Methods for recovering solvents and separating humic materials and compositions thereof

Abstract

A novel method for recovering solvents and separating humic substances or humate materials from 5-hydroxymethylfurfural (HMF) and 2,5-furandicarboxylic acid (FDCA) pathway processes is described. In some embodiments, the method utilizes a thin film evaporator, such as a horizontal thin film evaporator (HTFE).

Description

[0001] Priority declaration

[0002] This application claims priority to U.S. Provisional Patent Application No. 62 / 834,143, filed on April 15, 2019, which is expressly incorporated herein by reference in its entirety for all purposes. Technical Field

[0003] The present disclosure relates to methods for recovering solvents and separating humin or humate materials from 2,5-furandicarboxylic acid pathway products. Background Art

[0004] Low-cost and renewable sources of 2,5-furandicarboxylic acid (FDCA) and its derivatives have considerable commercial application potential. In certain applications, they have the potential to replace aromatic dicarboxylic acids (such as terephthalic acid and isophthalic acid). Methods for producing FDCA from various raw materials have been reported, but in these methods, it is difficult to effectively recover the solvent and remove impurities and / or by-products (such as humic substances or humate / ester compounds) from the raw materials. Therefore, there is still a need for improved systems and methods for recovering solvents and removing impurities during the 5-hydroxymethylfurfural (HMF) and FDCA pathway. Summary of the invention

[0005] In one aspect, a method for separating humic substances from a feed source is disclosed. The method includes providing a feed source to a thin film evaporator. The feed source comprises about 65-90 wt.% or 65-90 wt.% of a multi-component solvent, the multi-component solvent comprising water and a water-miscible aprotic organic solvent, and about 10-35 wt.% or 10-35 wt.% of a dissolved dry residue. The dissolved dry residue comprises, based on wt.% or ppm of the total feed source: a sugar content of about 30,000-120,000 ppm or 30,000-120,000 ppm, a furan-containing compound content of about 2-5 wt.% or 2-5 wt.%, a humic compound content of about 24,000-100,000 ppm or 24,000-100,000 ppm, an organic acid content of about 0.2-0.7 wt.%, homogeneous acids, salts and metals. The method further includes wherein the feed source has a pH between about 1-4 pH or 1-4 pH, and the feed source is treated in a thin film evaporator to provide a separated solid material. The separated solid material comprises: a moisture content of about 0.3-2wt.% or 0.3-2wt.%, a furan-containing compound content of about 0.9-5wt.% or 0.9-5wt.%, a sugar content of about 0.1-2wt.% or 0.1-2wt.%, a dioxane content of about 0.02-1wt.% or 0.02-1wt.%, and an ash content of about 0.1-6wt.% or 0.1-6wt.%.

[0006] In some embodiments, the method further includes washing and drying the separated solid material to produce a washed and dried solid material. In some embodiments, the method further includes exposing the washed and dried solid material to a high temperature carbonization process to produce a carbonized solid material. In some embodiments, the thin film evaporator is a horizontal thin film evaporator. In some embodiments, the thin film evaporator is oriented at an angle between 0 ° to 90 ° or between about 0 ° to 90 ° (e.g., about or at 5 °, 10 °, 15 °, 30 °, 45 °, 60 °, 75 °, 80 °, 85 ° or any numerical range therebetween), wherein 0 ° corresponds to the heated thin film evaporator being oriented vertically downward toward the earth's center of mass, and 180 ° corresponds to the heated thin film evaporator being oriented vertically upward away from the earth's center of mass.

[0007] In some embodiments, the organic acid is selected from the group consisting of levulinic acid, formic acid, acetic acid, and combinations thereof. In some embodiments, the homogeneous acid is selected from the group consisting of HCl, HBr, HI, H 2 SO 4 , H 3 PO 4, oxalic acid, trifluoromethanesulfonic acid, methanesulfonic acid, boron trihalide and combinations thereof. In some embodiments, the salt is selected from the group consisting of sodium bromide, calcium bromide, sodium chloride, calcium chloride, potassium chloride, magnesium chloride and combinations thereof.

[0008] In another aspect, a method for recovering a solvent from a feed source is disclosed. The method includes providing a feed source to a thin film evaporator. The feed source comprises about 65-90 wt.% or 65-90 wt.% of a multi-component solvent, and about 10-35 wt.% or 10-35 wt.% of a dissolved dry residue, wherein the multi-component solvent comprises water and a water-miscible aprotic organic solvent. The dissolved dry residue comprises, based on wt.% or ppm of the total feed source: a sugar content of about 30,000-120,000 ppm or 30,000-120,000 ppm, a furan-containing compound content of about 2-5 wt.% or 2-5 wt.%, a humic compound content of about 24,000-100,000 ppm or 24,000-100,000 ppm, an organic acid content of about 0.2-0.7 wt.%, homogeneous acids, salts and metals. The method further includes wherein the feed source has a pH between about 1-4 pH or 1-4 pH, and the feed source is treated in a thin film evaporator to provide a recovered solvent material. The separated solid material comprises: a sugar content of up to about 500 ppm or 500 ppm, a furan content of up to about 1.6 wt.% or 1.6 wt.%, a humic compound content of about 300-700 ppm or 300-700 ppm, and an organic acid content of up to about 2 wt.% or 2 wt.%.

[0009] In some embodiments, the method further includes providing the recovered solvent material to a condenser. In some embodiments, the method further includes providing the recovered solvent material to a continuous distillation column. In some embodiments, the recovered solvent is further purified or separated by fractionation. In some embodiments, the thin film evaporator is a horizontal thin film evaporator. In some embodiments, the thin film evaporator is oriented at an angle between 0 ° to 90 ° or between about 0 ° to 90 ° (e.g., about or at 5 °, 10 °, 15 °, 30 °, 45 °, 60 °, 75 °, 80 °, 85 ° or any range of values ​​therebetween), wherein 0 ° corresponds to the heated thin film evaporator being oriented vertically downward toward the center of mass of the earth, and 180 ° corresponds to the heated thin film evaporator being oriented vertically upward away from the center of mass of the earth.

[0010] In another aspect, a composition of solid material separated from a feed source is disclosed, the composition comprising a moisture content of less than 2 wt.%, a furan content of at least 0.9 wt.%, a sugar content of at least 0.1 wt.%, a moisture content of at most 2 wt.%, a dioxane content of at most 1 wt.%, and an ash content of at most 6 wt.%.

[0011] In some embodiments, the ash content is at most 1 wt.%. In some embodiments, the ash content is at most 0.5 wt.%. In some embodiments, the ash content is at most 0.1 wt.%.

[0012] In another aspect, a method for separating humic substances from a feed source is provided. The method comprises providing a feed source to a thin film evaporator, wherein the feed source comprises: a multi-component solvent comprising water and a water-miscible aprotic organic solvent; and a dissolved dry residue comprising humic compound material, wherein the feed source has a pH between about 1-4 pH or between 1-4 pH; and treating the feed source in the thin film evaporator to provide a separated solid material, wherein the separated solid material comprises a moisture content of about 0.3-2 wt.% or 0.3-2 wt.%, a furan-containing compound content of about 0.9-5 wt.% or 0.9-5 wt.%, a sugar content of about 0.1-2 wt.% or 0.1-2 wt.%, a dioxane content of about 0.02-1 wt.% or 0.02-1 wt.%, and an ash content of about 0.1-6 wt.% or 0.1-6 wt.%.

[0013] In another aspect, a method for recovering solvent from a feed source is provided. The method includes providing a feed source to a thin film evaporator, wherein the feed source comprises: a multi-component solvent, the multi-component solvent comprising water and a water-miscible aprotic organic solvent; and a dissolved dry residue, the dissolved dry residue comprising a humic compound material, wherein the feed source has a pH between about 1-4 pH or 1-4 pH, and treating the feed source within the thin film evaporator to provide a recovered solvent material, the recovered solvent material comprising a sugar content of up to about 500 ppm or 500 ppm, a furan content of up to about 1.6 wt.% or 1.6 wt.%, a humic compound content of about 300-700 ppm or 300-700 ppm, and an organic acid content of up to about 2 wt.% or 2 wt.%.

[0014] Preferred alternatives include, but are not limited to:

[0015] 1. A method for separating humus from a feed source, the method comprising:

[0016] A feed source is provided to the thin film evaporator, wherein the feed source comprises:

[0017] about 65-90 wt. % or 65-90 wt. % of a multi-component solvent comprising water and a water-miscible aprotic organic solvent; and

[0018] about 10-35 wt.% or 10-35 wt.% dissolved dry residue;

[0019] Expressed in wt.% or ppm of the total feed source, the dry residue comprises:

[0020] A sugar content of about 30,000-120,000 ppm or 30,000-120,000 ppm;

[0021] about 2-5 wt.% or 2-5 wt.% furan-containing compound content;

[0022] A humic compound content of about 24,000-100,000 ppm or 24,000-100,000 ppm;

[0023] About 0.2-0.7 wt.% or 0.2-0.7 wt.% organic acid content;

[0024] Homogeneous acid;

[0025] Salt; and

[0026] Metal;

[0027] wherein the feed source has a pH at or between about 1-4 pH; and

[0028] The feed source is processed within the thin film evaporator to provide a separated solid material, the separated solid material comprising:

[0029] A moisture content of about 0.3-2 wt.% or 0.3-2 wt.%;

[0030] about 0.9-5 wt.% or 0.9-5 wt.% furan-containing compound content;

[0031] A sugar content of about 0.1-2 wt.% or 0.1-2 wt.%;

[0032] About 0.02-1 wt.% or 0.02-1 wt.% dioxane content; and

[0033] An ash content of about 0.1-6 wt.% or 0.1-6 wt.%.

[0034] 2. The method of alternative 1 further comprising washing and drying the separated solid material to produce a washed and dried solid material.

[0035] 3. The method of alternative 2 further comprising exposing the washed and dried solid material to a high temperature carbonization process to produce a carbonized solid material.

[0036] 4. The method of any of alternatives 1-3, wherein the thin film evaporator is a horizontal thin film evaporator.

[0037] 5. A method as described in any of alternatives 1-4, wherein the thin film evaporator is oriented at an angle between 0° and 90° or between about 0° and 90° (for example, at about or at 5°, 10°, 15°, 30°, 45°, 60°, 75°, 80°, 85° or any range of values ​​therebetween), wherein 0° corresponds to the heated thin film evaporator being oriented vertically downward toward the center of mass of the earth, and 180° corresponds to the heated thin film evaporator being oriented vertically upward away from the center of mass of the earth.

[0038] 6. The method of any of alternatives 1-5, wherein the organic acid is selected from the group consisting of levulinic acid, formic acid, acetic acid, and combinations thereof.

[0039] 7. A method as described in any one of alternatives 1-6, wherein the homogeneous acid is selected from HCl, HBr, HI, H 2 SO 4 , H 3 PO 4 , oxalic acid, trifluoromethanesulfonic acid, methanesulfonic acid, boron trihalide and combinations thereof.

[0040] 8. The method of any of Alternatives 1-7, wherein the salt is selected from the group consisting of sodium bromide, calcium bromide, sodium chloride, calcium chloride, potassium chloride, magnesium chloride, and combinations thereof.

