US20130130331A1 - Method of producing sugars using a combination of acids to selectively hydrolyze hemicellulosic and cellulosic materials - Google Patents

Method of producing sugars using a combination of acids to selectively hydrolyze hemicellulosic and cellulosic materials Download PDF

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US20130130331A1
US20130130331A1 US13/521,462 US201113521462A US2013130331A1 US 20130130331 A1 US20130130331 A1 US 20130130331A1 US 201113521462 A US201113521462 A US 201113521462A US 2013130331 A1 US2013130331 A1 US 2013130331A1
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biomass
acid
materials
hemicellulosic
organic acid
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Thomas P. Binder
Paul D. Bloom
Perry H. Doane
Chi-Cheng Ma
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Archer Daniels Midland Co
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Archer Daniels Midland Co
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    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K13/00—Sugars not otherwise provided for in this class
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B10/00—Production of sugar juices
    • C13B10/003—Production of sugar juices using chemicals other than extracting agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B16/00—Regeneration of cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
    • C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P13/00—Preparation of nitrogen-containing organic compounds
    • C12P13/02—Amides, e.g. chloramphenicol or polyamides; Imides or polyimides; Urethanes, i.e. compounds comprising N-C=O structural element or polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06—Ethanol, i.e. non-beverage
    • C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
    • C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P2203/00—Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • This invention concerns an improved process for accomplishing the hydrolysis of materials containing cellulose and hemicellulose, and especially of lignocellulosic biomasses for further use in the synthesis of chemicals or the preparation of biobased fuels or fuel additives.
  • biomass of materials whose carbon content is of biological rather than fossil origin—for providing chemicals and fuel products presently derived from fossil-origin materials such as petroleum, or for providing acceptable biobased, functional alternatives to such chemicals and fuel products, has increasingly become a focus of research and development investment and effort in recent years as supplies of fossil-origin materials have been compromised or been more difficult or expensive to acquire and use.
  • non-food, lignocellulosic biomasses might be contemplated of this character, including, for example, purpose-grown non-food biomass crops (such as grasses, sweet sorghum, fast growing trees), or more particularly wood wastes (such as prunings, wood chips, sawdust) and green wastes (for instance leaves, grass clippings, vegetable and fruit wastes).
  • purpose-grown non-food biomass crops such as grasses, sweet sorghum, fast growing trees
  • wood wastes such as prunings, wood chips, sawdust
  • green wastes for instance leaves, grass clippings, vegetable and fruit wastes.
  • a first difficulty arises from the very different characteristics of the various components comprising lignocellulosic biomasses.
  • lignocellulosic biomasses are comprised mainly of cellulose, hemicellulose and lignin fractions, with cellulose being the largest of these three components.
  • Cellulose derives from the structural tissue of plants, and consists of long chains of beta glucosidic residues linked through the 1,4 positions. These linkages cause the cellulose to have a high crystallinity and thus a low accessibility to the enzymes or acid catalysts which have been suggested for hydrolyzing the cellulose to C6 sugars or hexoses for further processing.
  • Hemicellulose by contrast is an amorphous heteropolymer which is easily hydrolyzed, while lignin, an aromatic three-dimensional polymer, is interspersed among the cellulose and hemicellulose within a plant fiber cell and lends itself to still other process options.
  • lignin parenthetically in regards to the lignin fraction, the materials understood as encompassed within the term “lignin” and the method by which lignin content has been correspondingly quantified in a biomass have historically depended on the context in which the lignin content has been considered, “lignin” lacking a definite molecular structure and thus being determined empirically from biomass to biomass.
  • lignin lacking a definite molecular structure and thus being determined empirically from biomass to biomass.
  • an acid detergent lignin method Goering and Van Soest, Forage Fiber Analyses ( Apparatus, Reagents, Procedures, and Some Applications ), Agriculture Handbook No.
