METHODS FOR PRODUCING 5 - (HALOMETHYL) FURFUR AL

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application No.

62/135,086, filed March 18, 2015, which is incorporated herein by reference in its entirety.

FIELD

[0002] The present disclosure relates generally to the production of furfurals, and more specifically to the production of 5-(halomethyl)furfural, including, for example, 5- (chloromethyl)furfural or 5-(bromomethyl)furfural, from renewable biomass resources (e.g. , cellulose, hemicellulose, starch, and sugar).

BACKGROUND

[0003] Efforts to reduce dependence on fossil fuels for transportation fuel and as feedstock for industrial chemicals have been undertaken for decades, with a particular focus on enabling economic feasibility of renewable feedstocks. Heightened efforts are being made to more effectively utilize renewable resources and develop "green" technologies, due to continued long- term increases in the price of fuel, increased environmental concerns, continued issues of geopolitical stability, and renewed concerns for the ultimate depletion of fossil fuels.

[0004] Cellulose in biomass is commonly used as a feedstock for biofuel production. For example, cellulose can be used to produce ethanol. Cellulose can also be used to produce furan- based biofuels by way of 5-(halomethyl)furfural, such as 5-(chloromethyl)furfural (CMF). CMF can be converted into 5-(ethoxymethyl)furfural, a compound considered as a promising diesel fuel additive. Alternatively, CMF can also be converted into 5-methylfurfural, another compound considered as a promising a biofuel candidate.

[0005] The production of CMF from cellulose was first described in the early 1900s.

Currently, various synthetic routes are known in the art to produce CMF from biomass using concentrated hydrochloric acid. For example, U.S. Patent No. 7,829,732 describes a method of producing CMF from biomass using concentrated hydrochloric acid and 1 ,2-dichloroethane as a solvent. See also, Szmant & Chundury, /. Chem. Tech. Biotechnol. 1981, 31, 205-212; Liu et al , J. Phys. Chem. A, 2011, 115, 13628-13641. The use of concentrated hydrochloric acid, however, can present several challenges on a commercial scale. For example, use of concentrated hydrochloric acid can cause corrosion of the reactors.

[0006] Thus, what is needed in the art are commercially viable methods to produce 5- (halomethyl)furfural from biomass using other types of acids.

BRIEF SUMMARY

[0007] Provided herein are methods for producing halomethylfurfurals, such as 5- (chloromethyl)furfural (CMF) and 5-(bromomethyl)furfural (BMF).

[0008] In some aspects, provided is a method for producing 5-(halomethyl)furfural, that includes: a) combining a feedstock, an acid and a salt in a reaction vessel to form a reaction mixture, wherein:

the acid has a pKa greater than or equal to -8;

the salt is A ^r+ (X ^" ) _r , wherein:

A ^r+ is a Group I or Group II cation, and

X ^" is a halo anion; and

b) producing 5-(halomethyl)furfural from at least a portion of the feedstock in the reaction mixture.

[0009] In some variations, the reaction mixture has a [H ⁺ ] less than 12 M.

[0010] In certain aspects, provided is a method for producing a 5-(halomethyl)furfural, that includes: a) combining a feedstock, an acid and a salt, wherein:

the salt is A ^r+ (X ^" ) _r , wherein:

A ^r+ is a Group I or Group II cation, and

X ^" is a halo anion;

b) producing the 5-(halomethyl)furfural and water from at least a portion of the feedstock, wherein the feedstock, the acid, the salt, the 5-(halomethyl)furfural and the water form a mixture; and c) distilling the mixture to remove at least a portion of the water in the mixture, wherein the distilling minimizes loss of the acid in the mixture.

[0011] In certain aspects, provided is a method for producing a 5-(halomethyl)furfural, that includes: a) combining a feedstock, an acid and a salt, wherein:

the salt is A ^r+ (X ^" ) _r , wherein:

A ^r+ is a Group I or Group II cation, and

X ^" is a halo anion;

b) producing the 5-(halomethyl)furfural and water from at least a portion of the feedstock, wherein the feedstock, the acid, the salt, the 5-(halomethyl)furfural and the water form a mixture; and

c) distilling the mixture to remove at least a portion of the water in the mixture before removal of acid in the mixture.

[0012] In any of the foregoing aspects, the method further includes isolating the 5- (halomethyl)furfural produced.

[0013] In some aspects, provided is also a composition that includes any of the feedstocks, acids and salts described herein. In some variations, the composition further includes any of the solvents described herein. In certain variations, the composition further includes the halomethylfurfural, such as 5-(halomethyl)furfural.

[0014] Provided herein is also the use of the halomethylfurfural, such as 5- (halomethyl)furfural, to produce one or more downstream products. Examples of such downstream products include dimethylfuran, such as 2,5-dimethylfuran, which may be used in turn to produce para- xylene. The para-xylene may be used as as a precursor to produce terephthalic acid, and subsequently polyethylene terephthalate.

DESCRIPTION OF THE FIGURE

[0015] The present application can be understood by reference to the following description taken in conjunction with the accompanying figure.

[0016] FIG. 1 depicts an exemplary reaction for converting glucose into 5-

(halomethyl)furfural (where X is halo) using an acid and a salt. DETAILED DESCRIPTION

[0017] The following description sets forth exemplary methods, parameters and the like. It should be recognized, however, that such description is not intended as a limitation on the scope of the present disclosure but is instead provided as a description of exemplary embodiments.

[0018] With reference to FIG. 1, method 100 is an exemplary reaction for producing 5- (halomethyl)furfural (where X of compound 110 is halo) by contacting feedstock 102, acid 104, and salt 106. Feedstock 102 in this exemplary reaction is glucose. While the glucose is depicted in open-chain form in FIG. 1, it should be understood, however, any isomers of glucose may be used. For example, feedstock 102 may be a cyclic isomer of glucose. The open-chain form of glucose used in method 100 may exist in equilibrium with several cyclic isomers. Further, feedstock 102 may also be a monosaccharide (as depicted in FIG. 1), or in other variations, disaccharides or polysaccharides made up of monomelic units having six carbon atoms.

[0019] With reference to FIG. 1, acid 104 is used. In some variations, acid 104 is an organic acid. In certain variations, acid 104 has a pKa greater than or equal to -8. It should also be understood that, in other exemplary embodiments, acid 104 may be added to the reaction mixture as a reagent, or generated in situ by combining reagents that may form acid 104 in situ in the reaction mixture. Other suitable acids and suitable concentrations of the acid are described further herein.

[0020] With reference again to the exemplary method depicted in FIG. 1, salt 106 used is a halide salt. Suitable salts may include, for example, lithium chloride and calcium chloride. A combination of suitable salts may also be used. It should also be understood that, in other exemplary embodiments, salt 106 may be added to the reaction mixture as a reagent, or generated in situ by combining reagents that may form salt 106 in the reaction mixture. Other suitable salts and suitable concentrations of the salts are described further herein.

[0021] Exemplary method 100 may be carried out at an elevated temperature. For example, method 100 may be carried out at a reaction temperature of at least 80°C.

[0022] With reference again to the exemplary method depicted in FIG. 1, it should be understood that one or more additional reagents may be used in method 100. For example, in some variations, method 100 may include a solvent or mixture of solvents. Further, it should be understood that method 100 may employ one or more additional steps. For example, in other variations, method 100 may further include isolating the 5-(halomethyl)furfural from the reaction mixture.

[0023] The methods and compositions described herein employ various reagents and reaction conditions, each of which is described in further detail below.

Feedstocks

[0024] The feedstocks used in the methods described herein refer to the starting materials for such methods. Feedstocks suitable for producing halomethylfurfurals, such as 5- (halomethyl)furfural, may include any materials that contain saccharides. Examples of the feedstock include glucose, glucans, cellulose, hemicellulose, starch, or sucrose, or any mixtures thereof.

[0025] In some embodiments, the feedstock may include six-carbon (C6) saccharides. It should be understood that "six-carbon saccharides" or "C6 saccharides" refers to saccharides where the monomeric unit has six carbons. The feedstock may include monosaccharides, disaccharides, polysaccharides, or any mixtures thereof. In one variation, the feedstock includes one or more C6 monosaccharides. In another variation, the feedstock includes a disaccharide or polysaccharide comprising monomeric units having six carbon atoms. It should be understood that the monomeric units may the same or different.

[0026] In one embodiment, the feedstock includes a monosaccharide. Examples of suitable monosaccharides include glucose, fructose, and any other isomers thereof. In another embodiment, the feedstock includes a disaccharide. Examples of suitable disaccharides include sucrose. In yet another embodiment, the feedstock includes a polysaccharide. Examples of polysaccharides include cellulose, hemicellulose, cellulose acetate, and chitin. In other embodiments, the feedstock includes a mixture of monosaccharides, disaccharides,

polysaccharides. For example, in one variation, the feedstock may include glucose, sucrose, cellulose, or any combinations thereof. In another variation, the feedstock includes clucans, starch, cellulose, or hemicellulose, or any combinations thereof.

[0027] In some embodiments, the feedstock includes C6 saccharides selected from glucose, fructose (e.g. , high fructose corn syrup), cellobiose, sucrose, lactose, and maltose, or isomers thereof (including any stereoisomers thereof), or any mixtures thereof. In one embodiment, the feedstock includes glucose, or a dimer or polymer thereof, or an isomer thereof. In another embodiment, the feedstock includes fructose, or a dimer or polymer thereof, or an isomer thereof. In another variation, the feedstock is a saccharide composition. For example, the saccharide composition may include a single saccharide or a mixture of saccharides such as fructose, glucose, sucrose, lactose and maltose.

