separation operation is more particularly a settling. In the process for producing the epoxide according to the invention, the separation and the treatment of the other compounds of the reaction medium for the chlorination of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of they can be carried out according to modes 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 on the same day as the present 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, a polyhydroxylated aliphatic hydrocarbon ester, or a mixture thereof, the content of which alkali metal and / or alkaline earth metal 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 one part of the mixture obtained in step (a) at one or more treatments in steps subsequent to step (a) and (c) at least one of the steps subsequent to step (a) consists of an oxidation at a temperature greater than or equal to 800 ° C. Special mention is made a process in which in the subsequent step, a portion 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 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 obtained in the form of a mixture of compounds comprising the isomers of 1-chloropropan-2-ol and of

2-chloropropane-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 derived from chloropropanol production processes, such as residual reagents, reaction by-products, solvents and in particular water.

The mass ratio between the isomers 1-chloropropan-2-ol and 2-chloropropane-1-ol 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 obtained 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 obtained in the form of a mixture of compounds comprising the isomers of 1,3-dichloropropan-2-ol and 2,3-dichloropropane. -laugh out loud. This mixture generally contains more than 1% by weight of the two isomers, preferably more than 5% in weight and in particular 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 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 9.0. When the dichloropropanol is obtained from allyl alcohol, the weight ratio 1,3-dichloropropan-2-ol: 2,3-dichloro-propan-1-ol is often of the order of 0.1.

In the process according to the invention, when the chlorohydrin is dichloropropanol, the mixture of isomers has a weight ratio 1,3-dichloropropan-2-ol: 2,3-dichloropropan-1-ol generally greater than or equal to 0, 5, often greater than or equal to 3, and frequently greater than or equal to 20.

In the process for producing the epoxide according to the invention, the chlorohydrin 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 the contents of which are 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 thereof, a dehydrochlorination treatment and azeotropic distillation treatment of a halogenated water-ketone mixture for removing at least a portion of the halogenated ketones formed and a method of manufacture epichlorohydrin in which the halogenated ketone formed is chloroacetone.

In the process for producing an epoxide according to the invention, the chlorohydrin 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.

In the process for producing an epoxide according to the invention, the epoxide is formed during the dehydrochlorination reaction of chlorohydrin with the basic compound. In a first embodiment of the process for producing an epoxide according to the invention, a fraction of the reaction medium obtained in step (a), which has the same composition as the reaction medium obtained in step (a), is removed. ), and during the sampling, the basic compound is added thereto.

The content of chlorohydrin in this fraction is generally greater than or equal to 10 g / kg, often greater than or equal to 400 g / kg and in particular greater than or equal to 500 g / kg. This content is generally less than or equal to 750 g / kg, often less than or equal to 650 g / kg and in particular less than or equal to 600 g / kg.

The content of chlorination agent in the fraction of the mixture obtained in step (a) is generally greater than or equal to 10 g / kg, often greater than or equal to 20 g / kg and in particular greater than or equal to 30 g / kg . This content is generally less than or equal to 150 g / kg, often less than or equal to 130 g / kg and in particular less than or equal to 100 g / kg.

The total organic acid content in the fraction of the mixture obtained in step (a) is generally greater than or equal to 1 g / kg, often greater than or equal to 2 g / kg and in particular greater than or equal to 5 g / kg . This content is generally less than or equal to 40 g / kg, often less than or equal to 20 g / kg and in particular less than or equal to 10 g / kg. The term "total organic acid content" is intended to mean the sum of the organic acid contents as such, esters of the organic acid and salts of the organic acid, this sum being expressed as the organic acid as such.

In a second embodiment of the process for manufacturing an epoxide according to the invention, a fraction of the mixture obtained in step (a), which has the same composition as the reaction medium obtained in step (a), is taken. this fraction is subjected to one or more separation treatments, for example, evaporation, stripping, distillation, so as to obtain a portion enriched in chlorohydrin and water.

The concentrations of the different species present in this part can vary greatly, particularly as a function of the raw materials involved, for example the type of chlorinating agent, anhydrous hydrogen chloride or in aqueous solution, the water content of the polyaliphatic hydrocarbon. hydroxyl or the type of organic acid used as catalyst or depending on the separation treatment. Surprisingly, the method according to the present invention can be applied in all cases.

The content of chlorohydrin in the chlorohydrin-enriched part and in water is generally greater than or equal to 10 g / kg, often greater than or equal to 400 g / kg and in particular greater than or equal to 500 g / kg. This content is generally less than or equal to 750 g / kg, often less than or equal to 600 g / kg and in particular less than or equal to 700 g / kg.

