METHODS FOR CONVERSION OF CARBOHYDRATES IN IONIC LIQUIDS TO VALUE-ADDED CHEMICALS

Abstract

Methods are described for converting carbohydrates including, e.g., monosaccharides, disaccharides, and polysaccharides in ionic liquids to value-added chemicals including furans, useful as chemical intermediates and/or feedstocks. Fructose is converted to 5-hydroxylmethylfurfural (HMF) in the presence of metal halide and acid catalysts. Glucose is effectively converted to HMF in the presence of chromium chloride catalysts. Yields of up to about 70% are achieved with low levels of impurities such as levulinic acid.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 (Prior Art) illustrates a process for conversion of carbohydrates to HMF by conventional acid catalyzed dehydration.

FIG. 2 illustrates a reaction process for conversion of fructose to HMF in an exemplary ionic liquid, with added metal halide catalysts to promote desired chemistry, according to embodiments of the process of the invention.

FIG. 3 illustrates a reaction process for conversion of glucose to HMF in an exemplary ionic liquid, with added CrCl₂ metal halide catalyst to promote desired chemistry, according to another embodiment of the process of the invention.

FIG. 4 is a plot comparing conversion results for fructose and glucose to HMF as a function of temperature, according to different embodiments of the process of the invention.

FIG. 5 is a plot showing conversion results for fructose in an exemplary ionic liquid treated with various metal halide catalysts, according to different embodiments of the process of the invention.

FIG. 6 is a plot showing conversion results for glucose in an exemplary ionic liquid treated with various metal halide catalysts, according to different embodiments of the process of the invention.

FIG. 7 is a plot showing conversion results for glucose as a function of time in an exemplary ionic liquid treated with CrCl₂, CuCl₂, and FeCl₂ metal halide catalysts.

FIG. 8 is a plot presenting conversion results for glucose in an exemplary ionic liquid treated with CrCl₂ metal halide catalyst, according to a preferred embodiment of the process of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The term “Imidazoles” as used herein refers to the class of heterocyclic aromatic compounds of general structural formula [A]:

where R represents functional groups as will be understood by those of skill in the chemical art.

The term “Imidazole” [CAS No. 288-32-4] [Mol. Wt.: 68.08] as used herein refers to the chemical compound of chemical formula (C₃H₄N₂) having general structural formula [B]:

The term “Imidazolium” as used herein refers to the cationic portion of ion-forming salts from the imidazole class of organic compounds, having general structural formula [C]:

where R₁ and R₂ are alkyl groups of formula (C_xH_2x+1) where X=1 to 18.

The terms “Furans” and “a Furan” as used herein refer to compounds from the class of heterocyclic organic compounds having general structural formula [D1] and [D2]:

where R₁, R₂, R₃, and R₄ are functional groups including, e.g., H or C; C may further include O and/or H, defining, e.g., aldehyde or alcohol functional groups. “Furan” [CAS Number 110-00-9] (C₄H₄O) is included in this class of compounds having structural formula [D1], where R₁ and R₂ are H.

The term “Sugar Alcohols” as used herein refers to compounds of chemical formula [C_nH_2n+2O_n] where n=1, 2, 3, etc. General structural formulas for representative 5-carbon and 6-carbon sugar alcohols are illustrated in [E1] and [E2]:

The term “Anhydro sugar alcohols” as used herein refers to compounds having general structural formula [F1] and [F2]:

The term “Dianhydrosugar alcohols” as used herein refers to compounds having general structural formula [G]:

While preceding compounds have been illustrated using generalized structures, no limitation to specific stereoisomers is implied.

Abbreviation nomenclature used herein to denote ionic liquids identifies the cationic portion of the ionic liquid, e.g., 1-ethyl-3-methyl-imidazolium, by bracket, e.g., [EMIM] or [EMIM]⁺. The anionic portion of the ionic liquid, e.g., chloride (Cl or Cl⁻) is identified by placement outside the bracket (e.g., [EMIM]Cl or [EMIM]⁺Cl⁻). Unless otherwise noted, nomenclature for ionic liquids with or without ionic charges are used interchangeably, e.g., [EMIM]⁺Cl⁻ or [EMIM]Cl.

The term “triflates” has reference to chemical compounds that include a trifluoromethanesulfonate functional group (CF₃SO₃⁻) or a corresponding acid conjugate (CF₃SO₃H).

