NZ612188B2 - A method of producing sugar from paper - Google Patents

Abstract

The disclosure relates to a method of producing an alcohol product or intermediate, comprising: combining a slurry of paper with a saccharifying agent in a vessel, the paper having a filler content greater than about 10wt%; allowing at least a portion of the paper to saccharify producing sugar, while mixing the contents of the vessel with a jet mixer and fermenting at least a portion of the sugar with a microorganism, where the contents of the vessel comprise at least one shear sensitive ingredient and the jet mixer provides gentle mixing so as to minimize damage. le mixing the contents of the vessel with a jet mixer and fermenting at least a portion of the sugar with a microorganism, where the contents of the vessel comprise at least one shear sensitive ingredient and the jet mixer provides gentle mixing so as to minimize damage.

Description

A METHOD OF PRODUCING SUGAR FROM PAPER BACKGROUND Magazines, catalogs, and other paper products that contain high levels of coatings, pigments, and inks, are widely available as waste materials. While efforts are made to recycle this waste paper, generally by repulping it for use in recycled paper products, it would be advantageous ifthis waste paper could be economically utilized as a feedstock to make other types of products.

SUMMARY Generally, this invention relates to methods ofprocessing paper oclcs, and to intermediates and products made therefrom. In ular, the invention s generally to the processing of certain types of relatively heavy paper feedstocks, such as highly pigmented papers, and or loaded papers, such as paper that has been color printed (printed with colors other than or in on to black), e.g., magazines, and other papers.

Many ofthe methods disclosed herein e microorganisms or products produced by microorganisms, e.g., enzymes, to cess the feedstock, producing useful intermediates and products, e.g., energy, fuels, foods and other materials. For e, in some cases enzymes are used to saccharify the feedstocks, converting the feedstocks to sugars. The sugars may be used as an end product or intermediate, or processed further, e.g., by fermentation. For example xylose can be hydrogenated to xylitol and glucose can be hydrogenated to sorbitol.

In one aspect, the invention features methods for producing a sugar, e.g., in the form of a solution or suspension, that includes providing a paper feedstock, the paper feedstock ing offset printing paper e.g., offset printed paper, colored paper and/0r coated paper e.g., polycoated paper and optionally mixing the feedstock with a fluid and/or saccharifying agent.

Some implementations include one or more ofthe following features. The paper feedstock may have a basis weight greater than 35 lb, e.g., from about 35 lb to 330 lb and/or the paper may have a high filler content, e.g., r than about 10 wt.% e. g., greater than 20 wt.%. For e, the filler or any coating can be an nic material. The paper may also have a high grammage, e.g., greater than about 500 g/m2. The paper may comprise a pigment or printing ink, e.g., at a level greater than about 0.025 wt.%. The paper can have an ash content greater than about 8 wt.%.

The method can further include adding a microorganism, for example a yeast and/or a bacteria (e.g., from the genus Clostridium), to the paper feedstock or saccharified paper and producing a product or intermediate.

In one embodiment ofthe present invention there is provided a method of ing a t or intermediate, the method comprising:_combining a slurry of paper with a saccharifying agent in a vessel, the paper having a high filler t greater than about 10wt%;_allowing at least a portion of the paper to saccharify, ing a sugar, while mixing the contents ofthe vessel with a jet mixer; and fermenting at least a portion of the sugar with a microorganism, wherein the ts ofthe vessel comprise at least one shear sensitive ingredient and the jet mixer provides gentle mixing so as to ze damage to the at least one shear sensitive ingredient.

The product can be a fiJel, including, for example, alcohols (e.g., methanol, ethanol, propanol, isopropanol, itol, nol, isobutanol, sec—butanol, tert- butanol, ethylene glycol, propylene glycol, 1,4-butane diol and/or glycerin), sugar alcohols (e.g., erythritol, glycol, glycerol, sorbitol threitol, arabitol, ribitol, mannitol, dulcitol, fucitol, iditol, isomalt, maltitol, lactitol, xylitol and other polyols), organic . acids (e.g., formic acid, acetic acid, propionic acid, c acid, valeric acid, caproic acid, palmitic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, oleic acid, linoleic acid, glycolic acid, lactic acid and/or y—hydroxybutyric acid), hydrocarbons (methane, ethane, propane, isobutene, pentane, n-hexane, sels and/or bio—gasolines), hydrogen and mixtures of these.

The method can fmther include adding a ased nutrient source to the mixture, e.g., a nutrient source selected from the group consisting of grains, vegetables, residues of grains, residues of vegetables, and mixtures thereof, for example wheat, oats, barley, soybeans, peas, legumes, potatoes, corn, rice bran, corn meal, wheat bran, and mixtures thereof. In such cases, the mixture can finther include an enzyme system selected to release nts from the ased nutrient source, e.g., a system sing a protease and an amylase.

The method can include detoxifying the sugar solution or suspension. The method can include further processing the sugar, for example, by separating xylose and or PCT/U82012/024970 glucose from the sugar. In some cases, the saccharification can be conducted at a pH of about 3.8 to 4.2. The mixture can further e a nitrogen source.

In some cases, the method further includes physically ng the paper feedstock, for example mechanically treating to reduce the bulk density of the paper feedstock and/or se the BET surface area of the feedstock. Physically treating the paper feedstock can include irradiation, for e, with an electron beam. The method can e mixing the paper feedstock with a fluid. The method can include detOXifying the paper feedstock, sugar, and/or other products or ediates. The paper feedstock may be in the form of magazines. The paper feedstock may also be a laminate of at least one layer of a r and paper and may further include at least one layer of a metal e.g., aluminum. gh many embodiments include the use of relatively heavy paper feedstocks, e.g., containing fillers and/or coatings other papers can be used e.g., newsprint.

Unless ise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control.

In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

Other features and advantages of the invention will be apparent from the following detailed description, and from the claims.

DESCRIPTION OF DRAWINGS is a flow diagram illustrating sion of a feedstock to ethanol Via production of a glucose solution. is a tic diagram of an ethanol manufacturing facility. is a diagram illustrating the enzymatic hydrolysis of cellulose to glucose.

PCT/U52012/024970 DETAILED DESCRIPTION Using the methods and nutrient packages described herein, paper feedstocks that include high levels of pigments, colors, fillers and/or coatings, and/or that have a high basis , and the saccharified derivatives of such feedstocks, can be bioprocessed, e.g., using fermentation, to produce useful intermediates and ts such as those bed herein. In some cases, the feedstock includes high levels pigments and/or fillers such as those feedstocks used in printing, e.g., nes. es of such feedstocks are described herein. Feedstocks of this type are advantageous for a number of reasons, including their relatively low cost (if waste materials are used) and, in the case of high basis weight papers, their relatively high density, which contributes to ease of handling and sing.

CONVERTING CELLULOSIC AND LIGNOCELLULOSIC MATERIALS T0 ALCOHOLS Referring to a process for manufacturing an alcohol, e.g., ethanol, or a butanol e.g., isobutanol, sec—butanol, tert—butanol or n—bntanol, can inciude, for example, optionally mechanically treating the feedstock (step 110), before and/or after this ent, optionally treating the feedstock with another physical treatment, for example ation, to further reduce its itrance (step 112), saccharifying the feedstock to form a sugar solution (step 114), optionally transporting, e.g., by ne, railcar, truck or barge, the solution (or the feedstock, enzyme and water, if saccharification is performed en route) to a manufacturing plant (step 116), and then bio—processing the treated feedstock to produce a desired product (step 118), which is then processed further, e. g., by distillation (step 120). If d, lignin t can be measured (step 122) and process parameters can be set or adjusted based on this measurement (step 124), as described in U.S. Application Serial No 12/704,519, filed on February 11, 2010, the complete disclosure ofwhich is incorporated herein by reference.

Because paper feedstocks are generally low in, or entirely tack, nutrients to support bioprocesses, it is generally preferred that nutrients be added to the system, for example in the form of a food—based nutrient source or nutrient package, as disclosed in U.S. Application Serial No. 13/1 84,138, orated by reference herein in its entirety.

WO 12488 PCT/U82012/024970 When utilized, the food-based nutrient source or nutrient package is present during bio- processing (step 118), e.g., tation, and may in some preferred implementations also be t during the saccharification step (step 114). In some implementations, the food-based nutrient source or nutrient package is added at the ing of step 114, along with an enzyme ation suitable for saccharification, fermentation, and release of nutrients from the food—based nutrient source.

Saccharification is conducted under a first set of process conditions (e.g., ature and pH), and then when saccharification has proceeded to a d extent the process conditions may be adjusted (e.g., by ing pH from 4 to 5) to allow ‘10 fermentation to proceed.

In some cases the feedstock includes materials that are not beneficial to the processing of the feedstock or decrease the quality ofthe intermediates and/or products.

For example there may be materials that are toxic, and/or solid inorganic materials or insoluble organic materials. The toxic materials can be detrimental, for example, by reducing the effectiveness of enzymes and/or rganisms. Examples of toxic materials are pigments and inks described herein. Solid inorganic materials can be detrimental, for example, in increasing the total viscosity and density of solutions in various processes as well as forming slurries, sludge and settled material that may, for example, block openings, be difficult to remove, e.g., from the bottom of tanks, and/or increase the wear on . es of inorganic materials are fillers and coatings described herein. Insoluble organic materials can, for example, contaminate the final fuel products and/or cause foaming during mixing or other processing steps. Examples of insoluble organic materials are polymers used in polycoated paper described herein. It can therefore be advantageous to remove some of the insoluble solids and organic materials and to detoxify the feedstock at any point during the processing as described herein. Surprisingly, it has been found that in some cases materials in the feedstock that would be expected to be detrimental, as discussed above, do not significantly ely affect the s. For example, some yeasts that provide ethanol by fermentation of sugars derived from paper ocks appear to be very resilient to various pigments, inks and fillers.

