Process for preparing ethylene glycol from a carbohydrate source

Patent metadata

Field	Value
Publication number	US-10294180-B2
Application number	US-201615543091-A
Country	US
Kind code	B2
Filing date	Jan 13, 2016
Priority date	Jan 13, 2015
Publication date	May 21, 2019
Grant date	May 21, 2019

Abstract

Ethylene glycol is prepared from a carbohydrate source in a process,
wherein hydrogen, the carbohydrate source, a liquid diluent and a catalyst system are introduced as reactants into a reaction zone;
wherein the catalyst system comprises a tungsten compound and ruthenium as hydrogenolysis metal and further at least one promoter metal, selected from transition and post-transition metals;
wherein the carbohydrate source is reacted with hydrogen in the presence of the catalyst system to yield a product mixture comprising ethylene glycol and butylene glycol. Butylene glycol may selectively be removed from the product mixture by azeotropic distillation using an entraining agent.

First claim

The invention claimed is:

1. Process for preparing ethylene glycol from a carbohydrate source,
wherein hydrogen, the carbohydrate source, a liquid diluent and a catalyst system are introduced as reactants into a reaction zone;
wherein the catalyst system comprises a tungsten compound and ruthenium as hydrogenolysis metal and further at least one promoter metal selected from Cu, Fe, Ni, Co, Pt, Pd, Rh, and Ir;
wherein the carbohydrate source is reacted with hydrogen in the presence of the catalyst system to yield a product mixture comprising ethylene glycol and butylene glycol; and wherein butylene glycol is selectively removed from the product mixture by azeotropic distillation using an entraining agent, wherein the entraining agent is selected from the group consisting of glycerol, erythritol, sorbitol, methyl ethyl ketoxime and combinations thereof.

2. Process according to claim 1 , wherein the carbohydrate source is selected from the group consisting of polysaccharides, oligosaccharides, disaccharides, and monosaccharides.

3. Process according to claim 1 , wherein the catalyst system comprises a tungsten compound that has an oxidation state of at least +2.

4. Process according to claim 1 , wherein the catalyst system comprises a tungsten compound selected from the group consisting of tungstic acid (H 2 WO 4 ), ammonium tungstate, ammonium metatungstate, ammonium paratungstate, tungstate compounds comprising at least one Group 1 or 2 element, metatungstate compounds comprising at least one Group 1 or 2 element, paratungstate compounds comprising at least one Group 1 or 2 element, tungsten oxide (WO 3 ), heteropoly compounds of tungsten, and combinations thereof.

5. Process according to claim 4 , wherein the catalyst system comprises tungstic acid.

6. Process according to claim 1 , wherein ruthenium and the at least one promoter metal are present in the form of a catalyst supported on a carrier.

7. Process according to claim 6 , wherein the carrier is selected from the group supports, consisting of activated carbon, silica, alumina, silica-alumina, zirconia, titania, niobia, iron oxide, tin oxide, zinc oxide, silica-zirconia, zeolitic aluminosilicates, titanosilicates, magnesia, silicon carbide, clays and combinations thereof.

8. Process according to claim 1 , wherein the molar ratio of tungsten to ruthenium is in the range of 1 to 25.

9. Process according to claim 1 , wherein the concentration of the tungsten compound is in the range of 1 to 35% by wt, calculated as tungsten and based on the weight of the carbohydrate source.

10. Process according to claim 1 , wherein the amount of ruthenium as hydrogenolysis metal and the promoter metal or metals ranges from 0.2 to 1.0% by wt, calculated as the metals and based on the amount of carbohydrate source introduced into the reaction zone.

11. Process according to claim 1 , wherein the carbohydrate source comprises a combination of at least one pentose-containing carbohydrate and at least one hexose-containing carbohydrate.

12. Process according to claim 1 , wherein the diluent is a mixture of alkylene glycol and water, wherein the amount of alkylene glycol ranges from 2 to 25% by volume, based on the volume of water and alkylene glycol.

13. Process according to claim 12 , wherein the diluent further comprises one or more compounds selected from the group consisting of sulfoxides, alcohols other than alkylene glycols, amides and mixtures thereof.

14. Process according to claim 1 , wherein the temperature in the reaction zone ranges from 120 to 300° C.

15. Process according to claim 1 , wherein a hydrogen partial pressure in the reaction zone is in the range of 1 to 16 MPa.

16. Process according to claim 1 , wherein the average residence time of the catalyst system in the reaction zone is in the range of 5 min. to 6 hrs.

17. Process according to claim 1 , wherein the amount of promoter metal or metals is at most equal to 50% by weight, based on the weight of ruthenium.

18. Process according to claim 1 , wherein the weight ratio of ruthenium to promoter metal or metals is in the range of 2:1 to 100:1.

19. Process according to claim 1 , wherein the catalyst system comprises a tungsten compound and ruthenium as hydrogenolysis metal and further at least one promoter metal selected from Rh, Pt, Pd, and Ir.

Assignees

• Avantium Knowledge Centre Bv

Inventors

• Van Der Waal Jan Cornelis
• Gruter Gerardus Johannes Maria
• Ras Erik-Jan

Classifications

• C07C29/60

  by elimination of -OH groups, e.g. by dehydration (C07C29/34 takes precedence) · CPC title

• C07C29/132 Primary

  by reduction of an oxygen containing functional group · CPC title

• B01J23/626

  with tin · CPC title

• B01J23/462

  Ruthenium · CPC title

• C07C29/82

  by azeotropic distillation · CPC title