EP1885674A1 - Method for making chlorohydrin in corrosion-resistant equipment - Google Patents
Method for making chlorohydrin in corrosion-resistant equipmentInfo
- Publication number
- EP1885674A1 EP1885674A1 EP06755270A EP06755270A EP1885674A1 EP 1885674 A1 EP1885674 A1 EP 1885674A1 EP 06755270 A EP06755270 A EP 06755270A EP 06755270 A EP06755270 A EP 06755270A EP 1885674 A1 EP1885674 A1 EP 1885674A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aliphatic hydrocarbon
- polyhydroxylated aliphatic
- chlorohydrin
- process according
- alloys
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
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- 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
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- 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
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- 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. More specifically, the invention relates to a process for producing a chlorohydrin in equipment made of corrosion resistant materials.
- Chlorohydrins are reaction intermediates in the manufacture of epoxides and derived products.
- 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 application WO 2005/054167 of SOLVAY SA describes a process for the manufacture of dichloropropanol by reaction between glycerol and hydrogen chloride in the presence of an acid such as adipic acid as catalyst.
- the reaction is carried out in a reactor made of or covered with a material resistant to the chlorinating agent under the reaction conditions.
- the use of this type of material is, however, limited to the glycerol chlorination reactor.
- the invention relates to a process for producing a chlorohydrin comprising: (a) 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 (b) at least one other step performed in equipment, made of or covered with chlorinating agent resistant materials, under the conditions of completion of this step.
- the invention therefore also relates to the use of equipment, made of or coated with chlorine-resistant materials in a process for the manufacture of a chlorohydrin comprising a step in which a polyhydroxylated aliphatic hydrocarbon, an ester is subjected to of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof, to a reaction with a chlorinating agent containing hydrogen chloride, in at least one step other than the reaction step.
- Water can be water generated by the reaction between the polyhydroxylated aliphatic hydrocarbon and the chlorinating agent or water introduced into the process.
- the invention finally relates to a plant for the manufacture of a chlorohydrin comprising: (a) a part in which a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, is subjected to reaction with a chlorinating agent containing 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 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 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. - AT -
- 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, cyclohexanedimethanol, 1,2,3-propanetriol (also known as "glycerol” or "glycerin”), and mixtures thereof.
- 1,2-ethanediol ethylene glycol
- 1,2-propanediol propylene glycol
- 1,3-propanediol 1,3-propanedi
- 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 polyhydroxylated aliphatic hydrocarbon esters 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 beforehand.
- process for producing chlorohydrin examples 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 starting chlorohydrin.
- 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 is meant a glycerol generally obtained from petrochemical resources.
- polyhydroxylated aliphatic hydrocarbon is ethylene glycol
- ethylene and “synthetic" ethylene glycol are particularly preferred.
- synthetic ethylene glycol is meant an ethylene glycol generally obtained from petrochemical resources.
- 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.
- Another method is for example the catalytic hydrogenolysis of xylitol obtained by hydrogenation of xylose.
- the xylose can for example be obtained by hydrolysis of the hemicellulose contained in the corn fibers.
- glycerol obtained from renewable raw materials is meant in particular glycerol obtained during the manufacture of biodiesel or glycerol obtained during transformations of fats or oils of vegetable or animal origin in general such as saponification, transesterification or hydrolysis reactions.
- 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.
- partially modified oils for example by polymerization or oligomerization, for example the "standolies" of linseed oil, sunflower oil and blown vegetable oils.
- a particularly suitable glycerol can be obtained during the processing of animal fats.
- Another particularly suitable glycerol can be obtained during the manufacture of biodiesel.
- a third particularly suitable glycerol can be obtained during the transformation of fats or oils, animal or vegetable by trans-esterification in the presence of a heterogeneous catalyst, as described in documents FR 2752242, FR 2869612 and FR More specifically, the heterogeneous catalyst is chosen from mixed oxides of aluminum and zinc, mixed oxides of zinc and titanium, mixed oxides of zinc, titanium and aluminum, and mixed oxides of bismuth and of aluminum, and the heterogeneous catalyst is implemented in the form of a fixed bed. The latter process may be a biodiesel manufacturing process.
- 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.
- 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 polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them can be a crude product or a purified product, such as specifically disclosed in the application
- the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them may be a polyhydroxylated aliphatic hydrocarbon whose alkali and / or alkaline earth metals may be less than or equal to 5 g / kg as described in the application entitled "Process of manufacture of a chlorohydrin by chlorination of a polyhydroxylated aliphatic hydrocarbon "deposited in the name of SOLVAY SA on the same day as the present application, the contents of which are hereby incorporated by reference.
- the alkali metals can be selected from lithium, sodium, potassium, rubidium and cesium and the alkaline earth metals can be selected from magnesium, calcium, strontium and barium.
- 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 ⁇ 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, the polyhydric aliphatic hydrocarbon ester hydroxyl, or a 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 less than 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 lower 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 on page 6, line 2.
- a chlorinating agent which may be aqueous hydrochloric acid or preferably anhydrous hydrogen chloride.
- the hydrogen chloride may be derived from a process for the pyrolysis of chlorinated organic compounds such as, for example, vinyl chloride production, a process for the manufacture of 4,4-methylenediphenyl diisocyanate (MDI) or toluene diisocyanate (TDI), metal stripping processes or a reaction between an inorganic acid such as sulfuric or phosphoric acid and a metal chloride such as sodium chloride, potassium chloride or calcium chloride.
- MDI 4,4-methylenediphenyl diisocyanate
- TDI toluene diisocyanate
- 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.
- the chlorinating agent is gaseous hydrogen chloride or an aqueous solution of hydrogen chloride or a combination of both.
- the hydrogen chloride may be an aqueous solution of hydrogen chloride or preferably anhydrous hydrogen chloride, resulting from a chlorine-producing plant. allyl and / or manufacture of chloromethanes and / or chlorinolysis and / or high temperature oxidation of chlorinated compounds as described in the application entitled "Process for producing a chlorohydrin by reaction between a polyhydroxylated aliphatic hydrocarbon and a chlorinating agent "filed on behalf 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 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.
- organic hydrocarbon compound which is selected from aromatic hydrocarbons, saturated or unsaturated aliphatic and mixtures thereof.
- 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.
- 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.
- halogenated organic compound which is a fluorinated organic compound selected from fluoromethanes, fluoroethanes, vinyl fluoride, vinylidene fluoride, and mixtures thereof.
- an oxygenated organic compound which is chosen from alcohols, chloroalcohols, chloroethers and their mixtures
- a metal chosen from alkali metals, alkaline-earth metals, iron, nickel, copper, lead, arsenic, cobalt, titanium, cadmium, antimony, mercury, zinc, selenium, aluminum, bismuth, and mixtures thereof.Mention is more particularly made of a process in which the chlorinating agent is derived at least partially from a process for the production of chlorine. allyl and / or a process for producing chloromethanes and / or a chlorinolysis process and / or a process for the oxidation of chlorinated compounds at a temperature greater than or equal to 800 ° C.
- hydrogen chloride is a aqueous solution of hydrogen chloride and does not include gaseous hydrogen chloride.
- 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 SOLVAY SA application WO 2005/054167, on page 6, lines 3 to 23.
- 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 a carboxylic acid derivative having a boiling point atmospheric greater than or equal to 200 ° C, in particular adipic acid and derivatives of adipic acid.
- 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. Mention is especially made of a temperature of at least 20 ° C and at most 160 ° C, a pressure of at least 0.3 bar and at most 100 bar, and a residence time at least 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 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.
- 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 the polyaliphatic hydrocarbon.
- hydroxylated as described in the application entitled “Process for producing 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 aliphatic hydrocarbon polyhydroxylated and whose boiling point under 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 preferentially 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.
- the polyhydroxylated aliphatic hydrocarbon is glycerol
- 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.
- 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 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 steps (a) and (b) of the method 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.
- 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.
- EP 05104321.4 filed in the name of SOLVAY SA on May 20, 2005, the contents of which are hereby incorporated by reference.
- 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 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.
- 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 reaction with hydrogen chloride 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 from 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 the chloride concentrations of hydrogen / 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 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.
- 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.
- 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 from a polyhydroxylated aliphatic hydrocarbon 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 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 of the other compounds from the reaction medium of chlorination of the polyhydroxylated aliphatic hydrocarbon can be carried out according to the modes as described in the application entitled "Process of 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 process for preparing a chlorohydrin comprising the following steps: (a) reacting a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, with an agent chlorination process so as to obtain a mixture containing chlorohydrin, chlorohydrin esters and water, (b) subjecting at least a fraction of the mixture obtained in step (a) to a distillation treatment and / or stripping so as to obtain a concentrated portion of water, chlorohydrin and chlorohydrin esters and (c) subjecting at least a fraction of the portion obtained in step (b) to a separation operation in the presence of minus an additive so as to obtain a concentrated portion of chlorohydrin and chlorohydrin esters and which contains less than 40% by weight of water.
- the separation operation is more particularly a settling.
- 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.
- 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) 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.
- 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 weight ratio between the isomers 1-chloropropane-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 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 derived from chloropropanediol production processes, such as residual reagents, reaction by-products, solvents and in particular water.
- the weight ratio between the isomers 1-chloropropane-2,3-diol and 2-chloropropane-1,3-diol is usually greater than or equal to 0.01, preferably greater than or equal to 0.4. This ratio is usually less than or equal to 99 and preferably less than or equal to 25.
- 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 all especially 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.
- 2,3-dichloropropan-1-ol 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, so 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 chlorination reaction of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them can be carried out in the presence 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 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 20/20172005 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 chlorhdyrine obtained in the process according to the invention to azeotropic distillation in the presence of water or by subjecting the chlorohydrin to a dehydrochlorination treatment as described in this application, on page 4, line 1, 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.
- 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 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.
- 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 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 having the same composition as the reaction medium obtained in step (a), to one or more treatments in subsequent steps in step (a) and (c) adding a basic compound to at least one of the steps subsequent to step (a) to react at least partially with the chlorohydrin, the chlorohydrin esters, the chlorine 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.
- 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 other step is, for example, a stage of storage, supply, sampling, transfer, chemical treatment or physical treatment of compounds used or produced in the process.
- process for producing chlorohydrin Examples of these steps have been described above.
- the storage steps there may be mentioned, for example, the storage of the chlorinating agent containing hydrogen chloride and the polyhydroxylated aliphatic hydrocarbon, before use, the storage of purges before treatment, the storage of chlorohydrin produced, the storage of the catalyst and its preparations.
- the chemical treatment steps there may be mentioned, for example, a hydrolysis treatment for recovering the catalyst and a treatment for dissolving the catalyst.
- the physical treatment steps there may be mentioned, for example, the separation operations by stripping, distillation, evaporation, extraction, decantation and filtration, the heat exchange, heating and cooling operations.
- the steps of supply, withdrawal or transfer there may be mentioned, for example, operations for recycling, purging and discharge of effluents, the transport of fluids between the various pieces of equipment in which are performed chemical reactions, storage and chemical and physical treatments.
- equipment is understood to mean containers in which compound storage, chemical reactions and / or physical operations are carried out, the pipes and fittings connecting these containers, the sealing parts at the connections, the instruments necessary for the transfer of compounds between receptacles, instruments and measuring equipment of the various parameters necessary for the control of storage, the transfer of compounds and the carrying out of chemical reactions and physical operations.
- low temperature is meant a temperature which is less than or equal to 110 ° C, often less than or equal to 100 ° C and more particularly less than or equal to 95 ° C. This low temperature is generally greater than or equal to 0 ° C, frequently greater than or equal to 5 ° C and more particularly greater than or equal to 10 ° C.
- Equipment used at low temperature are, for example, storage equipment for acidic raw materials and chlorohydrin produced and decanters.
- High temperature means a temperature which is greater than 110 ° C. This high temperature is generally less than or equal to 200 ° C., frequently less than or equal to 160 ° C. and more particularly less than or equal to 140 ° C.
- Equipment used at high temperature are, for example, the reactors where the chlorination reaction of the polyhydroxylated aliphatic hydrocarbon is carried out, the treatment of purges, the recovery of the catalyst and the preparation of the catalyst, the heat exchangers, the apparatus separation by stripping, distillation, evaporation, extraction and filtration.
- low pressure is meant a pressure which is less than or equal to 3 bar absolute, often less than or equal to 2 bar and more preferably less than or equal to 1.5 bar. This low pressure is generally greater than or equal to 0.01 bar absolute, frequently greater than or equal to 0.05 bar and more preferably greater than or equal to 0.1 bar.
- Equipment used at low pressure are, for example, separating apparatus by stripping, distillation, evaporation, extraction and filtration.
- high pressure is meant a pressure which is greater than 3 bar absolute, often greater than or equal to 5 bar and more particularly greater than or equal to 7 bar This high pressure is generally less than or equal to 50 bar absolute, frequently less than or equal to at 20 bar and more preferably less than or equal to 10 bar.
- Equipment used at high pressure are, for example, the reactors in which the chlorination reaction of the polyhydroxylated aliphatic hydrocarbon is carried out, separation apparatuses by stripping, distillation, evaporation and filtration.
- the equipment may be covered with or made of chlorine-resistant material under the operating conditions of such equipment.
- the choice of the type of protection, by covering with or by realization in a material resistant to chlorinating agents depends on many factors related to the chlorinating agent, the nature and the method of implementation of the material resistant to chlorinating agents and the characteristics of the equipment to be protected.
- the factors related to the chlorinating agent are, for example, its chemical nature (chlorine, hydrogen chloride), its physical state (liquid, gas, in aqueous solution) and its purity (presence of water).
- Equipment factors are, for example, shape, size, complexity and access to the surfaces of the equipment to be protected.
- Suitable materials include, for example, metallic materials and non-metallic materials.
- Metallic materials include tantalum and tantalum alloys, zirconium and zirconium alloys, titanium and titanium alloys, platinum and platinum group metals, silver and alloys. silver-gold - palladium with a minimum of 30% gold, gold and gold-silver alloys and gold-platinum alloys, molybdenum and molybdenum alloys, nickel-molybdenum alloys, nickel-chromium-molybdenum alloys, copper (Silicon-bronze) alloys, copper-tantalum and copper-niobium alloys, tin-antimony alloys containing 5% antimony, tin-nickel alloys, niobium and niobium-tantalum alloys.
- platinum group metals include rhodium, iridium, ruthenium, palladium and osmium.
- metals and their alloys can be used either in the mass or in the form of a clade or by any method of recovery.
- non-metallic materials mention may be made of high-density polyethylene, elastomers based on fluoroelastomers, thermoplastics based on polypropylene, fluoropolymers, copolymers ABS (acrylonitrile-butadiene-styrene), acrylonitrile copolymer (40% ) -vinylchloride (60%), polysulfones, polyphenylene sulfides and polyphenylsulfones, glass-resin laminates based on polyester resins, phenolic resins, furan resins, epoxy resins and vinylester resins, based on ceramics alumina and corundum, metallo-ceramic materials based on hafnium carbide and titanium alloy, refractory materials based on silicon carbide, silica, aluminum silicates (with high silica content), zirconium silicate, zirconium oxide and sillimanite (AliO 3 -SiO
- Impregnated graphite polytetrafluoroethylene
- carbon, glass, quartz, enamel, porcelain, sandstone and anti-acid brick may also be suitable as non-metallic materials.
- Enamel can be used as the steel covering material, and the chlorinator resistant material is enamelled steel.
- polymers polyolefins such as high density polyethylene and polypropylene and in particular thermoplastics based on fluorinated polymers, polymers comprising sulfur such as polysulfones or polysulfides, in particular aromatic, graphite and impregnated graphite are well suited .
- thermoplastics based on fluoropolymers polyvinylidene fluoride, polytetrafluoroethylene, perfluoroalkoxyalkanes, ethylene-terafluoroethylene copolymers, tetrafluoroethylene-perfluoromethylvinylether copolymers and tetrafluoroethylenehexafluoropropylene copolymers are suitable.
- the polymers can be used in the mass state or reinforced with an envelope (steel, hooping).
- those based on epoxy resins or phenolic resins are particularly suitable.
- those based on epoxy resins or phenolic resins are particularly suitable.
- heat exchangers and pumps, graphite, impregnated or not, is particularly well suited.
- heat exchangers for heating or evaporation of the process fluids the impregnation with polytetrafluoroethylene is particularly well suited.
- Enamelled steel, tantalum, gold and perfluorinated polymers are well suited for the recovery or production of equipment operating at high temperatures.
- Polyolefins, fluoropolymers and metal alloys are well suited for the recovery or production of equipment operating at low temperatures.
- the polyhydroxylated aliphatic hydrocarbon is preferably glycerol and the chlorohydrin is preferably dichloropropanol.
- 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.
- Example 1 (not in accordance with the invention) Corrugated samples of Ti Gr 261 and Monel 400 were placed at 120 ° C. and for 90 days in a glycerol liquid hydrochlorination reaction medium constituted by 20% of dichloropropanol, 18% of glycerol monochlorohydrin and 2% of glycerol. 6% mono and polychlorinated glycerol oligomers, 6% water, 0.8% HCl, the remainder being the carboxylic acid catalyst and its esters. The test pieces were completely dissolved in the reaction medium.
