Patent Grant
11091815
All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference. PCT/IL2012/050118 filed on Apr. 2, 2012, PCT/US2013/039585 filed May 3, 2013, PCT/US2013/068824 filed Nov. 6, 2013, PCT/US2014/053956 filed Sep. 3, 2014, PCT/US2016/012384 filed Jan. 6, 2016, U.S. Provisional Patent Application No. 62/091,319 filed on Dec. 12, 2014, U.S. Provisional Patent Application No. 62/100,791 filed Jan. 7, 2015, and U.S. Provisional Patent Application No. 62/167,111 filed May 27, 2015, are each incorporated herein by reference.
Processes allowing for the production of cellulosic sugars from biomass at high purity and low cost that are competitive with sugars made from food and feed sources have yet to be developed, despite much effort directed toward this goal worldwide. Biomass is a complex composite material that requires varying degrees of severity to extract and hydrolyze the individual components, each having unique sensitivity to the reaction conditions employed. Thus, a one-step extraction cannot achieve both a high degree of extraction and a low degree of degradation, both essential to achieving high product yield. Furthermore, biomass contains high amounts of other components, including Klasson lignin, acid soluble lignin, inorganic ash compounds, organic extractives, and organic acids. The biorefinery products (i.e. sugars and lignin), are used as feedstock for further conversion processes. To be useful as fermentation or chemical catalysis feedstock, sugars need to be purified to a high degree concomitantly with the elimination of impurities known to be inhibitors of conversion processes. To be economically competitive, efficient low cost processes must be developed and scaled up at minimal capital investment. We disclose herein integrated industrial methods for treating biomass that facilitate the production of high purity sugars and lignin at competitive costs.
In one aspect, provided herein is a process for the production of hemicellulosic mixed sugars, lignin and glucose from a biomass, comprising: (i) extracting hemicellulose sugars from the biomass, thereby obtaining a hemi-depleted remainder, wherein the hemi-depleted remainder comprises lignin and cellulose; (ii) contacting the hemi-depleted remainder with a lignin extraction solution to produce a lignin extract and a cellulosic remainder; wherein the lignin extraction solution comprises a limited-solubility solvent, a limited-solubility organic acid and water, wherein the limited-solubility solvent and water form an organic phase and an aqueous phase; (iii) separating the lignin extract from the cellulosic remainder, wherein the lignin extract comprises lignin dissolved in the limited-solubility solvent and the cellulosic remainder comprises cellulose and residual lignin; and (iv) contacting the cellulosic remainder with a cellulose hydrolysis solution to hydrolyze cellulose and extract residual lignin; wherein the cellulose hydrolysis solution comprises the limited-solubility solvent, the limited-solubility organic acid and water, wherein the limited-solubility solvent and water form an organic phase and an aqueous phase.
In practicing any of the methods described herein, the cellulosic remainder may be treated with the lignin extraction solution before contacting the cellulosic remainder with a cellulose hydrolysis solution to increase porosity and reduce crystallinity, wherein the treatment comprises contacting the cellulosic remainder with the lignin extraction solution at elevated temperature and pressure and releasing the pressure rapidly to create a solvent explosion effect.
In some embodiments of the process, the limited-solubility organic acid may be recycled by applying one, two, three, or four step(s) selected from: (i) contacting the aqueous stream(s) after phase separation with CO2 at a pressure of at least 2 barg to convert calcium fumarate to fumaric acid and calcium carbonate; (ii) stripping the limited-solubility solvent from the aqueous phase comprising fumaric acid by evaporation to produce a solvent-depleted aqueous phase; (iii) concentrating the aqueous phase comprising glucose and fumaric acid; and (iv) cooling the solvent-depleted aqueous phase to less than 5° C. to cause precipitation of fumaric acid and filtering the precipitate to collect the fumaric acid for further use. In some embodiments, loss of the limited-solubility organic acid per kg of glucose produced may be less than 25 g.
In another aspect, provided herein is a highly purified glucose product characterized by one or more, two or more, three or more, four or more, five or more, or six or more characteristics selected from: (i) monosaccharides in a ratio to total dissolved sugars >0.50 weight/weight; (ii) glucose in a ratio to total monosaccharides >0.90 weight/weight; (iii) xylose in a ratio to total monosaccharides <0.10 weight/weight; (iv) fructose in a ratio to total monosaccharides <0.10 weight/weight; (v) fructose in a ratio to total monosaccharides >0.01 weight/weight; (vi) furfurals in amounts up to 0.01% weight/weight; (vii) phenols in amounts up to 500 ppm; (viii) hexanol in amounts up to 500 ppm; (ix) C4 carboxylic acid in a ratio to total saccharides <0.05 weight/weight; and (x) fumaric acid in a ratio to total saccharides <0.05 weight/weight. In some embodiments, the highly purified glucose product may comprise fumaric acid in an amount less than 0.05% weight/weight. The highly purified glucose product may be used as feed for a fermentation process or chemical conversion process to produce a product.
In still another aspect, provided herein is a process for the hydrolysis of cellulose pulp, comprising: (i) contacting the cellulose pulp with water, a limited-solubility solvent, and a limited-solubility acid; and (ii) heating the cellulose pulp to a temperature of about 200-400° C. In some embodiments, the limited-solubility acid may be a dicarboxylic acid. In some embodiments, the limited-solubility acid may have at least one pKa value between 1.9 and 3.5 in water. In some embodiments, the solubility of the limited-solubility acid in water at 4° C. may be less than 1% wt/wt. In some embodiments, the limited-solubility acid may be fumaric acid. In some embodiments, the limited-solubility solvent may comprise a 4- to 8-carbon ketone. In some embodiments, the limited-solubility solvent may be methylethyl ketone. In some embodiments, at least a portion of the limited-solubility acid may be recovered by precipitation.
In practicing any of the methods described herein, the cellulose pulp may be subjected to a pretreatment step. In some embodiments, the pretreatment step comprises: (i) contacting the cellulose pulp with water, solvent, and a limited-solubility organic acid; (ii) heating the cellulose pulp to a temperature of about 160-220° C. in a closed system; and (iii) opening the closed system to rapidly release pressure.
The present disclosure provides a process for the hydrolysis of cellulose pulp. In some embodiments, the process comprises: (i) contacting the cellulose pulp with water, a limited-solubility solvent, and a limited-solubility acid, thereby forming a slurry; (ii) heating the slurry to a temperature of about 200-400° C., thereby forming a treated slurry; and (iii) recovering a cellulosic hydrolysate from the treated slurry. Optionally, the process further comprises, prior to the contacting step: (a) extracting hemicellulose sugars from a lignocellulosic biomass, thereby obtaining a hemi-depleted remainder, the hemi-depleted remainder comprising lignin and cellulose; (b) treating the hemi-depleted remainder with a limited-solubility solvent, a limited-solubility acid, and water, wherein the limited-solubility solvent and the water form an organic phase and an aqueous phase; and (c) separating the organic phase from the aqueous phase, wherein the aqueous phase comprises the cellulose pulp.
