BR122017001932A2 - METHOD OF CONVERTING AN INTERMEDIARY TO A PRODUCT, PRODUCT AND BIOMASS FEED STOCK PROCESSING SYSTEMS - Google Patents

Abstract

The present invention relates to biomass (e.g., plant biomass, animal biomass, microbial biomass and municipal waste) that is processed to produce useful products such as fuels. For example, systems may use feedstock materials, such as cellulosic and / or lignocellulosic materials and / or starch or sugar materials, to produce ethanol and / or butanol, for example by fermentation.

Description

(54) Title: METHOD OF CONVERSION OF AN INTERMEDIATE TO A PRODUCT, PRODUCT AND BIOMASS STOCK PROCESSING SYSTEMS (51) Int. Cl .: C12P 7/10; C12P 5/02; C12P 7/06; C12P 7/16 (30) Unionist Priority: 03/04/2009 US 12 / 417,880, 04/03/2009 US 12/417, 88018/06/2008 US 61 / 073,496, 04/03/2009 US 12/417, 88018/06/2008 US 61/073, 49630/04/2008 US 61 / 049,419, 04/03/2009 US 12 / 417,88018 / 06/2008 US 61/073, 49630/04/2008 US 61/049, 41930/04/2008 US 61 / 049,415, 04/03/2009 US 12/417, 88018/06/2008 US 61 / 073,49630 / 04/2008 US 61 / 049,41930 / 04/2008 US 61/049, 41530/04/2008 US 61 / 049,413, (...) (73) Holder (s): XYLECO, INC.

(72) Inventor (s): MARSHALL MEDOFF (74) Attorney (s): DANNEMANN, SIEMSEN, BIGLER & IPANEMA MOREIRA (86) International Application: PCT US2009041942 of 28/04/2009 (87) International Publication: WO

2009/140057 de 19/11/2009 (57) Abstract: The present invention relates to biomass (for example, plant biomass, animal biomass, microbial biomass and municipal waste) that is processed to produce useful products, such as fuels. For example, systems may use feed stock materials, such as cellulosic and / or lignocellulosic materials and / or starch or sugar materials, to produce ethanol and / or butanol, for example, by fermentation.

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Invention Patent Descriptive Report for METHOD OF CONVERSION OF AN INTERMEDIATE TO A PRODUCT, PRODUCT AND BIOMASS STOCK PROCESSING SYSTEMS.

[001] Divided from PI0913013-6, deposited on April 28, 2009. TECHNICAL FIELD [002] The present invention relates to the processing of biomass, such as methods and systems for processing biomass.

BACKGROUND [003] Various carbohydrates, such as cellulosic and lignocellulosic materials, for example, in fibrous form, are produced, processed and used in large quantities in a number of applications. Often, such materials are used once and then discarded as waste or are simply considered to be waste materials, for example, sewage, bagasse, sawdust and maceration liquor.

SUMMARY [004] Biomass can be processed to change its structure at one or more levels. The processed biomass can then be used, for example, as a source of materials and / or fuel.

[005] In general, the invention relates to methods of altering a molecular and / or supramolecular structure of a biomass feed stock. As will be discussed below, in some implementations, the methods include irradiation and dissipation of the biomass feed stock. In other implementations, the methods include irradiation of the feed stock, cooling of the feed stock and again irradiation of the feed stock.

[006] Materials containing carbohydrates (for example,

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2/204 biomass or materials derived from biomass, such as starch materials, cellulosic materials, lignocellulosic materials or biomass materials that are or include significant amounts of low molecular weight sugars (for example, monosaccharides, disaccharides or trisaccharides) processed to alter its structure and products can be made from structurally altered materials. For example, many of the methods described here can provide cellulosic and / or lignocellulosic materials that have a lower molecular weight and / or crystallinity with respect to a native material. Many of the methods provide materials that can be more readily used by a variety of microorganisms to produce useful products, such as hydrogen, alcohols (eg, ethanol or butanol), organic acids (eg, acetic acid), hydrocarbons, by-products (e.g., proteins) or mixtures of any of these. Many of the products obtained, such as ethanol or n-butanol, can be used as a fuel to supply cars, trucks, tractors, ships or trains, for example, as a fuel for an internal combustion engine or as a supply cell supply fuel. Many of the products obtained can also be used to supply aircraft, such as airplanes, for example, having jet engines or helicopters. In addition, the products described here can be used for the generation of electrical energy, for example, in a conventional steam generation plant or in a fuel cell plant. [007] In one aspect, the invention is characterized by methods that include dissipating a biomass feed stock that has been irradiated to ionize the biomass feed stock, so that the feed stock has a first level of radicals. which are detectable with an electron orbital resonance spectrometer, to a point where the radicals are in

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3/204 a second level lower than the first level.

[008] In another aspect, the invention is characterized by methods that include irradiation of a biomass feed stock to ionize the biomass feed stock, so that the feed stock has a first level of radicals which are detectable with an electron orbital resonance spectrometer and dissipation of the irradiated biomass feed stock to a point where the radicals are at a second level lower than the first level in the dissipated biomass feed stock.

[009] Some methods still include processing the irradiated and dissipated biomass feed stock to produce a product.

[0010] Some implementations include one or more of the following features.

[0011] Dissipation dissipation may include the radicals to a level that is no longer detectable with the electron orbital resonance spectrometer, e.g., less than about 10 ¹⁴ orbitals. Dissipation can include applying pressure to the biomass, for example, a pressure of more than about 1000 psig. Pressure can be applied along with the application of heat. Dissipation may include contact of the biomass with a gas capable of reacting with the radicals, for example, contact of the biomass with a fluid capable of penetrating the biomass and reaction with the radicals. Dissipation can also or, alternatively, include contact of the biomass with an antioxidant. In some cases, the biomass feed stock includes an antioxidant dispersed in it and dissipation includes contact of the antioxidant dispersed in the biomass feed stock with radicals.

[0012] In another aspect, the invention is characterized by a method including irradiation of biomass feed stock that

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4/204 has been prepared by reducing one or more dimensions of individual parts of the biomass feed stock, using an apparatus comprising an accelerator configured to accelerate particles, such as electrons or ions, in which the apparatus is capable of processing more 1,000 tonnes of biomass material per year, for example, more than 10,000, 25,000, 50,000, 100,000 or even more than 1,000,000 tonnes of biomass per year.

[0013] In another aspect, the invention is characterized by irradiation of a biomass feed stock, for example, with electron or ion ionizing radiation, to alter a molecular and / or supramolecular structure of the biomass feed stock, cooling of the biomass feed stock and then re-radiation of the biomass feed stock. The two radiation applications can be the same or different, for example, of the same type, such as electrons, at the same level.

[0014] The invention is also characterized by products formed using these methods and systems for carrying out the methods. [0015] Some implementations of these methods include one or more of the following characteristics.

[0016] The biomass feed stock can be cooled to a point where, after cooling, the biomass is at a temperature below its initial temperature before irradiation. Cooling of biomass may include contact of the biomass with a fluid at a temperature below the initial temperature of the biomass or below the temperature of the biomass after irradiation.

[0017] Each irradiation of the biomass feed stock can be performed as the biomass feed stock is being pneumatically transported in a fluid. Radiation can be applied as the biomass falls under the influence of gravity. For example, biomass can be transported from one

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5/204 first belt at a first height and captured by a second belt to a second level, smaller than the first level, the leading edge of the first belt and the leading edge of the second belt defining a gap and ionizing radiation can be applied to the biomass feed stock in the defined span. During irradiation, the biomass can be transported by a particle gun and through a bundle of charged particles. The biomass feed stock can have a volumetric density of less than about 0.25 g / cm ³ in a region below and / or above the bundle.

[0018] In another aspect, the invention is characterized by methods of altering a molecular and / or supramolecular structure of a low-molecular-weight starch or sugar material, such as sucrose, in a biomass feed stock comprising at least least about 10 weight percent of low molecular weight sugar. The methods include processing the treated biomass feed stock to produce a product, the treated biomass feed stock having been prepared by pretreating a biomass feed stock using a pretreatment method that alters the structure molecular and / or supramolecular structure of the starch material of the low molecular weight sugar portion selected from radiation, ultrasound, pyrolysis and oxidation. [0019] In another aspect, the invention is characterized by methods of treating a biomass feed stock including a starch material to alter the molecular and / or supramolecular structure of the starch material with at least one method selected from the group consisting of radiation, ultrasound, pyrolysis and oxidation.

[0020] Any aspect of the invention may, in some implementations, include one or more of the following characteristics. [0021] The method may also include treatment of the biomass feed stock with one or more other pre-petition methods 870170006381, of 01/30/2017, p. 11/258

6/204 treatment, in which the other pre-treatment methods are selected from ultrasound, pyrolysis and oxidation.

[0022] Radiation can be in the form of an electron beam, which can be applied, for example, in a total dosage of between about 10 Mrad and about 50 Mrad. The radiation can be ionizing radiation.

[0023] Processing may include making a fuel. In some cases, processing includes conversion of the irradiated material using a microorganism having the ability to convert at least about 1 weight percent of the biomass into fuel.

[0024] In some implementations, processing comprises fermentation of the feed stock, aerobically or anaerobically, to produce a product, such as a fuel, for example, ethanol. For example, processing may comprise contact of the feed stock with a microorganism having the ability to convert at least a portion, for example, at least about 1 weight percent, from the feed stock to the product. The microorganism can be a natural microorganism or a manipulated microorganism. For example, the microorganism can be a bacterium, for example, a cellulolytic bacterium, a fungus, for example, a yeast, a plant or a protist, for example, an algae, a protozoan, or a fungus-like protist, for example example, a mud mold. When the organisms are compatible, mixtures can be used.

[0025] The product may include one or more of hydrogen, organic acids, hydrocarbons and alcohols, for example, ethanol, n-propanol, isopropanol, n-butanol and mixtures thereof. Other examples of products that can be produced using the methods described here include C1-C6 mono- and polyfunctional alkyl alcohols, acids

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7/204 mono- and poly-functional carboxylics, C1-C6 hydrocarbons and combinations thereof. Other examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, 1,4-butane diol, glycerin and combinations thereof. Carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, palmitic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, oleic acid, linoleic acid, glycolic acid, lactic acid , ghydroxybutyric acid and combinations thereof. Hydrocarbons include methane, ethane, propane, pentane, n-hexane and combinations thereof. Many of these products can be used as fuels. [0026] The method may also include preparing the biomass feed stock by reducing one or more dimensions of individual parts of the biomass feed stock.

[0027] In some cases, the biomass feed stock has internal fibers and the biomass feed stock has been sheared to a point where its internal fibers are substantially exposed. The biomass feed stock may, in some cases, include or be composed of different fibers and / or particles having a maximum dimension of no more than about 0.5 mm.

[0028] The biomass feed stock can be prepared and then pre-treated and then prepared. The pretreatment method can be selected, for example, from radiation, such as radiation from an electron or ion beam, ultrasound, pyrolysis and oxidation. In some modalities, at least one of the pretreatment methods, for example, radiation, is carried out on the biomass feed stock while the biomass feed stock is exposed to air, nitrogen, oxygen, helium or argon. In some embodiments, pre-treatment may include pre-treatment of the biomass feed stock with steam explosion.

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8/204 [0029] In some embodiments, biomass is prepared by reducing one or more dimensions of individual parts of the biomass, including shear, wet or dry grinding, cutting, compression or mixing of any of these processes. For example, shear can be performed with a rotary knife cutter. Shear can produce fibers having an average length-to-diameter ratio of more than 5/1. In some embodiments, the prepared biomass may have a BET surface area of more than 0.25 m ² / g. The biomass can be sheared to a point where the internal fibers of the biomass are substantially exposed. The biomass can be sheared to a point where it has a volumetric density of less than about 0.35 g / cm ³ . [0030] In some modalities, two or more pretreatment methods can be applied to the biomass feed stock, for example, radiation and ultrasound, radiation and oxidation, radiation and pyrolysis, ultrasound and oxidation, ultrasound and pyrolysis or oxidation and pyrolysis. The two or more processes can be performed in any order or at or around the same time.

[0031] In some embodiments, the change in the molecular structure and / or change in the supramolecular structure of biomass, for example, cellulosic or lignocellulosic material or low molecular weight sugar or starch material, may include a change in any one or more of an average molecular weight, average crystallinity, surface area, degree of polymerization, porosity, branching, grafting, size or domain number, a change in the type or number of functional chemical groups and a change in the weight of the formula. For example, the change in molecular structure and / or supramolecular structure may include a decrease in one or both of an average molecular weight and average crystallinity or an increase in one or both of the surface area and porosity.

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9/204 [0032] In some cases, functionalized biomass (biomass in which the number and / or type of functional groups has been changed) is more soluble and more readily used by microorganisms compared to non-functionalized biomass. In addition, many of the functionalized materials described here are less prone to oxidation and may have enhanced long-term stability under ambient conditions.

[0033] In some embodiments, at least one pretreatment method can be performed on a biomass in which less than about 25 weight percent of the biomass is in a swollen state, the swollen state being characterized as having a volume of more than about 2.5 percent larger than a non-swollen state. In other embodiments, the biomass is mixed with or includes a swelling agent. For example, in any method described here, the biomass can be mixed with and / or include a swelling agent and the biomass can receive a dose of less than about 10 Mrad of radiation.

[0034] The pre-treated biomass material may optionally also include a buffer, such as sodium bicarbonate or ammonium chloride, an electrolyte, such as potassium chloride or sodium chloride, a growth factor, such as biotin and / or a base pair, such as uracil, a surfactant, a mineral or a chelating agent. [0035] In some modalities, pre-treatment is carried out on the biomass feed stock while the biomass feed stock is exposed to air, nitrogen, oxygen, helium or argon. Pre-treatment can be carried out under pressure, for example, under a pressure of more than about 2.5 atmospheres. The methods described here can also include oxidation of the biomass before pretreatment.

[0036] The biomass feed stock may include, for example,

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10/204 example, paper, paper products, waste paper, wood, wood-related materials, particleboard, grasses, rice husks, bagasse, cotton, jute, hemp, linen, bamboo, sisal, abaca, straw, corn cobs, corn husks, rice husks, coconut fur, cotton, kelp, cotton, synthetic cellulose or mixtures of any of these. Biomass can, in some cases, include a synthetic material.

[0037] Biomass can, in some cases, include a carbohydrate that includes one or more b-1,4-bonds and has an average numerical molecular weight between about 3,000 and 50,000.

[0038] In some implementations, the biomass material includes a starch, for example, corn starch, wheat starch, potato starch or rice starch, a starch derivative or a material that includes starch, such as a food product edible or a vintage. For example, the starch material can be squid, wild wheat, banana, barley, cassava, kudzu, hollow, sago, sorghum, regular domestic potatoes, sweet potatoes, taro, yams or one or more types of beans, such as fava beans , lentils or peas.

[0039] In other implementations, the biomass material is or includes a low molecular weight sugar. For example, biomass materials can include at least about 0.5 weight percent of a low molecular weight sugar, for example, at least about 2, 3, 4, 5, 6, 7, 8, 9 , 10, 12.5, 25, 35, 50, 60, 70, 80, 90 or even at least about 95 weight percent of low molecular weight sugar. In some cases, biomass is composed substantially of low molecular weight sugar, for example, more than about 95 weight percent, such as 96, 97, 98, 99 or substantially 100 weight percent of low weight sugar molecular. Biomass materials that include low molecular weight sugars can be agricultural products or food products, such as caPetição 870170006381, from 01/30/2017, p. 16/258

11/204 in sugar and sugar beet or an extract thereof, for example, juice from each sugar or sugar beet. Specific examples of low molecular weight sugars include cellobiosis, lactose, sucrose, glucose and xylose, along with derivatives thereof. Processing of low molecular weight sugars using any of the methods described here can make the resulting products more soluble and / or easier for microbes to use.

[0040] In one aspect, a method of converting an intermediate to a product includes treating an intermediate product irradiated with a microorganism, the intermediate having been prepared by irradiating a starch material and treating the starch material with an enzyme.

[0041] In another aspect, a method of converting an intermediate to a product includes preparing an intermediate by irradiating a starch material and treating the starch material with an enzyme and treating the intermediate product irradiated with a microorganism.

[0042] Another aspect includes a product produced by any of the above methods.

[0043] In one aspect, a biomass feed stock processing system includes an irradiation device configured to ionize a biomass feed stock, so that the feed stock has a first level of detectable radicals with a biomass spectrometer. electron orbital resonance; and a dissipation device configured to dissipate the ionized biomass feed stock to a point where the radicals are at a lower second level than the first level. [0044] In another aspect, a biomass feed stock processing system includes one or more irradiation devices configured to irradiate a biPetition feed stock 870170006381, from 01/30/2017, p. 17/258

12/204 omass with at least two distinct doses of radiation; and a cooling device configured to cool the biomass feed stock between radiation doses.

[0045] In some implementations, a system also includes a biomass feed stock positioned to be ionized by the irradiation device (s).

[0046] In any of the methods or systems described here, radiation can be applied from a device that is in a dome.

[0047] The term fibrous material, as used here, is a material that includes numerous loose, distinct and separable fibers. For example, a fibrous material can be prepared from a source of Kraft paper fiber bleached by shearing, for example, with a rotary knife cutter.

[0048] The term sieve, as used here, means an element capable of sieving a material according to size. Examples of sieves include a perforated plate, cylinder or the like or a wire mesh or fabric.

[0049] The term pyrolysis, as used here, means to break bonds in a material through the application of thermal energy. Pyrolysis can occur while the material in question is under vacuum or immersed in a gaseous material, such as an oxidation gas, for example, air or oxygen or a reducing gas, such as hydrogen. [0050] The oxygen content is measured by means of elemental analysis taking a sample to pyrolysis in an oven operating at 1,300 ° C or above.

[0051] The term biomass refers to any non-fossilized organic matter, that is, renewable. The various types of biomass include plant biomass (defined below), microbial biomass, animal biomass (any animal by-product, animal waste, etc.) and biomass

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13/204 municipal waste (light commercial and residential refuse with recyclable products, such as metal and glass, removed).

[0052] The term plant biomass and lignocellulosic biomass refer to virtually any organic matter derived from plants (wood or non-wood). Plant biomass can include, but is not limited to, agricultural or food crops (for example, sugar cane, sugar beets or corn kernels), agricultural crop residues and remnants such as hay, wheat straw, bagasse sugar cane and the like. Plant biomass still includes, but is not limited to, trees, energy wood crops, wood waste and debris, such as softwood forest shavings, bark waste, sawdust, paper and pulp industry waste streams , wood fiber and the like. Additionally, grass crops, such as switchgrass and the like, have the potential to be produced on a large scale as another source of plant biomass. For urban areas, the best potential plant biomass feed stock includes garden waste (for example, grass clippings, leaves, tree branches and shrubs) and plant processing waste.

[0053] Lignocellulosic stock is any type of plant biomass such as, but not limited to, non-wood plant biomass, plant biomass, crops grown such as, but not limited to, grasses, for example, but not limited to , C4 grasses, such as switchgrass, silver grass, rye, miscantum, red phallus grass or a combination thereof or sugar processing residues, such as bagasse or beet pulp, agricultural residues, for example, soy straw, corn straw , rice straw, rice husks, barley straw, corn cobs, wheat straw, canola straw, rice straw, oat straw, oat husks, corn fiber, recycled paper pulp fiber, powder sawdust, a line

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14/204 hardwood, for example, poplar wood and sawdust, softwood and a combination thereof. In addition, the lignocellulosic feed stock may include cellulosic waste material such as, but not limited to, newspaper, cardboard, sawdust and similar materials. [0054] Lignocellulosic feed stock may include a kind of fiber or, alternatively, the lignocellulosic feed stock may include a mixture of fibers that originate from different lignocellulosic feed stocks. In addition, the lignocellulosic feed stock may comprise fresh lignocellulosic feed stock, partially dry lignocellulosic feed stock, fully dry lignocellulosic feed stock or a combination thereof.

[0055] For the purposes of the present description, carbohydrates are materials that are composed entirely of one or more saccharide units or that include one or more saccharide units. Saccharide units can be functionalized around the ring with one or more functional groups, such as carboxylic acid groups, amino groups, nitro groups, nitrous groups or nitrile groups and still be considered carbohydrates. Carbohydrates can be polymeric (for example, equal to or more than 10-mer, 100-mer, 1,000-mer, 10,000-mer or 100,000-mer), oligomeric (for example, equal to or greater than 4mer, 5- mer, 6-mer, 7-mer, 8-mer, 9-mer or 10-mer), quarterly, dimeric or monomeric. When carbohydrates are formed from more than a single repetition unit, each repetition unit can be the same or different.

[0056] Examples of polymeric carbohydrates include cellulose, xylan, pectin and starch, while cellobiose and lactose are examples of dimeric carbohydrates. Examples of monomeric carbohydrates include glucose and xylose.

[0057] Carbohydrates may be part of a supramole structurePetition 870170006381, from 01/30/2017, p. 20/258

15/204 cell, for example, covalently attached to the structure. Examples of such materials include lignocellulosic materials, such as those found in wood.

[0058] A starch material is one that is or includes significant amounts of starch or a starch derivative, such as more than about 5 weight percent of starch or starch derivative. For the purposes of the present description, a starch is a material that includes an amylose, an amylopectin or a physical and / or chemical mixture thereof, for example, a 22:80 or 30:70 weight percent mixture of amylose to amylopectin . For example, rice, corn and mixtures thereof are starch materials. Starch derivatives include, for example, maltodextrin, acid modified starch, base modified starch, bleached starch, oxidized starch, acetylated starch, acetylated and oxidized starch, phosphate modified starch, genetically modified starch and starch that is resistant to digestion.

[0059] For the purposes of the present description, a low molecular weight sugar is a carbohydrate or a derivative thereof that has a formula weight (excluding moisture) that is less than about 2,000, for example, less than about 1,800 , 1,600, less than about 1,000, less than about 500, less than about 350 or less than about 250. For example, low molecular weight sugar can be a monosaccharide, for example, glucose or xylose, a disaccharide, for example, cellobiosis or sucrose or a trisaccharide.

[0060] A combustible compound is a material capable of burning in the presence of oxygen. Examples of combustible materials include ethanol, n-propanol, n-butanol, hydrogen and mixtures of any two or more of these.

[0061] Swelling agents, as used here, are materials that cause discernible swelling, for example, a 2.5 percent increase in volume over a non

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16/204 swollen with cellulosic and / or lignocellulosic materials when applied to such materials as a solution, for example, an aqueous solution. Examples include alkaline substances, such as sodium hydroxides, potassium hydroxide, lithium hydroxide and ammonium hydroxides, acidifying agents, such as mineral acids (for example, sulfuric acid, hydrochloric acid and phosphoric acid), salts, such as chloride zinc, calcium carbonate, sodium carbonate, benzyltrimethyl ammonium sulfate and basic organic amines, such as ethylene diamine.

[0062] A shear material, as used here, is a material that includes distinct fibers in which at least about 50% of the distinct fibers have a length / diameter (L / D) ratio of at least about 5 and which have an uncompressed volumetric density of less than about 0.6 g / cm ³ . A sheared material is thus different from a material that has been cut, chopped or crushed. [0063] Changing a molecular structure of a biomass feed stock, as used here, means changing the chemical bonding configuration, such as the type and quantity of functional groups or structure conformation. For example, the change in molecular structure can include change in the supramolecular structure of the material, oxidation of the material, change in an average molecular weight, change in an average crystallinity, change in a surface area, change in a degree of polymerization, change in a porosity, alteration of a degree of branching, grafting on other materials, alteration of a crystalline domain size or alteration of an overall domain size.

[0064] This application incorporates, by reference here, all the contents of International Application No. PCT / US2007 / 022719, filed on October 26, 2007. The full descriptions of each of the following US Patent Applications are incorporated herein by reference 870170006381, of 01/30/2017, p. 22/258

17/204 reference: U.S. Provisional Orders Nos. Series 61 / 049.391; 61 / 049,394; 61 / 049,395; 61 / 049,404; 61 / 049,405; 61 / 049,406;

61 / 049,407; 61 / 049,413; 61 / 049,415; and 61 / 049,419, all deposited on April 30, 2008; U.S. Provisional Orders Nos. Series 61 / 073,432; 61 / 073,436; 61 / 073,496; 61 / 073,530; 61 / 073,665; and 61 / 073,674, all deposited on June 18, 2008; U.S. Provisional Application Serial No. 61 / 106,861, filed October 20, 2008; U.S. Provisional Orders Nos. Series 61 / 139,324 and 61 / 139,453, both filed on December 19, 2008 and U.S. Patent Application Nos. Ser. 12 / 417,707; 12 / 417,720; 12 / 417,840; 12 / 417,699; 12 / 417,731; 12 / 417,900; 12 / 417,880; 12 / 417,723;

12 / 417,786; and 12 / 417,904, all deposited on April 3, 2009. [0065] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those versed in the field to which the present invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, Appendices, patent applications, patents and other references mentioned here or attached to it, are incorporated by reference in full by everything they contain. In case of conflict, this specification, including definitions, will prevail. In addition, the materials, methods and examples are illustrative only and are not intended to be limiting.

[0066] Other features and advantages of the invention will be evident from the detailed description below and from the claims. DESCRIPTION OF THE DRAWINGS [0067] Figure 1 is a block diagram illustrating the conversion of biomass into products and co-products.

[0068] Figure 2 is a block diagram illustrating the conversion

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18/204 of a fiber source in first and second fibrous materials. [0069] Figure 3 is a cross-sectional view of a rotary knife cutter.

[0070] Figure 4 is a block diagram illustrating the conversion of a fiber source into a first, second and third fibrous material.

[0071] Figure 5 is a block diagram illustrating the densification of a material.

[0072] Figure 6 is a perspective view of a pellet mill.

[0073] Figure 7A is a fibrous material densified in the form of a pellet.

[0074] Figure 7B is a cross section of a hollow pellet in which the center of the hollow is in line with a center of the pellet.

[0075] Figure 7C is a cross section of a hollow pellet in which a center of the hollow is out of line with the center of the pellet.

[0076] Figure 7D is a cross section of a tri-lobal pellet. [0077] Figure 8 is a block diagram illustrating a treatment sequence for processing food stock. [0078] Figure 9 is a sectional perspective view of a gamma irradiator housed in a concrete vault.

[0079] Figure 10 is an enlarged perspective view of the region R of figure 9.

[0080] Figure 11 is a block diagram illustrating a sequence of pre-treatment of feed stock through electron beam irradiation.

[0081] Figure 11A is a schematic representation of a biomass that is being ionized and then oxidized or dissipated.

[0082] Figure 11B is a schematic side view of a system for irradiation of a material with low volumetric density, enPetição 870170006381, of 01/30/2017, p. 24/258

19/204 while figure 11C is a cross-sectional view of the system taken along 11C-11C.

[0083] Figure 11D is a schematic cross-sectional view of a fluidized bed system for irradiation of a low volumetric density material.

[0084] Figure 11E is a schematic side view of another system for irradiating a material with low volumetric density. [0085] Figure 12 is a schematic view of a system for ultrasound of a process stream of cellulosic material in a liquid medium.

[0086] Figure 13 is a schematic view of an ultrasound device having two transducers coupled to a single antenna in the shape of a horn.

[0087] Figure 14 is a block diagram illustrating a pyrolytic feed pre-treatment system.

[0088] Figure 15 is a cross-sectional side view of a chamber.

[0089] Figure 16 is a cross-sectional side view of a chamber.

[0090] Figure 17 is a cross-sectional side view of a pyrolysis apparatus chamber that includes a heated filament. [0091] Figure 18 is a schematic cross-sectional side view of a Curie-Point pyrolysis apparatus.

[0092] Figure 19 is a schematic cross-sectional side view of a pyrolysis apparatus with an oven.

[0093] Figure 20 is a schematic cross-sectional top view of a laser pyrolysis apparatus.

[0094] Figure 21 is a schematic cross-sectional upper side view of a tungsten filament flame pyrolysis apparatus.

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20/204 [0095] Figure 22 is a block diagram illustrating an oxidative feed stock pre-treatment system.

[0096] Figure 23 is a block diagram illustrating an overview of the process of converting a fiber source to a product, for example, ethanol.

[0097] Figure 24 is a cross sectional view of a steam explosion device.

[0098] Figure 25 is a schematic cross-sectional side view of a hybrid electron beam / ultrasound device.

[0099] Figure 26 is a block diagram illustrating a dry milling process for corn kernels.

[00100] Figure 27 is a block diagram illustrating a wet milling process for corn kernels.

[00101] Figure 28 is a scanning electron micrograph of a fibrous material produced from poly-coated paper at a magnification of 25 X. The fibrous material was produced on a rotary knife cutter using a sieve with 1 / 8 inches. [00102] Figure 29 is an electronically scanning micrograph of a fibrous material produced from bleached Kraft cardboard at a magnification of 25 X. The fibrous material was produced on a rotary knife cutter using a sieve with 1/8 openings inches.

[00103] Figure 30 is an electronically scanned micrograph of a fibrous material produced from bleached Kraft cardboard at a magnification of 25 X. The fibrous material was sheared twice over a rotary knife cutter using a sieve with openings of 1 / 16 inches during each shear.

[00104] Figure 31 is an electronically scanned micrograph of a fibrous material produced from bleached Kraft cardboard at a magnification of 25 X. The fibrous material was sheared three times on sPetition 870170006381, from 01/30/2017, p. 26/258

21/204 about a rotary knife cutter. During the first shear, a 1/8 inch sieve was used; during the second shear, a 1/16 inch sieve was used and, during the third shear, a 1/32 inch sieve was used.

[00105] Figure 32 is a schematic side view of an ultrasound device, while figure 33 is a cross-sectional view through the processing cell of figure 32.

[00106] Figure 34 is a scanning electron micrograph at 1000 X magnification of a fibrous material produced from shearing switchgrass over a rotary knife cutter and then passing the sheared material through a 1 / 32 inches.

[00107] Figures 35 and 36 are electronically scanned micrographs of the fibrous material in Figure 34 after gamma irradiation at 10 Mrad and 1000 Mrad, respectively, at a magnification of 1000 X. [00108] Figure 37 is a micrograph of electronic scan of the fibrous material of figure 34 after irradiation with 10 Mrad and ultrasound at a magnification of 1000 X.

[00109] Figure 38 is a scanning electron micrograph of the fibrous material of Figure 34 after irradiation with 100 Mrad and ultrasound at a magnification of 1000 X.

[00110] Figure 39 is an infrared spectrum of Kraft cardboard sheared over a rotary knife cutter.

[00111] Figure 40 is an infrared spectrum of the Kraft paper of figure 39 after irradiation with 100 Mrad of gamma radiation.

[00112] Figure 41 is a schematic view of a process for converting biomass.

[00113] Figure 42 is a schematic view of another process for converting biomass.

DETAILED DESCRIPTION

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22/204 [00114] Systems and processes are described here which can use various biomass materials, such as cellulosic materials, lignocellulosic materials, starch materials or materials that are or include low molecular weight sugars, such as stock materials from food. Such materials are often available, but they can be difficult to process, for example, through fermentation or they can provide sub-optimal yields at a slow rate. In some cases, the difficulty in processing stems, at least in part, from the recalcitrance of the feed stock. Processing steps are described which can reduce this recalcitrance and thus facilitate the conversion of the feed stock in biomass to a desired product.

[00115] In the processes described here, feed stock materials are first physically prepared for processing, often by reducing the size of raw feed stock materials. Physically prepared feed stock can then be pre-treated or processed using one or more of radiation (which can, in some cases, be under controlled thermal conditions), ultrasound, oxidation, pyrolysis and vapor explosion. The various pre-treatment systems and methods can be used in combinations of two, three or even four of these technologies. Other techniques which can be used to intensify the processing of the feed stock are described here, for example, cooling of the feed stock between irradiation steps and dissipation of the biomass feed stock after irradiation. [00116] Functionalized materials are also described here, having desired types and amounts of functionality, such as carboxylic acid groups, enol groups, aldehyde groups, ketone groups, nitrile groups, nitro groups or nitrous groups, which can be prepared using the methods described here. Such functionalized materials poPetição 870170006381, of 01/30/2017, p. 28/258

23/204 may, for example, be more soluble, easier to use by various microorganisms or may be more stable in the long run, for example, less prone to oxidation.

[00117] In some cases, the feed stock may include low molecular weight sugars or starch materials, as will be discussed in detail here.

TYPE OF BIOMASS [00118] In general, any biomass material that is or includes carbohydrates composed entirely of one or more saccharide units or that includes one or more saccharide units can be processed using any of the methods described here. For example, the biomass material can be cellulosic or lignocellulosic materials, starch materials, such as corn kernels, rice grains or other foods or materials that are or include one or more low molecular weight sugars, such as sucrose or cellobiosis .

[00119] For example, such materials may include paper, paper products, waste paper, wood, wood-related materials, particleboard, grasses, rice husks, bagasse, cotton, jute, hemp, linen, bamboo, sisal , abaca, straw, corn cobs, corn straw, rice husks, coconut hair, cotton, seaweed, cotton, synthetic cellulose or mixtures of any of these. Suitable materials include those listed in the Summary section above.

[00120] Fiber sources include cellulosic fiber sources, including paper and paper products (for example, poly-coated paper and Kraft paper) and lignocellulosic fiber sources, including wood and wood-related materials, for example, particleboard . Other suitable sources of fiber include sources of natural fiber, for example, grasses, rice husks, bagasse, cotton, jute, hemp, flax,

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24/204 bamboo, sisal, abaca, straw, corn cobs, rice husks, coconut hair; fiber sources with a high content of a-cellulose, for example, cotton; and synthetic fiber sources, for example, extruded yarn (oriented yarn or non-oriented yarn). Sources of natural or synthetic fiber can be obtained from cutouts of virgin textile materials, for example, remaining textile materials or they can be a post-consumer waste, for example, rags. When paper products are used as a fiber source, they can be virgin materials, for example, cutouts of virgin materials or they can be post-consumer waste. In addition to virgin raw materials, post-consumer, industrial (eg, refuse) and processing (eg, paper processing effluent) waste can also be used as fiber sources. Also, the fiber source can be obtained from or derived from the waste of a human (eg, sewage), animal or plant. Additional sources of fiber have been described in U.S. Patent Nos. 6,448,307, 6,258,876, 6,207,729, 5,973,035 and 5,952,105.

[00121] Microbial biomass includes biomass derived from naturally occurring or genetically modified single-celled organisms and / or multicellular organisms, for example, ocean organisms, lakes, bodies of water, for example, salt water or fresh water or on land and containing a carbohydrate source (for example, cellulose). Microbial biomass can include, but is not limited to, for example, protists (for example, animal (for example, protozoa, such as flagellates, ameboids, ciliate and sporozoans) and plant (for example, algae such as honeycombs, chloroachnophytes, cryptophytes , euglenoids, glaucophytes, haptophytes, red algae, stramenopils and viridaeplantae)), seaweed, plankton (e.g., macroplankton, mesoplankton, microplankton, nanoplankton, picoplankton, and phopltoplankton), bacteria, gram-positive bacteria, negative and extremophilic, yeast and / or mixed petition 870170006381, of 30/01/2017, page 30/258

25/204 ras of them. In some cases, microbial biomass can be obtained from culture systems, for example, wet and dry large-scale culture systems.

[00122] Animal biomass includes any organic waste material, such as animal-derived waste material or excrement or human-derived waste material or excrement (for example, manure and sewage).

[00123] In some embodiments, the carbohydrate is or includes a material having one or more b-1,4-bonds and having an average numerical molecular weight between about 3,000 and 50,000. Such carbohydrate is or includes cellulose (I), which is derived from (β-glucose 1) through condensation of β (1 ® 4) -glycosidic bonds. This bond contrasts, in itself, with that for (1 ® 4) -glycoside bonds present in starch and other carbohydrates.

STARCH MATERIALS [00124] Starch materials include starch itself, for example, corn starch, wheat starch, starch or rice starch, a starch derivative, or a material that includes starch, such as an edible food product or a harvest. The starch material can be squid, wild wheat, banana, barley, cassava, kudzu, hollow, sago, sorghum, regular domestic potatoes, sweet potatoes, taro, yams or one or more beans, such as broad beans, lentils or peas. A mixture of any two or more starch materials is also considered to be

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26/204 being a starch material. Starch sources include, for example, wheat, barley, corn and potatoes. In particular embodiments, the starch material is derived from corn. Various corn starches and derivatives are described in Corn Starch, Corn Refiners Association (11th Edition, 2006) which is herein attached as Appendix A.

[00125] A starch (eg CAS # 9005-25-8, has the chemical formula (C ₆ H ₁₀ O ₅ ) „) and generally comprises a mixture of amylose and amylopectin (usually in proportions of 20:80 or 30 : 70) and, in general, exists as a homopolymer of repeated anhydroglycoside units joined by a β-glycoside on the next starch unit via hemiacetal bonds. Starch molecules are typically composed of 1,4-bonds and are referred to as amylose, while 1,6-bonds serve as the branching point in branched starch molecules called amylopectin.