Abstract
The invention concerns a method for making chlorohydrin including a step which consists in reacting a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon or a mixture thereof, with a chlorinating agent containing hydrogen chloride and at least one step performed in an equipment made of or coated with materials resistant to the chlorinating agent, under conditions suitable for performing said step.
Description
Procédé de fabrication d'une chlorhydrine dans des équipements résistant à la corrosion Process for producing a chlorohydrin in corrosion resistant equipment
La présente demande de brevet revendique le bénéfice de la demande de brevet FR 05.05120 et de la demande de brevet EP 05104321.4, déposées le 20 mai 2005 et des demandes de brevet US provisoires 60/734659, 60/734627, 60/734657, 60/734658, 60/734635, 60/734634, 60/734637 et 60/734636, déposées le 8 novembre 2005, dont les contenus sont ici incorporés par référence.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.
La présente invention se rapporte à un procédé de fabrication d'une chlorhydrine. Plus spécifiquement, l'invention se rapporte à un procédé de fabrication d'une chlorhydrine dans des équipements réalisés en matériaux résistant à la corrosion.The present invention relates to a process for producing a chlorohydrin. More specifically, the invention relates to a process for producing a chlorohydrin in equipment made of corrosion resistant materials.
Les chlorhydrines sont des intermédiaires réactionnels dans la fabrication des époxydes et produits dérivés. Le dichloropropanol, par exemple, est un intermédiaire réactionnel dans la fabrication de l'épichlorhydrine et des résines époxy (Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, 1992, Vol. 2, page 156, John Wiley & Sons, Inc.).Chlorohydrins are reaction intermediates in the manufacture of epoxides and derived products. 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.) .
Selon des procédés connus, on peut obtenir le dichloropropanol notamment par hypochloration du chlorure d'allyle, par chloration de l'alcool allylique et par hydrochloration du glycérol. Ce dernier procédé présente l'avantage que le dichloropropanol peut être obtenu au départ de matières premières fossiles ou de matières premières renouvelables et il est connu que les ressources naturelles pétrochimiques, dont sont issues les matières fossiles, par exemple le pétrole, le gaz naturel ou le charbon, disponibles sur la terre sont limitées.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.
La demande WO 2005/054167 de SOLVAY SA décrit un procédé de fabrication de dichloropropanol par réaction entre du glycérol et du chlorure d'hydrogène en présence d'un acide tel que l'acide adipique comme catalyseur. La réaction est réalisée dans un réacteur fait en ou recouvert d'un matériau résistant à l'agent de chloration dans les conditions de réaction. L'utilisation de ce type de matériau est cependant limitée au réacteur de chloration du glycérol.The application WO 2005/054167 of SOLVAY SA describes a process for the manufacture of dichloropropanol by reaction between glycerol and hydrogen chloride in the presence of an acid such as adipic acid as catalyst. The reaction is carried out in a reactor made of or covered with a material resistant to the chlorinating agent under the reaction conditions. The use of this type of material is, however, limited to the glycerol chlorination reactor.
L'invention concerne un procédé de fabrication d'un chlorhydrine comprenant :
(a) une étape dans laquelle on soumet un hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique poly hydroxylé, ou un mélange d'entre eux, à une réaction avec un agent de chloration contenant du chlorure d'hydrogène (b) au moins une autre étape effectuée dans un équipement, réalisé en ou recouvert de, matériaux résistant à l'agent de chloration, dans les conditions de réalisation de cette étape.The invention relates to a process for producing a chlorohydrin comprising: (a) 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 (b) at least one other step performed in equipment, made of or covered with chlorinating agent resistant materials, under the conditions of completion of this step.
On a trouvé que dans le procédé selon l'invention, les avantages suivants sont réalisés : (a) la durée de vie des équipements est allongéeIt has been found that in the method according to the invention, the following advantages are realized: (a) the service life of the equipment is lengthened
(b) la gestion des flux du procédé est simplifiée(b) the flow management of the process is simplified
(c) le coût global du procédé est diminué(c) the overall cost of the process is decreased
(d) les procédés en aval du procédé de fabrication de la chlorhydrine, comme par exemple le traitement des purges par oxydation à haute température qui requiert de faibles teneurs en métaux, ne sont pas perturbés.(d) processes downstream of the process for producing chlorohydrin, such as the treatment of high temperature oxidation purges which require low metal contents, are not disturbed.
(e) la qualité de l' effluent aqueux d'une fabrication d'un époxyde alimentée avec des mélanges de chlorhydrine et d'eau issus du procédé de chloration de l'hydrocarbure aliphatique poly hydroxylé, n'est pas altérée par une teneur anormalement élevée en métaux et il n'est par conséquent pas nécessaire d'effectuer un traitement particulier d'épuration des rejets aqueux en vue d'en réduire la teneur en métaux.(e) the quality of the aqueous effluent from the manufacture of an epoxide fueled with mixtures of chlorohydrin and water from the process of chlorinating the polyhydroxylated aliphatic hydrocarbon is not impaired by an abnormally high high in metals and it is therefore not necessary to carry out a particular treatment of purification of aqueous discharges in order to reduce the metal content.
On a en effet trouvé de façon surprenante que des phénomènes de corrosion peuvent se produire dans le procédé ailleurs qu'à l'étape de chloration de l'hydrocarbure aliphatique poly hydroxylé, de l'ester d'hydrocarbure aliphatique poly hydroxylé, ou du mélange d'entre eux, et avoir un impact global défavorable sur l'économie du procédé.It has indeed been found, surprisingly, that corrosion phenomena can occur in the process other than at the stage of chlorination of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture. of them, and have an overall unfavorable impact on the economics of the process.
L'invention concerne dès lors également l'utilisation d'équipement, réalisé en ou recouvert de, matériaux résistant aux agents de chloration dans un procédé de fabrication d'une chlorhydrine comprenant une étape dans laquelle on soumet un hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique poly hydroxylé, ou un mélange d'entre eux, à une réaction avec un agent de chloration contenant du chlorure d'hydrogène, dans au moins une étape autre que l'étape de réaction..The invention therefore also relates to the use of equipment, made of or coated with chlorine-resistant materials in a process for the manufacture of a chlorohydrin comprising a step in which a polyhydroxylated aliphatic hydrocarbon, an ester is subjected to of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof, to a reaction with a chlorinating agent containing hydrogen chloride, in at least one step other than the reaction step.
On a en effet trouvé que l'utilisation de ce type d'équipement permet éviter la corrosion par le chlorure d'hydrogène en présence d'eau et de l 'hydrocarbure aliphatique poly hydroxylé. L'eau peut être de l'eau générée par la réaction entre
l 'hydrocarbure aliphatique poly hydroxylé et l'agent de chloration ou de l'eau introduite dans le procédé.It has in fact been found that the use of this type of equipment makes it possible to avoid corrosion by hydrogen chloride in the presence of water and of the polyhydroxylated aliphatic hydrocarbon. Water can be water generated by the reaction between the polyhydroxylated aliphatic hydrocarbon and the chlorinating agent or water introduced into the process.
L'invention concerne enfin une installation de fabrication d'une chlorhydrine comprenant : (a) une partie dans laquelle on soumet un hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique poly hydroxylé, ou un mélange d'entre eux, à une réaction avec un agent de chloration contenant du chlorure d'hydrogèneThe invention finally relates to a plant for the manufacture of a chlorohydrin comprising: (a) a part in which a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, is subjected to reaction with a chlorinating agent containing hydrogen chloride
(b) au moins une autre partie faite dans un équipement, réalisé en ou recouvert de, matériaux résistant à l'agent de chloration.(b) at least one other part made in equipment, made of or covered with chlorine-resistant materials.
L'expression « hydrocarbure aliphatique poly hydroxylé » se rapporte à un hydrocarbure qui contient au moins deux groupements hydroxyles attachés à deux atomes de carbone différents saturés. L'hydrocarbure aliphatique poly hydroxylé peut contenir, mais n'est pas limité à, de 2 à 60 atomes de carbone. Chacun des carbones d'un hydrocarbure aliphatique poly hydroxylé portant le groupement hydroxylé (OH) fonctionnel ne peut pas posséder plus d'un groupement OH, et doit être d'hybridation sp3. L'atome de carbone portant le groupement OH peut être primaire, secondaire ou tertiaire. L'hydrocarbure aliphatique poly hydroxylé utilisé dans la présente invention doit contenir au moins deux atomes de carbone d'hybridation sp3 portant un groupement OH. L'hydrocarbure aliphatique poly hydroxylé inclut n'importe quel hydrocarbure contenant un diol vicinal (1,2-diol) ou un triol vicinal (1,2,3-triol) y compris des ordres plus élevés de ces unités répétitives, vicinales ou contiguës. La définition de l'hydrocarbure aliphatique poly hydroxylé inclut aussi par exemple un ou plus de groupements fonctionnels 1,3-, 1,4-, 1,5- et 1,6-diol. L'hydrocarbure aliphatique poly hydroxylé peut aussi être un polymère tel que l'alcool polyvinylique. Les diols géminés, par exemple, sont exclus de cette classe d'hydrocarbures aliphatiques poly hydroxyles.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.
Les hydrocarbures aliphatiques poly hydroxyles peuvent contenir des entités aromatiques ou des hétéro atomes incluant par exemple les hétéro atomes de type halogène, soufre, phosphore, azote, oxygène, silicium et bore, et leurs mélanges.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.
L'expression « hydrocarbure aliphatique poly hydroxylé » se rapporte à un hydrocarbure qui contient au moins deux groupements hydroxyles attachés à deux atomes de carbone différents saturés. L'hydrocarbure aliphatique poly hydroxylé peut contenir, mais n'est pas limité à, de 2 à 60 atomes de carbone.
- A -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. - AT -
Chacun des carbones d'un hydrocarbure aliphatique poly hydroxylé portant le groupement hydroxylé (OH) fonctionnel ne peut pas posséder plus d'un groupement OH, et doit être d'hybridation sp3. L'atome de carbone portant le groupement OH peut être primaire, secondaire ou tertiaire. L'hydrocarbure aliphatique poly hydroxylé utilisé dans la présente invention doit contenir au moins deux atomes de carbone d'hybridation sp3 portant un groupement OH. L'hydrocarbure aliphatique poly hydroxylé inclut n'importe quel hydrocarbure contenant un diol vicinal (1,2-diol) ou un triol vicinal (1,2,3-triol) y compris des ordres plus élevés de ces unités répétitives, vicinales ou contiguës. La définition de l'hydrocarbure aliphatique poly hydroxylé inclut aussi par exemple un ou plus de groupements fonctionnels 1,3-, 1,4-, 1,5- et 1,6-diol. L'hydrocarbure aliphatique poly hydroxylé peut aussi être un polymère tel que l'alcool polyvinylique. Les diols géminés, par exemple, sont exclus de cette classe d'hydrocarbures aliphatiques poly hydroxylés. Les hydrocarbures aliphatiques poly hydroxylés peuvent contenir des entités aromatiques ou des hétéro atomes incluant par exemple les hétéro atomes de type halogène, soufre, phosphore, azote, oxygène, silicium et bore, et leurs mélanges.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.
Des hydrocarbures aliphatiques poly hydroxylés utilisables dans la présente invention comprennent par exemple, le 1,2-éthanediol (éthylène glycol), le 1,2-propanediol (propylène glycol), le 1,3-propanediol, le l-chloro-2,3-propanediol (chloropropanediol), le 2-chloro-l,3-propanediol (chloropropanediol), le 1,4-butanediol, le 1,5-pentanediol, les cyclohexanediols, le 1,2-butanediol, le 1,2-cyclohexanediméthanol, le 1,2,3-propanetriol (aussi connu comme « glycérol » ou « glycérine »), et leurs mélanges. De façon préférée, l 'hydrocarbure aliphatique poly hydroxylé utilisé dans la présente invention inclut par exemple le 1,2-éthanediol, le 1,2-propanediol, le 1,3-propanediol, le chloropropanediol et 1,2,3-propanetriol, et les mélanges d'au moins deux d'entre-eux. De façon plus préférée, l'hydrocarbure aliphatique poly hydroxylé utilisé dans la présente invention inclut par exemple le 1,2-éthanediol, le 1,2-propanediol, le chloropropanediol et 1,2,3-propanetriol, et les mélanges d'au moins deux d'entre-eux. Le 1,2,3-propanetriol ou glycérol est le plus préféré.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, 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.
Les esters d'hydrocarbure aliphatique poly hydroxylé peuvent être présents dans l'hydrocarbure aliphatique poly hydroxylé et/ou être produits dans le procédé de fabrication de la chlorhydrine et/ou être fabriqués préalablement au
procédé de fabrication de la chlorhydrine. Des exemples d'esters de l'hydrocarbure aliphatique poly hydroxylé comprennent le monoacétate de l'éthylène glycol, les monoacétates de propanediol, les monoacétates de glycérol, les monostéarates de glycérol, les diacétates de glycérol et leurs mélanges. L'expression « chorhydrine » est ici utilisée pour décrire un composé contenant au moins un groupement hydroxylé et au moins un atome de chlore attaché à des différents atomes de carbone saturés. Une chlorhydrine qui contient au moins deux groupements hydroxyles est aussi un hydrocarbure aliphatique poly hydroxylé. Donc, le matériau de départ et le produit de la réaction peuvent chacun être des chlorhydrines. Dans ce cas, la chlorohydrine « produit » est plus chlorée que la chlorhydrine de départ, c'est-à-dire qu'elle a plus d'atomes de chlore et moins de groupements hydroxyles que la chlorhydrine de départ. Des chlorhydrines préférées sont le chloroéthanol, le chloropropanol, le chloropropanediol, le dichloropropanol et les mélanges d'au moins deux d'entre-eux. Le dichloropropanol est particulièrement préféré. Des chlorhydrines plus particulièrement préférées sont le 2 -chloroéthanol, le l-chloropropane-2-ol, le 2-chloropropane-l-ol, le l-chloropropane-2,3-diol, le 2-chloropropane-l,3-diol, le l,3-dichloropropane-2-ol, le 2,3-dichloropropane-l-ol et les mélanges d'au moins deux d'entre-eux. L'hydrocarbure aliphatique poly hydroxylé, l'ester d'hydrocarbure aliphatique poly hydroxylé, ou le mélange d'entre eux, dans le procédé selon l'invention peuvent être obtenus au départ de matières premières fossiles ou au départ de matières premières renouvelables, de préférence au départ de matières premières renouvelables. Par matières premières fossiles, on entend désigner des matières issues du traitement des ressources naturelles pétrochimiques, par exemple le pétrole, le gaz naturel, et le charbon. Parmi ces matières, les composés organiques comportant 2 et 3 atomes de carbone sont préférés. Lorsque l 'hydrocarbure aliphatique poly hydroxylé est le glycérol, le chlorure d'allyle, l'alcool allylique et le glycérol « synthétique » sont particulièrement préférés. Par glycérolThe polyhydroxylated aliphatic hydrocarbon esters 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 beforehand. process for producing chlorohydrin Examples of polyhydroxylated aliphatic hydrocarbon esters include ethylene glycol monoacetate, propanediol monoacetates, glycerol monoacetates, glycerol monostearates, glycerol diacetates, and mixtures thereof. The term "chorhydrin" is used here to describe a compound containing at least one hydroxyl group and at least one chlorine atom attached to different saturated carbon atoms. A chlorohydrin which contains at least two hydroxyl groups is also a polyhydroxylated aliphatic hydrocarbon. Thus, the starting material and the product of the reaction can each be chlorohydrins. In this case, the "produced" chlorohydrin is more chlorinated than the starting chlorohydrin, that is to say that it has more chlorine atoms and fewer hydroxyl groups than the starting chlorohydrin. Preferred chlorohydrins are chloroethanol, chloropropanol, chloropropanediol, dichloropropanol and mixtures of at least two of them. Dichloropropanol is particularly preferred. More particularly preferred chlorohydrins are 2-chloroethanol, 1-chloropropan-2-ol, 2-chloropropan-1-ol, 1-chloropropane-2,3-diol, 2-chloropropane-1,3-diol. 1,3-dichloropropan-2-ol, 2,3-dichloropropan-1-ol and mixtures of at least two of them. The polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, in the process according to the invention can be obtained starting from fossil raw materials or starting from renewable raw materials, from preferably from renewable raw materials. Fossil raw materials are understood to mean materials from the processing of petrochemical natural resources, for example, petroleum, natural gas, and coal. Of these materials, organic compounds having 2 and 3 carbon atoms are preferred. When the polyhydroxylated aliphatic hydrocarbon is glycerol, allyl chloride, allyl alcohol and "synthetic" glycerol are particularly preferred. By glycerol
« synthétique », on entend désigner un glycérol généralement obtenu à partir de ressources pétrochimiques. Lorsque l'hydrocarbure aliphatique poly hydroxylé est l'éthylène glycol, l'éthylène et l'éthylène glycol « synthétique » sont particulièrement préférés. Par éthylène glycol « synthétique », on entend désigner un éthylène glycol généralement obtenu à partir de ressources pétrochimiques. Lorsque l 'hydrocarbure aliphatique poly hydroxylé est le
propylène glycol, le propylène et le propylène glycol « synthétique » sont particulièrement préférés. Par propylène glycol « synthétique », on entend désigner un propylène glycol généralement obtenu à partir de ressources pétrochimiques. Par matières premières renouvelables, on entend désigner des matières issues du traitement des ressources naturelles renouvelables. Parmi ces matières, l'éthylène glycol « naturel », le propylène glycol « naturel » et le glycérol « naturel » sont préférés. De l'éthylène glycol, du propylène glycol et du glycérol « naturels » sont par exemple obtenus par conversion de sucres via des procédés thermochimiques, ces sucres pouvant être obtenus au départ de biomasse, comme décrit dans "Industrial Bioproducts : Today and Tomorrow, Energetics, Incorporated for the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Office of the Biomass Program, JuIy 2003, pages 49, 52 to 56". Un de ces procédés est par exemple l'hydrogénolyse catalytique du sorbitol obtenu par conversion thermochimique du glucose. Un autre procédé est par exemple l'hydrogénolyse catalytique du xylitol obtenu par hydrogénation du xylose. Le xylose peut par exemple être obtenu par hydrolyse de l'hemicellulose contenue dans les fibres de maïs. Par « glycérol obtenu à partir de matières premières renouvelables » on entend désigner en particulier du glycérol obtenu au cours de la fabrication de biodiesel ou encore du glycérol obtenu au cours de transformations de graisses ou huiles d'origine végétale ou animale en général telles que des réactions de saponification, de trans- estérification ou d'hydrolyse."Synthetic" 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 the 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 "glycerol obtained from renewable raw materials" is meant in particular glycerol obtained during the manufacture of biodiesel or glycerol obtained during transformations of fats or oils of vegetable or animal origin in general such as saponification, transesterification or hydrolysis reactions.
