EP1885671A1

EP1885671A1 - Method for making a chlorohydrin starting with a polyhydroxylated aliphatic hydrocarbon

Info

Publication number: EP1885671A1
Application number: EP06755267A
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: BRPI0610744A2; KR101337048B1; TWI388542B; TWI332493B; EP1885673A1; TW200938519A; US20080161613A1; US20080194849A1; JP5419446B2; JP2008540616A; EP1885678A1; TW200700360A; JP5280842B2; KR20080036554A; TWI332941B; CA2608719A1; CN101031532B; CN1993307B; CN102531841A; TW200700367A

Abstract

The invention concerns a method for making a chlorohydrin by reacting a polyhydroxylated aliphatic hydrocarbon with a chlorinating agent in a reactor which is fed with one or more liquid flows containing at least 50 wt. % of polyhydroxylated aliphatic hydrocarbon relative to the total weight of the liquid flows.

Description

Process for producing a chlorohydrin from a polyhydroxylated aliphatic hydrocarbon

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 chlorohydrin. The present invention relates more specifically to a process for producing chlorohydrin by reaction between a polyhydroxylated aliphatic hydrocarbon and a chlorinating agent.

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.

The international application WO 2005/021476 describes a process for the manufacture of dichloropropanol by reaction between glycerol and gaseous hydrogen chloride in the presence of acetic acid as catalyst. A mixture containing the produced DCPoI, the reaction water and the residual hydrogen chloride is separated by distillation. 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 another catalyst such as adipic acid. A mixture of water, DCPoI and hydrogen chloride is also separated by distillation. In both processes, the presence of hydrogen chloride in the distillate can be the source of losses of this reagent and corrosion problem related to the presence of potentially corrosive liquid phases.

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

The invention therefore relates to 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 ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof relative to the weight of all the liquid streams introduced into the reactor.

The liquid stream (s) often contain less than 40% by weight of the polyhydroxylated aliphatic hydrocarbon, the ester of a polyhydroxylated aliphatic hydrocarbon, or the mixture of them with respect to the weight of all the liquid streams. introduced into the reactor, frequently less than 30% by weight, specifically less than 20% by weight and more specifically less than 10% by weight. The process for producing chlorohydrin according to the invention preferably comprises the following steps:

(a) A polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon or a mixture thereof is reacted with a chlorinating agent so as to obtain at least one medium containing chlorohydrin, water and chlorinating agent

(b) at least a fraction of the medium formed in step (a) is taken

(c) The fraction taken in step (b) is subjected 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). It has been found that the addition of the polyhydroxylated aliphatic hydrocarbon in step (c) has, inter alia, the following advantages: 1) a maintenance of the chlorinating agent in the medium of step (a) with a concomitant increase in the yield of the chlorohydrin formation reaction 2) an energy gain with equivalent separation efficiency following a lower reflux of water in the distillation and / or stripping column

3) less corrosivity of the liquid phases obtained after condensation of the mixture of step (c). 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-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 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 "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-chloropropane-1-ol, 1-chloropropane-2,3-diol, 2-chloropropane-1,3-diol. 1,3-dichloropropan-2-ol, 2,3-dichloropropan-1-ol and mixtures of at least two of them.

The polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated hydrocarbon ester, or the mixtures thereof, in the process according to the invention can be obtained from fossil raw materials or from 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 hydrocarbon Polyhydroxylated aliphatic 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. 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 plant or animal origin in general such as saponification, trans-esterification 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, soy, flax and crambe oils and all oils for example, 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 a chlorohydrin according to the invention, the polyhydroxylated aliphatic hydrocarbon may be as described in the patent application entitled "Process for preparing chlorohydrin by conversion of polyhydroxylated aliphatic hydrocarbons" deposited in the name of SOLVAY SA the same day as the present application, the contents of which are hereby incorporated by reference.

