EP1885678A1 - Continuous method for making chlorhydrines - Google Patents

Abstract

The invention concerns a continuous method for producing chlorhydrine which consists in reacting a polyhydroxylated aliphatic hydrocarbon, a polyhydroxylated aliphatic hydrocarbon ester or a mixture thereof, with a chlorinating agent and an organic acid in a liquid reaction medium whereof the composition in stationary state comprises polyhydroxylated aliphatic hydrocarbon and polyhydroxylated aliphatic hydrocarbon esters and whereof the sum of the contents expressed in mole of polyhydroxylated aliphatic hydrocarbon is higher than 1.1 mole % and not more than 30 mole %, the percentage being relative to the organic part of the liquid reaction medium.

Description

 Continuous process for producing chlorohydrins

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 No. 60/734659, 60/734627, 60/734657, 60/734658, 60/734635, 60/734634, 60/734637 and 60/734636, filed November 8, 2005 and the contents of which are hereby incorporated by reference.

The present invention relates to a continuous process for producing chlorohydrin.

Chlorohydrins are reaction intermediates in the manufacture of epoxides. Dichloropropanol, for example, is a reaction intermediate in the manufacture of epichlorohydrin and epoxy resins (Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, 1992, Vol 2, page 156, John Wiley & Sons, Inc.). .

According to known processes, dichloropropanol can be obtained in particular by hypochlorination of allyl chloride, by chlorination of allyl alcohol and by hydrochlorination of glycerol. The latter process has the advantage that dichloropropanol can be obtained from fossil raw materials or renewable raw materials, and it is known that petrochemical natural resources, from which fossil fuels are derived, for example petroleum, natural gas or coal, available on the earth are limited.

International application WO 2006/020234 describes a process for converting a polyhydroxylated aliphatic hydrocarbon or an ester thereof to a chlorohydrin. A composition comprising at most 1% polyhydroxylated aliphatic hydrocarbon and esters of the polyhydroxylated aliphatic hydrocarbon is disclosed. This composition is characteristic of a process that is not suitable for continuous operation.

The object of the invention is to provide a continuous process for producing chlorohydrin which does not have these disadvantages.

The invention therefore relates to 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 medium liquid reaction agent 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 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 The 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. In the process for the production of chlorohydrin according to the invention, the organic acid may be a product originating from the process for producing the polyhydroxylated aliphatic hydrocarbon, that is to say an impurity contained in the polyhydroxylated aliphatic hydrocarbon, 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 can also be a mixture of acid - AT -

organic material 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. .

The polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, in the process according to the invention can be obtained starting from fossil raw materials or starting from renewable raw materials, from 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 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 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, for example another method. catalytic hydrogenolysis of xylitol obtained by hydrogenation of xylose Xylose may, for example, be obtained by hydrolysis of hemicellulose contained in maize fibers By "glycerol obtained from renewable raw materials" is meant in particular glycerol obtained from 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 2869613. 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 oxides. mixed bismuth and 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 producing chlorohydrin according to the invention, the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, may be as described in the patent application entitled "Process for the preparation of chlorohydrin by conversion of polyhydroxylated aliphatic hydrocarbons "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 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 chlorohydrin according to the invention, the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, can be a crude product or a purified product, such as specifically disclosed in the application WO 2005/054167 of SOLVAY SA, from page 2, line 8, to page 4, line 2. In the process for the production of chlorohydrin according to the invention, the polyhydroxylated aliphatic hydrocarbon, the ester of polyhydroxylated aliphatic hydrocarbon, or the mixture of them, may have an alkali metal and / or alkaline earth metal content may be less than or equal to 5 g / kg as described in the application entitled "Process for the manufacture of 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. The alkali metals may be selected from lithium, sodium, potassium, rubidium and cesium and the alkaline earth metals may be selected from magnesium, calcium, strontium and barium. 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 chlorohydrin according to the invention, the chlorinating agent may be as described in SOLVAY SA application WO 2005/054167, page 4, line 25, to page 6, line 2.

In the process for producing a chlorohydrin according to the invention, the chlorinating agent may be hydrogen chloride may be as described in SOLVAY SA application WO 2005/054167, 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.