The term “Selectivity” as used herein is defined by equation [1]:

$\begin{array}{cc}\mathrm{Selectivity}=\left(\frac{\mathrm{Moles}\mathrm{Product}\mathrm{Formed}}{\mathrm{Moles}\mathrm{Starting}\mathrm{Material}\mathrm{Reacted}}\right)& \left[1\right]\end{array}$

The term “Conversion” as used herein is defined by equation [2]:

$\begin{array}{cc}\mathrm{Conversion}=1-\left(\frac{\mathrm{Moles}\mathrm{Unreacted}\mathrm{Starting}\mathrm{Material}}{\mathrm{Moles}\mathrm{Starting}\mathrm{Material}}\right)& \left[2\right]\end{array}$

The term “Yield” as used herein is defined by equation [3]:

$\begin{array}{cc}\mathrm{Yield}=\left(\frac{\mathrm{Moles}\mathrm{Product}\mathrm{Formed}}{\mathrm{Moles}\mathrm{Starting}\mathrm{Material}}\right)& \left[3\right]\end{array}$

Ionic Liquids

Ionic liquids (IL) suitable for use as solvents in conjunction with the invention provide solubility to the carbohydrates selected for conversion therein. Properties of the ionic liquid solvents vary according to the cationic, alkyl, and anionic group constituents of the liquids. Preferred ionic liquids include salts of the 1-R₁-3-R₂-imidazolium class of compounds, where R₁ and R₂ are alkyl groups of formula (C_xH_2x+1) where X=1 to 18, further including a stoichiometric quantity of a selected anion. In these ionic liquids, the cationic portion (or cation) of the ionic liquid includes a 5-member imidazolium ring and alkyl groups R₁ and R₂. The anionic portion (or anion) of the ionic liquid can vary. Anions include, but are not limited to, e.g., halides including, e.g., chloride (Cl⁻), bromide (Br⁻), and iodide (I⁻); halogen-free anions, including, e.g., sulfates, sulfonates (e.g., alkyl sulfonates), phosphates, acetates, and triflates (e.g., alkyl triflates); hexafluorophosphates (PF₆⁻); tetrafluoroborates (BF₄⁻); hexafluoroborates (BF₆—); and aluminum chloride (AlCl₄⁻). Other ionic liquids suitable for use include pyridinium salts (e.g., N-alkylpyridinium salts), phosphonium salts (e.g., P,P,P,P-tetraalkylphosphonium salts), and tetralkylammonium salts (e.g., N,N,N,N-tetraalkylammonium salts) that include a stoichiometric quantity of a suitable anion, described herein.

Ionic liquids can contain impurities that are catalytic. In an illustrative example, reactivity of a carbohydrate in an “as-received” [EMIM]CH₃SO₃ ionic liquid had high activity due to presence of contaminants and/or impurities in the ionic liquid. However, when the “as-received” ionic liquid was purified to remove contaminants and/or impurities, reactivity of the carbohydrate was negligible. In general, at low reaction temperatures, catalysts are required for conversion of carbohydrates in ionic liquids.

Conversion of fructose to HMF is demonstrated using three exemplary [AMIM]Cl ionic liquid solvent systems, where A is an alkyl group, including, but not limited to, e.g., ethyl, butyl, octyl, and the like. Corresponding ionic liquids are: 1-ethyl-3-methylimidazolium [EMIM]Cl; 1-butyl-3-methylimidazolium chloride [BMIM]Cl; and 1-octyl-3-methylimidazolium chloride [OMIM]Cl, but is not limited thereto. These ionic liquids are preferred ionic liquid (IL) solvent systems for conversion of carbohydrates to versatile chemicals at high yields, including, e.g., 5-hydroxymethylfurfural (HMF).

In one process, according to an embodiment of the invention, fructose is converted in the presence of metal halide catalysts to HMF at high yields. In another process, fructose is converted to HMF at selected reaction temperatures in the absence of any added catalyst. In another process, fructose is converted in the presence of a mineral acid to HMF at high yields.

Conversion of 6-Carbon Sugars

Conversion of 6-C sugars (e.g., glucose and fructose) to HMF in ionic liquids has been demonstrated.

FIG. 2 illustrates a reaction process for conversion of fructose to HMF in an exemplary ionic liquid, [EMIM]Cl, with metal halide catalysts or acid catalysts added to promote desired chemistry. While the furanose form of fructose is illustrated in the figure, other forms of fructose (e.g., pyranose forms) are equally converted. Thus, no limitations are intended.

In a preferred embodiment, in the ionic liquid [EMIM]Cl, reaction time and reaction temperature is about 1 h to 3 h at about 80° C., but is not limited thereto. For example, reaction times and reaction temperatures may be selected in the range from about 0.01 minutes at 400° C. to about 12 h at 80° C. Alternatively, reaction times and reaction temperatures may be selected in the range from about 0.01 minutes at 250° C. to about 8 h at 80° C.

In other ionic liquids, the melting point is lower, allowing for a lower reaction temperature. For example, [EMIM]CH₃SO₃ is a liquid at room temperature. Reaction times and reaction temperatures may be selected at between about 20 h at 20° C. and from about 0.01 minutes at 250° C.

Continued processing of product furans may lead to formation polymeric products that are easily separated from products of interest.

