OA17214A

OA17214A - Processing biomass.

Info

Publication number: OA17214A
Application number: OA1201500106
Authority: OA
Inventors: Marshall Medoff; Thomas Masterman; Robert Paradis
Original assignee: Xyleco, Inc.
Priority date: 2012-10-10
Filing date: 2013-10-10
Publication date: 2016-04-05

Abstract

Methods and systems are described for processing cellulosic and lignocellulosic materials into useful intermediates and products, such as energy and fuels. For example, conveying systems, such as highly efficient vibratory conveyors, are described for the processing of the cellulosic and lignocellulosic materials. Provided herein is an apparatus for producing a treated biomass material, that includes an ionizing radiation source.

Description

Provided herein are methods and apparatus for producing a treated biomass material with a vibratory conveyer. The methods and apparatus provide an advantage because the vibratory conveyor provides an efficient mode of conveying biomass material while it is 30 under an irradiation source.

An exemplaiy embodiment is shown in FIGs. 1A-1E. FIG. IA shows a front side view of a System for irradiation of particulate biomass. A spreader, for example a distributer such as a CIIRISTY SPREADER™ 110 containing a biomass drops a controlled stream of biomass 112 onto the trough of a covered vibratory conveyor 113 through an opening 114 in 35 the cover of the conveyor. This aids in providing a substantiaily uniform thîckness of the

material spread across the conveyer. The covered vibratory conveyor is supported by a support 184 and includes a transverse vibration system inciuding leaf springs. The transverse drive assembly 186 provides horizontal oscillating movement to the trough. The drive motor includes an ccccntric crank 198. The biomass is convcyed in the direction of the shown arrows (downstream to upstream) through a scanning électron beam 116 generated by an électron beam irradiation device with an accelerating tube 118 and a scanning hom 120. The électron beam is extracted from the high vacuum side of the Scan hom through a window foil, passes through an air gap, through a window mounted in the cover 115, and irradiâtes the material 178 being conveyed beneath. The irradiated material is then conveyed away from the irradiation area and drops into a collecting hopper 122. In preferred embodiments at least the irradiation zone (e.g., the région where the irradiation takes place) is in a vault, and optionally the entire vibratory conveyor and hoppers, for example as outlined by the dotted line in FIG. IA 192, can be in a vault The biomass can enter via ingress 188 and egress 190 respectively.

In the embodiment above, as shown schematically as a top view of the conveyor surface by FIG. IB, the area covered by the biomass below the opening of the hopper 124 is a small approximately rectangular area compared to the width of the trough, its size being primarily determined by the size and shape of the spreader opening and the vertical drop from the opening of the hopper to the trough surface. In some embodiments the opening width of the spreader is about the same as the width of the conveyor or it can be smallcr than the width of the conveyor (e.g,, smallcr than the conveyor by at least about 1%, smallcr than the conveyor by at least about 5%, smaller than the conveyor by at least about 10%, smaller than the conveyor by at least about 15%, smaller than the conveyor by at least about 20%, smaller than the conveyor by at least about 25%). As the biomass is conveyed in the direction indicated by the arrows, the biomass is spread out over the entire width of the trough so that at about the dashed line defined by AB and areas downstream of thîs line, the bîomass covers the entire width of the trough. Additionally to this spreading, the biomass forms a layer of substantially uniform thickness on the conveyor as the material moves down the conveyor. At some distance from line AB, the électron beam impinges on and through the biomass layer. The électron beam is raster scanned over an area 126, the radiation area (zone, field, électron shower). A detailed view of the raster scan area is shown as FIG. IC. The path of the raster (e.g., a locus of scanned électron beams) is shown projected on the surface of irradiated material wherein the arrows show the path of the raster scan. In other embodiments, the hopper opening is approximately commensurate in size with the trough so that the area 124 spans the entire width of the trough.

FIG. ID shows a right side eut out view of a system for irradiating biomass. As shown, the biomass particles 178 form a uniform layer 150 as they are conveyed through the électron beam 116 with minimal up and down motion of the particles. The électron beam is extracted out of the high vacuum side of the scan hom 120 through the scan hom window

174 and then through a window 115 mounted to the cover of the conveyor 113. The tumbling and changing orientation of biomass particles, the even spreading of the biomass along the whole width of the trough as previously discussed, and the rester scan of the ebeam ensures a substantially uniform irradiation of the biomass as it moves down the conveyor through the électron beam shower. The movement of the biomass can also belp in 10 cooling (e.g., air cooling) of the biomass.

FIG. 1E shows a cross sectional detailcd view of the scan hom and window mounted in the cover. The scan hom includes hom window cooler 170 and the conveyor indudes enclosure window cooler 172 to blow air at high velocity across the Windows as indicted by the small arrows. The électrons in the électron beam 116 pass through the high vacuum of 15 the scan hom 120 through the scan hom window 174, through the cooling air gap between the scan hom window and enclosure window, through the enclosure window 115 and impinge on and penetrate through the biomass material 178 on the conveyor surface. The scan hom window is curved towards the vacuum side of the scan hom, for example due to the vacuum. The enclosure window is shown curved towards the conveyed material. The 20 curvaturc of the Windows can hclp the cooling air path flow past the window for efficient cooling. The enclosure window is mounted on the covcr 179 of the enclosed conveyor.

Biomass can be manufactured into various products by the methods described berein, for exampie, by référencé to FIG. 2, showing a process for manufacturing an alcohol can include, for example, optionally mechanically treating a feedstock 210. Such treatment can 25 make the feedstock easier to convey, for example on with vibratoiy conveyor and/or pneumatic conveyor. Before and/or after this treatment, the feedstock can be treated with another physical treatment, for example irradiation while conveying on a vibratory conveyor as described herein, to reduce or further reduce its recalcitrance 212, and saccharifying the feedstock, to form a sugar solution 214. Optionally, the method may also include transporting, e.g., by pipeline, railcar. Iruck or barge, the solution (or the feedstock, enzyme and water, if saccharification is performed en route) to a manufacturing plant 216. In some cases the saccbarified feedstock ls further bîoprocessed (e.g., fermented) to produce a desired product 218 and byproduct 211. The resulting product may in some implémentations be processed further, e.g., hy distillation 220. If desired, the steps of measuring lignin content 222 and setting or adjusting process parameters based on this

measurement 224 can be performed at various stages of the process, as described in U.S. Patent Application Serial Number 12/704,519, filed on February 11,2010, the entire disclosure of which is incorporated herein by référencé.

Vibratoiy convcyors work by the principlc of applying an oscillating force or vibration to a material to be conveyed, and particularly to the trough of a conveyor onto which the material to be conveyed is placed. The oscillating force can be supplied by a driver assembly that is mechanically coupled to the trough, as well as elastic éléments also mechanically coupled to the trough e.g., springs, leaf spring and/or coil spring. The vibrations can be, for example, supplied by the driver assembly that can include one or more of the drive motors coupled to one or more eccentric cranks or eccentric fly wheels. In some embodiments the vibratory conveyors are naturel frequency vibrating conveyors based on obtaining a common frequency between the elastic éléments and the drive assembly, for example as disclosed in U.S. Patent No 4,813,532 filed Jan 15,1988 and published March 21,1989, the entire disclosure of which is incorporated herein by référencé.

The driver assembly, elastic éléments and coupling to the trough can provide motion to the surface of the trough, on which the feedstock to be conveyed is placed. The motions include ail combined directions and magnitudes of x, y and z vectors, where x is the direction of conveying biomass, y is the direction transverse to conveying and z is the direction peipendicular to and orthogonal to the x and y vectors. The dïsplacement distance of the trough can be varied for optimal performance. For example, displaccmcnt in the x direction is between about 1/16 inch and 12 inch ( c.g., between about 1/16 inch and 8 inch, between about 1/16 inch and 4 inch, between about 1/16 inch and 1 inch, between about 1/8 inch and 12 inch, between about 1/8 inch and 6 inch, between about 1/8 inch and 2 inch, between about 1/8 inch and 1 inch, between about 1/4 inch and 6 inch, between about 1/4 inch and 4 inch, between about 1/4 inch and 2 inch, between about 1/4 inch and 1 inch, between about 1/2 inch and 6 inch, between about 1/2 inch and 4 inch, between about 1/2 inch and 2 inch, between about 1/2 inch and 1 inch, between about 1 inch and 6 inch, between about 1 inch and 4 inch). Displacement in the z direction can be, for example, be between about 0 and 3 inch (e.g., between about 0.004 inch and 3 inch, between about 0.008 inch and 3 inch, between about 0.016 inch and 3 inch, between about 0.025 inch and 3 inch, between about 0.05 inch and 3 inch, between about 0.1 inch and 3 inch, between about 1/4 inch and 3 inch, between about 1/2 inch and 3 inch, between about 1 inch and 3 inch, between about 0.008 Inch and 1 inch, between about 0.016 inch and 1 inch, between about 0.025 inch and 1 inch, between about 0.05 inch and 1 inch, between about 0.1 inch and 1 inch, between about 1/4 inch and 1 inch, between about 1/2 inch and 1 inch, between about

1/16 inch and 3/4 inch, between about l/8 inch and 3/4 inch, between about l/4 inch and 3/4 inch, between about l/2 inch and 3/4 inch). For example, the displacement in the x direction can be greater than the displacement in the z direction by a ratio less than about 3000:1 (e.g., less than about 1000 to 1, less than about 500 to 1, less than about 100 to 1, less than about

50 to 1, less than about 10 to 1, less than about 5:1, less than about 2:1). The displacement in the y direction can be less than 1 inch (e.g., less than about 0.5 inch, less than about 0.1 inch, less than about 0.05 inch, less than about 0.005 inch, or even about 0). The frequency of the oscillations can be between 1 and 60 kHz. For example, the frequency can be between about I and 100 Hz (e.g., between about 10 and 100 Hz, between about 20 and 100 Hz, between about 40 and 100 Hz, between about 60 and 100 Hz, between about 10 and 80 Hz, between about 20 and 80 Hz, between about 40 and 80 Hz, between about 60 and 801 Iz, between about 20 and 60 Hz). The frequency of oscillation can be higher. for example, the frequency of oscillation can be between about 100 Hz and 20 kHz (e.g., between about 100 Hz and 15 kHz, between about 100 Hz and 10 kHz, between about 100 Hz and 5 kHz, between about

500 Hz and 20 kHz, between about 500 Hz and 15 kllz, between about 500 Hz and 10 kHz, between about 500 Hz and 5 kHz, between about 1 and 20 kHz, between about 1 and 15 kHz, between about 1 and 10 kHz, between about 1 and 5 kHz). The frequency can be even much higher, for example in the ultrasonic range (e.g., between about 20 and 60 kHz, between about 30 and 60 kHz, between about 40 and 60 kHz, between about 50 and 60 kHz, 20 between about 20 and 50 kHz, between about 30 and 50 kHz, between about 40 and 50 kHz, between about 20 and 40 kHz, between about 30 and 40kHz, between about 20 and 30 kHz).

There are at least three types of vibratory conveyors e.g., that can be utilized in the methods herein described. Combinations of these and alternatives can be designed. The three 25 types of conveyors are discussed below.

In one type of vibratory conveyor, as depicted in FIG. 3 A, a vertical force is applied to the trough 310 and the trough is inclined at an angle a (alpha) to the horizontal, for example at least 1° (arc degree) e.g., at least 5®, at least 10^e, at least 20^s). In another configuration the trough is formed into a downwards sériés of steps (not shown) with a downward incline of at least 1^B (e.g., at least 5®, at least 10°, at least 20®, ai least 30®, at least 40®, at least 50®, at least 60®). A material, for example shown as a particle 312 moves sequentially to positions, shown as open circles, the direction of movement shown by arrows. This movement occurs because an oscillatory force or vibrational force is applied perpendicular to the trough surface as shown by the two headed arrows. The oscillatory force

repeatedly lofis the material to be conveyed perpendicular to the trough while gravity acts on the material to move it down the incline, or altematively the steps, of the trough.

In a second type of vibratory conveyor, depicted in FIG. 3 B, the materials to be conveyed arc placed on a trough 320 and a purcly horizontal force, indicated by the two 5 headed arrow, causes a horizontal movement of the materials. The force is an oscillating force such that the maximum horizontal vibratory forces applied to the trough in the direction of conveyance is less than the static friction force acring between the trough and the material, while the forces applied to the material in the direction opposite to conveyance is higher than the staric friction. In this way adhérence is maintained between the material 10 and the trough in the direction of conveyance but not in the direction opposite conveyance and the material is conveyed forward in a shuffling manncr. A material, for example, shown as particle 322 moves sequenrially to positions, shown as open circles, the shuffling movement indicated by the single headed arrows. As well as horizontal and downwards conveying, these types of conveyors can convey materials in upwards direction of up to 15 about 25 degrees.

In a third type of vibratoiy conveyor, depicted by FIG. 3C, the material carrying trough 330 is vibrated, as shown by the two headed arrows, at an angle β (beta) to the horizontal, for example 45 degrees. The material is lofted upwards and in the horizontal direction of incline. Therefore, the material is conveyed forward in a bouncing manner as 20 depicted by the particle 332 the movement indicated by the single headed arrows. As well as horizontal and downwards, these vibratory conveyors can convcy materials upwards as well as downwards, for example at an upwards direction of up to about 25 degrees.

FIG. 4 is a perspective view of a vibratory conveyor of the third type described above. The trough 410 has side walls 412 and 414 and is supported by support arms, legs or 25 structures 416 that are pivotally connected to the trough on one end and pivotally connected to a base support 418 on the other end. Coil springs are 420 shown at a 45® to the trough and support oscillations at this angle of the trough. A drive assembly 422 coupled to the trough provides the force for the oscillatory motion. Many other configurations of vibratory conveyors are known. For example, instead of coil springs, leaf springs can be used.

FIG. 5 shows a perspective view of another example of a vibratory conveyor of the third type. This example of a vibratory conveyor includes a drive assembly 510, leaf springs 520, a trough 530, cover 540 and access ports 550. Covers for the conveyors can be added to mitigate, for ex ample, dust génération.

FIG. 6A shows a perspective view of a vibratory conveyor of the second type 610.