In one aspect, the present disclosure provides a process for the hydrolysis of cellulose pulp. In some embodiments, the process comprises: (i) extracting hemicellulose sugars from a lignocellulosic biomass, thereby obtaining a hemi-depleted remainder, the hemi-depleted remainder comprising lignin and cellulose; (ii) treating the hemi-depleted remainder with a limited-solubility solvent, a limited-solubility acid, and water, wherein the limited-solubility solvent and the water form an organic phase and an aqueous phase; (iii) separating the organic phase from the aqueous phase, wherein the aqueous phase comprises the cellulose pulp; (iv) contacting the cellulose pulp with water, the limited-solubility solvent, and the limited-solubility acid, thereby forming a slurry; (v) heating the slurry to a temperature of about 200-400° C., thereby forming a treated slurry; and (vi) recovering a cellulosic hydrolysate from the treated slurry.
In one aspect, the present disclosure provides a process for the hydrolysis of cellulose pulp, comprising: (i) contacting the cellulose pulp with water, a limited-solubility solvent, and a limited-solubility acid, thereby forming a slurry; (ii) heating the slurry to a temperature of about 200-400° C., thereby forming a treated slurry; and (iii) recovering a cellulosic hydrolysate from the heated slurry. Optionally, the limited-solubility solvent is a 4- to 8-carbon ketone having an aqueous solubility of 10-40% wt/wt at 20° C. Optionally, the limited-solubility acid is a dicarboxylic acid having an aqueous solubility of less than 1% wt/wt at 4° C.
In practicing any of the processes described herein, the limited-solubility acid may be a dicarboxylic acid, such as fumaric acid. Optionally, the limited-solubility acid has at least one pKa value between 1.9 and 3.5 in water. Optionally, solubility of the limited-solubility acid in water at 4° C. is less than 1% wt/wt.
In practicing any of the processes described herein, the limited-solubility solvent may be an organic solvent. Optionally, solubility of the limited-solubility solvent in water at 20° C. is less than 40% wt/wt, such as less than 30% wt/wt. Optionally, solubility of the limited-solubility solvent in water at 20° C. is 20-40% wt/wt. Preferably, the limited-solubility solvent comprises a 4- to 8-carbon ketone, such as methylethyl ketone.
Any process described herein may further comprise recovering the limited-solubility acid by precipitation. In some examples, at least 80% of the limited-solubility acid is recovered, such as at least 95% of the limited-solubility acid.
Any process described herein may further comprise pretreating the cellulose pulp prior to the contacting step. Optionally, the pretreating comprises: (a) contacting the cellulose pulp with water, a limited-solubility solvent, and a limited-solubility acid, thereby forming a pretreatment slurry; (b) heating the pretreatment slurry to a temperature of about 160-220° C. in a closed system; and (c) opening the closed system to rapidly release pressure.
In some embodiments, the cellulose pulp comprises: (i) cellulose; (ii) hemicellulose in an amount up to 5% weight/weight relative to total solids; (iii) ash in an amount up to 6% weight/weight relative to total solids; and (iv) sulfate in an amount up to 3% weight/weight relative to total solids. Optionally, the cellulose pulp may further comprise lignin. Optionally, the cellulose pulp comprises less than 5% water soluble carbohydrates at 20° C. Optionally, a process described herein comprises at least 10 kg of the cellulose pulp, such as at least 50 kg.
In some embodiments, the recovering the cellulosic hydrolysate comprises phase separation of an aqueous phase comprising the cellulosic hydrolysate from an organic phase comprising the limited-solubility solvent. Optionally, the process further comprises contacting the aqueous phase with CO2 at a pressure of at least 2 barg to produce a carbonated aqueous phase. Optionally, the process further comprises cooling the carbonated aqueous phase to less than 10° C., thereby forming a precipitate comprising the limited-solubility acid. Optionally, the process further comprises separating the precipitate from the cold carbonated aqueous phase.
The present disclosure provides a sugar composition comprising: (i) monosaccharides in a ratio to total dissolved sugars >0.50 weight/weight; (ii) glucose in a ratio to total monosaccharides >0.90 weight/weight; (iii) xylose in a ratio to total monosaccharides <0.10 weight/weight; (iv) fructose in a ratio to total monosaccharides <0.10 weight/weight; (v) furfurals in amounts up to 0.01% weight/weight; (vi) phenols in amounts up to 500 ppm; and (vii) hexanol or 2-ethyl-1-hexanol in amounts up to 500 ppm. Optionally, the composition comprises glucose in a ratio to total monosaccharides of 0.90 to 0.99 weight/weight. Optionally, the composition comprises fructose in a ratio to total monosaccharides of at least 0.01 weight/weight. Optionally, the composition comprises xylose in a ratio to total monosaccharides of at least 0.01 weight/weight. Optionally, any composition provided herein comprises at least 10 ppb fumaric acid. Optionally, the composition comprises at least 10 ppb furfural. Optionally, the composition comprises at least 10 ppb phenols. In some examples, the phenols are lignin decomposition products. Optionally, the composition comprises at least 10 ppb hexanol or 2-ethyl-1-hexanol. Optionally, the composition comprises at least 10 ppb methylethyl ketone. Optionally, the composition comprises C6 oligosaccharides in a ratio to total dissolved sugars of 0.01 to 0.10 weight/weight.
The present disclosure relates to the integrated processing and refining of lignocellulosic biomass to produce high purity sugars and lignin at high yields and low costs. The sugar products may comprise a hemicellulosic sugar product, a cellulosic sugar product, or a mixed sugar product. The relative parts of C6 and C5 saccharides in the sugar product depend on the biomass used as feedstock, and may be enriched with a specific saccharide by applying separation processes to the refined sugar products.
In some embodiments, the overall integrated process may comprise three extraction steps, each one designed and optimized to extract preferentially one crude component that can be refined to a pure product stream while minimizing degradation of the extracted component and the remaining solids.
Extraction 1, designated as process 200 in
Preferably, an aqueous acidic solution is used to extract and hydrolyze hemicellulosic sugars from lignocellulosic biomass. The aqueous acidic solution can contain any acids, inorganic or organic. Preferably, an inorganic acid is used. For example, the solution can be an acidic aqueous solution containing an inorganic or organic acid such as H2SO4, H2SO3 (which can be introduced as dissolved acid or as SO2 gas), HCl, or acetic acid. The acidic aqueous solution can contain an acid in an amount of 0 to 2% acid or more, e.g., 0-0.2%, 0.2-0.4%, 0.4-0.6%, 0.6-0.8%, 0.8-1.0%, 1.0-1.2%, 1.2-1.4%, 1.4-1.6%, 1.6-1.8%, 1.8-2.0% or more weight/weight. Preferably, the aqueous solution for the extraction includes 0.2-0.7% H2SO4 and 0-3,000 ppm SO2. The pH of the acidic aqueous solution can be, for example, in the range of 1-5, preferably 1-3.5, more preferably 1-2.