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 a chlorohydrin 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 chlorohydrin according to the invention, the hydrogen chloride may be an aqueous solution of hydrogen chloride or preferably gaseous hydrogen chloride, originating from an allyl chloride production plant and and / or the manufacture of chloromethanes and / or chlorinolysis and / or high temperature oxidation of chlorinated compounds as described in the application entitled "Process for producing a chlorohydrin by reaction between a polyhydroxylated aliphatic hydrocarbon and a chlorination "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 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 chosen 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 a particularly advantageous embodiment of the production process according to the invention, the hydrogen chloride is an aqueous solution of hydrogen chloride and does not comprise gaseous hydrogen chloride. In the process for producing chlorohydrin 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 a reactor as described in application WO 2005/054167 of SOLVAY SA, on page 6, lines 3 to 23. Mention is particularly made of an installation made of or covered with resistant materials under the conditions of the reaction chlorinating agents, in particular hydrogen chloride. Mention is more particularly made of an installation made of enamelled steel or tantalum.

In the process for the production of chlorohydrin 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, may 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 same day as the present application, the content of which is 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 chlorohydrin 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 of a catalyst as described in SOLVAY SA application WO 2005/054167, page 6, line 28, to page 8, line 5.

Particular mention is made 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 derivatives of adipic acid. .

In the process for producing a chlorohydrin 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 may be carried out at a 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 residence time at least 1 hour and not more than 50 hours. In the process for the production of chlorohydrin 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 effected by 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 the production of chlorohydrin 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 effected by presence of 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 request, the content of which is 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 the production of the chlorohydrin 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 is 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 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 production 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. The process for producing the chlorohydrin according to the invention is a continuous process. A continuous process generally has a period of operation, called the transient phase, during which the concentrations of the constituents of the reaction medium change over time and then a period of operation, called a stationary state, during which the concentrations of the constituents of the medium reaction evolve almost no more over time.

In the continuous process for the production of chlorohydrin according to the invention, the liquid reaction medium has a composition in the stationary state which comprises polyhydroxylated aliphatic hydrocarbon and esters of the polyhydroxylated aliphatic hydrocarbon, the sum of the contents of which are expressed in mole of polyhydroxylated aliphatic hydrocarbon is greater than 1.1 mol% and less than or equal to 30%, the percentage being related to the organic part of the liquid reaction medium. This sum is often greater than 2.0 mol% and frequently greater than or equal to 5 mol%. This sum is often less than or equal to 25 mol% of the liquid reaction medium, frequently less than or equal to 15 mol% and in particular less than or equal to 10 mol%.

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 continuous process for the production of chlorohydrin according to the invention, the liquid reaction medium has a composition in the stationary state which comprises chlorohydrin and chlorohydrin esters whose sum of the contents expressed in mol of chlorohydrin is greater than or equal to 10 mol% and less than or equal to 98 mol%, the percentage being based on the organic part of the liquid reaction medium. This sum is often greater than or equal to 15 mol% and frequently greater than or equal to 25 mol%. This sum of these average contents is often less than or equal to 80 mol%, frequently less than or equal to 75 mol%, in particular less than or equal to 65 mol% and more specifically less than or equal to 55 mol%.

In the continuous process for the production of chlorohydrin according to the invention, the reaction medium has a composition in the stationary state which contains chlorinated oligomers of the polyhydroxylated aliphatic hydrocarbon and esters of the chlorinated oligomers of the polyhydroxylated aliphatic hydrocarbon of which the sum of the contents expressed in moles of polyhydroxylated aliphatic hydrocarbon is greater than or equal to 0.1 mol% and less than or equal to 20 mol%, the percentage being related to the organic part of the liquid reaction medium. This sum is often greater than or equal to 1 mol% and in particular greater than or equal to 5 mol%. This sum is often less than or equal to 15 mol% of the liquid reaction medium, frequently less than or equal to 10 mol% and in particular less than or equal to 8 mol%.

In the continuous process for producing chlorohydrin according to the invention, the chlorohydrin may be a mixture of monochlorohydrin and dichlorohydrin. The chlorohydrin is preferably a mixture of monochloropropanediol and dichloropropanol.

In the continuous process for the production of chlorohydrin according to the invention, when the chlorohydrin is a mixture of mono- and dichlorohydrin, the composition of the liquid reaction medium in the stationary state contains monochlorohydrin and monochlorohydrin esters, the sum of contents expressed in moles of monochlorohydrin is greater than or equal to 11 mol% and less than or equal to 85 mol%, the percentage being related to the organic part of the liquid reaction medium. This sum is frequently greater than or equal to 15 mol% and in particular greater than or equal to 25 mol%. This sum is often less than or equal to 75 mol% of the medium liquid reaction, frequently less than or equal to 60 mol% and in particular less than or equal to 45 mol%.