The trough 612 carries biomass that has been delivered to the conveyor 630. At the upstream

end of the conveyor where the biomass is delivered, e.g., near 630, the biomass may fonn a pile with a peak. Downstream, e.g., near 640 the biomass is more uniformly spread. The trough is supported by support structures 616 which hâve pairs of longitudinally spaced vertical legs 617, cach pair of legs arc connected by horizontal cross members 618 and longitudinal base members 619. The trough 612 is suspended from the overhead structures 616 by vertical straps 621. The straps 621 are attached at one end to the horizontal cross members 618 and at the other end to trough support members 622. The straps 621 are constructed of a dimension in the direction transverse to the path of conveyance much larger than that of the direction parallel to the path of conveyance, and therefore the vertical straps 10 621 can act as résilient leaf-springs permitting displacement of the trough only in the direction of conveyance. The horizontal deflection of the bottoms of the straps 621 combine with the forces imparted by a vibration generating apparatus 623 creating motion of the trough 612 in substantially horizontal direction with very Utile vertical deflection. The vibration generating apparatus 623 can, for example, include an ecccntric fly wheels 683, 15 684,685 and 686 as shown in front side view FIG. 6B. US patent number 5,131,525 (pub.

July 21,1992) dcscribes vibratory conveyors, the entire disclosure thereof incorporated herein by référencé.

The vibratory conveyors described can include screens used for sieving and sorting materials. Port openings on the side or bottom of the troughs can be used for sorting, 20 sclccting or removing spécifie materials, for example, by size or shape. Some conveyors have countcrbalanccs to rcduce the dynamic forces on the support structure. Some vibratory conveyors are configured as spiral elevators, are desîgned to curve around surfaces and/or are designed to drop material from one conveyor to another (e.g., in a step, cascade or as a sériés of steps or a stair). Along with conveying materials conveyors can be used, by 25 themselves or coupled with other equipment or Systems, for screening, separating, sorting, classifying, distributing, sizing, inspection, picking, métal removing, freezing, blending, mixing, orienting, heating, cooking, drying, dewatering, clearing, washing, leaching, quenching, coating, de-dusting and/or feeding. The conveyors can also include covers (e.g., dust-tight covers), side discharge gates, bottom discharge gates, spécial liners (e.g., anti* 30 stick, stainless steel, rubber, custom stcal, and or grooved), divided troughs, quench pools, screens, perforated plates, detectors (e.g., métal detectors), high température designs, food grade designs, heaters, dryers and or coolers. In addition, the trough can be of various shapes, for example, fiat bottomed, vee shaped bottom, flanged at the top, curved bottom, fiat with ridges in any direction, tubular, half pipe, covered or any combinations of these. In 35 particuiar, the conveyors can bc coupled with an irradiation Systems and/or equipment.

The conveyors (e.g., vibratoiy conveyor) can be made of corrosion résistant materials. The conveyors can utilize structural materials that include stainless steel (e.g., 304,316 stainless steel, HASTELLOY® ALLOYS and INCONEL® Alloys). For example, HASTELLOY® Corrosion-Rcsistant alloys from Hyncs (Kokomo, Indiana, USA) such as

HASTELLOY® B-3® ALLOY, HASTELLOY® IIYBRID-BC1® ALLOY, HASTELLOY® C-4 ALLOY, HASTELLOY® C-22® ALLOY, HASTELLOY® C-22HS® ALLOY, HASTELLOY® C-276 ALLOY, HASTELLOY® C-2000® ALLOY, HASTELLOY® G-30® ALLOY, HASTELLOY® G-35® ALLOY, HASTELLOY® N ALLOY and HASTELLOY® ULTIMET® alloy.

The vïbratory conveyors can include non-stick release coatings, for example

TUFFLON™ (Dupont, Delaware, USA). The vïbratory conveyors can also include corrosion résistant coatings. For example coatings that can be supplied from Métal Coatings Corp (Houston, Texas, USA) and others such as Fluoropolymer, XYLAN®, Molybdenum Disulfide, Epoxy Phenolic, Phosphate- ferrous métal coating, Polyuiethane- high gloss topcoat forepoxy, inorganic zinc, Poly Tetrafluoro ethylene, PPS/RYTON®, fluorinated ethylene propylene, PVDF/DYKOR®, ECTFE/lïALAR® and Ceramic Epoxy Coating. The coatings can improve résistance to process gases (e.g., ozone), chemical corrosion, pitting corrosion, galling corrosion and oxidation.

In one embodiment, the conveyors include a cover. These enclosed conveyors are useful, for example, for the mitigation of dust génération. In some embodiments of these enclosed conveyors, a window that is transparent to the électron beam is mounted onto the cover, for example forming an integra! part of the cover. The window can be aligned with the électron beam so that the électrons can pass through the window and irradiate material being conveyed through the radiation field undemeath the widow (e.g. undemeath the électron beam). The Windows are typically foïls at least 10 um (micro meters) thick (e.g., at least 15 um, at least 20 um, at least 25 um, at least 30 um, at least 40 um). The électron beam generator also includes at least one window for extraction of électrons from the vacuum side of the generator to the atmospheric side. The distance between the facing surfaces of the window foîl mounted to the électron beam generator (e.g., mounted to the scanning hom) and window foil mounted to the enclosure of the vïbratory conveyor, when the System is being used to irradiate a feedstock, is at least about 0.1 cm (e.g. at least about 1 cm, at least about 2 cm, at least about 4 cm, at least about 5 cm, at least about 6 cm, at least about 7cm, at least about 8 cm, at least about 9 cm, or at least about 10 cm, at least about 12 cm, at least about 15 cm). Preferably the window foïls are cooled with a coolîng fluid, for example by using an air blower to blow air over the surface of the window foils.

It is generally preferred that the material be in a bed or layer of substantially uniform thickness or depth while being irradiated. For example, a desired thickness can be, 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 10 +/- 0.025 inches, 0.900 +/- 0.025 inches or 0. 900 +/- 0.025 inches.

Vibratory conveyors are particularly useful for spreading the material and producing a uniform layer on the conveyor trough surface. For example the initial feedstock can form a pile of material that can be at least four feet high (e.g., at least about 3 feet, at least about 2 feet, at least about 1 foot, al least about 6 inches, at least about 5 inches, at least about, 4 15 inches, at least about 3 inches, at least about 2 inches, at least about 1 inch, at least about ^lA inch) and spans less than the width ofthe conveyor(e.g., less than about 10%, less than about 20%, less than about 30%, less than about 40%, less than about 50%, less than about 60%, less than about 70%, less than about 80%, less than about 90%, less than about 95%, less than about 99%). The vibratory conveyor can spread the material to span the entire 20 width of the conveyor trough and hâve a uniform thickness, preferably as discussed above.

In some cases, an additional spreading method can be useful. For example, a sprcader such as a broadeast spreader, a drop spreader (e.g., a CHRISTY SPREADER™) or combinations thereof can be used to drop (e.g., place, pour, spill and/or sprinkle) the feedstock over a wide area. Optionally, the spreader can deliver the biomass as a wide shower or curtain onto the vibratory conveyor. Additionally, a second conveyor, upstream from the first conveyor (e.g., the first conveyor is used in the irradiation of the feedstock), can drop biomass onto the first conveyor, where the second conveyor can hâve a width transverse to the direction of conveying smaller than the first conveyor. In particular, when the second conveyor is a vibratory conveyor, the feedstock is spread by the action of the second and first conveyor. In some optional embodiments, the second conveyor ends in a bias cross eut discharge (e.g., a bias eut with a ratio of 4:1) so that the material can be dropped as a wide curtain (e.g., wider than the width of the second conveyor) onto the first conveyor. The initial drop area of the biomass by the sprcader (e.g._t broadeast spreader, drop spreader, conveyor, or cross eut vibratory conveyor) can span the entire width of the first vibratory conveyor, or il can span part of this width. Once dropped onto the conveyor, the material is spread even more

uniformly by the vibrations of the conveyor so that, preferably, the entire width of the conveyor is covered with a uni form layer of biomass. In some embodiments combinations of spreaders can be used. Some methods of spreading a feed stock are described in US Patent No. 7,153,533, filed July 23,2002 and publishcd Dcccmbcr 26,2006, the entire disclosure of 5 which is încoiporated herein by reference.

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 I ft/min, e.g., at least 2 ft/min, at least 3 ft/min, at least 4 ft/min, at least 5 ft/mîn, at least 10 ft/min, at least 15 ft/min, at least 20 ft/min, at least 25 ft/min, at least 30 ft/min, at least 40 ft/min, at least 50 ft/min, at least 60 ft/min, at least 70 ft/min, at least 80 ft/min, at least 90 ft/min. The rate of conveying is related to the beam current and targeted irradiation dose, for example, for a *4 inch thick biomass spread over a 5.5 foot wide conveyor and 100 mA, the conveyor can move at about 20 ft/min to provide a useful irradiation dosage (e.g. about 10 Mrad for a single pass), at 50 mA the conveyor can move at about 10 ft/min to provide approximately the same irradiation dosage.

The rate at which material can be conveyed dépends on the shape and mass of the material being conveyed. Flowing materials e.g., particulate materials, are particulariy amenable to conveying with vibratory convcyors. Conveying speeds can, for example be, at least 100 Ib/hr (e.g., at least 500 Ib/hr, at least 1000 Ib/hr, at least 2000 lb/hr, at least 3000 20 Ib/hr, at least 4000 Ib/hr, at least 5000 Ib/hr, at least 10,000 Ib/hr, at least 15,000 Ib/hr, or even at least 25,000 Ib/hr). Some typical conveying speeds can be between about 1000 and 10,000 Ib/hr, (e.g., between about 1000 Ib/hr and 8000 Ib/hr, between about 2000 and 7000 Ib/hr, between about 2000 and 6000 Ib/hr, between about 2000 and 50001b/hr, between about 2000 and 4500 Ib/hr, between about 1500 and 5000 Ib/hr, between about 3000 and 7000 25 Ib/hr, between about 3000 and 6000 Ib/hr, between about 4000 and 6000 Ib/hr and between about 4000 and 5000 Ib/hr). Typical conveying speeds dépend on the density of the material. For example, for a biomass with a density of about 35 lb/ft³, and a conveying speed of about 5000 Ib/hr, the material is conveyed at a rate of about 143 ft³/hr, if the material is *4” thick and is in a trough 5.5 fit wide, the material is conveyed at a rate of about 1250 ft/hr (about 21 30 ft/min). Rates of conveying the material can therefore vary greatly. Preferably, for example a *4” thick layer of biomass, is conveyed at speeds of between about 5 and 100 ft/min (e.g. between about 5 and 100 ft/min, between about 6 and 100 ft/min, between about 7 and 100 ft/min, between about 8 and 100 ft/min, between about 9 and 100 ft/min, between about 10 and 100 ft/min, between about 11 and 100 ft/min, between about 12 and 100 ft/min, between 35 about 13 and 100 ft/min, between about 14 and 100 ft/min, between about 15 and 100

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

HQ. 7 shows an irradiation process. This process can be part of the process described in HQ. 2 although it can altematively be part of a different process. Initial! y, biomass can be delivered to a vibratory conveyor 750. The biomass can be treated by a pre-irradiation process 752 prior to it being conveyed through an irradiation zone 754. After irradiation, the biomass can be post processed 756. The process can be repeated (e.g., dashed arrow A).

Biomass can be delivered to the vibratory conveyor 750 by using another vibratory conveyor, a belt conveyor, a pneumatic conveyor, a screw conveyor, a hopper, a dispersîng 20 machine (e.g., a spreader), a pipe, manually or by combination of these. The biomass can, for example, bc dropped, pourcd, sprinklcd and/or placed onto the vibratory conveyor by any of these methods. 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% or less about than 5%, less than about 4%, less than about 3%, less than about 2%, and even less 25 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 10 wt% solids (e.g. at least 20 wL%, at least 30 wt %, at least 40 wt%, at least 50 wL%, at least 60 wt%, at least 70 wL%).

In some cases, the pre-irradiation processing 752 includes screening of the biomass material. Screening can bc by a vibratory screener coupled to the vibratory conveyor. For 30 example a vibratory screener that has a mesh or perforated plate onto which the biomass falls with a desired opening size, for example, less than 6.35 mm (¼ inch, 0.25 inch), {e.g., less 3.18 mm (1/8 inch, 0.125 inch), less than 1.59 mm (1/16 inch, 0.0625 inch), is less than 0.79 mm (1/32 inch, 0.03125 inch), e.g„ less than 0.51 mm (1/50 inch, 0.02000 inch), less than 0.40 mm (1/64 inch, 0.015625 inch), less than 0.23 mm (0.009 inch), less than 0.20 mm 35 (1/128 inch, 0.0078125 inch), less than 0.18 mm (0.007 inch), less than 0.13 mm (0.005

inch), or even less than less than 0.10 mm (1/256 inch, 0.00390625 inch)). In one configuration the desired biomass falls through the perforations or screen and thus biomass larger than the perforations or screen are not irradiated. These larger materials can be reproccsscd, for exampie by comminuting, or they can simply bc 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 by some other means. In this kind of a configuration, the conveyor itself (for example a part of the conveyor) can be perfbrated or made with a mesh. For exampie, in a one particular embodiment the biomass material may be wet and the perforations or mesh allow water to drain away from the biomass before 10 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-irradiation processing 752 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 one side or more than one side, can be continuous or periodic and/or can be for only a portion of the material or ail the material. For exampie, a portion of the trough can be heated by use of a heating jackct. Heating can be, for exemple, for the purpose of drying the material. In the case of drying the material, this can also be facîlitated, with or without heating, by the movement of a gas (e.g., air, nitrogen, oxygen, CO2, Argon, He) over and/or through the biomass as it is being conveyed. Drying can also be in vacuo.

Pre-irradiation processing 752 can also be with reactive gases, for example ozone, ammonia, steam or a plasma. The gas can supplied above atmospheric pressure.

Optionally, pre-irradiation processing 752 can include cooiing the material. Cooiing material is described in US Patent No. 7,900,857 filed July 14,2009 and published March 8, 2011, the entire disclosure of which in incorporated herein by référencé.

