Method for recovering solvents, method for isolating humus, and compositions comprising solvents or humus

Abstract

To provide improved systems and approaches for solvent recovery and impurity removal in a 5-hydroxymethylfurfural (HMF) pathway process and an FDCA pathway process.SOLUTION: Described herein are novel methods for recovering solvents and isolating humic or humate materials from a 5-hydroxymethylfurfural (HMF) pathway process and a 2,5-furandicarboxylic acid (FDCA) pathway process. In some embodiments, the methods employ a thin film evaporator, such as a horizontal thin film evaporator (HTFE).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] Priority claims This application claims priority benefit of U.S. Provisional Patent Application No. 62 / 834,143, filed April 15, 2019, which is expressly incorporated herein by reference in its entirety for all purposes.

[0002] Field The present disclosure relates to methods for recovering solvent and isolating humic substances or humates from 2,5-furandicarboxylic acid pathway products. [Background technology]

[0003] 2. Description of Related Art 2,5-Furandicarboxylic acid (FDCA) and its derivatives, produced at low cost from renewable resources, have great potential for a variety of commercial applications. FDCA is considered to be a viable alternative to aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid in certain applications. Methods for producing FDCA from various feedstocks have been reported, but these methods often lack the ability to efficiently recover solvents and remove impurities and / or by-products, such as humic and humate compounds, derived from the feedstock. Therefore, improved systems and methods for solvent recovery and impurity removal in 5-hydroxymethylfurfural (HMF) and FDCA pathway processes are needed. Summary of the Invention [Means for solving the problem]

[0004] In one aspect, a method for isolating humus from a feedstock is disclosed. The method includes feeding the feedstock to a thin film evaporator. The feedstock comprises about 65-90 wt % or 65-90 wt % of a 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 contains, as wt% or ppm based on the total feedstock, about 30,000-120,000 ppm or 30,000-120,000 ppm sugars, about 2-5 wt% or 2-5 wt% furan-containing compounds, about 24,000-100,000 ppm or 24,000-100,000 ppm humic compounds, and about 0.2-0.7 wt% or 0.2-0.7 wt% organic acids, homogeneous acids, salts, and metals. The pH of the feedstock is between about 1-4 or 1-4, and the method further includes treating the feedstock in the thin film evaporator to provide an isolated solid. The isolated solid contains about 0.3 to 2 wt% or 0.3 to 2 wt% moisture, about 0.9 to 5 wt% or 0.9 to 5 wt% furan-containing compounds, about 0.1 to 2 wt% or 0.1 to 2 wt% sugars, about 0.02 to 1 wt% or 0.02 to 1 wt% dioxane, and about 0.1 to 6 wt% or 0.1 to 6 wt% ash.

[0005] In some embodiments, the method further includes washing and drying the isolated solids to obtain washed and dried solids. In some embodiments, the method further includes subjecting the washed and dried solids to a high-temperature carbonization process to obtain carbonized solids. 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° and 90° or between about 0° and about 90°, e.g., 5°, 10°, 15°, 30°, 45°, 60°, 75°, 80°, or 85°, about 5°, about 10°, about 15°, about 30°, about 45°, about 60°, about 75°, about 80°, or about 85°, or any angle therebetween. Here, 0° means that the heated thin-film evaporator is oriented directly downward toward the center of gravity of the Earth, and 180° means that the heated thin-film evaporator is oriented directly upward, away from the center of gravity of the Earth.

[0006] 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, HSO, HPO, oxalic acid, trifluoromethanesulfonic acid, methanesulfonic acid, boron trihalides, 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, potassium chloride, magnesium chloride, magnesium chloride, and combinations thereof.

[0007] In another aspect, a method for recovering solvent from a feedstock is disclosed. The method includes feeding the feedstock to a thin film evaporator. The feedstock comprises about 65-90 wt % or 65-90 wt % of a 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 contains, as wt% or ppm based on the total feedstock, about 30,000-120,000 ppm or 30,000-120,000 ppm sugars, about 2-5 wt% or 2-5 wt% furan-containing compounds, about 24,000-100,000 ppm or 24,000-100,000 ppm humic compounds, and about 0.2-0.7 wt% or 0.2-0.7 wt% organic acids, homogeneous acids, salts, and metals. The pH of the feedstock is between about 1-4 or 1-4, and the method further includes treating the feedstock in the thin film evaporator to provide a recovered solvent. The isolated solids contain up to about 500 ppm or up to 500 ppm sugars, up to about 1.6 wt% or up to 1.6 wt% furans, about 300-700 ppm or 300-700 ppm humic compounds, and up to about 2 wt% or up to 2 wt% organic acids.

[0008] In some embodiments, the method further comprises feeding the recovered solvent to a condenser. In some embodiments, the method further comprises feeding the recovered solvent to a continuous distillation column. In some embodiments, the recovered solvent is further purified or isolated by fractional distillation. 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° and 90° or between about 0° and about 90°, for example, 5°, 10°, 15°, 30°, 45°, 60°, 75°, 80°, or 85°, about 5°, about 10°, about 15°, about 30°, about 45°, about 60°, about 75°, about 80°, or about 85°, or any angle therebetween. Here, 0° means that the heated thin film evaporator is oriented straight down towards the Earth's center of gravity, and 180° means that the heated thin film evaporator is oriented straight up away from the Earth's center of gravity.

[0009] In another aspect, a composition is disclosed comprising solids isolated from a feedstock, the composition comprising less than 2 wt% moisture, at least 0.9 wt% furan, at least 0.1 wt% sugars, at most 2 wt% water, at most 1 wt% dioxane, and at most 6 wt% ash.

[0010] 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%.

[0011] In another aspect, a method for isolating humus from a feedstock is provided, the method comprising: providing a feedstock to a thin film evaporator, the feedstock comprising a multi-component solvent comprising water and a water-miscible aprotic organic solvent, and a dissolved dry residue, the dry residue comprising humus compounds, the feedstock having a pH between about 1 and 4, or between 1 and 4; and processing the feedstock in the thin film evaporator to provide an isolated solid, the isolated solid comprising about 0.3-2 wt. % or 0.3-2 wt. % moisture, about 0.9-5 wt. % or 0.9-5 wt. % furan-containing compounds, about 0.1-2 wt. % or 0.1-2 wt. % sugars, about 0.02-1 wt. % or 0.02-1 wt. % dioxane, and about 0.1-6 wt. % or 0.1-6 wt. % ash.

[0012] In another aspect, a method for recovering solvent from a feedstock is provided, the method comprising: providing a feedstock to a thin film evaporator, the feedstock comprising a multi-component solvent comprising water and a water-miscible aprotic organic solvent, and a dissolved dry residue, the dry residue comprising humic compounds, the pH of the feedstock being between about 1 and 4, or between 1 and 4; treating the feedstock in the thin film evaporator to provide a recovered sorbent, the recovered sorbent comprising at most about 500 ppm or at most 500 ppm sugars, at most about 1.6 wt % or at most 1.6 wt % furans, at most about 300-700 ppm or at most 300-700 ppm humic compounds, and at most about 2 wt % or at most 2 wt % organic acids.

[0013] Preferred embodiments include, but are not limited to, the following: 1. A method for isolating humus from a feedstock, comprising: The method includes providing a feedstock to a thin film evaporator; The feedstock is about 65-90 wt % or 65-90 wt % of a multicomponent solvent comprising water and a water-miscible aprotic organic solvent, and Dissolved dry residue approx. 10-35 wt% or 10-35 wt% Including, The dissolved dry residue is, as a wt% or ppm value based on the total feedstock, Approximately 30,000-120,000 ppm or 30,000-120,000 ppm sugars, about 2-5 wt % or 2-5 wt % of a furan-containing compound; Approximately 24,000-100,000 ppm or 24,000-100,000 ppm of humic compounds, about 0.2-0.7 wt% or 0.2-0.7 wt% organic acid; homogeneous acid, salt, and metal Including, the pH of the feedstock is between about 1 and 4 or between 1 and 4; the method further comprising processing the feedstock in the thin film evaporator to provide an isolated solid; The isolated solid is about 0.3-2 wt% or 0.3-2 wt% moisture; about 0.9-5 wt % or 0.9-5 wt % of a furan-containing compound; about 0.1-2 wt% or 0.1-2 wt% sugar; about 0.02-1 wt % or 0.02-1 wt % dioxane, and Ash content of approximately 0.1 to 6 wt% or 0.1 to 6 wt% A method comprising: 2. The method of embodiment 1, further comprising washing and drying the isolated solid to obtain a washed, dried solid. 3. The method of embodiment 2, further comprising subjecting the washed and dried solids to a high temperature carbonization process to obtain a carbonized solid. 4. The method of any one of embodiments 1 to 3, wherein the thin film evaporator is a horizontal thin film evaporator. 5. The method of any one of embodiments 1 to 4, wherein the thin film evaporator is oriented at an angle between or about 0° and 90°, for example, 5°, 10°, 15°, 30°, 45°, 60°, 75°, 80°, or 85°, about 5°, about 10°, about 15°, about 30°, about 45°, about 60°, about 75°, about 80°, or about 85°, or any angle therebetween, where 0° means that the heated thin film evaporator is oriented directly downward toward the center of gravity of the Earth, and 180° means that the heated thin film evaporator is oriented directly upward, away from the center of gravity of the Earth. 6. The method of any one of embodiments 1-5, wherein the organic acid is selected from the group consisting of levulinic acid, formic acid, acetic acid, and combinations thereof. 7. The method of any one of the preceding claims, wherein the homogeneous acid is selected from the group consisting of HCl, HBr, HI, H2SO4, H3PO4, oxalic acid, trifluoromethanesulfonic acid, methanesulfonic acid, boron trihalides, and combinations thereof. 8. The method of any one of the preceding embodiments, wherein the salt is selected from the group consisting of sodium bromide, calcium bromide, sodium chloride, calcium chloride, potassium chloride, potassium chloride, magnesium chloride, magnesium chloride, and combinations thereof. 9. A method for recovering a solvent from a feedstock, comprising: The method includes providing a feedstock to a thin film evaporator; The feedstock is about 65-90 wt % or 65-90 wt % of a multicomponent solvent comprising water and a water-miscible aprotic organic solvent, and Dissolved dry residue approx. 10-35 wt% or 10-35 wt% Including, The dissolved dry residue is, as a wt% or ppm value based on the total feedstock, Approximately 30,000-120,000 ppm or 30,000-120,000 ppm sugars, about 2-5 wt % or 2-5 wt % of a furan-containing compound; Approximately 24,000-100,000 ppm or 24,000-100,000 ppm of humic compounds, about 0.2-0.7 wt% or 0.2-0.7 wt% organic acid; homogeneous acid, salt, and metal Including, the pH of the feedstock is between about 1 and 4 or between 1 and 4; the method further comprising processing the feedstock in the thin film evaporator to provide a recovered solvent; The recovered solvent is Sugars up to about 500 ppm or up to 500 ppm; up to about 1.6 wt% or up to 1.6 wt% furan; about 300-700 ppm or 300-700 ppm of humic compounds, and Up to about 2 wt% or up to 2 wt% organic acids A method comprising: 10. The method of embodiment 9, further comprising feeding the recovered sorbent to a condenser. 11. The process of embodiment 9, further comprising feeding the recovered solvent product to a continuous distillation column. 12. The method of embodiment 9, wherein the recovered solvent is further purified or isolated by fractional distillation. 13. The method of any one of embodiments 9 to 12, wherein the thin film evaporator is a horizontal thin film evaporator. 14. The method of any one of embodiments 9 to 13, wherein the thin film evaporator is oriented at an angle between or about 0° and 90°, for example, 5°, 10°, 15°, 30°, 45°, 60°, 75°, 80°, or 85°, about 5°, about 10°, about 15°, about 30°, about 45°, about 60°, about 75°, about 80°, or about 85°, or any angle therebetween, where 0° means that the heated thin film evaporator is oriented directly downward toward the center of gravity of the Earth, and 180° means that the heated thin film evaporator is oriented directly upward, away from the center of gravity of the Earth. 15. A composition comprising solids isolated from a feedstock, comprising: less than 2 wt% moisture, at least 0.9 wt% furan; at least 0.1 wt% sugars, Maximum 2 wt% moisture, up to 1 wt% dioxane, and Ash content up to 6 wt% A composition comprising: 16. The composition of embodiment 15, wherein the ash content is at most 1 wt%. 17. The composition of embodiment 15, wherein the ash content is at most 0.5 wt%. 18. The composition of embodiment 15, wherein the ash content is at most 0.1 wt%. 19. A method for isolating humus from a feedstock, comprising: The method includes providing a feedstock to a thin film evaporator; The feedstock is a multicomponent solvent comprising water and a water-miscible aprotic organic solvent; and Dissolved dry residue Including, the dry residue comprises humic compounds; the pH of the feedstock is between about 1 and 4 or between 1 and 4; the method further comprising processing the feedstock in the thin film evaporator to provide an isolated solid; The isolated solid is about 0.3-2 wt% or 0.3-2 wt% moisture; about 0.9-5 wt % or 0.9-5 wt % of a furan-containing compound; about 0.1-2 wt% or 0.1-2 wt% sugar; about 0.02-1 wt % or 0.02-1 wt % dioxane, and Ash content of approximately 0.1 to 6 wt% or 0.1 to 6 wt% A method comprising: 20. A method for recovering a solvent from a feedstock, comprising: The method includes providing a feedstock to a thin film evaporator; The feedstock is a multicomponent solvent comprising water and a water-miscible aprotic organic solvent; and Dissolved dry residue Including, the dry residue comprises humic compounds; the pH of the feedstock is between about 1 and 4 or between 1 and 4; the method further comprising processing the feedstock in the thin film evaporator to provide a recovered solvent; The recovered solvent is Sugars up to about 500 ppm or up to 500 ppm; up to about 1.6 wt% or up to 1.6 wt% furan; about 300-700 ppm or 300-700 ppm of humic compounds, and Up to about 2 wt% or up to 2 wt% organic acids A method comprising: [Brief explanation of the drawings]

