UPGRADING PROCESS STREAMS

CROSS REFERENCE TO RELATED APPLICATIONS

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

BACKGROUND OF THE INVENTION

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

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

[0004] Generally, the methods and equipment used for producing useful products from a biomass material are described herein. Generally, many methods include treating a recalcitrant biomass, e. g. treating with electron beams, and then biochemically and/or chemically processing the reduced recalcitrance material to a mixture of sugars, for example, glucose, xylose, arabinose, fructose, sugar alcohols, e. g. xylitol and other products. Salts (e.g., ions) generated during processing of the feedstock can be removed via the process of electrodialysis, e. g. common or standard electrodialysis (ED), electrodialysis reversal (EDR) and/or bipolar membrane electrodialysis (EDBM). The method of electrodialysis can help in removing the bulk salts from the sugar solution, or electrodialysis can be used to separate the organic acids from other compounds in a mixture. Prior to and/or after electrodialysis the biomass liquids can be also treated to remove other impurities and color.

[0005] In one aspect the invention features methods for removing and/or separating salts, partially ionized acids or fully ionized acids, from saccharified biomass liquids, such as including sugars and/or fermented liquids utilizing an electrodialysis system. The methods can therefor provide a processed solution (e.g., purified solution, upgraded process steam, purified process stream). Optionally, the electrodialysis system utilizes standard electrodialysis or electrodialysis reversal. Also optionally, the saccharified biomass liquids includes a reduced recalcitrance cellulosic or lignocellulosic material that has been saccharified. For example, saccharification can be done by utilizing one or more enzymes and/or one or more acids, such as sulfuric acid. For example, saccharification can be done by using an enzyme, using an acid, using an acid and then an enzyme, using an enzyme and then an acid or using an enzyme and an acid concurrently. Optionally, the cellulosic or lignocellulosic material has had its recalcitrance reduced by treatment with ionizing radiation (e.g., with between about 10 and about 50 Mrad of radiation). For example, the ionizing radiation can be in the form of accelerated electrons.

[0006] In another embodiment the saccharified product is fermented and then electrodialysis is applied with or without purification. In this embodiment fermentation broth can often include a product from converting one of the sugars to specific product and another sugar that remains unconverted during the fermentation. The fermentation broth can be subject to electrodialysis to remove salts that it been formed. Then the product can be isolated by using a bipolar electrodialysis operation. [0007] In some implementation, while utilizing the electrodialysis system, a voltage of between about 10 and 600V across ion selective membranes can be applied while flowing the saccharified biomass liquids and/or the fermentation product liquids past the membranes. Optionally, the voltage can be between 25 and 500 V. Additionally, the voltage can be 40 to 450 V. These voltages can be across multiple membranes.

[0008] In some implementations, the saccharified biomass liquids can be further processed with a fermentation step to produce fermentation products, such as an alcohol, organic acids. Optionally, the saccharified biomass liquids are liquids wherein a fermentation product (e.g., an alcohol such as ethanol, propanol or butanol or an organic acid such as acetic acid, propionic acid, succinic acid, tartaric acid, butyric acid and lactic acid) has been removed therefrom by electrodialysis or other isolation means (e.g., by distillation).

[0009] In some implementations, the ionic strength of the saccharified liquid prior to electrodialysis is between about 500 and about 50,000 μ8Λ:ιη (microSiemens/cm), and wherein an ionic strength of the saccharified biomass liquids after utilizing the electrodialysis system (e.g., the processed solution, purified solution, upgraded process steam or purified process stream) is between 1 and 100 μ8 :ιη. Optionally the salts, partially ionized acids or fully ionized acids removed during electrodialysis include at least one element selected from P, K, Mg, Na, Ca, S, Mn, Al, Zn, Si, CI and Fe. For example, the ions can be phosphates, sulfates, chlorides, silicates, aluminates, K ⁺ , Na ⁺ , Mg ²⁺ , Al ³⁺ , Zn ²⁺ , Mn ²⁺ , Fe ³⁺ , Fe ²⁺ , and mixtures of these ions.

[0010] Alternatively or additionally, the saccharified biomass liquids include saccharification residues (e.g., cells, proteinaceous, lignin derived material and/or colored bodies). In a similar manner the saccharified biomass is fermented to obtain a fermentation product stream which had fermentation residues (e.g., cells, proteinaceous, lignin derived material and/or colored bodies). In some implementations, the method can further include purifying the saccharified biomass liquids or fermentation product stream before, during and/or after utilizing the electrodialysis system. For example, purifying by a method selected from any one of the following methods: chromatography, filtration, centrifugation, precipitation, distillation, complexation and combinations thereof. When precipitation is utilized in purifying, one or more solvents or non-solvents (e.g., methanol, ethanol, isopropanol, acetone, ethyl ether and tetrahydrofuran, and mixtures of these) can be used to precipitate one or more undesired components, such as an impurity. Some implementations include decolorizing the saccharified biomass liquids or fermentation product streams with a decolorizing agent before, during and/or after utilizing the electrodialysis system. For example, decolorizing utilizing any one of powdered carbon, granular carbon, extruded carbon, bone char carbon, bead activated carbon, styrenic resins, acrylic resins, magnetic resins, decolorizing clays, bentonite, attapulgite, montmorillonite, hormite and combinations of these. For example mixing the saccharified biomass liquids or fermentation product stream and filtering away the solids, or flowing (e.g., filtering) the saccharified biomass liquids these solids. The solution after decolorization can be less than about 100 color units (e.g., less than 50, less than about 40, less than about 30, less than about 20, less than about 10, less than about 5 and even less than about 1).

[0011] In some implementations, the saccharified biomass liquids include one or more saccharides, e.g., a monodisaccharide, an oligosaccharides and/or a polysaccharide. Optionally the saccharified biomass liquids include a sugar selected from xylose, glucose, arabinose, fructose and mixtures of these. Optionally, the sugar is xylose and the purity of the processed solution (e.g., purified solution, upgraded process steam, purified process stream) after utilizing the electrodialysis system is at least about 80 wt. xylose (e.g., the wt.% of the xylose to the total solids/dissolved solids in solution as determined analytically by HPLC). For example, after electrodialysis the xylose purity is at least 85 wt.%, at least 90 wt.%, at least 95 wt.%, at least 96 wt.%, at least 97 wt.% or even at least 98 wt.%). Optionally, the sugar includes arabinose, and the purity of the solution after utilizing the electrodialysis system is about 0.5 wt.% arabinose (e.g., about 1 to 0 wt.%, about 1 to 0.1 wt.%, about 0.8 to 0.1 wt.%, about 0.8 to 0.2 wt.%, about 0.5 to 1.0 wt.%, about 0.1 to 0.5 wt.%).

[0012] These saccharified biomass liquids with sugars present can be fermented to produce additional biomass liquids. Examples of the fermentation include adding microorganisms that selectively convert one sugar in preference to another. For instance, in a saccharified biomass liquid with glucose and xylose present a microorganism can be chosen which can selectively convert glucose to ethanol while leaving the xylose basically unreacted. In a similar manner glucose can be selectively converted to D- or L- lactic acid.

[0013] Removing the ions (e.g., salts, fully or partially dissociated acids) from the sugar solutions derived from cellulosic and lignocellulosic biomass liquids is

advantageous because it increases the purity of the processed solution (e.g., purified solution, upgraded process steam, purified process stream) and assists in subsequent separation of the various product steams such as sugars. This ultimately can aid in further transformations of these process streams into high value produces such as sugars, sugar alcohols (e.g., xylose, arabinose, xylitol and sorbitol). For example, it can be easier to crystalize sugars and other products without salts present. Other features and advantages of the invention will be apparent from the following detailed description, and from the claims.

[0014] Implementations of the embodiments can optionally include one or more of the following summarized features. In some implementations, the selected features can be applied or utilized in any order while in other implementations a specific selected sequence is applied or utilized. Individual features can be applied or utilized more than once in any sequence and even continuously. In addition, an entire sequence, or a portion of a sequence, of applied or utilized features can be applied or utilized once, repeatedly or continuously in any order. In some optional implementations, the features can be applied or utilized with different, or where applicable, the same set or varied, quantitative or qualitative parameters as determined by a person skilled in the art. For example, parameters of the features such as size, individual dimensions (e.g., length, width, height), location of, degree (e.g., to what extent such as the degree of

recalcitrance), duration, frequency of use, density, concentration, intensity and speed can be varied or set, where applicable, as determined by a person of skill in the art.

[0015] Features, for example, include: a method for removing salts, partially ionized acids or fully ionized acids, from saccharified biomass liquids utilizing an electrodialysis system; a method that utilizes electrodialysis; electrodialysis reversal; a method that utilizes bipolar membrane electrodialysis treating a liquid, where the liquid includes a reduced recalcitrance, cellulosic or lignocellulosic material that has been saccharified; treating a liquid, where the liquid includes a cellulosic or lignocellulosic material that has had its recalcitrance reduced by treatment with ionizing radiation; treating a liquid, where the liquid includes a cellulosic or lignocellulosic material that has had its recalcitrance reduced by treatment with accelerated electrons; treating a liquid, where the liquid includes a cellulosic or lignocellulosic material that has been saccharified utilizing one or more enzymes; treating a liquid, where the liquid includes a cellulosic or lignocellulosic material that has been saccharified utilizing one or more acids; treating a liquid, where the liquid includes a cellulosic or lignocellulosic material that has been saccharified utilizing sulfuric acid; an ionic strength of the saccharified biomass liquids prior to electrodialysis is between about 500 and about 50,000 μ8/οιη, and an ionic strength of the saccharified biomass liquids after electrodialysis is between 1 and 100 μ8/οιη; salts, partially ionized acids or fully ionized acids that include the element phosphorous are removed utilizing an electrodialysis system; salts, partially ionized acids or fully ionized acids that include the element potassium are removed utilizing an electrodialysis system; salts, partially ionized acids or fully ionized acids that include the element magnesium are removed utilizing an electrodialysis system; salts, partially ionized acids or fully ionized acids that include the element sodium are removed utilizing an electrodialysis system; salts, partially ionized acids or fully ionized acids including the element calcium are removed utilizing an electrodialysis system; salts, partially ionized acids or fully ionized acids that include the element S are removed utilizing an electrodialysis system; salts, partially ionized acids or fully ionized acids that include the element oxygen are removed utilizing an electrodialysis system; salts, partially ionized acids or fully ionized acids that include the element manganese are removed utilizing an electrodialysis system; salts, partially ionized acids or fully ionized acids that include the element aluminum are removed utilizing an electrodialysis system; salts, partially ionized acids or fully ionized acids that include the element zinc are removed utilizing an electrodialysis system; salts, partially ionized acids or fully ionized acids that include the element silicon are removed utilizing an electrodialysis system; salts, partially ionized acids or fully ionized acids that include the element chloride are removed utilizing an electrodialysis system; salts, partially ionized acids or fully ionized acids that include the element Fe are removed utilizing an electrodialysis system;

purifying a saccharified biomass liquids utilizing chromatography; purifying a saccharified biomass liquids utilizing filtration; purifying a saccharified biomass liquids utilizing centrifugation; purifying a saccharified biomass liquids utilizing precipitation; purifying a saccharified biomass liquids utilizing distillation; purifying a saccharified biomass liquids utilizing complexation; purifying a saccharified biomass liquids by the addition of one or more solvents or non-solvents to precipitate one or more undesired components; purifying a saccharified biomass liquids by the addition of methanol to precipitate one or more undesired component; purifying a saccharified biomass liquids by the addition of ethanol to precipitate one or more undesired components; purifying a saccharified biomass liquids by the addition of isopropanol to precipitate one or more undesired components; purifying a saccharified biomass liquids by the addition of acetone to precipitate one or more undesired components; purifying a saccharified biomass liquids by the addition of ethyl ether to precipitate one or more undesired components; purifying a saccharified biomass liquids by the addition of tetrahydrofuran to precipitate one or more undesired components; treating a saccharified biomass liquids that includes one or more fermentation products; treating a saccharified biomass liquids that includes liquids that have had a fermentation product and the fermentation product has been distilled therefrom; treating a saccharified biomass liquids that includes liquids that have had an alcohol fermentation product and the alcohol has been distilled therefrom; treating a saccharified biomass liquids that includes liquids that have had an ethanol fermentation product and the ethanol has been distilled therefrom; decolorizing a saccharified biomass liquids utilizing a decolorizing agent; decolorizing a saccharified biomass liquids utilizing a decolorizing agent including powdered carbon; decolorizing a saccharified biomass liquids utilizing a decolorizing agent including granular carbon; decolorizing a saccharified biomass liquids utilizing a decolorizing agent including extruded carbon; decolorizing a saccharified biomass liquids utilizing a decolorizing agent including bone char carbon; decolorizing a saccharified biomass liquids utilizing a decolorizing agent including bead activated carbon; decolorizing a saccharified biomass liquids utilizing a decolorizing agent including styrenic resins; decolorizing a saccharified biomass liquids utilizing a decolorizing agent including acrylic resins; decolorizing a saccharified biomass liquids utilizing a decolorizing agent including magnetic resins; decolorizing a saccharified biomass liquids utilizing a decolorizing agent including decolorizing clays; a method that includes decolorizing a saccharified biomass liquids utilizing a decolorizing agent including bentonite; a method that includes decolorizing a saccharified biomass liquids utilizing a decolorizing agent including attapulgite; decolorizing a saccharified biomass liquids utilizing a decolorizing agent including montmorillonite; decolorizing a saccharified biomass liquids utilizing a decolorizing agent including hormite; decolorizing a saccharified biomass liquids utilizing a decolorizing agent and after decolorizing the color of the solution is less than about 100 color units; decolorizing a saccharified biomass liquids utilizing a decolorizing agent and after decolorizing the color of the solution is less than about 10 color units; decolorizing a saccharified biomass liquids utilizing a decolorizing agent and after decolorizing the color of the solution is less than about 5 color units; treating a saccharified biomass liquid utilizing a electrodialysis system and applying a voltage of between about 10 and 600V across ion selective membranes of the electrodialysis system while flowing the saccharified biomass liquids past the membranes; treating a saccharified biomass liquids that includes one or more saccharides; treating a saccharified biomass liquids that includes xylose; treating a saccharified biomass liquids that includes glucose; treating a saccharified biomass liquids that includes arabinose; treating a saccharified biomass liquids that includes fructose; purifying a saccharified liquids utilizing an electrodialysis system, wherein the liquids includes xylose and the purity of the xylose after utilizing the electrodialysis system is at least about 80 wt.%; purifying a saccharified liquids utilizing an electrodialysis system, wherein the liquids includes arabinose and the purity of the arabinose after utilizing the electrodialysis system is at least about 0 to 1 wt.%.

[0016] Alternately, the saccharified biomass may be fermented and then

electrodialysis steps applied. An initial electrodialysis step can remove salts especially inorganic salts, followed by a second electrodialysis step using a bipolar electrolysis step to isolate valuable ionizable organic products from the fermentation system. Subsequent purification steps as described above may be used for further purify the ionizable organic products.

[0017] Other features and advantages of the invention will be apparent from the following detailed description, and from the claims.

DESCRIPTION OF DRAWINGS

[0018] FIG. 1A is a diagram showing an electrodialysis process.

[0019] FIG. IB is a diagrammatic view of an exemplary electrodialysis system.

[0020] FIG. 2 is a flow chart showing the steps of purifying (treating) the biomass before subjecting it to electrodialysis.

[0021] FIG. 3 is a plot showing conductivity vs time during an electrodialysis process.

[0022] FIG. 4 is flow chart showing the steps of purifying an ionizable organic product after a fermentation step; specifically D- or L-lactic acid.

[0023] FIG. 5 is a flow chart showing steps for using two electrodialysis steps for isolating an organic acid.

DETAILED DESCRIPTION

[0024] Using the methods and systems described herein, cellulosic and

lignocellulosic feedstock materials, for example that can be sourced from biomass (e.g., plant biomass, animal biomass, paper, and municipal waste biomass) and that are often readily available but difficult to process, can be converted to solutions containing sugars such as xylose and glucose, which can in some cases be further processed to produce other useful products (e.g., alcohols such as ethanol and butanol and organic acids such as acetic acid, propionic acid, succinic acid, tartaric acid, butyric acid and lactic acid). Methods and systems are discussed herein for removing unwanted components, such as salts (e.g. ions), and acids (e.g., organic acids) from these biomass liquids by

conventional electrodialysis, electrodialysis reversal and/or bipolar membrane electrodialysis.

[0025] Processes for manufacturing sugar solutions and products derived therefrom are described herein. These processes may include, for example, optionally mechanically treating a cellulosic and/or lignocellulosic feedstock. Before and/or after this treatment, the feedstock can be treated with another treatment, for example, irradiation, steam explosion, pyrolysis, sonication, chemical treatment (e.g., with and acid or a base) and/or oxidation to reduce, or further reduce its recalcitrance.

