Process for preparing ethylene glycol from a carbohydrate source

Patent metadata

Field	Value
Publication number	US-2017362145-A1
Application number	US-201615543091-A
Country	US
Kind code	A1
Filing date	Jan 13, 2016
Priority date	Jan 13, 2015
Publication date	Dec 21, 2017
Grant date	—

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

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 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.

2 . Process according to claim 1 , wherein butylene glycol is selectively removed from the product mixture by azeotropic distillation using an entraining agent.

3 . Process according to claim 2 , wherein the entraining agent is selected from the group of hydrocarbon compounds, consisting of ethyl benzene, p-xylene, n-propyl benzene, o-diethyl benzene, m-diethyl benzene, m-di-isopropyl benzene, cyclopentane, methyl cyclohexane, 3-methyl pentane, 2,3-dimethyl butane, heptane, 1-heptene, octane, 1-octene, 2,3,4-trimethyl pentane, decane, decalin, dicyclo pentadiene, alpha-phellandrene, beta-pinene, myrcene, terpinolene, p-mentha-1,5-diene, 3-carene, limonene and alpha-terpinene and combinations thereof.

4 . Process according to claim 2 , wherein the entraining agent is selected from the group consisting of glycerol, erythritol, sorbitol, methyl ethyl ketoxime and combinations thereof.

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

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

7 . 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.

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

9 . Process according to claim 1 , wherein the at least one other transition metal is selected from Cu and the other hydrogenolysis metal from groups 8, 9 or 10 of the Periodic Table of the Elements.

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

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

12 . Process according to claim 11 , 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.

13 . Process according to claim 1 , wherein the molar ratio of tungsten to ruthenium is in the range of 1 to 25, preferably from 2 to 20.

14 . 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.

15 . 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.

16 . 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.

17 . 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.

18 . Process according to claim 17 , 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.

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

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

21 . 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.

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

• B01J23/8926

  Copper and noble metals · CPC title

• C07C29/132 Primary

  by reduction of an oxygen containing functional group · CPC title

• B01J37/0236

  Drying, e.g. preparing a suspension, adding a soluble salt and drying · CPC title

• B01J23/626

  with tin · CPC title