Production of hydroxy ether hydrocarbons by liquid phase hydrogenolysis of cyclic acetals or cyclic ketals

Patent metadata

Field	Value
Publication number	US-9388105-B2
Application number	US-201113168304-A
Country	US
Kind code	B2
Filing date	Jun 24, 2011
Priority date	Jun 24, 2011
Publication date	Jul 12, 2016
Grant date	Jul 12, 2016

Abstract

A liquid phase hydrogenolysis of acetal compounds, such as cyclic acetals and cyclic ketals, is disclosed. The acetal compounds are fed to a reaction zone and reacted in the presence of a noble metal catalyst supported on a carbon or silica support to make hydroxy mono-ether compounds in high selectivity, without the necessity of using acidic co-catalysts such as phosphorus containing acids or stabilizers such as hydroquinone.

First claim

The invention claimed is:

1. A process for making a hydroxy mono-ether compound, comprising:
feeding a cyclic acetal or cyclic ketal compound and hydrogen, without feeding a carbonyl compound, into a reaction vessel;
reacting the cyclic acetal or cyclic ketal compound with the hydrogen in the presence of (i) a noble metal catalyst supported on carbon or silica and (ii) a solvent comprising a polyhydroxyl compound used to make the cyclic acetal or cyclic ketal compound, to form a hydroxy mono-ether compound,
wherein the reaction is carried out in the absence of an added acidic co-catalyst or promoter, and
wherein the molar ratio of the polyhydroxyl compound to the cyclic acetal or cyclic ketal compound is at least 2:1.

2. The process according to claim 1 , wherein the cyclic acetal or cyclic ketal compound has the structure of Formula I:

wherein R 1 , R 2 , R 3 , and R 4 are each independently H or a branched or un-branched C 1 -C 6 alkyl group;
wherein no more than one of R 1 and R 2 is H;
wherein R 5 is a branched or un-branched divalent alkyl group having 1 to 6 carbon atoms; and
wherein n is 0 or 1.

3. The process according to claim 1 , wherein the cyclic acetal or cyclic ketal compound comprises 2-propyl-1,3-dioxolane, 2-propyl-1,3-dioxane, 2-ethyl-1,3-dioxolane, 2-ethyl-1,3-dioxane, 2-methyl-1,3-dioxolane, 2-methyl-1,3-dioxane, 2-propyl-4-methyl-1,3-dioxane, 5,5-dimethyl-2-propyl-1,3-dioxane, 5,5-dimethyl-2-ethyl-1,3-dioxane, 2-ethyl-1,3-dioxepane, or 2-ethyl-1,3,6-trioxocane.

4. The process according to claim 1 , wherein the polyhydroxyl compound comprises ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, diethylene glycol, triethylene glycol, glycerin, trimethylolpropane, xylitol, arabitol, 1,2- or 1,3-cyclopentanediol, 1,2- or 1,3-cyclohexanediol, 2,3-norbornanediol, or combinations thereof.

5. The process according to claim 1 , wherein the polyhydroxyl compound comprises ethylene glycol, 1,2-propanendiol, 1,3-propanediol, or combinations thereof.

6. The process according to claim 1 , wherein the molar ratio of the polyhydroxyl compound to the cyclic acetal or cyclic ketal compound is from 3:1 to 20:1.

7. The process according to claim 1 , wherein the molar ratio of the polyhydroxyl compound to the cyclic acetal or cyclic ketal compound is from 5:1 to 20:1.

8. The process according to claim 1 , wherein the hydroxyl mono-ether compound comprises ethylene glycol monobutyl ether, 3-butoxy-1-propanol, ethylene glycol monopropyl ether, 3-propoxy-1-propanol, ethylene glycol monoethyl ether, 3-ethoxy-1-propanol, 3-butoxy-2,2-dimethyl-1-propanol, 4-propoxy-1-butanol, diethylene glycol monobutyl ether, or combinations thereof.