[0014] [Figure 1] A diagram of a horizontal thin film evaporator (HTFE) and its use. The HTFE is used to process the residual feed to produce dried humic solids and a solvent condenser is used to recover the solvent.

[0015] [Figure 2] A diagram of a horizontal thin film evaporator (HTFE) and its use. HTFE is used to process residual feed to obtain dried humic solids and recover purified solvent using continuous solvent distillation. DETAILED DESCRIPTION OF THE INVENTION

[0016] This disclosure relates to several approaches for recovering solvents and isolating humus or humates in 5-hydroxymethylfurfural (HMF) pathway processes and / or furandicarboxylic acid (FDCA) product pathway processes. Methods for producing HMF and FDCA pathway products are disclosed, for example, in U.S. Patent Publication Nos. 2017 / 0197930 and 2017 / 0158656, both of which are expressly incorporated by reference in their entirety for all purposes. Some FDCA production processes, such as those for producing 5-hydroxymethylfurfural (HMF) by dehydration of sugar feedstocks, produce humus and humates as by-products. It should be understood that there is no distinction between the terms humus and humates. Humus refers to polymerized sugars, polymerized dehydrated sugars, polymerized furan compounds, and / or other similar condensation by-products produced during sugar dehydration or HMF pathway processes. Humus is a condensation product, and its molecular weight increases as a result of the condensation reaction. Condensation reactions can occur with multiple reactants, potentially resulting in the production of multiple structurally diverse species with a wide molecular weight distribution. The specific structure and distribution of the resulting humus depend on the dehydration conditions, such as fructose concentration, acid, acid concentration, solvent, reaction temperature, and reaction time. As the molecular weight of the humus structure increases, it exceeds its solubility limit, resulting in precipitation of the humus in the reaction solution, making handling difficult, especially in the residual solution of a solvent recovery system. Furthermore, traditional methods isolate humus in the form of a thick, viscous liquid that solidifies upon cooling, typically posing challenges to its isolation and removal from solvent recovery systems. Viscous liquids that solidify upon cooling present obstacles for industrial processing applications. While several previous studies, such as U.S. Patent Publication No. 2018 / 0093894, have taught the isolation of solid furan resins, these traditionally isolated furan resins are unlikely to be further processed in an industrially feasible manner.

[0017] This disclosure describes several methods for isolating humus species from membrane retentate solutions using thin-film evaporators. Using thin-film evaporators, humus can be isolated as an easy-to-handle, free-flowing powder. This free-flowing humus can then be further processed to a form useful for downstream commercial applications. The resulting free-flowing powder can be used for high-throughput industrial processing. Furthermore, the evaporation methods of the present invention allow for >99% recovery of the solvent composition, making this method useful for reuse. Thus, this disclosure provides a cost-effective approach to separating and removing humus as a free-flowing powder and recovering the reaction solvent composition for reuse back in the HMF pathway process and / or the FDCA pathway process.

[0018] HMF Pathway Process In some embodiments, humus may be isolated from the residual stream of an HMF pathway process. In some embodiments, the HMF pathway process includes a sugar dehydration process. For example, a variety of sugar feedstocks or fructose-containing feedstocks may be used in the dehydration process. It will be understood that the terms sugar feedstock and fructose-containing feedstock are used interchangeably.

[0019] In some embodiments, the dehydration or conversion of the fructose-containing feedstock to HMF is carried out by contacting the sugar feedstock, including the sugar and a dehydration solvent, with a catalyst under conditions sufficient to form a (dehydration) reaction mixture for dehydrating the sugar to obtain a furan-based oxidation substrate (hereinafter referred to as the "dehydration process"). In some embodiments, the sugar is a hexose, such as glucose, galactose, mannose, idose, ketohexose, fructose, levulose, sorbose, tagatose, or allose; or a starch or cellulosic compound, or a carbohydrate derived from a starch or cellulosic compound that can be subjected to processing conditions to isomerize glucose. In some embodiments, the sugar is glucose or fructose. In some embodiments, the sugar is fructose.

[0020] As used herein, the term "dehydrating solvent" refers to an organic solvent in which the sugar and the furan-based oxidation substrate are each soluble in at least 2% by weight at the temperature at which the dehydration reaction is carried out. Typically, the dehydrating solvent is a solvent in which the furan-based oxidation substrate has a solubility of at least 3% by weight, at least 4% by weight, at least 5% by weight, at least 6% by weight, at least 7% by weight, at least 8% by weight, at least 9% by weight, at least 10% by weight, at least 11% by weight, at least 12% by weight, at least 13% by weight, at least 14% by weight, at least 15% by weight, at least 17% by weight, at least 19% by weight, at least 21% by weight, at least 23% by weight, or at least 25% by weight, as measured at the temperature at which the dehydration reaction is carried out. In some embodiments, the concentration of the furan-based oxidation substrate in the dehydrating solvent is 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%, 13-15 wt%, 14-16 wt%, 15-17 wt%, 16-18 wt%, 17-19 wt%, 18-20 wt%, 19-21 wt%, 20-22 wt%, 21-23 wt%, 22-24 wt%, or 23-25 ​​wt%, or any value within these ranges, or within a range defined by any two of these weight percentages. The dehydrating solvent typically contains water and / or a water-miscible organic solvent. More typically, the dehydration solvent is a multicomponent solvent. Typically, the multicomponent solvent used in the dehydration process comprises water and a water-miscible aprotic organic solvent. The compositions of the water-miscible aprotic organic solvent and multicomponent solvent suitable for use in the dehydration process are the same as those suitable for use in the aforementioned methods for producing FDCA pathway products. 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-based oxidation substrate comprises HMF.

[0021] Water-miscible aprotic solvents suitable for use as the dehydration solvent include tetrahydrofuran, glymes, dioxane, dioxolanes, dimethylformamide, dimethyl sulfoxide, sulfolane, acetone, N-methyl-2-pyrrolidone ("NMP"), methyl ethyl ketone ("MEK"), γ-valerolactone, or mixtures thereof. The water-miscible aprotic organic solvent is preferably an ether such as glymes, dioxane (1,4-dioxane), dioxolanes (e.g., 1,3-dioxolane), tetrahydrofuran, or mixtures thereof. Glymes suitable for use in the practice of the present disclosure include, for example, monoglyme (1,2-dimethoxyethane ("DME")), ethyl glyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme, butyl diglyme, tetraglyme, polyglymes, highly ethoxylated diethers of high molecular weight alcohols ("hyglyme"), or mixtures thereof. Often, the dehydrating solvent is a multicomponent solvent comprising a water-miscible aprotic organic solvent that is a glyme, diglyme, or dioxane, and water.

[0022] In some embodiments, the concentration of the water-miscible organic solvent species in the multi-component solvent is at least 5% by 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 95 vol%, and correspondingly, the concentration of water in the multi-component solvent system is typically less than 95 vol%, less than 90 vol%, less than 85 vol%, less than 80 vol%, less than 75 vol%, less than 70 vol%, less than 65 vol%, less than 60 vol%, less than 55 vol%, less than 50 vol%, less than 45 vol%, less than 40 vol%, less than 35 vol%, less than 30 vol%, less than 25 vol%, less than 20 vol%, less than 15 vol%, less than 10 vol% or less than 5 vol%.

[0023] In some embodiments, the multi-component solvent comprises 1-5 wt% water, or any value within this range, and 99-95 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 5-10 wt% water, or any value within this range, and 95-90 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 10-15 wt% water, or any value within this range, and 90-85 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 15-20 wt% water, or any value within this range, and 85-80 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent contains 20-25 wt% water, or any value within this range, and 80-75 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent contains 25-30 wt% water, or any value within this range, and 75-70 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent contains 30-35 wt% water, or any value within this range, and 70-65 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent contains 35-40 wt% water, or any value within this range, and 65-60 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 40-45 wt% water, or any value within this range, and 60-55 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 45-50 wt% water, or any value within this range, and 65-50 wt% water-miscible organic solvent, or any value within this range.In some embodiments, the multi-component solvent contains 50-55 wt% water, or any value within this range, and 50-45 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent contains 55-60 wt% water, or any value within this range, and 45-40 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent contains 60-65 wt% water, or any value within this range, and 40-35 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent contains 65-7 wt% water, or any value within this range, and 35-30 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 70-75 wt% water, or any value within this range, and 30-25 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 75-80 wt% water, or any value within this range, and 25-20 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 80-85 wt% water, or any value within this range, and 20-15 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 85-90 wt% water, or any value within this range, and 15-10 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 90-95 wt % water, or any value within this range, and 10-5 wt % water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 95-99 wt % water, or any value within this range, and 5-1 wt % water-miscible organic solvent, or any value within this range.

