초록 ▼

The invention relates to a process for the manufacture of epichlorohydrin (“ECH”) by catalytic oxidation of allyl chloride (“AC”) with an oxidant wherein the catalytic oxidation is performed in an aqueous reaction medium, wherein a water-soluble manganese complex is used as oxidation catalyst,follow

The invention relates to a process for the manufacture of epichlorohydrin (“ECH”) by catalytic oxidation of allyl chloride (“AC”) with an oxidant wherein the catalytic oxidation is performed in an aqueous reaction medium, wherein a water-soluble manganese complex is used as oxidation catalyst,followed by the isolation of epichlorohydrin.

대표청구항 ▼

1. A process for the manufacture of epichlorohydrin, comprising: reacting allyl chloride with an oxidant in the presence of a catalyst in an aqueous reaction medium, wherein the catalyst comprises a water-soluble manganese complex and the molar ratio of allyl chloride to oxidant is from 1:0.1 to 1:1

1. A process for the manufacture of epichlorohydrin, comprising: reacting allyl chloride with an oxidant in the presence of a catalyst in an aqueous reaction medium, wherein the catalyst comprises a water-soluble manganese complex and the molar ratio of allyl chloride to oxidant is from 1:0.1 to 1:1; and isolating an epichlorohydrin product, wherein the water-soluble manganese complex comprises a mononuclear manganese complex of the general formula (I): [LMnX3]Y  (I)or a binuclear manganese complex of the general formula (II): [LMn (μ−X )3MnL]Y2  (II)wherein Mn is a manganese; L or each L independently is a polydentate ligand; each X independently is a coordinating species: and each μ−X independently is a bridging coordinating species, selected from the group consisting of: RO−, Cl−, Br31 , I−, F−, NCS−, N3−, I3−, NH3, NR3, RCOO−, RSO3−, RSO4−, OH−, O2−, O22−, HOO−, H2O , SH−, CN−, OCN−, and S42−and combinations thereof, wherein R is a C1-C20 radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and combinations thereof, and Y is an oxidatively-stable counterion. 2. The process of claim 1, wherein the epichlorohydrin product or a part of the epichlorohydrin product is isolated as an organic phase, wherein the organic phase comprises epichlorohydrin product or a mixture of allyl chloride and epichlorohydrin product. 3. The process of claim 1, wherein each polydentate ligand is independently selected from acyclic compounds containing at least 7 atoms in the backbone or cyclic compounds containing at least 9 atoms in the ring, wherein each polydentate ligand having 3 nitrogen atoms with the nitrogen atoms separated by at least two carbon atoms. 4. The process of claim 1, wherein a binuclear water-soluble manganese complex is used as the catalyst. 5. The process of claim 1, wherein the catalyst is used in a molar ratio of the catalyst (Mn) to the allyl chloride from 1:10 to 1:10,000,000. 6. The process of claim 1, wherein the aqueous reaction medium is a water phase. 7. The process of claim 1, wherein the aqueous reaction medium further comprises a buffer system and a pH in the range of from 2.5 to 7. 8. The process of claim 1, wherein the reaction is carried out at temperatures in the range from −5° C. and 30° C. 9. The process of claim 1, wherein the oxidant is hydrogen peroxide. 10. The process of claim 9, wherein the hydrogen peroxide is used as an aqueous solution in a concentration from 15% to 98%. 11. The process of claim 1, wherein the allyl chloride and the oxidant are reacted at a molar ratio of the allyl chloride to the oxidant in the range from 1:0.2 to 0.8. 12. The process of claim 1, wherein the oxidant is added to the aqueous reaction medium at a rate about equal to the reaction rate. 13. The process of claim 1, wherein the reaction is performed in a batch process, in a continuous process or in a semi-continuous process. 14. The process of claim 1, wherein the aqueous reaction medium comprises a 100% aqueous medium excluding any dissolved epoxide and ally chloride. 15. The process of claim 1, wherein the wherein each L is independently a triazacyclononane or substituted triazacyclononane. 16. The process of claim 1, wherein the manganese complex comprises the formula [MnIV2(μ−O)3L2]Y2, wherein L is a triazacyclononane or substituted triazacyclononane and the counterion Y is PF6−or CH3CO2−. 17. The process of claim 1, wherein the catalyst comprises a mononuclear manganese complex of the general formula (I): [LMnX3]Y  (I)or a binuclear manganese complex of the general formula (II): [LMn (μ−X )3MnL]Y2  (II)wherein Mn is a manganese; L or each L independently is a polydentate ligand; each X independently is a coordinating species and each μ−X independently is a bridging coordinating species, selected from the group consisting of: RO−, Cl−, Br−, I−, F−, NCS−, N3−, I3−, NH3, NR3, RCOO−, RSO331 , RSO4−, OH−, O2−, O22−, HOO−, H2O , SH−, CN−, OCN−, and S42− and combinations thereof, wherein R is a C1-C20 radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and combinations thereof, and Y is an oxidatively-stable counterion;wherein the aqueous reaction medium further comprises a buffer system with a pH range from 2.5 to 7; andwherein the molar ratio of the terminal olefin to the hydrogen peroxide in the range of from 1:0.1 to 1.2:1. 18. The process of claim 1, wherein Y is an oxidatively-stable counterion selected from the group consisting of RO−, Cl−, Br−, I−, F−, SO42−, RCOO−, PF6−, acetate, tosylate, triflate (CF3SO3−) and a combination thereof.