WO2015091871A1 - Process for manufacturing an epoxide - Google Patents

Abstract

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.

Description

Process for manufacturing an epoxide

The present application claims benefit of European patent application n° 13199018.6 filed on December 20, 2013 the content of which is incorporated herein by reference for all purposes.

Should the disclosure of any of the patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

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.

In a first embodiment, 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.

This affords at least the following advantages:

o No need for an electrolysis plant in the vicinity of the epoxide

manufacture plant;

o Reduced costs related to electricity consumption;

o Reduced steam consumption;

o No electrolysis hazardous co-product to be valorized or disposed off; o No need for harsh treatment of the chlorinated co-product from the dehydrochlorination, prior to regeneration;

o Possibility of using essentially non aqueous dehydrochlorination conditions;

o Less aqueous effluent generation;

o Less steps for regenerating products which can be used in the process for manufacturing the epoxide and in the process for manufacturing the chlorohydrin.

In a second embodiment, the invention 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.

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.

Item 5. The process according to item 3 or 4, wherein the

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,

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, diisopentadecylisopropylamine, didodecyl-methylamine, dodecyl-diisopropylamine, and any mixture thereof, and the chlorinated co-product is a chlorohydrate of the tertiary amine, or, wherein the phosphine is a tertiary phosphine and the chlorinated co-product is a chlorohydrate of the tertiary phosphine, or, wherein the arsine is a tertiary arsine and the chlorinated co-product is a chlorohydrate of the tertiary arsine, or, 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 oxidechloride hydrate of the alkaline-earth metal, or, wherein the metal oxide is an earth metal oxide and the chlorinated by-product comprises the corresponding earth metal chloride and a mixed oxide chloride hydrate of the earth metal, or, wherein the metal oxide is a lanthanide metal oxide and the chlorinated co- product comprises the corresponding lanthanide metal chloride and a mixed oxide chloride hydrate of the lanthanide metal, or, wherein the metal oxide is a transition metal oxide and the chlorinated co-product comprises the

corresponding 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

or

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

or

more preferably, 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 and the epoxide is epichlorohydrin, 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.

In the following part of the description, the expressions "chlorinated by product" and "chlorinated co-product" are intended to designate the same compound.

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 example of 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.

In the process of the invention, the dehydrochlorination agent is preferably selected from a metal fluoride, an amine, a phosphine, an arsine, a metal oxide, and any mixture thereof.

Without willing to be tied by any theory, it is believed that those 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. Without willing to limit the list of selected dehydrochlorination agent above, 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. Examples of suitable dehydrochlorination agents are compounds for which the conjugated acid of the Bronsted acid/base couple exhibits an

"approximate pK_a value (relative to water)", which is usually lower than 15.74, preferably lower than 12, more preferably lower than 10, yet more preferably lower than 8, still more preferably lower than 6, and most preferably lower than 4. Such pKa value is usually higher than -1.74. Once more, without willing to limit the list of selected dehydrochlorination agent above, nucleophilicity can be understood as "n" as defined in March's Advanced Organic Chemistry,

Reactions, Mechanisms, and Structure, Sixth Edition, 2007, Chapter 10, Table 10.8., pages 490-495. 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. Such

nucleophilicity is usually higher than zero.

Still without willing to be tied by any theory, it is believed that 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.

Another essential feature of the invention resides therefore in the choice of the dehydrochlorinating agent which affords the following advantages:

o No need for an electrolysis operation;

o More simple regeneration process for the chlorinated co-product;

o Better selectivities for the epoxide;

o Lower formation of undesired products;

o Possibility of using essentially non aqueous dehydrochlorination

conditions;

o Less aqueous effluent generation;

o Lower amount of dehydrochlorinating agent used with respect to the amount of chlorohydrin.

These advantages are more particularly prominent when the

dehydrochlorinating agent is a metal fluoride, in particular potassium fluoride.

In the process of the invention, 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.

In the process of the invention, when the dehydrochlorination agent is a metal fluoride, 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.

In the process of the invention, 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,

diisopentadecylisopropylamine, didodecyl-methylamine, dodecyl- diisopropylamine, and any mixture thereof.