[0026] A solution rich in sugar can be produced by saccharifying the treated and irradiated feedstock by the addition of one or more enzymes. Many other products or biomass liquids may be derived from the sugar solution, for example, by fermentation to an alcohol such as ethanol, organic acids such as lactic acid or by reduction to a sugar alcohol such as xylitol, sorbitol etc. The solution also includes several unwanted ions, the bulk of which can be removed by electrodialysis. Before or after electrodialysis, the saccharification or fermentation product can be further purified.

[0027] Electrodialysis is a membrane separation process wherein the membrane is permeable to small species (e.g., ions) but not to larger species (e.g., molecules such as sugars). Electrodialysis differs from pressure driven membrane processes by utilizing electrical potential as the main driving force in matter separation making it useful for charged particles, for example, ions. Since the charged particles are mobile, the separation media transfers the electric current with relatively low resistance, electrodialysis is generally carried out in aqueous solutions. In the electrodialysis process, the liquid is made to flow through a separation cell (e.g., an area, a tube or chamber) enclosed by cation and anion selective membranes. In addition, while flowing the process liquid through the separation cell, the process liquid is subjected to an electrical potential using positively and negatively charged electrodes. The separation cell is generally configured so that the cations can migrate through the cation selective membrane towards the negatively polarized electrode, and the anions migrate through the anion selective membrane towards the positively charged electrode. The

arrangement of the cell ensures that ions are concentrated outside of the cell, and can be flowed away, while the ion depleted fluids can be collected. The process fluid can be circulated through the process cell repeatedly, for example, until a solution with the desired concentration of ions is be obtained. Multiple separation cells can be used in series or in parallel to achieve the optimum process results. [0028] A subset of electrodialysis is using bipolar membranes to separate materials. Bipolar membranes consist of an anion-permeable membrane and a cation permeable membrane laminated together. When this composite structure is oriented such that the cation-exchange layer faces the anode it is possible, by imposing a potential field across the membrane, to spit water into proton and hydroxyl ions. This results in the production of acidic and basic solutions at the surfaces of the bipolar membranes. Multiple bipolar membranes along with other ion permeable membranes can be placed between a single pair of electrodes in an electrodialysis stack for the production of acid and base from a neutral salt. For example, this strategy - - bipolar membrane electrodialysis may be used to isolate lactic acid or another organic acid from a fermentation product mixture. The lactic acid or other organic acids may be converted to its salt form processed through conventional electrodialysis followed by processing with bipolar membrane

electrodialysis to produce purified lactic acid (and/or organic acids) in its acid form.

[0029] FIG. 1A is a diagram showing how electrodialysis operates on a feed stream (e.g., containing sugars and salts). Feed stream 10 and makeup water 20 (brine makeup) enter the system. A potential 30 (DC voltage) is applied to the feed and makeup water which are separated by an ion selective membrane. The potential drives the ions preferentially into the makeup water. A demineralized product 40 exits the system, where the ions have been reduced as compared to the feed process stream. The ions that have been removed from the feed are brought out of the system as the brine blowdown 50. The process can be repeated, e.g. feeding the demineralized product back into the electrodialysis system to further remove ions (e.g., transfer them to brine blowdown). The process can be repeated until the desired reduction in ions is achieved, as will be further described below.

[0030] One possible arrangement of a membrane configuration in an electrodialysis system that can be utilized to purify saccharified lignocellulosic material is shown by FIG IB. This system utilizes alternating cation selective membranes 2101 and anion selective membranes 2102. Spacers (not shown) are placed between every membrane to ensure there is room between membranes for the process liquids to flow. The electrodes, 2103 and 2104, are not in physical contact with the process fluid but rather are in physical contact with a special conductive solution (electrolyte). The conductive solution serves the purpose of keeping unwanted reactions from occurring at the electrode. For example, a sulfuric solution splits water into hydrogen gas at the cathode and oxygen gas at the anode, both of which can be removed without damaging the electrodes or other components. The electrodes are therefore in electrical contact with the process fluids through the electrolyte.

[0031] Therefore, the arrangement as described above creates a series of flow channels (2105 and 2106) through which the process fluid (e.g., the sugar solution produced from a saccharified lignocellulosic material) is made to flow (e.g., by the action of a pump) while an electrical potential is applied to the flowing solution. Under operation, for example, the cations in every second flow channel 2105 flow towards the cathode 2103 and are able to migrate through the adjacent cation selective membrane 2101 into the next flow channel 2106. The cations are then trapped in flow channels 2105, unable to migrate through the anion selective membranes 2102. Conversely, the anions in the flow channels 2105 are able to migrate towards the anode 2104 through the anion selective membranes 2102 and into alternating flow channels 2106 where they are trapped, unable to migrate further, since they encounter the cation selective membranes 2101. In this arrangement, the cations and anions migrate out of every second flow channel 2105, such that the process fluid in the flow channels 2105 ends up substantially free of ions, while the process fluid in the remaining channels 2106 contains a high concentration of both cations and anions. The result is that by collecting the outlet of the flow channels 2105 and 2106 separately, a depleted-ion sugar solution (from flow channels 2105) and a separate enriched-ion sugar solution (from flow channels 2106) are obtained. Increasing the number of ion exchange membranes and flow channels greatly improves the efficiency of the system. For example, 10, 20, 50, 100 or even more membranes can be used.

[0032] In addition to sugars and products such as alcohols, the solutions derived from biomass by the processes such as saccharification and fermentation (described herein) can include various materials, for example, suspended or dissolved compounds and/or materials. For example, solutions can include enzymes (e.g., parts of enzymes, active enzymes, denatured enzymes), amino acids, nutrients, live cells, dead cells, cellular debris (e.g., lysed cells, yeast extract), acids, bases, salts (e.g., halides, sulfates, and phosphates, alkali, alkali earth, transition metal salts), partial hydrolysis products (e.g., cellulose and hemicellulose fragments), lignin, lignin residues, inorganic solids (e.g., siliceous materials, clays, carbon black, metals), remnants of saccharified and/or fermented biomass, and combinations thereof. The sugar solution may undergo purification processes, which may include a simulated bed chromatography, rotary drum filtration, filtration and or decolorization prior to being subjected to electrodialysis. Optionally, these impurities can be removed or reduced (e.g., decreased in concentration) prior to subjecting the biomass solution to electrodialysis. In particular, it may be beneficial to remove impurities (e.g., polymers, proteins, precipitants) that can coat, plug, fill or otherwise hinder the function of the electrodialysis membranes. In general, electrodialysis is subject to membrane fouling from particles and organic materials, for example, the organic impurities that can lead to color as previously discussed. Therefore, electrodialysis is preferably done after removing these materials. If fouling does occur, the membranes can be regenerated running the process in reverse by reversing the direction of constant current driving the separation and switching the dilution and concentration chambers.

[0033] A possible process for purifying biomass liquids, e. g. product liquids from saccharified feedstock or fermentation liquids before introducing it to electrodialysis, to avoid this fouling, is shown in FIG. 2. The saccharified feedstock is concentrated 210 under vacuum to remove solvents. In case of post-fermented feedstock, solvents including ethanol could be removed under vacuum or distilled away from the bulk of the solution and collected, leaving behind a solution (e.g., distillate bottom) comprising sugars where at least about 80 wt. of the sugars are xylose (e.g., at least 85 wt. , at least 90 wt.%, at least 95 wt.%, at least 96 wt.%, at least 97 wt.% or even at least 98 wt.%) and about 0.5 wt.% of the sugars are arabinose (e.g., about 1 to 0 wt.%, about 1 to 0.1 wt.%, about 0.8 to 0.1 wt.%, about 0.8 to 0.2 wt.%, about 0.5 to 1.0 wt.%, about 0.1 to 0.5 wt.%).

[0034] Some impurities (e.g., bi -products) are then precipitated 215 from the solution. This can be done by dilution with methanol, which induces precipitation of some impurities. The precipitates can be removed 220, for example, by use of a centrifuged and/or filtration. The filtered solution may then be decolorized 225 with activated carbon. The decolorizing agent is removed by filtration 230. A concentration step, 235 includes placing the solution under vacuum which removes methanol. The resulting solution can then be diluted with deionized water and subjected to

electrodialysis 240 to remove the salts.

[0035] A possible process for purifying an ionizable organic product (e.g., D- or L- lactic acid, succinic acid, tartaric acid) starts with saccharifying a biomass before fermentation and then introducing it to two steps of electrodialysis, as shown in FIG. 4. The saccharified feedstock is concentrated (410) under vacuum to remove solvents. Following saccharification the biomass is fermented (415) where the microorganism converts one sugar to a desired product while leaving other sugars unconverted. Prior to the electrodialysis steps the solids are removed from the fermentation product (420). The first electrodialysis is done to remove salts, especially inorganic salts (425). Then a bipolar membrane electrodialysis (430) is done to isolate the ionizable organic product (in this case, D- or L-lactic acid) from the unreacted sugars such as xylose. Subsequent purification (435) of the ionizable organic product by simulated moving bed

chromatography or similar isolation processes can lead to an isolated product of sufficient purity for its intended use.

[0036] Pertaining to FIG 6 two electrodialysis steps are shown as a purification strategy. To the fermentation product liquid mixture which has had solids removed from it (510), is added a base if needed to convert the organic acid to its salt form (520) and electrodialysis processing is done to separate the nonionic sugars from the salts

(including the organic acid salts). Then the salt is processed in the bipolar membrane electrodialysis unit (530) in which the organic acid salt is converted to its neutralized form and isolated from the salts.

[0037] Also present in the sugar solution, for example, prior to electrodialysis and/or some other purification method as described herein is applied, there can be intact or denatured enzymes utilized in the processing, or compounds derived from these enzymes (e.g., proteinaceous material such as proteins and amino acids). These can be dissolved/and or precipitated and suspended solids, can subsequently be removed by filtration or centrifugation. In some cases, the enzymes can be present in a functioning state and are denatured, e.g., by adding an acid, a base, heating, adding a denaturing agent. Denaturing the enzyme can facilitate its removal, e.g., by the methods described herein. The sugar solutions can have, for example, up to about 10 wt.% enzymes (e.g., up to 9 wt. %, up to 8 wt. %, up to 5 wt. %, up to 2 wt. %, up to 1 wt. %, between about 0.1 and 5 wt. %, between about 1 wt. % and 5 wt. %, between about 2 wt. % and 5 wt. %, between about 0.1 wt. % and 1 wt. %, between about 0.01 wt. % and 1 wt. %, between about 0.001 wt.% and 0.1 wt.%). Wherein the wt. % of enzymes is understood as the wt. % of proteinaceous material in the aqueous solution.

[0038] Some cellulolytic enzymes utilized for saccharification of a biomass operate best in the acidic region, e.g., between about pH 2 and 6 (e.g., between about 3 and 6, between about, 4 and 6, between about 4 and 5). The sugar solutions can be subjected to electrodialysis at these acidic pH, or optionally the pH can be adjusted up or down after saccharification and/or saccharification can be done at a higher or lower pH. Adjustment of the pH adds to the concentrations of ions in the solution. However, electrodialysis works well at pH values selected from a broad range. [0039] Solid impurities may be removed easily via filtration or centrifugation. Some of the dissolved impurities maybe precipitated out by treating the solution with solvents such as methanol, ethanol, isopropanol, acetone, ethyl ether and tetrahydrofuran and then removing the precipitates via filtration or centrifugation.

[0040] The sugar solutions derived from the processes described herein and used in the electrodialysis systems can include non-sugar suspended or dissolved solids present at concentrations up to about 50 wt. , for example between about 1 and 50 wt. , 2 and 40 wt. %, 3 and 25 wt.%, 5 and 25 wt.%, 40 and 50 wt.%, 30 and 40 wt.%, 10 and 20 wt.%, 1 and 5 wt.%, 10 and 40 wt.%, less than about 50 wt.%, less than about 40 wt.%, less than about 30 wt.%, less than about 20 wt.%, less than about 10 wt.%, less than about 5 wt.%, less than about 1 wt.%, less than about 0.5 wt.%, less than about 0.01 wt.%. These solutions can have high turbidity, for example, at least about 5

nephelometric turbidity units (NTU) (e.g., at least about 10 NTU, at least about 50 NTU, at least about 100 NTU, at least about 100 NTU, at least about 200 NTU, at least about 300 NTU, at least about 400 NTU and even greater than about 500 NTU). In some cases the solids are completely or partially removed prior to the solution being subjected to electrodialysis. For example, the solids can be removed by filtration, centrifuging, settling, floatation and combinations of these. In some cases the solids are derived from a previously soluble material that has been precipitated, for example, an enzyme that has been denatured. After removing the solids the turbidity of the solutions can be reduced by up to about 500 NTU (e.g., reduced by up to about 100 NTU, reduced by up to about 50 NTU, reduced by up to about 5 NTU).

[0041] In addition to being turbid, the sugar solutions produced from the processes described herein can be colored due to colored impurities (e.g., colored bodies) such as aromatic chromophores. For example, some metal ions and polyphenols and lignin- derived products produced or released during the processing of a lignocellulosic biomass can be highly colored. The solutions can be used directly in the electrodialysis system described herein or can be partially or completely decolorized prior to being used. For example, the colored impurities can be filtered out of the solution, destroyed (e.g., by chemical decomposition) and/or precipitated out of the solution. Some possible color removing agents that can be used are powdered, granular, extruded, bone char or bead activated carbon; styrenic, acrylic or magnetic resin; decolorizing clays such as bentonite, attapulgite, montmorillonite, hormite and combinations of these. After treating the solutions with these color removing agents, the color of the solution is less than about 200 (e.g., less than 100, less than 50, less than about 40, less than about 30, less than about 20, less than about 10, less than about 5 and even less than about 1) as measured by the Platinum-Cobalt method (ASTM Test Method D1209).

[0042] The ionic strength of the biomass derived sugar solutions can be highly dependent on the source of the biomass as well as the processing of the biomass as described herein. The solutions can be used directly or selectively or partially de-ionized prior to being used in the electrodialysis systems described herein.

[0043] An advantage of electrodialysis over, for example, ion exchange

chromatography, for removing ions in the processes described herein is throughput capacity. Ion exchange columns can become saturated quickly, requiring time consuming and costly regeneration cycles, while electrodialysis can run continuously without requiring regeneration, even with high conductivity process liquids. For example, solutions to be processed after the distillation steps described herein can have conductivities of greater than about 500 μδ/οιη (e.g., greater than about 1000 μδ/οιη, greater than about 2000 μδ/οιη, greater than about 3000 μδ/οιη, greater than about 4000 μδ/cm, greater than about 5000 μδ/οιη, greater than about 6000 μδ/οιη, greater than about 7000 μδ/οιη, greater than about 8000 μδ/αη, greater than about 9000 μδ/οιη, greater than about 10,000 μδ/οιη) or, for example, they can have conductivities between about 500 and 100,000 μδ :ιη (e.g., between about 500 and 50,000 μδ :ιη, between about 1000 and 20,000 μδ :ιη, between about 1000 and 20,000 μδ :ιη, between about 1000 and 15,000 μβ/αη, between about 5000 and 20,000 μβ/αη, between about 5000 and 10,000 μδ/οιη) and can be treated effectively by electrodialysis. For example, the conductivities after processing can be reduced by at least 10 fold (e.g., at least 20 fold, at least 30 fold, at least 50 fold, at least 100 fold, at least 500 fold, at least 1000 fold). After electrodialysis the conductivities can be between about 1- 100 μδ/οιη (e.g., between about 1-90 μδ/οιη, between about 1-80 μδ/οιη, between about 1-50 μδ/οιη, between about 1 -30 μδ/οιη, between about 1 -20 μδ/οιη, between about 2-60 μδ/οιη, between about 2-40 μδ/οιη, between about 2-20 μδ/οιη, between about 5- 100 μδ/οιη, between about 5-50 μδ/οιη, between about 5-25 μδ/οιη, between about 9-90 μδ/οιη, between about 9-50 μδ/οιη, between about 9-25 μδ/οιη, between about 9- 12 μδ/οιη, between about 15-60 μδ/οιη, between about 15-40 μδ/οιη, between about 15-30 μδ/οιη, between about 15-20 μδ/οιη, between about 27-100 μδ/οιη, between about 27-50 μδ/οιη, between about 27-30 μδ/οιη). Once the bulk of the ions have been removed by electrodialysis, a cation exchange column can be used. This final column is often designated as a "finishing" column. [0044] Electrodialysis and/or cation exchange can be effective to remove a variety of ions, for example, from biomass liquids such as saccharified biomass, fermentation liquids. In particular, the cations include alkali metals, alkali earths, transition metals, lanthanides and actinides, for example, lithium, sodium, potassium, magnesium, calcium, strontium, barium, scandium, titanium, chromium, manganese, iron, nickel, copper, zinc, aluminum, lanthanum, cerium, uranium. Cationic and anionic sulfides and oxides might also be present, and can be removed by the methods described. Anions may include fluoride, chloride, bromide, iodide, sulfate, sulfides, phosphate, nitrate, carbonate, borates (e.g., BO ₃ ^3" ), chlorates, arsinates and aluminates. In particular, Na ⁺ , and CI ^" are present in high concentrations and a high amount, for example about at least 50 %, of these ions should be removed (e.g., about at least 80%, about at least 85%, about at least 90%, about at least 95%, about at least 98%, about at least 99%). For example, chlorine can comprise about 1/3 of all ions present and can act as a xylose degradation catalyst. Other ions can be fouling to subsequent processes such as hydrogenation.

