OA17191A

OA17191A - Conversion of biomass.

Info

Publication number: OA17191A
Application number: OA1201400554
Authority: OA
Inventors: Christopher Cooper; Marshall Medoff; Jihan Khan; Thomas Craig Masterman
Original assignee: Xyleco, Inc.
Priority date: 2012-07-03
Filing date: 2013-07-03
Publication date: 2016-04-05

Abstract

Biomass feedstocks (e.g., plant biomass, animal biomass, and municipal waste biomass) are processed to produce useful products, such as fuels. For example, systems are described that can convert feedstock materials to a sugar solution, which can then be chemically converted to furfural and furfural-derived products.

Description

CONVERSION OF BIOMASS

BACKGROUND OF THE INVENTION

RELATED APPLICATIONS

1. This application claims priority to U.S. Provisional Application Serial No.

61/667,481, filed July 03,2012. The complété disclosure of this provisional application is hereby incorporated by référencé herein.

2. Various carbohydrates, such as cellulosic and lignocellulosic materials, e.g., in fibrous form, are produced, processed, and used in large quantifies in a number of applications. Often such materials are used once, and then discarded as waste, or are simply considered to be waste materials, e.g., sewage, bagasse, sawdust, and stover.

3. Various cellulosic and lignocellulosic materials, their uses, and applications hâve been described in U.S. Patent Nos. 7,846,295,7,307,108,7,074,918,6,448,307,6,258,876, 6,207,729,5,973,035 and 5,952,105; and in various patent applications, including “FIBROUS MATERIALS AND COMPOSITES,” PCT/US2006/010648, filed on March 23,2006, “FIBROUS MATERIALS AND COMPOSITES,” U.S. Patent Publication No. 2007/0045456 AND “SACCIIARIFYING BIOMASS, U.S. Patent Application No. 12/704,515. 12/417,720.

SUMMARY

4. Generally, this invention relates to processes for converting a cellulosic, starchy or lignocellulosic feedstock to use fui products, organic sugar derived products for example, furfural and furfural-derived products.

5. Xylose can be chemically converted into many use fui intermediates and products. The intermediates and products include but are not limited to furfural, furfuryl alcohol, methyl furan, methyl tetrahydrofuran, furan, tetrahydrofuran and similar structures. Xylose is shown in its hemiacetal structure as 1. Xylose can exist in various different chemical forms.

H0*V— O

OH

Xytose

6. The conversion can be by chemically converting the xylose the product or the intermediate. The xylose can be chemically converted, for example, by any one or more of

cyclization réactions, polymcrizaiion reactions, condensation reactions, réduction reactions, oxidation reactions, estérification reactions, alkylation reactions, and combinations thereof. The product of the conversion can be, for example, furfuntl. Optionally, the product can be isolated (e.g., by chromatography, crystallization, précipitation, filtering, centrifugation, évaporation, extraction, distillation, phase séparation, heating, vacuum distillation or combinations of these).

7. For instance, in the case of chemically converting xylose to furfural; furfural can be a product or an intermediate that can be, in tum, converted to wide array of products including but not Iimited to furfuryl alcohol, furoic acid, methyl furan, furan, methyl tetrahydrofuran and tetrahydro furan. The conversion of furfural to useful products often includes multiple chemical conversion steps and thus the term intermediate may mean a single intermediate or the several intermediates required to obtain the final furfural-derived product An example of the tetrahydrofuran product which requîtes a decarbonylation to furan followed by hydrogénation.

8. In some cases, converting can be by reacting the xylose or the chemical intermediate with an acid catalyst. Thus, for example, xylose can be dehydrated, losing 3 moles of water, to give furfural and the furfural can be hydrogenated to furfuryl alcohol. Optionally, the acid catalyst can be selected for example from acidified Zeolites, acidified silica, surface grafted silicas, acid clays, functionalized mesoporous silicas, poly acids, acid functionalïzed polymers, poly sulfonic acids, Nafion® perfluorinated sulfonic acid resin or membrane, poly acetic acids, poly phosphonic acids, polystyrène sulfonic acids, tetraorthosilicates, 3-(mercaptopropyl) trimethoxysilane, Lewis acids, microporous silicoaluminaphosphate, métal oxides, ZrO₂, A1₂O₃, T1O2, S1O2, V₂Oj, sulfate salts, (NILhSO-i, meta! halides, MgCb, LaClj, FeClj, métal carbonates, Cs₂COj, ionic liquida, Tungsten oxides, Tungstate, Phosphoric acid, Phosphonic acid, sulfuric acid, hydrochloric acid, ni trie acid and combinations thereof.

9. In some cases the methods include heating the xylose (e.g., to at least 50°C, at least 60°C, at least 70°C, at least 80°C at least 90°C, at least 100°C, at least, 120°C at least 140°C, at least 160°C, at least 180°C, at least 200°C, at least 220°C, at least 240°C, at least 260°C or at least 280°C or at least 300°C, e.g., between 200 and 320°C, between 250 and 300°C, between 260 and 29O°C), and/or subjecting the same to greater than atmospheric pressure (e.g., at least lOpsi, at least 100 psi, at least 500 psi, at least lOOOpsi, at least SOOOpsi, at least 12000 psi, e.g., between 10 and 12000 psi). The pressure can be derived

from the autogenous pressure generated by températures, but also by added pressure from added gases such as nitrogen.

10. In some aspects xylose is transformed, e.g., chemîcally, to a furfural-derived product For example, transforming can comprise a chemical reaction selected from the group consisting of, a réduction reaction, a decarbonylation reaction, a dc-aromatization reaction, a polymerization reaction or combinations thereof. The furfural-derived product can be furfury! alcohol, methytetrahydrofuran, furan, tetrahydrofuran, furancarbox aldéhyde, polyffurfuryl alcohol), a polyether or combinations of these. The products include al! possible stereoisomers including those that can be obtained by chemical conversions of prochiral centers. For example, the conversion of furfuryl alcohol to tetrahydrofurfiiryl alcohol results in a product with a stereocenter at the alpha carbon. Thus, both stereoisomers can be made.

11. The processes disclosed herein include saccharification of the feedstock, and transportation of the feedstock from a remote location, e.g., where the feedstock is produccd or stored, to the manufacturing facility. In some cases, saccharification can take place partially or entirely during transport. In some implémentations, the process further indudes reducing the recalcitrance of the feedstock, before or during saccharification. The process may include the further steps of measuring the lignin content of the feedstock and determining whether pretreatment is needed and under what conditions based on the measured lignin content.

12. Many of the methods described herein can provide cellulosic and/or lignocellulosic materials that hâve, for example, a lower recalcitrance level, a lower molecular weight, a different level of functionalization and/or crystallinity relative to a native material. Many of the methods provide materials that can be more readily utilized by a variety of microorganisms, such as one or more homoacctogens or heteroacetogens (with or without enzymatic hydrolysis assistance) to produce uscful products, such as energy, fuels, foods, sugars (e.g., xylose and glucose), organic products (e.g., derived from sugars), and materials. In addition, to the furfura! product describe above examples of products that can be derived from sugars include, but are not limited to, polyethers, hydrogen, alcohols (e.g., monohydric alcohols or dihydric alcohols, such as éthanol, n-propanol, iso propanol, propylene glycol, 1,4-butanediol, 1,3-propanediol, methyl or ethyl esters of any of these alcohols),, biodiesel, organic acids (e.g„ acetic acid and/or lactic acid), hydrocarbons, co· products (e.g., proteins, such as cellulolytic proteins (enzymes) or single cell proteins), and mixtures of any of these. Other examples include carboxylic acids, such as acetic acid or butyric acid, salts of a carboxylic acid, a mixture of carboxylic acids and salts of carboxylic

acids and esters of carboxylic acids (e.g., methyl, ethyl and n-propyl esters), ketones, aldéhydes, alpha, beta unsaturated acids, such as acrylic acid and olefins, such as ethylene. . Other products include methyl acrylate, methyl méthacrylate, lactic acid, propionic acid, butyric acid, succinic acid, 3-hydroxypropionic acid, a sait of any of the acids and a mixture . of any of the acids and respective sales.

13. Other intermediates and products, including food and pharmaceutical products, are described in U.S. Application Serial No. 12/417,723, ftlcd April 3,2009; the full disclosure of which is hcreby incorporated by référencé herein in its entirety.

14. Some of the products obtained by the methods disclosed herein, can be used

I q directly or as a chemical intermediate to a solvent (e.g., for refining lubricating oils), as a fongicide, as a weed killer, as transportation fuels, nylon, lubricants, solvents, adhesives, medicines, resta and plastics. Many of the products obtained by the methods disclosed herein, such as éthanol or n-butanol, can be utilized directly as a foel or as a blend with other components, such as gasoline, for powering cars, trucks, tractors, ships or trains, e.g., as an I g internai combustion fuel or as a fuel cell feedstock Other products (e.g., oiganic acids, such as acetic acid and/or lactic acid) can be converted to other moieties (e.g., esters or anhydrides) that can be converted and utilized as a fuel. Many of the products obtained can also be utilized to power watercraft and aircraft, such as planes, e.g., having jet engines, or helicopters. In addition, the products described herein can be utilized for electrical power génération, e.g., in a conventional steam generating plant or in a fuel cell plant.

15. In one aspect, the invention features a method including providing a cellulose, hemicellulose and/or lignocellulose-containing feedstock (e.g., a biomass that includes polysaccharides of glucose xylose and other saccharides), mixing the feedstock with a solvent, such as water, and an agent, such as a saccharifying enzyme or acid, and optionally transport!ng the resulting mixture. Suitable acids include minerai acids, e.g., sulforic acid or hydrochloric acid.

16. In one aspect, the invention features a method for converting a sugar, including converting xylose to a product or intermediate, the xylose being obtained by treating biomass with any one or more of sonication, irradiation, pyrolysis, oxidation, and saccharification. For example the biomass can be irradiated and then saccharified.

17. The invention can feature xylose that is derived from the treated material by a process including hydrolysis of the treated materiaL Hydrolysis can include contacting the treated biomass material with at least one of an acid, a base, heat, microwave energy, sonie energy, mechanical energy, shearing, milling or an enzyme. For example, the xylose can be denved from contacting material treated with at least one of oxidation, sonication, irradiation,pyroly sis and/or with at least one xylanase.

18. The methods can include producing glucose. Optionally the glucose and xylose are separated prior to converting the xylose to a product. Also optionally, the glucose can be fermented and then the xylose converted to an intermediate or a product

19. The biomass used in the methods herein described can include hemicellulose (e.g., xylan, glucuronoxylan, arabinoxylan, glucomannan and xyloglucan). The biomass can be selected from one or more of paper, paper products, paper waste, wood, particlc board, sawdust, a gri cul tu ral waste, sewage, silage, grasses, wheat straw, rice hulls, bagasse, cotton, jute, hemp, flax, bamboo, sisal, abaca, straw, corn cobs, corn stover, alfalfa, hay, coconut hair, seaweed, algae, and mixtures thereof.

20. In some aspects the method includes irradiating the biomass prior to saccharification with between 10 and 200 Mrad. Optionally, the irradiating can be 10 and 75 Mrad, or 20 and 50 Mrad. Additionally, the irradiation is provided by an électron beam (e.g., from an électron accelerator), for example, with an électron beam power between 0.5 and 10 MeV (e.g., 0.5-2MeV). Typical électron beam irradiation device power can be 50 kW to 500 kW, or 75 kW to 250 kW.