Another optional pre-irradiation processing 750 can include adding a material to the biomass. Vibratory conveying is very well suited to be coupled with the addition of a material, for example, by showering, sprinkling and or pouring a material onto the biomass as it is conveyed, because the vibratory conveyor provides agitation, tumbling and/or tuming of the biomass that allows for efficient mixing and/or homogenization of the biomass with any added material. Materials that can be added include, for example, metals, ceramics

and/or ions as described in US. Application Sériés No. 12/605,534 and US. Application Sériés No. 12/639,289 the complété disclosures of which are incorporated herein by refercnce. Other materiais that can be added include acids, bases, oxidants (cg., peroxides, chlorates), polymers, polymcrizable monomers (e.g., containing unsaturated bonds), water, catalysts, enzymes and/or organisms. Materiais can be added, for example, in pure form, as a solution in a solvent (e.g., water or an organic solvent) and/or as a solution. In some cases the solvent is volatile and can be made to evaporate e.g., by heating and/or blowing gas as prcviously described. The added material may form a uniform coating on the biomass or be a homogeneous mixture of different components (e.g., biomass and additional material). The added material can modulate the subséquent irradiation step by increasing the effïciency of the irradiation, damping the irradiation or changing the effect of the irradiation (e.g., from électron beams to X-rays or heat). The method may hâve no impact on the irradiation but may be useful for further downstream processing. The added material may help În conveying the material, for example, by lowering dust levels.

After optional pre-radiation treatment the material is conveyed by the vibratory conveyor through an irradiation zone (e.g., the radiation field) 754. Radiation can be by, for example électron beam, ion beam, 100 nm to 28 nm ultraviolet (UV) light, gamma or X-ray radiation. For example, radiation treatments and equipment are discussed below. Radiation treatments and Systems for treatments are also discussed in US. Patent 8,142,620, and US.

Patent Application Séries No. 12/417,731, the entire disclosures of which arc incorporated herein by référencé.

Referring again to FIG. 7, after the biomass material has been conveyed through the radiation zone optional post processing 756 can be done. The optional post processing can, for example, be a processes described with respect to the pre-irradiation processing. For example, the biomass can be screened, heated, cooled, and/or combined with additives. Uniquely to post-irradiation, quenching of the radicals can occur, for example, quenching of radicals by the addition of fluids (e.g., oxygen, réactivé liquids), using pressure, using heating and or addition of radical scavengers. Quenching of biomass that has been irradiated is described in US. Patent 8,083,906 and issued December 27,2011 the disclosure of which is incorporate herein by refercnce.

Il may be advantageous to repeat irradiation to more thoroughly reduce the recalcitrance of the biomass. For example, as shown by path A in FIG. 7. In particular the process parameters might be adjusted after a first (e.g., second, third, fourth or more) pass depending on the recalcitrance of the material. In some embodiments, the conveyor is a closed circular System where the biomass is conveyed multiple times through the various

processes described above. In some other embodiments multiple irradiation devices (e.g., électron beam generators) are used to irradiate the biomass multiple (e.g., 2,3,4 or more) limes. In yet other embodiments, a single électron beam generator may be the source of multiple bcams (e.g., 2,3,4 or more bcams) that can be used for irradiation of the biomass.

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

SYSTEMS FOR TREATING A FEEDSTOCK

Processes for conversion of a feedstock to sugars and other products, in which the conveying methods discuss above may be used, include, for example, optionally physically pre-treating the feedstock, e.g., to reduce its size, before and/or after this treatment, optionally treating the feedstock to reduce its recalcitrance (e.g., by irradiation), and saccharifying the feedstock to form a sugar solution. Saccharification can bc performed by mixing a dispersion of the feedstock in a liquid medium, e.g., water with an enzyme, as will bc discussed in detail herein. Prior to treatment with an enzyme, pretreated biomass can be subjected to hot water and pressure, e.g., 100-150 deg C, 100-140, or 110-130 deg C and associated pressure. Prior to treatment with the enzyme the material is cooled to about 50 deg C (e.g. between about 40 and 60 deg C). In addition or aitematively prior to the treatment with an enzyme the pretreated biomass can bc treated with an acid, such as hydrochloric, sulfuric or phosphoric acid e.g., less than 10% concentration (e.g., less than 5%, e.g. between about 0.01 and about 5%, between about 0.05 and about 1%, between about 0.05 and about 0.5%). During or after saccharification, the mixture (if saccharification is to be partially or completely performed en route) or solution can be transported, e.g., by pipeline, railcar, truck or barge, to a manufacturing plant At the plant the solution can be bioprocessed, e.g., fermented, to produce a desired product or intermediate, which can then be processed further, e.g., by distillation. The individual processing steps, materials used and examples of products and intermediates that may bc formed will bc described in detail below.

RADIATION TREATMENT

The feedstock can be treated with radiation to modify its structure to reduce its recalcitrance. Such treatment can, for example, reduce the average molecular weight of the

feedstock, change the crystalline structure of the feedstock, and/or increase the surface area and/or porosity of the feedstock· Radiation can be by, for exampie électron beam, ion beam, 100 nm to 28 nm ultraviolet (UV) lîght, gamma or X-ray radiation. Radiation treatments and Systems for treatments arc discussed in US. Patent 8,142,620, and US. Patent Application 5 Sériés No. 12/417, 731, the entire disclosures of which are incorporated herein by référencé.

Eaeh form of radiation ionizes the biomass via particular interactions, as determined by the energy of the radiation. Heavy charged particles primarily ionize matter via Coulomb scattering; furthermore, these interactions produce energetie électrons that may further ionize matter. Alpha particles are identieal to the nucléus of a hélium atom and are produced by the 10 alpha decay of various radioactive nuclei, such as isotopes of bismuth, polonium, astatine, radon, francium, radium, several actinides, such as actinium, thorium, uranium, neptunium, curium, californium, américium, and plutonium. Electrons interact via Coulomb scattering and bremsstrahlung radiation produced by changes in the velocity of électrons.

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

Gamma radiation has the advantage of a significant pénétration depth into a variety of material in the sample.

In embodiments in which the irradiating is performed with electromagnetic radiation, the electromagnetic radiation can hâve, e.g., energy per photon (in électron volts) of greater than 10² eV, e.g., greater than ΙΟ³,10⁴,10⁵,10^e, or even greater than 10⁷ eV. In some embodiments, the electromagnetic radiation has energy per photon of between 10⁴ and 10⁷, 30 e.g., between 10⁵ and 10⁶ eV. The electromagnetic radiation can hâve a frequency of, e.g., greater than 10’⁶ hz, greater than 10*⁷ hz, 10”, 10”, 10²⁰, or even greater than 10²¹ hz. In some embodiments, the electromagnetic radiation has a frequency of between 10¹⁸ and 10²²hz, e.g., between 10” to 10²¹ hz

Electron bombandment may be performed using an électron beam device that has a nominal energy of less than 10 MeV, e.g., less than 7 MeV, less than 5 MeV, or less than 2

MeV, e.g., from about 03 to about 4 MeV, from about 0.6 to about 3 MeV, from about 03 to 13 MeV, from about 0.8 to 1.8 MeV, from about 0.7 to about 23 MeV, or from about 0.7 to 1 MeV. In some implémentations the nominal energy is about 500 to 800 keV.

The électron beam may hâve a rclativcly high total beam power (the combined beam power of ail accelerating heads, or, if multiple accéléra tors are used, of ail accelerators and ail heads), e.g., at least 25 kW, e.g., at least 30, 40,50, 60,65,70, 80,100,125, or 150 kW. In some cases, the power is even as high as 500 kW, 750 kW, or even 1000 kW or more. In some cases the électron beam has a beam power of 1200 kW or more, e.g., 1400,1600, 1800, or even 300 kW.

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

It is generally preferred that the bed of biomass material has a relatively uniform thickness. In some embodiments the thickness is less than about 1 inch (e.g., less than about 0.75 inchcs, less than about 03 inches, less than about 0.25 inches, less than about 0.1 inches, between about 0.1 and 1 inch, between about 0.2 and 0.3 inches).

It îs désirable to beat the material as quickly as possible. In general, it is preferred that treatment be performed at a dose rate of greater than about 0.25 Mrad per second, e.g., greater than about 03,0.75,1,1.5,2,5,7,10, 12,15, or even greater than about 20 Mrad per second, e.g., about 0.25 to 2 Mrad per second. Higher dose rates allow a higher throughput for a target (e.g., the desired) dose. Higher dose rates generally require higher line speeds, to avoid thermal décomposition of the material. In one implémentation, the accelerator is set for 3 MeV, 50 mA beam carrent, and the line speed is 24 feet/minute, for a sample thickness of about 20 mm (e.g., conuninuted corn cob material with a bulk density of 0.5 g/cm³).

In some embodiments, électron bombardment is performed until the material rcceives a total dose of at least 0.1 Mrad, 0.25 Mrad, 1 Mrad, 5 Mrad, e.g., at least 10,20,30 or at least 40

Mrad. In some embodiments, the treatment is performed until the material rcceives a dose of from about 10 Mrad to about 50 Mrad, e.g., from about 10 to about 40 Mrad, from about 20 Mrad to about 40 Mrad, or from about 25 Mrad to about 30 Mrad. In some implémentations, a total dose of 25 to 35 Mrad is preferred, applied ideally over a couple of passes, e.g., at 5 Mrad/pass with each pass being applied for about one second. Cooling methods such as

cooling screw conveyors and cooled conveying troughs can also be utilized, for example after each in-adiation, after the total irradiation, during irradiation and/or before irradiation.

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

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

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

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

It may be advantageous to repeat the treatment to more thoroughly reduce the recalcitrance of the biomass and/or further modify the biomass. In particular the process parameters can be adjusted after a first («.g., second, third, fourth or more) pass depending on the recalcitrance of the material. In some embodiments, a conveyor can be used which includes a circulât system where the bïomass is conveyed multiple times through the various processes descnbcd above. In some other embodiments multiple treatment devices (e.g., électron beam generators) are used to treat the biomass multiple (e.g., 2,3,4 or more) times. In yet other embodiments, a single électron beam generator may be the source of multiple beams (e.g., 2,3,4 or more beams) that can be used for treatment of the biomass.

The effectiveness in changing the molecular/supermolccular structure and/or reducing the recalcitrance ofthe carbohydrate-containing biomass dépends on the électron energy used and the dose applied, while exposure time dépends on the power and dose. In some embodiments, the dose rate and total dose are adjusted so as not to destroy (e.g., char or bum) the biomass material. For example, the carbohydrates should not be damaged in the processing so that they can be released from the bîomass intact, e.g. as monomeric sugars. In some embodiments, the treatment (with any électron source or a combination of sources) is performed until the material receives a dose of at least about 0.05 Mrad, e.g., at least about 0.1, 0.25,0.5,0.75,1.0,2.5, 5.0,7.5,10.0,15,20,25,30,40, 50,60,70,80,90,100,125, 150,175, or 200 Mrad. In some embodiments, the treatment is performed until the material receives a dose of between 0.1-100 Mrad, 1-200,5-200, 10-200, 5-150, 50-150 Mrad, 5-100, 5-50,5-40, 10-50,10-75,15-50, 20-35 Mrad.

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

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

RADIATION OPAQUE MATERIALS

As previously discussed, the invention can include processing the material in a vault and/or bunker that is construetcd using radiation opaque materials. In some implémentations, the radiation opaque materials are seiected to be capable of shielding the components from X-rays with high energy (short wavelength), whieh can penetratc many materials. One important factor in designing a radiation shielding enclosure is the atténuation length of the materials used, which will détermine the required thickness for a particular material, blend of materials, or layered structure. The atténuation length is the pénétration distance at which the radiation is reduced to approximately 1/e (e = Eulers number) times that of the incident radiation. Although virtually ail materials are radiation opaque if thiek enough, materials containing a high compositional percentage (e.g., density) of éléments that hâve a high Z value (atoniic number) hâve a shorter radiation atténuation length and thus if such materials are used a thinner, lighter shielding can be provided.

Examples of high Z value materials that are used in radiation shielding are tantalum and lead. Another important parameter in radiation shielding is the halving distance, which is the thickness of a particular material that will reduce gamma ray intensity by 50%. As an example for X-ray radiation with an energy of 0.1 MeV the halving thickness is about 15.1 mm for concrète and about 2.7 mm for lead, while with an X-ray energy of 1 MeV the halving thickness for concrète is about 44.45 mm and for lead is about 7.9 mm. Radiation opaque materials can bc materials that are thîck or thin so long as they can reduce the radiation that passes through to the other side. Thus, if it is desired that a particular enclosure hâve a low wall thickness, e.g., for light weight or due to size constraints, the material chosen should hâve a sufficient Z value and/or atténuation length so that its halving length is Iess than or equal to the desired wall thickness of the enclosure.

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

A radiation opaque material can reduce the radiation passing through a structure (e.g., a wall, door, ceiling, enclosure, a sériés of these or combinations of these) formed of

the material by about at least about 10 %, (e g., at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, at least about 99.9%, at least about 99.99%, at least about

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

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, technetium, chromîum, gallium, indium, iodine, iron, krypton, samarium, sélénium, 20 sodium, thallium, and xénon.

Sources of X-rays include électron beam collision with métal taigets, 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 înfrared radiation include sapphire, zinc, or selenîde window ceramic lamps.

Sources for microwaves include klyslrons, 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 DE (e.g., electrostatic DC, electrodynamic DC), RF linear, magnetic induction linear or continuous wave. For example, various irradiating devices may be used in the methods disclosed

herein, including field ionization sources, electrostatic ion separators, field ionization généra tors, thermionic émission sources, microwave discharge ion sources, recirculating or static accelerators, dynamic lïnear accelerators, van de Graaff accelerators, Cockroft Walton accclcrators (e.g., PELLETRON® accelerators), LINACS, Dynamitrons (e.g,

DYNAMITRON® accelerators), cyclotrons, synchrotrons, betatrons, transformer-type accelerators, microtrons, plasma generators, cascade accelerators, and foldcd tandem accelerators. For example, cyclotron type accelerators are available from IB A, Belgium, such as the RI IODOTRON™ System, while DC type accelerators arc available from RDI, now IB A Industrial, such as the DYNAMITRON®. Other suitable accéléra tor 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 Iotron Industries (Canada); and ILU-bascd accelerators, available from Budker Laboratoires (Russia). Ions and ion accelerators are discussed in Introductory

Nuclear Physics, Kenneth S. Krane, John Wiley & Sons, Inc. (1988), Kisto Prelec, FIZIKA B 6 (1997) 4, 177-206, Chu, William T., Overview of Light-Ion Beam Therapy”, Columbus-Ohio, ICRU-IAEA Meeting, 18-20 March 2006, Iwata, Y. et al., “AltematingPhase-Focused IH-DTL for Heavy-Ion Medical Accelerators”, Proccedings of EPAC 2006, Edinburgh, Scotland,, and Leitner, CAI. et al., Status of the Superconducting ECR Ion

Source Venus”, Proccedings of EPAC 2000, Vienne, Austria. Some particle accelerators and their uses arc disclosed, for exemple, in U.S. Pat No. 7,931,784 to Mcdoff, the complète disclosure of which is incorporated herein by référencé.