9. The process according to claim 1 , which has a selectivity of at least 80% for the hydroxy mono-ether compound.

10. The process according to claim 1 , which has a selectivity of at least 90% for the hydroxy mono-ether compound.

11. The process according to claim 1 , which has a selectivity of at least 95% for the hydroxy mono-ether compound.

12. The process according to claim 11 , wherein the conversion of the cyclic acetal or cylic ketal compound is from 85% to 98%.

13. The process according to claim 1 , wherein the noble metal catalyst comprises palladium.

14. The process according to claim 1 , wherein the reaction is carried out in the absence of hydroquinone.

15. A process for preparing a hydroxy mono-ether compound, comprising:
(a) reacting a carbonyl compound with a polyhydroxyl compound in the presence of an acid catalyst to form a cyclic acetal or cyclic ketal compound;
(b) feeding the cyclic acetal or cyclic ketal compound and hydrogen, without feeding the carbonyl compound, into a reaction vessel; and
(c) reacting the cyclic acetal or cyclic ketal compound with the hydrogen in the presence of (i) a noble metal catalyst supported on carbon or silica and (ii) a solvent comprising the polyhydroxyl compound to form a hydroxy mono-ether compound,
wherein the reaction in step (c) is carried out in the absence of an added acidic co-catalyst or promoter, and
wherein the molar ratio of the polyhydroxyl compound to the cyclic acetal or cyclic ketal compound in step (c) is at least 2:1.

16. The process according to claim 15 , wherein the carbonyl compound comprises an aldehyde compound selected from the group consisting of acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, pentaldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde, hexaldehyde, benzaldehyde, 2-ethylhexaldehyde, octanal, and nonanal.

17. The process according to claim 15 , wherein the carbonyl compound comprises a ketone compound selected from the group consisting of acetone, methyl isobutyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, 2-heptanone, 4-heptanone, and 2-octonone.

18. The process according to claim 15 , wherein the polyhydroxyl compound comprises ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, diethylene glycol, triethylene glycol, glycerin, trimethylolpropane, xylitol, arabitol, 1,2- or 1,3-cyclopentanediol, 1,2- or 1,3-cyclohexanediol, 2,3-norbornanediol, or combinations thereof.

19. The process according to claim 15 , wherein the polyhydroxyl compound comprises ethylene glycol, 1,2-propanendiol, 1,3-propanediol, or combinations thereof.

20. The process according to claim 15 , wherein the molar ratio of the polyhydroxyl compound to the cyclic acetal or cyclic ketal compound in step (c) is from 5:1 to 20:1.

21. The process according to claim 15 , wherein the hydroxyl mono-ether compound comprises ethylene glycol monobutyl ether, 3-butoxy-1-propanol, ethylene glycol monopropyl ether, 3-propoxy-1-propanol, ethylene glycol monoethyl ether, 3-ethoxy-1-propanol, 3-butoxy-2,2-dimethyl-1-propanol, 4-propoxy-1-butanol, diethylene glycol monobutyl ether, or combinations thereof.

22. The process according to claim 15 , which has a selectivity of at least 90% for the hydroxy mono-ether compound.

23. The process according to claim 15 , which has a selectivity of at least 95% for the hydroxy mono-ether compound.

24. The process according to claim 23 , wherein the conversion of the cyclic acetal or cylic ketal compound is from 85% to 98%.

25. The process according to claim 15 , wherein the noble metal catalyst comprises palladium.

Assignees

• Billodeaux Damon Ray
• Devon Thomas James
• Penney Jonathan Michael
• Terrill Daniel Latham
• Hembre Robert Thomas
• Stavinoha Jr Jerome Leonard
• Eastman Chem Co

Inventors

• Billodeaux Damon Ray
• Devon Thomas James
• Penney Jonathan Michael
• Terrill Daniel Latham
• Hembre Robert Thomas
• Stavinoha Jr Jerome Leonard

Classifications

• C07C41/28 Primary

  from acetals, e.g. by dealcoholysis · CPC title

• C07C43/13

  containing hydroxy or O-metal groups (C07C43/11 takes precedence) · CPC title