[0041] 9. A method for recovering a solvent from a feed source, the method comprising:

[0042] A feed source is provided to the thin film evaporator, wherein the feed source comprises:

[0043] about 65-90 wt. % or 65-90 wt. % of a multi-component solvent comprising water and a water-miscible aprotic organic solvent; and

[0044] about 10-35 wt.% or 10-35 wt.% dissolved dry residue;

[0045] Expressed in wt.% or ppm of the total feed source, the dry residue comprises:

[0046] A sugar content of about 30,000-120,000 ppm or 30,000-120,000 ppm;

[0047] about 2-5 wt.% or 2-5 wt.% furan-containing compound content;

[0048] A humic compound content of about 24,000-100,000 ppm or 24,000-100,000 ppm;

[0049] About 0.2-0.7 wt.% or 0.2-0.7 wt.% organic acid content;

[0050] Homogeneous acid;

[0051] Salt; and

[0052] Metal;

[0053] wherein the feed source has a pH at or between about 1-4 pH; and

[0054] processing the feed source within the thin film evaporator to provide a recovered solvent material, the recovered solvent material comprising:

[0055] A sugar content of up to about 500 ppm or 500 ppm;

[0056] a furan content of up to about 1.6 wt.% or 1.6 wt.%;

[0057] A humic compound content of about 300-700 ppm or 300-700 ppm; and

[0058] Up to about 2 wt.% or 2 wt.% organic acid content.

[0059] 10. The method of Alternative Embodiment 9 further comprising providing the recovered solvent material to a condenser.

[0060] 11. The method of Alternative 9 further comprising providing the recovered solvent material to a continuous distillation column.

[0061] 12. A method as described in Alternative Scheme 9, wherein the recovered solvent is further purified or separated by fractional distillation.

[0062] 13. The method of any of alternatives 9-12, wherein the thin film evaporator is a horizontal thin film evaporator.

[0063] 14. A method as described in any of alternatives 9-13, wherein the thin film evaporator is oriented at an angle between 0° and 90° or between about 0° and 90° (for example, at about or at 5°, 10°, 15°, 30°, 45°, 60°, 75°, 80°, 85° or any range of values ​​therebetween), wherein 0° corresponds to the heated thin film evaporator being oriented vertically downward toward the center of mass of the earth, and 180° corresponds to the heated thin film evaporator being oriented vertically upward away from the center of mass of the earth.

[0064] 15. A composition of solid material separated from a feed source, the composition comprising:

[0065] Moisture content less than 2 wt.%;

[0066] A furan content of at least 0.9 wt.%;

[0067] A sugar content of at least 0.1 wt.%;

[0068] A moisture content of up to 2 wt.%;

[0069] Dioxane content up to 1 wt.%;

[0070] Ash content up to 6 wt.%.

[0071] 16. The composition of alternative 15 wherein the ash content is at most 1 wt.%.

[0072] 17. The composition of Alternative 15 wherein the ash content is at most 0.5 wt.%.

[0073] 18. The composition of Alternative 15 wherein the ash content is at most 0.1 wt.%.

[0074] 19. A method for separating humic substances from a feed source, the method comprising:

[0075] A feed source is provided to the thin film evaporator, wherein the feed source comprises:

[0076] a multi-component solvent comprising water and a water-miscible aprotic organic solvent; and

[0077] a dissolved dry residue, the dissolved dry residue comprising humic compound matter;

[0078] wherein the feed source has a pH at or between about 1-4 pH; and

[0079] The feed source is processed within the thin film evaporator to provide a separated solid material, the separated solid material comprising:

[0080] A moisture content of about 0.3-2 wt.% or 0.3-2 wt.%;

[0081] About 0.9-5 wt. % or 0.9-5 wt. % of a furan-containing compound;

[0082] A sugar content of about 0.1-2 wt.% or 0.1-2 wt.%;

[0083] About 0.02-1 wt.% or 0.02-1 wt.% dioxane content; and

[0084] An ash content of about 0.1-6 wt.% or 0.1-6 wt.%.

[0085] 20. A method for recovering a solvent from a feed source, the method comprising:

[0086] A feed source is provided to the thin film evaporator, wherein the feed source comprises:

[0087] a multi-component solvent comprising water and a water-miscible aprotic organic solvent; and

[0088] a dissolved dry residue, the dissolved dry residue comprising humic compound matter;

[0089] wherein the feed source has a pH at or between about 1-4 pH; and

[0090] processing the feed source within the thin film evaporator to provide a recovered solvent material, the recovered solvent material comprising:

[0091] A sugar content of up to about 500 ppm or 500 ppm;

[0092] a furan content of up to about 1.6 wt.% or 1.6 wt.%;

[0093] A humic compound content of about 300-700 ppm or 300-700 ppm; and

[0094] Up to about 2 wt.% or 2 wt.% organic acid content. BRIEF DESCRIPTION OF THE DRAWINGS

[0095] Figure 1 A horizontal thin film evaporator (HTFE) and a method for processing the retentate feed to obtain dry humic solids and collecting the solvent using a solvent condenser are described.

[0096] Figure 2A horizontal thin film evaporator (HTFE) and method for processing the retentate feed to obtain dry humic solids and collecting the purified solvent using continuous solvent distillation is described. DETAILED DESCRIPTION

[0097] The present disclosure relates to several methods for recovering solvent and separating humic acid or humate / ester in 5-hydroxymethylfurfural (HMF) and / or furandicarboxylic acid (FDCA) product pathway processes. Exemplary methods for producing HMF and FDCA pathway products are disclosed in U.S. Patent Publication No. 2017 / 0197930 and U.S. Patent Publication No. 2017 / 0158656, which are expressly incorporated herein by reference in their entirety for all purposes. In some FDCA product processes (e.g., processes for producing 5-hydroxymethylfurfural (HMF) by dehydration of sugar feedstock), humic acid or humate / ester byproducts are produced. It should be understood that the terms humic acid and humate / ester are interchangeable. Humic acid is a polymeric sugar, a polymerized dehydrated sugar, a polymerized furan compound, and / or other similar condensation reaction byproducts produced in sugar dehydration or HMF pathway processes. Because humic acid is a condensation product, they increase molecular weight by condensation reaction. Condensation reaction can be carried out with a variety of reaction species, and therefore a variety of structurally different species can be formed, which can have a wide range of molecular weight distributions. The exact structure and distribution of humic materials will depend on dehydration conditions, such as, for example, fructose concentration, acid, acid concentration, solvent, reaction temperature and reaction time. Along with the molecular weight increase of humic structure, their solubility limit may be exceeded, causing humic substances to precipitate from reaction solution, thereby causing operational difficulties, particularly in the retentate solution of solvent recovery system. In addition, separation and transportation of humic substances from solvent recovery system is usually problematic, because humic substances are separated in the form of viscous liquid, and when separated by conventional methods, the viscous liquid is cooled to solid. This viscous liquid cooled to solid material hinders industrial processing applications. For example, although other people (such as U.S. Patent Publication No. 2018 / 0093894) have taught the separation of solid furan resins, these traditionally separated furan resins are unlikely to be further processed with industrially feasible methods.

[0098] The present disclosure describes several methods for separating humic substances from membrane retentate solutions by using thin film evaporators. Thin film evaporators facilitate the separation of humic substances as convenient free-flowing powders, wherein the free-flowing humic substances can be further processed to have beneficial downstream commercial applications. The convenient access to the free-flowing powder allows for high-throughput industrial processing applications. In addition, the present evaporation method allows for the recovery of >99% of the solvent composition, which can then be used in a recovery procedure. Thus, the present disclosure provides a cost-effective method to separate and remove humic substances as free-flowing powders and recover the reaction solvent composition to recycle it into the HMF and / or FDCA pathway process.

[0099] HMF pathway process

[0100] In some embodiments, humic substances can be separated from the retentate stream of the HMF pathway process. In some embodiments, the HMF pathway process includes a sugar dehydration process. For example, any type of carbohydrate feedstock or fructose-containing feedstock can be used in the dehydration process. It should be understood that the terms carbohydrate feedstock or fructose-containing feedstock are used interchangeably.

[0101] In some embodiments, the fructose-containing feedstock is dehydrated or converted into HMF by contacting a carbohydrate feedstock comprising sugar and a dehydration solvent with a catalyst under conditions sufficient to form a (dehydration) reaction mixture for sugar dehydration to produce a furan oxidation substrate (referred to herein as a "dehydration process"). In some embodiments, the sugar is a hexose (such as, for example, glucose, galactose, mannose, idose, ketose, fructose (fructose or levulose), sorbose, tagatose or allose, etc.), or starch, cellulose and other forms of carbohydrates that can withstand treatment conditions that isomerize the glucose produced from starch or cellulose. In some embodiments, the sugar is glucose or fructose. In some embodiments, the sugar is fructose.

[0102] The term "dehydration solvent" refers to a solvent in which both the sugar and the furanic oxidation substrate are soluble at a minimum level of at least 2 wt.% at the temperature at which the dehydration reaction is carried out. Typically, the dehydration solvent is a solvent in which the furanic oxidation substrate has the following solubility measured at the temperature at which the dehydration reaction is carried out: at least 3 wt%, at least 4 wt%, at least 5 wt%, at least 6 wt%, at least 7 wt%, at least 8 wt%, at least 9 wt%, at least 10 wt%, at least 11 wt%, at least 12 wt%, at least 13 wt%, at least 14 wt%, at least 15 wt%, at least 17 wt%, at least 19 wt%, at least 21 wt%, at least 23 wt% or at least 25 wt%. In some embodiments, the concentration of furan oxidation substrate in the dehydration solvent is in the following range or any value therebetween: 2-4wt%, 3-5wt%, 4-6wt%, 5-7wt%, 6-8wt%, 7-9wt%, 8-10wt%, 9-11wt%, 10-12wt%, 11-13wt%, 12-14wt%, 13-15wt%, 14-16wt%, 15-17wt%, 16-18wt%, 17-19wt%, 18-20wt%, 19-21wt%, 20-22wt%, 21-23wt%, 22-24wt% or 23-25wt%, or in the range defined by any two of the above weight percentages. Typically, the dehydration solvent comprises water and / or a water-miscible organic solvent. More typically, the dehydration solvent is a multi-component solvent. Typically, the multi-component solvent used in the dehydration process comprises water and a water-miscible aprotic organic solvent. The water-miscible aprotic organic solvent and multi-component solvent composition suitable for the dehydration process are the same as those suitable for the above-mentioned FDCA pathway product production process. In some embodiments, the water-miscible aprotic organic solvent is N-methyl-2-pyrrolidone (NMP). In some embodiments, the carbohydrate feedstock comprises fructose and the furan oxidation substrate comprises HMF.

[0103] Exemplary water-miscible aprotic solvents suitable for the dehydrating solvent include tetrahydrofuran, glyme, dioxane, dioxolane, dimethylformamide, dimethyl sulfoxide, sulfolane, acetone, N-methyl-2-pyrrolidone ("NMP"), methyl ethyl ketone ("MEK"), or γ-valerolactone, or any mixture thereof. Preferably, the water-miscible aprotic organic solvent is an ether, such as, for example, glyme, dioxane (1,4-dioxane), dioxolane (e.g., 1,3-dioxolane), or tetrahydrofuran, or any mixture thereof. Glyme suitable for use in the practice of the present disclosure include, for example, monoglyme (1,2-dimethoxyethane, "DME"), ethylglyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme, butyl diglyme, tetraglyme, polyglyme, or a highly ethoxylated diether of a high molecular weight alcohol ("higlyme"), or any mixture thereof. Often, the dehydration solvent is a multi-component solvent comprising water and a water-miscible aprotic organic solvent, i.e., glyme, diglyme, or dioxane.