[0045] Electrodialysis and electrodialysis reversal can also be useful for removing acids. For example, mineral acids such as HCL, H2SO4, H ₃ PO4, HNO ₃ can be treated. Organic acids can also be treated, for example, acetic acid, formic acid, propionic acid, butyric acid, lactic acid and the like. The acids can be partially or fully de-ionized.

Bipolar membrane electrodialysis may be used for isolation of these organic acids

[0046] An electrodialysis unit that can be utilized in the methods, with equipment and with systems described herein is described in "Electrodialysis Cell Unit PCCell ED 64 0 02", by PCCell (Germany) Verions Jan 2006 pages 1 -12; the entire disclosure of which is incorporated by reference and attachment in the appendix. For example, the PCCell DE 64 described on pg. 10 of that document can be utilized to deionized saccharified materials described herein.

[0047] Some description of Electrodialysis Reversal that can be utilized in the methods, with equipment and with systems described herein is described in "High Water Recovery with Electrodialysis Reversal", by GE Power and Water, Technical paper 1071EN.doc, March 2010, pages 1-5; the full disclosure of which is incorporated by reference and attachment in the appendix. For example, Electrodialysis Reversal as described in the figure on page 1 of that document (figure 1 :EDR flow diagram) describes a system that can be utilized to process saccharified materials and waste streams derived from saccharified materials described herein.

[0048] Electrodialysis and Electrodialysis Reversal is described in "Electrodiolysis (ED) and Electrodialysis Reversal (EDR)", U.S Department of the Interior, Bureau of Reclamation, pages 1-4; the entire of which is incorporated by reference and attachment in the appendix. For example an treatment train using all or parts of this system (e.g., including raw water pumps, debris screens, rapid mix, slow mix flocculator, basin or clarifying, gravity filters and EDR membranes) as described on page 3 of that document can be utilized to process saccharified biomass and/or saccharified biomass waste streams.

[0049] Bipolar membrane electrodialysis equipment is available from for instance, Ameridia Somerset NJ; USA. The process was described by Ameridia in Membrane and Separation Technology News March 2006 the entire of which is incorporated by reference and attachment in the appendix.

[0050] Some more details and reiterations 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

[0051] Purification systems, methods and equipment (e.g., electrodialysis) can be applied to materials that have been processed as described above and also as described anywhere herein.

[0052] For example, processes for the conversion of a feedstocks to sugars and other products can 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 (e.g., as previously described and reiterated and expanded here).

Saccharification can be performed by mixing a dispersion of the feedstock in a liquid medium, e.g., water with an enzyme, as will be discussed in detail below. During or after saccharification, the mixture (e.g., 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, electrodialysis. The individual processing steps, materials used and examples of products and intermediates that may be formed will be described in detail below. Therefore, in addition to these methods, purification systems, methods and equipment (e.g., simulated moving bed chromatography) can be applied, for example, as an additional processing step. RADIATION TREATMENT

[0053] The feedstock can be treated with radiation to modify its structure to reduce its recalcitrance. Such treatment can, for example, reduce the average molecular weight of the feedstock, change the crystalline structure of the feedstock, and/or increase the surface area and/or porosity of the feedstock. Radiation can be by, for example, electron beam, ion beam, 100 nm to 280 nm ultraviolet (UV) light, gamma or X-ray radiation. Radiation treatments and systems for treatments are discussed in U.S. Patent 8,142,620, and U.S. Patent Application Series No. 12/417,731, the entire disclosures of which are incorporated herein by reference.

[0054] Each form of radiation ionizes the biomass via particular interactions, as determined by the energy of the radiation. Heavy charged particles primarily ionize matter via Coulomb scattering; furthermore, these interactions produce energetic electrons that may further ionize matter. Alpha particles are identical to the nucleus of a helium 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, americium, and plutonium. Electrons interact via Coulomb scattering and bremsstrahlung radiation produced by changes in the velocity of electrons.

[0055] When particles are utilized, they can be neutral (uncharged), positively charged or negatively charged. When charged, the charged particles can bear a single positive or negative charge, or multiple charges, e.g., one, two, three or even four or more charges. In instances in which chain scission is desired to change the molecular structure of the carbohydrate containing material, positively charged particles may be desirable, in part, due to their acidic nature. When particles are utilized, the particles can have the mass of a resting electron, or greater, e.g., 500, 1000, 1500, or 2000 or more times the mass of a resting electron. For example, the particles can have a mass of from about 1 atomic unit to about 150 atomic units, e.g., from about 1 atomic unit to about 50 atomic units, or from about 1 to about 25, e.g., 1, 2, 3, 4, 5, 10, 12 or 15 atomic units.

[0056] Gamma radiation has the advantage of a significant penetration depth into a variety of material in the sample.

[0057] In embodiments in which the irradiating is performed with electromagnetic radiation, the electromagnetic radiation can have, e.g., energy per photon (in electron volts) of greater than 102 eV, e.g., greater than 10 ³ , 10 ⁴ , 10 ⁵ , 10 ⁶ , or even greater than 10 ⁷ eV. In some embodiments, the electromagnetic radiation has energy per photon of between 10 ⁴ and 10 ⁷ , e.g., between 10 ⁵ and 10 ⁶ eV. The electromagnetic radiation can have a frequency of, e.g., greater than 10 ¹⁶ Hz, greater than 10 ¹⁷ Hz, 10 ¹⁸ , 10 ¹⁹ , 10 ²⁰ , or even greater than 10 ²¹ Hz. In some embodiments, the electromagnetic radiation has a frequency of between 10 ¹⁸ and 10 ²² Hz, e.g., between 10 ¹⁹ to 10 ²¹ Hz.

[0058] Electron bombardment may be performed using an electron 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 0.5 to 1.5 MeV, from about 0.8 to 1.8 MeV, or from about 0.7 to 1 MeV. In some implementations the nominal energy is about 500 to 800 keV.

[0059] The electron beam may have a relatively high total beam power (the combined beam power of all accelerating heads, or, if multiple accelerators are used, of all accelerators and all 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 electron beam has a beam power of 1200 kW or more, e.g., 1400, 1600, 1800, or even 3000 kW.

[0060] This high total beam power is usually achieved by utilizing multiple accelerating heads. For example, the electron beam device may include two, four, or more accelerating heads. The use of multiple heads, each of which has a relatively low beam power, prevents excessive temperature rise in the material, thereby preventing burning of the material, and also increases the uniformity of the dose through the thickness of the layer of material.

[0061] It is generally preferred that the bed of biomass material has a relatively uniform thickness. In some embodiments the thickness is less than about 1 inch (e.g., less than about 0.75 inches, less than about 0.5 inches, less than about 0.25 inches, less than about 0.1 inches, between about 0.1 and 1 inch, between about 0.2 and 0.3 inches).

[0062] It is desirable to treat the material as quickly as possible. In general, it is preferred that treatment be performed at a dose rate of greater than about 0.25 Mrad per second, e.g., greater than about 0.5, 0.75, 1, 1.5, 2, 5, 7, 10, 12, 15, or even greater than about 20 Mrad per second, e.g., about 0.25 to 2 Mrad per second. Higher dose rates allow a higher throughput for a target (e.g., the desired) dose. Higher dose rates generally require higher line speeds, to avoid thermal decomposition of the material. In one implementation, the accelerator is set for 3 MeV, 50 mA beam current, and the line speed is 24 feet/minute, for a sample thickness of about 20 mm (e.g., comminuted corn cob material with a bulk density of 0.5 g/cm ³ ). [0063] In some embodiments, electron bombardment is performed until the material receives a total dose of at least 0.1 Mrad, 0.25 Mrad, 1 Mrad, 5 Mrad, e.g., at least 10, 20, 30 or at least 40 Mrad. In some embodiments, the treatment is performed until the material receives a dose of from about 10 Mrad to about 50 Mrad, e.g., from about 20 Mrad to about 40 Mrad, or from about 25 Mrad to about 30 Mrad. In some

implementations, a total dose of 25 to 35 Mrad is preferred, applied ideally over a couple of passes, e.g., at 5 Mrad/pass with each pass being applied for about one second.

Cooling methods, systems and equipment can be used before, during, after and in between radiations, for example utilizing a cooling screw conveyor and/or a cooled vibratory conveyor.

[0064] Using multiple heads as discussed above, the material can be treated in multiple passes, for example, two passes at 10 to 20 Mrad/pass, e.g., 12 to 18 Mrad/pass, separated by a few seconds of cool-down, or three passes of 7 to 12 Mrad/pass, e.g., 5 to 20 Mrad/pass, 10 to 40 Mrad/pass, 9 to 11 Mrad/pass. As discussed herein, treating the material with several relatively low doses, rather than one high dose, tends to prevent overheating of the material and also increases dose uniformity through the thickness of the material. In some implementations, 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.

[0065] In some embodiments, electrons are accelerated to, for example, a speed of greater than 75 percent of the speed of light, e.g., greater than 85, 90, 95, or 99 percent of the speed of light.

[0066] In some embodiments, any processing described herein occurs on

lignocellulosic material that remains dry as acquired 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.%.

[0067] In some embodiments, two or more ionizing sources can be used, such as two or more electron sources. For example, samples can be treated, in any order, with a beam of electrons, 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 electrons, gamma radiation, and energetic UV light. The biomass is conveyed through the treatment zone where it can be bombarded with electrons.

[0068] It may be advantageous to repeat the treatment to more thoroughly reduce the recalcitrance of the biomass and/or further modify the biomass. In particular, the process parameters can be adjusted after a first (e.g., second, third, fourth or more) pass depending on the recalcitrance of the material. In some embodiments, a conveyor can be used which includes a circular system where the biomass is conveyed multiple times through the various processes described above. In some other embodiments, multiple treatment devices (e.g., electron beam generators) are used to treat the biomass multiple (e.g., 2, 3, 4 or more) times. In yet other embodiments, a single electron 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.

[0069] The effectiveness in changing the molecular/supermolecular structure and/or reducing the recalcitrance of the carbohydrate-containing biomass depends on the electron energy used and the dose applied, while exposure time depends 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 burn) the biomass material. For example, the carbohydrates should not be damaged in the processing so that they can be released from the biomass intact, e.g. as monomeric sugars.

[0070] In some embodiments, the treatment (with any electron 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.

[0071] In some embodiments, relatively low doses of radiation are utilized, e.g., to increase the molecular weight of a cellulosic or lignocellulosic material (with any radiation source or a combination of sources described herein). For example, a dose of at least about 0.05 Mrad, e.g., at least about 0.1 Mrad or at least about 0.25, 0.5, 0.75. 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, or at least about 5.0 Mrad. In some embodiments, the irradiation is performed until the material receives a dose of between 0.1 Mrad and 2.0 Mrad, e.g., between 0.5 Mrad and 4.0 Mrad or between 1.0 Mrad and 3.0 Mrad. [0072] It also can be desirable to irradiate from multiple directions, simultaneously or sequentially, in order to achieve a desired degree of penetration of radiation into the material. For example, depending on the density and moisture content of the material, such as wood, and the type of radiation source used (e.g., gamma or electron beam), the maximum penetration of radiation into the material may be only about 0.75 inch. In such a case, a thicker section (up to 1.5 inch) can be irradiated by first irradiating the material from one side, and then turning the material over and irradiating from the other side. Irradiation from multiple directions can be particularly useful with electron beam radiation, which irradiates faster than gamma radiation but typically does not achieve as great a penetration depth.

RADIATION OPAQUE MATERIALS

[0073] The radiation step can include processing a material in a vault and/or bunker that is constructed using radiation opaque materials. In some implementations, the radiation opaque materials are selected to be capable of shielding the components from X-rays with high energy (short wavelength), which can penetrate many materials. One important factor in designing a radiation shielding enclosure is the attenuation length of the materials used, which will determine the required thickness for a particular material, blend of materials, or layered structure. The attenuation length is the penetration distance at which the radiation is reduced to approximately 1/e (e = Euler's number) times that of the incident radiation. Although virtually all materials are radiation opaque if thick enough, materials containing a high compositional percentage (e.g., density) of elements that have a high Z value (atomic number) have a shorter radiation attenuation 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 concrete and about 2.7 mm for lead, while with an X-ray energy of 1 MeV the halving thickness for concrete is about 44.45 mm and for lead is about 7.9 mm. Radiation opaque materials can be materials that are thick or thin so long as they can reduce the radiation that passes through to the other side. Thus, if it is desired that a particular enclosure have a low wall thickness, e.g., for light weight or due to size constraints, the material chosen should have a sufficient Z value and/or attenuation length so that its halving length is less than or equal to the desired wall thickness of the enclosure.

[0074] 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 resistance, etc.). In some cases, the layered material may be a "graded-Z" laminate, e.g., including a laminate in which the layers provide a gradient from high-Z through successively lower-Z elements. As previously described herein, in some cases the radiation opaque materials can be interlocking blocks, for example, lead and/or concrete blocks can be supplied by NELCO Worldwide (Burlington, MA), and reconfigurable vaults can be utilized.

[0075] A radiation opaque material can reduce the radiation passing through a structure (e.g., a wall, door, ceiling, enclosure, a series 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), concrete, 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, 10 m).

RADIATION SOURCES

[0076] The type of radiation determines 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 utilize sources as described herein as well as any other useful sources.

[0077] Sources of gamma rays include radioactive nuclei, such as isotopes of cobalt, calcium, technetium, chromium, gallium, indium, iodine, iron, krypton, samarium, selenium, sodium, thallium, and xenon. [0078] Sources of X-rays include electron beam collision with metal targets, such as tungsten or molybdenum or alloys, or compact light sources, such as those produced commercially by Lyncean.

[0079] Alpha particles are identical to the nucleus of a helium 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, americium, and plutonium.

[0080] Sources for ultraviolet radiation include deuterium or cadmium lamps.

[0081] Sources for infrared radiation include sapphire, zinc, or selenide window ceramic lamps.

[0082] Sources for microwaves include klystrons, Slevin type RF sources, or atom beam sources that employ hydrogen, oxygen, or nitrogen gases.

[0083] Accelerators used to accelerate the particles (e.g., electrons or ions) can be DC (e.g., electrostatic DC or electrodynamic DC), RF linear, magnetic induction linear or continuous wave. For example, various irradiating devices may be used in the methods disclosed herein, including field ionization sources, electrostatic ion separators, field ionization generators, thermionic emission sources, microwave discharge ion sources, recirculating or static accelerators, dynamic linear accelerators, van de Graaff accelerators, Cockroft Walton accelerators (e.g., PELLETRON® accelerators), LINACS, Dynamitrons (e.g., DYNAMITRON® accelerators), cyclotrons, synchrotrons, betatrons, transformer-type accelerators, microtrons, plasma generators, cascade accelerators, and folded tandem accelerators. For example, cyclotron type accelerators are available from IBA, Belgium, such as the RHODOTRON™ system, while DC type accelerators are available from RDI, now IBA Industrial, such as the DYNAMITRON®. Other suitable accelerator systems include, for example: DC insulated core transformer (ICT) type systems, available from Nissin High Voltage, Japan; S-band LINACs, available from L3- PSD (USA), Linac Systems (France), Mevex (Canada), and Mitsubishi Heavy Industries (Japan); L-band LINACs, available from Iotron Industries (Canada); and ILU-based accelerators, available from Budker Laboratories (Russia). Ions and ion accelerators are discussed in Introductory Nuclear Physics, Kenneth S. Krane, John Wiley & Sons, Inc. (1988), Krsto Prelec, FIZIKA B 6 (1997) 4, 177-206, Chu, William T., "Overview of Light-Ion Beam Therapy", Columbus-Ohio, ICRU-IAEA Meeting, 18-20 March 2006, Iwata, Y. et al., "Alternating-Phase-Focused IH-DTL for Heavy-Ion Medical

Accelerators", Proceedings of EPAC 2006, Edinburgh, Scotland, and Leitner, CM. et al., "Status of the Superconducting ECR Ion Source Venus", Proceedings of EPAC 2000, Vienna, Austria. Some particle accelerators and their uses are disclosed, for example, in U.S. Pat. No. 7,931,784 to Medoff, the complete disclosure of which is incorporated herein by reference.