In some embodiments, an elevated temperature or pressure is preferred in the extraction. For example, a temperature in the range of 100-200° C., or more than 50° C., 60° C., 70° C., 80° C., 90° C., 100° C., 110° C., 120° C., 130° C., 140° C., 150° C., 160° C., 170° C., 180° C., 190° C., or 200° C. can be used. Preferably, the temperature is in the range of 110-160° C., 120-150° C., or 140-150° C. Preferably, the temperature is 135-165° C. The pressure can be in the range of 0.4-10 mPa, for example, 0.4-5 mPa. The solution can be heated for 0.1-5 hours, preferably 0.1-3 hours, 0.1-1 hour, 1-2 hours, or 2-3 hours. The extraction process may have a cooling down period of less than one hour.
Optionally, hemicellulose sugars are extracted from the biomass in an aqueous acidic solution comprising H2SO4 at a pH of 1-3.5. Optionally, hemicellulose sugars are extracted from the biomass in 0.1-3 hours at a temperature of 135-165° C. and a pressure of 0.4-5 mPa. Preferably, hemicellulose sugars are extracted from the biomass in an aqueous acidic solution comprising H2SO4 at a pH of 1-3.5, wherein the reaction mixture comprising the biomass and the aqueous acidic solution is heated for 0.1-3 hours to a temperature of 135-165° C.
In some embodiments, impurities such as ash, acid soluble lignin, fatty acids, organic acids such as acetic acid and formic acid, methanol, proteins and/or amino acids, glycerol, sterols, rosin acid and waxy materials may be extracted together with the hemicellulose sugars under the same conditions. These impurities can be separated from the aqueous phase by solvent extraction (e.g., using a solvent containing amine and alcohol).
In some embodiments, hemicellulose sugar extraction 200 can produce, in one single extraction process, a hemicellulose sugar stream 205 containing at least 80-95% monomeric sugars relative to total sugars. For example, the hemicellulose sugar stream can contain more than 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% wt/wt monomeric sugars relative to total sugars. In addition, the present method produces minimal amounts of lignocellulose degradation products such as furfural, levulinic acid, and formic acid. For example, the hemicellulose sugar stream may contain less than about 0.5, 0.4, 0.3, 0.2, or 0.1% wt/wt phenols. In some examples, the hemicellulose sugar stream may contain less than about 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1% wt/wt furfural. In some examples, the hemicellulose sugar stream may contain less than about 0.01 or 0.005% wt/wt HMF. In some examples, the hemicellulose sugar stream may contain less than about 0.05, 0.04, 0.03, or 0.02% wt/wt formic acid. In some examples, the hemicellulose sugar stream may contain less than about 0.05, 0.04, 0.03, or 0.02% wt/wt levulinic acid. In some embodiments, a xylose yield greater than 80% of theoretical value may be achieved. In some embodiments, at least 70%, 75%, 80%, or more of the hemicellulose sugars may be extracted using the present method.
The extraction of hemicellulose sugars from the biomass results in a lignocellulosic remainder comprising lignin and cellulose, with only a small residue of hemicellulose. In some embodiments, the extraction of hemicellulose sugars does not remove a substantial amount of the cellulosic sugars. For example, the extraction of hemicellulose sugars does not remove more than 1, 2, 5, 10, 15, 20, 30, 40, 50, or 60% weight/weight cellulose. In some embodiments, the lignocellulosic remainder contains less than 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, or 1% wt/wt hemicellulose. In some embodiments, the lignocellulose remainder contains less than 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1% wt/wt ash.
Hemicellulose sugar stream 205 is optionally refined and optionally fractionated according to the process disclosed in PCT/US2013/039585, incorporated herein by reference. Examples of compositions of refined hemicellulose sugar mixtures, xylose enriched sugar mixtures and xylose removed sugar mixtures are incorporated in this disclosure in the examples section.
Alternatively, stream 205 comprising acidic hemicellulose sugars may be combined before refining through stream 206 with acidic cellulosic sugar stream 405, which will be described below. In cases where the biomass feedstock used is high in C6 sugars, combining the two streams before purification is advantageous, as only one purification system is required to achieve a high purity sugar product rich in C6 sugars, thus reducing capital costs associated with this integrated process.
Next, as outlined in
Extraction 2 is designated as process 300 in
It is realized in the current disclosure and is a fundamental embodiment in this disclosure that it is advantageous to use in this process an acid that has limited solubility in water. In some embodiments, the acid is an organic acid. In some embodiments, the acid has limited solubility in an aqueous solution that is saturated with the limited-solubility solvent. In some embodiments, the acid has limited solubility in the limited-solubility solvent that is saturated with water. In some embodiments, the solubility of the acid in water, in solvent-saturated water or in water-saturated solvent is highly temperature dependent. In some embodiments, the solubility of the acid is higher in the limited-solubility solvent than in water, and is highest in water-saturated solvent. In some embodiments, the partition coefficient of the acid between the limited-solubility solvent and water is greater than 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In some embodiments, the solubility of the acid in water at 4° C. is less than 1%, 0.5%, or 0.3% wt/wt. In some embodiments, the solubility of the acid in water at 20° C. is less than 100, 75, 50, 40, 30, 25, 20, 15, 10, or 5 g/L. In some embodiments, the solubility of the acid in water at 20° C. is between 1-10, 1-5, or 3-5 g/L. In some embodiments, the solubility of the acid in water at 20° C. is about 4 g/L. In some embodiments, the acid has at least one pKa value lower than 4.8, 4.0, 3.7, 3.5, 3.2, or 3.0. In some embodiments, the acid has at least one pKa value between 1.9 and 3.5 in water. In some embodiments, the acid has at least one pKa value between 2.5 and 3.5 in water. In some embodiments, the acid is a dicarboxylic acid. In some embodiments, the acid is a C4 carboxylic acid. In some embodiments, the acid is selected form fumaric acid, maleic acid and malic acid. In some embodiments, the acid is fumaric acid. The acid used in lignin extraction may be referred to herein as a limited-solubility acid.
In some embodiments, the limited-solubility solvent is an organic solvent. In some embodiments, the limited-solubility solvent includes one or more of esters, ethers and ketones with 4- to 8-carbon atoms. In some embodiments, the limited-solubility solvent is a 4- to 8-carbon ketone, such as methylethyl ketone. Examples of limited-solubility solvents suitable for the present invention include methylethyl ketone, diethyl ketone, methyl isopropyl ketone, methyl propyl ketone, mesityl oxide, diacetyl, 2,3-pentanedione, 2,4-pentanedione, 2,5-dimethylfuran, 2-methylfuran, 2-ethylfuran, 1-chloro-2-butanone, methyl tert-butyl ether, diisopropyl ether, anisol, ethyl acetate, methyl acetate, ethyl formate, isopropyl acetate, propyl acetate, propyl formate, isopropyl formate, 2-phenylethanol, toluene, 1-phenylethanol, phenol, m-cresol, 2-phenylethyl chloride, 2-methyl-2H-furan-3-one, γ-butyrolactone, acetal, methyl ethyl acetal, dimethyl acetal, morpholine, pyrrole, 2-picoline, and 2,5-dimethylpyridine. In some embodiments, the solubility of the limited-solubility solvent in water is less than 50%, 45%, 40%, 35%, 30%, 29%, 28%, 27%, 26% or less than 25% weight/weight at 20° C., such as less than 40% weight/weight. Preferably, the solubility of the limited-solubility solvent in water is less than 30% weight/weight at 20° C. In some embodiments, the solubility of the limited-solubility solvent in water is 20-40% weight/weight at 20° C.
