OA17556A - Controlling process gases. - Google Patents

Abstract

Biomass (e.g., plant biomass, animal biomass, and municipal waste biomass) is processed to produce useful intermediates and products, such as energy, fuels, foods or materials. For example, equipment, systems and methods are described that can be used to treat feedstock materials, such as cellulosic and/or lignocellulosic materials, in a vault in which hazardous gases are removed, destroyed and/or converted. The treatments are efficient and can reduce the recalcitrance of the lignocellulosic material so that it is easier to produce an intermediate or product, e.g., sugars, alcohols, sugar alcohols and energy, from the lignocellulosic material.

Description

CONTROLLING PROCESS GASES

CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application claims priority from the following provisional applications: USSN 61/774,684, filed March 8, 2013; USSN 61/774,773, filed March 8, 2013; USSN 61/774,731, filed March 8, 2013; USSN 61/774,735, filed March 8, 2013; USSN 61/774,740, filed March 8, 2013; USSN 61/774,744, filed March 8, 2013; USSN 61/774,746, filed March 8, 2013; USSN 61/774,750, filed March 8, 2013; USSN 61/774,752, filed March 8, 2013; USSN 61/774,754, filed March 8, 2013; USSN 61/774,775, filed March 8, 2013; USSN 61/774,780, filed March 8, 2013; USSN 61/774,761, filed March 8, 2013; USSN 61/774,723, filed March 8, 2013; and USSN 61/793,336, filed March 15, 2013. The full disclosure of each of these provisional applications is incorporated by reference herein.

BACKGROUND OF THE INVENTION [0002] Many potential lignocellulosic feedstocks are available today, including agricultural residues, woody biomass, municipal waste, oilseeds/cakes and seaweed, to name a few. At présent, these materials are often under-utilized, being used, for example, as animal feed, biocompost materials, bumed in a co-generation facility or even landfilled.

[0003] Lignocellulosic biomass includes crystalline cellulose fibrils embedded in a hemicellulose matrix, surrounded by lignin. This produces a compact matrix that is difficult to access by enzymes and other chemical, biochemical and/or biological processes. Cellulosic biomass materials (e.g., biomass material from which the lignin has been removed) is more accessible to enzymes and other conversion processes, but even so, naturally-occurring cellulosic materials often hâve low yields (relative to theoretical yields) when contacted with hydrolyzing enzymes. Lignocellulosic biomass is even more récalcitrant to enzyme attack. Furthermore, each type of lignocellulosic biomass has its own spécifie composition of cellulose, hemicellulose and lignin.

SUMMARY [0004] Generally, the inventions relate to methods, equipment and Systems for treating materials, such as biomass. The inventions also relate to methods, Systems and processing equipment used for producing products from a biomass material. Generally, the methods include treating a récalcitrant biomass, (e.g., with électron beams or other ionizing radiation) to reduce the recalcitrance of the biomass, optionally while conveying the biomass using one or more conveyor(s) and optionally in an enclosure, such as a vault. Included in the methods, hazardous and/or noxious gases which are produced can be filtered or destroyed. In some implémentations, the methods further include biochemically and/or chemically processing the reduced recalcitrance material to, for 0 example, éthanol, xylitol and other useful and valuable products.

[0005] Radiation in a confined space containing gases and/or organic material (e.g., air, biomass and/or hydrocarbons), can create reactive gases, e.g., ozone, oxides of nitrogen and/or Volatile Organic Compounds (VOCs), such as methane, ethane, ethylene, formic acid, acetic acid, methanol, formaldéhyde, acetaldehyde and acetylene, and/or other airbom agents e.g., Hazardous Air Pollutants (HAPs), such as soot. In addition, accidentai release of processing gases from equipment, such as SFô, can be a hazard. The gases can dégradé processing equipment and cause equipment wear and failure, incurring costs due to downtime and necessary repairs. The gases also shouid be removed (e.g., removed, sequestered, filtered, concentrated) and/or destroyed before 2Q operators can access the interior of the confined spaces. Finally, the gases shouid be isolated (e.g., removed, sequestered, filtered) and/or destroyed prior to being released into the environment. Mitigation of these issues can be accomplished by controlling the atmosphère inside the confined space or near the processes, for example, by flushing and/or purging a processing vault with an inert gas (e.g., nitrogen or argon), and ensuring 25 that any process gases are removed from the vault. In addition, any hazardous gases can be filtered and/or destroyed by a filtering System.

[0006] In some instances, the invention relates to methods for processing materials (e.g., biomass including lignocellulosic, cellulosic or starchy material). The method includes impinging a substantially inert gas on a foil window of an électron beam hom 30 while passing électrons through the window and inert gas while processing the material.

The foil can hâve a surface communicating with a high vacuum side of an accelerator tube. The foil, along with a secondary foil can define a space about which the substantially inert gas traverses. Optionally, the pressure inside the space is greater than

atmospheric pressure (e.g., between about 50 and 200 psi). The inert gas can include nitrogen (e.g., at least 80% nitrogen, at least 90% nitrogen, at least 95% nitrogen, at least 99% nitrogen). Optionally the method includes recycling the inert gas, for example, the inert gas can be impinged on the foil window more than one time before it is discarded. The inert gas can be processed or treated, for example, prior to or before being utilized, or before using the gas again in the method that includes recycling the gas. Optionally, the inert case is treated after impinging électrons on the foil window. Optionally, treating the gas includes filtering the gas. For example, treating the inert gas can include removing from the inert gas contaminants or undesired components that include oxygen, ozone, oils, particulates, water and mixtures thereof. Treating can also include removing volatile organic compounds.

[0007] In some cases the invention relates to Systems for processing materials, e.g., biomass, where the System includes a flow path for providing a substantially inert gas through a space, wherein the space is defïned by, a first foil in communication with the vacuum side of a scanning hom of an électron beam accelerator and a secondary foil disposed facing the first foil window. Optionally, the secondary foil can be mounted on an enclosure. The flow path can optionally include a first conduit and inlet for flowing the inert gas into the space and a second conduit and outlet for flowing the inert gas out of the space. The first and second conduit are in fluid communication through the space. The first conduit and/or inlet and second conduit and/or outlet can be sized so that the pressure inside the space is above atmospheric pressure (e.g., between about 50 and 200 psi)· [0008] In another aspect of the invention, the methods include reducing the recalcitrance of biomass (e.g., biomass) while producing or generating a hazardous gas.

For example hazardous gases can include gases selected from the group consisting of ozone, volatile organic compounds, hazardous air pollutants, particulates, soot, nitrogen oxides and mixtures of these. The methods include flowing the hazardous gas through a filtering System. The hazardous gas can include a hazardous component and a nonhazardous component and the filtering System is configured to removed and/or destroy by the hazardous component. Optionally, the filter System can include a carbon filter disposed in the flow of the hazardous gas. Optionally, the method includes conveying the biomass while reducing its recalcitrance.

[0009] Optionally, reducing the recalcitrance of the biomass material occurs in a vault. For example, the concentration of hazardous gas can be reduced by flowing gas that is in the vault through the filter System to the exterior of the vault and flowing gas

from the exterior of the vault to the interior of the vault. For example, a make-up gas is flowed from the exterior of the vault to the interior of the vault while the hazardous gas is flowed from the interior of the vault to the exterior of the vault and through the filtering system. The filtering System can be disposed outside of the vault or inside the vault. Optionally, gas flowing from the exterior of the vault (e.g., a make-up gas) comprises an inert gas. Also optionally, the method can include maintaining a négative pressure in the vault by flowing the gas that is in the vault (e.g., through the filter system) to the exterior of the vault at a faster flow rate than flowing the gas from the exterior of the vault to the interior of the vault (e.g. the make-up gas). For example, the flow rate to the exterior of the vault is at least 2 times faster than the flow rate to the interior of the vault (e.g., at least 3 times faster, at least 4 times faster, at least 5 times faster). In some instances, the flow rate to the exterior of the vault is between about 1000 and 10000 CFM and the flow rate to the interior of the vault is between about 10 and 5000 CFM. Optionally, the method can include conveying the biomass from the interior of the vault to the exterior of the vault, extracting hazardous gases from the biomass, and flowing the hazardous gases through the filter system. For example, the hazardous gases can be extracted from the biomass in the vault or the hazardous gases can be extracted from the biomass once it has been conveyed out of the vault.

[0010] Optionally, the recalcitrance of the biomass material can be reduced by exposing the biomass material to ionizing radiation. For example, the ionizing radiation can be produced by an électron accelerator comprising a scanning hom equipped with a métal foil électron extraction window, and the method can further include directing a gas (e.g., a cooling gas) against the extraction side of the foil électron extraction window. [0011] In some aspects, the invention includes a system for processing a material in a vault. The vault can contain an électron irradiation device configured to irradiate a biomass material, e.g., while it is conveyed on a conveyor. The system can also include a process gas treating system, e.g., a system for treating gases produced during the processing of the biomass. Optionally the process gas treating system includes a gas path from the exterior of the vault to the interior of the vault, the gas path continuing through the vault, and then the gas path continuing from the interior of the vault to the exterior of the vault. A filter can be placed in the gas path. For example, the filter can be placed inside the vault in the gas path or outside of the vault in the gas path. The filter can be placed outside the vault and configured to process gasses that flow through the vault (e.g., process gases). The gas path through the vault can include a gas path through a window cooling System. For example, the window cooling system can include a

manifold configured to accept a gas from a conduit and the manifold can be also configured for impinging the gas against a first window mounted on the vacuum side of a scan hom of the irradiation device. The window cooling System can also include a second window facing the first window, wherein the first and second window define a space and the space includes an outlet configured to allow the gas to exit the space. For example, the gas path can include a path through the space. Optionally, the gas path through the vault includes a path through an intake manifold.

[0012] The equipment, Systems and methods described herein are effective in mitigating process gases produced during biomass processing.

[0013] Implémentations of the invention can optionally include one or more of the following summarized features. In some implémentations, the selected features can be applied or utilized in any order while in other implémentations a spécifie selected sequence is applied or utilized. Individual features can be applied or utilized more than once in any sequence and even continuously. In addition, an entire sequence, or a portion of a sequence, of applied or utilized features can be applied or utilized once repeatedly or continuously in any order. In some optional implémentations, the features can be applied or utilized with different, or where applicable the same, set or varied, quantitative or qualitative parameters as determined by a person skilled in the art. For example, parameters of the features such as size, individual dimensions (e.g., length, width, height), location of, degree (e.g., to what extent such as the degree of recalcitrance), duration, frequency of use, density, concentration, intensity and speed can be varied or set, where applicable as determined by a person of skill in the art.

[0014] Features, for example, include: a method of processing a material; impinging a substantially inert gas on a foil window of an électron beam hom and passing électrons through the window and inert gas while processing a material; a foil that has a surface communicating with a high vacuum side of an accelerator tube; a foil and a secondary foil that defines a space about which a substantially inert gas traverses; a pressure inside a space (e.g., defined by a foil and a secondary foil) that is greater than atmospheric pressure; an inert gas that comprises nitrogen; recycling an inert gas; impinging a substantially inert gas on a foil window more than one time before discarding it; treating an inert gas; treating an inert gas by a method that includes filtering the gas; removing oxygen from an inert gas; removing ozone from an inert gas; removing oils from an inert gas; removing particulates from an inert gas; removing water from an inert gas; processing a biomass material; processing a lignocellulosic material; processing a cellulosic material; utilizing vaults constructed with low porosity bricks.

[0015] Features, for example, can also include: a system for processing biomass; a flow path for providing a substantially inert gas through a space, wherein the space is defined by a first foil in communication with the vacuum side of a scanning hom of an électron beam accelerator and a secondary foil disposed facing the first foil; a secondary foil that is mounted on an enclosure; a flow path that includes a first conduit and an inlet for flowing an inert gas into a space and a second conduit and an outlet for flowing the inert gas out of the space, wherein the first conduit and second conduit are in fluid communication through the space; a first conduit and/or inlet and a second conduit and/or outlet that are sized so that the pressure inside the space is greater than atmospheric pressure.

[0016] Features, for example, can also include: a method for processing a biomass material; producing a hazardous gas while reducing the recalcitrance of a biomass material, and flowing the hazardous gas through a filtering system; reducing the recalcitrance of a biomass material in a vault; a filtering system disposed outside of a vault for filtering process gases generated inside the vault; a make-up gas that is flowed from the exterior of the vault to the interior of the vault while a hazardous gas is flowed from the interior of the vault to the exterior of the vault and through a filtering system; a make-up gas for a vault that comprises an inert gas; maintaining a négative pressure in a vault by flowing a gas that is in the vault through a filtering system to the exterior of the vault at a faster flow rate than flowing a make-up gas from the exterior of the vault to the interior of the vault; maintaining a négative pressure in a vault by flowing a gas that is in the vault through a filtering system to the exterior of the vault at a flow rate that is at least two times faster than flowing a make-up gas from the exterior of the vault to the interior of the vault; maintaining a négative pressure in a vault by flowing a gas that is in the vault through a filtering system to the exterior of the vault at a flow rate that is at least three times faster than flowing a make-up gas from the exterior of the vault to the interior of the vault; maintaining a négative pressure in a vault by flowing a gas that is in the vault through a filtering system to the exterior of the vault at a flow rate that is at least four times faster than flowing a make-up gas from the exterior of the vault to the interior of the vault; maintaining a négative pressure in a vault by flowing a gas that is in the vault through a filtering System to the exterior of the vault at a flow rate that is at least five times faster than flowing a make-up gas from the exterior of the vault to the interior of the vault; maintaining a négative pressure in a vault by flowing a gas that is in the vault to the exterior of the vault at a rate of between 1000 and 10,000 CFM and flowing a make-up gas from the exterior of the vault to the interior of the vault at a flow

rate of between about 10 and 5000 CFM; utilizing a vault constructed of low porosity materials; utilizing a vault constructed of low porosity concrète; utilizing a vault with walls constructed of low porosity bricks; conveying a biomass from the interior of a vault to the exterior of the vault, extracting hazardous gases from the biomass, and flowing the hazardous gases through a filter System; reducing the recalcitrance of the biomass material by exposing the biomass material to ionizing radiation; producing ionizing radiation by an électron accelerator comprising a scanning hom equipped with a métal foil électron extraction window, and directing a cooling gas against the extraction side of the foil électron extraction window; a gas fîltering System that includes a carbon filter disposed in the flow of a hazardous gas; a hazardous gas that includes ozone; a hazardous gas that includes volatile organic compounds; conveying a biomass material while reducing the recalcitrance of the biomass material; a hazardous gas that includes a hazardous component and a non-hazardous component and a fîltering System that is configured to remove the hazardous component; a hazardous gas that includes a hazardous component and a non-hazardous component and a filtering System that is configured to destroy the hazardous component.

[0017] Features, for example, can also include: a System for processing a material in a vault; a vault containing an électron irradiation device configured to irradiate a biomass material, and a process gas treating System comprising a gas path that includes a path from the exterior of the vault to the interior of the vault, through the vault, and to the exterior of the vault; a gas filter in a gas path; a gas path through a vault includes a gas path through a window cooling System and the window cooling System comprises a manifold configured to accept a gas from a conduit and impinging the gas against a first window mounted on the vacuum side of a scan hom of an irradiation device; a window cooling System that includes a first window mounted on the vacuum side of a scan hom of an irradiation device and a second window facing the first window, wherein the first and second window define a space and the space includes an outlet configured to allow the gas to exit the space; a gas path through a vault that includes a path through an intake manifold; a filter that is positioned outside of a vault and configured to filter a gas that has flowed through the vault [0018] Other features and advantages of the invention will be apparent from the following detailed description, and from the claims.

DESCRIPTION OF THE DRAWING [0019] FIG. 1 shows an embodiment of the invention, including a perspective view of a vault with its roof and ceiling not shown and some components of a process gas mitigation System.

[0020] FIG. 2 is a side view of the gas mitigation System components shown in FIG. 1.

[0021] FIG. 3A is a detailed side view showing part of the gas mitigation System including a System for air cooling window foils. FIG. 3B is a highly enlarged detail view of area 3B in FIG. 3A. FIG. 3C is an enlarged detailed perspective view of the électron scanning hom, window cooling System and conveyor.

DETAILED DESCRIPTION [0022] Using the equipment, methods and Systems described herein, cellulosic and lignocellulosic feedstock materials, for example, that can be sourced from biomass or processed biomass (e.g., plant biomass, animal biomass, paper, and municipal waste biomass) and that are generally readily available, can be tumed into useful products (e.g., sugars such as xylose and glucose, sugar alcohols and other alcohols such as éthanol and

5 butanol. Described herein are methods and Systems for removing (e.g., filtering, destroying, diluting, converting) process gases, for example, ozone and VOCs, produced during biomass processing, e.g., during irradiation of the biomass with an électron beam. [0023] Processes for manufacturing sugar solutions and products derived therefrom are described herein. These processes can include, for example, optionally mechanically 2Q treating a cellulosic and/or lignocellulosic feedstock. Before and/or after this treatment, the feedstock can be treated with another treatment, for example, irradiation, steam explosion, pyrolysis, sonication, chemical treatment (e.g., acid, base or solvents) and/or oxidation to reduce, or further reduce its recalcitrance. A sugar solution is formed by saccharifying the feedstock by, for example, the addition of one or more enzymes and/or 25 one of more acids. A product can be derived from the sugar solution, for example, by fermentation to an alcohol or hydrogénation to a sugar alcohol. Further processing can include purifying the solution, for example, by distillation. If desired, the steps of measuring lignin content and setting or adjusting process parameters (e.g., irradiation dosage) based on this measurement can be performed at various stages of the process, for

example, as described in U.S. Patent No. 8,415,122 issued April 9, 2013, the complété disclosure of which is incorporated herein by reference.

[0024] Since the recalcitrance reducing treatment step can be a high energy process, the treatment can be performed within an enclosure, e.g., a vault and/or bunker System to contain the energy and/or some of the products, e.g., process gases, derived from the energetic process, which could otherwise be hazardous. For example, the vault can be configured to contain heat energy, electrical energy (e.g., high voltages, electric discharges), radiation energy (e.g., X-rays, accelerated particles, gamma-rays, ultraviolet radiation), explosion energy (e.g., a shock wave, projectiles, blast wind), gases (e.g., ozone, steam, nitrogen oxides and/or volatile organic compounds) and combinations of these. Although this containment protects people and equipment outside of the vault, the equipment inside the vault is subjected to the energy and/or products derived from the energetic process. In some cases, this containment can exacerbate the négative effects, for example, by not allowing dissipation of gases and particulates (e.g., fines, dust, soot, carbon containing fine particles, ozone, steam, nitrogen oxides and/or volatile organic compounds). For example, many électron beam Systems hâve délicate window structures that can be damaged by process gases or particulates. The deleterious effects of hazardous gases and particulates can be mitigated by diluting, removing converting and/or destroying any process gases and/or particulates.

[0025] If treatment methods for reducing the recalcitrance include irradiation of a feedstock (e.g., cellulosic or lignocellulosic feedstock or even hydrocarbon-containing feedstocks), for example, with ionizing radiation, ozone may be produced by the irradiation of oxygen (e.g., oxygen présent in air). Oxides of nitrogen can also be produced by irradiation of air, as described in “Toxic Gas Production at Electron Linear Accelerators”, W.P. Swanson, SLAC-PUB_2470, February 1980, the entire disclosure of which is incorporated herein by reference. The irradiation can also cause heating and décomposition of the biomass material that can release and/or produce VOCs, HAPs and carbon-containing particulates (e.g., soot). Ozone is a strong oxidant with a redox potential of 2.07 V (vr the Standard Hydrogen Electrode : SHE), higher than other known strong oxidants such as hydrogen peroxide, permanganate, chlorine gas and hypochlorite with redox potentials of 1.77 V, 1.67 V, 1.36 V and 0.94 V, respectively. Therefore, materials, for example, organic materials, are susceptible to dégradation by ionizing radiation and oxidation by ozone. For example, the materials can dégradé through chain scission, cross-linking, oxidation and heating. In addition, métal components are susceptible to oxidation and dégradation by ozone causing them, for

example, to corrode/pit and/or rust. Soot and VOCs can be hazardous and/or damaging to equipment, for example, posing a breathing hazard and/or coating and interfering with the operation of equipment. Soot can also damage délicate Windows (e.g., window foils) utilized for électron extraction in irradiation devices.