[0084] Electrons may be produced by radioactive nuclei that undergo beta decay, such as isotopes of iodine, cesium, technetium, and iridium. Alternatively, an electron gun can be used as an electron source via thermionic emission and accelerated through an accelerating potential. An electron gun generates electrons, which are then accelerated through a large potential (e.g., greater than about 500 thousand, greater than about 1 million, greater than about 2 million, greater than about 5 million, greater than about 6 million, greater than about 7 million, greater than about 8 million, greater than about 9 million, or even greater than 10 million volts) and then scanned magnetically in the x-y plane, where the electrons are initially accelerated in the z direction down the accelerator tube and extracted through a foil window. Scanning the electron beams is useful for increasing the irradiation surface when irradiating materials, e.g., a biomass, that is conveyed through the scanned beam. Scanning the electron beam also distributes the thermal load homogenously on the window and helps reduce the foil window rupture due to local heating by the electron beam. Window foil rupture is a cause of significant down-time due to subsequent necessary repairs and re-starting the electron gun.

[0085] Various other irradiating devices may be used in the methods disclosed herein, including field ionization sources, electrostatic ion separators, field ionization generators, thermionic emission sources, microwave discharge ion sources, recirculating or static accelerators, dynamic linear accelerators, van de Graaff accelerators, and folded tandem accelerators. Such devices are disclosed, for example, in U.S. Pat. No. 7,931,784 to Medoff, the complete disclosure of which is incorporated herein by reference.

[0086] A beam of electrons can be used as the radiation source. A beam of electrons 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 have 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 emissions corresponding to the smaller amount of energy used. Electron beams can be generated, e.g., by electrostatic generators, cascade generators, transformer generators, low energy accelerators with a scanning system, low energy accelerators with a linear cathode, linear accelerators, and pulsed accelerators.

[0087] 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, electrons having energies of 0.5-10 MeV can penetrate low density materials, such as the biomass materials described herein, e.g., materials having a bulk density of less than 0.5 g/cm ³ , 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 electron of the electron beam is from about 0.3 MeV to about 2.0 MeV (million electron volts), e.g., from about 0.5 MeV to about 1.5 MeV, or from about 0.7 MeV to about 1.25 MeV. Methods of irradiating materials are discussed in U.S. Pat. App. Pub. 2012/0100577 Al , filed October 18, 2011, the entire disclosure of which is herein incorporated by reference.

[0088] Electron beam irradiation devices may be procured commercially or built. For example elements or components such inductors, capacitors, casings, power sources, cables, wiring, voltage control systems, current control elements, insulating material, microcontrollers and cooling equipment can be purchased and assembled into a device. Optionally, a commercial device can be modified and/or adapted. For example, devices and components can be purchased from any of the commercial sources described herein including Ion Beam Applications (Louvain-la-Neuve, Belgium), NHV Corporation (Japan), the Titan Corporation (San Diego, CA), Vivirad High Voltage Corp (Billerica, MA) and/or Budker Laboratories (Russia). Typical electron energies can be 0.5 MeV, 1 MeV, 2 MeV, 4.5 MeV, 7.5 MeV, or 10 MeV. Typical electron 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 series EPS-500 (e.g., 500 kV accelerator voltage and 65, 100 or 150 mA beam current), EPS-800 (e.g., 800 kV accelerator voltage and 65 or 100 mA beam current), or EPS- 1000 (e.g., 1000 kV accelerator voltage and 65 or 100 mA beam current). Also, accelerators from NHV's high energy series 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).

[0089] Tradeoffs in considering electron beam irradiation device power

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

[0090] The electron beam irradiation device can produce either a fixed beam or a scanning beam. A scanning beam may be advantageous with large scan sweep length and high scan speeds, as this would effectively replace a large, fixed beam width.

Further, available sweep widths of 0.5 m, 1 m, 2 m or more are available. The scanning beam is preferred in most embodiments describe herein because of the larger scan width and reduced possibility of local heating and failure of the windows.

ELECTRON GUNS - WINDOWS

[0091] The extraction system for an electron accelerator can include two window foils. The cooling gas in the two foil window extraction system can be a purge gas or a mixture, for example, air, or a pure gas. In one embodiment the gas is an inert gas such as nitrogen, argon, helium and or carbon dioxide. It is preferred to use a gas rather than a liquid since energy losses to the electron beam are minimized. Mixtures of pure gas can also be used, either pre-mixed or mixed in line prior to impinging on the windows or in the space between the windows. The cooling gas can be cooled, for example, by using a heat exchange system (e.g., a chiller) and/or by using boil off from a condensed gas (e.g., liquid nitrogen, liquid helium). Window foils are described in PCT/US2013/64332 filed October 10, 2013 the full disclosure of which is incorporated by reference herein.

HEATING AND THROUGHPUT DURING RADIATION TREATMENT

[0092] Several processes can occur in biomass when electrons from an electron beam interact with matter in inelastic collisions. For example, ionization of the material, chain scission of polymers in the material, cross linking of polymers in the material, oxidation of the material, generation of X-rays ("Bremsstrahlung") and vibrational excitation of molecules (e.g. phonon generation). Without being bound to a particular mechanism, the reduction in recalcitrance can be due to several of these inelastic collision effects, for example, ionization, chain scission of polymers, oxidation and phonon generation. Some of the effects (e.g., especially X-ray generation), necessitate shielding and engineering barriers, for example, enclosing the irradiation processes in a concrete (or other radiation opaque material) vault. Another effect of irradiation, vibrational excitation, is equivalent to heating up the sample. Heating the sample by irradiation can help in recalcitrance reduction, but excessive heating can destroy the material, as will be explained below.

[0093] The adiabatic temperature rise (ΔΤ) from adsorption of ionizing radiation is given by the equation: ΔΤ = D/Cp : where D is the average dose in kGy, Cp is the heat capacity in J/g °C, and ΔΤ is the change in temperature in °C. A typical dry biomass material will have a heat capacity close to 2. Wet biomass will have a higher heat capacity dependent on the amount of water since the heat capacity of water is very high (4.19 J/g °C). Metals have much lower heat capacities, for example, 304 stainless steel has a heat capacity of 0.5 J/g °C. The temperature change due to the instant adsorption of radiation in a biomass and stainless steel for various doses of radiation is shown below.

Calculated Temperature increase for biomass and stainless steel.

[0094] High temperatures 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 temperatures can become dark, sticky and give off odors indicating decomposition. The stickiness can even make the material hard to convey. The odors can be unpleasant and be a safety issue. In fact, keeping the biomass below about 200°C has been found to be beneficial in the processes described herein (e.g., below about 190°C, below about 180°C, below about 170°C, below about 160°C, below about 150°C, below about 140°C, below about 130°C, below about 120°C, below about 110°C, between about 60°C and 180°C, between about 60°C and 160°C, between about 60°C and 150°C, between about 60°C and 140°C, between about 60°C and 130°C, between about 60°C and 120°C, between about 80°C and 180°C, between about 100°C and 180°C, between about 120°C and 180°C, between about 140°C and 180°C, between about 160°C and

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

[0095] It has been found that irradiation above about 10 Mrad is desirable for the processes described herein (e.g., reduction of recalcitrance). A high throughput is also desirable so that the irradiation does not become a bottle neck in processing the biomass. The treatment is governed by a Dose rate equation: M = FP/D-time, where M is the mass of irradiated material (kg), F is the fraction of power that is adsorbed (unit less), P is the emitted power (kW= Voltage in MeV x Current in mA), time is the treatment time (sec) and D is the adsorbed dose (kGy). In an exemplary process where the fraction of adsorbed power is fixed, the Power emitted is constant and a set dosage is desired, the throughput (e.g., M, the biomass processed) can be increased by increasing the irradiation time. However, increasing the irradiation time without allowing the material to cool, can excessively heat the material as exemplified by the calculations shown above. Since biomass has a low thermal conductivity (less than about 0.1 Wm K ^" '), heat dissipation is slow, unlike, for example, metals (greater than about 10 Wm K ^" ') which can dissipate energy quickly as long as there is a heat sink to transfer the energy to.

ELECTRON GUNS - BEAM STOPS

[0096] In some embodiments the systems and methods include a beam stop (e.g., a shutter). For example, the beam stop can be used to quickly stop or reduce the irradiation of material without powering down the electron beam device. Alternatively the beam stop can be used while powering up the electron beam, e.g., the beam stop can stop the electron beam until a beam current of a desired level is achieved. The beam stop can be placed between the primary foil window and a secondary foil window. For example, the beam stop can be mounted so that it is movable, that is, so that it can be moved into and out of the beam path. Even partial coverage of the beam can be used, for example, to control the dose of irradiation. The beam stop can be mounted to the floor, to a conveyor for the biomass, to a wall, to the radiation device (e.g., at the scan horn), or to any structural support. Preferably the beam stop is fixed in relation to the scan horn so that the beam can be effectively controlled by the beam stop. The beam stop can incorporate a hinge, a rail, wheels, slots, or other means allowing for its operation in moving into and out of the beam. The beam stop can be made of any material that will stop at least 5% of the electrons, 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 electrons.

[0097] The beam stop can be made of a metal including, but not limited to, stainless steel, lead, iron, molybdenum, silver, gold, titanium, aluminum, tin, or alloys of these, or laminates (layered materials) made with such metals (e.g., metal-coated ceramic, metal- coated polymer, metal-coated composite, multilayered metal materials). [0098] The beam stop can be cooled, for example, with a cooling fluid such as an aqueous solution or a gas. The beam stop can be partially or completely hollow, for example with cavities. Interior spaces of the beam stop can be used for cooling fluids and gases. The beam stop can be of any shape, including flat, curved, round, oval, square, rectangular, beveled and wedged shapes.

[0099] The beam stop can have perforations so as to allow some electrons through, thus controlling (e.g., reducing) the levels of radiation across the whole area of the window, or in specific regions of the window. The beam stop can be a mesh formed, for example, from fibers or wires. Multiple beam stops can be used, together or

independently, to control the irradiation. The beam stop can be remotely controlled, e.g., by radio signal or hard wired to a motor for moving the beam into or out of position.

BEAM DUMPS

[00100] The embodiments disclosed herein can also include a beam dump when utilizing a radiation treatment. A beam dump's purpose is to safely absorb a beam of charged particles. Like a beam stop, a beam dump can be used to block the beam of charged particles. However, a beam dump is much more robust than a beam stop, and is intended to block the full power of the electron beam for an extended period of time. They are often used to block the beam as the accelerator is powering up.

[00101] Beam dumps are also designed to accommodate the heat generated by such beams, and are usually made from materials such as copper, aluminum, carbon, beryllium, tungsten, or mercury. Beam dumps can be cooled, for example, using a cooling fluid that can be in thermal contact with the beam dump.

BIOMASS MATERIALS

[00102] Lignocellulosic materials include, but are not limited to, wood, particle board, forestry wastes (e.g., sawdust, aspen wood, wood chips), grasses, (e.g., switchgrass, miscanthus, cord grass, reed canary grass), grain residues, (e.g., rice hulls, oat hulls, wheat chaff, barley hulls), agricultural waste (e.g., silage, canola straw, wheat straw, barley straw, oat straw, rice straw, jute, hemp, flax, bamboo, sisal, abaca, corn cobs, corn stover, soybean stover, corn fiber, alfalfa, hay, coconut hair), sugar processing residues (e.g., bagasse, beet pulp, agave bagasse), algae, seaweed, manure, sewage, and mixtures of any of these. [00103] In some cases, the lignocellulosic material includes corncobs. Ground or hammermilled corncobs can be spread in a layer of relatively uniform thickness for irradiation, and after irradiation are easy to disperse in the medium for further processing. To facilitate harvest and collection, in some cases the entire corn plant is used, including the corn stalk, corn kernels, and in some cases even the root system of the plant.

[00104] Advantageously, no additional nutrients (other than a nitrogen source, e.g., urea or ammonia) are required during fermentation of corncobs or cellulosic or lignocellulosic materials containing significant amounts of corncobs.

[00105] Corncobs, before and after comminution, are also easier to convey and disperse, and have a lesser tendency to form explosive mixtures in air than other cellulosic or lignocellulosic materials such as hay and grasses.

[00106] Cellulosic materials include, for example, paper, paper products, paper waste, paper pulp, pigmented papers, loaded papers, coated papers, filled papers, magazines, printed matter (e.g., books, catalogs, manuals, labels, calendars, greeting cards, brochures, prospectuses, newsprint), printer paper, polycoated paper, card stock, cardboard, paperboard, materials having a high ot-cellulose content such as cotton, and mixtures of any of these. For example paper products as described in U.S. App. No. 13/396,365 ("Magazine Feedstocks" by Medoff et al , filed February 14, 2012), the full disclosure of which is incorporated herein by reference.

[00107] Cellulosic materials can also include lignocellulosic materials which have been partially or fully de-lignified.

[00108] In some instances other biomass materials can be utilized, for example starchy materials. Starchy materials include starch itself, e.g., corn starch, wheat starch, potato starch or rice starch, a derivative 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, oca, sago, sorghum, regular household potatoes, sweet potato, taro, yams, or one or more beans, such as favas, lentils or peas. Blends of any two or more starchy materials are also starchy materials. Mixtures of starchy, cellulosic and or lignocellulosic materials can also be used. For example, a biomass can be an entire plant, a part of a plant or different parts of a plant, e.g., a wheat plant, cotton plant, a corn plant, rice plant or a tree. The starchy materials can be treated by any of the methods described herein.

[00109] Microbial materials that can be used as feedstock can include, but are not limited to, any naturally occurring or genetically modified microorganism or organism that contains or is capable of providing a source of carbohydrates (e.g., cellulose), for example, protists, e.g., animal protists (e.g., protozoa such as flagellates, amoeboids, ciliates, and sporozoa) and plant protists (e.g., algae such alveolates,

chlorarachniophytes, cryptomonads, euglenids, glaucophytes, haptophytes, red algae, stramenopiles, and viridaeplantae). Other examples include seaweed, plankton (e.g., macroplankton, mesoplankton, microplankton, nanoplankton, picoplankton, and femptoplankton), phytoplankton, bacteria (e.g., gram positive bacteria, gram negative bacteria, and extremophiles), yeast and/or mixtures of these. In some instances, microbial biomass can be obtained from natural sources, e.g., the ocean, lakes, bodies of water, e.g., salt water or fresh water, or on land. Alternatively or in addition, microbial biomass can be obtained from culture systems, e.g., large scale dry and wet culture and fermentation systems.

[00110] In other embodiments, the biomass materials, such as cellulosic, starchy and lignocellulosic feedstock materials, can be obtained from transgenic microorganisms and plants that have been modified with respect to a wild type variety. Such modifications may be, for example, through the iterative steps of selection and breeding to obtain desired traits in a plant. Furthermore, the plants can have 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 specific genes from parental varieties, or, for example, by using transgenic breeding wherein a specific gene or genes are introduced to a plant from a different species of plant and/or bacteria. Another way to create genetic variation is through mutation breeding wherein new alleles are artificially created from endogenous genes. The artificial genes can be created by a variety of ways including treating the plant or seeds with, for example, chemical mutagens (e.g., using alkylating agents, epoxides, alkaloids, peroxides, formaldehyde), irradiation (e.g., X-rays, gamma rays, neutrons, beta particles, alpha particles, protons, deuterons, UV radiation) and temperature shocking or other external stressing and subsequent selection techniques. Other methods of providing modified genes is through error prone PCR and DNA shuffling followed by insertion of the desired modified DNA into the desired plant or seed. Methods of introducing the desired genetic variation in the seed or plant include, for example, the use of a bacterial carrier, biolistics, calcium phosphate precipitation, electroporation, gene splicing, gene silencing, lipofection, microinjection and viral carriers. Additional genetically modified materials have been described in U.S. Application Serial No 13/396,369 filed February 14, 2012 the full disclosure of which is incorporated herein by reference. Any of the methods described herein can be practiced with mixtures of any biomass materials described herein.

BIOMASS MATERIAL PREPARATION - MECHANICAL TREATMENTS

[00111] The biomass can be in a dry form, for example with less than about 35% moisture content (e.g., less than about 20 %, less than about 15 %, less than about 10 % less than about 5 %, less than about 4%, less than about 3 %, less than about 2 % or even less than about 1 %). The biomass can also be delivered in a wet state, for example as a wet solid, a slurry or a suspension with at least about 10 wt.% solids (e.g., at least about 20 wt.%, at least about 30 wt. %, at least about 40 wt.%, at least about 50 wt.%, at least about 60 wt.%, at least about 70 wt.%).

[00112] The processes disclosed herein can utilize low bulk density materials, for example cellulosic or lignocellulosic feedstocks that have been physically pretreated to have a bulk density of less than about 0.75 g/cm ³ , 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/cm ³ . Bulk density is determined using ASTM D1895B. Briefly, the method involves filling a measuring cylinder of known volume with a sample and obtaining a weight of the sample. The bulk density is calculated by dividing the weight of the sample in grams by the known volume of the cylinder in cubic centimeters. If desired, low bulk density materials can be densified, for example, by methods described in U.S. Pat. No. 7,971,809 to Medoff, the full disclosure of which is hereby incorporated by reference.