21. The method can also include reducing the rccalcitrance of the feedstock prior to mixing the feedstock with the solvent and enzyme, e.g., by treating the feedstock with a physical treatment. The physical treatment can be, for example, selected from the group consisting of mechanical treatment, radiation, sonication, pyrolysis, oxidation, steam explosion, chemical treatment, and combinations thereof. Chemical treatment may include the use of a single chemical or two or more chemicals. Mechanical treatments include, for example, cutting, milling, pressing, grinding, shearing and chopping. Milling may include, for example, bail milling, hammer milling, or other types of milling.

22. The physical treatment can comprise any one or more of the treatments disclosed herein, applied alone or in any desired combination, and applied once or multiple times. In some cases, the physical treatment can comprise irradiating with ionizing radiation, alone or accompanied by mechanical treatment before and/or after irradiation. Irradiation can be performed, for example, with an électron beam.

23. In some cases, the method includes mechanically treating the feedstock to reduce the bulk density of the feedstock and/or increase the surface area of the feedstock, e.g., by performing a shearing process on the feedstock In some embodiments, after mechanical treatment the material has a bulk density of less than 0.6 g/cm³, 0.5 g/cm³,0.4 g/cm¹0.25

g/cm³, e.g., 0.20 g/cm³,0.15 g/cm³,0.10 g/cm³,0.05 g/cm³or less, e.g., 0.025 g/cm³. Bulk density is determined using ASTM D1895B. Bulk density is determined using ASTM D1895B. Briefly, the method involves filling a measuring cylinderof known volume with a sample and obtaining a weight of the sample. The bulk density is calculated by dividing the weight of the sample in grams by the known volume of the cylinder in cubic centimeters.

24. In yet another aspect, the invention featurcs a sugar concentrate made by saccharifying a dispersion that includes between about 10 percent by weight and about 90 percent by weight of a cellulosic or lignocellulosic material and converting this to another intermediate or product (e.g., furfural and furfural derived products).

25. In some implémentations, one or more components of the processing equipment, for example the mechanical treatment equipment, chemical (e.g., acid or base) treatment equipment, irradiai ing equipment, sonicaling, pyrolyzing, oxidizïng, steam exploding, saccharifying and/or fermenting equipment, or any of the other equipment described herein, may be portable, e.g., in the manner of the mobile processing equipment described in U.S. Patent Application Serial 12/374,549, and Publishcd International Application No. WO 2008/011598, the full disclosures of which are incorporated herein by reference.

26. Changïng a molecular structure of a material or molécules (e.g., molécules that are part of the material), as used herein, means to change the chemical bonding arrangement or conformation of the structure. For example, the change in the molecular structure can include changing the supramolecular structure of the material, oxidation of the material or molécule (e.g., adding oxygen or removing hydrogen), réduction of the material or molécules (e.g., hydrogénation), decarbonylation of a material or molécule, changing an average molecular weight, changing an average crystallïnity, changïng a surface area, changing a degree of polymerization, changing a porosity, changing a degree of branching, grafting on other materials, changing a crystalline domain size, or changing an overall domain size. A change in molecular structure may be effected using any one or more of the physical treatments described herein, alone or in any combination, applied once or repeatedly.

DESCRIPTION OF THE DRAWING

27. FIG. 1 is a diagram illustrating the enzymatic hydrolys is of cellulose and xylan to glucose and xylose respectively.

28. FIG. 2 is a flow diagram illustrating conversion of a fcedstock to various products.

29. FIG. 3 is a reaction scheme showing possible organic intermediates or products derived from a sugar.

DETAILED DESCRIPTION

30. Generally, this invention relates to processes for converting a cellulosic, starchy or lignocellulosic feedstock to useful products, organic sugar derived products (e.g., furfural and furfural-derived products).

I

31. Cellulosic, hemïcellulosic and lignocellulosic materials, such as biomass (e.g., plant biomass, animal biomass, paper, and municipal waste biomass), can be processed to a Iower level of rccalcitrance (if necessary) and converted into useful products such as those listed by way of example herein. Systems and processes are described herein that use readily abundant but often diffîcult to process cellulosic or lignocellulosic materials, e.g., municipal waste streams and waste paper streams, such as streams that include newspaper, kraft paper, corrugated paper or mixtures of these. Generally, if required, materials can be physically treated or processed using one or more of any of the methods described herein, such as mechanical treatment, chemical treatment, radiation, sonication, oxidation, pyrolysis and s team explosion.

32. In some cases, a manufacturing plant utilizi ng the processes described herein will obtain a variety of different feedstocks in the course of its operation. Some feedstocks may be relatively homogeneous in composition, for example a shipment of corn cobs, while other feedstocks may beof variable composition, for example municipal waste.

33. Feedstocks can include, for example, paper, paper products, wood, wood-related materials, particle board, grasses, rice hulls, bagasse, cotton, jute, hemp, flax, bamboo, wheat straw, sisal, abaca, straw, corn cobs, coconut haïr, algae, seaweed, altered celluloses, e.g., cellulose acetate, regenerated cellulose, and the like, or mixtures of any of these.

34. In some cases the biomass is a microbial material. Microbial sources include, but are not limited to, any naturally occurring or genetically modified microorganism or organism that contains or is capable of providing a source of carbohydrates (e.g., cellulose), for example, protists, e.g., animal protists (e.g., protozoa such as flagellâtes, amoeboids, ciliates, and sporozoa) and plant protists (e.g., algae such alveolates, chlorarachniophytes, cryptomonads, euglenids, glaucophytes, haptophytes, red algae, stramenopiles, and viridaeplantae). Other examples include seaweed, plankton (e.g., macroplankton, mesoplankton, microplankton, nanoplankton, picoplankton, and femptoplankton),

phytoplankton, bacteria (e.g., gram positive bacteria, gram négative bacteria, and extremophiles), yeast and/or mixtures of these. In some instances, microbial biomass can be obtained from natural sources, e.g., the océan, lakes, bodies of water, e.g., sait water or fresh water, or on land. Altematively or in addition, microbial biomass can be obtained from culture Systems, e.g., large scale dry and wet culture Systems.

35. In order to process the feedstock to a form that can be readily converted the cellulose in the feedstock is hydrolyzed to low molecular carbohydrates, such as sugars, by a saccharifying agent, e.g., by an enzyme, a process referred to as saccharification. In some implémentations, the saccharifying agent comprises an acid, e.g., a minerai acid. When an acid is used, co-products may be generated that are toxic to microorganisms, in which case the process can further include removing such co-products. Removal may be performed using an activated carbon, e.g., activated charcoal, or other suitable techniques.

36. The materials that include the cellulose are treated with the enzyme, e.g., by combining the material and the enzyme in a solvent, e.g., in an aqueous solution.

37. Enzymes and biomass-destroying organisais that break down biomass, such as the cellulose, hemicellulose and/or the lignin portions of the biomass, contain or manufacture various cellulolytic enzymes (cellulases), ligninases, xylanases, hemicellulases or various small molécule biomass-destroying métabolites. These enzymes may be a complex of enzymes that act synergistically to dégradé crystalline cellulose, xylan or the lignin portions of biomass. Examples of cellulolytic enzymes include: endoglucanases, cellobiohydrolases, and cellobiases (β-glucosidases). Referring to FIG. 1, a cellulosic substrate is initially hydrolyzed by endoglucanases at random locations producing oligomeric intermédiares. These intermediates are then substrates for exo-spütting glucanases such as cellobiohydrolase to produce cellobiose from the ends of the cellulose polymer. Cellobiose is a water-soluble 1,4-Iinked dimer of glucose. Finally cellobiase cleaves cellobiose to yield glucose. In the case of hemicellulose, xylanase (e.g., hemicellulase) act on this biopolymer and release xylose as one of the possible products. Hemicellulose is a class of complex polysaccharides, often components in plant cell walls, including xylose units and includes xylan, glucuronoxylan, arabinoxylan, glucomannan and xyloglucan. Xylanase are a class of enzymes the dégradé hemicellulose, e.g., dégradé beta 1,4-xylan bonds, into xylose, thus breaking down the hemicellulose.

38. Cellulase and/or xylanase are capable of degrading biomass and may be of fungal or bacterial origin. Suitable enzymes include cellulases and xylanases (hemicellulases) from the gênera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium,

Chrysosponum and Tnchoderma, and include species of Humicola, Coprinus, Thîelavia, Fusarium, Myceliophthora, Acremonium, Cephalosporium, Scytalidium, Pénicillium or Aspergillus (see, e.g., EP 458162), especialîy those produced by a strain selected from the species Humicola insolens (reclassified as Scytalidium thermophilum, see, e.g., U.S. Patent No. 4,435,307), Coprinus cinereus, Fusarium oxysporum, Myceliophthora thermophila, Meripilus giganteus, Thîelavia terrestris, Acremonium sp., Acremonium persicinum, Acremonium acremonium, Acremonium brachypenium, Acremonium dichromosporum, Acremonium obcîavatum, Acremonium pinkertoniae, Acremonium roseogriseum, Acremonium incoloratum, and Acremonium furatum; preferably from the species Humicola insolens DSM 1800, Fusarium oxysporum DSM 2672, Myceliophthora thermophila CBS 117.65, Cephalosporium sp. RYM-202, Acremonium sp. CBS 478.94, Acremonium sp. CBS 265.95, Acremonium persicinum CBS 169.65, Acremonium acremonium ABU 9519, Cephalosporium sp. CBS 535.71, Acremonium brachypenium CBS 866.73, Acremonium dichromosporum CBS 683.73, Acremonium obcîavatum CBS 311.74, Acremonium pinkertoniae CBS 157.70, Acremonium roseogriseum CBS 134.56, Acremonium incoloratum CBS 146.62, and Acremonium furatum CBS 299.7011. Cellulolytic enzymes may also be obtained from Chrysosponum, preferably a strain of Chrysosponum lucknowense. Additionally, Tnchoderma (particularly Trichoderma viride, Trichoderma reesei, and Tnchoderma koningii), alkalophïlic Bacillus (see, for example, U.S. Patent No. 3,844,890 and EP 458162), and Streptomyces (see, e.g., EP 458162) may be used.

39. The saccharification process can be partially or completely performed in a tank (e.g., a tank having a volume of at least 4000,40,000, or 400,000 L) in a manufacturing plant, and/or can be partially or completely performed in transit, e.g., in a rail car, tanker tnick, or in a supertanker or the hold of a ship. The time required for complété saccharification will dépend on the process conditions and the feedstock and enzyme used. If saccharification ls performed in a manufacturing plant under controlled conditions, the cellulose and hemicellulose may be substantially entïrely converted to glucose and xylose in about 12-96 hours. If saccharification is performed partially or completely in transit, saccharification may take longer.

40. It is generally preferred that the tank contents be mixed during saccharification, e.g., using jet mixing as described in U.S. Application No. 12/782,694, filed May 18,2010; the full disclosure of which is incorporated by référencé herein.

41. The addition of surfactants can enhance the rate of saccharification. Examples of surfactants include non-ionic surfactants, such as a Tween™ 20 or Tween™ 80 polyethylene glycol surfactants, ionic surfactants, or amphoteric surfactants.