GRANULAR STRUCTURE

Table 1. Granule size of various starches

Starch Species Granule size range (pm) (Coulter Counter) Average size (pm) Waxy rice 2-13 5.5 Corn with high amylose content 4-22 9.8 Corn 5-25 14.3 Cassava 3-28 14 Sorghum 3-27 16 Wheat 3-34 6.5, 19.5 Sweet potato 4-40 18.5 Arrowroot 9-40 23 Sago 15-50 33 Potato 10-70 36 Sugarcane (Arrowroot Aust.) 22-85 53

[00126] Plants store starch inside specialized organelles called amyloplasts, where it is deposited to form

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27/204 granules. These granules are comprised of starch recently synthesized in layers around a hilum core and vary, in diameter, from 2 to 130 microns. The granule size and shape are characteristic of the plant's origin and serve as a way of identifying the source of a particular starch (Table 1). The structure of the grain is crystalline, with the starch molecules orienting themselves in such a way as to form radially oriented crystals that give rise to the phenomenon of bi-refringence. When a beam of polarized light is directed through a starch granule, the granule is divided by dark lines into four wedge-shaped sections. This cross hatch or cross is characteristic of spherocrystalline structures.

[00128] Amylose molecules consist of single, mostly unbranched chains with 500-20,000 units of sucrose-dependent α - (1,4) -D glucose. The α (1,4) bonds promote the formation of a helix structure. The structural formula of amylose is represented in Figure 2 where the number of repeated glucose subunits (n) can be many thousands (usually in the range of 300 to 3000). Amylose starch is less readily digested than amylopectin; however, it takes up less space, so it is preferred for plant storage. Amylose makes up about 30% of the starch stored in plants. The digestive enzyme amylase works on the ends of the starch molecule, breaking it down into sugar. Petition 870170006381, of 1/30/2017, p. 33/258

28/204 cards.

[00129] Amylose molecules contribute to the formation of gel because the linear chains can orient themselves parallel to each other, moving close enough together for connection. Probably because of the ease with which amylose molecules pass over each other in the cooked paste, they do not contribute significantly to the viscosity.

Amylopectin

H [00130] Figure 3. Representative partial structure of amylopectin [00131] Amylopectin is formed by a- (1,6) -non-random branching of the structure of a- (1,4) -D-glucose of the amylose type. As can be seen in Figure 3, glucose units are connected in a linear fashion with α (1,4) bonds. Branching occurs with α (1,6) bonds occurring every 24 to 30 units of glucose and is determined by branching enzymes. Each amylopectin molecule contains one million or more residues, about 5% of which form the branch points.

[00132] The branched amylopectin molecules give viscosity to the cooked paste, due to the role it serves in maintaining the swollen granule. Its side chains and dense shape keep amylopectin molecules oriented closely enough for hydrogen bonding, so they usually do not contribute to gel formation.

SOURCE [00133] Plants hydrolyze starch, releasing the subunits of

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29/204 glucose when energy is required. So far, the biggest source of starch is maize (green maize), with other commonly used sources being wheat, potatoes, tapioca and rice. The relative proportions of amylose to amylopectin and 1,6-link branch points are genetically established and are relatively constant for each starch species. For example, starch contains more than 50% amylase, while waxy corn has almost none (~ 3%). UNprocessed starch [00134] Starch that is produced through the wet corn crushing process and then dried, is referred to as regular, unmodified or regular corn starch. Several forms of corn starch exist, including fine or thick powders, flakes, fine flakes or even larger particles. Unmodified starch can be minimally processed by adjusting the pH, through mild heat treatment or by adding small amounts of chemicals or adjuvants before or after drying in order to optimize performance. As an example, enzymatic conversion of starch to sugars can be accelerated by adjusting the pH of the starch.

[00135] So far, the most consumed polysaccharide in the human diet is starch. Starch (in particular corn starch) is used in cooking to thicken foods, such as sauces. In industry, it is used in the manufacture of adhesives, paper, textiles and as a mold in the manufacture of sweets, such as grape gums and jelly candies. Papermaking is the largest non-food application for starches globally, consuming millions of metric tons annually. In a typical xerographic sheet of paper, for example, the starch content can be as high as 8%. Modified and unmodified starches are used in paper making.

[00136] The chemical composition of starch, highly oxygenated carbon molecules, makes starch an excellent product for use

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30/204 as a chemical feed stock.

GENETICALLY MODIFIED STARCH [00137] Genetically modified starch, which refers to starch from genetically engineered plants, has been modified to reduce the need for chemical processing (cost reduction, toxicity or environmentally hazardous processes) or in order to produce new carbohydrates which might not occur naturally in the species of plant being harvested. The modification, in this sense, refers to the genetic manipulation of the plant's DNA and not to the subsequent process or treatment of starch or starch granules.

[00138] Genetically modified starch is of particular interest in the manufacture of biodegradable polymers and non-cellulosic feed stock in the paper industry, as well as in the creation of new food additives. For example, waxy maize was studied extensively in the 1950s for its desirable properties. Waxy corn starch, which is essentially 100% amylopectin, provides pastes that are almost clear when cold, do not freeze and, when dried on thin films, provide a translucent water-soluble coating often used to thicken a wide variety of foods prepared. Genetic modification of this starch to try to increase the amylose content could potentially result in an excellent film former and could be twisted into a fiber. Research in this area has resulted in the commercial development of two corn hybrids, one containing about 55%, the other about 70% amylose, and recently, recent research has resulted in the development of a starch with 80% amylose.

MODIFIED STARCH [00139] Modified starch is a food additive which is prepared by treating starch or starch granules, making

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31/204 with the starch being partially degraded. The modified starch is used as a thickening agent, stabilizer or an emulsifier. In addition to food products, modified starch is also found in pharmaceutical products. Starches are modified for a number of reasons, including increasing their stability to heat, acid and excessive freezing; change its texture; or prolong or reduce the gelatinization time.

ACID-MODIFIED STARCH [00140] Acid-modified starch, usually referred to simply as modified starch, is prepared by treating starch or starch granules with inorganic acids. The primary reaction that occurs during treatment with acid is hydrolysis of glycosidic bonds in the starch molecules. Acid modification reduces the chain length of the starch, but does not substantially alter the molecular configuration. In this method, a suspension of starch-water is stirred while being subjected to mild treatment with mineral acid diluted at elevated temperatures, but below the gelatinization temperature of the starch. When the desired viscosity is obtained, the acid is neutralized with sodium carbonate and the starch is filtered, washed and dried.

OXIDIZED CORN STARCH [00141] Another method for reducing viscosity is oxidation. Although oxidizing agents, such as chlorine, hydrogen peroxide and potassium permanganate, can be used, oxidized starches produced through the wet milling process are almost always made using sodium hypochlorite as the oxidizing agent. Aqueous stirred starch suspensions are treated with diluted sodium hypochlorite containing a small excess of sodium hydroxide (NaOH) and heated to 120 ° F. When the desired viscosity is obtained, the oxidized starch paste is treated with a reducing agent 870170006381, from 01/30/2017, p. 37/258

32/204 tion, such as sodium bisulfite, to remove excess hypochlorite, the pH is adjusted and the starch is filtered, washed and finally dried. Treatment of the starch with an oxidizing agent randomly converts the hydroxyl groups to carboxyl or carbonyl groups, which results in the cleavage of the adjacent glycosidic bond. Oxidized starches are used in pasta and bread, as they adhere very well to meats.

DEXTRINS [00142] Dextrins are a group of low molecular weight carbohydrates produced by dry heating or roasting unmodified starch, with or without an acid or alkaline catalyst. Other dextrinization methods use a fluid bed, in which unmodified starch is placed in a reactor and suspended or fluidized in a heated air stream. The starch is then acidified and heated until the desired final product is obtained. During dextrinization, the granule is not destroyed, but the granule's integrity is disrupted. When dextrins are suspended in water and heated, the granules swell and separate into layers that eventually break and disperse. Dextrins are mixtures of D- Glucose polymers a- (1,4) -linear bonds starting with an α- (1,6) bond. Industrial production, in general, is carried out by acid hydrolysis of potato starch. Dextrins are white to slightly yellow water-soluble solids that are optically active. Under analysis, dextrins can be detected with iodine solution, providing a red tint.

[00143] There are three main types of dextrins: white, yellow and British gum. Although dextrins are white in color and have low viscosities and cold water solubilities ranging from 5 to more than 90%, white dextrins are used to make very soft gels. Yellow dextrins (produced with less acid, higher temPetition 870170006381, from 01/30/2017, page 38/258

33/204 periods and longer) are yellow in color and have greater solubility in water. Yellow dextrins are used to make pastes with high levels of solids that are very viscous and, when applied to thin films, dry quickly. Finally, British gums are produced by adding little or no acid to the very dry starch and then toasting while gradually increasing the temperature. They are brown to light brown in color and are used to prepare almost solid gels to very soft gels and viscous liquids.

CYCLODEXTRINS [00144] Cyclodextrins are non-reducing cyclic glucose oligosaccharides resulting from starch degradation catalyzed by cyclomaltodextrin glucanotransferase. There are three common cyclodextrins with 6, 7 or 8 residues of D-glucopyranonsyl (α-, β- and γcyclodextrin, respectively) linked through α-1,4 glycosidic bonds (Figure 4). All three cyclodextrins have similar structures (lengths and connection orientations), in addition to the structural needs to accommodate a different number of glucose residues. They have a bottomless basin-shaped molecule (truncated cone) deflected by a hydrogen bond between the 3-OH and 2-OH groups around the outer edge. Cyclodextrins are used for encapsulation for controlled aroma release, disguise of odors and flavors, stabilization of emulsions, increased foaming power and color control or disguise.

STARCH DERIVATIVES (crosslinking and stabilization) [00145] Starch can be chemically derivatized in the primary and secondary hydroxyl positions, which gives different properties than those found in parental starch. This is presumably due to the breakdown of hydrogen bonds. Two types of derivatives are commercially prepared, cross-linked / inhibited and stabilized.

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34/204

Cross-linked starches, sometimes referred to as inhibited starches, are made by reacting hydroxyl groups on two different molecules within a granule, with a bifunctional agent. Reagents such as phosphorus oxychloride or sodium trimetaphosphate can be used as crosslinking agents. Very small amounts of these agents can have a marked effect on the behavior of cooked starch.

[00146] Starch can be stabilized against gelation using monofunctional reagents. These reagents react with hydroxyl groups on the starch to introduce substituent groups that interfere with the hydrogen bonding effects, thereby increasing their ability to combine with water or viscosity or giving a positive charge to the starch molecule. Reagents used in stabilizing starch through hydrogen bond disruption include ethylene oxide to produce hydroxyethyl starch, acetic anhydride to produce starch acetates, succinic anhydride to produce starch succinates, monosodium orthophosphate or sodium tripolyphosphate to produce starch phosphates and propylene oxide to produce hydroxypropyl starches. Reagents that give a positive charge to the starch molecule include tertiary or quaternary amines to produce cationic starches.

PREGELATINIZED STARCH [00147] Suspensions of many starches and starch derivatives can be gelatinized and dried to provide a wide variety of pregelatinized starches. This is done on a single drum dryer with applicator rollers. The starch paste is heated to gelatinize it, instantly dried and ground to the desired granulation requirement. Pre-gelatinized starch is used to thicken instant desserts, such as puddings, allowing the food to thicken with the addition of cold water or milk. Similarly, granules of

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35/204 cheese sauce (as in Macaroni and Cheese or lasagna) or granules of meat sauce to be thickened with boiling water without the product forming lumps. Commercial pizza toppings containing modified starch will thicken when heated in the oven, keeping them on top of the pizza and then become liquid when cold.

WHITE STARCHES [00148] Bleaching through very light oxidation is performed using sodium hypochlorite, sodium chloride, hydrogen peroxide, potassium permanganate, peracetic acid or ammonium persulfate with sulfur dioxide. Interactions with the starch molecules must be very small, since no change occurs in the physical properties of the starch or its solution, except for its color. Theoretically, there will be the production of few aldehyde or carboxyl groups. Only residual amounts of sodium chloride, sodium sulfate or sodium acetate remain in the final product. The bleached starch is recovered in continuous filters or centrifuges using copious amounts of water to remove residual amounts of inorganic salts formed from the bleach, dried and packaged.

LOW MOLECULAR WEIGHT SUGARS [00149] Biomass materials that include low molecular weight sugars can, for example, include at least about 0.5 weight percent of low molecular weight sugar, for example, at least about 2 , 3, 4, 5, 6, 7, 8, 9, 10, 12.5, 25, 35, 50, 60, 70, 80, 90 or even at least about 95 weight percent of low molecular weight sugar. In some cases, the biomass is composed substantially of low molecular weight sugar, for example, more than 95 weight percent, such as 96, 97, 98, 99 or substantially 100 weight percent of low molecular weight sugar.

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36/204 [00150] Biomass materials that include low molecular weight sugars can be agricultural products or food products such as sugar cane or sugar beet juice or an extract thereof, for example, sugar cane juice or sugar beet . Biomass materials that include low molecular weight sugars can be substantially pure extracts, such as crystallized (sucrose) or raw table sugar. Low molecular weight sugars include sugar derivatives. For example, low molecular weight sugars can be oligomeric (for example, equal to or more 4-mer, 5-mer, 6-mer, 7-mer, 8-mer, 9-mer or 10-mer), quarterly , dimeric or monomeric. When carbohydrates are formed from more than a single repetition unit, each repetition unit can be the same or different.

[00151] Specific examples of low molecular weight sugars include cellobiose, lactose, sucrose, glucose and xylose, along with derivatives thereof. In some cases, sugar derivatives are more quickly dissolved in solution or used by microbes to provide a useful material, such as ethanol or butanol. Several of such sugars and sugar derivatives are shown below

HLl ^

(Γ-γποποaccharide sucrose) 2-keto-alu conical acid

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37/204

HCK

ETHANOL FROM LOW MOLECULAR WEIGHT SUGARS [00152] More than half of the world's ethanol production is produced from sugar and sugar by-products, with Brazil being the world leader. Currently, there is no commercial production of ethanol from sugar cane or sugar beets in the United States, where 97 percent of ethanol is produced from corn.

[00153] Technologically, the process of producing ethanol from sugar is simpler than converting corn into ethanol. Converting corn into ethanol requires additional cooking (wet milling process) and the application of enzymes, while converting sugar requires only a yeast fermentation process. The energy requirement for converting sugar into ethanol is about half that for corn. However, technoPetition costs 870170006381, of 01/30/2017, p. 43/258

38/204 Logistics and direct energy are one of several factors that determine the viability of ethanol production. Other factors include relative production costs (including food stocks), conversion rates, proximity to installation units, alternative prices and government policies, construction of factories and processing costs. Since other countries have shown that it may be economically viable to produce ethanol from sugar and other new food stocks are being researched, interest in the United States on the production of ethanol from sugar has increased.

[00154] In response to the growing interest in sugar and ethanol, the USDA released a study in July 2006 entitled: The Economic Feasibility of Ethanol Production from Sugar in the United States, which is incorporated here by reference in its entirety. The report found that current market prices for ethanol, conversion of sugarcane, sugar beet and molasses into ethanol would be predictable (see Table 1).

Table 1. Current market prices for ethanol

Feed stock Total costs * Processing costs * Corn (wet shredding / dry shredding): $ 1.03 / 1.05 $ 0.63 / 0.52 Raw sugar cane $ 2.40 $ 0.92 Crude sugar beet $ 2.35 $ 0.77 Molasses** $ 1.27 $ 0.36 Raw sugar ** $ 3.48 $ 0.36 Refined sugar** $ 3.97 $ 0.36

* Per gallon ** Excluding shipping costs

SACARINIC BEET [00155] Sugar beets are an annual crop grown in 11

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39/204 states across a variety of climatic conditions, from the warm climate of California's Imperial Valley to the colder climates of Montana and North Dakota. Sugar beet by-products include beet pulp, which can be sold for animal feed and molasses, which is also sold for animal feed or further processed to extract more sugar.

[00156] Sugar beet processing units convert raw sugar beets directly into refined sugar in a 1-step process. Although the sugar beet fields planted have fallen slightly since the 1990s, sugar production has currently increased due to investments in new processing equipment, the adoption of new technologies, improved crop varieties and intensified technologies for sugar extraction of molasses. Sugar beets are very bulky and relatively expensive to transport and must be processed very quickly before sucrose deteriorates. Therefore, all sugar beet processing factories are located in the production areas.

SUGAR CANE [00158] Sugarcane is a perennial tropical crop produced in four states: Florida, Hawaii, Louisiana and Texas. By-products from sugarcane processing include molasses and bagasse, the fibrous material that remains after sugar is pressed from sugarcane. The bagasse is often burned as a fuel to help sugar cane mills. Sugarcane is initially processed into raw sugar in mills close to the cane fields. Like beets, cane is bulky and relatively expensive to transport and must be processed as soon as possible to minimize the deterioration of sucrose. Raw sugar is then sent to refineries to produce refined sugar.

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40/204 [00159] Sugar beet has achieved a greater share of sugar production in the United States over the past decade, now adding 58.8 percent of the nation's sugar production, while sugar cane has dropped to 41, 2 percent.

Molasses [00160] The most widely used sugar from ethanol fermentation is dark molasses, which contains about 35 - 40% by weight of sucrose, 15 - 20% by weight of inverted sugars, such as glucose and fructose and 28 - 35% by weight of non-sugar solids. Dark molasses (syrup) is collected as a by-product of the manufacture of sugar cane. The molasses is diluted to a puree containing approximately 10-20% by weight of sugar. After the pH of the puree is adjusted to about 4 - 5 with mineral acid, it is inoculated with the yeast and fermentation is carried out non-aseptically at 20 32 ° C for about 1 - 3 days. The fermented yeast, which contains approximately 6 - 10% by weight of ethanol, is then sent for product recovery in the purification section of the factory. [00161] Ethanol production (using 141 gallons per ton of sucrose conversion factor) was calculated for sugar cane, sugar beets and molasses below.

Sugar cane:

[00162] Recovery rate of 12.24% raw sugar, plus 41.6 pounds of sucrose from cane molasses [00163] 1 ton of sugarcane = 235.0 pounds of sucrose from sugar crude and 41.6 pounds of sucrose from molasses [00164] = 276.6 pounds (0.1383 tons) of sucrose [00165] = 19.5 gallons of ethanol [00166] or 0.051 tons of sugar cane per gallon of ethanol produced

Sugar beets:

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41/204 [00167] Recovery rate of 15.58% refined sugar, plus 40.0 pounds of sucrose from beet molasses [00168] 1 ton of sugar beet = 311.6 pounds of sucrose from sugar refined and 40.0 pounds of sucrose from beet molasses [00169] = 351.6 pounds (0.1758 tons) of sucrose [00170] = 24.8 gallons of ethanol [00171] or 0.040 tons of sugar beet per gallon of ethanol produced

Molasses:

[00172] 49.2% of total sugars as sucrose [00173] 1 ton of molasses = 984 pounds (0.492 tons) of sucrose [00174] = 69.4 gallons of ethanol [00175] or 28.8 pounds of molasses per gallon of ethanol produced [00176] or 2.45 gallons of molasses per gallon of ethanol produced [00177] (using a conversion of 1.0 gallons of molasses = 11.74 pounds in weight)

Raw sugar:

[00178] 96.0% of total sugars as sucrose [00179] 1 ton of raw sugar = 1920 pounds (0.96 tons) of sucrose [00180] = 135.4 gallons of ethanol [00181] or 14.77 pounds of raw sugar per gallon of ethanol produced

Refined beet sugar:

[00182] 100.0% of total sugars as sucrose [00183] 1 ton of refined sugar = 2000 pounds (1.0 ton) of sucrose [00184] = 141.0 gallons of ethanol

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42/204 [00185] or 14,18 pounds of refined sugar per gallon of ethanol produced [00186] The results of this study have several important implications regarding the production of ethanol from sugar crops in the United States. First, under the existing fermentation technology, corn is currently the cheapest feed stock available for use in ethanol production in the United States. Second, given current and projected future sugar and ethanol prices in the market, it appears that sugar production is the most predictable use for sugarcane or sugar beets. Third, cellulosic conversion of biomass into offers the potential for a wide variety of feed stocks to be used in ethanol production.

[00187] Systems and processes are described here, which can use these low molecular weight sugars to produce ethanol more quickly and more cost effectively.

[00188] Mixtures of any biomass materials described here can be used for the production of any of the products described here, such as ethanol. For example, mixtures of cellulosic materials and starch materials can be used to produce any product described here.

BIOMASS TREATMENT SYSTEMS [00189] Figure 1 shows a system 100 for converting biomass, particularly biomass with significant cellulosic and lignocellulosic components and / or starch components, into useful products and co-products. System 100 includes a feed preparation subsystem 110, a pretreatment subsystem 114, a primary process subsystem 118 and a postprocessing subsystem 122. Feed preparation subsystem 110 receives biomass in its raw form, it physically prepares the biomass

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43/204 for use as feed stock through downstream processes (for example, reduce the size and homogenize the biomass) and store the biomass in its raw form and as feed stock.

[00190] Biomass feed stock with cellulosic and / or lignocellulosic components or starch components may have a high average molecular weight and crystallinity which can make the processing of the feed stock into useful products (eg fermentation of the feed stock for producing ethanol) difficult. For example, others used acids, bases and enzymes to process cellulosic, lignocellulosic or starch food stocks. As described here, in some embodiments, such treatments are unnecessary or are needed only in small amounts or catalytic amounts.

[00191] The pretreatment subsystem 114 receives the feed stock from the feed preparation subsystem 110 and prepares the feed stock for use in primary production processes by, for example, reducing molecular weight and average crystallinity of the feed stock. The primary process subsystem 118 receives the pre-treated feed stock from the pretreatment subsystem 114 and produces useful products (for example, ethanol, other alcohols, pharmaceuticals and / or food products). In some cases, the product of the primary process subsystem 118 is directly useful, but in other cases, it requires additional processing provided by the post-processing subsystem 122. The post-processing subsystem 122 provides additional processing to the streams. product of the primary process system 118 which requires it (for example, ethanol distillation and denaturation), as well as treatment for residual streams from the other sub-systems. In some cases, co-products from subsystems 114, 118, 122 may

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44/204 may also be directly or indirectly useful as by-products and / or in increasing the overall efficiency of system 100. For example, post-processing subsystem 122 can produce treated water to be recycled for use as process water in others sub-systems and / or can produce a burnable residue which can be used as fuel for boilers that produce steam and / or electricity.

[00192] The optimal size for biomass conversion units is affected by factors, including economies of scale and the type and availability of biomass used as feed stock. Increasing the size of the unit tends to increase the economy of scale associated with processes in the unit. However, increasing the size of the unit also tends to increase costs (for example, transportation costs) per unit of food supply. Studies that analyzed these factors suggest that the appropriate size for biomass conversion units can range from 1000 to 10,000 or more dry tons of feed stock per day depending, at least in part, on the type of feed stock used. The type of feed stock can also have an impact on the unit's storage requirements with units designed primarily for feed stock processing, the availability of which varies periodically (for example, maize straw) which requires more storage of ethyl acetate in the or on the site than units designed to process feed stock whose availability is relatively constant (for example, waste paper).

PHYSICAL PREPARATION [00193] In some cases, processing methods start with a physical preparation of the feed stock, for example, reducing the size of raw feed stock materials, such as

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45/204 such as cutting, shredding, shearing, ball shredding, roll narrowing or chipping. In some cases, the material can be reduced to particles using a hammer mill, disc refiner or flake machine. In some cases, loose feed stock (for example, recycled paper, starch materials or switchgrass) is prepared by shearing or shearing. Sieves and / or magnets can be used to remove oversized or unwanted objects such as, for example, rocks or nails from the supply chain.

[00194] Material preparation systems can be configured to produce chains with specific characteristics such as, for example, maximum specific sizes, length for specific width or specific proportions of surface areas. As a part of the feed preparation, the volumetric density of ethyl acetate can be controlled (for example, increased). SIZE REDUCTION [00195] In some embodiments, the material to be processed is in the form of a fibrous material that includes fibers provided by shearing the fiber source. For example, shearing can be performed with a rotary knife cutter.

[00196] For example and with reference to figure 2, a fiber source 210 is sheared, for example, in a rotary knife cutter, to provide a first biomass material 212. The first fibrous material 212 is passed through a first screen 214 having an average opening size of 1.59 mm or less (1/16 inch, 0.0265 inch) to provide a second fibrous material 216. If desired, the fiber source can be cut prior to shearing, for example , with a mincer. For example, when a paper is used as the fiber source, the paper can first be cut into strips that are, for example, ¼ to ½ inches wide, using a

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46/204 chipper, for example, a counter-rotating thread chipper, such as the one manufactured by Munson (Utica, N.Y.). As an alternative to shredding, the paper can be reduced in size by cutting to a desired size using a guillotine cutter. For example, the guillotine cutter can be used to cut paper into sheets that are, for example, 10 inches wide by 12 inches long.

[00197] In some modalities, the cutting of the fiber source and the passage of the first resulting fibrous material through a first sieve are carried out concurrently. Shearing and passing can also be carried out sequentially, for example, in a batch-type process.

[00198] For example, a rotary knife cutter can be used to shear the fiber source concurrently and sieve the first fibrous material. Referring to Figure 3, a rotary knife cutter 220 includes a feeder container 222 that can be loaded with a chopped fiber source 224 prepared by shearing the fiber source. The chopped fiber source is sheared between stationary blades 230 and rotating blades 232 to provide a first fibrous material 240, The first fibrous material 240 passes through sieve 242 and the resulting second fibrous material 244 is captured in a container 250, To assist in the collection of the second fibrous material, the container may have a pressure below the nominal atmospheric pressure, for example, at least ten percent below the nominal atmospheric pressure, for example, at least 25 percent below the nominal atmospheric pressure, at least 50 percent percent below nominal atmospheric pressure or at least 75 percent below nominal atmospheric pressure. In some embodiments, a vacuum source 252 is used to keep the container below the rated atmospheric pressure.

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47/204 [00199] Shearing can be advantageous for opening, tensioning or even reducing the molecular weight of fibrous materials, making the cellulose of the materials more susceptible to chain splitting and / or reduced crystallinity. Open materials can also be more susceptible to oxidation when irradiated.

[00200] The fiber source can be sheared in a dry state, a hydrated state (for example, having up to ten percent by weight of absorbed water) or in a wet state, for example, having between about 10 percent and about 75 weight percent water. The fiber source can even be sheared while partially or completely submerged under a liquid, such as water, ethanol or isopropanol. [00201] The fiber source can also be sheared in a gas (such as a current or atmosphere other than air), for example, oxygen or nitrogen or steam.

[00202] Other methods of producing fibrous materials include, for example, stone grinding, mechanical tearing or tearing, pin grinding, ball grinding, roller narrowing or air friction grinding.

[00203] If desired, fibrous materials can be separated, continuously or in batches, in fractions according to their length, width, density, type of material or some combination of these attributes.

[00204] For example, ferrous materials can be separated from any of the fibrous materials by passing a fibrous material that includes a ferrous material over a magnet, for example, an electromagnet and then passing the resulting fibrous material through a series of sieves , each sieve having differently sized openings.

[00205] Fibrous materials can also be separated, for example, using a gas at high speed, for example, air. On such

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48/204 approach, the fibrous materials are separated by extracting different fractions which can be characterized photonically, if desired. Such a separation apparatus is discussed, for example, in Lindsey et al., U.S. Patent No. 6,883,667.

[00206] Fibrous materials may have a low moisture content, for example, less than about 7.5, 5, 3, 2.5, 2, 1.5, 1 or 0.5% by weight before processing. This material can be irradiated with a beam of particles, such as electrons or protons. The irradiation can be immediately after preparation of the material or after a moisture reduction step, for example, drying at approximately 105 ° C for 4-18 hours, so that the moisture content is, for example, less than about 0.5% before use.

[00207] If desired, lignin can be removed from any of the fibrous materials that include lignin. Also, to aid in the breakdown of materials including cellulose, the material can be treated before irradiation with heat, a chemical (for example, mineral acid, base or a strong oxidizer, such as sodium hypochlorite) and / or a enzyme.

[00208] In some embodiments, the average opening size of the first sieve is less than 0.79 mm (1/32 inch, 0.03125 inch), and, g ,, less than 0.51 mm (1/50 inch, 0.02000 inch), less than 0.40 mm (1/64 inch, 0.015625 inch), less than 0.23 mm (0.009 inch), less than 0.20 mm (1/128 inch, 0 , 0078125 inch), less than 0.18 mm (0.007 inch), less than 0.13 mm (0.005 inch) or even less than 0.10 mm (1/256 inch, 0.00390625 inch). The screen is prepared by interlacing monofilaments having an appropriate diameter to provide the desired opening size. For example, monofilaments can be made of a metal, for example, stainless steel. As the opening sizes become smaller, the structural demands on the 870170006381, from 01/30/2017, p. 54/258

49/204 bre monofilaments can be made larger. For example, for aperture sizes of less than 0.40 mm, it may be advantageous to make sieves from monofilaments made of a material other than stainless steel, for example, titanium, titanium alloys, amorphous metals, nickel, tungsten, rhodium, rhenium, ceramics or glass. In some embodiments, the sieve is made of a plate, for example, a metal plate having openings, for example, cut into a plate using a laser. In some modalities, the mesh opening area is less than 52%, for example, less than 41%, less than 36%, less than 31%, less than 30%.

[00209] In some embodiments, the second fibrous material is sheared and passed through the first sieve or a sieve of a different dimension. In some embodiments, the second fibrous material is passed through a second sieve having an average opening size equal to or less than that of the first sieve.

[00210] Referring to figure 4, a third fibrous material 220 can be prepared from the second fibrous material 216 by shearing the second fibrous material 216 and passing the resulting material through a second sieve 222 having an average opening size smaller than the first sieve 214. [00211] In general, fibers from fibrous materials can have a relatively large average length-to-diameter ratio (for example, greater than 20 to 1), even if they have been sheared more than one turn. In addition, the fibers of the fibrous materials described herein may have a relatively limited length-to-diameter ratio and / or length distribution.

[00212] As used here, average fiber widths (ie diameters) are those determined optically by selecting, at random, approximately 5,000 fibers. The average lengths

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50/204 fiber are weighted corrected lengths. The BET surface areas (Brunauer, Emmet and Teller) are multipoint surface areas and the porosities are those determined by means of mercury porosimetry.

[00213] The average length-to-diameter ratio of the second fibrous material 14 can be, for example, greater than 8/1, 10/1, 15/1, 20/1, 25/1 or even greater than 50 / 1, An average length of the second fibrous material 14 can be, for example, between about 0.5 mm and 2.5 mm, for example, between about 0.75 mm and 1.0 mm and an average width ( i.e., diameter) of the second fibrous material 14 can be, for example, between about 5 mm and 50 mm, for example, between about 10 mm and 30 mm.

[00214] In some embodiments, a standard deviation in the length of the second fibrous material 14 is less than 60 percent of an average length of the second fibrous material 14, for example, less than 50 percent of the average length, less than 40 percent the average length, less than 25 percent of the average length, less than 10 percent of the average length, less than 5 percent of the average length or even less than 1 percent of the average length.

[00215] In some embodiments, a BET surface area of the second fibrous material is greater than 0.1 m ² / g, for example, greater than 0.25 m ² / g, greater than 0.5 m ² / g, greater than 1.0 m ² / g, greater than 1.5 m ² / g, greater than 1.75 m ² / g, greater than 5.0 m ² / g, greater than 10 m ² / g, greater than 25 m ² / g, greater than 35 m ² / g, greater than 50 m ² / g, greater than 60 m ² / g, greater than 75 m ² / g, greater than than 100 m ² / g, greater than 150 m ² / g, greater than 200 m ² / g or even greater than 250 m ² / g. A porosity of the second fibrous material 14 can be, for example, greater than 20 percent, greater than 25 percent, greater than 35 percent, greater than 50 percent,

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51/204 greater than 60 percent, greater than 70 percent, for example, greater than 80 percent, greater than 85 percent, greater than 90 percent, greater than 92 percent, greater than than 94 percent, greater than 95 percent, greater than 97.5 percent, greater than 99 percent or even greater than 99.5 percent.

[00216] In some embodiments, an average length-to-diameter ratio of the first fibrous material to an average length-to-diameter ratio of the second fibrous material is, for example, less than 1.5, for example, less than 1.4, less than 1.25, less than 1.1, less than 1.075, less than 1.05, less than 1.025 or even substantially equal to 1.

[00217] In particular embodiments, the second fibrous material is sheared again and the resulting fibrous material passed through a second sieve having an average opening size smaller than the first sieve to provide a third fibrous material. In such cases, an average length to diameter ratio of the second fibrous material to the average length to diameter ratio of the third fibrous material can be, for example, less than 1.5, for example, less than 1.4, less than 1 , 25 or even less than 1.1.

[00218] In some embodiments, the third fibrous material is passed through a third sieve to produce a fourth fibrous material. The fourth fibrous material can, for example, be passed through a fourth sieve to produce a fifth material. Similar screening processes can be repeated as many times as desired to produce the desired fibrous material having the desired properties.

DENSIFICATION [00219] Densified materials can be processed or any processed materials can be densified through any

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52/204 one of the methods described here or any material described here, for example, any fibrous material described here, can be processed using any one or more of the methods described here and then densified, as described here.

[00220] A material, for example, a fibrous material having a low volumetric density can be densified into a product having a higher volumetric density. For example, a material composition having a volumetric density of 0.05 g / cm ³ can be densified by sealing the fibrous material in a relatively gas-impermeable structure, for example, a bag made of polyethylene or a bag made of alternating layers of polyethylene and a nylon and then evacuating the enclosed gas, for example, air, from the structure. After evacuation of air from the structure, the fibrous material may have, for example, a volumetric density greater than 0.3 g / cm ³ , for example, 0.5 g / cm ³ , 0.6 g / cm ³ , 0 , 7 g / cm ³ or more, for example, 0.85 g / cm ³ . After densification, the product can be processed using any of the methods described here, for example, irradiated, for example, with gamma radiation. This can be advantageous when it is desirable to transport the material to another location, for example, a remote factory, where the fibrous material composition can be added to a solution, for example, to produce ethanol. After drilling the substantially gas-impermeable structure, the densified fibrous material can revert to almost its initial volumetric density, for example, to more than 60 percent of its initial volumetric density, for example, 70 percent, 80 percent, 85 percent or more, for example, 95 percent of its initial volumetric density. To reduce static electricity in the fibrous material, an anti-static agent can be added to the material.

[00221] In some embodiments, the structure, for example, a bag, is formed of a material that dissolves in a liquid, such as

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53/204 water. For example, the structure can be formed of a polyvinyl alcohol, so that it dissolves when in contact with a water-based system. Such modalities allow densified structures to be added directly to solutions that include a microorganism, without first releasing the contents of the structure, for example, by cutting.

[00222] Referring to figure 5, a biomass material can be combined with any desired additives and binder and subsequently densified by applying pressure, for example, passing the material through a defined narrowing between counter pressure rollers rotating or passing the material through a pellet mill. During the application of pressure, heat can optionally be applied to assist in the densification of the fibrous material. The densified material can then be irradiated.

[00223] In some embodiments, the material, before densification, has a volumetric density of less than 0.25 g / cm ³ , for example, 0.20 g / cm ³ , 0.15 g / cm ³ , 0, 10 g / cm ³ , 0.05 g / cm ³ or less, for example, 0.025 g / cm ³ . The volumetric density is determined using ASTM D1895B. Briefly, the method involves filling a known volume measuring cylinder with a sample and obtaining a sample weight. The volumetric density is calculated by dividing the sample weight in grams by the known volume of the cylinder in cubic centimeters.

[00224] Preferred binders include binders that are water-soluble, water-swollen or that have a glass transition temperature of less than 25 ° C, as determined by differential scanning calorimetry. By water-soluble binders is meant binders having a solubility of at least about 0.05 weight percent in water. By water-swellable binders is meant binders that increase in volume

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54/204 by more than 0.5 percent when exposed to water.

