WO2015091871A1 - Procédé de fabrication d'un époxyde - Google Patents

Procédé de fabrication d'un époxyde Download PDF

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Publication number
WO2015091871A1
WO2015091871A1 PCT/EP2014/078586 EP2014078586W WO2015091871A1 WO 2015091871 A1 WO2015091871 A1 WO 2015091871A1 EP 2014078586 W EP2014078586 W EP 2014078586W WO 2015091871 A1 WO2015091871 A1 WO 2015091871A1
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Prior art keywords
chlorohydrin
chlorinated
oxide
fluoride
chloride
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PCT/EP2014/078586
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English (en)
Inventor
Patrick Gilbeau
Nicolas DEMOULIN
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Solvay Sa
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Publication of WO2015091871A1 publication Critical patent/WO2015091871A1/fr

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16K—VALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
    • F16K37/00—Special means in or on valves or other cut-off apparatus for indicating or recording operation thereof, or for enabling an alarm to be given
    • F16K37/0075—For recording or indicating the functioning of a valve in combination with test equipment
    • F16K37/0083—For recording or indicating the functioning of a valve in combination with test equipment by measuring valve parameters
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16K—VALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
    • F16K1/00—Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces
    • F16K1/12—Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces with streamlined valve member around which the fluid flows when the valve is opened
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16K—VALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
    • F16K31/00—Actuating devices; Operating means; Releasing devices
    • F16K31/02—Actuating devices; Operating means; Releasing devices electric; magnetic
    • F16K31/04—Actuating devices; Operating means; Releasing devices electric; magnetic using a motor
    • F16K31/047—Actuating devices; Operating means; Releasing devices electric; magnetic using a motor characterised by mechanical means between the motor and the valve, e.g. lost motion means reducing backlash, clutches, brakes or return means

Definitions

  • the present invention relates to a process for manufacturing an epoxide.
  • the present invention relates more specifically to a process for manufacturing an epoxide via reaction between a chlorohydrin and a dehydrochorination agent.
  • Epoxides are important reaction intermediates in the manufacture of chemicals.
  • Ethylene oxide is used in the manufacture of ethylene glycol, glycol ethers, surfactants, ethanolamine, etc. (Ullmann's Encyclopedia of Industrial Chemistry, Fifth Completely Revised Edition, Vol.10, pp.129- 130).
  • Propylene oxide is used in the manufacture of propylene glycol, polyether polyols, propylene glycol ethers, etc. (Ullmann's Encyclopedia of Industrial Chemistry, Fifth Completely Revised Edition, Vol.A22, pp. 255-256).
  • Epichlorohydrin is a reaction intermediate in the manufacture of epoxy resins, synthetic elastomers, glycidyl ethers, polyamide resins, etc. (Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition, Vol.A9, p.539).
  • Epoxides are usually manufactured by reacting a chlorohydrin with an aqueous basic agent. In such processes, a brine is obtained as co-product. The brine can be discharged in the environment after adequate treatment but due to more stringent environmental dispositions, alternatives to such disposal have been developed.
  • International application WO 2008/152043 of SOLVAY Societe Anonyme describes the manufacture of epichlorohydrin by reaction between dichloropropanol and a basic agent wherein a brine is obtained as co- product with epichlorohydrin. Said brine is fed to a chlor-alkali electrolysis process where the basic agent is regenerated and recycled to the manufacture of epichlorohydrin. Although being environmentally friendly, said regeneration process of the basic agent adds complexity and cost to the overall process for making the epoxide.
  • the objective of the present invention is to provide a process for manufacturing epoxides from chlorohydrins which does not have these disadvantages.
  • the invention hence relates to process for manufacturing an epoxide by reacting at least one chlorohydrin with at least one dehydrochlorinating agent in order to give the epoxide and at least one chlorinated co-product, said process comprising regenerating the
  • dehydrochlorinating agent from the chlorinated co-product by a treatment which does not comprise an electrolysis operation.
  • One of the essential features of the invention is that regeneration of the dehydrochlorinating agent from the chlorinated co-product is by a treatment which does not comprise an electrolysis operation.
  • the invention in a second embodiment, relates to a process comprising obtaining epichlorohydrin according to the first embodiment and further reacting the obtained epichlorohydrin with at least one polyol in order to manufacture an an epoxy resin.
  • the present invention therefore provides processes as described below.
  • Item 1 A process for manufacturing an epoxide by reacting at least one chlorohydrin with at least one dehydrochlorinating agent in order to give the epoxide and at least one chlorinated co-product, said process comprising regenerating the dehydrochlorinating agent from the chlorinated co-product by a treatment which does not comprise an electrolysis operation.
  • Item 2 The process according to item 1, wherein the dehydrochlorinating agent is selected from a metal fluoride, an amine, a phosphine, an arsine, a metal oxide, and any mixture thereof.
  • the dehydrochlorinating agent is selected from a metal fluoride, an amine, a phosphine, an arsine, a metal oxide, and any mixture thereof.
  • Item 3 The process according to item 2, wherein the dehydrochlorinating agent is a metal oxide.
  • Item 4 The process according to item 2, wherein the dehydrochlorinating agent is a metal fluoride.
  • dehydrochlorinating agent is a solid, preferably an unsupported solid.
  • Item 6 The process according to any one of items 1 to 5, wherein the chlorinated co-product is a salt.
  • Item 7 The process according to any one of items 2 to 6, wherein the metal fluoride is an alkali fluoride and the chlorinated co-product comprises an alkali chloride and an alkali bifluoride,or,wherein the amine is a tertiary amine, preferably selected from the group consisting of trihexylamine,
  • transition metal chloride and a mixed oxide chloride hydrate of the transition metal, or, any combination thereof.
  • Item 8 The process according to item 7, wherein the metal fluoride is an alkali fluoride and the chlorinated co-product comprises an alkali chloride and an alkali bifluoride.
  • Item 9 The process according to item 8, wherein the alkali fluoride is potassium fluoride and the chlorinated co-product comprises potassium chloride and potassium bifluoride.
  • Item 10 The process according to item 7, wherein the metal oxide is an alkaline-earth metal oxide and the chlorinated co-product comprises the corresponding alkaline-earth metal chloride and a mixed oxide chloride hydrate of the alkaline-earth metal.
  • Item 11 The process according to item 10, wherein the alkaline-earth metal oxide is magnesium oxide and the chlorinated co-product comprises magnesium chloride and a mixed oxide chloride hydrate of magnesium.
  • Item 12 The process according to any one of items 1 to 11, wherein the epoxide is ethylene oxide and the chlorohydrin is chloroethanol or wherein the epoxide is propylene oxide and the chlorohydrin is monochloropropanol or wherein the epoxide is epichlorohydrin and the chlorohydrin is dichloropropanol, or any combination thereof.
  • Item 13 The process according to any one of items 1 to 12, wherein at least part of the chlorohydrin has been obtained by reacting hydrogen chloride with a polyhydroxylated aliphatic hydrocarbon, optionally in the presence of a carboxylic acid catalyst.