  • lignocellulosic biomasses having at least a lignin content consistent with mature temperate grasses having relatively low nutritive value for ruminants and which consequently are diverted to other uses in the main, such grasses typically being characterized by 6% or more of acid detergent insoluble materials (on a dry weight basis).
  • one of the challenges to using corn stover as a biomass feed whether for producing ethanol by fermentation or other chemicals, biobased fuels or fuel alternatives that can be made starting from a corn stover feed (e.g., diols and polyols, acrylates, hydroxymethylfurfural and other furanics, levulinates, epichlorohydrin), has been determining how much of the stover should be collected, as well as how it should be chopped, packaged or bundled, stored and transported to provide a consistent biomass feed with the right qualities; in this regard, as with any transformative process, consistency of the feedstock is always a concern, and as biomass is derived from living organisms the quality of collected biomass is inherently somewhat changeable so that proximity to storage, transport and processing facilities has needed to be factored into biomass selection.
  • a corn stover feed e.g., diols and polyols, acrylates, hydroxymethylfurfural and other furanics, levulinates, epichlorohydrin
  • the present invention provides methods for processing lignocellulosic biomasses in ways that can address and overcome some or all of the above-mentioned difficulties.
  • the present invention concerns a method for producing sugars using a combination of acids to hydrolyze hemicellulosic and cellulosic materials in biomass, said combination of acids namely comprising a first, weak organic acid (such as acetic acid or formic acid) for providing a pentose product or stream from hydrolyzing hemicellulosic materials in the biomass on a batchwise, semi-continuous or continuous basis, and a second, strong mineral acid (such as sulfuric acid) for providing a hexose product or stream from hydrolyzing cellulosic materials in the biomass.
  • a first, weak organic acid such as acetic acid or formic acid
  • a second, strong mineral acid such as sulfuric acid
  • a first aspect after optionally preprocessing the biomass to isolate a component higher in protein that may be desirable for animal feed or fertilizer (by mechanically breaking down the biomass and by air classification, as one example) and/or to isolate a component or components which have a comparatively high content of a species or material that will be more difficult to remove downstream and that may interfere with or make intended downstream conversions more difficult and/or may adversely affect the contemplated products from further processing (for example, nitrogen compounds, sulfur compounds, higher ash components)—the first, weak organic acid is applied to the biomass, near a collection point for the biomass, under conditions (for example, in terms of acid concentrations, temperatures, pressures and residence times) sufficient to depolymerize hemicellulosic materials and solubilize lignins in the biomass.
  • the “cooked” acidified biomass is then dried to remove water therefrom to an extent whereby the dried solids can be pelletized for shipment to a central facility. Then, at the central facility, pelletized, weak acid-processed biomass is washed with a solvent or solvent mixture which is effective for separating the solubilized and depolymerized hemicelluloses and lignins from a cellulosic fraction of the biomass, and then the cellulosic fraction is contacted with the second, strong mineral acid (or acids) under conditions suited to providing a hexose product or stream.
  • the first, weak organic acid is applied to the biomass in a vapor form at elevated temperatures, in part to reduce the drying load prior to the pelletization step.
  • the first, weak organic acid which will be understood in common with references to the second, strong mineral acid to embrace both a single acid so characterized as well as combinations of acids so characterized—is applied to the biomass (or that portion of the biomass left after optionally preprocessing the biomass as a whole, as described above) under suitable conditions for hydrolyzing hemicellulosic materials in the biomass, and then the weak acid-processed biomass is washed with a solvent or solvent mixture to separate the pentose product or stream (from hydrolyzing the hemicellulosic materials in the biomass) from a remaining predominantly cellulosic solids fraction.
  • the cellulosic solids fraction is then dried, pelletized and shipped to a central location for further processing with the second, strong mineral acid, while solubilized hemicellulosic materials and lignins are retained and optionally further processed at the first site, near a collection point for the biomass.