The ratio of the limited-solubility solvent to water suitable for carrying out the lignin extraction can vary depending on the biomass material and the particular limited-solubility solvent used. In some embodiments, the solvent to water ratio is in the range of 100:1 to 1:100, e.g., 50:1 to 1:50, 20:1 to 1:20, and preferably 1:1.
Elevated temperatures and/or pressures are preferred in some lignin extraction embodiments. For example, the temperature of lignin extraction may be in the range of 50-300° C., preferably 160-220° C., e.g., 170-200° C. The pressure may be in the range of 1-30 mPa, preferably, 12-26 mPa. The solution may be heated for 0.5-24 hours, preferably 1-3 hours.
Optionally, lignin is extracted from a lignocellulosic remainder (i.e., a hemicellulose-depleted biomass) by contacting the lignocellulosic remainder with a lignin extraction solution to produce a lignin extract and a cellulosic remainder; wherein the lignin extraction solution comprises a limited-solubility solvent, a limited-solubility acid, and water, wherein the limited-solubility solvent and water form an organic phase and an aqueous phase. Preferably, solubility of the limited-solubility acid in water at 4° C. is less than about 1% wt/wt, and solubility of the limited-solubility solvent in water at 20° C. is less than about 30% wt/wt. Optionally, the limited-solubility acid is fumaric acid, and the limited-solubility solvent is methylethyl ketone.
Returning to
Optionally, the cellulose pulp comprises at least 70%, 80%, 85%, 90%, 95%, 96%, 97%, or at least 98% cellulose, such as at least 80% cellulose. Optionally, the cellulose pulp further comprises hemicellulose sugars in an amount up to 10%, 7.5%, 5%, 4%, 3%, 2%, 1%, or up to 0.5% weight/weight relative to total solids, such as up to 5% hemicellulose sugars. Optionally, the cellulose pulp comprises 0.01-5% hemicellulose sugars, such as 0.01-1% hemicellulose sugars. Optionally, the cellulose pulp further comprises ash in an amount up to 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or up to 0.1% weight/weight relative to total solids, such as up to 6% ash. Optionally, the cellulose pulp comprises 0.001-6% ash, such as 0.001-2% ash. Optionally, the cellulose pulp further comprises sulfate in an amount up to 5%, 4%, 3%, 2%, 1%, 0.5%, or up to 0.1% weight/weight relative to total solids, such as up to 3% sulfate. Optionally, the cellulose pulp further comprises lignin in an amount up to 20%, 15%, 10%, 7.5%, 5%, 4%, 3%, 2%, 1% or up to 0.5% weight/weight relative to total solids as determined by the NREL/TP-510-42618 method, such as up to 15% lignin. Optionally, the cellulose pulp comprises water soluble carbohydrates in an amount up to 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or up to 1% weight/weight relative to total solids, such as up to 5% water soluble carbohydrates, wherein the solubility is measured at 20° C. Optionally, the cellulose pulp comprises cellulose, hemicellulose in an amount up to 5% weight/weight relative to total solids, ash in an amount up to 4% weight/weight relative to total solids, and sulfate in an amount up to 3% weight/weight relative to total solids.
Optionally, the organic phase that contains the dissolved lignin is separated 308 from the aqueous phase that contains residual dissolved sugars and ionic species. Optionally, before separation 308, Ca(OH)2 is added to the solution to bring the pH of the aqueous phase to 3.5-3.8. Other suitable bases known in the art may be used to adjust the pH, including, for example, Mg(OH)2, NaOH, KOH, and others. In some embodiments, the separated organic phase comprises at least 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% lignin wt/wt.
The aqueous phase of separation 308 is optionally treated with high pressure CO2 gas, i.e. at 2-10, 3-8, or 4-5 barg, to convert any salts of the acid to the acid and carbonate salts. Optionally, Ca(OH)2 is added to the aqueous phase of separation 308 to raise the pH. The Ca(OH)2-treated aqueous phase may be treated with CO2 gas, i.e. at 2-10, 3-8, or 4-5 barg, to convert any calcium salts of the acid to the acid and calcium carbonate. In some embodiments, calcium carbonate is precipitated and removed by filtration.
Optionally, the acid is used in the lignin extraction process is fumaric acid. The aqueous phase of separation 308 is optionally treated with high pressure CO2 gas, i.e. at 2-10, 3-8, or 4-5 barg, to convert any calcium fumarate to fumaric acid and calcium carbonate. In some embodiments, calcium carbonate is precipitated and removed by filtration.
In some embodiments, the lignin containing organic phase is contacted 315 with a strongly acidic cation exchange resin (SAC) to remove residual cations. Lignin may be precipitated by flash evaporation 320 of the limited-solubility solvent in contact with hot water, and the collected lignin dried 330 to produce high purity lignin 340-P1. Detailed embodiments of the lignin refining process are disclosed in PCT/US2013/039585 and PCT/US2013/068824, incorporated herein by reference.
In some embodiments, the aqueous phase comprising limited-solubility acid, such as fumaric acid, is combined again with the solids (e.g., cellulose pulp) remaining from Extraction 2. Optionally, additional limited-solubility solvent is added. The combined slurry may be heated to a temperature sufficient to create high pressure, preferably 160 to 220° C., e.g., 170-200° C. The slurry may be maintained at high temperature for 1-30 minutes (e.g., 5-15 minutes) and the pressure released rapidly through a vent. In some embodiments, the vapors comprising limited-solubility solvent and water are collected in a condenser 382 and directed to be used in Extraction 3, 400 in
In some embodiments, a mixture of water and methylethyl ketone (MEK) is used as the limited-solubility solvent that is heated to create high pressure that is rapidly dropped to cause an explosive effect on the cellulose fibers. In some embodiments, the pressure difference between the high and low pressures is about 2.5, 3.0, 3.5, 4.0, 4.5, or 5.0 MPa. In some embodiments, the temperature required to achieve such pressure is about 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, or 190° C. In some embodiments, the use of a volatile solvent in the mixture allows for higher pressures at lower temperatures than steam alone. In some embodiments, the efficacy of solvent explosion is enhanced by applying pressure to cellulose pulp that is already well impregnated with the liquid phase from the previous process step (i.e., lignin extraction). In some embodiments, once exploded, the slurry is immediately transferred to Extraction 3.