[00113] In some cases, the pre-treatment processing includes screening of the biomass material. Screening can be through a mesh or perforated plate with a desired opening size, for example, less than about 6.35 mm (1/4 inch, 0.25 inch), (e.g., less than about 3.18 mm (1/8 inch, 0.125 inch), less than about 1.59 mm (1/16 inch, 0.0625 inch), is less than about 0.79 mm (1/32 inch, 0.03125 inch), e.g., less than about 0.51 mm (1/50 inch, 0.02000 inch), less than about 0.40 mm (1/64 inch, 0.015625 inch), less than about 0.23 mm (0.009 inch), less than about 0.20 mm (1/128 inch, 0.0078125 inch), less than about 0.18 mm (0.007 inch), less than about 0.13 mm (0.005 inch), or even less than about 0.10 mm (1/256 inch, 0.00390625 inch)). In one configuration the desired biomass falls through the perforations or screen and thus biomass larger than the perforations or screen are not irradiated. These larger materials can be re-processed, for example, by comminuting, or they can simply be removed from processing. In another configuration material that is larger than the perforations is irradiated and the smaller material is removed by the screening process or recycled. In this kind of a configuration, the conveyor itself (for example a part of the conveyor) can be perforated or made with a mesh. For example, in one particular embodiment the biomass material may be wet and the perforations or mesh allow water to drain away from the biomass before irradiation.

[00114] 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.

[00115] Optional pre-treatment processing can include heating the material. For example a portion of a conveyor conveying the material 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), resistive heating and/or inductive coils. The heat can be applied from at least one side or more than one side, can be continuous or periodic and can be for only a portion of the material or all the material. For example, a portion of the conveying trough can be heated by use of a heating jacket. Heating can be, for example, for the purpose of drying the material. In the case of drying the material, this can also be facilitated, with or without heating, by the movement of a gas (e.g., air, oxygen, nitrogen, He, C0 ₂ , Argon) over and/or through the biomass as it is being conveyed.

[00116] Optionally, pre-treatment processing can include cooling the material.

Cooling material is described in US Pat. No. 7,900,857 to Medoff, the disclosure of which in incorporated herein by reference. For example, cooling can be by supplying a cooling fluid, for example water (e.g., with glycerol), or nitrogen (e.g., liquid nitrogen) to the bottom of the conveying trough. Alternatively, a cooling gas, for example, chilled nitrogen can be blown over the biomass materials or under the conveying system.

[00117] Another optional pre-treatment processing method can include adding a material to the biomass or other feedstocks. The additional material can be added by, for example, by showering, sprinkling and or pouring the material onto the biomass as it is conveyed. Materials that can be added include, for example, metals, ceramics and/or ions as described in U.S. Pat. App. Pub. 2010/0105119 Al (filed October 26, 2009) and U.S. Pat. App. Pub. 2010/0159569 Al (filed December 16, 2009), the entire disclosures of which are incorporated herein by reference. Optional materials that can be added include acids and bases. Other materials that can be added are oxidants (e.g., peroxides, chlorates), polymers, polymerizable monomers (e.g., containing unsaturated bonds), water, catalysts, enzymes and/or organisms. Materials can be added, for example, in pure form, as a solution in a solvent (e.g., water or an organic solvent) and/or as a solution. In some cases the solvent is volatile and can be made to evaporate e.g., by heating and/or blowing gas as previously described. The added material may form a uniform coating on the biomass or be a homogeneous mixture of different components (e.g., biomass and additional material). The added material can modulate the subsequent irradiation step by increasing the efficiency of the irradiation, damping the irradiation or changing the effect of the irradiation (e.g., from electron beams to X-rays or heat). The method may have no impact on the irradiation but may be useful for further downstream processing. The added material may help in conveying the material, for example, by lowering dust levels.

[00118] Biomass can be delivered to a conveyor (e.g., vibratory conveyors 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 atmosphere and/or control dust and fines. Lofted or air suspended biomass fines and dust are undesirable because these can form an explosion hazard or damage the window foils of an electron gun (if such a device is used for treating the material).

[00119] The material can be leveled to form a uniform thickness between about 0.0312 and 5 inches (e.g., between about 0.0625 and 2.000 inches, between about 0.125 and 1 inches, between about 0.125 and 0.5 inches, between about 0.3 and 0.9 inches, between about 0.2 and 0.5 inches between about 0.25 and 1.0 inches, between about 0.25 and 0.5 inches, 0.100 +/- 0.025 inches, 0.150 +/- 0.025 inches, 0.200 +/- 0.025 inches, 0.250 +/- 0.025 inches, 0.300 +/- 0.025 inches, 0.350 +/- 0.025 inches, 0.400 +/- 0.025 inches, 0.450 +/- 0.025 inches, 0.500 +/- 0.025 inches, 0.550 +/- 0.025 inches, 0.600 +/- 0.025 inches, 0.700 +/- 0.025 inches, 0.750 +/- 0.025 inches, 0.800 +/- 0.025 inches, 0.850 +/- 0.025 inches, 0.900 +/- 0.025 inches, 0.900 +/- 0.025 inches.

[00120] Generally, it is preferred to convey the material as quickly as possible through the electron beam to maximize throughput. For example, the material can be conveyed at rates of at least 1 ft/min, e.g., at least 2 ft/min, at least 3 ft/min, at least 4 ft/min, at least 5 ft/min, at least 10 ft/min, at least 15 ft/min, 20, 25, 30, 35, 40, 45, 50 ft/min. The rate of conveying is related to the beam current, for example, for a ¼ 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.

[00121] 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, the biomass can be screened, heated, cooled, and/or combined with additives. Uniquely to post-irradiation, quenching of the radicals can occur, for example, quenching of radicals by the addition of fluids or gases (e.g., 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 (e.g., oxygen) where it is quenched, forming caboxylated groups. In one

embodiment the biomass is exposed during irradiation to the reactive gas or fluid.

Quenching of biomass that has been irradiated is described in U.S. Pat. No. 8,083,906 to Medoff, the entire disclosure of which is incorporate herein by reference.

[00122] If desired, one or more mechanical treatments can be used in addition to irradiation to further reduce the recalcitrance of the carbohydrate-containing material. These processes can be applied before, during and or after irradiation.

[00123] In some cases, the mechanical treatment may include an initial preparation of the feedstock as received, e.g., size reduction of materials, such as by comminution, e.g., cutting, grinding, shearing, pulverizing or chopping. For example, in some cases, loose feedstock (e.g., recycled paper, starchy materials, or switchgrass) is prepared by shearing or shredding. Mechanical treatment may reduce the bulk density of the carbohydrate- containing material, increase the surface area of the carbohydrate-containing material and/or decrease one or more dimensions of the carbohydrate-containing material.

[00124] Alternatively, or in addition, the feedstock material can be treated with another treatment, for example, chemical treatments, such as one with an acid (HC1, H ₂ SO ₄ , H ₃ PO ₄ ), a base (e.g., KOH and NaOH), a chemical oxidant (e.g., peroxides, chlorates, ozone), irradiation, steam explosion, pyrolysis, sonication, oxidation, chemical treatment. The treatments can be in any order and in any sequence and combinations. For example, 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 HC1, H ₂ SO ₄ , H ₃ PO ₄ ), radiation, sonication, oxidation, pyrolysis or steam explosion, and then mechanically treated. This sequence can be advantageous since materials treated by one or more of the other treatments, e.g., irradiation or pyrolysis, tend to be more brittle and, therefore, it may be easier to further change the structure of the material by mechanical treatment. As another example, a feedstock material can be conveyed through ionizing radiation using a conveyor as described herein and then mechanically treated. Chemical treatment can remove some or all of the lignin (for example, chemical pulping) and can partially or completely hydrolyze the material. The methods also can be used with pre -hydrolyzed material. The methods also can be used with material that has not been pre hydrolyzed. The methods can be used with mixtures of hydrolyzed and non-hydrolyzed materials, for example, with about 50% or more 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.

[00125] In addition to size reduction, which can be performed initially and/or later in processing, mechanical treatment can also be advantageous for "opening up,"

"stressing," breaking or shattering the carbohydrate-containing materials, making the cellulose of the materials more susceptible to chain scission and/or disruption of crystalline structure during the physical treatment.

[00126] Methods of mechanically treating the carbohydrate-containing material include, for example, milling or grinding. Milling may be performed using, for example, a hammer mill, ball mill, colloid mill, conical or cone mill, disk mill, edge mill, Wiley mill, 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 internal structure of the material that was initiated by the previous processing steps.

[00127] Mechanical feed preparation systems can be configured to produce streams with specific characteristics such as, for example, specific maximum sizes, specific length-to-width, or specific surface areas ratios. Physical preparation can increase the rate of reactions, improve the movement of material on a conveyor, improve the irradiation profile of the material, improve the radiation uniformity of the material, or reduce the processing time required by opening up the materials and making them more accessible to processes and/or reagents, such as reagents in a solution.

[00128] The bulk density of feedstocks can be controlled (e.g., increased). In some situations, it can be desirable to prepare a low bulk density material, e.g., by densifying the material (e.g., densification can make it easier and less costly to transport to another site) and then reverting the material to a lower bulk density state (e.g., after transport). The material can be densified, for example, from less than about 0.2 g/cc to more than about 0.9 g/cc (e.g., less than about 0.3 to more than about 0.5 g/cc, less than about 0.3 to more than about 0.9 g/cc, less than about 0.5 to more than about 0.9 g/cc, less than about 0.3 to more than about 0.8 g/cc, less than about 0.2 to more than about 0.5 g/cc). For example, the material can be densified by the methods and equipment disclosed in U.S. Pat. No. 7,932,065 to Medoff and International Publication No. WO 2008/073186 (which was filed October 26, 2007, was published in English, and which designated the United States), the full disclosures of which are incorporated herein by reference.

Densified materials can be processed by any of the methods described herein, or any material processed by any of the methods described herein can be subsequently densified.

[00129] In some embodiments, the material to be processed is in the form of a fibrous material that includes fibers provided by shearing a fiber source. For example, the shearing can be performed with a rotary knife cutter.

[00130] For example, a fiber source, e.g., that is recalcitrant or that has had its recalcitrance level reduced, can be sheared, e.g., in a rotary knife cutter, to provide a first fibrous material. The first fibrous material is passed through a first screen, e.g., having an average opening size of 1.59 mm or less (1/16 inch, 0.0625 inch), provide a second fibrous material. If desired, the fiber source can be cut 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 cut into strips that are, e.g., 1/4- to 1/2-inch wide, using a shredder, e.g., a counter- rotating screw shredder, such as those manufactured by Munson (Utica, N.Y.). As an alternative to shredding, the paper can be reduced in size by cutting to a desired size using a guillotine cutter. For example, the guillotine cutter can be used to cut the paper into sheets that are, e.g., 10 inches wide by 12 inches long.

[00131] In some embodiments, the shearing of the fiber source and the passing of the resulting first fibrous material through a first screen are performed concurrently. The shearing and the passing can also be performed in a batch-type process.

[00132] For example, a rotary knife cutter can be used to concurrently shear the fiber source and screen the first fibrous material. A rotary knife cutter includes a hopper that can be loaded with a shredded fiber source prepared by shredding a fiber source.

[00133] In some implementations, the feedstock is physically treated prior to saccharification and/or fermentation. Physical treatment processes can include one or more of any of those described herein, such as mechanical treatment, chemical treatment, irradiation, sonication, oxidation, pyrolysis or steam explosion. Treatment methods can be used in combinations of two, three, four, or even all 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 molecular structure of a biomass feedstock may also be used, alone or in combination with the processes disclosed herein.

[00134] Mechanical treatments that may be used, and the characteristics of the mechanically treated carbohydrate-containing materials, are described in further detail in U.S. Pat. App. Pub. 2012/0100577 Al, filed October 18, 2011, the full disclosure of which is hereby incorporated herein by reference.

SONICATION, PYROLYSIS, OXIDATION, STEAM EXPLOSION

[00135] If desired, one or more sonication, pyrolysis, oxidative, or steam explosion processes can be used instead of or in addition to irradiation to reduce or further reduce the recalcitrance of the carbohydrate-containing material. For example, these processes can be applied before, during and or after irradiation. These processes are described in detail in U.S. Pat. No. 7,932,065 to Medoff, the full disclosure of which is incorporated herein by reference.

INTERMEDIATES AND PRODUCTS

[00136] 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 internal combustion engines or feedstocks for fuel cells. Systems and processes are described herein that can use as feedstock cellulosic and/or lignocellulosic materials that are readily available, but often can be difficult to process, e.g., municipal waste streams and waste paper streams, such as streams that include newspaper, Kraft paper, corrugated paper or mixtures of these.

[00137] Specific examples of products include, but are not limited to, hydrogen, sugars (e.g., glucose, xylose, arabinose, mannose, galactose, fructose, disaccharides, oligosaccharides and polysaccharides), alcohols (e.g., monohydric alcohols or dihydric alcohols, such as ethanol, n-propanol, isobutanol, seobutanol, tert-butanol or n-butanol), hydrated or hydrous alcohols (e.g., containing greater than 10%, 20%, 30% or even greater than 40% water), biodiesel, organic acids, hydrocarbons (e.g., methane, ethane, propane, isobutene, pentane, n-hexane, biodiesel, bio-gasoline and mixtures thereof), co- products (e.g., proteins, such as cellulolytic proteins (enzymes) or single cell proteins), and mixtures of any of these in any combination or relative concentration, and optionally in combination with any additives (e.g., fuel additives). Other examples include carboxylic acids, salts of a carboxylic acid, a mixture of carboxylic acids and salts of carboxylic acids and esters of carboxylic acids (e.g., methyl, ethyl and n-propyl esters), ketones (e.g., acetone), aldehydes (e.g., acetaldehyde), alpha and beta unsaturated acids (e.g., acrylic acid) and olefins (e.g., ethylene). Other alcohols and alcohol derivatives include propanol, propylene glycol, 1 ,4-butanediol, 1,3 -propanediol, sugar alcohols (e.g., erythritol, glycol, glycerol, sorbitol threitol, arabitol, ribitol, mannitol, dulcitol, fucitol, iditol, isomalt, maltitol, lactitol, xylitol and other polyols), and methyl or ethyl esters of any of these alcohols. Other products include methyl acrylate, methyl methacrylate, D- lactic acid, L-lactic acid pyruvic acid, polylactic acid, citric acid, formic acid, acetic acid, propionic acid, lactic acid, tartaric acid, butyric acid, succinic acid, valeric acid, caproic acid, 3-hydroxypropionic acid, palmitic acid, stearic acid, oxalic acid, malonic acid, glutaric acid, oleic acid, linoleic acid, glycolic acid, gamma-hydroxybutyric acid, and mixtures thereof, salts of any of these acids, mixtures of any of the acids and their respective salts.

[00138] Any combination of the above products with each other, and/or of the above products with other products, which other products may be made by the processes described herein or otherwise, may be packaged together and sold as products. The products may be combined, e.g., mixed, blended or co-dissolved, or may simply be packaged or sold together.

[00139] Any of the products or combinations of products described herein may be sanitized or sterilized prior to selling the products, e.g., after purification or isolation or even after packaging, to neutralize one or more potentially undesirable contaminants that could be present in the product(s). Such sanitation can be done with electron

bombardment, for example, be 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.

[00140] The processes described herein can produce various by-product streams useful for generating steam and electricity to be used in other parts of the plant (co- generation) or sold on the open market. For example, steam generated from burning byproduct streams can be used in a distillation process. As another example, electricity generated from burning by-product streams can be used to power electron beam generators used in pretreatment.

[00141] The by-products used to generate steam and electricity are derived from a number of sources throughout the process. For example, anaerobic 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., burned, as a fuel.

[00142] Other intermediates and products, including food and pharmaceutical products, are described in U.S. Pat. App. Pub. 2010/0124583 Al, published May 20, 2010, to Medoff, the full disclosure of which is hereby incorporated by reference herein.

LIGNIN DERIVED PRODUCTS

[00143] The spent biomass (e.g., spent lignocellulosic material) from lignocellulosic processing by the methods described are expected to have a high lignin content and in addition to being useful for producing energy through combustion in a Co-Generation plant, may have uses as other valuable products. For example, the lignin can be used as captured as a plastic, or it can be synthetically upgraded to other plastics. In some instances, it can also be converted to lignosulfonates, which can be utilized as binders, dispersants, emulsifiers or as sequestrants.

[00144] 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 linoleum paste and as a soil stabilizer.

[00145] When used as a dispersant, the lignin or lignosulfonates can be used, for example in, concrete mixes, clay and ceramics, dyes and pigments, leather tanning and in gypsum board.

[00146] When used as an emulsifier, the lignin or lignosulfonates can be used, e.g., in asphalt, pigments and dyes, pesticides and wax emulsions.

[00147] As a sequestrant, the lignin or lignosulfonates can be used, e.g., in micro- nutrient systems, cleaning compounds and water treatment systems, e.g., for boiler and cooling systems. [00148] 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 have an energy content of between about 11,000 and 12,500 BTU per pound, compared to 7,000 an 8,000 BTU per pound of holocellulose. As such, lignin can be densified and converted into briquettes and pellets for burning. For example, the lignin can be converted into pellets by any method described herein. For a slower burning pellet or briquette, the lignin can be crosslinked, such as applying a radiation dose of between about 0.5 Mrad and 5 Mrad. Crosslinking can make a slower burning 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 desirable to crosslink the lignin to maintain structural integrity.

