METHODS FOR THE PRODUCTION OF REACTIVE INTERMEDIATES FROM BIOMASS AND FOR THE COMBINED SOLUBILIZATIO

专利摘要:
methods for producing reactive intermediates from biomass and for combined fractionation and catalytic conversion of biomass, and composition the present invention provides a system for producing reactive intermediates from lignocellulosic biomass. reactive intermediates can be used as platform chemicals for biological conversions or can be further catalytically enhanced to be used as "drop in" reagents for fuels. the disclosure provides methods and compositions useful for processing biomass into biofuels and intermediates.
公开号:BR112015026960B1
申请号:R112015026960-5
申请日:2014-04-25
公开日:2021-07-27
发明作者:Charles M. Cai；Charles E. Wyman；Taiying Zhang；Rajeev Kumar
申请人:The Regents Of The University Of California；
IPC主号:

专利说明:

CROSS REFERENCE TO RELATED ORDERS
[0001] This application claims priority over provisional US patent application No. 61/816,713, filed April 27, 2013, the description of which is incorporated herein by reference in its entirety. FIELD OF THE INVENTION
[0002] The disclosure refers to a single-phase aqueous co-solvent system to treat lignocellulosic biomass to extract lignin and produce reactive intermediates such as monomeric sugars, furfural, 5-HMF and levulinic acid that are important renewable precursors to produce transport and transport fuels. sustainable liquid chemicals. BACKGROUND
[0001] Declining oil supplies worldwide have led to the growing need to safeguard domestic oil supplies and develop an economical and highly effective renewable substitute for fossil fuels. Increased public awareness of the imbalance in atmospheric CO2 emissions resulting from the intensive use of non-renewable fossil fuels has put pressure on industrialized countries to demand the gradual integration of biomass-derived fuels into their transport sectors. Lignocellulosic biomass is the most abundant resource of organic carbon on Earth and is the only renewable resource that is cost effective enough to replace fossil fuels and sustain energy demand in the transportation sector. This biomass is composed of three main polymeric components: cellulose, hemicellulose and lignin. Cellulose has a crystalline structure and is composed of linearly linked β-1,4 glucose units known as glucan. Hemicellulose has an amorphous structure and is often comprised primarily of polymer chains of β-1.4 bonded xylose units known as xylan, an important component of hemicellulose in most hardwood species, agricultural residues and herbaceous crops for energy generation . Lignin is a heterogeneous cross-linked complex covalently linked to hemicellulose involving polymers of phenyl propanol units called monolignols. Only the maximum utilization of these three components from lignocellulosic biomass to produce reactive intermediates, including fuel precursors, will allow the cost-effective production of biofuels to sustain current and future energy demands. SUMMARY
[0002] The disclosure describes a method for biorefinery that increases the use of saccharides and carbonaceous material from all types of crude lignocellulosic biomass for the production of reactive intermediates in yields susceptible to conversion into biofuels and biochemicals. The method involves a one-step reaction of crude cellulosic biomass using a single-phase mixture of aqueous tetrahydrofuran (THF). In some embodiments, the mixture additionally includes an acid catalyst. Biomass is incubated at a temperature of about 100 °C or more. The reaction catalyzes and facilitates the production of hydrolyzed biomass sugars such as xylose and glucose and the like and the production of dehydration products from hydrolyzed biomass sugars (eg furfural (FF), 5-hydroxy-methylfurfural (5-HMF) ) and levulinic acid (LA)) and the removal of acid-insoluble lignin from the remaining hexose-rich unreacted solids. By changing the THF concentration, reaction temperature, reaction time, catalyst type and catalyst loading, the product distribution can be changed between these reactive intermediates. This process is advantageous to other cellulosic pretreatment and conversion technologies due to the low cost of operation and materials of this single-phase, one-step integrated approach, the high yields of dehydration and sugar products, the ease of scaling up such as a batch or continuous process, the unspecific need for the cellulosic material used as feed and the high recyclability of the solvent with a low boiling point.
[0003] The disclosure uses a water-miscible solvent, such as tetrahydrofuran, as a co-solvent in a one-pot reaction scheme to promote targeted production of primary and secondary reactive intermediates (RIs) such as monomeric sugars, furfural, 5-hydroxy -methylfurfural and levulinic acid, and isolated lignin, directly from lignocellulosic biomass. In some embodiments, the THF co-solvent mixture is used in conjunction with an acid-based catalyst. These reactive intermediates can be used as fuel precursors.
[0004] The disclosure provides a process in which a co-solvent such as THF can be used in an integrated biorefinery process to improve the production of reactive intermediates directly from lignocellulosic or cellulosic biomass. THF is a low boiling solvent that can be produced directly from furfural as a final co-product through catalytic decarbonylation to furan, followed by hydrogenation.
[0005] The revelation provides THF in a single phase solution with water and a suitable acid catalyst to promote (1) fractionation and (2) deconstruction/solubilization of crude biomass and (3) improve the production of RIs in a catalytic conversion in one step. THF as a co-solvent can (4) directly solubilize Klason's lignin as well as degrade tars that would normally accumulate without THF. By changing process conditions, (5) the solvent system can also allow the production of a glucan-rich pretreated solid that can be more readily enzymatically hydrolyzed to fermentable glucose than that of typical pretreatment technologies or further thermochemically converted to more levulinic acid.
[0006] The disclosure provides a method for the production of reactive intermediates from biomass, comprising: treating a biomass with a composition comprising a mixture of aqueous THF co-solvent under conditions to produce a material rich in solid glucan, monomeric sugars, furfural , 5-hydroxy-methylfurfural and lignin products. The disclosure also provides a method for producing reactive intermediates from biomass, comprising: treating a biomass with a composition comprising a mixture of aqueous tetrahydrofuran co-solvent and an acid catalyst under conditions to produce a material rich in solid glucan, monomeric sugars , furfural, 5-hydroxy-methylfurfural and lignin products. In one embodiment, the co-solvent mixture is single-phase under Normal Conditions of Temperature and Pressure (CNTP). In another embodiment, the acid catalyst is selected from the group consisting of mineral acids, organic acids, and metal halide acids. In yet another embodiment of any of the above, the acid catalyst is sulfuric acid, hydrochloric acid, nitric acid, acetic acid, formic acid, trifluoroacetic acid, or FeCl 3 . In another embodiment, the conditions include heating the combination of biomass and composition to 100°C to 220°C. In yet another embodiment, the method further comprises removing and/or recovering THF from the liquid phase after pretreatment of the biomass with cosolvent. In yet another embodiment, the method further comprises removing and/or recovering lignin from the cosolvent treated biomass by precipitation as a solid after removing THF from the liquid phase. In yet another embodiment, the method further comprises removing and/or recovering furfural from a liquid phase after treating the biomass with co-solvent by azeotropic distillation or solvent extraction. In yet another embodiment, the method further comprises removing and/or recovering furfural from the vapor phase during and/or after co-solvent treatment by boiling and/or steam stripping. In another embodiment of the above, furfural is further processed to be catalytically enhanced to produce THF and/or methyl-THF. In another embodiment, the method further comprises recovering a liquid product comprising C5 and C6 monosaccharides and/or their oligomers. In yet another embodiment, the liquid product is neutralized by a base. In yet another embodiment, the method further comprises recovering a solid product after treating the biomass with co-solvent, wherein the solid comprises a material rich in glucan. In yet another embodiment, the glucan-rich material is further treated with one or more enzymes that remove xylo-oligomers and higher xylose chain length polymers to produce xylose monomers. In yet another embodiment, the glucan-rich material is further treated with one or more enzymes that remove gluco-oligomers and higher glucose chain length polymers to produce glucose monomers. In yet another embodiment, the glucan rich material can be treated with low boiling point acids such as trifluoroacetic acid, formic acid, acetic acid and the like to produce glucose and related oligomers. In yet another embodiment, the glucan-rich solid is incubated with microorganisms and/or added enzymes to produce an alcohol, fatty acids, or other products through fermentation. In another embodiment, the glucan material can be used to produce a microcrystalline cellulose (MCC). In an additional modality, alcohol is ethanol. In yet another embodiment, alcohol contains 1 or more carbon molecules. In another embodiment, the microorganism is selected from the group consisting of a yeast, a bacterium, mold and a fungus. In yet another embodiment, the microorganism is manipulated to express a non-naturally occurring biosynthetic route to metabolize a carbon source from the treated biomass to produce an alcohol or other metabolite. In another embodiment, the glucan-rich material is used as paper pulp. In another embodiment, lignin is further processed and captured by THF or dimethyl sulfoxide (DMSO) as a liquid. In another embodiment, the acid catalyst is a Lewis acid and/or BrOnsted acid. In yet another embodiment, the acid catalyst is an acid metal halide. In yet another embodiment, the acid metal halide is selected from the group consisting of AlCl3, CuCl2, CrCl3, FeCl3 and ZrOCl2. In another embodiment, the aqueous THF co-solvent comprises a volume ratio of THF:water of from about 1:5 to about 7:1. In one embodiment, the treatment method has no added ionic salts or salts. In another embodiment, the treatment method does not include any THF:water ratio greater than 7:1 (eg, less than 7:1, 6:1, 5:1 etc.).
[0007] The disclosure also provides a method for the combined fractionation and catalytic conversion of biomass to produce reactive intermediates from biomass, comprising: treating a biomass with a co-solvent mixture comprising THF, water and an acid catalyst under conditions to produce furfural , 5-HMF, levulinic acid, glucan rich material, and lignin. In one embodiment, the co-solvent mixture is single-phase under Normal Conditions of Temperature and Pressure (CNTP). In another embodiment, the acid catalyst is selected from the group consisting of mineral acids, organic acids, metal halide acids and solid acid catalysts. In yet another embodiment, the acid catalyst is selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, formic acid, trifluoroacetic acid, FeCl3, AlCl3, CuCl2 and any combination thereof. In yet another embodiment, the conditions include heating the combination of the biomass and co-solvent mixture to 130 °C to 250 °C. In one embodiment, a dYigiia steam injection system is used to heat the reaction. In another embodiment, the method further comprises removing and/or recovering THF from the liquid phase after co-solvent treatment of the biomass. In another embodiment, the method further comprises removing and/or recovering lignin from treating the biomass with cosolvent by precipitation as a solid after removing THF from the liquid phase. In another embodiment, the method further comprises removing and/or recovering furfural and/or 5-HMF from a liquid phase of the biomass treatment with co-solvent by distillation. In another embodiment, the method further comprises removing and/or recovering furfural from the vapor phase during and/or after co-solvent treatment by boiling and/or steam stripping. In another embodiment, furfural is further processed to be catalytically decarbonyl and hydrogenated to produce THF. In another embodiment, the method further comprises extracting and/or recovering furfural and/or 5-HMF from a liquid phase of the biomass co-solvent treatment by a water-immiscible organic solvent. In another embodiment, the immiscible organic solvent is an ether, ketone, alcohol, alkane or any combination thereof. In another embodiment, the method further comprises recovering a solid product after treating the biomass with co-solvent, wherein the solid comprises a material rich in glucan. In another embodiment, the glucan-rich material is further treated with one or more enzymes that remove gluco-oligomers and higher glucose chain length polymers to produce glucose monomers. In a further embodiment, the glucan-rich solid is incubated with microorganisms and/or enzymes to produce an alcohol or other fermentation product. In a still further embodiment, the glucan-rich solid is further catalytically converted to 5-HMF and/or levulinic acid. In another embodiment, lignin is further processed and captured by THF or DMSO as a liquid. In another embodiment, the acid catalyst is a Lewis acid or BrOnsted acid. In yet another embodiment, the acid catalyst is a metal halide acid. In another embodiment, the metal halide acid is selected from the group consisting of AlCl3, CuCl2, CrCl3, FeCl3 and ZrOCl2. In one embodiment, the volume ratio of THF:water is about 1:1 to about 7:1. In one embodiment, the treatment method has no added ionic salts or salts. In another embodiment, the treatment method does not include any THF:water ratio greater than 7:1 (eg, less than 7:1, 6:1, 5:1 etc.).
[0008] The disclosure also provides a system for carrying out the methods of the present invention described herein. In one embodiment, the system comprises a vessel for mixing a biomass with an aqueous THF solution of co-solvent. One or more fluidly connected valves and tubes can be used to transport treated biomass in additional vessels for separation of solids and liquids. These additional vessels or chambers may include heating elements, settling systems, and the like (see, Figures 2A-D).
[0009] The disclosure also provides a composition comprising a biomass and an aqueous co-solvent of THF. In one embodiment, the composition can further include an acid catalyst. In another embodiment, the aqueous THF co-solvent comprises a volume ratio of THF:water of from about 1:3 to about 7:1. In yet another embodiment, the acid catalyst is a Lewis acid. In an additional embodiment, the Lewis acid is sulfuric acid. In another embodiment, the acid catalyst is a metal halide acid. In yet another embodiment, the acid catalyst is a Br0nsted acid. In a further embodiment, the metal halide acid is selected from the group consisting of AlCl3, CUCl2, CrCl3, FeCl3 and ZrOCl2.
[00010] Other features and advantages of the invention will become apparent from the following detailed description taken in conjunction with the attached drawings, which illustrate, by way of example, the elements of the invention. BRIEF DESCRIPTION OF THE DRAWINGS
[00011] Figure 1 shows a reaction network illustrating the primary and secondary reactive intermediates for the production of ethanol and gasoline, aromatic and hydrocarbon-based fuels for jet and diesel engines. 5-HMF: 5-hydroxy-methylfurfural; MF: 2-methylfuran; DMF: 2,5-dimethylfuran; MTHF: 2-methyltetrahydrofuran; Fur-Ale: furfuryl alcohol.
[00012] Figures 2A-D are exemplary process schematics of the description. (A) Conceptual process flow diagram of an approach to produce reactive intermediates and isolated lignin from lignocellulosic biomass using THF as a single-phase co-solvent to improve biomass fractionation and product yields. Process legend: (1) Pandia high solids screw reactor, (2) High pressure (HP) boiler (3) Removal of volatile substances and separation of solids (4) Continuous azeotropic distillation to recover furfural, THF and water, (5) Catalytic enhancement and hydrogenation of furfural, and (6) Production of levulinic acid from material enriched with glucose and glucan remaining in a concentrated solution. Dotted lines represent recycling and recovery streams. (B) Simplified process diagram of a proposed use of a THF co-solvent strategy for direct conversion of lignocellulosic biomass to furfural co-product and 5-HMF for catalytic enhancement in aromatic fuel products. Furfural and 5-HMF will be extracted by an organic solvent and hydrogenated (blue rectangle, right) to produce aromatic fuels such as MF and DMF. Lignin is precipitated by recovering THF. (1) Organic stream containing furfural and 5-HMF (2) Aqueous stream containing metal halide catalyst, furfural and 5-HMF. (C) Simplified process diagram of a proposed use of a THF co-solvent strategy for the pretreatment of lignocellulosic biomass to hydrolyze C5 and C6 sugars in high yields followed by simultaneous saccharification and fermentation (SSF) of C5 and C6 sugars to ethanol (or other alcohols) with high yield. In the first pre-treatment step (stage 1), the reaction with THF co-solvent hydrolyzes all hemicellulose sugars in the liquid phase as liquid products, extracts more than 90% of the acid-insoluble lignin as a highly oxidized lignin soluble product. THF and produces a glucan-rich pretreated solid that is highly digestible by enzymes. The pretreated solids or solid products are then separated from the liquid products and washed to remove any water-soluble contaminants. THF is then recovered and removed from the liquid stream to be recycled back to the first reaction step. Upon removal of THF, the extracted lignin product can be recovered as a solid precipitate. The liquid stream is then neutralized by a base such as calcium hydroxide, ammonium hydroxide (or equivalent) to be compatible for fermentation. The liquid products and solid products are then fed into a fermentor (stage 2) where a microorganism and saccharification enzymes are introduced to biologically convert the solid and liquid products into ethanol or other alcohol. (D) Shows a simplified process flow diagram of a possible continuous approach to produce reactive intermediates and isolated lignin from lignocellulosic biomass using THF as a single-phase co-solvent to improve biomass fractionation and product yields . Process legend: (1) High solids screw reactor, (2) High pressure (HP) boiler (3) Removal of volatile substances and separation of solids (4) Continuous azeotropic distillation to purify the products, (5 ) Catalytic enhancement and hydrogenation of furfural, and (6) Continuous production of levulinic acid from material enriched with glucan in a more concentrated acidic solution. Dotted lines represent recycling and recovery streams.
[00013] Figures 3A-E are graphs of the concentration profiles of RIs and glucan-rich solids produced from the THF co-solvent reaction at 170 °C. Concentration profiles of (A) glucose, (B) xylose + mannose + galactose, (C) LA, and (D) furfural over a 60 min reaction time (■ with THF, ▲ without THF). (E) Composition of crude maple wood and glucan-rich solids remaining after reaction with and without THF co-solvent. THF dissolved more than 90% (by weight) of the lignin and degradation tars that would otherwise accumulate in the case of non-solvent. Reaction conditions: 5% by weight of maple wood and 1% by weight of H2SO4 in batch reactions at 170 °C. The THF co-solvent solution contained a 1:1 ratio of THF and DI water.
[00014] Figures 4A-B show the ability of the reaction with THF co-solvent to improve the selectivity of furfural from xylose and protect furfural from degradation. (A) Furfural selectivity in reactions of 10 g L-1 of pure D-xylose (■ with THF, ▲ without THF) and remaining xylose in solution (□ with THF, Δ without THF). (B) Furfural remaining (%) for reactions of 6.5 g L-1 pure furfural (■ with THF, ▲ without THF).
[00015] Figure 5 is a graph of the product yields of crude maple wood reactions in a 1 L Parr® reactor at 170°C and 1% (w/w) H2SO4 solution in water only. The numbered markers represent the furfural yield at each reaction time.
[00016] Figure 6 is a graph of the product yields of crude maple wood reactions in a 1 L Parr® reactor at 170°C and 1% (w/w) H2SO4 in a solvent solution of 1 :3 (v/v) of tetrahydrofuran and water. The numbered markers represent the furfural yield at each reaction time. As shown, the presence of THF in the solution mixture allows for improvement of furfural yields in the reaction by up to 20%. Levulinic acid yields were also improved over water-only reactions by more than 11% at 60 min of reaction (the reaction temperature was optimal for furfural production).
[00017] [0001] Figure 7 is an initial graph comparing the calculated rate constants between an aqueous solution and a solvent solution of THF of pure xylose and 1% (by weight) of H2SO4. Reactions were performed using a 1 L Parr® reactor at 170°C. The THF solution is composed of a 50% (v/v) solvent mixture of tetrahydrofuran and water. The initial concentration of xylose (XO) was 10 g/L. The markers represent a linear regression of the normalized xylose conversion data and the reaction k value is represented by the slope and expressed in units of [min-1]. As shown, the xylose conversion rate is much faster in THF solvent solution than in water alone.
[00018] Figure 8 is a graph of a single experiment comparing the degradation profile of furfural between an aqueous solution and a THF solvent solution of furfural and 1% (by weight) of H2SO4. Reactions were performed using a 1 L Parr® reactor at 170°C. As shown, the THF solvent solution helps prevent up to 7% degradation of the furfural present in the solution.
[00019] Figure 9 represents a comparison of the maple wood composition of the Solid Fraction remaining over time after an acid catalyzed reaction in a 1 L Parr® reactor at 170°C between a solvent solution of THF and a aqueous solution. Comparison of reacted samples is based on the composition of 100 g of unreacted raw maple wood. As shown, up to 90% of the insoluble lignin and tars can be removed in reactions with THF. Without the solvent, the insoluble fraction of lignin and tars increases over time.
[00020] Figures 10A-E show the conversions and selectivities for pure sugar reactions with metal halide acid catalysts in THF co-solvent mixture plotted against the reaction time. Conversions of (A) xylose and (B) glucose and (C) furfural selectivity from xylose and (D) 5-HMF and (E) LA selectivity from glucose. Reaction conditions: 170°C, 20 g L-1 glucose or 10 g L-1 xylose, 1:1 THF:water ratio, 0.1 M catalyst charge and normalization of all solutions to pH 1.6 with the use of 72% sulfuric acid. Black squares represent the sulfuric acid control also titrated to pH 1.6.
[00021] Figure 11 shows the composition of raw maple wood and distribution of main components to the solids remaining after reaction with 1:1 THF co-solvent and various acid catalysts based on 100 g of initial maple wood fed to the systems . Metal halides improved the performance of sulfuric acid by releasing greater amounts of glucan-rich solids for enzymatic conversion to glucose or thermochemical reaction to glucose, 5-HMF and/or LA. Reaction conditions: 5% by weight maple wood, 0.1 M acid catalyst concentration, 1:1 THF:water, 170°C, batch reactions for 30 min.
[00022] Figure 12 shows the composition of raw maple wood and the distribution of the main components to the solids remaining after the reaction with THF co-solvent with FeCl3 • 6H2O at volume ratios of 1:1, 4:1, and 7: 1 of THF:water. The solid mass is based on 100 g of initial maple wood fed into the systems. Suspected phase separation at a 7:1 ratio is evident by a higher lignin fraction, less solids solubilization and higher fraction of glucans remaining after 60 min of reaction compared to the 4:1 ratio case. Reaction conditions: 5 wt. maple wood, 1 wt.% FeCl3 • 6H2O based on dry mass, 170°C.