Particular mention is made of a process for producing a chlorohydrin in which a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof, of which the total content of expressed metals, is reacted. in the form of elements is greater than or equal to 0.1 μg / kg and less than or equal to 1000 mg / kg, with a chlorinating agent.

In the process according to the invention, it is preferred to use glycerol, a glycerol ester or a mixture of them, obtained from renewable raw materials. In the process for producing a chlorhdyrine according to the invention, the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated hydrocarbon ester, or the mixture of them, can be raw products or purified products, such as specifically disclosed in SOLVAY SA application WO 2005/054167, page 2, line 8, to page 4, line 2. In the process for producing a chlorohydrin according to the invention, the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated hydrocarbon ester, or the mixture of them, may be a polyhydroxylated aliphatic hydrocarbon, a polyhydroxylated hydrocarbon ester, or a mixture thereof, the alkali metal content and / or alkaline earth may be less than or equal to 5 g / kg as described in the application entitled "Process for producing a chlorohydrin by chlorination of a polyhydroxylated aliphatic hydrocarbon" deposited in the name of SOLVAY SA the same day as this dem ande, the contents of which are hereby incorporated by reference. The alkali metals can be selected from lithium, sodium, potassium, rubidium and cesium and the alkaline earth metals can 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 a chlorohydrin according to the invention, the chlorinating agent may be as described in the application WO 2005/054167 of SOLVAY SA, of page 4, line 25, on 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.

Hydrogen chloride may be derived from a process of pyrolysis of chlorinated organic compounds such as vinyl chloride manufacture, 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 method 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 a chlorohydrin according to the invention, the hydrogen chloride may be an aqueous solution of hydrogen chloride or preferably anhydrous hydrogen chloride, from an installation for the production of allyl chloride and / or the production of chloromethanes and / or chlorinolysis and / or high temperature oxidation of chlorinated compounds as described in application entitled "Process for producing a chlorohydrin by reaction between a polyhydroxylated aliphatic hydrocarbon and a chlorinating agent" deposited in the name of SOLVAY SA on the same day as the present application, the contents of which are hereby incorporated by reference.

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 selected from alcohols, chloroalcohols, chloroethers and mixtures thereof. Particular mention is made of a metal selected from alkali metals, alkaline earth metals, iron, nickel , copper, lead, arsenic, cobalt, titanium, cadmium, antimony, mercury, zinc, selenium, aluminum, bismuth, and mixtures thereof. Particular mention is made of a process in which the chlorinating agent is derived at least partially from a process for producing allyl chloride and / or a process for producing chloromethanes and / or a process chlorinolysis and / or a process for the oxidation of chlorinated compounds at a temperature greater than or equal to 800 ° C.

In a particularly advantageous embodiment of the process for producing a chlorohydrin 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 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 can be carried out in a reactor as described in the application WO 2005/054167 SOLVAY SA, on page 6, lines 3 to 23. Mention is particularly made of an installation made of, or covered with, resistant materials under the conditions of the reaction with 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 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 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 the same 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 , the perfluoroalkoxyalkanes and poly (perfluoropropylvinylether), polysulfones and polysulfides, graphite and impregnated graphite.

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 can be carried out in a reaction medium, as described in the application entitled "Continuous process for the manufacture of chlorohydrins" filed in the name of SOLVAY SA on the same day as the present application, the content of which is 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 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 can be carried out in the presence of a catalyst as described in SOLVAY SA application WO 2005/054167, page 6, line 28, on 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 can be 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 of not less than 1 h and not more than 50 h.

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 can be carried out in the presence of a solvent as described in the application WO 2005/054167 of SOLVAY SA, on page 11, lines 12 to 36.