[0104] In some embodiments, the water-miscible organic solvent species is at least 5 volume % (vol%), at least 10 vol%, at least 15 vol%, at least 20 vol%, at least 25 vol%, at least 30 vol%, at least 35 vol%, at least 40 vol%, at least 45 vol%, at least 50 vol%, at least 55 vol%, at least 60 vol%, at least 65 vol%, at least 70 vol%, at least 75 vol%, at least 80 vol%, at least 85 vol%, at least 90 vol%, or at least 10 vol% of the multi-component solvent. 95vol%; correspondingly, water is usually less than 95vol%, less than 90vol%, less than 85vol%, less than 80vol%, less than 75vol%, less than 70vol%, less than 65vol%, less than 60vol%, less than 55vol%, less than 50vol%, less than 45vol%, less than 40vol%, less than 35vol%, less than 30vol%, less than 25vol%, less than 20vol%, less than 15vol%, less than 10vol% or less than 5vol% of the multi-component system, respectively.

[0105] In some embodiments, the multi-component solvent contains water in the range of 1-5 wt % or any value therebetween and a water-miscible organic solvent in the range of 99-95 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 5-10 wt % or any value therebetween and a water-miscible organic solvent in the range of 95-90 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 10-15 wt % or any value therebetween and a water-miscible organic solvent in the range of 90-85 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 15-20 wt % or any value therebetween and a water-miscible organic solvent in the range of 85-80 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 20-25 wt % or any value therebetween and a water-miscible organic solvent in the range of 80-75 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 25-30 wt % or any value therebetween and a water-miscible organic solvent in the range of 75-70 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 30-35 wt % or any value therebetween and a water-miscible organic solvent in the range of 70-65 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 35-40 wt % or any value therebetween and a water-miscible organic solvent in the range of 65-60 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 40-45 wt % or any value therebetween and a water-miscible organic solvent in the range of 60-55 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 45-50 wt % or any value therebetween and a water-miscible organic solvent in the range of 65-50 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 50-55 wt % or any value therebetween and a water-miscible organic solvent in the range of 50-45 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 55-60 wt % or any value therebetween and a water-miscible organic solvent in the range of 45-40 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 60-65 wt % or any value therebetween and a water-miscible organic solvent in the range of 40-35 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 65-70 wt % or any value therebetween and a water-miscible organic solvent in the range of 35-30 wt % or any value therebetween.In some embodiments, the multi-component solvent contains water in the range of 70-75 wt % or any value therebetween and a water-miscible organic solvent in the range of 30-25 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 75-80 wt % or any value therebetween and a water-miscible organic solvent in the range of 25-20 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 80-85 wt % or any value therebetween and a water-miscible organic solvent in the range of 20-15 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 85-90 wt % or any value therebetween and a water-miscible organic solvent in the range of 15-10 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 90-95 wt % or any value therebetween and a water-miscible organic solvent in the range of 10-5 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 95-99 wt %, or any value therebetween, and water-miscible organic solvent in the range of 5-1 wt %, or any value therebetween.

[0106] In some embodiments, the volume ratio of water to water-miscible organic solvent is in the range of 1:6 to 6:1 or any value therebetween. In certain embodiments, the volume ratio is 1:4 to 4:1 water: water-miscible organic solvent or any value therebetween. In other embodiments, the volume ratio is 1:4 to 3:1 water: water-miscible organic solvent or any value therebetween. In other embodiments, the volume ratio is 1:3 to 3:1 water: water-miscible organic solvent or any value therebetween. In certain embodiments, the volume ratio is 1:1 water: water-miscible organic solvent.

[0107] In some embodiments, the multi-component solvent comprises water and two different water-miscible organic solvents. Typically, two water-miscible organic solvents are water-miscible aprotic organic solvents. Each of the two water-miscible aprotic solvents can be independently selected from the group of tetrahydrofuran, glycol dimethyl ether, dioxane, dioxolane, dimethylformamide, dimethyl sulfoxide, cyclopentane, acetone, N-methyl-2-pyrrolidone ("NMP"), methyl ethyl ketone ("MEK") or γ-valerolactone. One or both of the water-miscible aprotic organic solvents can be ethers, such as glycol dimethyl ether, dioxane (e.g., 1,4-dioxane), dioxolane (e.g., 1,3-dioxolane) or tetrahydrofuran, etc. Glyme includes, for example, monoglyme (1,2-dimethoxyethane, "DME"), ethylglyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme, butyl diglyme, tetraglyme, polyglyme or highly ethoxylated diethers of high molecular weight alcohols ("high glymes"), and the like.

[0108] In some embodiments, the volume ratio of water to the first water-miscible organic solvent and the second water-miscible organic solvent is about 1:1:1 (v:v:v). In some embodiments, the volume ratio of water to the first water-miscible organic solvent and the second water-miscible organic solvent is about 1:2:1 (v:v:v). In some embodiments, the volume ratio of water to the first water-miscible organic solvent and the second water-miscible organic solvent is about 1:2:2 (v:v:v). In some embodiments, the volume ratio of water to the first water-miscible organic solvent and the second water-miscible organic solvent is about 2:1:1 (v:v:v).

[0109] The concentration of sugar in the carbohydrate raw material is generally in the range of 2wt% to 80wt% or any value therebetween, or in the range of 5wt% to 80wt% or any value therebetween. In various embodiments, the concentration of sugar is in the range of 20wt% to 80wt% or any value therebetween. In some embodiments, the concentration of sugar in the carbohydrate raw material is in the range of 5wt% to 20wt% or any value therebetween. In other embodiments, the concentration of sugar in the carbohydrate raw material is in the range of 5wt% to 40wt% or any value therebetween. In some embodiments, the concentration of sugars in the carbohydrate feedstock is within the range of 5-15wt%, 10-20wt%, 15-25wt%, 20-30wt%, 25-35wt%, 30-40wt%, 35-45wt%, 40-50wt%, 45-55wt%, 50-60wt%, 55-65wt%, 60-70wt%, 65-75wt% or 70-80wt%, or any value therebetween, or within the range defined by any two of the foregoing weight percentages.

[0110] In some embodiments, an aqueous fructose solution is used as a raw material for the reaction zone. In some embodiments, commercially available high fructose syrup (HFS) is dissolved in water to form a solution. For example, HFS-97 or HFS-90 can be used.

[0111] Catalysts suitable for the dehydration process include homogeneous catalysts (including, for example, homogeneous acid catalysts, etc.), and heterogeneous catalysts. In some embodiments, the acid catalyst is selected from HBr, H 2 SO 4 , HNO 3 , HCl, HI, H 3 PO 4 In some embodiments, the acid catalyst is HCl. In some embodiments, the acid catalyst is HCl and does not further comprise a bromide salt. In some embodiments, the acid catalyst is HCl and the dehydration solvent does not comprise N-methyl-pyrrolidone (NMP).

[0112] In some embodiments, the acid catalyst is HBr. In some embodiments, when the acid catalyst is not HBr, the dehydration reaction mixture further comprises a bromide salt. In some embodiments, when the acid catalyst is not HBr, the dehydration reaction mixture further comprises a bromide salt and the dehydration solvent comprises N-methyl-pyrrolidone (NMP). In some embodiments, the acid catalyst can be selected from H 2 SO 4 , HNO 3 , HCl, HI, H 3 PO 4 , trifluoromethanesulfonic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid, and wherein the dehydration reaction mixture comprises a bromide salt. In some embodiments, the bromide salt can be selected from the group consisting of LiBr, NaBr, KBr, MgBr 2 , CaBr 2 、ZnBr 2 , tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide and tetrabutylammonium bromide or any combination of two or more thereof. The acid catalyst may further comprise a Lewis acid. The Lewis acid may be selected from the group consisting of boron trihalide, organic boranes, aluminum trihalides, phosphorus pentafluoride, antimony pentafluoride, rare earth metal trifluoromethanesulfonates, metal halides, metal trifluoroacetates and metal cation ether complexes. The Lewis acid may be a metal halide. The metal halide may be ZnCl 2 or ZnBr 2 .

[0113] The amount of the acid catalyst used is typically in the range of 0.1 mol% to 25 mol% or any value therebetween, more typically in the range of 0.5 mol% to 5 mol% or any value therebetween (wherein mol% is calculated based on the number of moles of sugar (e.g., hexose)). In some embodiments, the amount of the acid catalyst in the reaction mixture for dehydrating sugars is such that the reaction mixture has an acidic pH. In some embodiments, the amount of the acid catalyst in the reaction mixture for dehydrating sugars is such that the reaction mixture has a pH of less than 6. In some embodiments, the amount of the acid catalyst in the reaction mixture for dehydrating sugars is such that the reaction mixture has a pH of less than 5. In some embodiments, the amount of the acid catalyst in the reaction mixture for dehydrating sugars is such that the reaction mixture has a pH of less than 4. In some embodiments, the amount of the acid catalyst in the reaction mixture for dehydrating sugars is such that the reaction mixture has a pH of less than 3. In some embodiments, the amount of the acid catalyst in the reaction mixture for dehydrating sugars is such that the reaction mixture has a pH of less than 2. In some embodiments, the amount of the acid catalyst in the reaction mixture for dehydrating sugars is such that the reaction mixture has a pH of less than 1.

[0114] The dehydration product solution can be used as a feedstock for producing FDCA pathway products or derivatives thereof, or as a feedstock for another subsequent process utilizing a furanic oxidation substrate. Typically, the furanic oxidation substrate is HMF.

[0115] In order to minimize the production of undesirable products and maximize the yield of the furanic oxidation substrate, it may be necessary to carry out the dehydration reaction to a partial conversion endpoint, as described in U.S. Patent Publication No. 2017 / 0158656 (which is expressly incorporated herein by reference in its entirety for all purposes), by quenching the reaction, and separating and recovering the unconverted sugars, for example, by filtration. When the dehydration reaction produces the furanic oxidation substrate, it is present in the dehydration product solution.

[0116] As used herein, the term "dehydrated product solution" or "crude oxidation feedstock" refers interchangeably to a solution comprising a furan oxidation substrate and a dehydration solvent. The dehydrated product solution may be a mixture comprising a dissolved furan oxidation substrate and one or more undissolved components, wherein the one or more undissolved components are selected from humus and unreacted sugars. The furan oxidation substrate may be optionally separated from one or more components selected from the group consisting of humus and unreacted sugars and / or separated from the dehydrated product solution, and optionally further purified. In one such embodiment, the dehydrated product solution is passed through a membrane to achieve separation of the furan oxidation substrate from one or more components selected from the group consisting of humus and unreacted sugars. Membranes suitable for such separation include nanofiltration membranes or ultrafiltration membranes, or combinations thereof. The term "purified oxidation feedstock" (e.g., permeate solution) may be used to refer to the separated oxidation feedstock, while the term "retentate solution" may be used to refer to a separation solution having an increased humus concentration.

[0117] In some embodiments, unconverted fructose, intermediates, and HMF are separated from other components of the composition withdrawn from the reaction zone using selective membrane separation techniques (e.g., ultrafiltration and / or nanofiltration). Selective membrane separation techniques for treating aqueous compositions withdrawn from the reaction zone as disclosed herein provide efficient recovery of unconverted fructose and intermediates for recycling, increased overall process yield, and a high degree of product recovery.

[0118] In some embodiments, aqueous reaction composition is contacted with one or more ultrafiltration membranes, to produce concentrate or retentate solution or liquid stream containing at least a portion (preferably, substantially all) humus from reaction composition, and permeate solution or liquid stream containing unconverted fructose, intermediate, catalyst and HMF and humus scarce relative to aqueous reaction composition.Then the retentate liquid stream can be fed to solvent and / or humus recovery unit to reclaim solvent from the retentate liquid stream containing humus.Humus can be separated as described in further detail herein, and the solvent recovered can be recycled.

