(19) TZZ Z_T

(11) EP 2 675 907 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C12P 7/10 (2006.01) C12P 19/02 (2006.01) 22.11.2017 Bulletin 2017/47 C12P 19/14 (2006.01) C13K 1/02 (2006.01)

(21) Application number: 12705586.1 (86) International application number: PCT/US2012/024970 (22) Date of filing: 14.02.2012 (87) International publication number: WO 2012/112488 (23.08.2012 Gazette 2012/34)

(54) PROCESSING FEEDSTOCKS VERARBEITUNG VON PAPIERROHSTOFFEN TRAITEMENT DE MATIÈRES PREMIÈRES DE PAPIER

(84) Designated Contracting States: US-A1- 2007 134 781 US-A1- 2010 297 705 AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO • LI KANG ET AL: "Bioconversion of PL PT RO RS SE SI SK SM TR Mill Sludges to Ethanol by SSF and SSCF", APPLIED BIOCHEMISTRY AND (30) Priority: 14.02.2011 US 201161442710 P BIOTECHNOLOGY, vol. 161, no. 1-8, 1 May 2010 (2010-05-01) , pages 53-66, XP055032190, ISSN: (43) Date of publication of application: 0273-2289, DOI: 10.1007/s12010-009-8893-4 25.12.2013 Bulletin 2013/52 • MORRIS WAYMAN ET AL: "Bioconversion of waste paper to ethanol", PROCESS (60) Divisional application: BIOCHEMISTRY, vol. 27, no. 4, 1 July 1992 17196529.6 (1992-07-01), pages239-245, XP055032173, ISSN: 1359-5113, DOI: 10.1016/0032-9592(92)80024-W (73) Proprietor: Xyleco, Inc. • DATABASE COMPENDEX [Online] Wakefield, MA 01880 (US) ENGINEERING INFORMATION, INC., NEW YORK, NY, US; June 2000 (2000-06), YAMADA N ET AL: (72) Inventors: "Decompositionbehavior ofwaste paperwith hot • MEDOFF, Marshall compressed water", XP002679607, Database Wakefield, MA 01880 (US) accession no. E2000445334468 & NIHON • MASTERMAN, Thomas ENERUGI GAKKAISHI/JOURNAL OF THE JAPAN Wakefield, MA 01880 (US) INSTITUTE OF ENERGY 2000 JUN MARUZEN CO LTD, vol. 79, no. 6, June 2000 (2000-06), pages (74) Representative: FRKelly 540-547, 27 Clyde Road • DASARI R K: "High-Solids Saccharification and Dublin D04 F838 (IE) Viscosity Studies in a Scraped Surface Bio-Reactor", DISSERTATION, B.TECH, (56) References cited: OSMANIA UNIVERSITY, INDIA, May 2008 JP-A- 2008 161 137 JP-A- 2010 041 923 (2008-05), pages i-243, JP-A- 2011 024 545 US-A- 5 876 505 • BERGERON P W, RILEY C J: "Wastepaper as a Feedstock for Ethanol Production, NREL/TP-232-4237", NATIONAL RENEWABLE ENERGY LABORATORY, USA, 1991, pages i-vi, 1-23,

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 675 907 B1

Printed by Jouve, 75001 PARIS (FR) 1 EP 2 675 907 B1 2

Description e.g., polycoated paper and optionally mixing the feed- stock with a fluid and/or saccharifying agent. BACKGROUND [0007] Some implementations include one or more of the following features. The paper feedstock may have a [0001] Magazines, catalogs, and other paper products 5 basis weight greater than 35 lb, e.g., from about 35 lb to that contain high levels of coatings, pigments, and inks, 330 lb and/or the paper may have a high filler content, are widely available as waste materials. While efforts are e.g., greater than about 10 wt.% e.g., greater than 20 made to recycle this waste paper, generally by repulping wt.%. For example, the filler or any coating can be an it for use in recycled paper products, it would be advan- inorganic material. The paper may also have a high gram- tageous if this waste paper could be economically utilized 10 mage, e.g., greater than about 500 g/m 2. The paper may as a feedstock to make other types of products. The pub- comprise a pigment or ink, e.g., at a level greater lished patent application JP2011024545 discloses a than about 0.025 wt.%. The paper can have an ash con- method for producing a saccharide from a -con- tent greater than about 8 wt.%. taining material containing calcium carbonate, such as [0008] The method can further include adding a micro- used paper, which method comprises a step of saccha- 15 organism, for example a yeast and/or a bacteria (e.g., rifying the material with a cellulase enzyme. from the genus Clostridium), to the paper feedstock or saccharified paper and producing a product or interme- SUMMARY diate. [0009] The product can be a fuel, including, for exam- [0002] Generally, this invention relates to methods of 20 ple, alcohols (e.g., methanol, ethanol, propanol, isopro- processing paper feedstocks, in particular certain types panol, erythritol, n-butanol, isobutanol, sec-butanol, tert- of relatively heavy paper feedstocks, such as highly pig- butanol, ethylene glycol, propylene glycol, 1,4-butane di- mented , and or loaded papers, such as paper ol and/or glycerin), sugar alcohols (e.g., erythritol, glycol, that has been color printed (printed with colors other than glycerol, sorbitol threitol, arabitol, ribitol, mannitol, dulci- or in addition to black), e.g., magazines, and other pa- 25 tol, fucitol, iditol, isomalt, maltitol, lactitol, xylitol and other pers. polyols), organic acids (e.g., formic acid, acetic acid, pro- [0003] More specifically, the present invention con- pionic acid, butyric acid, valeric acid, caproic acid, pal- cerns a method of producing a sugar, as defined in claim mitic acid, stearic acid, oxalic acid, malonic acid, succinic 1, which method comprises: acid, glutaric acid, oleic acid, linoleic acid, glycolic acid, 30 lactic acid and/or γ-hydroxybutyric acid), hydrocarbons providing a paper feedstock with a filler content of (methane, ethane, propane, isobutene, pentane, n-hex- greater than 10 wt.% and an ash content of at least ane, biodiesels and/or bio-gasolines), hydrogen and mix- 8 wt.%, and wherein the paper further comprises a tures of these. printing ink, [0010] The method can further include adding a food- combining the paper with a saccharifying agent35 based nutrient source to the mixture, e.g., a nutrient which is an enzyme, in a tank, and source selected from the group consisting of grains, veg- using jet mixing to mix the tank contents during sac- etables, residues of grains, residues of vegetables, and charification. mixtures thereof, for example wheat, oats, barley, soy- beans, peas, legumes, potatoes, corn, rice bran, corn [0004] Further aspects or embodiments disclosed40 meal, wheat bran, and mixtures thereof. In such cases, hereafter are part of the invention only insofar as they the mixture can further include an enzyme system se- are within the scope of said method according to claim 1. lected to release nutrients from the food-based nutrient [0005] Many of the methods disclosed herein utilize source, e.g., a system comprising a protease and an microorganisms or products produced by microorgan- amylase. isms, e.g., enzymes, to bioprocess the feedstock, pro- 45 [0011] The method can include detoxifying the sugar ducing useful intermediates and products, e.g., energy, solution or suspension. The method can include further fuels, foods and other materials. For example, in some processing the sugar, for example, by separating xylose cases enzymes are used to saccharify the feedstocks, and or glucose from the sugar. In some cases, the sac- converting the feedstocks to sugars. The sugars may be charification can be conducted at a pH of about 3.8 to used as an end product or intermediate, or processed 50 4.2. The mixture can further include a nitrogen source. further, e.g., by fermentation. For example xylose can be [0012] In some cases, the method further includes hydrogenated toxylitol and glucosecan be hydrogenated physically treating the paper feedstock, for example me- to sorbitol. chanically treating to reduce the bulk density of the paper [0006] In one aspect, the invention features methods feedstock and/or increase the BET surface area of the for producing a sugar, e.g., in the form of a solution or 55 feedstock. Physically treating the paper feedstock can suspension, that includes providing a paper feedstock, include irradiation, for example, with an electron beam. the paper feedstock including offset printing paper e.g., The method can include mixing the paper feedstock with offset printed paper, colored paper and/or a fluid. The method can include detoxifying the paper

2 3 EP 2 675 907 B1 4 feedstock, sugar, and/or other products or intermediates. enzyme and water, if saccharification is performed en The paper feedstock may be in the form of magazines. route) to a manufacturing plant (step 116), and then bio- The paper feedstock may also be a laminate of at least processing the treated feedstock to produce a desired one layer of a polymer and paper and may further include product (step 118), which is then processed further, e.g., at least one layer of a metal e.g., aluminum. 5 by distillation (step 120). If desired, content can be [0013] Although many embodiments include the use measured (step 122) and process parameters can be set of relatively heavy paper feedstocks, e.g., containing fill- or adjusted based on this measurement (step 124), as ers and/or coatings other papers can be used e.g., news- described in U.S. Application Serial No 12/704,519, filed print. on February 11, 2010. [0014] Other features and advantages of the invention 10 [0018] Because paper feedstocks are generally low in, will be apparent from the following detailed description, or entirely lack, nutrients to support bioprocesses, it is and from the claims. generally preferred that nutrients be added to the system, for example in the form of a food-based nutrient source DESCRIPTION OF or nutrient package, as disclosed in U.S. Application Se- 15 rial No. 13/184,138. When utilized, the food-based nutri- [0015] ent source or nutrient package is present during bio- processing (step 118), e.g., fermentation, and may in FIG. 1 is a flow diagram illustrating conversion of a some preferred implementations also be present during feedstock to ethanol via production of a glucose so- the saccharification step (step 114). In some implemen- lution. 20 tations, the food-based nutrient source or nutrient pack- FIG. 2 is a schematic diagram of an ethanol manu- age is added at the beginning of step 114, along with an facturing facility. enzyme combination suitable for saccharification, fer- FIG. 3 is a diagram illustrating the enzymatic hydrol- mentation, and release of nutrients from the food-based ysis of cellulose to glucose. nutrient source. 25 [0019] Saccharification is conducted under a first set DETAILED DESCRIPTION of process conditions (e.g., temperature and pH), and then when saccharification has proceeded to a desired [0016] Using the methods and nutrient packages de- extent the process conditions may be adjusted (e.g., by scribed herein, paper feedstocks that include high levels adjusting pH from 4 to 5) to allow fermentation to proceed. of pigments, colors, fillers and/or coatings, and/or that 30 [0020] In some cases the feedstock includes materials have a high basis weight, and the saccharified derivatives that are not beneficial to the processing of the feedstock of such feedstocks, can be bioprocessed, e.g., using fer- or decrease the quality of the intermediates and/or prod- mentation, to produce useful intermediates and products ucts. For example there may be materials that are toxic, such as those described herein. In some cases, the feed- and/or solid inorganic materials or insoluble organic ma- stock includes high levels pigments and/or fillers such as 35 terials. The toxic materials can be detrimental, for exam- those feedstocks used in printing, e.g., magazines. Ex- ple, by reducing the effectiveness of enzymes and/or mi- amples of such feedstocks are described herein. Feed- croorganisms. Examples of toxic materials are pigments stocks of this type are advantageous for a number of and inks described herein. Solid inorganic materials can reasons, including their relatively low cost (if waste ma- be detrimental, for example, in increasing the total vis- terials are used) and, in the case of high basis weight 40 cosity and density of solutions in various processes as papers, their relatively high density, which contributes to well as forming slurries, sludge and settled material that ease of handling and processing. may, for example, block openings, be difficult to remove, e.g., from the bottom of tanks, and/or increase the wear CONVERTING CELLULOSIC AND LIGNOCELLU- on mixers. Examples of inorganic materials are fillers and LOSIC 45 coatings described herein. Insoluble organic materials can, for example, contaminate the final fuel products MATERIALS TO ALCOHOLS and/or cause foaming during mixing or other processing steps. Examples of insoluble organic materials are pol- [0017] Referring to FIG. 1, a process for manufacturing ymers used in polycoated paper described herein. It can an alcohol, e.g., ethanol, or a butanol e.g., isobutanol, 50 therefore be advantageous to remove some of the insol- sec-butanol, tert-butanol or n-butanol, can include, for uble solids and organic materials and to detoxify the feed- example, optionally mechanically treating the feedstock stock at any point during the processing as described (step 110), before and/or after this treatment, optionally herein. Surprisingly, it has been found that in some cases treating the feedstock with another physical treatment, materials in the feedstock that would be expected to be for example irradiation, to further reduce its recalcitrance 55 detrimental, as discussed above, do not significantly ad- (step 112), saccharifying the feedstock to form a sugar versely affect the process. For example, some yeasts solution (step 114), optionally transporting, e.g., by pipe- that provide ethanol by fermentation of sugars derived line, railcar, truck or barge, the solution (or the feedstock, from paper feedstocks appear to be very resilient to var-