[0024] In some embodiments, the volume ratio of water to the water-miscible organic solvent is 1:6 to 6:1, or any value within this range. In certain embodiments, the volume ratio of water to the water-miscible organic solvent is 1:4 to 4:1, or any value within this range. In other embodiments, the volume ratio of water to the water-miscible organic solvent is 1:4 to 3:1, or any value within this range. In other embodiments, the volume ratio of water to the water-miscible organic solvent is 1:3 to 3:1, or any value within this range. In certain embodiments, the volume ratio of water to the water-miscible organic solvent is 1:1.

[0025] In some embodiments, the multi-component solvent comprises water and two different water-miscible organic solvents. Typically, the two different water-miscible organic solvents are both water-miscible aprotic organic solvents. The two different water-miscible aprotic solvents can be independently selected from the group consisting of tetrahydrofuran, glymes, dioxane, dioxolanes, dimethylformamide, dimethyl sulfoxide, sulfolane, acetone, N-methyl-2-pyrrolidone ("NMP"), methyl ethyl ketone ("MEK"), and γ-valerolactone. One or both of the water-miscible aprotic organic solvents can be, for example, ethers such as glymes, dioxanes (e.g., 1,4-dioxane), dioxolanes (e.g., 1,3-dioxolane), and tetrahydrofuran. Glymes include, for example, monoglyme (1,2-dimethoxyethane ("DME")), ethyl glyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme, butyl diglyme, tetraglyme, polyglymes, and highly ethoxylated diethers of high molecular weight alcohols ("hyglyme").

[0026] In some embodiments, the volume ratio of water to the first water-miscible organic solvent to 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 to 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 to 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 to the second water-miscible organic solvent is about 2:1:1 (v:v:v).

[0027] The concentration of sugars in the carbohydrate feedstock is typically between 2 wt% and 80 wt%, or any value within this range, or between 5 wt% and 80 wt%, or any value within this range. In various embodiments, the concentration of sugars is between 20 wt% and 80 wt%, or any value within this range. In some embodiments, the concentration of sugars in the carbohydrate feedstock is between 5 wt% and 20 wt%, or any value within this range. In other embodiments, the concentration of sugars in the carbohydrate feedstock is between 5 wt% and 40 wt%, or any value within this range. In some embodiments, the concentration of sugars in the carbohydrate feedstock is 5-15 wt%, 10-20 wt%, 15-25 wt%, 20-30 wt%, 25-35 wt%, 30-40 wt%, 35-45 wt%, 40-50 wt%, 45-55 wt%, 50-60 wt%, 55-65 wt%, 60-70 wt%, 65-75 wt%, or 70-80 wt%, or any value within these ranges, or within a range defined by any two of these weight percentages.

[0028] In some embodiments, an aqueous fructose solution is used as the feedstock for the reaction zone. In some embodiments, commercially available high fructose syrup (HFS) is dissolved in water to form the aqueous fructose solution. For example, HFS-97 or HFS-90 may be used.

[0029] Catalysts suitable for use in the dehydration process include homogeneous catalysts, such as homogeneous acid catalysts, and heterogeneous catalysts. In some embodiments, the acid catalyst is an acid selected from the group consisting of HBr, H2SO4, HNO3, HCl, HI, H3PO4, trifluoromethanesulfonic acid, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. 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).

[0030] 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 is selected from the group consisting of H2SO4, HNO3, HCl, HI, H3PO4, trifluoromethanesulfonic acid, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid, and the dehydration reaction mixture comprises a bromide salt. In some embodiments, the bromide salt is selected from the group consisting of LiBr, NaBr, KBr, MgBr2, CaBr2, ZnBr2, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, and 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 trihalides, organoboranes, 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 ZnCl2 or ZnBr2.

[0031] The amount of the acid catalyst used is typically 0.1 to 25 mol % or any value within this range, more typically 0.5 to 5 mol % or any value within this range (the molar concentration (mol %) is calculated relative to the number of moles of sugar (e.g., hexose)). In some embodiments, the amount of acid catalyst in the reaction mixture for dehydrating a sugar is such that the pH of the reaction mixture is acidic. In some embodiments, the amount of acid catalyst in the reaction mixture for dehydrating a sugar is such that the pH of the reaction mixture is less than 6. In some embodiments, the amount of acid catalyst in the reaction mixture for dehydrating a sugar is such that the pH of the reaction mixture is less than 5. In some embodiments, the amount of acid catalyst in the reaction mixture for dehydrating a sugar is such that the pH of the reaction mixture is less than 4. In some embodiments, the amount of acid catalyst in the reaction mixture for dehydrating a sugar is such that the pH of the reaction mixture is less than 3. In some embodiments, the amount of acid catalyst in the reaction mixture for dehydrating a sugar is such that the pH of the reaction mixture is less than 2. In some embodiments, the amount of acid catalyst in the reaction mixture for dehydrating the sugars is such that the pH of the reaction mixture is less than 1.

[0032] The dehydrated product solution may be used as a feedstock for producing an FDCA pathway product or derivative thereof, or in another downstream process that utilizes the furan-based oxidation substrate, which is typically HMF.

[0033] To minimize the formation of undesired products and maximize the yield of the furan-based oxidation substrate, it may be desirable to run the dehydration reaction to a point where conversion is partially complete by terminating the dehydration reaction and separating the unconverted sugars for recycling, e.g., by filtration, as described in U.S. Patent Publication No. 2017 / 0158656, which is expressly incorporated herein by reference in its entirety for all purposes. The furan-based oxidation substrate produced by the dehydration reaction is contained in the dehydration product solution.

[0034] The terms "dehydration product solution" and "crude oxidation feedstock" are used interchangeably herein and refer to a solution containing the furan oxidation substrate and the dehydration solvent. The dehydration product solution may be a mixture containing dissolved furan-based oxidation substrate and one or more undissolved components, where the one or more undissolved components are selected from humus and unreacted sugars. The furan-based oxidation substrate may be separated from the one or more components selected from the group consisting of humus and unreacted sugars and / or isolated from the dehydration product solution and further purified. In one such embodiment, the dehydration product solution is subjected to membrane separation to separate the one or more components selected from the group consisting of humus and unreacted sugars from the furan-based oxidation substrate. Membranes suitable for use in such separations include nanofiltration membranes, ultrafiltration membranes, and combinations thereof. A "purified oxidation feedstock," e.g., a permeate solution, may refer to the separated oxidation feedstock, and a "retentate solution" may refer to the separated solution with an enriched humus concentration.

[0035] In some embodiments, selective membrane separation techniques (e.g., ultrafiltration and / or nanofiltration) are utilized to separate the mixture recovered from the reaction zone into unconverted fructose, intermediates, HMF, and other components. As disclosed herein, the use of selective membrane separation techniques to treat the aqueous mixture recovered from the reaction zone allows for efficient recovery and recycling of unconverted fructose and intermediates, thereby improving overall process yield and achieving high product recovery rates.

[0036] In some embodiments, the aqueous reaction mixture is contacted with one or more ultrafiltration membranes to obtain a concentrate solution, retentate solution, concentrate stream, or retentate stream from the reaction mixture, which contains at least a portion (preferably substantially all) of the humus, and a permeate solution or permeate stream, which contains unconverted fructose, intermediates, catalyst, and HMF, and which is depleted in humus compared to the aqueous reaction mixture. This retentate stream may then be fed to a solvent recovery unit and / or a humus recovery unit to recover the solvent from the humus-containing retentate stream. As described in further detail herein, the humus may be isolated and the recovered solvent may be reused.

[0037] Solvent and humus recovery After the sugar dehydration process, the dehydration product solution may be separated into a purified oxidized feedstock and a residual solution, which may be subjected to a solvent recovery process. In some embodiments, the residual solution comprises a residual solvent and dissolved solids. In some embodiments, the residual solvent comprises a dehydration solvent as described herein. In some embodiments, the residual 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, glymes, dioxane, dioxolanes, dimethylformamide, sulfolane, acetone, N-methyl-2-pyrrolidinone, methyl ethyl ketone, γ-valerolactone, or any combination thereof. In some embodiments, the residual solvent comprises 1,4-dioxane, water, or a combination thereof.

[0038] In some embodiments, the dissolved solids comprise a carbohydrate feedstock, a carbohydrate feedstock intermediate, a carbohydrate feedstock by-product, an oxidized feedstock, an oxidized substrate, or a combination thereof, wherein the compositions of the carbohydrate feedstock, the carbohydrate feedstock intermediate, the carbohydrate feedstock by-product, the oxidized feedstock, and the oxidized substrate are described herein. For example, in some embodiments, the dissolved solids include sugars such as C6 monosaccharides (e.g., glucose, fructose, or mannose) and 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-furancarboxylic acid, furfuryl alcohol, or furylhydroxymethyl ketone), humic substances (e.g., polymerized sugars, dehydrated sugars, or polymerized furan compounds), organic acids (e.g., levulinic acid, formic acid, acetic acid, or combinations thereof), homogeneous acids (e.g., HCl, HBr, HI, HSO, HPO, oxalic acid, trifluoromethanesulfonic acid, methanesulfonic acid, boron trihalides, or combinations thereof), lithium, sodium, calcium, potassium, or magnesium salts of the above acids, or combinations thereof. In some embodiments, the residual solution comprises at least one of humus, sugar, organic acid, furan-containing organic compound, and salt, or a combination thereof. In some embodiments, the salt is selected from the group consisting of sodium bromide, calcium bromide, sodium chloride, calcium chloride, potassium chloride, potassium chloride, magnesium chloride, magnesium chloride, and combinations thereof. In some embodiments, the salt is sodium bromide and / or calcium bromide or a mixture thereof. In some embodiments, the salt is sodium chloride and / or calcium chloride or a mixture thereof.

[0039] In some embodiments, the retentate solution is further processed to obtain a depleted retentate stream having a reduced concentration of carbohydrate substrates and / or at least one dehydration pathway product relative to the retentate solution. In some embodiments, the depleted retentate solution is obtained by further processing the retentate solution with a membrane. In some embodiments, HMF is removed from the retentate solution to obtain the depleted retentate solution. In some embodiments, the depleted retentate solution is a solution enriched in humus, organic acids, sugars, or combinations thereof.