[0119] Solvent and humus recovery

[0120] When the dehydration product solution is separated into purified oxidation feedstock and retentate solution after the sugar dehydration process, the retentate solution can be used for a solvent recovery process. In some embodiments, the retentate solution comprises a retentate solvent and dissolved solids. In some embodiments, the retentate solvent comprises a dehydration solvent as described herein. In some embodiments, the retentate solvent is a multi-component solvent. In some embodiments, the multi-component solvent comprises water and a water-miscible aprotic organic solvent. In some embodiments, the water-miscible organic solvent is tetrahydrofuran, glycol dimethyl ether, dioxane, dioxolane, dimethylformamide, cyclopentane, acetone, N-methyl-2-pyrrolidone, methyl ethyl ketone or γ-valerolactone or any combination thereof. In some embodiments, the retentate solvent comprises 1,4-dioxane, water or a combination thereof.

[0121] In some embodiments, the dissolved solids include components of carbohydrate feedstocks, carbohydrate feedstock intermediates, carbohydrate feedstock byproducts, oxidized feedstocks, oxidized substrates, or combinations thereof. Combinations of carbohydrate feedstocks, carbohydrate feedstock intermediates, carbohydrate feedstock byproducts, oxidized feedstocks, and oxidized substrates are described herein. For example, in some embodiments, the dissolved solids include sugars, such as C6 monosaccharides (e.g., glucose, fructose, or mannose), C5 monosaccharides (e.g., xylose or arabinose), furan-containing organic compounds (e.g., 5-hydroxymethylfurfural, 5-hydroxymethyl-2-furancarboxylic acid, 2,5-furandicarboxylic acid, furfural, 2-furoic acid, furfuryl alcohol, or furan hydroxymethyl ketone), humus (e.g., polymerized sugars or dehydrated sugars, or polymerized furan compounds), organic acids (e.g., levulinic acid, formic acid, or acetic acid, and combinations thereof), homogeneous acids (e.g., HCl, HBr, HI, H 2 SO 4 , H 3 PO 4 In some embodiments, the retentate solution comprises at least one of humus, sugar, organic acid, furan-containing organic compound, salt or combination thereof. In some embodiments, the salt is selected from the group consisting of sodium bromide, calcium bromide, sodium chloride, calcium chloride, potassium chloride, magnesium chloride and a combination thereof. In some embodiments, the salt is sodium bromide and / or calcium bromide or a mixture of the two. In some embodiments, the salt is sodium chloride and / or calcium chloride or a mixture of the two.

[0122] In some embodiments, the retentate solution is further treated to form a lean retentate stream having a reduced concentration of carbohydrate substrate and / or at least one dehydration pathway product from the retentate solution. In some embodiments, the lean retentate solution is formed by further treating the retentate solution with a membrane. In some embodiments, HMF is removed from the retentate solution to form a lean retentate solution. In some embodiments, the lean retentate solution is enriched in humus, organic acids, or sugars, or any combination thereof.

[0123] The feed solution comprising the retentate solution and / or the lean retentate solution can be fed and processed by the solvent recovery method described herein. In some embodiments, the feed solution comprises about or comprises 1wt%, 3wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 31wt%, 32wt%, 35wt%, 40wt%, 50wt% or 60wt% dissolved solids, or dissolved solids in an amount within the range defined by any two of the above amounts. For example, in some embodiments, the feed solution comprises 5-40wt% dissolved solids. In some embodiments, the pH of the feed solution is about or is 0.5, 0.75, 1, 2, 3, 4, 5 or 6, or a pH within the range defined by any two of the above pHs. For example, in some embodiments, the feed solution has a pH of 1-4 or about 1-4. In some embodiments, the feed solution comprises a sugar concentration of about or comprising 15000 ppm, 20000 ppm, 22500 ppm, 25000 ppm, 28000 ppm, 30000 ppm, 31000 ppm, 35000 ppm, 40000 ppm, 50000 ppm, 60000 ppm, 70000 ppm, 80000 ppm, 90000 ppm, 100000 ppm, 110000 ppm, 120000 ppm, 150000 ppm, 200000 ppm, 250000 ppm, 300000 ppm or 400000 ppm, or a concentration within a range defined by any two of the above concentrations. In some embodiments, the feed solution contains about or comprises 1 wt.%, 1.5 wt.%, 2 wt.%, 2.3 wt.%, 2.5 wt.%, 2.7 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.%, 5 wt.%, 5.5 wt.%, 6 wt.%, 7 wt.% or 10 wt.% of a furanic compound concentration, or a concentration within a range defined by any two of the above concentrations. In some embodiments, the feed solution comprises a humic substance concentration of about or comprising 10000 ppm, 15000 ppm, 20000 ppm, 21000 ppm, 22000 ppm, 23000 ppm, 24000 ppm, 25000 ppm, 25300 ppm, 2600 ppm, 27000 ppm, 28000 ppm, 29000 ppm, 30000 ppm, 35000 ppm, 40000 ppm, 50000 ppm, 70000 ppm, 80000 ppm, 90000 ppm, 100000 ppm, 120000 ppm, 150000 ppm or 200000 ppm, or a concentration within a range defined by any two of the above concentrations.In some embodiments, the feed solution comprises an organic acid concentration of about or comprising 0.1 wt.%, 0.15 wt.%, 0.2 wt.%, 0.24 wt.%, 0.25 wt.%, 0.3 wt.%, 0.35 wt.%, 0.4 wt.%, 0.45 wt.%, 0.5 wt.%, 0.55 wt.%, 0.6 wt.%, 0.65 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1 wt.% or 2 wt.%, or a concentration within a range defined by any two of the above concentrations. In some embodiments, the feed solution comprises about or comprises 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 68 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 82 wt.%, 85 wt.%, 88.9 wt.%, 90 wt.%, 92 wt.%, 95 wt.%, 98 wt.%, or 99 wt.% of solvent concentration, or a concentration in a range defined by any two of the above concentrations. In some embodiments, the feed solution comprises about or comprises 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 10 wt.%, 11.6 wt.%, 12 wt.%, 15 wt.%, 17 wt.%, 19 wt.%, 20 wt.%, 25 wt.%, or 30 wt.% of dry residue concentration, or a concentration in a range defined by any two of the above concentrations.

[0124] The feed solution comprising the retentate solution and / or the lean retentate solution is then processed to recycle the retentate solvent and separate the dissolved solids as a dry free-flowing powder. In some embodiments, the feed solution is processed by a thin film evaporator or a heated thin film evaporator. In some embodiments, the thin film evaporator or the heated thin film evaporator is oriented vertically, horizontally or diagonally or at a fixed angle relative to the ground or the earth's center of mass. In some embodiments, the vertical orientation is at 0 ° of the normal or approximately at 0 ° of the normal, and the horizontal orientation is at 90 ° of the normal or approximately at 90 ° of the normal. In some embodiments, the thin film evaporator or the heated thin film evaporator is oriented relative to the ground at an angle between 0 ° to 90 ° of the normal or between about 0 ° to 90 ° of the normal (such as, for example, about or at 5 °, 10 °, 15 °, 30 °, 45 °, 60 °, 75 °, 80 ° or 85 °, or any numerical range therebetween). In some embodiments, the thin film evaporator or heated thin film evaporator is oriented at an angle of 0° to 180°, about 0° to 180°, between 0° to 180°, or between about 0° to 180°, such as at about or at 0°, 5°, 10°, 15°, 30°, 45°, 60°, 75°, 80°, 85°, 90°, 95°, 120°, 135°, 160°, or 180°, or any range of values ​​therebetween, wherein 0° corresponds to the thin film evaporator or heated thin film evaporator being oriented vertically downward toward the center of mass of the earth, and 180° corresponds to the thin film evaporator or heated thin film evaporator being oriented vertically upward away from the center of mass of the earth. In some embodiments, the feed solution is passed through a horizontal thin film evaporator (HTFE) or a heated HTFE (e.g., Artisan E thin film evaporator) for treatment. In some embodiments, the thin film evaporator system includes a feed pump to guide the feed solution to the thin film evaporator. In some embodiments, the thin film evaporator system includes a countercurrent horizontal thin film evaporator with a hot oil jacket. In some embodiments, the thin film evaporator system includes a condenser for solvent collection. In some embodiments, the thin film evaporator system includes a vacuum pump. In some embodiments, the thin film evaporator system includes a mass flow meter for inert gas injection. In some embodiments, the thin film evaporator system includes a bottom solid discharge valve. In some embodiments, the thin film evaporator system includes a control system. In some embodiments, the control system is configured to maintain the film temperature, pressure, inert gas injection or feed rate of the thin film evaporator system, or a combination thereof.

[0125] Figure 1 and Figure 2 An exemplary use of HTFE for processing the membrane retentate feed to obtain dry humic solids and collect the solvent is described. Figure 1An apparatus 100 is shown wherein a membrane retentate feed 102 is directed into a HTFE 104. In some embodiments, the HTFE 104 is a countercurrent HTFE. The HTFE 104 includes a rotating screw or slide 106, a hot inlet 108, and a hot outlet 110. When the HTFE 104 is operated with the addition of the membrane retentate feed 102, a dry free-flowing powder 112 is recovered from the processing of the membrane retentate feed 102. In some embodiments, the dry free-flowing powder 112 comprises dry humic substances. In addition, the processing of the membrane retentate feed 102 by the HTFE 104 produces a solvent vapor 114 that is directed to a solvent condenser 116, wherein the solvent condenser 116 produces a distillate 118.

[0126] Figure 2 An apparatus 200 is shown wherein a membrane retentate feed 202 is directed to a HTFE 204. In some embodiments, the HTFE 204 is a countercurrent HTFE. The HTFE 204 includes a rotating screw or slide 206, a hot inlet 208, and a hot outlet 210. When the HTFE 204 is operated with the addition of the membrane retentate feed 202, a dry free-flowing powder 212 is recovered from the processing of the membrane retentate feed 202. In some embodiments, the dry free-flowing powder 212 comprises dry humic substances. In addition, the processing of the membrane retentate feed 202 by the HTFE 204 produces a solvent vapor 214 that is directed to a continuous distillation column 216, wherein the solvent condenser 216 produces a bottoms collection 218 and a purified solvent distillate 220, respectively.

[0127] The feed solution is directed into a thin film evaporator, wherein the feed solution is maintained on a heated wall as a thin film by the centrifugal force applied by the rotor blades of the thin film evaporator, thereby evaporating the solvent. When the feed solution is continuously directed into the thin film evaporator, the film is constantly renewed and gradually becomes more concentrated with dissolved solids until the solids are precipitated from the solution as a solid product and are discharged to the bottom discharge valve by the incoming feed. In some embodiments, the feed rate of the feed solution entering the thin film evaporator is set so that the residence time of the feed solution is less than about or less than 10 minutes, 5 minutes, 4 minutes, 3 minutes, 2 minutes, 1 minute or 0.5 minutes, or any numerical range therebetween. In some embodiments, the feed rate is set so that the residence time of the feed solution is less than 2 minutes.

[0128] In some embodiments, the thin film evaporator is operated under an inert gas inside the evaporator. The inert gas can help to create a non-flammable atmosphere in the evaporator. In some embodiments, the thin film evaporator is operated under a nitrogen flow. The concentration of the feed and the evaporation of the solvent can be achieved under atmospheric pressure or vacuum. The feed can be fed directly from the membrane separation unit or can be pre-concentrated using standard evaporation techniques to increase the dissolved solids content and recover part of the multi-component solvent mixture.