[00023] Figure 13 shows an image: Left, lignin powder precipitated from maple wood after THF co-solvent with FeCl3 catalyst. Right, even lignin powder shown dissolved in a large droplet of DMSO suitable for catalytic enhancement for fuels or chemicals.
[00024] Figure 14 shows the concentration of liquid fructose from pure glucose THF co-solvent reactions. Reaction conditions: Reaction conditions: 20 g L-1 glucose, 1:1 THF: water (vol), 170 °C, 0.1 M catalyst loading based on dry mass.
[00025] Figure 15 shows the concentration of liquid xylulose from pure xylose THF co-solvent reactions. Reaction conditions: 10 g L-1 xylose, 1:1 THF: Water (vol), 170 °C, 0.1 M catalyst loading based on dry mass.
[00026] Figure 16 shows an exemplary product flow and a mass balance diagram describing the mass and yield of products recovered in the solid and liquid portion after the reaction. Data shown for the reaction conditions mentioned in Table 3, test 17 in the main article when the highest co-production yields of furfural and 5-HMF were obtained. The total recovery of C6 and C5 products is calculated from the liquid and solid yields.
[00027] Figure 17 shows a comparison between pretreatment with THF co-solvent (columns 2, 4, 5 and 7) and non-THF pretreatment with only dilute acid (DA) (col. 1, 3, and 6) 48 h yield of glucose for the enzymatic hydrolysis of corn forage (CS), maple wood (MW) and poplar wood (PW) at 50°C in 50 mM citrate buffer (pH 5, 0) Accellerase® 1500 cellulase loading of 15 mg protein/g glucan on pretreated solids. Pretreatment reaction conditions: (1) 5 wt% corn fodder, 170°C, water + 1 wt% H2SO4, 40 min; (2) 5 wt% corn fodder, 170°C, 1:1 THF:Water+ 1 wt% H 2 SO 4 , 40 min; (3) 5% by weight maple wood, 160°C, water + 0.5% by weight H2SO4, 30 min; (4) 5 wt% maple wood, 160°C, 1:1 THF:water+ 0.5 wt% H 2 SO 4 , 30 min; (5) 5% by weight maple wood, 170°C, 1:1 THF: Water + 1% by weight (anhydrous weight) FeCl3 • 6H2O, 30 min; (6) 5 wt% poplar wood, 160°C, water + 0.5 wt% H 2 SO 4 , 30 min; (7) 5 wt% poplar wood, 160°C, 1:1 THF: Water + 0.5 wt% H 2 SO 4 , 30 min; (8) Avicel® cellulose (97% pure alpha-cellulose).
[00028] Figure 18 shows a comparison between glucose released in various loads of cellulase enzyme (Accellerase® 1500) (mg enzyme protein/g glucan in pretreated sample) between pretreatment with THF co-solvent and non-THF pretreatment with only dilute acid (DA) (PT) of corn forage using dilute sulfuric acid at its optimal total sugar release conditions. The X axis represents the enzymatic hydrolysis time in hours. Pretreatment conditions for dilute acid only are 160°C and 0.5% H2SO4 for 20 min (Best). Pretreatment conditions for THF are 1:1 THF:water, 150 °C, 0.5% H 2 SO 4 for 25 min (Best).
[00029] Figure 19 shows a comparison between glucose, xylose and glucose plus the xylose yield obtained in stage 1 and stage 2 (% of total yield) combined in various loads of cellulase enzyme (Accellerase® 1500) (mg of enzyme protein/g glucan in pre-treated sample) between pre-treatment with THF co-solvent and pre-treatment (PT) with non-THF only with diluted acid (DA) of corn forage using dilute sulfuric acid as an acid catalyst. The X axis represents enzyme loading in mg protein/g glucan. Pretreatment conditions for dilute acid only are 160°C and 0.5% H2SO4 for 20 min (Best). Pretreatment conditions for THF are 1:1 THF:water, 150 °C, 0.5% H 2 SO 4 for 25 min (Best). The time in days is also indicated to be shown when the highest yields were obtained by enzymatic hydrolysis.
[00030] Figure 20 shows a comparison between ethanol yields from simultaneous saccharification and fermentation (SSF) with S. Cerevisiae (strain D5A) with the use of corn forage pretreated with THF (upper left side) and non-THF only with dilute acid (DA, upper right) and Avicel® cellulose. Comparison of broth component yields after 7 days of fermentation is also shown at the bottom. Two enzyme protein loadings (5 mg/g glucan and 15 mg/g glucan) are shown. Pretreatment conditions for dilute acid only are 160°C and 0.5% H2SO4 for 20 min (Best). Pretreatment conditions for THF are 1:1 THF:water, 150 °C, 0.5% H 2 SO 4 for 25 min (Best). SSF conditions: pre-hydrolysis at 50°C and 150 rpm for 18 h followed by fermentation at 37°C and 130 RPM, 4% by weight glucan loading, inoculation of S. Cerevisiae (strain D5A) at 0 0.5 OD (optical density) at 600 nm in 250 mL shake flasks. The X axis represents fermentation time.
[00031] Figure 21 shows a comparison between the solubilization of solids pretreated with C. thermocellum of THF co-solvent, ethanol-Organosolv, only dilute acid (DA) and Avicel® cellulose in CBP fermentation experiments. Pretreatment conditions are mentioned in the Table below the plot. CBP conditions: C. thermocellum DSM13131, incubation at 60°C on loading 5 g glucan/L solids in MTC medium and 2% (v/v) inoculum size. DETAILED DESCRIPTION
[00032] For use in the present invention and the appended claims, the singular forms "a" "and" and "the" include plural references unless the context clearly dictates otherwise. Thus, for example, reference to "an enzyme" includes a plurality of such enzymes, and reference to "the material" includes reference to one or more materials known to those of skill in the art, and so on.
[00033] Furthermore, the use of "or" means "and/or" unless otherwise stated. Similarly, "comprise," "comprises," "comprises," "includes," "includes," and "including" are interchangeable and are not intended to be limiting.
[00034] It should be further understood that when descriptions of various modalities use the term "comprises," those skilled in the art would understand that in some specific cases, a modality may alternatively be described using the language "consisting essentially of" or " consisting of."
[00035] Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as understood by one of ordinary skill in the art to which this disclosure belongs. While methods and materials similar or equivalent to those described herein can be used in practicing the disclosed methods and compositions, exemplary methods, devices, and materials are described in the present invention.
[00036] The publications discussed above and throughout the text are provided for description only prior to the filing date of this application. Nothing here should be construed as an admission that the inventors have no right to forego such disclosure by virtue of the prior disclosure.
[00037] The intense use of non-renewable fossil fuels in the last half of the century has been shaking the world's oil supplies and the environment. As a result, the United States and European countries have pushed the use of biofuels in their transportation sectors to alleviate foreign energy dependence and environmental concerns. While corn ethanol has been the most commercially successful biofuel in the United States, concerns about sustainability in corn growth and supply have necessitated a shift in focus toward fuel production from lignocellulosic feedstocks. Lignocellulosic biomass is the most abundant resource of organic carbon on Earth and is a renewable resource that can cost-effectively replace fossil fuels for the production of liquid fuels and sustain future energy demands in the transportation sector. A feasible conversion strategy requires effectively overcoming lignocellulose recalcitrance to increase the yield of reactive sugar intermediates and their derivatives that are suitable for transformation into final products by targeted conversion technologies. In this context, a reactive intermediate (RI) as used herein includes any sugar or sugar dehydration product that can be biologically, chemically or catalytically converted to fuels and chemicals.
[00038] Cellulosic waste and waste and lignocellulosic biomass, such as agricultural waste, wood, forestry waste, papermaking sludge, and municipal and industrial solid waste, provide a potentially large renewable raw material for the production of chemicals, plastics, fuels and feed. Cellulosic and lignocellulosic biomass residues and waste, composed of carbohydrate polymers comprising cellulose, hemicellulose, and lignin, can generally be treated by a variety of chemical, mechanical and enzymatic means to primarily release hexose and pentose sugars, which can be, then fermented into useful products including ethanol or dehydrated by acids into furfural, 5-HMf, and levulinic acid, which can then be catalytically upgraded to gasoline, diesel, and jet engine fuels.
[00039] Pretreatment methods are used to make carbohydrate polymers of cellulosic and lignocellulosic materials more readily available for saccharification enzymes or acid catalysts. Standard pretreatment methods have historically used mostly strong acids at high temperatures; however, due to high energy costs, high equipment costs, high cost of catalyst recovery from pretreatment, and incompatibility with saccharification enzymes, alternative methods are being developed, such as enzymatic pretreatment or the use of an acid or based on milder temperatures, where reduced hydrolysis of biomass carbohydrate polymers occurs during pretreatment, requiring improved enzymatic systems to saccharify cellulose and hemicellulose. For example, typical acid catalyzed or hydrothermal (water only) pretreatments that represent the least expensive pretreatment options are less effective on more recalcitrant lignocellulosic raw materials such as hard and soft woods. This means that higher enzyme loadings are needed to obtain higher sugar recovery yields which significantly increase process costs. The presence of lignin has also long been considered an enzyme inhibitor and its effective removal without significantly reducing the porosity of the pretreated material has been shown to significantly reduce the enzyme loadings required for high sugar recovery. Thus, there is still a need for an agnostic pretreatment process of more raw material that can simultaneously delignify the biomass, promote biomass solubilization, and obtain high total sugar yields with as little or no enzyme as possible.
[00040] Figure 1 depicts a reaction network for the production of ethanol and gasoline, fuel products for jet engines and diesel from primary and secondary reactive intermediates. As shown, hemicellulose xylose and glucose from cellulose can be fermented into ethanol or dehydrated with acid catalysts to produce the secondary reactive intermediates like furfural and 5-HMF. Additionally, the hydrolysis of 5-HMF results in the equimolar formation of the more stable products of levulinic acids (Las) and formic acid. LA can also be synthesized from furfural by a furfuryl alcohol intermediate. These secondary reactive intermediates can be catalytically enhanced into potential fuel products by selective hydrogenation over solid metal-based catalysts. As shown, catalytic hydrogenation of furfural and 5-HMF yields the promising gasoline blend products 2-methylfuran (MF, 131 Research Octane Number RON) and 2,5-dimethylfuran (DMF, 119 RON), respectively. 2-Methyltetrahydrofuran (MTHF, 86 RON) can be produced from the hydrogenation of LA and ethanol can be produced from sugars by fermentation by yeast and/or bacteria, both of which are major components in P series biofuels Ethanolysis of LA produces ethyl levulinate (EL), a diesel blending ingredient, while aldol addition using acetone and hydrodeoxygenation of secondary reactive intermediates with hydrogen can produce longer chain hydrocarbon fuels of up to 16 lengths. carbon for jet and diesel applications.
[00041] Alternatively, reactive intermediates such as furfural, hydroxy-methylfurfural, and levulinic acid, which are formed during the acid-catalyzed pretreatment of cellulosic biomass, can be hydrogenated and hydrodeoxygenated into alkanes that are compatible with the existing fuel infrastructure ( "drop-in" fuels) by the action of heterogeneous catalysts (Xing et al. 2010 and Huber et al. 2005). These RIs can be produced at higher concentrations from crude biomass by additional heating and the action of an acid catalyst under aqueous conditions (Zeitsch 2000). Figure 1 depicts the hydrolysis and dehydration pathways for glucan and xylan to form RIs (see also scheme 1). In the pentose route, xylan is first hydrolyzed to xylose, which is then dehydrated by removing three water molecules to form furfural. Further dehydration of furfural at high temperatures will produce formic acid. Similarly, for the hexose route, glucan is hydrolyzed to glucose, which is then dehydrated to form HMF. HMF is highly unstable in an aqueous environment and will rapidly degrade into equimolar amounts of levulinic acid and formic acid until HMF is consumed (Karinen 2011). Pentose hydrolysis and dehydration reaction route
Hexose dehydration and hydrolysis reaction pathway
Scheme 1
[00042] Furfural is a heterocyclic aldehyde that is produced from agricultural raw materials rich in pentosans and is useful as a furanic precursor. The maximum theoretical yield of furfural obtainable from xylan is 0.7273. Since the hydrolysis of pentosan occurs at a much faster rate than the formation of furfural from a pentose sugar, the kinetics of hydrolysis can be predominantly disregarded in optimizing furfural production. Because arabinose typically follows the same reaction route as xylose, it is reasonable to approximate that all pentosan content in most types of biomass except softwoods is xylan (Zeitsch 2000). Because furfural can degrade under an aqueous environment by self-resinification or condensation with a pentose-to-furfural intermediate, removing furfural from the catalytically active phase by vaporization can prevent loss reactions from occurring (Zeitsch 2000). Furfural is currently produced predominantly in China from various agricultural residues at reported yields of less than 50%, with higher yields due to continuous furfural removal by steam separation (Win 2005). Continuous distillation after separation by steam stripping allows for a product purity of up to 99.5% (Win 2005).
[00043] HMF is the 6 carbon analogue of furfural with an additional alcohol group on a branched carbon. The same can be produced by dehydration of fructose or glucose with higher yields compared to the previous one (Karinen 2011). The maximum theoretical yield of HMF from glucan is 0.7785. Due to the less stable ring structure of fructose than glucose, HMF formation is faster from fructose. Further hydrolysis of HMF in the aqueous phase leads to levulinic acid and formic acid, which are species stable without additional hydrolysis products (Küster 1990). Levulinic acid is also considered an important platform chemical for biofuel synthesis (Dautzenberg 2010; Werpy and Peterson 2004).
[00044] The improvement of furfural and HMF yields requires their protection from the catalytically active aqueous phase or the application of alternative reaction mechanisms.
[00045] IRs like furfural and levulinic acid, which can be produced directly from biomass sugars, are useful building blocks for the production of high value chemicals and fuels. Alkanes in the gasoline and diesel range can be catalytically produced from these RIs, and ongoing efforts to improve their synthesis have made this route attractive as an industrially relevant biofuels platform. Furfural is interesting as it is one of the only natural precursors of furan-based chemicals and today it is commercially produced in low yields (50% by mol) from xylan-rich lignocellulosic residues.
[00046] Current advances in catalysis have improved the selective conversion of secondary reactive intermediates into so-called "drop-in" fuel products that are compatible with existing fuel infrastructure, but achieving high total yields of reactive intermediates directly from of lignocellulosic biomass has been a long-standing barrier. Thus, there is a great need to develop effective strategies that integrate catalytic conversion with biomass deconstruction to co-produce FPs from C5 and C6 sugars so that “drop-in” biomass fuels have an impact. Obtaining total product yields from the main biomass fractions hemicellulose, cellulose, and lignin in an integrated process has the greatest potential to enable future biomass-in-fuel technologies. Several acid-catalyzed co-production schemes from biomass have been proposed, including co-production of furfural with levulinic acid, furfural with 5-HMF, furfural with cellulose, and LA from furfural and 5-HMF, but many suffer from lows yields due to the heterogeneous and complex nature of biomass. For example, furfural and 5-HMF produced early in biomass deconstruction are rapidly degraded before sufficient yields of LA from C6 sugars can be obtained. Consequently, LA production and recovery would have to accompany furfural removal, thus requiring multi-stage reactions with independent product recovery steps, costly steam separation to remove furfural, use of corrosive mineral acids, and/or biphasic reactions. Alternatively, co-production of furfural and 5-HMF would seem more desirable as both products could be recovered together by a suitable extraction solvent and converted simultaneously to drop-in fuels such as MF and DMF by a single catalyst.
[00047] Furfural is typically synthesized from the acid-catalyzed dehydration of C5 sugars (arabinose and xylose) while levulinic acid can be produced from C5 or C6 sugars (glucose, galactose and mannose). Water-soluble Br0nsted acids (eg acid catalysts) such as HCl and H2SO4 have typically been used to catalyze these dehydration reactions, but solid homogeneous and heterogeneous catalysts have also been successfully applied.
[00048] Various extraction solvents have been used to improve IR production by reducing side reactions that would otherwise occur in water. Yield improvements have been shown in two-phase systems for which the starting material was both extracted and pure sugars. In lignocellulosic biomass, C5 sugars in hemicellulose are more rapidly hydrolyzed and dehydrated than C6 sugars in cellulose and obtaining high yields of RIs from the cellulose and hemicellulose fractions simultaneously in a two-phase system would be challenging as furfural it degrades long before sufficient LA yields are obtained. Furthermore, it can be difficult to maintain two discernible liquid phases at the high solids concentrations required for reasonable thermal loads. Thus, a single-phase process that separates hemicellulose, cellulose and lignin fractions while obtaining high product yields from all fractions would be useful. The combination of pretreatment and enzymatic and/or catalytic hydrolysis is shown here as a promising approach for the extraction of cellulosic sugars and the conversion of xylose to furfural.
[00049] The main routes to convert cellulosic biomass into biofuels include gasification of biomass into synthesis gas and subsequent Fischer-Tropsch synthesis, pyrolysis and liquefaction of biomass into bio-oils, aqueous-phase catalytic processing of compounds from the dehydration of sugars, and sugar hydrolysis by pretreatment followed by enzymatic hydrolysis of solid waste for microbial fermentation (Yang and Wyman 2008). Yields, production costs and raw material availability are key constraints for these routes and high product yields must be obtained from biomass sugars, while using the simplest process that is effective for many types of raw material . For biological conversion, raw biomass needs to be pre-treated to increase the accessibility and utilization of sugars. Pretreatment technologies, such as with dilute acid, can recover pentose sugars from hemicellulose in high yields and reduce the recalcitrance of the remaining cellulose fraction. Acid neutralization must accompany pre-treatment with dilute acid and the presence of by-products other than sugar may inhibit downstream biocatalysts.
[00050] This disclosure provides the use of tetrahydrofuran (THF), a cyclic polar ether, as a miscible co-solvent in aqueous solution with or without an acid catalyst for the purpose of pre-treating lignocellulosic biomass. The disclosure shows that THF in a single-phase aqueous mixture (as a co-solvent) is extremely effective in performing the solubilization, fractionation, and pretreatment of lignocellulosic biomass to obtain high yields of total sugars and lignin product extracted for its efficient conversion into renewable chemicals and fuels. Pretreatment with THF co-solvent is beneficial over competing pretreatment technologies in at least the following ways: (1) THF co-solvent promotes the solubilization of hemicellulose and cellulose fractions and catalyzes their hydrolysis to directly obtain highs yields C5 and C6 sugars at lower severities than major pretreatments such as water only, dilute acid only, or Organosolv; (2) pretreatment with THF co-solvent dramatically improves the accessibility of lignocellulosic biomass to saccharification enzymes allowing higher total yields of C5 and C6 sugars to be obtained at lower enzymatic loads and reaction severities than pretreatment with just dilute acid; (3) the THF co-solvent can dissolve and depolymerize almost all of the lignin (greater than 90% delignification) to be efficiently recovered by precipitation from the liquid phase upon removal of THF; (4) the THF co-solvent can be used with mineral acids, organic acids, metal salt acids, and base catalysts to adjust product distribution for various co-production schemes; (5) material pretreated from the reaction with THF co-solvent can be used as direct feed for biological fermentation (for example, but not limited to simultaneous saccharification and SSF fermentation or consolidated CBP bioprocessing) to produce combustible products such as ethanol in higher yields than material pretreated with dilute acid alone; (6) THF in the co-solvent system can be easily recovered by low temperature or vacuum distillation for reuse, and (7) THF is renewable and can be synthesized by hydrogenation of furfural which is the product of direct acid dehydration of sugars of pentose from biomass.
[00051] As used herein, a "THF co-solvent" or "co-solvent" refers to a medium in which the co-solvent medium is single-phase (eg, single phase) under Normal Conditions of Temperature and Pressure (CNTP) and contains a aqueous medium and THF. The relative ratios, for example, of water and THF can be in the range of 1:5 to 7:1 of THF:water.
[00052] As used herein, an "acid catalyst" generally refers to a water-soluble acid. In various embodiments, the acid catalyst is selected from the group consisting of a mineral acid, a metal halide acid, a heteropolyacid, an organic acid, or a combination thereof. In one embodiment, the acid catalyst is a mineral acid selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid and any combination thereof. In another embodiment, the acid catalyst is an organic acid selected from the group consisting of acetic acid, an alkyl sulfonic acid, an aryl sulfonic acid, formic acid, a halogenated acetic acid, a halogenated alkyl sulfonic acid, a halogenated aryl sulfonic acid , oxalic acid and any combination thereof. Various metal halide acids are known and include, for example, AlCl3 • 6H2O, CUCI2 • 2H2O, CrCl3 • 6H2O, FeCl3 • 6H2O and ZrOCh • 8H2O
[00053] The disclosure provides a one-pot reaction scheme where a mixture of single-phase solvents, for example, water, tetrahydrofuran, and a mineral acid at a temperature of about 100 °C or more will catalyze and facilitate production of furanic compounds from hydrolyzed biomass sugars and removal of acid-insoluble lignin from remaining unreacted solids. The purpose of the invention is to use the single-phase solvent mixture to (1) hydrolyze all pentosans and some of the hexosans from the crude lignocellulosic biomass to their respective monomeric sugars, (2) catalyze the dehydration of the resulting monomeric sugars into furfural ( FF), hydroxy-methylfurfural (HMF), levulinic acid (LA), and formic acid (FA) in high yields, (3) dissolve and extract acid-insoluble Klason lignin from biomass in the liquid fraction for further conversion into high value by-products and (4) generate an easily hydrolysable hexose-rich solid fraction that can be used for enzymatic digestion, fermentation, or chemical conversion. From the results of the results shown below, there is sufficient evidence that purposes 1 to 4 can be achieved in a relevant biorefinery environment.