3 5 EP 2 675 907 B1 6 ious pigments, inks and fillers. be performed in transit. Such mobile processing is de- [0021] The manufacturing plant used in steps 118-120 scribed in U.S. Serial No. 12/374,549 and International (and in some cases all of the steps described above) can Application No. WO 2008/011598. be, for example, an existing starch-based or sugar-based [0027] Any or all of the method steps described herein ethanol plant or one that has been retrofitted by removing 5 can be performed at ambient temperature. If desired, or decommissioning the equipment upstream from the cooling and/or heating may be employed during certain bio-processing system (which in a typical ethanol plant steps. For example, the feedstock may be cooled during generally includes grain receiving equipment, a hammer- mechanical treatment to increase its brittleness. In some mill, a slurry mixer, cooking equipment and liquefaction embodiments, cooling is employed before, during or after equipment). In some cases, the feedstock received by 10 the initial mechanical treatment and/or the subsequent the plant can be input directly into the fermentation equip- mechanical treatment. Cooling may be performed as de- ment. A retrofitted plant is shown schematically in FIG. scribed in U.S. Serial No. 12/502,629, now U.S. Patent 2 and described below as well as, for example, in U.S. No. 7,900,857. Moreover, the temperature in the fermen- Serial No. 12/429,045, filed April 23, 2009. tation system 108 may be controlled to enhance saccha- [0022] FIG. 2 shows one particular system that utilizes 15 rification and/or fermentation. the steps described above for treating a feedstock and [0028] The individual steps of the methods described then using the treated feedstock in a fermentation proc- above, as well as the materials used, will now be de- ess to produce an alcohol. System 100 includes a module scribed in further detail. 102 in which a feedstock is initially mechanically treated (step 12, above), a module 104 in which the mechanically 20 PHYSICAL TREATMENT treated feedstock is structurally modified (step 14, above), e.g., by irradiation, and a module 106 in which [0029] Physical treatment processes can include one the structurally modified feedstock is subjected to further or more of any of those described herein, such as me- mechanical treatment (step 16, above). As discussed chanical treatment, chemical treatment, irradiation, son- above, the module 106 may be of the same type as the 25 ication, oxidation, pyrolysis or steam explosion. Treat- module 102, or a different type. In some implementations ment methods can be used in combinations of two, three, the structurally modified feedstock can be returned to four, or even all of these technologies (in any order). module 102 for further mechanical treatment rather than When morethan one treatment method isused, the meth- being further mechanically treated in a separate module ods can be applied at the same time or at different times. 106. 30 Other processes that change a molecular structure of a [0023] As described herein, many variations of system feedstock may also be used, alone or in combination with 100 can be utilized. the processes disclosed herein. [0024] After these treatments, which may be repeated as many times as required to obtain desired feedstock Mechanical Treatments properties, the treated feedstock is delivered to a fermen- 35 tation system 108. Mixing may be performed during fer- [0030] In some cases, methods can include mechan- mentation, in which case the mixing is preferably rela- ically treating the feedstock. Mechanical treatments in- tively gentle (low shear) so as to minimize damage to clude, for example, cutting, milling, pressing, grinding, shear sensitive ingredients such as enzymes and other shearing and chopping. Milling may include, for example, microorganisms. In some embodiments, jet mixing is40 ball milling, hammer milling, rotor/stator dry or wet milling, used, as described in U.S. Serial No. 12/782,694, freezer milling, blade milling, knife milling, disk milling, 13/293,977 and 13/293,985. roller milling or other types of milling. Other mechanical [0025] Referring again to FIG. 2, fermentation produc- treatments include, e.g., stone grinding, cracking, me- es a crude ethanol mixture, which flows into a holding chanical ripping or tearing, pin grinding or air attrition mill- tank 110. Water or other solvent, and other non-ethanol 45 ing. components, are stripped from the crude ethanol mixture [0031] Mechanical treatment can be advantageous for using a stripping column 112, and the ethanol is then "opening up," "stressing," breaking and shattering cellu- distilled using a distillation unit 114, e.g., a rectifier. Dis- losic or other materials in the feedstock, making the cel- tillation may be by vacuum distillation. Finally, the ethanol lulose of the materials more susceptible to chain scission can be dried using a molecular sieve 116 and/or dena- 50 and/or reduction of crystallinity. The open materials can tured, if necessary, and output to a desired shipping also be more susceptible to oxidation when irradiated. method. [0032] In some cases, the mechanical treatment may [0026] In some cases, the systems described herein, include an initial preparation of the feedstock as received, or components thereof, may be portable, so that the sys- e.g., size reduction of materials, such as by cutting, grind- tem can be transported (e.g., by rail, truck, or marine55 ing, shearing, pulverizing or chopping. For example, in vessel) from one location to another. The method steps some cases, loose feedstock (e.g., Machine Offset Paper described herein can be performed at one or more loca- and/or Polycoated Paper) is prepared by shearing or tions, and in some cases one or more of the steps can shredding.

4 7 EP 2 675 907 B1 8

[0033] Alternatively, or in addition, the feedstock ma- 50m2/g, greater than 60 m2/g, greater than 75 m2/g, terial can first be physically treated by one or more of the greater than 100 m2/g, greater than 150 m2/g, greater other physical treatment methods, e.g., chemical treat- than 200 m2/g, or even greater than 250 m 2/g. ment, radiation, sonication, oxidation, pyrolysis or steam [0040] In some situations, it can be desirable to pre- explosion,and thenmechanically treated.This sequence 5 pare a low bulk density material, densify the material can be advantageous since materials treated by one or (e.g., to make it easier and less costly to transport to more of the other treatments, e.g., irradiation or pyrolysis, another site), and then revert the material to a lower bulk tend to be more brittle and, therefore, it may be easier to density state. Densified materials can be processed by further change the molecular structure of the material by any of the methods described herein, or any material mechanical treatment. 10 processed by any of the methods described herein can [0034] In some embodiments, mechanical treatment be subsequently densified, e.g., as disclosed in U.S. Se- includes shearing to expose fibers of the material. Shear- rial No. 12/429,045 now U.S. Patent No. 7,932,065 and ing can be performed, for example, using a rotary knife WO 2008/0731 86. cutter. Other methods of mechanically treating the feed- stock include,for example, millingor grinding. Milling may 15 Radiation Treatment be performed using, for example, a hammer mill, ball mill, colloid mill, conical or cone mill, disk mill, edge mill, Wiley [0041] One or more radiation processing sequences mill or grist mill. Grinding may be performed using, for can be used to process the paper feedstock, and to pro- example, a stone grinder, pin grinder, coffee grinder, or vide a structurally modified material which functions as burr grinder. Grinding may be provided, for example, by 20 input to further processing steps and/or sequences. Irra- a reciprocating pin or other element, as is the case in a diation can, for example, reduce the molecular weight pin mill. Other mechanical treatment methods include and/or crystallinity of feedstock. Radiation can also ster- mechanical ripping or tearing, other methods that apply ilize the materials, or any media needed to bioprocess pressure to the material, and air attrition milling. Suitable the material. mechanical treatments further include any other tech- 25 [0042] In some embodiments, the radiation may be nique that changes the molecular structure of the feed- provided by (1) heavy charged particles, such as alpha stock. particlesor protons, (2) electrons,produced, for example, [0035] Ifdesired, themechanically treated material can in beta decay or electron beam accelerators, or (3) elec- be passed through a screen, e.g., having an average tromagnetic radiation, for example, gamma rays, x rays, opening size of 1.59 mm or less (1/16 inch, 0.0625 inch). 30 or ultraviolet rays. In one approach, radiation produced In some embodiments, shearing, or other mechanical by radioactive substances can be used to irradiate the treatment, and screening are performed concurrently. feedstock. In another approach, electromagnetic radia- For example, a rotary knife cutter can be used to concur- tion (e.g., produced using electron beam emitters) can rently shear and screen the feedstock. The feedstock is be used to irradiate the feedstock. In some embodiments, sheared between stationary blades and rotating blades 35 any combination in any order or concurrently of (1) to provide a sheared material that passes through a through (3) may be utilized. The doses applied depend screen, and is captured in a bin. on the desired effect and the particular feedstock. [0036] The paper feedstock can be mechanically treat- [0043] In some instances when chain scission is de- ed in a dry state (e.g., having little or no free water on its sirable and/or polymer chain functionalization is desira- surface), a hydrated state (e.g., having up to ten percent 40 ble, particles heavier than electrons, such as protons, by weight absorbed water), or in a wet state, e.g., having helium nuclei, argon ions, silicon ions, neon ions, carbon between about 10 percent and about 75 percent by ions, phosphorus ions, oxygen ions or nitrogen ions can weight water. The fiber source can even be mechanically be utilized. When ring-opening chain scission is desired, treated while partially or fully submerged under a liquid, positively charged particles can be utilized for their Lewis such as water, ethanol or isopropanol. 45 acid properties for enhanced ring-opening chain scis- [0037] The feedstock can also be mechanically treated sion. For example, when maximum oxidation is desired, under a gas (such as a stream or atmosphere of gas oxygen ions can be utilized, and when maximum nitration other than air), e.g., oxygen or nitrogen, or steam. is desired, nitrogen ions can be utilized. The use of heavy [0038] Mechanical treatment systems can be config- particles and positively charged particles is described in ured to produce streams with specific morphology char- 50 U.S. Serial No. 12/417,699, now U.S. Patent No. acteristics such as, for example, surface area, porosity, 7,931,784. In one method, a first material that is or in- bulk density, and length-to-width ratio. cludes cellulose having a first number average molecular

[0039] In some embodiments, a BET surface area of weight (MN1) is irradiated, e.g., by treatment with ionizing the mechanically treated material is greater than 0.1 radiation (e.g., in the form of gamma radiation, X-ray ra- m2/g, e.g., greater than 0.25 m 2/g, greater than 0.5 m 2/g, 55 diation, 100 nm to 280 nm ultraviolet (UV) light, a beam greater than 1.0 m 2/g, greater than 1.5 m 2/g, greater than of electrons or other charged particles) to provide a sec- 1.75 m2/g, greater than 5.0 m2/g, greater than 10 m2/g, ond material that includes cellulose having a second 2 2 greater than 25 m /g, greater than 35 m /g, greater than number average molecular weight (MN2) lower than the