[0129] In some embodiments, the feed solution is introduced into a heated thin film evaporator having a film temperature of about or at 170° C., 175° C., 180° C., 185° C., 190° C., 195° C., 200° C., 205° C., 210° C., 215° C., 220° C., 225° C., 230° C., 235° C., 240° C., or 250° C., or any range of values ​​therebetween. For example, in some embodiments, the film temperature is between 180-230° C. In some embodiments, the thin film evaporator is operated at a pressure of about or at 470torr, 480torr, 490torr, 500torr, 525torr, 550torr, 575torr, 600torr, 625torr, 650torr, 675torr, 700torr, 725torr, 750torr, 775torr, 800torr, 810torr, 820torr or 850torr, or any range of values ​​therebetween. For example, in some embodiments, the thin film evaporator is operated between 490-800torr.

[0130] In some embodiments, the collected solvent vapor or distillate exiting the thin film evaporator can be fed to a condenser connected to the thin film evaporator and collected, for example, as Figure 1 In some embodiments, the collected solvent vapor or distillate leaving the thin film evaporator can be fed as a vapor to a continuous distillation column to collect continuous fractions of solvent and light organic compounds, such as Figure 2 In some embodiments, the collected solvent distillate vapor can be further purified by fractional distillation at ambient pressure to obtain a purified or isolated solvent mixture.

[0131] In some embodiments, the solvent distillate has a pH of about or having a pH of 0.5, 0.75, 1, 2, 3, 4, 5, or 6, or any range of values ​​therebetween. In some embodiments, the solvent distillate comprises a sugar concentration of about or comprising 1 ppm, 5 ppm, 10 ppm, 20 ppm, 30 ppm, 50 ppm, 100 ppm, 150 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 800 ppm, or 10000 ppm, or any range of values ​​therebetween. In some embodiments, the solvent distillate comprises about or comprises 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1 wt.%, 1.1 wt.%, 1.2 wt.%, 1.3 wt.%, 1.4 wt.%, 1.5 wt.%, 2 wt.%, 2.3 wt.%, 2.5 wt.%, 2.7 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.%, or 5 wt.% furanic compound concentration, or any range of values ​​therebetween. In some embodiments, the solvent distillate comprises about or comprises 50ppm, 100ppm, 500ppm, 1000ppm, 2000ppm, 3000ppm, 4000ppm, 5000ppm, 6000ppm, 8000ppm or 10,000ppm of furanic compound concentration, or any range of furanic compound concentration therebetween. In some embodiments, the solvent distillate comprises about or comprises 200ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm or 900ppm of humic substance concentration, or any range of humic substance concentration therebetween. In some embodiments, the solvent distillate comprises an organic acid concentration of about or comprising <0.01 wt.%, 0.01 wt.%, 0.05 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.5 wt.%, 0.7 wt.%, 1 wt.%, 1.2 wt.%, 1.4 wt.%, 1.5 wt.%, 1.6 wt.%, 1.7 wt.%, 1.8 wt.%, 1.9 wt.%, 2 wt.%, 2.5 wt.%, or 3 wt.%, or any range of organic acid concentrations therebetween.In some embodiments, the solvent distillate comprises about or comprises 2 wt.%, 5 wt.%, 10 wt.%, 25 wt.%, 50 wt.%, 60 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 82 wt.%, 85 wt.%, 88.9 wt.%, 90 wt.%, 91 wt.%, 92 wt.%, 93 wt.%, 94 wt.%, 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.%, 98.5 wt.%, 99 wt.%, 99.5 wt.%, 99.8 wt.%, or 99.9 wt.% solvent concentration, or any range of solvent concentrations therebetween. In some embodiments, the solvent distillate comprises about or comprises 0.1 wt.%, 0.3 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1 wt.%, 1.2 wt.%, 1.5 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, or 10 wt.% dry residue concentration, or any range of values ​​therebetween.

[0132] In some embodiments, the solvent distillate is subjected to a fractionation process to form a fractionated distillate. In some embodiments, the fractionated distillate comprises an organic solvent, water, furan, or organic acid, or any combination thereof, with an increased concentration. In some embodiments, the solvent distillate recycles 70%, 80%, 85%, 90%, 92%, 95%, 97%, 98%, 99%, 99.5% or 99.9% of an organic solvent, or an organic solvent in an amount of solvent within a range defined by any two of the above percentages. In some embodiments, the organic solvent is a water-miscible aprotic organic solvent as described herein. In some embodiments, the organic solvent is 1,4-dioxane.

[0133] In some embodiments, the bottom solid product discharged from the thin film evaporator is dry. In some embodiments, the solid product comprises, comprises about, comprises less than about, or comprises less than 0.1wt.%, 0.33wt.%, 0.5wt.%, 0.62wt.%, 0.65wt.%, 1wt.%, 1.15wt.%, 1.88wt.%, 2wt.%, 3wt.%, 4wt.%, or 5wt.% moisture content, or any range of moisture content between them. In some embodiments, the solid product comprises about or comprises 0.80wt.%, 0.85wt.%, 0.90wt.%, 0.92wt.%, 0.95wt.%, 0.96wt.%, 0.97wt.%, 0.98wt.%, 0.99wt.%, 1wt.%, 1.2wt.%, or 1.5wt% furan content, or any range of furan content between them. In some embodiments, the solid product comprises about or comprises 0.05 wt.%, 0.1 wt.%, 0.15 wt.%, 0.17 wt.%, 0.20 wt.%, 0.5 wt.%, 1 wt.%, 1.3 wt.%, 1.5 wt.%, 1.6 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 4.5 wt.%, 5 wt.%, 6 wt.%, 8 wt.% or 10 wt.% sugar content, or any range of sugar content therebetween. In some embodiments, the solid product comprises about or comprises 0.01 wt.%, 0.05 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1 wt.% or 2 wt.% organic acid content, or any range of organic acid content therebetween. In some embodiments, the solid product comprises about or comprises 0.005 wt.%, 0.01 wt.%, 0.02 wt.%, 0.03 wt.%, 0.04 wt.%, 0.05 wt.%, 0.07 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1 wt.% or 2 wt.% organic solvent content, or any range of organic solvent content therebetween. In some embodiments, the solid product comprises about or comprises 50 wt.%, 55 wt.%, 56 wt.%, 57 wt.%, 58 wt.%, 59 wt.%, 60 wt.%, 61 wt.%, 62 wt.%, 63 wt.%, 65 wt.% or 70 wt.% carbon content, or any range of carbon contents therebetween.In some embodiments, the solid product comprises about or comprises 4 wt.%, 4.2 wt.%, 4.4 wt.%, 4.5 wt.%, 4.6 wt.%, 4.7 wt.%, 4.8 wt.%, 4.9 wt.%, 5 wt.% or 5.5 wt.% hydrogen content, or any range of values ​​therebetween. In some embodiments, the solid product comprises about or comprises 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.5 wt.%, 0.8 wt.%, 0.9 wt.%, 1 wt.%, 1.5 wt.% or 2 wt.% nitrogen content, or any range of values ​​therebetween. In some embodiments, the solid product comprises a low sulfur content. In some embodiments, the solid product comprises about or comprises 0 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.% or 0.5 wt.% sulfur content, or any range of values ​​therebetween. In some embodiments, the solid product comprises about or comprises 20wt.%, 25wt.%, 28wt.%, 29wt.%, 30wt.%, 31wt.%, 32wt.%, 33wt.%, 34wt.%, 35wt.% or 40wt.% oxygen content, or the oxygen content of any numerical range between them. In some embodiments, the solid product comprises low ash content. In some embodiments, the solid product comprises about or comprises 0.1wt.%, 0.5wt.%, 1wt.%, 2wt.%, 3wt.%, 4wt.%, 5wt.%, 6wt.%, 7wt.%, 8wt.%, 10wt.% or 15wt.% ash content when heated to 700°C, or the ash content of any numerical range between them. In some embodiments, the solid bottoms product is a fine carbonaceous powder. In some embodiments, the solid product comprises a low metal content. In some embodiments, the solid product comprises a high humus content.

[0134] In some embodiments, the solid product can be subsequently washed, the remaining solids are filtered and the collected liquid is dried to form a washed solid product. In some embodiments, the washed solid product comprises an ash content reduced relative to the unwashed solid product. In some embodiments, the washed solid product comprises a salt content reduced relative to the unwashed solid product. In some embodiments, the solid product is washed with at least one of water, an acid solution and / or an organic solvent. In some embodiments, the acidic solution comprises citric acid. In some embodiments, the organic solvent comprises ethanol. In some embodiments, the washed solid product comprises about or comprises 0.05wt.%, 0.1wt.%, 0.2wt.%, 0.3wt.%, 0.4wt.%, 0.5wt.%, 0.6wt.%, 0.7wt.%, 0.8wt.%, 0.9wt.%, 1wt.% or 2wt.% ash content when heated to 700°C, or an ash content within the range defined by any two of the above amounts.

[0135] In some embodiments, the solid product and / or the washed product may be subsequently carbonized to form a carbonized solid product. In some embodiments, the carbonization process includes exposing the product to high temperature. In some embodiments, the high temperature may be selected from about or selected from 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, 900°C, 1000°C, 1200°C, 1500°C or 2000°C, or in the range defined by any two of the above temperatures. In some embodiments, the carbonization process includes an inert atmosphere. In some embodiments, the inert atmosphere is a nitrogen atmosphere.

[0136] Additional processing of collected products

[0137] In some embodiments, the collected product can be further processed for downstream applications. In some embodiments, the collected product includes a solid product, a washed solid product or a carbonized product, or any combination thereof. In some embodiments, the collected product is further processed into a desired product. In some embodiments, the desired product can be used for soil applications (such as soil conditioners or fertilizers), energy storage applications, or for liquid and gas purification applications. In some embodiments, the desired product can be a soil conditioner, a soil enhancer, a soil conditioner, a soil purifier, a fertilizer, an anode material, or an activated carbon material.

[0138] In some embodiments, the desired product is an activated carbon material. In some embodiments, the activated carbon material can be used for gas purification, liquid purification, or electrode material applications. In some embodiments, the activated carbon material comprises at least about or at least 800 m 2 / g、900m 2 / g、1000m 2 / g、1200m 2 / g、1400m 2 / g、1600m 2 / g、1800m 2 / g or 2000m 2 / g of surface area, or a surface area within the range defined by any two of the above surface areas. In some embodiments, the activated carbon material is powdered activated carbon, or granular or spherical activated carbon. In some embodiments, forming powdered activated carbon from a solid product comprises washing a solid product as described herein, high temperature carbonization of the washed solid product as described herein, and activation of the carbonized solid product. In some embodiments, the activation of the solid product comprises steam and / or gas activation. In some embodiments, steam and / or gas activation comprises exposing the solid product to high temperature under a steam or combustion gas atmosphere. In some embodiments, the combustion gas atmosphere comprises CO 2 , CO or N 2 , or a combination thereof. In some embodiments, the high temperature used in steam and gas activation is about or is 600°C, 700°C, 800°C, 900°C, 1000°C, 1100°C or 1200°C, or within the range defined by any two of the above temperatures. In some embodiments, the activation of the solid product comprises chemical activation. In some embodiments, chemical activation comprises mixing the solid product with a strong base and then exposing it to a high temperature in an inert atmosphere. In some embodiments, the strong base may be KOH, or NaOH, or a combination thereof. In some embodiments, the high temperature used in chemical activation is about or is 400°C, 500°C, 600°C, 700°C, 800°C, 900°C or 1000°C, or within the range defined by any two of the above temperatures. In some embodiments, additional grinding of the activated particles is performed to obtain the desired particle size.