[00054] The disclosure demonstrates the use of tetrahydrofuran (THF) as a co-solvent and end product in an integrated biorefinery process to improve the production of furfural and other RIs from biomass. THF is a low boiling solvent that can be industrially produced from the cyclization of 1,4-butane diol and recovered as an azeotrope with water. However, it can also be synthesized directly from furfural through catalytic decarbonylation to furan followed by hydrogenation. THF is a versatile extraction solvent that has favorable properties to improve furfural yields from extracted hemicellulose sugars and crude biomass in a two-phase environment. However, THF is naturally miscible with water and would need to be saturated with solute to form an independent phase. The disclosure demonstrates that the application of THF in a single phase solution with water and catalysts (eg an acid catalyst such as a mineral acid catalyst (eg sulfuric acid (H2SO4) or nitric acid), an acid halide catalyst of metal (eg FeCl3), or an organic acid (eg acetic acid or formic acid)) provides a catalytic conversion in a raw maple wood step to fractionate the biomass and produce a combination of C5 and C6 monosaccharides, furfural, 5-HMF, and levulinic acid in high yields depending on the reaction conditions and the catalyst used. The THF co-solvent was also able to directly solubilize Klason lignin from rough maple wood as well as degradation tars that would normally build up without THF. As a result, the solvent system also produces a glucan-rich fraction of pretreated solids that can be more readily enzymatically hydrolyzed to fermentable glucose than typical pretreatment technologies or can be further chemically converted to additional levulinic acid.
[00055] The data below demonstrate that THF is an exceptionally effective single-phase co-solvent for integrated biomass reactions that improve yields of reactive intermediates during biomass deconstruction as well as delignification. For example, using dilute sulfuric acid in a miscible solution of THF and water, higher total yields of furfural, 5-HMF, and LA were obtained from maple wood than under previous reaction conditions. However, because sulfuric acid and furfural favor the production of LA, the regulation of this co-solvent system with different catalysts was examined and demonstrated to improve the yield for the co-production of furfural and 5-HMF. Because aqueous single-phase reactions with dilute mineral acids typically suffer from low yields of 5-HMF, as it easily hydrolyzes to form LA and formic acid, methyl isobutyl ketone (MIBK) was used as an extraction solvent in a two-phase reaction, but solvent recovery was a problem and the high energy demands for heating and stirring and the limited effective solids loading of a two-phase reaction for large-scale fuel production from solid biomass would likely prevent its commercial appeal. Thus, a single-phase reaction is beneficial if a more selective acid catalyst is used to optimize the biomass glucan selectivity to 5-HMF rather than LA.
[00056] Metal halides are inexpensive acid catalysts that are well studied to selectively promote alternative reaction mechanisms from xylose to furfural and glucose to 5-HMF compared to traditional mineral acids. In analogous ways, aldose-to-ketose isomerization of glucose to fructose and xylose to xylulose has been observed in the presence of certain bi- and trivalent metal cations that can be more easily subjected to acid-catalyzed dehydration. However, evidence also suggests that the strong Lewis acid character of metal halides accelerates several competing loss reactions that could potentially decrease product yields. When used in expensive two-phase ionic liquid co-solvent systems, metal halides have shown good performance with pure sugars, but poor performance in cellulose and biomass, requiring additional pre-treatment of the biomass.
[00057] Thus, the disclosure also demonstrates that acid metal halide catalysts in combination with THF are a miscible co-solvent that significantly improves yields for co-production of furfural and 5-HMF from lignocellulosic biomass, as shown with wood from maple and corn fodder. In this way, pre-treatment of biomass and catalytic dehydration of soluble sugars can be carried out in a one-pot reaction. Exemplary metal salt acid catalysts AlCl3, CuCl2, CrCl3, FeCl3 and ZrOCl2 can be used. For example, each of the aforementioned metal salt acid catalysts has been studied for sugar conversion and selectivity to furfural, 5-HMF and LA production by applying the co-solvent system to pure sugars. Through the use of the metal halide catalyst, reaction severity and solvent loadings (THF) can be optimized to scale to achieve higher furfural co-production and higher 5-HMF yields. The results reveal how different Br0nsted and Lewis acids can be applied in the THF co-solvent reaction strategy to increase the total furanic product yields for a biorefinery process.
[00058] The disclosure demonstrates that metal halides are highly selective and non-corrosive acid catalysts suitable for the co-production of furfural and 5-HMF directly from lignocellulosic biomass without a separate pretreatment step. The disclosure demonstrates that coupling metal halides with THF as a green co-solvent in a highly effective single-phase conversion strategy provides useful co-production yields of furfural and 5-HMF directly from biomass, producing an adequate clean product stream. for catalytic hydrogenation into final fuel products. Screening of several promising metal halides AICI3 • 6H2O, CuCh • 2H2O, CrCl3 • 6H2O, FeCl3 • 6H2O, and Z.rOCb • 8H2O based on sugar conversion and selectivity to secondary reactive intermediates showed that FeCl3 performed better in the THF co-solvent system due to its high Brensted acidity and moderate sugar conversion rate.
[00059] The volume ratio between THF and water can be adjusted in the system and can be in the range of 1:5 to more than 7:1 THF:water (eg 1:4, 1:3, 1: 2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1 etc. vol:vol). In addition, the percentage of acid catalyst can be varied to optimize the desired yield based on the amount of biomass, desired product, temperature, and THF:water ratio. For example, the acid catalyst loading range required for pretreatment with THF co-solvent ranges from 0 wt% to 10 wt% depending on the type of acid. In another example, a THF:water ratio of 4:1 and 1% by weight of FeCl3 reaction co-solvent obtained 95% furfural yield and 51% yield of 5-HMF directly from wood. maple and similar yields from corn forage after 60 min of reaction at 170°C. By reducing the concentration (or volume contribution) of THF in the reaction, one can adjust the biomass solubilization to increase the product mass of a glucan-rich solid residue that is suitable for further catalytic reaction, enzymatic digestion or a potential pulp and paper product. During the co-solvent reaction, THF extracted more than 90% of the lignin from the biomass that could be recovered as a fine powder. Due to its low boiling point, THF was recovered by vacuum distillation at room temperature. Furfural and 5-HMF can be concentrated by an immiscible extraction solvent and the catalyst can be recycled into the aqueous stream.
[00060] The disclosure also contemplates the use of THF co-solvent pretreatments in batch, continuous through flow, or piston flow configurations for (A) traditional biomass pretreatment followed by enzymatic hydrolysis or (B) direct solubilization of biomass to recover sugars without the need for an enzymatic hydrolysis step. In the latter case (B), the THF co-solvent can be applied to a heated through-flow reactor at ratios of THF:water >1:1 with little or no acid to effectively solubilize the biomass and release mono and oligosaccharides which are then , concentrated by removal and recovery of THF. Total sugar yields (stage 1 + stage 2) for typical pretreatments are calculated by adding the total yield of soluble sugar (C5 + C6 sugars) released after the heated reaction (stage 1, pretreatment) and the total yield of soluble sugar released after treatment of pretreated solids with saccharification enzymes (stage 2). Due to its overwhelming majority in the composition of biomass, it is generally safe to assume all C5 sugars as xylose and all C6 sugars as glucose. Sugars can be quantified by High Pressure Liquid Chromatography (HPLC). Total lignin is calculated by the mass of total lignin precipitated by solvent recovery of THF while delignification is calculated by the percentage of lignin remaining in the pretreated material as a function of the initial lignin content of the raw material.
[00061] The cellulosic material used as a source of biomass can be any material containing cellulose. Cellulose is generally found, for example, in the stems, leaves, hooves, bark, and cobs of plants or leaves, branches and wood of trees. Cellulosic material can be, but is not limited to, herbaceous material, agricultural waste, forest waste, municipal solid waste, used paper, and pulp and paper mill waste. The cellulosic material can be any type of biomass including, but not limited to, wood sources, municipal solid waste, waste paper, plantations, and agricultural waste (see, for example, Wiselogel et al., 1995, in Handbook on Bioethanol (Charles E. Wyman, editor), pp. 105 to 118, Taylor & Francis, Washington DC; Wyman, 1994, Bioresource Technology 50: 3-16; Lynd, 1990, Applied Biochemistry and Biotechnology 24/25: 695-719; Mosier et al., 1999, Recent Progress in Bioconversion of Lignocellulosics, in Advances in Biochemical Engineering/Biotechnology, T. Scheper, editor-in-chief, Volume 65, pp. 23-40, Springer-Verlag, New York, USA). It is understood here that the cellulose may be in the form of lignocellulose, a plant cell wall material containing lignin, cellulose and hemicellulose in a mixed matrix.
[00062] The optimization of the methods of the description can be obtained by adjusting the reaction temperature, quantity, type, condition, and particle size of the crude biomass, the type and concentration of acid involved, and the ratio between THF and water in the aqueous solvent mixture. Applying this invention in a continuous process in which product and solvent are continuously removed can further optimize the yields of RIs and allow for better integration into a large-scale production process. Furfural is also a known chemical precursor for the manufacture of THF and the integration of this invention with a downstream catalytic hydrogenation process can supply the THF needed in the reaction as well as provide a potential platform for the production of biochemicals and biofuels. The solid fraction rich in hexosane resulting from the process can be enzymatically digested to produce fermentable hexose sugars or can be used as a direct feed stream for simultaneous saccharification and fermentation (SSF) and consolidated bioprocessing (CPB) processes. After the solvent is recycled, the remaining lignin can be precipitated and used to produce new aromatic compounds or carbon-based compounds like carbon fiber or carbon nanotubes.
[00063] Figure 2A represents a process sketch that shows a possibility for the effective production of FPs and isolated lignin using the disclosed co-solvent system. Since THF is miscible in the aqueous phase, a higher solids charge can be achieved for greater thermal efficiency compared to a two-phase system. The highest % solids optimization will be determined by raw material type and moisture content and processing equipment options. As shown in Figure 2A, the crude biomass is first blended into a mixture containing the co-solvent (in this case THF), water and an acid catalyst. The slurry is then fed into a Pandia screw reactor, designated in Figure 2A as (1), much like those used in the 1960s for continuous furfural production to maintain reasonably uniform residence times and reduce unnecessary build-up. of by-products. Rapid heating of the reactor is provided by high pressure steam (HP) from an HP boiler (2). The hot slurry is quickly released at the reactor outlet in a separation unit (3). In this step, volatile aqueous components such as furfural and THF can be flashed together with dYigiia steam to a distillation unit (4). The THF azeotrope contains only about 4.6 wt% water, so its recovery in this composition is not as demanding as further drying is unnecessary. The dotted lines of (4) in Figure 2A show the THF and water recycle currents. 5-HMF and LA are not volatilized with water and are concentrated with some hydrolyzed glucose in the remaining aqueous layer in (3). For HMF and LA recovery, solvent extraction or vacuum distillation can reduce unwanted reactions. However, if only LA production is desired, the concentrated aqueous solution can be sent directly to a second continuous reactor (6) for a higher temperature reaction. Removal of THF from the liquid phase after the reaction causes the dissolved lignin to precipitate as a solid residue. Due to its sticky nature, a suitable solvent is likely needed to redissolve the extracted lignin for further processing and catalytic enhancement into fuels or chemicals. In line with this, pure THF readily redissolves recovered lignin. Assuming an effective continuous device is available to effectively separate the remaining glucan rich solid fraction, the solids can be washed, neutralized and enzymatically hydrolyzed to fermentable glucose or used as a processed feed stream for SSF or CBP operations. This approach has the additional benefit that the combination of high-severity reaction conditions with lignin removal makes the resulting solids more easily hydrolyzed with low doses of enzyme than has been obtained with other pretreatment systems that are constrained by the need for use low severities to avoid large losses of xylose to furfural when xylose fermentation is intended. Or, the glucan rich material can be sent directly to a second high temperature reactor to produce additional LA (6).
[00064] Sulfuric acid is a low cost mineral acid that is suitable for use as an acid catalyst in this co-solvent system. Other catalysts include, but are not limited to mineral acids, organic acids, metal halide acids and heterogeneous acid catalysts can all be applied in this co-solvent system. For example, FeCl3 is a solid acid catalyst that can be applied to selectively achieve high yields of furfural from xylose and high yields of 5-HMF from solubilized glucose while reducing LA formation. Under similar reaction conditions, the application of FeCl3 catalyst increases the amount of glucan-rich pretreated material that remains after the reaction compared to an equivalent mass charge of H2SO4. This will allow more glucose production by enzymatic hydrolysis. Since THF helps promote the deconstruction and solubilization of lignocellulosic biomass, heterogeneous solid catalysts such as porous membrane resins and zeolites can also be used to promote targeted FPs/RIs or specific reactions. Under 1:1 THF:water conditions, with the use of FeCl3 instead of sulfuric acid, a higher mass yield was obtained from the remaining pretreated glucan rich material (25 wt% of glucan initially present in maple wood for FeCl3 versus 21 wt% for H2SO4 as shown in Figure 11) and equivalent furfural production when compared to reactions with sulfuric acid (85% of theory for FeCl3 versus 87% of theory for H2SO4 , shown in Table 4). Furthermore, the production of levulinic acid (2% of theory) and higher production of 5-HMF (16%) were observed with FeCl3. A greater total recovery of these FPs was observed with the use of FeCl3 from sugars C5 (88% of theory) and C6 (99% of theory) initially present in maple wood than with sulfuric acid.
[00065] By using less stringent conditions (lower temperature, lower reaction time and/or less acid catalyst), the co-solvent system can be used specifically to target the release of xylose sugars, the extraction of insoluble lignin in acid, and improve the enzymatic digestibility of the remaining glucan-rich material for effective glucose production using lower enzymatic loads than typically required with traditional pretreatment strategies. This variation that increases the production of monosaccharides can then be integrated with downstream chemical and biological conversion routes to produce fuels.
[00066] As shown by Figure 2D, this variation represents moderately severe reaction conditions in the first stage (150 to 200 °C, 0.5 to 5% by weight acid catalyst loading) to drive furfural production to starting from xylose as it is the least stable RI in the catalytically active phase. Thus, by maximizing furfural recovery, total FP recovery can increase. Some 5-HMF will be produced from the hydrolyzed hexoses and the remaining glucan rich solids can be used for glucose production by enzymatic hydrolysis, levulinic acid production in a more severe second stage reaction (> 200 °C, > 1% by weight acid catalyst charge) or as a direct feed for SSF and CBP operations.
[00067] In another modality, the production of IR from lignocellulosic biomass is integrated with the simultaneous catalytic enhancement of IRs for combustible products such as "drop-in" hydrocarbon fuels and/or gasoline and diesel blended ingredient. Using moderate to high stringency conditions (150 to 220 °C) and appropriate catalysts, furfural and 5-HMF will first be produced and simultaneously recovered for catalytic conversion to drop-in fuels by selective hydrogenation and/or hydrodeoxygenation. The remaining glucose and glucan rich material will then be subjected to a second high stringency reaction (170 250 °C) to produce additional 5-HMF and/or LA for direct catalytic conversion to drop-in fuels also by hydrogenation selective and/or hydrodeoxygenation. As shown in Figure 2D, simultaneous catalytic enhancement of FPs at both stages can occur in the vapor phase above the reaction in each stage (Figure 2D), or directly in the liquid phase where sugar dehydration reactions are also taking place. If the final fuel products produced by the catalytic enhancement at each stage are more stable than the FPs from which they were produced, they can be returned to the reaction vessel for final recovery at the end of the second reaction stage, as shown in the 2D figure. The purpose of a two-stage reaction is to maximize the yields of stable fuel products from furfural in the first stage before producing fuel products from LA and/or 5-HMF in the second stage. Lignin will be extracted and recovered after furfural production.
[00068] In one embodiment, the cellulosic material is a herbaceous material. In another modality, the cellulosic material is agricultural waste. In another modality, the cellulosic material is forest residue. In another modality, the cellulosic material is municipal solid waste. In another embodiment, the cellulosic material is waste paper. In another modality, the cellulosic material is waste from pulp and paper mills.
[00069] In another embodiment, the cellulosic material is corn fodder. In another embodiment, the cellulosic material is corn fiber. In another modality, the cellulosic material is corn cob. In another modality, the cellulosic material is orange peel. In another embodiment, the cellulosic material is rice straw. In another embodiment, the cellulosic material is wheat straw. In another embodiment, the cellulosic material is fast-growing grass. In another embodiment, the cellulosic material is miscanthus. In another modality, the cellulosic material is sugarcane bagasse.
[00070] The following examples are intended to further illustrate, but not limit the aforementioned disclosure or the appended claims.ExamplesExample 1
[00071] The acid-catalyzed reactions of maple wood, D-xylose and furfural in this disclosure were performed in aqueous solutions of solvent and non-solvent. For most reactions, the solvent solution consisted of a 50% by volume (1:1) mixture of THF (>99% purity, Fisher Scientific, Pittsburgh, PA, USA) and deionized water (DI). Concentrated sulfuric acid (72% by weight, Ricca Chemical Company) was added to the solution to produce a 1% by weight acidic solution (approximately 0.1M). For the control experiments without solvent, only DI water was used to prepare the 1 wt% sulfuric acid solution. The reactions were then run in a 1 L continuously stirred high pressure Parr reactor (Parr Instrument Company). The reactor temperature was measured directly by an in-line thermocouple (Omega, type K). All reactions were maintained at 170°C (443K) by convective heating from a fluidized sand bath (Techne, Princeton, NJ) set at 340°C (613K) to reduce heating time. A PID controller regulated the temperature of the sand bath. Mixing was performed by 6-blade double propellers operating at 200 rpm by an upper electric motor. The reaction temperature was stabilized by using a mechanical crank to control the height of the reactor over the sand bath. At the end of a test, the reactor was cooled by quickly lowering it into a large bath of water at room temperature next to the sand bath. The start time was defined as when the temperature first reached 170 °C, and a final reaction time was recorded when the reactor first touched the cooling water bath. All used liquid-containing receptacles were made of glass to prevent the loss of furfural and THF that was observed when plastics were used for the experiments.
[00072] Maple wood reactions were performed using maple wood chips left to air dry (< 5% moisture content) obtained in northern New York by Mascoma Corporation (Lebanon, NH, USA) . The chips were crushed and sieved to a particle size of 1 mm. The dried and ground samples were then stored at room temperature in gallon-sized Ziploc® bags that were manually pressed to remove excess air. The composition of maple wood was measured according to the established procedure of the National Renewable Energy Laboratory (NREL) (version 8-03-2012) in triplicates with the result: 40.9 ± 0.3% by weight of glucan, 15.5 ± 0.2% xylan, 2.1 ± 0.1% mannan, 24.4 ± 0.3% K-lignin and 17.1% other material. The latter was not further characterized in this study, but is expected to be composed of ash, sugar acids and protein. Because arabinan and galactan are not present in significant amounts (<0.3%), it may be appropriate to consider that all maple wood pentosans are xylan and all hexosans are just glucan and mannan. For each test, 40 g (dry weight) of maple wood and 760 g of acidic solvent or non-solvent solution were first transferred to a sealed glass bottle for overnight pre-immersion at 4°C. The contents were then equilibrated to room temperature prior to reaction. After each reaction, 1 ml of the liquid was removed, centrifuged and analyzed by HPLC (Agilent 1200 system equipped with a Bio-Rad Aminex® HPX-87H column and an RI detector) with an eluent flow rate (sulfuric acid at 5 mM) of 0.6 ml/min. Since the HPX-87H column cannot distinguish between xylose, mannose and galactose sugars, the HPLC was also equipped with an Aminex® HPX-87P column for further analysis of the neutralized reaction samples to study the disappearance of xylose. The solids were then separated from the reaction liquid at room temperature by vacuum filtration through glass fiber filter paper (Fisher Scientific, Pittsburgh, PA, USA). The mass and density of the liquid fraction were measured to complete the accurate yield calculations below. For the solid fraction, mass, moisture content and composition were measured. Only tests with a total mass balance of 100 ± 5% were reported. Due to the difference in density between solvent and non-solvent solutions, densities were determined by weighing 25 ml of the liquid into a volumetric flask after each reaction for yield calculations. The calculation of RI yields is given by equation (1) where the molar equivalents (θRL); of furfural (Eq. 2), LA (Eq. 3), and HMF (Eq. 4) are calculated individually for their respective sugar sources.