The content of chlorinating agent in this part is generally greater than or equal to 10 g / kg, often greater than or equal to 20 g / kg and in particular greater than or equal to 30 g / kg. This content is generally less than or equal to 150 g / kg, often less than or equal to 130 g / kg and in particular less than or equal to 100 g / kg.

The total organic acid content in this part is generally greater than or equal to 1 g / kg, often greater than or equal to 2 g / kg and in particular greater than or equal to 5 g / kg. This content is generally less than or equal to 40 g / kg, often less than or equal to 25 g / kg and in particular less than or equal to 100 g / kg.

In a first variant of this second embodiment, the basic compound is added to this part enriched in chlorohydrin and in water. In a second variant of this second embodiment, the chlorochrin-enriched part and water are subjected to a decantation operation so as to obtain a first portion enriched with water and a second portion enriched with chlorohydrin. This settling may be carried out, for example, in the reflux tank of a distillation column or at any subsequent stage such as, for example, secondary storage or distillation for purification. The devices for carrying out this decantation are described for example in "Perry's Chemical Engineers' Handbook, Sixth Edition, Robert H. Perry, Don Green, 1984, section 21 -64 to 21 -68".

The contents of chlorohydrin, water and chlorinating agent of these two portions can be easily deduced from the ternary diagrams of compositions of the chlorohydrin-water-chlorinating agent mixtures. Such a ternary diagram for the 1,3-dichloropropanol-water-hydrogen chloride mixture can be found in "Gibson GP, The Preparation, Properties, and uses of glycerol derivatives." Part III. 975 ".

The first portion may contain chlorohydrin. The chlorohydrin content is generally less than or equal to 300 g / kg, often less than or equal to 250 g / kg and in particular less than or equal to 200 g / kg. The content of chlorinating agent in this first portion is generally greater than or equal to 1 g / kg, often greater than or equal to 10 g / kg and in particular greater than or equal to 20 g / kg. This content is generally less than or equal to 250 g / kg, often less than or equal to 200 g / kg and in particular less than or equal to 150 g / kg. The total organic acid content in this first portion is generally greater than or equal to 1 g / kg, often greater than or equal to 2 g / kg and in particular greater than or equal to 3 g / kg. This content is generally less than or equal to 100 g / kg, often less than or equal to 50 g / kg and in particular less than or equal to 30 g / kg. The content of chlorohydrin in the second portion is generally greater than or equal to 600 g / kg, often greater than or equal to 700 g / kg and in particular greater than or equal to 800 g / kg.

The content of chlorinating agent in this second portion is generally greater than or equal to 1 g / kg, often greater than or equal to 5 g / kg and in particular greater than or equal to 10 g / kg. This content is usually less than or equal to 50 g / kg, often less than or equal to 40 g / kg and in particular less than or equal to 30 g / kg.

The organic acid content in this second portion is generally greater than or equal to 1 g / kg, often greater than or equal to 5 g / kg and in particular greater than or equal to 10 g / kg. This content is generally less than or equal to 150 g / kg, often less than or equal to 70 g / kg and in particular less than or equal to 30 g / kg.

The content of chlorohydrin esters in this second portion is generally greater than or equal to 1 g / kg, often greater than or equal to 5 g / kg and in particular greater than or equal to 10 g / kg. This content is generally less than or equal to 140 g / kg, often less than or equal to 70 g / kg and in particular less than or equal to 30 g / kg.

In a first aspect of this second variant, the basic agent is added solely to the first portion enriched with water. In a second aspect of this second variant, the basic agent is added solely in the second portion enriched with chlorohydrin.

In a third aspect of this second variant, the basic agent is added in the first portion enriched with water and in the second portion enriched with chlorohydrin. In a fourth aspect of this second variant, the basic agent is added in a mixture of the first portion enriched with water and the second portion enriched with chlorohydrin. The mixture may contain varying proportions of these two portions. The ratio by weight of the first water-enriched portion and the second chlorohydrin-enriched portion generally ranges from 1/99 to 99/1, often from 89/11 to 11/89, frequently from 81/19 to

19/81, and in particular 41/59 to 59/41.

An advantage of this second variant is that it is possible to know exactly the composition of the portions involved in the dehydrochlorination reaction with the basic agent. The composition of each of the portions is in fact defined by the conditions in which the decantation is carried out, such as the temperature, the pressure and the composition of the fraction of the mixture obtained in step (a), in particular, the content of agent chlorine content, organic acid content and chlorohydrin ester content. Knowing the composition of each of the portions involved in the dehydrochlorination reaction in step (c) makes it possible to better control this step. In a third embodiment of the process for producing an epoxide according to the invention, a fraction of the mixture obtained in step (a), which has the same composition as the reaction medium obtained in step (a), is taken. this fraction is subjected to an evaporation, stripping or distillation treatment so as to obtain a part enriched in chlorohydrin, and the basic compound is added to this part.