Optionally, prior to Extraction 3, the cellulose pulp is pretreated. In some embodiments, the pretreating comprises (a) contacting the cellulose pulp with water, a limited-solubility solvent, and a limited-solubility acid, thereby forming a pretreatment slurry; (b) heating the pretreatment slurry to a temperature of about 160-220° C. in a closed system; and (c) opening the closed system to rapidly release pressure. The resultant cellulose pulp may be used directly in Extraction 3.
Extraction 3 is designated as process 400 in
In certain embodiments, provided herein is a process for the hydrolysis of cellulose pulp. The process may comprise: (i) contacting the cellulose pulp with water, a limited-solubility solvent, and a limited-solubility acid, thereby forming a slurry; (ii) heating the slurry to a temperature of about 200-400° C., thereby forming a treated slurry; and (iii) recovering a cellulosic hydrolysate from the treated slurry.
In certain embodiments, provided herein is a process for the hydrolysis of cellulose pulp. The process may comprise: (i) contacting the cellulose pulp with water, a limited-solubility solvent, and a limited-solubility acid, thereby forming a slurry; (ii) heating the slurry to a temperature of about 200-400° C., thereby forming a treated slurry; and (iii) recovering a cellulosic hydrolysate from the treated slurry, wherein the limited-solubility solvent is a 4- to 8-carbon ketone having an aqueous solubility of 10-40% wt/wt at 20° C., and wherein the limited-solubility acid is a dicarboxylic acid having an aqueous solubility of less than 1% wt/wt at 4° C. Optionally, the limited-solubility acid is fumaric acid. Optionally, the limited-solubility solvent is methylethyl ketone.
In some embodiments, recovering the cellulosic hydrolysate from the treated slurry comprises phase separation of an aqueous phase comprising the cellulosic hydrolysate from an organic phase comprising the limited-solubility solvent. Optionally, the aqueous phase is contacted with CO2 at a pressure of at least 2 barg to produce a carbonated aqueous phase. In some examples, the carbonated aqueous phase is cooled to less than 10° C., such as less than 5° C., thereby forming a precipitate comprising the limited-solubility acid. Optionally, the precipitate is separated from the aqueous phase.
In some embodiments, the process for the hydrolysis of cellulose pulp is conducted at an industrial scale. Optionally, at least 1 kg, 5 kg, 10 kg, 50 kg, 100 kg, 250 kg, 500 kg, or at least 1000 kg of cellulose pulp, such as at least 10 kg of cellulose pulp is hydrolyzed in a single batch. Optionally, the hydrolysis produces at least 1 kg, 5 kg, 10 kg, 50 kg, 100 kg, 250 kg, or at least 500 kg of glucose, such as at least 5 kg of glucose, in a single batch.
In some embodiments, the acid is a limited-solubility acid. In some embodiments, the acid has limited solubility in an aqueous solution that is saturated with the limited-solubility solvent. In some embodiments, the acid has limited solubility in the limited-solubility solvent that is saturated with water. In some embodiments, the solubility of the acid in water, in solvent-saturated water or in water-saturated solvent is highly temperature dependent. In some embodiments, the solubility of the acid is higher in the solvent than in water, and is highest in water-saturated solvent. In some embodiments, the partition coefficient of the acid between the limited-solubility solvent and water is greater than 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In some embodiments, the solubility of the acid in water at 4° C. is less than 1%, 0.5%, or 0.3% wt/wt. In some embodiments, the solubility of the acid in water at 20° C. is less than 100, 75, 50, 40, 30, 25, 20, 15, 10, or 5 g/L. In some embodiments, the solubility of the acid in water at 20° C. is between 1-10, 1-5, or 3-5 g/L. In some embodiments, the solubility of the acid in water at 20° C. is about 4 g/L. In some embodiments, the limited-solubility acid has at least one pKa value lower than 4.8, 4.0, 3.7, 3.5, 3.2, or 3.0. In some embodiments, the limited-solubility acid has at least one pKa value between 1.9 and 3.5 in water. In some embodiments, the limited-solubility acid has at least one pKa value between 2.5 and 3.5 in water. In some embodiments, the limited-solubility acid is a dicarboxylic acid. In some embodiments, the limited-solubility acid is a C4 carboxylic acid. In some embodiments, the limited-solubility acid is selected form fumaric acid, maleic acid and malic acid. In some embodiments, the limited-solubility acid is fumaric acid.
In some embodiments, Extraction 3 yields a hydrolysate aqueous phase and a lignin organic phase. In some embodiments, no solid remains at the end of Extraction 3. In some embodiments, any solid remaining at the end of Extraction 3 is collected and combined with the feed into solvent explosion 380 or the feed into Extraction 3. In some embodiments, the concentration of sugar in the hydrolysate (i.e. sugar/(sugar+water) concentration) is at least 5%, 8%, 10%, 12%, 15%, or 20% wt/wt. In some embodiments, the concentration of sugar in the hydrolysate is less than 25%, 20%, 15%, 12%, 10%, 8%, or 5% wt/wt. Optionally, the concentration of sugar in the hydrolysate is 1-25% wt/wt, such as 5-25% wt/wt. In some embodiments, the concentration of monomers relative to total sugars is at least 50%, 60%, 70%, 80%, 85%, 90%, or 95% wt/wt. In some embodiments, the concentration of lignin in the organic phase is at least 0.2%, 0.5%, 1%, 1.5%, 2%, 3%, 4%, or 5% lignin wt/wt.
In some embodiments, the concentration of monomers relative to total sugars in the hydrolysate is less than 95%, 90%, 85%, 80%, 70%, 60%, or 50% wt/wt. Optionally, the hydrolysate is heated to about 90-130° C. for about 20-120 minutes. The heating may cause hydrolysis of oligomers to monomers. In some embodiments, the concentration of total sugars in the solution is modified prior to the hydrolysis of oligomers to monomers. The concentration of total sugars in the solution may be reduced, optionally by dilution with water. The concentration of total sugars in the solution may be increased, optionally by the removal of water by evaporation. Preferably, the concentration of total sugars in the solution is modified to be less than 20%, 15%, 12%, 10%, 8%, or less than 6% wt/wt. In some embodiments, the further hydrolysis of oligomers to monomers described herein is done before treating the aqueous phase with base and/or CO2, as described below. In some embodiments, the further hydrolysis of oligomers to monomers described herein is done after treating the aqueous phase with base and/or CO2.
The stream coming out of Extraction 3 may be phase separated in process 408. Optionally, Ca(OH)2 is added before phase separation to adjust the pH to the range of 3.5-3.8. Other suitable bases known in the art may be used to adjust the pH, including, for example, Mg(OH)2, NaOH, KOH, and others. In some embodiments, the organic phase containing dissolved lignin is combined with lignin stream 305 of Extraction 2 for refining. In some embodiments, calcium fumarate formed in the aqueous stream is converted back to fumaric acid by applying CO2 gas, i.e. at 2-10, 3-8, or 4-5 barg. Calcium carbonate formed in this process may be removed by filtration.