42. It is generally preferred that the concentration of the resulting sugar (e.g. glucose and xylose) solution be relatively high, e.g., greatcr than 40%, or greater than 50,60,70,80, 90 or even greater than 95% by weight This reduces the volume to be shipped, and also inhibits microbial growth in the solution. Ilowever, lower concentrations may be used, in which case it may be désirable to add an antimicrobial additive, e.g., a broad spectrum antibiotic, in a low concentration, e.g., 50 to 150 ppm. Other suitable antibiotics include amphotericin D, ampicillin, chloramphenico], cîprofioxacin, gentamicin, hygromycin B, kanamycin, neomycin, penicillin, puromycin, streptomycin, Virginiamycin. Antibiotics will inhibit growth of microorganisms during transport and storage, and can be used at approprîate concentrations, e.g., between 15 and 1000 ppm by weight, e.g., between 25 and 500 ppm, or between 50 and 150 ppm. If desired, an antibiotic can be included even if the sugar concentration is relatively high.

43. A relatively high concentration solution can be obtained by limiting the amount of water added to the feedstock with the enzyme. The concentration can be controlled, e.g., by controliing how much saccharification takes place. For example, concentration can be increased by adding more feedstock to the solution. In order to keep the sugar that is being produced in solution, a surfactant can be added, e.g., one of those discussed above. Solubility can also be increased by incrcasing the température of the solution. For example, the solution can be maintained at a température of 40-50°C, 60-80°C, or even higher.

44. In some embodiments, the feedstock is processed to convert it to a convenient and concentrated solid material, e.g., in a powdered, granulate or particulate form, The concentrated material can be in a purified, or a raw,crude form. The concentrated form can hâve, for example, a total sugar concentration of between about 90 percent by weight and about 100 percent by weight, e.g., 92,94,96 or 98 percent by weight sugar. Such a form can be particularly cost effective to ship, e.g., to a bioprocessing facility, such as a biofuel manufacturing plant. Such a form can also be advantageous to store and handle, easier to manufacture and providing an option to the biorcfinery as to which products to manufacture.

45. In some instances, the powdered, granulate or particulate material can also include one or more of the materials, e.g., additives or chemicals, described herein, such as a nutrient.

a nitrogen source, e.g,, urea or a peptone, a surfactant, an enzyme, or any microorganism described herein. In some instances, ail materials needcd for a bio-process are combined in

the powdered, granulate or particulate material. Such a form can be a particularly convenient form for transport!ng to a remote bioprocessing facility, such as a remote biofuels manufacturing facility. Such a form can also be advantageous to store and handle.

46. In some instances, the powdered, granulate or particulate material (with or without added materials, such as additives and chemicals) can be treated by any of the physical treatments described herein. For exampie, irradiating the powdered, granulate or particulate material can increase its solubility and can sterilize the material so that a bioprocessing facility can integrate the material into their process directly as may be required.

47. In certain instances, the powdered, granulate or particulate material (with or without added materials, such as additives and chemicals) can be carried in a structure or a carrier for case of transport, storage or handling. For example, the structure or carrier can inciude or incorporate a bag or liner, such as a degradable bag or liner. Such a form can be particularly use fui for adding directly to a bioprocess System.

48. Referring to FIG. 2, a process for manufacturing a products from a biomass feedstock. For exampie, the biomass is converted by saccharification, bioprocessing and a chemical process, e.g., saccharification to xylose and glucose, fermentation of the glucose to an alcohol (e.g., éthanol), conversion of the un-fermented xylose to a product by a chemical réaction. The process, can inciude, for example, optionally mechanically treating the feedstock (step 210), before and/or after this treatment, optionally treating the feedstock with another physical treatment, for example irradiation, to further reduce its recalcitrance (step

212), saccharifying the feedstock to form a sugar solution (e.g., glucose and xylose) (step 214), transporting, e.g., by pipeline, railcar, truck or barge, the solution (or the feedstock, enzyme and waier, if saccharification is performed en route) to a manufacturing plant (step 216), and then bio-processïng the treated feedstock to produce a desired product such as an alcohol(step 218), further processing the unfermented xylose from the fermented solution to intermediates and products by chemical reactions, e.g., by steps induding hydrogénation, déhydration, polymerization and/or oxidation (step 220). The indïvidual steps of this process will be described in detail below. If desired, the steps of measuring lignin content (step 222) and setting or adjusting process parameters (step 224) can be performed at various stages of the process, for example just prior to the process step(s) used to change the structure of the feedstock, as shown. If thèse steps are included, the process parameters are adjusted to compensate for variability in the lignin content of the feedstock, as described in U.S. Patent 8,415,122, the complété disclosure of which is incorporated herein by référencé.

49. The manufacturing plant can be, for exampie, an existing starch-based or sugarbased éthanol plant or one that has been retrofïtted by removing or decommissïoning the equipment upstream from the bïo-processing System (which In a typical éthanol plant generally includes grain receiving equipment, a hammer mill, a slurry mixer, cooking equipment and liquéfaction equipment). Thus, the feedstock received by the plant is input directiy into the fermentation equipment.

BIOMASS MATERIALS

50. The biomass can be, e.g., a cellulosic, hemicellulosic or lignocellulosic material. Such materials include paper and paper products (e.g., polycoated paper and Kraft paper), wood, wood-related materials, e.g., paiticle board, grasses, rice hulls, bagasse, jute, hemp, flax, bamboo, sisal, abaca, straw, com cobs, wheat, wheat straw, coconut haïr; and materials hîgh in -cellulose content, e.g., cotton. Feedstocks can be obtained from virgin scrap textile materials, e.g., remuants, post-consumer waste, e.g., rags. When paper products are used they can be virgin materials, e.g., scrap virgin materials, or they can be post-consumer waste. Aside from virgin raw materials, post-consumer, industrial (e.g., offal), and processing waste (e.g., effluent from paper processing) can also be used as fiber sources. Biomass feedstocks can also be obtained or derived from human (e.g._t sewage), animal or plant wastes. Additional cellulosic and lignocellulosic materials hâve been described in U.S. Patent Nos. 6,448,307,6,258,876,6,207,729,5,973,035 and 5,952,105.

51. In some embodiments, the biomass material includes a carbohydrate that is or includes a material having one or more β- 1,4-linkages and having a number average molecular weight between about 3,000 and 50,000. Such a carbohydrate is or includes cellulose (Π), and xylan (ΙΠ) and which are derived from (β-glucose IV) and xylose respectively through condensation of p(l,4)-glycosidic bonds or by condensation of β-Dxylose units. This linkage contrasta itself with that for a(l,4)-glycosidic bonds présent in starch and other carbohydrates.

OH

1,4^-Xylan

III

β- Glucose

IV

52. Starchy materials include starch itself, e.g., coin starch, wheat starch, potato starch or rice starch, a dérivative of starch, or a material that includes starch, such as an edible food product or a crop. For example, the starchy material can be arracacha, buckwheat, banana, barlcy, cassava, kudzu, oca, sago, sorghum, regular household potatoes, sweet potato, taro, yams, or one or more beans, such as favas, lentils or peas. Blends of any two or more starchy materials are also starchy materials.

53. In some cases the biomass is a microbial material. Microbial sources include, but arc not limited to, any naturally occurring or genetically modified microorganism or organîsm that contains or is capable of providing a source of carbohydrates (e.g., cellulose), ₃ for example, protists, e.g., anima! protists (e.g., protozoa such as flagellâtes, amoeboids, ciliates, and sporozoa) and plant protists (e.g., algae such alveolates, chlorarachniophytes, cryptomonads, euglenids, glaucophytes, haptophytes, red algae, stramenopiles, and viridaeplantae). Other examples include seaweed, plankton (e.g., macroplankton, mesoplankion, microplankton, nanoplankton. picoplankton, and femptoplankton), phytoplankton, bacteria (e.g., gram positive bacteria, gram négative bacteria, and extremophiles), yeast and/or mixtures of these. In some instances, microbial biomass can be obtained from naturel sources, e.g., the océan, lakes, bodïes of water, e.g., sait water or fresh water, or on land. Altematively or in addition, microbial biomass can be obtained from culture Systems, e.g., large scale dry and wet culture Systems.

PHYSICAL TREATMENT

54. Physical treatment processes can include one or more of any of those described herein, such as mechanical treatment, chemical treatment, irradiation, sonication, oxidation,

pyrolysis or steam explosion. Treatment methods can be used in combinations of two, three, four, or even ail of these technologies (in any order). When more than one treatment methods is used, the methods can be applied at the same time or at different times. Other processes that change a molecular structure of a biomass feedstock may also be used, alone or in combination with the processes disclosed herein.

55. One or more of the treatment processes described below may be included in the recalcitrance reducing opéra tin g System discussed above. Altematively, or in addition, other processes for reducing recalcitrance may be included.

Mechanical Treatments

56. In some cases, methods can include mechanically treating the biomass feedstock. Mechanical treatments include, for example, cutting, milling, pressing, grinding, shearing and chopping. Milling may include, for example, bail milling, hammer milling, rotor/stator dry or wet milling, or other types of milling. Other mechanical treatments include, e.g., stone grinding, cracking, mechanical ripping or tearing, pin grinding or air attrition milling.

57. Mechanical treatment can t» advantageous for “opening up,” “stressing breakîng and shattering the cellulosic or lignocellulosic materiais, making the cellulose of the materiais more susceptible to chain scission and/or réduction of crystallinity. The open materiais can also be more susceptible to oxidatlon when irradiated. .

58. In some cases, the mechanical treatment may include an initial préparation of the feedstock as received, e.g., size réduction of materiais, such as by cutting, grinding, shearing, pulverizing or chopping. For example, in some cases, loose feedstock (e.g., recycled paper, starchy materiais, or switchgrass) is prepared by shearing or shredding.

59. Altematively, or in addition, the feedstock material can be physically treated by one or more of the other physical treatment methods, e.g., chemical treatment, radiation, sonication, oxidation, pyrolysis or steam explosion, and then mechanically treated. This sequence can t» advantageous since materiais treated by one or more of the other treatments, e.g., irradiation or pyrolysis, tend to be more brittle and, therefore, it may be easier to further change the molecular structure of the material by mechanical treatment.

60. In some embodiments, the feedstock material is in the form of a fibrous material, and mechanical treatment includes shearing to expose fibers of the fibrous material. Shearing can t» performed, for example, using a rotary knife cutter. Other methods of mechanically treating the feedstock include, for example, milling or grinding. Milling may be performed using, for example, a hammer mil], bail mill, colloid mill, conical or cône mill, disk mill, edge mill, Wiley mill or grist mill. Grinding may be performed using, for example, a stone

grinder, pin grinder, coffee grinder, or burr grinder. Grinding may be provided, for example, by a reciprocating pin or other élément, as is the case in a pin mill. Other mechanical treatment methods include mechanical ripping or tearing, other methods that apply pressure to the fibers, and air attrition milling. Suitable mechanical treatments further include any other technique that changes the molecular structure of the feedstock.

61. If desired, the mechanically treated material can be passed through a screen, e.g., having an average opening size of 1.59 mm or less (1/16 inch, 0.0625 inch). In some embodiments, shearing, or other mechanical treatment, and screening are performed concurrently. For example, a rotary knife cutter can be used to concuirently shear and screen the feedstock. The feedstock is sheared between stationary blades and rotating blades to provide a sheared material that passes through a screen, and is captured in a bin. The bin can hâve a pressure below nominal atmospheric pressure, e.g., at least 10 percent below nominal atmospheric pressure, e.g., at least 25 percent below nominal atmospheric pressure, at least 50 percent below nominal atmospheric pressure, or at least 75 percent below nominal atmospheric pressure. In some embodiments, a vacuum source is utilized to maintain the bin below nominal atmospheric pressure.

62. The cellulosic or lignocellulosic material can be mechanically treated in a dry state (e.g., having little or no free water on its surface), a hydrated state (e.g., having up to ten percent by weight absorbed water), or in a wet state, e.g., having between about 10 percent and about 75 percent by weight water. The fiber source can even be mechanically treated while partially or fully submerged under a liquid, such as water, éthanol or isopropanol.