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

In the process for producing 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 can be carried out in the presence of a liquid phase comprising heavy compounds other than the polyhydroxylated aliphatic hydrocarbon, as described in the application entitled "Process for the manufacture of a chlorohydrin in a liquid phase" deposited in the name of SOLVAY SA on 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, 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 a chlorohydrin according to the invention, the reaction between the polyhydroxylated aliphatic hydrocarbon and the hydrocarbon ester polyhydroxylated aliphatic, or the mixture of them, and the chlorinating agent 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 the water introduced into the process, for example via the polyaliphatic hydrocarbon hydroxyl and / or the chlorinating agent, as described in the application

WO 2005/054167 of SOLVAY SA, on page 2, lines 22 to 28, on page 3, lines 20 to 25, on page 5, lines 7 to 31 and on page 12, lines 14 to 19.

Among the by-products include, for example, partially chlorinated and / or esterified polyhydroxylated aliphatic hydrocarbon oligomers.

When the polyhydroxylated aliphatic hydrocarbon is glycerol, among the by-products, mention may be made, for example, of partially chlorinated and / or esterified glycerol oligomers.

The reaction intermediates and by-products may be formed in the various process steps such as, for example, during the chlorohydrin manufacturing step and during the chlorohydrin separation steps.

The liquid reaction medium may thus contain the polyhydroxylated aliphatic hydrocarbon, the dissolved or dispersed chlorination agent in the form of bubbles, the catalyst, the solvent, the impurities present in the reactants, the solvent and the catalyst, such as dissolved salts. or solids for example, the solvent, the catalyst, the reaction intermediates, the products and the by-products of the reaction.

The process for producing the chlorohydrin according to the invention can be carried out in batch mode or in continuous mode. Continuous mode is preferred.

The steps (a), (b) and (c) of the process according to the invention can be carried out in batch mode or in continuous mode. It is preferred to carry out all the steps in continuous mode.

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 May 20, 2005, the content of which is hereby incorporated by reference. Particular mention is made of a separation mode comprising at least one separation operation for removing the salt from the liquid phase.

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 a mixture thereof, used contains at least one sodium and / or potassium chloride and / or sulfate and wherein the separation operation for removing some 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 in a distillation step, in which 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 / water concentrations in the azeotropic hydrogen chloride / water binary composition to the temperature and the distillation pressure.

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

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

In the process for 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 can be carried out according to the modes as described in the "Conversion process" application. of polyhydroxylated aliphatic hydrocarbons to chlorohydrins "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 to obtain a mixture containing chlorohydrin, esters and of chlorohydrin and water, (b) at least a fraction of the mixture obtained in step (a) is subjected to a distillation and / or stripping treatment so as to obtain a concentrated portion of water, chlorohydrin and chlorohydrin esters and (c) at least a fraction of the portion 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 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 a 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 the production of a chlorohydrin by chlorination of a polyhydroxylated aliphatic hydrocarbon deposited in the name of SOLVAY SA 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, the alkali and / or alkaline-earth metal content is less than or equal to 5 g / kg, an oxidizing agent and an organic acid so as to obtain a mixture containing at least chlorohydrin and by-products, (b) subject to at least a portion of the mixture obtained in step (a) to one or more treatments in steps subsequent to step (a) and (c) at least one of the steps subsequent to step (a) consists of oxidation at a temperature greater than or equal to 800 ° C. More particular mention is made of a process in which in the subsequent step, a part of the mixture obtained in step (a) is taken and this part is subjected to oxidation at a temperature greater than or equal to 800 ° C. during the sampling. Particular mention is also made of a process in which the treatment of step (b) is a separation operation chosen from among the operations of decantation, filtration, centrifugation, extraction, washing, evaporation, stripping, distillation, adsorption or combinations of at least two of them.