[0026] Therefore, equipment that includes polymers and some metals (e.g., excluding perhaps corrosion résistant or noble metals) can be damaged. For example, damage can occur to belts that include organic material, for example, those used in equipment, e.g., as the coupling between a drive motor and an eccentric fly wheel of a vibratory conveyor. Systems and/or motor components that can be susceptible to damage by ozone and radiation include, for example, wheels, bearings, springs, shock absorbera, solenoids, actuators, switches, gears, axles, washers, adhesives, fasteners, bolts, nuts, screws, brackets, frames, pulleys, covers, vibration dampeners, sliders, fïlters, vents, pistons, fans, fan blades, wires, wire sheathing, valves, drive shafts, computer chips, microprocessors, circuit boards and cables. Some organic materials that can be degraded by ionizing radiation and ozone include thermoplastics and thermosets. For example, organic materials that can be susceptible to damage include phenolics (e.g., bakélite), fluorinated hydrocarbons (e.g., Teflon), thermoplastics, polyamides, polyesters, polyuréthanes, rubbers (e.g., butyl rubber, chlorinated polyethylene, poly norbomene), polyethers, polyethylene (linear low density polyethylene, high density polyethylene), polystyrènes, polyvinyls (e.g., poly vinyl chloride), cellulosics, amino resins (e.g., urea formaldéhyde), polyamines, polyamides, acrylics (e.g., methyl méthacrylate), acetals (e.g., polyoxymethylene) lubricants (e.g., oils and gels), polysiloxanes and combinations of these.

[0027] FIG. 1 depicts an embodiment of the invention shown as a top perspective view. The view shows enclosing walls 110 (in the form of blocks) of a vault with doors 112 and foundation 113. In the particular embodiment shown, the walls are made of blocks, the walls having a thickness of approximately six feet. The ceiling/roof is not shown so the interior of the vault can be more clearly described. The view includes a high voltage (e.g., 1 MV) power source 120 and an electrical conduit 122 connecting the power source to the électron accelerator 124. In this embodiment, the electrical conduit 122 is a “pipe in a pipe” design with insulating gas, e.g., SFô, between pipes. Distal (D) end of accelerator 124 has been leaded to prevent X-rays from emanating from the distal end of 124. The power source, electrical conduit and électron accelerator are supported by the concrète roof of the vault, outside the vault. The électron accelerator is connected to a scan hom 128 by a conduit 130 (high vacuum électron guide) that passes through the

concrète ceiling (e.g., 4 to 6 feet thickness). A conveyor 132 is positioned for conveying biomass under the scan hom while the scan hom irradiâtes the biomass. A window cooling air conduit 140 brings air from outside the vault through the ceiling and is connected to a System 200 for blowing the cooling air across an électron extraction window, e.g., a titanium foil window. The vault also includes an air conduit 144 for removing the air and other gases, such as process gases (e.g., hazardous gases, HAPs, VOCs), from the interior of the vault to the exterior of the vault. Air conduit 144 is fed by air intake manifold 182 that can include vents (e.g., configured as a screen, grill or mesh), for example 184. Component 182 can include screens, filters and/or air flow controllers. Ideally manifold 182 does not significantly reduce the air flow. In some instances air flow into the vault is on the order of 1000 CFM and air flow out is on the order of 5000 CFM, which maintains a négative pressure inside the vault. In this embodiment, the outer perimeter of the vault can be about 34 x 34 feet and the ceiling height can be about 8 feet. The interior volume of the vault is therefore about 4600 cubic feet. The turnover rate of the atmosphère can be at least about 0.25 turnover per minute (e.g., at least about 0.5 turnovers, at least 1 tumover per minute, at least about 2 turnovers per minute, at least about 3 turnovers per minute, at least 4 turnovers per minute, at least 5 turnovers per minute, or between 1 and 5 turnovers per minute, between about 2 and 4 turnovers per minute). The tumover rate is the rate of gas exchange in the vault.

[0028] Construction materials can be chosen to increase the containment of processes gases in vault and improve the lifetime of the vault (e.g., by reducing corrosion). For example, the porosity of the walls can be reduced by infusion of materials into the construction blocks. For example, concrète with lower permeability can generally be achieved by substituting between 25 to 65 percent slag cernent for Portland cernent. Finely-divided solids (e.g., lime, silicates and colloïdal silica) added to the cernent when the blocks are made can reduce permeability to water and gases by increasing the density or by filling up voids. Some crystalline admixtures react with water and cernent particles in the concrète to form calcium silicate hydrates and/or poreblocking précipitâtes in the existing microcracks and capillaries. The resulting crystalline deposits, which are analogous to calcium silicate hydrate formation, become integrally bound with the hydrated pastes. Porosity reducing additives can also include hydrophobie water-repellent chemicals based on soaps and long-chain fatty acids dérivatives, vegetable oils (tallows, soya-based materials, and greases), and petroleum (minerai oil, paraffin waxes, and bitumen émulsions). These materials are more useful

for providing a water repellency layer on the material and would be more usefully applied to the exterior portions of the vault to aid in decreasing interior vault humidity, which can exacerbate corrosion in the vault. In addition, to improve the life of the structures, the interior surfaces (e.g., of concrète blocks) can be coated or covered with a 5 corrosion résistant material, such as stainless steel.

[0029] FIG. 2 is a right side view of the process gas (e.g., hazardous gas) mitigation System components some of which were introduced in FIG. 1. In FIG. 2 the vault walls, foundation, irradiator power source and electrical conduit for the power source are omitted for clarity. A blower System 170 blows air into the vault in the direction shown θ by the arrows. For example, air is shown on the left side of the drawing being blown from the outside of the vault 171, though a ceiling inlet 172 (which is often leaded), and down a conduit 140, to an air outlet inside the vault 174 that is an outlet of a window cooling System to be described in detail with reference to FIG. 3 A. Therefore, an air flow path from outside the vault to the interior is provided through System 170, conduit 140, through the interior of the window cooling System (described with ref to FIG. 3A and 3B), and outlet 174 for this embodiment. Other gas inlets into the vault can be utilized if desired, for example, to cool a product or equipment in the vault.

[0030] Air in the vault is extracted out of the vault in the directions shown by the arrows on the right side of the drawing. In particular, air is drawn through grills (e.g., screen, mesh) disposed on exhaust manifold 182 as previously described. System 180 includes fans/blowers, and or grills (e.g., screens, mesh) and/or air pumps for drawing air into manifold 182, up conduit 144, and out of the vault. The air is made to pass through a process case, such as an ozone destruction System, e.g., a carbon filter that destroys any process gas, such as ozone (converting it to oxygen) and adsorbs or destroys volatile organic compounds. The destruction System can be disposed anywhere in the flowing air path that passes through 182,144 and 180 and before the air is vented to the atmosphère. In some embodiments, it is préférable to hâve destruction Systems in manifold 182 so that venting pipe 144 is not exposed to process gases, e.g., ozone. In other embodiments 3q it is preferred to hâve destructor Systems located in System 180 and configured to be quickly replaced so that minimal or no down time is required for maintenance. In some cases the destructor Systems (e.g., carbon filters) can be mounted to be automatically replaced when sensors indicated the need (e.g., ozone levels, VOCs and/or HAPs are higher than background levels). Vents on 180 (not shown), exhaust treated, e.g., de35 ozonized, air into the atmosphère 181. Accordingly, this embodiment provides a gas,

e.g., air, path from the interior of the vault to the exterior through a filtering (e.g., ozone

and VOC filtering) system. In some embodiments the air inside the vault is recirculated. For example, an air conduit 280, depicted with dashed Unes in FIG. 2, can optionally be added to the system to connect Systems 170 and 180. In this way, purified air exiting system 180 could be recirculated through the vault via system 170 rather than being vented to the atmosphère. In some cases the vault can include one or more recirculating loops of gas.

[0031] Air pollution control technologies can be used for the destruction of process gases, for example, in manifold 182 and/or as part of system 180 or anywhere therebetween, e.g. in the flow path between 180 and 182. Thermal oxidation can be utilized for the destruction of, for example, HAPs and VOCs. Since some HAPs and ail VOCs are carbon based, thermal oxidizer Systems can be used to destroy these gases by complété oxidation to carbon dioxide and water. Some types of thermal oxidizer Systems, for example, that can be utilized to treat the process gases as described herein, are regenerative thermal oxidizers, regenerative catalytic oxidizers, thermal recuperative oxidizers and direct fired thermal oxidizer. The first three thermal oxidizer Systems can be préférable when designing for high energy efficiency because they ail include some form of energy (e.g., heat) recovery and can hâve very high thermal efficiencies (e.g., greater than 95%). Air pollution control technologies for ozone generally include Systems that convert ozone to oxygen. Other process gases, for example, NO_X can also be treated with ammonia to produced nitrogen and water. Filtering or abatement Systems for SFô gas can also be included in the Systems to be included in some embodiments of the invention.

[0032] Air pollution technologies often utilize a métal or métal oxide catalyst. For example, métal and métal oxide catalysts (e.g., CuO-MnÛ2, vanadium oxides, tungsten oxides, Pd and Pt). The catalysts allow the conversion reactions (e.g., to CO2 and water, to O2, to N2 and water) to occur at relatively lower températures, for example, at températures as low as about 200 deg C (e.g., 100 to 400 deg C) lower than without the catalysts). Air pollution technologies also often utilize activated carbon. Ozone can be reduced to oxygen directly utilizing an activated carbon filter (e.g., bed, column). Activated carbons also act as an adsorbent for VOCs and HAPs, selectively removing and holding the gases on the surface until the carbon is regenerated. Activated carbons can be utilized in any useful form, for example, powdered carbon, granular carbon, extruded carbon, bead carbon, impregnated carbon (for example, impregnated with iodine, silver and métal ions, e.g., Al, Mn, Zn, Fe, Li, Ca métal ions), polymer coated carbon, polymer supported carbon, acid washed carbon, high purity carbon, aerogel

carbon, carbon cloth and/or activated forms of these. The carbon can be designed/formed into different configurations, for example, as a web filter, a pleated filter, a spiral filter, a layered filter, a packed column filter, and combinations of these.

[0033] The catalysts and activated carbon as described herein can be utilized in an any useful configuration, e.g., pelletized, extruded, supported (e.g., on silica, on alumina, on carbon, on graphite, on aluminosilicates, on clays, on a foam, on a sponge, on a mesh, on beads, on a honeycomb structure, on a ceramic, on a woven or non-woven cloth, on a pleated filter, on a spiral filter, on a layered filter), as a mesh, as a wire, as fibers, in a column and/or on an filtering bed.

[0034] Optionally, process gases (e.g., components to be removed and/or destroyed in the gas) can be concentrated using, for example, a rotor concentrator and/or a centrifuge and then this concentrated gas stream can be treated with the pollution control Systems described herein. Concentration can provide the advantage of not requiring a high throughput of gas through one of the air pollution control Systems as described herein, so that a smaller capacity (e.g., lower gas flow) System can be utilized. Optionally, the process gas stream can be split into two or more flows and each flow treated independently.

[0035] The air pollution technologies and Systems can be utilized in combinations and in any order to treat the process gases. For example, Systems for destruction and/or removal of VOCs and HAPs can be utilized prior to ozone destruction Systems. Additional Systems can be utilized, for example, particulate filters, in combinations with these Systems. Removal of particulates, then removal of VOCs and HAPs followed by Ozone removal can be preferred to reduce catalyst deactivation (e.g., fouling and catalyst poisoning can be reduced).

[0036] Some suppliers of process gas mitigation equipment (e.g., air pollution control technologies) and related supplies (e.g., filters, catalysts, activated carbon) include: Anguil Environmental Systems, Inc. (Milwaukee, WI); PureSphere Co., Inc. (Korea); General Air Products, Inc. (Exton, PA); Cabot Corp. (Boston, MA); Corporate Consulting Service Instruments, Inc. (Arkon, OH); Ozone Solutions, Inc. (Hull, IA); Columbus Industries, Inc. (Ashville, OH); California Carbon Co. Inc. (Wilmington, CA); Calgon Carbon Corporation (Pittsburgh, PA); and General Carbon Co. (Paterson, NJ). Some spécifie ozone destructor units that can be utilized in the methods described herein are; the NT-400 unit available from Auguil Environmental Systems Inc. and/or scaled up versions of this unit. An exemplary ozone destructor System that can be utilized in

manifold 182 is the NT-400 or a sealed up version of this System (e.g., so that high gas flow rates can be utilized), available from Ozone Solutions, Inc.

[0037] FIG. 3A is a detailed side view showing part of the process gas mitigation System including a System 200 for air-cooling window foils. In this air-cooling System, air entering the vault through conduit 140 is blown through manifold 210 and directed into an enclosed area 212 through conduit 178. The enclosed area 212 is positioned between the scan hom 128 and a conveyor System 132, which includes a trough 240 for carrying biomass and a conveyor cover 242. The enclosed area 212 is defined on one side by one or more foils 214 (e.g., titanium foils) on the scanning hom, and on the other side by one or more foils 216 (e.g., a window including titanium foil) mounted to the edges of an opening on the conveyor cover 242. The foils on the scanning hom allow électrons from the high vacuum side 215 of the scanning hom to flow through the high pressure area between the foils 219 and to the atmospheric side 217, as indicated by the e’ arrows in FIG. 3A. Outlet 174 (and/or gap 173 see FIG. 3B) is sized such that the pressure in the space 212 (high pressure area 219) is sufficient to keep the foils from fluttering in the air flows therein. For example, the pressure in 219 is higher than atmospheric pressure by at least about 0.1 psi, higher than atmospheric pressure by about lpsi or from about 50 - 200 psig (e.g., about 75-200 psig, about 80-150 psig). Foil 216 protects foil 214 from implosion, such as if particulates are projected towards the .q électron extraction Windows from the conveyor. For example, an outlet flow path, for example, the outlet 174 and/or gap 173, can hâve a minimum cross sectional area perpendicular to the flow path of the gas (e.g., air, nitrogen, argon, hélium) out of the space 212 that less than about 10% (e.g., less than about 20% the area, less than about 30% the area, less than about 40% the area, less than about 50% the area, less than about ?5 60% the area, less than about 70% the area, less than about 80% the area) the minimum cross sectional area of the flow path of the gas into the space 212 (e.g., through the opening of conduit 178). During biomass treatment, électrons pass from the vacuum side 215 of the scanning hom, through foil 214, through the high pressure area 219, through foil 216 and strike biomass 230 that is conveyed on conveyor surface (e.g., trough) 240.

3Q Heat is generated during these électron interactions, necessitating cooling of the foils. The flow of air from manifold 210 into the enclosed space assists with this cooling, maintaining efficient operation of the scanning head. For example, cooled window foils and window foils integrated with conveyors.

[0038] As discussed above, the électron interaction with the biomass can reduce the 35 recalcitrance of the biomass. Energy dissipation processes due to the électrons striking

the biomass or the conveyor surface can also occur. The heat produced, and/or the recalcitrance réduction of the biomass, can release (e.g., create, volatilize) volatile organic compounds (VOCs) and hazardous air pollutants (HAP), as indicated by the VOC/HAP arrow in FIG. 3A. Electrons can also interact with the components of air, for example, dioxygen, producing toxic gases, e.g., ozone. As shown in FIGS. 3A and 3B, ozone that is produced in the enclosed area 212 is vented out into the surrounding atmosphère, e.g., the vault, by way of the gap 173 (FIG. 3B) and through outlet 174. The gap 173 is defïned by sheet (e.g., stainless steel sheet) 175 and sheet 177 that are part of window cooling System and mounted to the manifold 210. The gap 173 defines a conduit between the space 212 and the outlet 174. The outlet 174 and manifold 210 are in fluid communication through the enclosure 212. FIG. 3C is a perspective view showing of the scan hom, manifold 210 and outlet 174.

[0039] Some of the ozone generated during irradiation of biomass can react (e.g., oxidize) the biomass, while some of the ozone can leak out of the enclosed conveyor 132 into the vault. However, some ozone may be carried out of the vault with the biomass. To control the ozone that exits the vault with the biomass, an ozone abatement System can be used, e.g., a closed loop air conveyor with ozone abatement Systems. For example, closed loop pneumatic conveyors and ozone abatement Systems.

[0040] In some embodiments an inert gas, for example nitrogen, argon, carbon dioxide, He, SFô, SiF4, CF4, or mixtures thereof (e.g., more than about 80% nitrogen, more than about 90% nitrogen, more than about 95% nitrogen, more than about 99% nitrogen), can be used to purge the vault. For example, with reference to FIG. 2 the inert gas is supplied to the vault through inlet 172. Processing the biomass in an atmosphère of inert gas, rather than air, can reduce or even eliminate the formation of ozone. An inert gas can be supplied by a tank, transported from a central location through a pipe and or generated close to the irradiation site. On site nitrogen génération technologies include membrane technology (e.g., hollow fiber membrane technology) and pressure swing adsorption technologies. The inert gas can be recycled, as described for other gases by drawing the vault atmosphère through manifold 182, through System 180 and then coupling the flows 181 and 171. Pressure adjustments and inert gas addition to compensate for any loss can be done by Systems such as 170 and 180 in addition to attachment to an inert gas compensation source (e.g., tank, supply in fluid communication with 170 and/or 180). Since the inert gas avoids the production of ozone no ozone destruction unit is necessary in this optional embodiment.

[0041] In some embodiments the pressure inside the vault is slightly lower than the pressure outside the vault. Ideally, the vault would be airtight so that no process gases escape into the atmosphère, however this would in practice be difficult to achieve. Thus, a similar resuit can be achieved by making the active flow out of the vault, and through a process gas abatement System, be higher than the air/gas made to flow into the vault,

e.g., using System 170 as discussed above. For example, the pressure in the vault can be at least about 0.001% lower than the pressure outside of the vault (e.g., at least about 0.002% lower, at least about 0.004% lower, at least about 0.006% lower, at least about 0.008% lower, at least about 0.01% lower, at least about 0.05% lower, at least about

1Q 0.1% lower, at least about 0.5% lower, at least about 1 % lower, at least about 2 % lower, at least about 5 % lower, at least about 10 % lower, at least about 50 % lower, or at least about 100 % lower). For example, if the pressure outside of the vault is 1 atm, and the pressure inside the vault is at least 0.1% lower than the pressure outside the vault, then the pressure inside the vault is at least 0.9 atm or lower. The pressure différences can be

5 achieved by controlling flow rate of air and/or gases into and out of the vault. For example, referring to FIG. 2, by adjusting Systems 170 and 180 so that the flow rate into the vault at 171 is at a lower rate than the flow rate out of the vault at 181. For example, the flow rate at an outlet to the vault, flowing air out of the vault, can be at least 0.1 times the flow rate at an inlet to the vault, flowing air into the vault (e.g., at least 0.5 times, at least 1 times, at least 2 times, at least 3 times, at least 4 times, at least 5 times, at least 10 times, at least 50 times, at least 100 times, or at least 200 times).

[0042] Some more details and réitérations of processes for treating a feedstock that can be utilized, for example, with the embodiments already discussed above, or in other embodiments, are described in the following disclosures.

RADIATION TREATMENT [0043] The feedstock can be treated with radiation to modify its structure to reduce its recalcitrance. Such treatment can, for example, reduce the average molecular weight of the feedstock, change the crystalline structure of the feedstock, and/or increase the surface area and/or porosity of the feedstock. Radiation can be by, for example, électron beam, ion beam, 100 nm to 280 nm ultraviolet (UV) light, gamma or X-ray radiation. Radiation treatments and Systems for treatments are discussed in U.S. Patent 8,142,620 and U.S. Patent Application Sériés No. 12/417,731, the entire disclosures of which are incorporated herein by reference.

[0044] Each form of radiation ionizes the biomass via particular interactions, as determined by the energy of the radiation. Heavy charged particles primarily ionize matter via Coulomb scattering; furthermore, these interactions produce energetic électrons that may further ionize matter. Alpha particles are identical to the nucléus of a 5 hélium atom and are produced by the alpha decay of various radioactive nuclei, such as isotopes of bismuth, polonium, astatine, radon, francium, radium, several actinides, such as actinium, thorium, uranium, neptunium, curium, californium, américium, and plutonium. Electrons interact via Coulomb scattering and bremsstrahlung radiation produced by changes in the velocity of électrons.