63. The cellulosic or lignocellulosic material can also be mechanically treated under a gas (such as a stream or atmosphère of gas other than air), e.g., oxygen or nitrogen, or steam.

64. If desired, lignin can be removed from any of the feedstock matériels that include lignin. Also, to aid in the breakdown of the materials that include cellulose, the material can be treated prior to or during mechanical treatment or irradiation with heat, a chemical (e.g., minerai acid, base or a strong oxidizer such as sodium hypochlorite) and/or an enzyme. For example, grinding can be performed in the presence of an acid.

65. Mechanical treatment Systems can be configured to produce streams with spécifie characteristics such as, for example, spécifie maximum sizes, spécifie length-to-width, or spécifie surface areas ratios. Mechanical treatment can increase the rate of reactions or reduce the processing time required by opening up the materials and making them more accessible to processes and/or reagents, such as reagents in a solution. The bulk density of feedstocks can also be controlled using mechanical treatment For example, in some embodiments, after mechanical treatment the material has a bulk density of less than 0.25 g/cm3, e.g., 0.20 g/cm3,0.15 g/cm3,0.10 g/cm3,0.05 g/cm3 or less, e.g., 0.025 g/cm3. Bulk density is determined using ASTM D1895B. Briefly, the method involves fïlling a measuring cylinder of known volume with a sample and obtaining a weight of the sample. The bulk density is calculated by dividing the weight of the sample in grams by the known volume of the cylinder in cubic centimeters.

66. If the feedstock is a fibrous material the fibers of the mechanically treated material can hâve a relatively large average length-to-diameter ratio (e.g., greater than 20-to-l), even if they hâve been sheared more than once. In addition, the fibers of the fibrous materials described herein may hâve a relatively narrow length and/or length-to-diameter ratio distribution.

67. As used herein, average fiber widths (e.g., diameters) are those determined optically by randomly selecting approximately 5,000 fibers. Average fiber lengths are corrected length-weighted lengths. BET (Brunauer, Emmett and Teller) surface areas are multi-point surface areas, and porosities are those determined by mercury porosimetry.

68. If the feedstock is a fibrous material the average length-to-diameter ratio of fibers of the mechanically treated material can be, e.g., greater than 8/1, e.g., greater than 10/1, greaterthan 15/1, greater than 20/1, greater than 25/1, or greater than 50/1. An average fiber length of the mechanically treated material can be, e.g., between about 0.5 mm and 2.5 mm, e.g., between about 0.75 mm and 1.0 mm, and an average width (e.g., diameter) of the second fibrous material 14 can be, e.g., between about 5 pm and 50 pm, e.g., between about 10 pm and 30 pm.

69. In some embodiments, if the feedstock is a fibrous material a standard déviation of the fiber length of the mechanically treated material is less than 60 percent of an average fiber length of the mechanically treated material, e.g., less than 50 percent of the average length, less than 40 percent of the average length, less than 25 percent of the average length, less than 10 percent of the average length, less than 5 percent of the average length, or even less than 1 percent of the average length.

70. In some embodiments, a BET surface area of the mechanically treated material is greater than 0.1 m²/g, e.g., greater than 0.25 m²/g, greater than 0.5 m²/g, greater than 1.0 m²/g, greater than 1.5 m²/g, greater than 1.75 m²/g, greater than 5.0 m²/g, greater than 10 m²/g, greater than 25 m²/g, greater than 35 m²/g, greater than 50 m²/g, greater than 60 m²/g,

greater than 75 m²/g, greater than 100 m2/g m²/g, greater than 150 m²/g, greater than 200 m²/g, or even greater than 250 m²/g.

71. A porosity of the mechanically treated material can be, e.g., greater than 20 percent, greater than 25 percent, greater than 35 percent, greater than 50 percent, greater than 60 percent, greater than 70 percent, greater than 80 percent, greater than 85 percent, greater than 90 percent, greater than 92 percent, greater than 94 percent, greater than 95 percent, greater than 97.5 percent, greater than 99 percent, or even greater than 99.5 percent.

72. In some situations, it can be désirable to prépare a low bulk density material, densify the material (e.g., to make it easîer and less costly to transport to another site), and then revert the material to a lower bulk density state. Densifïed materials can be processed by any of the methods described herein, or any material processed by any of the methods described herein can be subsequently densifïed, e.g., as disclosed in WO 2008/073186.

Radiation Treatment

73. One or more radiation processing sequences can be used to process the feedstock, and to provide a structurally modified material which fonctions as input to further processing steps and/or sequences. Irradiation can, for example, reduce the molecular weight and/or crystallinity of feedstock. In some embodiments, energy deposited in a material that rcleases an électron from its alomic orbital is used to irradiate the materials. The radiation may be provided by 1) heavy charged particies, such as alpha particies or protons, 2) électrons, produced, for example, in beta decay or électron beam accelerators, or 3) electromagnetic radiation, for example, gamma rays, x rays, or ultraviolet rays. In one approach, radiation produced by radioactive substances can be used to irradiate the feedstock. In some embodiments, any combination in any order or concurrently of (1) through (3) may be utilized. In another approach, electromagnetic radiation (e.g., produced using électron beam emitters) can be used to irradiate the feedstock The doses applied dépend on the desired effect and the particular feedstock. For example, high doses of radiation can break chemical bonds within feedstock components. In some instances when chain scission is désirable and/or polymer chain functionalization is désirable, particies heavier than électrons, such as protons, hélium nuclei, argon ions, silicon ions, néon ions, carbon ions, phosphores ions, oxygen ions or nitrogen ions can be utilized. When ring-opening chain scission is desired, positively charged particies can be utilized for their Lewis acid properties for enhanced ringopening chain scission. For example, when maximum oxidation is desired, oxygen ions can be utilized, and when maximum nitration is desired, nitrogen ions can be utilized.

74. In one method, a first material that is or includes cellulose having a first number average molecular weight (first Mn) is irradiated, e.g., by treatment with ïonizing radiation (e.g., in the form of gamma radiation, X-ray radiation, 100 nm to 280 nm ultraviolet (UV) light, a beam of électrons or other charged particlcs) to provide a second material that includes cellulose having a second number average molecular weight (second Mn) lower than the first number average molecular weight The second material (or the first and second material) can be combined with a microorganism (with or without enzyme treatment) that can utilize the second and/or first material or its constituent sugars or lignin to produce a fuel or other useful product that is or includes hydrogen, an alcohol (e.g., éthanol or butanol, such as n-, sec- or t-butanol), an organic acid, a hydrocarbon or mixtures of any of these.

75. Since the second material has cellulose having a reduced molecular weight relative to the first material, and in some instances, a reduced crystallinity as well, the second material is generally more dispersible, swellable and/or soluble in a solution containing a microorganism and/or an enzyme. These properties make the second material more susceptible to chemical, enzymatic and/or biological attack relative to the first material, which can greatly improve the production rate and/or production level of a desired product. e.g., éthanol. Radiation can also sterilize the materials or any media needed to bioprocess the material.

76. In some embodiments, the second number average molecular weight (second Mn ) is lower than the first number average molecular weight (first Mn ) by more than about 10 percent, e.g., 15,20,25,30,35,40,50 percent, 60 percent, or even more than about 75 percent.

77. In some instances, the second material has cellulose that has as crystallinity (C2) that is lower than the crystallinity (C 1) of the cellulose of the first material. For example, (C2) can be lower than (Cl) by more than about 10 percent, e.g., 15,20,25,30,35,40, or even more than about 50 percent

78. In some embodiments, the starting crystallinity index (prior to irradiation) is from about 40 to about 87.5 percent, e.g., from about 50 to about 75 percent or from about 60 to about 70 percent, and the crystallinity index after irradiation is from about 10 to about 50 percent, e.g., from about 15 to about 45 percent or from about 20 to about 40 percent However, in some embodiments, e.g., after extensive irradiation, it is possible to hâve a crystallinity index of lower than 5 percent. In some embodiments, the material after irradiation is substantially amorphous.

79. In some embodiments, the starting number average molecular weight (prior to irradiation) is from about 200.000 to about 3,200,000, e.g., from about 250,000 to about

1,000,000 or from about 250,000 to about 700,000, and the number average molecular weight after irradiation is from about 50,000 to about 200,000, e.g., from about 60,000 to about 150,000 or from about 70,000 to about 125,000. However, in some embodiments, e.g., after extensive irradiation, it is possible to hâve a number average molecular weight of less than about 10,000 or even less than about 5,000.

80. In some embodiments, the second material can hâve a level of oxidation (02) that is higher than the level ofoxidation (Ο I ) of the first material. A higher level of oxidation of the material can aid in its dispersability, swellability and/or solubility, further enhancing the material's susceptibility to chemical, enzymatic or biologicai attack. In some embodiments, to increase the level of the oxidation of the second material relative to the first material, the irradiation is performed under an oxidizing environment, e.g., under a blanket of air or oxygen, producing a second material that is more oxidized than the first material. For example, the second material can hâve more hydroxyl groups, aldéhyde groups, ketone groups, ester groups or carboxylic acid groups, which can increase its hydrophilicity.

Ionizing Radiation

81. Each form of radiation ionizes the carbon-containing material via particular interactions, as determined by the energy of the radiation. Heavy charged particles primarily ionize matter via Coulomb scattering; furthermore, these interactions produce energetic électrons that may further ionize matter. Alpha particles are identicaï to the nucléus of a hélium atom and are produced by the alpha decay of various radioactive nuclei, such as isotopes of bismuth, polonium, astatine, radon, francium, radium, several actinides, such as actinium, thorium, uranium, neptunium, curium, californium, américium, and plutonium.

82. When particles are utilized, they can be neutral (uncharged), positively charged or negatively charged. When charged, the charged particles can bear a single positive or négative charge, or multiple charges, e.g., one, two, three or even four or more charges. In instances in which chain scission is desired, positively charged particles may be désirable, in part due to their acidic nature. When particles are utilized, the particles can hâve the mass of a resting électron, or greater, e.g., 500, i 000,1500,2000,10,000 or even 100,000 limes the mass of a resting électron. For example, the particles can hâve a mass of from about I atomic unit to about 150 atomic units, e.g., from about I atomic unit to about 50 atomic units, or from about 1 to about 25, e.g., 1,2,3,4,5,10,12 or 15 amu. Accelcrators used to accelerate the particles can be electrostatic DC, elcctrodynamic DC, RF lincar, magnetic induction

linear or continuons wave. For example, cyclotron type accelerators are available from IBA, Belgium, such as the Rhodotron® E-beam Accelerator System, while DC type accelerators are available from RDI, now IBA Industrial, such as the Dynamitron®. Ions and ion accelerators are discussed in Introductoiy Nuclear Physics, Kenneth S. Krane, John Wiley & Sons, Inc. (1988), Krsto Prelec, ΡΙΖΙΚΑ B 6 (1997) 4,177-206, Chu, William T., “Overview of Light-Ion Beam Therapy” Columbus-Ohio, ICRU-IAEA Meeting, 18-20 March 2006, Iwata, Y. et al., “Altemating-Phase-Focused ΠΙ-DTL for Ileavy-Ion Medical Accelerators” Pioceedings of EPAC 2006, Edinburgh, Scotland and Leaner, C.M. et al., “Status of the Superconducting ECR Ion Source Venus” Proceedings of EPAC 2000, Vienna, Austria.