[00073] For the xylose dehydration studies, 10 g of D-xylose (99% purity, Sigma-Aldrich, St. Louis, MO, USA)) was transferred to a 1 L volumetric flask and dissolved with the solution THF solvent acid or non-solvent to obtain a concentration of 10 g L-1. A xylose concentration of 10 g L-1 was equivalent to the effective amount of xylose that would be hydrolyzed from a 40 g sample of biomass with a xylan content of 17.5% (average 14 to 21% typically found in biomass). As such, the calculated rate constants and selectivities would be relevant to current and future findings. A first-order approximation of xylose dehydration is represented by equation (5)
where D represents the dehydration products. The expression for the rate of xylose disappearance (X) and calculation of the rate constant are given in equations (6), (7) and (8). Since the acid concentration (A) was kept constant throughout the studies, it combined into the total rate constant k.
where k will be determined by linear fit of equation (8). Results after 30 min were not used in the linear fit as the xylose solution became too dilute for accurate quantification. Because not all dehydration products are furfural, the determination of furfural yield for each reaction was used to calculate furfural selectivity by equation (9):

[00074] A total of 800 g of xylose solution was used for each reaction in a 1 L Parr reactor and analysis was performed by HPLC.
[00075] Similarly, for furfural decomposition studies, reactions were performed with 6.4 g L-1 of furfural (99% purity, Sigma-Aldrich, St. Louis, MO, USA) in acidic solutions of THF and non-solvent solvent in a 1 L Parr reactor. Since 6.4 g L-1 is the molar equivalent of 10 g L-1 xylose at 100% conversion, these reactions provide insight into the amount of furfural lost by autoresinification compared to furfural loss by condensation reactions in the presence of xylose.
[00076] Two glass bottles, each with 5% by weight of maple wood were used. One contained a 1:1 ratio of THF to water and the other an aqueous solution without solvent. Aside from the pigmentation of the maple wood in the solvent solution, the two media were almost identical. The contents of these bottles were then transferred to a Parr reactor and reacted at 170 °C. A reaction temperature of 170 °C was found to be useful for studying furfural production in the presence of a solvent. A raw biomass often contains significant moisture content (up to ~50% by weight in woods), an adequate solvent to total water ratio needs to be selected to minimize thermal loads and maximize solids loading. Since the emphasis is on direct conversion of crude cellulosic biomass, a 1:1 or less solvent to water ratio is desirable in this case to minimize solvent use and maximize thermal efficiency. catalyzed by furfural acid, LA and HMF from maple wood and D-xylose in batch reactions with and without added THF