Electrons may bc produced by radioactive nuclei that undergo beta decay, such as isotopes of iodine, césium, technetium, and iridium. Altematively, an électron gun can be 25 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 potential (e.g., greaterthan about 500 thousand, greaterthan about lmillion, grcaterthan 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 30 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 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 hclps 35 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 restarting the électron gun.

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

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 15 as the bîomass 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 20 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 125 MeV. Methods of irradiating materials arc discussed in U.S. Pat. App. Pub. 2012/0100577 Al, filed October 18,2011, the entire disclosure of which is herein incorporated by référencé.

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, microcon troll ers and cooling equipment can be purchased and assembled into a device. Optionally, a commercial device can be modified and/or adapted. For example, devices and components can be purchased from any of the commercial sources described herein induding Ion Beam Applications (Louvain-la-Neuve, Belgium), NIIV Corporation (Japan), the Titan Corporation (San Diego, CA), Vivirad High Voltage Corp (Billeric, MA) and/or Budker Laboratoires (Russie). 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 beara currcnt), or EPS-1000 (e.g., 1000 kV accelerator voltage and 65 or 100 mA beam currcnt).

Also, accelerators from NIIV’s high eneigy 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 footprinL Tradeoffs in considering exposure dose levels of électron beam irradiation would be energy costs and environment, safety, and hcalth (ESII) concems. Typically, generators are houscd 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 wîdths 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 local heating and failurc of the Windows.

ELECTRON GUNS - WINDOWS

The extraction system for an électron accelerator can include two window foils. The 25 cooling gas in the two foil window extraction System can be a purge gas or a mixture, for example air, or a pure gas. In one embodiment the gas is an inert gas such as nitrogen, argon, hélium and or carbon dioxide. It is preferred to use a gas rather than a liquid since energy losses to the électron beam are minimized. Mixtures of pure gas can also be used, either pre-mixed or mixed in line prior to impinging on the Windows or in the space between 30 lhe Windows. The cooling gas can be cooled, for example, by using a heat exchange system (e.g., achiller) and/or by usingboil off from acondensed gas (e.g., liquid nitrogen, liquid hélium).

HEATING AND THROUGHPUT DURING RADIATION TREATMENT

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

The adiabatic température rise (ΔΤ) from adsorption of ionizing radiation is given by the équation: ΔΤ = D/Cp: where D is the average dose in kGy, C_P is the heat capacity in J/g °C, and ΔΤ is the change in température in °C. A typical dry biomass material will hâve a heat capacity close to 2. Wet biomass will hâve a higher heat capacity dépendent on the amount of water since the heat capacity of water is very high (4.19 J/g °C). Metals hâve much lower heat capacities, for exemple 304 stainlcss steel has a heat capacity of 0.5 J/g °C. The température change due to the instant adsorption of radiation in a biomass and stainless steel for various doses of radiation is shown in Table 1.

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

Dose (Mrad)	Est! mate d Biomass ΔΤ (°C)	Steel ΔΤ (°C)
10	50	200
50	250	1000
100	500	2000
150	750	3000
200	1000	4000

High températures can destroy and or modify the biopolymers in biomass so that the polymers (e.g., cellulose) are unsuitable for further processing. A biomass subjected to high températures can become dark, sticky and give off odors indicating décomposition. The

stickïness can even make the material hard to convey. The odors can be unpleasant and be a safety issue. In fact, keeping the biomass below about 200°C has been found to be bénéficiai in the processes described herein (e.g., below about 190°C, below about 180°C, below about 170°C, below about 160°C, below about 150°C, below about 140°C, below about 130°C, below about 120°C, below about 110°C, between about 60°C and 180°C, between about 60°C and 160°C, between about 60°C and 150°C, between about 60°C and 140°C, between about 60°C and 130°C, between about 60°C and 120°C, between about 80°C and !80°C, between about 100°C and 180°C, between about 120°C and 180°C, between about 140°C and 180°C, between about 160°C and 180°C. between about 100°C and 140°C, between about 80°C and 120°C).

It has been found that irradiation above about 10 Mrad is désirable for the processes described herein (e.g., réduction of recalcitrance). A high throughput is also désirable so that the irradiation does not become a bottle neck in processing the biomass. The treatment is govemed by a Dose rate équation: M = FP/D'time, where M is the mass of irradiated material (Kg), F is the fraction of power that is adsorbed (unit less), P is the emitted power (kW=Voltage in MeV X Current in mA), time is the treatment time (sec) and D is the adsorbed dose (kGy). In an exemplary process where the fraction of adsorbed power is fixed, the Power emitted is constant and a set dosage is desired, the throughput (e.g., M, the biomass processed) can be increased by increasing the irradiation time. However, increasing the irradiation time without allowîng the material to cool, can excessively heat the material as exemplified by the calculations shown above. Since biomass has a low thermal conductivity (less than about 0.1 Wnr’K'¹). heat dissipation is slow, unlike, for example metals (greater than about 10 Wm'¹ K^-1) which can dissipate energy quickly as long as there is a heat sink to transfer the energy to.

ELECTRON G UNS - 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 30 without powering down the électron beam device. Altematively the beam stop can be used while powering up the électron beam, e.g., the beam stop can stop the électron beam untii a beam current of a desired level is achîeved. The beam stop can be placed between the primary foil window and a secondary foil window. For example, the beam stop can be mounted so that it is movable, that is, so that it can be moved into and out of the beam path.

Even partial coverage of the beam can be used, for example, to control the dose of

irradiation. The beam stop can be mounted to the floor, to a conveyor for the biomass, to a wall, to the radiation device (e.g., at the scan hom), or to any structural support. Preferably the beam stop is fixed in relation to the scan hom so that the beam can be effectively controlled by the beam stop. The beam stop can incorporate a hinge, a rail, whccls, slots, or 5 other means allowing for its operation in moving into and out of the beam. The beam stop can be made of any material that will stop at least 5% of the électrons, e.g., at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, at least 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or even about 100% of the électrons.

The beam stop can be made of a métal including, but not limited to, stainless steel, lead, iron, molybdenum, sîlver, gold, titanium, aluminum, tin, or alloys of these, or laminates (layered materials) made with such metais (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 15 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 20 spécifie régions of the window. The beam stop can be a mesh formed, for exampie, from fibers or wïrcs. 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 orout of position.

BEAM DUMPS

The embodiments disclosed herein can also include a beam dump. A beam dump's purpose is to safely absorb a beam of charged particles. Like a beam stop, a beam dump can be used to block the beam of charged particles. However, a beam dump is much more robust 30 than a beam stop, and is intended to block the full power of the électron beam for an extended period of time. They are often used lo block the beam as the accelerator is powering up.

Beam dumps are also designed to accommoda te the heat generated by such beams, and are usually made from materials such as copper, aluminum, carbon, béryllium, tungsten,

or mercury. Beam dumps can be cooled, for example by using a cooling fluid that is in thermal contact with the beam dump.

BIOMASS MATERIALS

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, bariey straw, 10 oat straw, rice straw, jute, hemp, flax, bamboo, sisal, abaca, com cobs, corn stover, soybean stover, com fiber, alfalfa, hay, coco nu t haïr), sugar processing 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 uniform thickness for 15 irradiation, and after irradiation are easy to disperse in the medium for further processing.

To facilitate harvest and collection, in some cases the entire com plant is used, including the com 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 20 materials containing significant amounts of comcobs.

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

Cellulosic materials include, for example, paper, paper products, paper waste, paper 25 pulp, pigmented papers, loaded papers, coated papers, fil lcd papers, magazines, printed matter (e.g., books, catalogs, manuals, labels, calendars, grceting cards, brochures, prospcctuses, newsprint), printer paper, polycoated paper, caïd stock, caidboard, paperboaid, 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 Fccdstocks” 30 by Mcdoff et ai, filcd Fcbruary 14, 2012), the full disclosurc of which is incoiporatcd herein by reference.

Cellulosic materials can also include lignocellulosic materials which hâve been partially or fully dc-lignified.

In some instances other biomass materials can bc utilized, for example starchy materials. Starchy materials include starch itself, e.g., com starch, wheat starch, potato starch

or rice starch, a dérivative of starch, or a material that includes starch, such as an edible food product or a crop. For example, the starchy material can be arracacha, buckwheat, banana, barley, cassava, kudzu, ocra, sago, sorghum, regular household potatoes, sweet potato, tara, yams, or onc or more bcans, such as favas_t lentils or pcas. Blends of any two or more starchy materials are also starchy materials. Mixtures of starchy, cellulosîc 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 corn plant, rice plant or a tree. The starchy materials can be treated by any of the methods described herein.

Microbial materials that can be used as feedstock can include, but are not Iimited to, 10 any naturally occurring or genetically modified microorganism or organism that contains or is capable of providing a source of carbohydrates (e.g., cellulose), for example, protists, e.g., animal protists (e.g., protozoa such as flagellâtes, amoeboids, ciliates, and sporozoa) and plant protists (e.g, algae such alveolates, chlorarachnîophytes, 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 extremophïles), yeast and/or mixtures of these. In some instances, microbial biomass can be obtained from naturel sources, e.g., the océan, Iakes, 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 wct culture and fermentation Systems.

In other embodiments, the biomass materials, such as cellulosîc, starchy and lignocellulosic feedstock materials, can be obtained from transgenic microorganisms and plants that hâve been modified with respect to a wild type variety. Such modifications may 25 be, for example, through the itérative steps of sélection and brceding 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 varicties, or, for 30 exampie, by using transgenic breeding wherein a spécifie gene or genes are inlroduced to a plant from a different species of plant and/or bacteria. Another way to croate genetic variation is through mutation breeding wherein new alleles are artificially created from endogenous genes. The artificial genes can be created by a variety of ways including treating the plant or seeds with, for example, chemical mutagens (e.g., using alkylating agents, epoxides, alkaloids, peroxides, formaldéhyde), ircadiation (e.g., X-rays, gamma rays, neutrons, beta particles, alpha parucles, protons, deuterons, UV radiation) and température shocking or other externe] stressîng and subséquent sélection techniques. Other methods of providing modified genes is through error prône PCR and DNA shuflling followed by insertion of the desired modified DNA into the desired plant or sccd. Methods of introducing the desired genetic variation in the seed or plant include, for exampie, the use of a bacterial carrier, biolistics, calcium phosphate précipitation, electroporation, gene splicing, gene silencing, lipofection, microinjection and viral carriers. Additional genetically modified materiais hâve been described in U.S. Application Serial No 13/396,369 filed Fcbruary 14,2012 the fbll disclosure of which is incorporated herein by référence.

Any of the methods described herein can be practiced with mixtures of any biomass materiais described herein.

OTHER MATERIALS

Other materiais (e.g., naturai or synthetic materiais), for example polymers, can be treated and/or made utilizing the methods, equipment and Systems described herein._For example polyethylene (e.g., lincar low density ethylene and high density polyethylene), polystyrènes, sulfonated polystyrènes, poly (vinyl chloride), polyesters (e.g., nylons, DACRON™, KODEL™), polyalkylene esters, poly vinyl esters, polyamides (e.g., KEVLAR™), polyethylene tcrcphthalatc, cellulose acetate, acctal, poly acrylonitrile, polycarbonatcs (e.g., LEXAN™), acrylics [e.g., poly (methyl méthacrylate), poly(methyl méthacrylate), polyacrylnitriles], Poly urethanes, polypropylene, poly butadiene, polyisobutylene, polyacrylonitrile, polychloroprene (e.g. neoprene), poly(cis-l,4-isoprene) [e.g., naturai rubber], poly(txans-l,4-isoprenc) [e.g., gutta percha], phénol formaldéhyde, mel amine formaldéhyde, epoxides, polyesters, poly amines, polycarboxylic acids, polylactic acids, polyvinyl alcohols, polyanhydrides, poly fiuoro carbons (e.g., TEFLON™), silicons (e.g., silicone rubber), polysilanes, poly ethers (e.g., polyethylene oxide, polypropylene oxide), waxes, oils and mixtures of these . Also included are plastics, rubbers, elastomers, fibers, waxes, gels, oils, adhesives, thermoplastics, thermosets, biodégradable polymers, rcsins made with these polymers, other polymers, other materiais and combinations thereof. The polymers can be made by any useful method including cationic polymerization, anionic polymerization, radical polymerization, metathesis polymerization, ring opening polymerization, graft polymerization, addition polymerization. In some cases the treatments disclosed herein can be used, for example, for radically initiated graft polymerization and

cross linkîng. Composites of polymers, for example with glass, metals, biomass (e.g., fibers, particies), ceramîcs can also be treated and/or made.

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

In addition, manufactured mullipart or shaped materials (e.g., molded, extruded, welded, riveted, layered or combined in any way) can be treated, for example cables, pipes, boards, enclosures, integrated semiconductor chips, circuit boards, wires, tires, Windows, 10 laminated materials, geais, belts, machines, combinations of these. For example, treating a material by the methods described herein can modify the surfaces, for example, niaking them susceptible to further functionalization, combinations (e.g., welding) and/or treatment can cross link the materials.

BIOMASS MATERIAL PREPARATION - 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 20 about 1 %). The biomass can also be delivcrcd in a wet state, for example as a wct solid, a slurry or a suspension with at least about 10 wt% soiids (e.g., at least about 20 wt.%, at least about 30 WL %, at least about 40 wt.%, at least about 50 wt.%, at least about 60 wt.%, at least about 70 wt.%).

