IP Library Granted Patent US 11,919,840
Granted Patent B2
US 11,919,840 · App. 17/031,009 · Granted Mar 5, 2024

Methods for operating continuous, unmodulated, multiple catalytic step processes

Inventors: Ray Chrisman (Midland, MI); Donald Bunning (South Charleston, WV); Mark Nunley (Charleston, WV); Brooke Albin (Charleston, WV); Michael Bradford (Charleston, WV); David James Schreck (Lake City, MN); Louis A. Kapicak (Cross Lanes, WV)
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 11,919,840
App. No.
17/031,009
Granted
Mar 5, 2024
Kind
B2
Abstract

Control methods are disclosed for continuous, unmodulated, multiple catalytic conversion step processes using at least two catalysts, a first catalyst and a second catalyst, that accommodate changes in the performance of each catalyst and the relative performances of the catalysts. In the methods, certain process parameters are used in a manner that is indicative of changes in catalyst performance, and the control methods provide for adjustment of at least one of: the absolute amount of catalytically active species and relative amounts of each of the first catalyst and second catalyst and at least one of the rate of feed or concentration of the raw material to the reaction zone.

Claims (43)

1. A model predictive control method for operating a continuous, unmodulated, sequential, multi-catalytic reaction process wherein each catalyst is subject to changes in performance in the course of the process, the catalytic reaction process comprising:

(i) continuously or intermittently introducing at a feed rate at least one raw material, and optionally a tracer precursor, into a reaction zone containing a medium, wherein the medium is a liquid medium, and wherein the at least one raw material includes a carbohydrate and the tracer precursor is a ketone of 3 to 10 carbons,

(ii) maintaining the reaction zone under catalytic conversion conditions suitable for a first catalytic conversion to produce a medium containing an intermediate, said conditions including temperature, pressure, residence time, concentration of the first catalyst providing catalytically active species, and, optionally, pH and adjuvants,

(iii) contacting the medium containing the intermediate with a second catalyst providing catalytically active species under conditions suitable for the other conversion to produce a chemical product, said conditions including temperature, pressure, residence time, concentration of the second catalyst, and, optionally, pH and adjuvants, wherein the chemical product is at least and the tracer precursor is a ketone of 3 to 10 carbons; and

(iv) continuously or intermittently withdrawing medium containing the chemical product from contact with the second catalyst at a rate to provide a continuous process;

wherein at least one byproduct is produced, and wherein the catalytic activity of at least one of the first catalyst and second catalyst is subject to performance change during the continuous operation,

said control method comprising:

(a) continuously or intermittently inputting predetermined process parameters from the process operation into a model predictive control apparatus having a control model;

(b) adjusting, as necessary to meet a desired process objective, manipulative inputs to the process; and, optionally

(c) adjusting the control model,

wherein:

(A) in element (a) the predetermined process parameters inputted comprise (I) the rate and concentration of feed of raw material in step (i) and the conversion efficiency of the raw material to the chemical product and (II) at least one of concentration of at least one:

by-product in the withdrawn medium,

concentration of intermediate in the withdrawn medium and

concentration of at least one tracer in the withdrawn medium

to reflect in control model data pertaining to the performances of the catalysts; and

(B) in element (b) adjusting, as necessary to meet a desired process objective, at least one of: (I) the absolute amount of catalytically active species and relative amounts of each of the first catalyst and second catalyst, and (II) at least one of the rate of feed of the raw material and its concentration to the reaction zone as manipulative inputs.

2. The method of claim 1 wherein at least one of the first catalyst and the second catalyst are homogeneous.

3. The method of claim 1 wherein the reaction zone comprises two vessels in flow sequence.

4. The method of claim 1 wherein the adjustment of the absolute amount of catalytically active species of at least one of the catalysts is by addition of an additional amount of said catalyst to the reaction zone.

5. The method of claim 1 wherein the adjustment of the absolute amount of catalytically active species of at least one of the catalysts is by modulating the effectiveness of the catalyst in the reaction zone.

6. The method of claim 1 wherein the reaction zone is a single pot reaction zone.

7. The method of claim 1 wherein the process is for converting the carbohydrate to lower glycol of at least one of ethylene glycol and propylene glycol by sequential retro-aldol catalysis of carbohydrate to produce intermediates and hydrogenation catalysis of intermediates to the lower glycol.

8. The method of claim 7 wherein a concentration of at least one of a 1,2-butane diol, propylene glycol, at least one of an itol, hydroxyacetone and tracer in the withdrawn medium are used to reflect performances of the catalysts.