[00077] Table 1 compares yield data for the production of furfural, LA and HMF from maple wood and D-xylose between reactions with THF co-solvent and non-solvent. Tests 2 through 4 in Table 1 compare the highest furfural, LA, and HMF yields obtained from maple wood reactions using 1:3, 1:1, and 3:1 volume ratios of THF and water, respectively. Lower total RI yields were observed in the 1:3 mixture, identical furfural yields were obtained with 1:1 and 3:1 solutions and the highest yields of LA and HMF were obtained from the 3:1 mixture. While higher solvent ratios can result in marginal yield benefits, additional solvent recovery costs, higher heating requirements, and limited solids loading are likely detrimental to process economics. For these reasons, a 1:1 solvent ratio was chosen for further investigation. Tests 1 and 3 compare the reactions without solvent and with THF in 40 min when the furfural yield was the highest. Tests 5 and 6 compare solvent-free and THF reactions at 120 min when there was more LA production. Under identical process conditions, the presence of THF co-solvent significantly improved the yields of furfural (~25% mol improvement) and HMF (~10% mol) in 40 min and levulinic acid (yields ~8% mol ) in 120 min compared to the case without solvent.
[00078] HMF is an important platform chemical that is primarily produced from the acid-catalyzed dehydration of hexoses. When HMF is allowed to remain in the catalytically active aqueous phase, it will readily hydrolyze to form equimolar amounts of LA and formic acid (FA). Since LA is more stable than HMF in an aqueous environment, higher final yields of LA were observed in single-phase reactions. The application of solid acid catalysts has been shown to improve the selectivity of HMF when using THF. The highest yield of furfural, the primary RI targeted in this study, was 87 mol% of theory in 40 min in 1:1 and 3:1 THF co-solvent reactions. At that time, LA yields were approximately 11 mol% with 1:1 THF, 29 mol% with 3:1 THF and 7 mol% without (Table 1). The liquid densities at room temperature after 40 min reactions (0.9987 g L-1 with 1:1 THF and 1.0152 g L-1 without THF at 21 °C) took into account a 2% difference in maximum furfural yield. For both solvent and solventless reactions in Table 1, the highest furfural yield was obtained much earlier (40 min) than the highest LA yield (120 min). Due to the more acid-labile amorphous structure of hemicellulose, the rate of hydrolysis of xylan from hemicellulose was much higher than that of glucan from crystalline cellulose. By increasing the THF ratio to 3:1, the co-production yields of furfural and LA improved as more hydrolysis of the hexosans occurred.
[00079] Figures 2A-D compare the concentration profiles of IRs produced from maple wood reactions with and without THF as a co-solvent over 60 min of reaction. As shown, the higher initial concentration of glucose (10 min) in the THF reaction suggested that THF helped to increase cellulose hydrolysis to release glucose much earlier than the solventless case. Within 20 min, the glucose concentration in the reaction had started to decrease and LA formation and glucose consumption became significantly higher than in the case without solvent. As discussed above, the column used first could not differentiate between xylose, mannose and galactose monomers by their retention times, so an agglomerated concentration profile is shown. Due to the much slower decomposition rate of mannose relative to xylose, the exact concentration profile of xylose could not be determined. Instead, the xylose concentration was measured from separately neutralized reaction samples and it was observed that the xylose had been completely consumed within 40 min in the presence of THF and within 60 min in the case without solvent (compare with Figure 3A) . These results indicated that THF had a catalytic effect on the destruction of both glucose and xylose.
[00080] After 120 min of reaction, there was still some glucose remaining (<1 g L-1). By then, furfural yield had decreased to 69% (21% loss versus highest furfural observed at 40 min) with THF and 39% without (37% loss versus highest furfural observed at 40 min) . This was the first evidence that THF helped to reduce furfural loss in the catalytically active aqueous phase. However, the effective co-production of these IRs was still limited by the rapid degradation of furfural. Furfural losses can be attributed to condensation reactions between furfural and intermediate sugar products, the slow conversion of furfural to formic acid, and the formation of furfural resins and other degradation products. Because furfural concentrations drop sharply after 40 min in the presence of THF (Figure 3D), allowing the reaction to continue will further detract from yields. Thus, in order to increase the use of all cellulosic sugars, the optimization of less stable species is essential, and separate steps to independently target the production of furfural and levulinic acid will be necessary to obtain the highest total yield of the two combined.
[00081] Figure 3E shows the composition of the solid fraction remaining after reactions with and without tetrahydrofuran (THF) based on 100 g of crude maple wood. The almost complete removal of acid-insoluble lignin and degradation tars that accumulate with solvent-free reactions was unique to the THF co-solvent reactions. More than 90% (by weight) of the insoluble lignin was removed by THF and the amount of insolubles remaining in the solid fraction was minimal throughout the reaction (Figure 3E). Without THF, insoluble lignin was initially reduced, but the formation of insoluble tars and degradation products increased over the course of the reaction. Upon vacuum filtration of the reaction liquid, the unreacted solids in the THF reactions were almost exclusively composed of glucan (85% by weight in 40 min, Figure 3E). In fact, the THF system behaved similarly to an organosolv process. Due to the almost complete removal of the inhibitory hemicellulose and lignin fractions, these pretreated solids should be readily accessible for enzymatic attack and serve as an ideal feed stream for enzymatic hydrolysis to fermentable glucose. The higher initial glucose concentrations in the THF reactions (Figure 3A) suggest an improved digestibility of the pretreated solids. Although reactions using H2SO4 have been demonstrated by optimizing the reaction conditions and the type of acid catalyst used in the solvent reactions, the amount of solid residue rich in non-hydrolyzed glucan can be increased to favor the production of fermentable glucose. The washed solids could then be a potential feed stream for SSF or CB operations or directed towards the production of levulinic acid.
[00082] After the reaction, THF was recovered by vacuum distillation of the filtered liquid at room temperature to produce a dark brown sticky precipitate from the liquid phase that stuck to the walls of the glass bottle. This residue contained extracted lignin and degradation products that had been dissolved in the co-solvent solution. The now concentrated aqueous acidic solution was then poured out, and the solid precipitate of lignin was collected and washed with diethyl ether to yield the dark brown powdered lignin product. The lignin residue could then be redissolved by a suitable organic solvent to be catalytically enhanced. Applications of lignin for conversion to fuel products and valuable polymers are discussed elsewhere. Table 2. First-order rate constants for disappearance of D-xylose with and without THF and comparisons with previous literature