SACCHARIFICATION

[00149] In order to convert the feedstock to a form that can be readily processed, the glucan- or xylan-containing cellulose in the feedstock can be hydrolyzed to low molecular weight carbohydrates, such as sugars, by a saccharifying agent, e.g., an enzyme or acid, a process referred to as saccharification. The low molecular weight carbohydrates can then be used, for example, in an existing manufacturing plant, such as a single cell protein plant, an enzyme manufacturing plant, or a fuel plant, e.g., an ethanol manufacturing facility.

[00150] The feedstock can be hydrolyzed using an enzyme, e.g., by combining the materials and the enzyme in a solvent, e.g., in an aqueous solution.

[00151] Alternatively, 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 molecule biomass-degrading metabolites. These enzymes may be a complex of enzymes that act synergistically to degrade crystalline cellulose or the lignin portions of biomass. Examples of cellulolytic enzymes include: endoglucanases, cellobiohydrolases, and cellobiases (beta-glucosidases).

[00152] During saccharification a cellulosic substrate can be initially hydrolyzed by endoglucanases at random locations producing oligomeric intermediates. These intermediates are then substrates for exo-splitting glucanases such as cellobiohydrolase to produce cellobiose from the ends of the cellulose polymer. Cellobiose is a water- soluble 1 ,4-linked dimer of glucose. Finally, cellobiase cleaves cellobiose to yield glucose. The efficiency (e.g., time to hydrolyze and/or completeness of hydrolysis) of this process depends on the recalcitrance of the cellulosic material.

[00153] Therefore, the treated biomass materials can be saccharified, generally by combining the material and a cellulase enzyme in a fluid medium, e.g., an aqueous solution. In some cases, the material is boiled, steeped, or cooked in hot water prior to saccharification, as described in U.S. Pat. App. Pub. 2012/0100577 Al by Medoff and Masterman, published on April 26, 2012, the entire contents of which are incorporated herein.

[00154] 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 complete saccharification will depend 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.

[00155] It is generally preferred that the tank contents be mixed during

saccharification, e.g., using jet mixing as described in International App. No.

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

[00156] The addition of surfactants can enhance the rate of saccharification.

Examples of surfactants include non-ionic surfactants, such as a Tween® 20 or Tween® 80 polyethylene glycol surfactants, ionic surfactants, or amphoteric surfactants.

[00157] It is generally preferred that the concentration of the sugar solution resulting from saccharification be relatively high, e.g., greater than 40%, or greater than 50, 60, 70, 80, 90 or even greater than 95% by weight. Water may be removed, e.g., by evaporation, to increase the concentration of the sugar solution. This reduces the volume to be shipped, and also inhibits microbial growth in the solution.

[00158] Alternatively, sugar solutions of lower concentrations may be used, in which case it may be desirable to add an antimicrobial additive, e.g., a broad spectrum antibiotic, in a low concentration, e.g., 50 to 150 ppm. Other suitable antibiotics include amphotericin B, ampicillin, chloramphenicol, ciprofloxacin, gentamicin, hygromycin B, kanamycin, neomycin, penicillin, puromycin, streptomycin. Antibiotics will inhibit growth of microorganisms during transport and storage, and can be used at appropriate concentrations, e.g., between 15 and 1000 ppm by weight, e.g., between 25 and 500 ppm, or between 50 and 150 ppm. If desired, an antibiotic can be included even if the sugar concentration is relatively high. Alternatively, other additives with anti-microbial of preservative properties may be used. Preferably the antimicrobial additive(s) are food- grade.

[00159] A relatively high concentration solution can be obtained by limiting the amount of water added to the carbohydrate-containing material with the enzyme. The concentration can be controlled, e.g., by controlling how much saccharification takes place. For example, concentration can be increased by adding more carbohydrate- containing material to the solution. In order to keep the sugar that is being produced in solution, a surfactant can be added, e.g., one of those discussed above. Solubility can also be increased by increasing the temperature of the solution. For example, the solution can be maintained at a temperature of 40-50°C, 60-80°C, or even higher.

SACCHARIFYING AGENTS

[00160] Suitable cellulolytic enzymes include cellulases from species in the genera Bacillus, Coprinus, Myceliophthora, Cephalosporium, Scytalidium, Penicillium, Aspergillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium,

Chrysosporium and Trichoderma, especially those produced by a strain selected from the species Aspergillus (see, e.g., EP Pub. No. 0 458 162), Humicola insolens (reclassified as Scytalidium thermophilum, see, e.g., U.S. Pat. No. 4,435,307), Coprinus cinereus, Fusarium oxysporum, Myceliophthora thermophila, Meripilus giganteus, Thielavia terrestris, Acremonium sp. (including, but not limited to, A. persicinum, A. acremonium, A. brachypenium, A. dichromosporum, A. obclavatum, A. pinkertoniae, A. roseogriseum, A. incoloratum, and A. furatum). Preferred strains include Humicola insolens DSM 1800, Fusarium oxysporum DSM 2672, Myceliophthora thermophila CBS 117.65, Cephalosporium sp. RYM-202, Acremonium sp. CBS 478.94, Acremonium sp. CBS 265.95, Acremonium persicinum CBS 169.65, Acremonium acremonium AHU 9519, Cephalosporium sp. CBS 535.71, Acremonium brachypenium CBS 866.73, Acremonium dichromosporum CBS 683.73, Acremonium obclavatum CBS 311.74, Acremonium pinkertoniae CBS 157.70, Acremonium roseogriseum CBS 134.56, Acremonium incoloratum CBS 146.62, 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. Pat. No. 3,844,890 and EP Pub. No. 0 458 162), and Streptomyces (see, e.g., EP Pub. No. 0 458 162).

[00161] In addition to or in combination to enzymes, acids, bases and other chemicals (e.g., oxidants) can be utilized to saccharify lignocellulosic and cellulosic materials. These can be used in any combination or sequence (e.g., before, after and/or during addition of an enzyme). For example strong mineral acids can be utilized (e.g. HC1, H ₂ SO ₄ , H ₃ PO ₄ ) and strong bases (e.g., NaOH, KOH).

SUGARS

[00162] In the processes described herein, for example after saccharification, sugars (e.g., glucose and xylose) can be isolated. For example sugars can be isolated by precipitation, crystallization, chromatography (e.g., simulated moving bed

chromatography as described herein, high pressure chromatography), centrifugation, extraction, any other isolation method known in the art, and combinations thereof.

HYDROGENATION AND OTHER CHEMICAL TRANSFORMATIONS

[00163] The processes described herein can include hydrogenation. For example glucose and xylose can be hydrogenated to sorbitol and xylitol respectively.

Hydrogenation can be accomplished by use of a catalyst (e.g., Pt/gamma-Al ₂ C>3, Ru/C, Raney Nickel, or other catalysts know in the art) in combination with H ₂ under high pressure (e.g., 10 to 12000 psi). Other types of chemical transformation of the products from the processes described herein can be used, for example production of organic sugar derived products (e.g., furfural and furfural-derived products). Chemical transformations of sugar derived products are described in USSN 13/934,704 filed July 3, 2013, the entire disclosure of which is incorporated herein by reference.

FERMENTATION

[00164] Yeast and Zymomonas bacteria, for example, can be used for fermentation or conversion of sugar(s) to alcohol(s). Other microorganisms are discussed below. The optimum pH for fermentations is about pH 4 to 7. For example, the optimum pH for yeast is from about pH 4 to 5, while the optimum pH for Zymomonas is from about pH 5 to 6. Typical fermentation times are about 24 to 168 hours {e.g., 24 to 96 hrs) with temperatures in the range of 20°C to 40°C {e.g., 26°C to 40°C), however thermophilic microorganisms prefer higher temperatures.

[00165] In some embodiments, e.g., when anaerobic 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 N ₂ , Ar, He, C0 ₂ or mixtures thereof. Additionally, the mixture may have a constant purge of an inert gas flowing through the tank during part of or all of the fermentation. In some cases, anaerobic condition, can be achieved or maintained by carbon dioxide production during the fermentation and no additional inert gas is needed.

[00166] In some embodiments, all or a portion of the fermentation process can be interrupted before the low molecular weight sugar is completely converted to a product {e.g., ethanol). The intermediate fermentation products include sugar and carbohydrates in high concentrations. The sugars and carbohydrates can be isolated via any means known in the art. These intermediate fermentation products can be used in preparation of food for human or animal consumption. Additionally or alternatively, the intermediate fermentation products can be ground to a fine particle size in a stainless-steel laboratory mill to produce a flour- like substance. Jet mixing may be used during fermentation, and in some cases saccharification and fermentation are performed in the same tank.

[00167] Nutrients for the microorganisms may be added during saccharification and/or fermentation, for example the food-based nutrient packages described in U.S. Pat. App. Pub. 2012/0052536, filed July 15, 2011, the complete disclosure of which is incorporated herein by reference.

[00168] "Fermentation" includes the methods and products that are disclosed in application Nos. PCT/US2012/71093 published June 27, 2013, PCT/US2012/71907 published June 27, 2012, and PCT/US2012/71083 published June 27, 2012 the contents of which are incorporated by reference herein in their entirety.

[00169] Mobile fermenters can be utilized, as described in International App. No. PCT/US2007/074028 (which was filed July 20, 2007, was published in English as WO 2008/011598 and designated the United States) and has a US issued Patent No.

8,318,453, the contents of which are incorporated herein in its entirety. Similarly, the saccharification equipment can be mobile. Further, saccharification and/or fermentation may be performed in part or entirely during transit. FERMENTATION AGENTS

[00170] The microorganism(s) used in fermentation can be naturally-occurring microorganisms and/or engineered microorganisms. For example, the microorganism can be a bacterium (including, but not limited to, e.g., a cellulolytic bacterium), a fungus, (including, but not limited to, e.g., a yeast), a plant, a protist, e.g., a protozoa or a funguslike protest (including, but not limited to, e.g., a slime mold), or an alga. When the organisms are compatible, mixtures of organisms can be utilized.

[00171] Suitable fermenting microorganisms have 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, S. cerevisiae (baker's yeast), S. distaticus, S. uvarum), the genus

Kluyveromyces, (including, but not limited to, K. marxianus, K. fragilis), the genus Candida (including, but not limited to, C. pseudotropicalis, and C. brassicae), Pichia stipitis (a relative of Candida shehatae), the genus Clavispora (including, but not limited to, C. lusitaniae and C. opuntiae), the genus Pachysolen (including, but not limited to, P. tannophilus), the genus Bretannomyces (including, but not limited to, e.g., B. clausenii (Philippidis, G. P., 1996, Cellulose bioconversion technology, in Handbook on

Bioethanol: Production and Utilization, Wyman, C.E., ed., Taylor & Francis,

Washington, DC, 179-212)). Other suitable microorganisms include, for example, Zymomonas mobilis, Clostridium spp. (including, but not limited to, C. thermocellum (Philippidis, 1996, supra), C. saccharobutylacetonicum, C. tyrobutyricum C.

saccharobutylicum, C. Puniceum, C. beijernckii, and C. acetobutylicum), Moniliella spp. ( including but not limited to M. pollinis,M. tomentosa, M. madida, M. nigrescens, M. oedocephali, M. megachiliensis), Yarrowia lipolytica, Aureobasidium sp.,

Trichosporonoides sp., Trigonopsis variabilis, Trichosporon sp., Moniliellaacetoabutans sp., Typhula variabilis, Candida magnoliae, Ustilaginomycetes sp., Pseudozyma tsukubaensis, yeast species of genera Zygosaccharomyces, Debaryomyces, Hansenula and Pichia, and fungi of the dematioid genus Torula (e.g., Tcorallina).

[00172] Additional microorganisms include the Lactobacillus group. Examples include Lactobacillus casei, Lactobacillus rhamnosus, Lactobacillus delbrueckii, Lactobacillus plantarum, Lactobacillus coryniformis, e.g., Lactobacillus coryniformis subspecies torquens, Lactobacillus pentosus, Lactobacillus brevis. Other

microorganisms include Pediococus penosaceus, Rhizopus oryzae. [00173] Many such microbial strains are publicly available, either commercially or through depositories such as the ATCC (American Type Culture Collection, Manassas, Virginia, USA), the NRRL (Agricultural Research Service Culture Collection, Peoria, Illinois, USA), or the DSMZ (Deutsche Sammlung von Mikroorganismen und

Zellkulturen GmbH, Braunschweig, Germany), to name a few.

[00174] Commercially available yeasts include, for example, RED STAR®/Lesaffre Ethanol Red (available from Red Star/Lesaffre, USA), FALI ^® (available from

Fleischmann's Yeast, a division of Burns Philip Food Inc., USA), SUPERSTART ^® (available from Alltech, now Lalemand), GERT STRAND ^® (available from Gert Strand AB, Sweden) and FERMOL ^® (available from DSM Specialties).

DISTILLATION

[00175] After fermentation, the resulting fluids can be distilled using, for example, a "beer column" to separate ethanol and other alcohols from the majority of water and residual solids. The vapor exiting the beer column can be, e.g., 35% by weight ethanol and can be fed to a rectification column. A mixture of nearly azeotropic (92.5%) ethanol and water from the rectification column can be purified to pure (99.5%) ethanol using vapor-phase molecular sieves. The beer column bottoms can be sent to the first effect of a three-effect evaporator. The rectification column reflux condenser can provide heat for this first effect. After the first effect, solids can be separated using a centrifuge and dried in a rotary dryer. A portion (25%) of the centrifuge effluent can be recycled to fermentation and the rest sent to the second and third evaporator effects. Most of the evaporator condensate can be returned 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

[00176] In other embodiments utilizing the methods and systems described herein, hydrocarbon-containing materials, for example that are mixed with biomass can be processed. Any process described herein can be used to treat any hydrocarbon-containing material herein described. "Hydrocarbon-containing materials," as used herein, is meant to include oil sands, oil shale, tar sands, coal dust, coal slurry, bitumen, various types of coal, and other naturally-occurring and synthetic materials that include both hydrocarbon components and solid matter. The solid matter can include wood, rock, sand, clay, stone, silt, drilling slurry, or other solid organic and/or inorganic matter. The term can also include waste products such as drilling waste and by-products, refining waste and byproducts, or other waste products containing hydrocarbon components, such as asphalt shingling and covering, asphalt pavement, etc.

CONVEYING SYSTEMS

[00177] Various conveying systems can be used to convey the biomass material, for example, as previously discussed, to a vault, and under an electron beam in a vault. Exemplary conveyors are belt conveyors, pneumatic conveyors, screw conveyors, carts, trains, trains or carts on rails, elevators, front loaders, backhoes, cranes, various scrapers and shovels, trucks, and throwing devices can be used. For example, vibratory conveyors can be used in various processes described herein. Vibratory conveyors are described in PCT/US2013/64289 filed October 10, 2013 the full disclosure of which is incorporated by reference herein.

[00178] Vibratory conveyors are particularly useful for spreading the material and producing a uniform layer on the conveyor trough surface. For example the initial feedstock can form a pile of material that can be at least four feet high (e.g., at least about 3 feet, at least about 2 feet, at least about 1 foot, at least about 6 inches, at least about 5 inches, at least about, 4 inches, at least about 3 inches, at least about 2 inches, at least about 1 inch, at least about ½ inch) and spans less than the width of the conveyor (e.g., less than about 10%, less than about 20%, less than about 30%, less than about 40%, less than about 50%, less than about 60%, less than about 70%, less than about 80%, less than about 90%, less than about 95%, less than about 99%). The vibratory conveyor can spread the material to span the entire width of the conveyor trough and have a uniform thickness, preferably as discussed above. In some cases, an additional spreading method can be useful. For example, a spreader such as a broadcast spreader, a drop spreader (e.g., a CHRISTY SPREADER™) or combinations thereof can be used to drop (e.g., place, pour, spill and/or sprinkle) the feedstock over a wide area. Optionally, the spreader can deliver the biomass as a wide shower or curtain onto the vibratory conveyor. Additionally, a second conveyor, upstream from the first conveyor (e.g., the first conveyor is used in the irradiation of the feedstock), can drop biomass onto the first conveyor, where the second conveyor can have 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 cut discharge (e.g., a bias cut with a ratio of 4: 1) so that the material can be dropped as a wide curtain (e.g., wider than the width of the second conveyor) onto the first conveyor. The initial drop area of the biomass by the spreader (e.g., broadcast spreader, drop spreader, conveyor, or cross cut vibratory conveyor) can span the entire width of the first vibratory conveyor, or it can span part of this width. Once dropped onto the conveyor, the material is spread even more uniformly by the vibrations of the conveyor so that, preferably, the entire width of the conveyor is covered with a uniform layer of biomass. In some embodiments combinations of spreaders can be used. Some methods of spreading a feed stock are described in U.S. Patent No. 7,153,533, filed July 23, 2002 and published December 26, 2006, the entire disclosure of which is incorporated herein by reference.