W0 2012/112488 PCT/U52012/024970 The manufacturing plant used in steps 0 (and in some cases all of the steps bed above) can be, for example, an existing starch—based or sugar-based l plant or one that has been retrofitted by removing or decommissioning the equipment upstream from the bio-processing system (which in a typical ethanol plant generally includes grain receiving equipment, a hatmnermiil, a slurry mixer, cooking equipment and liquefaction equipment). In some cases, the feedstock received by the plant can be input directly into the fermentation equipment. A retrofitted plant is shown schematically in and described below as well as, for e, in US. Serial No. 12/429,045, filed Apiil 23, 2009, the complete disclosure ofwhich is incorporated herein by '10 reference. shows one particular system that utilizes the steps described above for treating a feedstock and then using the treated feedstock in a fermentation process to produce an alcohol. System 100 includes a module 102 in which a feedstock is initially mechanically treated (step 12, above), a module 104 in which the mechanically d feedstock is structurally modified (step 14, above), e.g., by irradiation, and a module 106 in which the urally modified feedstock is subjected to further mechanical treatment (step 16, above). As discussed above, the module 106 may be ofthe same type as the module 102, or a different type. In some implementations the urally modified ock can be returned to module 102 for further mechanical treatment rather than being further mechanically treated in a separate module 106.

As described herein, many variations ofsystem 100 can be utilized.

After these treatments, which may be repeated as many times as required to obtain desired feedstock properties, the treated feedstock is delivered to a fermentation system 108.

Mixing may be performed during tation, in which case the mixing is preferably relativeiy gentle (low shear) so as to ze damage to shear sensitive ingredients such as enzymes and other rganisms. In some embodiments, jet mixing is used, as described inU.S. Serial No. 12/782,694, ,977 and 13/293,985, the complete disclosures of which are incorporated herein by reference.

Referring again to fermentation es a crude ethanol mixture, which flows into a holding tank 110. Water or other solvent, and other non-ethanol components, are stripped from the crude ethanol mixture using a stripping column 112, and the ethanol is PCT/U82012/024970 then distilled using a distillation unit 1 14, e.g., a rectifier. Distillation may be by vacuum distillation. Finally, the l can be dried using a molecular sieve 116 and/or denatured, ifnecessary, and output to a desired shipping .

In some cases, the systems described herein, or components thereof, may be portable, so that the system can be orted (e.g., by rail, truck, or marine vessel) from one location to another. The method steps described herein can be performed at one or more locations, and in some cases one or more ofthe steps can be performed in transit.

Such mobile processing is described in US. Serial No. 12/374,549 and International ation No. W0 2008/01 1598, the full sures ofwhich are incorporated herein 1O by reference.

Any or all of the method steps described herein can be med at ambient temperature. If desired, cooling and/or heating may be ed during certain steps.

For example, the feedstock may be cooled during mechanical treatment to increase its brittleness. In some embodiments, cooling is employed before, during or after the initial mechanical ent and/or the subsequent mechanical treatment. Cooling may be performed as bed in US. Serial No. 12/502,629, now US. Patent No. 7,900,857 the full disclosure ofwhich is incorporated herein by reference. Moreover, the temperature in the fermentation system 108 may be controlled to enhance saccharification and/or fermentation.

The individual steps of the methods described above, as well as the materials used, will now be described in further detail.

PHYSICAL ENT 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 oftwo, three, four, or even all of these technologies (in any order). When more than one treatment method is used, the methods can be applied at the same time or at different times. Other processes that change a molecular structure of a feedstock may also be used, alone or in combination with the processes disclosed herein.

PCT/U82012/024970 Mechanical Treatments In some cases, methods can include mechanically treating the feedstock.

Mechanical treatments include, for example, cutting, milling, pressing, grinding, shearing and chopping. Milling may include, for example, ball milling, hammer milling, rotor/stator dry or wet g, freezer g, blade milling, knife milling, disk milling, roller g or other types of milling. Other mechanical treatments e, e.g., stone grinding, cracking, mechanical ripping or tearing, pin grinding or air attrition milling. ical treatment can be advantageous for “opening up,H (Cstressing,” ng and ring cellulosic or other materials in the feedstock, making the cellulose of the als more susceptible to chain scission and/or reduction of oiystallinity. The open materials can also be more tible to oxidation when irradiated.

In some cases, the mechanical treatment may include an initial preparation of the feedstock as received, e.g., size reduction of materials, such as by cutting, grinding, shearing, pulverizing or chopping. For example, in some cases, loose feedstock (e. g., e Offset Paper and/0r Polycoated Paper) is prepared by ng or shredding.

Alternatively, or in addition, the feedstock material can first be physically treated by one or more of the other physical treatment methods, cg, chemical treatment, radiation, sonication, oxidation, pyrolysis or steam explosion, and then mechanically treated. This sequence can be advantageous since materials 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.

In some embodiments, mechanical treatment includes shearing to expose fibers of the material. ng can be performed, for example, using a rotary knife cutter. Other methods of ically treating the feedstock include, for example, milling or grinding.

Milling may be performed using, for example, a hammer mill, ball mill, colloid mill, conical or cone mill, disk mill, edge mill, Wiley mill or grist mill. ng may be performed using, for example, a stone grinder, pin grinder, coffee grinder, or burr grinder. Grinding may be provided, for e, by a reciprocating pin or other element, PCT/U82012/024970 as is the ease in a pin mill. Other mechanical treatment methods include mechanical g or tearing, other methods that apply pressure to the material, and air attrition milling. Suitable mechanical treatments further include any other technique that changes the molecular ure ofthe feedstock.

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 ent, and screening are performed ' concurrently. For e, a rotary knife cutter can be used to concurrently shear and screen the feedstock. The feedstock is sheared between stationary blades and rotating blades to provide a d material that passes through a screen, and is captured in a bin.

The paper feedstock can be mechanically treated in a d1y 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 ically treated while partially or fully submerged under a liquid, such as water, l or isopropanoi.

The feedstock can also be mechanically treated under a gas (such as a stream or atmosphere of gas other than air), e.g., oxygen or nitrogen, or steam.

Mechanical ent systems can be configured to produce streams with specific morphology characteristics such as, for example, surface area, porosity, bulk density, and length-to-width ratio.

In some embodiments, a BET surface area of the mechanically treated material is greater than 0.1 mz/g, e.g., greater than 0.25 m2/g, greater than 0.5 nil/g, greater than 1.0 mZ/g, greater than 1.5 mZ/g, greater than 1.75 m2/g, greater than 5.0 mZ/g, greater than 10 m2/g, greater than 25 mZ/g, greater than 35 mz/g, greater than , greater than 60 mZ/g, greater than 75 mZ/g, greater than 100 mz/g, greater than 150 m2/g, greater than 200 nag/g, or even greater than 250 mz/g.

In some situations, it can be desirable to prepare a low bulk density material, densify the al (e.g., to make it easier and less costly to transport to another site), and then reveit the material to a lower bulk y state. Densified materials can be processed by any ofthe methods described herein, or any material processed by any of the s described herein can be subsequently ed, e.g., as disclosed in U.S.

PCT/U52012/024970 Serial No. 12/429, 045 now US. Patent No. 7,932,065 and , the full disclosures of which are incorporated herein by reference.

Radiation Treatment One or more radiation processing ces can be used to process the paper feedstock, and to provide a structurally d material which functions as input to further processing steps and/or sequences. Irradiation can, for e, reduce the molecular weight and/or crystallinity of feedstock. Radiation can also sterilize the materials, or any media needed to bioprocess the material.

In some embodiments, the radiation may be provided by (1) heavy charged particles, such as alpha particles or protons, (2) electrons, ed, for example, in beta decay or electron beam accelerators, or (3) electromagnetic radiation, for e, gamma rays, x rays, or ultraviolet rays. In one approach, radiation produced by ctive substances can be used to irradiate the feedstock. In another approach, electromagnetic radiation (e.g., ed using electron beam emitters) can be used to irradiate the feedstock. In some embodiments, any combination in any order or concurrently of (1) h (3) may be utilized. The doses applied depend on the desired effect and the particular feedstock.

In some instances when chain scission is desirable and/or polymer chain functionalization is desirable, particles r than electrons, such as protons, helium nuclei, argon ions, silicon ions, neon ions, carbon ions, phosphorus ions, Oxygen ions or nitrogen ions can be utilized. When ring-opening chain scission is desired, positively charged particles can be utilized for their Lewis acid properties for enhanced ring— opening 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.

The use ofheavy les and positively charged particles is described in US. Serial No. 12/417,699, now US. Patent No. 7,931,784, the full disclosure ofwhich is incorporated herein by nce.

In one method, a first al that is or includes cellulose having a first number average lar weight (Mm) is irradiated, e.g., by treatment with ionizing radiation (cg, in the form of gamma radiation, X—ray radiation, 100 nm to 280 nm ultraviolet (UV) light, a beam of electrons or other charged les) to provide a second material that includes cellulose having a second number e molecular weight (Mm) lower than the first number e 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 lig'nin to produce an intermediate or product, such as those described herein.

Since the second material includes 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, e.g., in a on containing a microorganism and/or an enzyme. These properties make the second material easier to process and 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., ethanol.

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

In some instances, the second material includes cellulose that has a crystallinity (C2) that is lower than the crystallinity (C1) of the cellulose ofthe first material. For example, (C2) can be lower than (C1) by more than about 10 percent, e.g., more than about 15, 20, 25, 30, 35, 40, or even more than about 50 percent.

In some embodiments, the second al can have 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 solubility, further enhancing the material’s susceptibility to chemical, enzymatic or biological attack. In some embodiments, to increase the level of the ion of the second material relative to the first material, the ation is performed under an oxidizing environment, e.g., under a t of air or oxygen, producing a second al that is more oxidized than the first al. For example, the second material can have more hydroxyl groups, aldehyde , ketone groups, ester groups or carboxylic acid groups, which can increase its hydrophilieity.

WO 12488 PCT/U82012/024970 Ionizing Radiation Each form of radiation ionizes the paper feedstock via particular interactions, as determined by the energy of the radiation. Heavy charged particles primarily ionize matter Via Coulomb scattering; furthermore, these interactions produce tic electrons that may r ionize matter. Alpha particles are identical to the nucleus of a helium atom and are produced by the alpha decay of various radioactive nuclei, such as isotopes of bismuth, polonium, astatine, radon, francium, , l actinides, such as actinium, m, uranium, neptunium, curium, californium, americium, and plutonium.

