Process for preparing ethylene glycol from a carbohydrate source

• US 10,233,138 B2
• Filed: 01/13/2016
• Issued: 03/19/2019
• 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, Claassens-Dekker, Paula
• Primary Examiner(s): Bakshi, Pancham
• Assistant Examiner(s): Luderer, Mark R
• Application Number:
  US15/543,116
• Publication Number:
  US 20170362146A1
• Time in Patent Office: 1,161 Days
• CPC Class Codes: B01J 23/6527 Tungsten
• 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 provided as reactants into a reaction zone;
  • wherein the catalyst system comprises a tungsten compound and at least one hydrogenolysis metal selected from the noble metals Pd, Pt, Ru, Rh, Ir and combinations thereof;
  • wherein the carbohydrate source is introduced into the reaction zone such that in the reaction zone the concentration of the carbohydrate source in the diluent is at least 4% wt, calculated as weight of carbohydrate source per weight of diluent;
  • wherein the amount of the at least one hydrogenolysis metal selected from the noble metals Pd, Pt, Ru, Rh, Ir and combinations thereof ranges from 0.2 to 1.0% wt, calculated as the metal and based on the amount of carbohydrate source introduced into the reaction zone;
  • wherein the molar ratio of tungsten to the at least one hydrogenolysis metal is in the range of 1 to 25; 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 provided as reactants into a reaction zone;

wherein the catalyst system comprises a tungsten compound and at least one hydrogenolysis metal selected from the noble metals Pd, Pt, Ru, Rh, Ir and combinations thereof;

wherein the carbohydrate source is introduced into the reaction zone such that in the reaction zone the concentration of the carbohydrate source in the diluent is at least 4% by wt, calculated as weight of carbohydrate source per weight of diluent;

wherein the amount of the at least one hydrogenolysis metal selected from the noble metals Pd, Pt, Ru, Rh, Ir and combinations thereof 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;

wherein the molar ratio of tungsten to the at least one hydrogenolysis metal is in the range of 1 to 25; 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 carbohydrate source is selected from the group consisting of polysaccharides, oligosaccharides, disaccharides, and monosaccharides.

3. Process according to claim 1, wherein the carbohydrate source comprises carbohydrate selected from the group consisting of cellulose, hemicellulose, hemicelluloses sugars, starch, sugars, such as sucrose, mannose, arabinose, glucose and mixtures thereof.

4. Process according to claim 1, wherein the carbohydrate source is derived from wood waste, paper waste, agricultural waste, municipal waste, paper, cardboard, sugar cane, sugar beet, wheat, rye, barley, other agricultural crops and combinations thereof.

5. Process according to claim 1, wherein the catalyst system comprises a tungsten compound 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 catalyst system comprises a mixture of two or more metals of the group consisting of Ru, Pt, Pd, Ir and Rh.

9. Process according to claim 1, wherein the at least one hydrogenolysis metal from the noble metals Pd, Pt, Ru, Rh, Ir and combinations thereof 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, based on the weight of the carbohydrate source.

14. 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.

15. Process according to claim 1, wherein the concentration of the carbohydrate source in the diluent is in the range of 7 to 25% by wt, calculated as weight of carbohydrate source per weight of diluent.

16. Process according to claim 1, wherein the diluent is selected from the group consisting of water, sulfoxides, alcohols, amides and mixtures thereof.

17. Process according to claim 16, wherein the diluent is selected from water and one or more of the organic diluents sulfoxides, alcohols and am ides.

18. Process according to claim 17, wherein the diluent is an alcohol.

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 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.