IP Library Granted Patent US 12,077,489
Granted Patent B2
US 12,077,489 · App. 17/735,813 · Granted Sep 3, 2024

Continuous, carbohydrate to ethylene glycol processes

Inventors: Ray Chrisman (Midland, MI); Donald Bunning (South Charleston, WV); Mark Nunley (Charleston, WV); Brooke Albin (Charleston, WV); Michael Bradford (Charleston, WV); Louis Kapicak (Cross Lanes, WV); David James Schreck (Lake City, MN)
Assignee: T.EN Process Technology Inc.
C07C29/132B01J19/0033B01J19/004B01J19/245B01J23/30C07C29/172B01J2219/00033B01J2219/0004B01J2219/00243B01J2523/69C07C31/202
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Quick Facts
Patent No.
US 12,077,489
App. No.
17/735,813
Granted
Sep 3, 2024
Kind
B2
Abstract

By this invention processes are provided for the conversion of carbohydrate to ethylene glycol by retro-aldol catalysis and sequential hydrogenation using control methods having at least one of acetol (hydroxyacetone) and a tracer as inputs.

Claims (33)

1. A continuous process controlled by a control system for the catalytic conversion of a carbohydrate feed in a reaction zone by sequential retro-aldol catalytic conversion the process including:

providing the carbohydrate feed to the reaction zone under retro-aldol conditions,

providing one or more catalysts to the reaction zone to catalytically convert at least a portion of the carbohydrate feed to a lower glycol;

controlling at least one operating parameter of the process using at least the concentration of acetol in the raw product is an input to the control system for the process; and

withdrawing continuously or intermittently a raw product from the reaction zone.

2. The process of claim 1 , wherein the raw carbohydrate containing feed contains at least aldose-yielding or ketose yielding carbohydrate, and wherein the lower glycol includes at least one of ethylene glycol and/or propylene glycol.

3. The process of claim 2 wherein in response to an increase in acetol concentration, at least one of (i) the hydrogenation catalytic activity is increased and (ii) at least one of the rate of supply of the carbohydrate feed and the concentration of carbohydrate in the feed is decreased.

4. The process of claim 2 , wherein providing one or more catalysts to the reaction zone further includes:

providing a retro-aldol catalyst a liquid medium in the reaction zone under retro-aldol conditions to convert at least a portion of the carbohydrate feed to intermediates in the reaction zone; and

providing a hydrogenation catalyst to the liquid medium under hydrogenation conditions to convert at least a portion of the intermediates to the lower glycol in the reaction zone, wherein the retro-aldol catalyst is homogeneous and the hydrogenation catalyst is heterogeneous.

5. The process of claim 2 wherein the concentration of acetol is compared with concentrations of at least one of itol, 1,2-butanediol, and pH in the raw product for purposes of process control.

6. The process of claim 5 wherein in response to an increase in acetol concentration and an increase in the concentration of at least one of sorbitol, 1,2-butanediol, and glycerol in the raw product, the retro-aldol catalytic activity is increased.

7. The process of claim 2 wherein the hydroxyacetone concentration is maintained less than about 0.15 mass percent of the raw product.

8. The process of claim 2 wherein in response to an increase in acetol accompanied by an increase in at least one of mannitol and glycerol, at least one of the rate of supply of the carbohydrate feed and the concentration of the carbohydrate in the feed, is decreased until retro-aldol catalytic activity is increased.

9. The process of claim 1 wherein the reaction zone is a cascade reaction zone.

10. A continuous process controlled by a control system for the catalytic conversion of a carbohydrate feed in a reaction zone by sequential retro-aldol catalytic conversion the process including:

providing the carbohydrate feed to the reaction zone under retro-aldol conditions,

providing one or more catalysts to the reaction zone to catalytically convert at least a portion of the carbohydrate feed to a lower glycol;

supplying a tracer precursor comprising a ketone of 3 to 6 carbons to the reaction zone from which at least one tracer is produced under conditions in the reaction zone;

controlling at least one operating parameter of the process using at least one component of the tracer in the raw product is an input to the control system for the process; and

withdrawing continuously or intermittently a raw product from the reaction zone.