  • this further processing will include at least a water wash, to effect a separation of water-insoluble lignins as a solids residue from the pentose product or stream resulting from hydrolysis of hemicellulosic materials in the biomass. It is also understood that pending local market conditions the “cooked” acidified biomass or cellulosic solids could be made available as a feed ingredient.
  • the first, weak organic acid is applied to the biomass (or to the remainder after optional preprocessing of the biomass, again), but then the weak acid-processed biomass is washed with a solvent or solvent mixture to separate the solubilized hemicellulosic materials and lignins from a predominantly cellulosic solids fraction, followed by contacting the cellulosic solids fraction with a strong mineral acid or acids, with the weak acid and strong acid hydrolyses occurring at the same location.
  • the first, weak organic acid is again applied to the biomass in a hot vapor form.
  • the location in question may ideally be near a grouping of collection points for the biomass, or may more preferably be at a central location relative to the biomass sources to be drawn upon for the facility and convenient to the markets and customers to be served by the facility.
  • FIG. 1 is a schematic drawing illustrating a process according to the present invention, according to the first aspect.
  • FIG. 2 is a schematic drawing illustrating a process according to the present invention, according to the second aspect.
  • FIG. 3 is a schematic drawing illustrating a process according to the present invention, according to the further aspect described above.
  • a lignocellulosic biomass in a preferred embodiment containing typically 6 percent or more of acid detergent insoluble lignin and preferably not having any substantial alternative use in or for making human food products, is initially collected in step 102 at a convenient location (Site A) close to where the biomass is grown or produced.
  • biomasses from various sources are obviously contemplated as well and should be considered as encompassed by the use of the singular “a lignocellulosic biomass”.
  • a purpose-grown non-food biomass or an agricultural waste biomass comprises the largest fraction of those several biomasses in the mixture.
  • An example of a mixed biomass feed would be comprised of corn stover and corn fiber, with preferably corn stover comprising a greater proportion of the feed than the corn fiber.
  • a mixed biomass feed may simply be whole plant silage, for example, whole plant corn harvested and stored largely anaerobically, ‘ensiled’ to form silage, as most facilities for making renewable source-based chemicals, fuels and fuel additives will require year-round access to the biomass or biomass-based feeds to those facilities, in the same manner as facilities relying on petroleum-dependent feeds, and silage represents much more of a “known commodity” for the operator of such facilities than other processed biomasses.
  • the present invention in embodiment 100 fundamentally partially processes (at Site A) the biomass collected in step 102 , in order to place the material in a condition to be more economically transported from Site A, a convenient location close to where the biomass is grown or produced, to a central processing facility (“Central Facility”) located typically closer to means for making and distributing the desired biobased chemical and fuel products and closer to the customers who would ultimately purchase these chemical and fuel products.
  • Central Facility central processing facility
  • a Site A and the Central Facility will be 50 or more kilometers (30 miles or more) from one another, and for a number of Sites A to be on average at least the same distance removed from a Central Facility.
  • the Sites A will be on average 80 km (50 miles) or more removed from a Central Facility.
  • the Central Facility and Site A are much closer geographically, for example, where the means for making a desired biobased chemical or fuel are already in place near a Site A—or where Site A is near a source of demand so that the embodiment of FIG. 3 would ordinarily be preferred, but considerations specific to Site A (for example, zoning and permitting considerations or space limitations) prevent the embodiment of FIG. 3 from being implemented.
  • biomass is collected and washed as necessary to remove dirt and other contaminants.
  • the materials are then optionally dried, preferably to a moisture content of 10% or less.
  • the biomass is then comminuted by any of a number of means, including without limitation by grinding, chopping and hammermilling.
  • preprocessing of the biomass may include separating out and recovering (through air classification or other known separatory methods) a higher protein portion of the biomass for use in animal feed and fertilizer, for example, the leaf fraction from corn stover has a greater content of nitrogen and the approximate nutritional value of hay.
  • preprocessing of the biomass may involve recovery of corn oil from the grain as an additional valued co-product.
