OA17372A - Treating biomass. - Google Patents

Abstract

Methods and systems are described for processing cellulosic and lignocellulosic materials and useful intermediates and products, such as energy and fuels. For example, irradiating methods and systems are described to aid in the processing of the cellulosic and lignocellulosic materials. The electron beam accelerator has multiple windows foils and these foils are cooled with cooling gas. In one configuration a secondary foil is integral to the electron beam accelerator and in another configuration the secondary foil is part of the enclosure for the biomass conveying system.

Description

This application daims priority to U.S. Provisional Application Serial No. 61/711,807 filed October 10, 2012, and U.S. Provisional Application Serial No. 61/711,801 filed October 10, 2012. The entire disclosures of these applications are incorporated by référencé herein.

BACKGROUND

As demand for petroleum increases, so too does interest in renewable feedstocks for manufacturing biofuels and biochemicals. The use of lignocellulosic biomass as a feedstock for such manufacturing processes has been studied since the 1970s. Lignocellulosic biomass 10 is attractive because it is abundant, renewable, domestically produced, and does not compete with food industry uses.

Many potential lignocellulosic feedstocks are available today, including agricullural residues, woody biomass, municipal waste, oilseeds/cakes and sea weeds, to name a few. At présent these materials are either used as animal feed, biocompost materials are bumed in a 15 cogénération facility or are landfilled.

Lignocellulosic biomass comprises 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 biological processes. Cellulosic biomass materials (i.e., 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 bioniass is even more récalcitrant to enzyme attack. Furthermore, each type of lignocellulosic bioniass has its own spécifie composition of cellulose, hemicellulose and lignin.

While a number of methods hâve been tried to extract structural carbohydrates from lignocellulosic biomass, they are either are too expensive, produce too low a yield, leave undesirable chemicals in the resulting product, or simply dégradé the sugars.

Monosaccharides from renewable biomass sources could become the basis of chemical and fuels industries by replacing, supplementing or substituting petroleum and other 30 fossil feedstocks. However, techniques need to be developed that will make these monosaccharides available in large quantities and at acceptable purities and prices.

SUMMARY

Described herein are methods for treating a biomass material, where the method includes passing an électron beam through multiple window foils and into the biomass material. The multiple window foils can include a System of cooled window foils.

In another implémentation the invention pertains to methods and Systems for cooling a primary and secondary foil window of a scanning type électron beam accelerator.

In one embodiment, the invention pertains to methods and Systems for cooling a primary and secondary foil window of a scanning type électron beam accelerator and irradiating a material (e.g., a biomass material).

A method is provided for producing a treated biomass material, where the method includes: providing a starting biomass material; and passing an électron beam through multiple window foils into starting biomass material; thereby producing a treated biomass material. The treated biomass material can hâve a lower level of recalcitrance relative to the starting biomass material. The multiple window foils can include a System of gas cooled window foils.

Also provided is a System for cooling multiple single-type window foils of an électron beam accelerator, where the system includes: a first flow path for providing a first cooling gas across a primary single-type window foil and second flow path for providing a second cooling gas across a secondary single-type window foil, where the primary and secondary 20 single-type window foils are positioned with a gap of less than about 9 cm between them.

Altemately, if the energy of électron beam accelerator is high, than larger gaps can be used. Gaps as large as 75 cm can be used.

Also provided is a method for cooling multiple single-type window foils of an électron beam accelerator, where the methods includes: passing a first cooling gas across a 25 primary single-type window foil and passing a second cooling gas across a secondary singletype window foil, where the primary and secondary single-type window foils are positioned facing each other with a gap of less than about 9 cm between them.

The System of gas cooled window foils can include: a primary single-type window foil attached to a scanning hom of an électron beam accelerator; a secondary single-type 30 window foil positioned on an atmospheric side of the scanning hom; a first flow path providing a first cooling gas across the primary single-type window foil; a second flow path providing a second cooling gas across the secondary single-type window foil; and a gap between the primary single-type window foil and the secondary single-type window foil. The System of gas cooled window foils can further include: a cooling chamber having an interior

volume defined by one or more walls, the primary single-type window foil and the secondary single-type window foil, wherein the cooling chamber include: a first inlet, which allows a first cooling gas to enter the interior volume; an optional second inlet, which allows optionally a second cooling gas to enter the interior volume; and at least one outlet, which allows the first and the second cooling gasses to exit the interior volume. The cooling chamber can include four walls and the interior volume can be approximately rectangular prism in shape. The system of gas cooled window foils can further include a treatment enclosure with a cover surface, where the enclosure is positioned on a side of the secondary single-type window foil opposite the électron beam accelerator. The secondary single-type o window foil can be mounted on the cover surface. The cover surface can be perpendicular to the électron beam accelerator. The treatment enclosure can hâve a first opening.

The methods and Systems can also include the steps of: conveying the biomass material through the first opening; positioning the biomass material under the secondary single-type window foil; and irradiating the biomass material; thereby producing a treated 15 biomass material. The treatment enclosure can include a second opening. The method can include the step of conveying the treated biomass material out of the treatment enclosure through the second opening. Positioning the biomass can be instantaneous, that is, the positioning step can include conveying the material on a conveyer belt that is continuously moving.

The method can also include purging the treatment enclosure with an inert gas, or a reactive gas.

The primary single-type window foil can be made from an element selected from the group consisting of: titanium, scandium, vanadium, chromium, nickel, zirconium, niobium, molybdenum, ruthénium, rhodium, palladium, hafnium, tantalum, tungsten, rhénium, platinum, iridium, and alloys or mixtures of any of these.

Alternatively, the secondary single-type window foil can be made from an element selected from the group consisting of: titanium, scandium, vanadium, chromium, nickel, zirconium, niobium, molybdenum, ruthénium, rhodium, palladium, hafnium, tantalum, tungsten, rhénium, platinum, iridium, béryllium, aluminum, silicon, and alloys or mixtures of 30 any of these.

The primary single-type window foil and the secondary single-type window foil can be made of tlie same element, alloy, or mixture, or they can be made of different éléments, alloys, or mixtures. The primary single-type window foil or the secondary single-type window foil or both can be made from a low Z element. The primary single-type window

foil can be made from a high Z element and the secondary single-type window foil can be made from a low Z element.

The primary single-type window foil can be from 10 to 50 microns thick, from 15 to 40 microns thick, from 20 to 30 microns thick, from 5 to 30 microns thick, from 8 to 25 microns thick, or from 10 to 20 microns thick. The single-type window foils can be the same thickness, or different thickness.

The starting biomass material is selected from the group consisting of: cellulosic material, lignocellulosic material, and starchy material. The biomass can be paper, paper products, paper waste, wood, particle board, sawdust, agricultural waste, sewage, silage, grasses, wheat straw, rice hulls, bagasse, cotton, jute, hemp, Ilax, bamboo, sisal, abaca, straw, corn cobs, corn stover, alfalfa, hay, coconut hair, seaweed, algae, and mixtures thereof.