83. Gamma radiation has the advantage of a significant pénétration depth into a variety of materials. Sources of gamma rays include radioactive nuclei, such as isotopes of cobalt, calcium, technetium, chromium, gallium, indium, iodine, iron, krypton, samarium, sélénium, sodium, thallium, and xénon.

84. Sources of x rays include électron beam collision with métal targets, such as tungsten or molybdenum or alloys, or compact light sources, such as those produced commercial)y by Lyncean Technologies, Inc.

85. Sources for ultraviolet radiation include deuterium or cadmium lamps.

86. Sources for infrared radiation include sapphire, zinc, or selenide window ce ramie lamps.

87. Sources for microwaves include klystrons, Slevin type RF sources, or atom beam sources thatemploy hydrogen, oxygen, or nitrogen gases.

88. In some embodiments, a beam of électrons is used as the radiation source. A beam of électrons has the advantages of high dose rates (e.g., 1,5, or even 10 Mrad per second), high throughput, less containment, and less confinement equipment Electrons can also be more efficient at causing chain scission. In addition, électrons having energies of 410 MeV can hâve a pénétration depth of 5 to 30 mm or more, such as 40 mm. Optionally, the électrons having energies of 0.8 to 2 MeV may be used.

89. Electron beams can be generated, e.g., by electrostatic generators, cascade generators, transformer generators, low energy accelerators with a scanning System, low energy accelerators with a linear cathode, linear accelerators, and pulsed accelerators. Electrons as an ionizing radiation source can be useful, e.g., for relatively thin piles of materials, e.g., less than 0.5 inch, e.g., less than 0.4 inch, 0.3 inch, 0.2 inch, or less than 0.1 inch. In some embodiments, the energy of each électron of the électron beam is from about

0.3 MeV to about 2.0 MeV (million électron volts), e.g., from about 0.5 MeV to about 1.5 MeV, or from about 0.7 MeV to about 1.25 MeV.

90. Electron beam irradiation devices may be procured commercially from Ion Beam Applications, Louvain-la-Neuve, Belgium or the Titan Corporation, San Diego, CA. Typical électron energies can be 1 MeV, 2 McV, 4.5 MeV, 7.5 MeV, or 10 MeV. Typical électron beam irradiation device power can be 1 kW, 5 kW, 10 kW, 20 kW, 50 kW, 100 kW. 250 kW, or 500 kW. The level of depolymerization of the feedstock dépends on the électron energy used and the dose applied, while exposure time dépends on the power and dose. Typical doses may take values of 1 kGy, 5 kGy, 10 kGy, 20 kGy, 50 kGy, 100 kGy, or 200 kGy.

Ion Partide Beams

91. Partides heavier than électrons can be utilized to irradiate materials, such as carbohydrates or materials that include carbohydrates, e.g., cellulosic materials, lignocellulosic materials, starchy materials, or mixtures of any of these and others described herein. For example, protons, hélium nuclei, argon ions, silicon ions, néon ions, carbon ions, phosphorus ions, oxygen ions or nitrogen ions can be utilized. In some embodiments, partides heavier than électrons can induce higher amounts of chain scission (relative to lighter partides). In some instances, positively charged partides can induce higher amounts of chain scission than negatively charged partides due to their acidity.

92. Heavier partide beams can be generated, e.g., using linear accéléra tors or cyclotrons. In some embodiments, the energy of each partide of the beam is from about 1.0 MeV/atomic unit to about 6,000 MeV/atomic unit, e.g., from about 3 MeV/ atomic unit to about 4,800 MeV/atomic unit, or from about 10 MeV/atomic unit to about 1,000 MeV/atomic unit

93. In certain embodiments, ion beams used to irradiate carbon-containing materials, e.g., biomass materials, can include more than one type of ion. For example, ion beams can indude mixtures of two or more (e.g., three, four or more) different types of ions. Exemplary mixtures can indude carbon ions and protons, carbon ions and oxygen ions, nitrogen ions and protons, and iron ions and protons. More generally, mixtures of any of the ions discussed herein (or any other ions) can be used to form irradiating ion beams. In particular, mixtures of relatively light and relatively heavier ions can be used in a single ion beam.

94. In some embodiments, ion beams for irradiating materials include positivelycharged ions. The positively charged ions can indude, for example, positively charged hydrogen ions (e.g., protons), noble gas ions (e.g., hélium, néon, argon), carbon ions, nitrogen ions, oxygen ions, silicon atoms, phosphorus ions, and métal ions such as sodium ions,

calcium ions, and/or iron ions. Without wtshing to be bound by any theory, it is believed that such positively-charged ions behave chemically as Lewis acid moieties when exposed to materials, initiating and sustaining cationic ring-opening chain scission reactions in an oxidative environment.

95. In certain embodiments, ion beams for irradiating materials include negativelycharged ions. Negatively charged ions can include, for example, negatively charged hydrogen ions (e.g., hydride ions), and negatively charged ions of various relatively electronegative nuclei (e.g., oxygen ions, nitrogen ions, carbon ions, silicon ions, and phosphorus ions). Without wishing to be bound by any theory, it is believed that such negatively-charged ions behave chemically as Lewis base moieties when exposed to materials, causing anionic ring-opening chain scission reactions in a reducing environment

96. In some embodiments, beams for irradiating materials can include neutral atoms. For example, any one or more of hydrogen atoms, hélium atoms, carbon atoms, nitrpgen atoms, oxygen atoms, néon atoms, silicon atoms, phosphorus atoms, argon atoms, and iron atoms can be included in beams that are used for irradiation of biomass materials. In general, mixtures of any two or more of the above types of atoms (e.g., three or more, four or more, or even more) can be présent in the beams.

97. In certain embodiments, ion beams used to irradiate maierials include singlycharged ions such as one or moreof II+, II-, IIe+, Ne+, Ar+, C+, C-, O+, Ο-, N+, N-, Si+, Si, P+, P-, Na+, Ca+, and Fe+. In some embodiments, ion beams can include multiply-charged ions such as one or more of C2+, C3+, C4+, N3+, N5+, N3-, O2+, 02-, 022-, Si2+, Si4+, Si2-, and Si4-. In general, the ion beams can also include more complex polynuclear ions that bear multiple positive or négative charges. In certain embodiments, by virtue of the structure of the polynuclear ion, the positive or négative charges can be effectively dïstributed over substantially the entire structure of the ions. In some embodiments, the positive or négative charges can be somewhat localized over portions of the structure of the ions. Electromagnetlc Radiation

98. In embodiments in which the inadiating is performed with electromagnetic radiation, the electromagnetic radiation can hâve, e.g., energy per photon (in électron volts) of greater than 10¹ eV, e.g., greater than ΙΟ³, ΙΟ⁴, ΙΟ⁵,10⁶, or even greater than 10^TeV. In some embodiments, the electromagnetic radiation has energy per photon of between 10⁴ and 10^T, e.g., between 10’ and 10⁶ eV. The electromagnetic radiation can hâve a frequency of, e.g., greater than 10¹⁶ Hz, greater than 10^I7IIz, 10™, ΙΟ™, 1O²⁰, or even greater than 10²¹ Hz.

In some embodiments, the electromagnetic radiation has a frequency of between 10¹⁸ and 10²²IIz, e.g., between 10¹’ to 10²¹ Hz.

99. In some embodiments, the irradiating (with any radiation source or a combination of sources) is performed until the material receives a dose of at least 0.25 Mrad, e.g., at least 1.0 Mrad, at least 23 Mrad, at least 5.0 Mrad, or at least 10.0 Mrad. In some embodiments, the irradiating is performed until the material receives a dose of between 1.0 Mrad and 6.0 Mrad, e.g., between 1.5 Mrad and 4.0 Mrad.

100. In some embodiments, the irradiating is performed at a dose rate of between 5.0 and 1500.0 kilorads/hour, e.g., between 10.0 and 750.0 kilorads/hour or between 50.0 and 350.0 kilorads/hours.

101. In some embodiments, two or more radiation sources are used, such as two or more ionizing radiations. For example, samples can be treated, in any order, with a beam of électrons, followed by gamma radiation and UV light having wavelengths from about 100 nm to about 280 nm. In some embodiments, samples are treated with three ionizing radiation sources, such as a beam of électrons, gamma radiation, and energetic UV light

Sonication

102. One or more sonication processing sequences can be used to process materials from a wide variety of different sources to extract useful substances from the materials, and to provide partially degraded organic material (when organic materials are employed) which fonctions as input to further processing steps and/or sequences. Sonication can reduce the molecular weight and/or crystallinity of the materials, such as one or more of any of the materials described herein, e.g., one or more carbohydrate sources, such as cellulosic or lignocellulosic materials, or starchy materials.

103. In one method, a first material that includes cellulose having a first number average molecular weight (M_ni) is dispersed in a medium, such as water, and sonicated and/or otherwise cavitated, to provide a second material that includes cellulose having a second number average molecular weight (M_n2) lower than the first number average molecular weight. The second material (or the first and second material in certain embodiments) can be combined with a microorganism (with or without enzyme treatment) that can utilize the second and/or first material to produce a fuel that ts or includes hydrogen, an alcohol, an organic acid, a hydrocarbon or mixtures of any of these.

104. Since the second material has cellulose having a reduced molecular weight relative to the first material, and in some instances, a reduced crystallinity as well, the second material is generally more dispersible, swellable, and/or soluble in a solution contammg the microorganism, e.g., at a concentration of greater than 106 microorganisms/mL These properties make the second material more susceptible to chemical, enzymatic, and/or microbial attack relative to the first material, which can grcally improve the production rate and/or production level of a desired product, e.g., éthanol. Sonication can also sterilize the materiais, but should not be used while the microorganisms are supposed to be alive.

105. In some embodiments, the second number average molecular weight (second M_n ) is lower than the first number average molecular weight (first M, ) by more than about 10 percent, e.g., 15,20,25,30,35,40,50 percent, 60 percent, or even more thon about 75 percent.

106. In some instances, the second material has cellulose that has as crystallinity (C2) that is lower than the crystallinity (Cl) of the cellulose of the first material For example, (C2) can be lower than (Cl) by more than about 10 percent, e.g., 15,20, 25,30,35, 40, or even more than about 50 percent.

107. In some embodiments. the starting crystallinity index (prior to sonication) is from about 40 to about 87.5 percent, e.g., from about 50 to about 75 percent or from about 60 to about 70 percent, and the crystallinity index after sonication is from about 10 to about 50 percent, e.g., from about 15 to about 45 percent or from about 20 to about 40 percent.

lowever, in certain embodiments, e.g., after extensive sonication, it is possible to hâve a crystallinity index of lower than 5 percent In some embodiments, the material after sonication is substantially amorphous.

108. In some embodiments. the starting number average molecular weight (prior to sonication) is from about 200,000 to about 3,200,000. e.g., from about 250,000 to about

1,000,000 or from about 250,000 to about 700,000, and the number average molecular weight after sonication is from about 50,000 to about 200,000, e.g., from about 60,000 to about 150,000 or from about 70,000 to about 125,000. Ilowever, in some embodiments, e.g., after extensive sonication, it is possible to hâve a number average molecular weight of less than about 10.000 or even less than about 5,000.

109. In some embodiments, the second material can hâve a level of oxidation (02) that is higher than the level of oxidation (01) of the first material. A higher level of oxidation of the material can aid in its dispersability, swellability and/or solubili ty, further enhancing the material's susceptibility to chemical, enzymatic or microbial attack In some embodiments, to increase the level of the oxidation of the second material relative to the first material, the sonication is performed in an oxidizing medium, producïng a second material that is more

oxidized than the first material. For example, the second material can hâve more hydroxyl groups, aldéhyde groups, ketone groups, ester groups or carboxylic acid groups, which can increase its hydrophilicity.