The material to be processed, e.g., biomass material, can be a particulate material.

For example, with an average particle size above at least about 0.25mm (e.g., at least about 0.5mm, at least about 0.75mm) and below about 6 mm (e.g., below about 3mm, below about 2mm). In some embodiments this is produced by mechanical means, for example as described herein.

The processes disclosed herein can utilize low bulk density materials, for example 30 cellulosic or lignocellulosic feedstocks that hâve been physically pretreated to hâve a bulk density of less than about 0.75 g/cm\ 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 35 by dividing the weight of the sample in grams by the known volume of the cylinder in cubic

centimeters. If desired, low bulk density materials can be densifled, for example, by methods described in US. Pat No. 7,971,809 published July 5,2011, lhe entîre disclosure of which is hereby incorporated by référencé.

In some cases, the prc-treatment processing includes screening of the biomass material. Screening can be through a mesh or perforated plate with a desired opening size, for example, less than about 6.35 mm(l/4 inch, 0.25 inch), {e.g., less than about 3.18 mm (1/8 inch, 0.125 inch), less than about 1.59 mm (1/16 inch, 0.0625 inch), is less than about 0.79 mm (1/32 inch, 0.03125 inch), e.g., less than about 0.51 mm (1/50 inch, 0.02000 inch), less than about 0.40 mm (1/64 inch, 0.015625 inch), less than about 0.23 mm (0.009 inch), less than about 0.20 mm (1/128 inch, 0.0078125 inch), less than about 0.18 mm (0.007 inch), less than about 0.13 mm (0.005 inch), or even less than about 0.10 mm (1/256 inch, 0.00390625 inch)). In one configuration lhe desired bîomass falls through lhe perforations or screen and thus biomass larger than lhe perforations or screen are not irradiated. These larger materials can be re-processed, for example by comminuling, or lhey can simpîy be removed from processing. In anolher configuration material lhat is larger than the perforations is irradiated and lhe smaller material is removed by lhe screening process or recycled. In this kind of a configuration, lhe conveyor, such as a vibratory conveyor, itself (for example a part of lhe conveyor) can be perforated or made wîlh a mesh. For example, in one particular embodiment lhe biomass material may be wet and lhe perforations or mesh allow water to drain away from the biomass beforc irradiation.

Screening of material can also be by a manual method, for example by an operator or mechanoîd (e.g., a robot equipped with a color, rcflectivity or other sensor) lhat removes unwanted material. Screening can also be by magnetic screening wherein a magnet is disposed near lhe conveyed material and the magnetic material is removed magnetically.

Option al pre-treatment processing can include heating lhe material. For example a portion of a conveyor conveying lhe biomass or other material can be sent through a heated zone. The heated zone can be created, for example, by IR radiation, microwaves, combustion {e.g., gas, coal, oil, biomass), résistive heating and/or inductive coîls. The heat can be applied from at least one side or more than one side, can bc continuous or periodic and can be for only a portion of lhe material or ail lhe material. For example, a portion of lhe conveying trough can be heated by use of a heating jacket Heaiing can bc, for example, for lhe purpose of drying lhe material. In lhe case of drying lhe material, this can also be facilitated, wilh or wilhout heating, by lhe movement of a gas {e.g., air, oxygen, nitrogen, He, CO2, Argon) over and/or through lhe biomass as it is being conveyed.

Optionally, pre-treatment processing can include cooling the material. Cooling material is described in US Pat. No. 7,900,857 published March 8,2011, the disclosure of which in incorporated herein by reference. For example, cooling can be by supplying a cooling fluid, for exemple water (e.g., with glyccrol), or nitrogen (e.g., liquid nitrogen) to the 5 bottom of the conveying trough. Altematively, a cooling gas, for example, chilied nitrogen can bc blown over the biomass materials or under the conveying System.

Another optional pre-treatment processing method can include adding a material to the biomass or other feedstocks. The additional material can bc added by, for example, by showering, sprinkling and or pouring the material onto the biomass as it is conveyed.

Materials that can be added include, for example, metals, cc ramies and/or ions as described in U.S. Pat App. Pub. 2010/0105119 Al (filed October 26,2009) and U.S. Pat App. Pub. 2010/0159569 Al (filed December 16, 2009), the entire disclosures of which are incorporated herein by reference. Optional materials that can be added include acids and bases, Other materials that ean be added are oxidants (e.g., peroxides, chlorates), polymers, polymerizable monomers (e.g., containîng unsaturated bonds), water, catalysts, enzymes and/or organisms. Materials can bc added, for example, in pure form, as a solution in a solvent (e.g., water or an organic solvent) and/or as a solution. In some cases the solvent is volatile and can be made to evaporate e.g., by heating and/or blowing gas as previously described. The added material may form a uniform coating on the biomass or be a homogeneous mixture of different components (e.g., biomass and additional material). The added material can modulatc the subséquent irradiation step by increasing the efficiency of the irradiation, damping the irradiation or changing the effect of the irradiation (e.g., from électron beams to X-rays or heat). The method may hâve no impact on the irradiation but may be useful for further downstream processing. The added material may help in conveying the material, for example, by lowering dust Ievels.

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

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 03 inches, between about 0.3 and 0.9 inches, between about 02 and 0.5 inches between about 0.25 and 1.0 inches, between about 0.25 and 0.5 inches, 0.100 5 +/- 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, 0350 +/- 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 throughpuL For example the material can be conveyed at rates of at least 1 ft/min, e.g., at least 2 ft/min, at least 3 ft/min, at least 4 ft/min, at least 5 ft/min, at least 10 ft/min, at least 15 ft/min, 20,25,30,35,40,45,50 ft/min. The rate of conveying is related to the beam current, for example, for a *4 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 the radiation zone, optional post-treatment processing can be done. The optional post-treatment processing can, for example, be a process described with respect to the pre-irradiation processing. For example, 20 the biomass can be sctccncd, heated, cooled, and/or combined with additives. Uniquclyto post-irradiation, qucnching of the radicals can occur, for example, quenching of radicals by the addition of fluids or gases (e.g., oxygen, nitrous oxide, ammonia, liquids), using pressure, heat, and/or the addition of radical scavengers. For example, the biomass can be conveyed out of the enclosed conveyor and exposed to a gas («.g., oxygen) where it is quenched, forming carboxylated groups. In one embodiment the biomass is exposed during irradiation to the reactive gas or fluid. Quenching of biomass that has been irradiated is described in U.S. PaL No. 8,083,906 published Dec 27,2011, 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-conlaining material. These processes 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., recyclcd paper, starchy materials, or switchgrass) is prepared by shearing or shredding.

Mechanicai treatment may reduce the bulk density of the carbohydrate-containing matenal, increase the surface area of the carbohydrate-containing material and/or decrease one or more dimensions of the carbohydrate-containing material.

Altcmativcly, or in addition, the feedstock material can be treated with another treatment, for example chemical treatments. such as with an acid (HCl, II2SO4, HjPCh). a base (e.g., KOHand NaOH), a chemical oxidant (e.g., peroxides, chlorates, ozone), irradiation, s team explosion, pyrolysis, sonication, oxidation, chemical treatment. The treatments can be in any order and in any sequence and combinations. For example, the feedstock material can first be physically treated by one or more treatment methods, e.g., chemical treatment including and in combination with acid hydrolysis (e.g., utilizing HCl, H2SO4, H3PO4). radiation, sonication, oxidation, pyrolysis or steam explosion, and then mechanlcally treated. This sequence can be advantageous since materials treated by one or more of the other treatments, e.g., irradiation or pyrolysis, tend to be more brittle and, therefore, it may be easier to further change the structure of the material by mechanicai treatment As another example, a feedstock material can be conveyed through ionizing radiation using a conveyor as described herein and then mcchanically 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 prehydrolyzed 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-hydrolyzcd materials, for example with about 50% or more non-hydrolyzed material, with about 60% or more non- hydrolyzed material, with about 70% or more non-hydrolyzed material, with about 80% or more non-hydrolyzed material or even with 90% or more non-hydrolyzed material.

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

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 mil!, Wiley mil], grist mill or other 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-to· width, or spécifie surface areas ratios. Physical préparation can increase the rate of reactions, improve the movement of material on a conveyor, improve the irradiation profile 10 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 rcagents, such as reagents in a solution.

The bulk density of feedstocks can be controlled (e.g., increased). In some situations, it can be désirable to prépare a low bulk density material, e.g., by densifytng the 15 material (e.g., densification can make it easîer and less costly to transport to another site) and then reverting the material to a lower bulk density state (e.g., after transport). The material can be densified, for example from less than about 0.2 g/cc to more than about 0.9 g/cc (e.g., less than about 0.3 to more than about 0.5 g/cc, less than about 0.3 to more than about 0.9 g/cc, less than about 0.5 to more than about 0.9 g/cc, less than about 0.3 to more than about 20 0.8 g/cc, less than about 0.2 to more than about 0.5 g/cc). For exampie, the material can be densified by the methods and equipment disclosed in U.S. Pat. No. 7,932,065 to Mcdoff 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 25 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 indudes fibers provided by shearing a fiber source. For exampie, the shearing can be performed with a rotary knife cutter.

For example, a fiber source, e.g., that is récalcitrant or that has had ils 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 screwshredder, such as those manufactured by Munson (Utica, N·Y.). As an alternative toshredding, 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 arc, e.g., 10 inches wide by 12 inches long.

In some embodiments, the shearing of the fiber source and the passîng 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 10 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.

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, 15 oxidation, pyrolysis or steam explosion. Treatment methods can be used în 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 times. Other processes that change a molccular structure of a biomass feedstock may also be used, alone or in combination with the processes disclosed herein.

Mechanical trcatments that may be used, and the characteristics of the mechanically treated carbohydratc-containing materials, are described in further detail in U.S. Pat. App. Pub. 2012/0100577 Al, filed October 18,2011, the full disclosure of which is hereby incorporated herein by référencé.

SONICATION, PYROLYSIS, OXIDATION, STEAM EXPLOSION, HEATING

If desired, one or more sonication, pyrolysis, oxidation, heating or steam explosion processes can be used instead of or in addition to irradiation to rcduce or further reduce the recalcitrance of the carbohydratc-containing material. For example, these processes can be 30 applied before, during and or after irradiation. These processes arc described in detail in U.S. Pat No. 7,932,065 to Medoff, the full disclosure of which is incorporated herein by reference.

Altematively, the biomass can be heated after the biomass is treated by one or more of sonication, pyrolysis, oxidation, radiation and steam explosion processes. For example the 35 biomass can be heated after the biomass is irradiated prior to a saccharification step. The

heating can be created, for example, by IR radiation, microwaves, combustion (e.g., gas, coal, oil, and/or biomass), résistive heating and/or inductive coils. This heating can be in a Iiquid, for example, in water or other water-based solvents. The heat can be applied from at least one side or more than onc side, can be continuons or pcriodic and can bc for only a portion of the material or ali the material. The biomass can be heated to températures above about 90 dcg C in an aqueous Iiquid that may hâve an acid or a base présent. For example, the aqueous biomass sluny can be heated to between about 90 and 150 deg C (e.g., between about 105-145 deg C., between about 110 to 140 deg C., or 115- 135 deg C). The lime that the aqueous biomass mixture is held at the targeted température range is 1 to 12 hours (e.g,,

1 to 6 hours, 1 to 4 hours). In some instances, the aqueous biomass mixture is alkaline and the pH is between 6 and 13 (e.g., 8-12, or 8-11)

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. For example, intermediates and products such as organic acids, salts of organic acids, anhydrides, esters of organic acids and fuels, e.g., fuels for internai combustion engines or feedstocks for fuel cells can be produced. Systems and processes are described herein that can use as feedstock cellulosic and/or lignoccllulosic materials that arc readiiy available, but oficn can bc difficult to process, e.g., municipal waste streams and waste paper streams, such as streams that include newspaper, kraft paper, corrugated paper or mixtures of these.

Spécifie examples of products include, but are not limited to, hydrogen, sugars (e.g., glucose, xylose, arabinosc, mannose, galactose, fructose, disaccharides, oligosaccharides and 25 polysaccharides), alcohols (e.g., monohydric alcohols or dihydric alcohols, such as éthanol, n-propanol, isobutanol, sec-butanol, tert-butanoi 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-hexanc, biodiesel, bio-gasoline and mixtures thereof), co-products (e.g., proteins, such as cellulolytic 30 proteins (enzymes) or single cell proteins), and mixtures of any of thèse in any combination or relative concentration, and optionally in combination with any additives (e.g., fuel additives). Other examplcs 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., acetaldchyde), alpha and 35 beta unsaturated acids (e.g., acrylic acid) and oleftns (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, ribito], mannitol, dulcitol, fucitol, iditol, isomalt, maltitoi, lactitol, xylitol and other polyols), and methyl or ethyl esters of any of these alcohols. Other products include methyl aerylatc, melhylmethacrylate, laetic acid, citric acid, formic acid, acetic acid, propionîc acid, butyric acid, succinic acid, valeric acid.caproic acid, 3-hydroxypropionic acid, palmitic acid, stearic acid, oxalic acid, malonîc acid, glutaric acid, oleic acid, linoleic acid, glycolic acid, gammahydroxybutyric acid, and mixtures thereof, salts of any of these acids, mixtures of any of the acids and their respective salts.

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

Any of the products or combinations of products described herein may be sanilized or sterilized prior to selling the products, e.g., after purification or isolation or even after packaging, to neutralize one or more potentially undesirable contaminants that could be présent in the product(s). Such sanitation can be done with électron bombardment, for exampie, by at a dosage of less than about 20 Mrad, e.g., from about 0.1 to 15 Mrad, from about 0.5 to 7 Mrad, or from about 1 to 3 Mrad.

The proccsscs described herein can producc various by-product streams useful for gênera ting steam and clectricity to bc used in other parts of the plant (co-gcncration) or sold on the open market For exampie, steam generated from buming by-product streams can be used in a distillation process. As another example, electricity generated from buming byproduct streams can be used to power électron beam generators used in pretreatment

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

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

LIGNIN DERIVED PRODUCTS

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

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

When used as a dispersant, the lignin or lignosulfonates can be used, e.g., concreLe · 15 mixes, clay and ceramics, dyes and pigments, leather tanning and in gypsum board.