The biomass can be treated with between 10 and 200 Mrad of radiation, between 10 and 75 Mrad of radiation, between 15 and 50 Mrad of radiation, or between 20 and 35 Mrad of radiation.

The électron beam can include électrons having an energy of about 0.5 - 10 MeV, about 0.8 - 5 MeV, about 0.8 - 3 MeV, about 1 - 3 MeV, or about lMeV.

The électron beam can hâve a beam current of at least about 50 mA, at least about 60 mA, at least about 70 mA, at least about 80 mA, at least about 90 mA, at least about 100 mA, at least about 125 mA, at least about 150 mA.

The électron beam can include électrons having an energy of about 1 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil can be less than about 30 centimeters. The électron beam can include électrons having an energy of about 1 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil can be less than 20 centimeters. The électron beam can include électrons having an energy of about 1 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil can be less than 10 centimeters.

Altematively, the électron beam comprises électrons can hâve an energy of about 5 MeV, and the spacing between the primary single-type window foil and the secondary single30 type window foil can be less than 75 centimeters. The électron beam comprises électrons can hâve an energy of about 5 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil can be less than 60 centimeters. The électron beam comprises électrons can hâve an energy of about 5 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil can be less than

centimeters. The électron beam comprises électrons can hâve an energy of about 5 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil can be less than 40 centimeters. The électron beam comprises électrons can hâve an energy of about 5 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil can be less than 30 centimeters. The électron beam comprises électrons can hâve an energy of about 5 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil can be less than 20 centimeters.

The methods and Systems described herein can include a beam stop.

One advantage of the methods and Systems discussed herein is that the processes are more robust and incur less down time from failure of foil Windows. In particular, multiple window Systems greatly reduce the likelihood of primary window failure/implosion, which can destroy expensive accelerator parts. Another advantage is that there can be a réduction in the production of toxic by-products, relative to some conventional processes. These advantages provide safer and more robust processing, e.g., higher and safer throughput in producing useful products. Yet another advantage of some of the methods and Systems described is that cooling of foil Windows can done with a high flow rate of cooling gas without disturbing the material targeted for irradiation. Another advantage of some of the methods and Systems is that the gap between window foils allows for a beam stop to be removable placed between the Windows.

Implémentations of tlie 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 others implémentations a spécifie selected sequence is applied or utilized. Individual features can be applied or utilized more than once in any sequence. In 25 addition, an entire sequence, or a poition of a sequence, of applied or utilized features can be applied or utilized once or repeatedly 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, 30 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.

A method irradiating a biomass material by passing an électron beam through multiple Windows into the biomass material. The recalcitrance of the biomass is reduced by

the irradiating. At least one of the multiple Windows is a metallic foil. The primary singletype window foil is on the high vacuum side of the scanning hom of the électron beam accelerator and a secondary window is positioned on the atmospheric side of the scanning horn. In one aspect, the primary single type window foil and the secondary window are part of the same électron beam structure and the foils are cooled by cooling gas. In one configuration both the primary and secondary window foil has cooling gas. In another aspect, the primary window foil is on the vacuum side of the scanning hom of the électron beam accelerator and there is a treatment enclosure with a cover surface, where the enclosure is positioned on a side of the secondary single-type window foil opposite the électron beam accelerator, and the secondary single-type window foil is mounted on the cover surface, perpendicular to the électron beam accelerator and mechanically intégral to the treatment enclosure.

A method of processing biomass where the biomass is conveyed into a first opening of the treatment enclosure, positioned under the secondary single type window foil and irradiating it, followed by conveying the irradiated biomass out the second opening of the enclosure. The gaseous space of treatment enclosure can be purged with an inert gas, a reactive gas or mixtures of these.

The window foils may be made from an element selected from the group consisting of: titanium, scandium, vanadium, chromium, nickel, zirconium, niobium, molybdenum, ruthénium, rhodium, palladium, hafnium, tantaluni, tungsten, rhénium, platinum, iridium, béryllium, aluminum, silicon, and alloys or mixtures of any of these. The window foils may be made up the same or different éléments, or alloys as listed previously. The window foils can be made of a low Z element and the single-type primary window can be made of a high Z element. The primary single-type window foil is from 10 to 50 microns thick, altemately 15 microns to 40 microns, optionally 20 to 30 microns thick. The secondary single-type window foil is from 5 to 30 microns thick, altemately 8 microns to 25 microns, optionally 10 to 20 microns thick. The window foils may be of different thickness.

The starting biomass material is selected from the group consisting of: cellulosic material, lignocellulosic material, and starchy material and can be selected from the group consisting of paper, paper products, paper waste, wood, particle board, sawdust, agricultural waste, sewage, silage, grasses, wheat straw, rice hulls, bagasse, cotton, jute, hemp, flax, barnboo, sisal, abaca, straw, corn cobs, corn stover, alfalfa, hay, coconut hair, seaweed, algae, and mixtures thereof. The biomass is treated with between 10 and 200 Mrad of radiation, optionally 10 to 75 Mrad, altematively 15 to 50 Mrad and further optionally 20 to

Mrad. The biomass is treated where the électron beam has an energy of between 0.5 to 10 MeV, optionally 0.8 to 5 MeV, altematively 0.8 to 3 MeV and further optionally 1 to 3 MeV. The biomass is treated where the électron beam has a beam current of at least 50 mA, altematively, at least 60 mA, optionally, at least 70, further optionally at least 80 mA, altemately, at least 90 mA, altemately, at least 100 mA, optionally at least 125 mA and further optionally at least 150 mA. The biomass is treated with an électron beam with électrons about lMeV and the spacing between the primary single-type window foil and secondary single-type window foil is less than 30 centimeters, altemately, where the spacing is less than 20 centimeters, and optionally where the spacing is less than 10 centimeters.

Altemately, when the an électron beam with électrons about 5 MeV and the spacing between the primary single-type window foil and secondary single-type window foil is less than 75 centimeters, altemately, where the spacing is less than 60 centimeters, and optionally, where the spacing is less than 50 centimeters, and optionally where the spacing is less than 40 centimeters, and altemately 30 and altemately less than 20 centimeters.

The method of treating where the électron beam accelerator has a beam stop which can be moveable to absorb different levels of électrons. The beam stop and its configuration can absorb 10 %, 20 %, 40 %, 60 % 80 % and 96 % of the incident électron energy.

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

DESCRIPTION OF DRAWINGS

FIG. 1 is a diagram showing exemplary processing of biomass materials to useful products.

FIG. 2 is a diagram showing exemplary processing including irradiation of biomass in an inert atmosphère.

FIG. 3 is an illustration of an enclosed conveyor for irradiating a biomass feedstock.