The chlorohydrin content in this slice is generally greater than or equal to 100 g / kg, often greater than or equal to 200 g / kg and in particular greater than or equal to 400 g / kg. The content of chlorinating agent in this slice is generally greater than or equal to 0.01 g / kg, often greater than or equal to 0.05 g / kg and in particular greater than or equal to 0.1 g / kg. This content is generally less than or equal to 110 g / kg, often less than or equal to 80 g / kg and in particular less than or equal to 65 g / kg. The organic acid content in this slice is generally greater than or equal to 0.01 g / kg, often greater than or equal to 0.1 g / kg and in particular greater than or equal to 1 g / kg. This content is generally less than or equal to 270 g / kg, often less than or equal to 200 g / kg and in particular less than or equal to 130 g / kg. Evaporation means the separation of a substance by heating, possibly under reduced pressure.

Stripping is understood to mean the separation of a substance by the entrainment by means of the vapor of a body which does not dissolve this substance. In the process according to the invention, this body may be any compound which is inert with respect to chlorohydrin such as, for example, water vapor, air, nitrogen and carbon dioxide. These same compounds may constitute the gas stream, optionally present in the evaporation treatment.

Distillation means the direct passage from the liquid state to the gaseous state and then condensation of the vapors obtained. Fractional distillation is understood to mean a series of distillations carried out on the successively condensed vapors. Fractional distillation treatment is preferred.

The different embodiments can be combined with each other in any way.

By basic compound is meant basic organic or basic inorganic. Basic inorganic compounds are preferred. These basic inorganic compounds may be oxides, hydroxides and metal salts, such as carbonates, hydrogen carbonates, phosphates or mixtures thereof, for example. Of the metals, the alkali and alkaline earth metals are preferred. Sodium, potassium and calcium and mixtures thereof are particularly preferred. The basic inorganic compounds may be in the form of aqueous or organic solids, liquids, solutions or suspensions. Aqueous solutions or suspensions are preferred. Solutions and suspensions of NaOH, Ca (OH) ₂ , purified alkaline brine and mixtures thereof are particularly preferred. By purified alkaline brine is meant caustic soda which contains NaCl such as that produced in a diaphragm electrolysis process. The content of basic compound in the solution or the suspension is generally greater than or equal to 1% by weight and preferably greater than or equal to 4% by weight. This content is usually less than or equal to 60% by weight. A content of about 50% by weight is particularly suitable. The basic compound can be used in superstoichiometric, substoichiometric or stoichiometric amounts with respect to the chlorohydrin. When the basic compound is used in substoichiometric amounts, generally not more than 2 moles of chlorohydrin per mole of base are used. Most often 1.5 moles of chlorohydrin are used per mole of base and preferably at most 1.05 moles of chlorohydrin per mole of base. When the basic agent is used in superstoichiometric amounts, at most 2 mole of base per mole of chlorohydrin is used. In this case, at least 1.05 mole of base is generally used per mole of chlorohydrin.

The method of manufacturing the epoxide according to the invention according to the invention can be integrated into a global epoxide manufacturing scheme as described in the application entitled "Process for the manufacture of an epoxide from a chlorohydrin Filed on behalf 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 the production of an epoxide comprising at least one step of purifying the epoxide formed, the epoxide being at least partly produced 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. In the process according to the invention, the polyhydroxylated aliphatic hydrocarbon is preferably glycerol, the chlorohydrin is preferably dichloropropanol and the epoxide is preferably epichlorohydrin.

When the epoxide is epichlorohydrin, the epoxide can be used in the manufacture of epoxy resins.

Figure 1 shows a particular installation scheme used to implement the separation method according to the invention.