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

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

For energy production lignin generally has a higher energy content than holocellulose (cellulose and hemicellulose) since it contains more carbon than homocellulose. For example, dry lignin can hâve an energy content of between about 11,000 and 12,500 BTU per pound, compared to 7,000 an 8,000 BTU per pound of holocellulose. As such, lignin can 25 be dcnsified and converted into briquettes and pellets for buming. For example, the lignin can be converted into pellets by any method described herein. For a slower buming pellet or ' briquette, the lignin can be crosslinked, such as applying a radiation dose of between about 0.5 Mrad and 5 Mrad. Crosslînking can make a slower buming form factor. The form factor, such as a pellet or briquette, can be converted to a “synthetic coal” or charcoal by pyrolyzing in the absence of air, e.g., at between 400 and 950 °C. Prior to pyrolyzing, it can be désirable to crosslink the lignin to maintain structural integrity.

SACCHARIFICATION

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. The low molecular weight carbohydrates can then be used, for example, in an existing manufacturing plant, such as a single cell protein plant, an enzyme manufacturing plant, or a fuel plant, e.g., an éthanol manufacturing facility.

The feedstock can be hydrolyzed using an enzyme, e.g., by combining the materials and the enzyme in a solvent, e.g., ïn 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 (betaglucosidases).

Du ring saccharification a cellulosic substrate can be ini tially hydrolyzed by endoglucanases atrandom locations producing oligomeric intermediates. These intermediates arc then substrates for cxo-splitting glucanases such as cellobiohydrolasc to producc cellobiose from the ends of the cellulose polymer. Ccllobiose is a water-soluble 1,4-linked dimer of glucose. Finally, cellobiase cleaves cellobiose to yield glucose. The efficiency (e.g., time to hydrolyze and/or completeness of hydrolysis) of this process dépends on the recalcitrance of the cellulosic material.

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

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 bc mixed during saccharification, e.g., using jet mixîng as described in International App. No. PCT/US201Q/035331, fïled May 18,

2010, which was published in English as WO 2010/135380 and desîgnated the United States, the full disclosure of which is incorporated by reference herein.

The addition ofsurfactants can enhance the rate ofsaccharification. Examples of surfactants include non-ionic surfactants, such as a Tween® 20 or Tween® 80 polyethylene 10 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 bc removed, e.g., by évaporation, to increase the concentration of the sugar solution. This reduces the volume to be shipped, and 15 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 anti microbial additive, e.g., a broad spectrum antibiotic, in a low concentration, e.g., 50 to 150 ppm. Other suitable antïbiotics include amphotericinB, ampicillin, chloramphenicol, ciprofloxacin, gentamicin, hygromycin B, kanamycin, neomycin, penicillin, puromycin, streptomycin. For example, antimicrobiais from Lallemand Biofuels and Distilled Spirits (Montreal, Quebec, Canada) can be used such as LACTOSIDE V™, BACTENIX® V300, BACTENIX® V300SP, ALLPEN™ SPECIAL, BACTENLX® V60, BACTENIX® V60SP, BACTENIX® V50 and/or LACTOSIDE 247™. 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 bc used. Preferably the antimicrobial additive(s) are food-grade.

A relatively high concentration solution can bc obtained by limiting the amount of water added to the carbohydratc-containing material with the enzyme. The concentration can be controlled, e.g., hy controlling how much saccharification takes place. Fbr 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 bc 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^eC, 60-80^eC, or even higher.

SACCHAR1FYING AGENTS

Suitable cellulolytic enzymes include celluloses from species in the généra Bacillus, Coprinus, Myceliophthora, Cephalosporium, Scytalidium, Pénicillium, Aspergillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, Chrysosporium and Trichoderma, especially those produced by a strain selected from the species Aspergillus (see, e.g., EP Pub. No. 0 458 162), Humicola insolens (reclassified as Scytalidium ihermophilum, see, e.g., U.S. Pat. No. 4,435,307), Coprinus cinereus, Fusarium oxysporum, Myceliophthora thermophila, Meripiius gtganteus, 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 AIIU 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 299.70H. Cellulolytic enzymes may also be obtained from Chrysosporium, preferably a strain of Chrysosporium lucknowense. Additional strains that can be used include, but are not limited to, Trichoderma (particularly T. viride, T. reesei, and T. koningii), alkalophilic

Bacillus (see, for example, U.S. PaL No. 3,844,890 and EP Pub. No. 0 458 162), and Streptomyces (see, e.g., EP Pub. No. 0 458 162).

In addition to or in combination to enzymes, acids, bases and other chemicals (e.g., oxidants) can be utilized to saccharify lignocellulosic and cellulosic materials. These can be used in any combination or sequence (e.g., before, after and/or during addition of an enzyme). For exampie strong minera! acids can be utilized (e.g. I1C1, II2SO4, HjPCh) and strong bases (e.g., NaOII, KOII).

SUGARS

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

HYDROGENATION AND OTHER CHEMICAL TRANSFORMATIONS

The processes described herein can inciude hydrogénation. For example glucose and xylose can be hydrogenated to sorbitol and xylîtol respectively. Hydrogénation can be accomplîshed by use of a catalyst (e.g., Pt/gamma-AhOj, Ru/C, Raney Nickel, or other catalysis 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 the 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 in USSN 13/934,704 filed July 3,2013, the entire disclosure of which is incoiporated herein by référencé 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, whiie the optimum pli 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 lhermophilic microorganisms prefer higher températures.

In some embodiments, e.g., when anaérobie organisms are used, at least a portion of the fermentation is conducted in the absence of oxygen, e.g., under a blanket of an inert gas such as N₂, Ar, He, 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 bc isolated via any means known in the art Thése intermediate fermentation products can be used in préparation offood for human or animal consumption. Addîtionally or altcmatively, the intermediate fermentation products can be ground to a fine particle size in a stainlcss-steel laboratory mill to produce a flour-like substance. Jet mixing may be used during fermentation, and in some cases saccharification and fermentation are performed in the same tank.

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

Fermentation*’ includes the methods and products that are disclosed in applications

No. PCT/US2012/71093 published June 27, 2013, PCT/ US2012/71907 published June 27, 2012, and PCT/US2012/71083 published June 27,2012 the contents of which are incorporated by référencé herein in their entirety.

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

FERMENTATION AGENTS

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

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

the genus Sacchromyces spp. (including, but not limited to, £ cerevisiae (baker’s yeast), S. distaticus, S. uvarum), the genus Kluyveromyces, (including, but not limited to, K. manàanus, K. fragilis), the genus Candida (including, but not limited to, C. pseudotropicalis, and C. brassicae), Pichla stipitis (a relative of Candida shehatae), the genus Clavispora (including, 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 Uandbook on Bioethanol: Production and Utilization, Wyman, C.E., ed., Taylor & Francis, Washington, DC, 179-212)). Other suitable microorganisms include, for example, Zymomonas mobilis, Clostridium spp. (including, but not limited to, C. thermocellum (Philippidis, 1996, supra), C. saccharobutylacetonicum, C. tyrobutyricum C. saccharobutyiicum, C. Puniceum, C. beijemckii, and C. acetobutylicum), Moniliella spp. (including but not limited to M. pollinisM tomentosa, M. madida, M. nigrescens, M. oedocephaiî, M. megachiliensis), Yarrowia iipolytica, Aureobasidium sp.,

Trichosporonoides sp„ Trigonopsis variabiiis, Trichosporon sp., Moniliellaacetoabutanssp., Typhuia variabiiis, Candida magnoliae, Ustilaginomycetes sp., Pseudozyma tsukubaensis, yeast species of généra Zygosaccharomyces, Debaryomyces, Hansenula and Pichia, and fungi of the dematioid genus Torula (e.g., T.coraliina).

Many such microbial strains are publicly available, either commercially or through dcposïtorics such as the ATCC (American Type Culture Collection, Manassas, Virginia, USA), the NRRL (Agricultural Rcscarch Scvicc Culture Collection, Pcoria, Illinois, USA), or the DSMZ (Deutsche Sammlung von Mikroorganismen und Zellkulturen Gmbll, 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 Specîalties).

DISTILLATION

After fermentation, the resulting fluids can be distilled using, for example, a “bcer column” to separate éthanol and other alcohols from the majority of water and resîdual solids. The vapor exiting the beer column can be, e.g., 35% by weight éthanol and can be

fed to a rectification column. Λ mixture of nearly azeotropic (92.5%) éthanol and water from the rectification column can be purified lo 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 providc heat for this first effect.

After the first effect, solids can be separated using a centrifuge and dried in a rotary dryer. A portion (25%) of the centrifuge effluent can be recycled to fermentation and the rest sent to the second and third evaporator effects. Most of the evaporator condensate can be retumed to the process as fairly clean condensate with a small portion split off to waste water treatment to prevent build-up of low-boiling compounds.

HYDROCARBON-CONTAINING MATERIALS

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

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

CONVEYING SYSTEMS

Various conveying Systems, including and in addition to the conveying Systems already discussed herein can be used to convey the biomass material, for example, as discussed, to a vault, and under an électron beam in a vaulL Exemplary conveyors are belt 35 conveyors, pneumatic conveyors, screw conveyors, carts, trains, trains or carts on rails, elevators, front loadcrs, backhoes, crânes, vanous scrapers and shovels, trucks, and throwing devices can be used.

Optionally, inciuding and in addition to the conveying Systems described herein, one or more other conveying Systems can be encloscd. When using an cnclosurc, the cncloscd conveyor can also be purged with an inert gas so as to maintain an atmosphère at a reduced oxygen level. Keeping oxygen Ievels 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%, less than about 1%, less than about 0.1%, less than about 0.01%, or even less than about 0.001% oxygen). Purging canbe done with an inert gas inciuding, 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 bc 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 Ievels low.

The enclosed conveyor can also be purged with a reactive gas that can react with the biomass. This can be done before, during or after the irradiation process. The reactive gas can be, but is not limited to, nitrous oxide, ammonia, oxygen, ozone, hydrocarbons, aromatic compounds, amides, peroxides, azides, halides, oxyhalides, phosphides, phosphines, arsines, sulfidcs, thiols, borancs and/or hydrides. The réactivé gas can bc activated in the cnclosurc, e.g.,by irradiation (e.g., élection beam, UV irradiation, microwavc irradiation,heating, IR radiation), so that it reacts with the biomass. The biomass itsclf can be activated, for example by irradiation. Preferably the biomass is activated by the électron beam, to produce radicals which then react with the activated or unactivated réactive 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 bc boiled off from a compressed gas such as liquid nitrogen or sublimed from solid carbon dioxide. As an alternative example, the gas can be cooled by a chiller or part of or the entire conveyor can be cooled.

OTHER EMBODIMENTS

Any material, processes or processed materials discussed herein can be used to make products and/or intermediates such as composites, fillcrs, binders, plastic additives,

adsorbcnts and controlled release agents. The methods can include densification, for example, by applying pressure and heat to the materials. For example composites can be made by combining fibrous materials with a resin or polymer. For exampie radiation crosslinkable resin, e.g., a thermoplastic resin ean bc combined with a fibrous material to providc 5 a fibrous material/cross-linkable resin combination. Such materials can be, for example, useful as building materials, piotective sheets, containers and other structural materials (e.g., molded and/or extruded products). Absorbents can bc, for example, in the form of pellets, chips, fibers and/or sheets. Adsorbents can be used, for example, as pet bedding, packaging material or in pollution contrat Systems. Controlled release matrices can also be the form of, 10 for example, pellets, chips, fibers and or sheets. The controlled release matrices can, for example, bc used to release drugs, biocides, fragrances. For example, composites, absorbents and control release agents and their uses are described in U.S. Serial No. PCT/US2006/010648, filed March 23, 2006, and US Patent No. 8,074,910 filed November 22,2011, the entire disclosures of which arc herein incorporated by référence.

In some instances the biomass material is treated at a first level to reduce recalcitrance, e.g., utilizing accelerated électrons, to selectively release one or more sugars (e.g., xylose). The biomass can then be treated to a second level to release one or more other sugars (e.g., glucose). Optionally the biomass can be dried between treatments. The treatments can include applying chemical and biochemical treatments to release the sugars.

For exampie, a biomass material can bc treated to a level of less than about 20 Mrad (e.g., less than about 15 Mrad, less than about 10 Mrad, less than about 5 Mrad, less than about 2 Mrad) and then treated with a solution of sulfuric acid, containing less than 10% sulfuric acid (e.g., less than. about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1%, less than about 0.75%, less than about 0.50 %, less than about 0.25%) to release xylose. Xylose, for example, that is released Into solution, can bc separated from solids and optionally the solids washed with a solvent/solution (e.g., with water and/or acidified water). Optionally, the solids can be dried, for example, in air and/or under vacuum optionally with heating (e.g., below about 150 deg C, below about 120 deg C) to a water content below about 25 wt% (below about 20 wL%, below about 15 wL%, below about 10 wt.%, below about 5 wt.%). The solids can then be treated with a level of less than about 30 Mrad (e.g., less than about 25 Mrad, less than about 20 Mrad, less than about 15 Mrad, less than about 10 Mrad, less than about 5 Mrad, less than about 1 Mrad or even not at ail) and then treated with an enzyme (e.g., a cellulase) to release glucose. The glucose (e.g., glucose in solution)

can be separated from the remaining soiids. The soiids can then be further processed, for example, utilized to make energy or other products (e.g,, lignin derived products).

FLAVORS, FRAGRANCES AND COLORANTS

Any of the products and/or intermediates described herein, for example, produced by the processes, Systems and/or equipment described herein, can be combined with flavors, fragrances, colorants and/or mixtures of these. For example, any one or more of (optionally along with flavors, fragrances and/or colorants) sugars, organic acids, fuels, polyols, such as 10 sugar alcohols, biomass, fibers and composites can be combined with (e.g., formulated, mixed or reacted) or used to make other products. For example, one or more such product can be used to make soaps, détergents, candies, drinks (e.g., cola, wine, beer, liquors such as gin or vodka, sports drinks, coffees, teas), pharmaceuticals, adhesives, sheets (e.g., woven, none woven, filters, tissues) and/or composites (e.g., boards). For example, one or more such 15 product can be combined with herbs, flowers, petals, spices, vitamins, potpourri, or candies.