FIG. 4A is a blow up cross section illustration of the enclosed conveyor and scanning hom with cooled Windows. FIG. 4B shows a different configuration of the blow up cross section including a beam stop. FIG. 4C is a blow up cross section illustration of the enclosed conveyor with the pivoting beam stop blocking the électrons.

FIG. 5 is a cross section view through the depth of a scanning hom.

DETAILED DESCRIPTION

Described herein is a method for irradiating biomass material, which facilitâtes the conversion of the material into useful products and improves the yield of those products from the biomass material. The treatment methods described herein are therefore useful in producing a biomass feedstock for use in other processes.

The methods disclosed herein can effectively lower the recalcitrance level of the biomass material, improving its utility as a feedstock in the production of useful intermediates and products. The claimed methods make the biomass material easier to process by methods such as bioprocessing (e.g., with any microorganism described herein, 10 such as a homoacetogen or a heteroacetogen, and/or any enzyme described herein), thermal processing (e.g., gasification or pyrolysis) or chemical processing (e.g., acid hydrolysis or oxidation). Biomass material intended for use as a feedstock can be treated or processed using one or more of any of the methods described herein, such as mechanical treatment, chemical treatment, radiation, sonication, oxidation, pyrolysis or steam explosion. The various treatment Systems and methods can be used in combinations of two, three, or even four or more of these technologies or others described herein and elsewhere.

Saccharified biomass can then be manufacturcd into various products. For example, FIG. 1, shows aprocess for manufacturing a sugar and other useful products (e.g., alcohol). The process can include, for example, optionally mechanically treating a feedstock (step

110), before and/or after this treatment, treating the feedstock with another physical treatment, for example irradiation by the methods described herein, to further reduce its recalcitrance (step 112), and saccharifying the feedstock, to form a sugar solution (step 114). Optionally, the method may also include transporting, e.g., by pipeline, railcar, truck or barge, the solution (or the feedstock, enzyme and water, if saccharification is performed en route) to a manufacturing plant (step 116). In some cases the saccharified feedstock is further bioprocessed (e.g., fermented) to produce a desired product (step 118) and byproduct (111). The resulting product may in some implémentations be processed further, e.g., by distillation (step 120). If desired, the steps of measuring lignin content (step 122) and setting or adjusting process parameters based on this measurement (step 124) can be performed at various stages of the process, as described in U.S. Pat. App. Pub. 2010/0203495 Al, filed on February 11,2010, the entire disclosure of which is incorporated herein by reference.

FIG. 2 shows an irradiation process. This process can be part of the process described in FIG. 1 or it can be part of a separate process. Initially, biomass can be delivered to a conveyor (150). Optionally, the conveyor can be enclosed. The biomass can be pre17372

irradiation processed while enclosed in the enclosed conveyor or prior to enclosing the material in the enclosed conveyor. Advantageously, the biomass on the conveyor when in an treatment enclosure, is protected from rapid air currents that can cause the biomass (e.g., fines and dust) to be lofted in the air. This can présent an explosion hazard or damage equipment.

The biomass can be conveyed through an irradiation zone (e.g., radiation field) (154). After irradiation, the biomass can be post processed (156). The process can be repeated (e.g., dashed arrow A). Finally the irradiated biomass is removed from the conveyor and either collected for later processing or sent directly to make useful products.

FIG. 3 shows one embodiment, an enclosed conveying System for irradiating a comminuted biomass. The enclosure has an enclosed distribution System (310), an enclosed conveyor (311), material removal System (318) where the irradiated material exits the conveyor and an irradiation vault and a Scan hom (322). The électron window foil (not shown) and enclosure window foil (not shown) hâve window coolers (320) and (326) respectively for blowing air across the surface of the Windows. The enclosed material distribution System (310) distributes the biomass onto the conveyor and brings the biomass from outside of the irradiation vault into the enclosed stainless steel conveyor without generating dust outside of the enclosure (e.g., protecting the biomass from air from the window cooling System). The distribution System can be equipped with a spreading System (not shown) to evenly distribute the biomass on the conveyor to a depth of about 0.25 inches.

The enclosed removal System (318) allows the material to fall off of the conveyor belt without generating dust outside of the enclosure, where the material can be collected (e.g., outside the irradiation vault) or directed elsewhere for further processing. The scan hom window and enclosure window can be brought together, or lined up so that the électron beams pass thought the scan hom window, through a small gap of cooling air and then through the enclosure window. For example, the conveyor can be aligned by moving it on casters and then fixing it in place. For example the casters can be blocked with a permanent break, a block, and or a dépréssion. The conveyor can also be aligned by other methods and equipment, for example rails, wheels, pulleys, shims e.g., in any combination. In this window arrangement the scan hom window and enclosure window do not touch, so that the remaining gap allows for efficient cooling. The scan hom window is part of the électron beam apparatus and the enclosure window is part of the treatment enclosure System.

A cross sectional detailed view of the scan hom and scan hom window of FIG. 3 are shown in FIG. 4A. The scan hom window cooler (426) and enclosure window cooler (420) blow air at high velocity across the Windows as indicted by the small arrows. The électrons à

m the électron beam (430) pass through the vacuum of the scan hom (422) through the scan hom window (428), through the cooling air gap between the scan hom window and enclosure window, through the enclosure window (429) and impinge on and penetrate the biomass material (444) on the conveyor surface (415). The scan hom window is shown as curved towards the vacuum side of the scan hom, for example due to the vacuum. In the embodiment illustrated, the enclosure window is curved towards the conveyed material. The curvature of the Windows can help the cooling air path flow past the window for efficient cooling. The enclosure window is mounted on the cover (412) of the endosed conveyor. The enclosure window is aligned with the cover surface.

FIG. 4B shows a different configuration of the detailed cross section view of the cnclosed conveyor including a beam stop. A beam stop (440) can be pivotally fîxed to the scan hom and is shown in the open position, e.g., allowing the e-beam to impinge on the conveyed material. FIG. 4C shows the cross sectional blowup of the scan hom and scan hom window with a beam stop (440) where the beam stop is in position for blocking the électrons. The cover surface is denoted by 414.

Optionally, the conveying System shown in FIG. 3 can be maintained under an atmosphère of an inert or reactive gas by a gentle purge through an inlet connected to a nitrogen gas source. The inlet can be positioned at different locations, for example, close to the zone where the biomass is irradiated to be more effective in reducing ozone formation if purging is with an inert gas; or further and downstream of the irradiation if a reactive gas is used that is designed to reacted with an irradiated material.