Parmi les huiles utilisables dans le procédé de l'invention, on peut citer toutes les huiles courantes, comme les huiles de palme, de palmiste, de coprah, de babassu, de colza ancien ou nouveau, de tournesol, de maïs, de ricin et de coton, les huiles d'arachide, de soja, de lin et de crambe et toutes les huiles issues par exemple des plantes de tournesol ou de colza obtenues par modification génétique ou hybridation. On peut même utiliser des huiles de friture usagées, des huiles animales variées, comme les huiles de poisson, le suif, le saindoux et même des graisses d'équarrissage.Among the oils that can be used in the process of the invention, mention may be made of all common oils, such as palm, palm kernel, coconut, babassu, old or new rapeseed, sunflower, corn, castor oil and cotton, peanut, soybean, flax and crambe oils and all oils derived for example from sunflower or rapeseed plants obtained by genetic modification or hybridization. You can even use used cooking oils, various animal oils, such as fish oils, tallow, lard and even rendering fats.
Parmi les huiles utilisées, on peut encore indiquer des huiles partiellement modifiées par exemple par polymérisation ou oligomérisation comme par exemple les "standolies" d'huiles de lin, de tournesol et les huiles végétales soufflées.
Un glycérol particulièrement adapté peut être obtenu lors de la transformation de graisses animales. Un autre glycérol particulièrement adapté peut être obtenu lors de la fabrication de biodiesel. Un troisième glycérol tout particulièrement bien adapté peut être obtenu lors de la transformation de graisses ou d'huiles, animales ou végétales, par trans-estérification en présence d'un catalyseur hétérogène, tel que décrit dans les documents FR 2752242, FR 2869612 et FR 2869613. Plus spécifiquement, le catalyseur hétérogène est choisi parmi les oxydes mixtes d'aluminium et de zinc, les oxydes mixtes de zinc et de titane, les oxydes mixtes de zinc, de titane et d'aluminium, et les oxydes mixtes de bismuth et d'aluminium, et le catalyseur hétérogène est mis en œuvre sous la forme d'un lit fixe. Ce dernier procédé peut être un procédé de fabrication de biodiesel.Among the oils used, it is also possible to indicate partially modified oils, for example by polymerization or oligomerization, for example the "standolies" of linseed oil, sunflower oil and blown vegetable oils. A particularly suitable glycerol can be obtained during the processing of animal fats. Another particularly suitable glycerol can be obtained during the manufacture of biodiesel. A third particularly suitable glycerol can be obtained during the transformation of fats or oils, animal or vegetable by trans-esterification in the presence of a heterogeneous catalyst, as described in documents FR 2752242, FR 2869612 and FR More specifically, the heterogeneous catalyst is chosen from mixed oxides of aluminum and zinc, mixed oxides of zinc and titanium, mixed oxides of zinc, titanium and aluminum, and mixed oxides of bismuth and of aluminum, and the heterogeneous catalyst is implemented in the form of a fixed bed. The latter process may be a biodiesel manufacturing process.
Dans le procédé de fabrication d'une chlorhydrine selon l'invention, l 'hydrocarbure aliphatique poly hydroxylé peut être tel que décrit dans la demande de brevet intitulée « Procédé de préparation de chlorhydrine par conversion d'hydrocarbures aliphatiques poly hydroxylés » déposée au nom de SOLVAY SA le même jour que la présente demande, dont le contenu est ici incorporé par référence.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.
Mention particulière est faite d'un procédé de fabrication d'une chlorhydrine dans lequel on fait réagir un hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique poly hydroxylé, ou un mélange d'entre eux, dont la teneur totale en métaux exprimés sous forme d'éléments est supérieure ou égale à 0,1 μg/kg et inférieure ou égale à 1 000 mg/kg, avec un agent de chloration. Dans le procédé selon l'invention, on préfère utiliser du glycérol obtenu au départ de matières premières renouvelables.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 obtained from renewable raw materials.
Dans le procédé de fabrication d'une chlorhdyrine selon l'invention, l 'hydrocarbure aliphatique poly hydroxylé, l'ester d'hydrocarbure aliphatique poly hydroxylé, ou le mélange d'entre eux, peut être un produit brut ou un produit épuré, tels que spécifiquement divulgués dans la demandeIn the process for producing a chlorhdyrine according to the invention, the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, can be a crude product or a purified product, such as specifically disclosed in the application
WO 2005/054167 de SOLVAY SA, de la page 2, ligne 8, à la page 4, ligne 2.WO 2005/054167 to SOLVAY SA, page 2, line 8, to page 4, line 2.
Dans le procédé de fabrication d'une chlorhydrine selon l'invention, l 'hydrocarbure aliphatique poly hydroxylé, l'ester d'hydrocarbure aliphatique poly hydroxylé, ou le mélange d'entre eux, peut être un hydrocarbure aliphatique poly hydroxylé dont la teneur en métaux alcalin et/ou alcalino-terreux peut être inférieure ou égale à 5 g/kg tel que décrit dans la demande intitulée « Procédé de
fabrication d'une chlorhydrine par chloration d'un hydrocarbure aliphatique poly hydroxylé » déposée au nom de SOLVAY SA le même jour que la présente demande, dont le contenu est ici incorporé par référence. Les métaux alcalins peuvent être sélectionnés parmi le lithium, le sodium, le potassium, le rubidium et le césium et les métaux alcalino-terreux peuvent être sélectionnés parmi le magnésium, le calcium, le strontium et le barium.In the process for producing a chlorohydrin according to the invention, the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, may be a polyhydroxylated aliphatic hydrocarbon whose alkali and / or alkaline earth metals may be less than or equal to 5 g / kg as described in the application entitled "Process of manufacture of a chlorohydrin by chlorination of a polyhydroxylated aliphatic hydrocarbon "deposited in the name of SOLVAY SA on the same day as the present application, the contents of which are hereby incorporated by reference. The alkali metals can be selected from lithium, sodium, potassium, rubidium and cesium and the alkaline earth metals can be selected from magnesium, calcium, strontium and barium.
Dans le procédé selon l'invention, la teneur en métaux alcalins et/ou alcalino-terreux de l'hydrocarbure aliphatique poly hydroxylé, de l'ester d'hydrocarbure aliphatique poly hydroxylé, ou du mélange d'entre eux, est inférieure ou égale à 5 g/kg, souvent inférieure ou égale à 1 g/kg, plus particulièrement inférieure ou égale à 0,5 g/kg et dans certains cas inférieure ou égale à 0,01 g/kg. La teneur métaux alcalins et/ou alcalino-terreux du glycérol est généralement supérieure ou égale à 0,1 μg/kg.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.
Dans le procédé selon l'invention, les métaux alcalins sont généralement le lithium, le sodium, le potassium et le césium, souvent le sodium et le potassium, et fréquemment le sodium.In the process according to the invention, the alkali metals are generally lithium, sodium, potassium and cesium, often sodium and potassium, and frequently sodium.
Dans le procédé de fabrication d'une chlorhydrine selon l'invention, la teneur en lithium de l'hydrocarbure aliphatique poly hydroxylé, de l'ester d'hydrocarbure aliphatique poly hydroxylé, ou du mélange d'entre eux, est généralement inférieure ou égale à 1 g/kg, souvent inférieure ou égale à 0,1 g/kg et plus particulièrement inférieure ou égale à 2 mg/kg. Cette teneur est généralement supérieure ou égale à 0,1 μg/kg.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.
Dans le procédé selon l'invention, la teneur en sodium de l'hydrocarbure aliphatique poly hydroxylé, de l'ester d'hydrocarbure aliphatique poly hydroxylé, ou du mélange d'entre eux, est généralement inférieure ou égale à 1 g/kg, souvent inférieure ou égale à 0,1 g/kg et plus particulièrement inférieure ou égale à 2 mg/kg. Cette teneur est généralement supérieure ou égale à 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.
Dans le procédé selon l'invention, la teneur en potassium de l 'hydrocarbure aliphatique poly hydroxylé, de l'ester d'hydrocarbure aliphatique poly hydroxylé, ou du mélange d'entre eux, est généralement inférieure ou égale à 1 g/kg, souvent inférieure ou égale à 0,1 g/kg et plus particulièrement inférieure ou égale à 2 mg/kg. Cette teneur est généralement supérieure ou égale à 0,1 μg/kg. Dans le procédé selon l'invention, la teneur en rubidium de l'hydrocarbure aliphatique poly hydroxylé, de l'ester d'hydrocarbure aliphatique poly
hydroxylé, ou du mélange d'entre eux, est généralement inférieure ou égale à 1 g/kg, souvent inférieure ou égale à 0,1 g/kg et plus particulièrement inférieure ou égale à 2mg/kg. Cette teneur est généralement supérieure ou égale à 0,1 μg/kg. Dans le procédé selon l'invention, la teneur en césium de l 'hydrocarbure aliphatique poly hydroxylé, de l'ester d'hydrocarbure aliphatique poly hydroxylé, ou du mélange d'entre eux, est généralement inférieure ou égale à 1 g/kg, souvent inférieure ou égale à 0,1 g/kg et plus particulièrement inférieure ou égale à 2 mg/kg. Cette teneur est généralement supérieure ou égale à 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, the polyhydric aliphatic hydrocarbon ester hydroxyl, or a 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.
Dans le procédé selon l'invention, les éléments alcalino-terreux sont généralement le magnésium, le calcium, le strontium et le barium, souvent le magnésium et le calcium et fréquemment le calcium.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.
Dans le procédé selon l'invention, la teneur en magnésium de l 'hydrocarbure aliphatique poly hydroxylé, de l'ester d'hydrocarbure aliphatique poly hydroxylé, ou du mélange d'entre eux, est généralement inférieure ou égale à 1 g/kg, souvent inférieure ou égale à 0,1 g/kg et plus particulièrement inférieure ou égale à 2 mg/kg. Cette teneur est généralement supérieure ou égale à 0,1 μg/kg. Dans le procédé selon l'invention, la teneur en calcium de l'hydrocarbure aliphatique poly hydroxylé, de l'ester d'hydrocarbure aliphatique poly hydroxylé, ou du mélange d'entre eux, est généralement inférieure ou égale à 1 g/kg, souvent inférieure ou égale à 0,1 g/kg et plus particulièrement inférieure ou égale à 2 mg/kg. Cette teneur est généralement supérieure ou égale à 0,1 μg/kg.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.
Dans le procédé selon l'invention, la teneur en strontium de l 'hydrocarbure aliphatique poly hydroxylé, de l'ester d'hydrocarbure aliphatique poly hydroxylé, ou du mélange d'entre eux, est généralement inférieure ou égale à 1 g/kg, souvent inférieure ou égale à 0,1 g/kg et plus particulièrement inférieure ou égale à 2 mg/kg. Cette teneur est généralement supérieure ou égale à 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.
Dans le procédé selon l'invention, la teneur en barium de l 'hydrocarbure aliphatique poly hydroxylé, de l'ester d'hydrocarbure aliphatique poly hydroxylé, ou du mélange d'entre eux, est généralement inférieure ou égale à 1 g/kg, souvent inférieure ou égale à 0,1 g/kg et plus particulièrement inférieure
ou égale à 2 mg/kg. Cette teneur est généralement supérieure ou égale à 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 lower or equal to 2 mg / kg. This content is generally greater than or equal to 0.1 μg / kg.
Dans le procédé selon l'invention, les métaux alcalins et/ou alcalino- terreux sont généralement présents sous la forme de sels, fréquemment sous la forme de chlorures, de sulfates et de leurs mélanges. Le chlorure de sodium est le plus souvent rencontré.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.
Dans le procédé de fabrication d'une chlorhydrine selon l'invention, l'agent de chloration peut être tel que décrit dans la demande WO 2005/054167 de SOLVAY SA, de la page 4, ligne 25, à la page 6, ligne 2. Dans le procédé de fabrication d'une chlorhydrine selon l'invention, l'agent de chloration peut être du chlorure d'hydrogène peut être tel que décrit dans la demande WO 2005/054167 de SOLVAY SA, de la page 4, ligne 30, à la page 6, ligne 2.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.
Mention particulière est faite d'un agent de chloration qui peut être de l'acide chlorhydrique aqueux ou du chlorure d'hydrogène de préférence anhydre.Particular mention is made of a chlorinating agent which may be aqueous hydrochloric acid or preferably anhydrous hydrogen chloride.
Le chlorure d'hydrogène peut provenir d'un procédé de pyrolyse de composés organiques chlorés comme par exemple d'une fabrication de chlorure de vinyle, d'un procédé de fabrication de 4,4-méthylènediphenyl diisocyanate (MDI) ou dede toluène diisocyanate (TDI), de procédés de décapage des métaux ou d'une réaction entre un acide inorganique comme l'acide sulfurique ou phosphorique et un chlorure métallique tel que le chlorure de sodium, le chlorure de potassium ou le chlorure de calcium.The hydrogen chloride may be derived from a process for the pyrolysis of chlorinated organic compounds such as, for example, vinyl chloride production, a process for the manufacture of 4,4-methylenediphenyl diisocyanate (MDI) or toluene diisocyanate ( TDI), metal stripping processes or a reaction between an inorganic acid such as sulfuric or phosphoric acid and a metal chloride such as sodium chloride, potassium chloride or calcium chloride.
Dans un mode de réalisation avantageux du procédé de fabrication d'une chlorhydrine selon l'invention, l'agent de chloration est du chlorure d'hydrogène gazeux ou une solution aqueuse de chlorure d'hydrogène ou une combinaison des deux.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.
Dans le procédé de fabrication d'une chlorhydrine selon l'invention, le chlorure d'hydrogène peut être une solution aqueuse de chlorure d'hydrogène ou du chlorure d'hydrogène de préférence anhydre, issu d'une installation de fabrication de chlorure d'allyle et/ou de fabrication de chlorométhanes et/ou de chlorinolyse et/ou d'oxydation à haute température de composés chlorés tels que décrit dans la demande intitulée « Procédé de fabrication d'une chlorhydrine par réaction entre un hydrocarbure aliphatique poly hydroxylé et un agent de chloration » déposée au nom de SOLVAY SA le même jour que la présente demande, dont le contenu est ici incorporé par référence.
Mention particulière est faite d'un procédé de fabrication d'une chlorhydrine à partir d'un hydrocarbure aliphatique poly hydroxylé, d'un ester d'un hydrocarbure aliphatique poly hydroxylé, ou d'un mélange d'entre eux, et d'un agent de chloration, ce dernier contenant au moins un des composés suivants : azote, oxygène, hydrogène, chlore, un composé organique hydrocarboné, un composé organique halogène, un composé organique oxygéné et un métal.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, resulting from a chlorine-producing plant. allyl and / or manufacture of chloromethanes and / or chlorinolysis and / or high temperature oxidation of chlorinated compounds as described in the application entitled "Process for producing a chlorohydrin by reaction between a polyhydroxylated aliphatic hydrocarbon and a chlorinating agent "filed on behalf of SOLVAY SA on the same day as the present application, the contents of which are hereby incorporated by reference. Particular mention is made of a process for producing a chlorohydrin from a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, and a chlorinating agent, the latter containing at least one of the following compounds: nitrogen, oxygen, hydrogen, chlorine, an organic hydrocarbon compound, a halogenated organic compound, an oxygenated organic compound and a metal.