11. The process of claim 10 wherein where the tracer in the raw product indicates a change in the portion of the tracer precursor hydrogenated, then at least one of (i) the absolute amounts of catalytically active species and relative amounts of each of the retro-aldol catalytic activity and hydrogenation catalytic activity, and (ii) at least one of the rate of feed and concentration of carbohydrate in the feed to the reaction zone are adjusted.

12. The process of claim 11 where the concentration of a tracer in the raw product indicates that a greater portion of the tracer precursor is hydrogenated, either or both the rate of feed to the reaction zone is increased or the hydrogenation catalyst activity in the reaction zone is decreased.

13. The process of claim 11 where the concentration of a tracer in the raw product indicates that a lesser portion of the tracer precursor is hydrogenated, either or both of (i) the hydrogenation catalyst activity in the reaction zone is increased and (ii) at least one of the rate of feed and the concentration of carbohydrate in the feed to the reaction zone is decreased.

14. The process of claim 10 , wherein providing one or more catalysts to the reaction zone further includes:

providing a retro-aldol catalyst a liquid medium in the reaction zone under retro-aldol conditions to convert at least a portion of the carbohydrate feed to intermediates in the reaction zone; and

providing a hydrogenation catalyst to the liquid medium under hydrogenation conditions to convert at least a portion of the intermediates to the lower glycol in the reaction zone, wherein the retro-aldol catalyst is homogeneous and the hydrogenation catalyst is heterogeneous.

15. The process of claim 10 , wherein the raw carbohydrate containing feed contains at least aldose-yielding or ketose yielding carbohydrate, and wherein the lower glycol includes at least one of ethylene glycol and/or propylene glycol, wherein the carbohydrate comprises aldose and the lower glycol comprises ethylene glycol, concentrations of at least one component of the tracer is compared with concentrations of at least one of itol, 1,2-butanediol, acetol and pH in the raw product for purposes of process control.

16. The process of claim 15 where the tracer in the raw product indicates a substantially constant in the portion of the tracer precursor being hydrogenated and an increase in the concentration of at least one of sorbitol and glycerol in the raw product, the retro-aldol catalytic activity is increased.

17. The process of claim 15 where the tracer in the raw product indicates a decrease in the portion of the tracer precursor being hydrogenated and no increase in the concentration of at least one of sorbitol, 1,2-butanediol, and glycerol in the raw product, one or both of (i) the hydrogenation catalytic activity is increased and (ii) at least one of the feed rate and the concentration of the carbohydrate in the feed is decreased.

18. The process of claim 10 wherein the process uses hydrogenation catalyst withdrawn from or intended to be used in a larger reaction zone for evaluating hydrogenation catalytic activity.

19. The process of claim 10 wherein the tracer precursor is added to trouble shoot the process.

20. The process of claim 10 wherein the tracer precursor comprises methylethylketone and the tracers comprise methylethylketone and iso-butanol.

Assignments (4)
CHANGE OF ADDRESS Recorded Feb 12, 2026
From: T.EN PROCESS TECHNOLOGY, INC.
To: T.EN PROCESS TECHNOLOGY, INC.
Reel/Frame 074818/0743 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 12, 2026
From: T.EN PROCESS TECHNOLOGY, INC.
To: TECHNIP ENERGIES FRANCE
Reel/Frame 073768/0584 →
CORRECTIVE ASSIGNMENT TO CORRECT THE RECEVING PARTY NAME PREVIOUSLY RECORDED AT REEL: 061121 FRAME: 0088. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Sep 21, 2022
From: IOWA CORN PROMOTION BOARD
To: T.EN PROCESS TECHNOLOGY, INC.
Reel/Frame 061497/0258 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 16, 2022
From: IOWA CORN PROMOTION BOARD
To: T.EN STONE & WEBSTER PROCESS TECHNOLOGY, INC.
Reel/Frame 061121/0088 →
Continuity (3)
Continuation 17031280 · Sep 24, 2020
Provisional Application 62905068 · Sep 24, 2019
Related Publication 20230091978A1 · Mar 23, 2023