5 9 EP 2 675 907 B1 10 first number average molecular weight. The second ma- [0049] When particles are utilized, they can be neutral terial (or the first and second material) can be combined (uncharged), positively charged or negatively charged. with a microorganism (with or without enzyme treatment) When charged, the charged particles can bear a single that can utilize the second and/or first material or its con- positive or negative charge, or multiple charges, e.g., stituent sugars or lignin to produce an intermediate or 5 one, two, three or even four or more charges. In instances product, such as those described herein. in which chain scission is desired, positively charged par- [0044] Since the second material includes cellulose ticles may be desirable, in part due to their acidic nature. having a reduced molecular weight relative to the first When particles are utilized, the particles can have the material, and in some instances, a reduced crystallinity mass of a resting electron, or greater, e.g., 500, 1000, as well, the second material is generally more dispersi- 10 1500, 2000, 10,000 or even 100,000 times the mass of ble, swellableand/or soluble,e.g., ina solution containing a resting electron. For example, the particles can have a microorganism and/or an enzyme. These properties a mass of from about 1 atomic unit to about 150 atomic make the second material easier to process and more units, e.g., from about 1 atomic unit to about 50 atomic susceptible to chemical, enzymatic and/or biological at- units, or from about 1 to about 25, e.g., 1, 2, 3, 4, 5, 10, tack relative to the first material, which can greatly im- 15 12 or 15 amu. Accelerators used to accelerate the parti- prove the production rate and/or production level of a cles can be electrostatic DC, electrodynamic DC, RF lin- desired product, e.g., ethanol. ear, magnetic induction linear or continuous wave. For [0045] In some embodiments, the second number av- example, cyclotron type accelerators are available from erage molecular weight (MN2) is lower than the first IBA, Belgium, such as the Rhodotron® system, while DC 20 number average molecular weight (MN1) by more than type accelerators are available from RDI, now IBA Indus- about 10 percent, e.g., more than about 15, 20, 25, 30, trial, such as the Dynamitron®. Ions and ion accelerators 35, 40, 50 percent, 60 percent, or even more than about are discussed in Introductory Nuclear Physics, Kenneth 75 percent. S. Krane, John Wiley & Sons, Inc. (1988), Krsto Prelec, [0046] In some instances, the second material in- FIZIKA B 6 (1997) 4, 177-206, Chu, William T., "Overview 25 cludes cellulose that has a crystallinity (C 2) that is lower of Light-Ion Beam Therapy" Columbus-Ohio, ICRU-IAEA than the crystallinity (C1) of the cellulose of the first ma- Meeting, 18-20 March 2006, Iwata, Y. et al., "Alternating- terial. For example, (C 2) can be lower than (C 1) by more Phase-Focused IH-DTL for Heavy-Ion Medical Acceler- than about 10 percent, e.g., more than about 15, 20, 25, ators" Proceedings of EPAC 2006, Edinburgh, Scotland 30, 35, 40, or even more than about 50 percent. and Leaner, C.M. et al., "Status of the Superconducting [0047] In some embodiments, the second material can 30 ECR Ion Source Venus" Proceedings of EPAC 2000, Vi- have a level of oxidation (O 2) that is higher than the level enna, Austria. of oxidation (O1) of the first material. A higher level of [0050] Gamma radiation has the advantage of a sig- oxidation of the material can aid in its dispersability, nificant penetration depth into a variety of materials. swellability and/or solubility, further enhancing the mate- Sources of gamma rays include radioactive nuclei, such rial’s susceptibility to chemical, enzymatic or biological 35 as isotopes of cobalt, calcium, technicium, chromium, attack. In some embodiments, to increase the level of gallium, indium, iodine, iron, krypton, samarium, seleni- the oxidation of the second material relative to the first um, sodium, thalium, and xenon. material, the irradiation is performed under an oxidizing [0051] Sources of x rays include electron beam colli- environment, e.g., under a blanket of air or oxygen, pro- sion with metal targets, such as tungsten or molybdenum ducing a second material that is more oxidized than the 40 or alloys, or compact light sources, such as those pro- first material. For example, the second material can have duced commercially by Lyncean. more hydroxyl groups, aldehyde groups, ketone groups, [0052] Sources for ultraviolet radiation include deute- ester groups or carboxylic acid groups, which can in- rium or cadmium lamps. crease its hydrophilicity. [0053] Sources for infrared radiation include sapphire, 45 zinc, or selenide window ceramic lamps. Ionizing Radiation [0054] Sources for microwaves include klystrons, Slevin type RF sources, or atom beam sources that em- [0048] Each form of radiation ionizes the paper feed- ploy hydrogen, oxygen, or nitrogen gases. stock via particular interactions, as determined by the [0055] In some embodiments, a beam of electrons is energy of the radiation. Heavy charged particles primarily 50 used as the radiation source. A beam of electrons has ionize matter via Coulomb scattering; furthermore, these the advantages of high dose rates (e.g., 1, 5, or even 10 interactions produce energetic electrons that may further Mrad per second), high throughput, less containment, ionize matter. Alpha particles are identical to the nucleus and less confinement equipment. Electrons can also be of a helium atom and are produced by the alpha decay more efficient at causing chain scission. In addition, elec- of various radioactivenuclei, such as isotopes of bismuth, 55 trons having energies of 4-10 MeV can have a penetra- polonium, astatine, radon, francium, radium, several ac- tion depth of 5 to 30 mm or more, such as 40 mm. tinides, such as actinium, thorium, uranium, neptunium, [0056] Electron beams can be generated, e.g., by elec- curium, californium, americium, and plutonium. trostatic generators, cascade generators, transformer

6 11 EP 2 675 907 B1 12 generators, low energy accelerators with a scanning sys- ions) can be used to form irradiating ion beams. In par- tem, low energy accelerators with a linear cathode, linear ticular, mixtures of relatively light and relatively heavier accelerators, and pulsed accelerators. Electrons as an ions can be used in a single ion beam. ionizing radiation source can be useful, e.g., for relatively [0061] In some embodiments, ion beams for irradiating thin sections of material, e.g., less than 0.5 inch, e.g., 5 paper feedstock include positively-charged ions. The less than 0.4 inch, 0.3 inch, 0.2 inch, or less than 0.1 positively charged ions can include, for example, posi- inch. In some embodiments, the energy of each electron tively charged hydrogen ions (e.g., protons), noble gas of the electron beam is from about 0.3 MeV to about 2.0 ions (e.g., helium, neon, argon), carbon ions, nitrogen MeV (million electron volts), e.g., from about 0.5 MeV to ions, oxygen ions, silicon atoms, phosphorus ions, and about 1.5 MeV, or from about 0.7 MeV to about 1.25 MeV. 10 metal ions such as sodium ions, calcium ions, and/or iron [0057] Electron beam irradiation devices may be pro- ions. Without wishing to be bound by any theory, it is cured commercially from Ion Beam Applications, Lou- believed that such positively-charged ions behave chem- vain-la-Neuve, Belgium or the Titan Corporation, San Di- ically as Lewis acid moieties when exposed to materials, ego, CA. Typical electron energies can be 1 MeV, 2 MeV, initiating and sustaining cationic ring-opening chain scis- 4.5 MeV, 7.5 MeV, or 10 MeV. Typical electron beam 15 sion reactions in an oxidative environment. irradiation device power can be 1 kW, 5 kW, 10 kW, 20 [0062] In certain embodiments, ion beams for irradiat- kW, 50 kW, 100 kW, 250 kW, or 500 kW. The level of ing paper feedstock include negatively-charged ions. depolymerization of the feedstock depends on the elec- Negatively charged ions can include, for example, neg- tron energy used and the dose applied, while exposure atively charged hydrogen ions (e.g., hydride ions), and time depends on the power and dose. Typical doses may 20 negatively charged ions of various relatively electroneg- take values of 1 kGy, 5 kGy, 10 kGy, 20 kGy, 50 kGy, ative nuclei (e.g., oxygen ions, nitrogen ions, carbon ions, 100 kGy, or 200 kGy. In a some embodiments energies silicon ions, and phosphorus ions). Without wishing to be between 0.25-10 MeV (e.g., 0.5-0.8 MeV, 0.5-5 MeV, bound by any theory, it is believed that such negatively- 0.8-4 MeV, 0.8-3 MeV, 0.8-2 MeV or 0.8-1.5 MeV) can charged ions behave chemically as Lewis base moieties be used. In some embodiment doses between 1-100 25 when exposed to materials, causing anionic ring-opening Mrad (e.g., 2-80 Mrad, 5-50 Mrad, 5-40 Mrad, 5-30 Mrad chain scission reactions in a reducing environment. or 5-20 Mrad) can be used. In some preferred embodi- [0063] In some embodiments, beams for irradiating pa- ments, an energy between 0.8-3 MeV (e.g., 0.8-2 MeV per feedstock can include neutral atoms. For example, or 0.8-1.5MeV) combined with dosesbetween 5-50 Mrad any one or more of hydrogen atoms, helium atoms, car- (e.g., 5-40 Mrad, 5-30 Mrad or 5-20 Mrad) can be used. 30 bon atoms, nitrogen atoms, oxygen atoms, neon atoms, silicon atoms, phosphorus atoms, argon atoms, and iron Ion Particle Beams atoms can be included in beams that are used for irradi- ation. In general, mixtures of any two or more of the above [0058] Particles heavier than electrons can be utilized types of atoms (e.g., three or more, four or more, or even to irradiate paper feedstock materials. For example, pro- 35 more) can be present in the beams. tons, helium nuclei, argon ions, silicon ions, neon ions [0064] In certain embodiments, ion beams used to ir- carbon ions, phosphorus ions, oxygen ions or nitrogen radiate paper feedstock include singly-charged ions such ions can be utilized. In some embodiments, particles as one or more of H+, H-, He+, Ne+, Ar+, C+, C-, O+, O-, heavier than electrons can induce higher amounts of N+, N-, Si+, Si-, P+, P-, Na+, Ca+, and Fe+. In some em- chain scission (relative to lighter particles). In some in- 40 bodiments, ion beams can include multiply-charged ions stances, positively charged particles can induce higher such as one or more of C 2+, C3+, C4+, N3+, N5+, N3-, O2+, 2- 2- 2+ 4+ 2- 4- amounts of chain scission than negatively charged par- O , O2 , Si , Si , Si , and Si . In general, the ion ticles due to their acidity. beams can also include more complex polynuclear ions [0059] Heavier particle beams can be generated, e.g., that bear multiple positive or negative charges. In certain using linear accelerators or cyclotrons. In some embod- 45 embodiments, by virtue of the structure of the polynuclear iments, the energy of each particle of the beam is from ion, the positive or negative charges can be effectively about 1.0 MeV/atomic unit (MeV/amu) to about 6,000 distributed over substantially the entire structure of the MeV/atomic unit, e.g., from about 3 MeV/ atomic unit to ions. In some embodiments, the positive or negative about 4,800 MeV/atomic unit, or from about 10charges can be somewhat localized over portions of the MeV/atomic unit to about 1,000 MeV/atomic unit. 50 structure of the ions. [0060] In certain embodiments, ion beams used to ir- radiate paper feedstock can include more than one type Electromagnetic Radiation of ion. For example, ion beams can include mixtures of two or more (e.g., three, four or more) different types of [0065] In embodiments in which the irradiating is per- ions. Exemplary mixtures can include carbon ions and 55 formed with electromagnetic radiation, the electromag- protons, carbon ions and oxygen ions, nitrogen ions and netic radiation can have, e.g., energy per photon (in elec- protons, and iron ions and protons. More generally, mix- tron volts) of greater than 10 2 eV, e.g., greater than 10 3, tures of any of the ions discussed above (or any other 104, 105, 106, or even greater than 10 7 eV. In some em-