[00225] In some embodiments, binders that are soluble or swollen by water include a functional group that is capable of forming a bond, for example, a hydrogen bond, with the fibers of the fibrous material, for example, cellulosic fibrous material . For example, the functional group can be a carboxylic acid group, a carboxylate group, a carbonyl group, for example, from an aldehyde or a ketone, a sulfonic acid group, a sulfonate group, a phosphoric acid group, a phosphate group, a amide group, an amine group, a hydroxyl group, for example, of an alcohol and combinations of these groups, for example, a carboxylic acid group and a hydroxyl group. Specific monomeric examples include glycerin, glyoxal, ascorbic acid, urea, glycine, pentaerythritol, a monosaccharide or a disaccharide, citric acid and tartaric acid. Suitable saccharides include glucose, sucrose, lactose, ribose, fructose, mannose, arabinose and erythrose. Polymeric examples include polyglycols, polyethylene oxide, polycarboxylic acids, polyamides, polyamines and polysulfonates of polysulfonic acids. Specific polymeric examples include polypropylene glycol (PPG), polyethylene glycol (PEG), polyethylene oxide, for example, POLYOX ^® , ethylene oxide and propylene oxide copolymers, polyacrylic acid (PAA), polyacrylamide, polypeptide, polyethylpyridine, polyvinyline, polyvinyline sodium (poly) -4-styrene sulfonate and (poly) -2-acrylamido-methyl-1-propane-sulfonic acid.

[00226] In some embodiments, the binder includes a polymer that has a glass transition temperature of less than 25 ° C. Examples of such polymers include thermoplastic elastomers (TPEs). Examples of TPEs include polyether block amides, such as those available under the trademark PEBAX ^® , polyester elastomers, such as those available under the trademark HYTREL ^® and styrenic block copolymers, such as those 870170006381, of 30 / 01/2017, p. 60/258

55/204 available on the KRATON® trademark. Other suitable polymers having a glass transition temperature of less than 25 ° C include ethylene vinyl acetate (EVA) copolymer, polyolefins, for example, polyethylene, polypropylene, ethylenepropylene copolymers and ethylene and alpha olefin copolymers, for example, 1octene, such as those available under the trademark ENGAGE®. In some embodiments, for example, when the material is a poly-coated paper in fiber, the material is densified without the addition of a low temperature transition polymer from the distinct glass. [00227] In a particular embodiment, the binder is a lignin, for example, a natural or synthetically modified lignin.

[00228] An adequate amount of binder added to the material, calculated on a dry weight basis is, for example, from about 0.01 percent to about 50 percent, for example, 0.03 percent, 0, 05 percent, 0.1 percent, 0.25 percent, 0.5 percent, 1.0 percent, 5 percent, 10 percent or more, for example, 25 percent, based on a weight of densified material. The binder can be added to the material as a pure liquid, as a liquid having the binder dissolved in it, as a dry binder powder or as binder pellets.

[00229] The densified fibrous material can be made in a pellet mill. Referring to Figure 6, a pellet mill 300 has a feeder container 301 for containing an un densified material 310 that includes carbohydrate containing materials, such as cellulose. The feed hopper communicates with a drill bit 312 that is driven by a variable speed motor 314, so that the non-densified material can be transported to a conditioner 320 that shakes the non-densified material with blades 322 which are rotated by a conditioner motor 330. Other ingredients, for example, any of the additives and / or fillers described here can be added to the

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56/204 entry 332. If desired, heat can be added while the fibrous material is in the conditioner. After being conditioned, the material passes from the conditioner through a drain chute 340 and to another drill 342. The drain chute, as controlled by an actuator 344, allows the unobstructed passage of the conditioner material to the drill. The drill is rotated by the motor 346 and controls the feeding of the fibrous material in the matrix and roller set 350. Specifically, the material is introduced in a hollow cylindrical matrix 352, which rotates about a horizontal axis and which has holes of matrix 250 that extend radially. The 352 matrix is rotated around the axis by a 360 engine, which includes a horsepower calibrator, which indicates the total energy consumed by the engine. Densified material 350, for example, in the form of pellets, falls from trough 372 and is captured and processed, such as by irradiation.

[00230] The material, after densification, can conveniently be in the form of pellets or chips having a variety of shapes. The pellets can then be irradiated. In some embodiments, the pellets or chips are cylindrical in shape, for example, having a maximum transverse dimension, for example, 1 mm or more, for example, 2 mm, 3 mm, 5 mm, 8 mm, 10 mm, 15 mm or more, for example, 25 mm. Other conventional shapes include pellets or chips that are shaped like a blade, for example, having a thickness of 1 mm or more, for example, 2 mm, 3 mm, 5 mm, 8 mm, 10 mm or more, for example , 25 mm; a width of, for example, 5 mm or more, for example, 10 mm, 15 mm, 25 mm, 30 mm or more, for example, 50 mm; and a length of 5 mm or more, for example, 10 mm, 15 mm, 25 mm, 30 mm or more, for example, 50 mm. [00231] Referring now to figures 7A-7D, pellets can be made so that they have a hollow interior. As shown, the hollow can, in general, be in-time with the center of the pellet (figuPetição 870170006381, of 01/30/2017, page 62/258

57/204 ra 7B) or out of line with the center of the pellet (figure 7C). Hollowing the inside of the pellet can increase the rate of dissolution in a liquid after irradiation.

[00232] Referring now to figure 7D, the pellet may have, for example, a cross-sectional shape that is multi-lobal, for example, trilobal as shown or tetra-lobal, penta-lobal, hexa-lobal or deca-lobal. Producing pellets with such transversal shapes can also increase the dissolution rate in a solution after irradiation. [00233] Alternatively, the densified material may be in any other desired shape, for example, the densified material may be in the form of a mat, roller or bale.

EXAMPLES [00234] In one example, half-gallon juice packs made of unprinted white Kraft cardboard having a volumetric density of 20 pounds / foot ³ can be used as a feed stock. The packages can be folded and then fed to a chipper to produce a confetti-like material having a width of between 0.1 inch and 0.5 inch, a length of between 0.25 inch and 1 inch and an equivalent thickness that of the starting material (about 0.075 inches). The confetti-like material can be fed to a rotary knife cutter, which cuts the confetti-like pieces, tearing the pieces apart and releasing the fibrous material.

[00235] In some cases, multiple chipper - shear trays can be arranged in series on the production line. In one embodiment, two shredder - shear trays can be arranged in series with the production line from the first shear fed as input to the second shredder. In another modality, three chipper - shear trays can be arranged in series with the production line from the first shear fed as enPetição 870170006381, from 01/30/2017, p. 63/258

58/204 brought to the second chipper and the production of the second shear fed as input to the third chipper. Multiple passes through the chopper - shear trays are expected to decrease particle size and increase the overall surface area within the feed stream.

[00236] In another example, the fibrous material produced from the crushing and shearing juice packaging can be treated to increase its volumetric density. In some cases, the fibrous material can be sprayed with water or a diluted stock solution of POLYOX® WSR N10 (polyethylene oxide) prepared in water. The wet fibrous material can then be processed using a pellet mill operating at room temperature. The pellet mill can increase the volumetric density of the feed stream. PRE-TREATMENT [00237] The physically prepared feed stock can be pre-treated for use in primary production processes, for example, by reducing the average molecular weight and crystallinity of the feed stock and / or increasing the surface area and / or porosity of the feed stock. In some embodiments, the cellulosic and / or lignocellulosic material includes a first cellulose having a first number average molecular weight and the resulting carbohydrate includes a second cellulose having a second number average molecular weight less than the first number average molecular weight. For example, the second average numerical molecular weight is less than the first average numerical molecular weight by more than about twenty-five percent, for example, a reduction of 2x, 3x, 5x, 7x, 10x, 25x, even by 100x.

[00238] In some embodiments, the first cellulose has a first crystallinity and the second cellulose has a second crystallinity less than the first crystallinity, such as less than

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59/204 about two, three, five, ten, fifteen or twenty-five percent less.

[00239] In some embodiments, the first cellulose has a first level of oxidation and the second cellulose has a second level of oxidation greater than the first level of oxidation, such as two, three, four, five, ten or even twenty-two five percent higher.

[00240] Pre-treatment processes may include one or more of irradiation, ultrasound, oxidation, pyrolysis and vapor explosion. The various pre-treatment systems and methods can be used in combinations of two, three or even four of these technologies. PRE-TREATMENT COMBINATIONS [00241] In some embodiments, biomass can be processed by applying two or more of any of the processes described here, such as two, three, four or more radiation, ultrasound (or any other rupture technique described here , for example, treatment with a rotor-stator rupture device), oxidation, pyrolysis and steam explosion, with or without prior, intermediate or subsequent preparation of the feed stock, as described here. The processes can be applied to biomass in any order or concurrently. For example, a carbohydrate can be prepared by applying radiation, ultrasound, oxidation, pyrolysis and optionally steam explosion to a cellulosic and / or lignocellulosic material (in any order or concurrently). The carbohydrate-containing material provided can then be converted by one or more microorganisms, such as bacteria, yeast or mixtures of yeast and bacteria, to a series of desirable products, as described herein. Multiple processes can provide materials that can be more readily used by a variety of microorganisms because of their lower molecular weight, less crystallinity and / or enhanced solubility. Multiple lawsuits can be provided 870170006381, from 01/30/2017, p. 65/258

60/204 provide synergies and can reduce the overall energy consumption required compared to any single process.

[00242] For example, in some modalities, food stocks are provided that include a carbohydrate that is produced through a process that includes irradiation and ultrasound, irradiation and oxidation, irradiation and pyrolysis or irradiation and explosion of steam (in any order or concurrently) of cellulosic and / or lignocellulosic material. The feed stock provided can then be contacted with a microorganism having the ability to convert at least a part, for example, at least about 1 weight percent, of the feed stock into product, such as the material fuel.

PRE-TREATMENT CONDITIONS [00243] In some embodiments, the process does not include hydrolysis of cellulosic and / or lignocellulosic material, such as with an acid, for example, a mineral acid, such as hydrochloric or sulfuric acid, an enzyme or a base. If desired, some or none of the feed stock can include a hydrolyzed material. For example, in some embodiments, at least about seventy percent by weight of the feed stock is non-hydrolyzed material, for example, at least 95 percent by weight of the feed stock is non-hydrolyzed material. In some embodiments, substantially the entire feed stock is a non-hydrolyzed material. For example, treatment with an alkali can be avoided.

[00244] Any feed stock or any reactor or fermenter loaded with a feed stock may include a buffer, such as sodium bicarbonate, ammonium chloride or Tris; an electrolyte, such as potassium chloride, sodium chloride or calcium chloride; a growth factor, such as biotin and / or a base pair, such as uracil or an equivalent thereof; a surfactant, such

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61/204 as Tween® or polyethylene glycol; a mineral, such as calcium, chromium, copper, iodine, iron, selenium or zinc; or a chelating agent, such as ethylene diamine, ethylene diamine tetraacetic acid (EDTA) (or its salt form, for example, sodium or potassium EDTA) or dimercaprol.

[00245] When irradiation is used, it can be applied to any sample that is dry or wet or even dispersed in a liquid, such as water. For example, irradiation can be carried out on cellulosic or lignocellulosic material in which less than about 25 weight percent of the cellulosic and / or lignocellulosic material has surfaces moistened with a liquid, such as water. In some embodiments, irradiation is carried out on a cellulosic and / or lignocellulosic material in which substantially none of the cellulosic and / or lignocellulosic material is moistened with a liquid, such as water. [00246] In some embodiments, any processing described here occurs with the remaining cellulosic and / or lignocellulosic material dried as purchased or after the material has been dried, for example, using heat and / or reduced pressure. For example, in some embodiments, cellulosic and / or lignocellulosic material has less than about five percent by weight of water remaining, measured at 25 ° C and a relative humidity of fifty percent.

[00247] The feed stock can be treated so that it has a low moisture content, for example, less than about 7.5, 5, 3, 2.5, 2, 1.5, 1 or 0, 5% by weight. This material can be irradiated with a beam of particles, such as electrons or protons. The irradiation can be immediately after preparing the material or after a moisture reduction step, for example, drying at approximately 105 ° C for 4-18 hours.

[00248] If desired, a swelling agent, as defined here, can be used in any process described here. In

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Some modalities, when a cellulosic and / or lignocellulosic material is processed using radiation, less than about 25 weight percent of the cellulosic and / or lignocellulosic material is in a swollen state, the swollen state being characterized as having a volume more than about 2.5 percent greater than a non-swollen state, for example, more than 5.0, 7.5, 10 or 15 weight percent greater than the non-swollen state. In specific embodiments, when radiation is used, the cellulosic and / or lignocellulosic material includes a swelling agent and the swollen cellulosic and / or lignocellulosic material receives a radiation dose of less than about 10 Mrad. In other embodiments, when radiation is used on a cellulosic and / or lignocellulosic material, substantially none of the cellulosic and / or lignocellulosic material is in a swollen state.

[00249] In some modalities, no chemical product, for example, no wetting agent, is added to the biomass before irradiation. For example, in some of these embodiments, no alkaline substance (such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxides), acidifying agents (such as mineral acids (for example, sulfuric acid, hydrochloric acid and phosphoric)), salts such as zinc chloride, calcium carbonate, sodium carbonate, benzyltrimethylammonium sulfate or basic organic amines, such as ethylene diamine, are added before irradiation or other processing. In some cases, no extra water is added. For example, biomass, before processing, can have less than 0.5 weight percent of chemicals added, for example, less than 0.4, 0.25, 0.15 or 0.1 weight percent of added chemicals. In some cases, biomass has no more than a residual amount, for example, less than 0.05 weight percent, of chemicals

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63/204 added, before irradiation. In other cases, biomass, before irradiation, has substantially no chemicals or wetting agents added. Avoiding the use of such chemicals can also be used throughout the processing, for example, at all times before fermentation or always. [00250] When radiation is used in any process, it can be applied while the cellulosic and / or lignocellulosic material is exposed to air, oxygen-enriched air or even oxygen itself or receive a stream of an inert gas, such as nitrogen, argon or helium. When maximum oxidation is desired, an oxidation environment is used, such as air or oxygen. The distance from the radiation source can also be optimized to maximize the formation of reactive gas, for example, ozone and / or nitrogen oxides.

[00251] When radiation is used, it can be applied to biomass, such as a cellulosic and / or lignocellulosic material, under a pressure of more than about 2.5 atmospheres, such as more than 5, 10, 15, 20 or even more than about 50 atmospheres.

[00252] When the process includes radiation, irradiation can be carried out using ionizing radiation, such as gamma rays, X-rays, energetic ultraviolet radiation, such as ultraviolet C radiation having a wavelength of about 100 nm to about 280 nm, a beam of particles, such as a beam of electrons, slow neutrons or alpha particles. In some embodiments, irradiation includes two or more sources of irradiation, such as gamma rays and an electron beam, which can be applied in any order or concurrently.

[00253] Any processing technique described here can be used at a pressure above or below normal atmospheric pressure. For example, any process that uses radiation, ultrasound, oxidation, pyrolysis, vapor explosion or combinations of any

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64/204 of these processes to provide materials that include a carbohydrate can be performed under high pressure, which can increase reaction rates. For example, any process or combination of processes can be performed at a pressure greater than about normal atmospheric pressure, for example, at a pressure of more than about 25 MPa, for example, greater than 50 MPa, 75 MPa, 100 MPa, 150 MPa, 200 MPa, 250 MPa, 350 MPa, 500 MPa, 750 MPa, 1,000 MPa or greater than 1,500 MPa.

RADIATION TREATMENT [00254] One or more irradiation processing sequences can be used to process a raw feed stock from a wide variety of different sources to extract useful substances from the feed stock and provide partially degraded organic material, which functions as an entry for other processing steps and / or sequences. Irradiation can reduce the molecular weight and / or crystallinity of the feed stock. In some embodiments, the energy deposited in a material that releases an electron from its atomic orbital is used to irradiate the materials. Radiation can be provided by 1) heavily charged particles, such as alpha particles or protons, 2) electrons produced, for example, in electron beam accelerators or beta decline or 3) electromagnetic radiation, for example, gamma rays, x-rays or ultraviolet rays. In one approach, radiation produced by radioactive substances can be used to irradiate the food supply. In some modalities, any combination in any order or concurrently (1) to (3) can be used. In another approach, electromagnetic radiation (for example, produced using electron beam emitters) can be used to irradiate the supply of food. For example, high radiation dose can break chemical bonds within the components of the feed stock and low

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65/204 doses of radiation can increase the chemical bond (eg, crosslinking) within the components of the feed stock. In some cases, when chain splitting is desirable and / or polymeric chain functionalization is desirable, particles heavier than electrons, such as protons, helium nuclei, argon ions, silicon ions, neon ions, carbon ions , phosphorus ions, oxygen ions or nitrogen ions can be used. When ring splitting is desired, positively charged particles can be used for their Lewis acid properties for enhanced ring splitting. For example, when functional groups containing oxygen are desired, irradiation in the presence of oxygen or even irradiation with oxygen ions can be performed. For example, when functional groups containing nitrogen are desirable, irradiation in the presence of nitrogen or even irradiation with nitrogen ions can be performed.

[00255] Referring to figure 8, in a method, a first material 2 that is or includes cellulose having a first numerical average molecular weight ( ^T MN1) is irradiated, for example, by treatment with ionizing radiation (for example, in the form gamma radiation, x-ray radiation, ultra-violet (UV) light from 100 nm to 280 nm, an electron beam or other charged particles to provide a second material 3 that includes cellulose having a second average numerical molecular weight ( ^T MN2 ) less than the first average numerical molecular weight The second material (or the first and second materials) can be combined with a microorganism (for example, a bacterium or yeast) that can use the second and / or the first material to produce a product, for example, a fuel 5 that is or includes hydrogen, an alcohol (for example, ethanol or butane, such as n-, sec- or tert-butanol), an organic acid, a hydrocarbon or mixtures of any of these.

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66/204 [00256] Since the second material 3 has cellulose having a molecular weight with respect to the first material and, in some cases, reduced crystallinity, the second material is, in general, more dispersible, swelling and / or soluble in a solution containing a microorganism. These properties make the second material 3 more susceptible to chemical, enzymatic and / or biological attack in relation to the first material 2, which can greatly improve the production rate and / or production level of a desired product, for example, ethanol. Radiation can also sterilize materials. [00257] In some embodiments, the second average numerical molecular weight (MN2) is less than the first average numerical molecular weight ( ^t M _N1 ) by more than about 10 percent, for example, 15, 20, 25, 30 , 35, 40, 50 percent, 60 percent or even more than about 75 percent.

[00258] In some cases, the second material has cellulose that has a crystallinity ( ^T C2) that is less than the crystallinity ( ^T C1) of the cellulose of the first material. For example, ( ^T C2) can be less than ( ^T C1) by more than about 10 percent, for example, 15, 20, 25, 30, 35, 40 or even more than about 50 percent.

[00259] In some embodiments, the initial crystallinity index (before irradiation) is about 40 to about 87.5 percent, for example, about 50 to about 75 percent or about 60 to about 70 percent and the crystallinity index after irradiation is about 10 to about 50 percent, for example, about 15 to about 45 percent or about 20 to about 40 percent. However, in some modalities, for example, after extensive irradiation, it is possible to have a crystallinity index of less than 5 percent. In some embodiments, the material after irradiation is substantially amorphous.

[00260] In some modalities, the numerical molecular weight average 870170006381, of 01/30/2017, p. 72/258

67/204 initial dio (before irradiation) is about 200,000 to about 3,200,000, for example, from about 250,000 to about 1,000,000 or from about 250,000 to about 700,000 and the average numerical molecular weight after irradiation it is about 50,000 to about 200,000, for example, about 60,000 to about 150,000 or about 70,000 to about 125,000. However, in some embodiments, after extensive irradiation, it is possible to have an average numerical molecular weight of less than about 10,000 or even less than about 5,000. [00261] In some embodiments, the second material may have an oxidation level ( ^T O2) that is higher than the oxidation level ( ^T O1) of the first material. A higher level of oxidation of the material can aid in its dispersibility, swelling capacity and / or solubility, further intensifying the material's susceptibility to chemical, enzymatic or biological attack. In some embodiments, to increase the level of oxidation of the second material with respect to the first material, irradiation is carried out under an oxidation environment, for example, under a current of air or oxygen, producing a second material that is more oxidized than the first material. For example, this second material can have more hydroxyl groups, aldehyde groups, ketone groups, ester groups or carboxylic acid groups, which can increase its hydrophilicity.

Lonizing radiation [00262] Each form of radiation ionizes biomass via particular interactions, as determined by the radiation energy. Heavily charged particles primarily ionize matter via Coulomb dispersion; in addition, these interactions produce energetic electrons that can further ionize matter. Alpha particles are identical to the nucleus of a helium atom and are produced by the alpha decline of several radioactive nuclei, such as isotopes of bismuth, polonium, astatin, radon, francium, radio, various actinides, such

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68/204 such as actinium, thorium, uranium, neptunium, curium, californium, americium and plutonium.

[00263] When particles are used, they can be neutral (not charged), positively charged or negatively charged. When charged, the charged particles can carry a single positive or negative charge or multiple charges, for example, one, two, three or even four or more charges. In cases where chain splitting is desired, positively charged particles may be desirable, in part, because of their acidic nature. When particles are used, the particles can have the mass of an electron at rest or greater, for example, 500, 1000, 1500 or 2000 or even more times the mass of an electron at rest. For example, particles can have a mass of about 1 atomic unit to about 150 atomic units, for example, from about 1 atomic unit to about 50 atomic units or from about 1 to about 25, for example, 1, 2, 3, 4, 5, 10, 12 or 15 amu. Acceleration used to accelerate particles can be electrostatic DC, electrodynamic DC, linear RF, linear or continuous magnetic induction wave. For example, cyclotron-type accelerators are available from IBA, Belgium, as is the Rhodotron® system, while DC-type accelerators are available from RDI, now IBA Industrial, such as Dynamitron®. Ions and ion accelerators are discussed in Introductory Nuclear Physics, Kenneth S. Krane, John Wiley & Sons, Inc. (1988), Krsto Prelec, FIZIKA B 6 (1997) 4, 177-206, a copy of which is attached as Appendix B, Chu, William T., Overview of Lightlon Beam Therapy, Columbus-Ohio, ICRU-IAEA Meeting, 18-20 March 2006, a copy of which is attached as Appendix C, Iwata, Y. et al. ., Alternating-Phase-Focusad IH-DTL for Heavy-Ion Medical Accelerators, Proceedings of EPAC 2006, Edinburgh, Scotland, a copy of which is attached as Appendix D and Leitner, CM et al.,

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69/204

Status of the Superconducting ECR lon Fonte Venus, Proceedings of EPAC 2000, Vienna, Austria, a copy of which is attached here as Appendix E.

[00264] Electrons interact via Coulomb dispersion and radiation and Bermsstrahlung produced by changes in electron speed. Electrons can be produced by radioactive nuclei that undergo beta decline, such as isotopes of iodine, cesium, technetium and iridium. Alternatively, an electron gun can be used as an electron source via thermionic emission.

[00265] Electromagnetic radiation interacts via three processes: photoelectric absorption, Compton dispersion and pair production. The dominant interaction is determined by the incident radiation energy and the atomic number of the material. The sum of the interactions that contribute to the radiation absorbed in cellulosic material can be expressed by the mass absorption coefficient.

[00266] Electromagnetic radiation is sub-classified as gamma rays, x-rays, ultraviolet rays, infrared rays, microwaves or radio waves, depending on their length.

[00267] For example, gamma radiation can be used to irradiate materials. Referring to figures 9 and 10 (an enlarged view of the R region), a gamma irradiator 10 includes sources of gamma radiation 408, for example, ⁶⁰ Co pellets, a work table 14 to contain the materials to be irradiated and storage 16 , for example, made of a plurality of iron plates, all of which are housed in a concrete containment chamber (vault) 20 that includes a maze entrance 22 behind a lead-lined door 26. Storage 16 includes a plurality of channels 30, for example, sixteen or more channels, which allow sources of gamma radiation to pass through storage on their proximal path to the work table.

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70/204 [00268] In operation, the sample to be irradiated is placed on a work table. The radiator is configured to distribute the desired dose rate and monitoring equipment is connected to an experimental block 31. The operator then leaves the containment chamber, passing through the labyrinth entrance and through the lead-lined door. The operator manipulates a control panel 32, instructing a computer 33 to raise the radiation sources 12 to the working position using a cylinder 36 attached to a hydraulic pump 40.

[00269] Gamma radiation has the advantage of a significant penetration depth in a variety of materials in the sample. Gamma ray sources include radioactive nuclei, such as isotopes of cobalt, calcium, technetium, chromium, gallium, indium, iodine, iron, krypton, samarium, selenium, sodium, butchery and xenon.

[00270] X-ray sources include electron beam collision with metal targets, such as tungsten or molybdenum or compact alloys or light sources, such as those commercially produced by Lyncean. Sources for ultraviolet radiation include deuterium or cadmium lamps. Sources for infrared radiation include sapphire, zinc or ceramic lamps with selenide elements. Microwave sources include RF sources such as Slevin, Klystrons, or atom beam sources that employ hydrogen, oxygen, or nitrogen gases.

[00271] Various other irradiation devices can be used in the methods described here, including field ionization sources, electrostatic ion separators, field ionization generators, thermionic emission sources, microwave discharge ion sources, recirculation accelerators or static, dynamic linear accelerators, van de Graaff accelerators and double random accelerators. Such devices are described, for example, in Provisional Application 870170006381, of 01/30/2017, p. 76/258

71/204 U.S. Serial No. 61 / 073,665, the complete description of which is incorporated herein by reference.

Electron Beam [00272] In some embodiments, an electron beam is used as the radiation source. An electron beam has the advantage of high dose rates (for example, 1, 5 or even 10 Mrad per second), high throughput, less containment and less containment equipment. Electron beams can also have up to 80 percent electrical efficiency, allowing for low energy consumption, which can translate into low operating costs and low greenhouse gas emissions corresponding to the small amount of energy used. Electrons can also be more efficient in causing chain fission.

[00273] In addition, electrons having energies of 4-10 MeV can have a penetration depth of 5 to 30 mm or more, such as 40 mm. In low density bulk materials, like many of the materials described in this document, for example, materials with a density of less than about 0.5 g / cm3, electrons with energy in the range of 40-10 MeV can penetrate 4-8 inches or more.

[00274] Electron beams can be generated, for example, through electrostatic generators, cascade generators, transforming generators, low-energy accelerators with a scanning system, low-energy accelerators with a linear cathode, linear accelerators and pulsed accelerators. Electrons as a source of ionizing radiation can be useful, for example, for relatively thin stacks of materials, for example, less than 0.5 inches, for example, less than 0.4 inches, 0.3 inches, 0.2 inches or less than 0.1 inch. In some embodiments, the energy of each electron in the electron beam is about 0.3 MeV to about 2.0 MeV (millions of electron volts), for example, about 0.5 MeV

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72/204 at about 1.5 MeV or from 0.7 MeV to about 1.25 MeV. [00275] Figure 11 shows a 3000 process flow chart that includes several steps in a pre-treatment sequence feed stock by electron beam irradiation. In the first step 310, a supply of dry feed stock is received from a power source. As discussed above, the dry feed stock of the power supply can be pre-processed before distribution to electron beam irradiation devices. For example, if the feed stock is derived from plant sources, certain parts of the plant material can be removed before the plant material is collected and / or before the plant material is distributed by the feed stock transport device. Alternatively or in addition, as expressed in optional step 3020, the biomass feed stock can be subjected to mechanical processing (for example, to reduce the average fiber length in the feed stock) prior to distribution to the beam irradiation devices electrons.

[00276] In step 3030, the dry feed stock is transferred to a feed stock transport device (for example, a conveyor belt) and is distributed over the cross sectional width of the feed stock transport device approximately uniform in volume. This can be achieved, for example, manually or by introducing a vibration movement located somewhere in the feed stock transport device before processing electron beam irradiation.

[00277] In step 3030, the dry feed stock is transferred to a feed stock transport device (for example, a conveyor belt) and is distributed over the cross sectional width of the stock feed devicePetition 870170006381, from 01/30/2017, p. 78/258

73/204 approximately uniformly in volume. This can be done, for example, manually or by inducing a vibration movement located at some point in the feed stock transport device before processing by electron beam irradiation.

[00278] In some embodiments, a mixing system introduces a 3045 chemical agent into the feed stock in an optional 3040 process step that produces a paste. Combining water with the feed stock processed in mixing step 3040 creates an aqueous feed stock slurry that can be transported, for example, through a pipeline instead of using, for example, a conveyor belt.

[00279] The next step 3050 is a loop that covers exposure of the feed stock (in dry or paste form) to electron beam radiation via one or more (say, N) electron beam irradiation devices. The feed stock folder is moved through each of the N electron beam showers in the step

3052. The movement can be at a continuous speed through and between the showers or there can be a pause through each shower, followed by a sudden movement to the next shower. A small part of the feed stock paste is exposed to each shower for some predetermined exposure time in the step

3053.

[00280] Electron beam irradiation devices can be commercially supplied by Ion Beam Applications, Louvain-laNeuve, Belgium or Titan Corporation, San Diego, CA. Typical electron energies can be 1 MeV, 2 MeV, 4.5 MeV, 7.5 MeV or 10 MeV. The typical energy of the electron beam irradiation device can be 1 kW, 5 kW, 10 kW, 20 kW , 50 kW, 100 kW, 250 kW or 500 kW. The efficacy of depolymerization of the food stock paste Petition 870170006381, of 01/30/2017, p. 79/258

74/204 tion depends on the electron energy used and the dose applied, while the exposure time depends on the energy and dose. Typical doses can have values of 1 kGy, 5 kGy, 10 kGy, 20 kGy, 50 kGy, 100 kGy or 200 kGy.

[00281] Impasses to consider regarding the energy specifications of the electron beam irradiation device include operating cost, financial costs, depreciation and device profile. Impasses to consider regarding dose levels of exposure to electron beam irradiation would be energy costs and concerns for the environment, safety and health (ESH). Typically, generators are housed in a vault, for example, of lead or lead-coated concrete. Impasses to consider about electron energies include energy costs; here, lower electron energy can be advantageous in encouraging depolymerization of certain food stock pastes (see, for example, Bouchard et al., Cellulose (2006) 13: 601-610).

[00282] It may be advantageous to provide a double pass of electron beam irradiation in order to confer a more efficient depolymerization process. For example, the feed stock transport device could direct the feed stock (in dry or paste form) down and in a reverse direction to its initial transport direction. Double-pass systems can allow thicker stock feed slots to be processed and can provide more uniform depolymerization through the thickness of the feed stock slurry.

[00283] The electron beam irradiation device can produce a fixed beam or a scanning beam. A scan beam can be advantageous with a long scan length and high scan speeds, as this effectively replaces a large fixed beam width. Still, scan widths available

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75/204 of 0.5 m, 1 m, 2 m or more are available.

[00284] Once a portion of the feed stock slurry has been transported through the N electron beam irradiation devices, it may be necessary, in some embodiments, as per step 3060, to mechanically separate the liquid and solid components of the slurry of food stock. In these embodiments, a liquid portion of the feed stock slurry is filtered to remove residual solid particles and recycled to the 3040 slurry preparation step. A solid portion of the feed stock slurry is then advanced to the next step processing 3070 via the feed stock transport device. In other modalities, the feed stock is kept in the form of paste for further processing.

Heavy Ion Particle Beams [00285] Particles heavier than electrons can be used to radiate carbohydrates or materials that include carbohydrates, for example, cellulosic materials, lignocellulosic materials, starch materials or mixtures of any of these and others described here. For example, protons, helium nuclei, argon ions, silicon ions, neon ions, carbon ions, phosphorus ions, oxygen ions or nitrogen ions can be used. In some embodiments, particles heavier than electrons can induce greater amounts of chain cleavage. In some cases, positively charged particles can induce greater amounts of chain cleavage than negatively charged particles due to their acidity.

[00286] Bundles of heavier particles can be generated, for example, using linear accelerators or cyclotrons. In some embodiments, the energy of each particle in the beam is about 1.0 MeV / atomic unit to about 6,000 MeV / atomic unit, for example.

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76/204 example, from about 3 MeV / atomic unit to about 4,800 MeV / atomic unit or from about 10 MeV / atomic unit to about 1,000 MeV / atomic unit.

Electromagnetic radiation [00287] In modalities in which irradiation is carried out with electromagnetic radiation, electromagnetic radiation can have, for example, energy by photons (in volts of electrons) of more than 10 ² eV, for example, more than 10 ³ , 10 ⁴ , 10 ⁵ , 10 ⁶ or even more than 10 ⁷ eV. In some embodiments, electromagnetic radiation has a photon energy of between 10 ⁴ and 10 ⁷ , for example, between 10 ⁵ and 10 ⁶ eV. Electromagnetic radiation may have a frequency, for example, greater than 10 ¹⁶ hz, greater than 10 ¹⁷ hz, 10 ¹⁸ , 10 ¹⁹ , 10 ²⁰ or even greater than 10 ²¹ hz. In some embodiments, electromagnetic radiation has a frequency of between 10 ¹⁸ and 10 ²² hz, for example, between 10 ¹⁹ to 10 ²¹ hz.

Doses [00288] In some embodiments, irradiation (with any radiation source or a combination of sources) is carried out until the material receives a dose of at least 0.05 Mrad, for example, at least 0.1 Mrad, 0 , 25, 1.0, 2.5, 5.0 or 10.0 Mrad. In some embodiments, irradiation is carried out until the material receives a dose of between 1.0 Mrad and 6.0 Mrad, for example, between 1.5 Mrad and 4.0 Mrad. In other embodiments, irradiation is carried out at a dose between about 0.1 Mrad and about 10 Mrad, for example, between about 0.25 Mrad and about 9 Mrad, between about 0.5 Mrad and about 7 , 5 Mrad or between about 0.75 Mrad and about 5 Mrad.

[00289] In some modalities, irradiation is carried out at a dose rate of between 5.0 and 1500.0 kilorads / hour, for example, between 10.0 and 750.0 kilorads / hour or between 50.0 and 350 , 0 kilorads / hours. [00290] In some modalities, two or more radiation sources

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77/204 are used, such as two or more ionizing radiation. For example, samples can be treated, in any order, with an electron beam, followed by gamma radiation and UV light having wavelengths from about 100 nm to about 280 nm. In some embodiments, the samples are treated with three sources of ionizing radiation, such as an electron beam, gamma radiation and energetic UV light. [00291] In an example of using radiation as a pretreatment, half-gallon juice packs made of unprinted poly-coated white Kraft cardboard having a volumetric density of 20 pounds / foot ³ are used as a feed stock. The packages are folded and then fed in a sequence of three shredder-shredder trays arranged in series with the output of the first shear fed as an entrance to the second shredder the output of the second shear fed as an entrance to the third shredder. The fibrous material produced by the chipper-shearer can be sprayed with water and processed through a pellet mill operating at room temperature. The densified pellets can be placed in a glass ampoule which is evacuated under high vacuum and then refilled with argon gas. The ampoule is sealed under argon. Alternatively, in another example, the ampoule is sealed under an atmosphere of air. The pellets in the ampoule are irradiated with gamma radiation for about 3 hours at a dose rate of about 1 Mrad per hour in order to provide an irradiated material in which cellulose has a lower molecular weight than the starting material. ADDITIVES TO INTENSIFY THE BREAKDOWN OF MOLECULAR WEIGHT DURING IRRADIATION [00292] In some modalities, before irradiation, various materials, for example, solid or liquid, can be added to the biomass to intensify the reduction of molecular weight. In those cases where a liquid is used, the liquid may be in contact with

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78/204 the outer surfaces of the biomass and / or the liquid may be in the inner portions of the biomass, for example, infused into the biomass. [00293] For example, the material can be a weak neutral base, such as alanine, ammonia, an ammonia / water mixture, for example, ammonia at 25 weight percent in water, water, methyl amine, dimethyl amine, trimethyl amine, pyridine or an anionic base, such as an acetic acid salt (for example, sodium acetate), sodium carbonate, sodium bicarbonate or a hydrogen sulfide ion salt (for example, sodium hydroxide) ).

[00294] Alternatively, the material may be a weak neutral acid, such as formic acid, acetic acid, trichloroacetic acid, water, hydrogen sulfide or a cationic acid, such as an ammonium salt.

Controlled Biomass Dissipation and Functionalization [00295] After treatment with one or more sources of ionizing radiation, such as photonic radiation (eg, X-rays or gamma rays), electron beam radiation or heavier electron particles that are positive or negative charged (for example, protons or carbon ions), any of the materials containing carbohydrates or mixtures described here become ionized; that is, they include radicals at levels that are detectable with an electron orbital resonance spectrometer. The current limit of detection of radicals is about 10 ¹⁴ orbitals at room temperature. After ionization, any biomass material that has been ionized can be dissipated to reduce the level of radicals in the ionized biomass, for example, so that the radicals are no longer detectable with the electron orbital resonance spectrometer. For example, radicals can be dissipated by applying sufficient pressure to the biomass and / or using a fluid in contact with the ionized biomass, such as a gas or liquid, which reacts with (dissipates)

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79/204 the radicals. The use of a gas or liquid to at least assist in the dissipation of radicals can be done to functionalize the ionized biomass with a desired number and types of functional groups, such as carboxylic acid groups, enol groups, aldehyde groups, nitro groups, nitrile groups , amino groups, alkylamino groups, alkyl groups, chloroalkyl groups or chlorofluoroalkyl groups. In some cases, such dissipation can improve the stability of some of the ionized biomass materials. For example, dissipation can improve the biomass's resistance to oxidation. Functionalization through dissipation can also improve the solubility of any biomass described here, can improve its thermal stability and can improve the use of material by different microorganisms. For example, the functional groups conferred to the biomass material by dissipation can act as receptor sites for attachment by microorganisms, for example, intensifying the hydrolysis of cellulose by various microorganisms.