Optionally, Ca(OH)2 is added to the aqueous phase of separation 408 to raise the pH. The Ca(OH)2-treated aqueous phase may be treated with CO2 gas, i.e. at 2-10, 3-8, or 4-5 barg, to convert any calcium salts of the acid to the acid and calcium carbonate. In some embodiments, calcium carbonate is precipitated and removed by filtration.
In some embodiments, the limited-solubility acid is recovered by precipitation. Preferably, at least 50%, 60%, 70%, 80%, 85%, 90%, 95%, 98% or 99% of the limited-solubility acid is recovered and optionally recycled, such as at least 80%, more preferably at least 95% of the limited-solubility acid is recovered and optionally recycled.
In some embodiments, the limited-solubility acid is recycled in the process by stripping the aqueous phase from dissolved solvent and cooling the remaining aqueous fraction to cause precipitation of the limited-solubility acid. In some embodiments, the precipitated acid is collected by filtration and is re-dissolved in solvent-saturated water for recycling. In a preferred embodiment of this invention, the limited-solubility solvent is 2-butanone (methylethyl ketone, MEK) and the limited-solubility acid is fumaric acid. Starr & King (Ind. Eng. Chem. Res. 1992, 31, 2572-2579) teach that the solubility of fumaric acid is greater in saturated solutions of ketones in water as compared to the solubility of fumaric acid in either pure water or dry ketone. While Starr & King did not test the combination of water and MEK, similar behavior is observed for this ternary mixture. As suggested by Starr & King, the recovery of fumaric acid is enhanced by stripping the solvent (MEK) from a solvent-saturated aqueous solution of the acid to cause its effective precipitation. Thus, precipitation and recovery of fumaric acid is enhanced by the removal or reduction of the solvent at a reduced energy cost as is required for the recovery of alternative acids commonly used in the art. In some embodiments, the concentration of the limited-solubility acid in the aqueous stream after acid recovery 450 is less than about 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, or 0.01% wt/wt. In some embodiments, at least about 80%, 85%, 90%, 95%, 96%, 97%, 98%, or 99% of the limited-solubility acid is recovered and recycled. In some embodiments, the glucose solution is optionally further concentrated by evaporation of water by any technique known to one skilled in the art to reduce further the total amount of organic acid loss. In some embodiments, the energy consumption of acid recovery 450 is reduced by at least 50%, 60%, 70%, 80%, or 90% compared to the recovery by distillation of organic acids that are soluble in water or water/MEK, including, for example, acetic acid and formic acid.
The refining process of crude glucose is presented in
The amine extractant may contain 10-90% or preferably 20-60% weight/weight of one or a plurality of amines having at least 20 carbon atoms. Such amine(s) can be primary, secondary, and tertiary amines. Examples of tertiary amines include tri-laurylamine (TLA; e.g. COGNIS ALAMINE 304 from Cognis Corporation; Tucson Ariz.; USA), tri-octylamine, tri-isooctylamine, tri-caprylylamine and tri-decylamine.
Diluents suitable for use in the amine extraction include an alcohol, such as butanol, isobutanol, hexanol, octanol, decanol, dodecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, eicosanol, docosanol, tetracosanol, or triacontanol. Preferably, the diluent is a long chain alcohol (e.g. C6, C8, C10, C12, C14, or C16 alcohol), or kerosene. The diluent can have additional components. More preferably, the diluent comprises n-hexanol or 2-ethyl-hexanol. Optionally, the diluent comprises hexanol. Most preferably, the diluent comprises 2-ethyl-hexanol. In some embodiments, the diluent consists essentially of, or consists of, 2-ethyl-hexanol.
Optionally, the amine is tri-laurylamine and the diluent is hexanol. The ratio of amine and diluent can be any ratio, e.g., between 3:7 and 6:4 weight/weight. In some methods, the amine extraction solution contains tri-laurylamine and hexanol in a ratio of 1:7, 2:7, 3:7, 6:4, 5.5:4.5, 4:7, 5:7, 6:7, 7:7, 5:4, 3:4, 2:4, or 1:4 weight/weight. Preferably, the amine extraction solution contains tri-laurylamine and hexanol in a ratio of 3:7 weight/weight.
Preferably, the amine is tri-laurylamine and the diluent is 2-ethyl-hexanol. The ratio of amine and 2-ethyl-hexanol can be any ratio, e.g., between 3:7 and 6:4 weight/weight. In some methods, the amine extraction solution contains tri-laurylamine and 2-ethyl-hexanol in a ratio of 1:7, 2:7, 3:7, 6:4, 5.5:4.5, 4:7, 5:7, 6:7, 7:7, 5:4, 3:4, 2:4, or 1:4 weight/weight. Preferably, the amine extraction solution contains tri-laurylamine and 2-ethyl-hexanol in a ratio of 3:7 weight/weight.
The amine extraction can be conducted at any temperature at which the amine is soluble, preferably at 50-70° C. Optionally, more than one extraction step (e.g., 2, 3, or 4 steps) can be used. The ratio of the amine extractant stream (organic phase) to the hemicellulose sugar stream (aqueous phase) can be 0.5-5:1, 1-2.5:1, or preferably, 1.5-3.0:1 weight/weight.
In some embodiments, the acid-depleted sugar stream can be further purified (see, e.g.,
Preferably, the acid-depleted sugar stream may then be contacted with a weak base anion (WBA) exchanger 486 to remove excess protons. The amine-removed and neutralized sugar stream may be pH adjusted and evaporated 490 to 25-65% and preferably 30-40% weight/weight dissolved sugars in any conventional evaporator, e.g., a multiple effect evaporator or a mechanical vapor recompression (MVR) evaporator.
The product of the refining process is optionally pure glucose solution 490-P1, which may be concentrated by one of several known evaporation techniques to the appropriate level. This pure glucose solution is highly suitable as feed for fermentation processes or catalytic conversion processes. For example, this product may be the feed for numerous fermentation processes applied in the industry, which currently employ dextrose made from corn, sugar cane or sugar beet. Some examples of such fermentation processes are disclosed in PCT/IL2012/050118, filed on Apr. 2, 2012, incorporated by reference herein. This glucose product may be the feed to a conversion process to HMF, as disclosed in U.S. Provisional Patent Application No. 62/091,319, filed on Dec. 12, 2014, incorporated by reference herein. In another alternative, the product is a combined sugar solution of high purity, comprising glucose, mannose, galactose, xylose and arabinose, with the ratios of different carbohydrates dependent on the biomass feedstock.