[0028] Feedstocks suitable for use in the methods and compositions described herein may also include derivatives of the sugars described above. In some embodiments, the feedstock may be aldoses, ketoses, or any mixtures thereof. In some embodiments, the feedstock includes C6 aldoses, C6 ketoses, or any mixtures thereof.

[0029] In some variations, the feedstock includes an aldose, or any polymers thereof. In one variation, the feedstock includes a C6 aldose, or any polymers thereof. Examples of suitable aldoses include glucose. In another variation, the feedstock includes polyaldoses.

[0030] In other variations, the feedstock includes a ketose, or any polymers thereof. In another embodiment, the feedstock includes a C6 ketose, or any polymers thereof. Examples of suitable ketoses include fructose. In another variation, the feedstock includes polyketoses.

[0031] In yet another embodiment, the feedstock includes a mixture of C6 aldoses and C6 ketoses. For example, in one variation, the feedstock may include glucose and fructose.

[0032] In some embodiments when the feedstock includes sugars, the sugars may be present in open-chain form, cyclic form, or a mixture thereof. For example, glucose as depicted in FIG. 1 is in open-chained form; however, cyclic isomers of glucose may also be used in the method or be present in the reaction mixture. One of skill in the art would recognize that, when the feedstock includes glucose, the open-chain form of glucose used may exist in equilibrium with several cyclic isomers in the reaction.

[0033] In other embodiments when the feedstock includes sugars, the sugars can exist as any stereoisomers, or as a mixture of stereoisomers. For example, in certain embodiments, the feedstock may include D-glucose, L-glucose, or a mixture thereof. In other embodiments, the feedstock may include D-fructose, L-fructose, or a mixture thereof.

[0034] In one variation, the feedstock includes hexose. One of skill in the art would recognize that hexose is a monosaccharide with six carbon atoms, having the chemical formula CelinOe- Hexose may be an aldohexose or a ketohexose, or a mixture thereof. The hexose may be in open-chain form, cyclic form, or a mixture thereof. The hexose may be any stereoisomer, or mixture of stereoisomers. Suitable hexoses may include, for example, glucose, fructose, galactose, mannose, allose, altrose, gulose, idose, talose, psicose, sorbose, and tagatose, or any mixtures thereof.

[0035] The feedstock used in the methods and compositions described herein may be obtained from any commercially available sources. For example, one of skill in the art would recognize that cellulose and hemicellulose can be found in biomass (e.g. , cellulosic biomass or lignocellulosic biomass). In some embodiments, the feedstock is biomass, which can be any plant or plant-derived material made up of organic compounds relatively high in oxygen, such as carbohydrates, and also contain a wide variety of other organic compounds. The biomass may also contain other materials, such as inorganic salts and clays.

[0036] Biomass may be pretreated to help make the sugars in the biomass more accessible, by disrupting the crystalline structures of cellulose and hemicellulose and breaking down the lignin structure (if present). Common pretreatments known in the art involve, for example, mechanical treatment (e.g. , shredding, pulverizing, grinding), concentrated acid, dilute acid, SO2, alkali, hydrogen peroxide, wet-oxidation, steam explosion, ammonia fiber explosion (AFEX), supercritical CO2 explosion, liquid hot water, and organic solvent treatments.

[0037] Biomass may originate from various sources. For example, biomass may originate from agricultural materials (e.g. , corn kernel, corn cob, corn stover, rice hulls, peanut hulls, and spent grains), processing waste (e.g. , paper sludge), and recycled cellulosic materials (e.g. , cardboard, old corrugated containers (OCC), old newspaper (ONP), and mixed paper). Other examples of suitable biomass may include wheat straw, paper mill effluent, newsprint, municipal solid wastes, wood chips, saw dust, forest thinnings, slash, miscanthus, switchgrass, sorghum, bagasse, manure, wastewater biosolids, green waste, and food/feed processing residues.

[0038] A combination of any of the feedstocks described herein may also be used. For example, in one variation, the feedstock may include glucose, corn kernel and wood chips. In another variation, the feedstock may include wood chips and cardboard. In yet another variation, the feedstock may include bagasse and cardboard. Acid

Types of acid

[0039] In some embodiments, the acids used in the methods and compositions described herein are organic acids.

[0040] In some variations, the acid includes trifluoroacetic acid, oxalic acid, chloroacetic acid, salicylic acid, fumaric acid, citric acid, malic acid, formic acid, lactic acid, acrylic acid, sebacic acid, acetic acid, levulinic acid, carbonic acid, and ammonium chloride. In other variations, the acid includes phosphoric acid, sulfuric acid, nitric acid, or boric acid. In certain embodiments, the acid is phosphoric acid or boric acid.

[0041] In some variations, the acid is a weak acid. In some embodiments, the acid has a pKa greater than or equal to -8, or greater than or equal to -5, or greater than or equal to 0. In other variations, the acid has a pKa between -8 and 10, or between 0 and 7, or between 0 and 6, or between 0 and 5. As used herein, the "pKa" of the acid is determined as described in March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 6 ^th edition.

[0042] In other embodiments, the acid has a higher vapor pressure than water, and distillation of the acid and water results in a vapor phase enriched with water, and the loss of acid is also minimized. Thus, in some embodiments of the methods described herein, when the feedstock, acid, salt, and optional solvent are combined to produce 5-(halomethyl)furfural and water, the feedstock, acid, salt, optional solvent, 5-(halomethyl)furfural and water form a mixture. In some variations, when this mixture is distilled, at least a portion of the water is removed, while minimizing the loss of acid in the mixture. In other variations, when this mixture is distilled, at least a portion of the water in the mixture is removed before the acid in the mixture. It should generally be understood that the mixture of the feedstock, acid, salt, optional solvent, 5-(halomethyl)furfural and water may be homogeneous or heterogeneous.

[0043] In other embodiments, the acid fed into the reactor or the reaction mixture is a gaseous acid. For example, at least a portion of such gaseous acid may be dissolved, or partially dissolved, in the reaction mixture to produce an aqueous acid.

Acid concentration

[0044] The concentration of the acid used in the methods and compositions described herein is typically less than 12 M. In some embodiments, the acid used in the methods and compositions described herein has a concentration less than 12 M, less than or equal to 11.5 M, less than or equal to 11 M, less than or equal to 10.5 M, less than or equal to 10 M, less than or equal to 9.5 M, less than or equal to 9 M, less than or equal to 8.5 M, less than or equal to 8 M, less than or equal to 7.5 M, less than or equal to 7 M, less than or equal to 6.5 M, less than or equal to 6 M, less than or equal to 5.5 M, less than or equal to 5 M, less than or equal to 4.5 M, less than or equal to 4 M, less than or equal to 3.5 M, less than or equal to 3 M, less than or equal to 2.5 M, less than or equal to 2 M, less than or equal to 1.5 M, or less than or equal to 1 M; or between 0.25 M and 10 M, between 0.25 M and 9 M, between 0.25 M and 8 M, between 0.25 M and 7 M, between 0.25 M and 6 M, between 0.25 M and 5 M, between 0.5 M and 10 M, between 0.5 M and 9 M, between 0.5 M and 8 M, between 0.5 M and 7 M, between 0.5 M and 6 M, between 0.5 M and 5 M, between 1 M and 10 M, between 1 M and 9 M, between 1 M and 8 M, between 1 M and 7 M, between 1 M and 6 M, between 1 M and 5 M, between 1 M and 4 M, or between 2 M and 4 M.

[0045] The concentration of the acid used herein may also vary depending on various factors, including the type of feedstock used. In some embodiments when the feedstock is or includes an aldose, the acid has a concentration less than 12 M, less than or equal to 11 M, less than or equal to 10 M, less than or equal to 9 M, less than or equal to 8 M, less than or equal to 7 M, less than or equal to 6 M, less than or equal to 5 M, less than or equal to 4 M, less than or equal to 3 M, or less than or equal to 2 M; or between 0.25 M and 11.5 M, between 0.25 M and 10 M, between 0.5 M and 8 M, between 0.5 and 6 M, or between 0.5 and 5 M.

[0046] In certain embodiments when the feedstock is or includes glucose, the acid has a concentration less than 12 M, less than or equal to 11 M, less than or equal to 10 M, less than or equal to 9 M, less than or equal to 8 M, less than or equal to 7 M, less than or equal to 6 M, less than or equal to 5 M, less than or equal to 4 M, less than or equal to 3 M, or less than or equal to 2 M; or between 0.25 M and 11.5 M, between 0.25 M and 10 M, between 0.5 M and 8 M, between 0.5 and 6 M, or between 0.5 and 5 M.

[0047] In other embodiments when the feedstock is or include ketose, the acid has a concentration less than or equal to 6 M, less than or equal to 5 M, less than or equal to 4 M, less than or equal to 3 M, less than or equal to 2 M, or less than or equal to 1 M; or between 0.25 M and 6 M, between 0.25 M and 5 M, between 0.25 M and 4 M, between 0.25 M and 3 M, between 0.25 M and 2 M, between 0.5 M and 6 M, between 0.5 M and 5 M, between 0.5 M and 4 M, between 0.5 M and 3 M, between 0.5 M and 2 M, between 1 M and 6 M, between 1 M and 5 M, between 1 M and 4 M, between 1 M and 3 M, or between 1 M and 2M.