[00296] Figure 11A illustrates changes in the molecular and / or supramolecular structure of a biomass feed stock through pre-treatment of the biomass feed stock with ionizing radiation, such as with sufficient electrons or ions of energy to ionize the biomass feed stock in order to provide a first level of radicals. As shown in figure 11A, if the ionized biomass remains in the atmosphere, it will be oxidized, such as to a point where the carboxylic acid groups are generated by the reaction with atmospheric oxygen. In some cases, with some materials, such oxidation is desired because it can assist in the extra decomposition of the molecular weight of the biomass containing carbohydrate and oxidation groups, for example, carboxylic acid groups, can be useful for solubility and use of microorganisms in some cases. However, since radicals can live for some

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80/204 time after irradiation, for example, more than 1 day, 5 days, 30 days, 3 months, 6 months or even more than 1 year, the properties of the materials may continue to change over time which, in some cases , may be undesirable. The detection of radicals in samples irradiated by electron orbital resonance spectroscopy and the life expectancy of radicals in such samples are discussed in Bartolotta et al., Physics in Medicine and Biology, 46 (2001), 461-471 and in Bartolotta et al., Radiation Protection Dosimetry, Vol. 84, Nos. 1-4, pages 293-296 (1999), which are incorporated into it as Appendix F and Appendix G, respectively. As shown in figure 11A, the ionized biomass can be dissipated to functionalize and / or stabilize the ionized biomass. At any point, for example, when the material is alive, partially alive or totally dissipated, the treated biomass can be converted into a product, for example, a fuel, a food or a compound.

[00297] In some embodiments, dissipation includes applying pressure to biomass, such as through mechanical deformation of biomass, for example, direct mechanical compression of biomass in one, two or three dimensions or applying pressure to a fluid in the which the biomass is immersed, for example, isostatic compression. In such cases, the deformation of the material itself maintains the radicals, which are often enclosed in crystalline domains, close enough that the radicals can recombine or react with another group. In some cases, pressure is applied along with the application of heat, such as a sufficient amount of heat to raise the temperature of the biomass above a melting point or softening point of a biomass component, such as lignin, cellulose or hemicellulose. Heat can improve molecular mobility in the polymeric material, which can assist in the dissipation of radicals. When pressure is used to

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81/204 dissipate, the pressure can be greater than about 1000 psi, such as greater than about 1250 psi, 1450 psi, 3625 psi, 5075 psi, 7250 psi, 10,000 psi or even greater than 15000 psi.

[00298] In some embodiments, dissipation includes contact of the biomass with a fluid, such as a liquid or gas, for example, a gas capable of reacting with radicals, such as acetylene or a mixture of acetylene in nitrogen, ethylene, chlorinated ethylenes or chlorofluoroethylenes, propylene or mixtures of these gases. In other particular embodiments, dissipation includes contact of the biomass with a liquid, for example, a soluble liquid or at least capable of penetrating the biomass and reaction with radicals, such as a diene, such as 1,5-cyclooctadiene. In some specific embodiments, dissipation includes contact of the biomass with an antioxidant, such as Vitamin E. If desired, the biomass feed stock may include an antioxidant dispersed in it and the dissipation may arise from contact of the antioxidant dispersed in the stock of biomass feed with radicals.

[00299] Other methods for dissipation are possible. For example, any method for dissipating radicals in polymeric materials described in Muratoglu et al., US Patent Application Publication No. 2008/0067724 and Muratoglu et al., US Patent No. 7,166,650, which are attached as Appendix H and Appendix I, respectively, can be used for the dissipation of any ionized biomass material described here. In addition, any dissipating agent (described as a sensitizing agent in the Muratoglu descriptions mentioned above) and / or any antioxidant described in any Muratoglu reference can be used to dissipate any ionized biomass material.

[00300] Functionalization can be intensified using heavy charged ions, such as any of the heavier ions. DisPetition 870170006381, from 01/30/2017, p. 87/258

82/204 written here. For example, if it is desired to intensify oxidation, charged oxygen ions can be used for irradiation. If nitrogen functional groups are desired, nitrogen ions or ions that include nitrogen can be used. Likewise, if sulfur or phosphorus groups are desired, sulfur or phosphorus ions can be used in irradiation.

[00301] In some embodiments, after dissipation, any of the dissipated ionized materials described here can be additionally treated with one or more radiation, such as ionizing or non-ionizing radiation, ultrasound, pyrolysis and oxidation to further alter the molecular structure and / or supramolecular.

Fluid Particle Beam Exposure [00302] In some cases, cellulosic or lignocellulosic materials may be exposed to a particle beam in the presence of one or more additional fluids (for example, gases and / or liquids). Exposure of a material to a particle beam in the presence of one or more additional fluids can increase the efficiency of the treatment.

[00303] In some embodiments, the material is exposed to a particle beam in the presence of a fluid such as air. Accelerated particles in any one or more of the types of accelerators described here (or another type of accelerator) are coupled outside the accelerator via an outlet orifice (for example, a thin membrane, such as a foil), pass through a volume of space taken up by the fluid and then focus on the material. In addition to direct treatment of the material, some of the particles generate additional chemical species through interaction with fluid particles (for example, ions and / or radicals generated from various constituents of the air, such as ozone and nitrogen oxides). These generated chemical species can also interact with the material and can act as initiators for a variety of different chemical bond disruption reactions 870170006381, from 01/30/2017, p. 88/258

83/204 mica in the material. For example, any oxidant produced can oxidize the material, which can result in reduced molecular weight. [00304] In certain embodiments, additional fluids can be selectively introduced into the path of a particle bundle before the bundle strikes the material. As discussed above, reactions between the beam particles and the particles of the introduced fluids can generate additional chemical species, which react with the material and can assist in the functionalization of the material and / or, otherwise, selectively alter certain material properties. The one or more additional fluids can be directed to the beam path from a supply tube, for example. The direction and flow rate of the fluid (s) that is / are being introduced can be selected according to the desired exposure rate and / or direction to control the overall treatment efficiency, including effects that result from particle-based treatment and effects that are due to the interaction of species dynamically generated from the fluid introduced with the material. In addition to air, exemplary fluids that can be introduced into the ion beam include oxygen, nitrogen, one or more noble gases, one or more halogens and hydrogen.

Irradiation of Low Volumetric Density Biomass Materials and Cooling of Irradiated Biomass [00305] During treatment of biomass materials with ionizing radiation, especially at high dose rates, such as at rates greater than 0.15 Mrad per second, for example 0.25 Mrad / s, 0.35 Mrad / s, 0.5 Mrad / s, 0.75 Mrad / s or even greater than 1 Mrad / sec, biomass materials can retain significant amounts of heat, so that the temperature of biomass materials becomes high. Although higher temperatures can, in some modalities, be advantageous, for example, when a reaction rate 870170006381, of 01/30/2017, p. 89/258

84/204 faster reaction is desired, it is advantageous to control the heating of biomass to retain control over chemical reactions initiated by ionizing radiation, such as crosslinking, chain splitting and / or grafting, for example, to maintain process control. Low volumetric density materials, such as those having a volumetric density of less than about 0.4 g / cm ³ , for example, less than about 0.35, 0.25 or less about 0.15 g / cm ³ , especially when combined with materials that have thin cross sections, such as fibers having small cross dimensions, are generally easier to cool. In addition, photons and particles can, in general, penetrate into and through materials having a relatively low volumetric density, which can allow the processing of larger volumes of materials at higher rates and can allow the use of photons and particles having lower energies. , for example, 0.25 Mev, 0.5 MeV, 0.75 MeV or 1.0 MeV, which can reduce security protection requirements. Many of the biomass materials described here can be processed in one or more of the systems shown in figures 11B, 11C, 11D and 11E, which are described below. The systems shown allow one or more types of ionizing radiation, such as relativistic electrons or electrons in combination with X-rays, to be applied to low volume density biomass materials at high dose rates, such as at a rate greater than 1 , 0, 1.5, 2.5 Mrad / s or even greater than about 5.0 Mrad / s, then allows biomass cooling before radiation application a second, third, fourth, fifth, sixth, seventh , eighth, ninth or even a tenth time.

[00306] For example, in a method of changing the molecular and / or supramolecular structure of a biomass feed stock, the biomass is pre-treated at a first temperature with ionizing radiation, such as photons, electrons or ions (for example , petition 870170006381, of 01/30/2017, page 90/258

85/204 tions or anions with single or multiple charge), for a sufficient time and / or a sufficient dose to raise the biomass feed stock to a second temperature higher than the first temperature. The pre-treated biomass is then cooled to a third temperature below the second temperature. Finally, if desired, cold biomass can be treated with radiation one or more times, for example, with ionizing radiation. If desired, cooling can be applied to the biomass after and / or during each radiation treatment.

[00307] The biomass feed stock can be physically prepared as discussed above, for example, by reducing one or more dimensions of individual parts of the biomass feed stock, so that the feed stock can be more efficiently processed, for example, more easily cooled and / or more easily penetrated by ionizing radiation. [00308] In some implementations, ionizing radiation is applied at a total dose of less than 25 Mrad or less than 10 Mrad, such as less than 5 Mrad or less than 2.5 Mrad and at a rate of more than 0.25 Mrad per second, such as more than 0.5, 0.75 or more than 1.0 Mrad / s, before biomass cooling.

[00309] Pre-treatment of the biomass feed stock with ionizing radiation can be carried out as the biomass feed stock is being pneumatically transported in a fluid, such as a gas, for example, nitrogen or air. To assist in the decomposition of molecular weight and / or functionalization of materials, the gas can be saturated with any swelling agent described here and / or water vapor. For example, acidic water vapor can be used. To aid in the decomposition of molecular weight, the water can be acidified with an organic acid, such as formic or acetic acid or a mineral acid, such as sulfuric acid

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86/204 or hydrochloric.

[00310] The pre-treatment of the biomass feed stock with ionizing radiation can be carried out as the biomass feed stock falls under the influence of gravity. This procedure can effectively reduce the volumetric density of the biomass feed stock as it is being processed and can assist in cooling the biomass feed stock. For example, biomass can be transported from a first belt at a first height above the ground and then it can be captured by a second belt at a second level above the ground that is smaller than the first level. For example, in some embodiments, the rear edge of the first belt and the front edge of the second belt define a gap. Advantageously, ionizing radiation, such as a beam of electrons, protons or other ions, can be applied to the gap to prevent damage to the biomass transport system.

[00311] Cooling of biomass can include contact of biomass with a fluid, such as a gas, at a temperature below the first or second temperature, such as nitrogen gas at or about 77 K. Even water, such as water at a temperature below the nominal ambient temperature (for example, 25 degrees Celsius) can be used.

[00312] Often, advantageously, the biomass feed stock has internal fibers and, before irradiation with ionizing radiation, the biomass feed stock was sheared to a point where its internal fibers are substantially exposed. This shear can provide a material with low volumetric density having small cross-sectional dimensions, which can assist in the rupture and / or functionalization of biomass. For example, in some modalities, biomass is or includes distinct fibers

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87/204 and / or particles having a maximum dimension of no more than about 0.5 mm, such as no more than about 0.25 mm, no more than about 0.1 mm or no more than than about 0.05 mm.

[00313] In some embodiments, the biomass feed stock to which ionizing radiation is applied has a volumetric density of less than about 0.35 g / cm ³ , such as less than about 0.3, 0.25 , 0.20 or less than about 0.15 g / cm ³ during the application of ionizing radiation. In such modalities, the biomass feed stock can be cooled and then ionizing radiation can be applied to cold biomass. In some advantageous embodiments, the biomass feed stock is or includes distinct fibers and / or particles having a maximum dimension of no more than about 0.5 mm, such as no more than about 0.25 mm, no more than about 0.1 mm, no more than about 0.05 mm or no more than about 0.025 mm.

[00314] Figures 11B and 11C show a device for generation, treatment, transport and irradiation of biomass material 1170 (protection not shown in the drawings). In operation, a sheet of 1173 paper, for example, bleached Kraft paper sheet, is supplied to a roll 1172 and distributed to a fiber forming apparatus 1174, such as a rotary shear. The sheet 1173 is converted to fibrous material 1112 and is distributed to a fiber loading zone 1180 by the conveyor 1178. If desired, the fibers of the fibrous material can be separated, for example, by sorting, into fractions having different proportions of L / D. In some embodiments, fibrous material 1112, generally of low volumetric density and, advantageously, thin cross sections, is distributed continuously to zone 1180 and, in other embodiments, the fibrous material is distributed in batches. A blower 1182 in loop 1184 is positioned adjacent to the 1180 fiber loading zone and is capable of moving 870170006381, from 01/30/2017, p. 93/258

88/204 of a fluid medium, for example, air, at a speed and volume sufficient to pneumatically circulate the fibrous material 1112 in a direction indicated by arrow 1188 through loop 1184.

[00315] In some modalities, the air velocity that travels in the loop is sufficient to uniformly disperse and transport the fibrous material around the entire 1184 loop. In some modalities, the flow velocity is greater than 2,500 feet / minute, for example, 5,000 feet / minute, 6,000 feet / minute or more, for example, 7,500 feet / minute or 8,500 feet / minute.

[00316] The fibrous material enclosed 1112 across the loop passes to an application zone 1190, which forms part of loop 1184. Here, any desired additives described here can be applied, such as a liquid, such as water, such as water acidified or basic. In operation, application zone 1190 applies an additive, such as a liquid solution 1196, to the fibrous material in circulation via nozzles 98, 99 and 11100. When a liquid is applied, the nozzles produce an atomized spray or mist, which collides with the fibers passing in close proximity to the nozzles. The 11102 valve is operated to control the flow of liquid to the respective nozzles 1198, 1199 and 11100. After a desired amount of additive is applied, the 11102 valve is closed.

[00317] In some embodiments, application zone 1190 is two to one hundred feet long or more, for example, 125 feet, 150 feet, 250 feet long or more, for example, 500 feet long. Longer application zones allow for a longer period of time during the passage of the fibrous material through the 1190 application zone. In some embodiments, the nozzles are spaced from about three to about four feet in length of the 1184 loop.

[00318] As the fibrous material moves in loop 1184 and

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89/204 through the irradiation portion of loop 11107 which includes the antenna in the form of horn 11109 for ionizing radiation distribution, ionizing radiation is applied to the fibrous material (protection is not shown).

[00319] As the irradiated fibrous material moves around loop 1184, it cools by the action of gases, such as air, which circulate at high speeds in the loop and is bathed in reactive gases, such as ozone and / or oxides nitrogen, which are produced by the action of ionizing radiation on circulating gases, such as air. After passing through the irradiation portion 11107, a cooling fluid, such as a liquid (for example, water) or a gas, such as 77 K liquid nitrogen, can be injected into loop 1184 to assist in cooling the fibrous material. This process can be repeated more than once if desired, for example 2, 3, 4, 5, 6, 7, 8, 9, 10 times or more, for example, 15 times, to distribute the desired dose to the fibrous material . Although, as shown, the long axis of the horn antenna is along the flow direction, in some implementations, the long axis of the horn antenna is transversal to the flow direction. In some implementations, an electron beam is used as the main source of ionizing radiation and X-rays as a source of secondary ionizing radiation. X-rays can be generated by having a metallic target, such as a tantalum target 11111, over the inside of loop 1184 so that when electrons collide on the target, X rays are emitted.

[00320] After a desired dose is distributed to the fibrous material, the fibrous material can be removed from 1184 via a separator 11112, which is selectively connected to loop 1184 through section 11114 and gate valve 11116. When valve 11116 is opened , another valve is also opened to allow air to enter the loop 1184 to compensate for the air leaving the separator 11112.

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90/204 [00321] Figure 11D shows a fibrous fluid bed irradiation device 11121 with protection. The fibrous material in a fluid, such as a gas, such as air under pressure, is distributed to a protected containment vessel 11123 via a 11125 pipeline and to a protected fluidized bed portion 11127. Counter current currents 11131 such as such as a gas and fluid 11133 cross-currents, such as a gas, which is the same or different from a distributed fluid countercurrent, combine to cause turbulence in the bed portion. Ionizing radiation is applied to the fluidized bed portion as the fibrous material is transported through the bed portion. For example, as shown, three electron beams from three Rhodotron® 11135, 11136 and 11137 machines can be used. Advantageously, each beam can penetrate the fluidized bed to a different depth and / or each beam can emit electrons of a different energy, such as 1, 3 and 5 MeV. As the fibrous material moves through the system, it cools down action of gases, such as air, circulating at high speeds in the system and is bathed in reactive gases, such as ozone and / or nitrogen oxides, which are produced by the action of ionizing radiation on circulating gases, such as air. If desired, the process can be repeated a desired number of times, until the fibrous material has received a desired dose. Although the fluidized bed has been illustrated so that its long axis is horizontal on the ground, in other implementations, the long axis of the bed is perpendicular to the ground, so that the fibrous material falls under the influence of gravity.

[00322] Figure 11E shows another device for transporting and irradiating fibrous material 11140 without protection. Fibrous material 11144 is distributed from a container 11142 to a first conveyor 11150 on a first level above the ground and then the material is transferred to a second conveyor 11152 at a height of 870170006381, from 01/30/2017, p. . 96/258

91/204 nor than the first carrier. The rear edge 11160 of the first conveyor and the front edge 11161 of the second conveyor 11152 define a gap with an S spacing. For example, the S spacing can be between 4 inches and about 24 inches. Material 11144 has enough momentum to fall freely under gravity and then be captured by the second conveyor 11152 without falling into the gap. During free fall, ionizing radiation is applied to the material. This configuration can be advantageous in the fact that ionizing radiation is less likely to damage the transport system because it is not directly contacted by the radiation.

[00323] After passing through the irradiation portion, a cooling fluid, such as a liquid (for example, water) or a gas, such as 77 K nitrogen liquid, can be applied to the material to assist in cooling the fibrous material . This process can be repeated more than once if desired, for example 2, 3, 4, 5, 6, 7, 8, 9, 10 times or more, for example, 15 times, to distribute the desired dose to the fibrous material . Although, as shown, the long axis of the horn antenna is transverse to the direction of flow of the material, other beam arrangements are possible. In some implementations, an electron beam is used as a source of primary ionizing radiation and X-rays as a source of secondary ionizing radiation. X-rays can be generated by having a metallic target, such as a tantalum target, in the gap on the opposite side of the material, so that electrons pass through the material as they collide with the target, generating X-rays.

ULTRASOUND AND OTHER BIOMASS BREAKING PROCESSES [00324] One or more ultrasound processing sequences can be used to process the raw feed stock from a wide variety of different sources to extract substances

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92/204 useful from the feed stock and in order to provide a partially degraded organic material, which acts as input for other steps and / or processing sequences. Ultrasound can reduce the molecular weight and / or crystallinity of the feed stock, such as one or more of any of the biomass materials described here, for example, one or more carbohydrate sources, such as cellulosic or lignocellulosic materials or starch materials .

[00325] Referring again to figure 8, in a method, a first material 2 that includes cellulose having a first numerical average molecular weight ( ^T MN1) is dispersed in a medium, such as water and subjected to ultrasound and / or otherwise cavitated, in order to provide a second material 3 which includes cellulose having a second average numerical molecular weight ( ^T MN2) less than the first average numerical molecular weight. The second material (or the first and second materials in certain embodiments) can be combined with a microorganism (for example, a bacterium or yeast) that can use the second and / or first material to produce a fuel 5 which is or includes hydrogen, an alcohol, an organic acid, a hydrocarbon or mixtures of any of these.

[00326] Since the second material has cellulose having a reduced molecular weight in relation to the first material and, in some cases, reduced crystallinity as well, the second material is, in general, more dispersible, swelling and / or soluble in a solution containing the microorganism, for example, at a concentration of more than 10 ⁶ microorganisms / mL. These properties make the second material 3 more susceptible to chemical, enzymatic and / or microbial attack compared to the first material 2, which can greatly improve the production rate and / or production level of a desired product, for example, ethanol. Ultrasound can also sterilize the materials, but it should not be used while the

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93/204 microorganisms are alive.

[00327] In some embodiments, the second average numerical molecular weight ( ^t MN2) is less than the first average numerical molecular weight ( ^t MN1) by more than about 10 percent, for example, 15, 20, 25, 30 , 35, 40, 50 percent, 60 percent or even more than about 75 percent.

[00328] In some cases, the second material has cellulose which has a crystallinity ( ^T C2) that is less than the crystallinity ( ^T C1) of the cellulose of the first material. For example, ( ^T C2) can be less than ( ^T C1) by more than about 10 percent, for example, 15, 20, 25, 30, 35, 40 or even more than about 50 percent.

[00329] In some embodiments, the initial crystallinity index (before ultrasound) is about 40 to about 87.5 percent, for example, about 50 to about 75 percent or about 60 to about 70 percent and a crystallinity index after ultrasound is about 10 to about 50 percent, for example, about 15 to about 45 percent or about 20 to about 40 percent. However, in certain modalities, for example, after extensive ultrasound, it is possible to have a crystallinity index of less than 5 percent. In some embodiments, the material, after ultrasound, is substantially amorphous.

[00330] In some modalities, the initial average numerical molecular weight (before ultrasound) is about 200,000 to about 3,200,000, for example, from about 250,000 to about 1,000,000 or from about 250,000 to about 700,000 and the average numerical molecular weight after ultrasound is about 50,000 to about 200,000, for example, from about 60,000 to about 150,000 or from about 70,000 to about 125,000, however, in some embodiments, for example, after extensive ultrasound, it is possible to have an average numerical molecular weight of less than about 10,000 or even less than

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94/204 about 5,000.

[00331] In some embodiments, the second material may have an oxidation level ( ^T O2) that is higher than the oxidation level ( ^T O1) of the first material. The higher level of oxidation of the material can aid in its dispersibility, swelling capacity and / or solubility, further intensifying the susceptibility of the materials to chemical, enzymatic or microbial attack. In some embodiments, to increase the level of oxidation of the second material in relation to the first material, ultrasound is performed in an oxidation medium, producing a second material that is more oxidized than the first material. For example, the second material may have more hydroxyl groups, aldehyde groups, ketone groups, ester groups or carboxylic acid groups, which can increase its hydrophilicity.

[00332] In some modalities, the ultrasound medium is an aqueous medium. If desired, the medium can include an oxidizer, such as a peroxide (for example, hydrogen peroxide), a dispersing agent and / or a buffer. Examples of dispersing agents include ionic dispersing agents, for example, sodium lauryl sulfate and non-ionic dispersing agents, for example, (poly) ethylene glycol.

[00333] In other modalities, the ultrasound medium is non-aqueous. For example, ultrasound can be performed on a hydrocarbon, for example, toluene or heptane, an ether, for example, diethyl ether or tetrahydrofuran or even on a liquefied gas, such as argon, xenon or nitrogen.

[00334] Without wishing to be bound by any particular theory, it is believed that ultrasound breaks bonds in the cellulose by creating bubbles in the medium containing the cellulose, which grow and then collapse violently. During the bubble's collapse, which can occur in less than a nano-second, the implosive force raises the local temperature inside the bubble to about 5100 K (still

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95/204 higher in some cases; see, for example, Suslick et al., Nature 434, 52-55) and generate pressures from a few hundred atmospheres to more than 1000 atmospheres or more. It is these high temperatures and pressures that break the connections. Furthermore, without wishing to be bound by any particular theory, it is believed that reduced crystallinity arises, at least in part, from extremely high cooling rates during bubble collapse, which can be greater than about 10 ¹¹ K /second. The high cooling rates do not, in general, allow the cellulose to organize and crystallize, resulting in materials that have reduced crystallinity. Ultrasonic and sonochemical systems are discussed, for example, in Olli et al., US Patent No. 5,766,764; Roberts, US Patent No. 5,828,156; Mason, Chemistry with Ultrasound, Elsevier, Oxford, (1990); Suslick (editor), Ultrasound: its Chemical, Physical and Biological Effects, VCH, Weinheim, (1988); Price, Current Trends in Sonochemistry Royal Society of Chemistry, Cambridge, (1992); Suslick et al., Ann. Rev. Mater. Sci. 29, 295, (1999); Suslick et al., Nature 353, 414 (1991); Hiller et al .., Phys. Rev. Lett. 69, 1182 (1992); Barber et al., Nature, 352, 414 (1991); Suslick et al., J. Am. Chem. Soc., 108, 5641 (1986); Tang et al., Chem. Comm., 2119 (2000); Wang et al., Avanced Mater., 12, 1137 (2000); Landau et al., J. of Catalysis, 201, 22 (2001); Perkas et al., Chem. Comm., 988 (2001); Nikitenko et al., Angew. Chem. Inter. Ed. (December 2001); Shafi et al., J. Phys. Chem B 103, 3358 (1999); Avivi et al., J. Amer. Chem. Soc. 121, 4196 (1999); and Avivi et al., J. Amer. Chem. Soc. 122, 4331 (2000).

Ultrasound systems [00335] Figure 12 shows a general system in which a stream of cellulosic material 1210 is mixed with a stream of water 1212 in a reservoir 1214 to form a process stream 1216. A first pump 1218 draws process stream 1216 of

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96/204 reservoir 1214 and toward a flow cell 1224. Ultrasonic transducer 1226 transmits ultrasonic energy to process stream 1216 as the process stream flows through flow cell 1224. A second pump 1230 extracts process current 1216 from flow cell 1224 and towards further processing.

[00336] Reservoir 1214 includes a first inlet 1232 and a second inlet 1234 in fluid communication with a volume 1236. A conveyor (not shown) distributes the stream of cellulosic material 1210 to reservoir 1214 through the first inlet 1232. The current of water 1212 enters reservoir 1214 through the second inlet 1234. In some embodiments, the water stream 1212 enters volume 1236 along a tangent that establishes a turbulent flow within volume 1236. In certain embodiments, the stream of cellulosic material 1210 and the water stream 1212 can be introduced into volume 1236 along opposite axes, intensifying the mixing within the volume.

[00337] Valve 1238 controls the flow of water current 1212 through the second inlet 1232 to produce a desired proportion of cellulosic material to water (e.g., cellulosic material approximately 10%, weight by volume). For example, 2000 tonnes / day of cellulosic material can be combined with 1 million to 1.5 million gallons / day, for example, 1.25 million gallons / day, of water.

[00338] Mixture of cellulosic material and water in reservoir 1214 is controlled by the size of volume 1236 and the flow rates of cellulosic material and water in the volume. In some embodiments, volume 1236 is sized to create a minimum mixing residence time for cellulosic material and water. For example, when 2000 tonnes / day of cellulosic material and 1.25 million gallons / day of

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97/204 water has to flow through reservoir 1214, volume 1236 can be about 32,000 gallons to produce a minimum mixing residence time of about 15 minutes.

[00339] Reservoir 1214 includes a mixer 1240 in fluid communication with volume 1236. Mixer 1240 shakes the contents of volume 1236 to disperse cellulosic material throughout the water in the volume. For example, mixer 1240 can be a rotating fin arranged in reservoir 1214. In some embodiments, mixer 1240 disperses the cellulosic material substantially evenly throughout the water.

[00340] Reservoir 1214 also includes an outlet 1242 in fluid communication with volume 1236 and process stream 1216. The mixture of cellulosic material and water in volume 1236 flows out of reservoir 1214 via outlet 1242. Exit 1242 it is arranged near the bottom of reservoir 1214 to allow gravity to push the mixture of cellulosic material and water out of reservoir 1214 and into process stream 1216.

[00341] The first 1218 pump (for example, any of the several recessed propellant swirl pumps made by Essco Pumps & Controls, Los Angeles, California) moves the contents of process stream 1216 towards flow cell 1224. In some embodiments, the first pump 1218 agitates the contents of process stream 1216, so that the mixture of cellulosic material and water is substantially uniform at inlet 1220 of flow cell 1224. For example, the first pump 1218 agitates the flow of process 1216 to create a turbulent flow that persists along the process stream between the first pump and inlet 1220 of flow cell 1224.

[00342] Flow cell 1224 includes a reactor volume 1244 in fluid communication with inlet 1220 and outlet 1222. In some case 870170006381, of 30/01/2017, pg. 103/258

98/204 but modalities, the volume of the 1244 reactor is a stainless steel tube capable of withstanding high pressures (for example, 10 bars). In addition or alternatively, the volume of the 1244 reactor includes a circular cross section.

[00343] Flow cell 1224 further includes a heat exchanger 1246 in thermal communication with at least a portion of the reactor volume 1244. Cooling fluid 1248 (eg water) flows into heat exchanger 1246 and absorbs the heat generated when process stream 1216 is subjected to ultrasound in the volume of reactor 1244. In some embodiments, the flow rate and / or temperature of cooling fluid 1248 to heat exchanger 1246 is controlled to maintain an approximately constant temperature in the volume of the reactor 1244. In some embodiments, the volume temperature of reactor 1244 is maintained at 20 to 50 ° C, for example, 25, 30, 35, 40 or 45 ° C. In addition or alternatively, heat transferred to the cooling fluid 1248 from reactor volume 1244 can be used in other parts of the overall process.

[00344] An adapter section 1226 creates fluid communication between the volume of the reactor 1244 and a voltage amplifier 1250 coupled (for example, mechanically coupled using a flange) to the ultrasonic transducer 1226. For example, the adapter section 1226 may include a flange and O-ring assembly arranged to create a leak-tight connection between the 1244 reactor volume and the 1250 voltage amplifier. In some embodiments, the 1226 ultrasonic transducer is a high power ultrasonic transducer manufactured by Hielscher Ultrasonics of Teltow, Germany.

[00345] In operation, a 1252 generator distributes electricity to the 1252 ultrasonic transducer. The 1226 ultrasonic transducer includes a piezoelectric element that converts electrical energy into sound in the ultrasonic range. In some modalities, the materials are subjected to

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99/204 ultrasound using sound having a frequency of about 16 kHz to about 110 kHz, for example, about 18 kHz to about 75 kHz or about 20 kHz to about 40 kHz (for example, sound having a frequency from 20 kHz to 40 kHz). In some implementations, ultrasound is performed, for example, at a frequency of between about 15 kHz and about 25 kHz, such as between about 18 kHz and 22 kHz. In specific modalities, ultrasound can be performed using a horn antenna of 1 KW or larger, for example, a horn antenna of 2, 3, 4, 5 or even 10 KW.

[00346] The ultrasonic energy is then distributed to the working medium through the 1248 voltage amplifier.

[00347] The ultrasonic energy traveling through the voltage amplifier 1248 in the volume of the reactor 1244 creates a series of compressions and rarefactions in a process current 1216 with an intensity sufficient to create cavitation in the process current 1216. Cavitation disaggregates the material cellulosic dispersed in process stream 1216. Cavitation also produces free radicals in the water of process stream 1216. These free radicals act to further decompose cellulosic material in process stream 1216.

[00348] In general, 5 to 4000 MJ / m ³ , for example, 10, 25, 50, 100, 250, 500, 750, 1000, 2000 or 3000 MJ / m ³ , of ultrasonic energy are applied to the current of process 16 that flows at a rate of about 0.2 m ³ / s (about 3200 gallons / min). After exposure to ultrasonic energy in reactor volume 1244, process stream 1216 leaves flow cell 1224 through outlet 1222. Second pump 1230 moves process stream 1216 for further processing (for example, any of several whirlwind with recessed thrusters made by Essco Pump & Controls, Los Angeles, California).

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100/204 [00349] Although certain modalities have been described, other modalities are possible.

[00350] As an example, although process stream 1216 has been described as a single flow path, other configurations are possible. In some embodiments, for example, process stream 1216 includes multiple parallel flow paths (for example, which flow at a rate of 10 gallons / min). In addition or alternatively, the multiple parallel flow paths of process stream 1216 flow to separate cells and are subjected to ultrasound in parallel (for example, using a plurality of 16 kW ultrasonic transducers).

[00351] As another example, although a single 1226 ultrasonic transducer has been described as being coupled to flow cell 1224, other configurations are possible. In some embodiments, a plurality of ultrasonic transducers 1226 are arranged in a flow cell 1224 (for example, ten ultrasonic transducers can be arranged in a flow cell 1224). In some embodiments, the sound waves generated by each of the plurality of ultrasonic transducers 1226 are synchronized (for example, synchronized out of phase with each other) to intensify the cavitation acting on the process current 1216.

[00352] As another example, although a single flow cell 1224 has been described, other configurations are possible. In some embodiments, the second pump 1230 moves the process current to a second flow cell where a second voltage amplifier and ultrasonic transducer additionally subject the process current 1216 to ultrasound.

[00353] As yet another example, although reactor volume 1244 has been described as a closed volume, reactor volume 1244 is open to ambient conditions in certain modes. Petition 870170006381, of 01/30/2017, p. 106/258

101/204 activities. In such modalities, pre-treatment with ultrasound can be performed substantially simultaneously with other pre-treatment techniques. For example, ultrasonic energy can be applied to process current 1216 in reactor volume 1244 while electron beams are simultaneously introduced into process current 1216.

[00354] As another example, although a continuous flow process has been described, other configurations are possible. In some modalities, ultrasound can be performed in a batch process. For example, a volume can be filled with a 10% (weight by volume) mixture of cellulosic material in water and exposed to sound with an intensity of about 50 W / cm ² to about 600 W / cm ² , for example , from about 75 W / cm ² to about 300 W / cm ² or from about 95 W / cm ² to about 200 W / cm ² . In addition or alternatively, the mixture in volume can be subjected to ultrasound for about 1 hour to about 24 hours, for example, about 1.5 hours to about 12 hours or about 2 hours to about 10 hours . In certain embodiments, the material is subjected to ultrasound for a predetermined time and then left to rest for a second predetermined time before ultrasound again. [00355] Referring now to figure 13, in some modalities, two electro-acoustic transducers are mechanically coupled to a single antenna in the shape of a horn. As shown, a pair of piezoelectric transducers 60 and 62 are coupled to a horn antenna with a slotted bar 64 via respective intermediate coupling horn antennas 70 and 72, the latter being also known as antenna shaped antennas. voltage amplification horn. The vibrations provided by the transducers, responsive to the high frequency electrical energy applied to them, are transmitted to the respective antennas in the form of

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102/204 coupling horn, which can be constructed to provide a mechanical gain, such as a 1 to 1.2 ratio. Horn antennas are provided with respective mounting flanges 74 and 76 to support the horn transducer and antenna assembly in a stationary housing.

[00356] The vibrations transmitted from the transducers through the antenna in the form of a coupling horn or voltage amplifier are coupled to the entrance surface 78 of the antenna in the shape of a horn and are transmitted, through the antenna in the shape of a horn, to the surface of oppositely located outlet 80 which, during operation, is in forced fit with a workpiece (not shown) to which the vibrations are applied.

[00357] The high frequency electrical energy supplied by the power supply 82 is fed to each of the transducers, electrically connected in parallel, via an equilibrium transformer 84 and a respective series of capacitors 86 and 90 connected, one capacitor connected in series with the electrical connection to each of the transducers. The balance transformer is also known as a balun, meaning unity of balance. The balance transformer includes a magnetic core 92 and a pair of identical windings 94 and 96, also called the primary winding and the secondary winding, respectively.

[00358] In some embodiments, the transducers include commercially available piezoelectric transducers, such as Branson Ultrasonics Corporation models 105 or 502, each designed for operation at 20 kHz and a maximum power rating of 3 kW. The power voltage for providing maximum moving excursion to the surface resulting from the transducer is 930 volts rms. The current flow through the transducer can vary between zero and 3.5 amps, depending on the load impedance. At 930 volts rms, the result movementPetition 870170006381, of 01/30/2017, p. 108/258

103/204 tant is approximately 20 microns. The maximum difference in terminal voltage for the same range of motion, therefore, can be 186 volts. Such a difference in voltage can give rise to large circulation currents that flow between the transducers. The balance unit 430 ensures a balanced condition by providing an equal current flow through the transducers, thereby eliminating the possibility of circulating currents. The wire size of the windings must be selected for the full load current mentioned above and the maximum voltage that appears through a winding input is 93 volts.

[00359] Although the 1226 ultrasonic transducer has been described as including one or more active piezoelectric elements to create ultrasonic energy, other configurations are possible. In some embodiments, the 1226 ultrasonic transducer includes active elements made from other types of magneto-restrictive materials (for example, ferrous metals). The design and operation of such a high power ultrasonic transducer are discussed in Hansen et al., U.S. Patent No. 6,624,539. In some embodiments, ultrasonic energy is transferred to the process stream 16 via an electro-hydraulic system.