7 13 EP 2 675 907 B1 14 bodiments, the electromagnetic radiation has energy per microorganisms, e.g., to enhance cellulose hydrolysis by photon of between 104 and 107, e.g., between 105 and various microorganisms. 106 eV. The electromagnetic radiation can have a fre- [0069] In some embodiments, quenching includes an quency of, e.g., greater than 1016 hz, greater than 1017 application of pressure to the ionized material, such as hz, 10 18, 10 19, 10 20, or even greater than 10 21 hz. Typical 5 by mechanically deforming the material, e.g., directly me- dosesmay take valuesof greater than1 Mrad (e.g., great- chanically compressing the material in one, two, or three er than 1 Mrad, greater than 2 Mrad). In some embodi- dimensions, or applying pressure to a fluid in which the ments, the electromagnetic radiation has a frequency of material is immersed, e.g., isostatic pressing. In such in- between 1018 and 1022 hz, e.g., between 1019 to 1021 stances, the deformation of the material itself brings rad- hz. In some embodiment doses between 1-100 Mrad 10 icals, which are often trapped in crystalline domains, in (e.g., 2-80 Mrad, 5-50 Mrad, 5-40 Mrad, 5-30 Mrad or close enough proximity so that the radicals can recom- 5-20 Mrad) can be used. bine, or react with another group. In some instances, the pressure is applied together with the application of heat, Quenching and Controlled Functionalization such as a sufficient quantity of heat to elevate the tem- 15 perature of the material to above a melting point or sof- [0066] After treatment with ionizing radiation, any of tening point of a component of the material, such cellu- the materials or mixtures described herein may become lose or another polymer. Heat can improve molecular ionized; that is, the treated material may include radicals mobility in the material, which can aid in the quenching at levels that are detectable with an electron spin reso- of the radicals. When pressure is utilized to quench, the nance spectrometer. If an ionized feedstock remains in 20 pressure can be greater than about 1000 psi, such as the atmosphere, it will be oxidized, such as to an extent greater than about 1250 psi, 1450 psi, 3625 psi, 5075 that carboxylic acid groups are generated by reacting psi, 7250 psi, 10000 psi or even greater than 15000 psi. with the atmospheric oxygen. In some instances with [0070] In some embodiments, quenching includes some materials, such oxidation is desired because it can contacting the ionized material with a fluid, such as a aid in the further breakdown in molecular weight of the 25 liquid or gas, e.g., a gas capable of reacting with the carbohydrate-containing biomass, and the oxidation radicals, such as acetylene or a mixture of acetylene in groups, e.g., carboxylic acid groups can be helpful for nitrogen, ethylene, chlorinated ethylenes or chlorofluor- solubility and microorganism utilization in some instanc- oethylenes, propylene or mixtures of these gases. In oth- es. However, since the radicals can "live" for some time er particular embodiments, quenching includes contact- after irradiation, e.g., longer than 1 day, 5 days, 30 days, 30 ing the ionized material with a liquid, e.g., a liquid soluble 3 months, 6 months or even longer than 1 year, material in, or at least capable of penetrating into the material and properties can continue to change over time, which in reacting with the radicals, such as a diene, such as 1,5- some instances, can be undesirable. Thus, it may be cyclooctadiene. In some specific embodiments, quench- desirable to quench the ionized material. ing includes contacting the material with an antioxidant, [0067] After ionization, any ionized material can be 35 such as Vitamin E. If desired, the feedstock can include quenched to reduce the level of radicals in the ionized an antioxidant dispersed therein, and the quenching can material, e.g., such that the radicals are no longer de- come from contacting the antioxidant dispersed in the tectable with the electron spin resonance spectrometer. feedstock with the radicals. For example, the radicals can be quenched by the appli- [0071] Functionalization can be enhanced by utilizing cation of a sufficient pressure to the material and/or by 40 heavy charged ions, such as any of the heavier ions de- utilizing a fluid in contact with the ionized material, such scribed herein. For example, if it is desired to enhance asa gas or liquid, that reactswith (quenches) theradicals. oxidation, charged oxygen ions can be utilized for the Using a gas or liquid to at least aid in the quenching of irradiation. If nitrogen functional groups are desired, ni- the radicals can be used to functionalize the ionized ma- trogen ions or anions that include nitrogen can be utilized. terial with a desired amount and kind of functional groups, 45 Likewise, if sulfur or phosphorus groups are desired, sul- such as carboxylic acid groups, enol groups, aldehyde fur or phosphorus ions can be used in the irradiation. groups, nitro groups, nitrile groups, amino groups, alkyl amino groups, alkyl groups, chloroalkyl groups or chlo- Doses rofluoroalkyl groups. [0068] In some instances, such quenching can im-50 [0072] In some instances, the irradiation is performed prove the stability of some of the ionized materials. For at a dosage rate of greater than about 0.25 Mrad per example, quenching can improve the resistance of the second, e.g., greater than about 0.5, 0.75, 1.0, 1.5, 2.0, material to oxidation. Functionalization by quenching can or even greater than about 2.5 Mrad per second. In some alsoimprove thesolubility of any materialdescribed here- embodiments, the irradiating is performed at a dose rate in, can improve its thermal stability, and can improve ma- 55 of between 5.0 and 1500.0 kilorads/hour, e.g., between terial utilization by various microorganisms. For example, 10.0 and 750.0 kilorads/hour or between 50.0 and 350.0 the functional groups imparted to the material by the kilorads/hour. In some embodiments, irradiation is per- quenching can act as receptor sites for attachment by formed at a dose rate of greater than about 0.25 Mrad

8 15 EP 2 675 907 B1 16 per second, e.g., greater than about 0.5, 0.75, 1, 1.5, 2, is an aqueous medium. If desired, the medium can in- 5, 7, 10, 12, 15, or even greater than about 20 Mrad per clude an oxidant, such as a peroxide (e.g., hydrogen per- second, e.g., about 0.25 to 2 Mrad per second. oxide), a dispersing agent and/or a buffer. Examples of [0073] In some embodiments, the irradiating (with any dispersing agents include ionic dispersing agents, e.g., radiation source or a combination of sources) is per-5 sodium lauryl sulfate, and non-ionic dispersing agents, formed until the material receives a dose of 0.25 Mrad, e.g., poly(ethylene glycol). e.g., at least 1.0, 2.5, 5.0, 8.0, 10, 15, 20, 25, 30, 35, 40, [0080] In other embodiments, the sonication medium 50, or even at least 100 Mrad. In some embodiments, is non-aqueous. For example, the sonication can be per- the irradiating is performed until the material receives a formed in a hydrocarbon, e.g., toluene or heptane, an dose of between 1.0 Mrad and 6.0 Mrad, e.g., between 10 ether, e.g., diethyl ether or tetrahydrofuran, or even in a 1.5 Mrad and 4.0 Mrad, 2 Mrad and 10 Mrad, 5 Mrad and liquefied gas such as argon, xenon, or nitrogen. 20 Mrad, 10 Mrad and 30 Mrad, 10 Mrad and 40 Mrad, or 20 Mrad and 50 Mrad. In some embodiments, the ir- Pyrolysis radiating is performed until the material receives a dose of from about 0.1 Mrad to about 500 Mrad, from about 15 [0081] One or more pyrolysis processing sequences 0.5 Mrad to about 200 Mrad, from about 1 Mrad to about can be used to process paper feedstock from a wide va- 100 Mrad, or from about 5 Mrad to about 60 Mrad. In riety of different sources to extract useful substances some embodiments, a relatively low dose of radiation is from the materials, and to provide partially degraded ma- applied, e.g., less than 60 Mrad. terials which function as input to further processing steps 20 and/or sequences. Pyrolysis can also be used to sterilize Sonication the materials. Pyrolysis conditions can be varied depend- ing on the characteristics of the feedstock and/or other [0074] Sonication can reduce the molecular weight factors. and/or crystallinity of the polymers comprising the paper [0082] In one example, a first material that includes feedstock, e.g., cellulose. Sonication can also be used 25 cellulose having a first number average molecular weight to sterilize the materials. As discussed above with regard (MN1) is pyrolyzed, e.g., by heating the first material in a to radiation, the process parameters used for sonication tube furnace (in the presence or absence of oxygen), to can be varied depending on various factors. provide a second material that includes cellulose having

[0075] In one method, a first material that includes cel- a second number average molecular weight (M N2) lower lulose having a first number average molecular weight 30 than the first number average molecular weight.

(MN1) is dispersed in a medium, such as water, and son- [0083] Since the second material includes cellulose icated and/or otherwise cavitated, to provide a second having a reduced molecular weight relative to the first material that includes cellulose having a second number material, and in some instances, a reduced crystallinity average molecular weight (MN2) lower than the first as well, the second material is generally more dispersi- number average molecular weight. The second material 35 ble, swellable and/or soluble, e.g., in a solution containing (or the first and second material in certain embodiments) a microorganism. can be combined with a microorganism (with or without [0084] In some embodiments, the second number av- enzyme treatment) that can utilize the second and/or first erage molecular weight (MN2) is lower than the first material to produce an intermediate or product. number average molecular weight (MN1) by more than [0076] Since the second material includes cellulose 40 about 10 percent, e.g., more than about 15, 20, 25, 30, having a reduced molecular weight relative to the first 35, 40, 50 percent, 60 percent, or even more than about material, and in some instances, a reduced crystallinity 75 percent. as well, the second material is generally more dispersi- [0085] In some instances, the second material in- ble, swellable, and/or soluble, e.g., in a solution contain- cludes cellulose that has a crystallinity (C 2) that is lower 45 ing a microorganism. than the crystallinity (C1) of the cellulose of the first ma- [0077] In some embodiments, the second number av- terial. For example, (C 2) can be lower than (C 1) by more erage molecular weight (MN2) is lower than the first than about 10 percent, e.g., more than about 15, 20, 25, number average molecular weight (MN1) by more than 30, 35, 40, or even more than about 50 percent. about 10 percent, e.g., more than about 15, 20, 25, 30, [0086] In some embodiments, the pyrolysis of the ma- 35, 40, 50 percent, 60 percent, or even more than about 50 terials is continuous. In other embodiments, the material 75 percent. is pyrolyzed for a pre-determined time, and then allowed [0078] In some instances, the second material in- to cool for a second pre-determined time before pyrolyz- cludes cellulose that has a crystallinity (C 2) that is lower ing again. than the crystallinity (C1) of the cellulose of the first ma- 55 terial. For example, (C 2) can be lower than (C 1) by more Oxidation than about 10 percent, e.g., more than about 15, 20, 25, 30, 35, 40, or even more than about 50 percent. [0087] One or more oxidative processing sequences [0079] In some embodiments, the sonication medium can be used to process paper feestock from a wide va-

9 17 EP 2 675 907 B1 18 riety of different sources to extract useful substances tween 2 and 5, between 2.5 and 5 or between about 3 from the feedstock, and to provide partially degraded and 5. Oxidation conditions can also include a contact and/or altered feedstock which functions as input to fur- period of between 2 and 12 hours, e.g., between 4 and ther processing steps and/or sequences. The oxidation 10 hours or between 5 and 8 hours. In some instances, conditions can be varied, e.g., depending on the lignin 5 temperature is maintained at or below 300 °C, e.g., at or content of the feedstock, with a higher degree of oxidation below 250, 200, 150, 100 or 50 °C. In some instances, generally being desired for higher lignin content feed- the temperature remains substantially ambient, e.g., at stocks. or about 20-25 °C. [0088] In one method, a first material that includes cel- [0095] In some embodiments, the one or more oxi- lulose having a first number average molecular weight 10 dants are applied as a gas, such as by generating ozone