θ [0045] When particles are utilized, they can be neutral (uncharged), positively charged or negatively charged. When charged, the charged particles can bear a single positive or négative charge, or multiple charges, e.g., one, two, three or even four or more charges. In instances in which chain scission is desired to change the molecular structure of the carbohydrate containing material, positively charged particles may be désirable, in part, due to their acidic nature. When particles are utilized, the particles can hâve the mass of a resting électron, or greater, e.g., 500, 1000, 1500, or 2000 or more times the mass of a resting électron. For example, the particles can hâve a mass of from about 1 atomic unit to about 150 atomic units, e.g., from about 1 atomic unit to about 50 atomic units, or from about 1 to about 25, e.g., 1, 2, 3, 4, 5, 10, 12 or 15 atomic units.

2q [0046] Gamma radiation has the advantage of a significant pénétration depth into a variety of material in the sample.

[0047] In embodiments in which the irradiating is performed with electromagnetic radiation, the electromagnetic radiation can hâve, e.g., energy per photon (in électron volts) of greater than 10² eV, e.g., greater than 10³, 10⁴, 10⁵, 10⁶, or even greater than 10⁷ 25 eV. In some embodiments, the electromagnetic radiation has energy per photon of between 10⁴ and 10⁷, e.g., between 10⁵ and 10⁶ eV. The electromagnetic radiation can hâve a frequency of, e.g., greater than 10¹⁶ Hz, greater than 10¹⁷ Hz, 10¹⁸, 10¹⁹, 10²⁰, or even greater than 10²¹ Hz. In some embodiments, the electromagnetic radiation has a frequency of between 10¹⁸ and 10²²Hz, e.g., between 10¹⁹ to 10²¹ Hz.

[0048] Electron bombardment may be performed using an électron beam device that OU has a nominal energy of less than 10 MeV, e.g., less than 7 MeV, less than 5 MeV, or less than 2 MeV, e.g., from about 0.5 to 1.5 MeV, from about 0.8 to 1.8 MeV, or from about 0.7 to 1 MeV. In some implémentations the nominal energy is about 500 to 800 keV.

[0049] The électron beam may hâve a relatively high total beam power (the combined beam power of ail accelerating heads, or, if multiple accelerators are used, of ail accelerators and ail heads), e.g., at least 25 kW, e.g., at least 30, 40, 50, 60, 65, 70, 80, 100, 125, or 150 kW. In some cases, the power is even as high as 500 kW, 750 kW, or even 1000 kW or more. In some cases the électron beam has a beam power of 1200 kW or more, e.g., 1400, 1600,1800, or even 3000 kW.

[0050] This high total beam power is usually achieved by utilizing multiple accelerating heads. For example, the électron beam device may include two, four, or more accelerating heads. The use of multiple heads, each of which has a relatively low beam power, prevents excessive température rise in the material, thereby preventing buming of the material, and also increases the uniformity of the dose through the thickness of the layer of material.

[0051] It is generally preferred that the bed of biomass material has a relatively uniform thickness. In some embodiments the thickness is less than about 1 inch (e.g., less than about 0.75 inches, less than about 0.5 inches, less than about 0.25 inches, less than about 0.1 inches, between about 0.1 and 1 inch, between about 0.2 and 0.3 inches). [0052] It is désirable to treat the material as quickly as possible. In general, it is preferred that treatment be performed at a dose rate of greater than about 0.25 Mrad per second, e.g., greater than about 0.5, 0.75, 1, 1.5, 2, 5, 7, 10, 12, 15, or even greater than about 20 Mrad per second, e.g., about 0.25 to 2 Mrad per second. Higher dose rates allow a higher throughput for a target (e.g., the desired) dose. Higher dose rates generally require higher line speeds, to avoid thermal décomposition of the material. In one implémentation, the accelerator is set for 3 MeV, 50 mA beam current, and the line speed is 24 feet/minute, for a sample thickness of about 20 mm (e.g., comminuted corn cob material with a bulk density of 0.5 g/cm³).

[0053] In some embodiments, électron bombardment is performed until the material receives a total dose of at least 0.1 Mrad, 0.25 Mrad, 1 Mrad, 5 Mrad, e.g., at least 10, 20, 30 or at least 40 Mrad. In some embodiments, the treatment is performed until the material receives a dose of from about 10 Mrad to about 50 Mrad, e.g., from about 20 Mrad to about 40 Mrad, or from about 25 Mrad to about 30 Mrad. In some implémentations, a total dose of 25 to 35 Mrad is preferred, applied ideally over a couple of passes, e.g., at 5 Mrad/pass with each pass being applied for about one second. Cooling methods, Systems and equipment can be used before, during, after and in between radiations, for example, utilizing a cooling screw conveyor and/or a cooled vibratory conveyor.

[0054] Using multiple heads as discussed above, the material can be treated in multiple passes, for example, two passes at 10 to 20 Mrad/pass, e.g., 12 to 18 Mrad/pass, separated by a few seconds of cool-down, or three passes of 7 to 12 Mrad/pass, e.g., 5 to 20 Mrad/pass, 10 to 40 Mrad/pass, 9 to 11 Mrad/pass. As discussed herein, treating the material with several relatively low doses, rather than one high dose, tends to prevent overheating of the material and also increases dose uniformity through the thickness of the material. In some implémentations, the material is stirred or otherwise mixed during or after each pass and then smoothed into a uniform layer again before the next pass, to further enhance treatment uniformity.

o [0055] In some embodiments, électrons are accelerated to, for example, a speed of greater than 75 percent of the speed of light, e.g., greater than 85, 90, 95, or 99 percent of the speed of light.

[0056] In some embodiments, any processing described herein occurs on lignocellulosic material that remains dry as acquired or that has been dried, e.g., using Ί 5 heat and/or reduced pressure. For example, in some embodiments, the cellulosic and/or lignocellulosic material has less than about 25 wt.% retained water, measured at 25°C and at fifty percent relative humidity (e.g., less than about 20 wt.%, less than about 15 wt.%, less than about 14 wt.%, less than about 13 wt.%, less than about 12 wt.%, less than about 10 wt.%, less than about 9 wt.%, less than about 8 wt.%, less than about 7 wt.%, less than about 6 wt.%, less than about 5 wt.%, less than about 4 wt.%, less than about 3 wt.%, less than about 2 wt.%, less than about 1 wt.%, or less than about 0.5 wt.%.

[0057] In some embodiments, two or more ionizing sources can be used, such as two or more électron sources. For example, samples can be treated, in any order, with a beam of électrons, followed by gamma radiation and UV light having wavelengths from about 100 nm to about 280 nm. In some embodiments, samples are treated with three ionizing radiation sources, such as a beam of électrons, gamma radiation, and energetic UV light. The biomass is conveyed through the treatment zone where it can be bombarded with électrons.

3Q [0058] It may be advantageous to repeat the treatment to more thoroughly reduce the recalcitrance of the biomass and/or further modify the biomass. In particular the process parameters can be adjusted after a first (e.g., second, third, fourth or more) pass depending on the recalcitrance of the material. In some embodiments, a conveyor can be used which includes a circular system where the biomass is conveyed multiple times through the various processes described above. In some other embodiments multiple

treatment devices (e.g., électron beam generators) are used to treat the biomass multiple (e.g., 2, 3, 4 or more) times. In yet other embodiments, a single électron beam generator may be the source of multiple beams (e.g., 2, 3, 4 or more beams) that can be used for treatment of the biomass.

[0059] The effectiveness in changing the molecular/supermolecular structure and/or reducing the recalcitrance of the carbohydrate-containing biomass dépends on the électron energy used and the dose appEed, while exposure time dépends on the power and dose. In some embodiments, the dose rate and total dose are adjusted so as not to destroy (e.g., char or bum) the biomass material. For example, the carbohydrates should o not be damaged in the processing so that they can be released from the biomass intact,

e.g. as monomeric sugars.

[0060] In some embodiments, the treatment (with any électron source or a combination of sources) is performed until the material receives a dose of at least about 0.05 Mrad, e.g., at least about 0.1, 0.25, 0.5, 0.75,1.0, 2.5, 5.0, 7.5, 10.0, 15,20, 25, 30,

40, 50, 60, 70, 80, 90, 100, 125, 150, 175, or 200 Mrad. In some embodiments, the treatment is performed until the material receives a dose of between 0.1-100 Mrad, 1200, 5-200, 10-200, 5-150, 50-150 Mrad, 5-100, 5-50, 5-40, 10-50, 10-75, 15-50, 20-35 Mrad.

[0061] In some embodiments, relatively low doses of radiation are utilized, e.g., to increase the molecular weight of a cellulosic or lignocellulosic material (with any radiation source or a combination of sources described herein). For example, a dose of at least about 0.05 Mrad, e.g., at least about 0.1 Mrad or at least about 0.25,0.5, 0.75. 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, or at least about 5.0 Mrad. In some embodiments, the irradiation is performed until the material receives a dose of between 0.1 Mrad and 2.0 Mrad, e.g., between 0.5 Mrad and 4.0 Mrad or between 1.0 Mrad and 3.0 Mrad.

[0062] It also can be désirable to irradiate from multiple directions, simultaneously or sequentially, in order to achieve a desired degree of pénétration of radiation into the material. For example, depending on the density and moisture content of the material, such as wood, and the type of radiation source used (e.g., gamma or électron beam), the maximum pénétration of radiation into the material may be only about 0.75 inch. In such a cases, a thicker section (up to 1.5 inch) can be irradiated by first irradiating the material from one side, and then tuming the material over and irradiating from the other side. Irradiation from multiple directions can be particularly useful with électron beam radiation, which irradiâtes faster than gamma radiation but typically does not achieve as great a pénétration depth.

RADIATION OPAQUE MATERIALS [0063] As previously discussed, the invention can include processing the material in a vault and/or bunker that is constructed using radiation opaque materials. In some implémentations, the radiation opaque materials are selected to be capable of shielding the components from X-rays with high energy (short wavelength), which can penetrate many materials. One important factor in designing a radiation shielding enclosure is the atténuation length of the materials used, which will détermine the required thickness for a particular material, blend of materials, or layered structure. The atténuation length is the pénétration distance at which the radiation is reduced to approximately 1/e (e = Euler’s number) times that of the incident radiation. Although virtually ail materials are radiation opaque if thick enough, materials containing a high compositional percentage (e.g., density) of éléments that hâve a high Z value (atomic number) hâve a shorter radiation atténuation length and thus if such materials are used a thinner, lighter shielding can be provided. Examples of high Z value materials that are used in radiation shielding are tantalum and lead. Another important parameter in radiation shielding is the halving distance, which is the thickness of a particular material that will reduce gamma ray intensity by 50%. As an example for X-ray radiation with an energy of 0.1 MeV the halving thickness is about 15.1 mm for concrète and about 2.7 mm for lead, while with an X-ray energy of 1 MeV the halving thickness for concrète is about 44.45 mm and for lead is about 7.9 mm. Radiation opaque materials can be materials that are thick or thin so long as they can reduce the radiation that passes through to the other side. Thus, if it is desired that a particular enclosure hâve a low wall thickness, e.g., for light weight or due to size constraints, the material chosen shouid hâve a sufficient Z value and/or atténuation length so that its halving length is less than or equal to the desired wall thickness of the enclosure.

[0064] In some cases, the radiation opaque material may be a layered material, for example having a layer of a higher Z value material, to provide good shielding, and a layer of a lower Z value material to provide other properties (e.g., structural integrity, impact résistance, etc.). In some cases, the layered material may be a graded-Z laminate, e.g., including a laminate in which the layers provide a gradient from high-Z through successively lower-Z éléments. In some cases the radiation opaque materials can be interlocking blocks, for example, lead and/or concrète blocks can be supplied by NELCO Worldwide (Burlington, MA), and reconfigurable vaults can be utilized.

[0065] A radiation opaque material can reduce the radiation passing through a structure (e.g., a wall, door, ceiling, enclosure, a sériés of these or combinations of these) formed of the material by about at least about 10 %, (e.g., at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about

70%, at least about 80%, at least about 90%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, at least about 99.9%, at least about 99.99%, at least about 99.999%) as compared to the incident radiation. Therefore, an enclosure made of a radiation opaque material can reduce the exposure of equipment/system/components by the same amount. Radiation opaque materials can q include stainless steel, metals with Z values above 25 (e.g., lead, iron), concrète, dirt, sand and combinations thereof. Radiation opaque materials can include a barrier in the direction of the incident radiation of at least about 1mm (e.g., 5 mm, 10mm, 5 cm, 10 cm, 100cm, lm and even at least 10 m).

RADIATION SOURCES [0066] The type of radiation détermines the kinds of radiation sources used as well as the radiation devices and associated equipment. The methods, Systems and equipment described herein, for example, for treating materials with radiation, can utilized sources as described herein as well as any other useful source.

[0067] Sources of gamma rays include radioactive nuclei, such as isotopes of cobalt, calcium, technetium, chromium, gallium, indium, iodine, iron, krypton, samarium, sélénium, sodium, thallium, and xénon.

[0068] Sources of X-rays include électron beam collision with métal targets, such as tungsten or molybdenum or alloys, or compact light sources, such as those produced commercially by Lyncean.

[0069] Alpha particles are identical to the nucléus of a hélium atom and are produced by the alpha decay of various radioactive nuclei, such as isotopes of bismuth, polonium, astatine, radon, francium, radium, several actinides, such as actinium, thorium, uranium, neptunium, curium, californium, américium, and plutonium.

[0070] Sources for ultraviolet radiation include deuterium or cadmium lamps.

[0071] Sources for infrared radiation include sapphire, zinc, or selenide window ceramic lamps.

[0072] Sources for microwaves include klystrons, Slevin type RF sources, or atom beam sources that employ hydrogen, oxygen, or nitrogen gases.

[0073] Accelerators used to accelerate the particles (e.g., électrons or ions) can be DC (e.g., electrostatic DC or electrodynamic DC), RF linear, magnetic induction linear or continuous wave. For example, various irradiating devices may be used in the methods disclosed herein, including field ionization sources, electrostatic ion separators, field ionization generators, thermionic émission sources, microwave discharge ion sources, recirculating or static accelerators, dynamic linear accelerators, van de Graaff accelerators, Cockroft Walton accelerators (e.g., PELLETRON® accelerators), LINACS, Dynamitrons (e.g., DYNAMITRON® accelerators), cyclotrons, synchrotrons, betatrons, transformer-type accelerators, microtrons, plasma generators, cascade accelerators, and q folded tandem accelerators. For example, cyclotron type accelerators are available from

IB A, Belgium, such as the RHODOTRON™ System, while DC type accelerators are available from RDI, now IBA Industrial, such as the DYNAMITRON®. Other suitable accelerator Systems include, for example: DC insulated core transformer (ICT) type Systems, available from Nissin High Voltage, Japan; S-band LINACs, available from L315 PSD (USA), Linac Systems (France), Mevex (Canada), and Mitsubishi Heavy Industries (Japan); L-band LINACs, available from Iotron Industries (Canada); and ILU-based accelerators, available from Budker Laboratories (Russia). 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, Chu, William T., “Overview of Light-Ion Beam Therapy”, Columbus-Ohio, ICRU-IAEA Meeting, 18-20 March 2006, Iwata, Y. et al., “Altemating-Phase-Focused EH-DTL for Heavy-Ion Medical Accelerators”, Proceedings of EPAC 2006, Edinburgh, Scotland,, and Leitner, C.M. et al., “Status of the Superconducting ECR Ion Source Venus”, Proceedings of EPAC 2000, Vienna, Austria. Some particle accelerators and their uses are disclosed, for example, in

U.S. Pat. No. 7,931,784 to Medoff, the complété disclosure of which is incorporated herein by reference.

[0074] Electrons may be produced by radioactive nuclei that undergo beta decay, such as isotopes of iodine, césium, technetium, and iridium. Altematively, an électron gun can be used as an électron source via thermionic émission and accelerated through 30 an accelerating potential. An électron gun generates électrons, which are then accelerated through a large potential (e.g., greater than about 500 thousand, greater than about 1 million, greater than about 2 million, greater than about 5 million, greater than about 6 million, greater than about 7 million, greater than about 8 million, greater than about 9 million, or even greater than 10 million volts) and then scanned magnetically in 35 the x-y plane, where the électrons are initially accelerated in the z direction down the

accelerator tube and extracted through a foil window. Scanning the électron beams is useful for increasing the irradiation surface when irradiating materials, e.g., a biomass, that is conveyed through the scanned beam. Scanning the électron beam also distributes the thermal load homogenously on the window and helps reduce the foil window rupture due to local heating by the électron beam. Window foil rupture is a cause of significant down-time due to subséquent necessary repairs and re-starting the électron gun.

[0075] Various other irradiating devices may be used in the methods disclosed herein, including field ionization sources, electrostatic ion separators, field ionization generators, thermionic émission sources, microwave discharge ion sources, recirculating or static accelerators, dynamic linear accelerators, van de Graaff accelerators, and folded tandem accelerators. Such devices are disclosed, for example, in U.S. Pat. No. 7,931,784 to Medoff, the complété disclosure of which is incorporated herein by reference.

[0076] A beam of électrons can be used as the radiation source. A beam of électrons has the advantages of high dose rates (e.g., 1, 5, or even 10 Mrad per second), high throughput, less containment, and less confinement equipment. Electron beams can also hâve high electrical efficiency (e.g., 80%), allowing for lower energy usage relative to other radiation methods, which can translate into a lower cost of operation and lower greenhouse gas émissions corresponding to the smaller amount of energy used. Electron beams can be generated, e.g., by electrostatic generators, cascade generators, transformer generators, low energy accelerators with a scanning System, low energy accelerators with a linear cathode, linear accelerators, and pulsed accelerators.

[0077] Electrons can also be more efficient at causing changes in the molecular structure of carbohydrate-containing materials, for example, by the mechanism of chain scission. In addition, électrons having energies of 0.5-10 MeV can penetrate low density materials, such as the biomass materials described herein, e.g., materials having a bulk density of less than 0.5 g/cm³, and a depth of 0.3-10 cm. Electrons as an ionizing radiation source can be useful, e.g., for relatively thin piles, layers or beds of materials, e.g., less than about 0.5 inch, e.g., less than about 0.4 inch, 0.3 inch, 0.25 inch, or less than about 0.1 inch. In some embodiments, the energy of each électron of the électron beam is from about 0.3 MeV to about 2.0 MeV (million électron volts), e.g., from about 0.5 MeV to about 1.5 MeV, or from about 0.7 MeV to about 1.25 MeV. Methods of irradiating materials are discussed in U.S. Pat. App. Pub. 2012/0100577 Al, filed October 18, 2011, the entire disclosure of which is herein incorporated by reference.

[0078] Electron beam irradiation devices may be procured commercially or built. For example, éléments or components such inductors, capacitors, casings, power sources,

cables, wiring, voltage control Systems, current control éléments, insulating material, microcontrollers and cooling equipment can be purchased and assembled into a device. Optionally, a commercial device can be modified and/or adapted. For example, devices and components can be purchased from any of the commercial sources described herein including Ion Beam Applications (Louvain-la-Neuve, Belgium), Wasik Associâtes Inc. (Dracut, MA), NHV Corporation (Japan), the Titan Corporation (San Diego, CA), Vivirad High Voltage Corp (Billerica, MA) and/or Budker Laboratoires (Russia). Typical électron energies can be 0.5 MeV, 1 MeV, 2 MeV, 4.5 MeV, 7.5 MeV, or 10 MeV. Typical électron beam irradiation device power can be 1 kW, 5 kW, 10 kW, 20 0 kW, 50 kW, 60 kW, 70 kW, 80 kW, 90 kW, 100 kW, 125 kW, 150 kW, 175 kW, 200 kW, 250 kW, 300 kW, 350 kW, 400 kW, 450 kW, 500 kW, 600 kW, 700 kW, 800 kW,

900 kW or even 1000 kW. Accelerators that can be used include NHV irradiators medium energy sériés EPS-500 (e.g., 500 kV accelerator voltage and 65, 100 or 150 mA beam current), EPS-800 (e.g., 800 kV accelerator voltage and 65 or 100 mA beam .|₅ current), or EPS-1000 (e.g., 1000 kV accelerator voltage and 65 or 100 mA beam current). Also, accelerators from NHV’s high energy sériés can be used such as EPS1500 (e.g., 1500 kV accelerator voltage and 65 mA beam current), EPS-2000 (e.g., 2000 kV accelerator voltage and 50 mA beam current), EPS-3000 (e.g., 3000 kV accelerator voltage and 50 mA beam current) and EPS-5000 (e.g., 5000 and 30 mA beam current).