[00360] Although the 1226 ultrasonic transducer has been described as using the electromagnetic response of magnetorestructive materials to produce ultrasonic energy, other configurations are possible. In some embodiments, acoustic energy in the form of an intense shock wave can be applied directly to the process stream 16 using a submerged purge. In some embodiments, ultrasonic energy is transferred to the process stream 16 via a thermo-hydraulic system. For example, high energy density acoustic waves can be produced by applying power through a closed volume of electrolyte,

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104/204 thereby heating the closed volume and producing an elevation of pressure which is subsequently transmitted via sound propagation medium (for example, process current 1216). The design and operation of such a thermo-hydraulic transducer are discussed in Hartmann et al., U.S. Patent 6,383,152.

[00361] Some modalities use a high frequency rotor-stator device can be used. This type of device produces high shear microcavitation forces, which can disintegrate the biomass in contact with such forces. Two commercially available high frequency rotor-stator devices are Supraton ^TM devices manufactured by Krupp Industrietechnik GmbH and marketed by Dorr-Oliver Deutschland GmbH of Connecticut and Dispax ^TM devices manufactured and marketed by IkaWorks, Inc. of Cincinnati, Ohio. The operation of such a microcavitation device is discussed in Stuart, US Patent No. 5,370,999.

[00362] In another biomass rupture technique, microwave or radio wave energy is applied to a treated or untreated biomass material, such as a lignocellulosic material, in a way that the water within the biomass material is vaporized but , in general, the biomass material over little volumetric heating. For example, a frequency from about 10 MHz to about 300,000 MHz can be applied to the biomass material. In some cases, microwave or radio wave energy is applied in short pulses, for example, having a duration of less than 0.1 second, for example, less than 0.05 seconds, less than 0.03 seconds, less 0.01 seconds or even less, for example, 0.005 seconds. Without wishing to be trapped by any particular theory, it is believed that when microwave or radio wave energy is applied in this way, water is vaporized into the biomass material with explosive force, which breaks down the lignin and flakes of the cellulose.

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105/204

At the same time, since application of such energy does not heat the dense material, lignin does not tend to be re-applied to cellulose, which could block access to cellulose, for example, by an enzyme or microbe. Many of the properties of lignin are described by Carter Fox in a thesis entitled Chemical and Thermal Characterization of Three Industrial Lignin and Their Corresponding Esters (May 2006, University of Idaho).

[00363] In another biomass rupture technique, treated biomass material (for example, using any treatment method described here) is subjected to a compressed, hot fluid, such as water. In such a method, the biomass is placed in a pressure vessel containing a fluid, such as water, at an elevated temperature, for example, above 50, 60, 70, 80, 90, 100, 110, 120, 130, 140 , 150, 160, 170 or above 180 ° C. The pressure vessel is placed under pressure of a gas, such as under argon, nitrogen or air and then stirred, for example, with a two-blade turbine propeller for a period of time, for example, 10 minutes, 20 minutes, 30 minutes, 45 minutes, 60 minutes or 90 minutes. In some embodiments, the pressure is between about 500 psig and 2000 psig, for example, between about 650 psig and about 1500 psig or between about 700 psig and about 1200 psig. In some embodiments, the temperature is at 5 or 10 ° C above the transition temperature from glass to lignin. Without wishing to be trapped by any particular theory, it is believed that when the temperature is above the transition temperature of the lignin glass, the conditions in the pressure vessel cause the lignin to peel off the cellulose, making the cellulose more exposed to disruption, for example, by an enzyme.

[00364] In another biomass rupture technique, treated biomass material, for example, irradiated or untreated is distributed to a defined narrowing between two pressure counter rolls Petition 870170006381, of 30/01/2017, p. 111/258

106/204 rotary, which can be optionally heated. The nip pressure can be adjusted by the amount of biomass material fed to the nip and the spacing between the pressure rollers. In some embodiments, the narrowing pressure may be greater than 1,000 psi per linear inch, for example, greater than 2,500 psi, greater than 5,000 psi, greater than 7,500 psi, greater than 10,000 psi or even greater than 15,000 psi per linear inch. In some embodiments, the pressure rollers are operated at an elevated temperature, for example, above 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170 or above 180 ° Ç. In some embodiments, the rollers are operated at a temperature above a transition temperature of the lignin glass. Without wishing to be trapped by any particular theory, it is believed that the pressure and heat in the narrowing can disrupt any lignin in the biomass material, making cellulose more accessible and available to an enzyme.

PYROLYSIS [00365] One or more pyrolysis processing sequences can be used to process the raw feed stock from a wide variety of different sources to extract useful substances from the feed stock and provide a partially degraded organic material which as input to others processing steps and / or sequences.

[00366] Referring again to such a general scheme in figure 8, a first material 2 that includes cellulose having a first numerical average molecular weight ( ^T MN1), undergoes pyrolysis, for example, by heating the first material in a pipe lathe in order to provide a second material 3 which includes cellulose having a second average numerical molecular weight ( ^T MN2) less than the first average numerical molecular weight. The second material (or the priPetition 870170006381, of 01/30/2017, page 112/258

107/204 first and second materials in certain modalities) is / are combined ^) with a microorganism (for example, a bacterium or a yeast) that can use the second and / or first material to produce a fuel 5 that is or includes hydrogen, an alcohol (for example, ethanol or butanol, such as n-, sec- or tert-butanol), an organic acid, a hydrocarbon or mixtures of any of these.

[00367] Since the second material has cellulose having a reduced molecular weight in relation to the first material and, in some cases, a reduced crystallinity as well, the second material is, in general, more dispersible, swelling and / or soluble in a solution containing the microorganism, for example, at a concentration of more than 10 ⁶ microorganisms / mL. These properties make the second material 3 more susceptible to chemical, enzymatic and / or microbial attack compared to the first material 2, which can greatly improve the production rate and / or production level of a desired product, for example, ethanol. Pyrolysis can also sterilize the first and second materials.

[00368] In some embodiments, the second average numerical molecular weight ( ^T MN2) is less than the first average numerical molecular weight ( ^T MN1) by more than about 10 percent, for example, 15, 20, 25, 30 , 35, 40, 50 percent, 60 percent or even more than about 75 percent.

[00369] In some cases, the second material has cellulose that has a crystallinity ( ^T C2) that is less than the crystallinity ( ^T C1) of the cellulose of the first material. For example, ( ^T C2) can be less than ( ^T C1) by more than about 10 percent, for example, 15, 20, 25, 30, 35, 40 or even more than about 50 percent.

[00370] In some embodiments, the initial crystallinity (before pyrolysis) is about 40 to about 87.5 percent, for example, about 50 to about 75 percent or about 60 to about 70

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108/204 percent and the crystallinity index, after pyrolysis, is about 10 to about 50 percent, for example, about 15 to about 45 percent or about 20 to about 40 percent . However, in certain embodiments, for example, after extensive pyrolysis, it is possible to have a crystallinity index of less than 5 percent. In some embodiments, the material, after pyrolysis, is substantially amorphous. [00371] In some embodiments, the initial average numerical molecular weight (before pyrolysis) is from about 200,000 to about 3,200,000, for example, from about 250,000 to about 1,000,000 or from about 250,000 to about 700,000 and the average numerical molecular weight, after pyrolysis, is about 50,000 to about 200,000, for example, from about 60,000 to about 150,000 or from about 70,000 to about 125,000, however, in some embodiments, for For example, after extensive pyrolysis, it is possible to have an average numerical molecular weight of less than about 10,000 or even less than about 5,000.

[00372] In some embodiments, the second material may have an oxidation level ( ^T O2) that is higher than the oxidation level ( ^T O1) of the first material. A higher level of oxidation of the material can assist in its dispersibility, swelling capacity and / or solution, further intensifying the susceptibility of the materials to chemical, enzymatic or microbial attack. In some embodiments, to increase the level of oxidation of the second material with respect to the first material, pyrolysis is performed in an oxidation environment, producing a second material that is more oxidized than the first material. For example, the second material can have more hydroxyl groups, aldehyde groups, ketone groups, ester groups or carboxylic acid groups, which can increase its hydrophilicity.

[00373] In some modalities, the pyrolysis of the materials is continuous. In other modalities, the material undergoes pyrolysis during a period of 870170006381, of 01/30/2017, p. 114/258

109/204 pre-determined and then allowed to cool for a second pre-determined time before pyrolysis once again.

Pyrolysis Systems [00374] Figure 14 shows a 6000 process flow chart that includes several steps in a feed stock pyrolytic pretreatment system. In step 6010, a supply of dry feed stock is received from a power source. [00375] As described above, the dry feed stock of the power supply can be pre-processed before distribution to the pyrolysis chamber. For example, if the feed stock is derived from plant sources, certain parts of the plant material can be removed before the plant material is collected and / or before the plant material is distributed by the feed stock transport device. Alternatively or in addition, the biomass feed stock can be subjected to 6020 mechanical processing (for example, to reduce the average length of fibers in the feed stock) before distribution to the pyrolysis chamber. [00376] After mechanical processing, the feed stock undergoes a moisture adjustment step 6030. The nature of the moisture adjustment step depends on the moisture content of the mechanically processed feed stock. Typically, feed stock pyrolysis occurs most efficiently when the moisture content of the feed stock is between about 10% and about 30% (for example, between 15% and 25%) by weight of the feed stock. If the moisture content of the feed stock is greater than about 40% by weight, the extra thermal load presented by the water content of the feed stock increases the energy consumption of subsequent pyrolysis steps.

[00377] In some modalities, if the feed stock has a moisture content which is greater than about 30% by weight,

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110/204 drier feed stock 6220, which has a low moisture content, can be mixed, creating a mix of feed stock in step 6030 with an average moisture content that is within the limits discussed above. In certain embodiments, feed stock with a high moisture content can simply be dried by dispersing the feed stock material on a moving conveyor that circulates the feed stock through an inline heating unit. The heating unit evaporates some of the water in the supply stock.

[00378] In some embodiments, if the feed stock of step 6020 has a moisture content which is very low (for example, less than about 10% by weight), the mechanically processed feed stock can be combined with the wetter feed stock material 6230 with a higher moisture content, such as sewage sludge. Alternatively or in addition, 6240 water can be added to the dry feed stock of step 6020 to increase its moisture content.

[00379] In step 6040, the feed stock - now with its moisture content adjusted to fall within suitable limits - can be preheated in an optional 6040 preheating step. The 6040 preheating step can be used to raise the temperature of the feed stock to between 75 ° C and 150 ° C in preparation for subsequent pyrolysis of the feed stock. Depending on the nature of the feed stock and the particular design of the pyrolysis chamber, preheating the feed stock can ensure that the heat distribution within the feed stock remains more uniform during pyrolysis and can reduce the thermal load on the feed chamber. pyrolysis.

[00380] The food supply is then transported to a

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111/204 pyrolysis chamber to undergo pyrolysis in step 6050. In some embodiments, transport of the supply stock is aided by the addition of one or more pressurized gases 6210 to the supply stock stream. The gases create a pressure gradient in the feed stock transport conduit, driving the feed stock into the pyrolysis chamber (and even through the pyrolysis chamber). In certain modalities, transportation of the food stock occurs mechanically; that is, a conveyor system that includes a conveyor, such as a drill, carries the feed stock to the pyrolysis chamber.

[00381] Other 6210 gases can also be added to the feed stock before the pyrolysis chamber. In some embodiments, for example, one or more catalyst gases can be added to the feed stock to assist in the decomposition of the feed stock during pyrolysis. In certain embodiments, one or more purifying agents can be added to the feed stock to capture volatile materials released during pyrolysis. For example, various sulfur-based compounds, such as sulfides, can be released during pyrolysis and an agent, such as hydrogen gas, can be added to the feed stock to cause sulfur removal from the pyrolysis products. Hydrogen combines with sulfides to form hydrogen sulphate gas, which can be removed from the pyrolysis-fed food supply.

[00382] Pyrolysis of the feed stock inside the chamber may include heating the feed stock to relatively high temperatures to cause partial decomposition of the feed stock. Typically, the feed stock is heated to a temperature ranging from 150 ° C to 1100 ° C. The temperature to which the feed stock is heated depends on a series of

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112/204 factors, including the composition of the feed stock, the average particle size of the feed stock, the moisture content and the desired pyrolysis products. For many types of biomass feed stock, for example, pyrolysis temperatures between 300 ° C and 550 ° C are used.

[00383] The residence time of the feed stock within the pyrolysis chamber generally depends on a number of factors, including the pyrolysis temperature, the composition of the feed stock, the average particle size of the feed stock, the moisture content and the desired pyrolysis products. In some embodiments, feed stock materials undergo pyrolysis at a temperature just above the decomposition temperature for the material in an inert atmosphere, for example, from about 2 ° C above to about 10 ° C above the decomposition temperature or from about 3 ° C above to about 7 ° C above the decomposition temperature. In such embodiments, the material is, in general, kept at that temperature for more than 0.5 hours, for example, more than 1.0 hours or more than about 2.0 hours. In other embodiments, the materials undergo pyrolysis at a temperature well above the decomposition temperature for the material in an inert atmosphere, for example, from about 75 ° C above to about 175 ° C above the decomposition temperature or about 85 ° C above about 150 ° C above the decomposition temperature. In such embodiments, the material is, in general, kept at that temperature for less than 0.5 hours, for example, less than 20 minutes, less than 10 minutes, less than 5 minutes or less than 2 minutes. In still other embodiments, the materials undergo pyrolysis at an extreme temperature, for example, from about 200 ° C above to about 500 ° C above the decomposition temperature of the material in an inert environment or from about 250 ° C above at about 400 ° C above the

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113/204 decomposition. In such embodiments, the material is, in general, kept at that temperature for less than 1 minute, for example, less than 30 seconds, 15 seconds, 10 seconds, 5 seconds, 1 second or less than 500 ms. Such modalities are typically referred to as flame pyrolysis.

[00384] In some embodiments, the feed stock is heated relatively quickly to the selected pyrolysis temperature inside the chamber. For example, the chamber can be created to heat the feed stock at a rate between 500 ° C / s and 11,000 ° C / s, for example, from 500 ° C / s to 1000 ° C / s.

[00385] A turbulent flow of feed stock material within the pyrolysis chamber is usually advantageous, as it ensures relatively efficient heat transfer to feed stock material from the heating subsystem. Turbulent flow can be obtained, for example, by blowing the feed stock material through the chamber using one or more injected vehicle gases 6210. In general, the carrier gases are relatively inert with respect to the feed stock material, even at high temperatures in the pyrolysis chamber. Exemplary carrier gases include, for example, nitrogen, argon, methane, carbon monoxide and carbon dioxide. Alternatively or in addition, mechanical transport systems, such as drills, can transport and circulate the feed stock within the pyrolysis chamber to create a turbulent flow of feed stock.

[00386] In some modalities, pyrolysis of the food supply occurs substantially in the absence of oxygen and other reactive gases. Oxygen can be removed from the pyrolysis chamber by periodically purging the chamber with high pressure nitrogen (for example, at nitrogen pressures of 2 bar or more). After purging the chamber, the gas mixture present in the pyrolysis chamber (for

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114/204 example, during feed stock pyrolysis) may include less than 4 mole% oxygen (for example, less than 1 mole% oxygen and even less than 0.5 mole% oxygen). The absence of oxygen ensures that inflammation of the feed stock does not occur at elevated pyrolysis temperatures.

[00387] In certain embodiments, relatively small amounts of oxygen can be introduced into the food supply and are present during pyrolysis. This technique is referred to as oxidative pyrolysis. Typically, oxidative pyrolysis occurs in multiple heating stages. For example, in a first heating stage, the feed stock is heated in the presence of oxygen to cause partial oxidation of the feed stock. This stage consumes the available oxygen in the pyrolysis chamber. Then, in subsequent stages of heating, the temperature of the feed stock is additionally high. With all the oxygen in the chamber consumed, however, combustion of the feed stock does not occur and pyrolytic decomposition without combustion of the feed stock (for example, to generate hydrocarbon products) occurs. In general, the process of heating the stock feed in the pyrolysis chamber in order to initiate decomposition is endothermic. However, in oxidative pyrolysis, the formation of carbon dioxide through oxidation of the feed stock is an exothermic process. The heat released from the formation of carbon dioxide can assist in additional stages of pyrolysis heating, thereby decreasing the thermal load presented by the supply stock. [00388] In some embodiments, pyrolysis occurs in an inert environment, such as while the stock feed materials are bathed in an argon or nitrogen gas. In certain embodiments, pyrolysis can occur in an oxidation environment, such as in air or air-enriched argon. In some modalities, piróliPetição 870170006381, of 01/30/2017, p. 120/258

115/204 can occur in a reducing environment, such as while the feed stock materials are bathed in hydrogen gas. To assist in pyrolysis, various chemical agents, such as oxidants, reducers, acids or bases, can be added to the material before or during pyrolysis. For example, sulfuric acid can be added or a peroxide (for example, benzoyl peroxide) can be added.

[00389] As discussed above, a variety of different processing conditions can be used, depending on factors, such as the composition of the feed stock and the desired pyrolysis products. For example, for feed stock material containing cellulose, relatively mild pyrolysis conditions can be employed, including flame pyrolysis temperatures between 375 ° C and 450 ° C and residence times of less than 1 second. As another example, for solid organic waste material, such as sewage sludge, flame pyrolysis temperatures between 500 ° C and 650 ° C are typically used, with residence times of between 0.5 and 3 seconds. In general, many of the pyrolysis process parameters, including residence time, pyrolysis temperature, feed stock turbulence, moisture content, feed stock composition, pyrolysis product composition and additive gas composition, can be regulated automatically by a regulator system and an automated control system.

[00390] After the 6050 pyrolysis step, the pyrolysis products undergo a 6250 dissipation step to reduce the temperature of the products before further processing. Typically, the 6250 dissipation step includes spraying the pyrolysis products with 6260 cooling water streams. The cooling water also forms a paste that includes resulting undissolved solid material and various dissolved products. Also present in the product chain

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116/204 is a mixture that includes various gases, including resultant gases, carrier gases and other types of process gases.

[00391] The product stream is transported, via the inline piping, to a gas separator that performs a 6060 gas separation step, in which the resulting gases and other gases are separated from the paste formed by dissipating the product from the pyrolysis. The separate gas mixture is optionally directed to a 6130 blower, which increases the gas pressure by blowing air into the mixture. The gas mixture can be subjected to a 6140 filtration step, in which the gas mixture passes through one or more filters (for example, activated carbon filters) to remove particles and other impurities. In a subsequent step 6150, the filtered gas can be compressed and stored for another use. Alternatively, the filtered gas can be subjected to other 6160 processing steps. For example, in some embodiments, the filtered gas can be condensed to separate different gaseous compounds within the gas mixture. The different compounds can include, for example, various hydrocarbon products (for example, alcohols, alkanes, alkenes, alkynes, ethers) produced during pyrolysis. In certain embodiments, the filtered gas containing a mixture of hydrocarbon components can be combined with 6170 steam gas (for example, a mixture of water vapor and oxygen) and subjected to a cracking process to reduce the molecular weights of the components of hydrocarbon.

[00392] In some embodiments, the pyrolysis chamber includes heat sources that burn hydrocarbon gases, such as methane, propane and / or butane, to heat the food supply. A 6270 portion of the separated gases can be recirculated to the pyrolysis chamber for combustion, to generate process heat to support the pyrolysis process.

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117/204 [00393] In certain embodiments, the pyrolysis chamber can receive process heat that can be used to increase the temperature of the feed stock materials. For example, irradiation of the food stock with radiation (for example, gamma radiation, electron beam radiation or other types of radiation) can heat the food stock materials to relatively high temperatures. Heated feed stock materials can be cooled through a heat exchange system that removes some of the excess heat from the irradiated feed stock. The heat exchange system can be configured to transport some of the thermal energy to the pyrolysis chamber to heat (or preheat) the feed stock material, thereby reducing energy costs for the pyrolysis process.

[00394] The paste containing liquid and solid pyrolysis products can undergo an optional 6070 dehydration step, in which excess water can be removed from the paste via processes such as mechanical compression and evaporation. Excess water 6280 can be filtered and then recirculated for further use in dissipating the pyrolysis decomposition products in step 6250.

[00395] The dehydrated paste then undergoes a mechanical separation step 6080, in which the resulting solid material 6110 is separated from the resulting liquid material 6090 through a series of increasingly fine filters. In step 6100, the resulting liquid material 6090 can then be condensed (for example, via evaporation) to remove residual water 6190 and purified through processes such as extraction. Extraction may include the addition of one or more 6180 organic solvents, for example, to separate products such as oils from products such as alcohols. Suitable organic solvents include, for example, various hydrocarbons and halohydrocarbons.

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118/204

The 6200 purified liquid products can then be subjected to further processing steps. Residual water 6190 can be filtered if necessary and recirculated for further use in dissipating the pyrolysis decomposition products in step 6250, [00396] After separation in step 6080, the resulting solid material 6110 is optionally subjected to a drying step 6120 which may include water evaporation. The 6110 solid material can then be stored for later use or subjected to further processing steps, as appropriate.

[00397] The parameters of the pyrolysis process discussed above are exemplary. In general, the values of these parameters can vary widely according to the nature of the feed stock and the desired products. In addition, a wide variety of different pyrolysis techniques, including use of heat sources, such as hydrocarbon flames and / or ovens, infrared lasers, microwave heaters, induction heaters, resistive heaters and other devices and configurations heating elements can be used.

[00398] A wide variety of different pyrolysis chambers can be used to break down the feed stock. In some embodiments, for example, pyrolysis of the feed stock may include heating the material using a resistive heating element, such as a metal filament or metal tape. Heating can take place through direct contact between the resistive heating element and the material.

[00399] In certain embodiments, pyrolysis may include heating the material through induction, such as using a Curie-Point pyrolysis apparatus. In some embodiments, pyrolysis may include heating the material by applying radiation, such as infrared radiation. The radiation can be generated by a laser,

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119/204 such as an infrared laser.

[00400] In certain embodiments, pyrolysis may include heating the material with convective heat. Convective heat can be generated by a stream of heated gas flow. The heated gas can be kept at a temperature of less than about 1200 ° C, such as less than 1000 ° C, less than 750 ° C, less than 600 ° C, less than 400 ° C or even less than 300 ° C . The heated gas can be kept at a temperature of over 250 ° C. Convective heat can be generated by a hot body that surrounds the first material, such as in an oven.

[00401] In some embodiments, pyrolysis may include heating the material with steam at a temperature above about 250 ° C. [00402] One embodiment, a pyrolysis chamber is shown in figure 15. The 6500 chamber includes an insulated chamber wall 6510 with a 6600 vent for exhaust gases, a plurality of 6520 burners that generate heat for the pyrolysis process, a 6530 transport duct for transporting the feed stock through the 6500 chamber, 6590 drills for moving the feed stock through the 6530 duct in turbulent flow and a 6540 dissipation system that includes a 6610 drill for moving pyrolysis products, jets of water 6550 for spraying pyrolysis products with cooling water and a gas separator to separate the 6580 gaseous products from the 6570 paste containing solid and liquid products.

[00403] Another embodiment of a pyrolysis chamber is shown in figure 16. Chamber 6700 includes a 6710 insulated chamber wall, a 6720 power supply supply duct, an inclined inner chamber wall 6730, 6740 burners that generate heat for the pyrolysis process, a 6750 vent for exhaust gases and a 6760 gas separator for product separation

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Gaseous 120/204 6770 of liquid and solid products 6780. Chamber 6700 is configured to rotate in the direction shown by arrow 6790 to ensure proper mixing and turbulent flow of the feed stock within the chamber.

[00404] Another embodiment of a pyrolysis chamber is shown in figure 17. The 1712 filament pyrolysis apparatus includes a sample container 1713 with a resistive heating filament 1714 in the form of a wire spiral through the open space defined by sample container 1713. Optionally, the heated element can rotate around axis 1715 (as indicated by the arrow 1716) to swirl the material that includes cellulosic material in sample container 1713. The space 1718 defined by containment 1719 is maintained at a temperature above room temperature, for example, 200 to 250 ° C. In a typical use, a carrier gas, for example, an inert gas or an oxidation or reduction gas, passes through the 1713 sample container, while the resistive heating element is rotated and heated to a desired temperature, for example, 325 ° Ç. After an appropriate time, for example, 5 to 10 minutes, the pyrolyzed material is emptied from the sample container. The system shown in figure 17 can be scaled and made continuous. For example, instead of a wire as the heating element, the heating element can be a drill thread. The material can fall continuously into the sample container, while a heated thread performs pyrolysis of the material. At the same time, the thread can push the pyrolysis material out of the sample container to allow fresh material that has not undergone pyrolysis to enter.

[00405] Another modality of a pyrolysis chamber is shown in figure 18, which is characterized by a CuriePoint 1820 pyrolysis apparatus that includes an 1821 sample chamber housing a foPetition 870170006381, from 01/30/2017, p. 126/258

121/204 ferromagnetic sheet 1822. Surrounding the sample chamber 1821 is an RF spiral 1823. The space 1824 defined by containment 1825 is maintained at a temperature above room temperature, for example, 200 to 250 ° C. In typical use, a carrier gas passes through sample chamber 1821, while sheet 1822 is inductively heated by an RF field applied to bring the material to pyrolysis at a desired temperature.

[00406] Yet another embodiment of a pyrolysis chamber is shown in figure 19. The pyrolysis apparatus with oven 130 includes a movable sample container 131 and an oven 132. In a typical use, the sample is lowered (as indicated by the arrow 137) to a hot zone 135 of oven 132, while a carrier gas fills the housing 136 and passes through the sample container 131. The sample is heated to the desired temperature for a desired time in order to provide a pyrolysed product. The pyrolyzed product is removed from the pyrolysis apparatus by lifting the sample container (as indicated by arrow 134).

[00407] In certain embodiments, as shown in figure 20, a cellulosic target 140 can undergo pyrolysis through treatment of the target, which is housed in a vacuum chamber 141, with laser light, for example, light having a length of wave from about 225 nm to about 1500 nm. For example, the target can be configured at 266 nm, using the fourth harmonic of an Nd-YAG laser (Spectra Physics, GCR170, San Jose, Calif.). The optical configuration shown allows the almost monochromatic light 143 generated by laser 142 to be directed using mirrors 144 and 145 on the target after passing through a lens 146 in vacuum chamber 141. Typically, pressure in the vacuum chamber is maintained at less about 10 ^-6 mm Hg. In some embodiments, infrared radiation is used, for example, 1.06 micron radiation from an Nd-YAG laser.

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In such embodiments, an infrared sensitive dye can be combined with the cellulosic material to produce a cellulosic target. The infrared dye can intensify the heating of the cellulosic material. Laser ablation is described by Blanchet-Fincher et al. In U.S. Patent No. 5,942,649.

[00408] Referring to figure 21, in some embodiments, a cellulosic material can be pyrolyzed to the flame by coating a tungsten filament 150, such as a tungsten filament from 5 to 25 thousand, with the desired cellulosic material while material is housed in a vacuum chamber 151. To perform pyrolysis, current is passed through the filament, which causes the filament to heat up quickly for a desired time. Typically, heating is continued for seconds before allowing the filament to cool. In some embodiments, heating is performed a number of times to achieve the desired amount of pyrolysis.

[00409] In certain modalities, material containing biomass carbohydrate can be heated in the absence of oxygen in a fluidized bed reactor. If desired, the carbohydrate-containing biomass can have relatively thin cross sections and can include any of the fibrous materials described here, for efficient heat transfer. The material can be heated by thermal transfer from a hot or ceramic metal, such as glass or sand globules in the reactor and the resulting pyrolysis liquid or oil can be transported to a central refinery for the production of combustible materials or other products Useful.

[00410] In some embodiments, irradiation of the biomass material, for example, with a beam of particles, such as electrons, before pyrolysis can decrease the pyrolysis temperature, resulting in less energy being consumed during pyrolysis.

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OXIDATION [00411] One or more oxidative processing sequences can be used to process the raw feed stock from a wide variety of different sources to extract useful substances from the feed stock and to provide a partially degraded organic material which functions as input to other processing steps and / or sequences.

[00412] Referring again to figure 8, a first material 2 that includes cellulose having a first average numerical molecular weight ( ^T MN1) and having a first oxygen content ( ^T O1) is oxidized, for example, by heating of the first material in a tube furnace in the air stream or oxygen-enriched air, in order to provide a second material 3 which includes cellulose having a second numerical average molecular weight ( ^T MN2) and having a second oxygen content ( ^T O2 ) higher than the first oxygen content ( ^T O1). The second material (or the first and second materials in certain embodiments) can, for example, be combined with a resin, such as a molten thermoplastic resin or a microorganism, in order to provide a compound 4 having desirable mechanical properties or a fuel 5.

[00413] Such materials can also be combined with a solid and / or a liquid. For example, the liquid can be in the form of a solution and the solid can be in the form of a particle. The liquid and / or solid can include a microorganism, for example, a bacterium and / or an enzyme. For example, the bacteria and / or enzyme can function on cellulosic or lignocellulosic material to produce a fuel, such as ethanol or a co-product, such as a protein. Fuels and co-products are described in FIBROUS MATERIALS AND COMPOSITES, USSN 11 / 453,951, filed on June 15, 2006. The contents of each of the previous orders

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124/204 are incorporated by reference.

[00414] In some embodiments, the second average numerical molecular weight is no more than 97 percent less than the first average numerical molecular weight, for example, no more than 95 percent, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 30, 20, 12.5, 10.0, 7.5, 5.0, 4.0, 3.0, 2.5, 2.0 or no more than 1.0 percent less than the first average numerical molecular weight. The amount of molecular weight reduction will depend on the application.

[00415] In some embodiments in which materials are used to produce a fuel or co-product, the initial average numerical molecular weight (before oxidation) is about 200,000 to about 3,200,000, for example, about 250,000 to about 1,000. 000 or about 250,000 to about 700,000 and the average numerical molecular weight, after oxidation, is about 50,000 to about 200,000, for example, from about 60,000 to about 150,000 or from about 70,000 to about 125,000 . However, in some embodiments, for example, after extensive oxidation, it is possible to have an average numerical molecular weight of less than about 10,000 or even less than about 5,000.

[00416] In some embodiments, the second oxygen content is at least about five percent higher than the first oxygen content, for example, 7.5 percent higher, 10.0 percent higher, 12.5 percent percent higher, 15.0 percent higher or 17.5 percent higher. In some preferred embodiments, the second oxygen content is at least about 20.0 percent greater than the oxygen content of the first material. The oxygen content is measured through elemental analysis through pyrolysis of the sample in an oven operating at 1300 ° C or higher. Suitable elemental analysis equipment is the LECO CHNS-932 analyzer with a high temperature pyrolysis oven VTF900.

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125/204 [00417] In some embodiments, oxidation of the first material 200 does not result in a substantial change in the crystallinity of the cellulose. However, in some cases, for example, after extreme oxidation, the second material has cellulose which has a crystallinity ( ^T C2) that is less than the crystallinity ( ^T C1) of the cellulose of the first material. For example, ( ^T C2) can be less than ( ^T C1) by more than about 5 percent, for example, 10, 15, 20 or 25 percent. It may be desirable to enhance the solubility of the materials in a liquid, such as a liquid that includes a bacterium and / or an enzyme. [00418] In some embodiments, the initial crystallinity index (before oxidation) is about 40 to about 87.5 percent, for example, about 50 to about 75 percent or about 60 to about 70 percent and a crystallinity index after oxidation is about 30 to about 75.0 percent, for example, about 35.0 to about 70.0 percent or about 37.5 about 65.0 percent. However, in certain embodiments, for example, after extensive oxidation, it is possible to have a crystallinity index of less than 5 percent. In some embodiments, the material, after oxidation, is substantially amorphous.

[00419] Without wishing to be bound by any particular theory, oxidation is believed to increase the number of hydrogen bonding groups on cellulose, such as hydroxyl groups, aldehyde groups, ketone groups, carboxylic acid groups or anhydride groups, which can increase its dispersibility and / or its solubility (for example, in a liquid). To further improve the dispersibility in a resin, the resin may include a component that includes hydrogen bonding groups, such as one or more anhydride groups, carboxylic acid groups, hydroxyl groups, amide groups, amine groups or mixtures of any of these groups . In some preferred embodiments, the component includes a polymer copolymerized with and / or

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126/204 grafted with maleic anhydride. Such materials are available from Dupont under the trademark FUSABOND®.

[00420] In general, oxidation of the first material 200 occurs in an oxidation environment. For example, oxidation can be performed or aided by pyrolysis in an oxidation environment, such as in air or air-enriched argon. To aid oxidation, various chemical agents, such as oxidants, acids or bases, can be added to the material before or during oxidation. For example, a peroxide (for example, benzoyl peroxide), can be added before oxidation.

Oxidation Systems [00421] Figure 22 shows a 5000 process flow chart that includes several steps in a feed stock oxidative pretreatment system. In the first step 5010, a supply of dry feed stock is received from a power source. The power supply may include, for example, a storage bed or container that is connected to an in-line oxidation reactor via a conveyor belt or other feed stock transport device.

[00422] As described above, the dry feed stock of the power supply can be processed before distribution to the oxidation reactor. For example, if the feed stock is derived from plant sources, certain parts of the plant material can be removed before the plant material is collected and / or before the plant material is distributed by the feed stock transport device. Alternatively or in addition, the biomass feed stock can be subjected to mechanical processing (for example, to reduce the average length of fibers in the feed stock) before distribution to the oxidation reactor. [00423] After 5020 mechanical processing, the food stock 870170006381, dated 01/30/2017, p. 132/258

127/204 batch 5030 is transported to a mixing system which introduces 5150 water to the feed stock in a mechanical mixing process. Combination of water with the feed stock processed in mixing step 5040 creates a 5050 aqueous feed stock slurry which can then be treated with one or more oxidizing agents.

[00424] Typically, one liter of water is added to the mixture for every 0.02 kg to 1.0 kg of dry feed stock. The proportion of feed stock to water in the mix depends on the source of the feed stock and the specific oxidizing agents used downstream in the overall process. For example, in typical industrial processing sequences for lignocellulosic biomass, the 5050 aqueous feed stock slurry includes from about 0.5 kg to about 1.0 kg of dry biomass per liter of water.

[00425] In some embodiments, one or more 5170 fiber protection additives can also be added to the feed stock paste in the 5040 feed stock mixing step. Fiber protection additives help reduce the degradation of certain types of feed stock. biomass fibers (eg cellulose fibers) during oxidation of the feed stock. Fiber protection additives can be used, for example, if a desired product from processing a lignocellulosic feed stock includes cellulose fibers. Exemplary fiber protection additives include magnesium compounds, such as magnesium hydroxide. The concentrations of fiber protection additives in the 5050 feed stock slurry can be from 0.1% to 0.4% of the dry weight of the biomass feed stock, for example.

[00426] In certain embodiments, the 5050 aqueous feed stock paste can be subjected to an optional 5180 extraction with an organic solvent to remove insoluble substances

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128/204 in paste water. For example, extraction of the 5050 slurry with one or more organic solvents provides a purified slurry and a 5210 organic residual stream that includes water-insoluble materials, such as fats, oils and other non-polar hydrocarbon-based substances. Suitable solvents for extracting the 5050 slurry include various alcohols, hydrocarbons and halohydrocarbons, for example.

[00427] In some embodiments, the 5050 aqueous feed stock may be subjected to an optional 5190 heat treatment to further prepare the feed stock for oxidation. An example of a heat treatment includes heating the stock feed slurry in the presence of pressurized steam. In a fibrous biomass feed stock, pressurized steam swells the fibers, exposing a larger fraction of the fiber surfaces to the aqueous solvent and oxidizing agents that are introduced in subsequent processing steps.

[00428] In certain embodiments, 5050 aqueous feed stock paste can be subjected to optional treatment with basic 5200 agents. Treatment with one or more basic agents helps to separate lignin from cellulose in the lignocellulosic biomass feed stock, thereby , improving the subsequent oxidation of the feed stock. Exemplary basic agents include alkaline and alkaline earth hydroxides, such as sodium hydroxide, potassium hydroxide and calcium hydroxide. In general, a variety of basic agents can be used, typically in concentrations of about 0.01% to about 0.5% of the dry weight of the feed stock.

[00429] 5050 aqueous feed stock paste is transported (for example, through an in-line piping system) to a chamber, which can be a pre-processing chamber for

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129/204 oxidation or an oxidation reactor. In the oxidation preprocessing step 5060, one or more oxidizing agents 5160 are added to the feed stock slurry 5050 to form an oxidation medium. In some embodiments, for example, 5160 oxidizing agents may include hydrogen peroxide. Hydrogen peroxide can be added to the 5050 slurry as an aqueous solution and in proportions ranging from 3% to between 30% and 35% by weight of 5050 slurry. Hydrogen peroxide has a number of advantages as an oxidizing agent. For example, aqueous hydrogen peroxide is relatively inexpensive, is relatively chemically stable and is not particularly dangerous with respect to other oxidizing agents (and therefore does not require problematic handling procedures and expensive safety equipment). In addition, hydrogen peroxide breaks down to form water during oxidation of the feed stock, so cleaning the residual stream is relatively straightforward and inexpensive.