  • Item 14 The process according to item 13, wherein the epoxide is ethylene oxide, the chlorohydrin is chloroethanol and the polyhydroxylated aliphatic hydrocarbon is ethylene glycol, or wherein the epoxide is propylene oxide, the chlorohydrin is monochloropropanol and the polyhydroxylated aliphatic hydrocarbon is 1,2-propanediol, or more preferably, wherein the epoxide is epichlorohydrin, the chlorohydrin is dichloropropanol and the polyhydroxylated aliphatic hydrocarbon is glycerol.
  • Item 15 The process according to item 12, wherein the epoxide is epichlorohydrin and the chlorohydrin is dichloropropanol.
  • Item 16 The process according to item 14, wherein the epoxide is epichlorohydrin, the chlorohydrin is dichloropropanol and the polyhydroxylated aliphatic hydrocarbon is glycerol.
  • Item 17 The process according to any one of items 1 to 16, wherein the reaction between the chlorohydrin and the dehydrochlorinating agent is carried out in the presence of water.
  • Item 18 The process according to any one of items 1 to 17, wherein the regeneration treatment comprises at least one operation of heating the chlorinated co-product, preferably at a temperature higher than or equal to 50 °C, optionally in the presence of at least one stripping agent .
  • Item 19 The process according to any one of items 2 to 18, wherein the dehydrochlorination is a metal fluoride and wherein the treatment comprises at least one operation carried out in the presence of hydrogen fluoride.
  • Item 20 The process according to item 19 wherein at least part of the hydrogen fluoride is generated in situ in the treatment of the chlorinated co- product.
  • Item 21 The process according to item 19 or 20, where the treatment comprises at least one other operation carried out in the absence of added hydrogen fluoride.
  • Item 22 The process according to any one of items 1 to 20, wherein at least one part of the regenerated dehydrochlorinating agent is recycled to the reaction with the chlorohydrin.
  • Item 23 The process according to item 22, wherein the molar ratio between the dehydrochlorinating agent produced during the regeneration of the dehydrochlorinating agent and the dehydrochlorinating agent used in the manufacture of the epoxide is higher than or equal to 0.5.
  • Item 24 The process according to item 22, wherein the recycled regenerated dehydrochlorinating agent accounts for at least 50 mol percent of the dehydrochlorinating agent used in the manufacture of the epoxide.
  • Item 25 The process according to any one of items 1 to 24, wherein hydrogen chloride is produced during the regeneration of the
  • dehydrochlorinating agent and at least part of the produced hydrogen chloride is used for manufacturing the chlorohydrin by reacting with the polyhydroxylated aliphatic hydrocarbon.
  • Item 26 The process according to any one of items 1 to 25, wherein the molar ratio between the hydrogen chloride produced during the regeneration of the dehydrochlorinating agent and the hydrogen chloride used in the manufacture of the chlorohydrin is higher than or equal to 0.5 and the epoxide is ethylene oxide, the chlorohydrin is chloroethanol and the
  • polyhydroxylated aliphatic hydrocarbon is ethylene glycol
  • the molar ratio between the hydrogen chloride produced during the regeneration of the dehydrochlorinating agent and the hydrogen chloride used in the manufacture of the chlorohydrin is higher than or equal to 0.5 and the epoxide is propylene oxide, the chlorohydrin is monochloropropanol and the polyhydroxylated aliphatic hydrocarbon is 1,2-propanediol
  • the chlorohydrin is
  • dichloropropanol and the polyhydroxylated aliphatic hydrocarbon is glycerol.
  • Item 27 The process according to item 26, wherein the epoxide is epichlorohydrin, the chlorohydrin is dichloropropanol and the polyhydroxylated aliphatic hydrocarbon is glycerol, and wherein the molar ratio between the hydrogen chloride produced during the regeneration of the dehydrochlorinating agent and the hydrogen chloride used in the manufacture of the chlorohydrin is higher than or equal to 0.25.
  • Item 28 A process for manufacturing an epoxy resin comprising obtaining epichlorohydrin by the process according to any one of items 12 to 27 and further reacting the obtained epichlorohydrin with at least one polyol.
  • chlorinated by product and “chlorinated co-product” are intended to designate the same compound.
  • electrolysis operation By electrolysis operation one intends to denote an operation comprising the decomposition of any compound, organic or inorganic, by means of an electrical current, preferably the decomposition of an inorganic compound in an aqueous solution by means of an electrical current, more preferably the decomposition of a salt in an aqueous solution by means of an electrical current, still more preferably the decomposition of a metal chloride in an aqueous solution by means of an electrical current and most preferably the decomposition of sodium chloride in an aqueous solution by means of an electrical current.
  • an electrical current preferably the decomposition of an inorganic compound in an aqueous solution by means of an electrical current, more preferably the decomposition of a salt in an aqueous solution by means of an electrical current, still more preferably the decomposition of a metal chloride in an aqueous solution by means of an electrical current and most preferably the decomposition of sodium chloride in an aqueous solution by means of an electrical current.
  • An electrolysis operation is such as disclosed in International Application WO 2008152043 of SOLVAY (Societe Anonyme), the content of which is incorporated herein by reference, more specifically, the passage from page 30, line 21 to page 37, line 13.
  • An electrolysis operation is more specifically an operation such as carried out in a process for producing chlorine, a metal hydroxide, preferably sodium hydroxide, and hydrogen, in a chlor-alkali electrolysis process, in particular a membrane chlor-alkali electrolysis process.
  • the dehydrochlorination agent is preferably selected from a metal fluoride, an amine, a phosphine, an arsine, a metal oxide, and any mixture thereof.
  • dehydrochlorination agents have suitable basic and nucleophilic properties, i.e. that such agents have a basicity strong enough to dehydrochlorinate the chlorohydrin but not too strong so as to allow easy recovery of hydrogen chloride, and have a nucleophilicity low enough to avoid side reactions.
  • basicity can be understood as defined in March's Advanced Organic Chemistry, Reactions, Mechanisms, and Structure, Sixth Edition, 2007, Chapter 8, Table 8.1., pages 359-364.
  • suitable dehydrochlorination agents are compounds for which the conjugated acid of the Bronsted acid/base couple exhibits an
  • nucleophilicity can be understood as "n" as defined in March's Advanced Organic Chemistry,
  • Suitable nucleophilic agents are compounds for which the nucleophilicity "n" is usually lower than 4.2, preferably lower than 4, more preferably lower than 3, and most preferably lower than 2.5.
  • nucleophilicity is usually higher than zero.
  • the basicity and nucleophilicity features of the dehydrochlorinating agent allows a regeneration of the dehydrochlorination agent from the corresponding chlorinated co-product with no need for comprising an electrolysis operation, hence a more simple regeneration process and in addition a better selectivity into the epoxides.
  • dehydrochlorinating agent is a metal fluoride, in particular potassium fluoride.
  • the dehydrochlorination agent is more preferably selected from a metal fluoride, an amine, a metal oxide, and any mixture thereof, still more preferably from a metal fluoride, a metal oxide, an amine and any mixture thereof, yet more preferably from a metal fluoride, a metal oxide, and any mixture thereof, and is most preferably a metal fluoride.
  • a metal oxide is also convenient.
  • the metal fluoride is preferably selected from the group consisting of alkali metal fluorides, alkaline-earth metal fluorides, alkali fluoroaluminates and any mixture thereof.
  • the alkali metal fluoride is preferably selected from the group consisting of lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride and any mixture thereof.
  • the alkali metal fluoride is more preferably selected from the group consisting of potassium fluoride, cesium fluoride, rubidium fluoride and any mixture thereof.