9. The method of claim 8 wherein the itol is one or more of erythritol, threitol, glycerin, mannitol, and sorbitol.

10. A method for operating a continuous, unmodulated, sequential, multi-catalytic reaction process wherein each catalyst is subject to changes in performance in the course of the process, which methods adjust manipulative inputs to provide outputs within predetermined ranges, the catalytic reaction process comprising:

(i) continuously or intermittently introducing at a feed rate and concentration at least one raw material, and optionally a tracer precursor, into a reaction zone containing liquid medium, wherein the at least one raw material includes a carbohydrate and the tracer precursor is a ketone of 3 to 10 carbons,

(ii) maintaining the reaction zone under catalytic conversion conditions suitable for a first catalytic conversion to produce a liquid medium containing an intermediate, said conditions including temperature, pressure, residence time, concentration of the first catalyst providing catalytically active species, and, optionally, pH and adjuvants,

(iii) contacting the liquid medium containing the intermediate with a second catalyst providing catalytically active species under conditions suitable for the other conversion to produce the chemical product, said conditions including temperature, pressure, residence time, concentration of the second catalyst, and, optionally, pH and adjuvants, wherein the chemical product is at least and the tracer precursor is a ketone of 3 to 10 carbons, and

(iv) continuously or intermittently withdrawing liquid medium containing chemical product from contact with the second catalyst at a rate to provide a continuous process;

wherein at least one byproduct is produced, and wherein the catalytic activity of at least one of the first catalyst and second catalyst is subject to performance change during the continuous operation,

the method comprises:

(a) continuously or intermittently comparing predetermined process parameters from the process operation to predetermined windows for such operation; and

(b) adjusting, as necessary to meet a desired process objective, manipulative inputs to the process,

wherein in element (a) the predetermined process parameters inputted comprise (I) the rate and concentration of feed of raw material in step (i) and the conversion efficiency of the raw material to the chemical product and (II) at least one of concentration of at least one by-product in the withdrawn liquid medium, concentration of intermediate in the withdrawn liquid medium and, if used, concentration of at least one tracer in the withdrawn liquid medium, and wherein in element (b) adjustment is made to at least one of: (I) the absolute amount of catalytically active species and relative amounts of each of the first catalyst and second catalyst, and (II) at least one of the rate of feed and concentration of the raw material to the reaction zone as the manipulative inputs.

11. The method of claim 10 wherein at least one of the first catalyst and the second catalyst are homogeneous.

12. The method of claim 10 wherein the reaction zone comprises two vessels in flow sequence.

13. The method of claim 10 wherein the adjustment of the absolute amount of catalytically active species of at least one of the catalysts is by addition of an additional amount of said catalyst to the reaction zone.

14. The method of claim 10 wherein the adjustment of the absolute amount of catalytically active species of at least one of the catalysts is by modulating the effectiveness of the catalyst in the reaction zone.

15. The method of claim 10 wherein the reaction zone is a single pot reaction zone.

16. The method of claim 10 wherein the process is for converting the carbohydrate to lower glycol of at least one of ethylene glycol and propylene glycol by sequential retro-aldol catalysis of carbohydrate to produce intermediates and hydrogenation catalysis of intermediates to the lower glycol.

17. The method of claim 16 wherein a 1,2-butane diol, propylene glycol, at least one itol, hydroxyacetone, pH and tracer in the withdrawn medium are used to reflect performances of the catalysts.

18. The method of claim 17 wherein the itol is one or more of erythritol, threitol, glycerin, mannitol, and sorbitol.

Assignments (5)
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 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 5, 2021
From: BUNNING, DONALD; KAPICAK, LOUIS A.; SCHRECK, DAVID JAMES; BRADFORD, MICHAEL; ALBIN, BROOKE; NUNLEY, MARK; CHRISMAN, RAY
To: IOWA CORN PROMOTION BOARD
Reel/Frame 055510/0459 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 26, 2021
From: ALBIN, BROOKE; BRADFORD, MICHAEL; BUNNING, DONALD; CHRISMAN, RAY
To: IOWA CORN PROMOTION BOARD
Reel/Frame 055421/0758 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 26, 2021
From: KAPICAK, LOUIS A.; NUNLEY, MARK
To: IOWA CORN PROMOTION BOARD
Reel/Frame 055426/0584 →
Continuity (2)
Provisional Application 62905068 · Sep 24, 2019
Related Publication 20210087127A1 · Mar 25, 2021