[00430] In certain embodiments, 5160 oxidizing agents may include oxygen (for example, oxygen gas), either alone or in combination with hydrogen peroxide. Oxygen gas can be bubbled into the 5050 slurry in proportions ranging from 0.5% to 10% by weight of the 5050 slurry. Alternatively or in addition, oxygen gas can also be introduced in a gas phase in equilibrium with the 5050 slurry (for example, a head and steam above the 5050 paste). Oxygen gas can be introduced into the oxidation preprocessing chamber or oxidation reactor (or both), depending on the configuration of the oxidative processing system. Typically, for example, the partial pressure of oxygen in the vapor above the 5050 slurry is greater than the ambient pressure of oxygen and ranges from 0.5 bar to 35 bar, depending on the nature of the feed stock.

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130/204 [00431] Oxygen gas can be introduced in pure form or it can be mixed with one or more carrier gases. For example, in some embodiments, high pressure air supplies oxygen in the vapor. In certain embodiments, oxygen gas can be supplied continuously to the vapor phase to ensure that the oxygen concentration in the vapor remains within certain predetermined processing limits of the supply stock. In some embodiments, oxygen gas can be introduced initially at a concentration sufficient to oxidize the feed stock and then the feed stock can be transported to a closed, pressurized vessel (for example, an oxidation reactor) for processing.

[00432] In certain embodiments, 5160 oxidizing agents may include nascent oxygen (eg, oxygen radicals). Typically, nascent oxygen is produced, as needed, in an oxidation reactor or in a fluid communicating chamber with an oxidation reactor through one or more decomposition reactions. For example, in some embodiments, nascent oxygen can be produced from a reaction between NO and O ₂ in a gas mixture or in solution. In certain modalities, nascent oxygen can be produced from the decomposition of HOCl in solution. Other methods by which nascent oxygen can be produced include, for example, electrochemical generation in electrolyte solution.

[00433] In general, nascent oxygen is an efficient oxidizing agent due to the relatively high reactivity of the oxygen radical. However, nascent oxygen can also be a relatively selective oxidizing agent. For example, when lignocellulosic feed stock is treated with nascent oxygen, selective lignin oxidation occurs in preference to other components of the feed stock, such as cellulose. As a result, it oxidizes Petition 870170006381, of 01/30/2017, p. 136/258

131/204 tion of nascent oxygen feed stock provides a method for the selective removal of the lignin fraction in certain feed stocks. Typically, concentrations of nascent oxygen of between about 0.5% and 5% of the dry weight of the feed stock are used to perform efficient oxidation.

[00434] Without wishing to be bound by theory, it is believed that nascent oxygen reacts with the lignocellulosic food supply according to at least two different mechanisms. In a first mechanism, the nascent oxygen undergoes an addition reaction with the lignin, resulting in partial oxidation of the lignin, which solubilizes the lignin in aqueous solution. As a result, the solubilized lignin can be removed from the rest of the feed stock via washing. In a second mechanism, the nascent oxygen disrupts the butane crosslink and / or opens aromatic rings that are connected via the butane crosslink. As a result, the solubility of lignin in aqueous solution increases and facilitates the separation of the lignin fraction from the rest of the feed stock via washing. [00435] In some embodiments, 5160 oxidizing agents include ozone (O3). The use of ozone can introduce several chemical manipulation considerations in the sequence of oxidation processing. If heated very vigorously, an aqueous ozone solution can decompose violently, with potentially adverse consequences for human system operators and system equipment. Consequently, ozone is typically generated in a thermally insulated thick-walled vessel separate from the vessel containing the feed stock paste and transported from it at the appropriate process stage.

[00436] Without wishing to be bound by theory, it is believed that ozone decomposes into oxygen and oxygen radicals and that the oxygen radicals (for example, nascent oxygen) are responsible for the properties 870170006381, of 30/01/2017, p. 137/258

132/204 ozone oxidation in the manner discussed above. Ozone oxidizes, preferably typically, the lignin fraction in lignocellulosic materials, leaving the cellulose fraction relatively unchanged. [00437] Conditions for ozone-based oxidation of biomass feed stock in general depend on the nature of the biomass. For example, for cellulosic and lignocellulosic feed stocks, ozone concentrations of 0.1 g / m ³ to 20 g / m ³ of dry feed stock provide efficient oxidation of feed stock. Typically, the water content in the 5050 slurry is between 10% by weight and 80% by weight (for example, between 40% by weight and 60% by weight). During ozone-based oxidation, the temperature of the 5050 slurry can be maintained between 0 ° C and 100 ° C to prevent violent ozone decomposition.

[00438] In some embodiments, the 5050 feed stock paste can be treated with an aqueous alkaline solution that includes one or more alkaline and alkaline earth hydroxides, such as sodium hydroxide, potassium hydroxide and calcium hydroxide and then treated then with a gas containing ozone in an oxidation reactor. It has been observed that this process significantly increases the decomposition of the biomass into 5050 paste. Typically, for example, a concentration of hydroxide ions in the alkaline solution is between 0.001% and 10% by weight of the 5050 paste. After the feed stock is moistened via In contact with the alkaline solution, the ozone-containing gas is introduced into the oxidation reactor, where it contacts and oxidizes the supply stock.

[00439] 5160 oxidizing agents can also include other substances. In some embodiments, for example, halogen-based oxidizing agents, such as chlorine and oxychlorine agents (eg, hypochlorite), can be introduced into the 5050 paste. In certain embodiments, oxidizing substances containing nitroPetition 870170006381, from 30/01 / 2017, p. 138/258

133/204 genius can be introduced into the 5050 slurry. Exemplary nitrogen-containing oxidation substances include NO and NO ₂ , for example. Nitrogen-containing agents can also be combined with oxygen in the 5050 slurry to create additional oxidizing agents. For example, NO and NO ₂ combine with oxygen in the 5050 slurry to form nitrate compounds, which are effective oxidizing agents for the biomass feed stock. Oxidizing agents based on halogen and nitrogen can, in some modalities, cause bleaching of the biomass feed stock, depending on the nature of the feed stock. Bleaching may be desirable for certain products derived from biomass that are extracted in subsequent processing steps. [00440] Other oxidizing agents may include, for example, various peroxy acids, peroxyacetic acids, persulfates, percarbonates, permanganates, osmium tetroxide and chromium oxides.

[00441] After the 5060 oxidation pre-processing step, the 5050 feed stock slurry is oxidized in step 5070, if 5160 oxidizing agents were added to the 5050 slurry in an oxidation reactor, then the oxidation takes place in the same reactor. Alternatively, if 5160 oxidizing agents were added to the 5050 slurry in a pre-processing chamber, then the 5050 slurry is transported to an oxidation reactor via an in-line piping system. Once inside the oxidation reactor, oxidation of the biomass feed stock takes place under a controlled environment of environmental conditions. Typically, for example, the oxidation reactor is a cylindrical vessel that is closed to the external environment and pressurized. Batch and continuous operation are possible, although environmental conditions are typically easier to control in in-line batch processing operations.

[00442] Oxidation of feed stock paste 5050 occurs,

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134/204 typically, at high temperatures in the oxidation reactor. For example, the temperature of the 5050 slurry in the oxidation reactor is typically kept above 100 ° C, for example, in a range of 120 ° C to 240 ° C. For many types of biomass feed stock, oxidation is particularly efficient if the temperature of the 5050 slurry is kept between 150 ° C and 220 ° C. The 5050 slurry can be heated using a variety of thermal transfer devices. For example, in some embodiments, the oxidation reactor contacts a heating bath that includes molten oil or salts. In certain embodiments, a series of heat exchange pipes surround and contact the oxidation reactor and the circulation of hot fluid within the pipes heats the 5050 slurry in the reactor. Other heating devices that can be used to heat the 5050 slurry include resistive heating elements, induction heaters and microwave sources, for example.

[00443] The residence time of the 5050 feed stock slurry in the oxidation reactor can be varied as desired to process the feed stock. Typically, the 5050 slurry takes from 1 minute to 60 minutes undergoing oxidation in the reactor. For a relatively soft biomass material, such as lignocellulosic material, the residence time in the oxidation reactor can be from 5 minutes to 30 minutes, for example, at an oxygen pressure of between 3 and 12 bars in the reactor and at a temperature between 160 ° C and 210 ° C. For other types of feed stock, however, residence times in the oxidation reactor can be longer, for example, as long as 48 hours. To determine appropriate residence times for the 5050 slurry in the oxidation reactor, aliquots of the slurry can be extracted from the reactor at specific intervals and analyzed to determine concentrations of products of particular interest, such as complex saccharides. Increase information

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135/204 in the concentrations of certain products in the 5050 slurry as a function of time can be used to determine residence times for particular classes of feed stock material.

[00444] In some embodiments, during oxidation of the feed stock paste 5050, the pH adjustment of the paste can be carried out by introducing one or more chemical agents into the oxidation reactor. For example, in certain embodiments, oxidation occurs most efficiently in a pH range of about 9-11. To maintain a pH in this range, agents such as alkaline and alkaline earth hydroxides, carbonates, ammonia and alkaline buffer solutions can be introduced into the oxidation reactor.

[00445] Circulation of 5050 slurry during oxidation may be important to ensure sufficient contact between the 5160 oxidizing agents and the feed stock. Circulation of the paste can be achieved using a variety of techniques. For example, in some embodiments, a mechanical stirring apparatus that includes propeller blades or a wheel of blades can be implemented in the oxidation reactor. In certain embodiments, the oxidation reactor can be a loop reactor, in which the aqueous solvent in which the feed stock is suspended is simultaneously drained from the bottom of the reactor and recirculated to the top of the reactor via a pump, thereby , ensuring that the paste is continuously re-mixed and does not stagnate inside the reactor.

[00446] After oxidation of the feed stock is complete, the paste is transported to a separation device, where a 5080 mechanical separation step occurs. Typically, the mechanical separation step 5080 includes one or more increasing stages of filtration of fines from the slurry to mechanically separate the solid and liquid constituents.

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136/204 [00447] The liquid phase 5090 is separated from the solid phase 500 and the two phases are processed independently afterwards. The solid phase 5100 can optionally undergo a drying step 5120 in a drying apparatus for example. The drying step 5120 may include, for example, mechanical dispersion of the solid material over a drying surface and evaporation of water from the solid phase 5100 by slightly heating the solid material. After drying step 5120 (or, alternatively, without undergoing drying step 5120), solid phase 5100 is transported to additional processing steps 5140.

[00448] The 5090 liquid phase can optionally undergo a 5110 drying step to reduce the water concentration in the liquid phase. In some embodiments, for example, drying step 5110 may include evaporation and / or distillation and / or extraction of water from liquid phase 5090 by slightly heating the liquid. Alternatively or in addition, one or more chemical drying agents can be used to remove water from the 5090 liquid phase. After the 5110 drying step (or alternatively, without undergoing the 5110 drying step), the 5090 liquid phase is carried into steps additional 5130 processors, which may include a variety of chemical and biological treatment steps, such as chemical and / or enzymatic hydrolysis.

[00449] Drying step 5110 creates a residual stream 5220, an aqueous solution that can include dissolved chemical agents, such as acids and bases in relatively low concentrations. Treatment of the 5220 residual stream may include, for example, pH neutralization with one or more mineral acids or bases. Depending on the concentration of salts dissolved in the 5220 residual stream, the solution can be partially deionized (for example, by passing the residual stream through an ion exchange system).

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Then, the residual stream - which primarily includes water - can be recirculated to the overall process (for example, as water 5150), diverted to another process or discharged.

[00450] Typically, for lignocellulosic biomass feed stocks, after separation step 5070, liquid phase 5090 includes a variety of soluble poly- and oligosaccharides which can then be separated and / or reduced to lower chain saccharides via other processing steps. The 5100 solid phase typically includes cellulose primarily, for example, with lesser amounts of products derived from hemicellulose and lignin.

[00451] In some embodiments, oxidation can be carried out at elevated temperature in a reactor, such as a pyrolysis chamber. For example, referring again to figure 17, feed stock materials can be oxidized in a 1712 filament pyrolysis apparatus. In a typical use, an oxidizing carrier gas, for example, air or a mixture of air / argon, passes through the sample container 1713, while the resistive heating element is rotated and heated to a desired temperature, for example, 325 ° C. After an appropriate time, for example, 5 to 10 minutes, the oxidized material is emptied from the sample container. The system shown in figure 17 can be scaled and made continuous. For example, instead of a wire as the heating element, the heating element can be a drill thread. The material can fall continuously into the sample container, tightening a heated thread that takes the material to pyrolysis. At the same time, the thread can push the oxidized material out of the sample container to allow fresh non-oxidized material to enter.

[00452] Feed stock materials can also be oxidized in any of the pyrolysis systems shown in figures 18-20 and described above in the Pyrolysis Systems section.

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138/204 [00453] Referring again to figure 21, feed stock materials can be quickly oxidized by coating with a tungsten filament 150, together with an oxidizer, such as a peroxide, with the desired cellulosic material, while the material is housed in a vacuum chamber 151. To carry out oxidation, current is passed through the filament, which causes a rapid heating of the filament for a desired time. Typically, heating is continued for seconds before allowing the filament to cool. In some embodiments, heating is performed a number of times to obtain a desired amount of oxidation.

[00454] Referring again to figure 12, in some embodiments, feed stock materials can be oxidized with the aid of sound and / or cavitation. In general, to perform oxidation, materials are subjected to ultrasound in an oxidation environment, such as water saturated with oxygen or another chemical oxidant, such as hydrogen peroxide.

[00455] Referring again to figures 9 and 10, in certain modalities, ionizing radiation is used to assist in the oxidation of feed stock materials. In general, to carry out oxidation, materials are irradiated in an oxidation environment, such as air or oxygen. For example, gamma radiation and / or electron beam radiation can be used to irradiate materials.

OTHER TREATMENT PROCESS [00456] Steam explosion can be used alone without any one or more of the processes described here or in combination with any of the processes described here.

[00457] Figure 23 shows an overview of the entire process of converting a fiber source or 400 power supply into

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139/204 a 450 product, such as ethanol, through a process that includes shear and steam explosion to produce a fibrous material

401 which is then hydrolyzed and converted, for example, fermented, to produce the product. The fiber source can be transformed into fibrous material 401 through a number of possible methods, including at least one shear process and at least one vapor explosion process.

[00458] For example, an option includes fiber source shear, followed by optional sieving step (s) and optional shear step (s) to produce a sheared fiber source

402 which can then be steam blown to produce the fibrous material 401. The steam blast process is optionally followed by a fiber recovery process to remove liquids or the liquor 404 resulting from the steam blast process. The material resulting from the steam explosion from the sheared fiber source can be further sheared through optional shearing step (s) and / or optional sieving step (s).

[00459] In another method, fibrous material 401 is first steam blown to produce a steam blown fiber source 410. The resulting steam blown fiber source is then subjected to an optional fiber recovery process to remove liquids or liquor. The resulting steam-blown fiber source can then be sheared to produce the fibrous material. The steam blown fiber source can also be subjected to one or more optional screening steps and / or one or more optional shearing steps. The process of shearing and steam explosion from the fiber source to produce the steam sheared and sheared fibrous material will be further discussed below.

[00460] The fiber source can be cut into pieces or strips of material in confetti before shearing or steam explosion. The

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140/204 shearing processes can occur with the material in a dry state (for example, having less than 0.25 percent by weight of absorbed water), a hydrated state or even while the material is partially or totally submerged in a liquid , such as water or isopropanol. The process can also optimally include drying steps of the product after steam explosion or shear to allow for additional drying or steam explosion steps. The shearing, sieving and steam explosion steps can occur with or without the presence of various chemical solutions.

[00461] In a steam explosion process, the fiber source or the sheared fiber source is contacted with steam under high pressure and the vapor diffuses into the structures of the fiber source (for example, lignocellulosic structures). The vapor then condenses under high pressure, thereby moistening the fiber source. The moisture in the fiber source can hydrolyze any acetyl groups in the fiber source (for example, the acetyl groups in the hemicellulose fractions), which form organic acids, such as acetic and uronic acids. The acids, in turn, can catalyze the depolymerization of hemicellulose, releasing xylan and limited amounts of glucan. The wet fiber source (or shear fiber source, etc.) is then blown up when the pressure is released. Condensed moisture evaporates instantly due to the sudden decrease in pressure and the expansion of water vapor exerts a shear force on the fiber source (or source of sheared fiber, etc.). a sufficient shear force will cause mechanical breakdown of the internal structures (for example, the lignocellulosic structures) of the fiber source.

[00462] The fibrous material sheared and blown up by steam is then converted into a useful product, such as ethanol. In some embodiments, the fibrous material is converted into a fuel. One method of converting fibrous material into fuel is through hiPetition 870170006381, dated 01/30/2017, p. 146/258

141/204 drolysis to produce fermentable sugars, 412 which are then fermented to produce the product. Other methods of converting fibrous materials to fuels can also be used.

[00463] In some embodiments, before combining with the microorganism, the steam-sheared and shredded fibrous material 401 is sterilized to kill any contaminating microorganisms that may be on the fibrous material. For example, the fibrous material can be sterilized by exposing the fibrous material to radiation, such as infrared radiation, ultraviolet radiation or ionizing radiation, such as gamma radiation. Microorganisms can also be killed using chemical sterilizing agents, such as bleaches (for example, sodium hypochlorite), chlorhexidine or ethylene oxide.

[00464] A method to hydrolyze the sheared and steam-blown fibrous material is through the use of cellulases. Cellulases are a group of enzymes that act synergistically to hydrolyze cellulose. The commercially available Accellerase® 1000 enzyme complex, which contains an enzyme complex that reduces lignocellulosic biomass in fermentable sugars, can also be used. [00465] According to the current understanding, the components of cellulase include endoglucanases, exoglucanases (cellobiohydrolases) and β-glucosidases (cellobiases). Synergism between cellulase components exists when the hydrolysis of a combination of two or more components exceeds the sum of the activities expressed by the individual components. The generally accepted mechanism of action of a cellulase system (particularly T. longibrachiatum) on crystalline cellulose is that endoglucanase hydrolyzes the internal β-1,4 glycosidic bonds in the amorphous regions, thereby increasing the number of non- reduction exposed. Exoglucanases, then, cleave the cellobiose units of the non-Petition ends 870170006381, of 01/30/2017, p. 147/258

142/204 reduction which, in turn, are hydrolyzed into individual glucose units by β-glucosidases. There are several configurations of endo- and exo-glucanases with different stereo-specificities. In general, the synergistic action of the components in various configurations is required for optimal cellulose hydrolysis. Cellulases, however, are more inclined to hydrolyze the amorphous regions of cellulose. There is a linear relationship between crystallinity and hydrolysis rates, so higher crystallinity rates correspond to lower rates of enzymatic hydrolysis. Amorphous regions of cellulose hydrolyze at twice the rate of crystalline regions. The hydrolysis of the sheared and steam-blown fibrous material can be carried out using any biomass hydrolysis process.

[00466] Biomass vapor explosion sometimes causes the formation of by-products, for example, toxins, which are inhibitory to enzymatic and microbial activities. The process of converting the sheared and steam-blown fibrous material into a fuel can therefore optionally include a step of excessive use of lime before fermentation to precipitate some of the toxins. For example, the pH of the sheared and steam-blown fibrous material can be raised to exceed the pH of 10 by adding calcium hydroxide (Ca (OH) 2), followed by a step of decreasing the pH to about 5 via addition of H ₂ SO ₄ . The fibrous material with excess lime can then be used as is without removing precipitates. As shown in figure 23, the optional step of excessive use of lime occurs just before the step of hydrolysis of the sheared and steam-blown fibrous material, but it is also considered to perform the step of excessive use of lime after the step of hydrolysis and before fermentation stage.

[00467] Figure 24 represents an example of a steam explosion device 460. The steam explosion device 460 includes a

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143/204 reaction chamber 462, in which the fiber source and / or fibrous material are placed through a fiber source inlet 464. The reaction chamber is closed by closing the 465 fiber source inlet valve. The reaction chamber also includes a pressurized steam inlet 466 that includes a steam valve 467. The reaction chamber also includes an explosive depressurizing outlet 468 that includes an outlet valve 469 in communication with cyclone 470 through the connecting pipe 472. Since the reaction chamber contains the fiber source and / or sheared fiber source and is sealed by closing valves 465, 467 and 469, steam is distributed to reaction chamber 462 by opening the inlet valve. steam 467, allowing steam to travel through the steam inlet 466. Once the reaction chamber reaches the target temperature, which can take about 20 - 60 seconds, the containment time begins. The reaction chamber is kept at the target temperature for the desired containment time, which typically lasts from about 10 seconds to 5 minutes. At the end of the containment period, the outlet valve is opened to allow explosive depressurization to occur. The explosive depressurization process pushes the contents of the reaction chamber 462 out of the explosive depressurization outlet 468, through connection piping 472 and into cyclone 470. The source of the steam-blown fiber or fibrous material then exits the cyclone in a sediment form in the collection container 474, while the remaining steam exits the cyclone into the atmosphere through ventilation 476. The steam blast apparatus still includes a flush outlet 478 with a flush outlet valve 479 in communication with the connection piping 472. The wash outlet valve 479 is closed when using the steam explosion apparatus 460 for steam explosion, but open when washing the reaction chamber 462. The target temperature of the reaction chamber

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Reaction 462 is preferably between 180 and 240 degrees Celsius or between 200 and 220 degrees Celsius. The containment time is preferably between 10 seconds and 30 minutes or between 30 seconds and 10 minutes or between 1 minute and 5 minutes.

[00468] The target temperature of reaction chamber 462 is preferably between 180 and 240 degrees Celsius or between 200 and 220 degrees Celsius. The containment time is preferably between 10 seconds and 30 minutes or between 30 seconds and 10 minutes or between 1 minute and 5 minutes.

[00469] Because the steam explosion process results in a steam-blown fibrous material sediment, the steam-blown fibrous material can optionally include a fiber recovery process where the liquor is separated from the steam-blown fibrous material. This fiber recovery step is useful in that it allows for additional shearing and / or screening processes and can allow the conversion of the fibrous material into a fuel. The fiber recovery process takes place using a gauze to separate the fibers from the liquor. Other drying processes can also be included to prepare the fibrous material or steam-blown fiber source for further processing.

IRRADIATION, PYROLYSIS, ULTRASOUND AND / OR DEVICES

COMBINED OXIDATION [00470] In some modalities, it may be advantageous to combine two or more different irradiation, ultrasound, pyrolysis and / or oxidation devices in a single hybrid machine. Using such a hybrid machine, multiple processes can be performed in close juxtaposition or even simultaneously, with the benefit of increased pre-treatment production and potential cost savings.

[00471] For example, consider the processes of electron beam irradiation and ultrasound. Each distinct process is effective in decreasing the

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145/204 average molecular weight of cellulosic material in an order of magnitude or more and in several orders of magnitude when performed serially.

[00472] Irradiation and ultrasound processes can be applied using an electron beam / ultrasound hybrid device, as shown in figure 25. The hybrid electron beam / ultrasound device 2500 is represented above a shallow reservoir (depth ~ 3 -5 cm) of a paste of cellulosic material 2550 dispersed in an aqueous oxidizing medium, such as hydrogen peroxide or carbamide peroxide. The 2500 hybrid device has a 2510 power source, which powers the 2540 electron beam emitter and 2530 horn-shaped ultrasound antennas.

[00473] The 2540 electron beam emitter generates electron beams, which pass through one of the 2545 electron beam objectifying devices to collide with the 2550 paste containing cellulosic material. The electron beam targeting device can be a scanner that scans a beam over a range of up to about 6 feet in a direction approximately parallel to the surface of the 2550 paste.

[00474] On either side of the 2540 electron beam emitter are 2530 horn-shaped ultrasound antennas, which distribute ultrasonic wave energy to the 2550 slurry. The 2530 horn-shaped ultrasound antennas terminate at a terminal part detachable 2535 that is in contact with the 2550 folder.

[00475] Horn-shaped ultrasound antennas 2530 are at risk of damage from long-term residual exposure to electron beam radiation. Thus, horn-shaped antennas can be protected with a standard 2520 shield, for example, made of lead or an alloy containing heavy metal, such as Lipowitz metal, which is impervious to electron beam radiation. Precautions should be

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146/204 taken, however, to ensure that ultrasonic energy is not affected by the presence of the shield. Detachable terminal parts 2535, which are constructed of the same material and attached to antennae in the shape of horn 2530, are in contact with cellulosic material 2550 during processing and are expected to be damaged. Consequently, the detachable end parts 2535 are constructed to be easily replaced.

[00476] Another benefit of such a simultaneous process with electron beam and ultrasound is that the two processes have complementary results. With electron beam irradiation alone, an insufficient dose can result in crosslinking of some of the polymers in the cellulosic material, which decreases the efficiency of the overall depolymerization process. Lower doses of electron beam irradiation and / or ultrasound radiation can also be used to obtain a degree of depolymerization similar to that obtained using electron beam and ultrasound irradiation separately.

[00477] An electron beam device can also be combined with one or more high frequency rotor-stator devices, which can be used as an alternative to ultrasound devices.

[00478] Other combinations of devices are also possible. For example, an ionizing radiation device that produces gamma radiation emitted, for example, from ⁶⁰ Co pellets, can be combined with an electron beam source and / or an ultrasonic wave source. Protection requirements may be more stringent in this case.

[00479] A radiation device for biomass pretreatment discussed above can also be combined with one or more devices that perform one or more processing sequences by pyrolysis. Such a combination may, once again, have the advantagePetition 870170006381, of 01/30/2017, p. 152/258

147/204 higher yield. However, care must be observed, since there may be conflicting requirements between some radiation and pyrolysis processes. For example, ultrasonic radiation devices may require the supply of food to be immersed in a liquid oxidation medium. On the other hand, as discussed earlier, it may be advantageous for the sample of feed stock to undergo pyrolysis to be of a particular moisture content. In this case, the new systems automatically measure and monitor a particular moisture content and regulate it. In addition, some or all of the above devices, especially the pyrolysis device, can be combined with an oxidation device, as discussed earlier.

PRIMARY PROCESSES

FERMENTATION [00480] In general, several microorganisms can produce a series of useful products, such as a fuel, operating, for example, on the fermentation of pre-treated biomass materials. For example, alcohols, organic acids, hydrocarbons, hydrogen, proteins or mixtures of any of these materials can be produced through fermentation or other processes.

[00481] The microorganism can be a natural microorganism or a manipulated microorganism. For example, the microorganism can be a bacterium, for example, a cellulolytic bacterium, a fungus, for example, a yeast, a plant or a protist, for example, an algae, a protozoan, or a fungus-like protist, for example example, a mud mold. When the organisms are compatible, mixtures of organisms can be used.

[00482] To assist in the decomposition of materials that include cellulose, one or more enzymes, for example, a cellulolytic enzyme, can be used. In some embodiments, materials that include

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148/204 cellulose is first treated with the enzyme, for example, by combining the material and the enzyme in an aqueous solution. This material can then be combined with the microorganism. In other embodiments, materials that include cellulose, one or more enzymes and the microorganism are combined concurrently, for example, by combining in an aqueous solution.

[00483] Also, to assist in the decomposition of materials including cellulose, the treated materials, post-irradiation, with heat, a chemical product (for example, mineral acid, base or a strong oxidizer, such as sodium hypochlorite) and / or an enzyme.

[00484] During fermentation, sugars released from the cellulolytic hydrolysis or saccharification stage are fermented, for example, in ethanol, by a fermentation micro-organism, such as yeast. Suitable fermentation microorganisms have the ability to convert carbohydrates, such as glucose, xylose, arabinose, mannose, galactose, oligosaccharides or polysaccharides, into fermentation products. Fermentation microorganisms include strains of the genus Sacchromyces spp. for example, Sacchromyces cerevisiae (baker's yeast), Saccharomyces distaticus, Saccharomyces uvarum; of the genus Kluyveromyces, for example, species Kluyveromyces marxianus and Kluyveromyces fragilis; of the genus Candida, for example, Candida pseudotropicalis and Candida brassicae, Pichia stipitis (a relative of Candida shehatae); of the genus Clavispora, for example, species Clavispora lusitaniae and Clavispora opuntiae; of the genus Pachysolen, for example, species Pachysolen tannophilus; of the Bretannomyces genus, for example, Bretannomyces clausenii species; (Philippidis G.P., 1996, Cellulose Bioconversion Technology, in Handbook on Bioethanol: Production and Utilization, Wyman, C.E., Ed., Taylor & Francis, Washington, DC, 179-212). In particular modalities, such as when xylose is present, Pichia stipitis (ATCC 66278) is used

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149/204 in fermentation.

[00485] Commercially available yeasts include, for example, Red Star® / Lesaffre Ethanol Red (available from Red Star / Lesaffre, USA), FALI® (available from Fleischmann's Yeast, a division of Burns Philip Food Inc., USA); SUPERSTART® (available from Alltech now Lallemand), GERT STRAND ^® (available from Gert Strand AB, Sweden); and FERMOL ^® (available from DSM Specialties).

[00486] Bacteria that can ferment biomass in ethanol and other products include, for example, Zymomonas mobilis and Clostridium thermocellum (Philippidis, 1996, supra). Leschine et al. (International Journal of Systematic and Evolutionary Microbiology 2002, 52, 11551160) isolated an anaerobic, mesophilic, cellulolytic bacterium from forest soil, Clostridium phytofermentans sp. nov., which converts cellulose to ethanol.

[00487] Fermentation of biomass in ethanol and other products can be carried out using certain types of thermophilic or genetically manipulated microorganisms, such as Thermoanaerobacter species, including T. mathranii and yeast species, such as Pichia species. An example of a T. mathranii strain is A3M4 described in Sonne-Hansen et al. (Applied Microbiology and Biotechnology 1993, 38, 537-541) or Ahring et al. (Arch. Microbiol. 1997, 168, 114-119). Other genetically engineered microorganisms are discussed in U.S. Patent No. 7,192,772.

[00488] Yeast and Zymomonas bacteria can be used for fermentation or conversion. The optimum pH for yeast is a pH of about 4 to 5, while the optimum pH for Zymomonas is a pH of about 5 to 6. Typical fermentation times are about 24 to 96 hours, with temperatures in the range of 26 ° C to 40 ° C, however thermophilic microorganisms prefer higher temperatures.

[00489] Enzymes which decompose biomass, such as cellulose 870170006381, of 01/30/2017, p. 155/258

150/204 lose, to decrease materials containing low molecular weight carbohydrates, such as glucose, during saccharification, are referred to as cellulolytic enzymes or cellulase. These enzymes can be a complex of enzymes that act synergistically to degrade crystalline cellulose. Examples of cellulolytic enzymes include: endoglucanases, cellobiohydrolases and cellobiases (β-glucosidases). A cellulosic substrate is initially hydrolyzed by endoglucanases at random locations that produce oligomeric intermediates. These intermediates are then substrates for exo-dividing glucanases, such as cellobiohydrolase, to produce cellobiose from the ends of the cellulose polymer. Cellobiosis is a water-soluble β-1,4 linked glucose dimer. Finally, celobiase cleaves cellobiosis to provide glucose.

[00490] A cellulase is capable of degrading biomass and can be of fungal or bacterial origin. Suitable enzymes include cellulases of the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, Chrysosporium and Trichoderma and include Humicola, Coprinus, Thielavia, Fusarium, Myceliophthora, Acremonium, Cephalosporium, Scytalidium, Penicillium or Asperg, eg 458162), especially those produced by a selected strain of the Humicola insolens species (re-classified as Scytalidium thermophilum; see, for example, US Patent No. 4,435,307), Coprinus cinereus, Fusarium oxysporum, Myceliophthora thermophila, Meripilus giganteus, Thielavia terrestris , Acremonium sp., Acremonium persicinum, Acremonium acremonium, Acremonium brachypenium, Acremonium dichromosporum, Acremonium obclavatum, Acremonium pinkertoniae, Acremonium roseogriseum, Acremonium incoloratum and Acremonium furatum; preferably from the species Humicola insolens DSM 1800, Fusarium oxysporum DSM 2672, Myceliophthora thermophila CBS 117.65, Cephalosporium sp. RYM-202,

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Acremonium sp. CBS 478.94, Acremonium sp. CBS 265.95, Acremonium persicinum CBS 169.65, Acremonium acremonium AHU 9519, Cephalosporium sp. CBS 535.71, Acremonium brachypenium CBS 866.73, Acremonium dichromosporum CBS 683.73, Acremonium obclavatum CBS 311.74, Acremonium pinkertoniae CBS 157.70, Acremonium roseogriseum CBS 134.56, Acremonium incoloratum CBS 146.62 and Acremonium furatum. Cellulolytic enzymes can also be obtained from Chrysosporium, preferably a lucknowense strain of Chrysosporium. In addition, Trichoderma (particularly Trichoderma viride, Trichoderma reesei and Trichoderma koningii), Alkalophilic Bacillus (see, for example, U.S. Patent No. 3,844,890 and EP 458162) and Streptomyces (see, for example, EP 458162). The bacterium Saccharophagus degradans, produces a mixture of enzymes capable of degrading a series of cellulosic materials and can also be used in this process.

[00491] Anaerobic cellulolytic bacteria have also been isolated from the soil, for example, a new cellulolytic species of Clostiridium, Clostridium phytofermentans sp. nov. (see Leschine et al., International Journal of Systematic and Evolutionary Microbiology (2002), 52, 1155-1160).

[00492] Cellulolytic enzymes using recombinant technology can also be used (see, for example, documents WO 2007/071818 and WO 2006/110891).

[00493] Other enzymes and enzyme formulations that can be used are discussed in Published Patent Applications Nos. 2006/0008885 and 2006/0068475 and in PCT Application No. WO 2006/128304.

[00494] Cellulolytic enzymes can be produced by fermenting the microbial strains mentioned above on a nutrient medium containing suitable carbon and nitrogen sources and

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152/204 inorganic salts, using procedures known in the field (see, for example, Bennett, J.W. and LaSure, L. (eds.), More Gene Manipulations in Fungi, Academic Press, CA 1991). Suitable media are available from commercial suppliers or can be prepared according to published compositions (for example, in catalogs of the American Type Culture Collection). Temperature ranges and other conditions suitable for cellulase growth and production are known in the field (see, for example, Bailey, J.E. and Ollis, D.F., Biochemical Engineering Fundamentals, McGraw-Hill Book Company, NY, 1986).

[00495] Treatment of cellulose with cellulase is usually carried out at temperatures between 30 ° C and 65 ° C. Cellulases are active over a pH range of about 3 to 7. A saccharification step can last up to 120 hours. The cellulase enzyme dosage achieves a sufficiently high level of cellulose conversion. For example, an appropriate cellulase dosage is typically between 5.0 and 50 Filter Paper Unit (FPU or IU) per gram of cellulose. FPU is a standard measure and is defined and measured according to Ghose (1987, Pure and Appl. Chem. 59: 257-268).

[00496] In particular modalities, the enzyme complex ACCELERASE ^® 1000 (Genencor) is used as the enzyme system in a loading of 0.25 ml per gram of substrate. The enzyme complex ACCELERASE® 1000 is a cocktail with multiple enzymes with multiple activities, mainly exoglucanase, endoglucanase, hemicellulase and beta-glucosidase. The cocktail has a minimum endoglucanase activity of 2500 CMC U / g and a minimum beta-glucosidase activity of 400 pNPG U / g. The pH of the cocktail is about 4.8 to about 5.2. In other particular embodiments, the enzyme system used is a mixture of CELLUCLAST® 1.5L and Novozyme 188. For example, 0.5 ml of CELLUCLAST® 1.5L and 0.1 ml

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153/204 of Novozyme 188 can be used for each gram of substrate. When increased hemicellulase (xylanase) activity is desired, OPTIMASH® BG can be used.

[00497] Mobile fermenters can be used, as described in U.S. Provisional Patent Application Serial No. 60 / 832,735, now Published International Application No. WO 2008/011598.

ETHANOL FERMENTATION [00498] Ethanol is a fermentation product. Fermentation is a sequence of reactions which release energy from organic molecules in the absence of oxygen. In this application of fermentation, energy is obtained when sugar is changed to ethanol and carbon dioxide. All drink ethanol and more than half of industrial ethanol is made through this process. Changing from corn to ethanol through fermentation occurs in many stages. Corn starch is broken down into simple sugars before fermentation can take place. This can be achieved, for example, by cooking the corn and adding the enzymes alpha amylase and gluco amylase. These enzymes act as catalysts to accelerate chemical changes. Once a simple sugar is obtained, yeast is added. Yeast is a single-celled fungus, which feeds on sugars and causes fermentation. As the funfo feeds on sugar, it produces alcohol (ethanol) and carbon dioxide. In fermentation, ethanol retains most of the energy that was originally in sugar, which explains why ethanol is an excellent fuel.