110, In some embodiments, the sonication medium is an aqueous medium. If desired, the medium can include an oxidant, such as a peroxide (e.g., hydrogen peroxide), a dispersing agent and/or a buffer. Examples of dispersing agents include ionic dispersing agents, e.g., sodium lauryl sulfate, and non-ionic dispersing agents, e.g., poly(ethy!ene glycol).

111. In other embodiments, the sonication medium is non-aqueous. For example, the sonication can be performed in a hydrocarbon, e.g., toluene or heptane, an ether, e.g., diethyl ether or tetrahydrofuran, or even in a îiquefied gas such as argon, xénon, or nitrogen

Pyrolysis of the Feedstock Materials

112. One or more pyrolysis processing sequences can be used to process carboncontaining materials from a wide variety of different sources to extract useful substances from the materials, and to provide partially degraded materials which fonction as input to further processing steps and/or sequences.

113. In one example, a first material that includes cellulose having a first number average molecular weight (MN1) is pyrolyzed, e.g., by heating the first material in a tube fomace (in the presence or absence of oxygen), to provide a second material that includes cellulose having a second number average molecular weight (MN2) lower than the first number average molecular weighL The second material (or the first and second material in certain embodiments) is/are combined with a microorganism (with or without acid or enzymatic hydrolysis) that can utilize the second and/or first material to produce a fuel that is or includes hydrogen. an alcohol (e.g., éthanol or butanol, such as n-, sec or t-butanol), an organic acid, a hydrocarbon or mixtures of any of these.

114. Since the second material has cellulose having a reduced molecular weight relative to the first material, and in some instances, a reduced crystallinity as well, the second material is generally more dispersible, swellable and/or soluble in a solution containing the microorganism, e.g., at a concentration of greater than 106 microorganisms/mL. These properties make the second material more susceptible to chemical, enzymatic and/or microbial attack relative to the first material, which can greatly improve the production rate and/or production level of a desired product, e.g., éthanol. Pyrolysis can also sterilize the first and second materials.

115. In some embodiments, the second number average molecular weight (second M_n ) is lower than the first number average molecular weight (first M„ ) by more than about 10 percent, e.g„ 15,20,25,30,35,40,50 percent, 60 percent, or even more than about 75 percent.

116. In some instances, the second material has cellulose that has as crystallinity (C2) that is lower than the crystallinity (Cl) of the cellulose of the first material For example, (C2) can be lower than (Cl) by more than about 10 percent, e.g., 15,20,25,30, 35,40, or even more than about 50 percent.

117. In some embodiments, the starting crystallinity (prior to pyrolysis) is from about 40 to about 87.5 percent, e.g., from about 50 to about 75 percent or from about 60 to about 70 percent, and the crystallinity index after pyrolysis is from about 10 to about 50 percent, e.g., from about 15 to about 45 percent or from about 20 to about 40 percent I fowever, in certain embodiments, e.g., after extensive pyrolysis, it is possible to hâve a crystallinity index of lower than 5 percent. In some embodiments, the material after pyrolysis is substantiaily amoiphous.

118. In some embodiments, the starting number average molecular weight (prior to pyrolysis) is from about 200,000 to about 3,200,000, e.g., from about 250,000 to about 1,000,000 or from about 250,000 to about 700,000, and the number average molecular weight after pyrolysis is from about 50,000 to about 200,000, e.g., from about 60,000 to about 150,000 or from about 70,000 to about 125,000. llowever, in some embodiments, e.g., after extensive pyrolysis, it is possible to hâve a number average molecular weight of less than about 10,000 or even less than about 5,000.

119. In some embodiments, the second material can hâve a level of oxidation (02) that is higher than the level ofoxidation (OI) of the first material A higher level of oxidation of the material can aid in its dispersability, swellabîlity and/or solubility, further enhancing the materials susceptibility to chemical, enzymatic or microbial attack. In some embodiments, to increase the level of the oxidation of the second material relative ta the first material, the pyrolysis is performed in an oxidizing environment, producing a second material that is more oxidized than the first material. For example, the second material can hâve more hydroxyl groups, aldéhyde groups, ketone groups, ester groups or caAoxylic acid groups, which can increase its hydrophilicity.

120. In some embodiments, the pyrolysis of the materials is continuous. In other embodiments, the material is pyrolyzed for a pre-determined time, and then allowed to cool for a second pre-determined time before pyrolyzing again.

Oxidation of the Feedstock Materials

121. One or more oxidative processing sequences can be used to process carboncontaining materials from a wide variety of different sources to extract useful substances from the materials, and to provide parti ally degraded and/or altered material which fonctions as input to further processing steps and/or sequences.

122. In one method, a first material that includes cellulose having a first number average molecular weight (first M_n) and having a first oxygen content (Ol) is oxidized, e.g., by heating the first material in a stream of air or oxygen-enriched air, to provide a second material that includes cellulose having a second number average molecular weight (second M_n) and having a second oxygen content (02) higher than the first oxygen content (Ol).

123. Such materials can also be combined with a solid and/or a liquid. The liquid and/or solid can include a microorganism, e.g., a bacterium, and/or an enzyme. For example, the bacterium and/or enzyme can work on the cellulosic or lignocellulosic material to produce a fuel, such as éthanol, or a coproduct, such as a protein. Fuels and coproducts are described in FIBROUS MATERIALS AND COMPOSITES,” U.S. Application No

11/453,951, filed June 15,2006. The entire contents of each of the foregoing applications are incorporated herein by référence.

124. In some embodiments, the second number average molecular weight is not more 97 percent lower than the first number average molecular weight, e.g., not more than 95 percent, 90, 85.80,75,70. 65,60,55, 50,45,40,30,20, 12.5,10.0, 7.5,5.0, 4.0,3.0,2.5,2.0 or not more than 1.0 percent lower than the first number average molecular weight. The amount of réduction of molecular weight will dépend upon the application. For example, in some preferred embodiments that provide composites, the second number average molecular weight is substantially the same as the first number average molecular weight. In other applications, such as making éthanol or another fuel or coproduct, a higher amount of molecular weight réduction is generally preferred.

125. In some embodiments in which the materials are used to make a fuel or a coproduct, the starting number average molecular weight (prior to oxidation) is from about 200,000 to about 3,200,000, e.g., from about 250,000 to about 1,000,000 or from about 250,000 to about 700,000, and the number average molecular weight after oxidation is from about 50,000 to about 200,000, e.g., from about 60,000 to about 150,000 or from about 70,000 to about 125,000. However, in some embodiments, e.g., after extensive oxidation, it is possible to hâve a number average molecular weight of less than about 10,000 or even less than about 5,000.

126. In some embodiments, the second oxygen content is at least about fïve percent higher than the first oxygen content, e.g., 7.5 percent higher, 10.0 percent higher, 12.5 ’ percent higher, 15.0 percent higher or 17.5 percent higher. In some prcferted embodiments, the second oxygen content is at least about 20.0 percent higher than the first oxygen content of the first material. Oxygen content is measured by elemental analysis by pyrolyzing a sample in a fumace operating at 1300 °C or higher. A suitable elemental analyzer is the LECO CIINS-932 analyzer with a VTF-900 hîgh température pyrolysis fumace.

127. Generally, oxidationof a material occurs in an oxidizing environment. For example, the oxidation can be effected or aided by pyrolysis in an oxidizing environment, such as in air or argon enriched in air. To aid in the oxidation, various chemical agents, such as oxîdants, acids or bases can be added to the material prior to or during oxidation. For example, a peroxide (e.g., benzoyl peroxide) can be added prior to oxidation.

128. Some oxidative methods of reducing recalcitrance employ Fenton or Fenton-type chemistry. Such methods are disclosed, for example, in U.S.Appiication No. 12/639,289, filed December 16,2009, the complété disclosure of which is incorporated herein by référencé.

129. Exemplary oxîdants inciude peroxides, such as hydrogen peroxide and benzoyl peroxide, persulfatcs, such as ammonium persulfate, activated forms of oxygen, such as ozone, permanganates, such as potassium permanganate, perchlorates, such as sodium perchlorate, and hypochlorites, such as sodium hypochlorite (household bleach).

130. In some situations, pli is maintained at or below about 5.5 during contact, such as between 1 and 5, between 2 and 5, between 2.5 and 5 or between about 3 and 5. Conditions can also inciude a contact period of between 2 and 12 hours, e.g., between 4 and 10 hours or between 5 and 8 hours. In some instances, conditions inciude not exceeding 300 °C, e.g., not exceeding 250,200,150,100 or 50 °C. In spécial désirable instances, the température remains substantially ambient, e.g., at or about 20-25 °C.In some désirable embodiments, the one or more oxîdants are appiied to a first ccliulosic or lignocellulosîc material and the one or more compounds as a gas, such as by generating ozone in-situ by irradiating the first cellulosic or lignocellulosîc material and the one or more compounds through air with a beam of particies, such as électrons.

131. In particular désirable embodiments, a first cellulosic or lignocellulosîc material is firstly dispersed in water or an aqueous medium that includes the one or more compounds dispersed and/or dissolved therein, water is removed after a soak time (e.g., loose and free water is removed by filtration), and then the one or more oxîdants are appiied to the

combination as a gas, such as by generating ozone in-si tu by irradiating the first cellulosic or lignocellulosic and the one or more compounds through air with a beam of particles, such as électrons (e.g., each being accelerated by a potentiai différence of between 3 MeV and 10 MeV). Soaking can open up interior portions to oxidation.

132. In some embodiments, the mixture includes one or more compounds and one or more oxidants, and a mole ratio of the one or more compounds to the one or more oxidants is from about 1:1000 to about 1:25, such as from about 1:500 to about 1:25 or from about 1:100 to about 1:25.

133. In some désirable embodiments, the mixture further includes one or more θ hydroquînones, such as 2,5-dimethoxyhydroquinone (DMIIQ) and/or one or more benzoquinones, such as 2,5-dimethoxy-l,4-benzoquinone (DMBQ), which can aid in électron transfer reactions.

134. In some désirable embodiments, the one or more oxidants are electrochemicallygenerated in-situ. Fbr example, hydrogen peroxide and/or ozone can be electro-chemically

I g produced within a contact or reaction vessel.

Other Processes to Solubilize, Reduce Recalcitrance Or To Functionalize

135. Any of the processes of this paragraph can be used alone without any of the processes described herein, or in combination with any of the processes described herein (in any order): steam explosion, acid treatment (including concentrated and dilute acid treatment ₂q with minerai acids, such as sulfuric acid, hydrochloric acid and organic acids, such as trifluoroacetic acid), base treatment (e.g., treatment with lime or sodium hydroxide), UV treatment, screw extrusion treatment (see, e.g., U.S. Patent Application No. 12/417,723, fïled November 18, 2008, solvent treatment (e.g., treatment with ionic liquids) and freeze milling (see, e.g., U.S. Patent No. 7,900,857)

Production of Fuels and/or other products by bioprocessing

136. After one or more of the processing steps discussed above hâve been performed on the biomass, the complex carbohydrates contained in the cellulose and hemicellulose fractions can be processed into sugars using a saccharification process, as discussed above.

137. The resulting sugar solution can be converted into a variety of products by fermentation, such as alcohols, e.g., éthanol, or organic acids. The product obtained dépends upon the microorganism utilized and the conditions under which the bioprocessing occurs. These steps can be performed, for example, utilizing the existing equipment of the com-based éthanol manufacturing faeïlity.