Tradeoffs in considering électron beam irradiation device power spécifications include cost to operate, capital costs, dépréciation, and device footprint. Tradeoffs in considering exposure dose levels of électron beam irradiation would be energy costs and environment, safety, and health (ESH) concerns. Typically, generators are housed in a vault, e.g., of lead or concrète, especially for production from X-rays that are generated in the process. Tradeoffs in considering électron energies include energy costs.

[0079] The électron beam irradiation device can produce either a fixed beam or a scanning beam. A scanning beam may be advantageous with large scan sweep length and high scan speeds, as this would effectively replace a large, fixed beam width. Further, available sweep widths of 0.5 m, 1 m, 2 m or more are available. The scanning 30 beam is preferred in most embodiments described herein because of the larger scan width and reduced possibility of local heating and failure of the Windows.

ELECTRON GUNS - WINDOWS [0080] The extraction System for an électron accelerator can include two window foils. The cooling gas in the two foil window extraction System can be a purge gas or a mixture, for example, air, or a pure gas. In one embodiment, the gas is an inert gas such as nitrogen, argon, hélium and/or carbon dioxide. It is preferred to use a gas rather than a liquid since energy losses to the électron beam are minimized. Mixtures of pure gas can also be used, either pre-mixed or mixed in line prior to impinging on the Windows or in the space between the Windows. The cooling gas can be cooled, for example, by using a heat exchange System (e.g., a chiller) and/or by using boil off from a condensed gas (e.g., liquid nitrogen, liquid hélium). Window foils are described in PCT/US2013/64332 filed October 10, 2013 the full disclosure of which is incorporated by reference herein.

HEATING AND THROUGHPUT DURING RADIATION TREATMENT [0081] Several processes can occur in biomass when électrons from an électron beam interact with matter in inelastic collisions. For example, ionization of the material, chain scission of polymers in the material, cross linking of polymers in the material, oxidation of the material, génération of X-rays (“Bremsstrahlung”) and vibrational excitation of molécules (e.g., phonon génération). Without being bound to a particular mechanism, the réduction in recalcitrance can be due to several of these inelastic collision effects, for example, ionization, chain scission of polymers, oxidation and phonon génération. Some of the effects (e.g., especially X-ray génération), necessitate shielding and engineering barriers, for example, enclosing the irradiation processes in a concrète (or other radiation opaque material) vault. Another effect of irradiation, vibrational excitation, is équivalent to heating up the sample. Heating the sample by irradiation can help in recalcitrance réduction, but excessive heating can destroy the material, as will be explained below.

[0082] The adiabatic température rise (ΔΤ) from adsorption of ionizing radiation is given by the équation: ΔΤ = D/Cp: where D is the average dose in kGy, Cp is the heat capacity in J/g °C, and ΔΤ is the change in température in °C. A typical dry biomass material will hâve a heat capacity close to 2. Wet biomass will hâve a higher heat capacity dépendent on the amount of water since the heat capacity of water is very high ( 4.19 J/g °C). Metals hâve much lower heat capacities, for example 304 stainless steel has a heat capacity of 0.5 J/g °C. The température change due to the instant adsorption of radiation in a biomass and stainless steel for various doses of radiation is shown in Table

1. At the higher températures biomass will décomposé causing extreme déviation from the estimated changes in température.

Table 1: Calculated Température increase for biomass and stainless steel.

Dose (Mrad)	Estimated Biomass ΔΤ (°C)	Steel AT (°C)
10	50	200
50	250 (decomposed)	1000
100	500 (decomposed)	2000
150	750 (decomposed)	3000
200	1000 (decomposed)	4000

[0083] High températures can destroy and/or modify the biopolymers in biomass so

- that the polymers (e.g., cellulose) are unsuitable for further processing. A biomass subjected to high températures can become dark, sticky and give off odors indicating décomposition. The stickiness can even make the material hard to convey. The odors can be unpleasant and be a safety issue. In fact, keeping the biomass below about 200°C has been found to be bénéficiai in the processes described herein (e.g., below about 190°C, below about 180°C, below about 170°C, below about 160°C, below about 150°C, below about 140°C, below about 130°C, below about 120°C, below about 110°C, between about 60°C and 180°C, between about 60°C and 160°C, between about 60°C and 150°C, between about 60°C and 140°C, between about 60°C and 130°C, between about 60°C and 120°C, between about 80°C and 180°C, between about 100°C and 180°C, between about 120°C and 180°C, between about 140°C and 180°C, between about 160°C and

180°C, between about 100°C and 140°C, between about 80°C and 120°C).

[0084] It has been found that irradiation above about 10 Mrad is désirable for the processes described herein (e.g., réduction of recalcitrance). A high throughput is also désirable so that the irradiation does not become a bottle neck in processing the biomass.

2Q The treatment is govemed by a Dose rate équation: M = FP/D time, where M is the mass of irradiated material (kg), F is the fraction of power that is adsorbed (unit less), P is the emitted power (kW=Voltage in MeV x Current in mA), time is the treatment time (sec) and D is the adsorbed dose (kGy). In an exemplary process where the fraction of adsorbed power is fixed, the Power emitted is constant and a set dosage is desired, the throughput (e.g., M, the biomass processed) can be increased by increasing the irradiation time. However, increasing the irradiation time without allowing the material to cool, can excessively heat the material as exemplified by the calculations shown

above. Since biomass has a low thermal conductivity (less than about 0.1 Wm 'K^-1), heat dissipation is slow, unlike, for example, metals (greater than about 10 Wm 'K¹) which can dissipate energy quickly as long as there is a heat sink to transfer the energy to.

ELECTRON GUNS - BEAM STOPS [0085] In some embodiments the Systems and methods include a beam stop (e.g., a shutter). For example, the beam stop can be used to quickly stop or reduce the irradiation of material without powering down the électron beam device. Alternatively the beam stop can be used while powering up the électron beam, e.g., the beam stop can stop the électron beam until a beam current of a desired level is achieved. The beam stop can be placed between the primary foil window and a secondary foil window. For example, the beam stop can be mounted so that it is movable, that is, so that it can be moved into and out of the beam path. Even partial coverage of the beam can be used, for example, to control the dose of irradiation. The beam stop can be mounted to the floor, to a conveyor for the biomass, to a wall, to the radiation device (e.g., at the scan hom), or to any structural support. Preferably the beam stop is fixed in relation to the scan hom so that the beam can be effectively controlled by the beam stop. The beam stop can incorporate a hinge, a rail, wheels, slots, or other means allowing for its operation in moving into and out of the beam. The beam stop can be made of any material that will stop at least 5% of the électrons, e.g., at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, at least 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or even about 100% of the électrons.

[0086] The beam stop can be made of a métal including, but not limited to, stainless steel, lead, iron, molybdenum, silver, gold, titanium, aluminum, tin, or alloys of these, or laminates (layered materials) made with such metals (e.g., metal-coated ceramic, metalcoated polymer, metal-coated composite, multilayered métal materials).

[0087] The beam stop can be cooled, for example, with a cooling fluid such as an aqueous solution or a gas. The beam stop can be partially or completely hollow, for example, with cavities. Interior spaces of the beam stop can be used for cooling fluids and gases. The beam stop can be of any shape, including fiat, curved, round, oval, square, rectangular, beveled and wedged shapes.

[0088] The beam stop can hâve perforations so as to allow some électrons through, thus controlling (e.g., reducing) the levels of radiation across the whole area of the window, or in spécifie régions of the window. The beam stop can be a mesh formed, for

example, from fibers or wires. Multiple beam stops can be used, together or independently, to control the irradiation. The beam stop can be remotely controlled, e.g., by radio signal or hard wired to a motor for moving the beam into or out of position.

BEAM DUMPS [0089] The embodiments disclosed herein can also include a beam dump when utilizing a radiation treatment. A beam dump’s purpose is to safely absorb a beam of charged particles. Like a beam stop, a beam dump can be used to block the beam of charged particles. However, a beam dump is much more robust than a beam stop, and is intended to block the full power of the électron beam for an extended period of time. They are often used to block the beam as the accelerator is powering up.

[0090] Beam dumps are also designed to accommodate the heat generated by such beams, and are usually made from materials such as copper, aluminum, carbon, béryllium, tungsten, or mercury. Beam dumps can be cooled, for example, using a cooling fluid that can be in thermal contact with the beam dump.

BIOMASS MATERIALS [0091] Lignocellulosic materials include, but are not limited to, wood, particle board, forestry wastes (e.g., sawdust, aspen wood, wood chips), grasses, (e.g., switchgrass, miscanthus, cord grass, reed canary grass), grain residues, (e.g., rice hulls, oat hulls, wheat chaff, barley hulls), agricultural waste (e.g., silage, canola straw, wheat straw, barley straw, oat straw, rice straw, jute, hemp, flax, bamboo, sisal, abaca, corn cobs, corn stover, soybean stover, corn fiber, alfalfa, hay, coconut hair), sugar processing residues (e.g., bagasse, beet pulp, agave bagasse), algae, seaweed, manure, sewage, and mixtures of any of these.

[0092] In some cases, the lignocellulosic material includes comcobs. Ground or hammermilled comcobs can be spread in a layer of relatively uniform thickness for irradiation, and after irradiation are easy to disperse in the medium for further processing. To facilitate harvest and collection, in some cases the entire corn plant is used, including the corn stalk, corn kernels, and in some cases even the root System of the plant.

[0093] Advantageously, no additional nutrients (other than a nitrogen source, e.g., urea or ammonia) are required during fermentation of comcobs or cellulosic or lignocellulosic materials containing signifîcant amounts of comcobs.

[0094] Comcobs, before and after comminution, are also easier to convey and disperse, and hâve a lesser tendency to form explosive mixtures in air than other cellulosic or lignocellulosic materials such as hay and grasses.

[0095] Cellulosic materials include, for example, paper, paper products, paper waste, paper pulp, pigmented papers, loaded papers, coated papers, filled papers, magazines, printed marier (e.g., books, catalogs, manuals, labels, calendars, greeting cards, g brochures, prospectuses, newsprint), printer paper, polycoated paper, card stock, cardboard, paperboard, materials having a high α-cellulose content such as cotton, and mixtures of any of these. For example, paper products as described in U.S. App. No. 13/396,365 (“Magazine Feedstocks” by Medoff et al., filed February 14, 2012), the full disclosure of which is incorporated herein by reference.

[0096] Cellulosic materials can also include lignocellulosic materials which hâve been partially or fully de-lignified.

[0097] In some instances other biomass materials can be utilized, for example, starchy materials. Starchy materials include starch itself, e.g., corn starch, wheat starch, potato starch or rice starch, a dérivative of starch, or a material that includes starch, such 2Q as an edible food product or a crop. For example, the starchy material can be arracacha, buckwheat, banana, barley, cassava, kudzu, ocra, sago, sorghum, regular household potatoes, sweet potato, taro, yams, or one or more beans, such as favas, lentils or peas.

Blends of any two or more starchy materials are also starchy materials. Mixtures of starchy, cellulosic and or lignocellulosic materials can also be used. For example, a biomass can be an entire plant, a part of a plant or different parts of a plant, e.g., a wheat plant, cotton plant, a com plant, rice plant or a tree. The starchy materials can be treated by any of the methods described herein.

[0098] Microbial materials that can be used as feedstock can include, but are not limited to, any naturally occurring or genetically modified microorganism or organism that contains or is capable of providing a source of carbohydrates (e.g., cellulose), for example, protists, e.g., animal protists (e.g., protozoa such as flagellâtes, amoeboids, ciliates, and sporozoa) and plant protists (e.g., algae such alveolates, chlorarachniophytes, cryptomonads, euglenids, glaucophytes, haptophytes, red algae, stramenopiles, and viridaeplantae). Other examples include seaweed, plankton (e.g., macroplankton, mesoplankton, microplankton, nanoplankton, picoplankton, and

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

[0099] In other embodiments, the biomass materials, such as cellulosic, starchy and lignocellulosic feedstock materials, can be obtained from transgenic microorganisms and plants that hâve been modified with respect to a wild type variety. Such modifications may be, for example, through the itérative steps of sélection and breeding to obtain desired traits in a plant. Furthermore, the plants can hâve had genetic material removed, modified, silenced and/or added with respect to the wild type variety. For example, genetically modified plants can be produced by recombinant DNA methods, where genetic modifications include introducing or modifying spécifie genes from parental varieties, or, for example, by using transgenic breeding wherein a spécifie gene or genes are introduced to a plant from a different species of plant and/or bacteria. Another way to create genetic variation is through mutation breeding wherein new alleles are artificially created from endogenous genes. The artificial genes can be created by a variety of ways including treating the plant or seeds with, for example, chemical mutagens (e.g., using alkylating agents, epoxides, alkaloids, peroxides, formaldéhyde), irradiation (e.g., X-rays, gamma rays, neutrons, beta particles, alpha particles, protons, deuterons, UV radiation) and température shocking or other external stressing and subséquent sélection techniques. Other methods of providing modified genes is through error prone PCR and DNA shuffling followed by insertion of the desired modified DNA into the desired plant or seed. Methods of introducing the desired genetic variation in the seed or plant include, for example, the use of a bacterial carrier, biolistics, calcium phosphate précipitation, electroporation, gene splicing, gene silencing, lipofection, microinjection and viral carriers. Additional genetically modified materials hâve been described in U.S. Application Serial No 13/396,369 filed February 14, 2012 the full disclosure of which is incorporated herein by reference.

[00100] Any of the methods described herein can be practiced with mixtures of any biomass materials described herein.

OTHER MATERIALS [00101] Other materials (e.g., natural or synthetic materials), for example, polymers, can be treated and/or made utilizing the methods, equipment and Systems described herein. For example, polyethylene (e.g., linear low density ethylene and high density polyethylene), polystyrènes, sulfonated polystyrènes, poly (vinyl chloride), polyesters (e.g., nylons, DACRON™, KODEL™), polyalkylene esters, poly vinyl esters, polyamides (e.g., KEVLAR™), polyethylene terephthalate, cellulose acetate, acetal, poly acrylonitrile, polycarbonates(LEXAN™), aciylics [e.g., poly (methyl méthacrylate), poly(methyl méthacrylate), polyacrylonitrile], Poly urethanes, polypropylene, poly butadiene, polyisobutylene, polyacrylonitrile, polychloroprene (e.g. neoprene), poly(cis1,4-isoprene) [e.g., natural rubber], poly(trans-l,4-isoprene) [e.g., gutta percha], phénol formaldéhyde, melamine formaldéhyde, epoxides, polyesters, poly amines, polycarboxylic acids, polylactic acids, polyvinyl alcohols, polyanhydrides, poly fluoro carbons (e.g., TEFLON™), silicons (e.g., silicone rubber), polysilanes, poly ethers (e.g., polyethylene oxide, polypropylene oxide), waxes, oils and mixtures of these. Also included are plastics, rubbers, elastomers, fibers, waxes, gels, oils, adhesives, thermoplastics, thermosets, biodégradable polymers, resins made with these polymers, other polymers, other materials and combinations thereof. The polymers can be made by any useful method including cationic polymerization, anionic polymerization, radical polymerization, metathesis polymerization, ring opening polymerization, graft

2Q polymerization, addition polymerization. In some cases the treatments disclosed herein can be used, for example, for radically initiated graft polymerization and cross linking. Composites of polymers, for example, with glass, metals, biomass (e.g., fibers, particles), ceramics can also be treated and/or made.

[00102] Other materials that can be treated by using the methods, Systems and equipment disclosed herein are ceramic materials, minerais, metals, inorganic compounds. For example, silicon and germanium crystals, silicon nitrides, métal oxides, semiconductors, insulators, cements and or conductors.

[00103] In addition, manufactured multipart or shaped materials (e.g., molded, extruded, welded, riveted, layered or combined in any way) can be treated, for example, 2Q cables, pipes, boards, enclosures, integrated semiconductor chips, circuit boards, wires, tires, Windows, laminated materials, gears, belts, machines, combinations of these. For example, treating a material by the methods described herein can modify the surfaces, for

example, making them susceptible to further functionalization, combinations (e.g., welding) and/or treatment can cross link the materials.

BIOMASS MATERIAL PREPARATION - MECHANICAL TREATMENTS [00104] The biomass can be in a dry form, for example, with less than about 35% moisture content (e.g., less than about 20 %, less than about 15 %, less than about 10 % less than about 5 %, less than about 4%, less than about 3 %, less than about 2 % or even less than about 1 %). The biomass can also be delivered in a wet state, for example as a wet solid, a slurry or a suspension with at least about 10 wt.% solids (e.g., at least about 20 wt.%, at least about 30 wt. %, at least about 40 wt.%, at least about 50 wt.%, at least about 60 wt.%, at least about 70 wt.%).

[00105] The processes disclosed herein can utilize low bulk density materials, for example cellulosic or lignocellulosic feedstocks that hâve been physically pretreated to hâve a bulk density of less than about 0.75 g/cm³, e.g., less than about 0.7, 0.65,0.60, 0.50, 0.35, 0.25, 0.20, 0.15, 0.10, 0.05 or less, e.g., less than about 0.025 g/cm³. Bulk density is determined using ASTM D1895B. Briefly, the method involves filling a measuring cylinder of known volume with a sample and obtaining a weight of the sample. The bulk density is calculated by dividing the weight of the sample in grams by the known volume of the cylinder in cubic centimeters. If desired, low bulk density materials can be densified, for example, by methods described in U.S. Pat. No. 7,971,809 to Medoff, the full disclosure of which is hereby incoiporated by reference.

[00106] In some cases, the pre-treatment processing includes screening of the biomass material. Screening can be through a mesh or perforated plate with a desired opening size, for example, less than about 6.35 mm (1/4 inch, 0.25 inch), (e.g., less than about 3.18 mm (1/8 inch, 0.125 inch), less than about 1.59 mm (1/16 inch, 0.0625 inch), is less than about 0.79 mm (1/32 inch, 0.03125 inch), e.g., less than about 0.51 mm (1/50 inch, 0.02000 inch), less than about 0.40 mm (1/64 inch, 0.015625 inch), less than about 0.23 mm (0.009 inch), less than about 0.20 mm (1/128 inch, 0.0078125 inch), less than about 0.18 mm (0.007 inch), less than about 0.13 mm (0.005 inch), or even less than about 0.10 mm (1/256 inch, 0.00390625 inch)). In one configuration the desired biomass falls through the perforations or screen and thus biomass larger than the perforations or screen are not irradiated. These larger materials can be re-processed, for example, by comminuting, or they can simply be removed from processing. In another configuration material that is larger than the perforations is irradiated and the smaller material is

removed by the screening process or recycled. In this kind of a configuration, the conveyor itself (for example, a part of the conveyor) can be perforated or made with a mesh. For example, in one particular embodiment the biomass material may be wet and the perforations or mesh allow water to drain away from the biomass before irradiation. [00107] Screening of material can also be by a manual method, for example, by an operator or mechanoid (e.g., a robot equipped with a color, reflectivity or other sensor) that removes unwanted material. Screening can also be by magnetic screening wherein a magnet is disposed near the conveyed material and the magnetic material is removed magnetically.

[00108] Optional pre-treatment processing can include heating the material. For example, a portion of a conveyor conveying the biomass or other material can be sent through a heated zone. The heated zone can be created, for example, by IR radiation, microwaves, combustion (e.g., gas, coal, oil, biomass), résistive heating and/or inductive coils. The heat can be applied from at least one side or more than one side, can be continuons or periodic and can be for only a portion of the material or ail the material. For example, a portion of the conveying trough can be heated by use of a heating jacket. Heating can be, for example, for the purpose of drying the material. In the case of drying the material, this can also be facilitated, with or without heating, by the movement of a gas (e.g., air, oxygen, nitrogen, He, CO2, Argon) over and/or through the biomass as it is being conveyed.