Mention particulière est faite d'un composé organique hydrocarboné qui est choisi parmi les hydrocarbures aromatiques, aliphatiques saturés ou insaturés et leurs mélanges.Particular mention is made of an organic hydrocarbon compound which is selected from aromatic hydrocarbons, saturated or unsaturated aliphatic and mixtures thereof.
Mention particulière est faite d'un hydrocarbure aliphatique insaturé qui est choisi parmi l'acétylène, l'éthylène, le propylène, le butène, le propadiène, le méthylacétylène, et leurs mélanges, d'un hydrocarbure aliphatique saturé qui est choisi parmi le méthane, l'éthane, le propane, le butane, et leurs mélanges, et d'un hydrocarbure aromatique qui est le benzène.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.
Mention particulière est faite d'un composé organique halogène qui est un composé organique chloré choisi parmi les chlorométhanes, les chloroéthanes, les chloropropanes, les chlorobutanes, le chlorure de vinyle, le chlorure de vinylidène, les monochloropropènes, le perchloroéthylène, le trichloréthylène, les chlorobutadiène, les chlorobenzènes et leurs mélanges.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.
Mention particulière est faite d'un composé organique halogène qui est un composé organique fluoré choisi parmi les fluorométhanes, les fluoroéthanes, le fluorure de vinyle, le fluorure de vinylidène, et leurs mélanges.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.
Mention particulière est faite d'un composé organique oxygéné qui est choisi parmi les alcools, les chloroalcools, les chloroéthers et leurs mélangesParticular mention is made of an oxygenated organic compound which is chosen from alcohols, chloroalcohols, chloroethers and their mixtures
Mention particulière est faite d'un métal choisi parmi les métaux alcalins, les métaux alcalino -terreux, le fer, le nickel, le cuivre, le plomb, l'arsenic, le cobalt, le titane, le cadmium, l'antimoine, le mercure, le zinc, le sélénium, l'aluminium, le bismuth, et leurs mélanges.Mention est plus particulièrement faite d'un procédé dans lequel l'agent de chloration est issu au moins partiellement d'un procédé de fabrication de chlorure d'allyle et/ou d'un procédé de fabrication de chlorométhanes et/ou d'un procédé de chlorinolyse et/ou d'un procédé d'oxydation de composés chlorés à une température supérieure ou égale à 800 °C. Dans un mode de réalisation particulièrement avantageux du procédé de fabrication d'une chlorhydrine selon l'invention, le chlorure d'hydrogène est une
solution aqueuse de chlorure d'hydrogène et ne comprend pas de chlorure d'hydrogène gazeux.Particular mention is made of a metal chosen from alkali metals, alkaline-earth metals, iron, nickel, copper, lead, arsenic, cobalt, titanium, cadmium, antimony, mercury, zinc, selenium, aluminum, bismuth, and mixtures thereof.Mention is more particularly made of a process in which the chlorinating agent is derived at least partially from a process for the production of chlorine. allyl and / or a process for producing chloromethanes and / or a chlorinolysis process 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, hydrogen chloride is a aqueous solution of hydrogen chloride and does not include gaseous hydrogen chloride.
Dans le procédé de fabrication d'une chlorhydrine selon l'invention, la réaction entre l 'hydrocarbure aliphatique poly hydroxylé, l'ester d'hydrocarbure aliphatique poly hydroxylé, ou le mélange d'entre eux, et l'agent de chloration, peut être effectuée dans un réacteur tel que décrit dans la demande WO 2005/054167 de SOLVAY SA, à la page 6, lignes 3 à 23.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 SOLVAY SA application WO 2005/054167, on page 6, lines 3 to 23.
Mention est particulièrement faite d'une installation réalisée en, ou recouverte de, matériaux résistants dans les conditions de la réaction aux agents de chloration, en particulier au chlorure d'hydrogène. Mention est plus particulièrement faite d'une installation réalisée en acier émaillé ou en tantale. Dans le procédé de fabrication de dichloropropanol selon l'invention, la réaction entre le glycérol et le chlorure d'hydrogène, peut être effectuée dans un milieu réactionnel, tel que décrit dans la demande intitulée « Procédé continu de fabrication de chlorhydrines » déposée au nom de SOLVAY SA le même jour que la présente demande, dont le contenu est ici incorporé par référence.Particular mention is made of an installation made of or covered with resistant materials under the conditions of the reaction with the chlorinating agents, in particular with hydrogen chloride. Mention is more particularly made of an installation made of enamelled steel or tantalum. In the process for producing dichloropropanol according to the invention, the reaction between glycerol and hydrogen chloride can be carried out in a reaction medium, as described in the application entitled "Continuous process for the manufacture of chlorhydrins" deposited in the name SOLVAY SA the same day as the present application, the content of which is hereby incorporated by reference.
Mention particulière est faite d'un procédé continu de production de chlorhydrine dans lequel on fait réagir un hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique poly hydroxylé ou un mélange d'entre eux, avec un agent de chloration et un acide organique dans un milieu réactionnel liquide dont la composition à l'état stationnaire comprend de l 'hydrocarbure aliphatique poly hydroxylé et des esters de l 'hydrocarbure aliphatique poly hydroxylé dont la somme des teneurs exprimée en mole d'hydrocarbure aliphatique poly hydroxylé est supérieure à 1,1 mol % et inférieure ou égale à 30 mol %, le pourcentage étant rapporté à la partie organique du milieu réactionnel liquide.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.
La partie organique du milieu réactionnel liquide consiste en l'ensemble des composés organiques du milieu réactionnel liquide c'est-à-dire les composés dont la molécule contient au moins 1 atome de carbone. Dans le procédé de fabrication d'une chlorhydrine selon l'invention, la réaction entre l 'hydrocarbure aliphatique poly hydroxylé, l'ester d'hydrocarbure aliphatique poly hydroxylé, ou le mélange d'entre eux, et l'agent de chloration, peut être effectuée en présence d'un catalyseur tel que décrit dans la demande WO 2005/054167 de SOLVAY SA, de la page 6, ligne 28, à la page 8, ligne 5. Mention est particulièrement faite d'un catalyseur basé sur un acide carboxylique ou sur un dérivé d'acide carboxylique ayant un point d'ébullition
atmosphérique supérieur ou égal à 200 °C, en particulier l'acide adipique et les dérivés de l'acide adipique.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, to page 8, line 5. Particular mention is made of an acid-based catalyst carboxylic acid or a carboxylic acid derivative having a boiling point atmospheric greater than or equal to 200 ° C, in particular adipic acid and derivatives of adipic acid.
Dans le procédé de fabrication d'une chlorhydrine selon l'invention, la réaction entre l 'hydrocarbure aliphatique poly hydroxylé, l'ester d'hydrocarbure aliphatique poly hydroxylé, ou le mélange d'entre eux, et l'agent de chloration peut être effectuée à une concentration en catalyseur, une température, à une pression et pour des temps de séjour tels que décrits dans la demande WO 2005/054167 de SOLVAY SA, de la page 8, ligne 6 à la page 10, ligne 10. Mention est particulièrement faite d'une température d'au moins 20 °C et d'au plus 160 °C, d'une pression d'au moins 0,3 bar et d'au plus, 100 bar, et d'un temps de séjour d'au moins 1 h et d'au plus 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 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. Mention is especially made of a temperature of at least 20 ° C and at most 160 ° C, a pressure of at least 0.3 bar and at most 100 bar, and a residence time at least 1 hour and not more than 50 hours.
Dans le procédé de fabrication d'une chlorhydrine selon l'invention, la réaction entre l 'hydrocarbure aliphatique poly hydroxylé, l'ester d'hydrocarbure aliphatique poly hydroxylé, ou le mélange d'entre eux, et l'agent de chloration peut être effectuée en présence d'un solvant tel que décrit dans la demande WO 2005/054167 de SOLVAY SA, à la page 11, lignes 12 à 36.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.
Mention est particulièrement faite d'un solvant organique tel qu'un solvant organique chloré, un alcool, une cétone, un ester ou un éther, un solvant non aqueux miscible avec l'hydrocarbure aliphatique polyhydroxylé tel que le chlroéthanol, le chloropropanol, le chloropropanediol, le dichloropropanol, le dioxanne, le phénol, le crésol, et les mélanges de chloropropanediol et de dichloropropanol, ou des produits lourds de la réaction tels que les oligomères de l 'hydrocarbure aliphatique poly hydroxylé au moins partiellement chlorés et ou estérifiés. Dans le procédé de fabrication d'une chlorhydrine selon l'invention, la réaction entre l'hydrocarbure aliphatique poly hydroxylé et l'agent de chloration peut être effectuée en présence d'une phase liquide comprenant des composés lourds autres que l'hydrocarbure aliphatique poly hydroxylé, comme décrit dans la demande intitulée « Procédé de fabrication d'une chlorhydrine dans une phase liquide » déposée au nom de SOLVAY SA le même jour que la présente demande, dont le contenu est ici incorporé par référence.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 and the chlorinating agent can be carried out in the presence of a liquid phase comprising heavy compounds other than the polyaliphatic hydrocarbon. hydroxylated, as described in the application entitled "Process for producing 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.
Mention particulière est faite d'un procédé de fabrication d'une chlorhydrine, dans lequel on soumet un hydrocarbure aliphatique poly hydroxylé, un ester d'hydrocarbure aliphatique poly hydroxylé, ou un mélange d'entre eux, à une réaction avec un agent de chloration, en présence d'une phase liquide comprenant des composés lourds autres que l 'hydrocarbure aliphatique
poly hydroxylé et dont la température d'ébullition sous une pression de 1 bar absolu est d'au moins 15 °C supérieure à la température d'ébullition de la chlorhydrine sous une pression de 1 bar absolu.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 aliphatic hydrocarbon polyhydroxylated and whose boiling point under 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.
Dans le procédé de fabrication de l'époxyde selon l'invention, la réaction entre l'hydrocarbure aliphatique poly hydroxylé, l'ester d'hydrocarbure aliphatique poly hydroxylé, ou le mélange d'entre eux, et l'agent de chloration est préférentiellement effectuée dans un milieu réactionnel liquide. Le milieu réactionnel liquide peut être mono- ou multiphasique.In the process for producing the epoxide according to the invention, the reaction between the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, and the chlorinating agent is preferentially carried out in a liquid reaction medium. The liquid reaction medium may be mono- or multiphasic.
Le milieu réactionnel liquide est constitué par l'ensemble des composés solides dissous ou dispersés, liquides dissous ou dispersés et gazeux dissous ou dispersés, à la température de la réaction.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.
Le milieu réactionnel comprend les réactifs, le catalyseur, le solvant, les impuretés présentes dans les réactifs, dans le solvant et dans le catalyseur, les intermédiaires de réaction, les produits et les sous-produits de la réaction. Par réactifs, on entend désigner l'hydrocarbure aliphatique poly hydroxylé, l'ester d'hydrocarbure aliphatique poly hydroxylé et l'agent de chloration.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.
Parmi les impuretés présentes dans l'hydrocarbure aliphatique poly hydroxylé, on peut citer les acides carboxyliques, les sels d'acides carboxyliques, les esters d'acide gras avec l'hydrocarbure aliphatique poly hydroxylé, les esters d'acides gras avec les alcools utilisés lors de la trans-estérification, les sels inorganiques tels que les chlorures et les sulfates alcalins ou alcalino-terreux.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.
Lorsque l'hydrocarbure aliphatique poly hydroxylé est le glycérol, on peut citer parmi les impuretés du glycérol les acides carboxyliques, les sels d'acides carboxyliques, les esters d'acide gras tels que les mono-, les di- et les triglycérides, les esters d'acides gras avec les alcools utilisés lors de la trans- estérification, les sels inorganiques tels que les chlorures et les sulfates alcalins ou alcalino-terreux.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.
Parmi les intermédiaires réactionnels on peut citer les monochlorhydrines de l'hydrocarbure aliphatique poly hydroxylé et leurs esters et/ou polyesters, les esters et/ou polyesters de l'hydrocarbure aliphatique poly hydroxylé et les esters des polychlorhydrines.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.
Lorsque la chlorhydrine est le dichloropropanol, on peut citer parmi les intermédiaires réactionnels, la monochlorhydrine de glycérol et ses esters et/ou polyesters, les esters et/ou polyesters de glycérol et les esters de dichloropropanol.
L'ester d'hydrocarbure aliphatique poly hydroxylé peut donc être selon le cas, un réactif, une impureté de l'hydrocarbure aliphatique poly hydroxylé ou un intermédiaire réactionnel.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.
Par produits de la réaction, on entend désigner la chlorhydrine et l'eau. L'eau peut être l'eau formée dans la réaction de chloration et/ou de l'eau introduite dans le procédé, par exemple via l 'hydrocarbure aliphatique poly hydroxylé et/ou l'agent de chloration, tel que décrit dans la demande WO 2005/054167 de SOLVAY SA, à la page 2, lignes 22 à 28, à la page 3, lignes 20 à 25, à la page 5, lignes 7 à 31 et à la page 12, lignes 14 à 19. Parmi les sous-produits, on peut citer par exemple, les oligomères l 'hydrocarbure aliphatique poly hydroxylé partiellement chlorés et/ou estérifiés. Lorsque l 'hydrocarbure aliphatique poly hydroxylé est le glycérol, parmi les sous-produits, on peut citer par exemple, les oligomères du glycérol partiellement chlorés et/ou estérifiés. Les intermédiaires réactionnels et les sous-produits peuvent être formés dans les différentes étapes du procédé comme par exemple, au cours de l'étape de fabrication de la chlorhydrine et au cours des étapes de séparation de la chlorhydrine.By products of the reaction is meant chlorohydrin and water. The water may be the water formed in the chlorination reaction and / or the water introduced into the process, for example via the polyhydroxylated aliphatic hydrocarbon and / or the chlorinating agent, as described in the application WO 2005/054167 of SOLVAY SA, on page 2, lines 22 to 28, on page 3, lines 20 to 25, on page 5, lines 7 to 31 and on page 12, lines 14 to 19. 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.
Le milieu réactionnel liquide peut ainsi contenir l'hydrocarbure aliphatique poly hydroxylé, l'agent de chloration dissous ou dispersé sous forme de bulles, le catalyseur, le solvant, les impuretés présentes dans les réactifs, le solvant et le catalyseur, comme des sels dissous ou solides par exemple, le solvant, le catalyseur, les intermédiaires réactionnels, les produits et les sous-produits de la réaction. Les étapes (a) et (b) du procédé selon l'invention peuvent être effectuées en mode batch ou en mode continu. On préfère effectuer toutes les étapes en mode continu.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 steps (a) and (b) of the method 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.
Dans le procédé selon l'invention, la séparation de la chlorhydrine et des autres composés du milieu réactionnel peut être effectuée selon les modes tels que décrits dans la demande WO 2005/054167 de SOLVAY SA, de la page 12, ligne 1, à la page 16, ligne 35 et à la page 18, lignes 6 à 13. Ces autres composés sont ceux mentionnés ci-dessus et comprennent les réactifs non consommés, les impuretés présentes dans les réactifs, le catalyseur, le solvant, les intermédiaires réactionnels, l'eau et les sous produits de la réaction. Mention particulière est faite d'une séparation par distillation azéotropique d'un mélange eau/chlorhydrine/agent de chloration dans des conditions
minimisant les pertes en agent de chloration suivie d'une séparation de la chlorhydrine par décantation.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 a separation by azeotropic distillation of a mixture of water / chlorohydrin / chlorinating agent under conditions minimizing losses of chlorinating agent followed by separation of chlorohydrin by decantation.
Dans le procédé de fabrication d'une chlorhydrine selon l'invention, la séparation de la chlorhydrine et des autres composés du milieu réactionnel, peut être effectuée selon des modes tels que décrits dans la demande de brevetIn the process for the production of a chlorohydrin according to the invention, the separation of the chlorohydrin and the other compounds from the reaction medium can be carried out according to modes as described in the patent application.