FIG. 5 is a cross sectional view of another embodiment of two foils window extraction system for a scanning électron beam. The primaiy foil window (510) in a scanning hom (520) is shown. The région indicated is a high vacuum area (525). Generally, the primary window is concave towards the high vacuum area (525). The secondary foil window (530) is flatter but is also concave in the same direction. This curvature helps provide structural support to the window and is mechanically stronger than a fiat window. Altematively the Windows can be fiat or curved in any direction. Sidewalls (540) and the primary and secondary Windows can define an interior space (550). Since the primary and secondary Windows are connected by sidewalls in this configuration both Windows are part of the électron beam apparatus. Electrons (560) travel through both Windows to impinge on and penetrate the biomass disposed beneath. A first inlet on one sidewall (512) is ananged to allow a cooling fluid (e.g., a liquid or a gas) to impinge on the primary window foil. The cooling fluid runs along the window and then reverses direction on meeting the far (opposite)

wall and flows back generally through the center of the intenor space as shown and then out through an exhaust port and or outlet (514). A second inlet (516) on the sidewall is airanged to allow cooling fluid to impinge on the secondary window foil in a similar fashion. Optionally more inlets (e.g., 2, 3, 4, 5, 6 or more) can bring cooling fluid to the primary and secondary window surfaces and more than one outlets (e.g., 2, 3, 4, 5, 6 or more) can allow the cooling fluid to exit the interior space. In some embodiments one or more side walls can even be a mesh, screen or grate with many openings through which cooling gas can flow while providing structural support to the Windows. The System can include a conveyor, with a conveying surface (570). A material, for example biomass (444), can be conveyed in the direction indicated as a thin pile (574), e.g., about 0.25 inches. Electrons irradiated the material as it is conveyed under tlie two foil extraction System.

The Windows

The biomass is irradiated as it passes under a window, which is generally a metallic foil (e.g., titanium, titanium alloy, aluminum and/or silicon). The window is imperméable to gases, yet électrons can pass with low résistance. The foil Windows are preferably between about 10 and 100 microns thick (e.g., about 10 microns thick to about 30 microns thick, about 15 - 40 microns, about 20 - 30 microns, about 5- 30 microns, about 8-25 microns, about 10 - 20 microns, about 20 - 25 microns thick, 11, 12, 13,14,15, 16, 17,18, 19, 20,21, 22,23, 24,25,26, 27, 28,29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 microns thick). Thin Windows are préférable to thick Windows since thin Windows dissipate less energy as an électron beam passes through them (e.g., the résistive heating is less since Power is the product of the square of the current and the résistance, P= I²R). Thin Windows are also less mechanically strong and more likely to fail which causes increased expense and more downtime for the equipment. The distance between the front surface of the primary window foil and back surface of the secondary window foil is preferably less than 30 cm, more preferably less than 20 cm, and most preferably less than 10 cm.

The foil window can be cooled by passing air or an inert gas over the window. When using an enclosure, it is generally preferred to mount the window to the enclosure and to cool the window front the side outside of the enclosed conveying System to avoid lofting up any particulates of the material being irradiated.

The System can include more than one window, e.g., a primary window and a secondary window. The two Windows may form the enclosure to contain the purging gases

and/or the cooling gases. The secondary window may serve a function as a “sacrifîcial” window, to protect the primary window. The électron beam apparatus includes a vacuum between the électron source and the primary window, and breakage of the primary window is likely to cause biomass material to be sucked up into the électron beam apparatus, resulting in 5 damage, repair costs, and equipment downtime.

The window can be polymer, ceramic, coated ceramic, composite or coated.

composite. The secondary window can be, for instance, a continuons sheet/roll of polymer or coated polymer, which can be advanced continuously or at intervals to provide a clean or new section to serve as the secondary window.

The primary window and the secondary window can be made from the same material, or different materials. For instance, the primaiy window foil can be made from titanium, scandium, vanadium, chromium, nickel, zirconium, niobium, molybdenum, ruthénium, rhodium, palladium, hafnium, tantalum, tungsten, rhénium, platinum, iridium, or alloys or mixtures of any of these. The secondary single-type window foil can be made from titanium, scandium, vanadium, chromium, nickel, zirconium, niobium, molybdenum, ruthénium, rhodium, palladium, hafnium, tantalum, tungsten, rhénium, platinum, iridium, béryllium, aluminum, silicon, or alloys or mixtures of any of these. The primary and secondary Windows can be of the same material, mixture of materials, or alloy, or different materials, mixtures of material or alloys. One or both of the Windows can be laminates of the same of different materials, mixtures of materials, or alloys.

One of more of the Windows can hâve a support structure across its face. The term “single-type window”, as used herein, means a window with no support structure across its face. The term “double-type window”, as used herein means a window with a support structure across its face, where the support structure effectively divides the surface of the window into two parts. Such a double-type window is shown in U.S. Pat. No. 5,877,582 to Nishimura. Additional support structures can also be used.

The primary window foil and the secondary window foil can both be made from low Z element. Altematively, the primary window foil can be made from a high Z element, and the secondary window foil can be made from a low Z element.

The embodiments described herein do not preclude the inclusion of additional

Windows, which may hâve a protective function, or may be included to modify the radiation exposure.

The Windows can be concave, fiat or convex. It is generally preferred that the window be slightly convex, in a direction away from the direction of the cooling fluid. This k

curvature improves the mechanical strength of the window and mcreases the permitted température levels as well as allowing a better flow path for the cooling fluid. On the side of the scanning hom the curvature tends to be towards the vacuum (e.g., away from the cooling fluid) due to the vacuum (e.g., about 10’⁵ to 10‘¹⁰ torr, about 10’⁶ to 10'⁹ torr, about 10'⁷ to 10' ⁸ torr).

The cooling of the window and/or concave shape of the window become especially important for high beam currents, for example at least about 100 mA électron gun currents (e.g., at least about 110 mA, at least about 120 mA, at least about 130 mA, at least about 140 mA, at least about 150 mA at least about 200 mA, at least about 500 mA, at least about 1000 mA) because résistive heating is approximately related to the square of (he current as discussed above. The Windows can be any shape but typically are approximately rectangular with a high aspect ratio of the width to the length (where the width direction is the same as the width of the conveying system perpendicular to the conveying direction, and the length is the same as the direction of conveying). The distance of the window to the conveyed material can be less than about 10 cm (e.g., less than about 5cm) and more than about 0.1cm (e.g., more than about 1cm, more than about 2 cm, more than about 3 cm, more titan about 4 cm). It is also possible to use multiple Windows (e.g., 3, 4, 5, 6 or more) with different and varied shapes and configured in different ways. For example, a primary or secondary foil ' window can include one, two or more Windows in the same plane or layered and can include one or more support structures. For example, support structures can be a bar or a grid in the same plane and contacting the Windows.

In some embodiments, the window that is mounted on the enclosed conveying system is a secondary foil window of a two foil window extraction system for a scanning électron beam. In other embodiments there is no enclosure for conveying the biomass material, e.g., the biomass is conveyed in air under the irradiation device.

