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1. (WO2012174089) CO-PRODUCTION OF BIOFUELS AND GLYCOLS
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C L A I M S

1. A method comprising:

(i) providing a bio-based feedstock stream containing carbohydrates and water;

(ii) contacting, in a first reaction system, the bio-based feedstock stream with an aqueous phase reforming catalyst at a temperature in the range of 120°C to 280°C and 0.1 to 150 bar of hydrogen to form a first intermediate stream containing plurality of oxygenated intermediates comprising at least 5 wt , based on the total oxygenates content, of glycols that comprises ethylene glycol (EG) and 1,2-propylene glycol (PG), and other monooxygenates;

(iii) contacting, in a second reaction system, at least a first portion of said first intermediate stream in the presence of a aqueous phase reforming catalyst at a temperature in the range of 160°C to 280°C to produce a second intermediate stream containing plurality of oxygenated intermediates stream and hydrogen;

(iv) providing at least a portion of said hydrogen to the first reaction system;

(v) processing at least a portion of the second intermediate stream to form a liquid fuel;

(vi) providing a second portion of said first intermediate stream to a first separation system;

(vii) separating a portion of said first intermediate stream, in the first separation system, to a monooxygenates stream comprising monooxygenates and a glycol rich stream comprising at least 10 wt , based on the total oxygenates, of glycols by flashing; and

(viii) recovering glycols from the glycol rich stream.

2. A method according to claim 1, wherein further comprising (ix) recycling at least a portion of said monooxygenates stream to the first reaction system.

3. A method according to claim 1 or claim 2, wherein glycols are recovered by separating finished glycol from the glycol rich stream.

4. A method according to any of claims 1 to 3, wherein the glycol content of the first intermediate stream produced in step (ii) is at least 25 wt , based on the total oxygenates content.

5. A method according to any of claims 1 to 4, wherein the ratio of the first intermediate stream provided to the first separation system and to the second reaction system is in the range of 1.5: 1 to 10: 1.

A method according to any of claims 1 to 5, wherein the maximum steady state temperature of the first reaction system is at least 10°C less than the maximum steady state temperature of the second reaction system;

A method according to any of claims 1 to 6, wherein no process heat from external source is added between the first and second reaction systems, or to the second reaction system, wherein the temperature increase in the second reaction system results from the exothermic heats from the first reaction system and the second reaction system.

A method according to any of claims 1 to 7, wherein the glycol rich stream in step (vii) comprises at least 25 wt%, based on the total oxygenates, of glycols.

A method according to any of claims 1 to 8, wherein a bio-based feedstock is subjected to a digestive solvent to provide bio-based feedstock stream comprising carbohydrates and water.

A method according to any of claims 1 to 9, wherein the conversion of carbohydrate or sugar alcohol in the first reaction system is limited to less than 80%, preferably limited to less than 70%, more preferably limited to less than 60%, further preferably limited to less than 50%.

A method according to any of claims 1 to 9, wherein the conversion of of carbohydrates and sugar alcohols to monooxygenated compounds across the first reaction system and the second reaction system is less than 90%;

A method according to any of claims 1 to 11, wherein the second intermediate stream from the second reaction system is flash distilled to provide a stream containing at least a portion of monooxygenate intermediates as feed for production of liquid fuels.

A method according to claim 12, wherein the bottoms from flashing containing enriched concentrations of unconverted carbohydrates, sugar alcohols, glycols, and some monooxygenates, are recycle to the first reaction system.

A method according to any of claims 1 to 13, wherein glycols are recovered by separating from the glycol rich stream glycols and remaining oxygenates stream; (vii) further contacting, in a third reaction system, at least a portion of said remaining oxygenates stream in the presence of a aqueous phase reforming catalyst at a temperature in the range of 160°C to 280°C to produce a recycle oxygenates stream and hydrogen; and (viii) providing at least a portion of said recycle

oxygenates stream and a portion of said hydrogen to the first reaction system.

A method according to any of claims 1 to 14, wherein the second intermediate stream is subjected to condensation to produce a liquid fuel.

A method according to any of claims 1 to 14, wherein the second intermediate stream is subjected to dehydration and alkylation to produce a liquid fuel

A method comprising:

(i) providing a bio-based feedstock stream containing carbohydrates and water;

(ii) contacting, in a first reaction zone, the bio-based feedstock stream with an aqueous phase reforming catalyst at a temperature in the range of 120°C to 280°C and 0.1 to 150 bar of hydrogen to produce a first intermediate stream containing plurality of oxygenated intermediates comprising at least 5 wt , based on the total oxygenates content, of glycols that comprises ethylene glycol (EG) and 1,2-propylene glycol (PG), and other monooxygenates;

(iii) contacting, in a second reaction zone, at least a first portion of said first intermediate stream in the presence of a aqueous phase reforming catalyst at a temperature in the range of 160°C to 280°C to produce a combined glycol and oxygenated intermediate stream comprising greater than 5wt glycols, based on the total oxygenates and hydrocarbons;

(iv) separating, by flashing, the combined glycol and oxygenated intermediate stream into a glycol rich stream comprising at least 10 wt , based on the total oxygenates, of glycols, and a mono-oxygenates- rich stream;

(v) processing at least a portion of the monooxygenates-rich stream to form a liquid fuel;

(vi) recovering glycols from the glycol rich stream.

A method according to claim 18, where the temperature of the second reaction zone is at least 10°C higher than the temperature of the first reaction zone.

A method according to claim 17 or claim 18, wherein at least a portion of either or both of the glycol-rich stream or mono-oxygenates rich stream is recycled to provide solvent for the first reaction zone or the recycled solvent is routed to a digestion zone to digest solid biomass to provide feed for the first reaction zone. A method according any of claims 17 to 19, wherein glycols are recovered by separating from the glycol rich stream glycols and remaining oxygenates stream; (vii) further contacting, in a third reaction system, at least a portion of said remaining oxygenates stream in the presence of a aqueous phase reforming catalyst at a temperature in the range of 160°C to 280°C to produce a recycle oxygenates stream and hydrogen; and (viii) providing at least a portion of said recycle oxygenates stream and a portion of said hydrogen to the first reaction zone.