  • the biomass can be preprocessed to separate out and remove portions of the whole biomass which have a comparatively high content of a species or material that will be more difficult to remove downstream and that may interfere with or make intended downstream conversions more difficult and/or may adversely affect the contemplated products from further processing.
  • an intended product from the processing of the biomass may be an animal feed, and the nitrates in a lignocellulosic biomass—if more highly concentrated in a portion of the biomass that can be separated out and removed prior to further processing—would be desirably removed by preprocessing the whole biomass.
  • the collected or preprocessed biomass is then contacted with weak, organic acid to at least partly solubilize/depolymerize hemicellulosic materials and preferably some of the lignins in the biomass as well in weak acid step 104 .
  • Preferred acids include formic acid, malic acid, acetic acid, succinic acid and propionic acid, with formic and acetic acids being more preferred.
  • the weak acid(s) are applied to the biomass in a hot vapor form to minimize water removal requirements in the subsequent drying step 106 .
  • a weak acid solution of 50 percent or more in water can, with sufficient heating, be sufficient to depolymerize the hemicellulosic and lignin materials in the biomass to an extent whereby the partly depolymerized materials can serve as a binder, in effect, in the subsequent pelletization or densification step.
  • no additional binders are required to achieve pellets having the desired durability as further discussed below.
  • the weak acid can thus be applied in a preferred embodiment in the form of a hot vapor of from 50 percent acid and greater, but more preferably is applied as a concentrated vapor containing from 70 percent acid up to in excess of 90 percent acid, at a temperature of from 50 degrees Celsius to 160 degrees Celsius, a pressure of from atmospheric pressure to 3.5 MPa, gauge (500 psig), and for a residence time of at least about thirty minutes, to break down the hemicellulosic fraction and at least some of the lignins in the biomass as much as possible without compromising the durability of the subsequently-formed pellets to an undue extent whereby significant amounts of a binder must be added.
  • the weak acid-processed biomass then undergoes a drying or dewatering step 106 to remove sufficient moisture for allowing the dried biomass to be pelletized in step 108 .
  • the drying/dewatering step 106 can be accomplished by a number of conventional devices or combinations of such devices for concentrating an aqueous slurry and removing water therefrom to a level suited for pelletization of the remaining solids, for example, centrifuges, hydroclones, belt filter press driers, fluid bed driers, indirect or direct rotary drum driers, spin flash driers and the like.
  • the biomass leaving the drying step 106 will have a moisture content of 10 percent by weight or less, more preferably 8 percent or less by weight and most preferably 6 percent or less by weight to facilitate its pelletization and reduce transportation costs.
  • Pelletization of the solids leaving drying step 106 can be accomplished in step 108 using methods and equipment conventionally known to those skilled in the art, as pelletization of animal feeds and of woody biomass for fuels has become well-established, and will preferably result in a material with sufficient cohesiveness and integrity to withstand transport pneumatically or by conveyor belts/systems, by truck, ship or rail, or by some other means or combination of means for conveying a material from Site A to the Central Facility.
  • the pelletized material's needed durability (principally meaning the pellet does not produce an excessive quantity of fines in handling, transport and storage—will depend more particularly on how the material is handled, transported and stored at a given Site A, between Site A and a given Central Facility, and at the Central Facility.
  • the pelletized material's needed durability will depend more particularly on how the material is handled, transported and stored at a given Site A, between Site A and a given Central Facility, and at the Central Facility.
  • there are several devices and related methods which have been developed for assessing pellet durability, so that precise numerical values for durability may not reasonably be assigned a priori.
  • the pelletized, partially processed biomass will be sufficiently durable so as not to experience more than five percent loss of mass by dusting or fines formation from the completion of the pelletizing step 108 to the start of solvent washing at the Central Facility, and preferably not more than three percent of the pelletized, partially processed biomass will be lost as fines in this transition.