Window Spacing

Although a large spacing between the Windows can be advantageous, for example, for the reasons described above, the large spacing poses some disadvantages. One disadvantage of a large spacing between Windows is that the électron beams will pass through a larger volume of cooling gas which can cause energy losses. For example, a lMeV beam loses about 0.2 MeV/m of energy, a 5 MeV beam loses about 0.23 MeV/rn and a 10 MeV beam loses about 0.26 MeV/m. Therefore with a 1 MeV beam of électrons passing through 1 cm of air, the beam loses only 0.2% of its energy, at 10 cm of air, the beam loses 2% of its energy,

at 20 cm this is 4% of its energy, while at 50 cm the energy loss is 10%. Since the électrons also hâve to travel from the secondary foil window to the biomass through additional air, the gap between the Windows must be carefully controlled. Preferably, energy losses are less that about 20% (e.g., less than 10%, less than 5% or even less than 1%). It is therefore advantageous to minimize the spacing between the Windows to decrease energy losses. Optimal spacing (e.g., average spacing) between the Windows (e.g., between the surface side of the électron window foil and the facing surface of the secondary window foil) for the benefit of cooling as described above and foi' the benefit of reducing energy loss are less than 30 cm (e.g., between about 2 and 20 cm, belween about 3 and 20 cm, between about 4 and

20 cm, between about 5 and 20 cm, between about 6 and 20 cm, between about 7 and 20 cm, between about 8 and 20 cm, between about 3 and 15 cm, between about 4 and 15 cm, between about 5 and 15 cm, between about 6 and 15 cm, between about 7 and 15 cm, between about 8 and 15 cm between about 3 and 10 cm, between about 4 and 10 cm, between about 5 and 10 cm, between about 6 and 10 cm, between about 7 and 10 cm, between about 8 and 10 cm, preferably less than 20 cm, and most preferably less than 10 cm.

Altematively, at higher MeV cquipment a greater gap can be tolerated. The higher gap can be as great as 75 cm. In some embodiments support structures for the Windows can be used across the Windows, although these types of structures are less preferred because of energy losses that can occur to the électron beam as it strikes these kinds of structures.

A large spacing between the Windows can be advantageous because it defines a larger volume between the Windows and allows for rapid flowing of a large volume cooling gasses for very efficient cooling. The inlets and outlets are between 1mm and 120 mm in diameter (e.g., about 2 mm, about 5 mm about 10 mm, about 20 mm, about 50 mm or even about 100 mm). The cooling gas flow can be at between about 500-2500 CFM (e.g., about 600 to 2500

CFM, about 700-2500 CFM, about 800 to 2500 CFM, about 1000 to 2500 CFM, about 600 to 2000 CFM, about 700-2000 CFM, about 800 to 2000 CFM, about 1000 to 2000 CFM, about 600 to 1500 CFM, about 700-1500 CFM, about 800 to 1500 CFM, about 1000 to 1500 CFM). In some embodiments, about 50% of the gas is exchanged per about 60 seconds or less (e.g., in about 50 sec or less, in about 30 sec or less, in about 10 sec or less, in about 1 sec or less).

Cooling and Purging Gases

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 some embodiments 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 Ene 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).

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 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%, 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 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.

The enclosure 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 radicale which then react with the activated or unactivated reactive gas, e.g., by radical coupling or quenching.

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 30 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.

Beam Stops

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. Altematively the beam stop can be used 5 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 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, to 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 15 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. Useful levels of stopping électrons can be 10%, 20%, 40 %, 60 %, 80% and 96%

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, metal-coated polymer, metal-coated composite, multilayered métal materials).

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.

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 30 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.

Radiation Sources

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.

Sources of gamma rays include radioactive nuclei, such as isotopes of cobalt, calcium, technicium, chromium, gallium, indium, iodine, iron, krypton, samarium, sélénium, sodium, thalium, and xénon.

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.

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.

Sources for ultraviolet radiation include deuterium or cadmium lamps.

Sources for infrared radiation include sapphire, zinc, or selenide window ceramic lamps. Sources for microwaves include klystrons, Slevin type RF sources, or atom beam sources that employ hydrogen, oxygen, or nitrogen gases.

Accelerators used to accelerate the particles (e.g., électrons or ions) can be electrostatic DC, e. g. electrodynamic DC, RF linear, magnetic induction linear or continuous wave. For example, various irradiating devices may be used in the methods disclosed herein, încluding 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, DYNAMTTRON® accelerators), cyclotrons, synchrotrons, betatrons, transformer-lype accelerators, microtrons, plasma generators, cascade accelerators, and folded tandem accelerators. For example, cyclotron type accelerators are available from IBA, 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 L3-PSD (USA), Linac Systems (France), Mevex (Canada), and Mitsubishi Heavy Industries (Japan); L-band LINACs, available from

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Iotron Industries (Canada); and ILU-based accelerators, available front 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, 5 18-20 March 2006, Iwata, Y. et al., “Altemating-Phase-Focused IH-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, lhe complété disclosure of which is incorporated herein by 10 reference.

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 an accelerating potential. An électron gun generates électrons, which are then accelerated through a large 15 potential (e.g., greater than about 500 thousand, greater than about lmillion, 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 the x-y plane, where the électrons are initially accelerated in the z direction down the accelerator tube and extracted through a foil 20 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 re25 starting the électron gun.

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, 30 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.

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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.

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 purchascd 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), NHV Corporation (Japan), the Titan

Corporation (San Diego, CA), Vivirad High Voltage Corp (Billeric, MA) and/or Budker Laboratori.es (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 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 current), or EPS1000 (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 EPS-1500 (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) concems. 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.

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 beam is preferred in most embodiments describe herein because of the larger scan width and reduced possibility of o local heating and failure of the Windows.

Subséquent Use of the Feedstocks

Using the methods described herein, a starting biomass material (e.g., plant biomass, animal biomass, paper, and municipal waste biomass) can be used as feedstock to produce 15 useful 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 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 20 newspaper, kraft paper, corrugated paper or mixtures of these.

In order to convert the feedstock to a form that can be readily processed, the glucanor 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, lire low molecular weight carbohydrates can then be used, for 25 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.

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.

Altematively, the enzymes can be supplied by organisms 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 biomassdegrading 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 (β-glucosidases).

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 1,4linked 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.

Biomass Material Préparation — Mechanical Treatments

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.%).

The processes disclosed herein can utilize low bulk density materials, for cxample 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 centinieters. If desired, low bulk density materials can be densified, for example, by methods described in US. Pat. No. 7,971,809 to Medoff, the full disclosure of which is hereby incorporated by reference.

In some cases, the pre-irradiation 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 (¼ 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 i

înch)). 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.

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.

Optional pre- processing can include heating the material. For example a portion of the conveyor 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 continuous 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.

Optionally, pre-irradiation processing can include cooling the material. Cooling material is described in US 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.