FIG. 3 illustrates a reaction process for conversion of glucose to HMF in an exemplary ionic liquid, e.g., ([EMIM]Cl), with CrCl₂ metal halide catalyst added, according to another embodiment of the process of the invention. As illustrated in the figure, in the ionic liquid treated with CrCl₂ metal halide catalyst, conversion of glucose to HMF occurs.

In a preferred embodiment, a reaction time and a reaction temperature are 3 h at about 100° C. are used, but is not limited thereto. For example, reaction temperatures and reaction times may be selected in the range from 1 minute to about 20 minutes at 150° C. or about 0.01 minutes at 250° C.; or 0.01 minutes at about 400° C.

In other embodiments, hydrolysis of cellulose to glucose, dehydration of glucose to HMF has been demonstrated. In a preferred embodiment, a reaction time and a reaction temperature of

In a preferred embodiment, a reaction time and reaction temperature are 0.5 h at about 140° C. is used, but is not limited thereto. For example, reaction temperatures and reaction times may be selected in the range from about 5 minutes and about 200° C.; or about 0.1 minutes at about 250° C.; or about 0.01 minutes at about 400° C.

FIG. 4 is a histogram that compares conversion results for fructose and glucose to HMF as a function of temperature in an exemplary ionic liquid, [EMIM]Cl, with no added catalyst. As shown in the figure, at sufficiently high temperatures, fructose is converted to HMF, with yields that decrease in the temperature range between about 120° C. and about 80° C. In contrast, glucose does not produce any significant quantity of HMF, even at 180° C. When water is added to the solvent ([EMIM]Cl) at a ratio of about 5:1, glucose is effectively inert.

A wide range of metal halide catalysts can be added to increase yields of desired end products. Fructose, for example, is rapidly converted to HMF in ionic liquids treated with metal halide catalysts. The catalysts provide efficient conversion. In such reactions, a very low quantity of levulinic acid impurity is formed, typically below about 1% and more particularly below about 0.1%.

In yet other processes, high yields of HMF are obtained from conversion of glucose in ionic liquids with a metal halide catalyst added. Chromium chlorides (e.g., CrCl₂ and CrCl₃) are uniquely effective catalysts for selective conversion of glucose to HMF, providing yields of greater than or equal to about 70%, described further herein.

In still yet other embodiments, HMF is produced from conversion of complex biomass materials, including e.g., cellulose in ionic liquid solvents Yields of approximately 50% are obtained.

While the exact mechanism for action of metal halide catalysts is unknown in these processes, at catalytic quantities of catalyst (e.g., 0.5% by weight), the ionic liquid solvent is believed to employ an equimolar amount of ionic liquid (e.g., [EMIM]Cl) and the associated metal halide. For purposes of illustration, addition of CrCl₂ in the ionic liquid [EMIM]Cl proceeds as denoted in equation [4]:

[EMIM]⁺Cl⁻+CrCl₂→[EMIM]⁺CrCl₃⁻  [4]

Experiments Demonstrating Conversion of Fructose to HMF in Ionic Liquids Treated with Metal Halide Catalysts

Fructose conversion in ionic liquids treated with and without addition of a catalyst demonstrates broad applicability and advantages of the processes of the invention described herein. For example, fructose can be selectively dehydrated to 5-hydroxymethylfurfural (HMF) with low yields of levulinic acid if treated with metal halide catalysts, described further hereafter.

Catalysts. Metal halide catalysts were tested using a high pressure reactor (e.g., a Symyx® high pressure reactor system equipped with a heated orbital shaker, Symyx Technologies Inc., Santa Clara, Calif., USA), but is not limited thereto. Ionic liquids and selected catalysts and were to reaction vials by mass. Vials were shaken at 700 rpm and heated at 150° C. between about 10 min. and 30 min. (0.5 h) to mix ionic liquid and catalyst.

Protocol. Fructose was added to reaction vials and introduced to the reactor. The reactor was purged at room temperature with N₂ or air, heated to an operating temperature of 80° C., and shaken at 700 rpm for 3 h, before cooling and venting.

Sample Analysis. 500 μL of water was added to each reaction vial followed by centrifugation at 3000 rpm for 30 min. Samples were then diluted with water by a factor of two for analysis by high pressure liquid chromatography (HPLC). For initial analyses, samples were injected onto an Aminex Fast Acid column and analyzed by refractive index on an Agilent 1100 series HPLC using a flow rate of 1 mL/min, column temperature of 60° C., and a 0.005M H₂SO₄ mobile phase. Select samples were chosen from the primary HPLC screen for a secondary HPLC analysis on a long column (e.g., an Aminex® model HPX-87H, 7.8 mm×300 mm, 9 μm particle size, column available commercially from Bio-Rad Laboratories, Richmond, Calif., USA) at a flow rate of 0.55 mL/min, a temperature of 60° C., and a 0.005M H₂SO₄ mobile phase. HPLC results were recorded and used to calculate feed conversion percentages, product selectivity, and molar balances. Catalysts were also ranked for effectiveness. Preferred catalysts, for example, exhibited high conversion and good selectivity yields to HMF.

