Method to convert biomass to 5-(hydroxymethyl)-furfural (HMF) and furfural using lactones, furans, and pyrans as solvents
Described is a process to produce hydroxymethyl furfural (HMF) from biomass-derived sugars. The process includes the steps of reacting a C5 and/or C6 sugar-containing reactant derived from biomass in a monophasic or biphasic reaction solution comprising water and a co-solvent. The co-solvent can be beta-, gamma-, and/or delta-lactones derived from biomass, tetrahydrofuran (THF) derived from biomass, and/or methyltetrahydrofuran (MTHF) derived from biomass. The reaction takes place in the presence of an acid catalyst and a dehydration catalyst for a time and under conditions such that at least a portion of glucose or fructose present in the reactant is converted to HMF.
1. A process to produce 5-hydroxymethylfurfural (HMF), the process comprising:
reacting a C6 sugar-containing reactant in a monophasic reaction solution comprising (i) an organic solvent selected from the group consisting of beta-, gamma-, and delta-lactones, hydrofurans, hydropyrans, and combinations thereof, and (ii) at least about 1 wt % water; in the presence of a heterogenous acid catalyst for a time and under conditions wherein at least a portion of the C6 sugar present in the reactant is converted to HMF.
2. The method of claim 1 , wherein the organic solvent is miscible with water.
3. The method of claim 1 , wherein the organic solvent can dissolve from 2 wt % to 25 wt % water.
4. The method of claim 1 , wherein the organic solvent is a combination of two or more solvents, wherein at least one of the solvents is miscible with water and at least one of the other solvents is not miscible with water.
5. The method claim 1 , further comprising subjecting the HMF to a hydrogenolysis reaction in the presence of a suitable catalyst, for a time and under conditions wherein at least a portion of the HMF is converted to dimethylfuran.
6. The method claim 1 , further comprising oxygenating the HMF in the presence of an oxygenation catalyst, for a time and under conditions wherein at least a portion of the HMF is converted to furandicarboxylic acid.
7. The method of claim 1 , wherein the heterogeneous acid catalyst is a solid acid catalyst selected from the group consisting of solid Brønsted acid catalysts, solid Lewis acid catalysts, and combinations thereof.
8. The method of claim 7 , wherein the solid acid catalyst is a heteropolyacid.
9. The method of claim 7 , wherein the solid acid catalyst is a mesoporous silica.
10. The method of claim 7 , wherein the solid acid catalyst is a zeolite.
11. The method of claim 7 , wherein the solid acid catalyst is an acidic material on a thermo-stable support.
12. The method of claim 11 , wherein the thermostable support is selected from the group consisting of tin oxide, alumina, niobia, zirconia, titania, and carbon.
13. The method of claim 7 , wherein the solid acid catalyst is a solid acidic metal oxide.
14. The method of claim 7 , wherein the solid acid catalyst is a solid acidic ion exchanger.
15. The method of claim 14 , wherein the acidic ion exchanger comprises cross-linked polystyrene-containing sulfonic acid groups.
16. The method of claim 14 , wherein the acidic ion exchanger comprises sulfonated tetrafluoroethylene-based fluoropolymer-copolymers.
17. The method claim 7 , further comprising subjecting the HMF to a hydrogenolysis reaction in the presence of a suitable catalyst for a time and under conditions wherein at least a portion of the HMF is converted to dimethylfuran.
18. The method claim 7 , further comprising oxygenating the HMF in the presence of an oxygenation catalyst, for a time and under conditions wherein at least a portion of the HMF is converted to furandicarboxylic acid.
19. The method of claim 1 , wherein the monophasic reaction solution comprises from about 5 wt % to about 20 wt % water.
20. The method of claim 1 , wherein the monophasic reaction solution comprises from about 5 wt % to about 12 wt % water.
21. The method of claim 1 , further comprising, after reacting the C6 sugar-containing reactant to yield HMF, adding a sufficient quantity of a mixture of water and hydrocarbon to the monophasic reaction solution to create a biphasic system having an organic phase and an aqueous phase, wherein at least a portion of the HMF is extracted into the resulting aqueous phase.
22. The method claim 21 , further comprising subjecting the HMF to a hydrogenolysis reaction in the presence of a suitable catalyst for a time and under conditions wherein at least a portion of the HMF is converted to dimethylfuran.
23. The method claim 21 , further comprising oxygenating the HMF in the presence of an oxygenation catalyst, for a time and under conditions wherein at least a portion of the HMF is converted to furandicarboxylic acid.
24. A process to produce 5-hydroxymethylfurfural (HMF), the process comprising:
reacting a C6 sugar-containing reactant in a biphasic reaction solution comprising (i) an aqueous phase, and (ii) an organic phase comprising a water-immiscible solvent selected from the group consisting of beta-, gamma-, and delta-lactones, hydrofurans, hydropyrans, and combinations thereof; in the presence of an acid catalyst for a time and under conditions wherein at least a portion of the C6 sugar present in the reactant is converted to HMF.
25. The method of claim 24 , wherein the aqueous phase comprises a saturating amount of a salt.
26. The method of claim 24 , wherein the acid catalyst is selected from the group consisting of Brønsted acid catalysts, Lewis acid catalysts, and combinations thereof.
27. The method of claim 24 , wherein the organic solvent has from five (5) carbon atoms to sixteen (16) carbon atoms.
28. The method of claim 24 , wherein the organic solvent has from five (5) carbon atoms to eleven (11) carbon atoms.
29. The method claim 24 , further comprising subjecting the HMF to a hydrogenolysis reaction in the presence of a suitable catalyst for a time and under conditions wherein at least a portion of the HMF is converted to dimethylfuran.
30. The method claim 24 , further comprising oxygenating the HMF in the presence of an oxygenation catalyst, for a time and under conditions wherein at least a portion of the HMF is converted to furandicarboxylic acid.