[0040] The residual solution and / or a feed solution containing the depleted residual solution may be fed to and processed in a solvent recovery process described herein. In some embodiments, the dissolved solids content of the feed solution is 1 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 31 wt%, 32 wt%, 35 wt%, 40 wt%, 50 wt%, or 60 wt%, or about 1 wt%, about 3 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 31 wt%, about 32 wt%, about 35 wt%, about 40 wt%, about 50 wt%, or about 60 wt%, or within a range defined by any two of these amounts. For example, in some embodiments, the feed solution contains 5-40 wt% dissolved solids. In some embodiments, the pH of the feed solution is 0.5, 0.75, 1, 2, 3, 4, 5, or 6, or about 0.5, about 0.75, about 1, about 2, about 3, about 4, about 5, or about 6, or within a range defined by any two of these pH limits. For example, in some embodiments, the pH of the feed solution is 1-4 or about 1-4.In some embodiments, the sugar content of the feed solution is 15,000 ppm, 20,000 ppm, 22,500 ppm, 25,000 ppm, 28,000 ppm, 30,000 ppm, 31,000 ppm, 35,000 ppm, 40,000 ppm, 50,000 ppm, 60,000 ppm, 70,000 ppm, 80,000 ppm, 90,000 ppm, 100,000 ppm, 110,000 ppm, 120,000 ppm, 150,000 ppm, 200,000 ppm, 250,000 ppm, 300,000 ppm, or 400,000 ppm, or about 15,000 ppm, about 2 The concentration is about 0,000 ppm, about 22,500 ppm, about 25,000 ppm, about 28,000 ppm, about 30,000 ppm, about 31,000 ppm, about 35,000 ppm, about 40,000 ppm, about 50,000 ppm, about 60,000 ppm, about 70,000 ppm, about 80,000 ppm, about 90,000 ppm, about 100,000 ppm, about 110,000 ppm, about 120,000 ppm, about 150,000 ppm, about 200,000 ppm, about 250,000 ppm, about 300,000 ppm or about 400,000 ppm, or within a range defined by any two of these concentrations. In some embodiments, the feed solution contains a furan compound at a concentration of 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 %, or about 1 wt %, 1.5 wt %, about 2 wt %, about 2.3 wt %, about 2.5 wt %, about 2.7 wt %, about 3 wt %, about 3.5 wt %, about 4 wt %, about 4.5 wt %, about 5 wt %, about 5.5 wt %, about 6 wt %, about 7 wt %, or about 10 wt %, or within a range defined by any two of these concentrations.In some embodiments, the humus content of the feed solution is 10,000 ppm, 15,000 ppm, 20,000 ppm, 21,000 ppm, 22,000 ppm, 23,000 ppm, 24,000 ppm, 25,000 ppm, 25,300 ppm, 2600 ppm, 27,000 ppm, 28,000 ppm, 29,000 ppm, 30,000 ppm, 35,000 ppm, 40,000 ppm, 50,000 ppm, 70,000 ppm, 80,000 ppm, 90,000 ppm, 100,000 ppm, 120,000 ppm, 150,000 ppm, or 200,000 ppm, or about 10,000 ppm, about 1 5000 ppm, about 20000 ppm, about 21000 ppm, about 22000 ppm, about 23000 ppm, about 24000 ppm, about 25000 ppm, about 25300 ppm, about 2600 ppm, about 27000 ppm, about 28000 ppm, about 29000 ppm, about 30000 ppm, about 35000 ppm, about 40000 ppm, about 50000 ppm, about 70000 ppm, about 80000 ppm, about 90000 ppm, about 100000 ppm, about 120000 ppm, about 150000 ppm or about 200000 ppm, or within a range defined by any two of these concentrations. In some embodiments, the organic acid content of the feed solution is 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 about 0.1 wt%, about 0.15 wt%, about 0.2 wt%, about 0.24 wt%, about 0.25 wt%, about 0.3 wt%, about 0.35 wt%, about 0.4 wt%, about 0.45 wt%, about 0.5 wt%, about 0.55 wt%, about 0.6 wt%, about 0.65 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, or about 2 wt%, or within a range defined by any two of these concentrations.In some embodiments, the solvent content of the feed solution is 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%, or about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 68 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 82 wt%, about 85 wt%, about 88.9 wt%, about 90 wt%, about 92 wt%, about 95 wt%, about 98 wt%, or about 99 wt%, or within a range defined by any two of these concentrations. In some embodiments, the feed solution has a dry residue content of 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%, or about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 10 wt%, about 11.6 wt%, about 12 wt%, about 15 wt%, about 17 wt%, about 19 wt%, about 20 wt%, about 25 wt%, or about 30 wt%, or within a range defined by any two of these concentrations.

[0041] The residual solution and / or the feed solution containing the depleted residual solution is then processed to recover the residual solvent and separately isolate the dissolved solids as a free-flowing dry powder. In some embodiments, the feed solution is processed in 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 obliquely, or at an angle relative to the bed or the center of gravity of the Earth. In some embodiments, a vertical orientation is at or about 0° relative to vertical, and a horizontal orientation is at or about 90° relative to vertical. In some embodiments, the thin film evaporator or heated thin film evaporator is oriented at an angle between 0° and 90° or between about 0° and about 90° relative to the vertical or floor, for example, 5°, 10°, 15°, 30°, 45°, 60°, 75°, 80°, or 85°, about 5°, about 10°, about 15°, about 30°, about 45°, about 60°, about 75°, about 80°, or about 85°, or any angle therebetween. In some embodiments, the thin film evaporator or heated thin film evaporator is oriented at an angle between 0° and 180° or between about 0° and about 180°, for example, 0°, 5°, 10°, 15°, 30°, 45°, 60°, 75°, 80°, 85°, 90°, 95°, 120°, 135°, 160°, or 180°, about 0°, about 5°, about 10°, about 15°, about 30°, about 45°, about 60°, about 75°, about 80°, about 85°, about 90°, about 95°, about 120°, about 135°, about 160°, or about 180°, or any angle therebetween. Here, 0° means that the thin film evaporator or the heated thin film evaporator is oriented directly downward toward the Earth's center of gravity, and 180° means that the thin film evaporator or the heated thin film evaporator is oriented directly upward away from the Earth's center of gravity. In some embodiments, the feed solution is processed in a horizontal thin film evaporator (HTFE) or heated HTFE, such as an Artisan Rototherm® E thin film evaporator. In some embodiments, the thin film evaporator system used in the present invention includes a feed pump that directs the feed solution into the thin film evaporator.In some embodiments, the thin film evaporator system comprises a hot oil jacketed counterflow horizontal thin film evaporator. In some embodiments, the thin film evaporator system comprises a solvent collection condenser. In some embodiments, the thin film evaporator system comprises a vacuum pump. In some embodiments, the thin film evaporator system comprises an inert gas injection mass flow meter. In some embodiments, the thin film evaporator system comprises a bottom solids delivery valve. In some embodiments, the thin film evaporator system comprises a control system. In some embodiments, the control system is configured to maintain the thin film temperature, pressure, inert gas injection, feed rate, or a combination thereof of the thin film evaporator system.

[0042] 1 and 2 illustrate the use of HTFE to treat a membrane retentate feed to obtain dry humus solids and capture the solvent. Figure 1 shows an apparatus 100. In this diagram, membrane retentate feed 102 is directed to HTFE 104. In some embodiments, HTFE 104 is a countercurrent HTFE. HTFE 104 includes a rotating screw or rotating wiper 106, a hot inlet 108, and a hot outlet 110. As HTFE 104 operates with the addition of membrane retentate feed 102, it processes the membrane retentate feed 102 to recover a free-flowing dry powder 112. In some embodiments, this free-flowing dry powder 112 comprises dry humus. Additionally, solvent vapor 114 resulting from the treatment of membrane retentate feed 102 with HTFE 104 is directed to a solvent condenser 116, which produces a distillate 118.

[0043] FIG. 2 illustrates an apparatus 200. In this diagram, a membrane retentate feed 202 is directed to an HTFE 204. In some embodiments, the HTFE 204 is a countercurrent HTFE. The HTFE 204 includes a rotating screw or wiper 206, a hot inlet 208, and a hot outlet 210. As the HTFE 204 operates with the addition of the membrane retentate feed 202, the membrane retentate feed 202 is processed to recover a free-flowing dry powder 212. In some embodiments, the free-flowing dry powder 212 comprises dry humus. Additionally, solvent vapor 214 resulting from the treatment of the membrane retentate feed 202 with the HTFE 204 is directed to a continuous distillation column 216, which separates a bottoms capture 218 and a purified solvent fraction 220.

[0044] The feed solution is directed into the thin-film evaporator, where the centrifugal force of the thin-film evaporator's rotating blades holds the feed solution as a thin film on the heated walls, and the solvent evaporates. As the feed solution is continuously directed through the thin-film evaporator, a new thin film is constantly formed, gradually concentrating the dissolved solids. The solids in the solution then precipitate out as a solid product, which is transported to the bottom discharge valve by the introduction of new feed. In some embodiments, the feed rate of the feed solution into the thin-film evaporator is set to provide a residence time of the feed solution of less than 10 minutes, less than 5 minutes, less than 4 minutes, less than 3 minutes, less than 2 minutes, less than 1 minute, or less than 0.5 minutes, or less than about 10 minutes, less than about 5 minutes, less than about 4 minutes, less than about 3 minutes, less than about 2 minutes, less than about 1 minute, or less than about 0.5 minutes, or any time therebetween. In some embodiments, the feed rate is set to provide a residence time of the feed solution of less than 2 minutes.

[0045] In some embodiments, the thin-film evaporator is operated with an inert atmosphere maintained inside. Maintaining an inert atmosphere can provide a non-flammable atmosphere inside the evaporator. In some embodiments, the thin-film evaporator is operated under a nitrogen flow. The feed concentration and solvent evaporation can be performed at atmospheric pressure or under reduced pressure. The feed can be supplied directly from a membrane separation unit. Alternatively, the feed can be pre-concentrated by standard evaporation techniques to increase the dissolved solids content and recover a portion of the multi-component solvent mixture before supplying it.

[0046] In some embodiments, the feed solution is introduced into the thin film evaporator heated to a thin film temperature of about 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, about 170°C, about 175°C, about 180°C, about 185°C, about 190°C, about 195°C, about 200°C, about 205°C, about 210°C, about 215°C, about 220°C, about 225°C, about 230°C, about 235°C, about 240°C, or about 250°C, or any temperature therebetween. For example, in some embodiments, the thin film temperature is between 180°C and 230°C. In some embodiments, the thin film evaporator is rated at 470 torr, 480 torr, 490 torr, 500 torr, 525 torr, 550 torr, 575 torr, 600 torr, 625 torr, 650 torr, 675 torr, 700 torr, 725 torr, 750 torr, 775 torr, 800 torr, 810 torr, 820 torr, or 850 torr, about 470 torr , about 480 torr, about 490 torr, about 500 torr, about 525 torr, about 550 torr, about 575 torr, about 600 torr, about 625 torr, about 650 torr, about 675 torr, about 700 torr, about 725 torr, about 750 torr, about 775 torr, about 800 torr, about 810 torr, about 820 torr, or about 850 torr, or any pressure therebetween. For example, in some embodiments, the thin film evaporator is operated between 490 torr and 800 torr.

[0047] In some embodiments, the solvent vapor or solvent fraction collected upon exiting the thin-film evaporator may be fed to and collected in a condenser connected to the thin-film evaporator, as shown, for example, in Figure 1. In some embodiments, the solvent vapor or solvent fraction collected upon exiting the thin-film evaporator may be fed as a vapor to a continuous distillation column for continuous fractionation to collect the solvent and light organic compounds, as shown, for example, in Figure 2. In some embodiments, the collected solvent vapor fraction may be further purified by fractional distillation at ambient pressure to obtain a purified or isolated solvent mixture.