[00109] Optionally, pre-treatment processing can include cooling the material. Cooling material is described in U.S. Pat. No. 7,900,857 to Medoff, the disclosure of which in incorporated herein by reference. For example, cooling can be by supplying a cooling fluid, for example, water (e.g., with glycerol), or nitrogen (e.g., liquid nitrogen) to the bottom of the conveying trough. Altematively, a cooling gas, for example, chilled nitrogen can be blown over the biomass materials or under the conveying system. [00110] Another optional pre-treatment processing method can include adding a material to the biomass or other feedstocks. The additional material can be added by, for example, by showering, sprinkling and or pouring the material onto the biomass as it is conveyed. Materials that can be added include, for example, metals, ceramics and/or ions as described in U.S. Pat. App. Pub. 2010/0105119 Al (filed October 26, 2009) and U.S. Pat. App. Pub. 2010/0159569 Al (filed December 16, 2009), the entire disclosures of which are incorporated herein by reference. Optional materials that can be added include acids and bases. Other materials that can be added are oxidants (e.g., peroxides, chlorates), polymers, polymerizable monomers (e.g., containing unsaturated bonds),

water, catalysts, enzymes and/or organisme. Materials can be added, for example, in pure form, as a solution in a solvent (e.g., water or an organic solvent) and/or as a solution. In some cases the solvent is volatile and can be made to evaporate e.g., by heating and/or blowing gas as previously described. The added material may form a uniform coating on the biomass or be a homogeneous mixture of different components (e.g., biomass and additional material). The added material can modulate the subséquent irradiation step by increasing the efficiency of the irradiation, damping the irradiation or changing the effect of the irradiation (e.g., from électron beams to X-rays or heat). The method may hâve no impact on the irradiation but may be useful for further downstream processing. The added material may help in conveying the material, for example, by lowering dust levels.

[00111] Biomass can be delivered to a conveyor (e.g., vibratory conveyors that can be used in the vaults herein described) by a belt conveyor, a pneumatic conveyor, a screw conveyor, a hopper, a pipe, manually or by a combination of these. The biomass can, for example, be dropped, poured and/or placed onto the conveyor by any of these methods. In some embodiments the material is delivered to the conveyor using an enclosed material distribution system to help maintain a low oxygen atmosphère and/or control dust and fines. Lofted or air suspended biomass fines and dust are undesirable because these can form an explosion hazard or damage the window foils of an électron gun (if such a device is used for treating the material).

[00112] The material can be leveled to form a uniform thickness between about 0.0312 and 5 inches (e.g., between about 0.0625 and 2.000 inches, between about 0.125 and 1 inches, between about 0.125 and 0.5 inches, between about 0.3 and 0.9 inches, between about 0.2 and 0.5 inches between about 0.25 and 1.0 inches, between about 0.25 and 0.5 inches, 0.100 +/- 0.025 inches, 0.150 +/- 0.025 inches, 0.200 +/- 0.025 inches, 0.250 +/- 0.025 inches, 0.300 +/- 0.025 inches, 0.350 +/- 0.025 inches, 0.400 +/- 0.025 inches, 0.450 +/- 0.025 inches, 0.500 +/- 0.025 inches, 0.550 +/- 0.025 inches, 0.600 +/0.025 inches, 0.700 +/- 0.025 inches, 0.750 +/- 0.025 inches, 0.800 +/- 0.025 inches, 0.850 +/- 0.025 inches, 0.900 +/- 0.025 inches, 0.900 +/- 0.025 inches.

[00113] Generally, it is preferred to convey the material as quickly as possible through the électron beam to maximize throughput. For example, the material can be conveyed at rates of at least 1 ft/min, e.g., at least 2 ft/min, at least 3 ft/min, at least 4 ft/min, at least 5 ft/min, at least 10 ft/min, at least 15 ft/min, 20, 25, 30, 35, 40,45, 50 ft/min. The rate of conveying is related to the beam current, for example, for a ^lA inch thick biomass and 100 mA, the conveyor can move at about 20 ft/min to provide a useful iiTadiation

dosage, at 50 mA the conveyor can move at about 10 ft/min to provide approximately the same irradiation dosage.

[00114] After the biomass material has been conveyed through the radiation zone, optional post-treatment processing can be done. The optional post-treatment processing 5 can, for example, be a process described with respect to the pre-irradiation processing.

For example, the biomass can be screened, heated, cooled, and/or combined with additives. Uniquely to post-irradiation, quenching of the radicals can occur, for example, by the addition of fluids or gases (e.g., oxygen, nitrous oxide, ammonia and/or liquids), using pressure, heat, and/or the addition of radical scavengers. For example, the biomass 10 can be conveyed out of the enclosed conveyor and exposed to a gas (e.g., oxygen) where it is quenched, forming carboxylated groups. In one embodiment, the biomass is exposed during irradiation to the reactive gas or fluid. Quenching of biomass that has been irradiated is described in U.S. Pat. No. 8,083,906 to Medoff, the entire disclosure of which is incorporate herein by reference.

₁₅ [00115] If desired, one or more mechanical treatments can be used in addition to irradiation to further reduce the recalcitrance of the carbohydrate-containing material. These processes can be applied before, during and/or after irradiation.

[00116] In some cases, the mechanical treatment may include an initial préparation of the feedstock as received, e.g., size réduction of materials, such as by comminution, e.g., 2Q cutting, grinding, shearing, pulverizing or chopping. For example, in some cases, loose feedstock (e.g., recycled paper, starchy materials, or switchgrass) is prepared by shearing or shredding. Mechanical treatment may reduce the bulk density of the carbohydratecontaining material, increase the surface area of the carbohydrate-containing material and/or decrease one or more dimensions of the carbohydrate-containing material.

[00117] Altematively, or in addition, the feedstock material can be treated with another treatment, for example, chemical treatments, such as an acid (HCl, H2SO4, H3PO4), a base (e.g., KOH and NaOH), a chemical oxidant (e.g., peroxides, chlorates, ozone), irradiation, steam explosion, pyrolysis, sonication, oxidation, chemical treatment. The treatments can be in any order and in any sequence and combinations. For example, 3q the feedstock material can first be physically treated by one or more treatment methods,

e.g., chemical treatment including and in combination with acid hydrolysis (e.g., utilizing HCl, H2SO4, H3PO4), radiation, sonication, oxidation, pyrolysis or steam explosion, and then mechanically treated. This sequence can be advantageous since materials treated by one or more of the other treatments, e.g., irradiation or pyrolysis, tend to be more brittle ₃₅ and, therefore, it may be easier to further change the structure of the material by

mechanical treatment. As another example, a feedstock material can be conveyed through ionizing radiation using a conveyor as described herein and then mechanically treated. Chemical treatment can remove some or ail of the lignin (for example, chemical pulping) and can partially or completely hydrolyze the material. The methods also can 5 be used with pre-hydrolyzed material. The methods also can be used with material that has not been pre-hydrolyzed. The methods can be used with mixtures of hydrolyzed and non-hydrolyzed materials, for example, with about 50% or more non-hydrolyzed material, with about 60% or more non- hydrolyzed material, with about 70% or more non-hydrolyzed material, with about 80% or more non-hydrolyzed material or even with 10 90% or more non-hydrolyzed material.

[00118] In addition to size réduction, which can be performed initially and/or later in processing, mechanical treatment can also be advantageous for “opening up,” “stressing,” breaking or shattering the carbohydrate-containing materials, making the cellulose of the materials more susceptible to chain scission and/or disruption of crystalline structure during the physical treatment.

[00119] Methods of mechanically treating the carbohydrate-containing material include, for example, milling or grinding. Milling may be performed using, for example, a hammer mill, bail mill, colloid mill, conical or cône mill, disk mill, edge mill, Wiley mill, grist mill or other mill. Grinding may be performed using, for example, a

2o cutting/impact type grinder. Some exemplary grinders include stone grinders, pin grinders, coffee grinders, and burr grinders. Grinding or milling may be provided, for example, by a reciprocating pin or other element, as is the case in a pin mill. Other mechanical treatment methods include mechanical ripping or tearing, other methods that apply pressure to the fibers, and air attrition milling. Suitable mechanical treatments further include any other technique that continues the disruption of the internai structure of the material that was initiated by the previous processing steps.

[00120] Mechanical feed préparation Systems can be configured to produce streams with spécifie characteristics such as, for example, spécifie maximum sizes, spécifie length-to-width, or spécifie surface areas ratios. Physical préparation can increase the 30 rate of reactions, improve the movement of material on a conveyor, improve the irradiation profile of the material, improve the radiation uniformity of the material, or reduce the processing time required by opening up the materials and making them more accessible to processes and/or reagents, such as reagents in a solution.

[00121] The bulk density of feedstocks can be controlled (e.g., increased). In some situations, it can be désirable to préparé a low bulk density material, e.g., by densifying

the material (e.g., densification can make it easier and less costly to transport to another site) and then reverting the material to a lower bulk density state (e.g., after transport). The material can be densified, for example, from less than about 0.2 g/cc to more than about 0.9 g/cc (e.g., less than about 0.3 to more than about 0.5 g/cc, less than about 0.3 to more than about 0.9 g/cc, less than about 0.5 to more than about 0.9 g/cc, less than about 0.3 to more than about 0.8 g/cc, less than about 0.2 to more than about 0.5 g/cc). For example, the material can be densified by the methods and equipment disclosed in U.S. Pat. No. 7,932,065 to Medoff and International Publication No. WO 2008/073186 (which was filed October 26, 2007, was published in English, and which designated the United States), the full disclosures of which are incorporated herein by reference. Densified materials can be processed by any of the methods described herein, or any material processed by any of the methods described herein can be subsequently densified.

[00122] In some embodiments, the material to be processed is in the form of a fibrous material that includes fibers provided by shearing a fiber source. For example, the shearing can be performed with a rotary knife cutter.

[00123] For example, a fiber source, e.g., that is récalcitrant or that has had its recalcitrance level reduced, can be sheared, e.g., in a rotary knife cutter, to provide a first fibrous material. The first fibrous material is passed through a first screen, e.g., having an average opening size of 1.59 mm or less (1/16 inch, 0.0625 inch), provide a second fibrous material. If desired, the fiber source can be eut prior to the shearing, e.g., with a shredder. For example, when a paper is used as the fiber source, the paper can be first eut into strips that are, e.g., 1/4- to 1/2-inch wide, using a shredder, e.g., a counterrotating screw shredder, such as those 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 eut the paper into sheets that are, e.g., 10 inches wide by 12 inches long.

[00124] In some embodiments, the shearing of the fiber source and the passing of the resulting first fibrous material through a first screen are performed concurrently. The shearing and the passing can also be performed in a batch-type process.

[00125] For example, a rotary knife cutter can be used to concurrently shear the fiber source and screen the first fibrous material. A rotary knife cutter includes a hopper that can be loaded with a shredded fiber source prepared by shredding a fiber source. [00126] In some implémentations, the feedstock is physically treated prior to saccharification and/or fermentation. Physical treatment processes can include one or

more of any of those described herein, such as mechanical treatment, chemical treatment, irradiation, sonication, oxidation, pyrolysis or steam explosion. Treatment methods can be used in combinations of two, three, four, or even ail of these technologies (in any order). When more than one treatment method is used, the methods can be applied at the 5 same time or at different times. Other processes that change a molecular structure of a biomass feedstock may also be used, alone or in combination with the processes disclosed herein.

[00127] Mechanical treatments that may be used, and the characteristics of the mechanically treated carbohydrate-containing materials, are described in further detail in

U.S. Pat. App. Pub. 2012/0100577 Al, filed October 18,2011, the full disclosure of which is hereby incorporated herein by reference.

SONICATION, PYROLYSIS, OXIDATION, STEAM EXPLOSION [00128] If desired, one or more sonication, pyrolysis, oxidative, or steam explosion processes can be used, instead of or in addition to, irradiation to reduce or further reduce the recalcitrance of the carbohydrate-containing material. For example, these processes can be applied before, during and/or after irradiation. These processes are described in detail in U.S. Pat. No. 7,932,065 to Medoff, the full disclosure of which is incoiporated herein by reference.

INTERMEDIATES AND PRODUCTS [00129] Using the processes described herein, the biomass material can be converted to one or more products, such as energy, fuels, foods and materials. For example, intermediates and products such as organic acids, salts of organic acids, anhydrides, esters of organic acids and fuels, e.g., fuels for internai combustion engines or feedstocks for fuel cells. Systems and processes are described herein that can use as feedstock

2g cellulosic and/or lignocellulosic materials that are readily available, but often can be difficult to process, e.g., municipal waste streams and waste paper streams, such as streams that include newspaper, Kraft paper, corrugated paper or mixtures of these. [00130] Spécifie examples of products include, but are not limited to, hydrogen, sugars (e.g., glucose, xylose, arabinose, mannose, galactose, fructose, disaccharides,

3Q oligosaccharides and polysaccharides), alcohols (e.g., monohydric alcohols or dihydric alcohols, such as éthanol, n-propanol, isobutanol, sec-butanol, tert-butanol or n-butanol),

hydrated or hydrous alcohols (e.g., containing greater than 10%, 20%, 30% or even greater than 40% water), biodiesel, organic acids, hydrocarbons (e.g., methane, ethane, propane, isobutene, pentane, n-hexane, biodiesel, bio-gasoline and mixtures thereof), coproducts (e.g., proteins, such as cellulolytic proteins (enzymes) or single cell proteins), and mixtures of any of these in any combination or relative concentration, and optionally, in combination with any additives (e.g., fuel additives). Other examples include carboxylic acids, salts of a carboxylic acid, a mixture of carboxylic acids and salts of carboxylic acids and esters of carboxylic acids (e.g., methyl, ethyl and n-propyl esters), ketones (e.g., acetone), aldéhydes (e.g., acetaldehyde), alpha and beta unsaturated acids (e.g., acrylic acid) and olefins (e.g., ethylene). Other alcohols and alcohol dérivatives include propanol, propylene glycol, 1,4-butanediol, 1,3-propanediol, sugar alcohols (e.g., erythritol, glycol, glycerol, sorbitol threitol, arabitol, ribitol, mannitol, dulcitol, fucitol, iditol, isomalt, maltitol, lactitol, xylitol and other polyols), and methyl or ethyl esters of any of these alcohols. Other products include methyl acrylate,

5 methylmethacrylate, D-lactic acid, L-lactic acid, pyruvic acid, poly lactic acid, citric acid, formic acid, acetic acid, propionic acid, butyric acid, succinic acid, valeric acid, caproic acid, 3-hydroxypropionic acid, palmitic acid, stearic acid, oxalic acid, malonic acid, glutaric acid, oleic acid, linoleic acid, glycolic acid, gamma-hydroxybutyric acid, and mixtures thereof, salts of any of these acids, mixtures of any of the acids and their respective salts.

[00131] Any combination of the above products with each other, and/or of the above products with other products, which other products may be made by the processes described herein or otherwise, may be packaged together and sold as products. The products may be combined, e.g., mixed, blended or co-dissolved, or may simply be packaged or sold together.

[00132] Any of the products or combinations of products described herein may be sanitized or sterilized prior to selling the products, e.g., after purification or isolation or even after packaging, to neutralize one or more potentially undesirable contaminants that could be présent in the product(s). Such sanitation can be done with électron bombardment, for example, be at a dosage of less than about 20 Mrad, e.g., from about vu

0.1 to 15 Mrad, from about 0.5 to 7 Mrad, or from about 1 to 3 Mrad.

[00133] The processes described herein can produce various by-product streams useful for generating steam and electricity to be used in other parts of the plant (cogeneration) or sold on the open market. For example, steam generated from buming by35 product streams can be used in a distillation process. As another example, electricity

generated from buming by-product streams can be used to power électron beam generators used in pretreatment.

[00134] The by-products used to generate steam and electricity are derived from a number of sources throughout the process. For example, anaérobie digestion of wastewater can produce a biogas high in methane and a small amount of waste biomass (sludge). As another example, post-saccharification and/or post-distillate solids (e.g., unconverted lignin, cellulose, and hemicellulose remaining from the pretreatment and primary processes) can be used, e.g., bumed, as a fuel.

[00135] Other intermediates and products, including food and pharmaceutical products, are described in U.S. Pat. App. Pub. 2010/0124583 Al, published May 20, 2010, to Medoff, the full disclosure of which is hereby incorporated by reference herein.

LIGNIN DERIVED PRODUCTS [00136] The spent biomass (e.g., spent lignocellulosic material) from lignocellulosic processing by the methods described are expected to hâve a high lignin content and in addition to being useful for producing energy through combustion in a Co-Generation plant, may hâve uses as other valuable products. For example, the lignin can be used as captured as a plastic, or it can be synthetically upgraded to other plastics. In some instances, it can also be converted to lignosulfonates, which can be utilized as binders, dispersants, emulsifiers or séquestrants.

[00137] When used as a binder, the lignin or a lignosulfonate can, e.g., be utilized in coal briquettes, in ceramics, for binding carbon black, for binding fertilizers and herbicides, as a dust suppressant, in the making of plywood and particle board, for binding animal feeds, as a binder for fiberglass, as a binder in linoléum paste and as a soil stabilizer.

[00138] When used as a dispersant, the lignin or lignosulfonates can be used, for example in, concrète mixes, clay and ceramics, dyes and pigments, leather tanning and in gypsum board.

[00139] When used as an emulsifier, the lignin or lignosulfonates can be used, e.g., in asphalt, pigments and dyes, pesticides and wax émulsions.

[00140] As a séquestrant, the lignin or lignosulfonates can be used, e.g., in micronutrient Systems, cleaning compounds and water treatment Systems, e.g., for boiler and cooling Systems.

[00141] For energy production lignin generally has a higher energy content than holocellulose (cellulose and hemicellulose) since it contains more carbon than homocellulose. For example, dry lignin can hâve an energy content of between about 11,000 and 12,500 BTU per pound, compared to 7,000 an 8,000 BTU per pound of holocellulose. As such, lignin can be densified and converted into briquettes and pellets for buming. For example, the lignin can be converted into pellets by any method described herein. For a slower buming pellet or briquette, the lignin can be crosslinked, such as applying a radiation dose of between about 0.5 Mrad and 5 Mrad. Crosslinking can make a slower buming form factor. The form factor, such as a pellet or briquette, can be converted to a “synthetic coal” or charcoal by pyrolyzing in the absence of air,

e.g., at between 400 and 950 °C. Prior to pyrolyzing, it can be désirable to crosslink the lignin to maintain structural integrity.

SACCHARIFICATION [00142] In order to convert the feedstock to a form that can be readily processed, the glucan- or xylan-containing cellulose in the feedstock can be hydrolyzed to low molecular weight carbohydrates, such as sugars, by a saccharifying agent, e.g., an enzyme or acid, a process referred to as saccharification. The low molecular weight carbohydrates can then be used, for example, in an existing manufacturing plant, such as a single cell protein plant, an enzyme manufacturing plant, or a fuel plant, e.g., an éthanol manufacturing facility.

[00143] The feedstock can be hydrolyzed using an enzyme, e.g., by combining the materials and the enzyme in a solvent, e.g., in an aqueous solution.

[00144] Alternatively, the enzymes can be supplied by organisme that break down biomass, such as the cellulose and/or the lignin portions of the biomass, contain or manufacture various cellulolytic enzymes (cellulases), ligninases or various small molécule biomass-degrading métabolites. These enzymes may be a complex of enzymes that act synergistically to dégradé crystalline cellulose or the lignin portions of biomass. Examples of cellulolytic enzymes include: endoglucanases, cellobiohydrolases, and cellobiases (beta-glucosidases).

[00145] During saccharification, a cellulosic substrate can be initially hydrolyzed by endoglucanases at random locations producing oligomeric intermediates. These intermediates are then substrates for exo-splitting glucanases such as cellobiohydrolase to produce cellobiose from the ends of the cellulose polymer. Cellobiose is a water-

soluble 1,4-linked dimer of glucose. Finally, cellobiase cleaves cellobiose to yield glucose. The efficiency (e.g., time to hydrolyze and/or completeness of hydrolysis) of this process dépends on the recalcitrance of the cellulosic material.

