Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
  • B01D3/14—Fractional distillation or use of a fractionation or rectification column
  • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
  • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
  • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
  • C07C29/82—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by azeotropic distillation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
  • C07C31/34—Halogenated alcohols
  • C07C31/36—Halogenated alcohols the halogen not being fluorine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
  • C07C31/34—Halogenated alcohols
  • C07C31/42—Polyhydroxylic acyclic alcohols
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D301/00—Preparation of oxiranes
  • C07D301/02—Synthesis of the oxirane ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D301/00—Preparation of oxiranes
  • C07D301/02—Synthesis of the oxirane ring
  • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
  • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
  • C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D301/00—Preparation of oxiranes
  • C07D301/02—Synthesis of the oxirane ring
  • C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
  • C07D301/26—Y being hydrogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
  • C07D303/02—Compounds containing oxirane rings
  • C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals

Definitions

• the present invention relates to a process for producing a chlorohydrin. It relates more specifically to a process for producing a chlorohydrin from 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.) .
• 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 and the application WO 2005/054167 of SOLVAY SA describe a process for the manufacture of dichloropropanol by reaction between glycerol and hydrogen chloride.
• the hydrogen chloride may be gaseous or in the form of aqueous solutions.
• the object of the invention is to provide a process for producing chlorohydrin from a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon or a mixture of them, and a chlorinating agent that does not have these disadvantages.
• the invention therefore relates to a process for producing a chlorohydrin from a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof, and a chlorinating agent, the chlorinating agent containing at least one of nitrogen, oxygen, hydrogen, chlorine, an organic hydrocarbon compound, a halogenated organic compound, an oxygenated organic compound and a metal.
• the hydrocarbon-based organic compound is chosen from aromatic, saturated or unsaturated aliphatic hydrocarbons and mixtures thereof.
• the unsaturated aliphatic hydrocarbon is chosen from acetylene, ethylene, propylene, butene, propadiene, methylacetylene and their mixtures
• the saturated aliphatic hydrocarbon is chosen from methane, ethane, propane, butane and mixtures thereof
• the aromatic hydrocarbon is benzene.
• the halogenated organic compound is a chlorinated organic compound chosen from chloromethanes, chloroethanes, chloropropanes, chlorobutanes, vinyl chloride, vinylidene chloride, monochloropropenes, perchlorethylene, trichlorethylene, chlorobutadiene, chlorobenzenes and mixtures thereof.
• the halogenated organic compound is a fluorinated organic compound chosen from fluoromethanes, fluoroethanes, vinyl fluoride, vinylidene fluoride, and mixtures thereof.
• the oxygenated organic compound is chosen from alcohols, chloroalcohols, chloroethers and their mixtures.
• the metal is chosen from alkali metals, alkaline earth metals, iron, nickel, copper, lead, arsenic, cobalt, titanium, cadmium, antimony, mercury, zinc, selenium, aluminum, bismuth, and mixtures thereof.
• the chlorinating agent is at least partially derived from a process for producing allyl chloride and / or a process for producing chloromethanes and / or a chlorinolysis process and or a process for oxidizing chlorinated compounds at a temperature greater than or equal to 800 ° C.
• the manufacturing processes can be carried out independently in batch mode or in continuous mode. It is preferred that at least one of the methods be conducted in a continuous mode. It is more particularly preferred that the continuous mode be used for all manufacturing processes considered.
• the chlorinating agent contains hydrogen chloride.
• 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 alcohol - AT -
• 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
• the polyhydroxylated aliphatic hydrocarbon used in the present invention includes, for example, 1,2-ethanediol, 1,2-propanediol,
• 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.
• 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.
• 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.
• the starting material and the product of the reaction can each be chlorohydrins.
• 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 chlorohydrin departure.
• Preferred chlorohydrins are chloroethanol, chloropropanol, chloropropanediol, dichloropropanol and mixtures of at least two of them. Dichloropropanol is particularly preferred.
• chlorohydrins are 2-chloroethanol, 1-chloropropan-2-ol, 2-chloropropan-1-ol, 1-chloropropane-2,3-diol, 2-chloropropane-1,3-diol. 1,3-dichloropropan-2-ol, 2,3-dichloropropan-1-ol and mixtures of at least two of them.
• the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, 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.
• the polyhydroxylated aliphatic hydrocarbon is glycerol, allyl chloride, allyl alcohol and "synthetic" glycerol are particularly preferred.
• synthetic glycerol is meant a glycerol generally obtained from petrochemical resources.
• the polyhydroxylated aliphatic hydrocarbon is ethylene glycol
• ethylene and “synthetic" ethylene glycol are particularly preferred.
• polyhydroxylated aliphatic hydrocarbon is propylene glycol
• propylene and synthetic propylene glycol are particularly preferred.
• 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.
• “natural” ethylene glycol, “natural” propylene glycol and “natural” glycerol are preferred.
• “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 corn fibers
• natural glycerol or “glycerol obtained from renewable raw materials” is intended to mean 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 reactions, trans-esterification or hydrolysis.
• oils that can be used to make natural glycerol are all common oils, such as palm, palm kernel, copra, babassu, old or new rapeseed, sunflower, maize, castor oil and cotton oils. , peanut, soybean, flax and crambe oils and all oils derived for example from sunflower or rapeseed plants obtained by genetic modification or hybridization.
• 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,
• 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.
• 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.
• 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 ⁇ g / kg and less than or equal to 1000 mg / kg, with a chlorinating agent.