[0048] In other embodiments when the feedstock is or include fructose, the acid has a concentration less than or equal to 6 M, less than or equal to 5 M, less than or equal to 4 M, less than or equal to 3 M, less than or equal to 2 M, or less than or equal to 1 M; or between 0.25 M and 6 M, between 0.25 M and 5 M, between 0.25 M and 4 M, between 0.25 M and 3 M, between 0.25 M and 2 M, between 0.5 M and 6 M, between 0.5 M and 5 M, between 0.5 M and 4 M, between 0.5 M and 3 M, between 0.5 M and 2 M, between 1 M and 6 M, between 1 M and 5 M, between 1 M and 4 M, between 1 M and 3 M, or between 1 M and 2M.

Ft concentration

[0049] The concentration of acid(s) used in the methods and compositions described herein affects the H ⁺ concentration in the reaction mixture. In some embodiments, the [H ⁺ ] in the reaction mixture is less than 12 M, less than or equal to 11.5 M, less than or equal to 11 M, less than or equal to 10.5 M, less than or equal to 10 M, less than or equal to 9.5 M, less than or equal to 9 M, less than or equal to 8.5 M, less than or equal to 8 M, less than or equal to 7.5 M, less than or equal to 7 M, less than or equal to 6.5 M, less than or equal to 6 M, less than or equal to 5.5 M, less than or equal to 5 M, less than or equal to 4.5 M, less than or equal to 4 M, less than or equal to 3.5 M, less than or equal to 3 M, less than or equal to 2.5 M, less than or equal to 2 M, less than or equal to 1.5 M, or less than or equal to 1 M; or between 0.25 M and 10 M, between 0.25 M and 9 M, between 0.25 M and 8 M, between 0.25 M and 7 M, between 0.25 M and 6 M, between 0.25 M and 5 M, between 0.5 M and 10 M, between 0.5 M and 9 M, between 0.5 M and 8 M, between 0.5 M and 7 M, between 0.5 M and 6 M, between 0.5 M and 5 M, between 1 M and 10 M, between 1 M and 9 M, between 1 M and 8 M, between 1 M and 7 M, between 1 M and 6 M, between 1 M and 5 M, between 1 M and 4 M, or between 2 M and 4 M.

[0050] In certain embodiments, the [H ⁺ ] in the reaction mixture is less than 0.6 M, less than 0.55 M, less than 0.5 M, less than 0.45 M, less than 0.4 M, less than 0.35 M, less than 0.3 M, less than 0.25 M, less than 0.2 M, less than 0.15 M, less than 0.1 M, less than 0.05M, or less than 0.01 M.

[0051] It should be understood that the [H ⁺ ] of the reaction mixture may depend on the concentration of acid or acids used in the methods and compositions described herein. [0052] It should also generally be understood that H is present in sufficient quantities in the methods described herein to allow the reaction to proceed. Thus, in some embodiments, the [H ⁺ ] is greater than 0 M. For example, in some variations, the [H ⁺ ] is greater than or equal to 0.0001 M, 0.001 M, or 0.1 M.

[0053] In other embodiments, the [H ⁺ ] in the reaction mixture is between the feedstock concentration and 5 M. The feedstock concentration refers to the molar concentration of C6 monosaccharides, or monomeric units have six carbon atoms.

[0054] The acid concentrations as described herein may refer to the initial concentrations, fed concentrations, or steady-state concentrations. Initial concentration refers to the

concentration of the reaction mixture at the point in time when the reaction begins. Fed concentration refers to the concentration when the reactants are combined before being fed into the reactor. Steady-state concentration refers to concentration at steady state of the reaction.

[0055] In some variations, the acid is added continuously to the reaction mixture at a rate to maintain a non-zero [H ⁺ ]. It should be understood that the acid is consumed in a stoichiometric amount. For example, 1 mole of CMF requires 1 mole of H ⁺ and 1 mole of glucose.

Salt

Types of salt

[0056] The salts used in the methods and compositions described herein may be inorganic salts and/or organic salts. An "inorganic salt" refers to a complex of a positively charged species and a negatively charged species, where neither species includes the element carbon. An "organic salt" refers to a complex of a positively charged species and a negatively charged species, where at least one species includes the element carbon.

[0057] The selection of the salt used may vary depending on the reaction conditions, as well as the acid and solvent used. In some embodiments, the salt is an inorganic salt. In ceratin embodiments, the salt is a halogen-containing acid.

[0058] The salts used may be halide salts or halogen-containing salts. In some embodiments, the salt is A ^r+ (X ^" ) _r , wherein:

A ^r+ is a Group I or Group II cation; and

X ^" is a halo anion. [0059] It should be understood that variable "r" refers to the ionic charge. In certain variations, the salt has a monovalent or divalent cation. In other words, in certain variations, r may be 1 or 2.

[0060] Examples of salts that may be used in certain embodiments include lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, and calcium salts. In some embodiments, the salt is a lithium salt. In other embodiments, the salt is a calcium salt. In some variations, A ^r+ is Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ , or Sr ²⁺ . In certain variations, A ^r+ is Li ⁺ , Mg ²⁺ , or Ca ²⁺ . In some variations, X ^" is CI ^" or Br ^" . In certain variations, the salt is LiX, NaX, KX, RbX, CsX, MgX ₂ , CaX ₂ , or SrX ₂ . In one variation, X is CI or Br. In some variations, the salt is LiCl, NaCl, KC1, RbCl, CsCl, MgCl ₂ , CaCl ₂ , SrCl ₂ , LiBr, NaBr, KBr, RbBr, CsBr, MgBr ₂ , CaBr ₂ , or SrBr ₂ . In certain variations, the salt is selected from LiCl, MgCl ₂ , CaCl ₂ , NaCl, KC1, CsCl, LiBr, MgBr ₂ , NaBr, KBr, and CsBr. In one variation, the salt is LiCl. In another variation, the salt is CaCl ₂ .

[0061] A combination of any of the salts described herein may also be used. For example, in some variations, LiCl and CaCl ₂ may be used together as the salt. In other variations, additional salts may also be used. Such additional salts may be selected from, for example, zinc salts, silicate salts, carbonate salts, sulfate salts, sulfide salts, phosphate salts, perchlorate salts, and triflate salts. In certain embodiments, the additional salt is selected from ZnCl ₂ , lithium triflate (LiOTf), and sodium triflate (NaOTf), or any combination thereof. In one variation, a combination of LiCl and LiOTf is used as the salt.

Salt concentration

[0062] The concentration of the salt used in the methods and compositions described herein may vary. In some embodiments, the concentration of the salt(s) is greater than 5 M, greater than 6 M, greater than 7 M, greater than 8 M, greater than 9 M, or greater than 10 M; or between 5 M and 20 M, between 5 M and 15 M, between 5.5 M and 10 M, between 7 M and 10 M, or between 7.5 M and 9 M; or about 10 M, about 11 M, about 12 M, about 13 M, about 14 M, or about 15 M.

[0063] For example, in some embodiments when LiCl is the salt used, the concentration of LiCl is greater than 5 M, greater than 6 M, greater than 7 M, greater than 8 M, greater than 9 M, or greater than 10 M; or between 5 M and 20 M, between 5 M and 15 M, between 5.5 M and 10 M, between 7 M and 10 M, or between 7.5 M and 9 M; or about 10 M, about 11 M, about 12 M, about 13 M, about 14 M, or about 15 M. In other embodiments, the LiCl is present from about 0.1% to 50% (w/w) of the aqueous phase.

[0064] In other embodiments when CaCl ₂ is the salt used, the concentration of CaCl ₂ is greater than 5 M, greater than 6 M, greater than 7 M, greater than 8 M, greater than 9 M, or greater than 10 M; or between 5 M and 20 M, between 5 M and 15 M, between 5.5 M and 10 M, between 7 M and 10 M, or between 7.5 M and 9 M; or about 10 M, about 11 M, about 12 M, about 13 M, about 14 M, or about 15 M. In other embodiments, the CaCl ₂ is present from about 0.1% to 50% (w/w) of the aqueous phase.

[0065] In other embodiments when MgCl ₂ is the salt used, the concentration of MgCl ₂ is greater than 5 M, greater than 6 M, greater than 7 M, greater than 8 M, greater than 9 M, or greater than 10 M; or between 5 M and 20 M, between 5 M and 15 M, between 5.5 M and 10 M, between 7 M and 10 M, or between 7.5 M and 9 M; or about 10 M, about 11 M, about 12 M, about 13 M, about 14 M, or about 15 M. In other embodiments, the MgCl ₂ is present from about 0.1% to 50% (w/w) of the aqueous phase.

[0066] In some embodiments when the salt used is LiCl, CaCl ₂ , MgCl ₂ , or a mixture thereof, the salt concentration is greater than 5 M, greater than 6 M, greater than 7 M, greater than 8 M, greater than 9 M, or greater than 10 M; or between 5 M and 20 M, between 5 M and 15 M, between 5.5 M and 10 M, between 7 M and 10 M, or between 7.5 M and 9 M; or about 10 M, about 11 M, about 12 M, about 13 M, about 14 M, or about 15 M. In other embodiments, the salt or mixture of salts is present from about 0.1% to 50% (w/w) of the aqueous phase.

[0067] In some embodiments when LiBr is the salt used, the concentration of LiBr is greater than 5 M, greater than 6 M, greater than 7 M, greater than 8 M, greater than 9 M, or greater than 10 M; or between 5 M and 20 M, between 5 M and 15 M, between 5.5 M and 10 M, between 7 M and 10 M, or between 7.5 M and 9 M; or about 10 M, about 11 M, about 12 M, about 13 M, about 14 M, or about 15 M. In other embodiments, the LiBr is present from about 0.1% to 50% (w/w) of the aqueous phase.