[00499] The fermentation reaction is represented by the simple equation:

C6H12O6 —— 2 CH ₃ CH ₂ OH + 2 CO ₂ [00500] Ethanol can be made from a wide variety of available feed stocks. Fuel ethanol can be

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154/204 made from crops which contain starch, such as feed grains, food grains, such as corn and tubers, such as potatoes and sweet potatoes. Sugar-containing crops, such as sugar beets, sugar cane and sweet sorghum could also be used for ethanol production. In addition, by-products from food processing, such as molasses, cheese whey and cellulosic materials, including grasses and wood, as well as agricultural and forest residues, can be processed into ethanol. As discussed above, these and other feed stocks can be treated as discussed here to facilitate ethanol production.

CONVERSION OF STARCH MATERIALS [00501] Figures 26 and 27 show block diagrams for a wet and dry grinding process, respectively, and illustrate the conversion, for example, fermentation, of corn kernels into ethanol and other valuable products.

[00502] Referring particularly to figure 26, in some implementations, a dry milling process for converting corn kernels into ethanol, for example, anhydrous ethanol, which can be used as a fuel, for example, fuel for automotive or aviation, can start with pre-treatment of dry corn kernels with any one or more pre-treatments described here, such as radiation, for example, any one or more types of radiation described here (for example, an electron beam in which each electron has an energy of about 5 MeV or a beam of protons in which the energy of each proton is about 3-100 MeV). After pre-treatment, the corn kernels can be crushed and / or sheared into a powder. Although any one or more of the pretreatments described here can be applied after milling and / or at any time during the dry milling process outlined in figure 26, pretreatment before milling and / or shearing can be applied. 870170006381, de 01/30/2017, p. 160/258

155/204 tajoso by the fact that the grains are, in general, more fragile after pretreatment and, as a result, they are easier and require less energy to crush and / or shear. In some embodiments, a selected pretreatment can be applied more than once during conversion, for example, before crushing and then after crushing. [00503] After crushing and / or shearing, the crushed dry grains can optionally be hydrated by adding the crushed material to a vessel containing water and, optionally, hydrating agents, such as surfactants. Optionally, such a reaction vessel may also include including one or more enzymes, such as amylase, to assist in further decomposition of the starch biomass or the reaction vessel may contain one or more acids, such as a mineral acid, for example, acid diluted sulfuric. If a hydration vessel is used, its contents are emptied into a conversion vessel, for example, a fermentation vessel, which includes one or more conversion microbes, such as one or more yeasts, bacteria or mixtures of yeasts and / or bacteria. If a hydration vessel is not used, the crushed material can be directly loaded into a conversion vessel, for example, for fermentation.

[00504] After conversion, the remaining solids are removed and dried to provide dry distillery grains (DDG), while ethanol is distilled. In some embodiments, a thermophilic microbe is used for the conversion and the ethanol is continuously removed by evaporation as it is produced. If desired, the distilled ethanol can be completely dehydrated, such as passing the wet ethanol through a zeolite bed or distilling with benzene. [00505] Referring particularly now to figure 27, in some implementations, the wet milling process for converting corn kernels into anhydrous ethanol begins with pretreatment of dry corn kernels with any one or more prePetition 870170006381, of 30/01 / 2017, p. 161/258

156/204 treatments described here, such as radiation, for example, any one or more types of radiation described here (for example, an electron beam in which each electron has an energy of about 5 MeV). After pre-treatment, the corn kernels are macerated in diluted sulfuric acid and gently agitated to decompose the corn kernels into their constituents. After maceration, the portions of fiber, oil and germ are fractionated and dried and then combined with any remaining solids after swelling to provide corn gluten (CGF) feed. After removing the germ and fiber, in some embodiments, the gluten is separated to provide corn gluten flour (CGM). The remaining starch can be pretreated again (or for the first time) through any pretreatment described here, for example, to reduce its molecular weight and / or functionalize the starch, so that it is more soluble. In some embodiments, the starch is then loaded into a reaction vessel containing water and, optionally, hydrating agents, such as surfactants. Optionally, that reaction vessel may also include one or more enzymes, such as amylase, to assist in further decomposition of starch or the reaction vessel may contain one or more acids, such as a mineral acid, for example, diluted sulfuric acid. As shown, saccharification can take place in several vessels and then the contents of the final vessel can be emptied into a conversion vessel, for example, a fermentation vessel, which includes one or more conversion microbes, such as one or more yeast or bacteria.

[00506] After conversion, ethanol is distilled. In some embodiments, a thermophilic microbe is used for the conversion and the ethanol is continuously removed by evaporation as it is produced. If desired, the distilled ethanol can be completely dehydrated, such as passing the wet ethanol through a zeolite bed.

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GASIFICATION [00507] In addition to using pyrolysis to pre-treat feed stock, pyrolysis can also be used to process pre-treated feed stock to extract useful materials. In particular, a form of pyrolysis known as gasification can be used to generate combustible gases along with various other gaseous, liquid and solid products. To perform gasification, the pre-treated feed stock is introduced into a pyrolysis chamber and heated to a high temperature, typically 700 ° C or more. The temperature used depends on a number of factors, including the nature of the feed stock and the desired products.

[00508] The amounts of oxygen (for example, as pure oxygen gas and / or as air) and steam (for example, superheated steam) are also added to the pyrolysis chamber to facilitate gasification. These compounds react with the carbon stock material in a multi-step reaction to generate a gas mixture called syngas (or syngas). Essentially, during gasification, a limited amount of oxygen is introduced into the pyrolysis chamber to allow some of the feed stock material to combust to form carbon monoxide and generate process heat. The process heat can then be used to promote a second reaction that converts the additional feed stock material into hydrogen and carbon monoxide.

[00509] In a first step of global reaction, heating the feed stock material produces a carbonization that can include a wide variety of different hydrocarbon-based species. Certain volatile materials can be produced (for example, certain gaseous hydrocarbon materials), resulting in a reduction in the overall weight of the stock material

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158/204 of feeding. Then, in a second stage of the reaction, some of the volatile material that is produced in the first stage reacts with oxygen in a combustion reaction to produce carbon monoxide and carbon dioxide. The combustion reaction releases heat, which promotes the third step of the reaction. In the third stage, carbon dioxide and steam (for example, water) react with the carbonization generated in the first stage to form carbon monoxide and hydrogen gas. Carbon monoxide can also react with steam, in a water / gas bypass reaction, to form carbon dioxide and more hydrogen gas.

[00510] Gasification can be used as a primary process to generate products directly from the pre-treated feed stock for subsequent transportation and / or sale, for example. Alternatively or in addition, gasification can be used as an auxiliary process for generating fuel for a global processing system. Hydrogen-rich syngas that are generated via the gasification process can be burned, for example, to generate electricity and / or process heat that can be directed for use elsewhere in the processing system. As a result, the overall processing system can be at least partially self-sufficient. A number of other products, including pyrolysis oils and hydrocarbon-based gaseous substances, can also be obtained during and / or after gasification; these can be separated and stored or transported, as desired.

[00511] A variety of different pyrolysis chambers are suitable for gasifying the pre-treated feed stock, including the pyrolysis chambers disclosed here. In particular, fluidized bed reactor systems, in which the pre-treated feed stock is fluidized in steam and oxygen / air, provide relatively high and direct product recovery. Solid carbonization

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159/204 that remains after gasification in a fluidized bed system (or in other pyrolysis chambers) can be burned to generate additional heat for the process in order to promote subsequent gasification reactions.

[00512] Syngas can be reformed using a Fischer-Tropsch process, which is a catalyzed chemical reaction in which the synthesis gas is converted into liquid alcohols and hydrocarbons. The most common catalysts are based on iron and cobalt, although nickel and ruthenium have also been used.

[00513] In an alternative process, a biofilm can be used to reform the syngas to produce liquid fuel instead of a chemical catalyst. Such a process has been described by Coskata, Inc. Any of the biomass materials described here can be used in the Coskata process.

[00514] In some embodiments, irradiation of the biomass material, for example, with a beam of particles, such as electrons, before gasification, can lower the gasification temperature, resulting in less energy being consumed during gasification and may result in less tar and pitch formation, resulting in an enhanced syngas yield.

POST-PROCESSING

DISTILLATION [00515] After fermentation, the resulting fluids can be distilled using, for example, a yeast column to separate ethanol and other alcohols from most water and residual solids. The steam leaving the yeast column can be, for example, 35% by weight of ethanol and can be fed to a rectifying column. A mixture of ethanol (92.5%) and quasi-azeotropic water from the rectification column can be purified to pure ethanol (99.5%) using molecular vapor sieves. The lower parts of the yeast column

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160/204 can be sent to the first stage of a three stage evaporator. The reflux condenser in the rectification column can provide heat for this first stage. After the first stage, solids can be separated using a centrifuge and dried in a rotary dryer. A portion (25%) of the effluent from the centrifuge can be recycled for fermentation and the rest sent to the second and third stages of the evaporator. Most of the condensate from the evaporator can be returned to the process as a reasonably clean condensate, with a small portion of the treated water diverted to prevent the development of low boiling compounds. WASTE WATER TREATMENT [00516] Waste water treatment is used to minimize plant water composition requirements by treating process water for reuse within the plant. Wastewater treatment can also produce fuel (for example, sediment and biogas) that can be used to improve the overall efficiency of the ethanol production process. For example, as described in more detail below, sediment and biogas can be used to create steam and electricity that can be used in various processes at the plant.

[00517] Residual water is initially pumped through a sieve (for example, a bar sieve) to remove large particles, which are collected in a feeder tank. In some embodiments, the large particles are sent to a landfill. Additionally or alternatively, the large particles are burned to create steam and / or electricity, as described in greater detail below. In general, the spacing on the bar sieve is between 1/4 inch to 1 inch spacing (for example, 1/2 inch spacing).

[00518] The residual water then flows into an equalization tank,

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161/204 where the organic concentration of the residual water is balanced during a retention time. In general, the retention time is between 8 hours and 36 hours (for example, 24 hours). A mixer is arranged inside the tank to stir the contents of the tank. In some embodiments, mixers arranged throughout the tank are used to stir the contents of the tank. In certain embodiments, the mixer substantially mixes the contents of the equilibration tank, so that the conditions (for example, concentration and temperature of the waste water) throughout the tank are uniform.

[00519] A first pump moves the water from the equalization tank through a liquid-to-liquid heat exchanger. The heat exchanger is controlled (for example, by controlling the rate of fluid flow through the heat exchanger) so that the residual water leaving the heat exchanger is at a desired temperature for anaerobic treatment. For example, the desired temperature for anaerobic treatment can be between 40 ° C to 60 ° C. [00520] After leaving the heat exchanger, the residual water enters one or more anaerobic reactors. In some embodiments, the sediment concentration in each anaerobic reactor is the same as the overall sediment concentration in the wastewater. In other embodiments, the anaerobic reactor has a higher concentration of sediment than the overall concentration of sediment in the wastewater.

[00521] A nutrient solution containing nitrogen and phosphorus is measured in each anaerobic reactor containing residual water. The nutrient solution reacts with the sediment in the anaerobic reactor to produce biogas, which can contain 50% methane and has a heating value of approximately 12,000 British thermal units (British Thermal Units) or Btu per pound. The biogas leaves each anaerobic reactor through ventilation and flows to a manifold, where several streams of biogas are combined into a single stream.

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A compressor moves the biogas stream to a boiler or combustion engine, as described in more detail below. In some embodiments, the compressor also moves the single biogas stream through a desulfurization catalyst. In addition or alternatively, the compressor can move the single biogas stream through a sediment trap.

[00522] A second pump moves the anaerobic effluent from the anaerobic reactors to one or more aerobic reactors (for example, activated sediment reactors). An aerator is arranged inside each aerobic reactor to mix the anaerobic effluent, sediment and oxygen (for example, oxygen contained in the air). Within each aerobic reactor, oxidation of cellular material in the anaerobic effluent produces carbon dioxide, water and ammonia.

[00523] The aerobic effluent moves (for example, via gravity) to a separator, where the sediment is separated from the treated water. Some of the sediment is returned to the one or more aerobic reactors to create a high concentration of sediment in the aerobic reactors, thereby facilitating the aerobic decomposition of cellular material in the waste water. A conveyor removes excess sediment from the separator. As described in more detail below, excess sediment is used as a fuel to create steam and / or electricity.

[00524] The treated water is pumped from the separator to a settlement tank. Solids dispersed throughout the treated water settle to the bottom of the settlement tank and are subsequently removed. After a settlement period, the treated water is pumped from the settlement tank through a fine filter to remove any residual solids remaining in the water. In some embodiments, chlorine is added to the treated water to kill pathogenic bc. In some modalities, one or more techniques of separationPetition 870170006381, of 01/30/2017, p. 168/258

163/204 physical-chemical feed are used to further purify treated water. For example, treated water can be pumped through a carbon adsorption reactor. As another example, treated water can be pumped through a reverse osmosis reactor.

[00525] In the processes described here, whenever water is used in any process, it can be gray water, for example, municipal gray water or black water. In some embodiments, gray or black water is sterilized before use. Sterilization can be performed using any desired technique, for example, by means of irradiation, steam or chemical sterilization.

WASTE COMBUSTION [00526] The production of alcohol from biomass can result in the production of various by-product streams useful for the generation of steam and electricity to be used elsewhere in the factory. For example, steam generated from burning by-product streams can be used in the distillation process. As another example, electricity generated from burning by-product currents can be used to drive electron beam generators and ultrasonic transducers used in pretreatment.

[00527] The by-products used to generate steam and electricity are derived from a number of sources throughout the process. For example, aerobic digestion of residual water produces biogas with a high methane content and a small amount of residual biomass (sediment). As another example, solid post-distillates (for example, unconverted lignin, cellulose and hemicellulose remaining from the primary and pretreatment processes) can be used as a fuel.

[00528] The biogas is diverted to a combustion engine connected to an electric generator to produce electricity. For example, biogas can be used as a fuel source for a spark-ignited natural gas engine. As another example, biogas can

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164/204 be used as a fuel source for a direct injection natural gas engine. As another example, biogas can be used as a fuel source for a combustion turbine. In addition or alternatively, the combustion engine can be configured in a cogeneration configuration. For example, residual heat from combustion engines can be used to provide hot water or steam to the entire plant.

[00529] The sediment and post-distilled solids are burned to heat a flow of water through a heat exchanger. In some embodiments, the flow of water through the heat exchanger is evaporated and overheated in steam. In certain embodiments, steam is used in the pretreatment reactor and in heat exchange in distillation and evaporation processes. Additionally or alternatively, the steam expands the power of a multistage steam turbine connected to an electric generator. The steam coming out of the steam turbine is condensed with the cooling water and returned to the heat exchanger for reheating in steam. In some embodiments, the rate of water flow through the heat exchanger is controlled to obtain a targeted production of electricity by the steam turbine connected to an electric generator. For example, water can be added to the heat exchanger to ensure that the steam turbine is operating above a threshold condition (for example, the turbine is rotating fast enough to start the electric generator).

[00530] Although certain modalities have been described, other modalities are possible.

[00531] As an example, although biogas is described as being diverted to a combustion engine connected to an electric generator, in certain embodiments, biogas can be passed through a fuel reformer to produce hydrogen. O

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165/204 hydrogen is then converted to electricity by a fuel cell.

[00532] As another example, although biogas is described as being burned separately from sediment and post-distilled solids, in certain embodiments, all residual by-products can be burned together to produce steam.

PRODUCTS / CO-PRODUCTS

ALCOHOLS [00533] The alcohol produced can be a monohydroxy alcohol, for example, ethanol or a polyhydroxy alcohol, for example, ethylene glycol or glycerin. Examples of alcohols that can be produced include methanol, ethanol, propanol, isopropanol, butanol, for example, n-, dried tert-butanol, ethylene glycol, propylene glycol, 1,4-butane diol, glycerin or mixtures of these alcohols.

[00534] Each of the alcohols produced by the factory has commercial value as an industrial food stock. For example, ethanol can be used in the manufacture of varnishes and perfume. As another example, methanol can be used as a solvent used as a fluid component for windshield wipers. As another example, butanol can be used in plasticizers, resins, lacquers and brake fluids.

[00535] The bioethanol produced by the factory is valuable as an ingredient used in the food and beverage industry. For example, ethanol produced by the factory can be purified in food grade alcohol and used as a primary ingredient in alcoholic beverages.

[00536] The bioethanol produced by the factory also has commercial value as a transport fuel. The use of ethanol as a transport fuel can be implemented with relatively little capital investment by engine manufacturers and owners

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166/204 from spark ignition (eg changes in timing, fuel-to-air ratio and fuel injection system components). Many automotive manufacturers currently offer flex vehicles capable of operation with ethanol / gasoline blends with up to 85% ethanol by volume (for example, standard equipment on a 4 x 4 Chevy Tahoe).

[00537] The bioethanol produced by this factory can be used as a motor fuel in order to improve environmental and economic conditions in addition to the factory location. For example, ethanol produced by this factory and used as a fuel can reduce greenhouse gas emissions from man-made sources (for example, transportation sources). As another example, the ethanol produced by this factory and used as a motor fuel can also replace the consumption of refined oil gasoline. [00538] Bioethanol has a higher number of octane than conventional gasoline and, thus, it can be used to improve the performance (for example, allow higher compression ratios) of spark ignition engines. For example, small amounts (eg 10% by volume) of ethanol can be mixed with gasoline to act as an octane intensifier for fuels used in spark ignition engines. As another example, larger amounts (eg 85% by volume) of ethanol can be mixed with gasoline to increase the fuel's octane number and replace large volumes of gasoline.

[00539] Strategies for bioethanol are discussed, for example, by DiPardo in Journal of Outlook for Biomass Ethanol Production and Demand (EIA Forecasts), 2002; Sheehan in Biotechnology Progress, 15: 8179, 1999; Martin in Enzyme Microbes Technology, 31: 274, 2002; Greer in BioCycle, 61-65, April 2005; Lynd in Microbiology and Molecular Biology Reviews, 66: 3, 506-577, 2002; Ljungdahl

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167/204 et al. in U.S. Patent No. 4,292,406; and Bellamy in U.S. Patent No. 4,094,742.

ORGANIC ACIDS [00540] The organic acids produced can include monocarboxylic acids or polycarboxylic acids. Examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, palmitic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, oleic acid, linoleic acid, glycolic acid, lactic acid, ghydroxybutyric acid or mixtures of these acids.

CO-PRODUCTS

Lignin Waste [00541] As described above, waste containing lignin from primary and pretreatment processes has value as a high / medium energy fuel and can be used to generate energy and steam for use in plant processes. However, such lignin residues are a new type of solid fuel and there is little demand for it outside the factory limits and the costs of drying it for transportation only subtract from its potential value. In some cases, gasification of lignin waste can convert it to a higher value product at a lower cost.

Other Co-Products [00542] Cellular matter, furfural and acetic acid have been identified as potential co-products of biomass fuel processing units. Interstitial cell material could be valuable, but it requires significant purification. The markets for furfuraldehyde and acetic acid exist, although they are unlikely to be large enough to consume the production of a fully commercialized ethanol lignocellulose industry.

EXAMPLES

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168/204 [00543] The following Examples are intended to illustrate and not to limit the teachings of the present description.

EXAMPLE 1 - PREPARATION OF FIBROUS MATERIAL FROM

POLY-COATED PAPER [00544] A load of 1500 pounds of virgin half-gallon juice packaging made of unprinted white poly-coated Kraft cardboard having a volumetric density of 20 pounds / foot ^{3 was} obtained from International Paper. Each package was folded and then fed to a 3 hp Flinch Baugh chipper at a rate of approximately 15 to 20 pounds per hour. The chipper was equipped with two 12-inch rotating blades, two fixed blades and a 0.30-inch discharge sieve. The gap between the rotating and fixed blades has been adjusted to 0.10 inches. The mincer product resembled confetti having a width of between 0.1 inch and 0.5 inch, a length of between 0.25 inch and 1 inch and a thickness equivalent to that of the starter material (about 0.075 inch).

[00545] The confetti-like material was fed to a Munson rotary knife cutter, Model SC30. The Model SC30 is equipped with four rotating blades, four fixed blades and a discharge screen having 1/8 inch openings. The gap between the rotating and fixed blades has been set to approximately 0.020 inches. The rotary knife cutter shears the confetti-like pieces across the edges of the knives, tearing the pieces apart and releasing a fibrous material at a rate of about a pound an hour. The fibrous material had a BET surface area of 0.9748 m ² / g +/- 0.0167 m ² / g, a porosity of 89.0437 percent and a volumetric density (@ 0.53 psia) of 0, 1260 g / ml. The average fiber length was 1.141 mm and the average fiber width was 0.027 mm, providing an average L / D of 42: 1. A scanning electron micrograph of the fibrous material is shown in figure 28 at a magnification of 25X.

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EXAMPLE 2 - PREPARATION OF FIBROUS MATERIAL FROM

WHITE KRAFT PAPER [00546] A load of 1500 pounds of bleached virgin white Kraft paper having a volumetric density of 30 pounds / foot ³ was obtained from International Paper. The material was folded and then fed to a 3 hp Flinch Baugh chipper at a rate of approximately 15 to 20 pounds per hour. The chipper was equipped with two 12-inch rotating blades, two fixed blades and a 0.30-inch discharge sieve. The gap between the rotating and fixed blades has been adjusted to 0.10 inches. The mincer product resembled confetti having a width of between 0.1 inch and 0.5 inch, a length of between 0.25 inch and 1 inch and a thickness equivalent to that of the starter material (about 0.075 inch). The confetti-like material was fed to a Munson rotary knife cutter, Model SC30. The discharge sieve had 1/8 inch openings. The gap between the rotating and fixed blades has been set to approximately 0.020 inches. The rotary knife cutter shears the confetti-like pieces, releasing a fibrous material at a rate of about a pound an hour. The fibrous material had a BET surface area of 1.1316 m ² / g +/- 0.0103 m ² / g, a porosity of 88.3285 percent and a volumetric density (@ 0.53 psia) of 0, 1497 g / ml. The average length of the fibers was 1.063 mm and the average width of the fibers was 0.0245 mm, providing an average L / D of 43: 1. A scanning electron micrograph of the fibrous material is shown in figure 29 at a magnification of 25X.

EXAMPLE 3 - PREPARATION OF SHEARED FIBROUS MATERIAL

TWO TIMES FROM BLEACHED KRAFT PAPER [00547] A load of 1500 pounds of bleached virgin white Kraft paper having a volumetric density of 30 pounds / foot ³ was obtained from International Paper. The material was folded and then fed to

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170/204 a 3 hp Flinch Baugh chipper at a rate of approximately 15 to 20 pounds per hour. The chipper was equipped with two 12-inch rotating blades, two fixed blades and a 0.30-inch discharge sieve. The gap between the rotating and fixed blades has been adjusted to 0.10 inches. The mincer product resembled confetti (as above). The confetti-like material was fed to a Munson rotary knife cutter, Model SC30. The discharge screen had 1/16 inch openings. The gap between the rotating and fixed blades has been set to approximately 0.020 inches. The rotary knife cutter confetti-like pieces, releasing a fibrous material at a rate of about one pound an hour. The material resulting from the first shear was re-fed in the same configuration described above and sheared again. The resulting fibrous material had a BET surface area of 1.4408 m ² / g +/- 0.0156 m ² / g, a porosity of 90.8998 percent and a volumetric density (@ 0.53 psia) of 0 , 1298 g / ml. The average fiber length was 0.891 mm and the average fiber width was 0.026 mm, providing an average L / D of 34: 1. A scanning electron micrograph of the fibrous material is shown in figure 30 at 25X magnification.

EXAMPLE 4 - PREPARATION OF SHEARED FIBROUS MATERIAL

THREE TIMES FROM BLEACHED KRASFT PAPER [00548] A load of 1500 pounds of bleached virgin white Kraft paper having a volumetric density of 30 pounds / foot ^{3 was} obtained from International Paper. The material was folded and then fed to a 3 hp Flinch Baugh chipper at a rate of approximately 15 to 20 pounds per hour. The chipper was equipped with two 12-inch rotating blades, two fixed blades and a 0.30-inch discharge sieve. The gap between the rotating and fixed blades has been adjusted to 0.10 inches. The chopper product resembled confetti (the

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171/204 above). The confetti-like material was fed to a Munson rotary knife cutter, Model SC30. The discharge sieve had 1/8 inch openings. The gap between the rotating and fixed blades has been set to approximately 0.020 inches. The rotary knife cutter shears the confetti-like pieces across the edges of the knives. The material resulting from the first shear was re-fed in the same configuration and the sieve was replaced by a 1/16 inch sieve. This material was sheared. The material resulting from the second shear was re-fed in the same configuration and the sieve was replaced with a 1/32 inch sieve. This material was sheared. The resulting fibrous material had a BET surface area of 1.6897 m ² / g +/- 0.0155 m ² / g, a porosity of 87.7163 percent and a volumetric density (@ 0.53 psia) of 0 , 1448 g / ml. The average length of the fibers was 0.824 mm and the average width of the fibers was 0.0262 mm, providing an average L / D of 32: 1. A scanning electron micrograph of the fibrous material is shown in figure 31 at a magnification of 25X. EXAMPLE 5 - PREPARATION OF DENSIFIED FIBROUS MATERIAL

FROM BLEACHED KRAFT PAPER WITHOUT BINDING

ADDED [00549] Fibrous material was prepared according to Example 2. Approximately 1 pound of water was sprayed on every 10 pounds of fibrous material. The fibrous material was densified using a Californium 1100 pellet mill operating at 75 ° C. Pellets were obtained having a volumetric density ranging from about 7 pounds / foot ³ to about 15 pounds / foot ³ .

EXAMPLE 6 - PREPARATION OF DENSIFIED FIBROUS MATERIAL

FROM BLANKED KRAFT PAPER WITH BINDING [00550] Fibrous material was prepared according to Example 2. [00551] A 2 percent by weight stock solution of POLIPetition 870170006381, from 01/30/2017, p. 177/258

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The X ^TM WSR N10 (polyethylene oxide) was prepared in water.

[00552] Approximately 1 pound of the stock solution was sprayed over every 10 pounds of fibrous material. The fibrous material was densified using a Californium 1100 pellet mill operating at 75 ° C. Pellets were obtained having a volumetric density ranging from about 15 pounds / foot ³ to about 40 pounds / foot ³ .

EXAMPLE 7 - CELLULOSE MOLECULAR WEIGHT REDUCTION

IN FIBROUS KRAFT PAPER THROUGH RANGE RADIATION WITH

MINIMUM OXIDATION [00553] Fibrous material is prepared according to Example 4. The fibrous kraft paper is densified according to Example 5.

[00554] The densified pellets are placed in a glass ampoule having a maximum capacity of 250 mL. The glass ampoule is evacuated under high vacuum (10 ^-5 torr) for 30 minutes and then refilled with argon gas. The ampoule is sealed under argon. The pellets in the ampoule are irradiated with gamma radiation for about 3 hours at a dose rate of about 1 Mrad per hour in order to provide an irradiated material in which the cellulose has a lower molecular weight than the Kraft initiation material fibrous.

EXAMPLE 8 - CELLULOSE MOLECULAR WEIGHT REDUCTION

IN FIBROUS KRAFT PAPER THROUGH RANGE RADIATION WITH

MAXIMUM OXIDATION [00555] Fibrous material is prepared according to Example 4. The fibrous Kfrat paper is densified according to Example 5.

[00556] The densified pellets are placed in a glass ampoule having a maximum capacity of 250 mL. The glass ampoule is sealed under an air atmosphere. The pellets in the ampoule are irradiated with gamma radiation for about 3 hours at a dose rate of about 1 Mrad per hour in order to provide an irradiated material in which cellulose has a lower molecular weight than the material of

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173/204 initiation of fibrous Kraft.

EXAMPLE 9 - METHODS OF DETERMINING THE MOLECULAR WEIGHT OF CELLULOSIS AND LIGNOCELLULOSIS MATERIALS THROUGH GEL-PERMEATION CHROMATOGRAPHY [00557] Cellulosic and lignocellulosic materials for analysis were treated according to the example in the following tables. (P), wheat straw (WS), alfalfa (A) and switchgrass (SG). Sample ID number 132 refers to the particle size of the material after shearing through a 1/32 inch sieve. The number after the dash refers to the radiation dosage (MRad) and US refers to ultrasonic treatment. For example, a sample ID P132-10 refers to Kraft paper that has been sheared to a particle size of 132 mesh and has been irradiated with 10 MRad.

Table 1. Average molecular weight of gamma irradiated Kraft paper

Source of sample ID sample Dosage ^{* 1} (MRad) Ultrasound ² Average MW ± Standard deviation Paper Kraft P132 0 Not 32853 ± 10006 P132-10 10 II 61398 ± 2468 ** P132-100 100 II 8444 ± 580 P132-181 181 II 6668 ± 77 P132-US 0 Yes 3095 ± 1013

** Low radiation doses appear to increase the molecular weight of some materials ¹ Dosage rate = 1MRad / hour ² Treatment for 30 minutes with ultrasound at 20 kHz using a 1000W horn antenna under recirculation conditions with the material dispersed in Water.

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Table 2. Average peak molecular weight of irradiated materials

Sample ID Peak # Dosage ^{* 1} (MRad) Ultrasound ² Average MW ± Standard Deviation WS132 1 0 Not 1407411 ± 175191 2 II II 39145 ± 3425 3 II II 2886 ± 177 WS132-10 * 1 10 II 26040 ± 3240 WS132-100 * 1 100 II 23620 ± 453 A132 1 0 II 1604886 ± 151701 2 II II 37525 ± 3751 3 II II 2853 ± 490 A132-10 * 1 10 II 50853 ± 1665 2 II II 2461 ± 17 A132-100 * 1 100 II 38291 ± 2235 2 II II 2487 ± 15 SG132 1 0 II 1557360 ± 83693 2 II II 42594 ± 4414 3 II II 3268 ± 249 SG132-10 * 1 10 II 60888 ± 9131 SG132-100 * 1 100 II 22345 ± 3797 SG132-10-US 1 10 Yes 86086 ± 43518 2 II II 2247 ± 468 SG132-100-US 1 100 II 4696 ± 1465

* Peaks coalesce after treatment ** Low doses of radiation appear to increase the molecular weight of some materials ¹ Dosage rate = 1MRad / hour ² Treatment for 30 minutes with 20 kHz ultrasound using a 1000W horn-shaped antenna under recirculation conditions with the material dispersed in water.

[00558] Gel Permeation Chromatography (GPC) is used to determine the molecular weight distribution of polymers. During GPC analysis, a solution of the polymer sample is passed through a packed column

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175/204 with small porous gel containment molecules. The sample is separated based on the molecular size, with larger molecules eluting before small molecules. The retention time of each component is most often detected by the refractive index (Refractive Index - RI), evaporative light scattering (Evaporative Light Scattering - ELS) or Ultraviolet (UV) and compared with a calibration curve. The resulting data is then used to calculate the molecular weight distribution for the sample.

[00559] A molecular weight distribution, instead of a single molecular weight, is used to characterize synthetic polymers. To characterize this distribution, statistical averages are used. The most common of these averages are the average numerical molecular weight (Mn) and the average gravimetric molecular weight (Mw). Methods for calculating these values are described in Example 9 of document PCT / US / 2007/022719.

[00560] The polydispersity index or PI (Polydispersivity Index) is defined as the proportion M _w / M _n . The larger the PI, the wider or more dispersed the distribution. The least value that a PI can have is 1. This represents a monodisperse sample; that is, a polymer with all molecules in the distribution having the same molecular weight. [00561] The peak molecular weight (M _P ) value is another descriptor defined as the mode of molecular weight distribution. It means the molecular weight that is most abundant in the distribution. This value also provides insight into the molecular weight distribution.

[00562] Most measurements by GPC are made with respect to a different polymeric standard. The accuracy of the results depends on how close the characteristics of the polymer being analyzed are to those of the standard used. The expected error in reproducibility between different series of determinations, calibrated separately Petition 870170006381, of 01/30/2017, p. 181/258

176/204 is approximately 5-10% and is characteristic of the limited precision of GPC determinations. Therefore, the GPC results are useful mainly when the comparison between the molecular weight distributions of different samples is made during the same series of determinations.

[00563] Lignocellulosic samples require sample preparation before analysis by GPC. First, a saturated solution (8.4% by weight) of lithium chloride (LiCl) was prepared in dimethyl acetamide (DMAc). Approximately 100 mg of each sample was added to approximately 10 g of a freshly prepared saturated LiCl / DMAc solution and each mixture was heated to approximately 150 ° C-170 ° C with stirring for 1 hour. The resulting solutions were generally light to dark yellow in color. The temperature of the solutions was lowered to approximately 100 ° C and the solutions were heated for an additional 2 hours. The temperature of the solutions was then lowered to approximately 50 ° C and each sample solution was heated for approximately 48 to 60 hours. Of note, samples irradiated at 100 MRad were more easily solubilized when compared to their untreated counterpart. In addition, the shear samples (denoted by the number 132) had slightly lower average molecular weights when compared to uncut samples.

[00564] The resulting sample solutions were diluted 1: 1 using DMAc as a solvent and were filtered through a 0.45 pm PTFE filter. The filtered sample solutions were then analyzed using GPC. The average peak molecular weight (Mp) of the samples, as determined by Gel Permeation Chromatography (GPC), is summarized in Tables 1 and 2. Each sample was prepared in duplicate and each sample preparation was analyzed in duplicate (two injections) for a total of four injections per

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177/204 sample. The EasiCal PS1A and PS1B polystyrene standards were used to generate a calibration curve for the molecular weight scale of about 580 to 7,500.00 Daltons.

Table 3. GPC analysis conditions

Instrument: Waters Alliance GPC 2000 Plgel 10μ Mixed -B Columns (3): S / N's: 10M-MB-148-83; 10M-MB-14884; 10M-MB-174-129 Mobile phase (solvent): 0.5% LiCl in DMAc (1.0 mL / min.) Column / Detector temperature: 70 Injector temperature: 70 Sample loop size: 323.5 μL EXAMPLE 15 - DETERMINATION OF CRYSTALLINITY OF MATERIALS

IRRADIATED RIALS THROUGH X-RAY DIFFERENCE [00565] X-ray diffraction (XRD) is a method by which a crystalline sample is irradiated with monoenergetic X-rays. The interaction of the matrix structure of the sample with these X-rays is recorded and provides information about the crystalline structure being irradiated. The resulting characteristic fingerprint allows the identification of crystalline compounds present in the sample. Using an entire pattern adaptation analysis (the Rietvelt Refining), it is possible to perform quantitative analyzes on samples containing more than one crystalline compound.

Table 4. XRD data including domain size and crystallinity% crystallinity

Sample ID

Domain size (A)

Crystallinity%

P132 55 55 P132-10 46 58 P132-100 50 55 P132-181 48 52 P132-US 26 40

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Sample ID Domain size (A) Crystallinity% A132 28 42 A132-10 26 40 A132-100 28 35 WS132 30 36 WS132-10 27 37 WS132-100 30 41 SG132 29 40 SG132-10 28 38 SG132-100 28 37 SG132-10-US 25 42 SG132-100-US 21 34

[00567] Each sample was placed on a zero-based fastener and placed on a Phillips PW1800 diffractometer using Cu radiation. Scans were then performed over the range of 5 ° to 50 ° with a step size of 0.05 ° and a containment time of 2 hours each.

[00568] Once the diffraction patterns were obtained, the phases were identified with the aid of the Powder Diffraction File published by the International Center for Diffraction Data. In all samples, the crystalline phase identified was cellulose - Ia, which has a triclinic structure.

[00569] The distinguishing feature among the 20 samples is the peak amplitude, which is related to the size of the crystallite domain. The experimental peak amplitude was used to compute the domain size and percentage crystallinity, which are reported in Table 4.

[00570] The percentage crystallinity (X _c %) is measured as a ratio of the crystalline area to the total area under the X-ray diffraction peaks, where:

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A _c = area of crystalline phase

A _a = amorphous phase area

X _c = percentage crystallinity [00571] To determine the percentage crystallinity for each sample, it was necessary to first extract the amount of the amorphous phase. This is done by estimating the area of each diffraction pattern that can be attributed to the crystalline phase (represented by the sharpest peaks) and the non-crystalline phase (represented by the wide valleys behind the pattern and centered at 22 ° and 38 °).

[00572] A systematic process was used to minimize the error in these calculations due to wide crystalline peaks, as well as high intensity of interference. First, a linear base was applied and then removed. Second, two Gaussian peaks centered at 22 ° and 38 ° with widths of 10-12 ° each have been adapted to the valleys behind the crystalline peaks. Third, the area behind the two broad Gaussian peaks and the rest of the pattern have been determined. Finally, the percentage crystallinity was calculated by dividing the area behind the crystalline peak by the total intensity (after subtracting the base). The domain size and crystallinity% of the samples, as determined by X-ray diffraction (XRD), are shown in Table 4.