In the continuous process for the production of chlorohydrin according to the invention, when the chlorohydrin is a mixture of mono- and dichlorohydrin, the composition of the liquid reaction medium in the stationary state contains dichlorohydrin and dichlorohydrin esters, the sum of contents expressed in moles of dichlorohydrin is greater than or equal to 0.5 mol% and less than or equal to 79%, the percentage being related to the organic part of the liquid reaction medium. This sum is often greater than or equal to 1 mol% of dichlorohydrin and its esters, and frequently greater than or equal to 5 mol%. This sum is often less than or equal to 55 mol% of the liquid reaction medium, frequently less than or equal to 45 mol% and in particular less than or equal to 35 mol%.

In the continuous process for the production of chlorohydrin according to the invention, the esters can come from the reaction between the chlorohydrin, the glycerol, the chlorinated oligomers of the polyhydroxylated hydrocarbon and the organic acid during the production step of chlorohydrin. The organic acid is as defined above.

The invention also relates to a liquid composition comprising a chlorohydrin, chlorohydrin esters, a polyhydroxylated aliphatic hydrocarbon, esters of the polyhydroxylated aliphatic hydrocarbon, chlorinated oligomers of the polyhydroxylated aliphatic hydrocarbon and esters of the chlorinated oligomers of the polyhydroxylated aliphatic hydrocarbon and wherein: (a) the sum of the contents of the polyhydroxylated aliphatic hydrocarbon and the esters of the polyhydroxylated aliphatic hydrocarbon, expressed as moles of polyhydroxylated aliphatic hydrocarbon in the organic part of the polyhydroxylated aliphatic hydrocarbon; liquid composition, is greater than 1.1 mol% and less than or equal to 30 mol% of the liquid composition (b) the sum of the contents of the chlorohydrin and of the chlorohydrin esters, expressed in mol of chlorohydrin in the organic part of the liquid composition, is greater than or equal to 10 mol% and less than 98 mol% of the liquid composition

(c) the sum of the chlorinated oligomer contents of the polyhydroxylated aliphatic hydrocarbon and the esters of the chlorinated oligomers of the polyhydroxylated aliphatic hydrocarbon, expressed as mole of aliphatic hydrocarbon poly hydroxylated in the organic part of the liquid composition, is greater than or equal to 0.1 mol% and less than 20 mol% of the liquid composition.

The invention also relates to a composition comprising 1,3-dichloropropan-2-ol and 2,3-dichloropropane-1-ol and having a total content of 1,3-dichloropropan-2-ol and 2,3-dichloropropane 1-ol relative to the organic part, greater than or equal to 800 g / kg.

The organic part is defined as above.

This liquid composition may contain water and hydrogen chloride.

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 the 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, the solvent, the 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 a chlorohydrin according to the invention, the separation of the chlorohydrin and the other compounds from the reaction medium can be carried out according to modes as described in the patent application EP 05104321.4 filed in the name of SOLVAY SA on 20/05/2005 whose content is hereby 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 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 method of manufacture of 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, an ester of a polyhydroxylated aliphatic hydrocarbon or a mixture thereof, used contains at least one chloride and / or sodium and / or potassium 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 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 a chlorohydrin according to the invention, the separation of the chlorohydrin and of 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 the manufacture of a chlorohydrin comprising the following steps: (a) a hydrocarbon is reacted polyhydroxylated aliphatic ester, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof, with a chlorinating agent and an organic acid so as 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 steps subsequent to step (a) and (c) adding polyhydroxylated aliphatic hydrocarbon to at least one of the subsequent steps in step (a), to react at a temperature of 20 ° C or higher with the chlorohydrin esters 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 a chlorohydrin 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 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. 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 such as 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) subjecting the fraction taken in step (b) to 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 the production of a chlorohydrin 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 converting 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 here incorporated by reference. Particular mention is made of a process for preparing a chlorohydrin 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 to obtain a mixture containing chlorohydrin, chlorohydrin esters and the 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 for the production of the chlorohydrin 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 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, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, of which the content of alkali and / or alkaline-earth metals 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) subjecting 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 monochloropropanol, it is generally obtained in the form of a mixture of compounds comprising the isomers of 1-chloropropan-2-ol and 2-chloropropan-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 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 weight 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 monochloroethanol, 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 from chloroethanol production processes, such as residual reagents, reaction byproducts, solvents and especially water. In the process according to the invention, when the chlorohydrin is monochloropropanediol, it is generally obtained in the form of a mixture of compounds comprising the isomers of 1-chloropropane-2,3-diol and 2-chloropropane-1 , 3-diol. 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 chloropropanediol production processes, such as residual reagents, reaction by-products, solvents and in particular water.