  • the pelletized, partially processed biomass is then conveniently shipped to the central facility for further processing, which includes at least washing with a solvent or combination of solvents in step 110 , the solvent or solvents being selected to effectively separate the at least partly depolymerized hemicellulosic materials in a product or stream 112 containing pentoses from the hydrolysis of hemicellulosic materials in the biomass, and a cellulosic solids fraction 114 .
  • the solvent wash step 110 can optionally comprise several iterations of washing and filtration, as desired.
  • an additional solvent wash step 116 (in one or more iterations of washing and filtration) is employed along with the solvent wash step 110 to separate out the lignins fraction 118 of the biomass.
  • the manner in which steps 110 and 116 are performed will depend on how the biomass has been processed at Site A, but in all cases will be conducted so as to provide a clean cellulosic pulp product or stream 114 which can then by hydrolyzed by exposure to the strong mineral acid in step 124 to yield a hexose product or stream 122 .
  • a preferred approach would be to use hot water to separate the at least partly depolymerized hemicelluloses and soluble salts from the cellulosic solids fraction 114 which would also contain the water-insoluble lignins.
  • the solvent wash step 116 would then be performed on the fraction 114 to solubilize and separate out the lignins in stream 118 and yield a material in product or stream 114 which can be acid hydrolyzed with a strong, mineral acid, a useful solvent for this purpose being a more concentrated organic acid solution applied at the requisite temperature to solubilize the lignins and separate the same from the remaining cellulosic fraction.
  • the clean cellulosic pulp 114 can be recovered in step 110 without the necessity of a further solvent wash step 116 .
  • Ethyl lactate has been found to be an effective solvent for use in step 110 in this embodiment.
  • Other effective solvents include tetrahydrofuran, 2-methyl tetrahydrofuran, ethyl formate and ethyl acetate.
  • the optional further solvent wash step 116 in this embodiment would be used to separate the lignins fraction 118 , preferably involving washing simply with hot water to recover the water-insoluble lignins in stream 118 .
  • Cellulosic solids fraction 114 recovered or fractionated out in this manner is then converted to a hexose product or substantially hexose stream 122 through conventional strong, mineral acid hydrolysis 124 under conditions suited to carry out this conversion.
  • the hexose product or stream produced by the present invention in its several embodiments will preferably be comprised substantially entirely of C6 monosaccharides, and of a character suited for upgrading to desired biobased chemical and fuel products with minimal further preprocessing or cleanup.
  • Exemplary biobased chemical and fuel products which have been suggested as derivable from the C6 monosaccharides include fuel additive products through hydrogenation and hydrotreating, or ethanol, lysine, threonine, lactic, gluconic or other organic acids through fermentation.
  • the pentose product or stream produced by the present invention in its several embodiments will preferably be comprised substantially entirely of C5 monosaccharides, and of a character suited for upgrading to those biobased chemical and fuel products which are derivable from such C5 monosaccharides, for example, ethanol, threonine, lysine, lactic, gluconic or other organic acids by fermentation, furfural, furfuryl alcohol, methyl tetrahydrofurfural, furfurylic acid and fuel additives generally by hydrogenation and hydrotreating.
  • C5 monosaccharides for example, ethanol, threonine, lysine, lactic, gluconic or other organic acids by fermentation, furfural, furfuryl alcohol, methyl tetrahydrofurfural, furfurylic acid and fuel additives generally by hydrogenation and hydrotreating.
  • a preferred strong, mineral acid for step 124 is sulfuric acid, applied as a 1 to 80, and preferably from 40 to 80, percent concentration aqueous sulfuric acid solution, at a temperature of from 25 degrees Celsius to 100 degrees Celsius, a pressure of from atmospheric pressure up to 0.7 MPa, gauge (100 psig), and a residence time of 15 minutes to 2 hours dependent primarily on the temperature conditions used.