When particles are ed, they can be neutral (uncharged), positively charged or negatively charged. When charged, the charged particles can bear a single positive or negative 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 ble, in part due to their acidic nature. When particles are utilized, the particles can have the mass of a resting electron, or greater, e.g., 500, 1000, l500, 2000, 10,000 or even 100,000 times the mass of a resting electron. For example, the particles can have a mass of from about 1 atomic unit to about 150 atomic units, e.g., from about 1 atomic unit to about 50 atomic units, or from about 1 to about 25, e.g., l, 2, 3, 4, 5, 10, 12 or 15 amu. Accelerators used to accelerate the particles can be electrostatic DC, electrodynarnic DC, RF linear, magnetic induction linear or continuous wave. For example, ron type accelerators are available from IBA, m, such as the Rhodotron® system, while DC type accelerators are available from RDI, now IBA Industrial, such as the Dynamitron®. Ions and ion accelerators are discussed in Introductory Nuclear s, Kenneth S. Krane, John Wiley & Sons, Inc. , Krsto Prelec, FIZIKA B 6 (1997) 4, l77-—206, Chu, William T., “Overview of Light-Ion Beam y” Columbus—Ohio, ICRU-IAEA Meeting, 18-20 March 2006,1wata, Y. et al., “Alternating—Phase-Focused IH—DTL for Heavy-Ion Medical Accelerators” Proceedings ofEPAC 2006, Edinburgh, Scotland and Leaner, C.M. et al., “Status of the Superconducting ECR Ion Source Venus” Proceedings ofEPAC 2000, Vienna, Austria.

Gamma radiation has the advantage of a significant penetration depth into a variety of materials. s of gamma rays include radioactive nuclei, such as isotopes PCTfU$2012/024970 of cobalt, calcium, technicium, chromium, gallium, indium, iodine, iron, krypton, samarium, selenium, sodium, m, and xenon.

Sources ofx rays include electron beam collision with metal targets, such as tungsten or molybdenum or alloys, or compact light sources, such as those produced commercially by Lyncean. s for ultraviolet radiation include deuterium or cadmium lamps.

Sources for infrared radiation include sapphire, zinc, or seienide window ceramic lamps.

Sources for aves include klystrons, Slevin type RF sources, or atom beam sources that employ hydrogen, oxygen, or nitrogen gases.

In some embodiments, a beam of electrons is used as the radiation . A beam of electrons has the advantages of high dose rates (e.g., l, 5, or even 10 Mrad per second), high hput, less containment, and less confinement equipment. Electrons can also be more efficient at causing chain scission. In addition, electrons having energies of 4—1 0 MeV can have a penetration depth of 5 to 30 mm or more, such as 40 Electron beams can be generated, e.g., by electrostatic generators, cascade generators, transformer generators, low energy rators with a scanning , low energy accelerators with a linear e, linear accelerators, and pulsed accelerators.

Electrons as an ionizing ion source can be useful, e.g., for relatively thin sections of material, 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 electron of the electron beam is from about 0.3 MeV to about 2.0 MeV (million electron volts), e.g., fi'om about 0.5 MeV to about 1.5 MeV, or from about 0.7 MeV to about 1.25 MeV.

Electron beam irradiation devices may be procured commercially from Ion Beam Applications, Louvain-la-Neuve, Belgium or the Titan Cmporation, San Diego, CA.

Typical electron energies can be 1 MeV, 2 MeV, 4.5 MeV, 7.5 MeV, or 10 MeV.

Typical on 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 ofthe feedstock depends on the electron energy used and the dose applied, while exposure time s on the power and dose. Typical doses may take values of 1 kGy, 5 kGy, 10 kGy, 20 kGy, PCT/U52012/024970 50 chy, 100 kGy, or 200 kGy. In a some ments energies between 0 MeV (e.g., 0.5—0.8 MeV, 0.5—5 MeV, 0.84 MeV, 0.8—3 MeV, 0.8-2 MeV or 5 MeV) can be used. In some embodiment doses between 1—100 Mrad (e.g., 2-80 Mrad, 5-50 Mrad, 5- 40 Mrad, 5-30 Mrad or 5-20 Mrad) can be used. In some preferred embodiments, an energy between 0.8~3 MeV (e.g., 0.8-2 MeV or 0.8—1.5 MeV) combined with doses between 5-50 Mrad (cg, 5—40 Mrad, 5—30 Mrad or 5—20 Mrad) can be used.

Ion Particle Beams Particles heavier than electrons can be utilized to irradiate paper feedstock als. For example, protons, helium nuclei, argon ions, silicon ions, neon ions carbon ions, phosphorus ions, oxygen ions or nitrogen ions can be utilized. In some embodiments, particles heavier than ons can induce higher amounts of chain scission (relative to lighter particles). In some instances, vely charged particles can induce higher amounts of chain scission than negatively charged particles due to their acidity.

Heavier particle beams can be generated, e.g., using linear accelerators or rons. In some embodiments, the energy of each particle of the beam is from about 1.0 MeV/atomic unit (MeV/emu) 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.

In certain embodiments, ion beams used to irradiate paper feedstock can include more than one type of ion. For e, ion beams can include mixtures of two or more (e. g., three, four or more) different types of ions. Exemplary mixtures can include carbon ions and protons, carbon ions and oxygen ions, nitrogen ions and protons, and iron ions and protons. More generally, mixtures of any ofthe ions discussed above (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.

In some embodiments, ion beams for irradiating paper ock include positively-charged ions. The positively charged ions can include, for example, positively charged hydrogen ions (cg, protons), noble gas ions (e.g., , neon, argon), carbon ions, nitrogen. ions, oxygen ions, silicon atoms, phosphorus ions, and metal ions such as PCT/U52012/024970 sodium ions, calcium ions, and/or iron ions. Without wishing to be bound by any theory, it is believed that such positively-charged ions behave ally as Lewis acid moieties when exposed to materials, initiating and sustaining cationic ring-opening chain scission reactions in an oxidative nment.

In certain embodiments, ion beams for irradiating paper feedstock include negatively—charged ions. Negatively charged ions can include, for example, negatively charged hydrogen ions (e.g., hydride ions), and negatively d ions of various relatively electronegative nuclei (cg, oxygen ions, nitrogen ions, carbon ions, n 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 nment.

In some embodiments, beams for irradiating paper feedstock can include neutral atoms. For example, any one or more of hydrogen atoms, helium atoms, carbon atoms, nitrogen atoms, oxygen atoms, neon atoms, silicon atoms, phosphorus atoms, argon atoms, and iron atoms can be included in beams that are used for irradiation. 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 present in the beams.

In certain embodiments, ion beams used to irradiate paper feedstock include singly—charged ions such as one or more of H“, H', He+, Ne+, Ari", C)”, C", 0+, 0", N, N, Si", Si', 13+, P", Na+, Ca+, and Fe”. In some embodiments, ion beams can e ly—charged ions such as one or more of C”, C“, C”, NEH", NSJ", N3“, 02+, 02', 022‘, Si2+, Si“, Si ', and Si“'. In general, the ion beams can also include more complex polynuclear ions that bear multiple positive or negative charges. In n embodiments, by virtue of the structure of the clear ion, the positive or negative charges can be effectively distributed over substantially the entire structure ofthe ions. In some embodiments, the positive or negative charges can be somewhat localized over ns ofthe structure of the ions.

PCT/U82012/024970 Electromagnetic ion In ments in which the irradiating is performed with electromagnetic radiation, the electromagnetic radiation can have, e.g., energy per photon (in electron volts) of r than 102 eV, e.g., greater than 103, 104, 105, 106, or even greater than 107 eV. In some embodiments, the electromagnetic radiation has energy per photon of between 104 and 107, e.g., between 105 and 106 eV. The electromagnetic radiation can have a ncy of, e.g., greater than 1016 hz, greater than 1017 hz, 1018, 1019, 1020, or even greater than 1021 hz. Typical doses may take values of greater than 1 Mrad (e.g., greater than 1 Mrad, greater than 2 Mrad). In some embodiments, the omagnetic 1O radiation has a frequency ofbetween 1018 and 1022 hz, e.g., between 1019 to 1021 hz. In some embodiment doses between 1-100 Mrad (e.g., 2—80 Mrad, 5-50 Mrad, 5-40 Mrad, -30 Mrad or 5—20 Mrad) can be used.

Quenching and Controlled Functionalization After treatment with ionizing radiation, any ofthe als or mixtures described herein may become ionized; that is, the treated material may include radicals at levels that are detectable with an electron spin resonance spectrometer. If an ionized feedstock remains in the atmosphere, it will be ed, such as to an extent that carboxylic acid groups are generated by reacting with the atmospheric oxygen. In some instances with some materials, such oxidation is desired e it can aid in the further breakdown in molecular weight of the carbohydrate—containing biomass, and the oxidation groups, e.g., carb0xylic acid groups can be helpful for solubility and microorganism utilization in some instances. However, since the radicals can “live” for some time after irradiation, e.g., longer than 1 day, 5 days, 30 days, 3 months, 6 months or even longer than 1 year, material properties can continue to change over time, which in some ces, can be undesirable. Thus, it may be desirable to quench the ionized material.

After ionization, any ionized material can be quenched to reduce the level of radicals in the ionized material, e.g., such that the radicals are no longer detectable with the electron spin reSOnance spectrometer. For example, the radicals can be quenched by the ation of a sufficient pressure to the material and/or by utilizing a fluid in contact with the ionized al, such as a gas or liquid, that reacts with (quenches) the radicals.

PCT/U82012/024970 Using a gas or liquid to at least aid in the quenching of the radicals can be used to functionalize the ionized material with a desired amount and kind of functional groups, such as carboxylic acid groups, enol groups, aldehyde groups, nitro groups, nitrile groups, amino , allryl amino groups, alkyl groups, chloroalkyl groups or chlorofluoroalkyl groups.