[0068] In other embodiments when CaB¾ is the salt used, the concentration of CaB¾ is greater than 5 M, greater than 6 M, greater than 7 M, greater than 8 M, greater than 9 M, or greater than 10 M; or between 5 M and 20 M, between 5 M and 15 M, between 5.5 M and 10 M, between 7 M and 10 M, or between 7.5 M and 9 M; or about 10 M, about 11 M, about 12 M, about 13 M, about 14 M, or about 15 M. In other embodiments, the CaBr ₂ is present from about 0.1% to 50% (w/w) of the aqueous phase.

[0069] In other embodiments when MgBr ₂ is the salt used, the concentration of MgBr ₂ is greater than 5 M, greater than 6 M, greater than 7 M, greater than 8 M, greater than 9 M, or greater than 10 M; or between 5 M and 20 M, between 5 M and 15 M, between 5.5 M and 10 M, between 7 M and 10 M, or between 7.5 M and 9 M; or about 10 M, about 11 M, about 12 M, about 13 M, about 14 M, or about 15 M. In other embodiments, the MgBr ₂ is present from about 0.1% to 50% (w/w) of the aqueous phase.

[0070] In some embodiments when the salt used is LiBr, CaBr ₂ , MgBr ₂ , or a mixture thereof, the salt concentration is greater than 5 M, greater than 6 M, greater than 7 M, greater than 8 M, greater than 9 M, or greater than 10 M; or between 5 M and 20 M, between 5 M and 15 M, between 5.5 M and 10 M, between 7 M and 10 M, or between 7.5 M and 9 M; or about 10 M, about 11 M, about 12 M, about 13 M, about 14 M, or about 15 M. In other embodiments, the salt or mixture of salts is present from about 0.1% to 50% (w/w) of the aqueous phase.

X concentration

[0071] The concentration of salt(s) and acid(s) used may affects the concentration of the positively charged ions and the negatively charged ions present in the reaction mixture. As discussed above, the salt may be depicted by the formula A ^r+ (X ^" ) _r , where A ^r+ is a cation having ionic charge "r", and X ^" is a halo anion. The cation concentration present in the reaction mixture may be defined by the following equation: cation concentration = | ΓΧΊ - ΓΗ ⁺ 1 | , where X is halo,

valence of cation

It should generally be understood that [H ⁺ ] refers to the H ⁺ concentration; and [X ] refers to the X ^" concentration.

[0072] In some embodiments, the [X ] in the reaction mixture is greater than 2 M, greater than 5 M, greater than 6 M, greater than 7 M, greater than 8 M, greater than 9 M, greater than 10 M; or between 2 M to 25 M, between 5 M and 20 M, between 5 M and 15 M, between 5 M and 12 M, between 6 M and 12 M, between 5.5 M and 10 M, between 7 M and 10 M, between 7.5 M and 9 M, or between 6 M and 12 M; or about 10 M, about 11 M, about 12 M, about 13 M, about 14 M, or about 15 M. [0073] For example, when the salt used is lithium chloride (LiCl), calcium chloride (CaC^), or a mixture thereof, X ^" is CI ^" . Thus, in one variation, the [CI ] in the reaction mixture is greater than 5 M, greater than 6 M, greater than 7 M, greater than 8 M, greater than 9 M, or greater than 10 M; or between 5 M and 20 M, between 5 M and 15 M, between 5.5 M and 10 M, between 7 M and 10 M, or between 7.5 M and 9 M; or about 10 M, about 11 M, about 12 M, about 13 M, about 14 M, or about 15 M.

[0074] In another example, when the salt used is lithium bromide (LiBr), calcium bromide (CaBr ₂ ), X ^" is Br ^" . Thus, in one variation, the [Br ] in the reaction mixture is greater than 5 M, greater than 6 M, greater than 7 M, greater than 8 M, greater than 9 M, or greater than 10 M; or between 5 M and 20 M, between 5 M and 15 M, between 5.5 M and 10 M, between 7 M and 10 M, or between 7.5 M and 9 M; or about 10 M, about 11 M, about 12 M, about 13 M, about 14 M, or about 15 M.

[0075] It is understood that any description of acid for use in the methods and compositions described herein may be combined with any descriptions of the salts the same as if each and every combination were individually listed. For example, in some embodiments, the acid is phosphoric acid, and the salt is lithium chloride, calcium chloride, or a mixture thereof. In one variation, the acid is phosphoric acid,, and the salt is lithium chloride. In another variation, the acid is phosphoric acid,, and the salt is calcium chloride. In yet another variation, the acid is phosphoric acid, and the salt is a mixture of lithium chloride and calcium chloride. In other variations, the acid is phosphoric acid, and the salt is lithium bromide and calcium bromide.

[0076] It is further understood that any description of acid concentration or [H ⁺ ] in the methods and compositions described herein may be combined with any description of the salt concentration or [X ] the same as if each and every combination were individually listed. In some embodiments, the [H ⁺ ] in the reaction mixture is greater than 0 M and less than 8M; and the [X ] in the reaction mixture is at least 5 M. In other embodiments, the [H ⁺ ] in the reaction mixture is greater than 0 M and less than 8M; and the [X-] in the reaction mixture is at least 10 M.

[0077] For example, in other embodiments where the salt is lithium chloride, the acid concentration is between 0.5 M and 9 M, and the lithium chloride concentration is between 5M and 20 M. In one variation, the acid concentration is between 0.5 M and 6 M, and the lithium chloride concentration is about 12 M. In other embodiments where the salt is lithium chloride, calcium chloride, or a mixture thereof, the reaction mixture has a [H ⁺ ] between 0.5 M and 9 M, and a [CI ] between 5M and 20 M. In one variation, the reaction mixture has a [H ] between 0.5 M and 6 M, and the reaction mixture has a [CI ] of about 12 M.

[0078] The salt used herein may be obtained from any commercially available source, or be produced in situ from providing suitable reagents to the reaction mixture.

[0079] The concentrations described herein for the salt or [X ] (e.g. , [CI ]) may refer to either initial concentrations, fed concentrations or steady-state concentrations.

Solvent System

[0080] A solvent, or a combination or mixture of solvents, may also be optionally added to the reaction mixture. The solvents used in the methods and compositions described herein may be obtained from any source, including any commercially available sources. In some embodiments, the methods described herein are performed neat (i. e. , without the use of any solvents). In other embodiments, the method includes combining a feedstock, an aqueous acid, a salt, and a solvent system in a reaction vessel to form a reaction mixture.

[0081] Any suitable solvent systems that can form a liquid / liquid biphase in the reaction mixture may be used, such that one phase is predominantly an organic phase and a separate phase is predominantly an aqueous phase. The 5-(halomethyl)furfural typically partitions between the organic phase and the aqueous phase such that the concentration of 5- (halomethyl)furfural in the organic phase is at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, or at least 60% of the 5- (halomethyl)furfural concentration in the aqueous phase.

[0082] The solvent systems used in the methods and compositions described herein may also be selected based on their dipole moment. One of skill in the art would understand that the dipole moment is a measure of polarity of a solvent. The dipole moment of a liquid can be measured with a dipole meter. In some embodiments, the solvent system used herein has a dipole moment less than 20.1 D, less than or equal to 20 D, less than or equal to 18 D, or less than or equal to 15 D.

[0083] The solvent system used in the methods and compositions described herein may also be selected based on their boiling points. In some embodiments, the solvent system has a boiling point of at least 110°C, at least 150°C, or at least 240°C. [0084] The solvent system used in the methods and compositions described herein may also be selected based on the partition coefficient of the 5-(halomethyl)furfural in the reaction mixture. As used herein, "partition coefficient" refers to the ratio of molar concentration of 5- (halomethyl)furfural in the organic phase to 5-(halomethyl)furfural in the aqueous phase in the reaction mixture. In some embodiments, the partition coefficient of the 5-(halomethyl)furfural in the reaction mixture is at least 0.2, at least 1, at least 10, or at least 100; or between 0.2 and 200, between 0.2 and 150, between 1 and 100.

[0085] The solvent system may include a solvent or a mixture of solvents. For example, in some embodiments, the solvent system includes one or more alkyl phenyl solvents, one or more alkyl solvents (e.g. , heavy alkyl solvents), one or more ester solvents, one or more aromatic solvents, one or more silicone oils, or any combinations or mixtures thereof. In other embodiments, the solvent system includes one or more hydrocarbons, one or more halogenated hydrocarbons, one or more ethers, one or more halogenated ethers, one or more cyclic ethers, one or more amides, one or more silicone oils, or any combinations or mixtures thereof.

[0086] In some embodiments, the solvent system includes p r -xylene, mesitylene, naphthalene, anthracene, toluene, dodecylbenzene, pentylbenzene, hexylbenzene, or other alkyl benzenes (e.g. , Wibaryl® A, Wibaryl® B, Wibaryl® AB, Wibaryl® F, Wibaryl® R, Cepsa Petrepar® 550-Q, Cepsa Petrepar® 900-Q, Santovac® 5, Santovac® 7, Marlican®, SynNaph® AB 3, SynNaph® AB4), sulfolane, hexadecane, heptadecane, octadecane, icosane, heneicosane, docosane, tricosane, tetracosane, or any combinations or mixtures thereof.

[0087] It should be understood that the solvent may fall into one or more of the classes listed herein. For example, the solvent system may include p r -xylene, which is an alkyl phenyl solvent and an aromatic solvent.