For example, the formulated, mixed or reacted combinations can hâve flavors/fragrances of grapefruit, orange, apple, raspberry, banana. lettuce, celery, cinnamon, chocolaté, vanilla, peppermint, mint, onion, garlic, pepper, saffron, ginger, milk, wine, beer, tea, Jean beef, fish, clams, olive oil, coconut fat, pork fat, butter fat, beef bouillon, legume, potatoes, 20 marmalade, ham, coffcc and chceses.

Flavors, fragrances and colorants can be added in any amount, such as between about 0.001 wt.% to about 30 wt.%, e.g., between about 0.01 to about 20, between about 0.05 to about 10, or between about 0.1 wt.% to about 5 wt.%. These can be formulated, mixed and or reacted (e.g., with any one of more product or intermediate described herein) by any means and in any order or sequence (e.g., agitated, mixed, emulsified, gelled, infused, heated, sonicated, and/or suspended). Fillers, binders, emulsifier, antioxidants can also be utilized, for example protein gels, starches and silica.

In one embodiment the flavors, fragrances and colorants can be added to the biomass immediately after the biomass is irradiated such that the reactive sites created by the irradiation may react with reactive compatible sites of the flavors, fragrances, and colorants.

The flavors, fragrances and colorants can be naturel and/or synthetic materials. These materials can be one or more of a compound, a composition or mixtures of these (e.g., a formulated or naturel composition of severa] compounds). Optionally the flavors, fragrances, antioxidants and colorants can be derived biologically, for example, from a fermentation process (e.g., fermentation of saccharified materials as described herein). Altematively, or additionally these flavors, fragrances and colorants can be harvested from a whole organism (e.g., plant, fungus, animal, bacteria or yeast) or a part of an organism. The organism can be collected and or extracted to provide color, flavors, fragrances and/or antioxidant by any means including utilizing the methods, Systems and equipment described herein, bot water extraction, supcrcritical fluid extraction, chemical extraction (e.g., solvent or reactive extraction including acids and bases), mechanical extraction (e.g., pressing, comminuting, filtering), utilizing an enzyme, utilizing a bacteria such as to break down a starting material, and combinations of these methods. The compounds can be derived by a cbemical reaction, for example, the combination of a sugar (e.g., as produced as described herein) with an amino acid (Maillard réaction). The flavor, fragrance, antioxidant and/or colorant can be an intermediate and or product produced by the methods, equipment or Systems described herein, for example and ester and a lignin derived product.

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

Among the colorants inorganic compounds, minerais or organic compounds can be used, for exampie titanium dioxidc, zinc oxide, aluminum oxide, cadmium ycllow (E.g., CdS), cadmium orange (e.g., CdS with some Se), alizarin crimson (e.g., synthetic ornonsynthetic rose madder), ultramarine (e.g., synthetic ultramarine, naturel uitramarine, synthetic ultramarine violet ), cobalt blue, cobalt yellow, cobalt green, viridian (e.g., hydrated chromium(III)oxide), chalcophylite, conicbalcite, comubitc, comwallite and lïroconite. Black pigments such as carbon black and self-dispersed blacks may be used.

Some flavors and fragrances that can be utilized include ACALEA TBIIQ, ACET C6, ALLYL AMYL GLYCOLATE, ALPI IA TERPINEOL, AMBRETTOLIDE, AMBRIN OL 95, ANDRANE, APHERMATE, APPLELIDE, BACDANOL®, BERGAMAL, BETA Ι0Ν0ΝΕ EPOXIDE, BETA NAPHTHYLISO-BUTYL ETHER, B1CYCLONONALACTONE, BORNAHX®, CANTHOXAL, CASHMERAN®, ' CASHMERAN® VELVET, CASSIFFIX®, CEDRAFIX, CEDRAMBER®, CEDRYL ACETATE, CELESTOLIDE, CINNAMALVA, CITRAL DLMETHYL ACETATE, CITROLATE™, CITRONELLOL 700, CITRONELLOL 950, CITRONELLOL COEUR, CTTRONELLYL ACETATE, CITRONELLYL ACETATE PURE, CITRONEIiYL

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

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

GALAXOLIDE® UNDILUTED, GALBASCONE, GERALDEIIYDE, GERANIOL 5020, GERANIOL 600 TYPE, GERANIOL 950, GERANIOL 980 (PURE), GERANIOL CFT COEUR, GERANIOL COEUR, GERANYL ACETATE COEUR, GERANYL ACETATE, PURE, GERANYL FORMATE, GRISALVA, GUAIYL ACETATE, HELIONAL™, IIERBAC. HERBAUME™ HEXADECANOLIDE, HEXALON, HEXENYL

SALICYLATE CIS 3-, HYACINTH BODY, HYACINTH BODY NO. 3, HYDRATROPIC ALDEHYDEDMA, HYDROXYOL, INDOLAROME, INTRELEVEN ALDEHYDE INTRELEVEN ALDEHYDE SPECIAL, IONONE ALPHA, IONONE BETA, ISO CYCLO CTTRAL, ISO CYCLO GERANIOL, ISO E SUPER®, ISOBUTYL QUINOLINE, JASMAL, JESSEMAL®, KIIARISMAL®, KHARISMAL® SUPER, KIIUSINIL,

KOAVONE®, KOHINOOL®, UFFAROME™, LIMOXAL, LINDENOL™, LYRAL®, LYRAME SUPER. MANDARIN ALD 10% TRI ETH, CITR, MARITIMA, MCK CHINESE, MEUIFF™, MELAFLEUR, MELOZONE, METHYL ANTHRANILATE, METHYL IONONE ALPHA EXTRA, METHYL IONONE GAMMA A, METHYL IONONE GAMMA COEUR, METHYL IONONE GAMMA PURE, METHYL

LAVENDER KETONE, MONTA VERDI®, MUGUESIA, MUGUET ALDEHYDE 50, MUSKZ4, MYRAC ALDEHYDE, MYRCENYL ACETATE, NECTARATE™, NEROL 900, NERYL ACETATE, OCIMENE, OCTACETAL, ORANGE FLOWER ETHER, ORIVONE,, ORRINIFF25%, OXASPIRANE, OZOFLEUR, PAMPLEFLEUR®, PEOMOSA, PHENOXANOL®, PICONIA, PRECYCLEMONE B, PRENYL ACETATE,

PRISMANTOL, RESEDA BODY, ROSALVA, ROSAMUSK, SANJINOL,

SANTALIFF™, SYVERTAL, TERPINEOL,TERPINOLENE 20. TERPINOLENE 90 PQ, TERPINOLENE RE CT.. TERPINYL ACETATE, TERPINYL ACETATE JAX, TETRAHYDRO, MUGUOL®, TETRAHYDRO MYRCENOL, TETRAMERAN, TIMBERSILK™, TOBACAROL. TRIMOFIX® O TT, TRIPLAL®, TRISAMBER®,

VANORIS, VERDOX™, VERDOX™ UC, VERTENEX®, VERTENEX® IIC.

VERTOFIX® COEUR, VERTOLIFF, VERTOLIFF ISO, VIOLIFF, VIVALDIE, ZENOLIDE, ABS INDIA 75 PCT MIGLYOL, ABS MOROCCO 50 PCT DPG, ABS MOROCCO 50 PCT TEC, ABSOLUTE FRENCII, ABSOLUTE INDIA, ABSOLUTE MD 50 PCT BB, ABSOLUTE MOROCCO, CONCENTRATE PG, TINCTURE 20 PCT,

AMBERGRIS, AMBRETTE ABSOLUTE, AMBRETTE SEED OIL, ARMOISE OIL 70 PCTTIIUYONE, BASIL ABSOLUTE GRAND VERT, BASIL GRAND VERT ABS MD, BASIL OIL GRAND VERT, BASIL OIL VER VEINA, BASIL OIL VIETNAM, BAY OIL TERPENELESS, BEESWAX ABS N G, BEESWAX ABSOLUTE, BENZOIN RESINOID SIAM, BENZOIN RESINOID SIAM 50 PCT DPG, BENZOIN RESINOID SIAM 50 PCT 10 PG, BENZOIN RESINOID SIAM 70.5 PCT TEC. BLACKCURRANT BUD ABS 65 PCT PG, BLACKCURRANT BUD ABS MD 37 PCT TEC, BLACKCURRANT BUD ABS MIGLYOL, BLACKCURRANT BUD ABSOLUTE BURGUNDY, BOIS DE ROSE OIL, BRAN ABSOLUTE, BRAN RESINOID, BROOM ABSOLUTE ITALY, CARDAMOM GUATEMALA CO2 EXTRACT, CARDAMOM OIL GUATEMALA, CARDAMOM OIL 15 INDIA, CARROT HEART, CASSŒ ABSOLUTE EGYPT, CASSIE ABSOLUTE MD 50 PCT IPM, CASTOREUM ABS 90 PCT TEC, CASTOREUM ABS C 50 PCT MIGLYOL, CASTOREUM ABSOLUTE, CASTOREUM RESINOID, CASTOREUM RESINOID 50 PCT DPG, CEDROL CEDRENE, CEDRUS ATLANTICA OIL REDIST, CIIAMOMILE OIL ROMAN, CIIAMOMILE OIL WILD, CHAMOMILE OIL WILD LOW LIMONENE, 20 CINNAMON BARK OIL CEYLAN, CISTE ABSOLUTE, CISTE ABSOLUTE COLORLESS, CITRONELLA OIL ASIA IRON FREE, CIVET ABS 75 PCT PG, CIVET ABSOLUTE, CIVET TINCTURE 10 PCT, CLARY SAGE ABS FRENCII DECOL, CLARY SAGE ABSOLUTE FRENCII, CLARY SAGE C'LESS 50 PCT PG. CLARY SAGE OIL FRENC11, COPAIBA BALSAM, COPAIBA BALSAM OIL, CORIANDER 25 SEED OIL, CYPRESS OIL, CYPRESS OIL ORGANIC. DAVANA OIL, GALBANOL, GALBANUM ABSOLUTE COLORLESS. GALBANUM OIL, GALBANUM RESINOID. GALBANUM RESINOID 50 PCT DPG, GALBANUM RESINOID IIERCOLYN BUT, GALBANUM RESINOID TEC BUT, GENTIANE ABSOLUTE MD 20 PCT BB, GENTIANE CONCRETE, GERANIUM ABS EGYPT MD, GERANIUM ABSOLUTE 30 EGYPT, GERANIUM OIL CIIINA, GERANIUM OIL EGYPT, GINGER OIL 624,

GINGER OIL RECTIFIED SOLUBLE, GUAIACWOOD HEART, HA Y ABS MD 50 PCT BB, IIAY ABSOLUTE, IIAY ABSOLUTE MD 50 PCT TEC, IIEALINGWOOD, HYSSOP OIL ORGANIC, IMMORTELLE ABS YUGO MD 50 PCT TEC, IMMORTELLE ABSOLUTE SPAIN, IMMORTELLE ABSOLUTE YUGO, JASMIN ABS 35 INDIA MD, JASMIN ABSOLUTE EGYPT, JASMIN ABSOLUTE INDIA, ASMIN

ABSOLUTE MOROCCO, JASMIN ABSOLUTE SAMBAC, JONQUILLE ABS MD 20 PCT BB. JONQUILIE ABSOLUTE France, JUNIPER BERRY OIL FLG, JUNIPER BERRY OIL RECTIFIED SOLUBLE, LABDANUM RESINOID 50 PCT TEC, LABDANUM RESINOID BB, LABDANUM RESINOID MD, LABDANUM RESINOID 5 MD 50 PCT BB, LAVANDIN ABSOLUTE II, LAVANDIN ABSOLUTE MD,

LAVANDIN OIL AB RIAL ORGANIC, LAVANDIN OIL GROSSO ORGANIC, LAVANDIN OIL SUPER, LAVENDER ABSOLUTE II, LAVENDER ABSOLUTE MD, LAVENDER OIL COUMARIN FREE, LAVENDER OIL COUMARIN FREE ORGANIC, LAVENDER OIL MAILLETTE ORGANIC, LAVENDER OIL MT, MA CE ABSOLUTE

BB, MAGNOLIA FLOWER OIL LOW METHYL EUGENOL, MAGNOLIA FLOWER OIL, MAGNOLIA FLOWER OIL MD, MAGNOLIA LEAF OIL, MANDARIN OIL MD, MANDARIN OIL MD B HT, MATE ABSOLUTE B B, MOSS TREE ABSOLUTE MD TEXIFRA 43, MOSS-OAK ABS MD TEC IFRA 43, MOSS-OAK ABSOLUTE IFRA 43, MOSS-TREE ABSOLUTE MD IPM IFRA 43, MYRRH RESINOID BB, MYRRH

RESINOID MD, MYRRH RESINOID TEC, MYRTLE OIL IR O N FREE, MYRTLE OIL TUNISIA RECTIFIED, NARCISSE ABS MD 20 PCT BB, NARCISSE ABSOLUTE FRENCH, NEROLI OIL TUNISIA, NUTMEG OIL TERPENELESS, OEILLET ABSOLUTE, OLIBANUM RESINOID, OLIBANUM RESINOID BB, OLIBANUM RESINOID DPG, OLIBANUM RESINOID EXTRA 50 PCT DPG, OLIBANUM

RESINOID MD, OLIBANUM RESINOID MD 50 PCT DPG, OLIBANUM RESINOID TEC, OPOPONAX RESINOID TEC, ORANGE BIGARADE OIL MD BUT, ORANGE BIGARADE OIL MD SCFC, ORANGE FLOWER ABSOLUTE TUNISIA, ORANGE FLOWER WATER ABSOLUTE TUNISIA, ORANGE LEAF ABSOLUTE, ORANGE LEAF WATER ABSOLUTE TUNISIA, ORRIS ABSOLUTE ITALY, ORRIS CONCRETE