[00146] Therefore, the treated biomass materials can be saccharifïed, generally by combining the material and a cellulase enzyme in a fluid medium, e.g., an aqueous solution. In some cases, the material is boiled, steeped, or cooked in hot water prior to saccharification, as described in U.S. Pat. App. Pub. 2012/0100577 Al by Medoff and Masterman, published on April 26, 2012, the entire contents of which are incorporated herein.

q [00147] The saccharification process can be partially or completely performed in a tank (e.g., a tank having a volume of at least 4000, 40,000, or 500,000 L) in a manufacturing plant, and/or can be partially or completely performed in transit, e.g., in a rail car, tanker truck, or in a supertanker or the hold of a ship. The time required for complété saccharification will dépend on the process conditions and the carbohydrateI g containing material and enzyme used. If saccharification is performed in a manufacturing plant under controlled conditions, the cellulose may be substantially entirely converted to sugar, e.g., glucose in about 12-96 hours. If saccharification is performed partially or completely in transit, saccharification may take longer. [00148] It is generally preferred that the tank contents be mixed during ,θ saccharification, e.g., using jet mixing as described in International App. No.

PCT/US2010/035331, filed May 18, 2010, which was published in English as WO 2010/135380 and designated the United States, the full disclosure of which is incorporated by reference herein.

[00149] The addition of surfactants can enhance the rate of saccharification.

Examples of surfactants include non-ionic surfactants, such as a Tween® 20 or Tween® polyethylene glycol surfactants, ionic surfactants, or amphoteric surfactants. [00150] It is generally preferred that the concentration of the sugar solution resulting from saccharification be relatively high, e.g., greater than 40%, or greater than 50, 60, 70, 80, 90 or even greater than 95% by weight. Water may be removed, e.g., by évaporation, to increase the concentration of the sugar solution. This reduces the volume to be shipped, and also inhibits microbial growth in the solution.

[00151] Altematively, sugar solutions of lower concentrations may be used, in which case it may be désirable to add an antimicrobial additive, e.g., a broad spectrum antibiotic, in a low concentration, e.g., 50 to 150 ppm. Other suitable antibiotics include amphotericin B, ampicillin, chloramphenicol, ciprofloxacin, gentamicin, hygromycin B,

kanamycin, neomycin, penicillin, puromycin, streptomycin. Antibiotics will inhibit growth of microorganisms during transport and storage, and can be used at appropriate concentrations, e.g., between 15 and 1000 ppm by weight, e.g., between 25 and 500 ppm, or between 50 and 150 ppm. If desired, an antibiotic can be included even if the sugar concentration is relatively high. Alternatively, other additives with anti-microbial preservative properties may be used. Preferably the antimicrobial additive(s) are foodgrade.

[00152] A relatively high concentration solution can be obtained by limiting the amount of water added to the carbohydrate-containing material with the enzyme. The concentration can be controlled, e.g., by controlling how much saccharification takes place. For example, concentration can be increased by adding more carbohydratecontaining material to the solution. In order to keep the sugar that is being produced in solution, a surfactant can be added, e.g., one of those discussed above. Solubility can also be increased by increasing the température of the solution. For example, the solution can be maintained at a température of 40-50°C, 60-80°C, or even higher.

SACCHARIFYING AGENTS [00153] Suitable cellulolytic enzymes include cellulases from species in the généra Bacillus, Coprinus, Myceliophthora, Cephalosporium, Scytalidium, Pénicillium, Aspergillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, Chrysosporium and Trichoderma, especially those produced by a strain selected from the species Aspergillus (see, e.g., EP Pub. No. 0 458 162), Humicola insolens (reclassified as Scytalidium thermophilum, see, e.g., U.S. Pat. No. 4,435,307), Coprinus cinereus, Fusarium oxysporum, Myceliophthora thermophila, Meripilus giganteus, Thielavia terrestris, Acremonium sp. (including, but not limited to, A. persicinum, A. acremonium, A. brachypenium, A. dichromosporum, A. obclavatum, A. pinkertoniae, A. roseogriseum, A. incoloratum, and A. furatum). Preferred strains include Humicola insolens DSM 1800, Fusarium oxysporum DSM 2672, Myceliophthora thermophila CBS 117.65, Cephalosporium sp. RYM-202, Acremonium sp. CBS 478.94, Acremonium sp. CBS 265.95, Acremonium persicinum CBS 169.65, Acremonium acremonium 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, Άηά Acremonium furatum CBS 299.70H. Cellulolytic

enzymes may also be obtained from Chrysosporium, preferably a strain of Chrysosporium lucknowense. Additional strains that can be used include, but are not limited to, Trichoderma (particularly T. viride, T. reesei, and T. koningiï), alkalophilic Bacillus (see, for example, U.S. Pat. No. 3,844,890 and EP Pub. No. 0 458 162), and Streptomyces (see, e.g., EP Pub. No. 0 458 162).

[00154] In addition to or in combination to enzymes, acids, bases and other chemicals (e.g., oxidants) can be utilized to saccharify lignocellulosic and cellulosic materials. These can be used in any combination or sequence (e.g., before, after and/or during addition of an enzyme). For example, strong minerai acids can be utilized (e.g. HCl, H2SO4, H3PO4) and strong bases (e.g., NaOH, KOH).

SUGARS [00155] In the processes described herein, for example, after saccharification, sugars (e.g., glucose and xylose) can be isolated. For example, sugars can be isolated by précipitation, crystallization, chromatography (e.g., simulated moving bed chromatography, high pressure chromatography), centrifugation, extraction, any other isolation method known in the art, and combinations thereof.

HYDROGENATION AND OTHER CHEMICAL TRANSFORMATIONS [00156] The processes described herein can include hydrogénation. For example, glucose and xylose can be hydrogenated to sorbitol and xylitol, respectively. Hydrogénation can be accomplished by use of a catalyst (e.g., Pt/gamma-AbOs, Ru/C, Raney Nickel, or other catalysts known in the art) in combination with H2 under high pressure (e.g., 10 to 12000 psi). Other types of chemical transformation of the products from the processes described herein can be used, for example, production of organic sugar derived products (e.g., furfural and furfural-derived products). Chemical transformations of sugar derived products are described in USSN 13/934,704 filed July 3, 2013, the entire disclosure of which is incorporated herein by reference.

FERMENTATION [00157] Yeast and Zymomonas bacteria, for example, can be used for fermentation or conversion of sugar(s) to alcohol(s). Other microorganisms are discussed below. The

optimum pH for fermentations is about pH 4 to 7. For example, the optimum pH for yeast is from about pH 4 to 5, while the optimum pH for Zymomonas is from about pH 5 to 6. Typical fermentation times are about 24 to 168 hours (e.g., 24 to 96 hrs) with températures in the range of 20°C to 40°C (e.g., 26°C to 40°C); however thermophilic microorganisms prefer higher températures.

[00158] In some embodiments, e.g., when anaérobie organisme are used, at least a portion of the fermentation is conducted in the absence of oxygen, e.g., under a blanket of an inert gas such as N₂, Ar, He, CO₂ or mixtures thereof. Additionally, the mixture may hâve a constant purge of an inert gas flowing through the tank during part of or ail of the fermentation. In some cases, anaérobie conditions can be achieved or maintained by carbon dioxide production during the fermentation and no additional inert gas is needed.

[00159] In some embodiments, ali or a portion of the fermentation process can be interrupted before the low molecular weight sugar is completely converted to a product (e.g., éthanol). The intermediate fermentation products include sugar and carbohydrates in high concentrations. The sugars and carbohydrates can be isolated via any means known in the art. These intermediate fermentation products can be used in préparation of food for human or animal consumption. Additionally or altematively, the intermediate fermentation products can be ground to a fine particle size in a stainless-steel laboratory mill to produce a flour-like substance. Jet mixing may be used during fermentation, and in some cases saccharification and fermentation are performed in the same tank.

[00160] Nutrients for the microorganisms may be added during saccharification and/or fermentation, for example, the food-based nutrient packages described in U.S. Pat. App. Pub. 2012/0052536, filed July 15, 2011, the complété disclosure of which is incorporated herein by reference.

[00161] “Fermentation” includes the methods and products that are disclosed in application Nos. PCT/US2012/71093 published June 27, 2013, PCT/US2012/71907 published June 27, 2012, and PCT/US2012/71083 published June 27, 2012 the contents of which are incorporated by reference herein in their entirety.

[00162] Mobile fermenters can be utilized, as described in International App. No. PCT/US2007/074028 (which was filed July 20, 2007, was published in English as WO 2008/011598 and designated the United States) and has a US issued Patent No. 8,318,453, the contents of which are incorporated herein in its entirety. Similarly, the saccharification equipment can be mobile. Further, saccharification and/or fermentation may be performed in part or entirely during transit.

FERMENTATION AGENTS [00163] The microorganism(s) used in fermentation can be naturally-occurring microorganisms and/or engineered microorganisms. For example, the microorganism can be a bacterium (including, but not limited to, e.g., a cellulolytic bacterium), a fungus, (including, but not limited to, e.g., a yeast), a plant, a protist, e.g., a protozoa or a funguslike protest (including, but not limited to, e.g., a. slime mold), or an alga. When the organisme are compatible, mixtures of organisms can be utilized.

[00164] Suitable fermenting microorganisms hâve the ability to convert carbohydrates, such as glucose, fructose, xylose, arabinose, mannose, galactose, oligosaccharides or polysaccharides into fermentation products. Fermenting microorganisms include strains of the genus Saccharomyces spp. (including, but not limited to, S. cerevisiae (baker’s yeast), 5. distaticus, S. uvarum), the genus Kluyveromyces, (including, but not limited to, K. marxianus, K. fragilis), the genus Candida (including, but not limited to, C. pseudotropicalis, and C. brassicae), Pichia stipitis (a relative of Candida shehatae), the genus Clavispora (including, but not limited to, C. lusitaniae and C. opuntiaé), the genus Pachysolen (including, but not limited to, P. tannophilus), the genus Bretannomyces (including, but not limited to, e.g., B. clausenii (Philippidis, G. P., 1996, Cellulose Bioconversion Technology, in Handbookon Bioethanol: Production and Utilization, Wyman, C.E., ed., Taylor & Francis, Washington, DC, 179-212)). Other suitable microorganisms include, for example, Zymomonas mobilis, Clostridium spp. (including, but not limited to, C. thermocellum (Philippidis, 1996, supra), C. saccharobutylacetonicum, C. tyrobutyricum C. saccharobutylicum, C. Puniceum, C. beijernckii, and C. acetobutylicum), Moniliella spp. (including but not limited to M. pollinis, M. tomentosa, M. madida, M. nigrescens, M. oedocephali, M. megachiliensis), Yarrowia lipolytica, Aureobasidium sp., Trichosporonoides sp., Trigonopsis variabilis, Trichosporon sp., Moniliellaacetoabutans sp., Typhula variabilis, Candida magnoliae, Ustilaginomycetes sp., Pseudozyma tsukubaensis, yeast species of généra Zygosaccharomyces, Debaryomyces, Hansenula and Pichia, and fungi of the dematioid genus Torula (e.g., T. corallina).

[00165] Additional microorganisms include the Lactobacillus group. Examples include Lactobacillus casei, Lactobacillus rhamnosus, Lactobacillus delbrueckii, Lactobacillus plantarum, Lactobacillus coryniformis, e.g., Lactobacillus coryniformis

subspecies torquens, Lactobacillus pentosus, Lactobacillus brevis. Other microorganisms include Pediococus penosaceus, Rhizopus oryzae.

[00166] Several organisms, such as bacteria, yeasts and fungi, can be utilized to ferment biomass derived products such as sugars and alcohols to succinic acid and similar products. For example, organisms can be selected from; Actinobacillus succinogenes, Anaerobiospirillum succiniciproducens, Mannheimia succiniciproducens, Ruminococcus flaverfaciens, Ruminococcus albus, Fibrobacter succinogenes, Bacteroides fragilis, Bacteroides ruminicola, Bacteroides amylophilus.Bacteriodes succinogenes, Mannheimia succiniciproducens, Corynebacterium glutamicum, Aspergillus niger, Aspergillus fumigatus, Byssochlamys nivea, Lentinus degener, Paecilomyces varioti, Pénicillium viniferum, Saccharomyces cerevisiae, Enterococcus faecali, Prevotella ruminicolas, Debaryomyces hansenii, Candida catenulata VKM Y-5, C. mycoderma VKM Y-240, C. rugosa VKM Y-67, C. paludigena VKM Y-2443, C. utilis VKM Y-74, C. utilis 766, C. zeylanoides VKM Y-6, C. zeylanoides VKM Y-14, C. zeylanoides VKM Y-2324, C. zeylanoides VKM Y-1543, C. zeylanoides VKM Y-2595, C. valida VKM Y-934, Kluyveromyces wickerhamii VKM Y-589, Pichia anomala VKM Y-118, P. besseyi VKM Y-2084, P. media VKM Y-1381, P. guilliermondii H-P-4, P. guilliermondii 916, P. inositovora VKM Y-2494, Saccharomyces cerevisiae VKM Y-381, Torulopsis candida 127, T. candida 420, Yarrowia lipolytica 12a, Y. lipolytica VKM Y-47, Y. lipolytica 69, Y. lipolytica VKM Y57, Y. lipolytica 212, Y. lipolytica 374/4, Y. lipolytica 585, Y. lipolytica 695, Y. lipolytica 704, and mixtures of these organisms.

[00167] Many such microbial strains are publicly available, either commercially or through depositories such as the ATCC (American Type Culture Collection, Manassas, Virginia, USA), the NRRL (Agricultural Research Service Culture Collection, Peoria, Illinois, USA), or the DSMZ (Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Braunschweig, Germany), to name a few.

[00168] 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 Bums Philip Food Inc., USA), SUPERSTART® (available from Alltech, now Lalemand), GERT STRAND® (available from Gert Strand AB, Sweden) and FERMOL® (available from DSM Specialties).

DISTILLATION [00169] After fermentation, the resulting fluids can be distilled using, for example, a “beer column” to separate éthanol and other alcohols from the majority of water and residual solids. The vapor exiting the beer column can be, e.g., 35% by weight éthanol and can be fed to a rectification column. A mixture of nearly azeotropic (92.5%) éthanol and water from the rectification column can be purified to pure (99.5%) éthanol using vapor-phase molecular sieves. The beer column bottoms can be sent to the first effect of a three-effect evaporator. The rectification column reflux condenser can provide heat for this first effect. After the first effect, solids can be separated using a centrifuge and dried in a rotary dryer. A portion (25%) of the centrifuge effluent can be recycled to fermentation and the rest sent to the second and third evaporator effects. Most of the evaporator condensate can be retumed to the process as fairly clean condensate with a small portion split off to waste water treatment to prevent build-up of low-boiling compounds.

HYDROCARBON-CONTAINING MATERIALS [00170] In other embodiments utilizing the methods and Systems described herein, hydrocarbon-containing materials can be processed. Any process described herein can be used to treat any hydrocarbon-containing material herein described. “Hydrocarboncontaining materials,” as used herein, is meant to include oil sands, oil shale, tar sands, coal dust, coal slurry, bitumen, various types of coal, and other naturally-occurring and synthetic materials that include both hydrocarbon components and solid matter. The solid matter can include wood, rock, sand, clay, stone, silt, drilling slurry, or other solid organic and/or inorganic matter. The term can also include waste products such as drilling waste and by-products, refining waste and by-products, or other waste products containing hydrocarbon components, such as asphalt shingling and covering, asphalt pavement, etc.

[00171] In yet other embodiments utilizing the methods and Systems described herein, wood and wood containing produces can be processed. For example lumber products can be processed, e.g. boards, sheets, laminates, beams, particle boards, composites, rough eut wood, soft wood and hard wood. In addition eut trees, bushes, wood chips, saw dust, roots, bark, stumps, decomposed wood and other wood containing biomass material can be processed.

CONVEYING SYSTEMS [00172] Various conveying Systems can be used to convey the biomass material, for example, as discussed, to a vault, and under an électron beam in a vault. Exemplary conveyors are belt conveyors, pneumatic conveyors, screw conveyors, carts, trains, trains or carts on rails, elevators, front loaders, backhoes, crânes, various scrapers and shovels, trucks, and throwing devices can be used. For example, vibratory conveyors can be used in various processes described herein. Vibratory conveyors are described in PCT/US2013/64289 filed October 10,2013 the full disclosure of which is incorporated by reference herein.

[00173] Vibratory conveyors are particularly useful for spreading the material and producing a uniform layer on the conveyor trough surface. For example the initial feedstock can form a pile of material that can be at least four feet high (e.g., at least about 3 feet, at least about 2 feet, at least about 1 foot, at least about 6 inches, at least about 5 inches, at least about, 4 inches, at least about 3 inches, at least about 2 inches, at least about 1 inch, at least about */2 inch) and spans less than the width of the conveyor (e.g., less than about 10%, less than about 20%, less than about 30%, less than about 40%, less than about 50%, less than about 60%, less than about 70%, less than about 80%, less than about 90%, less than about 95%, less than about 99%). The vibratory conveyor can spread the material to span the entire width of the conveyor trough and hâve a uniform thickness, preferably as discussed above. In some cases, an additional spreading method can be useful. For example, a spreader such as a broadcast spreader, a drop spreader (e.g., a CHRISTY SPREADER™) or combinations thereof can be used to drop (e.g., place, pour, spill and/or sprinkle) the feedstock over a wide area. Optionally, the spreader can deliver the biomass as a wide shower or curtain onto the vibratory conveyor. Additionally, a second conveyor, upstream from the first conveyor (e.g., the first conveyor is used in the irradiation of the feedstock), can drop biomass onto the first conveyor, where the second conveyor can hâve a width transverse to the direction of conveying smaller than the first conveyor. In particular, when the second conveyor is a vibratory conveyor, the feedstock is spread by the action of the second and first conveyor. In some optional embodiments, the second conveyor ends in a bias cross eut discharge (e.g., a bias eut with a ratio of 4:1) so that the material can be dropped as a wide curtain (e.g., wider than the width of the second conveyor) onto the first conveyor. The initial drop area of the biomass by the spreader (e.g., broadcast spreader, drop

spreader, conveyor, or cross eut vibratory conveyor) can span the entire width of the first vibratory conveyor, or it can span part of this width. Once dropped onto the conveyor, the material is spread even more uniformly by the vibrations of the conveyor so that, preferably, the entire width of the conveyor is covered with a uniform layer of biomass. In some embodiments combinations of spreaders can be used. Some methods of spreading a feed stock are described in U.S. Patent No. 7,153,533, filed July 23, 2002 and published December 26, 2006, the entire disclosure of which is incorporated herein by reference.

[00174] Generally, it is preferred to convey the material as quickly as possible through an électron beam to maximize throughput. For example, the material can be conveyed at rates of at least 1 ft/min, e.g., at least 2 ft/min, at least 3 ft/min, at least 4 ft/min, at least 5 ft/min, at least 10 ft/min, at least 15 ft/min, at least 20 ft/min, at least 25 ft/min, at least ft/min, at least 40 ft/min, at least 50 ft/min, at least 60 ft/min, at least 70 ft/min, at least 80 ft/min, at least 90 ft/min. The rate of conveying is related to the beam current and targeted irradiation dose, for example, for a ^lA inch thick biomass spread over a 5.5 foot wide conveyor and 100 mA, the conveyor can move at about 20 ft/min to provide a useful irradiation dosage (e.g. about 10 Mrad for a single pass), at 50 mA the conveyor can move at about 10 ft/min to provide approximately the same irradiation dosage. [00175] The rate at which material can be conveyed dépends on the shape and mass of the material being conveyed and the desired treatment. Flowing materials e.g., particulate materials, are particularly amenable to conveying with vibratory conveyors. Conveying speeds can, for example be, at least 100 lb/hr (e.g., at least 500 lb/hr, at least 1000 lb/hr, at least 2000 lb/hr, at least 3000 lb/hr, at least 4000 lb/hr, at least 5000 lb/hr, at least

10,000 lb/hr, at least 15, 000 lb/hr, or even at least 25,000 lb/hr). Some typical conveying speeds can be between about 1000 and 10,000 lb/hr, (e.g., between about 1000 lb/hr and 8000 lb/hr, between about 2000 and 7000 lb/hr, between about 2000 and 6000 lb/hr, between about 2000 and 50001b/hr, between about 2000 and 4500 lb/hr, between about

1500 and 5000 lb/hr, between about 3000 and 7000 lb/hr, between about 3000 and 6000 lb/hr, between about 4000 and 6000 lb/hr and between about 4000 and 5000 lb/hr). Typical conveying speeds dépend on the density of the material. For example, for a biomass with a density of about 35 lb/ft3, and a conveying speed of about 5000 lb/hr, the material is conveyed at a rate of about 143 ft3/hr, if the material is *4” thick and is in a trough 5.5 ft wide, the material is conveyed at a rate of about 1250 ft/hr (about 21 ft/min). Rates of conveying the material can therefore vary greatly. Preferably, for example, a *4” thick layer of biomass, is conveyed at speeds of between about 5 and 100

ft/min (e.g. between about 5 and 100 ft/min, between about 6 and 100 ft/min, between about 7 and 100 ft/min, between about 8 and 100 ft/min, between about 9 and 100 ft/min, between about 10 and 100 ft/min, between about 11 and 100 ft/min, between about 12 and 100 ft/min, between about 13 and 100 ft/min, between about 14 and 100 ft/min, between about 15 and 100 ft/min, between about 20 and 100 ft/min, between about 30 and 100 ft/min, between about 40 and 100 ft/min, between about 2 and 60 ft/min, between about 3 and 60 ft/min, between about 5 and 60 ft/min, between about 6 and 60 ft/min, between about 7 and 60 ft/min, between about 8 and 60 ft/min, between about 9 and 60 ft/min, between about 10 and 60 ft/min, between about 15 and 60 ft/min, between about 20 and 60 ft/min, between about 30 and 60 ft/min, between about 40 and 60 ft/min, between about 2 and 50 ft/min, between about 3 and 50 ft/min, between about 5 and 50 ft/min, between about 6 and 50 ft/min, between about 7 and 50 ft/min, between about 8 and 50 ft/min, between about 9 and 50 ft/min, between about 10 and 50 ft/min, between about 15 and 50 ft/min, between about 20 and 50 ft/min, between about 30 and 50 ft/min, _{1 5} between about 40 and 50 ft/min). It is préférable that the material be conveyed at a constant rate, for example, to help maintain a constant irradiation of the material as it passes under the électron beam (e.g., shower, field).