• glycerol obtained from renewable raw materials.
• the process for producing chlorohydrins according to the invention may be followed by the manufacture of an epoxide.
• epoxide is used herein to describe a compound having at least one oxygen bridged on a carbon-carbon bond.
• 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 process for producing the epoxide may be followed by a process for producing epoxy resins.
• the processes from which the chlorinating agent may be derived are often associated.
• the heavy by-products of the synthesis of allyl chloride and epichlorohydrin are advantageously employed as a source of raw materials in a high temperature chlorinolysis process to produce commercially valuable materials. These facilities may, however, have other sources of raw materials. Oxidation at or above 800 ° C is used to remove chlorinated or oxygenated organic waste.
• the processes from which the chlorinating agent can be generated generate hydrogen chloride or aqueous solutions of hydrogen chloride as co-produced. These acids are generally of poor quality, containing traces of organic matter. They are advantageously engaged in the aforementioned chlorohydrin manufacturing process as such or after treatment.
• an at least partial feed of the process for the manufacture of chorhydrin by the chlorinating agent from a process for producing allyl chloride and / or a chlorinolysis process and / or a manufacturing process chloromethane and / or a process for the oxidation of chlorinated compounds at a temperature greater than or equal to 800 ° C in addition to limiting the transport of hazardous materials with removal of the costs related to these transports, allows an advantageous alternative valuation of the acids co-products in these processes.
• plant sharing between various manufacturing processes of the same product can be envisaged, which also contributes to a reduction in the costs of these processes.
• 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 as specifically disclosed in SOLVAY SA application WO 2005/054167, page 2, line 8, to page 4, line 2.
• the polyhydroxylated aliphatic hydrocarbon the polyhydroxylated aliphatic hydrocarbon ester, or mixture thereof may have an alkali and / or alkaline earth metal content may be less than or equal to 5 g / kg as described in the application entitled " A process for producing a chlorohydrin by chlorination of a polyhydroxylated aliphatic hydrocarbon deposited in the name of SOLVAY SA on the same day as the present application, the contents of which are hereby incorporated by reference.
• 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.
• the content of alkaline and / or alkaline-earth metals of the polyhydroxylated aliphatic hydrocarbon, of the ester of polyhydroxylated aliphatic hydrocarbon or mixture thereof is less than or equal to 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 case 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 ⁇ g / kg.
• the alkali metals are generally lithium, sodium, potassium and cesium, often sodium and potassium, and frequently sodium.
• 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 ⁇ g / kg.
• 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 ⁇ g / kg.
• 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 ⁇ g / kg.
• 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 ⁇ g / kg.
• 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 lower or equal to 2 mg / kg. This content is generally greater than or equal to 0.1 ⁇ g / kg.
• the alkaline-earth elements are generally magnesium, calcium, strontium and barium, often magnesium and calcium and frequently calcium.
• 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 ⁇ g / kg.
• 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 ⁇ g / kg.
• 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 ⁇ g / kg.
• 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 ⁇ g / kg.
• 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.
• 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 .
• the chlorinating agent may be hydrogen chloride may be as described in SOLVAY SA application WO 2005/054167, page 4, line 30,
• the chlorinating agent is gaseous hydrogen chloride or an aqueous solution of hydrogen chloride or a hydrogen chloride. combination of both.
• This chlorinating agent is particularly advantageous since it is often obtained as a by-product in organic synthesis of chlorination, elimination or substitution, or by combustion.
• the present invention allows recovery of this by-product.
• the chlorinating agent comes at least partially from a process for producing allyl chloride.
• the allyl chloride can be obtained by chlorination of propylene.
• the process for producing allyl chloride is then fed with at least propylene and chlorine.
• Other compounds may also be present in the feed such as non-chlorinated hydrocarbons other than propylene, partially chlorinated hydrocarbons, totally chlorinated hydrocarbons or mixtures thereof.
• the allyl chloride can be obtained by dehydrochlorination of dichloropropane.
• the process for producing allyl chloride is then fed with at least partially chlorinated hydrocarbons, preferably containing dichloropropane, in particular 1,2-dichloropropane.
• the chlorinating agent comes at least partially from a process for producing chloromethanes.
• the manufacturing process is fed with methane and / or methyl chloride and chlorine.
• the process chlorination can be thermal, photochemical or catalytic. Thermal and photochemical processes are preferred.
• the chlorinating agent comes at least partially from a chlorinolysis process.
• chlorinolysis is meant any decomposition reaction with chlorine and more particularly decomposition reactions of organic compounds, carried out at temperatures greater than or equal to 300 ° C, preferably greater than or equal to 350 ° C.
• the chlorinolysis process is fed with at least chlorine and aliphatic or aromatic hydrocarbons, saturated or unsaturated, preferably aliphatic and selected from non-chlorinated aliphatic hydrocarbons, comprising from 1 to 6 carbon atoms, partially and / or totally chlorinated aliphatic hydrocarbons having 1 to 6 carbon atoms and 1 to 14 chlorine atoms, and mixtures thereof.
• the non-chlorinated hydrocarbons are, for example, propane, propylene, methyl acetylene, methane and ethylene.
• Partially chlorinated hydrocarbons are, for example, chloroform, trichloropropanes, chloropropenes, tetrachloroethanes, trichloroethanes, acetylene chloride and tetrachloropentane.
• the totally chlorinated hydrocarbons can be selected from carbon tetrachloride, hexachloroethane, and perchlorethylene.