Alkyl Phenyl Solvents

[0088] As used herein, "an alkyl phenyl solvent" refers to a class of solvents that may have one or more alkyl chains and one or more phenyl or phenyl-containing ring systems. The alkyl phenyl solvent may be referred to as an alkylbenzene or a phenylalkane. One skilled in the art would recognize that certain phenylalkanes may also be interchangeably referred to as an alkylbenzene. For example, (l-phenyl)pentane and pentylbenzene refer to the same solvent.

[0089] In some embodiments, the solvent system includes an alkylbenzene. Examples may include (monoalkyl)benzenes, (dialkyl)benzenes, and (poly alky l)benzenes. In certain embodiments, the alkylbenzene has one alkyl chain attached to one benzene ring. The alkyl chain may have one or two points of attachment to the benzene ring. Examples of alkylbenzenes with one alkyl chain having one point of attachment to the benzene ring include pentylbenzene, hexylbenzene and dodecylbenzene. In embodiments where the alkyl chain has two points of attachment to the benzene ring, the alkyl chain may form a fused cycloalkyl ring to the benzene. Examples of alkylbenzenes with one alkyl having two points of attachment to the benzene ring include tetralin. It should be understood that the fused cycloalkyl ring may be further substituted with one or more alkyl rings.

[0090] In other embodiments, the alkylbenzene has two or more alkyl chains (e.g. , 2, 3, 4, 5, or 6 alkyl chains) attached to one benzene ring.

[0091] In yet other embodiments, the alkylbenzene is an alkyl-substituted fused benzene ring system. The fused benzene ring system may include benzene fused with one or more heterocyclic rings. In one embodiment, the fused benzene ring system may be two or more fused benzene rings, such as naphthalene. The fused benzene ring system may be optionally substituted by one or more alkyl chains.

[0092] In some embodiments, the solvent system includes phenylalkane. Examples may include (monophenyl)alkanes, (diphenyl)alkanes, and (polyphenyl)alkanes. In certain embodiments, the phenylalkane has one phenyl ring attached to one alkyl chain. The phenyl ring may be attached to any carbon along the alkyl chain. For example, the phenyl alkyl having one alkyl chain may be (l-phenyl)pentane, (2-phenyl)pentane, (l-phenyl)hexane, (2-phenyl)hexane, (3-phenyl)hexane, (l-phenyl)dodecane, and (2-phenyl)dodecane.

[0093] In other embodiments, the phenylalkane has two or more phenyl rings attached to one alkyl chain.

[0094] In one embodiment, the solvent system includes Wibaryl® A, Wibaryl® B,

Wibaryl® AB, Wibaryl® F, Wibaryl® R, Cepsa Petrepar® 550-Q, or any combinations or mixtures thereof. In another embodiment, the solvent system includes p r -xylene, toluene, or any combinations or mixtures thereof.

[0095] In certain embodiments, the alkyl chain of a solvent may be 1 to 20 carbon atoms

(e.g. , Ci-20 alkyl). In one embodiment, the alkyl chain may be 4 to 15 carbons (e.g. , C _4- i ₅ alkyl), or 10 to 13 carbons (e.g. , Cio-13 alkyl). The alkyl chain may be linear or branched. Linear alkyl chains may include, for example, n-propyl, n-butyl, n-hexyl, n-heptyl, n-octyl, n-nonanyl, n- decyl, n-undecyl, and n-dodecyl. Branched alkyl chains may include, for example, isopropyl, sec -butyl, isobutyl, tert-butyl, and neopentyl. In some embodiments where the solvent includes two or more alkyl chains, certain alkyl chains may be linear, whereas other alkyl chains may be branched. In other embodiments where the solvent includes two or more alkyl chains, all the alkyl chains may be linear or all the alkyl chains may be branched.

[0096] For example, the solvent system includes a linear alkylbenzene ("LAB"). Linear alkylbenzenes are a class of solvents having the formula CeHsC _n tt _n+ i- For example, in one embodiment, the linear alkylbenzene is dodecylbenzene. Dodecylbenzene is commercially available, and may be "hard type" or "soft type". Hard type dodecylbenzene is a mixture of branched chain isomers. Soft type dodecylbenzene is a mixture of linear chain isomers. In one embodiment, the solvent system includes a hard type dodecylbenzene.

[0097] In some embodiments, the solvent system includes any of the alkyl phenyl solvents described above, in which the phenyl ring is substituted with one or more halogen atoms. In certain embodiments, the solvent system includes an alkyl(halobenzene). For example, the alkyl(halobenzene) may include alkyl(chlorobenzene). In one embodiment, the halo substituent for the phenyl ring may be, for example, chloro, bromo, or any combination thereof.

[0098] In other embodiments, the solvent system includes naphthalene, naphthenic oil, alkylated naphthalene, diphenyl, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, or haloginated hydrocarbons.

Aliphatic Solvents

[0099] In one embodiment, the solvent system includes an aliphatic solvent. The aliphatic solvent may be linear, branched, or cyclic. The aliphatic solvent may also be saturated (e.g. , alkane) or unsaturated (e.g. , alkene or alkyne). In some embodiments, the solvent system includes a Ci _-20 aliphatic solvent, a Ci_io, aliphatic solvent, or a Ci_6 aliphatic solvent. In certain embodiments, the solvent system includes a C4-30 aliphatic solvent, a C ₆ -3o aliphatic solvent, a C _6- 24 aliphatic solvent, or a C ₆ -2o aliphatic solvent. In certain embodiments, the solvent system includes Cs ₊ alkyl solvent, or a Cs-so alkyl solvent, a Cs-4o alkyl solvent, a Cs-3o alkyl solvent, a C8-20 alkyl solvent, or a C _8- i6 alkyl solvent. Suitable aliphatic solvents may include, for example, butane, pentane, cyclopentane, hexane, cyclohexane, heptane, cycloheptane, octane, cyclooctane, nonane, decane, undecane, dodecane, hexadecane, or any combinations or mixtures thereof. In certain embodiments, the aliphatic solvent is linear. [0100] The aliphatic solvent may be obtained from petroleum refining aliphatic fractions, including any isomers of the aliphatic solvents, and any mixtures thereof. For example, alkane solvents may be obtained from petroleum refining alkane fractions, including any isomers of the alkane solvents, and any mixtures thereof. In certain embodiments, the solvent system includes petroleum refining alkane fractions.

Aromatic Solvents

[0101] In another embodiment, the solvent system includes an aromatic solvent. In some embodiments, the solvent system includes a C ₆ -2o aromatic solvent, a C _6- i ₂ aromatic solvent, or a Ci ₃ _2o aromatic solvent. The aromatic solvent may be optionally substituted. Suitable aromatic solvents may include, for example, p r -xylene, mesitylene, naphthalene, anthracene, toluene, anisole, nitrobenzene, bromobenzene, chlorobenzene (including, for example, dichlorobenzene), dimethylfuran (including, for example, 2,5-dimethylfuran), and methylpyrrole (including, for example, N-methylpyrrole).

Ether Solvents

[0102] In other embodiments, the solvent system includes an ether solvent, which refers to a solvent having at least one ether group. For example, the solvent system includes a C2-2 ₀ ether, or a C2-1 ₀ ether. The ether solvent can be non-cyclic or cyclic. For example, the ether solvent may be alkyl ether (e.g. , diethyl ether, glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), or Methylene glycol dimethyl ether (triglyme)). In another example, the ether solvent may be cyclic, such as dioxane (e.g. , 1,4-dioxane), dioxin, tetrahydrofuran, or a cycloalkyl alkyl ether (e.g. , cyclopentyl methyl ether).

[0103] The solvent system may include an acetal such as dioxolane (e.g. , 1,3-dioxolane).

[0104] The solvent system may also include a polyether with two or more oxygen atoms. In some embodiments, the ether solvent has a formula as follows: where each R _a and ¾ are independently aliphatic moieties, and n and m are integers equal to greater than 1. In some embodiments, each R _a and ¾ are independently alkyl. In certain embodiments, each R _a and R _b are independently Ci_io alkyl, or Ci_6 alkyl. R _a and R _b may be the same or different. In other embodiments, each n and m are independently 1 to 10, or 1 to 6, where n and m may be the same or different.

[0105] The formula above includes proglymes (such as dipropylene glycol dimethylether), or glymes (such as glycol diethers based on ethylene oxide). In one embodiment, the solvent system includes glyme, diglyme, triglyme, or tetraglyme.

[0106] It should also be understood that a solvent having an ether group may also have one or more other functional groups. It should be understood, however, that the solvent may have an ether functional group in combination with one or more additional functional groups, such as alcohols. For example, the solvent system includes alkylene glycols (e.g. , ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol), phenyl ethers (e.g. , diphenyl ether, polyphenyl ethers), or alkylphenylethers (e.g. , alkyldiphenyl ether).

[0107] In certain embodiments, the solvent system includes a polyphenyl ether that includes at least one phenoxy or at least one thiophenoxy moiety as the repeating group in ether linkages. For example, in one embodiment, the solvent system includes Santovac®.

Ester Solvents

[0108] In yet other embodiments, the solvent system includes an ester solvent, which refers to a solvent having at least one ester group. For example, the solvent system includes a C2-2 ₀ ester, or a C2-1 ₀ ester. The ester solvent can be non-cyclic (linear or branched) or cyclic. For example, non-cyclic ester solvents may include alkyl acetate (e.g. , methyl acetate, ethyl acetate, propyl acetate, butyl acetate), triacetin, and dibutylphthalate. An example of cyclic ester is, for example, propylene carbonate. It should be understood, however, that a solvent having an ester group may also have one or more other functional groups. The ester solvent may also include alkyl lactate (e.g. , methyl lactate, ethyl lactate, propyl lactate, butyl lactate), which has both an ester group as well as a hydroxyl group.