[00179] Generally, it is preferred to convey the material as quickly as possible through an electron beam to maximize throughput. For example, the material can be conveyed at rates of at least 1 ft/min, e.g., at least 2 ft/min, at least 3 ft/min, at least 4 ft/min, at least 5 ft/min, at least 10 ft/min, at least 15 ft/min, at least 20 ft/min, at least 25 ft/min, at least 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 ¼ 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.

[00180] The rate at which material can be conveyed depends on the shape and mass of the material being conveyed, and the desired treatment. Flowing materials e.g., particulate materials, are particularly amenable to conveying with vibratory conveyors. Conveying speeds can, for example be, at least 100 lb hr (e.g., at least 500 lb hr, at least 1000 lb hr, at least 2000 lb hr, at least 3000 lb hr, at least 4000 lb hr, at least 5000 lb/hr, at least 10,000 lb hr, at least 15, 000 lb hr, or even at least 25,000 lb hr). Some typical conveying speeds can be between about 1000 and 10,000 lb/hr, (e.g., between about 1000 lb hr and 8000 lb/hr, between about 2000 and 7000 lb/hr, between about 2000 and 6000 lb hr, between about 2000 and 50001b hr, between about 2000 and 4500 lb hr, between about 1500 and 5000 lb hr, between about 3000 and 7000 lb hr, between about 3000 and 6000 lb hr, between about 4000 and 6000 lb hr and between about 4000 and 5000 lb hr). Typical conveying speeds depend on the density of the material. For example, for a biomass with a density of about 35 lb/ft3, and a conveying speed of about 5000 lb/hr, the material is conveyed at a rate of about 143 ft3/hr, if the material is ¼" thick and is in a trough 5.5 ft wide, the material is conveyed at a rate of about 1250 ft/hr (about 21 ft/min). Rates of conveying the material can therefore vary greatly. Preferably, for example, a ¼" thick layer of biomass, is conveyed at speeds of between about 5 and 100 ft/min (e.g. between about 5 and 100 ft/min, between about 6 and 100 ft/min, between about 7 and 100 ft/min, between about 8 and 100 ft/min, between about 9 and 100 ft/min, between about 10 and 100 ft/min, between about 11 and 100 ft/min, between about 12 and 100 ft/min, between about 13 and 100 ft/min, between about 14 and 100 ft/min, between about 15 and 100 ft/min, between about 20 and 100 ft/min, between about 30 and 100 ft/min, between about 40 and 100 ft/min, between about 2 and 60 ft/min, between about 3 and 60 ft/min, between about 5 and 60 ft/min, between about 6 and 60 ft/min, between about 7 and 60 ft/min, between about 8 and 60 ft/min, between about 9 and 60 ft/min, between about 10 and 60 ft/min, between about 15 and 60 ft/min, between about 20 and 60 ft/min, between about 30 and 60 ft/min, between about 40 and 60 ft/min, between about 2 and 50 ft/min, between about 3 and 50 ft/min, between about 5 and 50 ft/min, between about 6 and 50 ft/min, between about 7 and 50 ft/min, between about 8 and 50 ft/min, between about 9 and 50 ft/min, between about 10 and 50 ft/min, between about 15 and 50 ft/min, between about 20 and 50 ft/min, between about 30 and 50 ft/min, between about 40 and 50 ft/min). It is preferable 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 electron beam (e.g., shower, field).

[00181] 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, selecting or removing specific materials, for example, by size or shape. Some conveyors have counterbalances to reduce the dynamic forces on the support structure. Some vibratory conveyors are configured as spiral elevators, are designed to curve around surfaces and/or are designed to drop material from one conveyor to another (e.g., in a step, cascade or as a series of steps or a stair). Along with conveying materials conveyors can be used, by themselves or coupled with other equipment or systems, for screening, separating, sorting, classifying, distributing, sizing, inspection, picking, metal removing, freezing, blending, mixing, orienting, heating, cooking, drying, dewatering, cleaning, washing, leaching, quenching, coating, de-dusting and/or feeding. The conveyors can also include covers (e.g., dust-tight covers), side discharge gates, bottom discharge gates, special liners (e.g., anti-stick, stainless steel, rubber, custom steal, and or grooved), divided troughs, quench pools, screens, perforated plates, detectors (e.g., metal detectors), high temperature designs, food grade designs, heaters, dryers and or coolers. In addition, the trough can be of various shapes, for example, flat bottomed, vee shaped bottom, flanged at the top, curved bottom, flat with ridges in any direction, tubular, half pipe, covered or any combinations of these. In particular, the conveyors can be coupled with an irradiation systems and/or equipment.

[00182] The conveyors (e.g., vibratory conveyor) can be made of corrosion resistant 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-Resistant alloys from Hynes (Kokomo, Indiana, USA) such as HASTELLOY® B-3® ALLOY, HASTELLOY® HYBRID-BC1® ALLOY, HASTELLOY® C-4 ALLOY, HASTELLOY® C-22® ALLOY,

HASTELLOY® C-22HS® ALLOY, HASTELLOY® C-276 ALLOY, HASTELLOY® C-2000® ALLOY, HASTELLOY® G-30® ALLOY, HASTELLOY® G-35® ALLOY, HASTELLOY® N ALLOY and HASTELLOY® ULTIMET® alloy.

[00183] The vibratory conveyors can include non-stick release coatings, for example, TUFFLON™ (Dupont, Delaware, USA). The vibratory conveyors can also include corrosion resistant coatings. For example, coatings that can be supplied from Metal Coatings Corp (Houston, Texas, USA) and others such as Fluoropolymer, XYLAN®, Molybdenum Disulfide, Epoxy Phenolic, Phosphate- ferrous metal coating,

Polyurethane- high gloss topcoat for epoxy, inorganic zinc, Poly Tetrafluoro ethylene, PPS/RYTON®, fluorinated ethylene propylene, PVDF/DYKOR®, ECTFE/HALAR® and Ceramic Epoxy Coating. The coatings can improve resistance to process gases (e.g., ozone), chemical corrosion, pitting corrosion, galling corrosion and oxidation.

[00184] Optionally, in addition to the conveying systems described herein, one or more other conveying systems can be enclosed. When using an enclosure, the enclosed conveyor can also be purged with an inert gas so as to maintain an atmosphere at a reduced oxygen level. Keeping oxygen levels low avoids the formation of ozone which in some instances is undesirable due to its reactive and toxic nature. For example, the oxygen can be less than about 20% (e.g., less than about 10%, less than about 1 %, less than about 0.1 %, less than about 0.01 %, or even less than about 0.001 % oxygen).

Purging can be done with an inert gas including, but not limited to, nitrogen, argon, helium or carbon dioxide. This can be supplied, for example, from a boil off of a liquid source (e.g., liquid nitrogen or helium), generated or separated from air in situ, or supplied from tanks. The inert gas can be recirculated and any residual oxygen can be removed using a catalyst, such as a copper catalyst bed. Alternatively, combinations of purging, recirculating and oxygen removal can be done to keep the oxygen levels low.

[00185] The enclosed conveyor can also be purged with a reactive gas that can react with the biomass. This can be done before, during or after the irradiation process. The reactive gas can be, but is not limited to, nitrous oxide, ammonia, oxygen, ozone, hydrocarbons, aromatic compounds, amides, peroxides, azides, halides, oxyhalides, phosphides, phosphines, arsines, sulfides, thiols, boranes and/or hydrides. The reactive gas can be activated in the enclosure, e.g., by irradiation (e.g., electron beam, UV irradiation, microwave irradiation, heating, IR radiation), so that it reacts with the biomass. The biomass itself can be activated, for example by irradiation. Preferably the biomass is activated by the electron beam, to produce radicals which then react with the activated or unactivated reactive gas, e.g., by radical coupling or quenching.

[00186] Purging gases supplied to an enclosed conveyor can also be cooled, for example below about 25°C, below about 0°C, below about -40°C, below about -80°C, below about -120°C. For example, the gas can be boiled off from a compressed gas such as liquid nitrogen or sublimed from solid carbon dioxide. As an alternative example, the gas can be cooled by a chiller or part of or the entire conveyor can be cooled.

OTHER EMBODIMENTS

[00187] Any material, processes or processed materials discussed herein can be used to make products and/or intermediates such as composites, fillers, binders, plastic additives, adsorbents and controlled release agents. The methods can include densification, for example, by applying pressure and heat to the materials. For example composites can be made by combining fibrous materials with a resin or polymer. For example, radiation cross-linkable resin, e.g., a thermoplastic resin can be combined with a fibrous material to provide a fibrous material/cross-linkable resin combination. Such materials can be, for example, useful as building materials, protective sheets, containers and other structural materials (e.g., molded and/or extruded products). Absorbents can be, for example, in the form of pellets, chips, fibers and/or sheets. Adsorbents can be used, for example, as pet bedding, packaging material or in pollution control systems. Controlled release matrices can also be the form of, for example, pellets, chips, fibers and or sheets. The controlled release matrices can, for example, be used to release drugs, biocides, fragrances. For example, composites, absorbents and control release agents and their uses are described in International Serial No. PCT/US2006/010648, filed March 23, 2006, and U.S. Patent No. 8,074,910 filed November 22, 2011, the entire disclosures of which are herein incorporated by reference.

[00188] In some instances the biomass material is treated at a first level to reduce recalcitrance, e.g., utilizing accelerated electrons, to selectively release one or more sugars (e.g., xylose). The biomass can then be treated to a second level to release one or more other sugars (e.g., glucose). Optionally, the biomass can be dried between treatments. The treatments can include applying chemical and biochemical treatments to release the sugars. For example, a biomass material can be treated to a level of less than about 20 Mrad (e.g., less than about 15 Mrad, less than about 10 Mrad, less than about 5 Mrad, less than about 2 Mrad) and then treated with a solution of sulfuric acid, containing less than 10% sulfuric acid (e.g., less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1%, less than about 0.75%, less than about 0.50 %, less than about 0.25%) to release xylose. Xylose, for example, that is released into solution, can be separated from solids and optionally the solids washed with a solvent/solution (e.g., with water and/or acidified water). Optionally, the solids can be dried, for example in air and/or under vacuum optionally with heating (e.g., below about 150 deg C, below about 120 deg C) to a water content below about 25 wt.% (below about 20 wt.%, below about 15 wt.%, below about 10 wt.%, below about 5 wt.%). The solids can then be treated with a level of less than about 30 Mrad (e.g., less than about 25 Mrad, less than about 20 Mrad, less than about 15 Mrad, less than about 10 Mrad, less than about 5 Mrad, less than about 1 Mrad or even not at all) and then treated with an enzyme (e.g., a cellulase) to release glucose. The glucose (e.g., glucose in solution) can be separated from the remaining solids. The solids can then be further processed, for example, utilized to make energy or other products (e.g., lignin derived products).

FLAVORS. FRAGRANCES AND COLORS

[00189] Any of the products and/or intermediates described herein, for example, produced by the processes, systems and/or equipment described herein, can be combined with flavors, fragrances, colorants and/or mixtures of these. For example, any one or more of (optionally along with flavors, fragrances and/or colorants) sugars, organic acids, fuels, polyols, such as sugar alcohols, biomass, fibers and composites can be combined with (e.g., formulated, mixed or reacted) or used to make other products. For example, one or more such product can be used to make soaps, detergents, candies, drinks (e.g., cola, wine, beer, liquors such as gin or vodka, sports drinks, coffees, teas), syrups, pharmaceuticals, adhesives, sheets (e.g., woven, none woven, filters, tissues) and/or composites (e.g., boards). For example, one or more such product can be combined with herbs, flowers, petals, spices, vitamins, potpourri, or candles. For example, the formulated, mixed or reacted combinations can have flavors/fragrances of grapefruit, orange, apple, raspberry, banana, lettuce, celery, cinnamon, chocolate, vanilla, peppermint, mint, onion, garlic, pepper, saffron, ginger, milk, wine, beer, tea, lean beef, fish, clams, olive oil, coconut fat, pork fat, butter fat, beef bouillon, legume, potatoes, marmalade, ham, coffee and cheeses.

[00190] 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.

[00191] 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.

[00192] The flavors, fragrances and colorants can be natural and/or synthetic materials. These materials can be one or more of a compound, a composition or mixtures of these (e.g., a formulated or natural composition of several compounds). Optionally, the flavors, fragrances, antioxidants and colorants can be derived biologically, for example, from a fermentation process (e.g., fermentation of saccharified materials as described herein). Alternatively, 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, hot water extraction, supercritical fluid extraction, chemical extraction (e.g., solvent or reactive extraction including acids and bases), mechanical extraction (e.g., pressing, comminuting, filtering), utilizing an enzyme, utilizing a bacteria such as to break down a starting material, and combinations of these methods. The compounds can be derived by a chemical reaction, for example, the combination of a sugar (e.g., as produced as described herein) with an amino acid (Maillard reaction). The flavor, fragrance, antioxidant and/or colorant can be an intermediate and/or product produced by the methods, equipment or systems described herein, for example, and ester and a lignin derived product.

[00193] Some examples of flavor, fragrances or colorants are polyphenols.

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

[00194] Among the colorants inorganic compounds, minerals or organic compounds can be used, for example titanium dioxide, zinc oxide, aluminum oxide, cadmium yellow (E.g., CdS), cadmium orange (e.g., CdS with some Se), alizarin crimson (e.g., synthetic or non-synthetic rose madder), ultramarine (e.g., synthetic ultramarine, natural ultramarine, synthetic ultramarine violet ), cobalt blue, cobalt yellow, cobalt green, viridian (e.g., hydrated chromium(III)oxide), chalcophylite, conichalcite, cornubite, cornwallite and liroconite. Black pigments such as carbon black and self-dispersed blacks may be used.

[00195] Some flavors and fragrances that can be utilized include ACALEA TBHQ, ACET C-6, ALLYL AMYL GLYCOLATE, ALPHA TERPINEOL, AMBRETTOLIDE, AMBRINOL 95, ANDRANE, APHERMATE, APPLELIDE, BACDANOL®,

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

COEUR, CITRONELLYL ACETATE, CITRONELLYL ACETATE PURE,

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

DIHYDRO TERPINEOL, DIHYDRO TERPINYL ACETATE, DIMETHYL

CYCLORMOL, DIMETHYL OCTANOL PQ, DIMYRCETOL, DIOLA, DIPENTENE, DULCINYL® RECRYSTALLIZED, ETHYL-3-PHENYL GLYCIDATE,

FLEURAMONE, FLEURANIL, FLORAL SUPER, FLORALOZONE, FLORIFFOL, FRAISTONE, FRUCTONE, GALAXOLIDE® 50, GALAXOLIDE® 50 BB,

GALAXOLIDE® 50 IPM, GALAXOLIDE® UNDILUTED, GALBASCONE, GERALDEHYDE, GERANIOL 5020, GERANIOL 600 TYPE, GERANIOL 950, GERANIOL 980 (PURE), GERANIOL CFT COEUR, GERANIOL COEUR,

GERANYL ACETATE COEUR, GERANYL ACETATE, PURE, GERANYL

FORMATE, GRISALVA, GUAIYL ACETATE, HELIONAL™, HERBAC,

HERBALIME™, HEXADECANOLIDE, HEXALON, HEXENYL SALICYLATE CIS 3-, HYACINTH BODY, HYACINTH BODY NO. 3, HYDRATROPIC

ALDEHYDE.DMA, HYDROXYOL, INDOLAROME, INTRELEVEN ALDEHYDE, INTRELEVEN ALDEHYDE SPECIAL, IONONE ALPHA, IONONE BETA, ISO CYCLO CITRAL, ISO CYCLO GERANIOL, ISO E SUPER®, ISOBUTYL

QUINOLINE, JASMAL, JESSEMAL®, KHARISMAL®, KHARISMAL® SUPER, KHUSINIL, KOAVONE®, KOHINOOL®, LIFFAROME™, LIMOXAL,

LINDENOL™, LYRAL®, LYRAME SUPER, MANDARIN ALD 10% TRI ETH, CITR, MARITIMA, MCK CHINESE, MEIJIFF™, MELAFLEUR, MELOZONE, METHYL ANTHRANILATE, METHYL IONONE ALPHA EXTRA, METHYL IONONE GAMMA A, METHYL IONONE GAMMA COEUR, METHYL IONONE GAMMA PURE, METHYL LAVENDER KETONE, MONTA VERDI®, MUGUESIA, MUGUET ALDEHYDE 50, MUSK Z4, MYRAC ALDEHYDE, MYRCENYL ACETATE, NECTARATE™, NEROL 900, NERYL ACETATE, OCIMENE, OCTACETAL, ORANGE FLOWER ETHER, ORIVONE, ORRINIFF 25%,