In the process of the invention, when the dehydrochlorination agent is a phosphine, the 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. The following 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 . The following aryl groups are suitable: phenyl, tolyl, and xylyl.

In the process of the invention, 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.The following 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. The following aryl groups are suitable: phenyl and tolyl.

In the process of the invention, 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.

In the process of the invention, 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.

In the process of the invention, 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.

In the process of the invention, 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.

In the process of the invention, 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.

An alkaline-earth oxide is a more preferred metal oxide and magnesium oxide is the most preferred metal oxide.

In the process of the invention, the dehydrochlorination agent is more preferably magnesium oxide and most preferably potassium fluoride.

In the process of the invention, 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. The expression "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.

When 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.

When 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.

When the dehydrochlorinating agent is 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. When the

dehydrochlorinating agent is used in the form of a supported solid, it can be used as a catalyst for the dehydrochlorination reaction. In the process of the invention, the solid dehydrochlorinating agent, preferably magnesium oxide and most preferably potassium fluoride, is preferably unsupported. The

dehydrochlorination agent, magnesium oxide and most preferably potassium fluoride, is preferably not used as a catalyst for the dehydrochlorination reaction.

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 μιη, in many cases lower than or equal to 200 μιη, often lower than or equal to 100 μιη, frequently lower than or equal to 50 μιη. The size is usually higher than or equal to 0.1 μιη.

In the process of the invention, 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. In the process of the invention, the chlorinated co-product is preferably a salt. By 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.

When the dehydrochlorinating agent is a metal fluoride, the by-product can be for example a mixture of the corresponding metal chloride and the corresponding metal bifluoride. For potassium fluoride (KF), the by-product is preferably a mixture of potassium chloride (KC1) and potassium bifluoride (KHF₂).

When the dehydrochlorination agent is an amine, a phosphine or an arsine, the by-product can be respectively an amine chlorohydrate or an arsine chlorohydrate or a phosphine chlorohydrate.

When the dehydrochlorination agent is a metal oxide, 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. When the metal oxide is magnesium oxide, the co-product is preferably a mixture of magnesium chloride (MgCl₂), of a magnesium oxide magnesium chloride hydrate (xMgO.MgCl₂.yH₂0) and of magnesium hydroxychloride (Mg(OH)Cl).

In the process of the invention, 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.

In the process of the invention, when the dehydrochlorination agent is a metal fluoride, in particular potassium fluoride, 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.

In the process of the invention, when the dehydrochlorination agent is a metal oxide, in particular magnesium oxide, 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. In the process of the invention, 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.

In the process of the invention, hydrogen chloride is preferably formed during the regeneration treatment.

In the process of the invention, when the dehydrochlorination agent is a metal fluoride, preferably potassium fluoride, 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. When the operation of heating the chlorinated co product is carried out in the presence of hydrogen fluoride, which is preferred, hydrogen fluoride may be part of the stripping agent.

In a first variant, 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.

In that first step, the hydrogen fluoride can be liquid, gaseous or a mixture thereto. In that first step, 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.

By carrying out the step under continuous mode, one intends to denote a mode where the chlorinated by product is added continuously to that step and the regenerated dehydrochlorination agent is continuously withdrawn from that step. Any other mode of operation is considered as discontinuous. The continuous mode is preferred.

When carried out under batch 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.

When carried out under continuous mode, 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.

When carried out under continuous mode, 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.

Without willing to be tied by any theory, when the dehydrochlorination agent is potassium fluoride, it is believed that chlorinated co-product resulting from the reaction between the chlorohydrin and potassium fluoride comprises potassium chloride (KC1) and potassium bifluoride (KHF₂) and that the treatment with hydrogen fluoride (HF) generates hydrogen chloride (HC1) and a potassium bifluoride -hydrogen fluoride adduct (KHF₂.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.

Without willing to be tied by any theory, when the dehydrochlorination agent is potassium fluoride, it is believed that the potassium bifluoride-hydrogen fluoride adduct (KHF₂.nHF) obtained in the first step of the treatment is further decomposed in potassium fluoride (KF) and hydrogen fluoride (HF). This can be illustrated by the non-limiting following reactions:

(1) KC1.KHF₂ + (n+2)HF→ 2 KHF₂.nHF + HC1

(2) 2 KHF₂.nHF→ 2KF + (n+2) HF

In a second variant, 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.