Halogenated Solvents

[0109] In yet other embodiments, the solvent system includes halogenated solvents. For example, the solvent can be a chlorinated solvent. Suitable chlorinated solvents may include, for example, carbon tetrachloride, chloroform, methylene chloride, bromobenzene and

dichlorobenzene. Other Solvents

[0110] In some variations, the solvent includes water.

Solvent Combinations or Mixtures

[0111] A combination or mixture of solvents may also be used in the methods and compositions described herein. In some embodiments, an ether solvent may be combined with one or more other types of solvents listed above.

Amount of Solvents ) Used

[0112] The solvents used in the methods and compositions described herein may vary depending on the type and amount of feedstock used. For example, in some embodiments, the mass to volume ratio of feedstock to solvent system is between 1 g and 30 g feedstock per 100 mL solvent system.

[0113] It is further understood that any description of the solvents used in the methods and compositions described herein may be combined with any description of the acids and salts the same as if each and every combination were individually listed. For example, in some embodiments, the acid is phosphoric acid, the salt is lithium chloride or calcium chloride, or a combination thereof, and the solvent is an alkyl phenyl solvent. In certain variations, the acid is phosphoric acid, the salt is lithium chloride, the reaction mixture has a [H ⁺ ] between 0.5 M and 9 M and a [CI ] between 5M and 20 M, and the solvent is p r -xylene.

Reaction Conditions

[0114] As used herein, "reaction temperature" and "reaction pressure" refer to the temperature and pressure, respectively, at which the reaction takes place to convert at least a portion of the six-carbon sugars in the feedstock into 5-(halomethyl)furfural.

[0115] In some embodiments of the methods described herein, the reaction temperature is at least 15°C, at least 25°C, at least 30°C, at least 40°C, at least 50°C, at least 60°C, at least 70°C, at least 80°C, at least 90°C, at least 100°C, at least 110°C, at least 115°C, at least 120°C, at least 125°C, at least 130°C, at least 135°C, at least 140°C, at least 145°C, at least 150°C, at least 175 °C, at least 200°C, at least 250°C, or at least 300°C. In other embodiments, the reaction temperature is between 110°C and 300°C, between 110°C to 250°C, between 150°C and 300°C, or between 110°C and 250°C. [0116] The reaction temperature selected may vary depending on the various factors, including, for example, the type of feedstock and the concentration of acid used. In certain variation, when the feedstock is or includes ketose sugars, the reaction may be performed at lower temperatures compared to when the feedstock is or includes aldose sugars. For example, in one variation, when the feedstock includes fructose, the reaction may be performed at a temperature of at least 15°C. In another variation, when the feedstock include glucose, the reaction is performed at a temperature of at least 115°C, and the reaction proceeds at lower [H ⁺ ], e.g. , less than 1 M. 5-(Halomethyl)furfural was unexpectedly observed to be produced with improved selectivity under such conditions (e.g. , lower [H ⁺ ]).

[0117] In some embodiments of the methods described herein, the reaction pressure is between 0.1 atm and 10 atm. In other embodiments, the reaction pressure is atmospheric pressure.

[0118] It should be understood that temperature may be expressed as degrees Celsius (°C) or Kelvin (K). One of ordinary skill in the art would be able to convert the temperature described herein from one unit to another. Pressure may also be expressed as gauge pressure (barg), which refers to the pressure in bars above ambient or atmospheric pressure. Pressure may also be expressed as bar, atmosphere (atm), pascal (Pa) or pound- force per square inch (psi). One of ordinary skill in the art would be able to convert the pressure described herein from one unit to another.

[0119] The reaction temperature and reaction pressure of the methods described herein may also be expressed as a relationship. For example, in one variation, at least a portion of the feedstock is converted into 5-(chloromethyl)furfural at a reaction temperature T expressed in Kelvin and a reaction pressure P expressed in psi, wherein 10 < Ln[P/(l psi)] + 2702/(T/(l K)) < 13. In another variation, at least a portion of the feedstock is converted into 5-(

chloromethyl)furfural at a reaction temperature and a reaction pressure in region A of FIG. 3.

[0120] The residence time will also vary with the reaction conditions and desired yield. Residence time refers to the average amount of time it takes to produce 5-(halomethyl)furfural from the feedstock in the reaction mixture. The methods described herein can produce 5- (halomethyl)furfural with residence times less than 360 minutes, less than 240 minutes, less than 120 minutes, less than 60 minutes, less than 30 minutes, less than 20 minutes, less than 10 minutes, less than 5 minutes, or less than 2 minutes. In one variation, at least 50%, at least 60%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or at least 99% of the feedstock is converted into 5-(chloromethyl)furfural in less than 12 hours. In another variation, at least 50% of the feedstock is converted into 5-(chloromethyl)furfural in less than 12 hours, less than 11 hours, less than 10 hours, less than 9 hours, less than 8 hours, less than 7 hours, less than 6 hours, less than 5 hours, less than 4 hours, less than 3 hours, less than 2 hours, less than 60 minutes, less than 45 minutes, less than 30 minutes, less than 20 minutes or less than 10 minutes.

[0121] In certain embodiments, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or at least 99% of the feedstock is converted to 5-(halomethyl)furfural at a reaction temperature of at least 140°C in 20 minutes or less. In certain embodiments, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or at least 99% of the feedstock is converted to 5- (halomethyl)furfural at a reaction temperature of at least 170°C in 10 minutes or less.

Isolation of 5-(Halomethyl)furfural

[0122] The converting of at least a portion of the feedstock in the reaction mixture produces a product mixture that has one or more aqueous phases and one or more organic phases. The aqueous phase(s) and the organic phase(s) each independently has at least a portion of 5- (halomethyl)furfural.

[0123] At the completion of the reaction, at least a portion of the 5-(halomethyl)furfural produced is soluble in the organic phase of the biphasic reaction mixture. At the reaction temperature, the 5-(halomethyl)furfural and the organic solvent (if used) form one organic phase. The organic phase is separated from the aqueous phase to isolate the product-containing phase, and then cooled to a temperature at which at least a portion of the 5-(halomethyl)furfural and the organic solvent forms multiple phases. The 5-(halomethyl)furfural can then be isolated from the organic phase. Thus, in some embodiments, the methods described herein further includes isolating the 5-(halomethyl)furfural from the reaction mixture.

[0124] The methods described herein may also include purifying the isolated 5- (halomethyl)furfural. Any suitable methods known in the art may be employed to purify the isolated 5-(halomethyl)furfural, including for example column chromatography or

recrystallization. Reactors and Vessels

[0125] The methods described herein may be carried out batch-wise or continuously. The production of 5-(halomethyl)furfural from the feedstock may be performed in any suitable reactors, including open or closed reactors, that can contain the chemical reactions described herein. Suitable reactors may include, for example, a fed-batch stirred reactor, a batch stirred reactor, a continuous flow stirred reactor, a continuous plug-flow column reactor, an attrition reactor, a fluidized bed reactor. The reactor may include a continuous mixer, such as a screw mixer.

[0126] Additionally, the reactor may allow for addition and removal of certain components in the reaction mixture. For example, the reactor can have one or more outlets to add additional solvent or acid, or to remove the organic or aqueous phase from the reaction mixture. In some embodiments, the reactor may have one or more outlets that connecting the reactor to an isolation vessel, where the organic phase can be transferred from the reactor to the isolation vessel.

[0127] The reactors and vessels used herein may be generally made up of materials that are capable of withstanding the physical and chemical forces exerted during the methods described herein. In some embodiments, such materials used are capable of tolerating high concentrations of strong liquid acids. For example, the reactors and vessels may be made up of glass, metal or pyrex.

5-(Halomethyl)furfural and Downstream Products

[0128] The 5-(halomethyl)furfural produced according to the methods described herein may be used in other chemical reactions, or further converted into other furanic derivatives for biofuels, diesel additives, or plastics.

[0129] In some embodiments, the 5-(halomethyl)furfural is 5-(chloromethyl)furfural (CMF). For example, CMF may be converted into dimethylfuran and ethoxymethylfurfural. In other embodiments, the 5-(halomethyl)furfural is 5-(bromomethyl)furfural (BMF).

[0130] In some aspects, provided is a method of producing an alkylfuran, comprising:

converting 5-(halomethyl)furfural produced according to any of the methods described herein into an alkylfuran. Any suitable methods known in the art may be employed for this reaction. In one variation, provided is a method of producing 2,5-dimethylfuran, by: converting 5- (chloromethyl)furfural (CMF) produced according to any of the methods described herein into 2,5-dimethylfuran (DMF).

[0131] The DMF can be further converted into para-xylene using any suitable methods known in the art. For example, DMF may be converted into p r -xylene by Diels-Alder cycloaddition of ethylene. See e.g. , U.S. Patent No. 8,314,267; WO 2009/110402. Thus, in certain aspects, provided is a method of producing p r -xylene, by: converting 5- (chloromethyl)furfural (CMF) produced according to any of the methods described herein into 2,5-dimethylfuran (DMF); and combining the DMF with ethylene in the presence of any suitable catalysts, and optionally solvent, to produce p r -xylene. In certain variations, any suitable catalysts and optionally solvent described in WO 2013/040514, US 2013/0245316, and WO 2014/043468 may be employed. For example, in one variation, provided is a method of producing p r -xylene, by: converting 5-(chloromethyl)furfural (CMF) produced according to any of the methods described herein into 2,5-dimethylfuran (DMF); and combining the DMF with ethylene in the presence of a catalyst, and optionally solvent, to produce p r -xylene.