  • the alkali fluoride is most preferably potassium fluoride.
  • the alkaline-earth metal fluoride is preferably selected from the group consisting of magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride and any mixture thereof.
  • the alkali fluoroaluminate is preferably sodium hexafluoroaluminate.
  • An alkali fluoride is a more preferred metal fluoride and potassium fluoride is the most preferred metal fluoride.
  • Potassium fluoride can contain other metal salts like for example salts of Ca, Sr, Ba, B, Al, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, Fe, Co, Ni, Cu, Zn, Ag, Mn, Hg, Cd, Sn, Pb, Sb and mixture thereof.
  • the dehydrochlorination agent when the dehydrochlorination agent is an amine, the amine can be selected from the group consisting of an aliphatic amine, an alicyclic amine, an aromatic amine, and any mixture thereof.
  • the amine can be selected from the group consisting of a primary amine, a secondary amine, a tertiary amine, or any mixture thereof.
  • the amine is preferably a tertiary amine.
  • the amine is more preferably selected from the group consisting of trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, cyclohexyl- diisooctylamine, cyclohexyl-4-heptyloctylamine, cyclohexyl-2- ethylhexyloctylamine, 2-ethylhexyl-4-heptyloctylamine, tri-2-ethylhexylamine, di-2-ethylhexyl-methylamine, didecylethylamine, tridodecylamine, dodecyl- dibutylamine, dodecyl-diisobutylamine, dodecyl-isobutylmethylamine, diisopentadecyl-methylamine, diisopentadecyl-ethylamine,
  • the phosphine when the dehydrochlorination agent is a phosphine, can be selected from the group consisting of an aliphatic phosphine, an alicyclic phosphine, an aromatic phosphine, and any mixture thereof.
  • the phosphine can be selected from the group consisting of a primary phosphine, a secondary phosphine, a tertiary phosphine, or any mixture thereof.
  • the phosphine is preferably a tertiary phosphine.
  • the phosphine is preferably an aliphatic and/or alicyclic phosphine, preferably alkylated and/or arylated.
  • alkyl groups are suitable : methyl, ethyl, n-propyl, n- butyl, iso-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl (lauryl) , palmityl, stearyl as well as isomers .
  • aryl groups are suitable: phenyl, tolyl, and xylyl.
  • the dehydrochlorination agent when the dehydrochlorination agent is an arsine, the arsine can be selected from the group consisting of an aliphatic arsine, an alicyclic arsine, an aromatic arsine, and any mixture thereof.
  • the arsine can be selected from the group consisting of a primary arsine, a secondary arsine, a tertiary arsine, or any mixture thereof.
  • the arsine is preferably a tertiary arsine.
  • the arsine is preferably an aliphatic and/or alicyclic arsine, preferably alkylated and/or arylated.
  • alkyl groups are suitable: methyl, ethyl, n-propyl, n-butyl, iso-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n- undecyl, n-dodecyl (lauryl) as well as isomers.
  • aryl groups are suitable: phenyl and tolyl.
  • the dehydrochlorination agent when the dehydrochlorination agent is a metal oxide, the metal oxide is preferably selected from the group consisting of alkaline-earth metal oxides, earth metal oxides, lanthanide metal oxides, transition metal oxides, and any mixture thereof.
  • the alkaline-earth metal oxide is preferably selected from magnesium oxide, calcium oxide, strontium oxide, barium oxide and any mixture thereof.
  • the alkaline-earth metal oxide is more preferably magnesium oxide.
  • the alkaline-earth metal oxide, preferably magnesium oxide, can contain some alkali metal oxide.
  • the alkali metal oxide is preferably selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide and any mixture thereof.
  • the alkaline-earth metal oxide can contain aluminum oxide.
  • the earth metal oxide is preferably selected from boron oxide, aluminum oxide, gallium oxide, indium oxide, thallium oxide and any mixture thereof.
  • the earth metal oxide is preferably aluminum oxide.
  • the lanthanide metal oxide is preferably selected from lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, promethium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide and any mixture thereof.
  • the transition metal oxide is preferably selected from iron oxide, ruthenium oxide, osmium oxide, cobalt oxide, rhodium oxide, iridium oxide, nickel oxide, palladium oxide, platinum oxide, zinc oxide, zirconium oxide, titanium oxide and any mixture thereof.
  • Silver oxide is not a metal oxide according to the invention.
  • alkaline-earth oxide is a more preferred metal oxide and magnesium oxide is the most preferred metal oxide.
  • the dehydrochlorination agent is more preferably magnesium oxide and most preferably potassium fluoride.
  • the dehydrochlorinating agent can be used in the form of a liquid, of a solid, of an aqueous and/or organic solution or of an aqueous and/or organic suspension.
  • the solid is preferably an essentially anhydrous solid or a hydrated solid.
  • the expression "essentially anhydrous solid” is understood to mean a solid of which the water content is less than or equal to 20 g/kg, preferably less than or equal to 10 g/kg and more preferably less than or equal to 1 g/kg.
  • hydrated solid is understood to mean a solid of which the water content is at least 20 g/kg and at most 700 g/kg, preferably at least 50 g/kg and at most 650 g/kg and most particularly preferably at least 130 g/kg and at most 630 g/kg.
  • the hydrates which denote solid combinations of substances with one or more water molecules are examples of hydrated solids.
  • the dehydrochlorinating agent is a metal fluoride or a metal oxide or any mixture thereof, it is preferably used in the form of an essentially anhydrous solid or a hydrated solid, as defined above.
  • the dehydrochlorinating agent is an amine, a phosphine, an arsine or any mixture thereof, it is preferably used in the form of a liquid or of a solid, and more preferably in the form of a liquid.
  • An ion exchange resin functionalized with tertiary amine groups is an example of an amine in the form of a solid.
  • the dehydrochlorinating agent when used in the form of a solid, the dehydrochlorinating agent can be supported or unsupported.
  • the support can be inorganic, organic, or a combination thereof.
  • the support is preferably inorganic.
  • An example of such a support is alumina.
  • dehydrochlorinating agent is used in the form of a supported solid, it can be used as a catalyst for the dehydrochlorination reaction.
  • the solid dehydrochlorinating agent preferably magnesium oxide and most preferably potassium fluoride, is preferably unsupported.
  • dehydrochlorination agent magnesium oxide and most preferably potassium fluoride, is preferably not used as a catalyst for the dehydrochlorination reaction.
  • the dehydrochlorinating agent When the dehydrochlorinating agent is used in the form of a solid, the dehydrochlorinating agent can exhibit various particle sizes. Sizes obtained by sieving are usually lower than or equal to 1 mm, generally lower than or equal to 425 ⁇ , in many cases lower than or equal to 200 ⁇ , often lower than or equal to 100 ⁇ , frequently lower than or equal to 50 ⁇ . The size is usually higher than or equal to 0.1 ⁇ .
  • the chlorinated co-product is understood to mean a co-product containing chlorine whatever the form of chlorine is, like e.g. chloride or hydrogen chloride.
  • the chlorinated co-product is preferably a salt.
  • salt one intend to denote a product resulting from the reaction of a base with an acid, whatever the final structure of the reaction product is.
  • the by-product can be for example a mixture of the corresponding metal chloride and the corresponding metal bifluoride.