Without willing to be tied by any theory, when the dehydrochlorination agent is potassium fluoride, it is believed that chlorinated co-product resulting from the reaction between the chlorohydrin and potassium fluoride comprises potassium chloride (KC1) and potassium bifluoride (KHF₂) and that the heating treatment generates hydrogen fluoride (HF), which reacts with potassium chloride to produce hydrogen chloride (HCl) and potassium fluoride (KF). This can be illustrated by the non-limiting following reaction:

KCI.KHF₂→ 2 KF + HCl

In a third variant, 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.

Without willing to be tied by any theory, when the dehydrochlorination agent is potassium fluoride, it is believed that chlorinated co-product resulting from the reaction between the chlorohydrin and potassium fluoride comprises potassium chloride (KC1) and potassium bifluoride (KHF₂) and that the heating treatment generates potassium fluoride (KF) and hydrogen chloride. This can be illustrated by the non-limiting following reaction:

KCI.KHF₂ + nHF→ 2 KF + nHF + HCl

In the process of the invention, 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 %.

In the process of the invention, 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 %,

In the process of the invention, it is preferred that 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. In the process of the invention, 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.

In the process of the invention, the recycled regenerated

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.

In the process of the invention, 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.

In the process of the invention, 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. When the chlorinated by product is a solid, a filtration operation is preferred.

In the process of the invention, 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. In the process of the invention, the reaction of the chlorohydrin with the dehydrochlorinating agent is preferably carried out in a dehydrochlorination medium containing at least one gaseous phase.

The term "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.

In the process of the invention, the reaction between the chlorohydrin and the dehydrochlorinating agent is preferably carried out in the presence of water. By the expression "in the presence of water", one intends to denote that 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.

When the dehydrochlorination medium contains at least one liquid phase, the liquid phase preferably comprises the chlorohydrin in the form of a liquid and the dehydrochlorinating agent in the form of a solid. This is more specifically the case when the dehydrochlorinating agent is a metal fluoride or a metal oxide, and in particular a metal fluoride.

When the dehydrochlorination medium contains at least one liquid phase, 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.

When the dehydrochlorination medium contains at least one gaseous phase, this phase usually comprises the chlorohydrin in the form of a gas and the dehydrochlorinating agent in the form of a solid. This is more specifically the case when the dehydrochlonnating agent is a metal fluoride or a metal oxide, and in particular a metal fluoride.

In the process of the invention, the dehydrochlorination of the chlorohydrin can be carried out under discontinuous or under continuous mode.

By carrying out the dehydrochlorination of the chlorohydrin under continuous mode, one intends to denote a mode where the chlorohydrin and the dehydrochlorinating agent are added continuously to the dehydrochlorination medium, and the epoxide and the chlorinated co product are continuously withdrawn from that medium. Any other mode of operation is considered as discontinuous. The continuous mode is preferred.

In the process of the invention, the regeneration of the dehydrochlorinating agent can be carried out under discontinuous or under continuous mode.

By carrying out the regeneration of the dehydrochlorinating agent under continuous mode, one intends to denote a mode where the chlorinated by product is added continuously to the regeneration medium, and the regenerated dehydrochlorination agent is continuously withdrawn from that medium. Any other mode of operation is considered as discontinuous. The continuous mode is preferred.

In the process of the invention, the dehydrochlorination of the chlorohydrin and the regeneration of the dehydrochlorinating agent are preferably carried out under continuous mode.

In the process of the invention, the dehydrochlorination reaction can be carried out in any type of reactor. When the dehydrochlorinating agent is a solid, 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.

In the process of the invention, the regeneration treatment can be carried out in any type of reactor. When the chlorinated co product is a solid, 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.

In the process of the invention, the term "epoxide" is used to describe a compound containing at least one oxygen bridged on a carbon-carbon bond. In general 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.