EP 05104321.4 déposée au nom de SOLVAY SA le 20/05/2005 dont le contenu est ici incorporé par référence. Mention particlière est faite d'un mode de séparation comprenant au moins une opération de séparation destinée à enlever le sel de la phase liquide. Mention particulière est faite d'un procédé de fabrication d'une chlorhydrine par réaction entre un hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique poly hydroxylé ou un mélange d'entre eux, et un agent de chloration dans lequel l'hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique poly hydroxylé ou un mélange d'entre eux, utilisé contient au moins un sel métallique solide ou dissous, le procédé comprenant une opération de séparation destinée à enlever une partie du sel métallique. Mention est plus particulièrement est faite d'un procédé de fabrication d'une chlorhydrine par réaction entre un hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique poly hydroxylé ou un mélange d'entre eux, et un agent de chloration dans lequel l'hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique poly hydroxylé ou un mélange d'entre eux, utilisé contient au moins un chlorure et/ou un sulfate de sodium et/ou potassium et dans lequel l'opération de séparation destinée à enlever une partie du sel métallique est un opération de filtration. Mention est aussi particulièrement faite d'un procédé de fabrication d'une chlorhydrine dans lequel (a) on soumet un hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique poly hydroxylé ou un mélange d'entre eux, à une réaction avec un agent de chloration dans un milieu réactionnel, (b) on prélève en continu ou périodiquement une fraction du milieu réactionnel contenant au moins de l'eau et la chlorhydrine, (c) au moins une partie de la fraction obtenue à l'étape (b) est introduite dans une étape de distillation et (d) le taux de reflux de l'étape de distillation est contrôlé en fournissant de l'eau à ladite étape de distillation. Mention est tout particulièrement faite d'un procédé de fabrication d'une chlorhydrine dans lequel (a) on soumet un hydrocarbure aliphatique poly hydroxylé,un ester d'un hydrocarbure aliphatique poly hydroxylé ou un mélange d'entre eux, à une
réaction avec du chlorure d'hydrogène dans un milieu réactionnel, (b) on prélève en continu ou périodiquement une fraction du milieu réactionnel contenant au moins de l'eau et la chlorhydrine, (c) au moins une partie de la fraction obtenue à l'étape (b) est introduite dans une étape de distillation, dans lequel le rapport entre la concentration en chlorure d'hydrogène et la concentration en eau dans la fraction introduite dans l'étape de distillation est plus petit que le rapport de concentrations chlorure d'hydrogène/eau dans la composition binaire azéotropique chlorure d'hydrogène/eau à la température et à la pression de distillation. Dans le procédé de fabrication de l'époxyde selon l'invention, la séparation de la chlorhydrine et des autres composés du milieu réactionnel de chloration de l 'hydrocarbure aliphatique polyhydroxylé peut être effectuée selon les modes tels que décrits dans la demande intitulée « Procédé de fabrication d'une chlorhydrine » déposée au nom de SOLVAY SA, le même jour que la présente demande, et dont le contenu est ici incorporé par référence.EP 05104321.4 filed in the name of SOLVAY SA on May 20, 2005, the contents of which are 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 reaction with hydrogen chloride 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 from 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 the chloride concentrations of hydrogen / water in the azeotropic hydrogen chloride / water binary composition at the distillation temperature and pressure. In the process for the production of the epoxide according to the invention, the separation of the chlorohydrin and the other compounds from the reaction medium of chlorination of the polyhydroxylated aliphatic hydrocarbon can be carried out according to the modes as described in the application entitled "Process of manufacture of a chlorohydrin "deposited in the name of SOLVAY SA, the same day as the present application, and the contents of which are hereby incorporated by reference.
Mention particulière est faite d'un procédé de fabrication d'une chlorhydrine comprenant les étapes suivantes (a) on fait réagir un hydrocarbure aliphatique polyhydroxylé, un ester d'un hydrocarbure aliphatique polyhydroxylé, ou un mélange d'entre eux, avec un agent de chloration et un acide organique de façon à obtenir un mélange contenant de la chlorhydrine et des esters de la chlorhydrine, (b) on soumet au moins une partie du mélange obtenu à l'étape (a) à un ou plusieurs traitements dans des étapes ultérieures à l'étape (a)et (c) on ajoute de l'hydrocarbure aliphatique polyhydroxylé à au moins une des étapes ultérieures à l'étape (a), pour qu'il réagisse à une température supérieure ou égale à 20 °C, avec les esters de la chlorhydrine de façon à former au moins partiellement des esters de l'hydrocarbure aliphatique polyhydroxylé. Mention est plus particulièrement faite d'un procédé dans lequel l 'hydrocarbure aliphatique polyhydroxylé est le glycérol et la chlorhydrine est le dichloropropanol. Dans le procédé de fabrication de l'époxyde selon l'invention, la séparation de la chlorhydrine et des autres composés du milieu réactionnel de chloration de l 'hydrocarbure aliphatique polyhydroxylé peut être effectuée selon les modes tels que décrits dans la demande intitulée « Procédé de fabrication d'une chlorhydrine au départ d'un hydrocarbure aliphatique poly hydroxylé » déposée au nom de SOLVAY SA le même jour que la présente demande, et dont le contenu est ici incorporé par référence.
Mention particulière est faite d'un procédé de fabrication de chlorhydrine par réaction entre un hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique polyhydroxylé, ou un mélange d'entre eux, et un agent de chloration dans un réacteur qui est alimenté en un ou plusieurs flux liquides contenant moins de 50 % en poids de l'hydrocarbure aliphatique poly hydroxylé, de l'ester d'hydrocarbure aliphatique polyhydroxylé, ou du mélange d'entre eux, par rapport au poids de la totalité des flux liquides introduits dans le réacteur. Mention plus particulière est faite d'un procédé comprenant les étapes suivantes : (a) on fait réagir un hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique polyhydroxylé, ou un mélange d'entre eux, avec un agent de chloration de façon à obtenir au moins un milieu contenant du de la chlorhydrine, de l'eau et de l'agent de chloration, (b) on prélève au moins une fraction du milieu formé à l'étape (a) et (c) on soumet la fraction prélevée à l'étape (b) à une opération de distillation et/ou de stripping dans laquelle on ajoute de l 'hydrocarbure aliphatique poly hydroxylé de façon à séparer de la fraction prélevée à l'étape (b) un mélange contenant de l'eau et de la chlorhydrine présentant une teneur réduite en agent de chloration comparée à celle de la fraction prélevée à l'étape (b).Particular mention is made of a process for producing a chlorohydrin comprising the following steps: (a) reacting a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof, with a chlorination and an organic acid to obtain a mixture containing chlorohydrin and chlorohydrin esters, (b) subjecting at least a portion of the mixture obtained in step (a) to one or more treatments in subsequent steps in step (a) and (c) polyhydroxylated aliphatic hydrocarbon is added to at least one of the steps subsequent to step (a), so that it reacts at a temperature greater than or equal to 20 ° C, with the chlorohydrin esters so as to at least partially form esters of the polyhydroxylated aliphatic hydrocarbon. Particular mention is made of a process in which the polyhydroxylated aliphatic hydrocarbon is glycerol and the chlorohydrin is dichloropropanol. In the process for the production of the epoxide according to the invention, the separation of the chlorohydrin and the other compounds from the reaction medium of chlorination of the polyhydroxylated aliphatic hydrocarbon can be carried out according to the modes as described in the application entitled "Process of manufacture of a chlorohydrin from a polyhydroxylated aliphatic hydrocarbon deposited in the name of SOLVAY SA on the same day as the present application, and the contents of which are hereby incorporated by reference. Particular mention is made of a process for producing chlorohydrin by reaction between a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, and a chlorinating agent in a reactor which is fed with one or more liquid streams containing less than 50% by weight of the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, based on the weight of all the liquid streams introduced into the polyhydroxylated aliphatic hydrocarbon, the reactor. More particular mention is made of a process comprising the following steps: (a) reacting a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, with a chlorination agent such as to obtain at least one medium containing chlorohydrin, water and chlorinating agent, (b) removing at least a fraction of the medium formed in step (a) and (c) subjecting the fraction taken in step (b) to a distillation and / or stripping operation in which polyhydroxylated aliphatic hydrocarbon is added so as to separate from the fraction taken in step (b) a mixture containing water and chlorohydrin having a reduced content of chlorinating agent compared to that of the fraction taken in step (b).
Dans le procédé de fabrication d'une chlorhydrine selon l'invention, la séparation de la chlorhydrine et des autres composés du milieu réactionnel de chloration de l 'hydrocarbure aliphatique polyhydroxylé peut être effectuée selon les modes tels que décrits dans la demande intitulée « Procédé de conversion d'hydrocarbures aliphatiques poly hydroxylés en chlorhydrines » déposée au nom de SOLVAY SA le même jour que la présente demande et dont les contenus sont ici incorporés par référence. Mention particulière est faite d'un procédé de préparation d'une chlorhydrine comprenant les étapes suivantes : (a) on fait réagir un hydrocarbure aliphatique polyhydroxylé, un ester d'un hydrocarbure aliphatique polyhydroxylé , ou un mélange d'entre eux, avec un agent de chloration de façon à obtenir un mélange contenant de la chlorhydrine, des esters de chlorhydrine et de l'eau, (b) on soumet au moins une fraction du mélange obtenu à l'étape (a) à un traitement de distillation et/ou de stripping de façon à obtenir une partie concentrée en eau, en chlorhydrine et en esters de chlorhydrine et (c) on soumet au moins une fraction de la partie obtenue à l'étape (b) à une opération de séparation en présence d'au moins un additif de façon à obtenir une portion concentrée en chlorhydrine et en esters de chlorhydrine et qui contient moins de 40 % en poids d'eau.
L'opération de séparation est plus particulièrement une décantation. Dans le procédé de fabrication d'une chlorhydrine selon l'invention, la séparation et le traitement des autres composés du milieu réactionnel peuvent être effectués selon des modes tels que décrits dans la demande intitulée « Procédé de fabrication d'une chlorhydrine par chloration d'un hydrocarbure aliphatique poly hydroxylé » déposée au nom de SOLVAY SA le même jour que la présente demande. Un traitement préféré consiste à soumettre une fraction des sous-produits de la réaction à une oxydation à haute température.In the process for producing a chlorohydrin according to the invention, the separation of the chlorohydrin and of the other compounds from the reaction medium of chlorination of the polyhydroxylated aliphatic hydrocarbon can be carried out according to the modes as described in the application entitled "Process of conversion of polyhydroxylated aliphatic hydrocarbons to chlorhydrins "deposited in the name of SOLVAY SA on the same day as the present application and the contents of which are hereby incorporated by reference. Particular mention is made of a process for preparing a chlorohydrin comprising the following steps: (a) reacting a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, with an agent chlorination process so as to obtain a mixture containing chlorohydrin, chlorohydrin esters and water, (b) subjecting at least a fraction of the mixture obtained in step (a) to a distillation treatment and / or stripping so as to obtain a concentrated portion of water, chlorohydrin and chlorohydrin esters and (c) subjecting at least a fraction of the portion obtained in step (b) to a separation operation in the presence of minus an additive so as to obtain a concentrated portion of chlorohydrin and chlorohydrin esters and which contains less than 40% by weight of water. The separation operation is more particularly a settling. In the process for 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.
Mention particulière est faite d'un procédé de fabrication d'une chlorhydrine comprenant les étapes suivantes (a) on fait réagir un hydrocarbure aliphatique poly hydroxylé, un ester d' un hydrocarbure aliphatique poly hydroxylé, ou un mélange d'entre eux, dont la teneur en métaux alcalins et/ou alcalino -terreux est inférieure ou égale à 5 g/kg, un agent oxydant et un acide organique de façon à obtenir un mélange contenant au moins de la chlorhydrine et des sous-produits, (b) on soumet au moins une partie du mélange obtenu à l'étape (a) à un ou plusieurs traitements dans des étapes ultérieures à l'étape (a) et (c) au moins une des étapes ultérieures à l'étape (a) consiste en une oxydation à une température supérieure ou égale à 800 °C. Mention plus particulière est faite d'un procédé dans lequel dans l'étape ultérieure, on prélève une partie du mélange obtenu à l'étape (a) et on soumet cette partie à une oxydation à une température supérieure ou égale à 800 °C, pendant le prélèvement. Mention particulière est aussi faite d'un procédé dans lequel le traitement de l'étape (b) est une opération de séparation choisie parmi les opérations de décantation, de filtration, de centrifugation, d'extraction, de lavage, d'évaporation, de stripping, de distillation, d'adsorption ou les combinaisons d'au moins deux d'entre-elles.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.
Dans le procédé selon l'invention, lorsque la chlorhydrine est le chloropropanol, celui-ci est généralement mis en œuvre sous la forme d'un mélange de composés comprenant les isomères de 1 -chloropropane-2-ol et de 2-chloropropane-l-ol. Ce mélange contient généralement plus de 1 % en poids des deux isomères, de préférence plus de 5 % en poids et de manière particulière plus de 50 %. Le mélange contient usuellement moins de 99,9 % en poids des deux isomères, de préférence moins de 95 % en poids et tout particulièrement moins de 90 % en poids. Les autres constituants du mélange peuvent être des composés provenant des procédés de fabrication du chloropropanol, tels que des réactifs résiduels, des sous-produits de réaction, des solvants et notamment de l'eau.
Le rapport massique entre les isomères 1 -chloropropane-2-ol et 2-chloropropane-l-ol est usuellement supérieur ou égal à 0,01, de préférence supérieur ou égal 0,4. Ce rapport est usuellement inférieur ou égal à 99 et de préférence inférieur ou égal à 25. Dans le procédé selon l'invention, lorsque la chlorhydrine est le chloroéthanol, celui-ci est généralement mis en œuvre sous la forme d'un mélange de composés comprenant l'isomère 2-chloroéthanol. Ce mélange contient généralement plus de 1 % en poids de l' isomère, de préférence plus de 5 % en poids et de manière particulière plus de 50 %. Le mélange contient usuellement moins de 99,9 % en poids de l' isomère, de préférence moins de 95 % en poids et tout particulièrement moins de 90 % en poids. Les autres constituants du mélange peuvent être des composés provenant des procédés de fabrication du chloroéthanol, tels que des réactifs résiduels, des sous-produits de réaction, des solvants et notamment de l'eau. Dans le procédé selon l'invention, lorsque la chlorhydrine est le chloropropanediol, celui-ci est généralement mis en œuvre sous la forme d'un mélange de composés comprenant les isomères de l-chloropropane-2,3-diol et de 2-chloropropane-l,3-diol. Ce mélange contient généralement plus de 1 % en poids des deux isomères, de préférence plus de 5 % en poids et de manière particulière plus de 50 %. Le mélange contient usuellement moins de 99,9 % en poids des deux isomères, de préférence moins de 95 % en poids et tout particulièrement moins de 90 % en poids. Les autres constituants du mélange peuvent être des composés provenant des procédés de fabrication du chloropropanediol, tels que des réactifs résiduels, des sous-produits de réaction, des solvants et notamment de l'eau.In the process according to the invention, when the chlorohydrin is chloropropanol, it is generally used in the form of a mixture of compounds comprising the isomers of 1-chloropropan-2-ol and 2-chloropropane-1. ol. This mixture generally contains more than 1% by weight of the two isomers, preferably more than 5% by weight and more particularly more than 50%. The mixture usually contains less than 99.9% by weight of the two isomers, preferably less than 95% by weight and most preferably less than 90% by weight. The other constituents of the mixture may be compounds derived from chloropropanol production processes, such as residual reagents, reaction by-products, solvents and in particular water. The weight ratio between the isomers 1-chloropropane-2-ol and 2-chloropropane-1-ol is usually greater than or equal to 0.01, preferably greater than or equal to 0.4. This ratio is usually less than or equal to 99 and preferably less than or equal to 25. In the process according to the invention, when the chlorohydrin is chloroethanol, it is generally 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.
Le rapport massique entre les isomères l-chloropropane-2,3-diol et 2-chloropropane-l,3-diol est usuellement supérieur ou égal à 0,01, de préférence supérieur ou égal 0,4. Ce rapport est usuellement inférieur ou égal à 99 et de préférence inférieur ou égal à 25. Dans le procédé selon l'invention, lorsque la chlorhydrine est le dichloropropanol, celui-ci est généralement mis en œuvre sous la forme d'un mélange de composés comprenant les isomères de l,3-dichloropropane-2-ol et de 2,3-dichloropropane-l-ol. Ce mélange contient généralement plus de 1 % en poids des deux isomères, de préférence plus de 5 % en poids et de manière particulière plus de 50 %. Le mélange contient usuellement moins de 99,9 % en poids des deux isomères, de préférence moins de 95 % en poids et tout
particulièrement moins de 90 % en poids. Les autres constituants du mélange peuvent être des composés provenant des procédés de fabrication du dichloropropanol, tels que des réactifs résiduels, des sous-produits de réaction, des solvants et notamment de l'eau. Le rapport massique entre les isomères l,3-dichloropropane-2-ol etThe weight ratio between the isomers 1-chloropropane-2,3-diol and 2-chloropropane-1,3-diol is usually greater than or equal to 0.01, preferably greater than or equal to 0.4. This ratio is usually less than or equal to 99 and preferably less than or equal to 25. In the process according to the invention, when the chlorohydrin is dichloropropanol, it is generally 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 all especially 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 mass ratio between the 1,3-dichloropropan-2-ol isomers and
2,3-dichloropropane-l-ol est usuellement supérieur ou égal à 0,01, souvent, supérieur ou égal 0,4, fréquemment supérieur ou égal à 1,5, de préférence supérieur à ou égal à 3,0, de manière plus préférée supérieur ou égal à 7,0 et de manière tout particulièrement préférée supérieur ou égal à 20,0. Ce rapport est usuellement inférieur ou égal à 99 et de préférence inférieur ou égal à 25.2,3-dichloropropan-1-ol 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, so 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.