[0048] In some embodiments, the pH of the solvent fraction is 0.5, 0.75, 1, 2, 3, 4, 5, or 6, or about 0.5, about 0.75, about 1, about 2, about 3, about 4, about 5, or about 6, or any value therebetween. In some embodiments, the sugar content of the solvent fraction is 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 10,000 ppm, or about 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 10,000 ppm, or any concentration therebetween. In some embodiments, the concentration of furan compounds in the solvent fraction is 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%, or is less than about 0.1 %, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, about 1.1 wt%, about 1.2 wt%, about 1.3 wt%, about 1.4 wt%, about 1.5 wt%, about 2 wt%, about 2.3 wt%, about 2.5 wt%, about 2.7 wt%, about 3 wt%, about 3.5 wt%, about 4 wt%, about 4.5 wt%, or about 5 wt%, or any concentration therebetween.In some embodiments, the solvent fraction contains furan compounds at a concentration of 50 ppm, 100 ppm, 500 ppm, 1000 ppm, 2000 ppm, 3000 ppm, 4000 ppm, 5000 ppm, 6000 ppm, 8000 ppm, or 10,000 ppm, or about 50 ppm, about 100 ppm, about 500 ppm, about 1000 ppm, about 2000 ppm, about 3000 ppm, about 4000 ppm, about 5000 ppm, about 6000 ppm, about 8000 ppm, or about 10,000 ppm, or any concentration therebetween. In some embodiments, the humus content of the solvent fraction is 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, or 900 ppm, or about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, or about 900 ppm, or any concentration therebetween. In some embodiments, the organic acid content of the solvent fraction is <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 < about 0 0.01 wt%, about 0.01 wt%, about 0.05 wt%, about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.5 wt%, about 0.7 wt%, about 1 wt%, about 1.2 wt%, about 1.4 wt%, about 1.5 wt%, about 1.6 wt%, about 1.7 wt%, about 1.8 wt%, about 1.9 wt%, about 2 wt%, about 2.5 wt%, or about 3 wt%, or any concentration therebetween.In some embodiments, the solvent fraction has a solvent content of 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%, or about 2 wt%, or about 5 wt%, about 10 wt%, about 25 wt%, about 50 wt%, about 60 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 82 wt%, about 85 wt%, about 88.9 wt%, about 90 wt%, about 91 wt%, about 92 wt%, about 93 wt%, about 94 wt%, about 95 wt%, about 96 wt%, about 97 wt%, about 98 wt%, about 98.5 wt%, about 99 wt%, about 99.5 wt%, about 99.8 wt%, or about 99.9 wt%, or any concentration therebetween. In some embodiments, the dry residue content of the solvent fraction is 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%, or about 0 0.1 wt%, about 0.3 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, about 1.2 wt%, about 1.5 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt% or about 10 wt%, or any concentration therebetween.

[0049] In some embodiments, the solvent fraction is subjected to a fractional distillation process to obtain a fraction. In some embodiments, the fraction has a higher concentration of organic solvent, water, furan, organic acid, or any combination thereof than the solvent fraction. In some embodiments, 70%, 80%, 85%, 90%, 92%, 95%, 97%, 98%, 99%, 99.5%, or 99.9% of the organic solvent is recovered from the solvent fraction, or a range of any two of these limits. 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.

[0050] In some embodiments, the bottom solid product discharged from the thin film evaporator is dry. In some embodiments, the water content of the solid product is less than 0.1 wt%, less than 0.33 wt%, less than 0.5 wt%, less than 0.62 wt%, less than 0.65 wt%, less than 1 wt%, less than 1.15 wt%, less than 1.88 wt%, less than 2 wt%, less than 3 wt%, less than 4 wt%, or less than 5 wt%, or less than about 0.1 wt%, less than about 0.33 wt%, less than about 0.5 wt%, less than about 0.62 wt%, less than about 0.65 wt%, less than about 1 wt%, less than about 1.15 wt%, less than 1.88 wt%, less than about 2 wt%, less than about 3 wt%, less than about 4 wt%, or less than about 5 wt%, or any amount therebetween. In some embodiments, the furan content of the solid product is 0.80 wt%, 0.85 wt%, 0.90 wt%, 0.92 wt%, 0.95 wt%, 0.96 wt%, 0.97 wt%, 0.98 wt%, 0.99 wt%, 1 wt%, 1.2 wt%, or 1.5 wt%, or about 0.80 wt%, about 0.85 wt%, about 0.90 wt%, about 0.92 wt%, about 0.95 wt%, about 0.96 wt%, about 0.97 wt%, about 0.98 wt%, about 0.99 wt%, about 1 wt%, about 1.2 wt%, or about 1.5 wt%, or any amount therebetween. In some embodiments, the sugar content of the solid product is 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%, or is about 0.0 5 wt%, about 0.1 wt%, about 0.15 wt%, about 0.17 wt%, about 0.20 wt%, about 0.5 wt%, about 1 wt%, about 1.3 wt%, about 1.5 wt%, about 1.6 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 4.5 wt%, about 5 wt%, about 6 wt%, about 8 wt%, or about 10 wt%, or any amount therebetween.In some embodiments, the organic acid content of the solid product is 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%, or about 0.01 wt%, about 0.05 wt%, about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, or about 2 wt%, or any amount therebetween. In some embodiments, the organic solvent content of the solid product is 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%, or about 0. 0.005 wt%, about 0.01 wt%, about 0.02 wt%, about 0.03 wt%, about 0.04 wt%, about 0.05 wt%, about 0.07 wt%, about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, or about 2 wt%, or any amount therebetween. In some embodiments, the carbon content of the solid product is 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%, or about 50 wt%, about 55 wt%, about 56 wt%, about 57 wt%, about 58 wt%, about 59 wt%, about 60 wt%, about 61 wt%, about 62 wt%, about 63 wt%, about 65 wt%, or about 70 wt%, or any amount therebetween.In some embodiments, the hydrogen content of the solid product is 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%, or about 4 wt%, about 4.2 wt%, about 4.4 wt%, about 4.5 wt%, about 4.6 wt%, about 4.7 wt%, about 4.8 wt%, about 4.9 wt%, about 5 wt%, or about 5.5 wt%, or any amount therebetween. In some embodiments, the nitrogen content of the solid product is 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%, or about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.5 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, about 1.5 wt%, or about 2 wt%, or any amount therebetween. In some embodiments, the sulfur content of the solid product is low. In some embodiments, the sulfur content of the solid product is 0 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, or 0.5 wt%, or about 0 wt%, about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, or about 0.5 wt%, or any amount therebetween. In some embodiments, the solid product has an oxygen content of 20 wt%, 25 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, or 40 wt%, or about 20 wt%, about 25 wt%, about 28 wt%, about 29 wt%, about 30 wt%, about 31 wt%, about 32 wt%, about 33 wt%, about 34 wt%, about 35 wt%, or about 40 wt%, or any amount therebetween. In some embodiments, the solid product has a low ash content. In some embodiments, the ash content of the solid product when heated to 700° C. is 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 10 wt%, or 15 wt%, or about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 10 wt%, or about 15 wt%, or any amount therebetween.In some embodiments, the bottom solid product is a fine carbonaceous powder. In some embodiments, the solid product has a low metal content. In some embodiments, the solid product has a high humus content.

[0051] In some embodiments, the solid product may then be washed, the remaining solids filtered, and the collected liquid dried to obtain a washed solid product. In some embodiments, the washed solid product has a lower ash content than the unwashed solid product. In some embodiments, the washed solid product has a lower salt content than the unwashed solid product. In some embodiments, the solid product is washed with at least one of water, an acidic 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 ash content of the washed solid product when heated to 700°C is 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%, or about 0.05 wt%, about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, or about 2 wt%, or within a range defined by any two of these limits.

[0052] In some embodiments, the solid product and / or the washed product may then be carbonized to obtain a carbonized solid product. In some embodiments, the carbonization process includes exposing the product to an elevated temperature. In some embodiments, the elevated temperature may be 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, about 300°C, about 400°C, about 500°C, about 600°C, about 700°C, about 800°C, about 900°C, about 1000°C, about 1200°C, about 1500°C, or about 2000°C, or a range defined by any two of these temperatures. In some embodiments, the carbonization process includes an inert atmosphere. In some embodiments, the inert atmosphere is a nitrogen atmosphere.

[0053] Further processing of the collected product In some embodiments, the collected product may be further processed for downstream use. In some embodiments, the collected product includes a solid product, a washed solid product, a carbonized product, or a combination thereof. In some embodiments, the collected product is further processed into a desired product. In some embodiments, the desired product may be used for soil applications (e.g., soil conditioner or fertilizer), energy storage, or liquid or gas purification. In some embodiments, the desired product may be a soil conditioner, soil enhancer, soil amendment, soil remediation agent, fertilizer, anode material, or activated carbon material.

[0054] In some embodiments, the desired product is an activated carbon material. In some embodiments, the activated carbon material may be used in gas purification, liquid purification, or electrode material applications. In some embodiments, the activated carbon material has a surface area of ​​at least 800 m 2 / g, at least 900m 2 / g, at least 1000m 2 / g, at least 1200m 2 / g, at least 1400m 2 / g, at least 1600m 2 / g, at least 1800m 2 / g or at least 2000m 2 / g or at least about 800m 2 / g, at least about 900m 2 / g, at least about 1000m 2 / g, at least about 1200m 2 / g, at least about 1400m 2 / g, at least about 1600m 2 / g, at least about 1800m 2 / g or at least about 2000m 2 / g, or within a range defined by any two of these surface areas. In some embodiments, the activated carbon material is powdered activated carbon, granular activated carbon, or pelleted activated carbon. In some embodiments, producing powdered activated carbon from the solid product includes washing the solid product as described above, carbonizing the washed solid product at an elevated temperature as described above, and activating the carbonized solid product. In some embodiments, activating the solid product includes steam activation and / or gas activation. In some embodiments, the steam activation and / or gas activation includes exposing the solid product to an elevated temperature under a steam atmosphere or a combustion gas atmosphere. In some embodiments, the combustion gas atmosphere includes CO2, CO, N2, or a combination thereof. In some embodiments, the elevated temperature during the steam activation and the gas activation is 600°C, 700°C, 800°C, 900°C, 1000°C, 1100°C, or 1200°C, or about 600°C, about 700°C, about 800°C, about 900°C, about 1000°C, about 1100°C, or about 1200°C, or within a range defined by any two of these temperatures. In some embodiments, the activation of the solid product comprises chemical activation. In some embodiments, the chemical activation comprises mixing the solid product with a strong base and then exposing it to an elevated temperature in an inert atmosphere. In some embodiments, the strong base can be KOH, NaOH, or a combination thereof. In some embodiments, the elevated temperature during chemical activation is 400° C., 500° C., 600° C., 700° C., 800° C., 900° C., or 1000° C., or about 400° C., about 500° C., about 600° C., about 700° C., about 800° C., about 900° C., or about 1000° C., or within a range defined by any two of these temperatures. In some embodiments, the activated particles are further crushed to a desired particle size.

[0055] In some embodiments, granular or pelleted activated carbon is produced in a manner similar to that used to produce powdered activated carbon, except that the washed solid product is subjected to a granulation or compression process after the washing process and before the high-temperature carbonization process. In some embodiments, the production of granular or pelleted activated carbon includes washing the solid product as described above, combining the washed solid product with a bio-based binder, extruding, pelletizing, or granulating the binder and solid product mixture, then drying or oxidizing, optionally subjecting the binder to a high-temperature carbonization process as described above, activating the carbonized solid product as described above, and further washing and drying the activated product. In some embodiments, the bio-based binder is tall oil pitch, a water-containing mixture of sugars and / or cellulose derivatives, or a combination thereof. In some embodiments, the cellulose derivative is hydroxyethyl cellulose. In some embodiments, the drying or oxidation is carried out in air at 100°C, 150°C, 200°C, 250°C, or 300°C, or within a range of any two of these temperatures.

[0056] In some embodiments, the desired product is a hard carbon material. In some embodiments, the hard carbon material may be used in energy storage applications, such as an anode material in lithium-ion batteries. In some embodiments, the hard carbon material is characterized by a lower surface area than the starting solid product. In some embodiments, producing a hard carbon material from the solid product includes washing the solid product as described above, carbonizing the washed solid product at high temperature as described above, crushing and classifying the carbonized product, and coating and post-carbonization treating the crushed product.