  • the by-product is preferably a mixture of potassium chloride (KC1) and potassium bifluoride (KHF 2 ).
  • the by-product can be respectively an amine chlorohydrate or an arsine chlorohydrate or a phosphine chlorohydrate.
  • the by product can be the corresponding metal chloride, the corresponding metal chloride hydrate, a mixed metal chloride metal oxide hydrate of the metal, the corresponding metal hydroxychloride or any mixture thereof.
  • the metal oxide is magnesium oxide
  • the co-product is preferably a mixture of magnesium chloride (MgCl 2 ), of a magnesium oxide magnesium chloride hydrate (xMgO.MgCl 2 .yH 2 0) and of magnesium hydroxychloride (Mg(OH)Cl).
  • the regeneration treatment preferably comprises at least one operation of heating the chlorinated co-product.
  • the heating operation is preferably carried out at a temperature high enough to regenerate the dehydrochlorinating agent and is more preferably carried out at a temperature higher than or equal to 50 °C.
  • the heating operation is preferably carried out at a temperature higher than or equal to 100 °C, more preferably higher than or equal to 150 °C, yet more preferably higher than or equal to 200 °C and most preferably higher than 300°C. That temperature is usually lower than or equal to 600°C.
  • the heating operation is preferably carried out at a temperature higher than or equal to 300 °C, more preferably higher than or equal to 350 °C, yet more preferably higher than or equal to 400 °C and most preferably higher than 450 °C. That temperature is usually lower than or equal to 700°C.
  • at least one part of the operation of heating is preferably carried out in the presence of at least one stripping agent.
  • the stripping agent can be selected from air, nitrogen, oxygen, steam, and any mixture thereof.
  • hydrogen chloride is preferably formed during the regeneration treatment.
  • the regeneration treatment comprises preferably at least one operation carried out in the presence of hydrogen fluoride.
  • At least part of the hydrogen fluoride can be generated in situ in the treatment of the chlorinated co-product.
  • hydrogen fluoride which is preferred, hydrogen fluoride may be part of the stripping agent.
  • that regeneration treatment comprises a first step comprising heating the chlorinated co-product in the presence of added hydrogen fluoride in order to obtain a hydrogen fluoride treated chlorinated co-product and a second step comprising heating the hydrogen fluoride treated chlorinated co- product obtained from the first step in the absence of added hydrogen fluoride.
  • the temperature at which the first step of the treatment is carried out is usually higher than or equal to 20 °C, preferably higher than or equal to 40 °C, more preferably higher than or equal to 50 °C and most preferably higher than or equal to 60 °C, That temperature is usually lower than or equal to 300 °C, preferably lower than or equal to 200 °C, more preferably lower than or equal to 100 °C and most preferably lower than or equal to 80 °C. A value of 115 °C is also convenient.
  • the pressure at which the first step of the treatment is carried out is usually higher than or equal to 0.1 bar absolute (bara), preferably higher than or equal to 1 bara, more preferably higher than or equal to 5 bara and most preferably higher than or equal to 10 bara. That pressure is usually lower than or equal to 100 bara, preferably lower than or equal to 75 bara, more preferably lower than or equal to 50 bara and most preferably lower than or equal to 20 bara.
  • bara 0.1 bar absolute
  • the hydrogen fluoride can be liquid, gaseous or a mixture thereto.
  • the ratio between the added hydrogen fluoride and the chlorinated co-product expressed in weight is usually greater than or equal to 0.05, preferably greater than or equal to 0.1, more preferably greater than or equal to 0.5, yet more preferably greater than or equal to 1, still more preferably greater than or equal to 5, and most preferably greater than or equal to 10.
  • This ratio is usually lower than or equal to 1000, preferably lower than or equal to 500, more preferably lower than or equal to 100, yet more preferably lower than or equal to 75, still more preferably lower than or equal to 50, and most preferably lower than or equal to 25.
  • That first step can be carried out under continuous or discontinuous mode.
  • the duration of that first step of treatment is usually higher than or equal to 0.1 h, preferably higher than or equal to 1 h, more preferably higher than or equal to 2 h and most preferably higher than or equal to 5 h. That duration is usually lower than or equal to 100 h, preferably lower than or equal to 50 h, more preferably lower than or equal to 25 h and most preferably lower than or equal to 20 h.
  • the residence time of the gas phase is usually higher than or equal to 0.2 s, preferably higher than or equal to 2 s, more preferably higher than or equal to 4 s and most preferably higher than or equal to 10 s. That residence time is usually lower than or equal to 30 min, preferably lower than or equal to 15 min, more preferably lower than or equal to 10 min and most preferably lower than or equal to 1 min.
  • the residence time of the chlorinated by-product based on the inlet flow vs the volume occupied by the non-gaseous phase in the reactor is usually higher than or equal to 0.1 h, preferably higher than or equal to 1 h, more preferably higher than or equal to 2 h and most preferably higher than or equal to 5 h, That residence time is usually lower than or equal to 100 h, preferably lower than or equal to 50 h, more preferably lower than or equal to 25 h and most preferably lower than or equal to 20 h.
  • the duration and residence time can be easily adapted by monitoring the quantity of hydrogen chloride evolved during that step.
  • chlorinated co-product resulting from the reaction between the chlorohydrin and potassium fluoride comprises potassium chloride (KC1) and potassium bifluoride (KHF 2 ) and that the treatment with hydrogen fluoride (HF) generates hydrogen chloride (HC1) and a potassium bifluoride -hydrogen fluoride adduct (KHF 2 .nHF).
  • the second step is carried out under similar conditions that the first excepted that no hydrogen fluoride is added and that a stripping agent is possibly and preferably used, and that the temperature is as follows.
  • the temperature at which the second step of the treatment is carried out is usually higher than or equal to 50 °C, preferably higher than or equal to 100 °C, more preferably higher than or equal to 150 °C, yet more preferably higher than or equal to 200 °C, still more preferably higher than or equal to 250 °C and most preferably higher than or equal to 350 °C. That temperature is usually lower than or equal to 600 °C, preferably lower than or equal to 550 °C, more preferably lower than or equal to 500 °C and most preferably lower than or equal to 450 °C.
  • the dehydrochlorination agent is potassium fluoride
  • KHF 2 .nHF potassium bifluoride-hydrogen fluoride adduct
  • HF hydrogen fluoride
  • that regeneration treatment comprises a step comprising heating the chlorinated co-product in the absence of added hydrogen fluoride.
  • That step is carried out under similar conditions that the second step of the first variant.
  • chlorinated co-product resulting from the reaction between the chlorohydrin and potassium fluoride comprises potassium chloride (KC1) and potassium bifluoride (KHF 2 ) and that the heating treatment generates hydrogen fluoride (HF), which reacts with potassium chloride to produce hydrogen chloride (HCl) and potassium fluoride (KF).
  • KC1 potassium chloride
  • KHF 2 potassium bifluoride
  • HF hydrogen fluoride
  • HCl hydrogen chloride
  • KF potassium fluoride
  • that regeneration treatment comprises a step comprising heating the chlorinated co-product in the presence of added hydrogen fluoride.
  • That step is carried out under similar conditions that the second step of the first variant excepted that hydrogen fluoride is present.