138. Generally, fermentation utilizes various microorganisms. The sugar solution produced by saccharification of lignocellulosic materials will generally contain xylose as well as glucose. It may be désirable to remove the xylose, e.g., by chromatography, as some commonly used microorganisms (e.g., yeasts) do not act on xylose. The xylose may be collected and utilized in the manufacture ofother products, e.g., the sweetener Xylitol. The xylose may be removed prior to or after delivery of the sugar solution to the manufacturing facility where fermentation will be performed.

139. The microorganism can be a naturel microorganism or an engineered microorganism. For example, the microorganism can be a bacterium, e.g., a cellulolytic bacterium, a fungus, e.g., a yeast, a plant or a protist, e.g., an algae, a protozoa or a fungus- like protist, e.g., a slime mold. When the organisms are compatible, mixtures of organisms can be utilized. The microorganism can be an aerobe or an anaerobe. The microorganism can be a homofermentative microorganism (produces a single or a substantially single end product). The microorganism can be a homoacetogenic microorganism, a homolactic microorganism, a propionic acid bacterium, a butyric acid bacterium, a succinic acid bacterium or a 3-hydroxypropionic acid bacterium. The microorganism can be of a genus selected from the group Clostridium, Lactobacillus, Moorella, Thermoanaerobacter, Proprionibacterium, Propionispera, Anaerobiospirillum, and Bacteriodes. In spécifie instances, the microorganism can be Clostridium formicoaceticum. Clostridium butyricum, Moorella thermoacetica, Thermoanaerobacter kivui, Lactobacillus delbrukiî, .

Propionibacterium acidipropionici, Propionispera arboris, Anaerobiospirillum succinicproducens, Bacteriodes amylophilus or Bacteriodes ruminicola. For example, the microorganism can be a recombinant microorganism engineered to produce a desired product, such as a recombinant Escherichia coli transformed with one or more genes capable of encodîng proteins that direct the production of the desired product is used (see, e.g., U.S.

^î5 Pat No. 6,852,517, issued Feb. 8,2005).

140. Carboxylic acid groups generally Iower the pli of the fermentation solution, tending to inhibit fermentation with some microorganisms, such Pichia stipitis. Accordingly, it is in some cases désirable to add base and/or a buffer, before or during fermentation, to bring up the pli of the solution. For example, sodium hydroxide or lime can be added to the fermentation medium toelevate the pli of the medium to range that is optimum for the microorganism utilized.

141. Fermentation is generally conducted in an aqueous growth medium, which can contain a nitrogen source or other nutrient source, e.g., urea, along with vîtamins and trace

minerais and metals. It is generally préférable that the growth medium be stérile, or at least hâve a low microbial load, e.g., bacterial counL Sterilization of the growth medium may be accomplished in any desired manner. Ilowever, in preferred implémentations, sterilization is accomplished by irradiating the growth medium or the indivîdual components of the growth medium prior to mixing. The dosage of radiation is generally as low as possible while still obtaining adéquate results, in order to minimize energy consumption and resulting cosL For example, in many instances, the growth medium itself or components of the growth medium can be treated with a radiation dose of Iess than 5 Mrad, such as Iess than 4, 3,2 or 1 Mrad. In spécifie instances, the growth medium is treated with a dose of between about 1 and 3 Mrad.

Products by Chemical Reactions

142. Figure 3 shows various transformation of xylose (3a) in its open chain aldéhyde form to products. Chemical transformations using, for example, catalysts are useful to convert sugars (e.g., xylose) derived from biomass material as described herein into useful organic products. The products can be directly converted to a product (e.g., furfural 3b) or can be converted through various intennediates as depicted in Figure 3. Prior to conversion the, sugar (e.g., xylose) can be isolated, concentrated, and/or purified from the saccharified biomass using various methods such as distillation, crystallization, précipitation, chromatography (e.g., simulated moving bed chromatography or improved simulated moving bed chromatography), centrifugation, settling, sédimentation, fioatation, fermentation (e.g., fermentation of other sugars such as glucose to a greater degree than the xylose) or combinations of these and/or other methods.

143. Chemical conversions can be perfomied in the same tank as the saccharification (e.g., in situ right after saccharification) or transferred (optionally with a purification step) to a second tank for chemical reaction. For example the tank for the chemical reaction can be equippcd with température control units, mixing units, may be made to withstand corrosive or dissolving solvents, made to withstand higher than atmospheric pressure. These chemical conversions can also be done in a continuais fashion (e.g., using a tube reactor, continuous stirred tank reactor) or semi-continuous fashion.

144. Examples of chemical conversion of xylose to furfural and subséquent products is shown if Fig 3. While several of the products do not hâve any carbon atom that has stereochemistry, products 3d and 3f do hâve stereocenters. The chemistries envisaged hère can lead to pure stereoisomers or D,L mixtures that could be resolved.

145. The chemical conversion of xylose (3a) to methytetrahydrofuran (3D can be done in several steps. In a first step xylose (3a) is dehydrated and cyclization to furfural (3b) altematively called furancarboxaldehyde which is an oily, colorless heterocyclic aldéhyde. Several catalyst Systems can transform xylose to furfural successfully. Some possible acidic Systems are: Zeolite acidified with II3PO4/ H2SO4; Sulfonic acid, Silica surface grafted; 1Methylimidazole, i-BuC(=O)Me; Kl, KG; l-alkyl-3-methylimidazolium ionic liquids; NaCl, ΠΟ, SiO₂, Zeolite Beta, Sulfonic acid functionalized mesoporous silica MCM-4I; perfluorinated sulfonic acid resins (Nafion®), acidic clays, FeClj, NaCl; Mesoporous silica supported; SBA -!5 supported sulfonic acid, SiO₂,1I2SO4; Tetraethy! orthosilicate, 3(mercaptopropyl) trimethoxy silane, LaCh; Microporous silicoaluminophosphate; Z1O2, Tungstate; LSC resin; ΛΙ2Ο3, tungstate; TiO₂ sulfonated; VïOj, II3PO4; ZrOi, AI2O3, (NIl4)SO4i SiOî, MgGîî HCI. Microwave irradiation; Amberlyst 15; CS2CO3, S1O2. These réactions can be perfbrmed under higher températures and/or high pressure.

146. Furfural is used as a solvent for refining lubricating oils, as a fungicide and weed killer. Furfural is also a chemical intermediate in lhe production of melhyltetrahydrofuran (3f) which is an important industrial solvent In addition, furfural (3b) can serve as a building block for other potential transportation fuels. Furfural is an important renewable, nonpetroleum based, chemical feedstock. It is highly regardcd for its thermosetting properties, physical strcngth and corrosion résistance. It is consumed by the chemical industry as an intermediate product in synthesizing chemical products such as nylon, lubricants, solvents, adhesives, medicines and plastics.

147. Furfural is also a chemical intermediate to furfury! alcohol since réduction of the aldéhyde group of furfural provides furfuryl alcohol (3c). Furfuryl alcohol is also a use fui chemical intermediate and can be dearomatized to tetrahydrofurfuryl alcohol (3d). Some of the industrial processes are listed below:

148. In a two-step process, biomass (e.g., plant materials) contaînîng xylose is mixed with an acid (e.g., dilute sulphuric acid) or a saccharifying enzyme, producing sugars including xylose. The xylose is cyclohydrated losing three moles of water to furfural in the second step, e.g., with an acid (e.g., dilute sulphuric acid optionally from the first step). The product can be recovered by steam distillation from a mixture of acid and undigested biomass.

149. Furfural (3b) is a versatile chemical intermediate and can be used to make other furan chemlcals, such as furoic acid, via oxidation, and furan (3g) itself via palladium catalyzed vapor phase decarbonylation. Furfuryl alcohol (3c) can be manufactured by lhe

catalytic réduction of furfural. Réduction of the furfural aldéhyde group (3b) can yield furfuryl alcohol. For example, the aldéhyde can be reduced by using NaBI I4 in MeOH in one hour with (e.g., yielding greater than 10% product, e.g., greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%). Other reactants that can be used for this transformation include, FeClj, ZnCl₂; NiCl₂, A1₂O₂,; Pt, TiO₂, SiO₂; (NH₄)₂.HCO₂, Ni; IRhCl(COD)]₂; CuO, Cr₂O₃, SiO₂.

150. Furfuryl alcohol (3c), also called 2-furylmethanol or 2-furancarbinol (3c), is an organic compound containing a furan substitute hydroxymethyl group. It is a clear colorless liquid when pure, but becomes amber colored upon prolonged standing. It possesses a faint buming odor and a bitter taste. It is miscible with but unstable in water. It is soluble in common organic solvents. Upon treatment with acids, heat and/or catalysts, furfuryl alcohol can be made to polymerize into a resin, poly( furfuryl alcohol). It also can be used as a solvent and as an ingrédient in the manufacture of various chemical products such as foundry resins, adhesives, and wetting agents.

151. Furfuryl alcohol (3c) has been used in rocketry as a fuel, which ignites with white fuming nitric acid or red fuming ni trie acid oxidizer. Because of ils low molecular weight, furfuryl alcohol (3c) can impregnate the cells of wood, where it can be polymerized and bonded with the wood by heat, radiation, and/or catalysts or additional reactants (e.g., by the methods disclosed in US patent 7,846,295 the full disclosure incorporated herein by référencé). The treated wood has improved moisture stability, dimensional stability, hardness, microbial decay résistance and insect résistance; catalysts can include zinc chloride, citric or formic acid, or borates.

152. Dearomatization of furfuryl alcohol (3c) to tetrahydrofurfuryl alcohol (3d) can be performed using several métal catalysts under high pressures (e.g., between 10 and 8000psi) and températures (e.g., from 50 to 400°C). For exemple, catalysts can be selected from: Ilectorite supported Ru nanoparticles; nickel boride/SiO₂; Skeleton Ni; L-Serine, Alginic acid, platinum complex; Na₂O, ZnO, NiO, A1₂O3; Ni, Al, Mo, Si, Ca; Rh-PPhî complex; RuO₂; Ru; Ru/TiO₂; Al/Ni alloy; nickel bonde, nickel/cobalt bonde; NiO, amongst others. The hydrogénation reactions take from minutes (or hours) to a day (or several days). Tetrahydrofurfuryl alcohol is a hygroscopic, colorless liquid, miscible with water; used as a solvent for resins, in leather dyes, and in nylon. Tetrahydrofurfuryl alcohol can be used as a nonhazardous solvent in agriculture! formulations and as an adjuvant to help herbicides penetrate the leaf structure. Dihydropyran can be prepared by the déhydration of tetrahydrofurfuryl alcohol over alumina at 300-400 °C.

153. 2-Methyltetrahydrofuran (3f) is an organic compound with the molecular formula CU3C4II7O. It is a highly flammable mobile liquid. It is mainly used as a replacement for THF in specialized applications for its better performance in those applications, e.g., to obtain higher reaction températures, or easier séparations due to the solubility, changed acidity and changed donor properties of the ring oxygen of the 2-methyltetrahydrofuran. It also is used in the electrolyte formulation for secondary lithium électrodes and as a component in alternative fuels. It is a valued solvent for low température réactions. 2-Methyltetrahydrofuran forms a glass, which does not crystallize, and is frequently used as a solvent for spectroscopic studies at -196 °C. Methyltetrahydrofuran has a stereocenter alpha to the oxygen. The methyltetrahydrofuran produced by these chemistries may be a 50:50 mixture of stereoisomers or enriched in either enantiomer.