FIG. 5 is a histogram showing conversion results for fructose in an exemplary ionic liquid treated with various metal halide catalysts, according to different embodiments of the process of the invention. In the figure, metal halide catalysts included: CrCl₂, CrCl₃, FeCl₂, FeCl₃, CuCl, CuCl₂, VCl₃, MoCl₃, PdCl₂, PtCl₂, PtCl₄, RuCl₃, or RhCl₃. As shown, dehydration of fructose to HMF is catalyzed by many metal halide catalysts and mineral acids, e.g., sulfuric acid, (H₂SO₄). Two metal halides were ineffective, i.e., LaCl₃, and MnCl₂. Alkali metal halides (e.g., NaCl, and LiCl) were also ineffective. HMF yields from conversion of fructose ranged from about 63% to about 83% at reaction times of about 3 h at 80° C. Product mixtures were very clean, as evidenced by NMR analysis. For example, yields of levulinic acid and α-angelicalactone were low, typically less than about 0.1%.

Conversion of Glucose to HMF

Conversion experiments for fructose were repeated using glucose as a feed material. Temperature was raised to 100° C. due to a lower expected reactivity of glucose relative to fructose.

FIG. 6 is a histogram showing conversion results for glucose in an exemplary ionic liquid, [EMIM]Cl, pretreated with various metal halide catalysts. As shown in the figure, Glucose conversion was high for many of the metal halide catalysts tested, including AlCl₃, FeCl₃, CuCl₂, CuCl, VCl₃, MoCl₃, PtCl₂, PtCl₄, RuCl₃, and RhCl₃. These metal halides showed a conversion of glucose of 40% or greater. However, HMF yields were low. HMF yields from conversion of glucose were also low using acids (e.g., H₂SO₄) as catalysts. One catalyst, CrCl₂, gave HMF yields of 68-70%, a previously elusive efficiency for conversion of glucose. HMF yields for ionic liquid solvent systems not containing CrCl₂ or CrCl₃ were on the order of 10%. HMF yields could not be accounted for by product instability under reaction conditions. Results indicate that high conversion of glucose is achieved with various metal halide catalysts, in many ionic liquid systems. However, low product yields suggest these metal halides catalyze undesired reaction pathways.

Conversion of Glucose in Ionic Liquid Containing Metal Halide Catalysts CrCl₂, CuCl₂, and FeCl₂

In additional experiments, conversion of glucose was tested for three specific catalysts, CrCl₂, CuCl₂, and FeCl₂, at 100° C. To ensure uniform catalyst loading, each catalyst-ionic liquid mixture was prepared in a single batch and then added to the reaction vial (500 mg aliquots) containing glucose (50 mg). Following reaction times at selected reaction temperatures, samples were analyzed by HPLC.

FIG. 7 plots glucose conversion (mol %) in [EMIM]Cl ionic liquid treated with each of three metal halide catalysts, i.e., CrCl₂, CuCl₂, and FeCl₂, respectively, as a function of time. Glucose conversion is highest in ionic liquid containing CrCl₂. Glucose is reactive in ionic liquid containing CuCl₂, but does not provide a high yield of HMF. In ionic liquid containing FeCl₂, glucose shows essentially no reactivity. Results suggest chemistry for conversion of the carbohydrate differs for each of the metal halide catalysts tested. Effectiveness of CrCl₂ catalyst for conversion of glucose to HMF was unexpected.

FIG. 8 is a histogram showing results for conversion of glucose in two exemplary ionic liquids, [EMIM]Cl and [BMIM]Cl, treated with a preferred metal halide catalyst, CrCl₂. As shown in the figure, conversion of glucose is greater than 90% (mole basis), with yields of HMF of about 68% (in [EMIM]Cl) and 60% (in [BMIM]Cl), respectively.

Conversion of Cellulose

Conversion of cellulose in an ionic liquid is described hereafter optionally in conjunction with a catalyst. Ionic liquids catalyze all, or a majority, of the chain of necessary reactions, including, e.g., decrystallization, hydrolysis, and/or dehydration, yielding the desired conversion products. For example, hydrolysis of cellulose in ionic liquids that yields simple sugars including HMF with low yields of levulinic acid was an unexpected result. And, use of additional acids is not required for dehydration to occur. Further, conversion of cellulose and other complex carbohydrates in ionic liquids exhibits high selectivity to desired value-added products. Cellulose can also be converted selectively to other products in different ionic liquids systems. Thus, by appropriate selection of ionic liquid, product can be selectively tuned. Conversion in ionic liquids is applicable to conversion of other carbohydrates and polysaccharides including starch. Thus, the disclosure is not intended to be limited to exemplary embodiments and exemplary carbohydrates described herein.

