# US 11,299,468 B2 · Methods for producing 5-(halomethyl)furfural > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,299,468 B2 - Document ID: US11299468B2 - Status: Granted - Kind: B2 - Application number: 16/894,503 - Filed: 2020-06-05 - Published: 2021-03-25 - Granted: 2022-04-12 - Earliest claimed: 2013-09-20 - Assignees: Origin Materials Operating, Inc. - Applicants: Origin Materials Operating, Inc. - Inventors: Alex B. Wood; Makoto N. Masuno; Ryan L. Smith; John Bissell; Dimitri A. Hirsch-Weil; Robert Joseph Araiza; Daniel R. Henton; James H. Plonka - Web page: https://patentgrep.com/patent/US11299468B2 ## CPC - C07D 307/46: Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom - B01J 27/10: Chlorides - 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 - Y02E 50/10: Biofuels, e.g. bio-diesel - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION ## Abstract The present disclosure provides methods to produce 5-(halomethyl)furfural, including 5-(chloromethyl)furfural, by acid-catalyzed conversion of C6 saccharides, including isomers thereof, polymers thereof, and certain derivatives thereof. The methods make use of acids with lower concentrations, and allows for conversion of sugars into 5-(halomethyl)furfural at higher temperatures and faster reaction or residence times. ## Claims ### Claim 1 A method for producing 5-(halomethyl)furfural, comprising: combining feedstock, aqueous acid, and halide salt to produce 5-(halomethyl)furfural, wherein the feedstock comprises one or more C6 monosaccharides, disaccharides comprising monomeric units having six carbon atoms, or polysaccharides comprising monomeric units having six carbon atoms; wherein the aqueous acid and the halide salt react to provide a halogen-containing mineral acid in situ; and wherein the combination of the feedstock, the aqueous acid, and the halide salt has a hydrogen concentration of less than or equal to 8 M, and a halide concentration of at least 8 M. ### Claim 2 (depends on 1) The method of claim 1, wherein the aqueous acid comprises protic acid. ### Claim 3 (depends on 1) The method of claim 1, wherein the halide salt comprises lithium halide or calcium halide, or any combinations thereof. ### Claim 4 (depends on 1) The method of claim 1, wherein the salt comprises calcium chloride, calcium bromide or a combination thereof. ### Claim 5 (depends on 1) The method of claim 1, wherein the halogen-containing mineral acid provided in situ is a chloro-containing mineral acid. ### Claim 6 (depends on 1) The method of claim 1, wherein the halogen-containing mineral acid provided in situ comprises hydrochloric acid, or hydrobromic acid, or a combination thereof. ### Claim 7 (depends on 1) The method of claim 1, wherein the aqueous acid comprises protic acid; wherein the halide salt comprises lithium chloride, or calcium chloride, or a combination thereof; and wherein the aqueous acid and the halide salt react to provide hydrochloric acid in situ. ### Claim 8 (depends on 7) The method of claim 7, wherein the aqueous acid comprises acids with pKa less than 5. ### Claim 9 (depends on 1) The method of claim 1, wherein the hydrogen concentration is less than or equal to 2 M. ### Claim 10 (depends on 1) The method of claim 1, wherein the hydrogen concentration is greater than or equal to 0.5 M and less than or equal to 8 M. ### Claim 11 (depends on 1) The method of claim 1, wherein the halide concentration is at least 9 M. ### Claim 12 (depends on 1) The method of claim 1, wherein the hydrogen concentration is less than or equal to 5 M; and the halide concentration is at least 9 M. ### Claim 13 (depends on 1) The method of claim 1, wherein the aqueous acid is continuously added. ### Claim 14 (depends on 13) The method of claim 13, wherein the aqueous acid is continuously added at a rate to maintain an average hydrogen concentration greater than 0 M and less than or equal to 6 M. ### Claim 15 (depends on 1) The method of claim 1, wherein the combination of the feedstock, the aqueous acid, and the halide salt further produces humins, levulinic acid, formic acid, furfural, gamma valerolactone, or fulvic acid, or any combinations thereof. ### Claim 16 (depends on 1) The method of claim 1, wherein the feedstock, the aqueous acid, and the halide salt are further combined with solvent. ### Claim 17 (depends on 1) The method of claim 1, wherein the 5-(halomethyl)furfural is produced at a temperature of at least 110° C. ### Claim 18 (depends on 1) The method of claim 1, wherein the feedstock comprises glucose, fructose, sucrose, starch, inulin, cellulose, hemicellulose, cellulosic oligomers, or cellobiose, or any combinations thereof. ### Claim 19 (depends on 1) The method of claim 1, wherein the feedstock is selected from the group consisting of corn stover, corn cob, corn kernel, rice flour, whole cane, beet pulp, beet processing raffinate, empty palm fruit bunches, palm fronds, saw dust, wood pellets, rice hulls, peanut hulls, spent grains, paper sludge, cardboard, old corrugated containers (OCC), old newspaper (ONP), mixed paper, wheat straw, paper mill effluent, newsprint, municipal solid wastes, wood chips, forest thinnings, slash, miscanthus, switchgrass, sorghum, bagasse, manure, wastewater biosolids, green waste, and food or feed processing residues, and any combinations thereof. ### Claim 20 (depends on 16) The method of claim 16, wherein the solvent comprises one or more alkyl phenyl solvents, one or more heavy alkane solvents, one or more ester solvents, one or more aromatic solvents, one or more silicone oils, or any combinations or mixtures thereof. ### Claim 21 (depends on 2) The method of claim 2, wherein the protic acid comprises nitric acid, phosphoric acid, sulfuric acid, fluoroboric acid, or any combination thereof. ### Claim 22 (depends on 7) The method of claim 7, wherein the protic acid comprises nitric acid, phosphoric acid, sulfuric acid, or fluoroboric acid, or any combination thereof.