[0057] FDCA pathway process Any FDCA pathway process can be utilized in the present disclosure. As used herein, the terms "furandicarboxylic acid pathway product" and "FDCA pathway product" are used interchangeably to refer to 2,5-furandicarboxylic acid (FDCA) or a 2,5-furandicarboxylic acid pathway intermediate compound.

[0058] In some embodiments, the FDCA pathway product is FDCA. In some embodiments, the oxidation substrate is a sugar, HMF, and / or an FDCA pathway intermediate compound (e.g., DFF, HMFCA, or FFCA), or a mixture of any two or more thereof. In some embodiments, the oxidation feedstock may further contain other agents or residual components, which may or may not be soluble in the oxidation feedstock. For example, the oxidation feedstock may be a crude oxidation feedstock consisting of HMF or other oxidation substrate and an oxidation solvent. As used herein, the term "crude oxidation feedstock" refers to a feedstock that contains, in addition to the desired oxidation substrate, impurities and / or by-products associated with the production, isolation, and / or purification of the oxidation substrate. For example, the oxidation feedstock may contain, in addition to the desired oxidation substrate, certain biomass-related components, such as biomass-derived components and by-products generated during the conversion of biomass to sugars (e.g., by pyrolysis, chemical decomposition, mechanical decomposition, and / or enzymatic decomposition) that are then converted to HMF. Thus, the crude oxidized feedstock may further comprise components selected from the group consisting of polysaccharides (e.g., cellulose (e.g., lignocellulose, hemicellulose, etc.), starch, etc.), oligosaccharides (e.g., raffinose, maltodextrin, cellodextrin, etc.), monosaccharides (e.g., glucose, fructose, galactose, mannose, xylose, arabinose, etc.), disaccharides (e.g., sucrose, lactose, maltose, cellobiose, etc.), furan-based substrates such as furfural, humus in the form of oligomers or polymers as by-products, residual inorganic acids, and residual inorganic acid salts. Similarly, the oxidized feedstock may be a crude feedstock consisting of HMF oxidation products, including HMF and / or FDCA pathway intermediate compounds. The crude oxidized feedstock may be treated to increase the concentration of desired oxidized substrates and / or reduce the concentration of impurities and / or by-products. A crude oxidized feedstock treated in this manner may be referred to herein as a "purified oxidized feedstock."

[0059] As used herein, the term "oxidation solvent" refers to an organic or multi-component solvent in which the oxidation substrate and the desired FDCA pathway product are each soluble in at least 2% by weight at the temperature at which the contacting (oxidation) step is carried out. Typically, the oxidation solvent is a solvent in which the FDCA pathway product has a solubility of at least 3% by weight or at least 4% by weight, measured at the temperature at which the contacting step is carried out, and more typically, the FDCA pathway product has a solubility of at least 5% by weight, at least 6% by weight, at least 7% by weight, at least 8% by weight, at least 9% by weight, at least 10% by weight, at least 11% by weight, at least 12% by weight, at least 13% by weight, at least 14% by weight, or at least 15% by weight, or within a range defined by any two of these amounts. In some embodiments, the solubility of the FDCA pathway product is within 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 within a range bounded by any two of these weight percentages. The solubility of the FDCA pathway product in candidate organic or multicomponent solvents can be readily determined by known methods.

[0060] An organic solvent exhibiting the minimum necessary solvating power for the oxidation substrate and FDCA can be used alone or as one component of a multicomponent solvent. In some embodiments, the oxidation solvent comprises an aprotic organic solvent (e.g., ethers, esters, ketones, etc.) alone (i.e., as a single-component solvent) or as one component of a multicomponent solvent. When the aprotic organic solvent is used as one component of a multicomponent solvent, the aprotic organic solvent is typically miscible with the other components in the multicomponent solvent. As used herein, the term "multicomponent solvent" refers to a mixture of two, three, or more solvent species. The multicomponent solvent used in the practice of the present disclosure may contain 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 multicomponent solvent comprises water and an organic solvent, the organic solvent is a water-miscible organic solvent. The water-miscible organic solvent is typically a water-miscible aprotic organic solvent.

[0061] In some embodiments, candidate solvents for the components of the multi-component solvent are not limited to those in which the oxidized substrate and the desired FDCA pathway product are highly soluble. Even if FDCA has low solubility in any of the solvent components of the multi-component solvent, the multi-component solvent may exhibit a synergistic solvation effect on FDCA. For example, even if FDCA has low solubility in water, combining water with a water-miscible organic solvent that has low solvation power for FDCA can improve the solvation power for FDCA.

[0062] Multicomponent solvents that exhibit this effect include multicomponent solvents containing water and a water-miscible aprotic organic solvent. Water-miscible aprotic solvents suitable for use in the practice of the present disclosure include tetrahydrofuran, glymes, dioxane, dioxolanes, dimethylformamide, dimethyl sulfoxide, sulfolane, acetone, N-methyl-2-pyrrolidone ("NMP"), methyl ethyl ketone ("MEK"), γ-valerolactone, and the like. The water-miscible aprotic organic solvent is preferably an ether, such as glymes, dioxane (1,4-dioxane), dioxolanes (e.g., 1,3-dioxolane), or tetrahydrofuran. Glymes suitable for use in the practice of the present disclosure include, for example, monoglyme (1,2-dimethoxyethane ("DME")), ethyl glime, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme, butyl diglyme, tetraglyme, polyglymes, highly ethoxylated diethers of high molecular weight alcohols ("hyglyme"), etc. Often, the oxidation solvent is a multicomponent solvent comprising a water-miscible aprotic organic solvent that is a glyme, diglyme, or dioxane, and water.

[0063] In some embodiments, the composition of the oxidation solvent may be determined taking into account the requirements of further downstream processes (e.g., processes for product recovery, purification, etc.) or the requirements of upstream processes (e.g., conversion of sugars to furan-based oxidation substrates). For example, in certain embodiments, it may be desirable to use a multi-component solvent comprising a light solvent and a heavy solvent as the oxidation solvent. A "light solvent" refers to a solvent that has a lower boiling point (boiling temperature) at a specific pressure than a heavy solvent. Conversely, a "heavy solvent" refers to a solvent that has a higher boiling point (boiling temperature) at a specific pressure than a light solvent. When the multi-component solvent comprises water and a water-miscible organic solvent, the water-miscible organic solvent may be a water-miscible light organic solvent (e.g., a water-miscible organic solvent with a lower boiling point than water) or a water-miscible heavy organic solvent (e.g., a water-miscible organic solvent with a higher boiling point than water). Typically, the water-miscible light organic solvent is an aprotic light organic solvent, and the water-miscible heavy organic solvent is an aprotic heavy organic solvent. Examples of water-miscible (and aprotic) light organic solvents that are combined with water in the multicomponent solvent include glymes, dioxolanes (e.g., 1,3-dioxolane), tetrahydrofuran, and the like. Examples of water-miscible (and aprotic) heavy organic solvents that are combined with water in the multicomponent solvent include dioxane, ethyl glyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme, butyl diglyme, tetraglyme, polyglymes, and the like. In some embodiments (e.g., continuous reactor systems), all or a portion of the oxidation solvent, or components thereof, may be removed from the product solution (e.g., via distillation) and recycled to the reaction mixture. In such embodiments, it may be desirable to use a multicomponent solvent having a composition that corresponds to or is capable of forming an azeotrope (i.e., an "azeotropic composition") at the temperature at which the oxidation step (i.e., contacting step) described above is carried out or at the temperature at which processes upstream or downstream of the oxidation step are carried out.The use of such multi-component solvents with azeotropic compositions may facilitate the recycling of the oxidation solvent (as part of the azeotropic composition) to the oxidation step or to processes upstream and / or downstream of the oxidation step.

[0064] In some embodiments, the concentration of the water-miscible organic solvent species in the multi-component solvent is at least 5% by 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 95 vol%, and correspondingly, the concentration of water in the multi-component solvent system is typically less than 95 vol%, less than 90 vol%, less than 85 vol%, less than 80 vol%, less than 75 vol%, less than 70 vol%, less than 65 vol%, less than 60 vol%, less than 55 vol%, less than 50 vol%, less than 45 vol%, less than 40 vol%, less than 35 vol%, less than 30 vol%, less than 25 vol%, less than 20 vol%, less than 15 vol%, less than 10 vol% or less than 5 vol%.

[0065] In some embodiments, the multi-component solvent comprises 1-5 wt% water, or any value within this range, and 99-95 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 5-10 wt% water, or any value within this range, and 95-90 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 10-15 wt% water, or any value within this range, and 90-85 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 15-20 wt% water, or any value within this range, and 85-80 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent contains 20-25 wt% water, or any value within this range, and 80-75 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent contains 25-30 wt% water, or any value within this range, and 75-70 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent contains 30-35 wt% water, or any value within this range, and 70-65 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent contains 35-40 wt% water, or any value within this range, and 65-60 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 40-45 wt% water, or any value within this range, and 60-55 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 45-50 wt% water, or any value within this range, and 65-50 wt% water-miscible organic solvent, or any value within this range.In some embodiments, the multi-component solvent contains 50-55 wt% water, or any value within this range, and 50-45 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent contains 55-60 wt% water, or any value within this range, and 45-40 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent contains 60-65 wt% water, or any value within this range, and 40-35 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent contains 65-70 wt% water, or any value within this range, and 35-30 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 70-75 wt% water, or any value within this range, and 30-25 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 75-80 wt% water, or any value within this range, and 25-20 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 80-85 wt% water, or any value within this range, and 20-15 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 85-90 wt% water, or any value within this range, and 15-10 wt% water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 90-95 wt % water, or any value within this range, and 10-5 wt % water-miscible organic solvent, or any value within this range. In some embodiments, the multi-component solvent comprises 95-99 wt % water, or any value within this range, and 5-1 wt % water-miscible organic solvent, or any value within this range.

[0066] In some embodiments, the volume ratio of water to the water-miscible organic solvent is 1:6 to 6:1, or any value within this range. In certain embodiments, the volume ratio of water to the water-miscible organic solvent is 1:4 to 4:1, or any value within this range. In other embodiments, the volume ratio of water to the water-miscible organic solvent is 1:4 to 3:1, or any value within this range. In other embodiments, the volume ratio of water to the water-miscible organic solvent is 1:3 to 3:1, or any value within this range. In certain embodiments, the volume ratio of water to the water-miscible organic solvent is 1:1.

[0067] In some embodiments, the multi-component solvent comprises water and two different water-miscible organic solvents. Typically, the two different water-miscible organic solvents are both water-miscible aprotic organic solvents. The two different water-miscible aprotic solvents can be independently selected from the group consisting of tetrahydrofuran, glymes, dioxane, dioxolanes, dimethylformamide, dimethyl sulfoxide, sulfolane, acetone, N-methyl-2-pyrrolidone ("NMP"), methyl ethyl ketone ("MEK"), and γ-valerolactone. One or both of the water-miscible aprotic organic solvents can be, for example, ethers such as glymes, dioxanes (e.g., 1,4-dioxane), dioxolanes (e.g., 1,3-dioxolane), and tetrahydrofuran. Glymes include, for example, monoglyme (1,2-dimethoxyethane ("DME")), ethyl glyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme, butyl diglyme, tetraglyme, polyglymes, and highly ethoxylated diethers of high molecular weight alcohols ("hyglyme").