Following examples provide a further understanding of the invention

EXAMPLE 1

Conversion of Fructose to HMF in [EMIM]Cl

Metal Halide or Acid Catalyst

Fructose (99.9%) was supplied by Mallinckrodt. [EMIM]Cl (99%) was supplied by Solvent-Innovation (GmbH, Cologne, GE). Metal halide catalysts were CuCl, CuCl₂, CuBr₂, MOCl₃, FeCl₂, FeCl₃, CrCl₂, CrCl₃, VCl₃, AlCl₃, MnCl₃, PdCl₂, PtCl₂, PtCl₄, RuCl₃, RhCl₃ were supplied by Sigma-Aldrich (St. Louis, Mo., USA) Acid catalyst was H₂SO₄, supplied by Sigma-Aldrich (St. Louis, Mo., USA). 500 mg [EMIM]Cl was loaded into reaction vials. Metal halide catalysts were added to respective vials at a concentration of ˜6 mol % with respect to fructose. 2 mg CrCl₂ was added to its reaction vial. Vials were installed into the high pressure reactor, heated at 150° C. and shaken at 700 rpm to mix contents. After cooling, 50 mg fructose was added to each vial and heated at 80° C. for 3 h. After cooling, 2.0 mL of water was added for analysis by HPLC. Results are presented in TABLE 1 (see FIG. 5).

TABLE 1
Conversion of Fructose to HMF, and product yields.
			Feedstock	Product
Example	Feedstock	Catalyst	conversion (%)	yields (%)*
1.1	Fructose	None	10.92	HMF: 1.36
1.2	Fructose	CuCl	91.25	HMF: 78.81
1.3	Fructose	CuCl2	99.54	HMF: 76.02
1.4	Fructose	CuBr2	99.59	HMF: 77.48
1.5	Fructose	MoCl3	98.67	HMF: 70.88
1.6	Fructose	FeCl2	76.40	HMF: 63.15
1.7	Fructose	FeCl3	99.80	HMF: 77.08
1.8	Fructose	CrCl2	95.32	HMF: 65.26
1.9	Fructose	CrCl3	95.41	HMF: 69.28
1.10	Fructose	VCl3	100.00	HMF: 77.03
1.11	Fructose	AlCl3	99.00	HMF: 76.00
1.12	Fructose	MnCl3	10.22	HMF: 5.02
1.13	Fructose	PdCl2	92.00	HMF: 77.00
1.14	Fructose	PtCl2	99.00	HMF: 83.00
1.15	Fructose	PtCl4	99.00	HMF: 80.00
1.16	Fructose	RuCl3	98.00	HMF: 79.00
1.17	Fructose	RhCl3	99.00	HMF: 83.00
1.18	Fructose	H2SO4	99.00	HMF: 80.00
*Yields of levulinic acid and α-angelicalactone were less than 0.1% for all experiments.

EXAMPLE 2

Conversion of Fructose to HMF in Alternate Ionic Liquids

Metal Halide or Acid Catalyst

Fructose was processed as in Example 1 in various ionic liquids containing a metal halide or acid catalyst. Ionic liquids were [EMIM]CH₃SO₃ (Solvent-Innovations, GmbH, Cologne, GE); tetrabutylammonium chloride (Fluka-Sigma-Aldrich, Steinheim, GE); tetrabutylphosphonium chloride (ionic Liquid Technologies, GmbH, Denzlingen, GE); 1,2,4-trimethylpyrazolium methyl sulfate (Fluka-Sigma-Aldrich, Steinheim, GE). [EMIM]CH₃SO₃, tetrabutylphosphonium chloride, and 1,2,4-trimethylpyrazolium methyl sulfate each contained a catalytic quantity of acid. Results are presented in TABLE 2.

TABLE 2
Conversion of Fructose to HMF, and product yields.
			Feedstock	Product
		Ionic Liquid (IL)	conversion	Yields
Example	Feedstock	and Catalyst	(%)	(%)
2.1	Fructose	IL: [EMIM]CH3SO3;	99.6	HMF: 86.5
		Catalyst: acid
2.2	Fructose	IL: tetrabutylammonium chloride;	—	HMF: 59.1
		Catalyst: VCl3
2.3	Fructose	IL: tetrabutylphosphonium chloride;	—	HMF: 65.2
		Catalyst: acid
2.4	Fructose	IL: 1,2,4-trimethylpyrazolium methyl	—	HMF: 52.1
		sulfate;
		Catalyst: acid

EXAMPLE 3

Carbohydrate Reactivity in “As-Received” and Purified Ionic Liquid

Carbohydrate reactivity was compared in both “as-received” (as purchased) and purified ionic liquid. Fructose was processed as in Example 1 in 99% [EMIM]CH₃SO₃ (Solvent-Innovation, GmbH, Cologne, GE) in both the “as-received” ionic liquid and the ionic liquid purified with basic alumina to remove any contaminants (e.g., methane sulfonic acid). Reaction time and temperature was 3 h at 80° C. Conversion of fructose in the “as-received” ionic liquid was 99.9%; yield of HMF was 83.9%. Conversion of fructose in purified ionic liquid was 0%; yield of HMF was 0%. Results demonstrate that some impurities present in ionic liquids (e.g., as purchased) are sufficient to catalyze reaction of carbohydrates. When purified, the ionic liquid does not exhibit reactivity at the same temperature.

