# US 8,772,515 B2 · Method to convert biomass to 5-(hydroxymethyl)-furfural (HMF) and furfural using lactones, furans, and pyrans as solvents > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,772,515 B2 - Document ID: US8772515B2 - Status: Granted - Kind: B2 - Application number: 13/649,891 - Filed: 2012-10-11 - Published: 2014-04-17 - Granted: 2014-07-08 - Earliest claimed: 2012-10-11 - Assignees: Wisconsin Alumni Research Foundation - Applicants: Wisconsin Alumni Research Foundation - Inventors: James A. Dumesic; Jean Marcel Ribeiro Gallo; David Alonso - Web page: https://patentgrep.com/patent/US8772515B2 ## CPC - C07D 307/46: Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom - C07D 307/36: with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms - C07D 307/50: Preparation from natural products - C07D 307/68: Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) ## Abstract 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. ## Claims ### Claim 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. ### Claim 2 (depends on 1) The method of claim 1, wherein the organic solvent is miscible with water. ### Claim 3 (depends on 1) The method of claim 1, wherein the organic solvent can dissolve from 2 wt % to 25 wt % water. ### Claim 4 (depends on 1) 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. ### Claim 5 (depends on 1) 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. ### Claim 6 (depends on 1) 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. ### Claim 7 (depends on 1) 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. ### Claim 8 (depends on 7) The method of claim 7, wherein the solid acid catalyst is a heteropolyacid. ### Claim 9 (depends on 7) The method of claim 7, wherein the solid acid catalyst is a mesoporous silica. ### Claim 10 (depends on 7) The method of claim 7, wherein the solid acid catalyst is a zeolite. ### Claim 11 (depends on 7) The method of claim 7, wherein the solid acid catalyst is an acidic material on a thermo-stable support. ### Claim 12 (depends on 11) The method of claim 11, wherein the thermostable support is selected from the group consisting of tin oxide, alumina, niobia, zirconia, titania, and carbon. ### Claim 13 (depends on 7) The method of claim 7, wherein the solid acid catalyst is a solid acidic metal oxide. ### Claim 14 (depends on 7) The method of claim 7, wherein the solid acid catalyst is a solid acidic ion exchanger. ### Claim 15 (depends on 14) The method of claim 14, wherein the acidic ion exchanger comprises cross-linked polystyrene-containing sulfonic acid groups. ### Claim 16 (depends on 14) The method of claim 14, wherein the acidic ion exchanger comprises sulfonated tetrafluoroethylene-based fluoropolymer-copolymers. ### Claim 17 (depends on 7) 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. ### Claim 18 (depends on 7) 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. ### Claim 19 (depends on 1) The method of claim 1, wherein the monophasic reaction solution comprises from about 5 wt % to about 20 wt % water. ### Claim 20 (depends on 1) The method of claim 1, wherein the monophasic reaction solution comprises from about 5 wt % to about 12 wt % water. ### Claim 21 (depends on 1) 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. ### Claim 22 (depends on 21) 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. ### Claim 23 (depends on 21) 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. ### Claim 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. ### Claim 25 (depends on 24) The method of claim 24, wherein the aqueous phase comprises a saturating amount of a salt. ### Claim 26 (depends on 24) 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. ### Claim 27 (depends on 24) The method of claim 24, wherein the organic solvent has from five (5) carbon atoms to sixteen (16) carbon atoms. ### Claim 28 (depends on 24) The method of claim 24, wherein the organic solvent has from five (5) carbon atoms to eleven (11) carbon atoms. ### Claim 29 (depends on 24) 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. ### Claim 30 (depends on 24) 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.