In some instances, such quenching can improve the stability of some of the ionized materials For example, quenching can improve the resistance of the material to oxidation. Functionalization by quenching can also improve the solubility of any material described herein, can improve its thermal stability, and can improve al utilization by various microorganisms. For example, the functional groups imparted to the material by the quenching can act as receptor sites for attachment by microorganisms, c.g., to enhance ose ysis by various microorganisms.

In some embodiments, quenching includes an application of pressure to the ionized material, such as by mechanically deforming the material, e.g., directly ically compressing the al in one, two, or three dimensions, or applying re to a fluid in which the material is immersed, e.g., isostatic pressing. In such instances, the ation of the material itself brings radicals, which are often trapped in crystalline s, in close enough proximity so that the radicals can recombine, or react with another group. In some instances, the pressure is applied together with the ation of heat, such as a ent ty ofheat to elevate the temperature of the material to above a melting point or softening point of a component of the material, such ose or another polymer. Heat can improve molecular mobility in the al, which can aid in the quenching of the radicals. When pressure is utilized to quench, the pressure can be greater than about 1000 psi, such as greater than about 1250 psi, 1450 psi, 3625 psi, 5075 psi, 7250 psi, 10000 psi or even greater than 15000 psi.

In some embodiments, quenching includes contacting the ionized material with a fluid, such as a liquid or gas, e.g., a gas capable of ng with the radicals, such as acetylene or a mixture of acetylene in nitrogen, ethylene, chlorinated ethylenes or chlorofluoroethylenes, propylene or mixtures of these gases. In other particular embodiments, quenching includes contacting the ionized material with a liquid, e.g., a liquid soluble in, or at least capable of penetrating into the material and reacting with the PCT/U52012/024970 radicals, such as a diene, such as 1,5—eyclooctadiene. In some specific embodiments, quenching includes contacting the material with an antioxidant, such as Vitamin E. If desired, the feedstock can include an antioxidant dispersed therein, and the quenching can come from contacting the antioxidant dispersed in the feedstock with the radicals.

Functionalization can be ed by utilizing heavy charged ions, such as any of the heavier ions described herein. For example, if it is desired to enhance oxidation, charged oxygen ions can be utilized for the irradiation. If nitrogen functional groups are d, nitrogen ions or anions that e nitrogen can be utilized. Likewise, if sulfur or phosphorus groups are desired, sulfur or phosphorus ions can be used in the 1O irradiation.

Doses In some instances, the irradiation is performed at a dosage rate of greater than about 0.25 Mrad per , e.g., greater than about 0.5, 0.75, 1.0, 1.5, 2.0, or even greater than about 2.5 Mrad per second. 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 kiiorads/hour or between 50.0 and 350.0 kilorads/hour. In some embodiments, ation is performed at a dose rate of greater than about 0.25 Mrad per second, e.g., greater than about 0.5, 0.75, 1, 1.5, 2, 5, 7, 10, 12, 15, or even greater than about 20 Mrad per second, e.g., about 0.25 to 2 Mrad per second.

In some embodiments, the ating (with any radiation source or a combination of sources) is performed untii the material receives a dose of 0.25 Mrad, e.g., at least 1.0, 2.5, 5.0, 8.0, 10, 15, 20, 25, 30, 35, 40, 50, or even at least 100 Mrad. In some embodiments, the ating is performed until the material receives a dose of between 1.0 Mrad and 6.0 Mrad, e.g., n 1.5 Mrad and 4.0 Mrad, 2 Mrad and 10 Mrad, 5 Mrad and 20 Mrad, 10 Mrad and 30 Mrad, 10 Mrad and 40 Mrad, or 20 Mrad and 50 Mrad. In some embodiments, the irradiating is performed until the material receives a dose of from about 0.1 Mrad to about 500 Mrad, fi'orn about 0.5 Mrad to about 200 Mrad, from about 1 Mrad to about 100 Mrad, or from about 5 Mrad to about 60 Mrad. In some ments, a relatively low dose of radiation is applied, e.g., less than 60 Mrad. 2012/024970 Sonication can reduce the lar weight and/or crystallinity of the polymers comprising the paper feedstock, e.g., cellulose. Sonication can also be used to sterilize the materials. As discussed above with regard to radiation, the process parameters used for sonication can be varied depending on various factors.

In one method, a first material that includes cellulose having a first number average molecular weight (Mm) is dispersed in a medium, such as water, and ted and/or otherwise cavitated, to provide a second material that includes ose having a second number average molecular weight (Mm) lower than the first number average molecular weight. The second material (or the first and second al in n embodiments) can be combined with a microorganism (with or without enzyme treatment) that can utilize the second and/or first material to produce an intermediate or product.

Since the second material includes 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 sible, swellable, and/or soluble, e.g., in a solution containing a microorganism.

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

In some instances, the second material es cellulose that has a crystallinity (C2) that is lower than the crystallinity (C1) of the cellulose of the first material. For e, (C2) can be lower than (C1) by more than about 10 percent, e.g., more than about 15, 20, 25, 30, 35, 40, or even more than about 50 t.

In some embodiments, the sonication medium is an s 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(ethylene glycol).

PCT/U32012/024970 In other embodiments, the sonication medium is non—aqueous. For example, the sonication can be med in a hydrocarbon, e.g., toluene or heptane, an ether, e.g., diethyl ether or tetrahydrofuran, or even in a liquefied gas such as argon, xenon, or nitrogen. flrolysis One or more pyrolysis processing sequences can be used to process paper feedstock from a wide variety of different s to extract useful nces from the materials, and to provide partially degraded materials which function as input to further 1O processing steps and/or sequences. Pyrolysis can also be used to ize the materials.

Pyrolysis conditions can be varied depending on the characteristics of the feedstock and/or other factors.

In one example, a first material that includes cellulose having a first number average molecular weight (Mm) is pyrolyzed, e.g., by heating the first material in a tube furnace (in the presence or e of oxygen), to provide a second material that includes cellulose having a second number average molecular weight (Mm) lower than the first number average lar .

Since the second material includes cellulose having a reduced molecular weight relative to the first al, and in some instances, a reduced crystallinity as well, the second material is generally more dispersible, swellablc and/or soluble, e.g., in a on containing a microorganism.

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

In some instances, the second material includes cellulose that has a crystallinity (C2) that is lower than the llinity (C1) ofthe cellulose ofthe first material. For example, (C2) can be lower than (C1) by more than about 10 percent, e. g., more than about 15, 20, 25, 30, 35, 40, or even more than about 50 percent.

PCT/U52012/024970 In some embodiments, the pyrolysis ofthe materials is continuous. In other ments, the material is pyrolyzed for a pre-determined time, and then allowed to cool for a second pie-determined time before pyrolyzing again.

Oxidation One or more oxidative processing sequences can be used to process paper ck from a wide variety of different sources to extract useful substances from the feedstock, and to provide partially degraded and/or altered feedstock which functions as input to fiirther processing steps and/or sequences. The oxidation conditions can be varied, e.g., depending on the lignin content of the feedstock, with a higher degree of oxidation generally being desired for higher lignin content feedstocks.

In one method, a first al that es ose having a first number average molecular weight (Mm) and having a first oxygen content (01) is oxidized, e.g., by heating the first al in a stream of air or oxygen-enriched air, to provide a second material that includes cellulose having a second number average molecular weight (Mm) and having a second oxygen t (02) higher than the first oxygen content (01).

The second number average molecular weight of the second material is generally lower than the first number average lar weight of the first material. For example, the molecular weight may be reduced to the same extent as discussed above with respect to the other physical treatments. The llinity ofthe second material may also be reduced to the same extent as discussed above with respect to the other physical treatments.

In some embodiments, the second oxygen content is at least about five percent higher than the first oxygen content, e.g., 7 .5 percent higher, 10.0 t higher, 12.5 percent higher, 15.0 percent higher or 17.5 percent higher. In some preferred embodiments, the second oxygen content is at least about 20.0 percent higher than the first oxygen content ofthe first material. Oxygen content is measured by elemental analysis by pyrolyzing a sample in a furnace operating at 1300 °C or higher. A suitable elemental analyzer is the LEGO 32 analyzer with a VTF-900 high temperature pyrolysis furnace.

PCT/U52012/024970 Generally, oxidation of a al occurs in an oxidizing environment. For example, the oxidation can be ed 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 oxidants, 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.

Some oxidative methods ofreducing recalcitrance in a paper feedstock employ Fenton-type chemistry. Such methods are disclosed, for example, in US. Serial No. ,289, the complete disclosure of which is incorporated herein by reference. ary oxidants include peroxides, such as hydrogen per0xide and l peroxide, persulfates, 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).

In some situations, pH is maintained at or below about 5.5 during contact, such as between 1 and 5, between 2 and 5, n 2.5 and 5 or between about 3 and 5.

Oxidation conditions can also include a contact period ofbetween 2 and 12 hours, e.g., between 4 and 10 hours or between 5 and 8 hours. In some instances, temperature is ined at or below 300 °C, e.g., at or below 250, 200, 150, 100 or 50 °C. In some instances, the temperature remains substantially t, e.g., at or about 20—25 °C.

In some embodiments, the one or more oxidants are d as a gas, such as by generating ozone in-sz'tu by irradiating the al through air with a beam of particles, such as electrons.

In some embodiments, the mixture further es one or more hydroquinones, such as 2,5-dimethoxyhydroquinone (DMI-IQ) and/or one or more benzoquinones, such as 2,5-dimethoxy—l,4-benzoquinone (DMBQ), which can aid in electron transfer reactions.

In some embodiments, the one or more oxidants are electrochemically—generated in—sz‘tu. For example, hydrogen peroxide and/0r ozone can be electro—chemically produced within a contact or reaction vessel.

WO 12488 PCT/U82012/024970 Other ses To Solubilize, Reduce Reealeitrance Or To Funetionalize Any ofthe processes of this aph 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, chemical treatment (e.g., acid treatment (including concentrated and dilute acid treatment with mineral acids, such as sulfuric acid, hydrochloric acid and organic acids, such as trifluoroaeetic acid) and/or base ent (e.g., treatment with lime or sodium hydroxide)), UV treatment, screw ion treatment (see, e.g., U.S. Serial No. 13/099,151, solvent treatment (e.g., treatment with ionic liquids) and freeze milling (see, e.g., U.S. Serial No. 12/502,629 now US. Patent No. 7,900,857).