(MN1) and having a first oxygen content (O 1) is oxidized, in-situ by irradiating the material through air with a beam e.g., by heating the first material in a stream of air or of particles, such as electrons. oxygen-enriched air, to provide a second material that [0096] In some embodiments, the mixture further in- includes cellulose having a second number average mo- cludes one or more hydroquinones, such as 2,5-dimeth- 15 lecular weight (M N2) and having a second oxygen content oxyhydroquinone (DMHQ) and/or one or more benzoqui- (O2) higher than the first oxygen content (O 1). nones, such as 2,5-dimethoxy-1,4-benzoquinone (DM- [0089] The second number average molecular weight BQ), which can aid in electron transfer reactions. of the second material is generally lower than the first [0097] In some embodiments, the one or more oxi- number average molecular weight of the first material. dants are electrochemically-generated in-situ. For exam- For example, the molecular weight may be reduced to 20 ple, hydrogen peroxide and/or ozone can be electro- the same extent as discussed above with respect to the chemically produced within a contact or reaction vessel. other physical treatments. The crystallinity of the second material may also be reduced to the same extent as dis- Other Processes To Solubilize, Reduce Recalci- cussed above with respect to the other physical treat- trance Or To Functionalize ments. 25 [0090] In some embodiments, the second oxygen con- [0098] Any of the processes of this paragraph can be tent is at least about five percent higher than the first used alone without any of the processes described here- oxygen content, e.g., 7.5 percent higher, 10.0 percent in, or in combination with any of the processes described higher, 12.5 percent higher, 15.0 percent higher or 17.5 herein (in any order): steam explosion, chemical treat- percent higher. In some preferred embodiments, the sec- 30 ment (e.g., acid treatment (including concentrated and ond oxygen content is at least about 20.0 percent higher dilute acid treatment with mineral acids, such as sulfuric than the first oxygen content of the first material. Oxygen acid, hydrochloric acid and organic acids, such as trif- content is measured by elemental analysis by pyrolyzing luoroacetic acid) and/or base treatment (e.g., treatment a sample in a furnace operating at 1300 °C or higher. A with lime or sodium hydroxide)), UV treatment, screw ex- suitable elemental analyzer is the LECO CHNS-932 an- 35 trusion treatment (see, e.g., U.S. Serial No. 13/099,151, alyzer with a VTF-900 high temperature pyrolysis fur- solvent treatment (e.g., treatment with ionic liquids) and nace. freeze milling (see, e.g., U.S. Serial No. 12/502,629 now [0091] Generally, oxidation of a material occurs in an U.S. Patent No. 7,900,857). oxidizing environment. For example, the oxidation can be effected or aided by pyrolysis in an oxidizing environ- 40 Saccharification ment, such as in air or argon enriched in air. To aid in the oxidation, various chemical agents, such as oxidants, [0099] In order to convert the paper feedstock to fer- acids or bases can be added to the material prior to or mentable sugars, the cellulose in the feedstock is hydro- during oxidation. For example, a peroxide (e.g., benzoyl lyzed by a saccharifying agent, e.g., an enzyme, a proc- peroxide) can be added prior to oxidation. 45 ess referred to as saccharification. The materials that [0092] Some oxidative methods of reducing recalci- include the cellulose are treated with the enzyme, e.g., trance in a paper feedstock employ Fenton-type chem- by combining the material and the enzyme in a solvent, istry. Such methods are disclosed, for example, in U.S. e.g., in an aqueous solution. Serial No. 12/639,289. [0100] Enzymes and organisms that break down cel- [0093] Exemplary oxidants include peroxides, such as 50 lulose contain or manufacture various cellulolytic en- hydrogen peroxide and benzoyl peroxide, persulfates, zymes (cellulases), ligninases or various small molecule such as ammonium persulfate, activated forms of oxy- biomass-destroying metabolites. These enzymes may gen, such as ozone, permanganates, such as potassium be a complex of enzymes that act synergistically to de- permanganate, perchlorates, such as sodium perchlo- grade crystalline cellulose. Examples of cellulolytic en- rate, and hypochlorites, such as sodium hypochlorite55 zymes include: endoglucanases, cellobiohydrolases, (household bleach). and cellobiases (β-glucosidases). Referring to FIG. 3, a [0094] In some situations, pH is maintained at or below cellulosic is initially hydrolyzed by endogluca- about 5.5 during contact, such as between 1 and 5, be- nases at random locations producing oligomeric interme-

10 19 EP 2 675 907 B1 20 diates. These intermediates are then substrates for exo- creased by adding more feedstock to the solution. In or- splitting glucanases such as cellobiohydrolase to pro- der to keep the sugar that is being produced in solution, duce cellobiose from the ends of the cellulose polymer. a surfactant can be added, e.g., one of those discussed Cellobiose is a water-soluble 1,4-linked dimer of glucose. above. Solubility can also be increased by increasing the Finally cellobiase cleaves cellobiose to yield glucose. 5 temperature of the solution. For example, the solution [0101] Suitable saccharifying agents are described, for can be maintained at a temperature of 40-50°C, 60-80°C, example, in the Materials section below. or even higher. [0102] As noted above, a food-based nutrient source [0107] In some embodiments, the feedstock is proc- or nutrient package is preferably added prior to or during essed to convert it to a convenient and concentrated solid saccharification, and an enzyme is added that is selected 10 material, e.g., in a powdered, granulate or particulate to release nutrients from the food-based nutrient source. form. The concentrated material can be in a purified, or Suitable enzymes are described, for example, in the Ma- a raw or crude form. The concentrated form can have, terials section below. for example,a total sugar concentration ofbetween about [0103] The saccharification process can be partially or 90 percent by weight and about 100 percent by weight, completely performed in a tank (e.g., a tank having a15 e.g., 92, 94, 96 or 98 percent by weight sugar. Such a volume of at least 4000, 40,000, 400,000 L or 1,000,000 form can be particularly cost effective to ship, e.g., to a L) in a manufacturing plant, and/or can be partially or bioprocessing facility, such as a biofuel manufacturing completely performed in transit, e.g., in a rail car, tanker plant. Such a form can also be advantageous to store truck, or in a supertanker or the hold of a ship. The time and handle, easier to manufacture and becomes both an required for complete saccharification will depend on the 20 intermediate and a product, providing an option to the process conditions and the feedstock and enzyme used. biorefinery as to which products to manufacture. If saccharification is performed in a manufacturing plant [0108] In some instances, the powdered, granulate or under controlled conditions, the cellulose may be sub- particulate material can also include one or more of the stantially entirely converted to glucose in about 12-96 materials, e.g., additives or chemicals, described herein, hours. If saccharification is performed partially or com- 25 such as the food-based nutrient or nutrient package, a pletely in transit, saccharification may take longer. The nitrogen source, e.g., urea, a surfactant, an enzyme, or tank contents are mixed during saccharification, using any microorganism described herein. In some instances, jet mixing, e.g. as described in U.S. Applications Serial all materials needed for a bio-process are combined in Nos. 12/782,694, 13/293,985 and 13/293,977. the powdered, granulate or particulate material. Such a [0104] The addition of surfactants can enhance the 30 form can be a particularly convenient form for transport- rate of saccharification. Examples of surfactants include ing to a remote bioprocessing facility, such as a remote non-ionic surfactants, such as a Tween® 20 or Tween® biofuels manufacturing facility. Such a form can also be 80 polyethylene glycol surfactants, ionic surfactants, or advantageous to store and handle. amphoteric surfactants. [0109] In some instances, the powdered, granulate or [0105] It is generally preferred that the concentration 35 particulate material (with or without added materials, of the resulting glucose solution be relatively high, e.g., such as additives and chemicals) can be treated by any greater than 40%, or greater than 50, 60, 70, 80, 90 or of the physical treatments described in U.S. Serial No. even greater than 95% by weight. This reduces the vol- 12/429,045. For example, irradiating the powdered, ume to be shipped, if saccharification and fermentation granulate or particulate material can increase its solubility are performed at different locations, and also inhibits mi- 40 and can sterilize the material so that a bioprocessing fa- crobial growth in the solution. However, lower concen- cility can integrate the material into their process directly trations may be used, in which case it may be desirable as may be required for a contemplated intermediate or to add an antimicrobial additive, e.g., a broad spectrum product. antibiotic, in a low concentration, e.g., 50 to 150 ppm. [0110] In certain instances, the powdered, granulate Other suitable antibiotics include amphotericin B, ampi- 45 or particulate material (with or without added materials, cillin, chloramphenicol, ciprofloxacin, gentamicin, hygro- such as additives and chemicals) can be carried in a mycin B, kanamycin, neomycin, penicillin, puromycin, structure or a carrier for ease of transport, storage or streptomycin. Antibiotics will inhibit growth of microor- handling. For example, the structure or carrier can in- ganisms during transport and storage, and can be used clude or incorporate a bag or liner, such as a degradable at appropriate concentrations, e.g., between 15 and 1000 50 bag or liner. Such a form can be particularly useful for ppm by weight, e.g., between 25 and 500 ppm, or be- adding directly to a bioprocess system. tween 50 and 150 ppm. If desired, an antibiotic can be included even if the sugar concentration is relatively high. Fermentation [0106] A relatively high concentration solution can be obtained by limiting the amount of water added to the 55 [0111] Microorganisms can produce a number of use- feedstock with the enzyme. The concentration can be ful intermediates and products by fermenting a low mo- controlled, e.g., by controlling how much saccharification lecular weight sugar produced by saccharifying the paper takes place. For example, concentration can be in- feedstock materials. For example, fermentation or other

11 21 EP 2 675 907 B1 22 bioprocesses can produce alcohols, organic acids, hy- (25%) of the centrifuge effluent can be recycled to fer- drocarbons, hydrogen, proteins or mixtures of any of mentation and the rest sent to the second and third evap- these materials. orator effects. Most of the evaporator condensate can be [0112] Yeast and Zymomonas bacteria, for example, returned to the process as fairly clean condensate with can be used for fermentation or conversion. Other micro- 5 a small portion split off to waste water treatment to pre- organisms are discussed in the Materials section, below. vent build-up of low-boiling compounds. The optimum pH for fermentations is about pH 4 to 7. For example, the optimum pH for yeast is from about pH Other Possible Processing of Sugars 4 to 5, while the optimum pH forZymomonas is from about pH 5 to 6. Typical fermentation times are about 24 10 [0117] Processing during or after saccharification can to 168 hours (e.g., 24 to 96 hrs) with temperatures in the include isolation and/or concentration of sugars by chro- range of 20 °C to 40 °C (e.g., 26 °C to 40 °C), however matography e.g., simulated moving bed chromatogra- thermophilic microorganisms prefer higher tempera- phy, precipitation, centrifugation, crystallization, solvent tures. evaporation and combinations thereof. In addition, or op- [0113] In some embodiments e.g., when anaerobic or- 15 tionally, processing can include isomerization of one or ganisms are used, at least a portion of the fermentation more of the sugars in the sugar solution or suspension. is conducted in the absence of oxygen e.g., under a blan- Additionally, or optionally, the sugar solution or suspen- ket of an inert gas such as N2, Ar, He, CO2 or mixtures sion can be chemically processed e.g., glucose and xy- thereof. Additionally, the mixture may have a constant lose can be hydrogenated to sorbitol and xylitol respec- purge of an inert gas flowing through the tank during part 20 tively. Hydrogenation can be accomplished by use of a of or all of the fermentation. In some cases, anaerobic catalyst e.g., Pt/γ-Al2O3, Ru/C, Raney Nickel in combi- condition can be achieved or maintained by carbon di- nation with H 2 under high pressure e.g., 10 to 12000 psi. oxide production during the fermentation and no addi- tional inert gas is needed. REMOVING OF FILLERS, INKS, AND COATINGS [0114] In some embodiments, all or a portion of the 25 fermentation process can be interrupted before the low [0118] Paper feedstock used in the processes de- molecular weight sugar is completely converted to a scribed can contain fillers, coatings, laminated material, product (e.g, ethanol). The intermediate fermentation pigments, inks and binders. These can be removed and products include high concentrations of sugar and car- either discarded or recycled as described here. bohydrates. The sugars and carbohydrates can be iso- 30 [0119] Inorganic fillers and coatings e.g., those de- lated as discussed below. These intermediate fermenta- scribed in the materials section below can be removed tion products can be used in preparation of food for hu- at any point during the process. For example, the inor- man or animal consumption. Additionally or alternatively, ganic filler and coating can be removed from the feed- the intermediate fermentation products can be ground to stock after a mechanical, physical or chemical treatment a fine particle size in a stainless-steel laboratory mill to 35 to reduce the recalcitrance of the feedstock; after com- produce a flour-like substance. bination with a fluid; after, during or before saccharifica- [0115] Mobile fermentors can be utilized, as described tion; after, during or before a purification step; after, dur- in U.S. Provisional Patent Application Serial 60/832,735, ing or before a fermentation step; and/or after, during or now Published International Application No. WObefore a chemical conversion step. The fillers and coat- 2008/011598. Similarly, the saccharification equipment 40 ings can be removed by any means e.g., by sedimenta- can be mobile. Further, saccharification and/or fermen- tion, precipitation, ligand sequestration, filtration, floata- tation may be performed in part or entirely during transit. tion, chemical conversion and centrifugation. Some of the physical treatments discussed herein (see Physical Distillation Treatment section) can aid in separating the cellulosic 45 materials from the inorganic fillers and coatings (e.g., me- [0116] After fermentation, the resulting fluids can be chanical treatments, chemical treatments, irradiation, py- distilled using, for example, a "beer column" to separate rolysis, sonication and/or oxidiation). The recovered in- ethanol and other alcohols from the majority of water and organic fillers can be recycled or discarded. residual solids. The vapor exiting the beer column can [0120] Inks that are present can be removed from the be, e.g., 35% by weight ethanol and can be fed to a rec- 50 feedstock at any point during the process. Inks can be a tification column. A mixture of nearly azeotropic (92.5%) complex medium composed of several components e.g., ethanol and water from the rectification column can be solvents, pigments, dyes, , lubricants, solubilizers, purified to pure (99.5%) ethanol using vapor-phase mo- surfactants, particulate matter and/or fluorescers. For ex- lecular sieves. The beer column bottoms can be sent to ample, printed papers, e.g., magazines and catalogs, the first effect of a three-effect evaporator. The rectifica- 55 may include high levels of the pigments generally used tion column reflux condenser can provide heat for this in printing inks. In some cases the papers include metal- first effect. After the first effect, solids can be separated based pigments, organic pigments, and/or Lake pig- using a centrifuge and dried in a rotary dryer. A portion ments. For example, pigments that can be used are Yel-