• An example of such a process is the process of pyrolysis of chlorinated hydrocarbons containing from one to three carbon atoms in the presence of chlorine for the production of perchlorethylene and carbon tetrachloride. Generally, these hydrocarbons do not contain other heteroatoms than chlorine.
• the chlorinating agent comes at least partially from a process for the oxidation of chlorinated compounds at a temperature greater than or equal to 800 ° C. This temperature is often greater than or equal to 900 ° C. and more particularly greater than or equal to 1000 ° C. Thereafter, this process will be referred to as a process
• the oxidation process is fed with at least one oxidizing agent and at least one chlorinated compound.
• the oxidizing agent may be selected from oxygen, chlorine oxides, nitrogen oxides, their mixtures and their mixtures with nitrogen. Water can be usefully added to the oxidizing agent especially to facilitate the oxidation of chlorinated compounds.
• the chlorinated compounds can be inorganic or organic compounds. Chlorinated organic compounds are preferred. These chlorinated organic compounds are hydrocarbons chosen from partially chlorinated hydrocarbons comprising from 1 to 10 carbon atoms and from 1 to 21 chlorine atoms, the totally chlorinated hydrocarbons comprising from 1 to 4 carbon atoms and mixtures thereof.
• chlorinated compounds from processes for producing allyl chloride, epichlorohydrin, dichloroethane, propylene oxide, vinylidene chloride, vinyl chloride, are oxidized at high temperature.
• 1-trichloroethane, chloromethanes, trichlorethylene and chlorinolysis process to enhance the energy content of chlorinated compounds in the form of CO 2 and generating hydrogen chloride in the form of aqueous solutions of hydrogen chloride (hydrochloric acid) "Technical”) that can be purified or not.
• the chlorinating agent resulting from a process for producing allyl chloride and / or a process for producing chloromethanes and / or a chlorinolysis process and or a high temperature oxidation process which feeds the manufacture of dichloropropanol contains hydrogen chloride, liquid or gaseous, preferably gaseous.
• Hydrogen chloride is particularly preferably substantially anhydrous.
• substantially anhydrous hydrogen chloride is meant hydrogen chloride whose water content is generally less than or equal to 15 mol%, preferably less than or equal to 10 mol% and particularly preferably preferred less than or equal to 8 mol%. This water content is generally greater than or equal to 0.01 ppm in mole.
• the nitrogen content of the chlorinating agent is generally greater than or equal to 0.1 ppm vol, often greater than or equal to 10 ppm vol and in particular greater than or equal to 20 ppm flight .
• This content is generally less than or equal to 50 000 ppm vol, often less than or equal to 40 000 ppm vol and in particular less than or equal to 30 000 ppm vol.
• the oxygen content of the chlorinating agent is generally greater than or equal to 0 , 1 ppm volume and often greater than or equal to 0.5 ppm vol. This content is generally less than or equal to 5% vol, often less than or equal to 2% vol and in particular less than or equal to 1% vol.
• the hydrogen content of the chlorinating agent is generally greater than or equal to 0. , 1 ppm vol and often greater than or equal to 0.5 ppm vol. This content is generally less than or equal to 0.1% vol and often less than or equal to 500 ppm vol.
• the chlorine content of the chlorinating agent is generally greater than or equal to 0 , 1 ppm vol and often greater than or equal to 0.5 ppm vol.
• This content is generally less than or equal to 2000 ppm vol, often less than or equal to 1000 ppm vol and in particular less than or equal to 500 ppm vol.
• the methane content of the chlorinating agent is generally greater than or equal to 0.1 ppm vol, often greater than or equal to 1 ppm vol and in particular greater than or equal to 5 ppm vol.
• This content is generally less than or equal to 10,000 ppm vol, often less than or equal to 5,000 ppm vol and in particular less than or equal to 40,000 ppm vol.
• the carbon monoxide content of the chlorinating agent is generally greater or equal to 0.1 ppm vol, often greater than or equal to 0.5 ppm vol and in particular greater than or equal to 1 ppm vol.
• This content is generally less than or equal to 10,000 ppm vol, often less than or equal to 5,000 ppm vol and in particular less than or equal to 4,000 ppm vol.
• the carbon dioxide content of the chlorinating agent is generally greater or equal to 0.1 ppm vol, often greater than or equal to 0.5 ppm vol and in particular greater than or equal to 1 ppm vol.
• This content is generally less than or equal to 10,000 ppm vol, often less than or equal to 5,000 ppm vol and in particular less than or equal to 4,000 ppm vol.
• the overall content of chlorinated organic products such as, for example, chloromethanes, ethyl chloride, dichloroethane, vinyl chloride and chlorobenzene, in the chlorinating agent, in not taking into account the water and nitrogen present in the chlorinating agent, is generally greater than or equal to 0.1 ppm vol, often greater than or equal to 1 ppm vol and in particular greater than or equal to 5 ppm flight .
• This content is generally less than or equal to 50,000 ppm vol, often less than or equal to 20,000 ppm vol and in particular less than or equal to 10,000 ppm vol.
• the overall content of non-chlorinated organic products such as, for example, ethylene, acetylene, ethane, propylene, methylacetylene and propane, in the chlorinating agent , without taking into account the water and nitrogen present in the chlorinating agent, is generally greater than or equal to 0.1 ppm vol, often greater than or equal to 1 ppm vol and in particular greater than or equal to 5 ppm vol.
• This content is generally less than or equal to 50,000 ppm vol, often less than or equal to 20,000 ppm vol and in particular less than or equal to 10,000 ppm vol.