Saccharification In order to convert the paper feedstock to fermentable sugars, the cellulose in the feedstock is hydrolyzed by a saccharifying agent, e.g., an enzyme, a process referred to as saccharification. 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 s solution.

Enzymes and organisms that break down cellulose contain or manufacture various cellulolytic s (cellulases), ligninascs or various small molecule biomassdestroying metabolites. These enzymes may be a compiex of enzymes that act synergistically to degrade crystalline cellulose. es of ccllulolytic enzymes include: endoglucanases, cellobiohydrolases, and cellobiases (B—glucosidases). Referring to a ccllulosic substrate is initially hydrolyzed by endoglucanases at random locations producing oligomeric intermediates. These intermediates are then ates for exo—splitting ases such as cellobiohydrolase to produce cellobiose from the ends of the cellulose polymer. Cellobiose is a water-soluble nked dimer of glucose. Finally ccllobiasc cleaves cellobiose to yield glucose.

Suitable saccharifying agents are bed, for example, in the Materials section below.

As noted above, a food—based nutrient source or nutrient package is preferably added prior to or during saccharification, and an enzyme is added that is selected to WO 12488 PCT/USZOl2/024970 e nts from the food-based nutrient source. Suitable enzymes are described, for example, in the Materials section below.

The saccharifrcation process can be partially or completely med in a tank (e.g., a tank having a volume of at least 4000, 40,000, 400,000 L or 1,000,000 L) in a manufacturing plant, and/or can be partially or completely performed in transit, e.g., in a rail car, tanker truck, or in a supertanker or the hold of a ship. The time required for complete saccharification will depend on the process conditions and the feedstock and enzyme used. If saccharification is performed in a manufacturing plant under controlled conditions, the cellulose may be substantially entirely converted to glucose in about 12— 96 hours. If rification is performed partially or completely in transit, saccharification may take longer.

It is generally preferred that the tank contents be mixed during saccharification, e.g., using jet mixing as bed in US. Applications Serial Nos. 12/782,694, 13/293,985 and ,977, the full disclosure ofwhich are incorporated by reference herein.

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.

It is generally preferred that the concentration ofthe resulting glucose solution be relatively high, e.g., greater than 40%, or greater than 50, 60, 70, 80, 90 or even greater than 95% by weight. This reduces the volume to be shipped, if saccharification and fermentation are med at different locations, and also inhibits microbial growth in the solution. However, lower concentrations may be used, in which case it may be ble to add an antimicrobial additive, e.g., a broad spectrum otic, in a low concentration, e.g., 50 to 150 ppm. Other le antibiotics include amphotericni B, ampicillin, chlorarnphenicol, ciprofloxacin, gentamicin, hygromycin B, kanamycin, neomycin, penicillin, puromycin, streptomycin. Antibiotics will inhibit growth of microorganisms during transport and storage, and can be used at appropriate concentrations, e.g., between 15 and 1000 ppm by weight, e.g., between 25 and 500 ppm, or between 50 and 150 ppm. If d, an antibiotic can be included even if the sugar concentration is relatively high.

PCT/U52012/024970 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 lled, e.g., by controlling how much saccharification takes place. For example, concentration can be increased by adding more ock to the solution. In order to keep the sugar that is being produced in solution, a surfactant can be added, e.g., one ofthose sed above.

Solubility can also be increased by increasing the temperature of the solution. For example, the solution can be ined at a temperature of 40—50°C, 60-80°C, or even higher.

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 or crude form. The concentrated form can have, for example, a total sugar concentration ofbetween about 90 t by weight and about 100 percent by weight, e.g., 92, 94, 96 or 98 t 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 , easier to manufacture and becomes both an intermediate and a product, providing an option to the biorefinery as to which products to manufacture.

In some instances, the powdered, granulate or ulate material can also include one or more of the materials, e.g., additives or chemicals, described , such as the food—based nutrient or nt package, a nitrogen source, e. g., urea, a surfactant, an enzyme, or any microorganism described herein. In some instances, all materials needed for a bio-process are combined in the powdered, granulate or particulate material.

Such a form can be a particularly convenient form for transporting to a remote cessing facility, such as a remote biofuels manufacturing facility. Such a form can also be advantageous to store and handle.

In some instances, the powdered, granulatc or ulate material (with or Without added materials, such as additives and chemicals) can be treated by any of the physical treatments described in US. Serial No. 12/429,045, incorporated by reference above. For e, ating the powdered, granulate or particulate material can increase its solubility and can sterilize the material so that a bioprocessing facility can WO 12488 PCT/U52012/024970 integrate the material into their process directly as may be required for a contemplated ediate or product.

In certain ces, the powdered, granulate or particulate material (with or without added materials, such as additives and chemicals) can be carried in a ure or a carrier for ease of transport, storage or handling. For example, the structure 01' carrier can include or incorporate a bag or liner, such as a degradable bag or liner. Such a form can be ularly useful for adding directly to a cess system.

Fermentation ‘10 Microorganisms can produce a number of useful intermediates and products by fermenting a low molecular weight sugar produced by saccharifying the paper feedstock materials. For example, fermentation or other bioprocesses can produce alcohols, organic acids, hydrocarbons, hydrogen, proteins or mixtures of any of these materials.

Yeast and Zymomonas ia, for example, can be used for fermentation or conversion. Other microorganisms are discussed in the Materials section, below. The optimum pH for fermentations is about pH 4 to 7. For example, the optimum pH for yeast is from about pH 4 to 5, while the optimum pH for Zymomonas is from about pH 5 to 6.

Typical fermentation times are about 24 to 168 hours (cg, 24 to 96 hrs) with temperatures in the range of 20 °C to 40 °C (e.g., 26 °C to 40 °C), however philic microorganisms prefer higher temperatures.

In some embodiments e.g., when anaerobic organisms are used, at least a portion of the fermentation is conducted in the absence of oxygen e.g., under a blanket of an inert gas such as N2, Ar, He, C02 or mixtures thereof. Additionally, the mixture may have a constant purge of an inert gas flowing through the tank during part of or all of the fermentation. In some cases, anaerobic condition can be achieved or maintained by carbon dioxide production during the fermentation and no additional inert gas is needed.

In some embodiments, all or a n of the fermentation process can be interrupted before the low molecular weight sugar is completely ted to a t (cg, ethanol). The intermediate fermentation products include high concentrations of Sugar and carbohydrates. The sugars and carbohydrates can be isolated as discussed below. These ediate fermentation products can be used in preparation of food for PCT/U82012/024970 human or animal consumption. Additionally or alternatively, the intermediate fermentation products can be ground to a fine particle size in a stainless—steel laboratory mill to produce a flour—like substance.

The fermentations include the methods and products that are disclosed in US.

Provisional Application Serial No. ,559, filed December 22, 2012, and U.S. application 61/579,576, filed December 22, 2012 incorporated by nce herein in its Mobile fermentors can be utilized, as described in US. Provisional Patent Application Serial 60/832,735, now Published International Application No. WO 2008/011598. Similarly, the sacchariiication equipment can be mobile. Further, saccharification and/or fermentation may be performed in part or entirely during transit.

Distillation After fermentation, the resulting fluids can be distilled using, for example, a “beer column” to te ethanol and other alcohols from the majority of water and residual solids. The vapor g the beer column can be, c.g., 35% by weight ethanol and can be fed to a rectification column. A e of nearly azeotropic (92.5%) ethanol and water from the rectification column can be purified to pure (99.5%) ethanol using vapor-phase molecular sieves. The beer column bottoms can be sent to the first effect of a effect evaporator. The ication column reflux ser can provide heat for this first effect. After the first effect, solids can be separated using a centrifuge and dried in a rotary dryer. A portion (25%) of the centrifuge effluent can be recycled to fermentation and the rest sent to the second and third evaporator effects. Most of the evaporator condensate can be returned to the process as fairly clean condensate with a small portion split offto waste water treatment to prevent build-up of low—boiling compounds.

Other Possible Processing of Sugars Processing during or after saccharifieation can include isolation and/or concentration of sugars by chromatography e.g., simulated moving bed chromatography, precipitation, fugation, crystallization, solvent evaporation and combinations thereof. In on, or optionally, processing can include isomerization of one or more of PCT/U82012/024970 the sugars in the sugar solution or suspension. Additionally, or ally, the sugar solution or suspension can be chemically sed e.g., glucose and xylose can be hydrogenated to sorbitol and xylitol respectively. Hydrogenation can be accomplished by use of a catalyst e.g., Pt/y—Alzog, Ru/C, Raney Nickel in ation with H2 under high pressure e.g., 10 to 12000 psi.

Some le processing steps are sed in in US. Provisional Application Serial No. 61/579,552, filed December 22, 2012, and in US. Provisional Application Serial No. 61/5 79,576 filed December 22, 2012, incorporated by reference herein in its entirety above.

REMOVING 0F FILLERS, INKS, AND COATINGS Paper feedstock used in the processes described can contain fillers, gs, laminated material, pigments, inks and binders. These can be rem0ved and either discarded or recycled as described here.

Inorganic fillers and coatings e. g., those described in the materials section below can be d at any point during the process. For example, the inorganic filler and coating can be removed from the ock after a mechanical, physical or chemical treatment to reduce the recalcitrance of the feedstock; after ation with a fluid; afier, during or before iification; after, during or before a purification step; after, during or before a fermentation step; and/or after, during or before a chemical conversion step. The fillers and coatings can be removed by any means e.g., by sedimentation, precipitation, ligand sequestration, filtration, ion, chemical conversion and centrifugation. Some of the physical treatments discussed herein (see Physical Treatment section) can aid in separating the cellulosic mateiials from the inorganic fillers and coatings (e. g., mechanical treatments, chemical treatments, irradiation, pyrolysis, sonication and/or oxidiation). The recovered inorganic fillers can be recycled or discarded.

