Production of alpha-hydroxy carboxylic acids and esters from higher sugars using tandem catalyst systems
The present disclosure is directed to methods and composition used in the preparation of alpha-hydroxy carboxylic acids and esters from higher sugars using a tandem catalyst system comprising retro-aldol catalysts and Lewis acid catalysts. In some embodiments, these alpha-hydroxy carboxylic acids may be prepared from pentoses and hexoses. The retro-aldol and Lewis catalysts may be characterized by their respective ability to catalyze a 1,2-carbon shift reaction and a 1,2-hydride shift reaction on an aldose or ketose substrate.
1. A method comprising contacting a carbohydrate feedstock with a tandem catalyst system at a temperature in a range of from 60° C. to 200° C., the contacting resulting in the formation of an α-hydroxy carboxylic acid or α-hydroxy carboxylic acid ester, wherein the carbohydrate feedstock comprises a monosaccharide; and
wherein the tandem catalyst system comprises two materially different discrete catalysts, the catalysts being:
(a) a first retro-aldol catalyst, wherein the first retro-aldol catalyst comprises
(i) an optionally substituted oxo(hydroxy)molybdate, an optionally substituted sulfomolybdate, an optionally substituted oxy(hydroxy)tungstate;
(ii) a Ni(II) diamine complex;
(iii) an alkali-exchanged hafno-, stanno-, titano-, or zirconosilicate, an optionally substituted amorphous hafnium-, tin-, titanium-, or zirconium-silicate co-precipitate; or
(iv) a combination thereof; and
(b) a second Lewis acid catalyst, wherein the Lewis acid catalyst comprises a crystalline microporous hafno-, stanno-, titano-, or zirconosilicate containing pores equal to or greater than 10-MR.
2. The method of claim 1 , wherein the carbohydrate feedstock comprises a pentose or hexose monosaccharide, and the contacting results in the conversion of the pentose or hexose monosaccharide to the corresponding α-hydroxy carboxylic acid or α-hydroxy carboxylic acid ester.
3. The method of claim 1 , wherein carbohydrate feedstock comprises an aldose or ketose monosaccharide, and the contacting results in the conversion of the aldose or ketose monosaccharide to the corresponding α-hydroxy carboxylic acid or α-hydroxy carboxylic acid ester.
4. The method of claim 1 , wherein carbohydrate feedstock comprises glucose, mannose, fructose, psicose, sorbose, tagatose, or a combination thereof, and the contacting results in the conversion of the glucose, mannose, fructose, psicose, sorbose, tagatose, or a combination thereof, to the corresponding α-hydroxy carboxylic acid or α-hydroxy carboxylic acid ester.
5. The method of claim 1 , wherein the first retro-aldol catalyst is capable of converting a pentose or hexose monosaccharide to a diose, triose, or tetrose intermediate.
6. The method of claim 1 , wherein the first retro-aldol catalyst is derived from an oxomolybdate or sulfomolybdate precursor of MoO 3 , MoO 2 , MoS 2 , MoS 3 , Mo 2 S 5 , MoO(OH) 2 , MoO 4 2− , Mo 5 O 14 , Mo 2 O 7 2− , Mo 17 O 47 , H 3 PMo 12 O 40 , [Mo 7 O 24 ] 6− , or a combination thereof.
7. The method of claim 1 , wherein the first retro-aldol catalyst comprises an ethylenediamine complex of Ni(II).
8. The method of claim 1 , wherein the second Lewis acid catalyst is capable of converting a diose, triose, or tetrose intermediate to an α-hydroxy carboxylic acid or α-hydroxy carboxylic acid ester.
9. The method of claim 1 , wherein the second Lewis acid catalyst comprises a tin-substituted silicate of beta or MFI topology.
10. The method of claim 1 , where in the tandem catalyst system comprises a composite catalyst, comprising both the first retro-aldol catalyst and the second Lewis acid catalyst.
11. The method of claim 1 , wherein the tandem catalyst system comprises polar aprotic solvent.
12. The method of claim 1 , wherein the tandem catalyst system comprises an aqueous solvent.
13. The method of claim 1 , wherein the tandem catalyst system comprises a solvent comprising at least one C 1-6 alcohol.
14. The method of claim 13 , wherein the alcoholic solvent is substantially anhydrous.
15. The method of claim 1 , wherein
(a) the carbohydrate feedstock comprises a C5 or C6 aldose or ketose monosaccharide;
(b) the first retro-aldol catalyst comprises an oxo(hydroxy)molybdate; and
(c) the second Lewis acid catalyst comprises a Sn-beta or Sn-MFI zeolite; and
(d) the tandem catalyst system further comprises an alcoholic solvent;
wherein the contacting is done at a temperature in a range of from 60° C. to 140° C., so as to produce an α-hydroxy carboxylic acid or α-hydroxy carboxylic acid ester.