EXAMPLE 11 - POROSIMETRY ANALYSIS OF IRRADIATED MATERIALS [00573] Analysis of pore volume and pore size by mercury (Table 21) is based on forcing mercury (a non-wetting liquid) into a porous structure under hermetically controlled pressures. Since mercury does not wet most substances and will not spontaneously penetrate the pores through capillary action, it must be forced into the sample voids by applying external pressure. The pressure required to fill the voids is

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180/204 inversely provide pore size. Only a small amount of force or pressure is required to fill large voids, while greater pressure is required to fill very small pore voids.

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Table 5. Pore size and volumetric distribution through mercury porosimetry

Sample ID Volume total of intrusion (mL / g) Total pore area (m ² / g) Median pore diameter (Volume) (pm) Diameter median pore (area) (pm) Average pore diameter (4V / A) (pm) Density volumetric @ 0.50 psia (g / mL) Apparent density (skeletal) (g / mL) Porosity (%) P132 6.0594 1,228 36.2250 13.7278 19.7415 0.1448 1.1785 87.7163 P132-10 5.5436 1,211 46.3463 4.5646 18.3106 0.1614 1.5355 89.4875 P132-100 5.3985 0.998 34.5235 18,2005 21.6422 0.1612 1.2413 87.0151 P132-181 3.2866 0.868 25.3448 12.2410 15,1509 0.2497 1.3916 82.0577 P132-US 6,0005 14,787 98.3459 0.0055 1.6231 0.1404 0.8894 84.2199 A132 2.0037 11,759 64.6308 0.0113 0.6816 0.3683 1.4058 73.7990 A132-10 1.9514 10,326 53.2706 0.0105 0.7560 0.3768 1.4231 73.5241 A132-100 1.9394 10.205 43.8966 0.0118 0.7602 0.3760 1.3889 72.9264 SG132 2.5267 8.265 57.6958 0.0141 1.2229 0.3119 1.4708 78.7961 SG132-10 2.1414 8.643 26.4666 0.0103 0.9910 0.3457 1.3315 74.0340 SG132-100 2.5142 10,766 32.7118 0.0098 0.9342 0.3077 1.3590 77.3593 SG132-10-US 4.4043 1,722 71.5734 1.1016 10.2319 0.1930 1.2883 85.0169 SG132-100-US 4.9665 7.358 24.8462 0.0089 2.6998 0.1695 1.0731 84.2010 WS132 2.9920 5.477 76.3675 0.0516 2.1971 0.2773 1.6279 82.9664 WS132-10 3.1338 2.901 57.4727 0.3630 4.2940 0.2763 1.9808 86.0484 WS132-100 3.2077 3,114 52.3284 0.2876 4.1999 0.2599 1.5611 83.3538

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182/204 [00574] AutoPore® 9520 can reach a maximum pressure of 414 MPa or 60,000 psia. There were four low pressure stations for sample preparation and data collection from 0.2 psia to 50 psia macropore. There were two high pressure chambers which collect data from 25 psia to 60,000 psia. The sample is placed in a device similar to the vat called a penetrometer, which is connected to a glass capillary rod with a metal coating. As the mercury invades the voids in and around the sample, it moves down the capillary rod. The loss of mercury from the hair shaft results in a change in electrical capacitance. The change in capacitance during the experiment is converted to a volume of mercury knowing the volume of the rod of the penetrometer in use. A variety of penetrometers with different tub sizes (sample) and capillaries are available to accommodate most sample sizes and configurations. Table 22 below defines some of the key parameters calculated for each sample.

Table 6. Definition of parameters

Parameter

description

Total intrusion volume:

Total pore area:

Median pore diameter (volume): Median pore diameter (area):

The total volume of mercury that penetrates during an experiment. This can include interstitial filling between small particles, sample porosity and sample compression volume. The total volume of intrusion converted to an area admitting pores of cylindrical shape.

The size in the 50th percentile on a cumulative volume chart.

The size in the 50th percentile on the cumulative area chart.

Average pore diameter:

The total pore volume divided by the total pore area (4V / A).

„....... The mass of the sample divided by the dense volume.

Volumetric density The dense volume is determined in the pressure of ca:

filling, typically 0.5 psia.

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Parameter Description

The mass of the sample divided by the volume of the apparent density: sample measured at the highest pressure, typically

60,000 psia.

_ ... (Volumetric density / Apparent density) x

Porosity:

100%

EXAMPLE 12 - PARTICLE SIZE ANALYSIS OF IRRADIATED MATERIALS [00575] The particle sizing technique using static light scattering is based on Mie's theory (which also covers Fraunhofer's theory). Mie's theory predicts the relationship of intensity vs. Angle as a function of size for spherical dispersion particles, as long as other system variables are known and kept constant. These variables are the wavelength of the incident light and the relative refractive index of the sample material. Application of Mie's theory provides detailed information about particle size. Table 23 summarizes the particle size using the median diameter, average diameter and modal diameter as parameters.

Table 7. Particle size through laser light scattering (dry sample scattering)

Sample ID Median diameter (pm) Average diameter (pm) Modal diameter (pm) A132 380,695 418,778 442,258 A132-10 321,742 366,231 410,156 A132-100 301,786 348,633 444,169 SG132 369,400 411,790 455.508 SG132-10 278,793 325,497 426,717 SG132-100 242,757 298,686 390,097 WS132 407,335 445,618 467,978 WS132-10 194,237 226,604 297,941 WS132-100 201,975 236,037 307,304

[00576] The particle size was determined through DisperPetição 870170006381, of 01/30/2017, p. 189/258

184/204 are Laser Light (Dry Sample Dispersion) using a Malvern Mastersizer 2000 using the following conditions:

Feed rate: 35%

Disperser pressure: 4 Bar

Optical model: (2,610, 1,000i), 1,000 [00577] An appropriate amount of sample was placed on a vibrating tray. The feed rate and air pressure were adjusted to ensure that the particles were properly dispersed. The key component is selecting an air pressure that will break up agglomerations, but will not compromise the integrity of the sample. The amount of sample required varies, depending on the size of the particles. In general, samples with fine particles require less material than samples with thick particles. EXAMPLE 13 - ANALYSIS OF MATERIALS SURFACE AREA

IRRADIATES [00578] The surface area of each sample was analyzed using a Micromeritics ASAP 2420 Acelerated Surface Area and Porosimetry system. The samples were first prepared by degassing for 16 hours at 40 ° C. Then, the free space (hot and cold) with helium is calculated and then the sample tube is evacuated again to remove the helium. Data collection begins after this second evacuation and consists of defining target pressures, which controls how much gas is metered into the sample. At each target pressure, the amount of gas adsorbed and the actual pressure are determined and recorded. The pressure inside the sample tube is measured with a pressure transducer. Additional doses of gas will continue until the target pressure is obtained and allowed to equilibrate. The amount of adsorbed gas is determined by adding multiple doses over the sample. Pressure and quantity define a gas adsorption isotherm and are used to calculate a number of parameters, including BET surface area

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185/204 (Table 24).

Table 8. Summary of the surface area by means of gas adsorption

Sample ID Surface area over a single point (m ² / g) BET surface area (m ² / g) P132 @ P / Po = 0.250387771 1.5253 1.6897 P132-10 @ P / Po = 0.239496722 1.0212 1.2782 P132-100 @ P / Po = 0.240538100 1.0338 1.2622 P132-181 @ P / Po = 0.239166091 0.5102 0.6448 P132-US @ P / Po = 0.217359072 1.0983 1.6793 A132 @ P / Po = 0.240040610 0.5400 0.7614 A132-10 @ P / Po = 0.211218936 0.5383 0.7212 A132-100 @ P / Po = 0.238791097 0.4258 0.5538 SG132 @ P / Po = 0.23789893 0.6359 0.8350 SG132-10 @ P / Po = 0.238576905 0.6794 0.8689 SG132-100 @ P / Po = 0.241960361 0.5518 0.7034 SG132-10-US @ P / Po = 0.225692889 0.5693 0.7510 SG132-100-US @ P / Po = 0.225935246 1.0983 1.4963 WS132 @ P / Po = 0.23823664 0.6582 0.8663 WS132-10 @ P / Po = 0.2381212476 0.6191 0.7912 WS132-100 @ P / Po = 0.238398832 0.6255 0.8143

[00579] The BET Model for isotherms is a theory widely used for calculating the specific surface area. The analysis involves determining the surface monolayer capacity of the sample by calculating the amount required to cover the entire surface with a single densely packed layer of krypton. The monolayer capacity is multiplied by the cross sectional area of the probe gas molecule to determine the total surface area. The specific surface area is the surface area of the sample aliquot divided by the mass of the sample.

EXAMPLE 14 - DETERMINATION OF FIBER LENGTH OF

IRRADIATED MATERIALS [00580] Fiber length distribution testing was carried out 870170006381, from 01/30/2017, p. 191/258

186/204 in triplicate on samples sent using the Techpap MorFi LB01 system. The average length and width of fiber are reported in Table 9.

Table 9. Summary of lignocellulosic fiber width and length data

Sample ID ai Average rhythm (mm) Weighted average length (mm) Statistically corrected weighted average length (mm) Width (micrometers) (pm) P132-10 0.484 0.615 0.773 24.7 P132-100 0.369 0.423 0.496 23.8 P132-181 0.312 0.342 0.392 24.4 A132-10 0.382 0.423 0.650 43.2 A132-100 0.362 0.435 0.592 29.9 SG132-10 0.328 0.363 0.521 44.0 SG132-100 0.325 0.351 0.466 43.8 WS132-10 0.353 0.381 0.565 44.7 WS132-100 0.354 0.371 0.536 45.4 EXAMPLE 15 - SWITCHGRASS ULTRASONIC TREATMENT

IRRADIATED AND NON-RADIATED [00581] Switchgrass was sheared according to Example 4. The switchgrass was treated by means of ultrasound alone or irradiation with 10 Mrad or 100 Mrad of gamma rays and then subjected to ultrasound. The resulting materials correspond to G132-BR (non-irradiated), G132-10-BR (10 Mrad and ultrasound) and G132-100-BR (100 Mrad and ultrasound), as shown in Table 1. Ultrasound was performed on each sample during 30 minutes using ultrasound at 20 kHz from the antenna in the shape of a 1000W horn under re-circulation conditions. Each sample was dispersed in water at a concentration of about 0.10 g / mL.

[00582] Figures 32 and 33 show the device used for ultrasound. The apparatus 500 includes a converter 502 connected to a voltage amplifier 504 that communicates with the antenna in the form of

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187/204 horn 506 made of titanium or a titanium alloy. The horn antenna, which has a 510 seal made of VITON® around its perimeter on its processing side, forms a liquid-tight seal with a 508 processing cell. The processing side of the antenna The horn is immersed in a liquid, such as water, which has, dispersed in it, the sample to be submitted to ultrasound. The pressure in the cell is monitored with a 512 manometer. In operation, each sample is moved by pump 517 in tank 516 through the processing cell and subjected to ultrasound. After ultrasound, the sample is captured in tank 520. The process can be reversed, so the contents of tank 520 can be sent through the processing cell and captured in tank 516. This process can be repeated a number of times, until that a desired level of processing is given to the sample.

EXAMPLE 16 - ELECTRONIC SCAN MICROGRAPHIES OF

NON-RADIATED SWITCHGRASS IN COMPARISON WITH RADIATED AND RADIATED AND ULTRASOUND [00583] Switchgrass samples for the electronically scanned micrographs were applied to a carbon ribbon and coated with a gold discharge device (70 seconds). The images were taken with a JEOL 6500 field-scanning electron microscope.

[00584] Figure 34 is a scanning electron micrograph at 1000 X magnification of a fibrous material produced from shearing switchgrass over a rotary knife cutter and then passing the sheared material through a 1 / 32 inches.

[00585] Figures 35 and 36 are scanning electron micrographs of the fibrous material of figure 32 after irradiation with gamma rays at 10

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Mrad and 100 Mrad, respectively, at 1000 X magnification. [00586] Figure 37 is an electronically scanned micrograph of the fibrous material in Figure 32 after irradiation with 10 Mrad and ultrasound at 1000 X magnification.

[00587] Figure 38 is a scanning electron micrograph of the fibrous material in Figure 32 after irradiation with 100 Mrad and ultrasound at a magnification of 1000 X.

EXAMPLE 17 - PAPER INFRARED SPECTRUM

IRRADIATED KRAFT IN COMPARISON WITH NO KRAFT PAPER

IRRADIATED [00588] The FTERC-IR analysis was performed on a Nicolet / Impact 400. The results indicate that all samples reported in Table 1 are consistent with a cellulose-based material.

[00589] Figure 39 is an infrared spectrum of Kraft paper shear according to Example 4, while Figure 40 is an infrared spectrum of Kraft paper of Figure 37 after irradiation with 100 Mrad of gamma radiation. The irradiated sample shows an additional peak in region A (centered around 1730 cm ^-1 ) that is not found in the non-irradiated material.

EXAMPLE 18 - PRE-TREATMENT COMBINATION WITH BEAM

ELECTRONIC AND ULTRASOUND [00590] Switchgrass is used as the feed stock and is sheared with a Munson rotary knife cutter in a fibrous material. The fibrous material is then evenly distributed on an open tin-based tray with an area of more than about 500 in ² . The fibrous material is distributed so that it has a depth of about 1 - 2 inches in the open tray. The fibrous material can be distributed in plastic bags in smaller doses of irradiation (under 10 MRad) and left uncovered on the

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189/204 metal tray in higher radiation doses.

[00591] Different samples of the fibrous material are then exposed to successive doses of electron beam radiation to obtain a total dose of 1 Mrad, 2 Mrad, 3, Mrad, 5 Mrad, 10 Mrad, 50 Mrad and 100 Mrad. Some samples are kept under the same conditions as the remaining samples, but are not irradiated to serve as controls. After cooling, the irradiated fibrous material is sent for further processing via an ultrasound device. [00592] The ultrasound device includes a converter connected to a voltage amplifier that communicates with the horn-shaped antenna made of titanium or a titanium alloy. The horn-shaped antenna, which has a seal made of VITON® around its perimeter on its processing side, forms a liquid-tight seal with a processing cell. The processing side of the horn antenna is immersed in a liquid, such as water, in which the irradiated fibrous material to be subjected to ultrasound is immersed. The pressure in the cell is monitored with a manometer. In operation, each sample is moved by the pump through the processing cell and subjected to ultrasound.

[00593] To prepare the irradiated fibrous material for ultrasound, the irradiated fibrous material is removed from any container (for example, plastic bags) and is dispersed in water at a concentration of about 0.10 g / mL. Ultrasound is performed on each sample for 30 minutes using 20 kHz ultrasound from a 1000 W horn antenna under recirculation conditions. After ultrasound, the irradiated fibrous material is captured in a tank. This process can be repeated a number of times, until a desired level of processing is achieved based on monitoring the structural change in the switchgrass. Again, some irradiated samples are kept under the same conditions as the samples

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190/204 remaining, but not subjected to ultrasound, to serve as controls. In addition, some samples that have not been irradiated are subjected to ultrasound, again to serve as controls. Thus, some controls are not processed, some are just irradiated and some are subjected to ultrasound.

EXAMPLE 19 - PRE-TREATED BIOMASS MICROBIAL TESTING [00594] Specific pre-treated lignocellulosic materials as described here are analyzed for toxicity by common strains of yeast and bacteria used in the biofuel industry for the fermentation stage in ethanol production. In addition, the sugar content and compatibility with cellulase enzymes are examined to determine the viability of the treatment process. Testing of pre-treated materials is carried out in two stages, as follows.

I: Toxicity and Sugar Content [00595] The toxicity of pre-treated grass and paper feed stocks is measured in the yeast Saccharomyces cerevisiae (grape yeast) and Pichia stipitis (ATCC 66278), as well as in the bacteria Zymomonas mobilis (ATCC 31821) and Clostridium thermocellum (ATCC 31924). A growth study is carried out with each of the organisms to determine the optimal incubation and sampling time. [00596] Each of the food stocks is then incubated, in duplicate, with S. cerevisiae, P. stipitis, Z. mobilis and C. thermocellum in a standard microbiological medium for each organism. YM broth is used for the two strains of yeast, S. cerevisiae and P. stipitis. RM medium is used for Z. mobilis and CM4 medium for C. thermocellum. A positive control, with pure sugar added, but without food supply, is used for comparison. During incubation, a total of five samples are taken every 12 hours at times 0, 3, 6, 9

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191/204 and 12 hours and analyzed for viability (plaque counts for Z. mobilis and direct counts for S. cerevisiae) and ethanol concentration.

[00597] The sugar content of feed stocks is measured using High Performance Liquid Chromatography (HPLC) equipped with a Shodex® SP0810 or Biorad Aminax® HPX-87P sugar column. Each of the feed stocks (approx. 5 g) is mixed with water subjected to reverse osmosis (RO) for 1 hour. The liquid portion of the mixture is removed and analyzed for glucose, galactose, xylose, mannose, arabinose and cellobiosis. The analysis is performed according to the protocol of the National Bioenergy Center Determination of Structural Carbohydrates and Lignin in Biomass.

II. Cellulase Compatibility [00598] Food stocks are tested, in duplicate, with commercially available Accellerase® 1000 enzyme complex, which contains an enzyme complex that reduces lignocellulosic biomass in fermentable sugars, at the recommended temperature and concentration in an Erlenmeyer flask . The flasks are incubated with moderate shaking at around 200 rpm for 12 hours. During this time, samples are taken every three hours at times 0, 3, 6, 9 and 12 hours to determine the concentration of reducing sugars (Hope and Dean, Biotech J., 1974, 144: 403) in the liquid portion of the bottles.

EXAMPLE 20 - ALCOHOL PRODUCTION USING ULTRASOUND IRRADIATION PRE-TREATMENT [00599] The optimum size for biomass conversion plants is affected by factors including economies of scale and the type and availability of biomass used as feed stock. Increasing the size of the plant tends to increase the economy of scale associated with processes in the plant. However, factory size increase 870170006381, from 01/30/2017, p. 197/258

192/204 ca also tends to increase costs (for example, transportation costs) per unit of biomass feed stock. Studies analyzing these factors suggest that the appropriate size for biomass conversion plants can range from 2000 to 10,000 tonnes of dry biomass feed stock per day. The plant described below is sized to process 2000 tons of dry biomass feed stock per day.

[00600] Figure 41 shows a schematic process of a biomass conversion system configured to process switchgrass. The storage preparation subsystem processes raw biomass feed stock to remove foreign objects and provides particles of consistent size for further processing. The pretreatment subsystem alters the molecular structure (for example, reduces the average molecular weight and crystallinity) of the biomass feed stock by irradiating the biomass feed stock, mixing the irradiated biomass feed stock with water to form a paste and applying ultrasonic energy to the paste. Irradiation and ultrasound convert the cellulosic and lignocellulosic components of the biomass feed stock into fermentable materials. The primary process subsystem ferments glucose and other low-weight sugars present after pretreatment to form alcohols.

EXAMPLE 21 - ELECTRON BEAM PROCESSING OF THE

SUGAR IN THE TABLE (SACAROSE) [00601] Sucrose was treated with an electron beam using a Rhodotron® TT200 continuous wave accelerator with dome that distributes electrons from 5 MeV to 80 kW of output power. The Table below describes the nominal parameters for the TT200. The nominal doses (in Mrad) and actual doses (in kgy) distributed to the samples are also provided below.

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Beam

Produced beam:

Beam energy:

Energy dispersion at 10 Mev:

Power beam at 10 MeV:

Energy consumption

Stand-by condition (vacuum and cooling ON):

Beam energy at 50 kW:

Beam energy at 80 kW: Continued ...

Accelerated electrons

Nominal (fixed): 10 MeV (+0 keV250 keV)

Half the maximum complete width (FWHM) 300 keV

Guaranteed operating range 1 to 80 kW <15 kW <210 kW <260 kW

RF System

Frequency:

Tetrode type:

Scanning horn antenna

107.5 ± 1 MHz Thomson TH781

Nominal scan length (measured 25-35 cm from the window):

Scan range:

Nominal scan frequency (at max. Scan length): Scan uniformity (through 90% of the nominal scan length)

120 cm

Nominal scan length from 30% to 100%

100 Hz ± 5% ± 5%

Dosages Distributed to Sucrose Samples

Total dosage (Mrad) (Number associated with the sample ID) Distributed dose (kgy) ¹ 1 9.9 3 29.0 5 50.4

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Total dosage (Mrad) (Number associated with the sample ID) Distributed dose (kgy) ¹ 7 69.2 10 100.0 15 150.3 20 198.3 30 330.9 50 529.0 70 695.9 100 993.6

[00603] ¹ For example, 9.9kgy were distributed in 11 seconds at a beam current of 5mA and a line speed of 12.9 feet / minute. The time to cool down between treatments was around 2 minutes.

[00604] The solubility of sucrose samples treated above 30 Mrad was enhanced and at or above 30 Mrad, sucrose appeared to be visually devoid of crystallinity. Above 70 Mrad, the sucrose was converted to a solid mass of material.

Feed Preparation [00605] The standard feed rate selected for the plant is 2,000 dry tons per day of switchgrass biomass. The standard feed is chopped and / or sheared switchgrass.

[00606] Biomass feed stock in the form of switchgrass bales is received by the factory. In some cases, switchgrass bales are wrapped with a plastic net to ensure that they do not fall apart when handled and can also be wrapped in plastic wrap to protect the bales from the weather. The bales are square or round. The bales are received at the off-site storage factory on large truck trailers. As the trucks are received, they are weighed and unloaded by forklifts. Some bales are shipped

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195/204 for on-site storage, while others are taken directly to conveyors.

[00607] Since switchgrass is only available periodically, long-term storage is required in order to provide power to the factory annually. Long-term storage is likely to consist of 400-500 acres of stacked bale rows discovered at a location (or multiple locations) reasonably close to the ethanol plant. Short-term on-site storage is provided equivalent to 72 hours of production in an external storage area. Surrounding bales and access roads, as well as the conveyors are on a concrete slab. The concrete slab is used due to the volume of traffic required to distribute the large amount of biomass feed stock required. The concrete slab will minimize the amount of water standing in the storage area, as well as reduce the exposure of the biomass feed stock to dirt. The stored material provides a short-term supply for weekends, holidays and when normal direct distribution of material in the process is interrupted.

[00608] The bales are unloaded by forklifts and are placed directly on bale conveyors or to the short-term storage area. The bales are also taken for short-term storage by forklifts and loaded onto the bale conveyors.

[00609] Bales travel to one of two bale unpacking stations. Unpacked bales are decomposed using a spreader bar and then unloaded on a conveyor that passes a magnetic separator to remove metal before chopping. A retaining iron magnet is provided to capture the loose magnetic metal and a sieving screen removes the material

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196/204 strange and grossly oversized above multiple chipper-shear trays, which reduce the biomass feed stock to the appropriate size for pre-treatment. Chipper-shear trays include rotary knife chippers and cutters. Chippers reduce the size of the raw biomass feed stock and feed the resulting material to rotary knife cutters. Rotary knife cutters concurrently shear the biomass feed stock and sieve the resulting material. Finally, the biomass feed stock is transported to the pretreatment subsystem.

[00610] Three storage silos are provided to limit overall system downtime due to required maintenance and / or equipment outages of the storage preparation sub-system. Each silo can hold approximately 55,000 cubic feet of biomass feed stock (~ 3 hours of plant operation).

Pretreatment [00611] A conveyor belt transports the biomass feed stock from storage preparation subsystem 110 to pretreatment subsystem 114. As shown in figure 42, in pretreatment subsystem 114, the biomass feed stock is irradiated using electron beam emitters, mixed with water to form a paste and subjected to the application of ultrasonic energy. As discussed above, irradiation of the biomass feed stock alters the molecular structure (for example, reduces recalcitrance, average molecular weight and crystallinity) of the biomass feed stock. Mixing the irradiated biomass feed stock in a slurry and applying ultrasonic energy to the slurry further alters the molecular structure of the biomass feed stock. Application of radiation and ultrasound

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197/204 in sequence can have synergistic effects due to the fact that the combination of techniques seems to achieve greater changes in the molecular structure (for example, reduces recalcitrance, average molecular weight and crystallinity) than any technique can achieve the same in isolation from efficiently. Without wishing to be bound by theory, in addition to reducing the polymerization of the biomass feed stock by breaking the intramolecular links between segments of cellulosic and lignocellulosic components of the biomass feed stock, irradiation can make the overall physical structure of the feed stock more fragile biomass. After the fragile biomass feed stock is mixed into a slurry, the application of ultrasonic energy further alters the molecular structure (for example, reduces the average molecular weight and crystallinity) and can also reduce the size of the stock particles of biomass feed.

ELECTRON BEAM IRRADIATION [00612] The 491 conveyor belt that transports the biomass feed stock to the pretreatment subsystem distributes the biomass feed stock into multiple feed streams (for example, 50 feed streams) each one leading to distinct 492 electron beam emitters. In this modality, the biomass feed stock is irradiated while it is dry. Each feed stream is transported on a separate conveyor belt to an associated electron beam emitter. Each irradiation feed conveyor belt can be approximately one meter wide. Before reaching the electron beam emitter, localized vibration is induced on each conveyor belt to evenly distribute the dry biomass feed stock over the cross sectional width of the conveyor belt.

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198/204 [00613] The 492 electron beam emitter (for example, commercially available electron beam irradiation devices from Titan Corporation, San Diego, CA) is configured to apply a 100 kilo-Gray electron dose applied to a power of 300 kW. Electron beam emitters are scan beam devices with a scan width of 1 meter to match the width of the conveyor belt. In some embodiments, electron beam emitters with large fixed beam widths are used. Factors, including beam / belt width, desired dose, density of the biomass feed stock and applied power, guide the number of electron beam emitters required for the plant to process 2,000 tons per day of dry feed. ULTRASOUND [00614] The irradiated biomass feed stock is mixed with water to form a paste before ultrasonic energy is applied. There may be a separate ultrasound system associated with each electron beam feed stream, or multiple electron beam streams can be aggregated as feed for a single ultrasound system.

[00615] In each ultrasound system, the irradiated biomass feed stock is fed to a reservoir 1214 through a first inlet 1232 and water is fed into reservoir 1214 through the second inlet 1234. Appropriate valves (manual or automatic) control the flow of biomass feed stock and water flow to produce a desired ratio of biomass feed stock to water (eg 10% cellulosic material, weight by volume). Each reservoir 1214 includes a mixer 1240 to stir the contents of volume 1236 and disperse the biomass feed stock throughout the water.

[00616] In each ultrasound system, the paste is pumped (for

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199/204 example, using a reciprocating impeller vortex pump 1218) from reservoir 1214 to and through a flow cell 1224 including an ultrasonic transducer 1226. In some embodiments, pump 1218 is configured to agitate slurry 1216 so that the mix of biomass and water feed stock is substantially uniform at inlet 1220 of flow cell 1224. For example, pump 1218 can agitate slurry 1216 to create a turbulent flow that persists through the tubing between the first pump and inlet 1220 of flow cell 1224.

[00617] Inside flow cell 1224, ultrasonic transducer 1226 transmits ultrasonic energy to paste 1216 as the paste flows through flow cell 1224. Ultrasonic transducer 1226 converts electrical energy into mechanical energy high frequency (for example, ultrasonic energy), which is then distributed to the pulp via voltage amplifier 48. Ultrasonic transducers are commercially available (for example, from Hielscher USA, Inc. of Ringmadeira, New Jersey) that are capable of delivering a continuous power of 16 kilowatts.

[00618] The ultrasonic energy that travels through the voltage amplifier 1248 in the volume of the reactor 1244 creates a series of compressions and rarefactions in the process current1216 with an intensity sufficient to create cavitation in the process current1216. Cavitation disaggregates the components of the biomass feed stock including, for example, cellulosic and lignocellulosic material dispersed in process stream 1216 (for example, pulp). Cavitation also produces free radicals in the water of the 1216 process stream (for example, paste). These free radicals act to further decompose the cellulosic material in process stream 1216. In general, about 250 MJ / m ³ of ultrasonic energy is applied to process stream 1216 containing fragments of slivers of

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200/204 poplar. Other levels of ultrasonic energy (between about 5 and about 4000 MJ / m ³ , for example, 10, 25, 50, 100, 250, 500, 750, 1000, 2000 or 3000) can be applied to other stocks biomass feed. After exposure to ultrasonic energy in reactor volume 1244, process current 1216 leaves flow cell 24 through outlet 1222.

[00619] Flow cell 1224 also includes a heat exchanger 1246 in thermal communication with at least a portion of reactor volume 1244. Cooling fluid 1248 (eg water) flows into heat exchanger 1246 and absorbs heat generated when process stream 1216 (for example, slurry) is ultrasounded in reactor 1244 volume. In some embodiments, the flow of cooling fluid 1248 to heat exchanger 1246 is controlled to maintain an approximately constant temperature in the volume of the reactor 1244. In addition or alternatively, the temperature of cooling fluid 1248 flowing to heat exchanger 1246 is controlled to maintain an approximately constant temperature in the volume of reactor 1244.

[00620] Output 1242 of flow cell 1224 is arranged near the bottom of reservoir 1214 to induce gravity feeding of process stream 1216 (e.g., slurry) out of reservoir 1214 towards the entrance of a second pump 1230 which pumps process stream1216 (eg, slurry) towards the primary process subsystem.

[00621] Ultrasound systems can include a single flow path (as described above) or multiple parallel flow paths each with an associated individual ultrasound unit. Multiple ultrasound units can also be arranged in series to increase the amount of sonic energy applied to the paste. Primary Processes

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201/204 [00622] A rotary vacuum drum filter removes the solids from the paste before fermentation. The filter liquid is pumped cold before entering the fermenters. The filtered solids are passed to the post-processing subsystem for further processing. [00623] The fermentation tanks are large low pressure stainless steel vessels with low speed agitators and tapered bottom. Fermentation tanks with multiple first stages can be arranged in series. The temperature in the first stage fermentation tanks is controlled to 30 degrees centigrade using external heat exchangers. Yeast is added to the first stage fermentation tank at the top of each series of tanks and transports it through the other tanks in the series. [00624] Second fermentation consists of two continuous fermenters in series. Both fermenters are continuously stirred with low speed mechanical mixers. The temperature is controlled with water cooled in external exchangers with continuous recirculation. Recirculation pumps are of the progressive cavity type due to the high concentration of solids.

[00625] Exhaust gas from fermentation tanks and fermenters are combined and washed in a column of counter-current water before being released into the atmosphere. The exhaust gas is flushed to recover ethanol instead of controlling air emissions.

Post-Processing

Distillation [00626] Distillation and adsorption on a molecular sieve are used to recover ethanol from crude fermentation yeast and produce 99.5% ethanol. Distillation is carried out in two columns - the first, called the yeast column, removes dissolved CO ₂ and most of the water and the second concentrates ethanol for a composition

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202/204 almost azeotropic.

[00627] All the water in the almost azeotropic mixture is removed by means of adsorption of molecular sieve in vapor phase. Regeneration of the adsorption columns requires an aqueous ethanol mixture to be recycled to distillation for recovery.

[00628] Fermentation vents (containing mainly CO ₂ , but also a little ethanol), as well as the ventilation of the yeast column are purified in a water purifier, recovering almost all of the ethanol. The effluent from the purifier is fed to the first distillation column along with the fermentation yeast.

[00629] The bottom part of the first distillation contains all the insoluble and dissolved solids not converted. Insoluble solids are dehydrated by a pressure filter and sent to a combustor. The pressure filter liquid that is not recycled is concentrated in a multi-effect evaporator using residual heat from the distillation. The evaporator's concentrated syrup is mixed with the solids that are sent to the combustion and the evaporated condensate is used as relatively clean recycling water for the process.

[00630] Due to the fact that the amount of vinasse water that can be recycled is limited, an evaporator is included in the process. The total amount of water in a pressure filter that is directly recycled is set at 25%. Organic salts, such as ammonium acetate or lactate, components of the maceration water not used by the organism or inorganic compounds in the biomass are found in this stream. Recycling too much of this material can result in levels of ionic resistance and osmotic pressure that can be detrimental to the efficiency of the fermentation organism. For water that is not recycled, the evaporator concentrates the dissolved solids in a syrup that can be sent to the combustor, minimizing the load for wastewater treatment.

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Wastewater treatment [00631] The wastewater treatment section treats process water for reuse to reduce the plant's composition water requirements. The wastewater is initially separated to remove large particles, which are collected in a feeder and sent to a landfill. The separation is followed by anaerobic and aerobic digestion to digest organic matter in the stream. Anaerobic digestion produces a biogas stream that is rich in methane, which is fed to the combustion. Aerobic digestion produces a relatively clear stream of water for reuse in the process, as well as a sediment that is primarily composed of cell mass. The sediment is also burned in the combustor. This separation / anaerobic digestion / aerobic digestion scheme is standard within the current ethanol industry and units in the range 1-5 million gallons per day can be obtained as off-the-shelf units from vendors.

Combustor, Boiler and Turbo-generator [00632] The purpose of the combustion, boiler and turbogenerator subsystem is to burn various by-product streams for steam and electricity generation. For example, some lignin, cellulose and hemicellulose remains unconverted through pretreatment and primary processes. Most of the waste water from the process is concentrated to a syrup in soluble solids. Anaerobic digestion of the remaining waste water produces biogas with a high methane content. Aerobic digestion produces a small amount of residual biomass (sediment). Burning these by-product streams to generate steam and electricity allows the plant to be self-sufficient in energy, reduces solid waste disposal costs and generates additional resources by selling excess electricity.

[00633] Three primary fuel streams (powder solidsPetition 870170006381, from 01/30/2017, page 209/258

204/204 distillate, biogas and evaporator syrup) are fed to a circulating fluidized bed combustor. The small amount of residual biomass (sediment) from wastewater treatment is also sent to the combustor. A fan moves the air into the combustion chamber. Treated water enters the heat exchanger circuit in the combustor and is evaporated and superheated to 510 ° C (9501 ³ ) and steam at 86 atm (1265 psia). Combustible gas from the combustor preheats the combustion air at the entrance and then enters a housing to remove particles, which are grounded. The gas is released through a chimney.

[00634] A turbine and generator with multiple stages are used to generate electricity. Steam is extracted from the turbine in three different conditions for injection into the pretreatment reactor and heat exchange in distillation and evaporation. The remaining steam is condensed with cooling water and returned to the boiler feed water system along with condensate from the various heat exchangers in the process. Treated well water is used as a composition to replace the steam used for direct injection.

OTHER MODALITIES [00635] A number of modalities of the invention have been described. However, it should be understood that various modifications can be made without departing from the spirit and scope of the invention.

[00636] Consequently, other modalities are within the scope of the following claims.

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Claims (5)

1. Method of converting an intermediate to a product, characterized by the fact that it comprises: treating an intermediate product irradiated with a microorganism, the intermediate having been prepared by irradiating a starch material and treating the starch material with an enzyme. 2. Product, characterized by the fact that it is produced through: (i) one comprising the dissipation of a biomass feed stock that has been irradiated to ionize the biomass feed stock, so that the feed stock has a first level of radicals, the dissipation carried out to a point where the radicals they are at a second level, less than the first level, in the dissipated biomass feed stock; (ii) a method comprising: irradiation of a biomass feed stock to alter a molecular and / or supramolecular structure of the biomass feed stock; cooling of the irradiated biomass feed stock; and, then re-irradiation of the biomass feed stock with a second dose of ionizing radiation. (iii) a method comprising: treating a biomass feed stock comprising a starch material to alter the molecular and / or supramolecular structure of the starch material, with at least one method selected from the group consisting of radiation, ultrasound, pyrolysis and oxidation; or Petition 870170006381, of 01/30/2017, p. 211/258 2/2 (iv) a method of converting an intermediary to a product comprising: treating an intermediate product irradiated with a microorganism, the intermediate having been prepared by irradiating a starch material and treating the starch material with an enzyme. 3. Biomass feed stock processing system, characterized by the fact that it comprises: an irradiation device configured to ionize a biomass feed stock, so that the feed stock has a first level of radicals detectable with an electron orbital resonance spectrometer; and a dissipation device configured to dissipate the ionized biomass feed stock to a point where the radicals are at a lower second level than the first level. 4. Biomass feed stock processing system, characterized by the fact that it comprises: one or more irradiation devices configured to irradiate one and similar biomass with at least two distinct doses of radiation; and a cooling device configured to cool and similar biomass similars between radiation doses. 5. System according to claim 3 or 4, characterized by the fact that it comprises biomass feed stock positioned to be ionized by the irradiation device (s). Petition 870170006381, of 01/30/2017, p. 212/258 1/39 Petition 870170006381, of 01/30/2017, p. 214/258 2/39