Another optional pre-irradiation processing can include adding a material to the biomass. The additional material can be added by, for example, by showering, sprinkling and or pouring the material onto tlie 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

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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 5 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 thebiomass orbe ahomogeneous mixture of differentcomponents (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., front 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.

Biomass can be treated as described herein, e.g. with électron beam radiation, while being conveyed. The biomass can be delivered to the conveyor by using, a belt conveyor, a pneumatic conveyor, a screw conveyor, a hopper, a pipe, manually or by 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 tlie window foils.

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.

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

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

After the biomass material has been conveyed through a treatment area, e.g., a radiation zone, optional post processing can be done. The optional post processing can, for example, be any process described herein. 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, quenching of radicals by the addition of fluids or gases (e.g., o oxygen, nitrous oxide, ammonia, liquids), using pressure, heat, and/or the addition of radical scavengers. For example, the biomass can be conveyed out of an enclosed conveyor and exposed to a gas (e.g., oxygen) where it is quenched, forming carboxylated groups. In one embodiment the biomass can be exposed during irradiation to a 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.

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 processcs can be applied before, during and or after irradiation.

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., 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 carbohydrate-containing material, increase the surface area of the carbohydrate-containing material and/or decrease one or more dimensions of the carbohydrate-containing material.

Altematively, or in addition, the feedstock material can first be physically treated by one or more of the other physical treatment methods, e.g., chemical treatment, radiation, sonication, oxidation, pyrolysis or steam explosion, and then mechanically treated. This sequence can be advantageous since materials treated by one or more of the other treatments, 30 e.g., irradiation or pyrolysis, tend to be more brittle and, therefore, it may be easier to further change the structure of the material by mechanical treatment. For 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 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 nonhydrolyzed material, with about 60% or more non- hydrolyzed material, with about 70% or 5 more non-hydrolyzed material, with about 80% or more non-hydrolyzed material or even with 90% or more non-hydrolyzed material.

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 1 o materials more susceptible to chain scission and/or disruption of crystalline structure during the physical treatment.

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 15 mill. Grinding may be performed using, for example, a 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.

Mechanical feed préparation Systems can be configured to produce streams with spécifie characteristics such as, for example, spécifie maximum sizes, spécifie length-towidth, or spécifie surface areas ratios. Physical préparation can increase the rate of reactions, 25 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.

The bulkdensity of feedstocks can be controlled (e.g., increased). In some situations, 30 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 Üien 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 référencé. 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.

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

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 counter-rotating 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.

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.

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. The shredded fiber source. 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 same time or at different tunes.

i

Other processes that change a molecular structure of a biomass feedstock may also be used, alone or in combination with the processes disclosed herein.

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. 2012/01000577 Al, filed October 18,2011, the full disclosure of which is hereby incorporated herein by reference.

Sonication, Pyrolysis, Oxidation, Steam Explosion

If desired, one or more sonication, pyrolysis, oxidative, or steam explosion processes 10 can be used in addition to irradiation to further reduce the recalcitrance of the carbohydratecontaining material. 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 incorporated herein by reference.

Biomass Processing after Irradiation

After irradiation the biomass may be transferred to a vessel for saccharification. Altcrnately, the biomass can be heatcd after the biomass is irradiated prior to the saccharification step. The biomass can be, for example, by IR radiation, microwaves, combustion (e.g., gas, coal, oil, biomass), résistive heating and/or inductive coils. This heating can be in a liquid, for 20 example, in water or other water-based solvents. The heat can be applied from at least one side or more than one side, can be continuous or periodic and can be for only a portion of the material or ail the material. The biomass may be heated to températures above 90°C in an aqueous liquid that may hâve an acid or a base présent. For example, the aqueous biomass slurry may be heated to 90 to 150°C, altematively, 105 to 145°C, optionally 110 to 140°C or 25 further optionally from 115 to 135°C. The time that the aqueous biomass mixture is held at the peak température is 1 to 12 hours, alternately, 1 to 6 hours, optionally 1 to 4 hours at the peak température. In some instances, the aqueous biomass mixture is acidic, and the pH is between 1 and 5, optionally 1 to 4, or alternately, 2 to 3. In other instances, the aqueous biomass mixture is alkaline and the pH is between 6 and 13, alternately, 8 to 12, or optionally, 8 to 11.

Saccharification

The treated biomass materials can be saccharified, 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. 2012/01000577 Al, filed October 18,2011.

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 carbohydrate-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.

It is generally preferred that the tank contents be mixed during 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.

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

It is generally preferred that the concentration 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.

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. Altematively, other additives with anti-microbial of preservative properties may be used. Preferably the antimicrobial additive(s) are food-grade.

i

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 carbohydrate-containing 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.

Sugars

In tlie 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 15 combinations thereof.

Hydrogénation and Other Chemical Transformations

The processes described herein can include hydrogénation. For example, glucose and xylose can be hydrogenated to sorbitol and xylitol respectively. Hydrogénation can be 20 accomplished by use of a catalyst (e.g., Pt/gamma-AhOi, Ru/C, Raney Nickel, or other catalysts know 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 ±e processes described herein can be used, for example production of organic sugar derived products such (e.g., furfural and furfural-derived products). Chemical transformations of sugar derived products are described 25 in US Prov. App. No. 61/667,481, filed July 3,2012, the disclosure of which is incorporated herein by reference in its entirety.

Fermentation

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.

In some embodiments, e.g., when anaérobie organisais 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 condition, can be achieved or maintained by carbon dioxide production during the fermentation and no additional inert gas is needed.

In some embodiments, ail 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 fermentation products can be ground to a appropriate particle size by comminution.

Jet mixing may be used during fermentation, and in some cases saccharification and fermentation are performed in the same tank.

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.

Fermentation includes the methods and products that are disclosed in U.S. Prov. App. No. 61/579,559, filed December 22,2012, and U.S. Prov. App. No. 61/579,576, filed December 22, 2012, the contents of both of which are incorporated by reference herein in their entirety.

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), the contents of which is 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.

Distillation

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 rotaiy 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 o build-up of low-boiling compounds.

Intermediates and Products

Using the processes described herein, the biomass material can be converted to one or more products, such as energy, fuels, foods and materials. Spécifie examples of products include, but are not limited to, hydrogen, sugars (e.g., glucose, xylose, arabinose, mannose, galactose, fructose, disaccharides, oligosaccharides and polysaccharides), alcohols (e.g., monohydric alcohols or dihydric alcohols, such as éthanol, n-propanol, isobutanol, secbutanol, 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), co-products (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 betaunsaturated 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, methylmethacrylate, 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. Many of the products obtained, such as éthanol or n-butanol, can be utilized as a fuel for powering cars, trucks, tractors, ships or trains, e.g., as an internai combustion fuel or as a fuel cell feedstock. Many of the products obtained can also be utilized to power aircraft, such as planes, e.g., having jet engines or helicopters. In addition, the products described herein can be utilized for electrical power génération, e.g., in a conventional steam generating plant or in a fuel cell plant.