[00176] The vibratory conveyors described can include screens used for sieving and sorting materials. Port openings on the side or bottom of the troughs can be used for 2Q sorting, selecting or removing spécifie materials, for example, by size or shape. Some conveyors hâve counterbalances to reduce the dynamic forces on the support structure. Some vibratory conveyors are configured as spiral elevators, are designed to curve around surfaces and/or are designed to drop material from one conveyor to another (e.g., in a step, cascade or as a sériés of steps or a stair). Along with conveying materials conveyors can be used, by themselves or coupled with other equipment or Systems, for screening, separating, sorting, classifying, distributing, sizing, inspection, picking, métal removing, freezing, blending, mixing, orienting, heating, cooking, drying, dewatering, cleaning, washing, leaching, quenching, coating, de-dusting and/or feeding. The conveyors can also include covers (e.g., dust-tight covers), side discharge gates, bottom discharge gates, spécial liners (e.g., anti-stick, stainless steel, rubber, custom steal, and or grooved), divided troughs, quench pools, screens, perforated plates, detectors (e.g., métal detectors), high température designs, food grade designs, heaters, dryers and or coolers. In addition, the trough can be of various shapes, for example, fiat bottomed, vee shaped bottom, flanged at the top, curved bottom, fiat with ridges in any direction, tubular, half

pipe, covered or any combinations of these. In particular, the conveyors can be coupled with an irradiation Systems and/or equipment.

[00177] The conveyors (e.g., vibratory conveyor) can be made of corrosion résistant materials. The conveyors can utilize structural materials that include stainless steel (e.g., 304, 316 stainless steel, HASTELLOY® ALLOYS and INCONEL® Alloys). For example, HASTELLOY® Corrosion-Résistant alloys from Hynes (Kokomo, Indiana, USA) such as HASTELLOY® B-3® ALLOY, HASTELLOY® HYBRID-BC1® ALLOY, HASTELLOY® C-4 ALLOY, HASTELLOY® C-22® ALLOY, HASTELLOY® C-22HS® ALLOY, HASTELLOY® C-276 ALLOY, HASTELLOY®

C-2000® ALLOY, HASTELLOY® G-30® ALLOY, HASTELLOY® G-35® ALLOY,

HASTELLOY® N ALLOY and HASTELLOY® ULTIMET® alloy.

[00178] The vibratory conveyors can include non-stick release coatings, for example, TUFFLON™ (Dupont, Delaware, USA). The vibratory conveyors can also include corrosion résistant coatings. For example, coatings that can be supplied from Métal

5 Coatings Corp (Houston, Texas, USA) and others such as Fluoropolymer, XYLAN®,

Molybdenum Disulfide, Epoxy Phenolic, Phosphate- ferrous métal coating, Polyuréthane- high gloss topcoat for epoxy, inorganic zinc, Poly Tetrafluoro ethylene, PPS/RYTON®, fluorinated ethylene propylene, PVDF/DYKOR®, ECTFE/HALAR® and Ceramic Epoxy Coating. The coatings can improve résistance to process gases (e.g., 2Q ozone), chemical corrosion, pitting corrosion, galling corrosion and oxidation.

[00179] Optionally, in addition to the conveying Systems described herein, one or more other conveying Systems can be enclosed. When using an enclosure, the enclosed conveyor can also be purged with an inert gas so as to maintain an atmosphère at a reduced oxygen level. Keeping oxygen levels low avoids the formation of ozone which 25 in some instances is undesirable due to its reactive and toxic nature. For example, the oxygen can be less than about 20% (e.g., less than about 10%, less than about 1%, less than about 0.1%, less than about 0.01%, or even less than about 0.001% oxygen). Purging can be done with an inert gas including, but not limited to, nitrogen, argon, hélium or carbon dioxide. This can be supplied, for example, from a boil off of a liquid 2Q source (e.g., liquid nitrogen or hélium), generated or separated from air in situ, or supplied from tanks. The inert gas can be recirculated and any residual oxygen can be removed using a catalyst, such as a copper catalyst bed. Altematively, combinations of purging, recirculating and oxygen removal can be done to keep the oxygen levels low. [00180] The enclosed conveyor can also be purged with a reactive gas that can react with the biomass. This can be done before, during or after the irradiation process. The

reactive gas can be, but is not limited to, nitrous oxide, ammonia, oxygen, ozone, hydrocarbons, aromatic compounds, amides, peroxides, azides, halides, oxyhalides, phosphides, phosphines, arsines, sulfides, thiols, boranes and/or hydrides. The reactive . gas can be activated in the enclosure, e.g., by irradiation (e.g., électron beam, UV irradiation, microwave irradiation, heating, IR radiation), so that it reacts with the biomass. The biomass itself can be activated, for example by irradiation. Preferably the biomass is activated by the électron beam, to produce radicals which then react with the activated or unactivated reactive gas, e.g., by radical coupling or quenching.

[00181] Purging gases supplied to an enclosed conveyor can also be cooled, for example below about 25°C, below about 0°C, below about -40°C, below about -80°C, below about -120°C. For example, the gas can be boiled off from a compressed gas such as liquid nitrogen or sublimed from solid carbon dioxide. As an alternative example, the gas can be cooled by a chiller or part of or the entire conveyor can be cooled.

OTHER EMBODIMENTS [00182] Any material, processes or processed materials discussed herein can be used to make products and/or intermediates such as composites, fillers, binders, plastic additives, adsorbents and controlled release agents. The methods can include densification, for example, by applying pressure and heat to the materials. For example composites can be made by combining fibrous materials with a resin or polymer. For example radiation cross-linkable resin, e.g., a thermoplastic resin can be combined with a fibrous material to provide a fibrous material/cross-linkable resin combination. Such materials can be, for example, useful as building materials, protective sheets, containers and other structural materials (e.g., molded and/or extruded products). Absorbents can be, for example, in the form of pellets, chips, fibers and/or sheets. Adsorbents can be used, for example, as pet bedding, packaging material or in pollution control Systems. Controlled release matrices can also be the form of, for example, pellets, chips, fibers and or sheets. The controlled release matrices can, for example, be used to release drugs, biocides, fragrances. For example, composites, absorbents and control release agents and their uses are described in International Serial No. PCT/US2006/010648, filed March 23, 2006, and U.S. Patent No. 8,074,910 filed November 22, 2011, the entire disclosures of which are herein incorporated by reference.

[00183] In some instances the biomass material is treated at a first level to reduce recalcitrance, e.g., utilizing accelerated électrons, to selectively release one or more

sugars (e.g., xylose). The biomass can then be treated to a second level to release one or more other sugars (e.g., glucose). Optionally the biomass can be dried between treatments. The treatments can include applying chemical and biochemical treatments to release the sugars. For example, a biomass material can be treated to a level of less than about 20 Mrad (e.g., less than about 15 Mrad, less than about 10 Mrad, less than about 5 Mrad, less than about 2 Mrad) and then treated with a solution of sulfuric acid, containing less than 10% sulfuric acid (e.g., less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1%, less than about 0.75%, less than about 0.50 %, less than about 0.25%) to release xylose. Xylose, for example that is released into solution, can be separated from solids and optionally the solids washed with a solvent/solution (e.g., with water and/or acidified water). Optionally, the Solids can be dried, for example in air and/or under vacuum optionally with heating (e.g., below about 150 deg C, below about 120 deg C) to a water content below about 25 wt.% (below about 20 wt.%, below about 15 wt.%, below about 10 wt.%, below about 5 wt.%). The solids can then be treated with a level of less than about 30 Mrad (e.g., less than about 25 Mrad, less than about 20 Mrad, less than about 15 Mrad, less than about 10 Mrad, less than about 5 Mrad, less than about 1 Mrad or even not at ail) and then treated with an enzyme (e.g., a cellulase) to release glucose. The glucose (e.g., glucose in solution) can be separated from the remaining solids. The solids can then be further processed, for example utilized to make energy or other products (e.g., lignin derived products).

FLAVORS, FRAGRANCES AND COLORANTS [00184] Any of the products and/or intermediates described herein, for example, produced by the processes, Systems and/or equipment described herein, can be combined with flavors, fragrances, colorants and/or mixtures of these. For example, any one or more of (optionally along with flavors, fragrances and/or colorants) sugars, organic acids, fuels, polyols, such as sugar alcohols, biomass, fibers and composites can be combined with (e.g., formulated, mixed or reacted) or used to make other products. For example, one or more such product can be used to make soaps, détergents, candies, drinks (e.g., cola, wine, beer, liquors such as gin or vodka, sports drinks, coffees, teas), syrups, pharmaceuticals, adhesives, sheets (e.g., woven, none woven, filters, tissues) and/or composites (e.g., boards). For example, one or more such product can be combined with herbs, flowers, petals, spices, vitamins, potpourri, or candies. For

example, the formulated, mixed or reacted combinations can hâve flavors/fragrances of grapefruit, orange, apple, raspberry, banana, lettuce, celery, cinnamon, chocolaté, vanilla, peppermint, mint, onion, garlic, pepper, saffron, ginger, milk, wine, beer, tea, lean beef, fish, clams, olive oil, coconut fat, pork fat, butter fat, beef bouillon, legume, potatoes, marmalade, ham, coffee and cheeses.

[00185] Flavors, fragrances and colorants can be added in any amount, such as between about 0.001 wt.% to about 30 wt%, e.g., between about 0.01 to about 20, between about 0.05 to about 10, or between about 0.1 wt.% to about 5 wt.%. These can be formulated, mixed and or reacted (e.g., with any one of more product or intermediate described herein) by any means and in any order or sequence (e.g., agitated, mixed, emulsified, gelled, infused, heated, sonicated, and/or suspended). Fillers, binders, emulsifier, antioxidants can also be utilized, for example protein gels, starches and silica. [00186] In one embodiment the flavors, fragrances and colorants can be added to the biomass immediately after the biomass is irradiated such that the reactive sites created by the irradiation may react with reactive compatible sites of the flavors, fragrances, and colorants.

[00187] The flavors, fragrances and colorants can be natural and/or synthetic materials. These materials can be one or more of a compound, a composition or mixtures of these (e.g., a formulated or natural composition of several compounds). Optionally the 2θ flavors, fragrances, antioxidants and colorants can be derived biologically, for example, from a fermentation process (e.g., fermentation of saccharified materials as described herein). Altematively, or additionally these flavors, fragrances and colorants can be harvested from a whole organisai (e.g., plant, fungus, animal, bacteria or yeast) or a part of an organism. The organisai can be collected and or extracted to provide color, flavors, fragrances and/or antioxidant by any means including utilizing the methods, Systems and equipment described herein, hot water extraction, supercritical fluid extraction, chemical extraction (e.g., solvent or reactive extraction including acids and bases), mechanical extraction (e.g., pressing, comminuting, filtering), utilizing an enzyme, utilizing a bacteria such as to break down a starting material, and combinations of these methods.

The compounds can be derived by a chemical reaction, for example, the combination of a sugar (e.g., as produced as described herein) with an amino acid (Maillard reaction).

The flavor, fragrance, antioxidant and/or colorant can be an intermediate and or product produced by the methods, equipment or Systems described herein, for example and ester and a lignin derived product.

[00188] Some examples of flavor, fragrances or colorants are polyphenols. Polyphenols are pigments responsible for the red, purple and blue colorants of many fruits, vegetables, cereal grains, and flowers. Polyphenols also can hâve antioxidant properties and often hâve a bitter taste. The antioxidant properties make these important preservatives. On class of polyphenols are the flavonoids, such as Anthocyanidines, flavanonols, flavan-3-ols, s, flavanones and flavanonols. Other phenolic compounds that can be used include phenolic acids and their esters, such as chlorogenic acid and polymeric tannins.

[00189] Among the colorants inorganic compounds, minerais or organic compounds θ can be used, for example titanium dioxide, zinc oxide, aluminum oxide, cadmium yellow (E.g., CdS), cadmium orange (e.g., CdS with some Se), alizarin crimson (e.g., synthetic or non-synthetic rose madder), ultramarine (e.g., synthetic ultramarine, natural ultramarine, synthetic ultramarine violet ), cobalt blue, cobalt yellow, cobalt green, viridian (e.g., hydrated chromium(III)oxide), chalcophylite, conichalcite, comubite, g comwallite and liroconite. Black pigments such as carbon black and self-dispersed blacks may be used.

[00190] Some flavors and fragrances that can be utilized include ACALEA TBHQ, ACET C-6, ALLYL AMYL GLYCOLATE, ALPHA TERPINEOL, AMBRETTOLIDE, AMBRINOL 95, ANDRANE, APHERMATE, APPLELIDE, BACDANOL®,

BERGAMAL, BETA IONONE EPOXEDE, BETA NAPHTHYLISO-BUTYL ETHER, BICYCLONONALACTONE, BORNAFIX®, CANTHOXAL, CASHMERAN®, CASHMERAN® VELVET, CASSIFFIX®, CEDRAFIX, CEDRAMBER®, CEDRYL ACETATE, CELESTOLIDE, CINNAMALVA, CITRAL DIMETHYL ACETATE, CITROLATE™, CITRONELLOL 700, CITRONELLOL 950, CITRONELLOL

COEUR, CITRONELLYL ACETATE, CITRONELLYL ACETATE PURE, CITRONELLYL FORMATE, CLARYCET, CLONAL, CONIFERAN, CONIFERAN PURE, CORTEX ALDEHYDE 50% PEOMOSA, CYCLABUTE, CYCLACET®, CYCLAPROP®, CYCLEMAX™, CYCLOHEXYL ETHYL ACETATE, DAMASCOL, DELTA DAMASCONE, DIHYDRO CYCLACET, DIHYDRO MYRCENOL,

DIHYDRO TERPINEOL, DIHYDRO TERPINYL ACETATE, DIMETHYL CYCLORMOL, DIMETHYL OCTANOL PQ, DIMYRCETOL, DIOLA, DIPENTENE, DULCINYL® RECRYSTALLIZED, ETHYL-3-PHENYL GLYCIDATE, FLEURAMONE, FLEURANIL, FLORAL SUPER, FLORALOZONE, FLORIFFOL, FRAISTONE, FRUCTONE, GALAXOLIDE® 50, GALAXOLIDE® 50 BB,

GALAXOLIDE® 50 IPM, GALAXOLIDE® UNDILUTED, GALBASCONE,

GERALDEHYDE, GERANIOL 5020, GERANIOL 600 TYPE, GERANIOL 950, GERANIOL 980 (PURE), GERANIOL CFT COEUR, GERANIOL COEUR, GERANYL ACETATE COEUR, GERANYL ACETATE, PURE, GERANYL FORMATE, GRISALVA, GUAIYL ACETATE, HELIONAL™, HERBAC,

HERBALIME™, HEXADECANOLIDE, HEXALON, HEXENYL SALICYLATE CIS

3-, HYACINTH BODY, HYACINTH BODY NO. 3, HYDRATROPIC ALDEHYDE.DMA, HYDROXYOL, INDOLAROME, INTRELEVEN ALDEHYDE, INTRELEVEN ALDEHYDE SPECIAL, IONONE ALPHA, IONONE BETA, ISO CYCLO CITRAL, ISO CYCLO GERANIOL, ISO E SUPER®, ISOBUTYL

QUINOLINE, JASMAL, JESSEMAL®, KHARISMAL®, KHARISMAL® SUPER,

KHUSINIL, KOAVONE®, KOHINOOL®, LIFFAROME™, LIMOXAL, LINDENOL™, LYRAL®, LYRAME SUPER, MANDARIN ALD 10% TRI ETH, CITR, MARITIMA, MCK CHINESE, MEIJIFF™, MELAFLEUR, MELOZONE, METHYL ANTHRANILATE, METHYL IONONE ALPHA EXTRA, METHYL

IONONE GAMMA A, METHYL IONONE GAMMA COEUR, METHYL IONONE

GAMMA PURE, METHYL LAVENDER KETONE, MONTAVERDI®, MUGUESIA, MUGUET ALDEHYDE 50, MUSKZ4, MYRAC ALDEHYDE, MYRCENYL ACETATE, NECTARATE™, NEROL 900, NERYL ACETATE, OCIMENE, OCTACETAL, ORANGE FLOWER ETHER, ORIVONE, ORRINIFF 25%,

OXASPIRANE, OZOFLEUR, PAMPLEFLEUR®, PEOMOSA, PHENOXANOL®, PICONIA, PRECYCLEMONE B, PRENYL ACETATE, PRISMANTOL, RESEDA BODY, ROSALVA, ROSAMUSK, SANJINOL, SANTALIFF™, SYVERTAL, TERPINEOL,TERPINOLENE 20, TERPINOLENE 90 PQ, TERPINOLENE RECT., TERPINYL ACETATE, TERPINYL ACETATE JAX, TETRAHYDRO, MUGUOL®,

TETRAHYDRO MYRCENOL, TETRAMERAN, TIMBERSILK™, TOBACAROL,

TRIMOFIX® O TT, TRIPLAL®, TRISAMBER®, VANORIS, VERDOX™, VERDOX™ HC, VERTENEX®, VERTENEX® HC, VERTOFIX® COEUR, VERTOLIFF, VERTOLIFF ISO, VIOLIFF, VIVALDIE, ZENOLIDE, ABS INDIA 75 PCT MIGLYOL, ABS MOROCCO 50 PCT DPG, ABS MOROCCO 50 PCT TEC, ₃₀ ABSOLUTE FRENCH, ABSOLUTE INDIA, ABSOLUTE MD 50 PCT BB,

ABSOLUTE MOROCCO, CONCENTRATE PG, TINCTURE 20 PCT, AMBERGRIS, AMBRETTE ABSOLUTE, AMBRETTE SEED OIL, ARMOISE OIL 70 PCT THUYONE, BASIL ABSOLUTE GRAND VERT, BASIL GRAND VERT ABS MD, BASIL OIL GRAND VERT, BASIL OIL VER VEINA, BASIL OIL VIETNAM, BAY

OIL TERPENELESS, BEESWAX ABS N G, BEESWAX ABSOLUTE, BENZOIN

RESINOID SIAM, BENZOIN RESINOID SIAM 50 PCT DPG, BENZOIN RESINOID SIAM 50 PCT PG, BENZOIN RESINOID SIAM 70.5 PCT TEC, BLACKCURRANT BUD ABS 65 PCT PG, BLACKCURRANT BUD ABS MD 37 PCT TEC, BLACKCURRANT BUD ABS MIGLYOL, BLACKCURRANT BUD ABSOLUTE