Inks that are present can be removed from the feedstock at any point during the process. Inks can be a complex medium composed of several components e.g., solvents, pigments, dyes, resins, lubricants, solubilizers, surfactants, particulate matter and/or fluorescers. For e, printed papers, e.g., magazines and catalogs, may include high levels of the pigments generally used in printing inks. In some cases the papers include metal—based ts, organic pigments, and/or Lake pigments. For example, pigments that can be used are Yellow Lakes, Tartrazine Yellow Lake, Hansa Yellows, Diarylide' s, Yellow azo pigments, Fluorescent Yellow, Diarylide Orange, DNA Orange, Pyrazolone , Fast Orange FZG, Benzimidazolone Orange HL, Ethyl Lake Red C, Para Reds, ine Red, Carmine F.B., Naphthol Reds and Rubines, Permanent Red PRC, Bordeaux FRR, Rubine Reds, Lithol Reds, BON Red, Lithol Rubine 4B, BON Maroon, Rhodamine 6G, Lake Red C, BON Aiylamide Red, Quinacrinone Magentas, Copper Ferrocyanide Pink, Benzimidazolone es and Reds, Azo Magenta G, Anthraquinone Scarlet, Madder Lakes, Phthalocyanine Blues, PMTA Victoria Blue, Victoria Blue CFA, Ultramarine Blue, Indanthrene Blue, Alkali Blues, k Blue, Benzimz‘dazolone Bordeaux HF 3R, PMTA Rhodarnine, PMTA Violet, Dioxazine Violet, Carbazole Violet, Crystal Violet, ine Violet B, Thioindigoid Red, Phthalocyanine , PMTA Greens, Benzirnidazolone Brown HFR, Cadmium Red, Cadmium Yellow, Cadmium Oranges, m—Mercury Reds, Iron Oxide Yellows, Irons Oxide Blues, Iron Oxide browns, Iron Oxide Reds, Ultramarine Blues, Ultramarine Violet, Chromium Antimony Titanium Buff, copper phthalocyanine blue, green copper phthalocyanine pigments, potash blue and soda blue pigments. The removal of ink may help improve certain parts in the process. For example, some ink can be toxic to microorganisms used in the process. The inks can also impart an undesirable coloration or toxicity to the final product. Furthermore, ng the inks may allow these to be recycled, improving the cost benefits to the process and lessening the environmental impact of the paper feedstock. The inks can be removed by any means. For example, removal may include sion, floatation, ng and/or washing steps, extraction with solvents (e. g., supercritical C02, alcohol, water and organic solvents), settling, al means, sieving and/or precipitation. Some of the physical treatments discussed herein (see Physical Treatment section) can aid in separating the cellulosic materials from the inks (e.g., mechanical treatments, chemical treatments, irradiation, pyrolysis, sonication and/or oxidiation). In addition enzymatic deinking technologies such as those disclosed in US. patent 224 hereby incorporated by reference herein, can be used.

PCT/U82012/024970 Coating materials, e.g., those found in poly-coated paper described in the materials section below, can be d from the feedstock at any point during the process. This can be done by, for example, the s mentioned above for removal of pigments and inks and inorganic materials. In some cases, where polycoated paper is a laminate, de—lamination can be done by, for example, chemical and/or mechanical means.

The non~cellulosic laminate portions can then be ted from the cellulose containing layers and discarded and/or ed.

INTERMEDIATES AND TS The processes and nts discussed herein can be used to convert paper feedstocks to one or more products, Such as energy, fuels, foods and materials. Specific examples of products include, but are not d to, hydrogen, sugars (e.g., glucose, xylose, arabinose, mannose, galactose, fructose, disaccharides, oligosaccharides and polysaccharides), alcohols (cg, monohydric alcohols or ic alcohols, such as ethanol, n-propanol, isobutanol, sec—butanol, tert—butanol or n-butano l), hydrated or hydrous alcohols, e.g., containing greater than 10%, 20%, 30% or even greater than 40% water, sugars, biodiesel, c acids (e.g., acetic acid and/or lactic acid), hydrocarbons, e.g., methane, , propane, isobutene, e, n—hexane, biodiesel, bio-gasoline and mixtures thereof, co-products (e.g., proteins, such as cellulolytic proteins (enzymes) or single cell proteins), and mixtures of any ofthese in any combination or relative concentration, and optionally in combination with any additives, e.g., fiiel additives.

Other examples include carboxylic acids, such as acetic acid or butyric acid, salts of a ylic 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, aldehydes, alpha, beta unsaturated acids, such as acrylic acid and olefins, such as ethylene. Other alcohols and alcohol derivatives include propanol, propylene glycol, 1,4-butanediol, 1,3-propanediol, sugar alcohols (e.g., crythritol, glycol, ol, sorbitol threitol, arabitol, ribitol, mannitol, dulcitol, fucitol, iditol, isomalt, maltitol, lactitol, xylitol and other polyols), methyl or ethyl esters of any of these alcohols. Other products e methyl te and methylrnethacrylate. The product may also be an organic acid, e.g., lactic acid, formic acid, acetic acid, propionic acid, butyric acid, succinic acid, valeric acid, caproic, PCT/U82012/024970 palmitic acid, stearic acid, oxalic acid, e acid, glutaric acid, oleic acid, linoleic acid, glycolic acid, 'y—hydroxybutyric acid, a mixture thereof, a salt of any of these acids, or a mixture of any of the acids and their respective salts.

Other intermediates and products, including food and ceutical products, are described in US. Serial No. ,900, the full disclosure of which is hereby incorporated by nce herein.

Paper Feedstocks Suitable paper feedstocks include paper that is highly pigmented, coated or filled and can have a low calorific value. Sources of such paper include magazines, catalogs, books, manuals, labels, calendars, greeting cards and other high quality printed materials such as prospectuses, brochures and the like. The papers may include at least 0.025% by weight ofpigment, filler or coating, e.g., from 0 to 80%, 0 to 50%, 0.1 to 50%, 0.1 to %, 0.1 to 20%, 0.5 to 2.5%, 0.2 to 15%, 0.3 to 10%, 0.5 to 5%.

Other le paper feedstocks include high basis weight coated. paper and/or paper with a high filler content i.e., at least 10 wt.%. These papers can be printed or unprinted. Examples of this type of feedstock include paper having a basis weight, as defined as the weight in pounds (lb) for a ream (500 ) of 25” X 38” sheets, of at least 35 1b., for example at least 45 1b., at least 50 1b., at least 60 lb, at least 70 lb. or at least 80 lb. The feedstock includes paper having a basis weight below 330 1b., for example below about 300 lb, below about 250 lb, below about 200 1b, below about 150 1b, below about 120 lb, below about 110 1b, below about 105 lb or below about 100 lb.

For example the basis weight may be between 35 lb and 330 lb, 35 lb and 120 lb, n 35 lb and 110 lb, between 35 lb and 100 lb, between 35 lb and 90 lb, between 45 lb and 120 lb, between 45 lb and 110 lb, between 45 lb and 100 lb, between 45 lb and 90 lb, between 50 lb and 120 lb, between 50 lb and 110 lb, between 50 lb and 100 lb, between 50 lb and 90 1b, between 60 lb and 120 lb, between 60 lb and 110 lb, between 60 lb and 100 lb, between 60 lb and 90 1b, between 60 lb and 120 1b, between 60 lb and 110 lb, between 60 lb and 100 lb, between 60 lb and 90 lb, n 70 1b and 1201b, between 70 lb and 110 lb, between 70 lb and 100 lb, between 70 lb and 90 lb, between 90 lb and PCTfUS2012/024970 330 lb, between 90 lb and 300 lb, between 90 1b and 250 lb, between 90 lb and 200 lb, between 90 lb and 150 lb, between 90 lb and 110 1b, between 110 lb and 330 11), between 110 lb and 300 lb, between 110 lb and 250 lb, between 110 lb and 200 lb, between 110 lb and 150 lb, between 130 lb and 330 lb, between 130 lb and 300 lb, between 130 lb and 250 lb, between 130 lb and 200 lb, or between 130 lb and 150 lb, In some embodiments, the papers have relatively high density, e.g., greater than 1.11 g/cm3, in some cases from about 1.11 to 2 g/crn3 e.g., 1.11 to 1.8 g/cm2, 1.11 to 1.6 g/cm2, 1.11 to 1.52 g/cm2, 1.2 to 1.8 g/cm2, 1.2 to 1.6 g/emz, 1.2 to 1.52 g/cm2, 1.3 to 1.8 g/cm2, 1.3 to 1,6 g/crn2 or 1.3 to 1.52 g/cm2 Such papers often have a high ash content e.g., at least 8wt.%, at least 10 wt.%, at least 15 wt.% at least 20 wt.% or at least 50 wt.%. The ash content can be between 8 and 50%, e.g., between 10 and 50%, between 20 and 50%, between 30 and 50%, between 10 and 40%, between 20 and 40%, between 10 and 30% or between 10 and 20%. The papers can have a high filler content, e.g., at 0% by , e.g., at least 20 wt%, at least 30 wt%, at least 40 wt% or at least 50 wt%. Filler contents can be between 10 and 80%, e.g., between 20 and 80%, between 30 and 80%, between 40 and 80%, between 10 and 70%, between 20 and 70%, n 30 and 70%, between 40 and 70%, between 10 and 60%, between 20 and 60%, between 30 and 60% and n 40 and 60%. Suitable fillers include clays, oxides (e.g., titania, silica, alumina), carbonates (e.g., m carbonate), tes (e.g., Talc) and aluminosilicates (e.g., Kaolin). One suitable grade of coated paper is referred to in the industry as Machine Finished Coated (MFC) paper. In other ments the paper can have a high surface density (i.e., Grammage), for example, at least 50 g/m2, at least 60 g/m2, at least 70 g/m2, at least 80 g/m2 or at least 90 g/m2.The Grammage can be between 50 g/m2 and 200 g/m2, between 50 g/rn2 and 175 g/m2, between 50 g/m2 and 150 g/m2, between 50 g/rn2 and 125 g/m2, between 50 g/m2 and 100 g/m2, between 60 g/m2 and 200 g/m2, between 60 g/m2 and 175 g/m2, between 60 g/m2 and 150 g/m2, between 60 g/m2 and 125 g/m2, between 60 g/m2 and 100 g/m2, between 70 g/m2 and 200 g/m2, between 70 g/m2 and 175 g/m2, between 70 g/m2 and 150 g/m2, between 70 g/m2 and 125 g/m2, between 70 g/rn2 and 100 g/m2, between 80 g/m2 and 200 g/m2, n 80 g/m2 and 175 g/m2, between 80 g/m2 and 150 g/ml, between 80 gi’m2 and 125 g/m2, between 80 g/m2 and 100 g/m2, between 130 g/m2 and 500 g/m2, between 130 g/m2 and 450 g/m2, between 130 g/m2 and 350 g/m2, between 130 g/m2 and 300 g/m2, between 130 g/m2 and 250 g/m2, between 130 g/m2 and 200 g/m2, between 130 g/m2 and 175 g/m2, between 130 g/m2 and 150 g/m2, between 200 g/m2 and 500 g/m2, between 200 g/m2 and 450 g/m2, between 200 g/m2 and 350 g/m2, between 200 g/m2 and 300 g/m2, between 200 g/m2 and 250 g/m2, between 250 g/m2 and 500 g/m2, between 250 g/m2 and 450 g/ml, between 250 g/m2 and 350 g/m2, between 250 g/m2 and 300 g/m2, between 200 g/m2 and 250 g/m2, between 300 g/m2 and 500 g/m2, between 300 g/m2 and 450 g/m2, or between 300 g/m2 and 350 g/m2.

