PROCESS WITH INTEGRATED RECYCLE FOR MAKING ETHYLENE GLYCOL AND/OR PROPYLENE GLYCOL FROM ALDOSE- AND/OR KETOSE- YIELDING CARBOHYDRATES
Processes are disclosed for the catalytic conversion of carbohydrate feed to one or both of ethylene glycol and propylene glycol. In the disclosed processes, a portion of the aqueous medium in the reaction zone of the catalytic process is withdrawn and recycled and the recycle is integrated to enhance the overall process.
1 . A catalytic process for producing a lower glycol of at least one of ethylene glycol and propylene glycol from a carbohydrate-containing feed comprising at least one of aldose- and ketose-yielding carbohydrate, said process comprising continuously or intermittently supplying the feed to a reaction zone containing an aqueous medium having therein one or more catalysts for converting said carbohydrate to said glycol, wherein at least one of the catalysts is dissolved or suspended in the aqueous medium, said aqueous medium being at catalytic conversion conditions including the presence of dissolved hydrogen, to produce a reaction product containing said lower glycol, wherein
(i) continuously or intermittently at least a portion of the aqueous medium containing said dissolved or suspended catalyst is withdrawn from the reaction zone;
(ii) at least a portion of the withdrawn aqueous medium is subjected to one or more unit operations to remove a portion of the lower glycol in a separated fraction and provide a retained liquid phase containing at least about 10 mass percent of the lower glycol that was contained in the aqueous medium as withdrawn from the reaction zone and said dissolved or suspended catalyst; and
(iii) at least a portion of the liquid phase containing the dissolved or suspended catalyst from the one or more unit operations is passed to the reaction zone.
2 . The process of claim 1 wherein the reaction product contains organic acid, and at least about 25 mass percent of the organic acid is, in the one or more unit operations to remove a portion of the lower glycol, separated to a separated fraction.
3 . The process of claim 1 wherein the one or more unit operations is a vapor/liquid separator and wherein water is added to the liquid phase from the vapor/liquid separator to provide a liquid phase comprising at least about 25 mass percent water.
4 . The process of claim 1 wherein the mass ratio of lower glycol to water in the retained liquid phase is at least about 20:1.
5 . The process of claim 1 wherein the catalyst for the catalytic process comprises a homogeneous retro-aldol catalyst and a heterogeneous hydrogenation catalyst, and the retained liquid phase contains the retro-aldol catalyst and at least a portion of the retro-aldol catalyst is passed with the liquid phase to the reaction zone.
6 . The process of claim 1 wherein at least a portion of the retained liquid phase is continuously or intermittently removed as a liquid phase purge.
7 . The process of claim 1 wherein the one or more unit operations to remove lower glycol from the withdrawn aqueous medium is a vapor/liquid separation.
8 . A catalytic process for producing a lower glycol of at least one of ethylene glycol and propylene glycol from a carbohydrate-containing feed comprising at least one of aldose- and ketose-yielding carbohydrate, said process comprising continuously or intermittently supplying the feed to a reaction zone containing an aqueous medium having therein one or more catalysts for converting said carbohydrate to said glycol, said aqueous medium being at catalytic conversion conditions including the presence of dissolved hydrogen, to produce a reaction product containing said lower glycol and organic acid, wherein
(i) continuously or intermittently at least a portion of the aqueous medium is withdrawn from the reaction zone;
(ii) at least a portion of the withdrawn aqueous medium is subjected to at least one unit operation sufficient to remove at least about 25 mass percent of the organic acid contained in the withdrawn aqueous medium and provide a retained liquid phase; and
(iii) at least a portion of the liquid phase is passed to the reaction zone.
9 . The process of claim 8 wherein the one unit operation comprises a vapor/liquid separation providing a vapor phase that removes a portion of the lower glycol to the vapor phase and at least about 35 mass percent of the organic acid is separated to the vapor phase.
10 . A catalytic process for producing a lower glycol of at least one of ethylene glycol and propylene glycol from a carbohydrate-containing feed comprising at least one of aldose- and ketose-yielding carbohydrate, said process comprising continuously or intermittently supplying the feed to a reaction zone containing an aqueous medium having therein one or more catalysts for converting said carbohydrate to said glycol, said aqueous medium being at catalytic conversion conditions including the presence of dissolved hydrogen, to produce a reaction product containing said lower glycol and wherein solids are generated, wherein
(i) continuously or intermittently at least a portion of the aqueous medium is withdrawn from the reaction zone;
(ii) at least a portion of the withdrawn aqueous medium is subjected to one or more separation unit operations, preferably comprising a vapor/liquid separation, to remove at least a portion of the lower glycol and provide a remaining liquid phase;
(iii) a portion of the remaining liquid phase is passed to the reaction zone, and
(iv) continuously or intermittently a portion of the liquid phase is purged to maintain the mass of solids per unit volume of the aqueous medium substantially constant.
11 . The process of claim 10 wherein the purge is subjected to one or more unit operations to recover catalytic metals from the purge.
12 . The process of claim 11 wherein catalytic metals are components of the heterogeneous catalyst
13 . The process of claim 11 wherein retro-aldol catalyst is used and retro-aldol catalyst is recovered from the purge.
14 . The process of claim 11 wherein the catalytic metals are metal-containing ions and are recovered by ion exchange or through chemical treatment by at least one of:
(i) introducing counter ions to precipitate and
(ii) causing an oxidation or reduction of the metal-containing ions into solid form.