• the overall content of fluorinated organic products such as, for example, vinyl fluoride, fluoroethane, vinylidene fluoride and fluoromethanes, in the chlorinating agent, by not taking account of the water and nitrogen present in the chlorinating agent, is generally greater than or equal to 0.1 ppm vol, often greater than or equal to 1 ppm vol and in particular greater than or equal to 5 ppm vol.
• This content is generally less than or equal to 500 ppm vol, often less than or equal to 20 000 ppm vol and in particular less than or equal to 100 000 ppm vol.
• the overall content of organic products comprising heteroatoms other than chlorine and fluoro such as, for example, alcohols and acids, in the chlorinating agent, without taking into account the water and nitrogen present in the chlorinating agent is generally greater than or equal to 0.1 ppm vol, often greater than or equal to 1 ppm vol and in particular greater than or equal to 5 ppm vol.
• This content is generally less than or equal to 50,000 ppm vol, often less than or equal to 20,000 ppm vol and in particular less than or equal to 10,000 ppm vol.
• the propylene content of the chlorinating agent is generally greater than or equal to 0.1 ppm vol, often greater than or equal to 1 ppm vol and in particular greater than or equal to 5 ppm vol. This content is generally less than or equal to
• the monochloropropene content of the chlorinating agent is generally greater than or equal to 0.1 ppm vol, often greater than or equal to 1 ppm vol and in particular greater than or equal to 5 ppm vol.
• This content is generally less than or equal to 5000 ppm vol, often less than or equal to 1000 ppm vol and in particular less than or equal to 500 ppm vol.
• the sum of the chloropropane contents of the chlorinating agent, without taking into account the water and nitrogen present in the chlorinating agent, is generally greater or equal to 0.1 ppm vol, often greater than or equal to 1 ppm vol and in particular greater than or equal to 5 ppm vol.
• This content is generally less than or equal to 10,000 ppm vol, often less than or equal to 4,000 ppm vol and in particular less than or equal to 3,000 ppm vol.
• the content of isopropanol, chloroalcohols and chloroethers of the chlorinating agent is generally greater than or equal to 0.1 ppm vol, often greater than or equal to 1 ppm vol and in particular greater than or equal to 5 ppm vol.
• This content is generally less than or equal to 5,000 ppm vol, often less than or equal to 4,000 ppm vol and in particular less than or equal to 3,000 ppm vol.
• the hydrogen chloride is an aqueous solution of hydrogen chloride.
• the hydrogen chloride solution content is generally at least 10% by weight. Preferably, this content is greater than or equal to 15% by weight. In this case, the content of the hydrogen chloride solution is generally at most 37% by weight.
• This second aspect allows the development of aqueous solutions of hydrogen chloride of low quality, resulting for example from the pyrolysis of chlorinated organic compounds or having been used for the pickling of metals.
• a concentrated aqueous solution of hydrogen chloride is used, generally comprising from 28 to 37% by weight of hydrogen chloride as the primary source of the chlorinating agent and said concentrated solution is separated off. for example by evaporation in at least two fractions, the first consisting essentially of anhydrous hydrogen chloride and the second comprising hydrogen chloride and water in proportions in which they form an azeotrope, said azeotrope being at a pressure of 101.3 kPa of 19 to 25% of hydrogen chloride, and 75 to 81% by weight of water, in particular of about 20% by weight of hydrogen chloride and about 80% water.
• the aqueous solution of 20% hydrogen chloride may optionally be used to absorb hydrogen chloride produced by the allyl chloride production process, the chlorinolysis process, the chloromethane production process and the process oxidation at high temperature, so as to generate an aqueous solution of hydrogen chloride at 33% by weight of hydrogen chloride.
• this aspect allows the use of a transportable chlorination agent in an easy manner while allowing an effective control of the water content in the reaction medium, particularly when the reaction between the glycerol and the chlorinating agent is carried out in several steps.
• the aqueous solution of hydrogen chloride used in this second aspect of the process according to the invention may contain compounds other than water and hydrogen chloride. These compounds can be, inter alia, chlorinated or non-chlorinated inorganic compounds and saturated organic compounds or unsaturated, non-chlorinated, partially chlorinated or totally chlorinated. These compounds may be different depending on the manufacturing process from which the aqueous solution of hydrogen chloride is derived.
• the individual contents of metals and in particular of alkali metals, alkaline earth metals, iron, nickel, copper, lead, arsenic, cobalt, titanium, cadmium, antimony, mercury, zinc, selenium aluminum and bismuth are generally greater than or equal to 0.03 ppb by weight, often greater than or equal to 0.3 ppb by weight and frequently greater than 1 ppb by weight. weight. These contents are generally less than or equal to 5 ppm by weight and preferably less than or equal to 1 ppm by weight.
• the chlorinating agent fraction which feeds the manufacture of dichloropropanol and which is derived from a process for producing allyl chloride and / or a process for chlorinolysis and / or a process for producing chloromethane and / or a high temperature oxidation process is generally greater than or equal to 0% by weight of the chlorinating agent, often greater than or equal to 10% by weight and frequently greater than or equal to at 20% by weight.
• This fraction is generally less than or equal to 100% by weight of the chlorinating agent, often less than or equal to 90% by weight and frequently less than 80% by weight.
• the reaction between the polyhydroxylated aliphatic hydrocarbon, the ester of the polyhydroxylated aliphatic hydrocarbon, or the mixture of them, and the chlorination can be carried out in a reactor as described in the application WO 2005/054167 SOLVAY SA, on page 6, lines 3 to 23.