  • the lignins fraction (as stream 118 in FIG. 1 , stream 212 in FIG. 2 and stream 318 in FIG. 3 ) can in like manner be put to practical further use, for example, ozonolysis to an aromatic fuel additive based, for example, on the teachings of United States Published Patent Application No. 2009/0718498A1, as a gasification feed for producing synthesis gas, as a combustion fuel, or ozonolysis to produce an aromatic sulfonation feed for producing biobased linear alkylbenzene sulfonates.
  • FIG. 2 an alternate embodiment 200 is shown schematically.
  • the embodiment 200 only the cellulosic fraction from the biomass is collected in solid form and pelletized for shipment and processing at a central facility to produce a hexose product or stream, while the hemicellulosic and lignin fractions are hydrolyzed at a first site, Site A, that is preferably convenient to where the biomass has been produced or grown.
  • Site A a first site
  • the alternate embodiment 200 would be advantageous where the biomass has a comparatively high lignin content but no ready outlet for the products to be made from the cellulosic or lignin fractions.
  • lignocellulosic biomass is collected and prepared for subsequent weak acid hydrolysis in step 202 , in the same manner as described above for step 102 of embodiment 100 .
  • the collected and preprocessed biomass then undergoes a weak acid hydrolysis step 204 , again preferably corresponding to the weak acid hydrolysis step 104 of embodiment 100 .
  • the weak acid hydrolyzed biomass comprising at least partly depolymerized lignins and hemicellulosic materials and a cellulosic solids fraction, is in one or more iterations solvent washed and filtered in a solvent wash step 206 , just as in the solvent wash step 110 described above for embodiment 100 .
  • a pentose product or stream 208 (“product” being understood herein as contemplative of a batchwise or generally discontinuous mode of operation, and “stream” being conventionally understood as referencing a continuous mode of operation) from the weak acid hydrolysis of hemicelluloses in the biomass is then optionally washed in step 210 in one or more iterations of washing and filtering, to produce a solid lignin product or stream 212 and a liquid pentose product or stream 214 .
  • the cellulosic solids from the solvent wash step 206 are dried in a drying step 216 , to remove moisture from the solids prior to their being pelletized in step 218 for shipment to a second venue—denominated a “Central Facility” in FIG. 2 .
  • Drying step 216 and pelletizing step 218 will for embodiment 200 generally be carried out as described above for drying step 106 and pelletizing step 108 of FIG. 1 .
  • pelletized cellulosic solids from step 218 at a given Site A will preferably be combined with pelletized cellulosic solids from steps 218 at other localized Site A's and hydrolyzed in a strong, mineral acid hydrolysis step 222 .
  • Strong, mineral acid hydrolysis step 222 in embodiment 200 will preferably be as described above for embodiment 100 , for step 124 .
  • a third general embodiment 300 is schematically illustrated and may be briefly described as comprising the same basic biomass collection and preprocessing, weak acid hydrolysis, solvent washing, optional water washing and strong acid hydrolysis steps performed in common with embodiments 100 and 200 , but, for example, omitting the drying and pelletization steps from embodiment 200 , as the embodiment 300 is contemplated for practice at a given, localized site, ideally near where the biomass to be processed is grown or produced.
  • the biomass is collected and preprocessed in a collection step 302 , then undergoes a weak acid hydrolysis step 304 followed by a solvent wash and filtration process 306 for substantially separating the solid cellulosic fraction 308 from the solubilized/hydrolyzed hemicellulosic and lignin fractions 310 .
  • the cellulosic solids 308 are in turn hydrolyzed in a strong acid hydrolysis step 312 to yield a hexose product or stream 314 , while the water-soluble pentoses and water-insoluble lignins are optionally separated and recovered as products (or streams) 316 and 318 through a wash step 320 performed on the stream 310 .
  • Embodiment 300 is thus advantageously employed where the biomass to be processed is grown or produced near a source of demand for the pentoses and/or hexoses to be produced therefrom, for example, for making biobased chemicals, fuels and/or fuel additives.