[00083] In addition to maple wood applications, acid-catalyzed dehydration reactions with pure D-xylose were also done to determine the specific effects of THF on the rate of xylose disappearance, as shown in Table 2, and selectivity of furfural, shown in Figure 4A. The reactions were carried out with 10 g L-1 of xylose solutions under the same conditions as the maple wood reactions to study the conversion of xylose to furfural without interference from other biomass components. The amounts of xylose remaining from the solvent and solvent-free reactions are also shown in Figure 4A. The rate constants reported in Table 2 were then determined by a linear fit of a first-order rate expression. To ensure that the reaction system was not limited by mass transfer and represented the actual kinetics, the rate constant of the solvent-free control reactions was compared with the calculated result of an empirical model reported in the previous literature, also shown in Table 2 , and was observed being very close. The results demonstrated that THF greatly improved (~2 times) the rate of xylose disappearance, which suggested that the presence of THF had a catalytic effect on xylose dehydration.
[00084] Because not all dehydration products are furfural, equation (9) was used to calculate the furfural selectivity for these reactions. For reactions without solvent, furfural selectivity was initially higher (72% in 10 min) (Figure 4A), but as the reaction proceeded, furfural selectivity drastically decreased to only 59% within 50 min. As more furfural was produced, the formation of irreversible by-products increased. For reactions with THF, the furfural selectivity was initially lower (67% in 10 min), but continued to grow over the course of the reaction, surpassing the solvent-free selectivity in 20 min to reach a maximum of 74% in up to 40 min. Although the exact reason for these differences is not clear, the lower initial selectivity of furfural for solvent reactions may be caused by the higher rate of xylose dehydration resulting in competing xylose intermediates. Subsequently, as xylose was more rapidly consumed in THF, the selectivity of furfural increased as the opportunity for condensation reactions with the intermediate products was reduced. In any case, the reduced total by-product formation in the presence of THF resulted in a higher maximum yield of furfural from xylose of 73% mol with THF compared to the 60% mol yield of the solvent-free system (Table 1 ). However, compared to maple wood reactions, furfural yields from pure xylose were lower, specifically for the solvent case. This phenomenon was also observed in crushed poplar wood chips. Higher initial xylose concentrations in pure xylose reactions could increase the degree of cross-polymerization with furfural earlier while slower release of xylose from maple wood could reduce this effect.
[00085] Figure 4B shows the degradation of 6.5 g L-1 of pure furfural at 170 °C under solvent and solvent-free conditions. After 50 min of reaction, furfural loss was only about 3% with THF in the solution, whereas the case without solvent had furfural losses of up to 16%. The 13% difference in furfural loss between the two cases in Figure 4B took into account most of the furfural yield difference between solvent and solvent-free reactions with pure xylose, which shows that THF plays an important role in prevention of furfural loss by resinification. Interestingly, the formation of formic acid accounted for almost all the furfural lost in the THF reactions but less than half of the furfural lost in the solventless reactions. Although the reaction severities were too mild to effectively study the kinetics of furfural destruction in just 50 min, the data correlated roughly with the proposed first-order loss approximation for the case without solvent, while the furfural loss in THF did not appear to follow first-order kinetics.
[00086] The application of THF as a co-solvent in a biomass conversion process to optimize RI yields can be done by adding THF to an acid-catalyzed process. The combined benefits of higher RI yields and complete fractionation of biomass from this solvent system can be achieved on a commercial scale by modifying existing continuous furfural technologies with additional separation and recycling processes to collect the pretreated biomass, isolate the fraction of lignin for enhancement and solvent recovery with low boiling point. As an example of the possibilities, Figure 2D shows a simplified conceptual process flow diagram for the integrated production of reactive intermediates and lignin from cellulosic biomass using THF as a co-solvent. Since THF is dissolved in the aqueous phase, a higher solids charge can be achieved for greater thermal efficiency compared to a two-phase system.
[00087] The highest weight % solids optimization will be determined by the type and moisture content of the raw material and the processing equipment options.
[00088] As shown in figure 2D, a suitable raw material, such as ground wood chips, is first immersed in a solution containing THF and an acid catalyst. The slurry is then fed into a Pandia screw reactor (1), much like those used in the 1960s for continuous furfural production to maintain reasonably uniform residence times to reduce unnecessary by-product formation. Rapid heating of the reactor is provided by high pressure (HP) steam from an HP boiler (2) at temperatures around 170 °C or more, depending on the life of the vessel. The hot aqueous slurry is rapidly released at the exit of the Pandia reactor in a separation unit (3) at reduced pressures. In this step, volatile aqueous components, such as furfural and THF, can be flashed or boiled together with the steam for distillation (4). The THF azeotrope contains only about 4.6 wt% water, so its recovery in this composition is not as demanding as further drying is unnecessary. The dotted lines of (4) in Figure 2D show the recycling streams for THF and water. HMF, LA and sulfuric acid are not volatilized with water and are concentrated with some hydrolyzed glucose in the remaining aqueous layer in (3). For HMF and LA recovery, solvent extraction or vacuum distillation can be applied to reduce unwanted reactions. However, if only LA production is desired, the concentrated aqueous solution can be sent directly to a continuously stirred reactor (6) for a higher temperature reaction (> 200 °C).
[00089] From the previous observations, the removal of THF from the liquid phase caused the lignin to precipitate as a solid residue. Due to its sticky nature, a suitable solvent is likely needed to redissolve the extracted lignin for further processing and catalytic enhancement into high-value products. Accordingly, pure THF readily redissolves recovered lignin. Assuming an effective continuous device such as Hydroclone® is available to effectively collect the remaining glucan-rich solid fraction, the solids can be washed, neutralized, and enzymatically hydrolyzed to fermentable glucose or used as a processed feed stream for CBP and SSF operations. . In that case, high stringency conditions that would be undesirable when xylose and other hemicellulose sugars are targeted can be applied to produce furfural. This approach has the additional benefit that combining high stringency reaction conditions with lignin removal should make the resulting solids more easily hydrolyzed with low doses of enzyme than has been achieved with other pretreatment systems that are constrained by need. of using low severities to avoid large losses of xylose to furfural when xylose fermentation is intended. Or, the glucan rich material can be sent directly to the high temperature CSTR for additional LA production (6), as shown by the solid line (Figure 2D).
[00090] As shown by test 9 in Table 1, LA with yields up to 75% in mol of theoretical could be obtained from maple wood enriched in cellulose after the extraction of hemicellulose by hydrothermal pretreatment. The production of LA in this case was obtained from a batch reaction at 200 °C with a higher solids loading (10% by weight) plus concentrated sulfuric acid (1.5% by weight) and without the use of solvents. These results demonstrate that high yields of LA can be obtained from the glucan-rich material without hemicellulose that remains from the THF reactions if the reaction temperatures are increased to specifically target LA production.
[00091] The purified furfural product can be sold as is or decarbonylated and hydrogenated to produce more THF. Hydrogenation remains the most versatile option for enhancing furfural and levulinic acid for fuel products, but the source and cost of hydrogen for catalytic enhancement of these RIs must be carefully considered. Furfural can be upgraded to furfuryl alcohol (FFA), tetrahydrofurfuryl alcohol, and dihydropyran. Methylfuran and methyltetrahydrofuran are hydrogenated FFA products that can directly serve as gasoline additives. Aldol condensation and dimerization of furfural followed by hydrodeoxygenation can produce alkanes to tridecanes. The diversity of potential furfural products greatly improves its marketability in the high yields obtained from this process. Since LA is more stable than HMF in aqueous solution, it is an important primary cellulose product in this process that can be a valuable chemical precursor to levulinate esters, GVL, MTHF, and other potential hydrogenation fuel products. The high boiling point of LA (245 °C) makes it difficult to distill off without applying a vacuum, so maintaining a concentrated LA product stream will improve separation economics and allow solvent extraction. Since LA production benefits from more severe reaction conditions, a two-stage production strategy for furfural and LA will achieve the highest RI yields from biomass.
[00092] Although most of the THF is recovered, some THF was lost to acid-catalyzed ring opening reactions. Thus, the reduction in reaction time should reduce THF losses. Fortunately, THF itself is a versatile chemical that has commercial application as a solvent for the manufacture of plastics and is closely related to 1,4-butanediol (BDO) and Y-butyrolactone (GBL). Since THF polymers (PolyTHF and PTMEG) are also important commercial products, further investigation into the application of these products will be interesting, particularly for the potential production of THF from furfural.
[00093] To investigate the possibility of furfural production from glucose in the system, 18.7 g L-1 of glucose solution containing THF and 1% by weight of sulfuric acid were reacted at 170 °C. After 40 min of reaction, trace amounts of a substance that eluted at the same time as furfural (approximately 44 min) on the Aminex® HPX-87H column were observed, however, they were not present in the solvent-free reactions. Since certain compounds are known to have similar retention times on this column, further quantification of this furfural-like compound by GC-MS is needed to confirm its identity. The contribution of this trace compound (0.12 g L-1) could take into account approximately 2.5% of the furfural yield measured at 40 min from maple wood reactions. However, since this amount resulted from the pure glucose reaction in the absence of glucan hydrolysis, it provides an upper bound for the possible enhancement in furfural yields reported in this document. Furthermore, in glucose reactions with THF, a more significant amount (0.97 g L-1) of another glucose-derived compound was measured at the same elution time as xylose (approximately 9.7 min). This saccharide other than xylose (or some other unidentified compound) could explain why similar minute concentrations in Figure 3B were still observed in maple wood reactions after 40 min when xylose had been completely consumed. The persistence of this compound and the much lower production of furfural from glucose suggested that an alternative glucose intermediate was responsible.
[00094] The disclosure demonstrates the application of THF as a single-phase co-solvent to significantly increase the yields of RIs from aqueous processing of lignocellulosic biomass such as maple wood or corn fodder. For the first time the disclosure shows that a single-phase solution of THF and water can (1) improve the hydrolysis of hemicellulose and cellulosic polysaccharides; (2) help catalyze the dehydration of the resulting monomeric sugars to FF, hydroxymethylfurfural (HMF), and levulinic acid (LA) in high yields; (3) dissolving acid-insoluble lignin and biomass degradation products in the liquid fraction for conversion to high-value by-products; and (4) generate an easily hydrolyzable glucan-rich solid fraction that can be used for enzymatic digestion, fermentation, or further chemical conversion. The targeted production of reactive intermediates from lignocellulosic biomass by an integrated single-phase solvent process with THF allows for the effective utilization of all important constituents of lignocellulose, including lignin. The light energy strategy proposed here is designed to complement the latest advances in catalytic technology while providing an effective solution for handling raw material. Greater flexibility in end-product types allows continuous advances to improve the deconstruction and catalytic enhancement of lignocellulosic biomass for conversion to renewable fuels and chemicals.Example 2
[00095] Reagent grade THF (>99% purity, Fisher Scientific, Pittsburgh, PA, USA) was used in all THF co-solvent reactions. The THF solution and co-solvent was prepared based on volume increasing the amount of THF additions to obtain ratios from 1:1 (THF 50% v/v) to 7:1 (THF 87.5% v/v) between THF and water. Metal halide catalysts were purchased from Sigma Aldrich (St Louis, MO, USA). The hydrated form of each metal halide catalyst (AICI3 • 6H2O, CuCh • 2H2O, CrCl3 • 6H2O, FeCl3 • 6H2O, and ZrOCh • 8H2O) was used, but were loaded based on their dry mass equivalent to obtain 0.1 M or 1% by weight catalyst loading. Concentrated sulfuric acid (72% by weight H2SO4) was purchased from Ricca Chemical Company (Arlington, TX) and used to make the dilute sulfuric acid solutions.
[00096] Maple wood chips obtained in upstate New York were supplied by Mascoma Corporation (Lebanon, NH, USA), and Kramer corn fodder left to air dry was supplied by the National Renewable Energy Laboratory (NREL, Golden, CO, lot no. 33A14). The relatively dry biomass (10 to 15% moisture) was knife crushed to pass through a 1 mm particle size internal sieve using a laboratory mill (Model 4, Arthur H. Thomas Company, Philadelphia, PA , USA). The composition of biomass was determined according to the procedure established by the National Renewable Energy Laboratory (TP-510-42618, ver. 8-03-2012) in triplicates with a resulting composition of 40.9 ± 0.3%, in weight of glucan, 15.5 ± 0.2% of xylan, 2.1 ± 0.1% of mannan, 24.4 ± 0.3% of K-lignin and 17.1% of other material for wood from maple and 32.7 ± 0.4% by weight of glucan, 20.7 ± 0.2% of xylan, 2.6 ± 0.1% of arabinan, 16.0 ± 0.1% of K-lignin , and 28.0% of other corn forage material. Other materials required for biomass composition for the total of 100% were not characterized in this study, but were expected to include secondary saccharides, ash, sugar acids, acetate and protein. Because arabinan, galactan and mannan are not present in significant amounts and the specific quantification of these secondary sugars is difficult by HPLC, a decision was made to treat all pentosans quantified in biomass as xylan and all hexosans as glucan .
[00097] The pure sugar reaction mixtures were prepared in 1:1 solutions of THF co-solvent: water containing 20 g/L of glucose or 10 g/L of xylose and loading at 0.1 M (anhydrous) of the catalyst. metal halide based on the total volume of liquids. Due to the different Br0nsted acidity of each catalyst (Table 3), all solutions were normalized to pH 1.6 by titration with 72% by weight of concentrated sulfuric acid. An acidity of pH 1.6 was selected because it was close to the Br0nsted acidity of the mixture containing ZrOCb plus acidic at 0.1 M (Table 3). Pure sugar solutions containing only sulfuric acid were also prepared and titrated to pH 1.6 to compare directly with metal halide acid catalysts as an acid control.

[00098] Reactions were performed in unstirred 14.3 mL Hastelloy tubing reactors (Hastelloy C-276, 0.0127 m or 0.5 inch OD) with a wall thickness of 0.0008890 m (0.035 inches) and length 0.1524 m (6 inches) to provide a working reaction liquid volume of 10 mL. The pipe reactors were loaded into a heavy-duty custom steam chamber produced from stainless steel for steam (up to a steam pressure of 1 MPa) 316 readily available with 0.102 m (4 inch) ID fittings (McMaster , Santa Fe Springs, CA). A high-pressure steam boiler (FB-075-L, Fulton Companies, Pulaski, NY) supplied water steam for the rapid and stable heating of triplicate tube reactors. The temperature was monitored by in-line pressure gauges and two type K thermosensors (Omega Engineering Co., Stamford, CT) and controlled by a PID controller through vapor pressure. Due to the longitudinal construction of the tube reactors and the application of steam for heating and cold water for cooling, heat transfer was relatively fast even for shorter reaction times (<10 min). The start time was defined when a reaction temperature of 170 °C was reached. At the end of the reaction, the water vapor supply was turned off and the vapor chamber was filled with tap water to stop the reaction.
[00099] The liquid content of each reaction tube was transferred to 2 mL glass vials. These samples were centrifuged (2500 rpm for 20 min) and the supernatant was transferred to HPLC glass vials for HPLC analysis by an Agilent 1200 system equipped with a Bio-Rad Aminex® HPX-87H column and an RI detector with a eluent flow (5 mM sulfuric acid) of 0.6 ml/min. Calculations for the conversion of sugars and the selectivity of the secondary reactive intermediates are shown below, where Q is the molar ratio of equivalence of the initial sugar:

[000100] Solid loads of corn forage or maple wood were calculated based on the total reaction mass (800 g) so that each reaction contained 5%, by weight of solids (40 g of dry basis) and 1%, in weight of acid (7.6 g by dry weight) based on the weight of the THF:water mixture (760 g). The biomass mixtures were then left to pre-wet overnight at 4°C to ensure an even distribution of the acid catalyst within the pores of the biomass. The contents were then left in the laboratory for one hour for the temperature to reach about room temperature before the reaction.
[000101] The complete biomass aqueous slurry was then transferred to a 1 L continuously stirred high pressure Parr reactor (Parr Instrument Company, Moline, IL) heated by a 4 kW fluidized sand bath (model SBL-2D , Techne, Princeton, NJ, USA). Mixing was done by 6-blade double helices operating at 200 rpm by an upper electric motor and the reactor temperature was measured directly by an in-line thermocouple (Omega, type K). At the end of a test, the reactor was cooled by quickly lowering it into a large bath of water at room temperature. All liquid-containing receptacles were made of glass to prevent the loss of furfural and THF that was observed when plastics were used. The solids were then separated from the reaction liquid by vacuum filtration through fiberglass filter paper (Fisher Scientific, Pittsburgh, PA, USA). The mass and density of the liquid fraction were measured to complete accurate yield calculations. Due to the difference in density between the co-solvent and pure water mixtures, the final densities were determined by weighing 25 ml of the reacted liquid into a volumetric flask after each reaction.
[000102] The liquid samples were analyzed by an Agilent 1200 HPLC system equipped with a Bio-Rad Aminex® HPX-87H column and an RI detector with an eluent (5 mM sulfuric acid) at a flow rate of 0.6 ml/min. Since the HPX-87H column cannot distinguish between xylose, mannose and galactose sugars, the HPLC was also equipped with an Aminex® HPX-87P column to differentiate xylose from other C6 sugars for yield calculations. The calculation of yields of reactive intermediates is given by equation (15) where the number of molar equivalents (θ) of furfural (Eq. 16), LA (Eq. 17), and 5-HMF (Eq. 18) is calculated individually and divided by the fraction of the total glucan or xylan in the raw material.