• the reaction between the polyhydroxylated aliphatic hydrocarbon, the ester of the polyhydroxylated aliphatic hydrocarbon, or mixture thereof, 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 producing a chlorohydrin in corrosion-resistant equipment "deposited in the name of SOLVAY SA on the same day as the present application, the contents of which are hereby incorporated by reference.
• 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.
• 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.
• non-metallic materials such as high density polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene , perfluoroalkoxyalkanes and poly (perfluoropropylvinylether), polysulfones and polysulfides, graphite and impregnated graphite.
• 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 a reaction medium, as described in the application entitled “Continuous process for the manufacture of chlorhydrins" filed in the name of SOLVAY SA on the same day as the present application, the content of which is hereby incorporated by reference.
• 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.
• 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.
• 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.
• a catalyst as described in SOLVAY SA application WO 2005/054167, page 6, line 28, to page 8, line 5.
• an acid-based catalyst carboxylic acid or on a carboxylic acid derivative having an atmospheric boiling point greater than or equal to 200 ° C, in particular adipic acid and adipic acid derivatives.
• 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 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.
• a temperature of at least 20 ° C and not more than 160 ° C a pressure of not less than 0.3 bar and not more than 100 bar, and a time of stay of not less than 1 hour and not more than 50 hours.
• 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 the presence of a solvent as described in the application WO 2005/054167 of SOLVAY SA, on page 11, lines 12 to 36.
• 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.
• 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.
• the reaction between the polyhydroxylated aliphatic hydrocarbon and the chlorinating agent can be carried out in the presence of a liquid phase comprising heavy compounds other than hydrocarbon polyhydroxylated aliphatic, as described in the application entitled "Process for manufacturing a chlorohydrin in a liquid phase" filed in the name of SOLVAY SA on the same day as the present application, the contents of which are hereby incorporated by reference.
• 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.
• the reaction between the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, 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.
• reagents is meant the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, and the chlorinating agent.
• 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.
• polyhydroxylated aliphatic hydrocarbon is glycerol
• 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.
• 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.
• chlorohydrin is 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.
• 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.
• By-products include, for example, partially chlorinated and / or esterified polyhydroxylated aliphatic hydrocarbon oligomers.
• the polyhydroxylated aliphatic hydrocarbon is glycerol
• 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 separation of the chlorohydrin and of 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 page 16, line 35 and to the 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, the water and the by-products of the invention. reaction.
• the separation of the chlorohydrin and the other compounds from the reaction medium can be carried out according to the methods described in the patent application EP 05104321.4 filed in the name of SOLVAY. SA, 20/20172005, 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.
• a process for producing a chlorohydrin in which (a) a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon or a mixture are subjected to of them, 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 a 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.
• 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.
• 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 may be carried out according to the modes as described in the application entitled "Process for the manufacture of a chlorohydrin" deposited in the name of SOLVAY SA, the same day as the present application, and the contents of which are hereby incorporated by reference .
• 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 aliphatic hydrocarbon polyhydroxylated. Mention is more particularly made of a process in which the polyhydroxylated aliphatic hydrocarbon is glycerol and the chlorohydrin is dichloropropanol.
• 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.
• 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).
• the separation of the chlorohydrin and the other compounds from the reaction medium of chlorination of the polyhydroxylated aliphatic hydrocarbon can be carried out according to the modes as described in the application entitled "Process of conversion of polyhydroxylated aliphatic hydrocarbons to chlorhydrins "deposited in the name of SOLVAY SA on the same day as the present application and the contents of which are hereby incorporated by reference.
• a method of preparation of 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 chlorinating agent so as to obtain a mixture containing chlorohydrin, chlorohydrin esters and water, (b) subjecting at least a fraction of the mixture obtained in step (a) to a distillation and / or stripping treatment so as to obtain a concentrated portion in water, chlorohydrin and chlorohydrin esters and (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 portion concentrated to chlorohydrin and chlorohydrin esters and contains less than 40% by weight of water.
• the separation operation is more particularly a settling.
• 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 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.
• 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.
• step (b) 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.
• the treatment of step (b) is a separation operation selected from the settling, filtration, centrifugation, extraction, washing, evaporation, stripping, distillation, adsorption or combinations of at least two of them.
• the chlorohydrin when the chlorohydrin is chloropropanol, it is generally used in the form of a mixture of compounds comprising the isomers of 1-chloropropan-2-ol and 2-chloropropane-1. ol.
• This mixture generally contains more than 1% by weight of the two isomers, preferably more than 5% by weight and more particularly more than 50%.
• the mixture usually contains less than 99.9% by weight of the two isomers, preferably less than 95% by weight and most preferably less than 90% by weight.
• the other constituents of the mixture may be compounds derived from chloropropanol production processes, such as residual reagents, reaction by-products, solvents and in particular water.
• the mass ratio between the isomers 1-chloropropan-2-ol and 2-chloropropane-1-ol is usually greater than or equal to 0.01, preferably greater than or equal to 0.4. This ratio is usually less than or equal to 99 and preferably less than or equal to 25.
• the chlorohydrin 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.
• the chlorohydrin 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 from the manufacturing processes of the chloropropanediol, 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.
• the chlorohydrin when 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 generally contains more than 1% by weight of the two isomers, preferably more than 5% by weight and more particularly more than 50%.
• the mixture usually contains less than 99.9% by weight of the two isomers, preferably less than 95% by weight and most preferably less than 90% by weight.