In the process according to the invention, the content of chlorinating agent of the fraction taken in step (b) is generally greater than or equal to 0.035 percent by weight, preferably greater than or equal to 0.35 percent by weight. and particularly preferably greater than or equal to 3.5 percent by weight. This content is generally less than or equal to 30 percent by weight, preferably less than or equal to 20 percent by weight, and particularly preferably less than or equal to 10 percent by weight. The chlorinating agent is preferably hydrogen chloride. In the process according to the invention, the chlorinating agent content of the fraction taken in step (b) is generally smaller than the concentration of chlorinating agent in the binary azeotropic chlorinating agent / water composition at the temperature and at the distillation and / or stripping pressure. The chlorinating agent is preferably hydrogen chloride. When the chlorinating agent is hydrogen chloride, the ratio of the hydrogen chloride content to the water content of the fraction taken in step (b) is less than or equal to the ratio of the chloride content of hydrogen and the water content in the azeotropic binary hydrogen chloride / water composition at the temperature and at the distillation and / or stripping pressure. Stripping is understood to mean the separation of a substance by entrainment with the vapor of a body which does not dissolve it. Distillation means the direct passage from the liquid state to the gaseous state of the substance to be separated and the condensation of the vapors obtained. The distillation is preferably a fractional distillation, that is to say a series of distillations carried out on the successively condensed vapors.

In the process according to the invention, the ratio between the chlorinating agent content of the mixture separated in step (c) and the chlorinating agent content of the fraction taken in step (b) is generally less than or equal to at 0.95, in particular less than or equal to 0.70, most often less than or equal to 0.5. The chlorinating agent is preferably hydrogen chloride.

Step (c) of the process according to the invention is generally carried out at a temperature greater than or equal to 50 ° C., frequently greater than or equal to 70 ° C. and most often greater than or equal to 90 ° C. This temperature is generally less than or equal to 180 ° C., often less than or equal to 150 ° C. and in particular less than or equal to 120 ° C.

Step (c) of the process according to the invention is generally carried out at a pressure greater than or equal to 0.1 bar, often greater than or equal to 0.5 bar and more particularly greater than or equal to 0.9 bar. This pressure is generally less than or equal to 20 bar, frequently less than or equal to 10 bar and in some cases less than or equal to 5 bar. Stage (c) of the process according to the invention is carried out at a ratio of masses between the polyhydroxylated hydrocarbon and the fraction taken in stage (b) generally greater than or equal to 0.02, often greater than or equal to 0.05 and in particular greater than or equal to 0.1. This mass ratio is generally less than or equal to 2 and frequently less than or equal to 1.

Step (c) of the process according to the invention can be carried out in any container, such as, for example, a distillation and / or stripping column, with reflux. This column may be of any type and generally comprises at least one feed point of the fraction taken in step (b), at least one feed point of the polyhydroxylated aliphatic hydrocarbon, at least one reflux feed point and at least one theoretical plateau below the reflux feed point.

The distillation or stripping column may be located at any point relative to the reactor where the process step (a) according to the invention is carried out.

In the case of a stripping operation, the stripping gas may be any inert gas with respect to the chlorohydrin such as, for example, water vapor, air, nitrogen and carbon dioxide.

In a first configuration, the column is located above the reactor in which the process step (a) according to the invention is carried out. The fraction taken in step (b) is then a fraction of the gaseous phase in contact with the liquid phase in which the reaction of step (a) is carried out.

In a second configuration, the column is not situated above the container in which the process step (a) according to the invention is carried out, but for example in a loop for withdrawing the liquid phase.

In the process according to the invention, the addition of the polyhydroxylated hydrocarbon to step (c) can be carried out at any level of the distillation column. This addition is preferably performed at a level corresponding to at least 1 and at most 4 theoretical plates below the reflux feed point.

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

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

The weight ratio between the 1,3-dichloropropan-2-ol and 2,3-dichloropropan-1-ol isomers is usually greater than or equal to 0.01, often greater than or equal to 0.4, frequently greater than or equal to 1 , 5, preferably greater than or equal to 3.0, more preferably greater than or equal to 7.0 and most preferably greater than or equal to 20.0. This ratio is usually less than or equal to 99 and preferably less than or equal to 25. In the process for producing a chlorohydrin according to the invention, the reaction between the polyhydroxylated hydrocarbon and the polyhydroxylated aliphatic hydrocarbon ester or the mixture of them, and the chlorinating agent can be carried out in the presence of an organic acid as a catalyst. The organic acid may be a product from the process for producing the polyhydroxylated aliphatic hydrocarbon or a product not from this process. In the latter case, it may be an organic acid used to catalyze the reaction between the polyhydroxylated aliphatic hydrocarbon and the chlorinating agent. The organic acid may also be a mixture of organic acid from the process for producing the polyhydroxylated aliphatic hydrocarbon and an organic acid not originating from the process for producing the polyhydroxylated aliphatic hydrocarbon.