[000103] For the recovery of the extracted lignin, the reaction liquid was transferred to a glass bottle with a screw cap which was capped with a 0.64 cm (0.25 inch) metal hose barb fitting. The fitting was connected by a flexible hose to a vacuum pump to perform vacuum distillation of THF. The liquid was stirred by a magnetic stir bar on a stir plate as the THF was boiled at room temperature under vacuum. When THF is removed from the aqueous liquid, lignin precipitates out of solution as a black resinous solid. The solid residue of lignin was then separated from the liquid and crushed to a fine powder by a ceramic pestle and mortar. The powder was then rinsed with water, allowed to air dry, and then rinsed with diethyl ether. The resulting fine lignin powder product is shown in Figure 13.
[000104] Table 3 shows the measured pH for sugar co-solvent solutions containing 0.1 M of each metal halide prior to reaction. It is known that metal oxide species form when metal halides are hydrolyzed by water at elevated temperatures and the formation of OH ligands (as electron pair donors) during the hydrolysis of metal cations increases their acidity. The resulting pH of the solution is related to the first hydrolysis constant of the cationic species, where Zr and Fe cations are the strongest. Metal chlorides are also known to form stable adducts with THF, which can influence their ionizability and catalytic activity. As Bronsted acidity typically dominates sugar dehydration kinetics, the pH was normalized for all sugar solutions to 1.6 with the use of sulfuric acid (close to that of the more acidic metal halide) before each reaction. Doing so allowed a better understanding of how the relative Lewis strength of each catalyst influenced its selectivity to secondary reactive intermediates, the propensity for degradation of end products, and the ability of catalysts to adjust to optimize the co-production of furfural and 5-HMF from of biomass.
[000105] In order to characterize the catalyst performance with this co-solvent system, pure glucose and xylose were reacted in 1:1 (v:v) THF:water solutions using different metal halides to compare the conversion of sugar and the selectivity for furfural, 5-HMF and LA. The metal halides AlCl3 • 6H2O, CUCI2 • 2H2O, CrCl3 • 6H2O, FeCl3 • 6H2O, and ZrOCh • 8H2O were selected for this comparison. The sugar co-solvent solutions contained either 20 g L-1 glucose or 10 g L-1 xylose to simulate likely sugar concentrations from actual biomass reactions at 5% loading by weight solids. Each metal halide was added based on its anhydrous catalyst mass at a concentration of 0.1 M for each reaction. The sugar solutions were then loaded into reactors and Hastelloy tube (10 mL working volume) and heated to 170°C by a custom designed stainless steel steam chamber. The reaction continued until the water vapor was turned off and the chamber was filled with cold running water to cool the reaction. As shown in Figures 10A and 10B, the conversion of xylose and glucose was significantly improved by all acid metal catalysts beyond what was possible for sulfuric acid alone in the THF co-solvent system. The relative performances of metal halides were also very consistent for glucose and xylose. The most active metals were Cr, Zr, and Al due to their high Lewis acid strength, obtaining almost complete conversion of xylose in 5 min and glucose in 10 min. Cu and Fe-based catalysts were especially slower to convert sugar, but still achieved almost complete conversion after 20 min.
[000106] In all THF co-solvent sugar reactions, it was observed the accumulation of secondary sugar species whose retention times on HPLC were compatible with those of fructose and xylulose. Their concentrations were also consistent with the disappearance of glucose and xylose over the course of the reaction, suggesting that aldose-to-ketosis isomerization occurred at a faster rate than sugar dehydration (concentrations shown in figures 14 to 15) . This result agrees with what is known about metal halide-catalyzed sugar reactions: an open-chain dehydration mechanism is prevalent and ketosis sugars dehydrate to furfural and 5-HMF more readily and faster than their aldose counterparts. Interestingly, ketosis sugars were present in sulfuric acid reactions, suggesting that THF may also interact with sugars to promote isomerization and support earlier observations that the THF co-solvent helped to catalyze the dehydration of aldose sugars over the course of a comparable solvent-free reaction using sulfuric acid alone. By promoting the most kinetically favorable open-chain dehydration pathway, THF can help metal halides obtain high yields of reactive intermediates.
[000107] The selectivity to secondary FPs was then calculated based on their concentrations after each reaction. In terms of the selectivity of furfural from xylose (Figure 10C), sulfuric acid achieved a maximum of about 70% selectivity at 10 min which outperformed all other metal salt catalysts. This result suggested that although the Lewis acid character of metal halides accelerated the destruction of sugars, it also promoted concurrent loss reactions that decreased the accumulation of furfural in solution. These loss reactions can be attributed to condensation reactions between intermediate sugar species and furan products to form humins. Due to the fast sugar conversion, the Cr catalyst obtained the highest furfural selectivity of about 65% earlier in 5 min, while the FeCl3 required 20 min to obtain a maximum furfural selectivity also of about 65%. ZrOCl2 had the lowest selectivity to furfural despite its ability to rapidly degrade xylose, probably due to the high formation of loss products.
[000108] In the case of selectivity of 5-HMF for glucose (Figure 10D), all metal salts except CuCl2 obtained higher selectivities (~ 40%) to sulfuric acid (~ 22%) in the co-solvent system, with the metals of Al , Cr and Fe having the best performance. Again, the Fe-based catalyst required the longest reaction time and continuously increased the 5-HMF selectivity throughout, reaching 38% after 20 min. Interestingly, for all catalysts except CuCl2, the highest selectivity for furfural and 5-HMF occurred at approximately the same time with the best co-production of furfurals demonstrated by the Al, Cr and Fe metals. Overall, however, the selectivity of 5-HMF was significantly lower than furfural selectivity due to significant loss reactions for both the condensation products and LA. This was evident by the more drastic drop in selectivity of 5-HMF than was observed with furfural over the course of the reaction for all metal halides except FeCl3.
[000109] In the case of LA selectivity from glucose (Figure 10E), all metal halides showed lower selectivity for LA formation than sulfuric acid, according to the purpose of this study. LA is produced from the hydrolysis of 5-HMF in this system, CuCl2 and sulfuric acid obtained the highest LA selectivity since its selectivity for 5-HMF was the lowest. By extrapolating the increasing trend of LA selectivity over longer reaction times, furfural and LA are probably not compatible co-products based on their formation kinetics. Instead, furfural and 5-HMF can be produced together, whereas LA production would be more effectively directed in a furfural-independent reaction. The faster sugar conversions observed with Cr, Zr and Al based halides compared to slower Fe and Cu based halides are important differences between these catalysts, which may help explain their performance when reacting to real biomass revealed in next section. Quantifiable parameters in sugar reactions such as sugar conversion, reactive intermediate selectivity, and acidity of these metal halide catalysts will affect the biomass conversion to obtain high combined yields of furfural and 5-HMF.
[000110] The primary lignocellulosic biomass fractions of interest for catalytic conversion to platform chemicals are cellulose, hemicellulose and lignin. The xylan contained within the amorphous hemicellulose presents the most readily available source of sugars as it can be completely hydrolyzed in a mild to moderate severity reaction. Cellulose, on the other hand, is composed of polymeric and crystalline glucose chains that are a primary source of C6, but it remains the most recalcitrant sugar fraction for acid hydrolysis and is usually treated with cellulase enzymes after pretreatment to obtain highs. yields of glucose monomers in solution. Because the hemicellulose fraction of lignocellulosic biomass is much more acid-labile than crystalline cellulose, furfural is produced much earlier than 5-HMF and LA. Thus, an integrated conversion strategy to co-produce furfural and 5-HMF directly from biomass must be adjustable to minimize competing side reactions from less stable products to increase product yields. For this reason, optimization for high furfural yields is a primary concern as the glucan remaining in the slower solubilizing cellulose fraction can be recovered as a solid product for further enzymatic and/or acid hydrolysis to glucose, biological conversion to fuels of alcohol (eg ethanol) or thermochemical conversion to 5-HMF and/or LA.
[000111] In addition to manipulating the temperature, time, and acid charges (severity of the combined reaction) to optimize the yields of a biomass reaction, the THF co-solvent strategy allowed for additional adjustment by increasing the concentrations of THF in water to obtain greater selectivity for 5-HMF and increased biomass solubilization. The data compared the performance of metal halide catalysts against sulfuric acid in 1 L THF co-solvent reactions with 5% by weight of maple wood or corn fodder filler. Table 4 lists the reaction conditions under which the highest total yields of furfural and 5-HMF were obtained from the biomass reactions. The THF:water ratio was also varied from 1:1 to 7:1 (by volume) to determine the extent of improved product yields and the limit of the single-phase regime. The catalysts were loaded based on mass similar to the commercial operation at 1% by weight, diluted in terms of the total net mass contained in the reaction. Table 4 is the acid-catalyzed co-production of furfural, 5-HMF and LA from wood maple and corn forage in batch reactions with TFa co-solvent

[000112] As shown in Table 4 (tests 1 to 9), with the exception of CrCl3 and ZrOCl2, the metal halide catalysts demonstrated very consistent performance in maple wood and corn forage, obtaining maximum furfural yields close to those of sulfuric acid to a 1:1 mixture of THF:water. 5-HMF yields were more comparable between catalysts, but metal halides produced lower LA yields compared to sulfuric acid due to its greater selectivity for 5-HMF, as found for pure sugar reactions. FeCl3 showed the best performance due to its higher Br0nsted acidity, slower xylose conversion rates and higher furfural selectivity in longer reaction times. AlCl3 and CuCl2 had an intermediate performance due to their more moderate Br0nsted character, with exchanges between high 5-HMF yields or high furfural yields, respectively, compatible with their selectivity with pure sugar reactions.
[000113] In order to investigate the extent of biomass solubilization for each catalyst, maple wood was reacted for 30 min in a 1:1 mixture of THF co-solvent and 5% initial charge, by weight of biomass and charge of 0.1 M catalyst equivalent in the 1 L Parr reactor. Figure 11 shows the composition of rough maple wood solids and the distribution of major components in the solids remaining after the reaction based on the mass of 100 g feed stream of rough maple wood. As shown, the solubilization of biomass with metal halides was reduced compared to sulfuric acid. Also shown, over 90% of the maple wood lignin K was removed during all metal halide reactions except with ZrOCl2, leaving behind a substantial amount of glucan-rich solids that did not contain hemicellulose and small amounts of other components . In 1:1 THF reactions, increasing solids recovery from the co-solvent reaction is crucial to increase the economics of this process as cleanly fractionated solids are suitable as a direct feed stream to produce fermentable or used glucose to produce more 5-HMF or LA. The non-sugar fraction may have resulted from the accumulation of polymeric degradation products in the solids as the actual glucan remaining in the solids was much smaller than that of the sulfuric acid catalyzed reactions.
[000114] Greater biomass solubilization at the highest solvent ratio of 3:1 (as shown in Table 4, tests 10 to 16) can support a reaction strategy that is more focused on producing furfural and 5-HMF with less solids. recoverable. At a 3:1 volume ratio of THF-water, the three best performing metal halide catalysts (Al, Cu, Fe) greatly increased the co-production of furfural and 5-HMF from maple wood and forage. corn compared to sulfuric acid. In these reactions, FeCl3 performed better than CuCl2 and AlCl3 in the production of furfural (97% yield for maple wood and corn forage) and 5-HMF (41% yield for maple wood and 42% for corn forage) corn) and biomass solubilization (11% remaining solids). CuCl2 was unable to solubilize biomass as quickly as FeCl3, and its lower 5-HMF yields from maple wood and corn forage reactions could be explained by its lower selectivity to 5-HMF (Figure 10D) from glucose in sugar reactions. For AlCl3, adjusting the reaction to obtain co-production of high furfural and 5-HMF content was difficult as the optimal reaction time for furfural was 20 min shorter than for 5-HMF. Thus, higher furfural yields were obtained with CuCl2 at the expense of higher 5-HMF losses and higher 5-HMF yields were obtained with AlCl3 at the expense of lower furfural yields. Overall, the consistency in performance between corn forage and maple wood in all reactions indicated that the THF co-solvent system can be very feedstock agnostic and capable of achieving high yields in heterogeneous feedstock streams. or mixed, appealing to commercial viability.
[000115] At a 4:1 solvent ratio (Table 4, tested 17), FeCl3 performed significantly better than sulfuric acid and other metal halides and had the highest reported co-production yields of furfural (95 % for maple wood and corn forage) and 5-HMF (51% for maple wood and 45% for corn forage) from lignocellulosic biomass by a single-phase reaction in one vessel. The higher solvent ratio was also beneficial to further reduce LA yields (6 to 7% in the 4:1 ratio), the most difficult product to recover due to its high boiling point. Thus, FeCl3 proved to be the best metal halide to catalyze the co-production of furfural and 5-HMF in a biomass process using THF as a miscible co-solvent. Its strong acid strength allowed for reasonably fast deconstruction of maple wood and corn fodder, and the close reaction time for optimal production of furfural and 5-HMF was beneficial in getting good yields of both in a biomass reaction. . As shown in Figure 12, the 10% solids remaining after the 4:1 maple wood co-solvent reaction were very rich in glucan and could be recovered for an efficient conversion to glucose by enzymes or another thermochemical reaction of 5-HMF and/or LA. A mass balance is shown for this test in figure 16, ensuring accountability for 80% of the C6 products and 95% of the C5 products in the soluble and insoluble products after the reaction.
[000116] The data show that at a 7:1 THF-solvent ratio (Table 4, test 19) or more, the reaction behavior suddenly changed to resemble a two-phase regimen. Although this was not determined qualitatively (such as by a sight glass in the reactor), the kinetics of the reaction and the composition of the resulting solid material strongly suggested that the system was two-phase at such high THF ratios. In such a two-phase reaction, the dehydration kinetics of the aqueous phase is not largely affected by the presence of the extracting solvent. Thus, THF would no longer be able to accelerate the biomass solubilization, as is evident from the much larger fraction of solids that remained after the reaction (21% for test 19 in Table 4). As shown in Figure 12, the compositional analysis of this solid fraction also revealed that a large portion of the glucan remained unsolubilized and most of the lignin was still intact and unextracted, as would be expected in a single-phase reaction with THF. Operating pressures of about 1.83 MPa (about 265 psig) were also the highest observed and close to the sum of the water saturated vapor pressures and THF, which is consistent with expectations for a two-phase system. Furthermore, because biomass often has moisture contents of up to 50% by weight for woods, high solvent ratios would likely hurt the economics of biomass processing by consuming more heat, which is an important consideration when comparing others co-solvent systems.
[000117] Figure 2B describes an integrated THF co-solvent strategy proposed for the application of metal halide catalysts to improve the direct conversion of biomass into furfural and 5-HMF followed by two possibilities for its hydrogenation into MF and DMF, respectively . Experimental work in this study focused on producing high yields of FP so as to be more compatible with major downstream catalytic enhancement operations. In the process concept illustrated in the Figure, the crude biomass and acid catalyst are loaded into a reactor along with THF co-solvent. After the reaction, high yields of furfural and 5-HMF are obtained, and the reacted slurry is then collected and filtered to separate solid residues. As THF is a low boiling point solvent (66°C) and forms a 95.4% azeotrope with water, it could easily be flashed in a biorefinery to be recovered and recycled. In fact, vacuum distillation at room temperature was sufficient to recover THF from the aqueous phase.
[000118] The removal of THF also precipitates the lignin extracted from the biomass as a solid that can be recovered and rinsed with diethyl ether to produce a very pure lignin powder, as shown in Figure 13. This powder can, in turn, be redissolved in THF or DMSO and is suitable for catalytic enhancement of valuable chemicals. Then, a suitable organic solvent, such as MTHF, can be used as an immiscible solvent to extract and concentrate furfural and 5-HMF in the organic layer, leaving most of the trace sugars and contaminants in the aqueous layer. Alternatively, the aqueous stream resulting from THF removal could be fed directly into a catalytic reactor, if desired, depending on the catalyst system chosen for furfural and 5-HMF enhancement. The aqueous stream containing the catalyst could be recycled as it has been shown that aqueous streams containing FeCl3 remain effective through various reactions in other systems.Example 3
[000119] THF is an effective co-solvent for the pretreatment of lignocellulosic biomass between solvent-to-water ratios of 1:5 (by volume) or more, up to 7:1 (vol:vol) to specifically maximize sugar yields monomeric from biomass. Operating temperatures for THF co-solvent pretreatment are in the range of 100°C to 220°C. The acid catalyst loading range required for THF co-solvent pretreatment is in the range of 0% by weight to 10% by weight, depending on the type of acid. For this function, THF co-solvent pretreatments can be operated in batch, continuous flow or piston flow configurations for (A) traditional biomass pretreatment followed by enzymatic hydrolysis or (B) direct biomass solubilization to recover sugars without the need for an enzymatic hydrolysis step. In the latter case (B), the THF co-solvent can be applied to a heated flow-through reactor at ratios of THF:water >1:1 with little or no acid to effectively solubilize the biomass and release mono and oligosaccharides which are, then, concentrated by removal and recovery of THF. The total sugar yields (stage 1 + stage 2) for typical pretreatments are calculated by adding the total yield of soluble sugar (C5 + C6 sugars) released after the heated reaction (stage 1, pretreatment) and the total yield of soluble sugar released after treatment of the pre-treated solids with saccharification enzymes (stage 2).
[000120] Consecutive batch reactions at 170 °C were carried out using dilute sulfuric acid (1% by weight, also known as dilute acid only or without THF). From the mass and composition of the remaining solids (per base of 100 g of raw maple wood) shown in Figure 3E, a significantly higher degree of biomass solubilization was observed in the presence of THF than without. For reactions containing a 1:1 mixture of THF and water, more than 90% by weight, the acid-insoluble Klason lignin (lignin K) initially present in maple wood was removed to the liquid phase for 10 min, producing a solid residue that was highly rich in glucan (>85% by weight glucan). In contrast, the composition of the remaining solids from the reactions without THF shows that the lignin K content was only slightly reduced in 30 min, but then increased rapidly over time due to the formation of pseudolignin and other acid-insoluble degradation products (Figure 12). Furthermore, the increased disappearance rate of glucan (cellulose) from the pretreatments with THF co-solvent compared to the case without THF with only dilute acid suggests that THF also catalyzes and promotes the hydrolysis of cellulose and probably also hemicellulose.
[000121] Table 5 shows a comparison between the solubilization of hemicellulose, cellulose, and poplar wood lignin fractions by pretreatment with only dilute acid, organosolv, and methods with THF co-solvent under the same reaction conditions. Because the reaction condition in these experiments has lower severity than shown in Figure 3, it can be seen that pretreatment with THF co-solvent catalyzes and enhances the solubilization of all major lignocellulosic fractions beyond what is possible. by an equivalent Organosolv (ethanol) or pre-treatment with dilute acid only. This means that reaction conditions with much lower stringency are required with THF co-solvent pretreatment to hydrolyze the same amount of sugars as the other two main pretreatment methods.Table 5. Solubilization of hemicellulose, cellulose, fractions and poplar lignin by pretreatment with only dilute acid, organosolv, and THF co-solvent methods