When hemicellulosic sugars are not combined into the stream, the highly purified glucose product may be characterized by one or more, two or more, three or more, four or more, five or more, or six or more characteristics, including: (i) monosaccharides in a ratio to total dissolved sugars >0.50 weight/weight; (ii) glucose in a ratio to total monosaccharides >0.90 weight/weight; (iii) xylose in a ratio to total monosaccharides <0.10 weight/weight; (iv) fructose in a ratio to total monosaccharides <0.10 weight/weight; (v) fructose in a ratio to total monosaccharides >0.01 weight/weight; (vi) furfurals in amounts up to 0.01% weight/weight; (vii) phenols in amounts up to 500 ppm; (viii) hexanol in amounts up to 500 ppm; (ix) C4 carboxylic acid in a ratio to total saccharides <0.05 weight/weight; and (x) fumaric acid in a ratio to total saccharides <0.05 weight/weight. For example, the glucose product may be a mixture having a high monosaccharides to total dissolved sugars ratio, a high glucose content, and a low xylose content. In some embodiments, the sugar mixture is a mixture having a high monosaccharides to total dissolved sugars ratio, a high glucose content, a low xylose content, and a low impurity content (e.g., low furfurals and phenols). In some embodiments, the mixture is characterized by a high monosaccharides to total dissolved sugars ratio, a high glucose content, a low xylose content, a low impurity content (e.g., low furfurals and phenols), and a trace amount of hexanol. In some embodiments, the glucose product is provided as an aqueous solution. The aqueous solution may comprise at least 1%, 5%, 10%, 15%, 20%, 25%, or at least 30% total sugars weight/weight relative to the total weight of the composition.
In certain embodiments, the product of the cellulose pulp extraction process is a sugar composition comprising: (i) monosaccharides in a ratio to total dissolved sugars >0.50 weight/weight; (ii) glucose in a ratio to total monosaccharides >0.80, such as >0.90, weight/weight; (iii) xylose in a ratio to total monosaccharides <0.10 weight/weight; (iv) fructose in a ratio to total monosaccharides <0.10 weight/weight; (v) furfurals in amounts up to 0.01% weight/weight; (vi) phenols in amounts up to 500 ppm; and optionally (vii) hexanol or 2-ethyl-1-hexanol in amounts up to 500 ppm. Optionally, the composition comprises glucose in a ratio to total monosaccharides of 0.80 to 0.99, such as 0.90 to 0.99, weight/weight. Optionally, the composition comprises fructose in a ratio to total monosaccharides of at least 0.0001, 0.001, 0.01, 0.05, 0.08, or 0.09 weight/weight, such as at least 0.01 weight/weight. Optionally, the composition comprises xylose in a ratio to total monosaccharides of at least 0.0001, 0.001, 0.01, 0.05, 0.08, or 0.09 weight/weight, such as at least 0.01 weight/weight. Optionally, the composition further comprises at least 1, 5, 10, 50, 100, 250, 500, 1000, 5000, or 10,000 ppb fumaric acid, such as at least 10 ppb fumaric acid. Optionally, the composition further comprises at least 1, 5, 10, 50, 100, 250, 500, 1000, 5000, or 10,000 ppb furfural, such as at least 10 ppb furfural. Optionally, the composition further comprises at least 1, 5, 10, 50, 100, 250, 500, 1000, 5000, or 10,000 ppb phenols, such as at least 10 ppb phenols. Optionally, the composition further comprises at least 1, 5, 10, 50, 100, 250, 500, 1000, 5000, or 10,000 ppb hexanol or 2-ethyl-1-hexanol, such as at least 10 ppb hexanol or 2-ethyl-1-hexanol. Optionally, the composition further comprises at least 1, 5, 10, 50, 100, 250, 500, 1000, 5000, or 10,000 ppb methylethyl ketone, such as at least 10 ppb methylethyl ketone. Optionally, the composition further comprises C6 oligosaccharides in a ratio to total dissolved sugars of 0.001 to 0.30, 0.001 to 0.20, 0.01 to 0.20, 0.001 to 0.10, 0.01 to 0.10, 0.001 to 0.05, or 0.01 to 0.05 weight/weight, such as 0.01 to 0.10 weight/weight. In some embodiments, the sugar composition is provided as an aqueous solution. The aqueous solution may comprise at least 1%, 5%, 10%, 15%, 20%, 25%, or at least 30% total sugars weight/weight relative to the total weight of the composition.
When hemicellulosic sugars are combined, the highly purified cellulosic sugar product may be characterized by one or more, two or more, three or more, four or more, five or more, or six or more characteristics, including (i) monosaccharides in a ratio to total dissolved sugars >0.50 weight/weight; (ii) glucose in a ratio to total monosaccharides >0.50 weight/weight; (iii) glucose in a ratio to total monosaccharides >0.80 weight/weight; (iv) fructose in a ratio to total monosaccharides <0.10 weight/weight; (v) fructose in a ratio to total monosaccharides >0.01 weight/weight; (vi) xylose in a ratio to total monosaccharides <0.10 weight/weight; (vii) furfurals in amounts up to 0.01% weight/weight; (viii) phenols in amounts up to 500 ppm; (ix) hexanol in amounts up to 500 ppm; (x) C4 carboxylic acid in a ratio to total saccharides <0.05 weight/weight; and (xi) fumaric acid in a ratio to total saccharides <0.05 weight/weight. For example, the sugar mixture may be a mixture having a high monosaccharides to total dissolved sugars ratio, a high glucose content, and a low xylose content. In some embodiments, the sugar mixture is a mixture having a high monosaccharides to total dissolved sugars ratio, a high glucose content, a low xylose content, and a low impurity content (e.g., low furfurals and phenols). In some embodiments, the mixture is characterized by a high monosaccharides to total dissolved sugars ratio, a high glucose content, a low xylose content, a low impurity content (e.g., low furfurals and phenols), and a trace amount of hexanol. In some embodiments, the sugar product is provided as an aqueous solution. The aqueous solution may comprise at least 1%, 5%, 10%, 15%, 20%, 25%, or at least 30% total sugars weight/weight relative to the total weight of the composition.
It is understood that the examples and embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the claimed invention. It is also understood that various modifications or changes in light of the examples and embodiments described herein will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims. All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety for all purposes.
Bagasse sugar composition (DB4D01): Bagasse was shredded in a wood shredder. In a temperature controlled tank, bagasse (60 lbs, dry base) was then treated with an aqueous solution containing 0.5% H2SO4 (wt/wt) at a liquid to solid ratio of 14:2. The average temperature of the temperature controlled tank was maintained at 130-135° C. for 3 hours. The solution was circulated by pumping. The resulting liquor was collected and the solids washed with water. The wash water was then used to prepare the acid solution for the next batch by adding acids as needed. The hemicellulose-depleted lignocellulosic matter was collected and dried.
The acidic hemicellulose sugar stream was run through a SAC column. The sugar stream was then extracted continuously in a series of mixer settlers (2 countercurrent stages) with an extractant having tri-laurylamine:hexanol at a ratio of 30:70. The extractant to sugar stream ratio was kept in the range of 2:1 to 1.5:1. The resulting aqueous phase was further purified by using a SAC resin, a WBA resin, and a mixed bed resin. The pH of the resulting stream was adjusted to 4.5 with 0.5% HCl and the sugar solution evaporated to a concentration of ˜30% dissolved solids (DS). The resulting sugar stream contained about 7% arabinose, 2.5% galactose, 6.5% glucose, 65% xylose, 1.5% mannose, 4% fructose and 14% oligosaccharides (all % weight/total sugars). This sugar solution was further processed by fractionation on an SSMB system, resulting in a xylose rich fraction and a xylose depleted fraction. Each fraction was concentrated by evaporation. Table 1 provides a chemical analysis of the resulting xylose rich sugar solution.