Coated papers are well known in the paper art, and are disclosed, for example, in US. Patent Nos. 6,777,075; 6,783,804, and 441, the full disclosures of which are incorporated herein by reference.

Coated papers suitable as feedstock can include paper coated with an inorganic material, for e the same materials used as fillers can be used in coatings. onally, coated papers can include paper coated with a polymer coated paper).

Such paper can be made, for example, by extrusion g, brush coating, Curtain coating, blade coating, air knife coating, cast coating or roller coating paper. For example, sources ofsuch poly—coated paper include a variety of food containers, including juice s, condiment s (e.g., sugar, salt, pepper), plates, pet food bags, cups, bowls, trays and boxes for frozen foods. The poly-coated paper can, in addition to paper, contain, for example, polymers, (e.g., polyethylene, polypropylene, biodegradable polymers, silicone), latexes, binders, wax, and, in some cases, one or more layers of aluminum. The poly coated papers can be multi layered laminate, for example, made with one or more, e.g., two, three, four, five or more, layers of polyethylene and paper and one or more, e.g., two, three or more layers of aluminum.

The paper feedstocks typically have a low gross calorie value e.g., below 7500 Btu/lb e.g, below 7400 Btu/lb, below 7200 Btu/lb, below 7000 Btu/lb, below 6800 , beiow 6600 Btu/lb, below 6400 Btu/lb, below 6200 Btu/lb, below 6000 Btu/lb, below 5800 Btu/lb, below 5600 Btu/lb, below 5400 Btu/lb or below 5200 Btu/lb. The gross calorific value can be between about 5200 and 7500 Btu/lb e.g., between 6800 and 7000 Btu/1b, n 6700 and 7100 Btu/lb, between 6400 and 7100 Btu/lb, between 6600 and 6800 Btu/lb, between 6100 and 6700 Btu/lb, between 6100 and 6300 Btu/lb, between 6000 and 6350 Btu/lb, between 5600 and 6400 Btu/lb or n 5200 and 5500 Btu/lb.

PCT/U82012/024970 The gross calorific value can be measure using a bomb meter e. g., as outlined in ASTM method E71 1.

The paper feedstock can have a basis weight between 35 1b and 330 lb, e.g. 45 lb and 330 lb, 60 and 330 lb, 80 and 330 lb, 60 and 200 lb, 60 and 100 lb; optionally a filler content greater than about 10 wt.%, e.g., between 10 and 80 wt.%, between 20 and 80 wt.%, between 30 and 80 wt.%, between 30 and 70 wt.%, between 230 and 60 wt.%; optionally a grammage between 50 and 500 g/m2, e.g., 70 and 500 g/m2, 90 and 500 g/m2, 90 and 400 g/m2, 90 and 300 g/m2, 90 and 200 g/m2; and optionally a calorific value between 7500 and 4000 Btu/lb, e.g., 7000 and 4000 Btu/lb, 6500 and 4000 , 5000 and 4000 Btu/lb, 6000 and 4500 Btu/lb; optionally an ash t between 8 and 50 wt.%, e.g., 10 and 80 wt.%, 10 and 60 wt.%, 10 and 50 wt.%, 20 and 50 wt.%.

Some suitable paper feedstock can include a homogeneous sheet formed by irregularly intertwining cellulose fibers. These can include, for example, Abrasive Papers, Absorbent Paper, Acid Free Paper, Acid ProofPaper, t Book Paper, Adhesive Paper, Air Dried Paper, Air Filter Paper, Album Paper, Albumin Paper, Alkaline Paper, Alligator Imitation Paper, Aluminum Foil Laminated paper, Ammunition Paper, Announcement Card Paper, Anti Rust Paper, Anti—Tarnish Paper, Antique Paper, Archival Paper, Art Paper, Asphalt Laminated Paper, Azurelaid Paper, Back Liner Paper, Bacon Paper, Bagasse Paper, Bakers‘ Wrap, Balloon Paper, Banknote or Currency Paper, Barograph Paper, Barrier Paper, Baiyta Paper, Beedi Wrap Paper, Bible Paper, Black WaterproofPaper, Blade Wrapping Paper, Bloodproof Paper or r Paper, Blotting Paper, Blueprint Paper, Board, Bogus Paper, Bond Paper, Book Paper, Boxboard, e Printing Paper, Bread Wrapping Paper, Bristol Board, Business Form Paper, Butter Wrapping Paper, Burnt Paper, Cable Paper, Calf Paper, Calico Paper, Candy Twisting Tissue, Canvas Paper, less Paper, ard, Corrugated Cardboard, Carton board, Cartridge paper, Cast Coated Paper, Catalogue Paper, Chart Paper, Check Paper, Cheese Wrapping Paper, Chipboard, Chromo, Coarse Paper (also Industrial Paper), Coated freesheet, Coated Paper, Coated White Top Liner, Cockle Finish Paper, Color— fast papers, Commodity Paper, Colored Kraft, Condenser Tissue, Construction Paper, nerboard, Copier Paper or Laser Paper, Correspondence Papers, Corrugated Board, Corrugated Medium or Fluting Media or Media,Cotton Paper or Rag Paper, Cover Paper PCT/U82012/024970 or Cover Stock, Creamwove Paper, Cut Sheet, Damask Paper, Decalcomania Paper, Diazo Base Paper, Document Paper, Drawing Paper, Duplex Board, Duplex Paper, End— leaf Paper, Envelop Paper, Esparto Paper, Extensible Kraft, Extrusion Coated Board, Fax Base Paper,Flarne Resistant, d Paper, Fluorescent Paper, Folding Boxboard, Form Bond, Freesheet, Fruit Wrapping Paper, Gasket Board, Glassine Paper, Glazed Paper, Granite Paper, Gravure Paper, Gray Board, Greaseproof Paper, Green Paper, Groundwood Papers, Gummed Paper, Gypsum Board, Handmade Paper, Hanging Paper, Hard Sized Paper, Heat Seal Paper, Heat er Paper, Hi—Fi (High Finish) Paper, Industrial Papers, Insect Resistant, Insulating Board, Ivory Board, Japan Paper, Jute 1O Paper, Kraft Bag Paper, Kraft liner, Kraft Paper, Kraft Waterproof Paper, Kraft ng Paper, Label Paper, Lace Paper, Laid Paper, Laminated Paper, Laminated Linerboard, Latex Paper, Ledger Paper, Lightproof Paper, Liner, Linerboard, Litmus Paper, On Machine Coated, Magazine Paper, Manila, Map Paper, Marble Paper, Matrix Paper, Matt ed Paper, Mechanical Paper, Mellow Paper, Metalization Base Paper, Machine Finished Paper, Machine glazed Paper, Millboard, Mulberry Paper, Natural Colored Papers or Self Colored , Newsprint, Oatmeal Paper, Offset Paper, Packaging Paper, Paperboard, Pattern Paper, Permanent Paper, Photographic Paper, Playing Card Stock, Pleading Paper, Poly Extrusion Paper, Postcard Board, Post—Consumer Waste Paper, Poster Paper, Pre—Consumer Waste Paper, Pressure Sensitive Coated Paper, Publishing Paper, Pulp Board, Release Paper, Roofing Paper, Safety Paper, Security paper, Self Adhesive Paper, Self Contained Paper, Silicon Treated Paper, Single Faced ated Board, Sized Paper, Stamp Paper, Strawboard, Suede Paper, Supercalendered Paper, Surface-Sized, Super Art Paper, Synthetic Fiber Paper, Tag Paper, ner, Text Paper, Thermal Paper, Translucent Drawing Paper, Transparent Paper, Treated Paper, Union Kraft, Unglazed Paper, Un-sized Paper, Vaporproof Paper, Varnish—Label Paper, Vegetable Parchment, Vellum Paper, Velour Paper, Velvet Finish Paper, Vulcanizing Paper, Wadding, Wall Paper, Water—Color Paper, Water Finished Paper, Water ant Paper, Waterleaf, Waxed Paper, Wet Strength Paper, White Top Liner, Willesden Paper, Wipes or Wiper, Wove, Wrapper, Writing Paper and Xerographic Paper.

The feedstocks described herein can be used in combination with any of the biomass feedstocks described in US. Application Serial No. 12/417,880, filed April 3, 2009, incorporated by reference herein in its entirety.

Saccharifying Agents Suitable enzymes include cellobiases and cellulases capable of degrading biomass.