[0132] The p r -xylene can be further oxidized to produce terephthalic acid. Any suitable methods to produce terephthalic acid from p r -xylene may be employed. Thus, in certain aspects, provided is a method of producing terephthalic acid, by: converting 5- (chloromethyl)furfural (CMF) produced according to any of the methods described herein into 2,5-dimethylfuran (DMF); combining the DMF with ethylene in the presence of any suitable catalysts, and optionally solvent, to produce p r -xylene; and oxidizing the p r -xylene to produce terephthalic acid.

[0133] The terephthalic acid is a precursor of polyethylene terephthalate (PET), which may be used to manufacture polyester fabrics. Any suitable methods to produce PET from terephthalic acid may be employed. Thus, in certain aspects, provided is a method of producing polyethylene terephthalate (PET), by: converting 5-(chloromethyl)furfural (CMF) produced according to any of the methods described herein into 2,5-dimethylfuran (DMF); combining the DMF with ethylene in the presence of any suitable catalysts, and optionally solvent, to produce p r -xylene; oxidizing the p r -xylene to produce terephthalic acid; and producing PET from the terephthalic acid. For example, in some variations, PET can be produced by polymerizing terephthalic acid and ethylene glycol to produce polyethylene terephthalate.

[0134] Further, one or more additional products may also be produced according to the methods described herein. For example, humins, levulinic acid, formic acid, furfural, gamma valerolactone, or fulvic acid, or any combinations or mixtures thereof, may be produced. It should generally be understood that the humins may include Hydro thermal Carbon (HTC). The methods described herein can reduce or minimize the amount of such additional product(s) present in the reaction mixture. For example, in some embodiments, the reaction mixture has less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, or less than 5% of the one or more additional products described above.

[0135] In some variations, less than 20%, less than 15%, less than 10%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% by weight of humins are produced relative to the amount of feedstock used. In other variations, less than3 0%, less than 20%, less than 15%, less than 10%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% by weight of levulinic acid is produced relative to the amount of feedstock used.

Yield, Conversion, Selectivity

[0136] The methods described herein produce 5-(halomethyl)furfural at commercially viable yields. The yield of a product takes into account the conversion of the starting materials into the product, and the selectivity for the product over other byproducts that may be formed.

[0137] The difference between yield, conversion and selectivity is explained in the examples provided below. For example, with respect to the conversion of glucose into 5- (halomethyl)furfural, the reaction can be generalized as follows, where "A" represents the moles of glucose; "B" represents the moles of 5-(halomethyl)furfural produced; and "a" and "b" are stoichiometric coefficients. aA — - bB.

[0138] Conversion of A is the percentage of reactant A that has been consumed during the reaction shown above, as expressed by the following equation:

where A ₀ is the initial number of moles of reactant A; and A _f is the final number of moles of reactant A.

[0139] Selectivity is the stoichiometrically relative amount of product B produced from the converted amount of reactant A, as expressed as a percentage by the following equation: Selectivity (%) =

where A ₀ is the starting moles of reactant A; A _f is the final number of moles of reactant A; and B _f is the number of moles of product B. In some embodiments where "a/b" = 1, and the equation can be simplified to:

Selectivity (%) = Ao™ i x 100%.

It should be understood, however, that depending on the type of feedstock used, the selectivity may be based on the total number of C6 monosaccharides or monomeric units having six carbons atoms.

[0140] The yield of product B is the percentage of reactant A that is converted into product B, as expressed by the following equation:

Yield (%) = [Conversion (%)] x [Selectivity (%)]

[0141] In certain embodiments, the methods described herein have a 5-(halomethyl)furfural yield of at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or at least 99% by weight. In other embodiments, the yield is between 10% to 100%, between 10% to 90%, between 20% to 80%, between 30% to 80%, between 40% to 80%, between 50%-80%, or between 60%-80% by weight.

[0142] In certain embodiments, the methods described herein have a 5-(halomethyl)furfural selectivity of at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 99%. In other embodiments, the selectivity is between 40% to 99%, between 40% to 95%, between 40% to 90%, between 40% to 80%, between 50% to 99%, between 50% to 95%, between 50% to 90%, between 50% to 80%, between 60% to 99%, between 60% to 95%, between 60% to 90%, between 60% to 80%, between 70% to 99%, between 70% to 95%, between 70% to 90%, or between 70% to 80%.

Compositions

[0143] Provided herein are also compositions that include any of the feedstocks, acids, and salts described herein. For example, in some aspects, provided is a composition that includes: a feedstock, an acid having a pKa greater than or equal to -8, and a salt. In certain aspects, provided is a composition that includes: feedstock, wherein the feedstock comprises C6 saccharides; an acid having a pKa greater than or equal to -8; lithium chloride or calcium chloride, or a combination thereof.

[0144] In some variations, the composition has a [H ⁺ ] less than 12 M. In certain variations, the composition has a [H ⁺ ] between 0.5 M and 9 M, and a [CI ] between 5M and 20 M.

[0145] It should be understood that that any description of the feedstocks, acids, and salts described herein for the methods may be applied to the compositions the same as if each and every combination were individually listed.

[0146] For example, in some embodiments, the composition has a [H ⁺ ] between 1 M and 6 M; between 1 M and 5 M; or between 2 M and 4 M. In some embodiments where 5- (chloromethyl)furfural is produced, the composition has a [CI ] of about 12 M. In some embodiments where 5-(bromomethyl)furfural is produced, the composition has a [Br ] of about 12 M.

[0147] The composition may further include a solvent system. The solvent system may include, for example, 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, as described above. In certain embodiments of the composition, the solvent system includes one or more linear alkyl benzenes as described herein. In one embodiment of the composition, the solvent system includes toluene, other alkyl benzenes (e.g. , Wibaryl ^® A, Wibaryl ^® B, Wibaryl ^® AB, Wibaryl ^® F, Wibaryl ^® R, Cepsa Petrepar ^® 550-Q, Cepsa Petrepar ^® 900-Q, Santovac ^® 5, Santovac ^® 7, Marlican®, Synnaph AB 3, Synnaph AB4), sulfolane, hexadecane, heptadecane, octadecane, icosane, heneicosane, docosane, tricosane, tetracosane, or any combinations or mixtures thereof.

[0148] In some embodiments of the composition, the feedstock is selected from corn stover, corn kernel, corn cob, 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, saw dust, saw dust pellets, forest thinnings, slash, miscanthus, switchgrass, sorghum, bagasse, whole cane, empty palm fruit bunches, palm frond, beet pulp, beet process rafinate, manure, wastewater biosolids, green waste, agriculture residues, and food or feed processing residues, or any combinations thereof. [0149] The composition may further include one or more additional compounds. For example, the compositions may further include humins, levulinic acid, formic acid, furfural, gamma valerolactone, or fulvic acid, or any combinations or mixtures thereof. In certain embodiments, the composition has less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, or less than 5% of the one or more additional compounds described above.

[0150] It should be understood that reference to "about" a value or parameter herein includes (and describes) embodiments that are directed to that value or parameter per se. For example, description referring to "about x" includes description of "x" per se. In other instances, the term "about" when used in association with other measurements, or used to modify a value, a unit, a constant, or a range of values, refers to variations of +/- 5%.

[0151] It should also be understood that reference to "between" two values or parameters herein includes (and describes) embodiments that include those two values or parameters per se. For example, description referring to "between x and y" includes description of "x" and "y" per se.

ENUMERATED EMBODIMENTS

[0152] The following enumerated embodiments are representative of some aspects of the invention.

1. A method for producing 5-(halomethyl)furfural, comprising:

a) combining a feedstock, an acid, and a salt in a reaction vessel to form a reaction mixture, wherein:

the acid has a pKa greater than or equal to -8;

the salt is A ^r+ (X ^" ) _r , wherein:

A ^r+ is a Group I or Group II cation, and

X ^" is a halo anion; and

b) producing 5-(halomethyl)furfural from at least a portion of the feedstock in the reaction mixture.

2. A method for producing a 5-(halomethyl)furfural, comprising:

a) combining a feedstock, an acid and a salt, wherein:

the salt is A ^r+ (X ^" ) _r , wherein: A ^r is a Group I or Group II cation, and

X ^" is a halo anion;

b) producing the 5-(halomethyl)furfural and water from at least a portion of the feedstock, wherein the feedstock, the acid, the salt, the 5-(halomethyl)furfural and the water form a mixture; and

c) distilling the mixture to remove at least a portion of the water in the mixture, wherein the distilling minimizes loss of the acid in the mixture.

3. A method for producing a 5-(halomethyl)furfural, comprising:

a) combining a feedstock, an acid and a salt, wherein:

the salt is A ^r+ (X ^" ) _r , wherein:

A ^r+ is a Group I or Group II cation, and

X ^" is a halo anion;

b) producing the 5-(halomethyl)furfural and water from at least a portion of the feedstock, wherein the feedstock, the acid, the salt, the 5-(halomethyl)furfural and the water form a mixture; and

c) distilling the mixture to remove at least a portion of the water in the mixture before removal of acid in the mixture.

4. The method of any one of embodiments 1 to 3, further comprising isolating the 5- (halomethyl)furfural produced.

5. The method of any one of embodiments 1 to 4, wherein the acid has a pKa greater than or equal to -5, or greater than or equal to 0, or between -8 and 10.