[0139] In some embodiments, granular or spherical activated carbon is formed by the same process as forming powdered activated carbon, except that after the washing process and before the high temperature carbonization process, the washed solid product is subjected to a granulation or compaction process. In some embodiments, forming granular or spherical activated carbon includes washing the solid product as described herein, mixing the washed solid product with a bio-based binder, extrusion, spheroidization or granulation of the binder-solid product mixture, subsequent drying or oxidation, and then optionally exposed to a high temperature carbonization process as described herein, followed by activation of the carbonized solid product as described herein, and subsequent washing and drying of the activated product. In some embodiments, the bio-based binder is an aqueous mixture of tall oil pitch, sugar and / or cellulose derivatives, or a combination thereof. In some embodiments, the cellulose derivative is hydroxyethyl cellulose. In some embodiments, drying or oxidation is carried out in air at 100°C, 150°C, 200°C, 250°C or 300°C, or within a range defined by any two of the above temperatures.

[0140] In some embodiments, the desired product is a hard carbon material. In some embodiments, the hard carbon material can be used for energy storage applications (e.g., as an anode material in a lithium ion battery). In some embodiments, the hard carbon material is characterized by a low surface area relative to the solid product starting material. In some embodiments, forming the hard carbon material from the solid product includes washing a solid product as described herein, high temperature carbonization of the washed solid product as described herein, grinding and sorting of the carbonized product, and coating and carbonization post-treatment of the ground product.

[0141] FDCA pathway process

[0142] In the present disclosure, any and all FDCA pathway processes may be utilized.As used herein, the terms "furandicarboxylate pathway product" and "FDCA pathway product" are used interchangeably herein to refer to 2,5-furandicarboxylic acid (FDCA) or a 2,5-furandicarboxylate pathway intermediate compound.

[0143] In some embodiments, the FDCA pathway product is FDCA. In some embodiments, the oxidation substrate is sugar, HMF and / or FDCA pathway intermediate compound (such as DFF, HMFCA or FFCA), or a mixture of any two or more thereof. In some embodiments, the oxidation feedstock may also include residual components or other reagents that are soluble or insoluble in the oxidation feedstock. For example, the oxidation feedstock may be a crude oxidation feedstock of an oxidation solvent and HMF or other oxidation substrates. The term "crude oxidation feedstock" refers herein to a raw material that includes impurities and / or by-products related to the production, separation and / or purification of the desired oxidation substrate in addition to the desired oxidation substrate. For example, the oxidation feedstock may additionally include some biomass-derived or biomass-related components as a by-product, which are produced in the conversion of biomass to sugar (such as by heat, chemical, mechanical, and / or enzymatic degradation methods), and such sugars are subsequently converted into HMF. Thus, the crude oxidation feedstock may also contain a component selected from the group consisting of: a polysaccharide (including, for example, cellulose (e.g., lignocellulose or hemicellulose, etc.) or starch, etc.), or an oligosaccharide (e.g., raffinose, maltodextrin or cellodextrin, etc.), or a monosaccharide (e.g., glucose, fructose, galactose, mannose, xylose or arabinose, etc.), or a disaccharide (e.g., sucrose, lactose, maltose or cellobiose, etc.), or a furanic substrate (e.g., furfural, oligomeric or polymeric humic byproducts (humins)), or a residual inorganic acid, or a salt of a corresponding inorganic acid. Similarly, the oxidation feedstock may be a crude feedstock of HMF oxidation products comprising HMF and / or FDCA pathway intermediate compounds. The crude oxidation feedstock may be treated to increase the concentration of the desired oxidation substrate and / or reduce the concentration of impurities and / or byproducts, wherein the crude oxidation feedstock treated in this manner may be referred to as a "purified oxidation feedstock" as described herein.

[0144] As used herein, the term "oxidation solvent" refers to a solvent that is an organic solvent or a multi-component solvent in which the oxidation substrate and the desired FDCA pathway product can each be dissolved at a minimum level of at least 2 wt% at the temperature at which the contacting (oxidation) step is performed. Typically, the oxidation solvent is a solvent in which the FDCA pathway product has a solubility of at least 3 wt%, at least 4 wt%, more typically at least 5 wt%, at least 6 wt%, at least 7 wt%, at least 8 wt%, at least 9 wt%, at least 10 wt%, at least 11 wt%, at least 12 wt%, at least 13 wt%, at least 14 wt% or at least 15 wt%, or a solubility within the range defined by any two of the above amounts, as measured at the temperature at which the contacting step is performed. In some embodiments, the FDCA pathway product has a solubility in the range of 2-4 wt%, 3-5 wt%, 4-6 wt%, 5-7 wt%, 6-8 wt%, 7-9 wt%, 8-10 wt%, 9-11 wt%, 10-12 wt%, 11-13 wt%, 12-14 wt%, or 13-15 wt%, or a solubility in the range defined by any two of the above weight percentages. The solubility of the FDCA pathway product in a candidate organic solvent or candidate multi-component solvent can be readily determined using known methods.

[0145] Organic solvents that exhibit the necessary minimum solvating requirement for oxidation substrates and FDCA are suitable for use alone or as a component of a multi-component solvent. In some embodiments, the oxidation solvent comprises an aprotic organic solvent (e.g., ether, ester, or ketone, etc.) alone (i.e., as a single-component solvent) or as a component of a multi-component solvent. When used in a multi-component solvent, the aprotic organic solvent is generally miscible with the other components of the multi-component solvent. The term "multi-component solvent" refers to a mixture of two, three or more solvent species in this article. The multi-component solvent used in the practice of the present disclosure may include two or more solvent species selected from the group consisting of a first organic solvent species, a second organic solvent species, and water. When the multi-component solvent contains water and an organic solvent, the organic solvent is a water-miscible organic solvent. Typically, a water-miscible organic solvent is a water-miscible aprotic organic solvent.

[0146] In some embodiments, the candidate component solvents of the multi-component solvent are not limited to solvents in which the oxidation substrate and the desired FDCA pathway product are highly soluble, because even when FDCA has poor solubility in each component solvent, the multi-component solvent can also exhibit a synergistic solvating effect relative to FDCA. For example, FDCA has poor solubility in water. However, even when paired with a water-miscible organic solvent with poor FDCA solvating ability, the combination of water and a water-miscible organic solvent also exhibits enhanced FDCA solvating ability.

[0147] Exemplary multi-component solvents that exhibit this effect include multi-component solvents containing water and a water-miscible aprotic organic solvent. Exemplary water-miscible aprotic solvents suitable for use in the practice of the present disclosure include tetrahydrofuran, glyme, dioxane, dioxolane, dimethylformamide, dimethyl sulfoxide, sulfolane, acetone, N-methyl-2-pyrrolidone ("NMP"), methyl ethyl ketone ("MEK"), or γ-valerolactone, and the like. Preferably, the water-miscible aprotic organic solvent is an ether, such as, for example, glyme, dioxane (1,4-dioxane), dioxolane (e.g., 1,3-dioxolane), or tetrahydrofuran, and the like. Glyme suitable for use in the practice of the present disclosure include, for example, monoglyme (1,2-dimethoxyethane, "DME"), ethylglyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme, butyl diglyme, tetraglyme, polyglyme, or highly ethoxylated diethers of high molecular weight alcohols ("higlyme"), etc. Typically, the oxygenate solvent is a multicomponent solvent comprising water and a water-miscible aprotic organic solvent, which is glyme, diglyme, or dioxane.

[0148] In some embodiments, the composition of the oxidation solvent can take into account the requirements of further downstream processes (e.g., promoting product recovery, purification, etc.) or upstream processes (e.g., converting sugars into furan oxidation substrates). For example, in certain embodiments, it may be desirable to use an oxidation solvent that is a multi-component solvent comprising a light solvent and a heavy solvent. The term "light solvent" refers to a solvent having a boiling point that occurs at a temperature lower than the boiling point (temperature) of a heavy solvent at the same pressure under a certain pressure. On the contrary, the term "heavy solvent" refers to a solvent having a boiling point that occurs at a temperature higher than the boiling point (temperature) of a light solvent at the same pressure under a certain pressure. When the multi-component solvent comprises water and a water-miscible organic solvent, the water-miscible organic solvent can be a light water-miscible organic solvent (e.g., a water-miscible organic solvent having a boiling point that occurs at a temperature lower than the boiling point of water), or it can be a heavy water-miscible organic solvent (e.g., a water-miscible organic solvent having a boiling point that occurs at a temperature higher than the boiling point of water). Typically, light and heavy water-miscible organic solvents are light and heavy aprotic organic solvents, respectively. Exemplary light water-miscible (and aprotic) organic solvents used with water in a multi-component solvent include, for example, glycol dimethyl ether, dioxolane (e.g., 1,3-dioxolane) or tetrahydrofuran, etc. Exemplary heavy water-miscible (and aprotic) organic solvents used with water in a multi-component solvent include, for example, dioxane, ethyl glycol dimethyl ether, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme, butyl diglyme, tetraglyme or polyglyme, etc. In some embodiments (e.g., continuous reactor systems), all or part of the oxidation solvent or its components can be removed from the production solution (e.g., via distillation) and recycled to the reaction mixture. In such embodiments, it may be desirable to use a multi-component solvent having a composition that corresponds to an azeotrope or is capable of forming an azeotrope at the temperature used during the oxidation step (i.e., the contacting step) or at the temperature used in a process upstream or downstream of the oxidation step (i.e., an "azeotropic composition"). The use of such a multi-component solvent having an azeotropic composition can facilitate the recycling of the oxidation solvent (as part of the azeotropic composition) to the oxidation step or to processes occurring upstream and / or downstream of the oxidation step.

[0149] In some embodiments, the water-miscible organic solvent species is at least 5 volume % (vol%), at least 10 vol%, at least 15 vol%, at least 20 vol%, at least 25 vol%, at least 30 vol%, at least 35 vol%, at least 40 vol%, at least 45 vol%, at least 50 vol%, at least 55 vol%, at least 60 vol%, at least 65 vol%, at least 70 vol%, at least 75 vol%, at least 80 vol%, at least 85 vol%, at least 90 vol%, or at least 10 vol% of the multi-component solvent. 95vol%; correspondingly, water is usually less than 95vol%, less than 90vol%, less than 85vol%, less than 80vol%, less than 75vol%, less than 70vol%, less than 65vol%, less than 60vol%, less than 55vol%, less than 50vol%, less than 45vol%, less than 40vol%, less than 35vol%, less than 30vol%, less than 25vol%, less than 20vol%, less than 15vol%, less than 10vol% or less than 5vol% of the multi-component system, respectively.

[0150] In some embodiments, the multi-component solvent contains water in the range of 1-5 wt % or any value therebetween and a water-miscible organic solvent in the range of 99-95 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 5-10 wt % or any value therebetween and a water-miscible organic solvent in the range of 95-90 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 10-15 wt % or any value therebetween and a water-miscible organic solvent in the range of 90-85 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 15-20 wt % or any value therebetween and a water-miscible organic solvent in the range of 85-80 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 20-25 wt % or any value therebetween and a water-miscible organic solvent in the range of 80-75 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 25-30 wt % or any value therebetween and a water-miscible organic solvent in the range of 75-70 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 30-35 wt % or any value therebetween and a water-miscible organic solvent in the range of 70-65 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 35-40 wt % or any value therebetween and a water-miscible organic solvent in the range of 65-60 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 40-45 wt % or any value therebetween and a water-miscible organic solvent in the range of 60-55 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 45-50 wt % or any value therebetween and a water-miscible organic solvent in the range of 65-50 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 50-55 wt % or any value therebetween and a water-miscible organic solvent in the range of 50-45 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 55-60 wt % or any value therebetween and a water-miscible organic solvent in the range of 45-40 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 60-65 wt % or any value therebetween and a water-miscible organic solvent in the range of 40-35 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 65-70 wt % or any value therebetween and a water-miscible organic solvent in the range of 35-30 wt % or any value therebetween.In some embodiments, the multi-component solvent contains water in the range of 70-75 wt % or any value therebetween and a water-miscible organic solvent in the range of 30-25 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 75-80 wt % or any value therebetween and a water-miscible organic solvent in the range of 25-20 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 80-85 wt % or any value therebetween and a water-miscible organic solvent in the range of 20-15 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 85-90 wt % or any value therebetween and a water-miscible organic solvent in the range of 15-10 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 90-95 wt % or any value therebetween and a water-miscible organic solvent in the range of 10-5 wt % or any value therebetween. In some embodiments, the multi-component solvent contains water in the range of 95-99 wt %, or any value therebetween, and water-miscible organic solvent in the range of 5-1 wt %, or any value therebetween.