The weight ratio between the isomers 1-chloropropane-2,3-diol and 2-chloropropane-1,3-diol 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 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% by weight and more particularly more than 50%. The mixture usually contains less than 99.9% by weight of both isomers. 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.

The invention also relates to a composition comprising 1,3-dichloropropan-2-ol and 2,3-dichloropropan-1-ol and other organic compounds having a total content of 1,3-dichloropropan-2-ol. and 2,3-dichloropropan-1-ol based on the total organic compound content greater than or equal to 800 g / kg. This content is often greater than or equal to 850 g / kg, frequently greater than or equal to 900 g / kg, in particular greater than or equal to 950 g / kg, specifically greater than or equal to 975 g / kg and very particularly greater than or equal to 985 g / kg. This composition may also contain water and hydrogen chloride. 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 chlorhdyrine 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. 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 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. The preferred epoxides are ethylene oxide, propylene oxide, glycidol, epichlorohydrin and mixtures of at least two of them. 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 the production of the chlorohydrin according to the invention can be integrated into an overall scheme for the manufacture of an epoxide as described in the application entitled "Process for the production of an epoxide from 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 the production of an epoxide comprising at least one stage of purification of the epoxide formed, the epoxide being at least partly manufactured by a process for the dehydrochlorination of a chlorohydrin, the latter being at least partly made by a process for the chlorination of 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 and the chlorohydrin is preferably dichloropropanol.

When the chlorohydrin is dichloropropanol, the process according to the invention can be followed by the manufacture of epichlorohydrin by dehydrochlorination of dichloropropanol and epichlorohydrin can be used in the manufacture of epoxy resins.

The following example intends to illustrate the invention without limiting it. Single example

The example according to the invention was carried out in an installation shown schematically in FIG. 1. A reactor equipped with a stirring device (4) was fed continuously with a flow of 20 kg / h of glycerin (1). and a flow of 47.2 kg / h of 33% concentrated hydrochloric acid (2). The adipic acid catalyst is introduced into the reactor via line (3). The reactor was operated at a temperature of 125 ° C and at atmospheric pressure with a reaction liquid volume of 625 L. A distillation column (6) was fed via line (5) with vapors produced in the reactor (4). ). A stream was withdrawn from the column (6) via the line (7) and was introduced into a condenser (8). The flow from the condenser (8) was introduced via the line (9) into a decanter (10) in which aqueous and organic phases were separated. A fraction of the separated aqueous phase was recycled via line (11) to the top of column (6) to maintain sufficient reflux for separation. The less volatile compounds were condensed in the column and were recycled to the reactor (4) via line (12). The production of dichloropropanol consisted of a saturated aqueous phase of dichloropropanol withdrawn via line (13) and an organic phase saturated with water withdrawn via line (14). The overall production of dichloropropanol which contains a little hydrogen chloride has an organic purity of 99.6% by weight.

A fraction of the reaction mixture was regularly drawn off the line (15) so as to keep a constant volume of liquid in the reactor (4). The overall stationary catalyst content was 1.87 moles of weak acid and ester functions associated with adipic acid per kg of reaction mixture. The organic part of the constituents of the reaction mixture comprises 35.5 mol% of dichloropanols and their esters, 48.5 mol% of monochloropropanediols and of their esters, 5.5 mol% of glycerol and its esters, 9.1 mol% of diglycerols and chlorinated diglycerols and 1.4 mol% acid

Claims

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

A continuous process for the production of chlorohydrin in which 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 in a liquid reaction medium the stationary composition 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 lower or equal to 30 mol%, the percentage being related to the organic part of the liquid reaction medium.

Process according to Claim 1, in which the composition of the liquid reaction medium in the stationary state contains chlorohydrin and chlorohydrin esters whose sum of the contents expressed in moles of chlorohydrin is greater than or equal to 10 mol% and less than or equal to at 98 mol%, the percentage being related to the organic part of the liquid reaction medium.

The process according to claim 1 or 2, wherein the composition of the stationary liquid reaction medium contains chlorinated oligomers of the polyhydroxylated aliphatic hydrocarbon and esters of the chlorinated oligomers of the polyhydroxylated aliphatic hydrocarbon whose sum of contents expressed in moles of polyhydroxylated aliphatic hydrocarbon is greater than or equal to 0.1 mol% and less than or equal to 20 mol%, the percentage being related to the organic part of the liquid reaction medium.