• the other constituents of the mixture may be compounds from dichloropropanol production processes, such as residual reagents, reaction by-products, solvents and in particular water.
• the weight ratio between the 1,3-dichloropropan-2-ol and 2,3-dichloropropan-1-ol isomers is usually greater than or equal to 0.01, often greater than or equal to 0.4, frequently greater than or equal to 1 , 5, preferably greater than or equal to 3.0, more preferably greater than or equal to 7.0 and most preferably greater than or equal to 20.0.
• This ratio is usually less than or equal to 99 and preferably less than or equal to 25.
• the reaction between the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, and the chlorinating agent can take place in the presence of an organic acid.
• the organic acid can 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 an organic acid mixture derived from the process for producing the polyhydroxylated aliphatic hydrocarbon and an organic acid not derived from the process for producing the polyhydroxylated aliphatic hydrocarbon.
• the esters of the polyhydroxylated aliphatic hydrocarbon can come from the reaction between the aliphatic hydrocarbon polyhydroxy and the organic acid, before, during or in the steps following the reaction with the chlorinating agent.
• 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 20/20172005 filed in the name of the Applicant, and whose content is hereby incorporated by reference.
• the content of halogenated ketone can be reduced by subjecting the chlorohydrin obtained in the process according to the invention to azeotropic distillation in the presence of water or by subjecting the chlorohydrin to a dehydrochlorination treatment as described in this application, on page 4, line 1, on page 6, line 35.
• 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 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.
• 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 chlorination agent, the medium reaction containing at least 10 g of chlorohydrin per kg of reaction medium, to a subsequent chemical reaction without intermediate treatment.
• Epoxide manufacturing 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) is added a basic compound to at least one of the steps subsequent to step (a); ) so that he at least partially reacts with the chlorohydrin, the chlorohydrin esters, the chlorinating agent and the organic acid to form epoxide
• the process for the manufacture of chlorohydrin can be integrated into an overall scheme for the manufacture of an epoxide as described in the application entitled “Process for the manufacture of a epoxide from a chlorohydrin "deposited in the name of SOLVAY SA the same day as the present application, and whose content is here incorporated by reference.
• 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.
• the various processes involved in the process for producing a chlorohydrin according to the invention may or may not be part of an integrated process for producing chlorinated organic products. An integrated method is preferred.
• the invention also relates to an installation for implementing an integrated process comprising: (a) an allyl chloride production unit and / or a chloromethane production unit and / or a chlorinolysis unit and / or an oxidation unit chlorinated compounds from which a chlorinating agent containing hydrogen chloride
• This installation may include:
• the various manufacturing units are preferably distributed on the same industrial site or on nearby sites, and more preferably on the same site.
• the industrial scheme comprising these units on the same site or on nearby sites is particularly advantageous, such as, for example, a unit according to the above-mentioned method of manufacturing chlorohydrin in the vicinity of allyl chloride production units and epoxides to which there may be added a chlorinolysis unit and / or a chloromethane production unit and / or a high temperature oxidation unit of chlorinated compounds.
• nearby sites it is meant in particular to designate industrial sites close enough that the transport of materials between facilities can be done economically by collectors.
• the polyhydroxylated aliphatic hydrocarbon is preferably glycerol
• the chlorohydrin is preferably dichloropropanol
• the epoxide is preferably epichlorohydrin.
• the epoxide is epichlorohydrin, it can be used in the manufacture of epoxy resins.
• Figure 1 shows a particular scheme of installation used to implement the method according to the invention, in the case where the polyhydroxylated aliphatic hydrocarbon is glycerol, the chlorohydrin is dichloropropanol and the epoxide is epichlorohydrin.
• a dehydrochlorination unit of dichloropropanol (1) is supplied with dichloropropanol via line (2) and dehydrochlorination agent via line (3).
• Epichlorohydrin is withdrawn via line (4) and organic compounds other than epichlorohydrin via line (5). At least a fraction these compounds can feed a chlorinolysis plant (21) via the line (33) and / or a high temperature oxidation plant of chlorinated compounds (23) via the line (34).
• Epichlorohydrin feeds an epoxy resin manufacturing unit (8) via line (6) and / or a polyglycerol production unit (9) via line (7).
• the dichloropropanol is from a hypochlorination unit of allyl chloride (10) via line (11) and / or a glycerol chlorination unit (12) via line (13).
• the glycerol chlorination unit (12) is fed with crude and / or purified glycerol via line (14).
• the crude / and / or purified glycerol comes from a biodiesel production unit (15) from which biodiesel is also withdrawn via the line (37) and which is fed with vegetable and / or animal fats and / or oils via the line ( 16) and alcohol, preferably methanol via line (17).
• the glycerol chlorination unit (12) is supplied with hydrogen chloride and / or with an aqueous solution of hydrogen chloride via line (18).
• the hydrogen chloride and / or the aqueous solution of hydrogen chloride come from an allyl chloride production unit by chlorination of the propylene (19) via the line (20) and / or a production unit of chloromethanes (35) via line (36) and / or a chlorinolysis unit (21) via line (22) and / or a high temperature oxidation unit (23) via line (24).
• Allyl chloride is withdrawn from the unit (19) and at least one fraction of this allyl chloride is fed to the hypochlorination unit (10) via line (25).
• the allyl chloride (19) production unit extracts organic compounds other than allyl chloride via line (26), at least one fraction of which serves to feed the chlorinolysis unit (21) via the line (27) and / or the high temperature oxidation unit of chlorinated compounds (23) via line (28).