[0068] In some embodiments, the volume ratio of water to the first water-miscible organic solvent to 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 to 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 to 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 to the second water-miscible organic solvent is about 2:1:1 (v:v:v).

[0069] In some embodiments, the oxidation catalyst used in the oxidation of the oxidation substrate to the FDCA pathway product typically comprises a precious metal dispersed on the inner and / or outer surface of a support. As used herein, "precious metal" refers to ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, or gold. In some embodiments, the precious metal is selected from the group consisting of platinum, gold, and combinations thereof. In some embodiments, the precious metal is platinum. In some embodiments, the precious metal is gold. The heterogeneous oxidation catalyst may further comprise a promoter to improve the performance of the catalyst. When the precious metal is platinum or gold, or a combination thereof, suitable promoters include, for example, Pd, Ir, Mo, Bi, Te, Sn, W, etc.

[0070] The solid support component of the oxidation catalyst may comprise any type of material known to those skilled in the art to be suitable for use as a catalyst support that satisfies 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 materials made therefrom. Metal oxides include, for example, silicon oxide (silica), zirconium oxide (zirconia), titanium oxide (titania), aluminum oxide (alumina), and the like. As used herein, "carbonaceous" refers to graphite and carbon black. Metal silicates include, for example, orthosilicates, borosilicates, aluminosilicates (e.g., zeolites), and the like. Metal carbides include, for example, silicon carbide. Suitable polymeric solid support materials include polystyrene, polystyrene-co-divinylbenzene, polyamides, polyacrylamides, and the like.

[0071] When carrying out the FDCA pathway process, pure oxygen (i.e., consisting only of O2 and no other gases) may be supplied, or oxygen may be supplied as a component of a mixed gas (e.g., air, oxygen-enriched air, oxygen-deficient air, nitrogen-oxygen mixture, etc.). The molar ratio of oxygen to the oxidized substrate in the contacting step is typically 2:1 to 10:1. In some embodiments, the molar ratio of oxygen to the oxidized substrate is 2:1 to 10:1 or 3:1 to 5:1. The partial pressure of the oxygen in the contacting step is typically 40 psig to 1000 psig, or any value within this range. More typically, the partial pressure of the oxygen is 40 psig to 200 psig, or any value within this range. In some embodiments, the partial pressure of the oxygen is 40 to 200 psig, 100 to 300 psig, 200 to 400 psig, 300 to 500 psig, 400 to 600 psig, 500 to 700 psig, 600 to 800 psig, 700 to 900 psig, or 800 to 1000 psig, or any value within these ranges, or within a range defined by any two of these partial pressures.

[0072] In some embodiments, the oxidation of the oxidation substrate to the FDCA pathway product is carried out at a temperature of 50°C to 200°C, or any value within this range. In some embodiments, the oxidation step is carried out at a temperature of 80°C to 180°C, or any value within this range, and in other embodiments, the oxidation step is carried out at a temperature of 90°C to 160°C, or any value within this range, or at a temperature of 100°C to 160°C, or any value within this range. In some embodiments, the oxidation step is carried out at a temperature of 90°C to 180°C, or any value within this range, and in some cases, the oxidation step is carried out at a temperature of 110°C to 160°C, or any value within this range.

[0073] The process of the present disclosure may be carried out in a batch reactor process, a semi-batch reactor process, or a continuous reactor process using reactors known in the art, such as fixed bed reactors, trickle bed reactors, slurry phase reactors, moving bed reactors, etc. The relatively high solubility of reactants and products (particularly the FDCA pathway products) in the oxidation solvent facilitates the use of any of the foregoing reactor processes, and particularly the fixed bed reactor process.

[0074] The FDCA pathway product may be recovered from the reaction mixture by separating the catalyst used to produce the FDCA pathway product from a product solution containing the FDCA pathway product and the oxidation solvent. The resulting product solution contains the oxidation solvent and dissolved components of the reaction mixture, but does not contain the oxidation catalyst. Furthermore, the dissolved components may be concentrated by removing a portion of the oxidation solvent from the product solution. The oxidation solvent may be removed by evaporation (e.g., using an evaporator), distillation, or the like.

[0075] Alternatively, or as a further isolation step, the FDCA pathway product may be purified. Preferably, the FDCA pathway product is purified by crystallization. The purification and crystallization of the FDCA pathway product can be carried out by known methods. The FDCA pathway product crystals can be separated from the crystallization solvent using known methods for separating solids and liquids, such as filtration, centrifugation, or both. [Example]

[0076] Described below are various exemplary embodiments of a method for separating and recovering process solvent and solid organic impurities from a by-product-enriched membrane retentate stream obtained from a dehydration process using a thin-film evaporator.

[0077] Common analytical methods The humus content in all effluents was determined by UV-visible spectrophotometry (absorbance in the 360-460 nm range) using humus isolated by precipitation as a standard. Furan-containing compounds were determined by HPLC-UV using known commercially available compounds as standards. Water content was determined by Karl Fischer titration. 1,4-Dioxane content was determined by GC using commercially available 1,4-dioxane as a standard. Organic acids were determined by HPLC-UV using commercially available compounds as standards. For the dried residue, samples were freeze-dried and the residual weight was measured. The residual water content of the collected bottom fraction was determined gravimetrically by heating the sample at 105 °C until a constant weight was reached. Residual organic compounds in the collected solid fraction were determined by stirring a solid sample (1 g) in deionized water (20 g), filtering, and analyzing the aqueous phase using the method described above. The ash content of the collected solids was determined gravimetrically by heating the samples to 700°C in a flow of ambient air. CHNSO was analyzed using a Thermo Flash 2000 organic elemental analyzer.

[0078] Example 1 Example 1 describes the separation and recovery of solvent and solids by treating a feed in a thin-film evaporator. The feed used contained humus, sugars, organic acids, furan-containing organic compounds, sodium bromide, and a multicomponent solvent consisting of 1,4-dioxane and water. The feed was introduced into the thin-film evaporator under conditions of varying feed rate and thin-film temperature. The distillate and dried bottom fraction were collected in a pre-weighed, dry glass container for a set period of time.

[0079] The main equipment used in the test was the following: peristaltic feed pump; internal volume 465 cm 2 A hot oil jacketed countercurrent horizontal thin film evaporator with a motor-driven rotor, a 5 cm bottom outlet, and a 5 cm steam outlet; steam flows on the shell side and cooling water on the tube side; internal volume 0.37 m 2 The equipment used in Tests 1-1 to 1-7 includes a U-tube condenser, a dry ice cooling trap for liquefying the vapor bypass, a vacuum pump, and a mass flow meter for nitrogen injection. All metal parts in these devices that become wet during processing are made of 316 stainless steel. The setup parameters for the equipment used in Tests 1-1 to 1-7 are shown in Table 1. [Table 1]

[0080] Table 2 shows analytical data for the feed (Feed-1) and the solvent fractions of Tests 1-1 to 1-7. [Table 2]

[0081] The analytical data for the solid bottom fractions of Tests 1-2 and 1-3 are shown in Table 3 as Solids 1-2 and 1-3, respectively. [Table 3]

[0082] Example 2 Example 2 describes the separation and recovery of solvent and solids by treating a feed in a thin-film evaporator. The feed used contained humus, sugars, organic acids, furan-containing organic compounds, sodium bromide, and a multicomponent solvent consisting of 1,4-dioxane and water. The feed was introduced into the thin-film evaporator under conditions of varying feed rate, thin-film temperature, nitrogen injection rate, and reactor pressure. The distillate and dry bottom fraction were collected over a set period in a pre-weighed, dry glass container.

[0083] The following main equipment was used for the test: a 300 L stirred feed tank; a peristaltic feed pump; and an internal volume of 930 cm. 2 A hot oil jacketed countercurrent horizontal thin film evaporator with a motor-driven rotor, a 10 cm bottom outlet, and a 10 cm steam outlet; steam flows on the shell side and cooling water on the tube side; internal volume 0.7 m 2 The equipment consisted of a U-tube condenser, a dry ice cold trap for liquefying the vapor bypass, a vacuum pump, and a mass flow meter for nitrogen injection. All metal parts in these devices that were wetted during processing were made of 316 stainless steel. The setup parameters for the equipment used in Tests 2-1 to 2-6 are shown in Table 4. [Table 4]

[0084] Table 5 shows analytical data for the feed (Feed-2) and the solvent fractions of Tests 2-1 to 2-6. [Table 5]

[0085] The analytical data for the solid bottom fractions of Tests 2-1, 2-2, 2-5, and 2-6 are shown in Table 6 as Solids 2-1, 2-2, 2-5, and 2-6. [Table 6]

[0086] Example 3 Example 3 describes a washing method to reduce the amount of ash in the bottom fraction.

[0087] Solid 3-1: Solid 1-3 described in Example 1 was stirred in deionized water (20 x sample weight) at ambient temperature for 16 hours. The solid was filtered and dried overnight at 105°C to obtain solid 3-1.

[0088] 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 and dried overnight at 105° C. to give solid 3-2 (82 g, 85.7 wt %).

[0089] 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 and dried overnight at 105°C, and then the residue was stirred in absolute ethanol (240 g) at ambient temperature for 26 hours. The solid was filtered and dried overnight at 105°C to give solid 3-3 (81.3 g, 84.5 wt%).

[0090] Solid 3-4: Solid 2-5 described in Example 2 was stirred in deionized water (4× sample weight) for 6 hours at 60° C. The solid was filtered and dried overnight at 105° C. to give solid 3-4.

[0091] Solid 3-5: Solid 2-5 described in Example 2 was stirred in a citric acid solution (5 wt % aqueous solution, 4× sample weight) for 6 hours at 60° C. The solid was filtered, washed with deionized water, and dried overnight at 105° C. to obtain solid 3-5.

[0092] The difference in ash content between the washed and unwashed solid samples represents the amount of residual NaBr removed. The results are shown in Table 7. [Table 7]

[0093] Example 4 Example 4 describes the carbonization of Solid 3-1 from Example 3 at high temperatures to obtain Solid 4-1. A fine powder of Solid 3-1 (3.2 g) was heated to a maximum temperature of 1000°C under a N2 stream at a flow rate of 10 K / min and held at this maximum temperature for 1 hour. The heating was then stopped and the solid was allowed to cool to room temperature under a N2 stream. 1.45 g (45.3 wt% of 1-3) of residual Solid 4-1 was collected as a black fine powder. The elemental and ash analyses of Solids 3-1 and 4-1 are shown in Table 8. [Table 8]

[0094] Example 5 Example 5 describes the carbonization of solid 3-2 at high temperatures to obtain solid 5-1 and solid 5-2. The fine powder of solid 3-2 (50.5 g) described in Example 3 was heated to a maximum temperature of 500 °C under a N2 stream at a flow rate of 10 K / min and held at this maximum temperature for 1 hour. The heating was then stopped and the solid was allowed to cool to room temperature under a N2 stream. 28.2 g (55.8 wt%) of solid 5-1 was collected as a brown / black fine powder.