  • lignocellulosic biomasses that can be processed according to the present invention, numerous other similar examples can be considered wherein a sufficient supply of a suitable biomass exists near a source of demand for the pentoses and/or hexoses.
  • the embodiment 300 may be relatively more limited, while for economies with developed or developing chemical and fuel industries and fewer large population centers—or wherein the chemical and fuel industries have developed away from large population centers and nearer agrarian areas—the embodiment 300 may be preferred. In any event, those skilled in the art will be well able to determine which of the three embodiments described herein is to be preferred in a particular set of circumstances.
  • the embodiments 100 , 200 and 300 may comprise additional steps as well, of course. It will typically be desirable, for instance, to include acid recovery and recycle for recovering and recycling for reuse either or both of the weak, organic acid(s) and the strong, mineral acid(s), and those skilled in the art will be well able to select and employ suitable means for accomplishing the separation of the acid(s) from the sugar streams in the inventive process.
  • Acetic acid when used as the weak acid can be recovered by simple distillation, whereas formic acid forms an azeotrope with water and so requires azeotropic distillation methods when formic acid is applied as in the pulping art, as a concentrated aqueous liquid solution.
  • the formic acid is applied as a very concentrated vapor with small amounts of steam
  • the formic acid can be recovered, recycled and reused in concentrated form without the need of separating out the included water through simple distillation, preferably employing ethyl formate as an entrainer.
  • Various methods for recovering and reusing the strong mineral acid, sulfuric acid are described in U.S. Pat. No. 5,562,777 to Farone et al.
  • either or both of the weak, organic acid(s) and strong, mineral acid(s) may be simply neutralized.
  • the amount of such acid employed may be insufficient to justify the expense of recovery and recycle, so that neutralization may be preferred.
  • a further refinement to simplify recovery of the acid used in the weak acid hydrolysis step in each of the embodiments 100 , 200 and 300 would involve preparing the biomass leading into the weak acid hydrolysis step as an aqueous slurry, and providing the weak acid in a solid form that can be recovered by filtration.
  • a zeolite would be exemplary of the types of acidic solids that could be used.
  • an enzymatic hydrolysis can be employed in addition to or alongside the referenced acid hydrolyses to improve the efficiency of the fractionation of certain biomasses.
  • silage is used for the biomass
  • anaerobic fermentation of the silage feed itself over a period of time produces lactic acid, and this lactic acid can be used as a weak organic acid for the initial hydrolysis either alone or in combination with weak organic acids from other sources.
  • Still other variations will be evident to those skilled in the art, which do not depart from the true scope of the present invention, as expressed in the claims that follow.

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US9919939B2 (en) 2011-12-06 2018-03-20 Delta Faucet Company Ozone distribution in a faucet
US10947138B2 (en) 2011-12-06 2021-03-16 Delta Faucet Company Ozone distribution in a faucet
US8715765B2 (en) * 2012-06-18 2014-05-06 Randal Myers Process of treating biomass
US20140186903A1 (en) * 2012-12-28 2014-07-03 Api Intellectual Property Holdings, Llc Processes and apparatus for producing furfural, levulinic acid, and other sugar-derived products from biomass
US11458214B2 (en) 2015-12-21 2022-10-04 Delta Faucet Company Fluid delivery system including a disinfectant device
IT201700123012A1 (it) * 2017-10-30 2019-04-30 Versalis Spa Procedimento per la produzione di zuccheri da biomassa derivante da piante di guayule
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WO2011097065A3 (en) 2011-11-17
EP2531528A2 (en) 2012-12-12
BR112012019121A2 (pt) 2016-06-28
US20130102045A1 (en) 2013-04-25
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EP2531528A4 (en) 2014-04-02
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JP2013518972A (ja) 2013-05-23
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DK2531528T3 (en) 2015-05-26
ES2538669T3 (es) 2015-06-23

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