• the chlorinolysis unit (21) is withdrawn from perchlorethylene and carbon tetrachloride via line (29) and organic compounds other than perchlorethylene and carbon tetrachloride via line (30) and at least a fraction of these are removed.
• the compounds can be recycled to the chlorinolysis unit via the line (31) and / or fed to the high temperature oxidation unit of chlorinated compounds (23) via the line (32).
• Chlorinolysis and high temperature oxidation units of chlorinated compounds can be fed with organic products from other manufacturing units than those mentioned.
• the dichloropropanol production unit can be fed with hydrogen chloride and / or hydrochloric acid from manufacturing processes other than those mentioned above.
• the benefits of this scheme include:
• Process water is, for example, water from pumps or ejectors used to maintain the vacuum in the facilities. It can also be water obtained after decantation of organic.

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  • 2006-05-19 EP EP06755270A patent/EP1885674A1/fr not_active Withdrawn
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  • 2006-05-19 EP EP06755267A patent/EP1885671A1/fr not_active Withdrawn
  • 2006-05-19 EP EP06755271A patent/EP1885706A2/fr not_active Withdrawn
  • 2006-05-19 EP EP06755264A patent/EP1890988A2/fr not_active Withdrawn
  • 2006-05-19 US US11/914,862 patent/US7615670B2/en not_active Expired - Fee Related
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  • 2006-05-19 CA CA002608937A patent/CA2608937A1/en not_active Abandoned
  • 2006-05-19 CA CA002608722A patent/CA2608722A1/en not_active Abandoned
  • 2006-05-19 TW TW095117970A patent/TW200700403A/zh unknown
  • 2006-05-19 TW TW095117946A patent/TWI313261B/zh not_active IP Right Cessation
  • 2006-05-19 CA CA002608732A patent/CA2608732A1/en not_active Abandoned
  • 2006-05-19 CA CA002608723A patent/CA2608723A1/en not_active Abandoned
  • 2006-05-19 US US11/914,836 patent/US7893193B2/en active Active
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  • 2006-05-19 EP EP06763200A patent/EP1891032A2/fr not_active Withdrawn
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  • 2006-05-19 EP EP10182403A patent/EP2284163A3/en not_active Withdrawn
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  • 2006-05-19 EP EP06755262.0A patent/EP1885705B1/fr active Active
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  • 2006-05-19 EA EA200702561A patent/EA200702561A1/ru unknown
  • 2006-05-19 EP EP10182309A patent/EP2275417A3/en not_active Withdrawn
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  • 2006-05-19 CA CA002608953A patent/CA2608953A1/en not_active Abandoned
  • 2006-05-19 EA EA200702553A patent/EA200702553A1/ru unknown
  • 2006-05-19 EP EP06755269.5A patent/EP1885673B1/fr not_active Not-in-force
  • 2006-05-19 EP EP10182191.6A patent/EP2284162B1/en active Active
  • 2006-05-19 EP EP06755263A patent/EP1904427A2/en not_active Withdrawn
  • 2006-05-19 US US11/914,891 patent/US8106245B2/en not_active Expired - Fee Related
  • 2006-05-19 EP EP06763198A patent/EP1885678A1/fr not_active Withdrawn
  • 2006-05-19 JP JP2008511717A patent/JP5259390B2/ja not_active Expired - Fee Related
  • 2006-05-19 JP JP2008511714A patent/JP2008545640A/ja active Pending
  • 2006-05-19 CN CN2006800006073A patent/CN101006068B/zh not_active Ceased
  • 2006-05-19 CA CA002608719A patent/CA2608719A1/en not_active Abandoned
  • 2006-05-19 EA EA201300253A patent/EA201300253A1/ru unknown
  • 2006-05-19 TW TW095117952A patent/TW200700401A/zh unknown
  • 2006-05-19 US US11/914,879 patent/US8173823B2/en active Active
  • 2006-05-19 CN CN201110379336XA patent/CN102531841A/zh active Pending
  • 2006-05-19 BR BRPI0610799-0A patent/BRPI0610799A2/pt not_active IP Right Cessation
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  • 2006-05-19 US US11/915,053 patent/US8389777B2/en not_active Expired - Fee Related
  • 2006-05-19 US US11/915,067 patent/US20080200701A1/en not_active Abandoned
  • 2006-05-19 KR KR1020077029668A patent/KR101345965B1/ko active IP Right Grant
  • 2006-05-19 CA CA2608946A patent/CA2608946C/en not_active Expired - Fee Related
  • 2006-05-19 US US11/914,874 patent/US7906692B2/en not_active Expired - Fee Related
  • 2006-05-19 WO PCT/EP2006/062437 patent/WO2006100311A2/fr not_active Application Discontinuation
  • 2006-05-19 MY MYPI20062337A patent/MY148295A/en unknown
  • 2006-05-19 CN CN2012100221306A patent/CN102603475A/zh active Pending
  • 2006-05-19 CN CN2012100221382A patent/CN102659511A/zh active Pending