Bagasse was extracted and refined according to Example 1. The process was conducted at pilot scale at Virdia PDU, Danville Va. Table 2 summarizes the sugar profile of the refined sugar stream.
Refined bagasse produced according to Example 2 was fractionated by chromatography (as per PCT/US2013/039585) to produce a xylose enriched extract stream (Table 3A) and xylose depleted raffinate stream (Table 3B).
Water and methylethyl ketone (MEK) were shaken for several minutes to allow saturation of each phase. The phases were separated. An excess amount of fumaric acid was stirred at 40° C. in each phase for 5 hours in a closed container. A sample of the solution was diluted with water and filtered. The concentration of fumaric acid was determined by HPLC by injecting 1-20 μL onto a Bio-Rad Aminex HPX-87H 7.2 mm column, using 0.003 M H2SO4 as eluent, flow rate 0.6 mL/min, temperature 65° C., and an RI detector. The saturated solution was held in a thermostated bath at 25° C., 10° C., 4° C. and 0° C. and allowed to equilibrate at each temperature. A sample of each solution was taken, diluted with water and injected onto the HPLC to determine fumaric acid concentration. Similarly, excess amounts of fumaric acid and Ca(OH)2 were shaken with each phase and the concentration of fumaric acid determined by HPLC in a diluted, filtered sample. The solubility curves of fumaric acid and calcium fumarate are shown in
An excess amount of fumaric acid was shaken overnight at 4° C. in a biphasic system of water and MEK. The fumaric acid concentration in each phase was determined by HPLC as described in Example 4. Similarly, excess amounts of both fumaric acid and calcium hydroxide were equilibrated with a biphasic system of water and MEK. The partition coefficient was calculated as:
K was determined to be 8.6 for fumaric acid and 0.5 for calcium fumarate.
Hemicellulose-depleted bagasse (treated as described in the examples above) of DS-47% was contacted for 2 hours with a mixture of water, MEK and fumaric acid using reaction conditions summarized in Table 6. The liquid to solid ration was maintained at 17:1 and the MEK to water ratio was 1:1. The mixture was heated in a Parr 5500 pressure reactor with a 4848 reactor controller. After the reactor was cooled down, the solids were filtered, washed with water saturated MEK, dried, and the solids weighed. The dried cellulosic-remainder was characterized by NREL/TP-510-42618 method to determine the cellulose and lignin content. The amount of ash in the lignin could not be determined at the available quantities, but is estimated to be about 5%, i.e., if the % lignin+ash is reported as 20%, then mixture comprises about 15% lignin and about 5% ash.
The liquid phase is split into two fractions. Fraction A is separated to obtain the organic phase and the aqueous phase. A sample of the organic phase is evaporated to dryness to determine the amount of dissolved lignin. Fraction B is first titrated with Ca(OH)2 to pH 3.5-3.8 and is then treated similarly to Fraction A.
The solid separated in Example 6 having DS of 30-50% wt/wt is introduced into a high pressure lab reactor equipped with a stirrer and thermostated heating system (Autoclave Engineers). Alternatively, a reaction vessel fabricated in the lab from metal piping and Swagelock® fittings allowing for the rapid conduction of heating and cooling is heated by dipping it into a hot oil bath using DowTherm A thermal fluid and cooled by dipping into a water bath. The reaction vessel is loaded with a water/MEK solution at 13:1 ratio to dry solids. The solution comprises MEK:water at about 35:65% wt/wt and fumaric acid as indicated in Table 7, and the reaction is conducted for 10-40 minutes at the reaction temperature.
After the reaction is cooled down, the content of the reactor is tested to determine if all of the solid have been hydrolyzed to liquid, and any remaining solid is filtered, dried and its weight measured. The liquid phase is split into two fractions. Fraction A is separated to obtain the organic phase and the aqueous phase. A sample of the organic phase is evaporated to dryness to determine the amount of dissolved lignin. Fraction B is first titrated with Ca(OH)2 to pH 3.5-3.8 and is then treated similarly to Fraction A. The aqueous phase is analyzed for total sugars, for monomer/oligomer composition and for carbohydrate composition.
1. A process of producing hemicellulosic mixed sugars, lignin and glucose from a biomass, comprising:
2. The process of embodiment 1, wherein before contacting the cellulosic remainder with the cellulose hydrolysis solution, the cellulosic remainder is treated with the lignin extraction solution to increase porosity and reduce crystallinity, wherein the treatment comprises contacting the cellulosic remainder with the lignin extraction solution at elevated temperature and pressure and releasing the pressure rapidly to create a solvent explosion effect.
3. The process according to embodiment 1 or 2, wherein the limited-solubility organic acid is recycled by applying one, two, three, or four step(s) selected from:
4. The process of embodiment 3, wherein loss of the limited-solubility organic acid per kg of glucose produced is less than 25 g.
5. A highly purified glucose product characterized by one or more, two or more, three or more, four or more, five or more, or six or more characteristics selected from:
6. The use of the highly purified glucose product of embodiment 5 as feed for a fermentation process or chemical conversion process to produce a product.
7. The highly purified glucose product of embodiment 5, comprising fumaric acid in an amount less than 0.05% weight/weight.
8. A process for the hydrolysis of cellulose pulp, comprising:
9. The process of embodiment 8, wherein the limited-solubility acid is a dicarboxylic acid.
10. The process of embodiment 8 or 9, wherein the limited-solubility acid has at least one pKa value between 1.9 and 3.5 in water.
11. The process of any one of embodiments 8-10, wherein the solubility of the limited-solubility acid in water at 4° C. is less than 1% wt/wt.
12. The process of any one of embodiments 8-11, wherein the limited-solubility acid is fumaric acid.
13. The process of any one of embodiments 8-12, wherein the limited-solubility solvent comprises a 4- to 8-carbon ketone.
14. The process of any one of embodiments 8-13, wherein the limited-solubility solvent is methylethyl ketone.
15. The process of any one of embodiments 8-14, wherein at least a portion of the limited-solubility acid is recovered by precipitation.
16. The process of any one of embodiments 8-15, wherein the cellulose pulp has undergone a pretreatment step.
17. The process of embodiment 16, wherein the pretreatment step comprises:
This application is a National Stage Entry of PCT/US2016/034194, filed May 25, 2016, which claims the benefit of U.S. Provisional Application No. 62/167,111, filed on May 27, 2015, each incorporated herein by reference in its entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2016/034194 | 5/25/2016 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2016/191503 | 12/1/2016 | WO | A |
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| Number | Date | Country | |
|---|---|---|---|
| 20180148804 A1 | May 2018 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62167111 | May 2015 | US |