EXAMPLE 4

Conversion of Fructose to HMF in [EMIM]CH₃SO₃

Acid Catalyst

Fructose was processed as in Example 1 in (99%) [EMIM]CH₃SO₃ (Solvent-Innovation, GmbH, Cologne, GE) ionic liquid, containing a catalytic quantity of CH₃SO₃. Liquid products were analyzed by HPLC. Conversion of fructose was 99.6%; yield of HMF was 86.5%; yield of levulinic acid yield was 0.5%. Yields of HMF in repeat experiments ranged from 86% to 90%.

EXAMPLE 5

Conversion of Fructose to HMF in [EMIM]Cl

No Metal Halide or Acid Catalyst

Fructose was processed as in Example 1 in [EMIM]Cl at a reaction temperature of 120° C. for 3 h. Conversion of fructose was 98%; yield of HMF was 73% (see FIG. 4).

EXAMPLE 6

Conversion of Glucose to HMF in [EMIM]Cl

CrCl₂ Metal Halide Catalyst

Glucose was processed as in Example 1 at a reaction temperature of 100° C. for 3 h in [EMIM]Cl. Metal halide catalyst was CrCl₂. Results are listed in FIG. 6 and TABLE 3.

EXAMPLE 7

Conversion of Glucose to HMF in [EMIM]Cl

CrCl₃ Metal Halide Catalyst

Glucose was processed as in Example 1 at a reaction temperature of 100° C. for 3 h in [EMIM]Cl. Metal halide catalyst was CrCl₃. Results are listed in FIG. 6 and TABLE 3.

EXAMPLE 8

Conversion of Glucose to HMF in [EMIM]Cl

Various Metal Halide and Acid Catalysts

Glucose was processed as in Example 1 in [EMIM]Cl at a reaction temperature of 100° C. for 3 h. Metal halide catalysts were CuCl, CuCl₂, CuBr₂, MOCl₃, FeCl₂, FeCl₃, CrCl₂, CrCl₃, VCl₃, AlCl₃, MnCl₃, PdCl₂, PtCl₂, PtCl₄, RuCl₃, RhCl₃. Acid catalyst was H₂SO₄. Results are presented in FIG. 6 and TABLE 3.

TABLE 3
Conversion of Glucose to HMF, and product yields.
			Feedstock	Product
Example	Feedstock	Catalyst	conversion (%)	yields (%)*
6	Glucose	CrCl2	94.4	HMF: 68.0
7	Glucose	CrCl3	71.5	HMF: 44.3
8.1	Glucose	None	0	HMF: 0
8.2	Glucose	CuCl	0	HMF: 0
8.3	Glucose	CuCl2	85.0	HMF: 6.4
8.4	Glucose	CuBr2	40.4	HMF: 4.7
8.5	Glucose	MoCl3	46.8	HMF: 7.2
8.6	Glucose	FeCl2	0	HMF: 0
8.7	Glucose	FeCl3	47.8	HMF: 6.4
8.8	Glucose	VCl3	61.2	HMF: 8.1
8.9	Glucose	AlCl3	97.3	HMF: 10.8
8.10	Glucose	MnCl3	0	HMF: 0
8.11	Glucose	PdCl2	20.0	HMF: 0.7
8.12	Glucose	PtCl2	65.0	HMF: 7.6
8.13	Glucose	PtCl4	88.0	HMF: 13.0
8.14	Glucose	RuCl3	65.0	HMF: 7.1
8.15	Glucose	RhCl3	55.0	HMF: 3.9
8.16	Glucose	H2SO4	94.4	HMF: 11.0
*Yields of levulinic acid and α-angelicalactone were less than 0.1% for all experiments.

EXAMPLE 9

Conversion of Cellulose to HMF in [EMIM]Cl

CrCl₂ Metal Halide Catalyst

500 mg [EMIM]Cl, (99.5%) (Solvent-Innovation GmbH, Cologne, Germany) and 0.037 mmol/mL of CrCl₂ metal halide catalyst were added to a reaction vial. The vial was heated to 180° C. to create a homogenous catalyst system. 50 mg of cellulose (Sigma-Aldrich, St. Louis, Mo., USA) was added and mixed at 700 rpm to swell the cellulose. Vial was heated at 180° C. for 1 h. 50 μL of water was added for analysis by HPLC. Yield of HMF was 49.8%.

