Membrane-supported catalyst removal in the epoxidation of cyclic unsaturated C12 compounds, for example cyclododecene (CDEN)

Patent metadata

Field	Value
Publication number	US-9643153-B2
Application number	US-201514714985-A
Country	US
Kind code	B2
Filing date	May 18, 2015
Priority date	May 19, 2014
Publication date	May 9, 2017
Grant date	May 9, 2017

Abstract

A homogeneous catalyst system is removed from a reaction mixture of two liquid phases by separating the two liquid phases with a membrane having at least one separation-active layer in such a way that the homogeneous catalyst system is at least partially concentrated in a membrane retentate; wherein the reaction mixture contains at least one partially epoxidized cyclic unsaturated compound having twelve carbon atoms; and wherein the membrane separation-active layer contains crosslinked a silicone acrylate and/or polydimethylsiloxane and/or polyimide.

First claim

The invention claimed is:

1. A method to prepare an epoxidized cyclic unsaturated compound comprising twelve carbon atoms, comprising:
epoxidizing a cyclic unsaturated compound comprising 12 carbon atoms with hydrogen peroxide in a two phase organic aqueous system in the presence of a homogeneous catalyst and phase transfer reagent;
separating and removing the aqueous phase to obtain an organic phase containing the epoxidized cyclic unsaturated compound comprising twelve carbon atoms, the homogeneous catalyst and the phase transfer reagent;
contacting the organic phase with a membrane under a transmembrane pressure of 5 to 80 bar to obtain a permeate comprising the epoxidized cyclic unsaturated compound comprising twelve carbon atoms and a retentate comprising the homogeneous catalyst and phase transfer reagent;
wherein the membrane is a composite membrane comprising a support material and a membrane separation-active layer comprising a crosslinked silicone acrylate and
the homogeneous catalyst comprises an oxide, a mixed oxide, an oxoacid, a salt of an oxoacid, a carbonyl derivative, a sulphide, a chloride, an oxychloride or a stearate of an element selected from the group consisting of tungsten, molybdenum and vanadium.

2. The method according to claim 1 , wherein the aqueous phase comprises the hydrogen peroxide.

3. The method according to claim 1 , wherein the cyclic unsaturated compound comprising twelve carbon atoms is cyclododecene.

4. The method according to claim 3 , wherein the phase transfer reagent is a tertiary or quaternary ammonium compound.

5. The method according to claim 4 , wherein the phase transfer reagent is a quaternary ammonium compound and is an esterquat of formula (I)

wherein the substituents R are independently identical or different alkyl or alcohol groups comprising from 1 to 4 carbon atoms and at least one of the substituents R is an alcohol group which comprises from 1 to 4 carbon atoms and which has been esterified with a saturated or unsaturated fatty acid comprising from 1 to 30 carbon atoms and X 31 is a counteranion.

6. The method according to claim 4 , wherein the phase transfer reagent is a quaternary ammonium compound and is a quaternary ammonium compound ester according to formulae (II) and (III)

wherein Z denotes one or more saturated or unsaturated fatty acids comprising from 1 to 30 carbon atoms and X 31 is a counteranion.

7. The method according to claim 1 , wherein the silicone acrylate is of formula IV:

wherein
a is from 1 to 500, b is from 1 to 25 and c is from 0 to 20,
the substituents R 1 are independently identical or different alkyl or aryl groups which comprise from 1 to 30 carbon atoms and which may bear at least one ether, ester, epoxy and/or hydroxy group,
the substituents R 2 are independently identical or different substituents selected from the group consisting of R 1 , R 3 and R 4 ,
the substituents R 3 are independently identical or different acrylate groups of formulae V or VI:

wherein d is from 0 to 12, e is from 0 to 1, f is from 0 to 12, g is from 0 to 2, h is from 1 to 3 and g+h is 3,
the substituents R 6 are independently identical or different alkyl or aryl groups comprising from 1 to 30 carbon atoms or hydrogen,
the groups R 7 are identical or different divalent hydrocarbon radicals,
the substituents R 4 are independently identical or different polyether groups of formula (VII):

wherein i is from 0 to 12, j is from 0 to 50, k is from 0 to 50 and l is from 0 to 50,
the substituents R 8 are identical or different alkyl or aryl groups comprising from 2 to 30 carbon atoms and
R 9 is an alkyl, aryl or acyl group comprising from 2 to 30 carbon atoms or hydrogen.

8. The method according to claim 1 , wherein the separation-active layer is arranged on a carrier material selected from the group consisting of polyacrylonitrile, polyimide, polyether ether ketone, polyvinylidene fluoride, polyamide, polyamide-imide, polyethersulphone, polybenzimidazole, sulphonated polyether ketone, polyethylene, polypropylene and mixtures thereof.

9. The method according to claim 1 , wherein the the applied transmembrane pressure is from 10 to 60 bar.

10. The method according to claim 1 , wherein the separation is carried out at a temperature of from 25° C. to 160° C.

11. The method according to claim 7 , wherein the groups R 7 are identical or different divalent hydrocarbon radicals of the formula —CR 6 2 —.

12. The method according to claim 7 , wherein the groups R 7 are CH 2 .

13. The method according to claim 1 , wherein the epoxidizing and the separating are carried out simultaneously.

Assignees

• Meier Ralf
• Micoine Kévin
• Kreis Peter
• Gluth Frederik
• Priske Markus
• Evonik Degussa Gmbh

Inventors

• Meier Ralf
• Micoine Kévin
• Kreis Peter
• Gluth Frederik
• Priske Markus

Classifications

• B01J2219/24

  Stationary reactors without moving elements inside · CPC title

• B01J2231/72

  Epoxidation · CPC title

• B01J31/4061 Primary

  involving membrane separation · CPC title

• C07D301/32

  Separation; Purification · CPC title

• B01J2531/985

  in a water / organic solvent system · CPC title