Suitable cellobiases include a cellobiase from Aspergillus niger sold under the tradename NOVOZYME 188W. ases are capable of ing biomass, and may be of fimgal or bacterial origin. Suitable s include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonz'zmz, Chin/sosporz‘um and Trichoderma, and include species of Humicala, Coprz'nus, Thielavia, ‘um, Myceliophthora, Acremom‘um, Cephalospommz, Scytalz‘dz'um, llium or Aspergillus (see, e.g., EP 458162), especially those produced by a strain selected from the species Humz’cola insolens ssified as Scytalz‘dium philum, see, e.g., US. Patent No. 4,435,307), Coprz'nus cinereus, 'zmz oxysporum, fifircelz'ophthora themzophila, Merz'pilus giganteus, Thielavia terrestris, Acremom‘um sp., Acremonium persicinum, Acremonz‘um m'um, nium brachypenium, m‘um dichromospomm, Acremom'um obclavatum, Acremonium pinkertonz’ae, Acremom’um roseogrz'seum, Acremom’um incoloratum, and Acremom’zmzfirratzmz; preferably from the species Hzmzz'cola insolens DSM 1800, Fusarz'um oxysporum DSM 2672, ophz‘hora thermophila CBS 117.65, Cephalosporium sp. RYM—202, nium Sp. CBS 478.94, Acremom'um Sp. CBS 265.95, Acremonium persicinum CBS 169.65, Acremonizmz acremonium AHU 9519, Cephalosporium Sp. CBS 535.71, Acremonium brachypenium CBS 866.73, Acremom'zmr dichromosporum CBS 683.73, Acremoniwn obclavatum CBS 311.74, m'um pinkertom'ae CBS 157.70, Acremoniunz roseogrz'seum CBS 134.56, Acremom'um incoloratum CBS , and Acremoniumfuratum CBS 299.7011. Cellulolytic enzymes may also be obtained from Chms’osporz'zmz, preferably a strain of Chrysosporz'um Iucknowense. Additionally, Trichodemza (particularly Trichoderma viride, Trichoderma reesei, and Trichoderma kom'ngz'z'), alkalophilic us (see, for example, US. Patent No. 3,844,890 and EP 458162), and Streptomyces (see, e.g., RP 458162) may be used.

PCT/U82012/024970 Enzyme complexes may be utilized, such as those available from Genencm® under the tradename ACCELLERASE®, for example, Accellerase® 1500 enzyme complex. Accellerase 1500 enzyme complex contains multiple enzyme activities, mainly exoglucanase, endoglucanase (2200~2800 CMC U/g), ellulase, and beta- glucosidase 75 pNPG U/g), and has a pH of 4.6 to 5.0. The endoglucanase activity of the enzyme x is expressed in carboxymethylcellulose activity units (CMC U), while the beta-glucosidase activity is reported in pNP—glucoside ty units (pNPG U).

In one embodiment, a blend of Accellerase® 1500 enzyme complex and METM 188 cellobiase is used.

Fermentation Agents The microorganism(s) used in fermentation can be natural microorganisms and/or engineered microorganisms. For example, the microorganism can be a bacterium, e.g., a olytic bacterium, a fungus, e.g., a yeast, a plant or a protist, e.g., an algae, a protozoa or a fungus-like t, e.g., a slime mold. When the organisms are compatible, mixtures of organisms can be utilized.

Suitable fermenting microorganisms have the ability to convert carbohydrates, such as glucose, fi'uctose, xylose, arabinose, mannose, gaiactose, oligosaccharides or polysaccharides into fermentation products. Fermenting microorganisms include strains of the genus Sacchromyces spp. e.g., Sacchromyces cerevz'sz'ae (baker’s , Saccharomyces distaticus, Saccharomyces uvarum; the genus Klzgiveromyces, cg, species Kluyveromyces marxiamls, romycesfi'agilz's; the genus Candida, e.g., Candida pseudotropz'calz's, and Candida brassicae, Pichia stipitis (a relative of Candida Shehatae, the genus Clavispora, e.g., species Clavispora lusz‘tam'ae and Clavz'spora 'ae, the genus Pachysolen, e.g., species Pachysolen tannophz‘lus, the genus Bretannomyces, e.g., species Bretannomyces clausem‘i (Philippidis, G. P., 1996, ose bioconversion technology, in Handbook on Biocthanol: Production and Utilization, Wyman, C.E., ed., Taylor & Francis, Washington, DC, 179—212). Other suitable microorganisms include, for example, Zymomonas lz's, Clostrz'dz'um thermocellmn (Philippidis, 1996, supra), Clostridz'um saccharobutylacetonicum, idium saccharobutylicun-z, Clostridium Pum'ceum, Clostridium beijernckii, Clostridz'um acetobutylicmn, Moniliella is, Yarrowia Zz'polytica, Aureobasidz‘um sp., Trichosporonoides sp., Trigonopsis variabilis, Trichosporon sp., Moniliellaacetoabutans, Typhula variabilis, Candida iae, gz'nomycetes, Pseudozyma aensz's, yeast species of genera Zygosaccharomyces, Debazyomyces, Hansenula and Pichz'a, and fiingi of the dematioid genus Torula.

Commercially available yeasts include, for example, Red Sta1®/Lesaffre Ethanol Red able from Red Star/Lesaffre, USA), FALI® (available from Fleischmann’s Yeast, a division of Burns Philip Food Inc., USA), SUPERSTART® (available from Alltech, now Lalemand), GERT STRAND® (available from Gert Strand AB, Sweden) and FERMOL® (available from DSM Specialties).

Nutrient e Ingredients As discussed above, it may be preferred to include a nutrient package in the system during saccharification and/or fermentation. Preferred nt packages contain a food-based nutrient source, a nitrogen source, and in some cases other ingredients, e.g., phosphates. Suitable food-based nutrient s e grains and vegetables, including those discussed above and many others. The food—based nutrient source may include mixtures of two or more grains and/or vegetables. Such nutrient sources and packages are disclosed in U.S. Application Serial No. 13/184,138, incorporated by reference herein in its entirety above.

Enzymes for Releasing nts When a food—based nutrient source is utilized, it is preferred that the saccharification and/or fermentation mixture further include an enzyme system selected to release nutrients, e.g., en, amino acids, and fats, from the food-based nutrient source. For example, the enzyme system may e one or more enzymes selected from the group consisting of amylases, pretenses, and mixtures thereof. Such systems are disclosed in U.S. Application Serial No. 13/184,138, incorporated by reference herein in its entirety.

Fuel Cells Where the methods described herein produce a sugar solution or suspension, this solution or suspension can uently be used in a fuel cell. For example, fuel cells utilizing sugars derived from cellulosic or lignocellulosic materials are disclosed in US.

Provisional Application Serial No. 61/579,568, filed December 22, 2011, the complete disclosure of which is incorporated herein by reference.

Throughout the specification and claims, unless the t es otherwise, the word ise” or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other r or group of integers.

Each document, reference, patent application or patent cited in this text is expressly incorporated herein in their entirety by reference, which means that it should be read and considered by the reader as part ofthis text. That the document, reference, patent application or patent cited in this text is not repeated in this text is merely for reasons of conciseness.

Reference to cited material or information contained in the text should not be understood as a concession that the material or information was part of the common l5 general knowledge or was known in Australia or any other country.

OTHER MENTS A number of embodiments of the invention have been described. Nevertheless, it Will be understood that various modifications may be made without departing from the spirit and scope of the invention.

For e, while it is possible to perform all the processes described herein at one physical location, in some embodiments, the processes are ted at multiple sites, and/or may be performed during transport.

Accordingly, other embodiments are within the scope of the following claims.

Claims (21)

WHAT IS CLAIMED IS:

1. A method of producing a product or intermediate, the method comprising: combining a slurry ofpaper with a rifying agent in a vessel, the paper having a high filler content greater than about 10wt%; allowing at least a portion of the paper to saccharify, producing a sugar, While mixing the contents of the vessel with a jet mixer; and fermenting at least a portion ofthe sugar with a rganism, wherein the contents of the vessel comprise at least one shear sensitive ingredient and the jet mixer provides gentle mixing so as to minimize damage to the at least one shear sensitive ingredient.

2. The method of claim 1, wherein the filler content is at least 20wt.%.

3. The method of claim 1 or 2, wherein the paper has an ash content of at least 8 wt.%.

4. The method of any ofthe above claims, wherein the paper r comprises a printing ink.

5. The method of any of the above claims, wherein the paper is in the form of magazines.

6. The method of any ofthe above claims, further comprising adding a food—based nutrient source to the mixture.

7. The method of claim 6, wherein the food—based nutrient source is selected from the group consisting of grains, vegetables, es of grains, residues of vegetables, and mixtures thereof.

8. The method of any of the above claims, wherein the product comprises a fuel selected from the group consisting of hydrogen, alcohols, organic acids, hydrocarbons, and mixtures thereof.

9. The method of any ofthe above claims, wherein the microorganism comprises a yeast and/or a ia.

10. The method of any of the above claims, further comprising physically treating the paper prior to the combining step.

11. The method of any of the above claims, further comprising processing the sugar.

12. The method of claim 12, wherein sing comprises separating xylose and/or glucose from the sugar.

13. The method of any of the above claims, n saccharification is conducted at a pH of about 3.8 to 4.2.

14. The method of claim 11, wherein the physically treating step comprises mechanically treating the paper to reduce the bulk density of the paper and/or increase the BET surface area of the paper.

15. The method of claim 6, wherein the food-based nutrient source is ed from the group consisting of wheat, oats, barley, soybeans, peas, s, potatoes, corn, rice bran, corn meal, Wheat bran, and mixtures thereof.

16. The method of any of the above , wherein the paper has a basis weight of at least 35 lb.

17. The method of_any of the above claims, wherein the paper has a basis weight between 35 lb and 330 lb.

18. The method of any one of the above claims, wherein the paper has an ash content of at least 8 wt.%.

19. The method of any one of claims 5-9, wherein the paper further comprises a printing ink.

20. The method of any one of the above claims, wherein the paper is in the form of magazines.

21. The method ing to claim 1 substantially as herein before described with reference to the Examples.