154. Other common uses of 2-mcthyltetrahydrofuran is as a solvent for Grignard reagents used in organometallic and biphasic chemical processes, because of the oxygen atom's ability to coordinate to the magnésium ion component of the Grignard reagent, or to azeotropically dry products. The use of 2-methyltetrahydrofuran provides very clean organicwater phase séparations. It is a popular, but costlier substitute for tetrahydrofuran.

155. 2-Methyl tetrahydrofuran has been approved by the United Statcs Department of Energy as an additive to gasoline. Furfural and other partially hydrogenated/reduced furyl compounds between it and 2-methyltetrahydrofuran (furfuryl alcohol, methylfuran, tetrahydrofuryl alcohol) hâve a tendency to polymerize and are quite volatile. 2methyltetrahydrofuran itself, however, is more stable and less volatile, and thus is suitable for use as a motor fuel.

156. 2-Methyltetrahydrofuran has one stereocenter, so it exists in two enantiomeric forms. In some processes involving hydrogénation a racemic mixture of the two enantiomers is formed. The asymmetric synthesis of (S>(+)-2-methyltetrahydrofuran can be achieved by using chiral catalytic hydrogénation, e.g., using supported catalysts such as wool-rhodium complex.

157. The conversion of 3c to 3e involves hydrogenolysis. 3e can be converted to 3f by vapor phase hydrogénation using Raney Ni under 200°C.

Furfural (3b) can be catalytically converted to Furan (3g) by métal complexes. For examples, the reactions can be made to proceed via metal-acyl hydrides. Cu/Mo fixed bed complex can catalyze this conversion under high pressures and températures (e.g., between 10 and 20000psi and 50 to 400°C) with continuous flow of hydrogen. Catalyst complexes of Pd and

Ni hâve also been used but they hâve pioven to be less sélective (leading to ring opening and C4 compounds). The hydrogénation of Furan (3g) to tetrahydrofuran (3h) can be performed under high pressure and température under hydrogen using meta! based catalysts such as Raney Ni, Ru and Pt.

158. The furfural-derived products are extensive and include, but are not limited to furfuryl alcohol, levulinic acid, tetrahydrofurfuryl alcohol, dihydropyran,, furoic acid, methyl furan, me thytetrahydrofuran, furan, tetrahydrofuran, pynole, thiofuran, 1,4-butanediol, maleic anhydride, furfuryl amine, furanacrylic acid, furanacrylonitrile, furfuryliden acrolein, alkyl furfurylidene ketone, Diels Aider product with cyclopentadiene and other diene and q dienophiles, and polyfurfuryl alcohol.

159. The furfural-derived products can be the product of a multiple step reaction scheme. The intermediates along the reaction scheme may be isolated before subséquent reactions. For example, the furfural can be isolated and purified prior to conversion of furfural alcohol.

EXAMPLES

160. Unless otherwise noted the chemicals were obtained from Alfa Chemical, Rings

Point New York; Sigma Aldrich Chemical, St Louis, Missouri.

Example I: Xylose conversion to furfural with acetic acid

161. To a 1-Liter pressure vessel equipped with a vent condenser (Pair stainless steel reactor, Pair Instrument Company, Moline Illinois.) 20 grams of xylose, 0.2mLof glacial acetic acid and 400 mL of water was added. The vessel was heated to 185°C and liquids dîstiUed from the reactor. The total heating time was two hours. Most of the furfural was recovered from the distillate. The furfural yield was determined by gas chromatography to be 39 percent

Example 2: Xylose conversion to furfural

162. To a 1-Liter pressure vessel equipped with a vent condenser (Pair stainless steel reactor, Pair Instrument Company, Moline Illinois.) 50 grams of xylose, and 500 mLof water was added. The reactor was heated to 185°C, agitated at 350 rpm and the pressure was 145 psig. The furfural yield was 45 percent

Example 3: Xylose conversion to furfural, calcium chloride added.

163. To a 1-Liter pressure vessel equipped (Parr stainless steel reactor, Parr Instrument Company, Moline Illinois.) 30 grams of xylose ( from Cascade Analytical Reagents and wU

Biochemicals, Corvallis, Oregon), 300mL of methyltetrahydrofuran, calcium chloride, 30 grams and 150 mL of water was added. The reactor was heated to 200°C for four hours. The furfural yield was 55 percent.

Example 4: Xylose conversion to furfural; continuous processing.

164. Xy lose was dissolved in water at 0.66 moles/liter. This solution was pumped through a heated tubular reactor. At 180°C the furfural yield was less than 5 percent. At 200°C the yield wasl3 % at a 10 minute résidence time. At 220“C at a 10 min residence time reached 40 %.

165. Other than în the examples herein, or unless otherwise expressly specified, ail of the numerical ranges, amounts, values and percentages, such as those for amounts of materials, elemental contents, times and températures of réaction, ratios of amounts, and others, in the following portion of the spécification and attached claims may be read as if prefaccd by the word “about even though the term “about” may not expressly appear with the value, amount, or range. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following spécification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limît the application of the doctrine of équivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of rcported significant digits and by applying ordinary rounding techniques.

166. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the spécifie examples are rcported as prccisely as possible. Any numerical value, however, inherently contains error necessarily resulting from the standard déviation found in its underlying respective testing measurements. Furthermore, when numerical ranges are set forth herein, these ranges are inclusive of the recited range end points (e.g., end points may be used). When percentages by weight are used herein, the numerical values rcported are relative to the total weight

167. Also, it should be understood that any numerical range recited herein is intended to include ail sub-ranges subsumed therein. For example, a range of “1 to 10 is intended to include ail sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10. The ternis “one,” “a,” or “an” as used herein are intended to include “at least one” or “one or more,” unless otherwise indicated.

♦ 37

168. Any patent, publication, or other disclosure material, in whole or in part, that is said to be incorporated by référencé herein is incorporated herein only to the extent that the incorporated material does not conilict with existing définitions, statements, or other disclosure material set forth in this disclosure. As such, and to the extent necessary, the disclosure as explicitly set forth herein supersedes any conflicting material incorporated herein by référencé. Any material, or portion thereof, that is said to be incorporated by référencé herein, but which conflicts with existing définitions, statements, or other disclosure material set forth herein will only be incorporated to the extent that no conflict anses between that incorporated material and the existing disclosure material.

169. While this invention has been particularly shown and described with référencés to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made thereîn without departing from the scope of the invention encompassed by the appended daims.

Claims

1. Λ method for converting a sugar, the method comprising;

chemically converting xylose to a product or an intermediate, the xylose being obtained by treating biomass with irradiation and saccharification.

2. The method of claim 1 where the product or intermediate comprises furfural.

3. The method ofclaim 1 wherein chemical converting further comprises converting the xylose over an acid catalyst

4. The method of claim 2 where the furfural is further chemically converted to a furfural-derived product.

5. The method of claim 4 wherein the chemically converted furfural comprises reactions selected from the group consisting of cyclization reactions, polymerization reactions, condensation reactions, réduction reactions, oxidation reactions, estérification reactions, alkylation reactions, decarbonylation reactions, aldol reactions, amination reactions, hydrogénation reactions, disproportionation reactions, dearomatization reaction, Diels Aider reactions, and combinations thereof.

6. The method of claim 4 chemically converted furfural comprises at least two successive reactions selected from the group consisting of cyclization reactions, polymerization reactions, condensation reactions, réduction reactions, oxidation reactions, estérification reactions, alkylation reactions, decarbonylation reactions, aldol reactions, amination reactions, hydrogénation réactions, disproportionation réactions, dearomatization reaction, Diels Aider reactions, and combinations thereof.

7. The method of claim 3 wherein the acid catalyst is selected from the group consisting of acidified Zeolites, acidified silica, surface grafted silicas, functionalized mesoporous silicas, poly acids, acid functionalized polymers, poly sulfonic acids, poly acetic acids, poly phosphonic acids, polystyrène sulfonic acids, tetraorthosilicates, 3(mercaptopropyl)trimethoxysilane, Lewis acids, microporous silicoaluminaphosphatc, métal oxides, ZtOî, A12Oj, T1O2, SÎO2, V2OJ, sulfate salts, (NlUbSCh, métal halides, MgCh, LaClj, FeClj, métal carbonates, CS2CO3, ionic liquids, Tungtscn oxides, Tungstate, Phosphoric acid, Phosphonic acid, sulfuric acid, hydrochloric acid, nitric acid, perfluorinated resin-sulfonic acid, and combinations thereof.

8. The method of daim 1 or 3 wherein converting comprises applying greater than atmospheric pressure to the xylose.

9. The method of daim 1 or 3 wherein converting comprises heating the xylose to a température greater than 50°C up to 320°C.

10. The method of claim 1 further comprising isolating the product or the intermediate.

11. The method of claim 4 wherein the furfural-derived product is selected from the group consisting of furfuryl alcohol, Ievulinic acid, tetrahydrofurfuryl alcohol, dihydropyran, , furoic acid, methyl furan, methytetrahydro furan, furan, tetrahydrofuran, pyrrole, thiofuran, 1,4-butanedioI, maJeic anhydride, furfuryl amine, furanacrylic acid, furanacrylonitrile, θ furfuryliden acrolein, alkyl furfurylidene ketone, Diels Aider adduct with cyclopentadiene, poly(furfuryl alcohol).

12. The method of daim 1 wherein the xylose is derived from the treated biomass material by a process comprising hydrolysis of the treated biomass material.

13. The method of daim 12 wherein hydrolysis comprises contacting the treated

15 biomass material with at least one of an acid, a base, heat, microwave energy, sonie energy, mechanical energy, shearing, milling or an enzyme.

14. The method of claim 12 wherein hydrolysis comprises contacting the treated biomass with an enzyme.

15. The method of claim 14 wherein the enzyme is an enzyme complex including xylanase.

16. The method of any one of the above claims further comprising producing glucose.

17. The method of claim 16 further comprising separating the glucose from the xylose prior to chemically converting the xylose.

18. The method of claim 16 or 17 further comprising fermenting the glucose.

25

19. The method of claim 1 wherein biomass comprises hemicellulose further comprising xylan, glucuronoxylane, arabinoxylan, glucomannan and/or xyloglucan.

. «

20. The method of any one of the above daims wherein the irradiation comprises a radiation dosage ofbetween 10 and 200 Mrad.

21. The method of claim 1 wherein the irradiation is provided by an électron beam.

22. The method of claim 21 wherein the électron beam has a power between 0.5 and ₅ 10 MeV.

23. The method of any one of the above daims wherein the biomass is selected from the group consisting of paper, paper products, paper waste, wood, particle board, sawdust, agricultural waste, sewage, silage, grasses, wheat straw, rice hulls, bagasse, cotton, jute, hemp, flax, bamboo, sisal, abaca, straw, com cobs, com stover, alfalfa, hay, coconut hair,

0 seaweed, algae, and mixtures thereof.

24. A method for converting a sugar, the method comprising:

chemîcally converting xylose to a product or an intermediate, the xylose beîng obtained by treating biomass with irradiation and saccharification, wherein the product comprises furfural which is further converted to a furfuralderived product, and wherein the furfural-deiived product is selected from the group consisting of furfuryl alcohol, levulinic acid, tetrahydrofurfuryl alcohol, dihydropyran,, furoic acid, methyl furan, methytetrahydrofuran, furan, tetrahydro furan, pyTrole, thiofuran, 1,4-butanediol, maleic anhydride, furfuryl amine, furanacrylic acid, furanacrylonitrile, furfurylïden acrolein, alkyl furfurylidene ketone, Diels Aider product with cyclopentadiene, and polyfurfuryl alcohol.