EXAMPLE 10

Conversion of Cellulose in [EMIM]Cl

CrCl₃ Metal Halide Catalyst

Cellulose was processed as in Example 9 in [EMIM]Cl at 140° C. for 0.5 h. Metal halide catalyst was CrCl₃. Products were analyzed by HPLC. Yield of HMF was 50.7%; yield of levulinic acid was 1.4%; yield of formic acid was 2.5%. Results for Examples 9-10 are listed in TABLE 4.

TABLE 4
Conversion of Cellulose to HMF, and product yields.
		Process
		conditions for	Feedstock
		hydrolysis and	conversion	Product
Example	Feedstock	dehydration	(%)	yields (%)
9	Cellulose	Temp: 180° C.,	—	HMF: 49.8
		Time: 3 h
		Catalyst: CrCl2
10	Cellulose	Temp: 140° C.,	—	HMF: 50.7
		Time: 0.5 h,		Levulinic acid: 1.4
		Catalyst: CrCl3		Formic acid: 2.3

EXAMPLE 11

Conversion of Sorbitol in [OMIM]Cl

No Metal Halide Catalyst

50 mg sorbitol and 500 mg [OMIM]Cl were introduced to a vial. The vial was installed into a high pressure reactor, evacuated, purged with N₂. The vial was shaken at 700 rpm and heated at 150° C. under 25-torr vacuum for 1 h. The vial was cooled and 2.0 mL water was added for analysis by HPLC. Conversion of sorbitol was 97.2%, yield of 1,4-sorbitan was 51.6%; yield of isosorbide was 20.0%.

EXAMPLE 12

Conversion of Sorbitol in [OMIM]Cl

CuCl₂ Metal Halide Catalyst

Sorbitol was processed as in Example 9 in [OMIM]Cl with 50 mg CuCl₂ added as catalyst. Conversion of sorbitol was 95.8%; yield of 1,4-sorbitan was 36.3%; and yield of isosorbide was 37.3%.

EXAMPLE 13

Conversion of Sorbitol in [EMIM]CH₃SO₃

No Metal Halide Catalyst

Sorbitol was processed as in Example 9 in [EMIM]CH₃SO₃. Liquid products were analyzed by HPLC. Conversion of sorbitol was 82.4%; yield of 1,4-sorbitan was 63.8%; yield of isosorbide was 1.6%.

EXAMPLE 14

Conversion of Sorbitol in [EMIM]Cl

ZnCl₂ Metal Halide Catalyst

Sorbitol was processed as in Example 9 in [EMIM]Cl with 50 mg ZnCl₂ added as catalyst. Products were analyzed by HPLC. Conversion of sorbitol was 92.1%; yield of 1,4-sorbitan was 76.0%; yield of isosorbide was 3.8%.

Results of Examples 11-14 are summarized in TABLE 5.

TABLE 4
Conversion of Sorbitol, and product yields.
Ex-			Feedstock
am-		Ionic Liquid	conversion	Product
ple	Feedstock	and Catalyst	(%)	yields (%)
11	Sorbitol	IL: [OMIM]Cl,	97.2	1,4-sorbitan: 51.6
		Catalyst: None		Isosorbide: 20.0
12	Sorbitol	IL: [OMIM]Cl,	95.8	1,4-sorbitan: 36.3
		Catalyst: CuCl2		Isosorbide: 37.3
13	Sorbitol	IL: [EMIM]CH3SO3,	82.4	1,4-sorbitan: 63.8
		Catalyst: None		Isosorbide: 1.6
14	Sorbitol	IL: [EMIM]Cl,	92.1	1,4-sorbitan: 76.0
		Catalyst: ZnCl2		Isosorbide: 3.8

As demonstrated in Examples 11-14, sorbitol is dehydrated to products including, e.g., isosorbide and 1,4-sorbitan. Yields are selectively tunable by choices of ionic liquid and catalyst.

While Examples presented herein demonstrate conversion of carbohydrates using a single batch process and reactor, the invention is not limited thereto. Those of skill in the art will appreciate that many reactors and reactor configurations are suitable for use in conjunction with the invention, including, e.g., step-wise and/or serial processing, multistage processing and reactors, continuous flow processing and reactors, and/or tandem stage processing and reactors. All reactor configurations and processes as will be contemplated and implemented by those of skill in the art in view of the present disclosure are within the scope of the invention.

While preferred embodiments of the invention have been shown and described herein, many changes and modifications may be made without departing from the invention in its broader aspects. The appended claims are therefore intended to cover all such changes and modifications as fall within the scope of the invention.