Other intermediates and products, including food and pharmaceutical products, are described in U.S. App. No. 12/417,900 filed April 3, 2009, the full disclosure of which is hereby incorporated by reference herein.

Carbohydrate Containing Materials (Biomass Materials)

As used herein, the term “biomass materials” is used interchangeably with the term “carbohydrate-containing materials”, and includes lignocellulosic, cellulosic, starchy, and microbial materials. Any of the methods described herein can be practiced with mixtures of any biomass materials described herein.

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), sugarprocessing residues (e.g., bagasse, beet pulp, agave bagasse),, algae, seaweed, manure, sewage, and mixtures of any of these.

In some cases, the lignocellulosic material includes comcobs. Ground or hammermilled comcobs can be spread in a layer of relatively unifonn 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, com kernels, and in some cases even the root System of the plant.

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 significant amounts of comcobs.

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.

À

Cellulosic materials include, for example, paper, paper products, paper waste, paper pulp, pigmented papers, loaded papers, coated papers, filled papers, magazines, printed matter (e.g., books, catalogs, manuals, labels, calendars, greeting cards, 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.

Cellulosic materials can also include lignocellulosic materials which hâve been delignified.

Starehy materials include starch itself, e.g., com starch, wheat starch, potato starch or rice starch, a derivative of starch, or a material that includes starch, such as an edible food product or a crop. For example, the starehy material can be airacacha, buckwheat, banana, barley, cassava, kudzu, oca, sago, sorghum, regular household potatoes, sweet potato, taro, yams, or one or more beans, such as favas, lentils or peas. Blends of any two or more starehy materials are also starehy materials. Mixtures of starehy, 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 starehy materials can be treated by any of the methods described herein.

Microbial materials 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) andplant 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 femtoplankton), 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.

In other embodiments, the biomass materials, such as cellulosic, starehy 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 transgenîc 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 front endogenous genes. The artificial genes can be created by a variety of ways including treating tlie plant or seeds with, for example, chemical mulagens (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 extemal 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 examplc, 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 încorporated herein by référencé.

Saccharifying Agents

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 (reclassifîed 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, Acremoniumpersicinum CBS

169.65, Acremonium acremonium AHU 9519, Cephalosporium sp. CBS 535.71, Acremonium brachypenium CBS 866.73, Acremonium dichromosporum CBS 683.73, Acremonium obclavatum CBS 311.74, Acremonium pinkertoniae CBS 157.70, Acremonium roseogriseum CBS 134.56, Acremonium incoloratum CBS 146.62, and Acremonium furatum CBS 299.7011.

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).

Fermentation Agents

The microorganism(s) used in fermentation can be naturally-occurring microorganisms and/or engineered microorganisms. For example, the microorganism can be abacterium (including, but not limited to, e.g., a cellulolytic bacterium), afungus, (including, 15 but not limited to, e.g., a yeast), a plant, a protist, e.g., a protozoa or a fungus-like protest (including, but not limited to, e.g., a slime mold), or an alga. When the organisais are compatible, mixtures of organisais can be utilized.

Suitable fermenting microorganisms hâve the ability to convert carbohydrates, such as glucose, fructose, xylose, arabinose, mannose, galactose, oligosaccharides or polysaccharides 20 into fermentation products. Fermenting microorganisms include strains of the genus

Sacchromyces spp. (including, but not limited to, S. cerevisiae (baker’s yeast), S. 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, 25 but not limited to, C. lusitaniae and C. opuntiae), 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 Handbook on Bioethanol: Production and Utilization, Wyman, C.E., ed., Taylor & Francis, Washington, DC, 179-212)). Other suitable microorganisms include, for example, Zymomonas mobilis, 30 Clostridium spp. (including, but not limited to, C. thermocellum (Philippidis, 1996, supra), C.

saccharobutylacetonicum, C. saccharobutylicum, C. Puniceum, C. beijernckii, and C. acetobutylicum), Moniliella pollinis, 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.

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 Sevice Culture Collection, Peoria, Illinois, USA), or the DSMZ (Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Braunschweig, Germany), to name a few.

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® (Lallemand Biofuels and Distilled Spirits, Canada), EAGLE C6 FUEL™ or C6 FUEL™ (available from Lallemand Biofuels and Distilled Spirits, Canada), GERT STRAND® (available from Gert Strand AB, Sweden) and FERMOL® (available from DSM Specialties).

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.

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. When percentages by weight are used herein, the numerical values reported aie relative to the total weight.

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 încluding) 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.

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 o 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.

While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various 15 changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended daims.

Claims (66)

1. CLAIMS:

   1. A method of producing a treated biomass material, the method comprising: irradiating a biomass material by passing an électron beam through multiple Windows into the biomass material.
2. 2. The method of claim 1, wherein one or more of the Windows is in the form of a metallic foil.
3. 3. The method of claim 1, wherein irradiating the biomass material reduces the recalcitrance of the biomass material.
4. 4. The method of claim 1, wherein the multiple window foils comprise a System of gas cooled window foils wherein a primary single-type window foil communicates with a high vacuum side of a scanning hom of an électron beam accelerator and a secondary single-type window foil is positioned on an atmospheric side of the scanning hom.
5. 5. The method of claim 4, wherein the System of gas cooled window foils define a gap between the primary and secondary window and a first flow path providing cooling to the primary window foil;

   a second flow path providing cooling to the secondary window foil.
6. 6. The method of claim 5, wherein the System of gas cooled window foils further comprises where both the primary window foil and the secondary window foil are part of the scanning hom of the électron beam accelerator, where at least one inlet, which allows a cooling gas to enter the gap defined between the primary and the secondary window and at least one outlet, to extract cooling gases from the gap defined between the primary and secondary window.
7. 7. The method of claim 6, wherein the cooling chamber comprises four walls and the interior volume is approximately rectangular prism in shape.
8. 8. The method of claim 4, wherein the System further comprises a treatment enclosure with a cover surface, where the enclosure is positioned on a side of the secondary single-type window foil opposite the électron beam accelerator.
9. 9. The method of claim 8, wherein the secondary single-type window foil is mounted on the cover surface and is intégral to the treatment enclosure.
10. 10. The method of claim 9, wherein the cover surface is perpendicular to the électron beam accelerator.
11. 11. The method of claim 8, wherein the treatment enclosure has a first opening.
12. 12. The method of claim 11, further comprising:

    conveying the biomass material through the first opening; positioning the biomass material under the secondary single-type window foil; and irradiating the biomass material.
13. 13. The method of claim 11, wherein the treatment enclosure comprises a second opening.
14. 14. The method of claim 12, further comprising:

    conveying the treated biomass material out of the treatment enclosure through the second opening.
15. 15. The method of claims 12 or 14, further comprising purging the treatment enclosure with an inert gas.
16. 16. The method of claims 12 or 14, further comprising purging the treatment enclosure with a reactive gas.
17. 17. The method of claim 4, wherein the primary single-type window foil is made from an element selected from the group consisting of: titanium, scandium, vanadium, chromium, nickel, zirconium, niobium, molybdenum, ruthénium, rhodium, palladium, hafnium, tantalum, tungsten, rhénium, platinum, iridium, and alloys or mixtures of any of these.
18. 18. The method of claim 4, wherein the secondary single-type window foil is made from an element selected from the group consisting of: titanium, scandium, vanadium, chromium, nickel, zirconium, niobium, molybdenum, ruthénium, rhodium, palladium, hafnium, tantalum, tungsten, rhénium, platinum, iridium, béryllium, aluminum, silicon, and alloys or mixtures of any of these.
19. 19. The method of claim 4, wherein the primary single-type window foil and the secondary single-type window foil are made of the same element, alloy, or mixture.
20. 20. The method of claim 4, wherein the primary single-type window foil and the secondary single-type window foil are made of different éléments, alloys, or mixtures.
21. 21. The method of claim 4, wherein the primary single-type window foil or the secondary single-type window foil or both are made from a low Z element.
22. 22. The method of claim 4, wherein the primary single-type window foil is made from a high Z element and the secondary single-type window foil is made from a low Z element.
23. 23. The method of claim 4, wherein the primary single-type window foil is from 10 to 50 microns thick.
24. 24. The method of claim 23, wherein the primary single-type window foil is from 15 to

    40 microns thick.
25. 25. The method of claim 23, wherein the primary single-type window foil is from 20 to

    30 microns thick.
26. 26. The method of claim 23, wherein the secondary single-type window foil is from 5 to 30 microns thick.
27. 27. The method of claim 23, wherein the secondary single-type window foil is from 8 to 25 microns thick.
28. 28. The method of claim 23, wherein the secondary single-type window foil is from 10 to 20 microns thick.
29. 29. The method of claim 23, wherein the primary single-type window foils are the same thickness.
30. 30. The method of claim 23, wherein the single-type window foils are different thicknesses.
31. 31. The method of claim 1, wherein the starting biomass material is selected from the group consisting of: ccllulosic material, lignocellulosic material, and starchy material.
32. 32. The method of claim 31, wherein the biomass is selected from the group consisting of paper, paper products, paper waste, wood, particle board, sawdust, agricultural waste, sewage, silage, grasses, wheat straw, rice hulls, bagasse, cotton, jute, hemp, flax, bamboo, sisal, abaca, straw, corn cobs, corn stover, alfalfa, hay, coconut hair, seaweed, algae, and mixtures thereof.
33. 33. The method of claim 1, wherein the biomass is treated with between 10 and 200 Mrad of radiation.
34. 34. The method of claim 33, wherein the biomass is treated with between 10 and 75 Mrad of radiation.
35. 35. The method of claim 33, wherein the biomass is treated with between 15 and 50 Mrad of radiation.
36. 36. The method of claim 33, wherein the biomass is treated with between 20 and 35 Mrad of radiation.
37. 37. The method of claim 1, wherein the électron beam comprises électrons having an energy of about 0.5 -10 MeV.
38. 38. The method of claim 37, wherein ±e électron beam comprises électrons having an energy of about 0.8 - 5 MeV.
39. 39. The method of claim 37, wherein the électron beam comprises élections having an energy of about 0.8 - 3 MeV.
40. 40. The method of claim 37, wherein the électron beam comprises électrons having an energy of about 1-3 MeV.
41. 41. The method of claim 37, wherein the électron beam comprises électrons having an energy of about lMeV.
42. 42. The method of claim 1, wherein the électron beam has a beam current of at least about 50 mA.
43. 43. The method of claim 42, wherein the électron beam has a beam current of at least about 60 mA.
44. 44. The method of claim 42, wherein the électron beam has a beam current of at least about 70 mA.
45. 45. The method of claim 42, wherein the électron beam has a beam current of at least about 80 mA.
46. 46. The method of claim 42, wherein the électron beam has a beam current of at least about 90 mA.
47. 47. The method of claim 42, wherein the électron beam has a beam current of at least about 100 mA.
48. 48. The method of claim 42, wherein the électron beam has a beam current of at least about 125 mA.
49. 49. The method of claim 42, wherein the électron beam has a beam current of at least about 150 mA.
50. 50. The method of claim 4, wherein the électron beam comprises électrons having an energy of about 1 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil is less than 30 centimeters.
51. 51. The method of claim 50, wherein the électron beam comprises électrons having an energy of about 1 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil is less than 20 centimeters.
52. 52. The method of claim 50, wherein the électron beam comprises électrons having an energy of about 1 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil is less than 10 centimeters.
53. 53. The method of claim 4, wherein the électron beam comprises électrons having an energy of about 5 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil is less than 75 centimeters.
54. 54. The method of claim 53, wherein the électron beam comprises électrons having an energy of about 5 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil is less than 60 centimeters.
55. 55. The method of claim 53, wherein the électron beam comprises électrons having an energy of about 5 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil is less than 50 centimeters.
56. 56. The method of claim 53, wherein the électron beam comprises électrons having an energy of about 5 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil is less than 40 centimeters.
57. 57. The method of claim 53, wherein the électron beam comprises électrons having an energy of about 5 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil is less than 30 centimeters.
58. 58. The method of claim 53, wherein the électron beam comprises électrons having an energy of about 5 MeV, and the spacing between the primary single-type window foil and the secondary single-type window foil is less than 20 centimeters.
59. 59. The method of claim 4, where the method further comprises a beam stop.
60. 60. A System for cooling multiple single-type window foils of an électron beam accelerator comprising:

    a first flow path for providing a first cooling gas across a primary single-type window foil and second flow path for providing a second cooling gas across a secondary single-type window foil, wherein the primary and secondary single-type window foils are positioned with a gap of less than about 9 cm between them.
61. 61. A method for cooling multiple single-type window foils of an électron beam accelerator, the method comprising:

    passing a first cooling gas across a primary single-type window foil and passing a second cooling gas across a secondary single-type window foil, wherein the primary and secondary single-type window foils are positioned facing each other with a gap of less than about 9 cm between them.
62. 62. The method of claim 59, where the beam stop is moveable to absorb different amounts of the électron beam.
63. 63. The method of claim 59, where the beam stop absorbs at least 20 % of the incident électrons.
64. 64. The method of claim 59, where the beam stop absorbs at least 40 % of the incident électrons.

    5
65. 65. The method of claim 59, where the beam stop absorbs at least 60 % of the incident électrons.
66. 66. The method of claim 59, where the beam stop absorbs at least 80 % of the incident électrons.