In the process of the invention, the term "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),

1.2- propanediol (propylene glycol), l-chloro-2,3-propanediol

(chloropropanediol), 2-chloro-l,3-propanediol (chloropropanediol), 1,2,3- propanetriol (also known as "glycerol" or "glycerin"), and any mixture thereof. 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.

In the process of the invention, the term "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,

1.3- dichloropropan-2-ol, 2,3-dichloropropan-l-ol and mixtures of at least two thereof. 2-chloroethanol, 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 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. The general name monochloropropanol refers to l-chloropropan-2-ol, 2-chloropropan-l-ol, and any mixture thereof. The general name

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.

In the process of the invention, 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.

In the process of the invention, the chlorohydrin may have been obtained by any processes like olefin hypochlorination, olefin chlorination,

polyhydroxylated aliphatic hydrocarbons hydrochlorination, and any

combination thereof. 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 .

In the process of the invention, 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. l-chloropropane-2,3-diol, 2-chloropropane-l,3-diol, l,3-dichloropropan-2-ol, 2,3-dichloropropan-l-ol from glycerol hydrochlorination, chloroethanol from ethylene glycol

hydrochlorination, l-chloropropan-2-ol and 2-chloropropan-l-ol from propylene glycol hydrochlorination), and any combination thereof. Polyhydroxylated aliphatic hydrocarbon hydrochlorination is preferred.

In the process of the invention, the chlorohydrin is preferably

l,3-dichloropropan-2-ol, 2,3-dichloropropan-l-ol and mixtures of at least two thereof, obtained by hydrochlorination of glycerol.

In the process of the invention, 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. In the process of the invention, the epoxide is more preferably ethylene oxide, the chlorohydrin is preferably 2-chloroethanol and the polyhydroxylated aliphatic hydrocarbon is preferably ethylene glycol.

In the process of the invention, 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.

In the process of the invention, the epoxide is most preferably

epichlorohydrin, the chlorohydrin is most preferably dichloropropanol and the polyhydroxylated aliphatic hydrocarbon is most preferably glycerol.

In the process of the invention, the epoxide is most preferably

epichlorohydrin, 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.

Any combination of the above triads is also convenient.

In the process of the invention, when the epoxide is epichlorohydrin, 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.

Therefore, in a further embodiment, 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 polyol is preferably selected from Bisphenol A (4,4'- dihydroxy-2,2- diphenylpropane, 4,4'-isopropylidenediphenol), tetrabromo Bisphenol A (4,4'- isopropylidenebis(2,6-dibromophenol)), Bisphenol AF (4,4'- [2,2,2-trifluoro-l- (trifluoromethyl)ethylidene]bisphenol) = hexafluorobisphenol A (4,4'-dihydroxy- 2,2-diphenyl-l,l,l,3,3,3-hexafluoropropane), l,l,2,2-tetra(p- hydroxyphenyl)ethane, hexafluorobisphenol A, tetramethylbisphenol (4,4'- dihydroxy-3,3',5,5'-tetramethyl bisphenol), 1,5-dihydroxynaphthalene, 1,1 ',7,7'- tetrahydroxy-dinaphthyl methane, 4,4'-dihydroxy-alpha-methylstilbene, a condensation product of Bisphenol A with formaldehyde (Bisphenol A novolac), a condensation product of phenol with formaldehyde, preferably Bisphenol F (mixture of ο,ο', ο,ρ' and ρ,ρ' isomers of dihydroxy diphenylmethane), a condensation product of cresol with formaldehyde (mixtures of ο,ο', ο,ρ' and ρ,ρ' isomers of methyl hydroxy diphenylmethane), an alkylation product of phenol and dicyclopentadiene (2,5-bis[(hydroxy phenyl] octahydro-4,7-methano-5H- indene), a condensation product of phenol and glyoxal (tetrakis(4-hydroxy- phenyl)ethane), a condensation product of phenol and a hydroxybenzaldehyde (e.g., tris(4-hydroxyphenyl)methane), l,l,3-tris-(p-hydroxyphenyl)-propane, isosorbide and mixtures thereof.

In the process of the invention, 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.