12 23 EP 2 675 907 B1 24 low Lakes, Tartrazine Yellow Lake, Hansa Yellows, Di- can be used to convert paper feedstocks to one or more arylide Yellows, Yellow azo pigments, Fluorescent Yel- products, such as energy, fuels, foods and materials. low, Diarylide Orange, DNA Orange, Pyrazolone Or- Specific examples of products include, but are not limited ange, Fast Orange F2G, Benzimidazolone Orange HL, to, hydrogen, sugars (e.g., glucose, xylose, arabinose, Ethyl Lake Red C, Para Reds, Toluidine Red, Carmine 5 mannose, galactose, fructose, disaccharides, oligosac- F.B., Naphthol Reds and Rubines, Permanent Red FRC, charides and polysaccharides), alcohols (e.g., monohy- Bordeaux FRR, Rubine Reds, Lithol Reds, BON Red, dric alcohols or dihydric alcohols, such as ethanol, n- Lithol Rubine 4B, BON Maroon, Rhodamine 6G, Lake propanol, isobutanol, sec-butanol, tert-butanol or n-bu- Red C, BON Arylamide Red, Quinacrinone Magentas, tanol), hydrated or hydrous alcohols, e.g., containing Copper Ferrocyanide Pink, Benzimidazolone Carmines 10 greater than 10%, 20%, 30% or even greater than 40% and Reds, Azo Magenta G, Anthraquinone Scarlet, Mad- water, sugars, biodiesel, organic acids (e.g., acetic acid der Lakes, Phthalocyanine Blues, PMTA Victoria Blue, and/or lactic acid), hydrocarbons, e.g., methane, ethane, Victoria Blue CFA, Ultramarine Blue, Indanthrene Blue, propane, isobutene, pentane, n-hexane, biodiesel, bio- Alkali Blues, Peacock Blue, Benzimidazolone Bordeaux gasoline and mixtures thereof, co-products (e.g., pro- HF 3R, PMTA Rhodamine, PMTA Violet, Dioxazine Vi- 15 teins, such as cellulolytic proteins (enzymes) or single olet, Carbazole Violet, Crystal Violet, Dioxazine Violet B, cell proteins), and mixtures of any of these in any com- Thioindigoid Red, Phthalocyanine Greens, PMTA bination or relative concentration, and optionally in com- Greens, Benzimidazolone Brown HFR, Cadmium Red, bination with any additives, e.g., fuel additives. Other ex- Cadmium Yellow, Cadmium Oranges, Cadmium-Mercu- amples include carboxylic acids, such as acetic acid or ry Reds, Iron Oxide Yellows, Irons Oxide Blues, Iron Ox- 20 butyric acid, salts of a carboxylic acid, a mixture of car- ide browns, Iron Oxide Reds, Ultramarine Blues, Ultra- boxylic acids and salts of carboxylic acids and esters of marine Violet, Chromium Antimony Titanium Buff, copper carboxylic acids (e.g., methyl, ethyl and n-propyl esters), phthalocyanine blue, green copper phthalocyanine pig- ketones, aldehydes, alpha, beta unsaturated acids, such ments, potash blue and soda blue pigments. The removal as acrylic acid and olefins, such as ethylene. Other alco- of ink may help improve certain parts in the process. For 25 hols and alcohol derivatives include propanol, propylene example, some ink can be toxic to microorganisms used glycol, 1,4-butanediol, 1,3-propanediol, sugar alcohols in the process. The inks can also impart an undesirable (e.g., erythritol, glycol, glycerol, sorbitol threitol, arabitol, coloration or toxicity to the final product. Furthermore, ribitol, mannitol, dulcitol, fucitol, iditol, isomalt, maltitol, removing the inks may allow these to be recycled, im- lactitol, xylitol and other polyols), methyl or ethyl esters proving the cost benefits to the process and lessening 30 of any of these alcohols. Other products include methyl the environmental impact of the paper feedstock. The acrylate and methylmethacrylate. The product may also inks can be removed by any means. For example, re- be an organic acid, e.g., lactic acid, formic acid, acetic moval may include dispersion, floatation, pressing and/or acid, propionic acid, butyric acid, succinic acid, valeric washing steps, extraction with solvents (e.g., supercriti- acid, caproic, palmitic acid, stearic acid, oxalic acid, 35 cal CO2, alcohol, water and organic solvents), settling, malonic acid, glutaric acid, oleic acid, linoleic acid, gly- chemical means, sieving and/or precipitation. Some of colic acid, γ-hydroxybutyric acid, a mixture thereof, a salt the physical treatments discussed herein (see Physical of any of these acids, or a mixture of any of the acids and Treatment section) can aid in separating the cellulosic their respective salts. materials from the inks (e.g., mechanical treatments, [0123] Other intermediates and products, including chemical treatments, irradiation, pyrolysis, sonication40 food and pharmaceutical products, are described in U.S. and/or oxidiation). In addition enzymatic tech- Serial No. 12/417,900. nologies such as those disclosed in U.S. patent 7,297,224 can be used. MATERIALS [0121] Coating materials, e.g., those found in poly- coated paper described in the materials section below, 45 Paper Feedstocks can be removed from the feedstock at any point during the process. This can be done by, for example, the meth- [0124] Suitable paper feedstocks include paper that is ods mentioned above for removal of pigments and inks highly pigmented, coated or filled and can have a low and inorganic materials. In some cases, where polycoat- calorific value. Sources of such paper include maga- ed paper is a laminate, de-lamination can be done by, 50 zines, catalogs, books, manuals, labels, calendars, for example, chemical and/or mechanical means. The greeting cards and other high quality printed materials non-cellulosic laminate portions can then be separated such as prospectuses, brochures and the like. The pa- from the cellulose containing layers and discarded and/or pers may include at least 0.025% by weight of pigment, recycled. filler or coating, e.g., from 0 to 80%, 0 to 50%, 0.1 to 50%, 55 0.1 to 30%, 0.1 to 20%, 0.5 to 2.5%, 0.2 to 15%, 0.3 to INTERMEDIATES AND PRODUCTS 10%, 0.5 to 5%. According to the method of the invention, the paper feedstock has a filler content of greater than [0122] The processes and nutrients discussed herein 10 wt. % and an ash content of at least 8 wt. %, and

13 25 EP 2 675 907 B1 26 comprises a printing ink. Other suitable paper feedstocks density (i.e., ), for example, at least 50 g/m 2, include high basis weight coated paper and/or paper with at least 60 g/m2, at least 70 g/m2, at least 80 g/m2 or at a high filler content i.e., at least 10 wt.%. These papers least 90 g/m2.The Grammage can be between 50 g/m2 can be printed or unprinted. Examples of this type of feed- and 200 g/m 2, between 50 g/m 2 and 175 g/m 2, between stock include paper having a basis weight, as defined as 5 50 g/m2 and 150 g/m2, between 50 g/m2 and 125 g/m2, the weight in pounds (lb) for a ream (500 sheets) of 25" X between 50 g/m2 and 100 g/m2, between 60 g/m2 and 38" sheets, of at least 35 lb., for example at least 45 lb., 200 g/m2, between 60 g/m2 and 175 g/m2, between 60 at least 50 lb., at least 60 lb, at least 70 lb. or at least 80 g/m2 and 150 g/m 2, between 60 g/m 2 and 125 g/m 2, be- lb. The feedstock includes paper having a basis weight tween 60 g/m2 and 100 g/m 2, between 70 g/m 2 and 200 below 330 lb., for example below about 300 lb, below 10 g/m2, between 70 g/m2 and 175 g/m2, between 70 g/m2 about 250 lb, below about 200 lb, below about 150 lb, and 150 g/m 2, between 70 g/m 2 and 125 g/m 2, between below about 120 lb, below about 110 lb, below about 105 70 g/m2 and 100 g/m2, between 80 g/m2 and 200 g/m2, lb or below about 100 lb. For example the basis weight between 80 g/m2 and 175 g/m2, between 80 g/m2 and may be between 35 lb and 330 lb, 35 lb and 120 lb, be- 150 g/m2, between 80 g/m2 and 125 g/m2, between 80 tween 35 1b and 110 lb, between 35 1b and 100 lb, be- 15 g/m2 and 100 g/m2, between 130 g/m2 and 500 g/m2, tween 35 1b and 90 lb, between 45 lb and 120 lb, between between 130 g/m 2 and 450 g/m 2, between 130 g/m 2 and 45 lb and 110 lb, between 45 lb and 100 lb, between 45 350 g/m 2, between 130 g/m 2 and 300 g/m 2, between 130 lb and 90 lb, between 50 lb and 120 lb, between 50 lb g/m2 and 250 g/m2, between 130 g/m2 and 200 g/m2, and 110 lb, between 50 lb and 100 lb, between 50 lb and between 130 g/m 2 and 175 g/m 2, between 130 g/m 2 and 90 lb, between 60 lb and 120 lb, between 60 lb and 110 20 150 g/m 2, between 200 g/m 2 and 500 g/m 2, between 200 lb, between 60 lb and 100 lb, between 60 lb and 90 lb, g/m2 and 450 g/m2, between 200 g/m2 and 350 g/m2, between 60 lb and 120 lb, between 60 lb and 110 lb, between 200 g/m 2 and 300 g/m 2, between 200 g/m 2 and between 60 lb and 100 lb, between 60 lb and 90 lb, be- 250 g/m 2, between 250 g/m 2 and 500 g/m 2, between 250 tween 70 lb and 120 lb, between 70 lb and 110 lb, be- g/m2 and 450 g/m2, between 250 g/m2 and 350 g/m2, tween 70 lb and 100 lb, between 70 lb and 90 lb, between 25 between 250 g/m 2 and 300 g/m 2, between 200 g/m 2 and 90 lb and 330 lb, between 90 lb and 300 lb, between 90 250 g/m 2, between 300 g/m 2 and 500 g/m 2, between 300 lb and 250 lb, between 90 lb and 200 lb, between 90 lb g/m2 and 450 g/m 2, or between 300 g/m 2 and 350 g/m 2. and 150 lb, between 90 lb and 110 lb, between 110 lb [0125] Coated papers are well known in the paper art, and 330 lb, between 110 lb and 300 lb, between 110 lb and are disclosed, for example, in U.S. Patent Nos. and 250 lb, between 110 lb and 200 lb, between 110 lb 30 6,777,075; 6,783,804, and 7,625,441. and 150 lb, between 130 lb and 330 lb, between 130 lb [0126] Coated papers suitable as feedstock can in- and 300 lb, between 130 lb and 250 lb, between 130 lb clude paper coated with an inorganic material, for exam- and 200 lb, or between 130 lb and 150 lb, In some em- ple the same materials used as fillers can be used in bodiments, the papers have relatively high density, e.g., coatings. Additionally, coated papers can include paper greater than 1.11 g/cm 3, in some cases from about 1.11 35 coated with a polymer (poly-coated paper). Such paper to 2 g/cm 3 e.g., 1.11 to 1.8 g/cm 2, 1.11 to 1.6 g/cm 2, 1.11 can be made, for example, by extrusion coating, brush to 1.52 g/cm2, 1.2 to 1.8 g/cm2, 1.2 to 1.6 g/cm2, 1.2 to coating, curtain coating, blade coating, air knife coating, 1.52 g/cm2, 1.3 to 1.8 g/cm2, 1.3 to 1.6 g/cm2 or 1.3 to cast coating or roller coating paper. For example, sources 1.52 g/cm2 Such papers often have a high ash content of such poly-coated paper include a variety of food con- e.g., at least 8wt.%, at least 10 wt.%, at least 15 wt.% , 40 tainers, including juice , condiment pouches (e.g., at least 20 wt.% or at least 50 wt.%. The ash content can sugar, salt, pepper), plates, pet food bags, cups, bowls, be between 8 and 50%, e.g., between 10 and 50%, be- trays and boxes for frozen foods. The poly-coated paper tween 20 and 50%, between 30 and 50%, between 10 can, in addition to paper, contain, for example, polymers, and 40%, between 20 and 40%, between 10 and 30% or (e.g., polyethylene, polypropylene, biodegradable poly- between 10 and 20%. The papers can have a high filler 45 mers, silicone), latexes, binders, wax, and, in some cas- content, e.g., at least10% by weight, e.g., at least 20 wt%, es, one or more layers of aluminum. The poly coated at least 30 wt%, at least 40 wt% or at least 50 wt%. Filler papers can be multi layered laminate, for example, made contents can be between 10 and 80%, e.g., between 20 withone or more, e.g.,two, three,four, five ormore, layers and 80%, between 30 and 80%, between 40 and 80%, of polyethylene and paper and one or more, e.g., two, between 10 and 70%, between 20 and 70%, between 30 50 three or more layers of aluminum. and 70%, between 40 and 70%, between 10 and 60%, [0127] The paper feedstocks typically have a low gross between 20 and 60%, between 30 and 60% and between caloric value e.g., below 7500 Btu/lb e.g, below 7400 40 and 60%. Suitable fillers include clays, oxides (e.g., Btu/lb, below 7200 Btu/lb, below 7000 Btu/lb, below 6800 titania, silica, alumina),carbonates (e.g., calcium carbon- Btu/lb, below 6600 Btu/lb, below 6400 Btu/lb, below 6200 ate), silicates (e.g., Talc) and aluminosilicates (e.g., Ka- 55 Btu/lb, below 6000 Btu/lb, below 5800 Btu/lb, below 5600 olin). One suitable grade of coated paper is referred to Btu/lb, below 5400 Btu/lb or below 5200 Btu/lb. The gross in the industry as Machine Finished Coated (MFC) paper. calorific value can be between about 5200 and 7500 In other embodiments the paper can have a high surface Btu/lb e.g., between 6800 and 7000 Btu/lb, between 6700