Dans le procédé de fabrication d'une chlorhydrine selon l'invention, la réaction de chloration de l 'hydrocarbure aliphatique poly hydroxylé, de l'ester d'hydrocarbure aliphatique poly hydroxylé, ou du mélange d'entre eux, peut être menée en présence d'un acide organique. L'acide organique peut être un produit provenant du procédé de fabrication de l 'hydrocarbure aliphatique poly hydroxylé ou un produit ne provenant pas de ce procédé. Dans ce dernier cas, il peut s'agir d'un acide organique utilisé pour catalyser la réaction entre l 'hydrocarbure aliphatique poly hydroxylé et l'agent de chloration. L'acide organique peut aussi être un mélange d'acide organique provenant du procédé de fabrication de l 'hydrocarbure aliphatique poly hydroxylé et d'un acide organique ne provenant pas du procédé de fabrication l 'hydrocarbure aliphatique poly hydroxylé.In the process for producing a chlorohydrin according to the invention, the chlorination reaction of the polyhydroxylated aliphatic hydrocarbon, of the polyhydroxylated aliphatic hydrocarbon ester, or of the mixture of them, can be carried out in the presence 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.
Dans le procédé selon l'invention, les esters de l 'hydrocarbure aliphatique polyhydroxylé peuvent provenir de la réaction entre l 'hydrocarbure aliphatique polyhydroxylé et l'acide organique, avant, pendant ou dans les étapes qui suivent la réaction avec l'agent de chloration.In the process according to the invention, the esters of the polyhydroxylated aliphatic hydrocarbon can come from the reaction between the polyhydroxylated aliphatic hydrocarbon and the organic acid before, during or in the steps which follow the reaction with the chlorinating agent. .
La chlorhydrine obtenue dans le procédé selon l'invention peut contenir une teneur élevée en cétones halogénées, en particulier en chloroacétone, comme décrit dans la demande de brevet FR 05.05120 du 20/05/2005 déposée au nom de la demanderesse, et dont le contenu est ici incorporé par référence. La teneur en cétone halogénée peut être réduite en soumettant la chlorhdyrine obtenue dans le procédé selon l'invention à une distillation azéotropique en présence d'eau ou en soumettant la chlorhydrine à un traitement de déshydrochloration comme décrit dans cette demande, de la page 4, ligne 1, à la page 6, ligne 35. Mention particulière est faite d'un procédé de fabrication d'un époxyde dans lequel des cétones halogénées sont formées comme sous-produits et qui
comprend au moins un traitement d'élimination d'au moins une partie des cétones halogénées formées. Mention est plus particulièrement faite d'un procédé de fabrication d'un époxyde par déshydrochloration d'une chlorhydrine dont au moins une fraction est fabriquée par chloration d'un hydrocarbure aliphatique poly hydroxylé, d'un ester d'un hydrocarbure aliphatique poly hydroxylé, ou d'un mélange d'entre eux, d'un traitement de déshydrochloration et d'un traitement par distillation azéotropique d'un mélange eau-cétone halogénée destinés à éliminer au moins une partie des cétones halogénées formées et d'un procédé de fabrication d'épichlorhydrine dans lequel la cétone halogénée formée est la chloroacétone.The chlorohydrin obtained in the process according to the invention may contain a high content of halogenated ketones, in particular chloroacetone, as described in the patent application FR 05.05120 of 20/05/2005 filed in the name of the Applicant, and whose content is hereby incorporated by reference. The content of halogenated ketone can be reduced by subjecting the chlorhdyrine obtained in the process according to the invention to azeotropic distillation in the presence of water or by subjecting the chlorohydrin to a dehydrochlorination treatment as described in this application, on page 4, line 1, page 6, line 35. Special mention is made of a process for producing an epoxide in which halogenated ketones are formed as by-products and which comprises at least one treatment for removing at least a portion of the halogenated ketones formed. Mention is more particularly made of a process for producing an epoxide by dehydrochlorination of a chlorohydrin of which at least one fraction is produced by chlorination of a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture thereof, a dehydrochlorination treatment and azeotropic distillation treatment of a halogenated water-ketone mixture for removing at least a portion of the halogenated ketones formed and a method of manufacture epichlorohydrin in which the halogenated ketone formed is chloroacetone.
La chlorhydrine obtenue dans le procédé selon l'invention peut être soumise à une réaction de déshydrochloration pour produire un époxyde comme décrit dans les demandes de brevet WO 2005/054167 et FR 05.05120 déposées au nom de SOLVAY SA. L'expression « époxyde » est utilisée ici pour décrire un composé comportant au moins un oxygène ponté sur une liaison carbone-carbone. Généralement les atomes de carbone de la liaison carbone-carbone sont adjacents et le composé peut contenir d'autres atomes que des atomes de carbone et d'oxygène, tels que des atomes d'hydrogène et des halogènes. Les époxydes préférés sont l'oxyde d'éthylène, l'oxyde de propylène et l'épichlorhydrine.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 and epichlorohydrin.
La déshydrochloration de la chlorhydrine peut être effectuée comme décrit dans la demande intitulée « Procédé de fabrication d'un époxyde au départ d'un hydrocarbure aliphatique poly hydroxylé et d'un agent de chloration » déposée au nom de SOLVAY SA le même jour que la présente demande, et dont le contenu est ici incorporé par référence.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.
Mention particulière est faite d'un procédé de fabrication d'un époxyde dans lequel on soumet un milieu réactionnel résultant de la réaction entre un hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique poly hydroxylé, ou un mélange d'entre eux, et un agent de chloration, le milieu réactionnel contenant au moins 10 g de chlorhydrine par kg de milieu réactionnel, à une réaction chimique ultérieure sans traitement intermédiaire.Particular mention is made of a process for producing an epoxide in which a reaction medium resulting from the reaction between a polyhydroxylated aliphatic hydrocarbon, an ester of a polyhydroxylated aliphatic hydrocarbon, or a mixture of them, is subjected to and a chlorinating agent, the reaction medium containing at least 10 g of chlorohydrin per kg of reaction medium, to a subsequent chemical reaction without intermediate treatment.
Mention est également faite de fabrication d'un époxyde comprenant les étapes suivantes : (a) on fait réagir un hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique poly hydroxylé, ou un mélange d'entre eux, avec un agent de chloration et un acide organique de façon à former de la chlorhydrine et des esters de chlorhydrine dans un milieu réactionnel contenant
de l'hydrocarbure aliphatique poly hydroxylé, de l'ester d'hydrocarbure aliphatique poly hydroxylé, de l'eau, l'agent de chloration et l'acide organique, le milieu réactionnel contenant au moins 10 g de chlorhydrine par kg de milieu réactionnel, (b) on soumet au moins une fraction du milieu réactionnel obtenu à l'étape (a), fraction qui a la même composition que le milieu réactionnel obtenu à l'étape (a), à un ou plusieurs traitements dans des étapes ultérieures à l'étape (a) et (c) on ajoute un composé basique à au moins une des étapes ultérieures à l'étape (a) pour qu'il réagisse au moins partiellement avec la chlorhydrine, les esters de chlorhydrine, l'agent de chloration et l'acide organique de façon à former de l'époxyde et des sels.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 having the same composition as the reaction medium obtained in step (a), to one or more treatments in subsequent steps in step (a) and (c) adding a basic compound to at least one of the steps subsequent to step (a) to react at least partially with the chlorohydrin, the chlorohydrin esters, the chlorine and the organic acid to form epoxide and salts.
Le procédé de fabrication de la chlorhydrine selon l'invention peut être intégré dans un schéma global de fabrication d'un époxyde tel que décrit dans la demande intitulée « Procédé de fabrication d'un époxyde au départ d'une chlorhydrine » déposée au nom de SOLVAY SA le même jour que la présente demande, et dont le contenu est ici incorporé par référence.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.
Mention particulière est faite d'un procédé de fabrication d'un époxyde comprenant au moins une étape de purification de l'époxyde formé, l'époxyde étant au moins en partie fabriqué par un procédé de déshydrochloration d'une chlorhydrine, celle-ci étant au moins en partie fabriquée par un procédé de chloration d'un hydrocarbure aliphatique poly hydroxylé, d'un ester d'un hydrocarbure aliphatique poly hydroxylé, ou d'un mélange d'entre eux.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.
Dans le procédé de fabrication d'une chlorhydrine selon l'invention, l'autre étape est par exemple une étape de stockage, d'approvisionnement, de prélèvement, de transfert, de traitement chimique ou de traitement physique de composés utilisés ou produits dans le procédé de fabrication de la chlorhydrine. Des exemples de ces étapes ont été décrits ci-dessus.In the process for producing a chlorohydrin according to the invention, the other step is, for example, a stage of storage, supply, sampling, transfer, chemical treatment or physical treatment of compounds used or produced in the process. process for producing chlorohydrin Examples of these steps have been described above.
Parmi les étapes de stockage, on peut citer par exemple, les stockages de l'agent de chloration contenant le chlorure d'hydrogène et de l'hydrocarbure aliphatique poly hydroxylé, avant utilisation, le stockage des purges avant traitement, les stockages de la chlorhydrine produite, le stockage du catalyseur et de ses préparations. Parmi les étapes de traitement chimique, on peut citer par exemple un traitement d'hydrolyse destiné à récupérer le catalyseur et un traitement de mise en solution du catalyseur. Parmi les étapes de traitement physique, on peut citer par exemple, les opérations de séparation par stripping, distillation, évaporation, extraction, décantation et filtration, les opérations d'échange de chaleur, chauffage et refroidissement.
Parmi les étapes d'approvisionnement, de prélèvement ou de transfert, on peut citer par exemple, les opérations de recyclage, de purge et de mise en décharge d'effluents, le transport des fluides entre les différents pièces d'équipements dans lesquelles sont effectués les réactions chimiques, les stockages et les traitements chimiques et physiques.Amongst the storage steps, there may be mentioned, for example, the storage of the chlorinating agent containing hydrogen chloride and the polyhydroxylated aliphatic hydrocarbon, before use, the storage of purges before treatment, the storage of chlorohydrin produced, the storage of the catalyst and its preparations. Among the chemical treatment steps, there may be mentioned, for example, a hydrolysis treatment for recovering the catalyst and a treatment for dissolving the catalyst. Amongst the physical treatment steps, there may be mentioned, for example, the separation operations by stripping, distillation, evaporation, extraction, decantation and filtration, the heat exchange, heating and cooling operations. Among the steps of supply, withdrawal or transfer, there may be mentioned, for example, operations for recycling, purging and discharge of effluents, the transport of fluids between the various pieces of equipment in which are performed chemical reactions, storage and chemical and physical treatments.
Dans le procédé de fabrication de chlorhydrine selon l'invention, on entend par « équipement » les récipients où l'on effectue des stockages de composés, des réactions chimiques et/ou des opérations physiques, les tuyauteries et les raccords connectant ces récipients, les pièces assurant l'étanchéité au niveau des raccords, les instruments nécessaires au transfert de composés entre les récipients, les instruments et les appareillages de mesure des différents paramètres nécessaires au contrôle des stockages, au transfert des composés et à la réalisation des réactions chimiques et des opérations physiques.In the process for the manufacture of chlorohydrin according to the invention, the term "equipment" is understood to mean containers in which compound storage, chemical reactions and / or physical operations are carried out, the pipes and fittings connecting these containers, the sealing parts at the connections, the instruments necessary for the transfer of compounds between receptacles, instruments and measuring equipment of the various parameters necessary for the control of storage, the transfer of compounds and the carrying out of chemical reactions and physical operations.
Les conditions de température et de pression auxquelles sont soumis ces équipements dépendent de leur utilisation dans le procédé.The temperature and pressure conditions to which these devices are subjected depend on their use in the process.
Certains équipements sont utilisés à basse température. Par basse température, on entend désigner une température qui est inférieure ou égale à 110 °C, souvent inférieure ou égale à 100 °C et plus particulièrement inférieure ou égale à 95 °C. Cette basse température est généralement supérieure ou égale à 0 °C, fréquemment supérieure ou égale à 5 °C et plus particulièrement supérieure ou égale à 10 °C. Des équipements utilisés à basse température sont par exemple, les équipements de stockages des matières premières acides et de la chlorhydrine produite et les décanteurs.Some equipment is used at low temperatures. By low temperature is meant a temperature which is less than or equal to 110 ° C, often less than or equal to 100 ° C and more particularly less than or equal to 95 ° C. This low temperature is generally greater than or equal to 0 ° C, frequently greater than or equal to 5 ° C and more particularly greater than or equal to 10 ° C. Equipment used at low temperature are, for example, storage equipment for acidic raw materials and chlorohydrin produced and decanters.
Certains équipements sont utilisés à haute température. Par haute température, on entend désigner une température qui est supérieure à 110 °C. Cette haute température est généralement inférieure ou égale à 200 °C, fréquemment inférieure ou égale à 160 °C et plus particulièrement inférieure ou égale à 140 °C. Des équipements utilisés à haute température sont par exemple, les réacteurs où s'effectuent la réaction de chloration de l'hydrocarbure aliphatique poly hydroxylé, le traitement des purges, la récupération du catalyseur et la préparation du catalyseur, les échangeurs de chaleur, les appareils de séparation par stripping, distillation, évaporation, extraction et filtration.Some equipment is used at high temperatures. High temperature means a temperature which is greater than 110 ° C. This high temperature is generally less than or equal to 200 ° C., frequently less than or equal to 160 ° C. and more particularly less than or equal to 140 ° C. Equipment used at high temperature are, for example, the reactors where the chlorination reaction of the polyhydroxylated aliphatic hydrocarbon is carried out, the treatment of purges, the recovery of the catalyst and the preparation of the catalyst, the heat exchangers, the apparatus separation by stripping, distillation, evaporation, extraction and filtration.
Certains équipements sont utilisés à basse pression. Par basse pression, on entend désigner une pression qui est inférieure ou égale à 3 bar absolu, souvent inférieure ou égale à 2 bar et plus particulièrement préférée inférieure ou égale à 1.5 bar. Cette basse pression est généralement supérieure ou égale à 0,01 bar
absolu, fréquemment supérieure ou égale à 0,05 bar et plus particulièrement préférée supérieure ou égale à 0,1 bar. Des équipements utilisés à basse pression sont par exemple, les appareils de séparation par stripping, distillation, évaporation, extraction et filtration. Certains équipements sont utilisés à haute pression. Par haute pression, on entend désigner une pression qui est supérieure à 3 bar absolu, souvent supérieure ou égale à 5 bar et plus particulièrement supérieure ou égale à 7 bar Cette haute pression est généralement inférieure ou égale à 50 bar absolu, fréquemment inférieure ou égale à 20 bar et plus particulièrement préférée inférieure ou égale à 10 bar. Des équipements utilisés à haute pression sont par exemple, les réacteurs où s'effectuent la réaction de chloration de l'hydrocarbure aliphatique poly hydroxylé, des appareils de séparation par stripping, distillation, évaporation et filtration.Some equipment is used at low pressure. By low pressure is meant a pressure which is less than or equal to 3 bar absolute, often less than or equal to 2 bar and more preferably less than or equal to 1.5 bar. This low pressure is generally greater than or equal to 0.01 bar absolute, frequently greater than or equal to 0.05 bar and more preferably greater than or equal to 0.1 bar. Equipment used at low pressure are, for example, separating apparatus by stripping, distillation, evaporation, extraction and filtration. Some equipment is used at high pressure. By high pressure is meant a pressure which is greater than 3 bar absolute, often greater than or equal to 5 bar and more particularly greater than or equal to 7 bar This high pressure is generally less than or equal to 50 bar absolute, frequently less than or equal to at 20 bar and more preferably less than or equal to 10 bar. Equipment used at high pressure are, for example, the reactors in which the chlorination reaction of the polyhydroxylated aliphatic hydrocarbon is carried out, separation apparatuses by stripping, distillation, evaporation and filtration.
Les équipements peuvent être recouvert de ou réalisés en matériau résistant aux agents de chloration dans les conditions de fonctionnement de ces équipements. Outre les conditions de fonctionnement de température et de pression citées plus haut, le choix du type de protection, par recouvrement avec ou par réalisation dans un matériau résistant aux agents de chloration, dépend de nombreux facteurs liés à l'agent de chloration, à la nature et à la méthode de mise en œuvre du matériau résistant aux agents de chloration et aux caractéristiques des équipements à protéger.The equipment may be covered with or made of chlorine-resistant material under the operating conditions of such equipment. In addition to the operating conditions of temperature and pressure mentioned above, the choice of the type of protection, by covering with or by realization in a material resistant to chlorinating agents, depends on many factors related to the chlorinating agent, the nature and the method of implementation of the material resistant to chlorinating agents and the characteristics of the equipment to be protected.