A reactor (4) is supplied in continuous mode or in batch mode with polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them via line (1) and as a catalyst via the line (2), the supply of chlorinating agent is carried out in continuous mode or in batch mode via line (3), a distillation column (6) is fed via line (5) with vapors produced in the reactor (4), a stream is withdrawn from the column (6) via the line (7) and is introduced into a condenser (8), the flow from the condenser is introduced via the line (9) into a decanter (10). ) in which aqueous and organic phases are separated. A fraction of the flow of the line (7) can be withdrawn and sent to the dehydrochlorination reactor (31) via the line (37). The dehydrochlorination reactor (31) is supplied with basic agent via line (32). A stream containing epoxide is withdrawn from the reactor (31) via the line (40). A fraction of the separated aqueous phase in the decanter (10) is optionally recycled via line (11) to the top of the column to maintain reflux. Fresh water can be introduced into the line (11) via the line (12). The production of chlorohydrin is distributed between the organic phase withdrawn via line (14) and the aqueous phase withdrawn via line (13). A fraction of the flow of the line (13) can be withdrawn and sent to a dehydrochlorination reactor (31) via the line (38). A fraction of the flow of the line (14) can be withdrawn and sent to a dehydrochlorination reactor (31) via line (39). Another part of the flow of the line (14) can optionally be sent to the reflux of the column (6) via the line (30). The residue of the column (6) can be recycled to the reactor (4) via line (15). A fraction of the heavy products is withdrawn from the reactor and is introduced via the line (17) into an evaporator (18) in which a partial evaporation operation is carried out for example by heating or gas flushing with nitrogen or nitrogen. water vapor, the gaseous phase containing most of the flow chlorinating agent (17) is recycled via the line (19) to the column (6) or via the line (20) to the reactor (4). Another fraction of the products heavy is withdrawn from the reactor (4) via the line (16), a portion of which is sent to a dehydrochlorination reactor (31) via the line (34). A fraction of the flow of the line (17) can be withdrawn and sent to a dehydrochlorination reactor (31) via line (35). A fraction of the flow of the line (21) can be withdrawn and sent to a dehydrochlorination column (31) via the line (33). A distillation or stripping column (22) is fed with the liquid phase from the stripping apparatus (18) via the line (21), most of the chlorohydrin is collected at the top of the column (22) via line (23) and the residue which contains esters of polyhydroxylated aliphatic hydrocarbon and chlorohydrin is introduced via line (24) into the filter column (25) in which liquid and solid phases are separated, the liquid phase is recycled via the line (26) to the reactor (4). A fraction of the flow of the line (23) can be withdrawn and sent to a dehydrochlorination column (31) via the line (36). A solid can be withdrawn from the filtration unit (25) via the line (27) in the form of a solid or a solution. Solvents may be added to the filter unit (25) via lines (28) and (29) for washing and / or dissolving the solid and withdrawn via line (27).

The following examples intend to illustrate the invention without limiting it.

Example 1 (in accordance with the invention)

A mixture containing 80 g of dichloropropanol (0.62 mol), 9.7 g of hydrogen chloride (0.27 mol), 30 g of water and 1.3 g of acetic acid is preheated to 95 ° C. C in a reactor surmounted by a distillation column. 132 g of an aqueous solution of caustic soda at 280 g / kg at a temperature of 95 ° C. and a pressure of 0.59 bar are added over 30 minutes. A mixture containing epichlorohydrin and water is continuously removed. After an additional 20 min of reaction after the end of the addition, 53.9 g of epichlorohydrin (0.58 mol) are recovered. Example 2 (in accordance with the invention)

A mixture containing 80 g of dichloropropanol (0.62 mol), 9.7 g of hydrogen chloride (0.27 mol), 900 g of water and 1.3 g of acetic acid is preheated to 95 ° C. C in a reactor surmounted by a distillation column. 132 g of an aqueous solution of caustic soda at 280 g / kg, at a temperature of 95 ° C. and at a pressure of

0.59 bar. A mixture containing epichlorohydrin and the water. After 40 minutes of additional reaction after the end of the addition, 52.2 g of epichlorohydrin (0.56 mol) are recovered.

Claims

R E V E N D I C A T IO N S

1 - 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, and a chlorinating agent are subjected to the reaction medium containing at least 10 g of chlorohydrin per kg of reaction medium, to a subsequent chemical reaction without intermediate treatment.

2 - Process according to claim 1 wherein the subsequent chemical reaction is a dehydrochlorination reaction.

3 - Process according to claim 2 wherein the dehydrochlorination reaction is carried out by adding a basic compound to the reaction medium.

4 - Process for 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. 5 - Process according to claim 4, wherein, in the subsequent step, a fraction of the reaction medium obtained in step (a), which fraction has the same composition as the reaction medium obtained in step (a), is removed. ), and during the sampling, the basic compound is added thereto.

6 - Process according to claim 4 or 5, wherein, in the subsequent step, is taken a fraction of the reaction medium obtained in step (a), which fraction has the same composition as the reaction medium obtained in step (a), this fraction is subjected to an evaporation and / or stripping and / or distillation treatment so as to obtain an enriched portion of chlorohydrin, of chlorohydrin esters and of water, and the basic compound is added to the part enriched in chlorohydrin, in chlorohydrin esters and in water.