BURGUNDY, BOIS DE ROSE OIL, BRAN ABSOLUTE, BRAN RESINOID,

BROOM ABSOLUTE ITALY, CARDAMOM GUATEMALA CO2 EXTRACT, CARDAMOM OIL GUATEMALA, CARDAMOM OIL INDIA, CARROT HEART, CASSIE ABSOLUTE EGYPT, CASSIE ABSOLUTE MD 50 PCT IPM, CASTOREUM ABS 90 PCT TEC, CASTOREUM ABS C 50 PCT MIGLYOL, CASTOREUM q ABSOLUTE, CASTOREUM RESINOID, CASTOREUM RESINOID 50 PCT DPG,

CEDROL CEDRENE, CEDRUS ATLANTICA OIL REDIST, CHAMOMILE OIL ROMAN, CHAMOMILE OIL WILD, CHAMOMILE OIL WILD LOW LIMONENE, CINNAMON BARK OIL CEYLAN, CISTE ABSOLUTE, CISTE ABSOLUTE COLORLESS, CITRONELLA OIL ASIA IRON FREE, CIVET ABS 75 PCT PG,

CIVET ABSOLUTE, CIVET TINCTURE 10 PCT, CLARY SAGE ABS FRENCH

DECOL, CLARY SAGE ABSOLUTE FRENCH, CLARY SAGE C'LESS 50 PCT PG, CLARY SAGE OIL FRENCH, COPAIBA BALSAM, COPAIBA BALSAM OIL, CORIANDER SEED OIL, CYPRESS OIL, CYPRESS OIL ORGANIC, DAVANA OIL, GALBANOL, GALBANUM ABSOLUTE COLORLESS, GALBANUM OIL,

GALBANUM RESINOID, GALBANUM RESINOID 50 PCT DPG, GALBANUM RESINOID HERCOLYN BHT, GALBANUM RESINOID TEC BHT, GENTIANE ABSOLUTE MD 20 PCT BB, GENTIANE CONCRETE, GERANIUM ABS EGYPT MD, GERANIUM ABSOLUTE EGYPT, GERANIUM OIL CHINA, GERANIUM OIL EGYPT, GINGER OIL 624, GINGER OIL RECTIFIED SOLUBLE, GUAIACWOOD ₂₅ HEART, HAY ABS MD 50 PCT BB, HAY ABSOLUTE, HAY ABSOLUTE MD 50

PCT TEC, HEALINGWOOD, HYSSOP OIL ORGANIC, IMMORTELLE ABS YUGO MD 50 PCT TEC, IMMORTELLE ABSOLUTE SPAIN, IMMORTELLE ABSOLUTE YUGO, JASMIN ABS INDIA MD, JASMIN ABSOLUTE EGYPT, JASMIN ABSOLUTE INDIA, ASMIN ABSOLUTE MOROCCO, JASMIN ABSOLUTE ₃₀ SAMBAC, JONQUILLE ABS MD 20 PCT BB, JONQUILLE ABSOLUTE France, JUNIPER BERRY OIL FLG, JUNIPER BERRY OIL RECTIFIED SOLUBLE, LABDANUM RESINOID 50 PCT TEC, LABDANUM RESINOID BB, LABDANUM RESINOID MD, LABDANUM RESINOID MD 50 PCT BB, LAVANDIN ABSOLUTE H, LAVANDIN ABSOLUTE MD, LAVANDIN OIL ABRIAL ORGANIC,

LAVANDIN OIL GROSSO ORGANIC, LAVANDIN OIL SUPER, LAVENDER

ABSOLUTE H, LAVENDER ABSOLUTE MD, LAVENDER OIL COUMARIN FREE, LAVENDER OIL COUMARIN FREE ORGANIC, LAVENDER OIL MAILLETTE ORGANIC, LAVENDER OIL MT, MACE ABSOLUTE BB, MAGNOLIA FLOWER OIL LOW METHYL EUGENOL, MAGNOLIA FLOWER OIL, MAGNOLIA FLOWER OIL MD, MAGNOLIA LEAF ODL, MANDARIN OIL MD, MANDARIN OIL MD BHT, MATE ABSOLUTE BB, MOSS TREE ABSOLUTE MD TEXIFRA 43, MOSS-OAK ABS MD TEC IFRA 43, MOSS-OAK ABSOLUTE IFRA 43, MOSS-TREE ABSOLUTE MD IPM IFRA 43, MYRRH RESINOID BB, MYRRH RESINOID MD, MYRRH RESINOID TEC, MYRTLE OIL IRON FREE, MYRTLE OIL TUNISIA RECTIFIED, NARCISSE ABS MD 20 PCT BB, NARCISSE ABSOLUTE FRENCH, NEROLI OIL TUNISIA, NUTMEG OIL TERPENELESS, OEILLET ABSOLUTE, OLIBANUM RESINOID, OLIBANUM RESINOID BB, OLIBANUM RESINOID DPG, OLIBANUM RESINOID EXTRA 50 PCT DPG, OLIBANUM RESINOID MD, OLIBANUM RESINOID MD 50 PCT DPG, OLIBANUM RESINOID TEC, OPOPONAX RESINOID TEC, ORANGE BIGARADE OIL MD BHT, ORANGE BIGARADE OIL MD SCFC, ORANGE FLOWER ABSOLUTE TUNISIA, ORANGE FLOWER WATER ABSOLUTE TUNISIA, ORANGE LEAF ABSOLUTE, ORANGE LEAF WATER ABSOLUTE TUNISIA, ORRIS ABSOLUTE ITALY, ORRIS CONCRETE 15 PCT IRONE, ORRIS CONCRETE 8 PCT IRONE, ORRIS NATURAL 15 PCT IRONE 4095C, ORRIS NATURAL 8 PCT IRONE 2942C, ORRIS RESINOID, OSMANTHUS ABSOLUTE, OSMANTHUS ABSOLUTE MD 50 PCT BB, PATCHOULI HEART N°3, PATCHOULI OIL INDONESIA, PATCHOULI OIL INDONESIA IRON FREE, PATCHOULI OIL INDONESIA MD, PATCHOULI OIL REDIST, PENNYROYAL HEART, PEPPERMINT ABSOLUTE MD, PETITGRAIN BIGARADE OIL TUNISIA, PETITGRAIN CITRONNIER OIL, PETITGRAIN OIL PARAGUAY TERPENELESS, PETITGRAIN OIL TERPENELESS STAB, PIMENTO BERRY OIL, PIMENTO LEAF OIL, RHODINOL EX GERANIUM CHINA, ROSE ABS BULGARIAN LOW METHYL EUGENOL, ROSE ABS MOROCCO LOW METHYL EUGENOL, ROSE ABS TURKISH LOW METHYL EUGENOL, ROSE ABSOLUTE, ROSE ABSOLUTE BULGARIAN, ROSE ABSOLUTE DAMASCENA, ROSE ABSOLUTE MD, ROSE ABSOLUTE MOROCCO, ROSE ABSOLUTE TURKISH, ROSE OIL BULGARIAN, ROSE OIL DAMASCENA LOW METHYL EUGENOL, ROSE OIL TURKISH, ROSEMARY OIL CAMPHOR ORGANIC, ROSEMARY OIL TUNISIA, SANDALWOOD OIL INDIA, SANDALWOOD OIL INDIA RECTIFIED,

SANTALOL, SCHINUS MOLLE OIL, ST JOHN BREAD TINCTURE 10 PCT, STYRAX RESINOID, STYRAX RESINOID, TAGETE OIL, TEA TREE HEART, TONKA BEAN ABS 50 PCT SOLVENTS, TONKA BEAN ABSOLUTE, TUBEROSE ABSOLUTE INDIA, VETIVER HEART EXTRA, VETIVER OIL HAITI, VETIVER OIL HAITI MD, VETIVER OIL JAVA, VETIVER OIL JAVA MD, VIOLET LEAF ABSOLUTE EGYPT, VIOLET LEAF ABSOLUTE EGYPT DECOL, VIOLET LEAF ABSOLUTE FRENCH, VIOLET LEAF ABSOLUTE MD 50 PCT BB, WORMWOOD OIL TERPENELESS, YLANG EXTRA OIL, YLANGΙΠ OIL and combinations of these.

o [00191] The colorants can be among those listed in the Color Index International by the Society of Dyers and Colourists. Colorants include dyes and pigments and include those commonly used for coloring textiles, paints, inks and inkjet inks. Some colorants that can be utilized include carotenoids, arylide yellows, diarylide yellows, β-naphthols, naphthols, benzimidazolones, disazo condensation pigments, pyrazolones, nickel azo g yellow, phthalocyanines, quinacridones, perylenes and perinones, isoindolinone and isoindoline pigments, triarylcarbonium pigments, diketopyrrolo-pyrrole pigments, thioindigoids. Cartenoids include, for example, alpha-carotene, beta-carotene, gammacarotene, lycopene, lutein and astaxanthin, Annatto extract, Dehydrated beets (beet powder), Canthaxanthin, Caramel, p-Apo-8'-carotenal, Cochineal extract, Carminé,

Sodium copper chlorophyllin, Toasted partially defatted cooked cottonseed flour,

Ferrous gluconate, Ferrous lactate, Grape color extract, Grape skin extract (enocianina), Carrot oil, Paprika, Paprika oleoresin, Mica-based pearlescent pigments, Riboflavin, Saffron, Titanium dioxide, Tomato lycopene extract; tomato lycopene concentrate, Turmeric, Turmeric oleoresin, FD&C Blue No. 1, FD&C Blue No. 2, FD&C Green No.

3, Orange B, Citrus Red No. 2, FD&C Red No. 3, FD&C Red No. 40, FD&C Yellow

No. 5, FD&C Yellow No. 6, Alumina (dried aluminum hydroxide), Calcium carbonate, Potassium sodium copper chlorophyllin (chlorophyllin-copper complex), Dihydroxyacetone, Bismuth oxychloride, Ferrie ammonium ferrocyanide, Ferrie ferrocyanide, Chromium hydroxide green, Chromium oxide greens, Guanine,

Pyrophyllite, Talc, Aluminum powder, Bronze powder, Copper powder, Zinc oxide,

D&C Blue No. 4, D&C Green No. 5, D&C Green No. 6, D&C Green No. 8, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11, FD&C Red No. 4, D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31,

D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, D&C Red No. 39, D&C Violet

No. 2, D&C Yellow No. 7, Ext. D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. 11, D&C Black No. 2, D&C Black No. 3 (3), D&C Brown No. 1, Ext. D&C, Chromium-cobalt-aluminum oxide, Ferrie ammonium citrate, Pyrogallol, Logwood extract, l,4-Bis[(2-hydroxy-ethyl)amino]-9,10-anthracenedione bis(2propenoic)ester copolymers, 1,4-Bis [(2-methylphenyl)amino] -9,10-anthracenedione,

I, 4-Bis[4- (2-methacryloxyethyl) phenylamino] anthraquinone copolymers, Carbazole violet, Chlorophyllin-copper complex, Chromium-cobalt-aluminum oxide,, C.I. Vat Orange 1, 2-[[2,5-Diethoxy- 4-[(4-methylphenyl)thiol] phenyl]azo] -1,3,5-benzenetriol, 16,23-Dihydrodinaphtho [2,3-a:2',3'-i] naphth [2',3':6,7] indolo [2,3-c] carbazole5,10,15,17,22,24-hexone, N,N'-(9,10-Dihydro- 9,10-dioxo- 1,5-anthracenediyl) bisbenzamide, 7,16-Dichloro- 6,15-dihydro- 5,9,14,18-anthrazinetetrone, 16,17Dimethoxydinaphtho (l,2,3-cd:3',2',r-lm) perylene-5,10-dione, Poly(hydroxyethyl méthacrylate) -dye copolymers(3), Reactive Black 5, Reactive Blue 21, Reactive Orange 78, Reactive Yellow 15, Reactive Blue No. 19, Reactive Blue No. 4, C.I. Reactive Red

II, C.I. Reactive Yellow 86, C.I. Reactive Blue 163, C.I. Reactive Red 180, 4-[(2,4dimethylphenyl)azo]- 2,4-dihydro- 5-methyl-2-phenyl- 3H-pyrazol-3-one (solvent Yellow 18), 6-Ethoxy-2- (6-ethoxy-3-oxobenzo[b] thien-2(3H)- ylidene) benzo[b]thiophen- 3(2H)-one, Phthalocyanine green, Vinyl alcohol/methyl methacrylatedye reaction products, C.I. Reactive Red 180, C.I. Reactive Black 5, C.I. Reactive Orange 78, C.I. Reactive Yellow 15, C.I. Reactive Blue 21, Disodium l-amino-4-[[4-[(2bromo-l-oxoallyl)amino]-2-sulphonatophenyl]amino]-9,10-dihydro-9,10dioxoanthracene-2-sulphonate (Reactive Blue 69), D&C Blue No. 9, [Phthalocyaninato(2-)J copper and mixtures of these.

[00192] Other than in the examples herein, or unless otherwise expressly specified, ail of the numerical ranges, amounts, values and percentages, such as those for amounts of materials, elemental contents, times and températures of reaction, ratios of amounts, and others, in the following portion of the spécification and attached claims may be read as if prefaced by the word “about” even though the term “about” may not expressly appear with the value, amount, or range. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following spécification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the présent invention. At the very least, and not as an attempt to limit the application of the doctrine of équivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[00193] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the spécifie examples are reported as precisely as possible. Any numerical value, however, inherently contains error necessarily resulting from the standard déviation found in its underlying respective testing measurements. Furthermore, when numerical ranges are set forth herein, these ranges are inclusive of the recited range end points (e.g., end points may be used). When percentages by weight are used herein, the numerical values reported are relative to the total weight.

[00194] Also, it should be understood that any numerical range recited herein is intended to include ail sub-ranges subsumed therein. For example, a range of “1 to 10” is intended to include ail sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10. The terms “one,” “a,” or “an” as used herein are intended to include “at least one” or “one or more,” unless otherwise indicated.

[00195] Any patent, publication, or other disclosure material, in whole or in part, that is said to be incorporated by reference herein is incorporated herein only to the extent that the incorporated material does not conflict with existing définitions, statements, or other disclosure material set forth in this disclosure. As such, and to the extent necessary, the disclosure as explicitly set forth herein supersedes any conflicting material incorporated herein by reference. Any material, or portion thereof, that is said to be incorporated by reference herein, but which conflicts with existing définitions, statements, or other disclosure material set forth herein will only be incorporated to the extent that no conflict arises between that incorporated material and the existing disclosure material.

[00196] While this invention has been particularly shown and described with référencés to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended daims.

Claims (42)

1. A method of processing a material, the method comprising:

impinging a substantially inert gas on a foil window of an électron beam hom while passing électrons through the window and inert gas while processing a material.

2. The method of claim 1, wherein the foil has a surface communicating with a high vacuum side of an accelerator tube.

3. The method of claims 1 or 2, wherein the foil, along with a secondary foil, defines a space about which the substantially inert gas traverses.

4. The method of claim 3, wherein the pressure inside the space is greater than atmospheric pressure.

5. The method of any one of the previous claims, wherein the inert gas comprises nitrogen.

6. The method of any one of the previous claims, further comprising recycling the inert gas.

7. The method of claim 6, wherein recycling comprises impinging the substantially inert gas on the foil window more than one time before discarding it.

8. The method of any one of the previous claims, further comprising treating the inert gas.

9. The method of claim 8, wherein treating the inert gas comprises filtering the gas.

10. The method of claim 8 or 9, wherein treating the inert gas comprises removing from the inert gas contaminants selected from oxygen, ozone, oils, particulates,

5 water and mixtures thereof.

11. The method of any one of the previous claims, wherein the material is a biomass material.

12. The method of any one of the previous claims, wherein the material includes a lignocellulosic or cellulosic material.

10

13. A System for processing biomass, the System comprising:

a flow path for providing a substantially inert gas through a space, wherein the space is defined by a first foil in communication with the vacuum side of a scanning hom of an électron beam accelerator and a secondary foil disposed facing the first foil.

14. The System of claim 13, wherein the secondary foil is mounted on an

15 enclosure.

15. The System of claims 13 or 14, wherein the flow path includes a first conduit and an inlet for flowing the inert gas into the space and a second conduit and an outlet for flowing the inert gas out of the space, and wherein the first conduit and second conduit are in fluid communication through the space.

16. The System of claim 15, wherein the first conduit and/or inlet and second conduit and/or outlet are sized so that the pressure inside the space is greater than atmospheric pressure.

17. A method for processing a biomass material, the method comprising;

5 producing a hazardous gas while reducing the recalcitrance of a biomass material, and flowing the hazardous gas through a filtering System.

18. The method of claim 17, wherein reducing the recalcitrance of the biomass material occurs in a vault.

19. The method of claim 18, wherein the filtering System is disposed outside of the vault.

20. The method of claim 19, wherein a make-up gas is flowed from the exterior of the vault to the interior of the vault while the hazardous gas is flowed from the interior of the vault to the exterior of the vault and through the filtering System.

15

21. The method of claim 20, wherein the make-up gas comprises an inert gas.

22. The method of any one of claims 19 through 21, further comprising maintaining a négative pressure in the vault by flowing the gas that is in the vault through the filtering System to the exterior of the vault at a faster flow rate than flowing the make-up gas from the exterior of the vault to the interior of the vault.

23. The method of claim 22, wherein the flow rate to the exterior of the vault is at least 2 times faster than the flow rate to the interior of the vault.

24. The method of claim 22, wherein the flow rate to the exterior of the vault is at least 3 times faster than the flow rate to the interior of the vault.

5

25. The method of claim 22, wherein the flow rate to the exterior of the vault is at least 4 times faster than the flow rate to the interior of the vault.

26. The method of claim 22, wherein the flow rate to the exterior of the vault is at least 5 times faster than the flow rate to the interior of the vault.

27. The method of claim 22, wherein the flow rate to the exterior of the vault is

10 between about 1000 and 10,000 CFM and the flow rate to the interior of the vault is between about 10 and 5000 CFM.

28. The method of any one of daims 18 through 27, further comprising conveying the biomass from the interior of the vault to the exterior of the vault, extracting hazardous gases from the biomass, and flowing the hazardous gases through

15 the filter system.

29. The method of any one of daims 17 through 28, wherein the recalcitrance of the biomass material is reduced by exposing the biomass material to ionizing radiation.

30. The method of claim 29, wherein the ionizing radiation is produced by an électron accelerator comprising a scanning horn equipped with a métal foil électron ™ extraction window, and the method further comprises directing a cooling gas against the extraction side of the foil électron extraction window.

31. The method of any one of claims 17 through 30, wherein the filtering system comprises a carbon filter disposed in the flow of the hazardous gas.

5

32. The method of any one of claims 17 through 31, wherein the hazardous gas comprises ozone.

33. The method of any one of claims 17 through 32, wherein the hazardous gas comprises volatile organic compounds.

34. The method of any one of claims 17 through 33, further comprising

1 o conveying the biomass material while reducing the recalcitrance of the biomass material.

35. The method of any one of claims 17 through 34, wherein the hazardous gas comprises a hazardous component and a non-hazardous component and the filtering system is configured to remove the hazardous component.

36. The method of any one of claims 17 through 35, wherein the hazardous gas

15 comprises a hazardous component and a non-hazardous component and the filtering system is configured to destroy the hazardous component.

37. A system for processing a material in a vault, the system comprising;

a vault containing an électron irradiation device configured to irradiate a biomass material, and a process gas treating System comprising a gas path that includes a path from the exterior of the vault to the interior of the vault, through the vault, and to the exterior of the vault.

38. The System of claim 37, further comprising a gas filter in the gas path.

39. The System of claim 37 or 38, wherein the gas path through the vault includes a gas path through a window cooling System, wherein the window cooling System comprises a manifold configured to accept a gas from a conduit and impinging the gas against a first window mounted on the vacuum side of a scan hom of the irradiation device.

40. The System of claim 39, wherein the window cooling System includes a second window facing the first window, wherein the first and second window define a space and the space includes an outlet configured to allow the gas to exit the space.

41. The System of any one of claims 38 through 40, wherein the gas path through the vault includes a path through an intake manifold.

42. The System of any one of claims 38 through 41, wherein the filter is positioned outside of the vault and configured to filter a gas that has flowed through the vault.