6. The method of any one of embodiments 1 to 4, wherein the acid is selected from the group consisting of trifluoroacetic, oxalic acid, phosphoric acid, chloroacetic acid, salicylic acid, fumaric acid, citric acid, malic acid, formic acid, lactic acid, acrylic acid, sebacic acid, acetic acid, levulinic acid, carbonic acid, boric acid, and ammonium chloride, or any combinations thereof.

7. The method of any one of embodiments 1 to 4, wherein the acid is phosphoric acid or acetic acid, or a combination thereof.

8. The method of any one of embodiments 1 to 7, wherein the acid is added continuously. 9. The method of any one of embodiments 1 to 8, wherein A ^r is Li , Na , K , Rb , Cs , Mg ²⁺ , Ca ²⁺ , or Sr ²⁺ .

10. The method of embodiment 9, wherein A ^r+ is Li ⁺ or Ca ²⁺ .

11. The method of any one of embodiments 1 to 10, wherein the reaction mixture has a [H ⁺ ] less than 12 M.

12. The method of any one of embodiments 1 to 10, wherein the reaction mixture has a [H ⁺ ] less than or equal to 5 M.

13. The method of any one of embodiments 1 to 10, wherein the reaction mixture has a [H ⁺ ] less than or equal to 1 M.

14. The method of any one of embodiments 1 to 13, wherein the reaction mixture has a [X ] of at least 5 M.

15. The method of any one of embodiments 1 to 10, wherein the reaction mixture has:

a [H ⁺ ] less than or equal to 8 M; and

a [X ] of at least 5M.

16. The method of any one of embodiments 1 to 10, wherein the reaction mixture has:

a [H ⁺ ] less than or equal to 8 M; and

a [XT] of at least 10 M.

17. The method of any one of embodiments 1 to 16, wherein the 5-(halomethyl)furfural is produced at a temperature of at least 115°C.

18. The method of embodiment 17, wherein the reaction mixture has a [H ⁺ ] less than or equal to 0.6 M.

19. The method of any one of embodiments 1 to 10, wherein the feedstock and the [H ⁺ ] is present in the reaction mixture at a molar ratio of 1 : 1.

20. The method of any one of embodiments 1 to 10, wherein the reaction mixture has a [H ⁺ ] between the feedstock concentration and 5 M.

21. The method of embodiment 20, wherein the 5-(halomethyl)furfural is produced at a temperature of at least 110°C.

22. The method of any one of embodiments 1 to 10, wherein:

the reaction mixture has a [H ⁺ ] between the feedstock concentration and 2 M; and the 5-(halomethyl)furfural is produced at a temperature of at least 135°C.

23. The method of any one of embodiments 1 to 10, wherein the reaction mixture has a [H ⁺ ] between 0.1 times the feedstock concentration and 5M.

24. The method of any one of embodiments 1 to 23, wherein the feedstock, acid, and salt are further combined with additional salt, wherein the additional salt is a silicate salt, a carbonate salt, a sulfate salt, a sulfide salt, a phosphate salt, a perchlorate salt, or a triflate salt.

25. The method of embodiment 24, wherein the triflate salt is lithium triflate or sodium triflate.

26. The method of any one of the preceding embodiments, wherein the feedstock, the acid and the salt are further combined with a solvent system.

27. The method of embodiment 26, wherein the solvent system comprises polar aprotic solvents.

28. The method of embodiment 26, wherein the solvent system comprises dimethylsulfoxide, tetrahydrofuran, methyl tetrahydrofuran, or acetronitrile, or any combinations or mixtures thereof.

29. The method of embodiment 26, wherein the solvent system 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.

30. The method of embodiment 26, wherein the solvent system comprises one or more linear alkyl benzenes.

31. The method of embodiment 26, wherein the solvent system comprises p r -xylene, mesitylene, naphthalene, anthracene, toluene, dodecylbenzene, pentylbenzene, hexylbenzene, sulfolane, hexadecane, heptadecane, octadecane, icosane, heneicosane, docosane, tricosane, tetracosane, or any combinations or mixtures thereof.

32. The method of embodiment 26, wherein the solvent system comprises one or more phenyl ether solvents.

33. The method of any one of embodiments 1 to 32, wherein the feedstock comprises an aldose, or any polymers thereof.

34. The method of any one of embodiments 1 to 32, wherein the feedstock comprises glucose, glucans, starch, sucrose, cellulose, or hemicellulose, or any combinations thereof. 35. The method of any one of embodiments 1 to 32, wherein the feedstock comprises glucans, starch, cellulose, or hemicellulose, or any combinations thereof.

36. The method of any one of embodiments 1 to 32, 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.

37. The method of any one of embodiments 1 to 32, 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, or any combinations thereof.

38. The method of any one of the preceding embodiments, wherein the acid is produced in situ.

39. The method of any one of the preceding embodiments, wherein the salt is produced in situ.

40. The method of any one of the preceding embodiments, wherein the 5- (halomethyl)furfural is produced at a temperature of at least 80°C, at least 110°C, or at least 115°C.

41. The method of any one of the preceding embodiments, wherein the 5- (halomethyl)furfural is 5-(chloromethyl)furfural (CMF).

42. The method of any one of the preceding embodiments, wherein the 5- (halomethyl)furfural is 5-(bromomethyl)furfural (BMF).

EXAMPLES

[0153] The following Examples are merely illustrative and are not meant to limit any aspects of the present disclosure in any way. Example 1

Synthesis of 5-(Chloromethyl)furfural

[0154] This example demonstrates the synthesis of 5-(chloromethyl)furfural from glucose using phosphoric acid.

[0155] To a 100 ml volumetric flask was added 93.15 ml of 12 M LiCl, and 6.85 ml of 85% wt/wt phosphoric acid. To a 500 ml round bottom pressure vessel was added 4.0052

g of glucose 40 ml of 1 M Phosphoric acid 11.2 M LiCl aqueous just made. The reaction mixture was allowed to stir for 10 minutes, and glucose was observed to be dissolved. 80 ml of toluene was then added. The reaction vessel was heated to 135°C in a 150°C oil bath for 16

minutes. After 16 minutes, the reaction vessel was cooled to 40-50°C and the reaction mixture filtered using a glass fritted funnel and 1.6 micron glass fiber filter paper. The filter cake obtained is a resin, which was washed with 150 ml of toluene. The resin is made up of

Hydrothermal Carbon (HTC), which is also known in the art as humins. The catch flask was removed, and the resin was washed with 250 ml of deionized (DI) water, which was then put into a 500 ml volumetric flask. After filtration, the filtrate was put into a separatory funnel, and the aqueous was removed and set aside. The organic was put into 500 ml volumetric flask. The aqueous was put back into the separatory funnel and washed with 60-80 ml of toluene. The aqueous was then removed and 1 ml was submitted to titration for H ⁺ , and the rest was combined with the 150 ml water wash into the 500 ml voluemtric flask. The aqueous and water wash were then diluted to the 500 ml line with DI water. The toluene wash from the separatory flask was then put into the 500 ml volumetric flask with the organic from the reaction and diluted with toluene until the 500 ml line was reached. The glass filter was dried in an oven for 3 days, and the dry mass was obtained.

[0156] The following samples from this example were further analyzed by GC-FID (to identify furfural and CMF), HPLC (to identify levulinic acid and glucose) and gravimetrically (to identify the resin): (1) the organic phase diluted in toluene combined with the toluene obtained from the resin wash, and (2) the aqueous phase diluted in water combined with the water obtained from the resin wash. Table 1 below summarizes the results of this example. Table 1.

Example 2

Synthesis of 5-(Chloromethyl)furfural

[0157] This example demonstrates the synthesis of 5-(chloromethyl)furfural from glucose using acetic acid.

[0158] To a 500 ml round bottom pressure vessel was added 4.0456 g of glucose 40 ml of 4 M acetic acid, and an aqueous solution of 5.1 M Ca ²⁺ and 10.2 M CI ^" . The reaction mixture was allowed to stir for 10 minutes, and the glucose was observed to dissolve. 80 mL of toluene was then added. The reaction vessel was heated to 135°C in a 150°C oil bath for 40 minutes. After 40 minutes, the reaction vessel was cooled to 40-50°C and filtered using a glass fritted funnel and 1.6 micron glass fiber filter paper. The filter cake (resin) was washed with 150 ml of toluene. The resin is made up of Hydrothermal Carbon (HTC), which is also known in the art as humins. The catch flask was removed, and the resin was washed with 250 ml of deionized (DI) water, which was then put into a 500 ml volumetric flask. After filtration, the filtrate was put into a separatory funnel and the aqueous phase was removed and set aside. The organic phase was put into 500 ml volumetric flask and fitted with a glass stopper. The aqueous phase was put back into the separatory funnel and washed with 60-80 ml of toluene. The aqueous phase was then removed and 1 ml was collected for H ⁺ concentration determination, and the rest was combined with the 250 ml water wash into the 500 ml volumetric flask. The aqueous phase and water wash were then diluted to the 500 ml line with DI water. The toluene wash from the separatory flask was then put into the 500 ml volumetric flask with the organic from the reaction and diluted with toluene until the 500 ml line was reached. The glass filter was dried in an oven for 3 days and the dry mass was obtained.

[0159] The following samples from this example were further analyzed by GC-FID (to identify furfural and CMF) and HPLC (to identify levulinic acid and glucose): (1) the organic phase diluted in toluene combined with the toluene obtained from the resin wash, and (2) the aqueous phase diluted in water combined with the water obtained from the resin wash. Table 2 below summarizes the results of this example.

Table 2.