[000122] Figure 12 compares the composition of the remaining solids with the use of different acid catalysts after pretreatment with THF co-solvent with maple wood on a basis of 100 g of raw material. In Figure 12, reaction severities were significantly higher than typically used for pretreatment to recover sugars as metal halide catalysts can be used to adjust the pretreatment method to produce high furfural yields from of hydrolyzed C5 sugars. As shown, over 93% of the maple wood lignin K was removed during all metal halide reactions except ZrOCl2, and over 90% sulfuric acid delignification in a reaction of just 30 min leaving behind a glucan-rich solid suitable for enzymatic hydrolysis to glucose or to direct the feed stream for fermentation processes such as concurrent saccharification and fermentation (SSF) and consolidated bioprocessing (CBP). Adjustment of the THF co-solvent with different catalysts is possible for co-production schemes from biomass such as co-production of xylose with glucose and furfural with glucose.
[000123] As cellulase enzymes are the main force to hydrolyze and convert the glucan in biomass into fermentable glucose, the accessibility of the pretreated material to these enzymes indicates the effectiveness of the pretreatment strategy. The amount of cellulases used also contributes to a significant cost in the total process, so reducing the enzyme loads needed to obtain high sugar yields is beneficial. As shown in Figure 17, acid-catalyzed THF co-solvent pretreated material is much more amenable to enzymatic hydrolysis than reactions without THF under the same reaction conditions for multiple raw materials of corn fodder, poplar wood, and maple wood. In just 48 h of enzymatic hydrolysis with a moderate enzyme load of 15 mg protein/g glucan, complete conversion of glucan to glucose is achieved from corn forage pretreated with THF. Even for more recalcitrant biomass such as hardwoods, the material pretreated with THF was able to release 5x more glucose than the case without THF under the same conditions, obtaining glucose yields similar to those of the almost pure Avicel® cellulose. As also shown in Figure 17 (column 5), when THF co-solvent is used in conjunction with a metal halide catalyst under more severe reaction conditions suitable for the production of furfural and 5-HMF, the glucan rich material remnant (shown in Figure 12) is still highly digestible by enzymes for conversion to glucose.
[000124] In Figures 18 and 19, both THF and non-THF corn forage pretreatments were optimized for maximum total sugar recovery at an enzyme load of 30 mg/g. It was observed that the optimal conditions for pretreatment with THF co-solvent (150°C, 25 min, 0.5% by weight, acid) are much less stringent (less energy requirement) than pretreatment without THF with dilute acid only (160°C, 20 min, 0.5% by weight acid) at the same acid charges. Enzyme loads were then reduced (see Figure 18) to see how the glucose conversion yield responded. As shown in Figure 18, corn forage pretreated with THF co-solvent demonstrated significantly improved response to reduced charges of Accellerase® 1500 (DuPont) cellulase than corn forage pretreated with water only when dilute sulfuric acid was used. as a catalyst. In the case of the THF co-solvent, at protein glucan cellulase loads of 5 and 15 mg/g, almost all of the glucan in the pretreated corn forage was released with glucose after 100 h. Furthermore, by extrapolating the glucose release curve to the 2 mg/g case, this low enzyme load can also achieve almost complete glucose release at longer hydrolysis times, as shown in figure 18 (diamonds).
[000125] The total sugar yields (xylose and glucose) obtained from corn forage pretreated with THF and without THF are compared in Figure 19. As shown, the total sugar yield was theoretical effectively (~97%) at enzyme loads of only 2 mg/g glucan for corn forage pretreated with THF (after 20 days), whereas corn forage pretreated with dilute acid only required 30 mg/g to obtain ~89% of total sugar yield (after 14 days). This means that pretreatment with THF co-solvent effectively reduced enzyme demand by < 10X compared to traditional dilute acid only pretreatment for corn forage. At just 15 mg/g glucan enzyme loading, corn forage pretreated with THF co-solvent achieved maximum yields (97%) in just 1 day compared to the maximum yield of pretreatment with dilute acid alone ( 85%) obtained after 14 days. Not only is the maximum total sugar yield higher for THF co-solvent pretreatment, but conversion to enzyme is much faster. This is an indication that the THF co-solvent is effective in maximizing accessibility by removing hemicellulose and lignin fractions and does not inhibit the enzyme function that is observed by pretreatment with dilute acid alone. The high xylose yields observed also indicate that the THF co-solvent is highly effective in maximizing sugar yields from hemicellulose and cellulose biomass fractions.
[000126] Figure 20 compares ethanol yields from SSF of corn forage pretreated with THF and without THF and Avicel® cellulose by S. Cerevisiae in 250 mL scale shake flask experiments (working volume of 50 ml). In these experiments, flasks were loaded with 4% by weight of glucan, autoclaved for 30 minutes, pre-hydrolyzed with Accellerase 1500 cellulase at 15 mg/g glucan load for 18 h (150 rpm, 50°C), and inoculated at an optical density (OD) of 0.5 to 600 nm (130 RPM, 37°C). As shown, corn forage pretreated with THF co-solvent achieved higher ethanol yields earlier in SSF than corn forage pretreated with only dilute acid and Avicel® cellulose. With sufficient rinsing of the pretreated material with water (4 volume rinses through a vacuum filter), the material pretreated with THF did not demonstrate important inhibitory effects on ethanol titers. A maximum yield of 87% ethanol was obtained by corn fodder pretreated with THF, while only 80% ethanol yield was obtained by corn fodder pretreated with dilute acid alone, and 75% yield of ethanol from cellulose Avicel® as a control.
[000127] Figure 21 compares the solids solubilization capacity yields from pretreated poplar wood CBP using C. thermocellum as the biological catalyst to perform saccharification of sugars and the simultaneous conversion of sugars to ethanol . In CBP, solids solubilization is a metric used to determine substrate performance. The greater solubilization of solids obtained by poplar wood pretreated with THF co-solvent (Figure 21; legend D) is comparable and better than that of organosolv-ethanol pretreatment (Figure 21; legend B) and far superior to that of pretreatment with dilute acid only (Figure 21; legend A). The reaction conditions and the identities of the markers are mentioned in the Table below the plot in Figure 21.
[000128] Other features and advantages of the invention will become apparent from the following detailed description of the invention, taken in conjunction with the accompanying exemplifying drawings. Additional modifications and enhancements can be made in addition to the system and methods presented here without departing from the scope of the description. Accordingly, it is not intended that the invention be limited by the embodiments disclosed in the present invention.

权利要求:
Claims (26)
[0001]
1. Method for the production of reactive intermediates from biomass, characterized in that it comprises: treating a biomass with a composition comprising a mixture of 50-70% and 0.05-0.1 tetrahydrofuran (THF) cosolvents M of an acid catalyst at 120°C to 200°C to produce a liquid phase comprising dissolved monosaccharides, furfural and lignin products; and a solid material comprising glucan; and wherein biomass treatment removes more than 70% of the lignin from the biomass, removing and/or recovering THF from the liquid phase to produce a solid lignin product.
[0002]
2. Method according to claim 1, characterized in that the mixture of cosolvents is single-phase under Normal Conditions of Temperature and Pressure (CNTP).
[0003]
3. Method according to claim 1, characterized in that the acid catalyst is selected from the group consisting of mineral acids, organic acids and metal halide acids.
[0004]
4. Method according to claim 1, characterized in that the acid catalyst is selected from the group consisting of sulfuric acid, hydrochloric acid, formic acid, acetic acid, trifluoroacetic acid, FeCl3 and any combination thereof.
[0005]
5. Method according to claim 1, characterized in that it further comprises recovering the lignin by THF or DMSO for further processing.
[0006]
6. Method according to claim 1, characterized in that it further comprises removing and/or recovering furfural from a liquid phase after treating the biomass with co-solvent by azeotropic distillation or solvent extraction.
[0007]
7. Method according to claim 6, characterized in that furfural is further processed to be catalytically enhanced to produce THF and/or methyl-THF.
[0008]
8. Method according to claim 1, characterized in that it further comprises recovering a liquid product comprising C5 and C6 monosaccharides and their oligomers.
[0009]
9. Method according to claim 8, characterized in that the liquid product is neutralized by a base.
[0010]
10. Method according to claim 1, characterized in that it further comprises recovering a solid product after treating the biomass with co-solvent, wherein the solid comprises a material rich in glucan.
[0011]
11. Method according to claim 10, characterized in that the glucan-rich material is further treated with one or more enzymes that remove xylo-oligomers and polymers with longer xylose chain length to produce xylose monomers.
[0012]
12. Method according to claim 10, characterized in that the glucan-rich material is further treated with one or more enzymes that remove gluco-oligomers and polymers with longer glucose chain length to produce glucose monomers.
[0013]
13. Method according to claim 10, characterized in that the solid rich in glucan is incubated with microorganisms and/or with added enzymes to produce an alcohol or other products by fermentation.
[0014]
14. Method according to claim 13, characterized in that the alcohol is ethanol.
[0015]
15. Method according to claim 13, characterized in that the alcohol contains 1 or more carbon molecules.
[0016]
16. Method according to claim 13, characterized in that the microorganism is selected from the group consisting of a yeast, a bacterium, a mold and a fungus.
[0017]
17. Method according to claim 10, characterized in that the glucan-rich material is used to produce paper pulp or dissolve pulp.
[0018]
18. The method of claim 10, characterized in that the glucan-rich material is hydrolyzed to glucose and glucose-rich oligomers using an acid selected from the group consisting of formic acid, acetic acid, trifluoroacetic acid and any combination thereof .
[0019]
19. Method according to claim 1, characterized in that the solid lignin product is at least 93% lignin.
[0020]
20. Method according to claim 1, characterized in that the solid lignin product is at least 90% lignin.
[0021]
21. A method for the combined solubilization and catalytic conversion of biomass to produce reactive intermediates from biomass, characterized in that it comprises: treating a biomass with a composition comprising an aqueous mixture of cosolvents containing 63 - 83% tetrahydrofuran (THF) , water and 0.1 - 0.2 M of an acid catalyst at a treatment temperature between 170°C to 220°C to produce a liquid phase comprising furfural, 5-hydroxymethylfurfural, levulinic acid and lignin; and removing and/or recovering THF from the liquid phase to produce a solid lignin product by removing more than 70% of the lignin from the biomass, where (i) the co-solvent mixture is single-phase under Normal Temperature and Pressure Conditions; ( ii) the acid catalyst is selected from the group consisting of mineral acids, organic acids, metal halide acids and solid acid catalysts; (iii) the acid catalyst is selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, formic acid , acetic acid, trifluoroacetic acid, FeCl3, AlCl3, CuCl2 and any combination thereof; (iv) further comprising removing and/or recovering THF from the liquid phase after treating the biomass with cosolvent; (v) further comprising removing and /or recovering lignin from the treatment of biomass with cosolvent by precipitation as a solid after the distillation of THF from the liquid phase; (vi) further comprising removing and/or recovering fur fural and/or 5-HMF from a liquid phase of the biomass treatment with co-solvent by distillation; (vii) further comprising removing and/or recovering furfural during and/or after co-solvent treatment by boiling and/or separation by drag the steam; or (viii) further comprising extracting and/or recovering furfural and/or 5-HMF from a liquid phase of the biomass co-solvent treatment by a water-immiscible organic solvent.
[0022]
22. Method according to claim 21, characterized in that the lignin is further processed and captured by THF or DMSO as a liquid.
[0023]
23. Method according to claim 21, characterized in that the immiscible organic solvent is an ether, a ketone, an alcohol, an alkane or any combination thereof.
[0024]
24. Method according to claim 22, characterized in that the solid lignin product is at least 93% lignin.
[0025]
25. Method according to claim 22, characterized in that the solid lignin product is at least 93% lignin.
[0026]
26. Method for the production of reactive intermediates from biomass, characterized in that it comprises: treating a biomass with a composition comprising a mixture of aqueous tetrahydrofuran (THF) single-phase cosolvents and an acid catalyst under conditions to produce a liquid phase comprising monomeric sugars, oligosaccharides and lignin products derived from biomass and a solid material comprising polysaccharides derived from biomass; and removing and/or recovering lignin from the cosolvent treated biomass by precipitation as a solid after removal of THF from the liquid phase.

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同族专利:

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公开号 | 公开日

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AU2014256941B2|2018-05-17|

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WO2014176531A3|2015-01-08|

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JP6535321B2|2019-06-26|

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US20160076112A1|2016-03-17|

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AU2018217276B2|2020-07-02|

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CN105264080A|2016-01-20|

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CN105264080B|2020-02-07|

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JP2016524525A|2016-08-18|

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AU2014256941A1|2015-11-05|

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CA2910274C|2022-01-18|

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EP2989207A4|2016-11-23|

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BR112015026960A8|2019-12-31|

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BR112015026960A2|2017-07-25|

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WO2014176531A2|2014-10-30|

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CA2910274A1|2014-10-30|

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EP2989207B1|2018-11-28|

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EP2989207A2|2016-03-02|

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US20200399722A1|2020-12-24|

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US10774394B2|2020-09-15|

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AU2018217276A1|2018-08-30|

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法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-08-11| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-06-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-07-13| B350| Update of information on the portal [chapter 15.35 patent gazette]|

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2021-07-27| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/04/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201361816713P| true| 2013-04-27|2013-04-27|

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US61/816,713|2013-04-27|

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PCT/US2014/035506|WO2014176531A2|2013-04-27|2014-04-25|Co-solvent to produce reactive intermediates from biomass|

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