In the process of the invention, when the epoxide is epichlorohydrin, 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. In the process of the invention, when the epoxide is epichlorohydrin and the chlorohydrin is dichloropropanol, 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

dehydrochlorination agent.

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). Optionally, 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

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).

Figure 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, MgCl₂, xMgO.MgCl₂.yH₂0 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, MgCl₂,

xMgO.MgCl₂.yH₂0 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 examples below are intended to illustrate the invention without, however, limiting it.

1. Dehydrochlorination of chlorohydrins

1.1. Dehydrochlorination of dichloropropanol

The examples were conducted, unless otherwise indicated, under a nitrogen atmosphere at 1 bar absolute in a round bottom flask equipped with an oil bath, a magnetic stirrer or a mechanical stirring device, and a condenser on top of which an outlet tube was connected to a gas scrubber containing aqueous caustic soda or water. Aliquots were taken from the liquid reaction medium overtime, filtered or centrifuged for gas chromatography (GC) analysis. Each sample has been dissolved in ethanol. GC has been performed on a CP sil 5 CB column

(50m*0.32mm*1.2um) using an appropriate temperature program and flame ionization detection. Quantification has been done using an internal standard and relative response factors, determined using standard reference products.

GC conditions:

- Injector temperature: 250°C

Detector temperature: 300°C

- Oven temperature : 40°C (5 min) - 8 °C/min - 300 °C (5 min)

- Split flow: 100 ml/min

Helium flow rate: 2 ml/min (constant)

All reactants employed were anhydrous or essentially anhydrous.

The examples have been carried out as follows.

To the round bottom flask were added the dehydrochlorination agent (DHC agent) and l,3-dichloropropan-2-ol (1,3-DCPol) along with an additive when specified. Unless otherwise indicated, the 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%, BaF₂ Sigma- Aldrich 99.99% on metal basis, CsF Sigma-Aldrich, > 99%, NaF Sigma-Aldrich > 99%, RbF Alfa Aesar > 99.7 % on metal basis, CaF₂ Alfa Aesar > 98 %, Na₃AlF₆ Sigma-Aldrich > 97%, KBF₄ Alfa Aesar > 98 %, NH₄F Sigma-Aldrich ACS reagent > 98%, MgO Sigma-Aldrich 99.99% on metal basis. Unless otherwise indicated, the MgO used as a DHC agent was obtained by

prehydrating commercial MgO at reflux for 24 h with demineralized water in a 1: 12.5 molar ratio, next filtered on Whatman 40 Ashless 125 mm filter, dried at 100°C under 100 torr for 20 h and then calcinated in an oven at 600°C for 20 hours.

The 1,3-DCPol conversion is calculated as follows:

100 X (number of moles of reaction products at the time of the

sampling)/(number of moles of 1,3-DCPol introduced in the flask). 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.

The epichlorohydrin (ECH) selectivity is calculated as follows:

100 X (number of moles of ECH 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 examples conditions and results are summarized in Table 1 and 3 here below.

Table 1

DHC agent: dehydrochlorination agent ; 1,3-DCPol : l,3-dichloropropan-2-ol ; (a) : magnetic, (b) mechanical,

* : the concentration of water in 1,3-DCPol has been adjusted according to Table 2; 3': 2,3-DCPol was used instead of 1,3-DCPol

Table 2

Example Water concentration (g/kg)

20 6.5

21 10.9

22 25.9

23 0.5

24 0.34

Table 3

a: DCP: 1,2-dichloropropane

β: reactions carried out in a 1 L autoclave under pressure, DCM: dichloromethane

y: the DHC agent used was the solid obtained from the example 33 after it was filtered and dried at 100°C under 100 Torr δ: commercial MgO used without any pretreatment

(a) : magnetic, (b) mechanical

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 AgN0₃ 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(N0₃)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.

1.2. Dehydrochlorination of other chlorohydrins

The examples of 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:

100 X (number of moles of reaction products at the time of the

sampling )/(number of moles of the chlorohydrin introduced in the flask). 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 examples conditions and results are described as below.