Les facteurs liés à l'agent de chloration sont par exemple sa nature chimique (chlore, chlorure d'hydrogène), son état physique (liquide, gaz, en solution aqueuse) et sa pureté (présence d'eau). Les facteurs liés aux équipements sont par exemple la forme, la taille, la complexité et l'accès aux surfaces des équipements à protéger.The factors related to the chlorinating agent are, for example, its chemical nature (chlorine, hydrogen chloride), its physical state (liquid, gas, in aqueous solution) and its purity (presence of water). Equipment factors are, for example, shape, size, complexity and access to the surfaces of the equipment to be protected.
Les matériaux tels que divulgués tel que décrit dans la demande WO 2005/054167 de SOLVAY SA, à la page 6, lignes 3 à 23, sont particulièrement préférés. A titre de matériau approprié, on peut citer par exemple les matériaux métalliques et les matériaux non-métalliques.The materials as disclosed as described in SOLVAY SA application WO 2005/054167, at page 6, lines 3 to 23, are particularly preferred. Suitable materials include, for example, metallic materials and non-metallic materials.
Ces matériaux peuvent être utilisés soit dans la masse, soit sous forme de clade ou encore par un procédé de recouvrement quelconque.These materials can be used either in the mass or in the form of a clade or by any method of recovery.
Parmi les matériaux métalliques, on peut citer le tantale et les alliages de tantale, le zirconium et les alliages de zirconium, le titane et les alliages de titane, le platine et les métaux du groupe du « platine », l'argent et les alliages argent-or
- palladium avec un minium de 30 % en or, l'or et les alliages or-argent et les alliages or-platine, le molybdène et les alliages de molybdène, les alliages nickel- molybdène, les alliages nickel-chrome-molybdène, les alliages de cuivre (Silicon-bronze), les alliages cuivre-tantale et cuivre-niobium, les alliages étain- antimoine contenant 5% d'antimoine, les alliages étain-nickel, le niobium et les alliages niobium-tantale.Metallic materials include tantalum and tantalum alloys, zirconium and zirconium alloys, titanium and titanium alloys, platinum and platinum group metals, silver and alloys. silver-gold - palladium with a minimum of 30% gold, gold and gold-silver alloys and gold-platinum alloys, molybdenum and molybdenum alloys, nickel-molybdenum alloys, nickel-chromium-molybdenum alloys, copper (Silicon-bronze) alloys, copper-tantalum and copper-niobium alloys, tin-antimony alloys containing 5% antimony, tin-nickel alloys, niobium and niobium-tantalum alloys.
Parmi les métaux du groupe du platine, on peut citer le rhodium, l'iridium, le ruthénium, le palladium et l'osmium.Among the platinum group metals include rhodium, iridium, ruthenium, palladium and osmium.
Parmi les matériaux métalliques, l'or et le tantale sont préférés. Les métaux et leurs alliages peuvent être utilisés soit dans la masse, soit sous forme de clade ou encore par un procédé de recouvrement quelconque.Of the metallic materials, gold and tantalum are preferred. The metals and their alloys can be used either in the mass or in the form of a clade or by any method of recovery.
Parmi les matériaux non-métalliques, on peut citer le polyéthylène haute densité, les élastomères à base de fluoroelastomères, les thermoplastiques à base de polypropylène, de polymères fluorés, les copolymères ABS (acrylonitrile- butadiène-styrène), le copolymère acrylonitrile (40%)-vinylchloride (60%), les polysulfones, les polyphenylène sulfure et les polyphénylsulfones, les stratifiés verre-résine à base de résines de polyester, de résines phénoliques, de résines furanes, de résines époxy et de résines vinylester, les céramiques à base d'alumine et de corindon, les matériaux métallo-céramiques à base de carbure de hafnium et de niture de titane, les matériaux réfractaires à base de carbure de silicium, de silice, de silicates d'aluminium (à teneur en silice élevée), de silicate de zirconium, d'oxyde de zirconium et de sillimanite (AIiO3-SiOi), les révêtements à base de résine époxy, de Sâkaphen, de Brauthite (sur base de résine formo-phénolique) et d'isolémail, les ciments anti-acides à base de silicates, de résine phénol- formaldéhyde et de sulfure (mélangé avec du sable de quartz), les « self-curing » ciments anti-acides à base de résines phénol- formaldéhyde additionnées de graphite, de résines d'alcool de furfuryl additionnées de graphite, de résines époxy additionnées de carbone, de résines polyester additionnées de quartz. Dans le cas des ciments, le substrat devrait être protégé par une feuille additionnelle en plastique. Le graphite imprégné (par du polytétrafluoroéthylène), le carbone, le verre, le quartz, l'émail, la porcelaine, le grès et la brique anti-acide peuvent également convenir comme matériaux non- métalliques.Among the non-metallic materials, mention may be made of high-density polyethylene, elastomers based on fluoroelastomers, thermoplastics based on polypropylene, fluoropolymers, copolymers ABS (acrylonitrile-butadiene-styrene), acrylonitrile copolymer (40% ) -vinylchloride (60%), polysulfones, polyphenylene sulfides and polyphenylsulfones, glass-resin laminates based on polyester resins, phenolic resins, furan resins, epoxy resins and vinylester resins, based on ceramics alumina and corundum, metallo-ceramic materials based on hafnium carbide and titanium alloy, refractory materials based on silicon carbide, silica, aluminum silicates (with high silica content), zirconium silicate, zirconium oxide and sillimanite (AliO 3 -SiOi), the epoxy resin, Sâkaphen, Brauthite (based on resin form) coatings o-phenolic) and isolemail, anti-acid cements based on silicates, phenol-formaldehyde resin and sulphide (mixed with quartz sand), the "self-curing" anti-acid cements based on resins phenol-formaldehyde added with graphite, graphite-added furfuryl alcohol resins, carbon-added epoxy resins, polyester resins supplemented with quartz. In the case of cements, the substrate should be protected by an additional sheet of plastic. Impregnated graphite (polytetrafluoroethylene), carbon, glass, quartz, enamel, porcelain, sandstone and anti-acid brick may also be suitable as non-metallic materials.
L'émail peut être utilisé comme matériau de recouvrement de l'acier, et le matériau résistant aux agents de chloration est l'acier émaillé.
Parmi les polymères, les polyoléfines tels que le polyéthylène haute densité et le polypropylène et en particulier les thermoplastiques à base de polymères fluorés, les polymères comprenant du soufre tels que les polysulfones ou polysulfures, en particulier aromatiques, le graphite et le graphite imprégné conviennent bien.Enamel can be used as the steel covering material, and the chlorinator resistant material is enamelled steel. Among the polymers, polyolefins such as high density polyethylene and polypropylene and in particular thermoplastics based on fluorinated polymers, polymers comprising sulfur such as polysulfones or polysulfides, in particular aromatic, graphite and impregnated graphite are well suited .
Parmi les thermoplastiques à base de polymères fluorés, le polyfluorure de vinylidène, le polytétrafluoroéthylène, les perfluororalcoxy alcanes, les copolymères éthylène-térafluoroéthylène, les copolymères tétrafluoroéthylène- perfluorométhylvinyléthere t les copolymères tétrafluoroéthylène- hexafluoropropylène conviennent bien.Of the thermoplastics based on fluoropolymers, polyvinylidene fluoride, polytetrafluoroethylene, perfluoroalkoxyalkanes, ethylene-terafluoroethylene copolymers, tetrafluoroethylene-perfluoromethylvinylether copolymers and tetrafluoroethylenehexafluoropropylene copolymers are suitable.
Les polymères peuvent être employés à l'état massique ou renforcés par une enveloppe (acier, frettage).The polymers can be used in the mass state or reinforced with an envelope (steel, hooping).
Parmi les revêtements au moyen de résines, ceux à base résines époxy ou de résines phénoliques conviennent particulièrement bien. Pour certaines pièces particulières, par exemple des échangeurs de chaleur et des pompes, le graphite, imprégné ou non est particulièrement bien adapté. Pour les échangeurs de chaleur permettant un chauffage ou une évaporation des fluides du procédé, l'imprégnation par du polytétrafluoroéthylène est particulièrement bien adaptée. L'acier émaillé, le tantale, l'or et les polymères perfluorés conviennent bien pour le recouvrement ou la réalisation d'équipements opérant à haute température.Among the coatings by means of resins, those based on epoxy resins or phenolic resins are particularly suitable. For certain particular parts, for example heat exchangers and pumps, graphite, impregnated or not, is particularly well suited. For heat exchangers for heating or evaporation of the process fluids, the impregnation with polytetrafluoroethylene is particularly well suited. Enamelled steel, tantalum, gold and perfluorinated polymers are well suited for the recovery or production of equipment operating at high temperatures.
Les polyoléfines, les polymères fluorés et les alliages de métaux conviennent bien pour le recouvrement ou la réalisation d'équipements opérant à basse température.Polyolefins, fluoropolymers and metal alloys are well suited for the recovery or production of equipment operating at low temperatures.
Dans le procédé, l'utilisation et l'installation selon l'invention, l'hydrocarbure aliphatique polyhydroxylé est de préférence le glycérol et la chlorhydrine est de préférence le dichloropropanol.In the process, use and installation according to the invention, the polyhydroxylated aliphatic hydrocarbon is preferably glycerol and the chlorohydrin is preferably dichloropropanol.
Lorsque la chlorhydrine est le dichloropropanol, le procédé selon l'invention peut être suivi d'une fabrication d'épichlorhydrine par déshydrochloration de dichloropropanol et l'épichlorhdyrine peut entrer dans la fabrication de résines époxy.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.
Les exemples ci-après entendent illustrer l'invention sans toutefois la limiter. Exemple 1 (non-conforme à l'invention)
Des éprouvettes de corrosion en Ti Gr 261 et Monel 400 on été placées, à 120 °C et pendant 90 jours dans un milieu réactionnel liquide hydrochloration du glycérol constitué par 20 % de dichloropropanol, 18% de monochlorhydrine de glycérol, 2 % de glycérol, 6 % d'oligomères de glycérol mono et polychlorés, 6 % d'eau, 0,8 % d'HCl, le solde étant constitué de l'acide carboxylique servant de catalyseur et de ses esters. Les éprouvettes se sont complètement dissoutes dans le milieu réactionnel.The following examples intend to illustrate the invention without limiting it. Example 1 (not in accordance with the invention) Corrugated samples of Ti Gr 261 and Monel 400 were placed at 120 ° C. and for 90 days in a glycerol liquid hydrochlorination reaction medium constituted by 20% of dichloropropanol, 18% of glycerol monochlorohydrin and 2% of glycerol. 6% mono and polychlorinated glycerol oligomers, 6% water, 0.8% HCl, the remainder being the carboxylic acid catalyst and its esters. The test pieces were completely dissolved in the reaction medium.
Exemple 2 (conforme à l'invention)Example 2 (in accordance with the invention)
Plongées dans le milieu réactionnel en phase liquide, les parties en acier émaillées du réacteur d'hydrochloration du glycérol, celles en graphite des échangeurs de chaleurs ainsi que celles en PTFE des colonnes de distillation n'ont pas montré de signe de corrosion.
Plunging into the reaction medium in the liquid phase, the enamelled steel parts of the glycerol hydrochlorination reactor, the graphite heat exchanger and the PTFE distillation columns did not show signs of corrosion.
Claims
R E V E N D I C A T I O N SR E V E N D I C A T IO N S
1 - Procédé de fabrication d'une chlorhydrine comprenant :1 - Process for the manufacture of a chlorohydrin comprising:
(a) une étape dans laquelle on soumet un hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique poly hydroxylé, ou un mélange d'entre eux, à une réaction avec un agent de chloration contenant du chlorure d'hydrogène(a) 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
(b) au moins une autre étape effectuée dans un équipement réalisé en ou recouvert de matériaux résistant à l'agent de chloration, dans les conditions de réalisation de cette étape.(b) at least one other step carried out in equipment made of or covered with materials resistant to the chlorinating agent, under the conditions of completion of this step.
2 - Procédé selon la revendication 1 dans lequel l 'hydrocarbure aliphatique poly hydroxylé, l'ester d'hydrocarbure aliphatique poly hydroxylé, ou le mélange d'entre eux, est obtenu au départ de matières premières renouvelables.2 - Process according to claim 1 wherein the polyhydroxylated aliphatic hydrocarbon, the polyhydroxylated aliphatic hydrocarbon ester, or the mixture of them, is obtained from renewable raw materials.
3 - Procédé selon la revendication 1 ou 2 dans lequel le chlorure d'hydrogène est une combinaison de chlorure d'hydrogène gazeux et d'une solution aqueuse de chlorure d'hydrogène ou une solution aqueuse de chlorure d'hydrogène.3 - Process according to claim 1 or 2 wherein the hydrogen chloride is a combination of gaseous hydrogen chloride and an aqueous solution of hydrogen chloride or an aqueous solution of hydrogen chloride.
4 - Procédé selon l'une quelconque des revendications 1 à 3 dans lequel l'autre étape est une étape de stockage, d'approvisionnement, de prélèvement, de transfert, de traitement chimique ou de traitement physique de composés utilisés ou produits dans le procédé de fabrication de la chlorhydrine.4 - Process according to any one of claims 1 to 3 wherein the other step is a storage step, supply, sampling, transfer, chemical treatment or physical treatment of compounds used or produced in the process of manufacture of chlorohydrin.
5 - Procédé selon l'une quelconque des revendications 1 à 4 dans lequel l'équipement est sélectionné parmi les récipients où l'on effectue des stockages de composés, des réactions chimiques et/ou des opérations physiques, les tuyauteries et les raccords connectant ces récipients, les pièces assurant l'étanchéité au niveau des raccords, les instruments nécessaires au transfert de composés entre les récipients, les instruments et les appareillages de mesure des différents paramètres nécessaires au contrôle des stockages, au transfert des composés et à la réalisation des réactions chimiques et des opérations physiques.5 - Process according to any one of claims 1 to 4 wherein the equipment is selected from the containers where one carries out storage of compounds, chemical reactions and / or physical operations, the pipes and fittings connecting these containers, sealing parts at the connections, instruments necessary for the transfer of compounds between receptacles, instruments and measuring equipment of the various parameters necessary for the control of storage, the transfer of compounds and the realization of reactions chemical and physical operations.
6 - Procédé selon l'une quelconque des revendications 1 à 5 dans lequel les équipements sont maintenus à une température supérieure ou égale à 0 °C et
inférieure ou égale à 200 °C et à une pression supérieure ou égale à 0,01 bar absolu et inférieure ou égale à 50 bar.6 - Process according to any one of claims 1 to 5 wherein the equipment is maintained at a temperature greater than or equal to 0 ° C and less than or equal to 200 ° C and a pressure greater than or equal to 0.01 bar absolute and less than or equal to 50 bar.
7 - Procédé selon l'une quelconque des revendications 1 à 6 dans lequel les matériaux résistant aux agents de chloration sont sélectionnés parmi les matériaux métalliques et les matériaux non-métalliques à base d'élastomères, de thermosplastiques, de stratifié verre-résine, de céramiques, de matériaux métallo- céramiques, de matériaux réfractaires, de révêtements, de ciments anti-acides, de « self-curing » ciments anti-acides, de graphite imprégné, de carbone, de verre, de quartz, d'émail, de porcelaine, de grès et de brique anti-acide.7 - Process according to any one of claims 1 to 6 wherein the chlorinator-resistant materials are selected from metal materials and non-metallic materials based on elastomers, thermosplastics, glass-resin laminate, ceramics, metallo-ceramics, refractories, coatings, anti-acid cements, self-curing, anti-acid cements, impregnated graphite, carbon, glass, quartz, enamel, porcelain, sandstone and anti-acid brick.
8 - Procédé selon l'une quelconque des revendications 1 à 7 dans lequel les matériaux résistant aux agents de chloration sont utilisés dans la masse, sous forme de clade ou par un procédé de recouvrement quelconque.8 - Process according to any one of claims 1 to 7 wherein the chlorine-resistant materials are used in the mass, in the form of a clade or by any method of recovery.
9 - Procédé selon la revendication 7 ou 8, dans lequel les matériaux métalliques sont sélectionnés parmi le tantale et les alliages de tantale, le zirconium et les alliages de zirconium, le titane et les alliages de titane, le platine et les métaux du groupe du « platine », l'argent et les alliages argent-or- palladium avec un minimum de 30 % en or, l'or et les alliages or-argent et les alliages or-platine, le molybdène et les alliages de molybdène, les alliages nickel- molybdène, les alliages nickel-chrome-molybdène, les alliages de cuivre (Silicon-bronze), les alliages cuivre -tantale et cuivre-niobium, les alliages étain- antimoine contenant 5% d'antimoine, les alliages étain-nickel, le niobium et les alliages niobium-tantale.9 - Process according to claim 7 or 8, wherein the metallic materials are selected from tantalum and tantalum alloys, zirconium and zirconium alloys, titanium and titanium alloys, platinum and metals from the group of "Platinum", silver and silver-gold-palladium alloys with a minimum of 30% gold, gold and gold-silver alloys and gold-platinum alloys, molybdenum and molybdenum alloys, alloys nickel-molybdenum, nickel-chromium-molybdenum alloys, copper (Silicon-bronze) alloys, copper-tantalum and copper-niobium alloys, tin-antimony alloys containing 5% antimony, tin-nickel alloys, niobium and niobium-tantalum alloys.
