Process for the manufacture of epichlorohydrin
View Patent ↗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.
1. A process for the manufacture of epichlorohydrin, comprising:
reacting allyl chloride with an hydrogen peroxide in the presence of a catalyst in an aqueous reaction medium in a system having one or two organic phases, wherein the catalyst comprises a water-soluble manganese complex and the molar ratio of allyl chloride to hydrogen peroxide is from 1:0.1 to 1:1; and
isolating an epichlorohydrin product in the one or two organic phases, and wherein the water-soluble manganese complex is selected from a mononuclear manganese complex of the formula (I):
[LMnX 3 ]Y (I)
or a binuclear manganese complex of the formula (II):
[LMn(μ-X) 3 MnL]Y 2 (II)
wherein Mn is a manganese atom; L or each L independently is a polydentate ligand of triazacyclononane or a substituted triazacyclononane; each X independently is a coordinating species selected from the group consisting of: RO − , Cl − , Br − , I − , F − , NCS − , N 3 − , I 3 − , NH 3 , NR 3 , RCOO − , RSO 3 − , RSO 4 − , OH − , O 2− , O 2 2− , HOO − , H 2 O, SH − , CN − , OCN − , and S 4 2− and combinations thereof, wherein R is a C 1 -C 20 radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and combinations thereof and each μ-X independently is a bridging coordinating species selected from the group consisting of: RO − , Cl − , Br − , I − , F − , NCS − , N 3 − , I 3 − , NH 3 , NR 3 , RCOO − , RSO 3 − , RSO 4 − , OH − , O 2− , O 2 2− , HOO − , H 2 O, SH − , CN − , OCN − , and S 4 2− and combinations thereof, wherein R is a C 1 -C 20 radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and combinations thereof, and Y is an anion counterion selected from the group consisting of RO − , Cl − , Br − , I − , F − , SO 4 2− , RCOO − , PF 6 − , acetate, tosylate, triflate (CF 3 SO 3 − ) and a combination thereof, wherein R is a C 1 -C 20 radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and combinations thereof, wherein the aqueous reaction medium further comprises a buffer system so as to stabilize the pH and a pH in the range of from 3 to 6.5.
2. The process of claim 1 , wherein the one or two organic phases comprise epichlorohydrin product or a mixture of allyl chloride and epichlorohydrin product.
3. The process of claim 1 , wherein the manganese complex comprises the formula [LMn(μ-X) 3 MnL]Y 2 , wherein Mn is a manganese atom; L is a L is a triazacyclononane or substituted triazacyclononane; 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 − , F − , NCS − , N 3 − , I 3 − , NH 3 , NR 3 , RCOO − , RSO 3 − , RSO 4 − , OH − , O 2− , HOO − , H 2 O, SH − , CN − , OCN − , and S4 2− and combinations thereof, wherein R is a C 1 -C 20 radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and combinations thereof, and Y is SO 4 2− , PF 6 − , acetate, or a combination thereof.
4. The process of claim 1 , further comprising agitating the aqueous reaction medium and the one or two organic phases.
5. The process of claim 4 , wherein the stirring the aqueous reaction medium comprises stirring the system with a stirrer at between 100 rpms and 650 rpm.
6. The process of claim 1 , wherein the aqueous reaction medium further comprises a buffer system at a buffer to catalyst ratio from 10:1 to 100:1.
7. The process of claim 6 , wherein the buffer system comprises an acid-salt combination.
8. The process of claim 7 , wherein the acid-salt combination comprises oxalic acid-oxalate salt or acetic acid-acetate salt.
9. The process of claim 1 , wherein the catalyst is present in a concentration from 0.001 mmol/L to 10 mmol/L.
10. 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.
11. The process of claim 1 , wherein the aqueous reaction comprises a pH in the range of from 3 to 6.5.
12. The process of claim 1 , wherein the aqueous reaction comprises a pH in the range of from 3 to 4.2.
13. The process of claim 1 , wherein the allyl chloride and the hydrogen peroxide are reacted at a molar ratio of the allyl chloride to the hydrogen peroxide in the range from 1:0.2 to 1:0.8.
14. The process of claim 1 , wherein the reaction is performed in a batch process, in a continuous process or in a semi-continuous process.
15. The process of claim 1 , wherein the aqueous reaction medium comprises a 100% aqueous medium excluding any dissolved epoxide and allyl chloride.
16. The process of claim 1 , wherein the manganese complex comprises the formula [LMn(μ-X) 3 MnL]Y 2 , wherein L is a triazacyclononane or substituted triazacyclononane and the counterion Y is PF 6 − or CH 3 CO 2 − .
17. The process of claim 1 , wherein the catalyst comprises
a binuclear manganese complex of the general formula (II):
[LMn(μ-X) 3 MnL]Y 2 (II),
wherein Mn is a manganese; L or each L independently is a polydentate ligand of triazacyclononane or a substituted triazacyclononane; each μ-X independently is a bridging coordinating species of: O 2− , RCOO − , RSO 3 − , RSO 4 − , wherein R is selected from the group consisting of C 1 -C 20 alkyl, C 1 -C 20 cycloalkyl, C 1 -C 20 aryl, benzyl and combinations thereof, and Y is an anion selected from the group consisting of SO 4 2− , PF 6 − , acetate, and a combination thereof;
wherein the aqueous reaction medium further comprises a buffer system with a pH range from 3 to 4.2; and
wherein the molar ratio of the terminal olefin to the hydrogen peroxide in the range of from 1:0.1 to 1.2:1.