Example 39

To a 100 mL round bottom flask were added 7.43 g (127.9 mmol) KF and 40.61 g (531.0 mmol) 2-chloroethanol. The reactor was heated at 120°C and the condenser cooled down to -5°C. After vigorous stirring for 90 minutes and continuous distillation, the contents were sampled and conversion of 2- chloroethanol was found to be superior to 6 % with a selectivity to ethylene oxide of 97%.

Example 40

To a 100 mL round bottom flask were added 7.54 g (129.8 mmol) KF and 47,37 g (523.4 mmol) l-chloro-2-propanol. The reactor was heated at 110°C and the condenser cooled down to 10°C. After vigorous stirring for 75 minutes and continuous distillation, the contents were sampled and conversion of l-chloro-2- propanol was found to be 13 % with a selectivity to propene oxide of 96%.

2. Regeneration of chlorinated co-product

The regeneration of the chlorinated co-product has firstly been carried out according to a two steps procedure.

In the first step, 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).

All reactants employed were anhydrous or essentially anhydrous.

The conversion of KCl is calculated as follows:

100 X (the difference between the number of moles of KCl at the time of the sampling and the number of moles of KCl introduced in the flask)/(number of moles of KCl introduced in the flask).

The regeneration conditions and results are summarized in Table 4 here below.

Table 4

a: The reaction was run in 4 periods of 16 hours each, at the beginning of which at -25°C, 12.6 g, 12.8 g, 14,6 g and 16,1 g of HF were introduced and at the end of which at 120°C the gaseous phase was removed for analysis

b: The reaction was run in the presence of stainless coils to elevate the salts at the beginning of the reaction and allow the introduction of HF through the autoclave dip tube

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. At the end of the heating program, 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.

All reactants employed were anhydrous or essentially anhydrous.

Example 47

To a 10 mL platinum nacelle was added 3.8275 g of solids from the first step of the regeneration of the DHC agent KF according to example 44 .The nacelle was heated in the tube furnace at 105°C for 2 hours, 30 minutes at 250°C and 5 hours at 400°C with a rate of 10°C/min between each range of

temperature. After cooling down to room temperature, the white solid content was weighed (1,915 g) and did not show any residual HF. No residual chloride was found in the solid. The regeneration of the chlorinated co-product has secondly been carried out according to a one step procedure.

In the first step, 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.

Example 48

To a 10 mL platinum nacelle was added 4.0820 g of solids composed of a 1/1 ratio of KHF₂ and KCl and obtained from the DHC of 1,3-DCPol and according to example 6'. The nacelle was heated in the tube furnace from room

temperature to 250°C with a rate of 20°C/min and heated at 250°C for 4 hours then to 400°C with a rate of 10°C/min and heated at 400°C for 5 hours. After cooling down to room temperature, 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).

3. Reuse of regenerated chlorinated by-product

The solids obtained after the regeneration process of the DHC agent KF were used in a DHC process as described above.

The 1,3-DCPol conversion, the epichlorohydrin (ECH) selectivity and the number of moles of the reaction products are calculated as above.

Example 49

To a 25 mL round bottom flask were added 1.41 g of the solids obtained after the regeneration process of the DHC agent KF in example 47 and 6.30 g (48.9 mmol) l,3-dichloropropan-2-ol. The reactor was heated at 80°C. After vigorous stirring for 1 hour, the contents were sampled and conversion of 1,3- dichloropropan-2-ol was found to be 24% with a selectivity to epichlorohydrin of 93%.

Example 50

To a 25 mL round bottom flask were added 1.03 g of the solids obtained after the regeneration process of the DHC agent KF in example 48 and 3.43 g (26,6 mmol) l,3-dichloropropan-2-ol. The reactor was heated at 80°C. After vigorous stirring for 1 hour, the contents were sampled and conversion of 1,3- dichloropropan-2-ol was found to be 12% with a selectivity to epichlorohydrin of 91%.

Claims

C L A I M S

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.

2. The process according to claim 1, wherein the dehydrochlorinating agent is selected from a metal fluoride, an amine, a phosphine, an arsine, a metal oxide, and any mixture thereof, wherein the dehydrochlorinating agent is preferably a metal oxide or a metal fluoride and wherein the

dehydrochlorinating agent is more preferably a metal fluoride.