10 - Procédé selon la revendication 9, dans lequel les matériaux métalliques sont sélectionnés parmi l'or et le tantale.The method of claim 9, wherein the metallic materials are selected from gold and tantalum.
11 - Procédé selon la revendication 9, dans lequel les métaux du groupe du11 - Process according to claim 9, wherein the metals of the group of
« platine » sont sélectionnés parmi le rhodium, l'iridium, le ruthénium, le palladium et l'osmium."Platinum" are selected from rhodium, iridium, ruthenium, palladium and osmium.
12 - Procédé selon la revendication 7 ou 8, dans lequel les matériaux non- métalliques sont sélectionnés parmi l'émail, le polyéthylène haute densité, les élastomères à base de fluoroélastomères, les thermoplastiques à base de polypropylène, de polymères fluorés, les copolymères acrylonitrile-butadiène- styrène, le copolymère acrylonitrile (40%)-vinylchloride (60%), les polysulfones,
les polyphenylène sulfure et les polyphénylsulfones, les stratifiés verre-résine à base de résines de polyester, de résines phénoliques, de résines furanes, de résines époxy et de résines vinylester, les céramiques à base d'alumine et de corindon, les matériaux métallo-céramiques à base de carbure de hafnium et de niture de titane, les matériaux réfractaires à base de carbure de silicium, de silice, de silicates d'aluminium à teneur en silice élevée, de silicate de zirconium, d'oxyde de zirconium et de sillimanite (AIiO3-SiOi), les révêtements à base de résine époxy, de Sâkaphen, de Brauthite sur base de résine formo-phénolique et d'isolémail, les ciments anti-acides à base de silicates, de résine phénol- formaldéhyde et de sulfure mélangé avec du sable de quartz, les « self-curing » ciments anti-acides à base de résines phénol- formaldéhyde additionnées de graphite, de résines d'alcool de furfuryl additionnées de graphite, de résines époxy additionnées de carbone, de résines polyester additionnées de quartz.12 - Process according to claim 7 or 8, wherein the non-metallic materials are selected from enamel, high density polyethylene, elastomers based on fluoroelastomers, thermoplastics based on polypropylene, fluoropolymers, acrylonitrile copolymers -butadiene-styrene, acrylonitrile copolymer (40%) - vinylchloride (60%), polysulfones, polyphenylene sulfide and polyphenylsulfones, glass-resin laminates based on polyester resins, phenolic resins, furan resins, epoxy resins and vinylester resins, alumina and corundum ceramics, metallocene materials, ceramic based on hafnium carbide and titanium alloy, refractory materials based on silicon carbide, silica, high silica aluminum silicates, zirconium silicate, zirconium oxide and sillimanite (AIiO 3 -SiOi), the coatings based on epoxy resin, Sakaphen, Brauthite based on formophenolic resin and isolemail, the antacidic cements based on silicates, phenol-formaldehyde resin and sulfide mixed with quartz sand, the "self-curing" anti-acid cements based on phenol-formaldehyde resins supplemented with graphite, furfuryl alcohol resins added with graphite, resins carbon-added epoxy, polyester resins supplemented with quartz.
13 - Procédé selon la revendication 12, dans lequel les matériaux ,non- métalliques sont sélectionnés parmi l'émail, le polyéthylène haute densité, le polypropylène, les thermoplastiques à base de polymères fluorés, les polysulfones et les polysulfures, le graphite et le graphite imprégné.13 - Process according to claim 12, wherein the non-metallic materials are selected from enamel, high density polyethylene, polypropylene, thermoplastics based on fluoropolymers, polysulfones and polysulfides, graphite and graphite impregnated.
14 - Procédé selon la revendication 13, dans lequel les thermoplastiques à base de polymères fluorés sont sélectionnés parmi le polyfluorure de vinylidène, le polytétrafluoroéthylène, les perfluororalcoxy alcanes, les copolymères éthylène-tétrafluoroéthylène, les copolymères tétrafluoroéthylène- perfluorométhylvinyléther et les copolymères tétrafluoroéthylène- hexafluoropropylène.14 - Process according to claim 13, wherein the thermoplastics based on fluoropolymers are selected from polyvinylidene fluoride, polytetrafluoroethylene, perfluoroalkoxyalkanes, ethylene-tetrafluoroethylene copolymers, tetrafluoroethylene-perfluoromethylvinylether copolymers and tetrafluoroethylenehexafluoropropylene copolymers.
15 - Procédé selon la revendication 13, dans lequel l'émail est utilisé comme matériau de recouvrement de l'acier, et le matériau résistant aux agents de chloration est l'acier émaillé.The method of claim 13, wherein the enamel is used as a steel covering material, and the chlorinator resistant material is enamelled steel.
16 - Procédé selon l'une quelconque des revendications 1 à 15, selon lequel l 'hydrocarbure aliphatique polyhydroxylé est choisi parmi l'éthylène glycol, le propylène glycol, le chloropropanediol, le glycérol et les mélanges d'au moins deux d'entre-eux.16 - Process according to any one of claims 1 to 15, wherein the polyhydroxylated aliphatic hydrocarbon is selected from ethylene glycol, propylene glycol, chloropropanediol, glycerol and mixtures of at least two of them.
17 - Procédé selon l'une quelconque des revendications 1 à 16, selon lequel la chlorhydrine est choisie parmi le chloroéthanol, le chloropropanol, le
chloropropanediol, le dichloropropanol et les mélanges d'au moins deux d'entre- eux.17 - Process according to any one of claims 1 to 16, wherein the chlorohydrin is selected from chloroethanol, chloropropanol, chloropropanediol, dichloropropanol and mixtures of two or more of them.
18 - Procédé selon la revendication 16 ou 17 selon lequel l 'hydrocarbure aliphatique polyhydroxylé est le glycérol et la chlorhydrine est le dichloropropanol.18 - The method of claim 16 or 17 wherein the polyhydroxy aliphatic hydrocarbon is glycerol and the chlorohydrin is dichloropropanol.
19 - Procédé selon la revendication 18 suivi d'une fabrication d'épichlorhydrine par déshydrochloration de dichloropropanol19 - Process according to claim 18 followed by a manufacture of epichlorohydrin by dehydrochlorination of dichloropropanol
20 - Procédé selon la revendication 19 dans lequel l'épichlorhdyrine entre dans la fabrication de résines époxy.20 - Process according to claim 19 wherein epichlorohydrin is used in the manufacture of epoxy resins.
21 - Utilisation d'équipement réalisé en ou recouvert de matériaux résistant aux agents de chloration dans un procédé de fabrication d'une chlorhydrine comprenant une étape dans laquelle on soumet un hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique poly hydroxyl, ou un mélange d'entre eux, à une réaction avec un agent de chloration contenant du chlorure d'hydrogène, dans au moins une étape autre que l'étape de réaction.21 - Use of equipment made of or coated with chlorine-resistant materials in 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 of them, in a reaction with a chlorinating agent containing hydrogen chloride, in at least one step other than the reaction step.
22 - Utilisation selon la revendication 20 pour éviter la corrosion par le chlorure d'hydrogène en présence d'eau et de l'hydrocarbure aliphatique poly hydroxylé.22 - Use according to claim 20 to prevent corrosion by hydrogen chloride in the presence of water and the polyhydroxylated aliphatic hydrocarbon.
23- Utilisation selon la revendication 22 dans laquelle l'hydrocarbure aliphatique polyhydroxylé est le glycérol et la chlorhydrine est le dichloropropanol.23. Use according to claim 22 wherein the polyhydroxylated aliphatic hydrocarbon is glycerol and the chlorohydrin is dichloropropanol.
24 - Installation de fabrication d'une chlorhydrine comprenant :24 - Plant for the manufacture of a chlorohydrin comprising:
(a) une partie dans laquelle on soumet un hydrocarbure aliphatique poly hydroxylé, un ester d'un hydrocarbure aliphatique poly hydroxyl, ou un mélange d'entre eux, à une réaction avec un agent de chloration contenant du chlorure d'hydrogène(a) a part 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
(b) au moins une autre partie faite dans un équipement réalisé en ou recouvert de matériaux résistant à l'agent de chloration.
25 - Installation selon la revendication 24 dans laquelle l'hydrocarbure aliphatique polyhydroxylé est le glycérol et la chlorhydrine est le dichloropropanol.(b) at least one other part made in equipment made of or covered with chlorine-resistant materials. 25. The plant according to claim 24, wherein the polyhydroxylated aliphatic hydrocarbon is glycerol and the chlorohydrin is dichloropropanol.
26 - Procédé de fabrication de dichloropropanol dans lequel on soumet du glycérol à une réaction avec un agent de chloration contenant de l'acide chlorhydrique et dans lequel toutes les étapes du procédé sont effectuées dans des équipements réalisés en ou recouverts de matériaux résistant aux agents de chloration, dans les conditions de réalisation de ces étapes.
26 - Process for producing dichloropropanol in which glycerol is subjected to a reaction with a chlorinating agent containing hydrochloric acid and in which all the steps of the process are carried out in equipment made of or covered with materials resistant to chlorination, under the conditions of completion of these steps.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP06755270A EP1885674A1 (en) | 2005-05-20 | 2006-05-19 | Method for making chlorohydrin in corrosion-resistant equipment |
Applications Claiming Priority (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0505120A FR2885903B1 (en) | 2005-05-20 | 2005-05-20 | PROCESS FOR THE PRODUCTION OF EPICHLORHYDRIN |
EP05104321A EP1762556A1 (en) | 2005-05-20 | 2005-05-20 | Process for producing dichloropropanol from glycerol |
US73465805P | 2005-11-08 | 2005-11-08 | |
US73465905P | 2005-11-08 | 2005-11-08 | |
US73463505P | 2005-11-08 | 2005-11-08 | |
US73462705P | 2005-11-08 | 2005-11-08 | |
US73463405P | 2005-11-08 | 2005-11-08 | |
US73463705P | 2005-11-08 | 2005-11-08 | |
US73465705P | 2005-11-08 | 2005-11-08 | |
US73463605P | 2005-11-08 | 2005-11-08 | |
PCT/EP2006/062447 WO2006100317A1 (en) | 2005-05-20 | 2006-05-19 | Method for making chlorohydrin in corrosion-resistant equipment |
EP06755270A EP1885674A1 (en) | 2005-05-20 | 2006-05-19 | Method for making chlorohydrin in corrosion-resistant equipment |
Publications (1)
Publication Number | Publication Date |
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EP1885674A1 true EP1885674A1 (en) | 2008-02-13 |
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Family Applications (16)
Application Number | Title | Priority Date | Filing Date |
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EP06755270A Withdrawn EP1885674A1 (en) | 2005-05-20 | 2006-05-19 | Method for making chlorohydrin in corrosion-resistant equipment |
EP06755267A Withdrawn EP1885671A1 (en) | 2005-05-20 | 2006-05-19 | Method for making a chlorohydrin starting with a polyhydroxylated aliphatic hydrocarbon |
EP06755271A Withdrawn EP1885706A2 (en) | 2005-05-20 | 2006-05-19 | Method for making an epoxide starting with a polyhydroxylated aliphatic hydrocarbon and a chlorinating agent |
EP06755264A Withdrawn EP1890988A2 (en) | 2005-05-20 | 2006-05-19 | Method for making a chlorohydrin |
EP06755268A Withdrawn EP1885672A2 (en) | 2005-05-20 | 2006-05-19 | Method for making a chlorohydrin by chlorinating a polyhydroxylated aliphatic hydrocarbon |
EP06763200A Withdrawn EP1891032A2 (en) | 2005-05-20 | 2006-05-19 | Method for making an epoxy starting from a chlorhydrine |
EP10182403A Withdrawn EP2284163A3 (en) | 2005-05-20 | 2006-05-19 | Process for producing dichloropropanol |
EP06755262.0A Active EP1885705B1 (en) | 2005-05-20 | 2006-05-19 | Method for making an epoxide |
EP10182309A Withdrawn EP2275417A3 (en) | 2005-05-20 | 2006-05-19 | Process for producing dichloropropanol |
EP06755269.5A Not-in-force EP1885673B1 (en) | 2005-05-20 | 2006-05-19 | Method for making chlorohydrin in liquid phase in the presence of heavy compounds |
EP10182191.6A Active EP2284162B1 (en) | 2005-05-20 | 2006-05-19 | Process for producing dichloropropanol |
EP06755263A Withdrawn EP1904427A2 (en) | 2005-05-20 | 2006-05-19 | Process for producing a chlorhydrin from a multihydroxylated aliphatic hydrocarbon and/or ester thereof in the presence of metal salts |
EP06763198A Withdrawn EP1885678A1 (en) | 2005-05-20 | 2006-05-19 | Continuous method for making chlorhydrines |
EP06763189A Withdrawn EP1885677A2 (en) | 2005-05-20 | 2006-05-19 | Method for making a chlorhydrine by reaction between a polyhydroxylated aliphatic hydrocarbon and a chlorinating agent |
EP06755272A Withdrawn EP1885675A1 (en) | 2005-05-20 | 2006-05-19 | Method for preparing chlorohydrin by converting polyhydroxylated aliphatic hydrocarbons |
EP06755273A Withdrawn EP1885676A2 (en) | 2005-05-20 | 2006-05-19 | Method for converting polyhydroxylated aliphatic hydrocarbons into chlorohydrins |
Family Applications After (15)
Application Number | Title | Priority Date | Filing Date |
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EP06755267A Withdrawn EP1885671A1 (en) | 2005-05-20 | 2006-05-19 | Method for making a chlorohydrin starting with a polyhydroxylated aliphatic hydrocarbon |
EP06755271A Withdrawn EP1885706A2 (en) | 2005-05-20 | 2006-05-19 | Method for making an epoxide starting with a polyhydroxylated aliphatic hydrocarbon and a chlorinating agent |
EP06755264A Withdrawn EP1890988A2 (en) | 2005-05-20 | 2006-05-19 | Method for making a chlorohydrin |
EP06755268A Withdrawn EP1885672A2 (en) | 2005-05-20 | 2006-05-19 | Method for making a chlorohydrin by chlorinating a polyhydroxylated aliphatic hydrocarbon |
EP06763200A Withdrawn EP1891032A2 (en) | 2005-05-20 | 2006-05-19 | Method for making an epoxy starting from a chlorhydrine |
EP10182403A Withdrawn EP2284163A3 (en) | 2005-05-20 | 2006-05-19 | Process for producing dichloropropanol |
EP06755262.0A Active EP1885705B1 (en) | 2005-05-20 | 2006-05-19 | Method for making an epoxide |
EP10182309A Withdrawn EP2275417A3 (en) | 2005-05-20 | 2006-05-19 | Process for producing dichloropropanol |
EP06755269.5A Not-in-force EP1885673B1 (en) | 2005-05-20 | 2006-05-19 | Method for making chlorohydrin in liquid phase in the presence of heavy compounds |
EP10182191.6A Active EP2284162B1 (en) | 2005-05-20 | 2006-05-19 | Process for producing dichloropropanol |
EP06755263A Withdrawn EP1904427A2 (en) | 2005-05-20 | 2006-05-19 | Process for producing a chlorhydrin from a multihydroxylated aliphatic hydrocarbon and/or ester thereof in the presence of metal salts |
EP06763198A Withdrawn EP1885678A1 (en) | 2005-05-20 | 2006-05-19 | Continuous method for making chlorhydrines |
EP06763189A Withdrawn EP1885677A2 (en) | 2005-05-20 | 2006-05-19 | Method for making a chlorhydrine by reaction between a polyhydroxylated aliphatic hydrocarbon and a chlorinating agent |
EP06755272A Withdrawn EP1885675A1 (en) | 2005-05-20 | 2006-05-19 | Method for preparing chlorohydrin by converting polyhydroxylated aliphatic hydrocarbons |
EP06755273A Withdrawn EP1885676A2 (en) | 2005-05-20 | 2006-05-19 | Method for converting polyhydroxylated aliphatic hydrocarbons into chlorohydrins |
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EP (16) | EP1885674A1 (en) |
JP (13) | JP2008545643A (en) |
KR (7) | KR100978436B1 (en) |
CN (13) | CN102690168A (en) |
BR (8) | BRPI0610789A2 (en) |
CA (13) | CA2608725A1 (en) |
EA (14) | EA014241B1 (en) |
MX (7) | MX2007014525A (en) |
MY (4) | MY148345A (en) |
TW (16) | TWI321129B (en) |
WO (13) | WO2006100320A2 (en) |
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