  • chlorinated co-product resulting from the reaction between the chlorohydrin and potassium fluoride comprises potassium chloride (KC1) and potassium bifluoride (KHF 2 ) and that the heating treatment generates potassium fluoride (KF) and hydrogen chloride.
  • KC1 potassium chloride
  • KHF 2 potassium bifluoride
  • KF potassium fluoride
  • the conversion of the chlorinated co- product into the regenerated dehydrochlorination agent after regeneration is usually higher than or equal to 10 , preferably higher than or equal to 20 , more preferably higher than or equal to 30 , and most preferably higher than or equal to 40 ,
  • This conversion is usually lower than or equal to 90 , preferably lower than or equal to 80 , more preferably lower than or equal to 70 , and most preferably lower than or equal to 60 %.
  • the conversion of the chlorinated co- product into the regenerated dehydrochlorination agent after regeneration is usually higher than or equal to 10 , preferably higher than or equal to 50 , more preferably higher than or equal to 70 , and most preferably higher than or equal to 80 , This conversion is usually lower than or equal to 99 , preferably lower than or equal to 95 , and most preferably lower than or equal to 90 %,
  • At least part of the regenerated dehydrochlorinating agent is recycled to the dehydrochlorination reaction.
  • This part is usually higher than or equal to 50 % of the regenerated dehydrochlorinating agent, preferably higher than or equal to 75 , more preferably higher than or equal to 90 , yet more preferably higher than or equal to 95 % and most preferably higher than or equal to 99 %. It is convenient to recycle essentially all the regenerated dehydrochlorinating agent to the dehydrochlorination reaction.
  • the ratio between the dehydrochlorinating agent produced during the regeneration of the dehydrochlorinating agent and the dehydrochlorinating agent used in the manufacture of the epoxide is usually higher than or equal to 0.5, preferably higher than or equal to 0.75, more preferably higher than or equal to 0.90 and most preferably higher than or equal to 0.95.
  • dehydrochlorinating agent usually accounts for at least 30 mol percent of the dehydrochlorinating agent used in the manufacture of the epoxide, preferably for at least 50 mol percent, more preferably for at least 70 mol percent and most preferably for at least 80 mol percent. This recycled regenerated
  • dehydrochlorinating agent usually accounts for at most 99 mol percent of the dehydrochlorinating agent used in the manufacture of the epoxide, preferably for at most 98 mol percent, more preferably for at most 95 mol percent and most preferably for at most 90 mol percent.
  • hydrogen chloride is preferably produced during the regeneration of the dehydrochlorinating agent. At least part of the produced hydrogen chloride is preferably used for manufacturing the
  • chlorohydrin by reacting with a polyhydroxylated aliphatic hydrocarbon, optionally in the presence of a carboxylic acid catalyst.
  • At least one other part of the produced hydrogen chloride is preferably used in a process for manufacturing a chlorinated organic product, more preferably 1,2-dichloroethane, still more preferably 1,2-dichloroethane by oxychlorination of ethylene, optionally in the presence of a catalyst.
  • the chlorinated co-product may be submitted to at least one operation prior to the regeneration treatment.
  • Such operation is preferably selected from a filtration, a centrifugation, a decantation, a cyclonic separation, a washing with a solvent, a drying, a stripping and combination thereof.
  • a filtration operation is preferred.
  • the reaction of the chlorohydrin with the dehydrochlorinating agent can be carried out in a dehydrochlorination medium containing at least one liquid phase or in a dehydrochlorination medium containing at least one gaseous phase, or any combination thereof.
  • the reaction of the chlorohydrin with the dehydrochlorinating agent is preferably carried out in a dehydrochlorination medium containing at least one gaseous phase.
  • dehydrochlorination medium refers to the medium in which the dehydrochlorination reaction of the process according to the invention takes place and is understood to mean a medium comprising at least the chlorohydrin and the dehydrochlorinating agent.
  • the reaction between the chlorohydrin and the dehydrochlorinating agent is preferably carried out in the presence of water.
  • the dehydrochlorination medium preferably contains at least 0.01 % by weight of water, more preferably at least 0.1 % by weight, even more preferably at least 1 % by weight, yet more preferably at least 5 % by weight and most preferably at least 10 % by weight.
  • This content of water is at most 50 % by weight of water, preferably at most 40 % by weight, more preferably at most 30 % by weight and yet more preferably at most 20 % by weight.
  • the water can come from the dehydrochlorinating agent, the chlorohydrin, the solvent or any combination thereof.
  • the water can also be added separately.
  • the water can also be generated during the dehydrochlorination reaction.
  • the liquid phase preferably comprises the chlorohydrin in the form of a liquid and the dehydrochlorinating agent in the form of a solid.
  • the dehydrochlorinating agent is a metal fluoride or a metal oxide, and in particular a metal fluoride.
  • the liquid phase can contain at least one solvent.
  • the solvent is preferably an organic solvent.
  • the solvent is preferably inert with respect to the chlorohydrin, the dehydrochlorination agent, the epoxide and the chlorinated co product.
  • the solvent is more preferably selected from aliphatic hydrocarbons linear or branched, cycloaliphatic hydrocarbons, aromatic hydrocarbons, alkyl aromatic hydrocarbons, aliphatic ketones linear or branched, cycloaliphatic ketones, aromatic ketones, alkyl aromatic ketones or mixture thereof.
  • this phase usually comprises the chlorohydrin in the form of a gas and the dehydrochlorinating agent in the form of a solid.
  • the dehydrochlonnating agent is a metal fluoride or a metal oxide, and in particular a metal fluoride.
  • the dehydrochlorination of the chlorohydrin can be carried out under discontinuous or under continuous mode.
  • the regeneration of the dehydrochlorinating agent can be carried out under discontinuous or under continuous mode.
  • the dehydrochlorination of the chlorohydrin and the regeneration of the dehydrochlorinating agent are preferably carried out under continuous mode.
  • the dehydrochlorination reaction can be carried out in any type of reactor.
  • the reactor can be selected from a slurry reactor, a fixed bed reactor, a fluidized- bed reactor, a loop reactor, a cyclonic reactor, a moving bed reactor, and any combination thereof.
  • the regeneration treatment can be carried out in any type of reactor.
  • the reactor can be selected from a slurry reactor, a fixed bed reactor, a fluidized-bed reactor, a loop reactor, a cyclonic reactor, a moving bed reactor, and any combination thereof.
  • the term "epoxide” is used to describe a compound containing at least one oxygen bridged on a carbon-carbon bond.
  • the carbon atoms of the carbon-carbon bond are adjacent and the compound may contain atoms other than carbon and oxygen atoms, such as hydrogen atoms and halogens.
  • the preferred epoxides are ethylene oxide, propylene oxide, glycidol and epichlorohydrin, and mixtures of at least two thereof.
  • the more preferred epoxides are ethylene oxide, propylene oxide and epichlorohydrin, and mixtures of at least two thereof.
  • the yet more preferred epoxides are propylene oxide and epichlorohydrin, and mixtures thereof.
  • Epichlorohydrin is the most preferred epoxide.
  • polyhydroxylated aliphatic hydrocarbon refers to a hydrocarbon which contains at least two hydroxyl groups attached to two different saturated carbon atoms.