Claims

1. A method for selective conversion of a carbohydrate producing a furan at a substantial yield, comprising the steps: mixing said carbohydrate up to a limit of solubility with an ionic liquid;heating said carbohydrate in the presence of a catalyst at a reaction temperature and a reaction time sufficient for conversion of same;wherein conversion of said carbohydrate produces said furan at a substantial yield.

2. The method of claim 1, wherein said ionic liquid has a chemical formula 1-R1-3-R2-imidazolium chloride, where R1 and R2 are alkyl groups of formula (CxH2x+1) where X=1 to 18.

3. The method of claim 1, wherein said ionic liquid includes a cation of chemical formula 1-R1-3-R2-imidazolium where R1 and R2 are alkyl groups of formula (CxH2x+1) where X=1 to 18, and an anion.

4. The method of claim 3, wherein said anion is selected from the group consisting of halides, sulfates, sulfonates, phosphates, acetates, phosphates, triflates, hexafluorophosphates, tetrafluoroborates, hexafluoroborates, and aluminum chloride.

5. The method of claim 3, wherein said anion is selected from the group consisting of methanesulfonate or trifluoromethanesulfonate.

6. The method of claim 1, wherein said ionic liquid is selected from the group consisting of pyridinium salts, phosphonium salts, tetralkylammonium salts, and combinations thereof.

7. The method of claim 1, wherein said carbohydrate is fructose.

8. The method of claim 7, wherein fructose is converted to 5-hydroxylmethylfurfural in the absence of a catalyst.

9. The method of claim 8, wherein said reaction temperature is about 100° C. and said reaction time is between about 3 hours and about 8 hours.

10. The method of claim 8, wherein said reaction temperature is about 120° C. and said reaction time is between about 1 hour and about 3 hours.

11. The method of claim 7, wherein said catalyst is an acid.

12. The method of claim 7, wherein said catalyst is a metal halide.

13. The method of claim 7, wherein said metal halide is selected from the group consisting of AlCl3, CrCl2, CrCl3, FeCl2, FeCl3, CuCl, CuBr, CuCl2, CuBr2, VCl3, MoCl3, PdCl2, PtCl2, PtCl4, RuCl3, RhCl3, and combinations thereof.

14. The method of claim 7, wherein said reaction temperature is about 80° C. and said reaction time is between about 1 hour and about 4 hours.

15. The method of claim 7, wherein said ionic liquid is 1-ethyl-3-methylimidazolium methanesulfonate and said catalyst is methane sulfonate or its conjugate acid; and wherein said reaction temperature and said reaction time are between about 80° C. for 2 hours and about 30° C. for 12 hours.

16. The method of claim 7, wherein yield of levulinic acid and α-angelicalactone is below about 0.1 percent by weight.

17. The method of claim 1, wherein said carbohydrate is glucose.

18. The method of claim 17, wherein said catalyst is a chromium halide.

19. The method of claim 18, wherein said reaction temperature and said reaction time are about 100° C. and about 3 hours, respectively.

20. The method of claim 18, wherein yield of levulinic acid and α-angelicalactone is below about 0.1 percent by weight.

21. The method of claim 1, wherein said carbohydrate is sucrose, maltose, lactose, or cellobiose.

22. The method of claim 1, wherein said carbohydrate is maltodextrin, starch, or cellulose.

23. The method of claim 22, wherein said catalyst is a chromium halide.

24. The method of claim 23, wherein said reaction time and said reaction temperature are about 0.5 hours at about 140° C., respectively.

25. The method of claim 1, wherein said furan is 5-hydroxymethylfurfural.

26. The method of claim 1, wherein said carbohydrate is arabinose, xylose, ribose, or lyxose.

27. The method of claim 26, wherein said furan is furfural.

28. The method of claim 1, wherein said carbohydrate is converted in a continuous flow reactor or a continuous flow reactor system.

29. The method of claim 1, wherein said carbohydrate is converted in a batch reactor or a batch reactor system.

30. The method of claim 1, wherein said carbohydrate is a sugar alcohol and said furan is an anhydrosugar alcohol or a dianhydrosugar alcohol.

31. The method of claim 30, wherein said sugar alcohol is sorbitol.

32. The method of claim 1, wherein conversion of said carbohydrate is greater than or equal to about 80 percent and said yield of said furan is greater than or equal to about 50 percent on a mole basis.

33. The method of claim 1, wherein said yield of said furan is at least about 35 percent by weight.

34. The method of claim 1, wherein yield of levulinic acid and α-angelicalactone is less than about 3 percent by weight.

35. The method of claim 1, wherein the step of heating said carbohydrate includes a reaction time of from about 0.01 minutes to about 5 hours and a reaction temperature of from about 400° C. down to about 20° C.

36. The method of claim 1, wherein the step of heating said carbohydrate includes a reaction time and a reaction temperature of between about 0.01 minutes at about 250° C. and about 12 hours at about 20° C.