15 . A catalytic process for producing a lower glycol of at least one of ethylene glycol and propylene glycol from a carbohydrate-containing feed comprising at least one of aldose- and ketose-yielding carbohydrate, said process comprising continuously or intermittently supplying the feed to a reaction zone containing an aqueous medium having therein catalyst for converting said carbohydrate to said glycol, said aqueous medium being at catalytic conversion conditions including the presence of dissolved hydrogen, to produce a reaction product containing said glycol, wherein
(i) continuously or intermittently at least a portion of the aqueous medium is withdrawn from the reaction zone, and
(ii) at least a portion of the withdrawn aqueous medium from the reaction zone is recycled to the reaction zone,
wherein in step (ii) the aqueous medium recycling to the reaction zone is subjected to at least one unit operation to enhance the catalytic process in the reaction zone.
16 . The process of claim 15 wherein the aqueous medium withdrawn from the reaction zone comprises catalytic metals and the at least one unit operation to enhance the catalytic process comprises subjecting the aqueous medium to a unit operation that selectively reduces concentration of catalytic metals.
17 . The process of claim 16 wherein the unit operation is a density separation.
18 . The process of claim 16 wherein the catalyst for converting the carbohydrate to glycol comprises retro-aldol catalyst and the retro-aldol catalyst comprises a soluble tungsten-containing catalyst that is, or is converted during the process to, a tungsten-containing anion that can be converted to tungstic acid at low pH, the pH of the aqueous medium is sufficiently reduced that tungstic acid is precipitated and then removed by a solids separation unit operation.
19 . The process of claim 18 wherein the precipitated tungstic acid is reacted with base to form a soluble tungstate anion.
20 . The process of claim 16 wherein a soluble tungsten-containing catalyst is used in the catalytic conversion, reduced tungsten-containing species form in the reaction zone, and the aqueous medium being recycled to the reaction zone is subjected to an oxidation unit operation to convert solid tungsten-containing species to soluble tungstate species.
21 . The process of claim 20 wherein one or more of oxygen, ozone, peroxides, and soluble peracid and peroxyanion compounds are passed to the oxidation unit operation.
22 . The process of claim 16 wherein organic acid is contained in the aqueous medium and at least a portion of the withdrawn aqueous medium is subjected to carboxylic acid hydrogenation conditions including the presence of a carboxylic acid hydrogenation catalyst and hydrogen at elevated temperature and pressure.
23 . The process of claim 16 wherein at least one unit operation to enhance the catalytic process in the reaction zone comprises increasing the hydrogen partial pressure of the aqueous medium.
24 . A catalytic process for producing a lower glycol of at least one of ethylene glycol and propylene glycol from a carbohydrate-containing feed comprising at least one of aldose- and ketose-yielding carbohydrate, said process comprising continuously or intermittently supplying the feed to a reaction zone containing an aqueous medium having therein catalyst for converting said carbohydrate to said glycol, said catalyst comprising heterogeneous hydrogenation or hydrogenolysis catalyst, and said aqueous medium being at catalytic conversion conditions including the presence of dissolved hydrogen, to produce a reaction product containing said glycol, wherein
(i) continuously or intermittently at least a portion of the aqueous medium is withdrawn from the reaction zone, said withdrawn aqueous medium containing heterogeneous catalyst, and
(ii) recycling at least a portion of the withdrawn aqueous medium from the reaction zone to the reaction zone, said recycled aqueous medium containing heterogeneous catalyst from the reaction zone, and prior to being introduced into the reaction zone, hydrogen is admixed with the recycling aqueous medium to provide a hydrogen-laden aqueous medium.
25 . A catalytic process for producing a lower glycol of at least one of ethylene glycol and propylene glycol from a carbohydrate-containing feed comprising at least one of aldose- and ketose-yielding carbohydrate, said process comprising continuously or intermittently supplying the feed to a reaction zone containing an aqueous medium having therein a homogeneous, tungsten-containing retro-aldol catalyst and heterogeneous hydrogenation catalyst for converting said carbohydrate to said glycol, said aqueous medium being at catalytic conversion conditions including the presence of dissolved hydrogen, to produce a reaction product containing said lower glycol, wherein
(i) tungsten compound precipitates on the hydrogenation catalyst during the process;
(ii) continuously or intermittently at least a portion of the aqueous medium containing said hydrogenation catalyst is withdrawn from the reaction zone;
(iii) at least a portion of the withdrawn aqueous medium containing hydrogenation catalyst is subjected to at least one unit operation to remove a portion of the water and the lower glycol to a separated phase and provide a retained liquid phase containing at least about 10 mass percent of the lower glycol contained in the aqueous medium as withdrawn from the reaction zone and less than 10 volume percent water, and said hydrogenation catalyst wherein at least of the portion of the tungsten compound precipitated on the hydrogenation catalyst is solubilized;
(iv) maintaining the pH of the retained liquid phase from about 4 to 10 to maintain solubilized tungsten compound; and
(v) at least a portion of the retained liquid phase containing the solubilized tungsten compound is passed to the reaction zone.
26 . The process of claim 25 wherein water is added to the retained liquid phase after step (a).
27 . The process of claim 25 wherein the at least one unit operation comprises a vapor/liquid separation.