14 27 EP 2 675 907 B1 28 and 7100 Btu/lb, between 6400 and 7100 Btu/lb, between per, Fluorescent Paper, , Form Bond, 6600 and 6800 Btu/lb, between 6100 and 6700 Btu/lb, Freesheet, Fruit Wrapping Paper, Gasket Board, Glass- between 6100 and 6300 Btu/lb, between 6000 and 6350 ine Paper, Glazed Paper, Granite Paper, Gravure Paper, Btu/lb, between 5600 and 6400 Btu/lb or between 5200 Gray Board, , Green Paper, Ground- and 5500 Btu/lb. The gross calorific value can be meas- 5 wood Papers, Gummed Paper, Gypsum Board, Hand- ure using a bomb calorimeter e.g., as outlined in ASTM made Paper, Hanging Paper, Hard Sized Paper, Heat method E711. Seal Paper, Heat , Hi-Fi (High Finish) Pa- [0128] The paper feedstock can have a basis weight per, Industrial Papers, Insect Resistant, Insulating Board, between 35 lb and 330 lb, e.g. 45 lb and 330 lb, 60 and Ivory Board, Japan Paper, Jute Paper, Kraft Bag Paper, 330 lb, 80 and 330 lb, 60 and 200 lb, 60 and 100 lb;10 Kraft liner, Kraft Paper, Kraft , Kraft optionally a filler content greater than about 10 wt.%, e.g., Wrapping Paper, Label Paper, Lace Paper, , between 10 and 80 wt.%, between 20 and 80 wt.%, be- Laminated Paper, Laminated Linerboard, Latex Paper, tween 30 and 80 wt.%, between 30 and 70 wt.%, between Ledger Paper, Lightproof Paper, Liner, Linerboard, Lit- 230 and 60 wt.%; optionally a grammage between 50 mus Paper, On Machine Coated, , Ma- and 500 g/m2, e.g., 70 and 500 g/m2, 90 and 500 g/m2, 15 nila, Map Paper, Marble Paper, Matrix Paper, Matt Fin- 90 and 400 g/m2, 90 and 300 g/m2, 90 and 200 g/m2; ished Paper, Mechanical Paper, Mellow Paper, Metali- and optionally a calorific value between 7500 and 4000 zation Base Paper, Machine Finished Paper, Machine Btu/lb, e.g., 7000 and 4000 Btu/lb, 6500 and 4000 Btu/lb, glazed Paper, Millboard, Mulberry Paper, Natural Color- 5000 and 4000 Btu/lb, 6000 and 4500 Btu/lb; optionally ed Papers or Self Colored Papers, , Oatmeal an ash content between 8 and 50 wt.%, e.g., 10 and 80 20 Paper, Offset Paper, Packaging Paper, , Pat- wt.%, 10 and 60 wt.%, 10 and 50 wt.%, 20 and 50 wt.%. tern Paper, Permanent Paper, , [0129] Some suitable paper feedstock can include a Playing , Pleading Paper, Poly Extrusion Pa- homogeneous sheet formed by irregularly intertwining per, Postcard Board, Post-Consumer Waste Paper, cellulose fibers. These can include, for example, Abra- Poster Paper, Pre-Consumer Waste Paper, Pressure sive Papers, Absorbent Paper, Acid Free Paper, Acid 25 Sensitive Coated Paper, Publishing Paper, Board, Proof Paper, Account , Adhesive Paper, Air Release Paper, Roofing Paper, Safety Paper, Security Dried Paper, Air , Album Paper, Albumin Pa- paper, Self Adhesive Paper, Self Contained Paper, Sili- per, Alkaline Paper, Alligator Imitation Paper, Aluminum con Treated Paper, Single Faced Corrugated Board, Foil Laminated paper, Ammunition Paper, Announce- Sized Paper, Stamp Paper, Strawboard, Suede Paper, ment Card Paper, Anti Rust Paper, Anti-Tarnish Paper, 30 Supercalendered Paper, Surface-Sized, Super Art Pa- Antique Paper, Archival Paper, Art Paper, Asphalt Lam- per, Synthetic Fiber Paper, Tag Paper, Testliner, Text inated Paper, Azurelaid Paper, Back Liner Paper, Bacon Paper, , Translucent Paper, Paper, Paper, Bakers’ Wrap, Balloon Paper, Transparent Paper, Treated Paper, Union Kraft, Un- or Currency Paper, Barograph Paper, Barrier glazed Paper, Un-sized Paper, Vaporproof Paper, Var- Paper, Baryta Paper, Beedi Wrap Paper, , 35 nish-Label Paper, Vegetable Parchment, Vellum Paper, Black Waterproof Paper, Blade Wrapping Paper, Blood- Velour Paper, Velvet Finish Paper, Vulcanizing Paper, proof Paper or , , Blueprint Wadding, Wall Paper, Water-Color Paper, Water Fin- Paper, Board, Bogus Paper, , Book Paper, ished Paper, Water Resistant Paper, Waterleaf, Waxed Boxboard,Braille PrintingPaper, BreadWrapping Paper, Paper, Paper, White Top Liner, Willesden , Business Form Paper, Butter Wrapping 40 Paper, Wipes or Wiper, Wove, Wrapper, Writing Paper Paper, Burnt Paper, Cable Paper, Calf Paper, Calico Pa- and Xerographic Paper. per, Candy Twisting Tissue, Canvas Paper, Carbonless [0130] The feedstocks described herein can be used Paper, , Corrugated Cardboard, in combination with any of the biomass feedstocks de- board, Cartridge paper, Cast Coated Paper, Catalogue scribed in U.S. Application Serial No. 12/417,880, filed Paper, Chart Paper, Check Paper, Cheese Wrapping Pa- 45 April 3, 2009. per, Chipboard, Chromo, Coarse Paper (also Industrial Paper), Coated freesheet, Coated Paper, Coated White Saccharifying Agents Top Liner, Cockle Finish Paper, Color-fast papers, Com- modity Paper, Colored Kraft, Condenser Tissue, Con- [0131] Suitable enzymes include cellobiases and cel- struction Paper, , Copier Paper or Laser 50 lulases capable of degrading biomass. Paper, Correspondence Papers, Corrugated Board, Cor- [0132] Suitable cellobiases include a cellobiase from rugated Medium or Fluting Media or Media, Aspergillus niger sold under the tradename NOVOZYME or Rag Paper, Cover Paper or Cover Stock, Creamwove 188™. Paper, Cut Sheet, Damask Paper, Decalcomania Paper, [0133] Cellulases are capable of degrading biomass, Diazo Base Paper, Document Paper, Drawing Paper, 55 and may be of fungal or bacterial origin. Suitable en- Duplex Board, Duplex Paper, End-leaf Paper, Envelop zymes include cellulases from the genera Bacillus, Pseu- Paper, Esparto Paper, Extensible Kraft, Extrusion Coat- domonas, Humicola, Fusarium, Thielavia, Acremonium, ed Board, Fax Base Paper,Flame Resistant, Flocked Pa- Chrysosporium and Trichoderma, and include species

15 29 EP 2 675 907 B1 30 of Humicola, Coprinus, Thielavia, Fusarium, Mycelioph- charides or polysaccharides into fermentation products. thora, Acremonium, Cephalosporium, Scytalidium, Pen- Fermenting microorganisms include strains of the genus icillium or Aspergillus (see, e.g., EP 458162), especially Sacchromycesspp. e.g., Sacchromyces cerevisiae (bak- those produced by a strain selected from the species er’s yeast), Saccharomyces distaticus, Saccharomyces Humicola insolens (reclassified asScytalidium ther- 5 uvarum; the genus Kluyveromyces, e.g., species Kluy- mophilum, see, e.g., U.S. Patent No. 4,435,307), Copri- veromyces marxianus, Kluyveromyces fragilis; the ge- nus cinereus, Fusarium oxysporum, Myceliophthora nus Candida, e.g., Candida pseudotropicalis, and Can- thermophila, Meripilus giganteus, Thielavia terrestris, dida brassicae, Pichia stipitis (a relative of Candida she- Acremonium sp., Acremonium persicinum, Acremonium hatae, the genus Clavispora, e.g., species Clavispora acremonium, Acremonium brachypenium, Acremonium 10 lusitaniae and Clavispora opuntiae, the genus Pachyso- dichromosporum, Acremonium obclavatum, Acremoni- len, e.g., species Pachysolen tannophilus, the genus um pinkertoniae, Acremonium roseogriseum, Acremoni- Bretannomyces, e.g., species Bretannomyces clausenii um incoloratum, and Acremonium furatum; preferably (Philippidis, G. P., 1996, Cellulose bioconversion tech- from the species Humicola insolens DSM 1800, Fusari- nology, in Handbook on Bioethanol: Production and Uti- um oxysporum DSM 2672, Myceliophthora thermophila 15 lization, Wyman, C.E., ed., Taylor & Francis, Washing- CBS 117.65, Cephalosporium sp. RYM-202, Acremoni- ton, DC, 179-212). Other suitable microorganisms in- um sp. CBS 478.94, Acremonium sp. CBS 265.95, Acre- clude, for example, Zymomonas mobilis, Clostridium monium persicinum CBS 169.65, Acremonium acremo- thermocellum (Philippidis, 1996, supra), Clostridium sac- nium AHU 9519, Cephalosporium sp. CBS 535.71, Acre- charobutylacetonicum, Clostridium saccharobutylicum, monium brachypenium CBS 866.73, Acremonium di- 20 Clostridium Puniceum, Clostridium beijernckii, Clostrid- chromosporum CBS 683.73, Acremonium obclavatum ium acetobutylicum, Moniliella pollinis, Yarrowia lipolyti- CBS 311.74, Acremonium pinkertoniae CBS 157.70, ca, Aureobasidium sp., Trichosporonoides sp., Trigonop- Acremonium roseogriseum CBS 134.56, Acremonium sis variabilis, Trichosporon sp., Moniliellaacetoabutans, incoloratum CBS 146.62, and Acremonium furatum CBS Typhula variabilis, Candida magnoliae, Ustilaginomyc- 299.70H. Cellulolytic enzymes may also be obtained25 etes, Pseudozyma tsukubaensis, yeast species of gen- from Chrysosporium, preferably a strain of Chrysospori- era Zygosaccharomyces, Debaryomyces, Hansenula um lucknowense. Additionally, Trichoderma (particularly and Pichia, and fungi of the dematioid genus Torula. Trichoderma viride, Trichoderma reesei, and Trichoder- [0137] Commercially available yeasts include, for ex- ma koningii), alkalophilic Bacillus (see, for example, U.S. ample, Red Star®/Lesaffre Ethanol Red (available from Patent No. 3,844,890 and EP 458162), and Streptomy- 30 Red Star/Lesaffre, USA), FALI® (available from Fleis- ces (see, e.g., EP 458162) may be used. chmann’s Yeast, a division of Bums Philip Food Inc., [0134] Enzyme complexes may be utilized, such as USA), SUPERSTART® (available from Alltech, now La- those available from Genencor® under the tradename lemand), GERT STRAND® (available from Gert Strand ACCELLERASE®, for example, Accellerase® 1500 en- AB, Sweden) and FERMOL® (available from DSM Spe- zyme complex. Accellerase 1500 enzyme complex con- 35 cialties). tains multiple enzyme activities, mainly exoglucanase, endoglucanase (2200-2800 CMC U/g), hemi-cellulase, Nutrient Package Ingredients and beta-glucosidase (525-775 pNPG U/g), and has a pH of 4.6 to 5.0. The endoglucanase activity of the en- [0138] As discussed above, it may be preferred to in- zyme complex is expressed in carboxymethylcellulose 40 clude a nutrient package in the system during sacchari- activity units (CMC U), while the beta-glucosidase activity fication and/or fermentation. Preferred nutrient packages is reported in pNP-glucoside activity units (pNPG U). In contain a food-based nutrient source, a nitrogen source, one embodiment, a blend of Accellerase® 1500 enzyme and in some cases other ingredients, e.g., phosphates. complex and NOVOZYME™ 188 cellobiase is used. Suitable food-based nutrient sources include grains and 45 vegetables, including those discussed above and many Fermentation Agents others. The food-based nutrient source may include mix- tures of two or more grains and/or vegetables. Such nu- [0135] The microorganism(s) used in fermentation can trient sources and packages are disclosed in U.S. Appli- be natural microorganisms and/or engineered microor- cation Serial No. 13/184,138. ganisms. For example, the microorganism can be a bac- 50 terium, e.g., a cellulolytic bacterium, a fungus, e.g., a Enzymes for Releasing Nutrients yeast, a plant or a protist, e.g., an algae, a protozoa or a fungus-like protist, e.g., a slime mold. When the organ- [0139] When a food-based nutrient source is utilized, isms are compatible, mixtures of organisms can be uti- it is preferred that the saccharification and/or fermenta- lized. 55 tion mixture further include an enzyme system selected [0136] Suitable fermenting microorganisms have the to release nutrients, e.g., nitrogen, amino acids, and fats, ability to convert carbohydrates, such as glucose, fruc- from the food-based nutrient source. For example, the tose, xylose, arabinose, mannose, galactose, oligosac- enzyme system may include one or more enzymes se-

