US 11,655,200 B2
Continuous processes for the selective conversion of aldohexose-yielding carbohydrate to ethylene glycol using low concentrations of retro-aldol catalyst
David James Schreck, Lake City, MN (US); Mark Nunley, Charleston, WV (US); Donald Bunning, South Charleston, WV (US); Brooke Albin, Charleston, WV (US); Louis A. Kapicak, Cross Lanes, WV (US); and Michael Bradford, Charleston, WV (US)
Assigned to T.EN PROCESS TECHNOLOGY, INC., Houston, TX (US)
Filed on Jul. 16, 2021, as Appl. No. 17/378,340.
Application 17/378,340 is a continuation of application No. 17/031,701, filed on Sep. 24, 2020, granted, now 11,319,269.
Prior Publication US 2022/0089515 A1, Mar. 24, 2022
This patent is subject to a terminal disclaimer.
Int. Cl. C07C 29/136 (2006.01); C07C 29/74 (2006.01); B01J 23/755 (2006.01); B01J 35/00 (2006.01); B01J 23/30 (2006.01); B01J 8/18 (2006.01); B01J 19/00 (2006.01); C07C 31/20 (2006.01)
CPC C07C 29/136 (2013.01) [B01J 8/1854 (2013.01); B01J 19/0066 (2013.01); B01J 23/30 (2013.01); B01J 23/755 (2013.01); B01J 35/006 (2013.01); B01J 35/0093 (2013.01); C07C 29/74 (2013.01); B01J 2219/00033 (2013.01); C07C 31/202 (2013.01)] 27 Claims
1. A continuous, catalytic process for producing ethylene glycol from an aldose-yielding carbohydrate-containing feed, comprising:
(a) continuously or intermittently supplying the feed to a reaction zone containing a liquid medium having therein heterogeneous, nickel-containing hydrogenation catalyst, wherein the feed is supplied at a rate of at least about 50 grams per hour of carbohydrate per liter of liquid medium, and wherein said liquid medium is at catalytic conversion conditions including the presence of dissolved hydrogen, a temperature of at least about 235° C., a pH greater than 3 and a residence time sufficient to react at least 99 mass percent of the aldose-yielding carbohydrate, wherein:
(i) the heterogeneous hydrogenation catalyst has a maximum particle dimension of less than about 100 microns, and
(ii) the hydrogenation catalyst is dispersed in the liquid medium in an amount of less than about 100 grams per liter thereby providing a spatial relationship among catalytically active hydrogenation sites in the liquid medium;
(b) continuously or intermittently supplying to the reaction zone homogeneous, tungsten-containing retro-aldol catalyst the concentration of solubilized tungsten compounds, calculated as tungsten atoms, in the liquid medium in the reactor is between about 200 and 1500 milligrams per liter, wherein the relative amounts of hydrogenation catalyst and retro-aldol catalyst are sufficient to provide, under the catalytic conversion conditions, a cumulative conversion efficiency of the aldose-containing carbohydrate to ethylene glycol of at least 75 percent for a duration of 100 hours; and
(c) continuously or intermittently withdrawing from the reaction zone a raw product stream containing ethylene glycol wherein the feed comprises carbohydrate and a portion of the liquid medium from the reaction zone that has an absence of hydrogenation catalyst.