In the process according to the invention, the polyhydroxylated aliphatic hydrocarbon ester 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 chlorohydrin obtained in the process according to the invention may contain a high content of halogenated ketones, in particular chloroacetone, as described in the patent application FR 05.05120 of 20/05/2005 filed in the name of the Applicant, and whose content is hereby incorporated by reference. The content of halogenated ketone can be reduced by subjecting the chlorohydrin obtained in the process according to the invention to azeotropic distillation in the presence of water or subjecting the chlorohydrin to a dehydrochlorination treatment as described in this application, from page 4, line 1, to 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 manufacture of 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. Preferred epoxides are ethylene oxide, propylene oxide, glycidol and epichlorohydrin.

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. Epoxide manufacturing is also described 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, the chlorinating agent and the organic acid, the reaction medium containing at least 10 g of chlorohydrin per kg of reaction medium, (b) subjecting at least a fraction of the reaction medium obtained in step (a), which fraction has the same composition as the reaction medium obtained in step (a), one or more treatments in steps subsequent to step (a), and (c) adding a basic compound to at least one of the steps subsequent to step ( a) for i It reacts at least partially with the chlorohydrin, the chlorohydrin esters, the chlorinating agent and the organic acid 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 producing an epoxide as described in the application entitled "Process for producing 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 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. 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.

In the process according to the invention, the polyhydroxylated aliphatic hydrocarbon is preferably glycerol and the chlorohydrin is preferably dichloropropanol.

Figure 1 shows a particular installation scheme used to implement the separation method according to the invention. A reactor (4) is fed continuously or in batch mode with a polyhydroxylated aliphatic hydrocarbon, a polyhydroxylated dicarboxylic acid ester, or a mixture of them via the line (1) and into 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 supplied 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. Part of the separated aqueous phase 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). The residue of the column (6) can be recycled to the reactor (4) via line (15). Polyhydroxylated aliphatic hydrocarbon may be introduced into the distillation column (6) under the reflux feed point (11) via line (33). A portion of the heavy products is withdrawn from the reactor (4) via the purge (16) and is introduced via line (17) into an evaporator (18) in which a partial evaporation operation is carried out for example by heating or by sweeping gaseous with nitrogen or water vapor, the gaseous phase containing most of the hydrogen chloride of the stream (17) is recycled via line (19) to column (6) or via the line (20) to the reactor (4), a distillation or stripping column (22) is fed with the liquid phase from the evaporator (18) via the line (21), the line (21) and / or the distillation column (22) and / or the evaporator (18) and / or the line (17) are supplied with polyhydroxylated aliphatic hydrocarbon via line (32) and / or line (31) and / or line respectively. (33) and / or line (34), most of the chlorohydrin is collected at the top of column (22) via line (23) and the residue that contains the ester s of the polyhydroxylated aliphatic hydrocarbon is introduced via the line (24) into the filtration column (25) in which liquid and solid phases are separated, the liquid phase is recycled via line (26) to the reactor (4) . The 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).

Optionally, a stream is withdrawn from the purge (16) and introduced via the line (30) in the filtration column (25). The evaporator (18) and the distillation column (22) are then short-circuited.

Claims

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

1 - 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 streams liquids containing less than 50% by weight of the polyhydroxylated aliphatic hydrocarbon, the ester of a polyhydroxy hydrocarbon, or the mixture of them, based on the weight of all the liquid flows introduced into the reactor.