15 PCT IRONE, ORRIS CONCRETE 8 PCT IRONE, ORRIS NATURAL 15 PCT IRONE

4095C, ORRIS NATURAL 8 PCT IRONE 2942C, ORRIS RESINOID, OSMANTHUS ABSOLUTE, OSMANTHUS ABSOLUTE MD 50 PCT BB, PATCHOULI HEARTN°3, PATCHOULI OIL INDONESIA, PATCHOULI OIL INDONESIA IRON FREE, PATCHOULI OIL INDONESIA MD, PATCHOULI OIL REDIST, PENNYROYAL

IIEART, PEPPERMINT ABSOLUTE MD, PETITGRAIN BIGARADE OILTUNISIA, PETITGRAIN CITRONNIER OIL, PETITGRAIN OIL PARAGUAY TERPENELESS, PETITGRAIN OIL TERPENELESS STAB, PIMENTO BERRY OIL, PIMENTO LEAF OIL, RHODINOL EX GERANIUM CHINA, ROSE ABS BULGARIAN LOW METHYL EUGENOL, ROSE ABS MOROCCO LOW METHYL EUGENOL, ROSE ABS TURKISH

LOW METHYL EUGENOL, ROSE ABSOLUTE, ROSE ABSOLUTE BULGARIAN,

ROSE ABSOLUTE DAMASCENA, ROSE ABSOLUTE MD, ROSE ABSOLUTE MOROCCO, ROSE ABSOLUTE TURKISH, ROSE OIL BULGARIAN, ROSE OIL DAMASCENA LOW METHYL EUGENOL, ROSE OIL TURKISH, ROSEMARY OIL CAMPIIOR ORGANIC, ROSEMARY OILTUNISIA, SANDALWOOD OIL INDIA,

SANDALWOOD OIL INDIA RECITHED, SANTALOL, SCHINUS MOLLE OIL, ST JOHN BREAD TINCTURE 10 PCT, STYRAX RESINOID, STYRAX RESINOID, TAGETE OIL, TEA TREEIIEART, TONKA BEAN ABS 50 PCT SOLVENTS, TONKA BEAN ABSOLUTE, TUBEROSE ABSOLUTE INDIA, VETIVER IIEART EXTRA, VETIVER OIL HAITI, VETIVER OIL HAITI MD, VETIVER OIL JAVA, VETIVER OIL 10 JAVA MD, VIOLET LEAF ABSOLUTE EGYPT, VIOLET LEAF ABSOLUTE EGYPT DECOL, VIOLET LEAF ABSOLUTE FRENCII, VIOLET LEAF ABSOLUTE MD 50 PCT BB, W0RMW00D OIL ITRPENELESS, YLANG EXTRA OIL, YLANGΙΠ OIL and combinations of these.

The colorants can be among those Iisted in the Colour Index International by the

Society of Dyeis and Colourists. Colorants include dyes and pigments and include those commonly used for coloring textiles, paints, inks and inkjet inks. Some colorants that can be utilized include carotenoids, arylide yellows, diarylide yellows, β-naphthols, naphthols, benzimidazolones, disazo condensation pigments, pyrazolones, nickel azo yellow, phthalocyanines, quinacridones, perylenes and perinones, isoindolinone and isoindoline 20 pigments, triarylcarbonium pigments, diketopyrrolo-pyrrole pigments, thioindigoids.

Cartenoids includc.g., alpha-carotene, bcta-carotcne, gamma-carotcne, lycopcnc, lutein and astaxanthin Annatto extract, Dehydrated bects (beet powder), Canthaxanthin, Caramel, βApo-8'-carotenal, Cochineal extract, Carminé, Sodium copper chlorophyllin, Toasted partially defatted cooked cottonseed flour, Ferrous gluconate, Ferrous lactate, Grape color 25 extract, Grape skin extract (enocianina), Carrot oil. Paprika, Paprika oleoresin, Mica-based pearlescent pigments, Riboflavin, Saffron, Titanium dioxide, Tomato lycopene extract; tomato lycopene concentrate, Turmeric, Tumieric oleoresin, FD&C Blue No. I, FD&C Blue No. 2, FD&C Green No. 3, Orange B, Citrus Red No. 2, FD&C Red No. 3, FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No. 6, Alumina (dried aluminum hydroxide),

Calcium carbonate, Potassium sodium copper chlorophyllin (chlorophyllin-copper complex), Dihydroxyacetone, Bismuth oxychloride, Ferrie ammonium ferrocyanide, Ferrie ferrocyanide, Chromium hydroxide green, Chromium oxide greens. Guanine, Pyrophyllite, Talc, Aluminum powder, Bronze powder, Copper powder, Zinc oxide, D&C Blue No. 4, D&C Green No. 5, D&C Green No. 6, D&C Green No. 8, D&C Orange No. 4, D&C Orange 35 No. 5, D&C Orange No. 10, D&C Orange No. 11, FD&C Red No. 4, D&C Red No. 6, D&C

Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, D&C Red No. 39, D&C Violet No. 2, D&C Yellow No. 7, Ext D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. 11, D&C Black No. 2, 5 D&C Black No. 3 (3), D&C Brown No. 1, ExL D&C, Chromium-cobalt-aluminum oxide,

Ferrie ammonium citrate, Pyrogallo], Logwood extract, l,4-Bis[(2-hydroxy-ethyl)amino]-

9.10- anthracenedionebis(2-propenoic)estercopolymers, 1,4-Bis [(2-methylphenyl)amino] -

9.10- anthraccnedione, 1,4-Bis [4- (2-methacryloxyethyl) phenylamino] anthraquinone copolymers, Carbazole violet, Chlorophyllin-copper complex, Chromium-cobalt-aluminum oxide,, C.I. Vat Orange 1,2-[[2,5-Diethoxy- 4-[(4-methyIphenyl)thiol] phenyljazo] -1,3,5benzenetriol, 16,23-Dihydrodinaphtho [2,3-a:2’,3'-i] naphth [2',3’;6,7] indolo [2,3-c] carbazole-5,10,15,17,22,24-hexone, N,N'-(9,10-DihydLro- 9,10-dioxo- 1,5-anthracenediyl) bisbenzamide, 7,16-Dichloro- 6,15-dihydro- 5,9,14,18-anthrazinetetrone, 16,17Dimethoxydinaphtho (l,2,3-cd:3',2'_tl'-lm) pcry!ene-5,10-dione, Po]y(hydroxyethyl méthacrylate) -dye copolymers(3), Reactive Black 5, Reactive Blue 21, Reactive Orange 78, Réactivé Yellow 15, Reactive Blue No. 19, Reactive Blue No. 4, C.L Reactive Red 11, C.I. Reactive Yellow 86, C.I. Reactive Blue 163, C.I. Reactive Red 180,4-((2,4dimethylphenyljazo]- 2,4-dihydro- 5-methyl-2-phenyl- 3II-pyrazol-3-one (solvent Yellow 18), 6-Ethoxy-2- (6-ethoxy-3-oxobenzo[b] thien-2(3H)- ylidene) benzo[b]thiophen- 3(2H)20 one, Phthalocyaninc grcen, Vinyl alcohol/methyl mcthacrylatc-dyc reaction products, C.I. Réactive Red 180, C.I. Reactive Black 5, C.I. Réactive Orange 78, C.I. Réactive Yellow 15, C.I. Réactivé Blue 21, Disodium l-amino-4-[[4-[(2-bromo-l-oxoally])amino]-2sulphonatophenyl]amino]-9,10-dihydro-9,10-dioxoanthracenc-2-sulphonate (Reactive Blue 69), D&C Blue No. 9, (Phthalocyaninato(2-)] copper and mixtures of these.

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 materiais, 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 b y the 30 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 paramelers 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 numencal 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 arc 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. Furthemiore, when numerical ranges are set forth herein, these ranges are inclusive of the reeïted range end points (e.g„ end points may be used). When percentages by weight are used herein, the numerical values reported are relative to the total weight.

Also, il should be understood that any numerical range recited herein is intended to include al] sub-ranges subsumed therein. For example, a range of “1 to 10” is intended to include ail sub-ranges between (and including) the recitcd minimum value of 1 and the recited maximum value of 10, lhat is, having a minimum value equal to or greater than l and a maximum value of equal to or less lhan 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, thaï is said to be incorporated by référencé herein is incorporated herein only to the extent that the incorporated material does noi conflict with existing définitions, statements, or other disclosure material set forth in thîs disclosure. As such, and to the extent nccessary, the disclosure as cxplicîtly set forth herein supersedes any conflicting material incorporated herein by référencé. Any material, or portion thereof, that is said to be incorporated by référencé 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 référencés to preferred embodiments thereof, il will be understood by those skilled in the art that various changes in form and details may be made therein without depaiting from lhe scope of the invention encompassed by the appendcd claims.

Claims

1. A method comprising:

5 exposing δ biomass material to ionîzing radiation while the biomass material is being conveyed upon a vibratoiy conveyer.

2. The method of claim 1, wherein the biomass material defines a substantially uniform thickness bed on the conveyor as it is being exposed to the ionizing radiation.

3. Ihe method of claim 1 or 2, further comprising distributing the biomass material prior to conveying the biomass material upon the vibratory conveyer and exposing the bïomass to the ionizing radiation.

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4. The method of claim 3, wherein distributing the biomass material utilizes a feeder conveying System.

5. The method of claim 4, wherein the feeder conveying system comprises a second vibratory conveying System.

6. The method of any one of claims 1-3, wherein 75% or more of the biomass material is distribu ted to be at the level of the average bed thickness.

7. The method of any one of claims 1-3, wherein 80% or more of biomass material is 25 distributed to be at the level of the average bed thickness.

8. The method of any one of claims 1-3, wherein 85% or more of the biomass material is distributed to be at the level of the average bed thickness.

30

9. The method of any one of claims 1 -3, wherein 90% or more of the biomass material is distributed to be at the level of the average bed thickness.

10. The method of any one of claims 1-3, wherein 95% or more of the biomass material is distributed to be at the level of the average bed thickness.

11. The method of any one of the preceding claims, further comprising comminuting the biomass prior to exposing the biomass to the ionizing radiation.

12. The method of claim 11, wherein comminuting is selected from the group consisting

5 of shearïng, chopping, grinding, hammermilling and combinations thereof.

13. The method of claim 11 or 12, wherein comminuting produces a biomass material with particles, and more than 80 % of the particles hâve at least one dimension that is less than about 0.25 inches.

14. The method of claim 13, wherein greater than 90 % of the particles hâve at least one dimension that is less than about 0.25 inches.

15. The method of claim 13, wherein greater than 95 % of the particles hâve at least one 15 dimension that is less than about 0.25 inches.

16. The method of any one of claims 13-15, wherein no more than 5 % of the particles are less than 0.03 inches in their greatest dimension.

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17. The method of any one of the preceding claims, wherein the source of the ionizing radiation is selected from the group consisting of an clectron beam, an ion beam, ultraviolet light with a wavelength of between lOOnm and 280nm, gamma radiation, X-ray radiation and combinations thereof.

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18. The method of any one of the preceding claims, wherein the source of the ionizing radiation is an électron beam.

19. The method of claim 18, wherein the biomass is irradiated with 10 to 200 Mrad of radiation.

20. The method of claim 18 wherein the biomass is irradiated with 10 to 25 Mrad of radiation.

21. The method of claim 18, wherein the biomass is irradiated with 10 to 75 Mrad of

35 radiation.

22. The method of claim 18, wherein the biomass is irradiated with 15 to 50 Mrad of radiation.

5

23. The method of claim 18, wherein the biomass is irradiated with 20 to 35 Mrad of radiation.

24. The method of any one of claims 18-23, wherein the energy of the électron beam is between 0.3 and 2 MeV.

25. The method of any one of claims 18-24, wherein the électron beam is supplied by an électron accelerator equipped with a scanning horn disposed above the conveyor and configured to direct the électron beam onto the biomass upon the vibratory conveyor.

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26. The method of any one of the precedïng claims, wherein the biomass material receives a substantially uniform level of ionizing radiation.

27. The method of any one of the preceding claims, wherein the biomass material comprises a cellulosic or lignocellulosic material.

28. The method of claim 27, wherein the cellulosic or lignocellulosic material comprises a lignocellulosic material selected from the group consisting of wood, paper, paper products, cotton, grasses, grain residues, bagasse, jute, hemp, flax, bamboo, sisal, abaca, corn cobs, corn stover, coconut hair, algae, seaweed, straw, wheat straw and mixtures thereof.

29. The method of any one of the preceding claims, wherein at least a portion of the conveyor comprises an enclosure.

30. The method of any one of the preceding claims, wherein exposing the biomass

30 material to ionizing radiation reduccs the recalcitrance of the biomass material.

31. The method of any one of the preceding claims, wherein the vibratory conveyer conveys the biomass material at an average speed of 3 to 100 ft/min.

32. The method of claim 31, wherein the vibratory conveyer conveys the biomass material at an average speed of 9 to 50 ft/min.

33. The method of claim 31, wherein the vibratory conveyer convcys the biomass

5 material at an average speed of 12 to 25 ft/min.

34. The method of any one of the above daims, wherein the biomass material is irradiated with an irradiator with a power output of at least 50 kW.

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35. The method of any one of the above daims, wherein the biomass material is conveyed at a rate of about 1000 to about 8000 lb/hr.

36. The method of any one of the above daims, wherein the biomass is exposed to ionizing radiation more than one lime.

37. An apparatus for producing a treated biomass material, comprising:

an ionizing radiation source; and a vibratory conveying System, wherein the vibratory conveying system is capable of conveying biomass material past the ionizing radiation source,

38. The apparatus of claim 37, further comprising an enclosure surrounding the biomass material when the biomass material is proximate to the radiation source.

39. The apparatus of daim 38, wherein the enclosure comprises a window foil integrated 25 into a wall of the enclosure, and wherein the window foil is disposed beneath the radiation source and allows passage of the électrons through the window foil and onto the biomass material.

40, The apparatus of any one of daims 37-39, further comprising a feeder conveying

30 system upstream from the vibratory conveying System, wherein the feeder conveying system is configured to spread the biomass material to form a bed of biomass material of substantially uniform depth, and where the feeder conveying system feeds the biomass material to the vibratory conveying system upstream of the radiation field.

41. The apparatus as in claim 40, wherein the feederconveying System is a vibratory conveying System.

42. The apparatus as in any one of claims 37-41, wherein the conveyor system comprises 5 structural materials including steel.