3. The process according to claim 2, wherein the dehydrochlorinating agent is a solid, preferably an unsupported solid.

4. The process according to claim 2 or 3, wherein the metal fluoride is an alkali fluoride and the chlorinated co-product comprises an alkali chloride and an alkali bifluoride or the amine is a tertiary amine, 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,

diisopentadecylisopropylamine, didodecyl-methylamine, dodecyl- diisopropylamine, and any mixture thereof, and the chlorinated co-product is a chlorohydrate of the tertiary amine or the phosphine is a tertiary phosphine and the chlorinated co-product is a chlorohydrate of the tertiary phosphine or the arsine is a tertiary arsine and the chlorinated co-product is a chlorohydrate of the tertiary arsine or the metal oxide is an alkaline-earth metal oxide and the chlorinated co- product comprises the corresponding alkaline-earth metal chloride and a mixed oxidechloride hydrate of the alkaline-earth metal, or the metal oxide is an earth metal oxide and the chlorinated by-product comprises the corresponding earth metal chloride and a mixed oxide chloride hydrate of the earth metal or the metal oxide is a lanthanide metal oxide and the chlorinated co-product comprises the corresponding lanthanide metal chloride and a mixed oxide chloride hydrate of the lanthanide metal or the metal oxide is a transition metal oxide and the chlorinated co-product comprises the corresponding transition metal chloride and a mixed oxide chloride hydrate of the transition metal or any combination thereof.

5. The process according to claim 4, wherein the metal fluoride is an alkali fluoride and the chlorinated co-product comprises an alkali chloride and an alkali bifluoride, and wherein preferably the alkali fluoride is potassium fluoride and the chlorinated co-product comprises potassium chloride and potassium bifluoride.

6. The process according to claim 4, 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 oxidechloride hydrate of the alkaline-earth metal, and wherein preferably the alkaline-earth metal oxide is magnesium oxide and the chlorinated co-product comprises magnesium chloride and a mixed oxide chloride hydrate of magnesium.

7. The process according to any one of claims 1 to 6, 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.

8. The process according to claim 7, wherein at least part of the chlorohydrin has preferably been obtained by reacting hydrogen chloride with a polyhydroxylated aliphatic hydrocarbon, optionally in the presence of a carboxylic acid catalyst, wherein preferably the epoxide is ethylene oxide, the chlorohydrin is

chloroethanol and the polyhydroxylated aliphatic hydrocarbon is ethylene glycol, or preferably the epoxide is propylene oxide, the chlorohydrin is

monochloropropanol and the polyhydroxylated aliphatic hydrocarbon is 1,2- propanediol, or more preferably the epoxide is epichlorohydrin, the chlorohydrin is dichloropropanol and the polyhydroxylated aliphatic hydrocarbon is glycerol.

9. The process according to any one of claims 1 to 8, wherein the reaction between the chlorohydrin and the dehydrochlorinating agent is carried out in the presence of water.

10. The process according to any one of claims 1 to 9, 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.

11. The process according to any one of claims 2 to 10, wherein the dehydrochlorination agent is a metal fluoride, preferably an alkali fluoride and more preferably potassium fluoride, wherein the treatment comprises at least one operation carried out in the presence of hydrogen fluoride, at least part of the hydrogen fluoride being optionally generated in situ in the treatment of the chlorinated co-product.

12. The process according to claim 11, where the treatment comprises at least one other operation carried out in the absence of added hydrogen fluoride.

13. The process according to any one of claims 1 to 12, wherein at least part of the regenerated dehydrochlorinating agent is recycled to the reaction with the chlorohydrin and preferably 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.

14. The process according to any one of claims 1 to 13, 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 a polyhydroxylated aliphatic hydrocarbon, wherein preferably 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 or preferably 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, or more preferably 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 and the epoxide is epichlorohydrin, the chlorohydrin is dichloropropanol and the polyhydroxylated aliphatic hydrocarbon is glycerol .

15. A process for manufacturing an epoxy resin comprising obtaining epichlorohydrin by the process according to any one of claims 7 to 14 and further reacting the obtained epichlorohydrin with at least one polyol.