  • Polyhydroxylated aliphatic hydrocarbons which can be used in the present invention comprise, for example, 1,2-ethanediol (ethylene glycol),
  • the polyhydroxylated aliphatic hydrocarbon is preferably obtained from renewable raw materials as described in WO 2005/054167 of SOLVAY SA, more specifically from page 1, line 26 to page 4, line 2, the content of which is incorporated herein by reference and as described in WO 2006/100312 of SOLVAY SA, especially from page 3, line 29 to page 5, line 24, the content of which is incorporated herein by reference.
  • 1,2,3-Propanetriol or glycerol is the most preferred polyhydroxylated aliphatic hydrocarbon.
  • Glycerol which has been obtained from renewable raw materials, in particular in the manufacture of biodiesel is the most preferred.
  • chlorohydrin is used in order to describe a compound containing at least one hydroxyl group and at least one chlorine atom attached to different saturated carbon atoms.
  • Chlorohydrins which are more particularly preferred are 2-chloroethanol, l-chloropropan-2-ol, 2-chloropropan-l-ol, l-chloropropane-2,3-diol, 2-chloropropane-l,3-diol,
  • l,3-dichloropropan-2-ol, 2,3-dichloropropan-l-ol and mixtures of at least two thereof are yet more preferred, l-chloropropan-2-ol, 2-chloropropan-l-ol, l,3-dichloropropan-2-ol, 2,3-dichloropropan-l-ol and mixtures of at least two thereof are still more preferred. l,3-dichloropropan-2-ol, 2,3-dichloropropan-l-ol and mixtures thereof are the most particularly preferred.
  • a mixture consisting essentially of l,3-dichloropropan-2-ol, 2,3-dichloropropan-l-ol , with a content of l,3-dichloropropan-2-ol higher than or equal to 90 % is particularly well suited.
  • monochloropropanol refers to l-chloropropan-2-ol, 2-chloropropan-l-ol, and any mixture thereof.
  • chloropropanediol refers to l-chloropropane-2,3-diol, 2-chloropropane-l,3-diol, and any mixture thereof.
  • the general name dichloropropanol refers to l,3-dichloropropan-2-ol, 2,3-dichloropropan-l-ol, and any mixture thereof.
  • the chlorohydrin preferably
  • dichloropropanol can contain hydrogen chloride and exhibit a composition as defined in International application PCT/EP2013/068223, the content of which is hereby incorporated by reference, more specifically the passage from page 17, line 27 to page 19, line 1.
  • the chlorohydrin may have been obtained by any processes like olefin hypochlorination, olefin chlorination,
  • the olefin is preferably selected from the group of ethylene, propylene, allyl chloride, allyl alcohol and any mixture thereof, more preferably from the group of ethylene, propylene and allyl chloride and any mixture thereof, yet more preferably from the group of propylene and ally chloride, and any mixture thereof, and is most preferably allyl chloride .
  • the chlorohydrin may have been obtained by hypochlorination, e.g. l-chloropropan-2-ol and 2-chloropropan-l-ol from propylene hypochlorination, or l,3-dichloropropan-2-ol and 2,3-dichloropropan- l-ol from allyl chloride hypochlorination, by olefin chlorination e.g. 2,3- dichloropropan-l-ol from allyl alcohol chlorination, by polyhydroxylated aliphatic hydrocarbons hydrochlorination (e.g.
  • hydrochlorination l-chloropropan-2-ol and 2-chloropropan-l-ol from propylene glycol hydrochlorination), and any combination thereof.
  • Polyhydroxylated aliphatic hydrocarbon hydrochlorination is preferred.
  • the chlorohydrin is preferably
  • the epoxide is preferably glycidol
  • the chlorohydrin is preferably l-chloropropane-2,3-diol, 2-chloropropane-l,3-diol, and mixture thereof and the polyhydroxylated aliphatic hydrocarbon is preferably glycerol.
  • the epoxide is more preferably ethylene oxide
  • the chlorohydrin is preferably 2-chloroethanol
  • the polyhydroxylated aliphatic hydrocarbon is preferably ethylene glycol.
  • the epoxide is still more preferably propylene oxide
  • the chlorohydrin is more preferably l-chloropropan-2-ol
  • 2-chloropropan-l-ol, or any mixture thereof and the polyhydroxylated aliphatic hydrocarbon is more preferably 1,2-propanediol.
  • the epoxide is most preferably
  • epichlorohydrin is most preferably dichloropropanol and the polyhydroxylated aliphatic hydrocarbon is most preferably glycerol.
  • the epoxide is most preferably
  • the chlorohydrin is most preferably dichloropropanol and the polyhydroxylated aliphatic hydrocarbon is most preferably glycerol obtained from renewable raw materials, more preferably in the manufacture of biodiesel.
  • the chlorohydrin is dichloropropanol and the polyhydroxylated aliphatic
  • hydrocarbon is glycerol
  • the epichlorohydrin can be further reacted with at least one polyol in order to produce an epoxy resin.
  • the invention also relates to a process for manufacturing an epoxy resin comprising obtaining epichlorohydrin by reacting dichlorpropanol with at least one dehydrochlorinating agent in order to give epichlorohydrin and at least one chlorinated co-product, said process for obtaining epichlorohydrin comprising regenerating the dehydrochlorinating agent from the chlorinated co-product by a treatment which does not comprise an electrolysis operation, and further reacting the obtained epichlorohydrin with at least one polyol.
  • the dehydrochlorinating agent, the chlorinated co-product, the process for obtaining epichlorohydrin and the regeneration treatment are as described above.
  • the polyol is as described in International application WO 2008/ 152044 of SOLVAY (Societe Anonyme), the content of which is incorporated herein by reference, more specifically the passage from page 16, line 31 to page 17, line 12 and in International application WO 2012/041816 of SOLVAY SA, the content of which is incorporated herein by reference, more specifically the passage from page 12, line 1 to page 15, line 33.
  • the chlorohydrin when the epoxide is glycidol, the chlorohydrin is l-chloropropane-2,3-diol, 2-chloropropane-l,3-diol, and mixture thereof and the polyhydroxylated aliphatic hydrocarbon is glycerol or when ethylene oxide, the chlorohydrin is chloroethanol and the polyhydroxylated aliphatic hydrocarbon is ethylene glycol or when the epoxide is propylene oxide, the chlorohydrin is monochloropropanol and the polyhydroxylated aliphatic hydrocarbon is 1,2-propanediol, the molar ratio between the hydrogen chloride produced during the regeneration of the dehydrochlorinating agent and the hydrogen chloride used in the manufacture of the chlorohydrin is higher than or equal to 0.5, preferably higher than or equal to 0.9 and most preferably higher than or equal to 0.99.
  • the chlorohydrin is dichloropropanol and the polyhydroxylated aliphatic
  • hydrocarbon is glycerol
  • the molar ratio between the hydrogen chloride produced during the regeneration of the dehydrochlorinating agent and the hydrogen chloride used in the manufacture of the chlorohydrin is higher than or equal to 0.25, preferably higher than or equal to 0.45 and most preferably higher than or equal to 0.495.
  • a preferred dehydrochlorinating agent is potassium fluoride.
  • Potassium fluoride combines several advantages over other dehydrochlorination agents like for instance other metal fluorides: cheap metal fluoride, fast and selective reaction allowing low reaction times and low production of by-products, poor solubility of the fluoride and of the chlorinated co-product in the reaction medium allowing easy separation by filtration for example, decomposition temperature of the co-product higher than the boiling point of the dichloropropanol allowing the clean recovery of the unreacted chlorohydrin before the co-product treatment for recovering the
  • Figure 1 shows a non-limiting embodiment of the process according to the invention.