7 - Process according to claim 6 wherein the portion enriched in chlorohydrin, chlorohydrin ester and water is subjected to a settling treatment so as to obtain a first portion enriched with water and a second portion enriched in chlorohydrin and ester chlorohydrin, and the basic agent is added in the first portion, in the second portion or in a mixture of the two portions.

8 - Process according to claim 7 wherein the mass ratio between the first and the second portion in the mixture is greater than or equal to 1/99 and less than or equal to 99/1.

9 - Process according to any one of claims 4 to 8 wherein, in the subsequent step, is removed a fraction of the reaction medium obtained in step (a), which fraction has the same composition as the reaction medium obtained in step (a), this fraction is subjected to a distillation treatment so as to obtain an enriched part of chlorohydrin and chlorohydrin ester, and the basic compound is added to this part.

10 - Process according to any one of claims 4 to 9 wherein the fraction of the reaction medium obtained in step (a) has a chlorohydrin content greater than or equal to 100 g / kg and less than or equal to 700 g / kg , a chlorinating agent content greater than 1 g / kg or less or 200 g / kg and a total organic acid content greater than or equal to 1 g / kg and less than or equal to 500 g / kg. - ss -

11 - The method of claim 6 wherein the portion enriched in chlorohydrin and water, has a chlorohydrin content greater than or equal to 10 g / kg and less than or equal to 850 g / kg, a chlorinating agent content greater than 0 , 01 g / kg and less than or equal to 110 g / kg of chlorinating agent and a total organic acid content greater than or equal to 0.01 g / kg and less than or equal to 270 g / kg of organic acid.

12 - Process according to claim 7 wherein the portion enriched with water has a chlorohydrin content less than or equal to 500 g / kg of chlorohydrin, a chlorinating agent content greater than 5 g / kg and less than or equal to 500 g / kg and a total organic acid content greater than or equal to 0.01 g / kg and less than or equal to 5 mol / kg and the portion enriched in chlorohydrin contains at least 400 g / kg of chlorohydrin, dl ppm by weight to 50 g / kg of chlorinating agent and from 0.0001 to 5 mol / kg of organic acid.

13 - Process according to claim 9 wherein the portion enriched in chlorohydrin, contains has a chlorohydrin content greater than or equal to 100 g / kg, a chlorinating agent content greater than 0.01 g / kg and less than or equal to 110 g / kg and a total organic acid content greater than or equal to 0.01 g / kg and less than or equal to 270 g / kg.

14 - Process according to any one of claims 1 to 13 wherein the polyhydroxylated aliphatic hydrocarbon, the ester of a polyhydroxylated aliphatic hydrocarbon, or the mixture of them, is obtained from renewable raw materials.

15 - Process according to any one of claims 1 to 14 wherein the chlorinating agent contains hydrogen chloride.

16 - Process according to claim 15 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.

17 - Process according to any one of claims 4 to 16 wherein the reaction of step (a) is catalyzed by the organic acid and the organic acid is not obtained during a manufacturing process of the polyhydroxylated aliphatic hydrocarbon. 18 - Process according to any one of claims 4 to 17 wherein the organic acid is acetic acid or adipic acid.

19 - Process according to any one of claims 3 to 18 wherein the basic compound is selected from aqueous solutions or suspensions of NaOH, Ca (OH) ₂ , purified alkaline brine and mixtures thereof and wherein the molar ratio between the basic compound and the chlorohydrin is greater than or equal to 0.5 and less than or equal to 2.

20 - Process according to any one of claims 1 to 19, wherein the polyhydroxylated aliphatic hydrocarbon is selected from ethylene glycol, propylene glycol, chloropropanediol, glycerol and mixtures of at least two of them.

21 - Process according to any one of claims 1 to 20, wherein the chlorohydrin is selected from chloroethanol, chloropropanol, chloropropanediol, dichloropropanol and mixtures of at least two of them.

22 - Process according to any one of claims 1 to 21, wherein the epoxide is selected from ethylene oxide, propylene oxide, glycidol, epichlorohydrin and mixtures of at least two d 'between them..

23. A process according to any one of claims 20 to 22, wherein the polyhydroxylated aliphatic hydrocarbon is glycerol, the chlorohydrin is dichloropropanol and the epoxide is epichlorohydrin.

24. The process as claimed in claim 23, in which epichlorohydrin is used in the manufacture of epoxy resins.

25 - Process for producing epichlorohydrin in which a mixture containing dichloropropanol, hydrogen chloride and an organic acid is reacted with an aqueous solution of a basic agent.