16 31 EP 2 675 907 B1 32 lected from the group consisting of amylases, proteases, 10. The method of any of the above claims further com- and mixtures thereof. Such systems are disclosed in U.S. prising processing the sugar. Application Serial No. 13/184,138. 11. The method of claim 10 wherein processing com- Fuel Cells 5 prises separating xylose and/or glucose from the sugar. [0140] Where the methods described herein produce a sugar solution or suspension, this solution or suspen- 12. The method of any of the above claims wherein sac- sion can subsequently be used in a fuel cell. charification is conducted at a pH of about 3.8 to 4.2. 10 OTHER EMBODIMENTS 13. The method of claim 9 wherein the physical treat- ment comprises mechanically treating the paper to [0141] While it is possible to perform all the processes reduce the bulk density of the paper and/or increase described herein at one physical location, in some em- the BET surface area of the paper. bodiments, the processes are completed at multiple15 sites, and/or may be performed during transport. 14. The method of claim 4 wherein the food-based nu- trient source is selected from the group consisting of wheat, oats, barley, soybeans, peas, legumes, po- Claims tatoes, corn, rice bran, corn meal, wheat bran, and 20 mixtures thereof. 1. A method of producing a sugar comprising providing a paper feedstock with a filler content of greater than 10 wt.% and an ash content of at least Patentansprüche 8 wt.%, and wherein the paper further comprises a printingink, combining the paperwith a saccharifying 25 1. Verfahren zum Herstellen eines Zuckers, umfas- agent which is an enzyme, in a tank, and using jet send Bereitstellen eines Papierrohstoffs mit einem mixing to mix the tank contents during saccharifica- Füllstoffanteil von mehr als 10 Gewichtsprozent und tion. einem Aschegehalt von mindestens 8 Gewichtspro- zent, und wobei das Papier ferner eine Druckfarbe 2. The method of claim 1 wherein the filler content is 30 umfasst, Mischen des Papiers mit einem Verzucke- at least 20wt.%. rungsmittel, welches ein Enzym ist, in einem Tank, und 3. The method of any of the above claims wherein the Verwenden von Strahlmischung, um die Tankinhalte paper is in the form of magazines. während der Verzuckerung zu vermischen. 35 4. The method of any of the above claims further com- 2. Verfahren nach Anspruch 1, wobei der Füllstoffanteil prising adding a food-based nutrient source to the mindestens 20 Gewichtsprozent beträgt. mixture. 3. Verfahren nach einem der vorhergehenden Ansprü- 5. The method of any of the above claims further com- 40 che, wobei das Papier in Form von Magazinen vor- prising adding a microorganism to the saccharified liegt. paper and producing a product or intermediate. 4. Verfahren nach einem der vorhergehenden Ansprü- 6. The method of claim 4 wherein the food-based nu- che, ferner umfassend Hinzufügen einer nahrungs- trient source is selected from the group consisting 45 mittelbasierten Nährstoffquelle zur Mischung. of grains, vegetables, residues of grains, residues of vegetables, and mixtures thereof. 5. Verfahren nach einem der vorhergehenden Ansprü- che, ferner umfassend Hinzufügen eines Mikroorga- 7. The method of claim 5 wherein the product compris- nismus zum verzuckerten Papier und Herstellen ei- es a fuel selected from the group consisting of hy- 50 nes Produkts oder Zwischenprodukts. drogen, alcohols, organic acids, hydrocarbons, and mixtures thereof. 6. Verfahren nach Anspruch 4, wobei die nahrungsmit- telbasierte Nährstoffquelle aus der Gruppe ausge- 8. The method of claim 5 wherein the microorganism wählt wird, die aus Getreide, Gemüse, Getreideres- comprises a yeast and/or a bacteria. 55 ten, Gemüseresten und Mischungen daraus be- steht. 9. The method of any of the above claims further com- prising physically treating the paper. 7. Verfahren nach Anspruch 5, wobei das Produkt ei-

17 33 EP 2 675 907 B1 34

nen Kraftstoff enthält, der aus der Gruppe ausge- 4. Procédé selon l’une quelconque des revendications wählt wird, die aus Wasserstoff, Alkoholen, organi- précédentes comprenant en outre l’ajout d’une sour- schen Säuren, Kohlenwasserstoffen und Mischun- ce de nutriments au mélange. gen daraus besteht. 5 5. Procédé selon l’une quelconque des revendications 8. Verfahren nach Anspruch 5, wobei der Mikroorga- précédentes comprenant en outre l’ajout d’un micro- nismus eine Hefe und/oder eine Bakterie umfasst. organisme au papier saccharifié et la fabrication d’un produit ou d’un intermédiaire. 9. Verfahren nach einem der vorhergehenden Ansprü- che, ferner umfassend die physikalische Behand- 10 6. Procédé selon la revendication 4, dans lequel la lung des Papiers. source de nutriments est choisie dans le groupe composé des céréales, des légumes, des résidus 10. Verfahren nach einem der vorhergehenden Ansprü- de céréales, des résidus de légumes et de leurs mé- che, ferner umfassend die Verarbeitung des Zu- langes. ckers. 15 7. Procédé selon la revendication 5 dans lequel le pro- 11. Verfahren nach Anspruch 10, wobei die Verarbei- duit comprend un combustible choisi dans le groupe tung die Abspaltung von Xylose und/oder Glucose composé de l’hydrogène, des alcools, des acides vom Zucker umfasst. organiques, des hydrocarbures et de leurs mélan- 20 ges. 12. Verfahren nach einem der vorhergehenden Ansprü- che, wobei die Verzuckerung bei einem pH-Wert von 8. Procédé selon la revendication 5 dans lequel le mi- ungefähr 3,8 bis 4,2 durchgeführt wird. cro-organisme comprend une levure et/ou une bac- térie. 13. Verfahren nach Anspruch 9, wobei die physikalische 25 Behandlung die mechanische Behandlung des Pa- 9. Procédé selon l’une quelconque des revendications piers umfasst, um die Rohdichte des Papiers zu re- précédentes comprenant en outre le traitement phy- duzieren und/oder die BET-Oberfläche des Papiers sique du papier. zu vergrößern. 30 10. Procédé selon l’une quelconque des revendications 14. Verfahren nach Anspruch 4, wobei die nahrungsmit- précédentes comprenant en outre le traitement du telbasierte Nährstoffquelle aus der Gruppe ausge- sucre. wählt wird, die aus Weizen, Hafer, Gerste, Sojaboh- nen, Erbsen, Leguminosen, Kartoffeln, Mais, Reis- 11. Procédé selon la revendication 10 dans lequel le trai- kleie, Maismehl, Weizenkleie und Mischungen dar- 35 tement comprend la séparation du xylose et/ou du aus besteht. glucose du sucre.

12. Procédé selon l’une quelconque des revendications Revendications précédentes dans lequel la saccharification est ef- 40 fectuée à un pH d’environ 3,8 à 4,2. 1. Procédé de production d’un sucre comprenant la fourniture d’une matière première de papier d’une 13. Procédé selon la revendication 9 dans lequel le trai- teneur en matières de remplissage supérieure à 10 tement physique comprend le traitement mécanique % en poids et d’une teneur en cendres d’au moins du papier pour réduire la densité en vrac du papier 8 % en poids, et dans lequel le papier comprend en 45 et/ou pour augmenter la surface BET du papier. outre une encre d’impression, l’associationdu papierà un agentde saccharification 14. Procédé selon la revendication 4 dans lequel la sour- qui est une enzyme, dans un réservoir, et cede nutriments estchoisie dans le groupe composé l’utilisation du malaxage à jet pour mélanger le con- du blé, de l’avoine, de l’orge, du soja, des pois, des tenu du réservoir pendant la saccharification. 50 légumes, des pommes de terre, du maïs, du son de riz, de la semoule de maïs, du son de blé et de leurs 2. Procédé selon la revendication 1 dans lequel la te- mélanges. neur en matières de remplissage est d’au moins 20 % en poids. 55 3. Procédé selon l’une quelconque des revendications précédentes dans lequel le papier se présente sous la forme de magazines.

18 EP 2 675 907 B1

19 EP 2 675 907 B1

20 EP 2 675 907 B1

21 EP 2 675 907 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

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Non-patent literature cited in the description

• KENNETH S. KRANE. Introductory Nuclear Physics. • IWATA, Y. et al. Alternating-Phase-Focused IH-DTL John Wiley & Sons, Inc, 1988 [0049] for Heavy-Ion Medical Accelerators. Proceedings of • KRSTO PRELEC. FIZIKA B, 1997, vol. 6 (4), 177-206 EPAC, 2006 [0049] [0049] • LEANER, C.M. et al. Status of the Superconducting • CHU, WILLIAM T. Overview of Light-Ion Beam Ther- ECR Ion Source Venus. Proceedings of EPAC, 2000 apy. Columbus-Ohio, ICRU-IAEA Meeting, 18 March [0049] 2006 [0049] • Cellulose bioconversion technology. PHILIPPIDIS, G. P. Handbook on Bioethanol: Production and Utili- zation. Taylor & Francis, 1996, 179-212 [0136]

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