[0151] In some embodiments, the volume ratio of water to water-miscible organic solvent is in the range of 1:6 to 6:1 or any value therebetween. In certain embodiments, the volume ratio is 1:4 to 4:1 water: water-miscible organic solvent or any value therebetween. In other embodiments, the volume ratio is 1:4 to 3:1 water: water-miscible organic solvent or any value therebetween. In other embodiments, the volume ratio is 1:3 to 3:1 water: water-miscible organic solvent or any value therebetween. In certain embodiments, the volume ratio is 1:1 water: water-miscible organic solvent.

[0152] In some embodiments, the multi-component solvent contains water and two different water-miscible organic solvents. Typically, two water-miscible organic solvents are water-miscible aprotic organic solvents. Each of the two water-miscible aprotic solvents can be independently selected from the group of tetrahydrofuran, glycol dimethyl ether, dioxane, dioxolane, dimethylformamide, dimethyl sulfoxide, cyclopentane, acetone, N-methyl-2-pyrrolidone ("NMP"), methyl ethyl ketone ("MEK") or γ-valerolactone. One or both of the water-miscible aprotic organic solvents can be ethers, such as glycol dimethyl ether, dioxane (e.g., 1,4-dioxane), dioxolane (e.g., 1,3-dioxolane) or tetrahydrofuran, etc. Glyme includes, for example, monoglyme (1,2-dimethoxyethane, "DME"), ethylglyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme, butyl diglyme, tetraglyme, polyglyme or highly ethoxylated diethers of high molecular weight alcohols ("high glymes"), and the like.

[0153] In some embodiments, the volume ratio of water to the first water-miscible organic solvent and the second water-miscible organic solvent is about 1:1:1 (v:v:v). In some embodiments, the volume ratio of water to the first water-miscible organic solvent and the second water-miscible organic solvent is about 1:2:1 (v:v:v). In some embodiments, the volume ratio of water to the first water-miscible organic solvent and the second water-miscible organic solvent is about 1:2:2 (v:v:v). In some embodiments, the volume ratio of water to the first water-miscible organic solvent and the second water-miscible organic solvent is about 2:1:1 (v:v:v).

[0154] In some embodiments, the oxidation catalyst is used to oxidize the oxidation substrate to the FDCA pathway product, and generally has a noble metal dispersed on the inner surface and / or outer surface of the carrier. The term "noble metal" refers to ruthenium, rhodium, palladium, silver, osmium, iridium, platinum or gold in this article. In some embodiments, the metal is selected from the group consisting of platinum, gold and a combination thereof. In some embodiments, the metal is platinum. In some embodiments, the metal is gold. The heterogeneous oxidation catalyst may further include a promoter to enhance the performance of the heterogeneous oxidation catalyst. When the metal is platinum, gold or a combination thereof, suitable promoters include, for example, Pd, Ir, Mo, Bi, Te, Sn or W.

[0155] The solid support component of the oxidation catalyst can include any type of material known to those of ordinary skill in the art that is suitable for use as a catalytic support and also has the specific surface area requirements described herein. In some embodiments, suitable materials include, for example, metal oxides, carbonaceous materials, polymers, metal silicates, metal carbides, or any composite material prepared therefrom. Exemplary metal oxides include silicon oxide (silicon dioxide), zirconium oxide (zirconium oxide), titanium oxide (titania) or aluminum oxide (aluminum oxide), etc. As used herein, the term "carbonaceous" refers to graphite and carbon black. Exemplary metal silicates include, for example, orthosilicates, borosilicates or aluminosilicates (e.g., zeolites), etc. Exemplary metal carbides include, for example, silicon carbide, etc. Suitable polymer solid support materials include polystyrene, polystyrene-to-divinylbenzene, polyamide or polyacrylamide, etc.

[0156] In the process of implementing the FDCA pathway, oxygen can be used in a neat form (i.e., only O 2 , no other gases) or as a component of a gas mixture (e.g., air, oxygen-enriched air, oxygen-depleted air, oxygen, etc. mixed in nitrogen). The molar ratio of oxygen to the oxidation substrate during the contacting step is typically in the range of 2:1 to 10:1. In some embodiments, the molar ratio of oxygen to the oxidation substrate is 2:1 to 10:1, or 3:1 to 5:1. During the contacting step, oxygen is typically present at a partial pressure in the range of 40 psig to 1000 psig, or any value therebetween. More typically, oxygen is present at a partial pressure in the range of 40 psig to 200 psig, or any value therebetween. In some embodiments, oxygen is present at a partial pressure in the range of 40-200 psig, 100-300 psig, 200-400 psig, 300-500 psig, 400-600 psig, 500-700 psig, 600-800 psig, 700-900 psig, or 800-1000 psig, or any value therebetween, or in a range bounded by any two of the foregoing partial pressures.

[0157] In some embodiments, the oxidation of the oxidized substrate to the FDCA pathway product is carried out at a temperature in the range of 50°C to 200°C, or any value therebetween. In some embodiments, the oxidation step is carried out at a temperature in the range of 80°C to 180°C, or any value therebetween; in other embodiments, the oxidation step is carried out at a temperature in the range of 90°C to 160°C, or any value therebetween, or at a temperature in the range of 100°C to 160°C, or any value therebetween. In some embodiments, the oxidation step is carried out at a temperature in the range of 90°C to 180°C, or any value therebetween, and sometimes the contacting step is carried out at a temperature in the range of 110°C to 160°C, or any value therebetween.

[0158] The process of the present disclosure can be carried out in batch, semi-batch or continuous reactor form using reactors known in the art, such as, for example, fixed bed reactors, trickle flow reactors, slurry reactors or moving bed reactors, etc. The relatively high solubility of reactants and products (particularly FDCA pathway products) in the oxidation solvent facilitates the use of all of these reactor forms, particularly the fixed bed reactor form.

[0159] The FDCA pathway product can be recovered from the reaction mixture by separating the catalyst used to form the FDCA pathway product from a product solution comprising the FDCA pathway product and the oxidation solvent. The product solution comprises the soluble components of the reaction mixture and the oxidation solvent, and is catalyst-free. The product solution can be further concentrated relative to the soluble components by removing a portion of the oxidation solvent. Removal of the oxidation solvent can be accomplished by evaporation (e.g., by using an evaporator) or distillation, etc.

[0160] As an alternative to or further to the separation step, the FDCA pathway product can be purified. Preferably, the FDCA pathway product is purified by crystallization. The purification and crystallization of the FDCA pathway product can be accomplished using known methods. The separation of the FDCA pathway product crystals from the crystallization solvent can be accomplished using known methods for separating solids from liquids, such as, for example, filtration or centrifugation, or both.

[0161] Example

[0162] Various exemplary embodiments of a thin film evaporator process for separating and recovering process solvent and solid organic impurities from a byproduct-rich membrane retentate stream obtained from a dehydration process are described herein.

[0163] General analytical methods

[0164] The humic content in all liquid streams was determined using UV-vis spectrophotometry (absorbance in the range of 360-460nm) with the precipitated humic substances as reference standard. Furan-containing compounds were determined using the HPLC-UV method with known commercially available compounds as reference standards. The water content was determined using the Karl-Fischer titration method. The content of 1,4-dioxane was determined using the GC method with commercially available 1,4-dioxane as reference standard. Organic acids were determined using the HPLC-UV method with commercially available compounds as reference standards. The dry residue was determined by freeze-drying the sample and recording the weight of the residue. The residual moisture content of the collected bottom fraction was determined gravimetrically by heating the sample to 105°C until a constant weight was obtained. The residual organic compounds in the collected solid fraction were determined by stirring the solid sample (1 g) in deionized water (20 g) and analyzing the filtered aqueous phase using the above method. The ash content of the collected solid was determined gravimetrically by heating the sample to 700°C in an ambient air stream. CHNSO was analyzed using a Thermo Flash2000 organic element analyzer.

[0165] Example 1

[0166] Example 1 describes the solvent and solid separation and recovery of a feed processed by a thin film evaporator. The feed contained humic substances, sugars, organic acids, furan-containing organic compounds and sodium bromide, as well as a multi-component solvent of 1,4-dioxane and water. The feed was introduced into the thin film evaporator at different feed rates and film temperatures. For each timed run, the distillate and the dried bottom fraction were collected in a dry, pre-weighed glass container.

[0167] The test apparatus used the following major equipment, with all process wetted metal parts being 316 stainless steel: Peristaltic feed pump; 465 cm 2 (internal), hot oil jacketed, countercurrent horizontal thin film evaporator with motor driven rotor, 5 cm bottom outlet and 5 cm steam outlet; 0.37 m 2 (Internal) U-tube condenser with steam on the shell side and cold water on the tube side; dry ice cold trap condensing steam branch; vacuum pump and mass flow meter for nitrogen sparging. The equipment setup parameters for test runs 1-1 to test runs 1-7 are shown in Table 1 herein.

[0168] Table 1: Parameters

[0169]

[0170]

[0171] The analytical data of the feed material (Feed-1) and the solvent distillate for Test Run 1-1 to Test Run 1-7 are shown in Table 2 herein:

[0172] Table 2: Feed and solvent distillate

[0173]

[0174] The analytical data for the solid bottoms fractions of Test Run 1-2 and Test Run 1-3 are shown in Table 3 herein as Solids 1-2 and Solids 1-3, respectively.

[0175] Table 3: Solid bottom fraction

[0176]

[0177] Example 2

[0178] Example 2 describes the solvent and solid separation and recovery of a feed processed by a thin film evaporator. The feed contained humic substances, sugars, organic acids, furan-containing organic compounds, and sodium bromide, as well as a multi-component solvent of 1,4-dioxane and water. The feed was introduced into the thin film evaporator at various feed rates, film temperatures, nitrogen sparge rates, and reactor pressures. For each timed run, the distillate and dried bottom fraction were collected in a dry, pre-weighed glass container.

[0179] The test apparatus uses the following main equipment, of which all process wetted metal parts are 316 stainless steel: 300L stirring feed tank; peristaltic feed pump; 930cm 2 (internal), hot oil jacketed, countercurrent horizontal thin film evaporator with motor driven rotor, 10 cm bottom outlet and 10 cm steam outlet; 0.7 m 2 (Internal) U-tube condenser with steam on the shell side and cold water on the tube side; dry ice cold trap condensing steam branch; vacuum pump; and mass flow meter for nitrogen sparging. The equipment setup parameters for Test Runs 2-1 to 2-6 are shown in Table 4 herein.

[0180] Table 4: Parameters

[0181]

[0182] The analytical data for the feed material (Feed-2) and solvent distillate for Test Run 2-1 to Test Run 2-6 are shown in Table 5 herein:

[0183] Table 5: Feed and solvent distillate

[0184]

[0185] The analytical data for the solid bottoms fractions of Test Run 2-1, Test Run 2-2, Test Run 2-5, and Test Run 2-6 are shown in Table 6 herein as Solid 2-1, Solid 2-2, Solid 2-5, and Solid 2-6, respectively.