  • a polyhydroxylated aliphatic hydrocarbon such as a glycerol feed stream is introduced in a sector (1) via line (2).
  • the sector generally includes the equipment required for carrying out chemical reactions, separations and any combination thereof.
  • a hydrogen chloride feed stream is introduced in sector (1) via line (3).
  • a water stream is withdrawn from sector (1) via line (4).
  • a chlorohydrin such as a dichloropropanol stream is withdrawn from sector (1) and introduced to a second sector (6) via line (5).
  • a dehydrochlorination agent such as a potassium fluoride feed stream is introduced in sector (6) via line (7).
  • An epoxide such as an epichlorohydrin stream is withdrawn from sector (6) via line (8).
  • a chlorinated co-product such as a mixture of potassium chloride and potassium bifluoride stream is withdrawn from sector (6) and introduced to sector (10) via line (9).
  • a regenerated hydrogen chloride stream is withdrawn from sector (10) via line (11).
  • at least a part of the regenerated hydrogen chloride stream is recycled to sector (1) via line (12).
  • the regenerated hydrogen chloride stream could be recycled into the hydrogen chloride feed (3) stream via line (13). Another part of the regenerated hydrogen chloride stream could be used in another process via line (14).
  • a regenerated co-product such as a mixture of potassium chloride and potassium bifluoride stream
  • a regenerated hydrogen chloride stream is withdrawn from sector (10) via line (11).
  • at least a part of the regenerated hydrogen chloride stream is recycled to sector (1) via line (12).
  • the regenerated hydrogen chloride stream could be recycled into the hydrogen chloride feed
  • dehydrochlorination agent stream such as a potassium fluoride is withdrawn from sector (10) and recycled to sector (6) via line (15).
  • the regenerated dehydrochlorination agent stream could be recycled to dehydrochlorination agent feed stream (7) via line (16).
  • FIG. 2 shows another non limiting embodiment of the process according to the invention.
  • a potassium chloride potassium bifluoride feed stream arising from a process for making an epoxide by reacting potassium fluoride with a chlorhydrin is introduced in a sector (20) via line (21).
  • a hydrogen fluoride feed stream is introduced in sector (20) via line (22).
  • a gaseous stream comprising hydrogen chloride and hydrogen fluoride is withdrawn from sector (20) via line (23).
  • the gaseous stream is separated in a purified hydrogen chloride stream (24) and in a purified hydrogen fluoride stream (25) in the separation sector (26).
  • the purified hydrogen fluoride stream is introduced in sector (20) via line (27).
  • the purified hydrogen fluoride stream could be recycled to the hydrogen fluoride feed stream (22) via line (28).
  • a potassium bifluoride stream is withdrawn from sector (20) and fed to sector (29) via line (30).
  • a potassium fluoride stream is withdrawn from sector (29) via line (31).
  • a regenerated hydrogen fluoride stream is withdrawn from sector (29) and introduced in sector (20) via line (32).
  • the regenerated hydrogen fluoride stream could be recycled to the hydrogen fluoride feed stream (22) via line (33).
  • Figure 3 shows another non limiting embodiment of the process according to the invention.
  • a chlorohydrin such dichloropropanol feed stream is introduced in a sector (40) via line (41).
  • a dehydrochlorination agent such as magnesium oxide feed stream is introduced in sector (40) via line (42).
  • a nitrogen feed stream is introduced in sector (40) via line (43).
  • a stream containing a chlorinated co product such as a mixture comprising MgO, MgCl 2 , xMgO.MgCl 2 .yH 2 0 and Mg(OH)Cl, unreacted chlorohydrin and the epoxide such as epichlorohydrin is withdrawn from sector (40) and introduced to sector (44) via line (45).
  • a chlorinated co product such as a mixture comprising MgO, MgCl 2 ,
  • xMgO.MgCl 2 .yH 2 0 and Mg(OH)Cl stream is withdrawn from sector (44) and is introduced in a sector (46) via line (47).
  • An epoxide such as epichlorohydrin stream is withdrawn from sector (44) via line (48) and sent to storage or to further purification.
  • a chlorohydrin such dichloropropanol stream is withdrawn from sector (44) and is introduced into sector (40) via line (49). A part of said stream can be introduced in the chlorohydrin feed stream (41) via line (50).
  • a feed stream containing nitrogen and/or water is introduced in sector (46) via line (51).
  • a feed stream containing hydrogen chloride is withdrawn from sector (46) via line (52) and optionally sent to the process for preparing the chlorohydrin by reaction with polyhydroxylated aliphatic hydrocarbon such as glycerol.
  • a regenerated dehydrochlorinating agent such as magnesium oxide stream is withdrawn from sector (46) and introduced in sector (40) via line (53).
  • a part of said stream (53) can be introduced in the dehydrochlorinating agent such as magnesium oxide stream (42) via line (54).
  • the dehydrochlorination agent DHC agent
  • l,3-dichloropropan-2-ol 1,3-DCPol
  • 1,3-DCPol contained 0.97 g/kg of water.
  • the flask was heated to the desired temperature under stirring. The content of the flask was sampled overtime and analyzed as described above.
  • the reagents used were 1,3-DCPol Merck > 98% (containing 2.2 g of 2,3- dichloropropan-l-ol, 2,3-DCPol, per kg), 2,3-DCPol TCI > 98 % (containing 7.3 g of l,3-dichloropropan-2-ol per kg), KF Sigma- Aldrich puriss pa > 99% or Sigma-Aldrich ACS reagent > 99%, KC1 Sigma-Aldrich 99.99% on metal basis or formed during the process, KHF2 Sigma-Aldrich, > 99%, BaF 2 Sigma- Aldrich 99.99% on metal basis, CsF Sigma-Aldrich, > 99%, NaF Sigma-Aldrich > 99%, RbF Alfa Aesar > 99.7 % on metal basis, CaF 2 Alfa Aesar > 98 %, Na 3 AlF 6 Sigma-Aldrich > 97%, KBF 4 Alfa Aesar > 98 %, NH 4
  • the 1,3-DCPol conversion is calculated as follows:
  • the moles of reaction products is the sum of the moles of epichlorohydrin, l-chloro-3- fluoropropan-2-ol, epifluorohydrin, l,3-difluoropropan-2-ol, 3-chloro-l,2- propanediol and several unidentified by products.
  • the number of moles of the unidentified by products is expressed as moles of epichlorohydrin from the quantification by GC using the response factor of epichlorohydrin.
  • ECH epichlorohydrin
  • the number of moles of the reaction products is calculated as above.
  • DHC agent dehydrochlorination agent ; 1,3-DCPol : l,3-dichloropropan-2-ol ; (a) : magnetic, (b) mechanical,
  • the DHC agent used was the solid obtained from the example 33 after it was filtered and dried at 100°C under 100 Torr ⁇ : commercial MgO used without any pretreatment
  • the mixture After the dehydrochloration of DCPol, the mixture has been filtered or centrifuged.
  • the recovered solid has been washed with an organic solvent, or dried with a nitrogen stripping or under vacuum or by heating, or submitted to a combination of these different treatments, and further submitted to mineral analysis.
