Process for preparing ethylene glycol from a carbohydrate

• US 10,131,600 B2
• Filed: 01/13/2016
• Issued: 11/20/2018
• Est. Priority Date: 01/13/2015
• Status: Active Grant

• Current Assignee: Avantium Knowledge Centre B.V. (Avantium NV)
• Original Assignee: Avantium Knowledge Centre B.V. (Avantium NV)
• Inventors: Van Der Waal, Jan Cornelis, Gruter, Gerardus Johannes Maria
• Primary Examiner(s): Witherspoon, Sikarl A
• Application Number:
  US15/543,064
• Publication Number:
  US 20180002258A1
• Time in Patent Office: 1,042 Days
• Field of Search: 568863
• CPC Class Codes: B01J 21/18 Carbon
• CPC Class Codes: B01J 23/30 Tungsten
• CPC Class Codes: B01J 23/462 Ruthenium
• CPC Class Codes: B01J 35/19 Catalysts containing parts with different compositions
• CPC Class Codes: C07C 29/132 by reduction of an oxygen containing functional group
• CPC Class Codes: C07C 29/74 Separation; Purification; Use of additives, e.g. for stabilisation
• CPC Class Codes: C07C 31/202 Ethylene glycol
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

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 at least one hydrogenolysis metal selected from the groups 8, 9 or 10 of the Periodic Table of the Elements;
  • wherein the diluent that is introduced into the reaction zone comprises an alkylene glycol; and
  • wherein the carbohydrate source is reacted with hydrogen in the presence of the catalyst system to yield an ethylene glycol-containing product.

Claims

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 at least one hydrogenolysis metal selected from the groups 8, 9 or 10 of the Periodic Table of the Elements;

wherein the diluent that is introduced into the reaction zone comprises an alkylene glycol; and

wherein the carbohydrate source is reacted with hydrogen in the presence of the catalyst system to yield an ethylene glycol-containing product.

2. Process according to claim 1, wherein the diluent comprises ethylene glycol.

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

4. Process according to claim 1, wherein the carbohydrate source is selected from the group consisting of cellulose, starch, hemicellulose, hemicellulose sugars, glucose and combinations thereof.

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

6. Process according to claim 1, wherein the catalyst system comprises a tungsten compound selected from the group consisting of tungstic acid (H₂WO₄), 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 (WO₃), heteropoly compounds of tungsten, and combinations thereof.

7. Process according to claim 6, wherein the catalyst system comprises tungstic acid.

8. Process according to claim 1, wherein the hydrogenolysis metal from groups 8, 9 or 10 of the Periodic Table of the Elements is selected from the group consisting of Cu, Fe, Ni, Co, Pd, Pt, Ru, Rh, Ir, Os and combinations thereof.

9. Process according to claim 1, wherein the at least one hydrogenolysis metal from the groups 8, 9 or 10 of the Periodic Table of the Elements is present in the form of a catalyst supported on a carrier.

10. Process according to claim 9, 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.

11. Process according to claim 8, wherein the catalyst system comprises ruthenium on activated carbon.

12. Process according to claim 1, wherein the molar ratio of tungsten to the at least one hydrogenolysis metal is in the range of 1 to 25.

13. 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.

14. Process according to claim 1, wherein the amount of the at least one hydrogenolysis metal selected from the groups 8, 9 or 10 of the Periodic Table of the Elements ranges from 0.2 to 1.0% by wt, calculated as the metal and based on the amount of carbohydrate source introduced into the reaction zone.

15. 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.

16. 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 vol, based on the volume of water and alkylene glycol.

17. Process according to claim 16, 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.

18. Process according to claim 17, wherein the diluent is glycerol, xylytol, sorbitol or erythritol.

19. Process according to claim 1, wherein the ethylene glycol-containing product is purified.

20. Process according to claim 19, wherein the ethylene-glycol-containing product is purified by using one or more entraining agents.

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

C.

22. Process according to claim 1, wherein a hydrogen partial pressure in the reaction zone is in the range of 1 to 6 MPa.

23. 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.

24. Process according to claim 1, wherein a diluent already containing an alkylene glycol is introduced in the reaction zone before a reaction of the carbohydrate source with hydrogen in the presence of the catalyst system to yield an ethylene glycol-containing product is started in such reaction zone.

25. Continuous process comprising a first step starting the continuous process,

wherein the first step comprises a 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 at least one hydrogenolysis metal selected from the groups 8, 9 or 10 of the Periodic Table of the Elements;

wherein the diluent that is introduced into the reaction zone comprises an alkylene glycol; and

wherein the carbohydrate source is reacted in a reaction with hydrogen in the presence of the catalyst system to yield an ethylene glycol-containing product; and

wherein the reaction is started with a mixture of carbohydrate, diluent, catalyst system and hydrogen, wherein the diluent comprises an alkylene glycol.