  • 2006-05-19 BR BRPI0610745-1A patent/BRPI0610745A2/pt not_active Application Discontinuation
  • 2006-05-19 JP JP2008511728A patent/JP5280842B2/ja not_active Expired - Fee Related
  • 2006-05-19 BR BRPI0610744-3A patent/BRPI0610744A2/pt not_active Application Discontinuation
  • 2006-05-19 MX MX2007014527A patent/MX2007014527A/es active IP Right Grant
  • 2006-05-19 WO PCT/EP2006/062463 patent/WO2006106154A1/fr not_active Application Discontinuation
  • 2006-05-19 CN CN200680000523XA patent/CN1993306B/zh not_active Expired - Fee Related
  • 2006-05-19 JP JP2008511713A patent/JP5777268B2/ja active Active
  • 2006-05-19 TW TW095117942A patent/TWI333945B/zh not_active IP Right Cessation
  • 2006-05-19 EA EA200702555A patent/EA200702555A1/ru unknown
  • 2006-05-19 EA EA200702546A patent/EA200702546A1/ru unknown
  • 2006-05-19 BR BRPI0610751-6A patent/BRPI0610751A2/pt not_active Application Discontinuation
  • 2006-05-19 CA CA002608956A patent/CA2608956A1/en not_active Abandoned
  • 2006-05-19 US US11/914,868 patent/US8344185B2/en not_active Expired - Fee Related
  • 2006-05-19 WO PCT/EP2006/062448 patent/WO2006106153A2/fr not_active Application Discontinuation
  • 2006-05-19 EA EA200702550A patent/EA018479B1/ru not_active IP Right Cessation
  • 2006-05-19 CN CN2006800005511A patent/CN101098843B/zh not_active Expired - Fee Related
  • 2006-05-19 KR KR1020077029658A patent/KR100982605B1/ko active IP Right Grant
  • 2006-05-19 TW TW095117963A patent/TWI320037B/zh not_active IP Right Cessation
  • 2006-05-19 CA CA2608961A patent/CA2608961C/en not_active Expired - Fee Related
  • 2006-05-19 BR BRPI0610748-6A patent/BRPI0610748A2/pt not_active IP Right Cessation
  • 2006-05-19 BR BRPI0610791-5A patent/BRPI0610791A2/pt active Search and Examination
  • 2006-05-19 WO PCT/EP2006/062445 patent/WO2006100316A1/fr not_active Application Discontinuation
  • 2006-05-19 TW TW095117962A patent/TWI332493B/zh not_active IP Right Cessation
  • 2006-05-19 WO PCT/EP2006/062461 patent/WO2006100319A1/fr not_active Application Discontinuation
  • 2006-05-19 MX MX2007014516A patent/MX2007014516A/es not_active Application Discontinuation
  • 2006-05-19 WO PCT/EP2006/062444 patent/WO2006100315A2/fr not_active Application Discontinuation
  • 2006-05-19 KR KR1020077029670A patent/KR101337048B1/ko not_active IP Right Cessation
  • 2006-05-19 WO PCT/EP2006/062439 patent/WO2006100313A2/fr not_active Application Discontinuation
  • 2006-05-19 TW TW095117967A patent/TWI322142B/zh active
  • 2006-05-19 EA EA200702565A patent/EA200702565A1/ru unknown
  • 2006-05-19 EP EP06763189A patent/EP1885677A2/fr not_active Withdrawn
  • 2006-05-19 KR KR1020077029659A patent/KR100982618B1/ko not_active IP Right Cessation
  • 2006-05-19 CA CA002608720A patent/CA2608720A1/en not_active Abandoned
  • 2006-05-19 MY MYPI20062328A patent/MY158842A/en unknown
  • 2006-05-19 EA EA200702554A patent/EA200702554A1/ru unknown
  • 2006-05-19 BR BRPI0610746-0A patent/BRPI0610746A2/pt not_active IP Right Cessation
  • 2006-05-19 EA EA200702551A patent/EA200702551A1/ru unknown
  • 2006-05-19 TW TW095117957A patent/TWI332940B/zh not_active IP Right Cessation
  • 2006-05-19 US US11/915,056 patent/US7557253B2/en not_active Expired - Fee Related
  • 2006-05-19 EA EA200702562A patent/EA013681B1/ru not_active IP Right Cessation
  • 2006-05-19 JP JP2008511725A patent/JP2008540613A/ja active Pending
  • 2006-05-19 WO PCT/EP2006/062459 patent/WO2006100318A2/fr not_active Application Discontinuation
  • 2006-05-19 JP JP2008511730A patent/JP2008540617A/ja active Pending
  • 2006-05-19 TW TW095117968A patent/TWI388542B/zh not_active IP Right Cessation
  • 2006-05-19 MX MX2007014530A patent/MX2007014530A/es not_active Application Discontinuation
  • 2006-05-19 TW TW095117961A patent/TWI320036B/zh not_active IP Right Cessation
  • 2006-05-19 KR KR1020077029669A patent/KR101331367B1/ko not_active IP Right Cessation
  • 2006-05-19 US US11/915,046 patent/US20080194850A1/en not_active Abandoned
  • 2006-05-19 JP JP2008511727A patent/JP5551359B2/ja not_active Expired - Fee Related
  • 2006-05-19 EP EP06755272A patent/EP1885675A1/fr not_active Withdrawn
  • 2006-05-19 MX MX2007014514A patent/MX2007014514A/es active IP Right Grant
  • 2006-05-19 EP EP06755273A patent/EP1885676A2/fr not_active Withdrawn
  • 2006-05-19 CA CA002608816A patent/CA2608816A1/en not_active Abandoned
  • 2006-05-19 WO PCT/EP2006/062442 patent/WO2006100314A1/fr not_active Application Discontinuation
  • 2006-05-19 WO PCT/EP2006/062438 patent/WO2006100312A2/en not_active Application Discontinuation

Non-Patent Citations (1)

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