  • Each solid sample has been dissolved in demineralized water in presence or not of nitric acid.
  • the mineral analyses have been performed by titrating chloride and fluoride anions as well as proton cations.
  • Potentiometric titrations of chloride anions were performed with a titroprocessor equipped with titrating aqueous solution of AgN0 3 and a silver electrode.
  • Colorimetric titrations of chloride anions were performed in presence of bromophenol blue, nitric acid and diphenylcarbazole solutions, and with a titrating aqueous solution of Hg(N0 3 ) 2 .
  • Potentiometric titrations of fluoride anions were performed with a fluoride selective electrode in the presence of an ISE buffer (TISAB II - Chem Lab). Potentiometric titrations of proton cations were performed with a pH electrode and a titrating caustic solution.
  • DHC of other chlorohydrines such as 2-chloroethanol and l-chloro-2-propanol with KF were also conducted in a round bottom flask equipped with an oil bath, a magnetic stirrer, and a Vigreux condenser on top of which a condenser was connected to collect distilled fractions. Aliquots were taken from the distilled fractions overtime and from the liquid reaction medium at the end of the reaction, filtered or centrifuged for gas chromatography (GC) analysis. To the round bottom flask were added the dehydrochlorination agent (DHC agent) and the chlorohydrin. The flask was heated to the desired temperature under stirring. The content of the flask was sampled overtime and analyzed as described above. The reagents used were 2-chloroethanol Merck > 98%, and l-chloro-2-propanol Alfa Aesar, tech. 75%.
  • the chlorohydrin conversion is calculated as follows:
  • the moles of reaction products is the sum of the moles of the epoxide being formed and several unidentified by products.
  • the number of moles of the unidentified by products is expressed as moles of the epoxide formed from the chlorohydrin from the quantification by GC using the response factor of the epoxide.
  • the epoxide selectivity in distillates is calculated as follows: 100 X (number of moles of the epoxide in the flask at the time of the sampling )/( (number of moles of reaction products at the time of the sampling).
  • the number of moles of the reaction products is calculated as above.
  • the regeneration of the chlorinated co-product has firstly been carried out according to a two steps procedure.
  • the solids formed during the dehydrochloration of DCPol according to example 6' of Table 1 has been recovered by filtration and the recovered solid has been heated under a nitrogen stream at 160°C.
  • the solid after heating comprising KC1 and KHF2 in a 1/1 ratio (as measured by XRD and elementary analyses) and a water content 0.18 g/kg and a Total Organic Carbon of 1.05 g/kg.
  • the solid was placed in an autoclave and heated or cooled to a first temperature (starting temperature).
  • Anhydrous HF was then added in a batch mode (autogenously pressure) or continuous mode (regulated pressure).
  • the autoclave was then heated to a scond temperature (final temperature) ranging between 20°C and 300°C for 4 to 64 hours.
  • the composition of the gas phase at the outlet was obtained overtime by quenching through a scrubber of KOH and analyzing the scrubber chloride and fluoride contents. Then the reaction was stopped and the autoclave was cooled down to room temperature.
  • the content of the autoclave was collected and submitted to elementary (K, CI " , F " , H + ) analyses to determine its composition. It was found that the residue in the autoclave comprises KCl and KF.nHF (n > 1.0).
  • the second step of the regeneration of the DHC agent KF was conducted as follow.
  • the solids formed during the first step of the regeneration of the DHC agent KF, containing KCl and KF.nHF were placed in a platinum nacelle and heated, under a continuous flow of nitrogen at a linear velocity of 4 to 10 m/h, in a tube furnace.
  • the furnace was programmed to reach different temperatures above the platinum nacelle up to 400°C for different ranges of time, up to 10 h.
  • the gas exiting the tube was sent to a gas scrubber containing an aqueous solution of KOH.
  • the furnace was allowed to cool to room temperature overnight and under nitrogen.
  • the content of the nacelle was collected and submitted to mineral analyses.
  • the solids formed during the dehydrochloration of DCPol according to example 6' of Table 1 have been recovered by filtration and the recovered solid has been heated under a nitrogen stream at 160°C.
  • the solid after heating comprising KCl and KHF2 in a 1/1 ratio (as measured by XRD and elementary analyses) and a water content 0.18 g/kg and a Total Organic Carbon of 1.05 g/kg.
  • the solid was submitted to a treatment similar to the treatment of the second step of regeneration disclosed here above.
  • the white solid was weighed (3.5595 g) and did not show any residual HF.
  • the chloride content of the residual solid was 7.46 mol/kg (559 g KCl/kg).
  • the fluoride content of the residual solid was 7.2 mol/kg (412 g KF/kg).

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Abstract

L'invention concerne un procédé de fabrication d'un époxyde par mise en réaction d'au moins une chlorhydrine de butylène avec au moins un agent de déshydrochloration afin de produire l'époxyde et l'au moins un co-produit chloré, ce procédé consistant à régénérer l'agent de déshydrochloration du co-produit chloré par un traitement qui n'inclut pas d'électrolyse.
PCT/EP2014/078586 2013-12-20 2014-12-18 Procédé de fabrication d'un époxyde WO2015091871A1 (fr)

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EP13199018 2013-12-20

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1404675A (fr) * 1963-05-29 1965-07-02 Shell Int Research Procédé pour préparer des composés époxy par déshalogénhydratation
US4410714A (en) * 1979-05-03 1983-10-18 The Lummus Company Production of epoxy compounds from olefinic compounds
US6403840B1 (en) * 2001-06-20 2002-06-11 Grt, Inc. Process for synthesizing olefin oxides
WO2005054167A1 (fr) * 2003-11-20 2005-06-16 Solvay (Société Anonyme) Procede de production de dichloropropanol avec du glycerol, le glycerol provenant de la conversion de graisses animales dans la fabrication de biodiesel
WO2008152043A1 (fr) * 2007-06-12 2008-12-18 Solvay (Société Anonyme) Composition aqueuse contenant un sel, procédé de fabrication et utilisation
WO2008152044A1 (fr) * 2007-06-12 2008-12-18 Solvay (Société Anonyme) Produit contenant de l'épichlorhydrine, préparation de celui-ci et utilisation de celui-ci dans différentes applications

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1404675A (fr) * 1963-05-29 1965-07-02 Shell Int Research Procédé pour préparer des composés époxy par déshalogénhydratation
US4410714A (en) * 1979-05-03 1983-10-18 The Lummus Company Production of epoxy compounds from olefinic compounds
US6403840B1 (en) * 2001-06-20 2002-06-11 Grt, Inc. Process for synthesizing olefin oxides
WO2005054167A1 (fr) * 2003-11-20 2005-06-16 Solvay (Société Anonyme) Procede de production de dichloropropanol avec du glycerol, le glycerol provenant de la conversion de graisses animales dans la fabrication de biodiesel
WO2008152043A1 (fr) * 2007-06-12 2008-12-18 Solvay (Société Anonyme) Composition aqueuse contenant un sel, procédé de fabrication et utilisation
WO2008152044A1 (fr) * 2007-06-12 2008-12-18 Solvay (Société Anonyme) Produit contenant de l'épichlorhydrine, préparation de celui-ci et utilisation de celui-ci dans différentes applications

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