2 - Process for the manufacture of chlorohydrin according to claim 1, comprising the following steps:

(a) reacting a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof, with a chlorinating agent to obtain at least one medium containing chlorohydrin, water and chlorinating agent

(b) at least a fraction of the medium formed in step (a) is taken

(c) The fraction taken in step (b) is subjected 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).

3 - Process according to claim 1 or 2 wherein a carboxylic acid, a carboxylic acid anhydride, a carboxylic acid chloride, a carboxylic acid salt or a carboxylic acid ester preferably having a boiling point atmospheric greater than or equal to 200 ° C, is used as catalyst in step (a).

4 - Process according to any one of claims 1 to 3 wherein the reaction of step (a) is carried out in a liquid phase.

5 - Process according to any one of claims 2 to 4 wherein the distillation operation and / or stripping is carried out in a distillation column and / or stripping comprising at least one feed point of the fraction taken in step (b), at least one feed point of the polyhydroxylated aliphatic hydrocarbon, at least one reflux feed point and at least one theoretical plateau below the reflux feed point.

6 - Process according to claim 5 wherein the addition of the polyhydroxylated aliphatic hydrocarbon in step (c) is carried out at a level corresponding to at least 1 and at most 4 theoretical trays below the feed point of the reflux.

7 - Process according to any one of claims 2 to 6 wherein the content of chlorination agent of the fraction taken in step (b) is greater than or equal to 0.035 percent by weight and less than or equal to 30 percent in weight.

8 - Process according to any one of claims 2 to 7 wherein the chlorinating agent is hydrogen chloride and the ratio between the hydrogen chloride content and the water content of the fraction taken in step (b) is less than or equal to the ratio between the hydrogen chloride content and the water content in the binary hydrogen chloride / water binary azeotropic composition at the temperature and at the distillation and / or stripping pressure.

9 - Process according to any one of claims 2 to 8 wherein the ratio between the content of chlorination agent of the mixture separated in step (c) and the content of chlorinating agent of the fraction taken in step (b) is less than or equal to 0.95 and greater than or equal to 0.0015.

10 - Process according to any one of claims 2 to 9 wherein step (c) is carried out at a temperature greater than or equal to 50 ° C and less than or equal to 180 ° C, at a pressure greater than or equal to 0 , 1 bar and less than or equal to 20 bar and a mass ratio between the polyhydroxylated aliphatic hydrocarbon and the fraction taken in step (b) greater than or equal to 0.1 and less than or equal to 1.5.

11 - Process according to any one of claims 2 to 10 wherein steps (a), (b) and (c) are conducted continuously.

12 - Process according to any one of claims 1 to 11 wherein the polyhydroxylated aliphatic hydrocarbon, the ester of a hydrocarbon polyhydroxylate, or the mixture of them, is obtained from renewable raw materials.

13 - Process according to any one of claims 1 to 12, wherein the polyhydroxylated aliphatic hydrocarbon is selected from ethylene glycol, propylene glycol, chloropropanediol, glycerol and mixtures of at least two of them.

14 - Process according to any one of claims 1 to 13, wherein the chlorohydrin is selected from chloroethanol, chloropropanol, chloropropanediol, dichloropropanol and mixtures of at least two of them.

15. The process according to claim 14, wherein the polyhydroxylated aliphatic hydrocarbon is glycerol and the chlorohydrin is chloropropanediol and / or dichloropropanol.

16 - Process according to claim 15 followed by a manufacture of epichlorohydrin by dehydrochlorination of dichloropropanol

17 - The method of claim 16 wherein epichlorohydrin is used in the manufacture of epoxy resins.

18 - Process according to any one of claims 1 to 17 wherein the chlorinating agent contains hydrogen chloride.

19 - Process according to claim 18 wherein the hydrogen chloride is a combination between gaseous hydrogen chloride and an aqueous solution of hydrogen chloride or an aqueous solution of hydrogen chloride.