[0186] Table 6: Solid bottom fraction

[0187]

[0188] Example 3

[0189] Example 3 describes a washing procedure for reducing the ash content in the bottoms fraction.

[0190] Solid 3-1: Solid 1-3 described in Example 1 was stirred in deionized water (20× sample weight) at ambient temperature for 16 hours. The solid was filtered off and dried at 105° C. overnight to obtain solid 3-1.

[0191] Solid 3-2: Solid 2-2 (95.7 g) described in Example 2 was stirred in deionized water (300 g) at ambient temperature for 19 hours. The solid was filtered off and dried at 105° C. overnight to obtain solid 3-2 (82 g, 85.7 wt %).

[0192] Solid 3-3: Solid 2-5 (96.2 g) described in Example 2 was stirred in deionized water (300 g) at ambient temperature for 19 hours. The solid was filtered off and dried at 105° C. overnight, and then the residue was stirred in abs. ethanol (240 g) at ambient temperature for 26 hours. The solid was filtered off and dried at 105° C. overnight to obtain solid 3-3 (81.3 g, 84.5 wt%).

[0193] Solid 3-4: Solid 2-5 described in Example 2 was stirred in deionized water (4 x sample weight) at 60° C. for 6 hours. The solid was filtered off and dried at 105° C. overnight to obtain solid 3-4.

[0194] Solid 3-5: Solid 2-5 described in Example 2 was stirred in citric acid solution (5 wt.% in water, 4× sample weight) at 60° C. for 6 hours. The solid was filtered off, washed with deionized water and dried at 105° C. overnight to obtain solid 3-5.

[0195] The difference in ash content between the washed and unwashed solid samples corresponds to the removal of residual NaBr and is shown in Table 7 herein.

[0196] Table 7: Washing of solid fraction

[0197]

[0198] Example 4

[0199] Example 4 describes the high temperature carbonization of the solid 3-1 described in Example 3 to form solid 4-1. 2 The fine powder of solid 3-1 (3.2 g) was heated to a temperature of 1000°C at a rate of 10 K / min. max , in T max The holding time was 1 hour. Then the heat source was removed and the 2 The temperature of the material was allowed to cool to room temperature under 40 °C. The residual solid 4-1, 1.45 g (45.3 wt. % of 1-3) was collected as a fine black powder. The elemental and ash content analyses of solid 3-1 and solid 4-1 are shown in Table 8 herein.

[0200] Table 8: High temperature carbonization

[0201]

[0202] Example 5

[0203] Example 5 describes the high temperature carbonization of solid 3-2 to form solid 5-1 and solid 5-2. The fine powder (50.5 g) of solid 3-2 described in Example 3 was heated to 400 °C at N 2 The sample was heated at a rate of 10 K / min to a temperature of 500 °C. max , in T max The holding time under N 2 The temperature of the material was allowed to cool to room temperature. Solid 5-1, 28.2 g (55.8 wt%) was collected as a fine brown / black powder.

[0204] Then solid 5-1 (25.2 g) was stirred at N 2 The sample was heated at a rate of 10 K / min to a temperature of 1000 °C. max , in T max The holding time was 1 hour. Then the heat source was removed and the 2 The temperature of the material was allowed to cool to room temperature. Solid 5-2 was collected as a fine black powder, 20.2 g (80.2 wt%), with an overall yield of 44.8 wt%. The elemental and ash content analysis and particle size distribution of Solid 3-2, Solid 5-1 and Solid 5-2 are shown in Table 9 herein.

[0205] Table 9: High temperature carbonization

[0206]

[0207] *Measured in ambient airflow, 925°C

[0208] Example 6

[0209] Example 6 describes the high temperature carbonization of solid 3-3 to form solid 6-1 and solid 6-2. A fine powder (50.3 g) of solid 3-3 described in Example 3 was heated to 400 °C at N 2 The sample was heated at a rate of 10 K / min to a temperature of 500 °C. max , in T max The holding time under N 2 The temperature of the material was allowed to cool to room temperature. Solid 6-1, 30.4 g (60.4 wt.%) was collected as a fine brown / black powder.

[0210] Then solid 6-1 (27.6 g) was stirred at N 2 The sample was heated at a rate of 10 K / min to a temperature of 1000 °C. max , in T max The holding time under N 2 The temperature of the material was allowed to cool to room temperature. Solid 6-2 was collected as a fine black powder, 22.1 g (80.1 wt%), with an overall yield of 48.4 wt%. The elemental and ash content analysis and particle size distribution of Solid 3-3, Solid 6-1 and Solid 6-2 are shown in Table 10 herein.

[0211] Table 10: High temperature carbonization

[0212]

[0213] Example 7

[0214] Example 7 describes the fractionation of the collected solvent distillate. 363.8 g of solvent 2-6 described in Example 2 was heated to reflux in a 1 L round bottom flask equipped with a Vigreux column, a distillation head with a thermometer connected to the condenser, and a fraction collector. The solvent distillate was distilled and two fractions of solvent 7-1 and solvent 7-2 were collected. The analytical data are shown in Table 11 herein.

[0215] Table 11: Fractionated solvent distillates

[0216]

[0217] Summary of Examples 1-7

[0218] Embodiment 1-7 shows that horizontal thin film evaporator can be effectively used for separation of solvent (as vapour fraction) and organic impurity (as solid bottom fraction) and allows to recover solvent and remove impurity from sugar dehydration process (for example fructose dehydration is HMF and wood sugar dehydration is furfural).These processes show that when feed comprises humus, residual sugar, furan-containing organic compound and organic acid, based on the low residual solvent content in solid bottom fraction, high solvent recovery rate (90-100%) can be achieved.The solvent recovered has the lower residual organic impurity content of <4wt%, sometimes <2wt%.This recovery solvent with lower residual impurity can be further purified (>99%) (for example by the sequential fractionation of continuous distillation of steam feed or condensation distillate).

[0219] The recovery and discharge of organic impurities as a dry solid bottom fraction shows <2 wt% residual moisture and a low ash and sulfur free solid fraction after water washing. These solid bottom fractions can be further processed and used as anode materials for energy storage applications, activated carbon for purification processes, or can be added to soil enhancers, conditioners, fertilizers or soil purifiers.

[0220] Although the preferred embodiments of the present disclosure have been shown and described, it should be understood that various changes can be made without departing from the spirit and scope of the present disclosure. Therefore, it should be clearly understood that the forms disclosed herein are only exemplary and are not intended to limit the scope of the present disclosure.

Claims

1. A method for separating humus from a feed source, the method comprising: A feed source is provided to a horizontal thin film evaporator, wherein the feed source comprises: 65-90 wt.% of a multi-component solvent, the multi-component solvent comprising water and a water-miscible aprotic organic solvent; and 10-35 wt.% dissolved dry residue; Expressed in wt.% or ppm of the total feed source, the dry residue comprises: 30,000-120,000ppm sugar content; 2-5wt.% furan-containing compound content; 24,000-100,000 ppm of humic compounds; 0.2-0.7wt.% organic acid content; Homogeneous acid; Salt; and Metal; wherein the feed source has a pH between 1-4 pH; and processing the feed source within the horizontal thin film evaporator to provide a separated solid material, the separated solid material comprising: 0.3-2wt.% moisture content; 0.9-5wt.% furan-containing compound content; 0.1-2wt.% sugar content; 0.02-1 wt.% dioxane content; and 0.1-6wt.% ash content; wherein the separated solid material further comprises humic compounds, and wherein the humic compounds are separated into a free-flowing powder; and The film temperature is between 180-230° C., the film evaporator is operated between 490-800 torr, and the feed rate is set so that the residence time of the feed solution is between 0.5 minutes and 10 minutes.

2. The method of claim 1, further comprising washing and drying the separated solid material to produce a washed and dried solid material.

3. The method of claim 2, further comprising exposing the washed and dried solid material to a high temperature carbonization process to produce a carbonized solid material.

4. The method according to any one of claims 1 to 3, wherein: The organic acid is selected from the group consisting of levulinic acid, formic acid, acetic acid and combinations thereof.

5. The method according to any one of claims 1 to 3, wherein: The homogeneous acid is selected from the group consisting of HCl, HBr, HI, H2SO4, H3PO4, oxalic acid, trifluoromethanesulfonic acid, methanesulfonic acid, boron trihalide and combinations thereof.

6. The method according to any one of claims 1 to 3, wherein: The salt is selected from the group consisting of sodium bromide, calcium bromide, sodium chloride, calcium chloride, potassium chloride, magnesium chloride and combinations thereof.

7. A method for recovering a solvent from a feed source, the method comprising: A feed source is provided to a horizontal thin film evaporator, wherein the feed source comprises: 65-90 wt.% of a multi-component solvent, the multi-component solvent comprising water and a water-miscible aprotic organic solvent; and 10-35 wt.% dissolved dry residue; Expressed in wt.% or ppm of the total feed source, the dry residue comprises: 30,000-120,000ppm sugar content; 2-5wt.% furan-containing compound content; 24,000-100,000 ppm of humic compounds; 0.2-0.7wt.% organic acid content; Homogeneous acid; Salt; and Metal; wherein the feed source has a pH between 1-4 pH; and processing the feed source within the horizontal thin film evaporator to provide a recovered solvent material, the recovered solvent material comprising: Sugar content up to 500 ppm; A furan content of up to 1.6 wt.%; 300-700 ppm of humic compounds; and Up to 2 wt.% organic acid content; The film temperature is between 180-230° C., the film evaporator is operated between 490-800 torr, and the feed rate is set so that the residence time of the feed solution is between 0.5 minutes and 10 minutes.

8. The method of claim 7, further comprising providing the recovered solvent material to a condenser.

9. The method of claim 7, further comprising providing the recovered solvent material to a continuous distillation column.

10. The method of claim 9, wherein: The recovered solvent is further purified or separated by fractional distillation.

11. A method for separating humic substances from a feed source, the method comprising: A feed source is provided to a horizontal thin film evaporator, wherein the feed source comprises: a multi-component solvent comprising water and a water-miscible aprotic organic solvent; and a dissolved dry residue, the dissolved dry residue comprising humic compound matter; wherein the feed source has a pH between 1-4 pH; and processing the feed source within the horizontal thin film evaporator to provide a separated solid material, the separated solid material comprising: 0.3-2wt.% moisture content; 0.9-5wt.% of furan-containing compounds; 0.1-2wt.% sugar content; 0.02-1 wt.% dioxane content; and 0.1-6wt.% ash content; wherein the separated solid material further comprises humic compounds, and wherein the humic compounds are separated into free-flowing powders; The film temperature is between 180-230° C., the film evaporator is operated between 490-800 torr, and the feed rate is set so that the residence time of the feed solution is between 0.5 minutes and 10 minutes.

12. A method for recovering a solvent from a feed source, the method comprising: A feed source is provided to a horizontal thin film evaporator, wherein the feed source comprises: a multi-component solvent comprising water and a water-miscible aprotic organic solvent; and a dissolved dry residue, the dissolved dry residue comprising humic compound matter; wherein the feed source has a pH between 1-4 pH; and processing the feed source within the horizontal thin film evaporator to provide a recovered solvent material, the recovered solvent material comprising: Sugar content up to 500 ppm; A furan content of up to 1.6 wt.%; 300-700 ppm of humic compounds; and Up to 2 wt.% organic acid content; The film temperature is between 180-230° C., the film evaporator is operated between 490-800 torr, and the feed rate is set so that the residence time of the feed solution is between 0.5 minutes and 10 minutes.

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