[0095] Next, solid 5-1 (25.2 g) was heated to a maximum temperature of 1000 °C under a N2 stream at a flow rate of 10 K / min and held at this maximum temperature for 1 hour. Heating was then stopped and the solid was allowed to cool to room temperature under N2. 20.2 g (80.2 wt%) of solid 5-2 was collected as a fine black powder. The overall yield was 44.8 wt%. The elemental analysis, ash content analysis, and particle size distribution of solid 5-2, solid 5-1, and solid 5-2 are shown in Table 9. [Table 9]

[0096] Example 6 Example 6 describes the high-temperature carbonization of Solid 3-3 to obtain Solid 6-1 and Solid 6-2. The fine powder of Solid 3-3 (50.3 g) described in Example 3 was heated to a maximum temperature of 500 °C under a N2 stream at a flow rate of 10 K / min and held at this maximum temperature for 1 hour. The heating was then stopped and the solid was allowed to cool to room temperature under a N2 stream. 30.4 g (60.4 wt%) of Solid 6-1 was collected as a brown / black fine powder.

[0097] Next, solid 6-1 (27.6 g) was heated to a maximum temperature of 1000 °C under a N2 stream at a flow rate of 10 K / min and held at this maximum temperature for 1 hour. Heating was then stopped and the solid was allowed to cool to room temperature under N2. 22.1 g (80.1 wt%) of solid 6-2 was collected as a fine black powder. The overall yield was 48.4 wt%. The elemental analysis, ash analysis, and particle size distribution of solids 3-3, 6-1, and 6-2 are shown in Table 10. [Table 10]

[0098] Example 7 Example 7 describes the fractional distillation of the collected solvent fraction. 363.8 g of Solvent 2-6, as described in Example 2, was heated to reflux in a 1 L round-bottom flask equipped with a Vigreux column and a thermometer-equipped distillation head connected to a condenser and fraction collector. The solvent fraction was distilled to collect two fractions: Solvent 7-1 and Solvent 7-2. Analytical data are shown in Table 11. [Table 11]

[0099] Summary of Examples 1 to 7 Examples 1-7 demonstrate the effective use of horizontal thin-film evaporators to separate solvent (as a vapor fraction) and organic impurities (as a solid bottom fraction) for solvent recovery and impurity removal from sugar dehydration processes, such as the dehydration of fructose to HMF and xylose to furfural. These methods demonstrate that high solvent recoveries (90-100%) can be achieved when the feed contains humus, residual sugars, furan-containing organic compounds, and organic acids, based on the low residual solvent content in the solid bottom fraction. The residual organic impurity content in the recovered solvent was low, <4 wt%, and in some cases <2 wt%. Due to this low residual impurity content, the recovered solvent can be further purified (>99%) by methods such as continuous steam-fed distillation or sequential fractional distillation of the condensed distillate.

[0100] The organic impurities were collected and sent as a dry solid bottom fraction, resulting in a low ash, sulfur-free solid fraction with a residual moisture of <2 wt% after washing. This solid bottom fraction can be further processed for use as an anode material for energy storage, activated carbon for purification, or blended into soil enhancers, soil conditioners, fertilizers, or soil purifiers.

[0101] While preferred embodiments of the present disclosure have been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the present disclosure. It is therefore to be understood that the forms disclosed herein are illustrative only and are not intended to limit the scope of the present disclosure.

Claims

1. 1. A method for isolating humus from a feedstock, wherein the humus is polymerized sugars, polymerized dehydrated sugars, polymerized furan compounds and / or other similar condensation reaction by-products produced in a sugar dehydration process or an HMF pathway process; The method includes providing a feedstock to a horizontal thin-film evaporator; The feedstock is 65-90 wt% of a multi-component solvent containing water and a water-miscible aprotic organic solvent, and 10-35 wt% of the dissolved dry residue Including, The dissolved dry residue is, as a wt% or ppm value based on the total feedstock, 30,000 to 120,000 ppm sugars; 2 to 5 wt % of a furan-containing compound, the furan-containing compound being 5-hydroxymethylfurfural, 5-hydroxymethyl-2-furancarboxylic acid, 2,5-furandicarboxylic acid, furfural, 2-furancarboxylic acid, furfuryl alcohol, or furylhydroxymethyl ketone; 24,000 to 100,000 ppm humus; 0.2 to 0.7 wt% organic acid, homogeneous acid, salt, and metal Including, the pH of the feedstock is between 1 and 4; the method further comprising processing the feedstock in the horizontal thin film evaporator to provide an isolated solid; The isolated solid is 0.3 to 2 wt% moisture, 0.9 to 5 wt % of a furan-containing compound, the furan-containing compound being 5-hydroxymethylfurfural, 5-hydroxymethyl-2-furancarboxylic acid, 2,5-furandicarboxylic acid, furfural, 2-furancarboxylic acid, furfuryl alcohol, or furylhydroxymethyl ketone; 0.1 to 2 wt% sugar, 0.02 to 1 wt% dioxane, 0.1 to 6 wt% ash, and Humus, which is produced in the sugar dehydration process or the HMF pathway process. polymerized sugars, polymerized dehydrated sugars, polymerized furan compounds and / or other similar condensation reaction by-products resulting from the The humus is isolated as a free-flowing powder, the thin film temperature of the horizontal thin film evaporator is between 180 and 230°C, the horizontal thin film evaporator operates at between 490 and 800 torr, and the amount of feed solution supplied to the horizontal thin film evaporator is set so that the residence time of the feed solution is between 0.5 and 10 minutes; method.

2. 10. The method of claim 1, further comprising washing and drying the isolated solids to obtain washed, dried solids.

3. 3. The method of claim 2, further comprising subjecting the washed and dried solids to a high temperature carbonization process to obtain carbonized solids.

4. 4. The method of claim 1, wherein the horizontal thin-film evaporator is oriented at an angle between 0° and 90°, where 0° means that the heated horizontal thin-film evaporator is oriented straight down towards the center of gravity of the Earth, and 180° means that the heated horizontal thin-film evaporator is oriented straight up away from the center of gravity of the Earth.

5. 4. The method of claim 1, wherein the organic acid is selected from the group consisting of levulinic acid, formic acid, acetic acid, and combinations thereof.

6. The homogeneous acid may be HCl, HBr, HI, H 2 SO 4 , H 3 PO 4 4. The method of claim 1, wherein the hydroxybenzoate is selected from the group consisting of oxalic acid, trifluoromethanesulfonic acid, methanesulfonic acid, boron trihalides, and combinations thereof.

7. 4. The method of claim 1, 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.

8. 1. A method for recovering a solvent from a feedstock, comprising: The method includes providing a feedstock to a horizontal thin-film evaporator; The feedstock is 65-90 wt% of a multi-component solvent containing water and a water-miscible aprotic organic solvent, and 10-35 wt% of the dissolved dry residue Including, The dissolved dry residue is, as a wt% or ppm value based on the total feedstock, 30,000 to 120,000 ppm sugars; 2 to 5 wt % of a furan-containing compound, the furan-containing compound being 5-hydroxymethylfurfural, 5-hydroxymethyl-2-furancarboxylic acid, 2,5-furandicarboxylic acid, furfural, 2-furancarboxylic acid, furfuryl alcohol, or furylhydroxymethyl ketone; 24,000 to 100,000 ppm humus, said humus being polymerized sugars, polymerized dehydrated sugars, polymerized furan compounds and / or other similar condensation reaction by-products produced in a sugar dehydration process or an HMF pathway process; 0.2 to 0.7 wt% organic acid, homogeneous acid, salt, and metal Including, the pH of the feedstock is between 1 and 4; the method further comprising processing the feedstock in the horizontal thin-film evaporator to provide a recovered solvent; The recovered solvent is Maximum 500 ppm sugar, up to 1.6 wt% furan; 300-700 ppm humus, said humus being present in the sugar dehydration process or HMF Polymerized sugars, polymerized dehydrated sugars, polymerized furan compounds and / or are other similar condensation reaction by-products, up to 2 wt% organic acids, and Humus powder with good flowability Including, the thin film temperature of the horizontal thin film evaporator is between 180 and 230°C, the horizontal thin film evaporator operates at between 490 and 800 torr, and the amount of feed solution supplied to the horizontal thin film evaporator is set so that the residence time of the feed solution is between 0.5 and 10 minutes; method.

9. 10. The method of claim 8, further comprising feeding the recovered solvent to a condenser.

10. 10. The method of claim 8, further comprising feeding the recovered solvent product to a continuous distillation column.

11. 9. The method of claim 8, wherein the recovered solvent is further purified or isolated by fractional distillation.

12. 12. The method of any one of claims 8 to 11, wherein the horizontal thin-film evaporator is oriented at an angle between 0° and 90°, where 0° means that the heated horizontal thin-film evaporator is oriented straight down towards the center of gravity of the Earth, and 180° means that the heated horizontal thin-film evaporator is oriented straight up, away from the center of gravity of the Earth.

13. 1. A method for isolating humus from a feedstock, wherein the humus is polymerized sugars, polymerized dehydrated sugars, polymerized furan compounds and / or other similar condensation reaction by-products produced in a sugar dehydration process or an HMF pathway process; The method includes providing a feedstock to a horizontal thin-film evaporator; The feedstock is a multicomponent solvent comprising water and a water-miscible aprotic organic solvent; and Dissolved dry residue Including, the dry residue comprises humus; the pH of the feedstock is between 1 and 4; the method further comprising processing the feedstock in the horizontal thin film evaporator to provide an isolated solid; The isolated solid is 0.3 to 2 wt% moisture, 0.9 to 5 wt % of a furan-containing compound, the furan-containing compound being 5-hydroxymethylfurfural, 5-hydroxymethyl-2-furancarboxylic acid, 2,5-furandicarboxylic acid, furfural, 2-furancarboxylic acid, furfuryl alcohol, or furylhydroxymethyl ketone; 0.1 to 2 wt% sugar, 0.02 to 1 wt% dioxane, 0.1 to 6 wt% ash, and Humus, which is polymerized sugars, polymerized dehydrated sugars, polymerized furan compounds and / or other similar condensation reaction by-products produced in sugar dehydration processes or HMF pathway processes; The humus is isolated as a free-flowing powder, the thin film temperature of the horizontal thin film evaporator is between 180 and 230°C, the horizontal thin film evaporator operates at between 490 and 800 torr, and the amount of feed solution supplied to the horizontal thin film evaporator is set so that the residence time of the feed solution is between 0.5 and 10 minutes; method.

14. 1. A method for recovering a solvent from a feedstock, comprising: The method includes providing a feedstock to a horizontal thin-film evaporator; The feedstock is a multicomponent solvent comprising water and a water-miscible aprotic organic solvent; and Dissolved dry residue Including, the dry residue comprises humus, the humus being polymerized sugars, polymerized dehydrated sugars, polymerized furan compounds and / or other similar condensation reaction by-products produced in a sugar dehydration process or an HMF pathway process; the pH of the feedstock is between 1 and 4; the method further comprising processing the feedstock in the horizontal thin-film evaporator to provide a recovered solvent; The recovered solvent is Maximum 500 ppm sugar, up to 1.6 wt% furan; 300 to 700 ppm humus, said humus being polymerized sugars, polymerized dehydrated sugars, polymerized furan compounds and / or other similar condensation reaction by-products produced in the sugar dehydration process or HMF pathway process; up to 2 wt% organic acids, and Humus powder with good flowability, Including, the thin film temperature of the horizontal thin film evaporator is between 180 and 230°C, the horizontal thin film evaporator operates at between 490 and 800 torr, and the amount of feed solution supplied to the horizontal thin film evaporator is set so that the residence time of the feed solution is between 0.5 and 10 minutes; method.

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