Process according to any one of claims 1 to 3 wherein the chlorohydrin is a mixture of mono- and dichlorohydrin.

The method of claim 4 wherein the composition of the liquid reaction medium in the stationary state contains monochlorohydrin and monochlorohydrin esters, the sum of the contents expressed in moles of monochlorohydrin is greater than or equal to 11 mol% and lower or equal to 85 mol%, the percentage being related to the organic part of the liquid reaction medium.

The process according to claim 4 or 5 wherein the composition of the liquid reaction medium in the stationary state contains dichlorohydrin and of dichlorohydrin esters whose sum of the contents expressed in mol of dichlorohydrin is greater than or equal to 0.5 mol% and less than or equal to 79 mol%, the percentage being related to the organic part of the liquid reaction medium.

A process according to any one of claims 1 to 6 wherein the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester or the mixture thereof is obtained from renewable raw materials.

The process according to any one of claims 1 to 7 wherein the chlorinating agent is a combination of gaseous hydrogen chloride and an aqueous solution of hydrogen chloride, or an aqueous solution of hydrogen chloride.

The process according to any one of claims 1 to 8 wherein the organic acid is an impurity contained in the polyhydroxylated aliphatic hydrocarbon, the ester of a polyhydroxylated aliphatic hydrocarbon or the mixture of them.

The process of any one of claims 1 to 9 wherein the organic acid is used as a catalyst for the chlorination reaction.

The process of any one of claims 3 to 10 wherein the esters of the polyhydroxylated aliphatic hydrocarbon, chlorohydrin and chlorinated oligomers of the polyhydroxylated aliphatic hydrocarbon result from reactions between the organic acid and the hydrocarbon polyhydroxylated aliphatic acid, chlorohydrin and chlorinated oligomers of the polyhydroxylated aliphatic hydrocarbon.

The process according to any one of claims 1 to 11 wherein the polyhydroxylated aliphatic hydrocarbon is selected from ethylene glycol, propylene glycol, chloropropanediol, glycerol and mixtures of two or more of them.

Process according to any one of claims 1 to 12 wherein the chlorohydrin is selected from chloroethanol, chloropropanol, chloropropanediol, dichloropropanol and mixtures of at least two of them. The process of claim 12 or 13 wherein the polyhydroxylated aliphatic hydrocarbon is glycerol and the chlorohydrin is chloropropanediol and / or dichloropropanol.

Process according to claim 14 followed by production of epichlorohydrin by dehydrochlorination of dichloropropanol

The process of claim 15 wherein epichlorohydrin is used in the manufacture of epoxy resins.

A liquid composition comprising a chlorohydrin, chlorohydrin esters, a polyhydroxylated aliphatic hydrocarbon, esters of the polyhydroxylated aliphatic hydrocarbon, chlorinated oligomers of the polyhydroxylated aliphatic hydrocarbon and esters of the chlorinated oligomers of the polyhydric aliphatic hydrocarbon hydroxylated and wherein:

(a) the sum of the contents of the polyhydroxylated aliphatic hydrocarbon and the esters of the polyhydroxylated aliphatic hydrocarbon, expressed as moles of polyhydroxylated aliphatic hydrocarbon, in the organic part of the liquid composition, is greater than 1.1 mol% and less than or equal to 30 mol%

(b) the sum of the contents of chlorohydrin and chlorohydrin esters, expressed as moles of chlorohydrin, in the organic part of the liquid composition, is greater than or equal to 10 mol% and less than 98 mol%

(c) The sum of the chlorinated oligomer contents of the polyhydroxylated aliphatic hydrocarbon and the esters of the chlorinated oligomers of the polyhydroxylated aliphatic hydrocarbon, expressed in moles of polyhydroxylated aliphatic hydrocarbon, in the organic part of the liquid composition, is greater than or equal to 0.1 mol% and less than 20 mol%.

A composition comprising 1,3-dichloropropan-2-ol and 2,3-dichloropropan-1-ol and having a total content of 1,3-dichloropropan-2-ol and 2,3-dichloropropan-1-ol reported in the organic part, greater than or equal to 800 g / kg. The composition of claim 18 comprising water and hydrogen chloride.

The composition of claim 18 or 19 wherein the 2,3-dichloropropan-1-ol content is based on the sum of 1,3-dichloropropan-2-ol and 2,3-dichloropropan-1-ol contents. is less than or equal to 20% by weight.