OXASPIRANE, OZOFLEUR, PAMPLEFLEUR®, PEOMOSA, PHENOXANOL®, PICONIA, PRECYCLEMONE B, PRENYL ACETATE, PRISMANTOL, RESEDA BODY, ROSALVA, ROSAMUSK, SANJINOL, SANTALIFF™, SYVERTAL, TERPINEOL,TERPINOLENE 20, TERPINOLENE 90 PQ, TERPINOLENE RECT., TERPINYL ACETATE, TERPINYL ACETATE JAX, TETRAHYDRO, MUGUOL®, TETRAHYDRO MYRCENOL, TETRAMERAN, TIMBERSILK™, TOBACAROL, TRIMOFFX® O TT, TRIPLAL®, TRISAMBER®, VANORIS, VERDOX™,

VERDOX™ HC, VERTENEX®, VERTENEX® HC, VERTOFFX® COEUR, VERTOLIFF, VERTOLIFF ISO, VIOLIFF, VIVALDIE, ZENOLIDE, ABS INDIA 75 PCT MIGLYOL, ABS MOROCCO 50 PCT DPG, ABS MOROCCO 50 PCT TEC, ABSOLUTE FRENCH, ABSOLUTE INDIA, ABSOLUTE MD 50 PCT BB,

ABSOLUTE MOROCCO, CONCENTRATE PG, TINCTURE 20 PCT, AMBERGRIS, AMBRETTE ABSOLUTE, AMBRETTE SEED OIL, ARMOISE OIL 70 PCT

THUYONE, BASIL ABSOLUTE GRAND VERT, BASIL GRAND VERT ABS MD, BASIL OIL GRAND VERT, BASIL OIL VERVEINA, BASIL OIL VIETNAM, BAY OIL TERPENELESS, BEESWAX ABS N G, BEESWAX ABSOLUTE, BENZOIN RESINOID SIAM, BENZOIN RESINOID SIAM 50 PCT DPG, BENZOIN RESINOID SIAM 50 PCT PG, BENZOIN RESINOID SIAM 70.5 PCT TEC, BLACKCURRANT BUD ABS 65 PCT PG, BLACKCURRANT BUD ABS MD 37 PCT TEC,

BLACKCURRANT BUD ABS MIGLYOL, BLACKCURRANT BUD ABSOLUTE BURGUNDY, BOIS DE ROSE OIL, BRAN ABSOLUTE, BRAN RESINOID,

BROOM ABSOLUTE ITALY, CARDAMOM GUATEMALA C02 EXTRACT, CARDAMOM OIL GUATEMALA, CARDAMOM OIL INDIA, CARROT HEART, CASSIE ABSOLUTE EGYPT, CASSIE ABSOLUTE MD 50 PCT IPM, CASTOREUM ABS 90 PCT TEC, CASTOREUM ABS C 50 PCT MIGLYOL, CASTOREUM

ABSOLUTE, CASTOREUM RESINOID, CASTOREUM RESINOID 50 PCT DPG, CEDROL CEDRENE, CEDRUS ATLANTICA OIL REDIST, CHAMOMILE OIL ROMAN, CHAMOMILE OIL WILD, CHAMOMILE OIL WILD LOW LIMONENE, CINNAMON BARK OIL CEYLAN, CISTE ABSOLUTE, CISTE ABSOLUTE

COLORLESS, CITRONELLA OIL ASIA IRON FREE, CIVET ABS 75 PCT PG, CIVET ABSOLUTE, CIVET TINCTURE 10 PCT, CLARY SAGE ABS FRENCH DECOL, CLARY SAGE ABSOLUTE FRENCH, CLARY SAGE C'LESS 50 PCT PG, CLARY SAGE OIL FRENCH, COPAIBA BALSAM, COPAIBA BALSAM OIL, CORIANDER SEED OIL, CYPRESS OIL, CYPRESS OIL ORGANIC, DA V ANA OIL, GALBANOL, GALBANUM ABSOLUTE COLORLESS, GALBANUM OIL,

GALBANUM RESINOID, GALBANUM RESINOID 50 PCT DPG, GALBANUM RESINOID HERCOLYN BHT, GALBANUM RESINOID TEC BHT, GENTIANE ABSOLUTE MD 20 PCT BB, GENTIANE CONCRETE, GERANIUM ABS EGYPT MD, GERANIUM ABSOLUTE EGYPT, GERANIUM OIL CHINA, GERANIUM OIL EGYPT, GINGER OIL 624, GINGER OIL RECTIFIED SOLUBLE, GUAIACWOOD HEART, HAY ABS MD 50 PCT BB, HAY ABSOLUTE, HAY ABSOLUTE MD 50 PCT TEC, HEALINGWOOD, HYSSOP OIL ORGANIC, IMMORTELLE ABS YUGO MD 50 PCT TEC, IMMORTELLE ABSOLUTE SPAIN, IMMORTELLE ABSOLUTE YUGO, JASMIN ABS INDIA MD, JASMIN ABSOLUTE EGYPT, JASMIN

ABSOLUTE INDIA, ASMIN ABSOLUTE MOROCCO, JASMIN ABSOLUTE

SAMBAC, JONQUILLE ABS MD 20 PCT BB, JONQUILLE ABSOLUTE France, JUNIPER BERRY OIL FLG, JUNIPER BERRY OIL RECTIFIED SOLUBLE, LABDANUM RESINOID 50 PCT TEC, LABDANUM RESINOID BB, LABDANUM RESINOID MD, LABDANUM RESINOID MD 50 PCT BB, LAVANDIN ABSOLUTE H, LAVANDIN ABSOLUTE MD, LAVANDIN OIL ABRIAL ORGANIC,

LAVANDIN OIL GROSSO ORGANIC, LAVANDIN OIL SUPER, LAVENDER ABSOLUTE H, LAVENDER ABSOLUTE MD, LAVENDER OIL COUMARIN FREE, LAVENDER OIL COUMARIN FREE ORGANIC, LAVENDER OIL

MAILLETTE ORGANIC, LAVENDER OIL MT, MACE ABSOLUTE BB,

MAGNOLIA FLOWER OIL LOW METHYL EUGENOL, MAGNOLIA FLOWER OIL, MAGNOLIA FLOWER OIL MD, MAGNOLIA LEAF OIL, MANDARIN OIL MD, MANDARIN OIL MD BHT, MATE ABSOLUTE BB, MOSS TREE ABSOLUTE MD TEX IFRA 43, MOSS-OAK ABS MD TEC IFRA 43, MOSS-OAK ABSOLUTE IFRA 43, MOSS-TREE ABSOLUTE MD IPM IFRA 43, MYRRH RESINOID BB, MYRRH RESINOID MD, MYRRH RESINOID TEC, MYRTLE OIL IRON FREE, MYRTLE OIL TUNISIA RECTIFIED, NARCISSE ABS MD 20 PCT BB, NARCISSE ABSOLUTE FRENCH, NEROLI OIL TUNISIA, NUTMEG OIL TERPENELESS, OEILLET ABSOLUTE, OLIBANUM RESINOID, OLIBANUM RESINOID BB, OLIBANUM RESINOID DPG, OLIBANUM RESINOID EXTRA 50 PCT DPG, OLIBANUM RESINOID MD, OLIBANUM RESINOID MD 50 PCT DPG,

OLIBANUM RESINOID TEC, OPOPONAX RESINOID TEC, ORANGE BIGARADE OIL MD BHT, ORANGE BIGARADE OIL MD SCFC, ORANGE FLOWER

ABSOLUTE TUNISIA, ORANGE FLOWER WATER ABSOLUTE TUNISIA, ORANGE LEAF ABSOLUTE, ORANGE LEAF WATER ABSOLUTE TUNISIA, ORRIS ABSOLUTE ITALY, ORRIS CONCRETE 15 PCT IRONE, ORRIS

CONCRETE 8 PCT IRONE, ORRIS NATURAL 15 PCT IRONE 4095C, ORRIS NATURAL 8 PCT IRONE 2942C, ORRIS RESINOID, OSMANTHUS ABSOLUTE, OSMANTHUS ABSOLUTE MD 50 PCT BB, PATCHOULI HEART N°3,

PATCHOULI OIL INDONESIA, PATCHOULI OIL INDONESIA IRON FREE, PATCHOULI OIL INDONESIA MD, PATCHOULI OIL REDIST, PENNYROYAL HEART, PEPPERMINT ABSOLUTE MD, PETITGRAIN BIGARADE OIL TUNISIA, PETITGRAIN CITRONNIER OIL, PETITGRAIN OIL PARAGUAY TERPENELESS, PETITGRAIN OIL TERPENELESS STAB, PIMENTO BERRY OIL, PIMENTO LEAF OIL, RHODINOL EX GERANIUM CHINA, ROSE ABS BULGARIAN LOW

METHYL EUGENOL, ROSE ABS MOROCCO LOW METHYL EUGENOL, ROSE ABS TURKISH LOW METHYL EUGENOL, ROSE ABSOLUTE, ROSE ABSOLUTE BULGARIAN, ROSE ABSOLUTE DAMASCENA, ROSE ABSOLUTE MD, ROSE ABSOLUTE MOROCCO, ROSE ABSOLUTE TURKISH, ROSE OIL BULGARIAN, ROSE OIL DAMASCENA LOW METHYL EUGENOL, ROSE OIL TURKISH, ROSEMARY OIL CAMPHOR ORGANIC, ROSEMARY OIL TUNISIA,

SANDALWOOD OIL INDIA, SANDALWOOD OIL INDIA RECTIFIED,

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

[00196] The colorants can be among those listed in the Color Index International by the Society of Dyers and Colourists. Colorants include dyes and pigments and include those commonly used for coloring textiles, paints, inks and inkjet inks. Some colorants that can be utilized include carotenoids, arylide yellows, diarylide yellows, β-naphthols, naphthols, benzimidazolones, disazo condensation pigments, pyrazolones, nickel azo yellow, phthalocyanines, quinacridones, perylenes and perinones, isoindolinone and isoindoline pigments, triarylcarbonium pigments, diketopyrrolo-pyrrole pigments, thioindigoids. Cartenoids include, e.g., alpha-carotene, beta-carotene, gamma-carotene, lycopene, lutein and astaxanthinAnnatto extract, Dehydrated beets (beet powder), Canthaxanthin, Caramel, -Apo-8'-carotenal, Cochineal extract, Carmine, Sodium copper chlorophyllin, Toasted partially defatted cooked cottonseed flour, Ferrous gluconate, Ferrous lactate, Grape color extract, Grape skin extract (enocianina), Carrot oil, Paprika, Paprika oleoresin, Mica-based pearlescent pigments, Riboflavin, Saffron, Titanium dioxide, Tomato lycopene extract; tomato lycopene concentrate, Turmeric, Turmeric oleoresin, FD&C Blue No. 1, FD&C Blue No. 2, FD&C Green No. 3, Orange B, Citrus Red No. 2, FD&C Red No. 3, FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No. 6, Alumina (dried aluminum hydroxide), Calcium carbonate, Potassium sodium copper chlorophyllin (chlorophyllin-copper complex), Dihydroxy acetone, Bismuth oxychloride, Ferric ammonium ferrocyanide, Ferric ferrocyanide, Chromium hydroxide green, Chromium oxide greens, Guanine, Pyrophyllite, Talc, Aluminum powder, Bronze powder, Copper powder, Zinc oxide, D&C Blue No. 4, D&C Green No. 5, D&C Green No. 6, D&C Green No. 8, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11, D&C Red No. 4, D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, D&C Red No. 39, D&C Violet No. 2, D&C Yellow No. 7, Ext. D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. 11, D&C Black No. 2, D&C Black No. 3 (3), D&C Brown No. 1, Ext. D&C, Chromium-cobalt- aluminum oxide, Ferric ammonium citrate, Pyrogallol, Logwood extract, 1,4-Bis[(2- hydroxy-ethyl)amino]-9,10-anthracenedione bis(2-propenoic)ester copolymers, 1,4-Bis [(2-methylphenyl)amino] -9,10-anthracenedione, 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- methylphenyl)thiol] phenyljazo] -1,3,5-benzenetriol, 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- Dihydro- 9,10-dioxo- 1,5-anthracenediyl) bisbenzamide, 7,16-Dichloro- 6,15-dihydro- 5,9,14,18-anthrazinetetrone, 16,17-Dimethoxydinaphtho (l,2,3-cd:3',2',l'-lm) perylene- 5,10-dione, Poly(hydroxyethyl methacrylate) -dye copolymers(3), Reactive Black 5, Reactive Blue 21, Reactive Orange 78, Reactive Yellow 15, Reactive Blue No. 19, Reactive Blue No. 4, C.I. Reactive Red 11, C.I. Reactive Yellow 86, C.I. Reactive Blue 163, C.I. Reactive Red 180, 4-[(2,4-dimethylphenyl)azo]- 2,4-dihydro- 5-methyl-2- phenyl- 3H-pyrazol-3-one (solvent Yellow 18), 6-Ethoxy-2- (6-ethoxy-3-oxobenzo[b] thien-2(3H)- ylidene) benzo[b]thiophen- 3(2H)-one, Phthalocyanine green, Vinyl alcohol/methyl methacrylate-dye reaction products, C.I. Reactive Red 180, C.I. Reactive Black 5, C.I. Reactive Orange 78, C.I. Reactive Yellow 15, C.I. Reactive Blue 21, Disodium 1 -amino-4- [[4- [(2-bromo- 1 -oxoallyl)amino] -2-sulphonatophenyl]amino] -9 , 10- dihydro-9,10-dioxoanthracene-2-sulphonate (Reactive Blue 69), D&C Blue No. 9,

[Phthalocyaninato(2-)] copper and mixtures of these.

EXAMPLES

[00197] Concentrations were determined by HPLC in aqueous diluted and filtered solutions with appropriate standards.

Saccharification

[00198] A cylindrical tank with a diameter of 32 Inches, 64 Inches in height and fit with ASME dished heads (top and bottom) was used in the saccharification. The tank was also equipped with a hydrofoil mixing blade 16" wide. Heating was provided by flowing hot water through a half pipe jacket surrounding the tank.

[00199] The tank was charged with 200 Kg water, 80 Kg of biomass, and 18 Kg of Duet™ Cellulase enzyme. Biomass was corn cob that had been hammer milled and screened to a size of between 40 and 10 mesh. The biomass was irradiated with an electron beam to a total dosage of 35 Mrad. The pH of the mixture was adjusted and maintained automatically throughout the saccharification at 4.8 using Ca(OH) ₂ . This combination was heated to 53 °C, stirred at 180 rpm (1.8 Amp at 460V) for about 24 hours after which the saccharification was considered completed.

A portion of this material was screened through a 20 mesh screen and the solution stored in an 8 gal carboy at 4 °C.

Biomass Produced Ethanol and Xylose Stream

[00200] About 400 mL of the saccharified material was decanted into a 1L New Brunswick BioFlow 115 Bioreactor. The Material was aerated and heated to 30 °C prior to inoculation. Stirring was set at 50 rpm. The pH was measured at 5.2, which is acceptable for fermentation so it was not adjusted. Aeration was discontinued and the contents of the bioreactor were inoculated with 5 mg of Thermosacc Dry Yeast

(Lallemand, Inc.). Fermentation was allowed to proceed for about 24 hours.

[00201] After fermentation the glucose concentration was below the detection limit, the ethanol concentration was about 25 g/L, and the xylose concentration was 30 g/L.

Purification of Ethanol and Xylose Stream using Desalination Electrodialvsis

[00202] Four liters of post fermentation solution was concentrated under vacuo to about 1 ¹¹ ₃ L. The concentrated, ethanol free, solution was then diluted back to its original volume with methanol. Addition of the methanol caused immediate formation and precipitation of solids. It was found that the precipitate can be effectively removed by centrifugation or filtration.

[00203] The solid free solution was then treated with 5% (by weight/volume) activated carbon to decolorize the solution. The carbon was removed by filtration and the filtrate was then concentrated in vacuo to remove methanol. The solution was subsequently diluted to its original volume with de-ionized water.

[00204] Two Liters of the decolorized solution was then subjected to electrodialysis. The voltage across a stack of 20 membranes was 40 V. The conductivity, temperature and pH were measured. FIG. 3 is a plot of the conductivity vs time in the dilute streams. The experiment lasted for 71 min wherein the conductivity decreased from 7830 μ8 :ιη to 9 μ8/οηι, the temperature increased from to 25 deg. C to 33 deg. C and the measured pH decreased from about 4.8 to 4.0.

[00205] Elemental analysis (ICP) showed the improvement in reducing the ions throughout the processing. Elemental analysis was done in duplicate or triplicate.

Table 1: Post Fermentation Elemental Analysis.

Table 2: Elemental Analysis post Methanol Treatment

Table 3: Elemental Analysis Post Electrodialysis Treatment. [00206] Throughout the post fermentation processing the Xylose concentration remained constant at about 30 g/L with no apparent degradation.

Biomass Produced L-lactic acid and Xylose Stream with Lactobacillus rhamnosus

[00207] Saccharified biomass made utilizing similar steps as described above was used as the sugar source to produce an L-lactic acid/xylose stream.

[00208] The glucose to L-Lactic acid fermenting organism Lactobacillus rhamnosus

NRRL B-445 was grown in 25 mL of MRS medium (BD Diagnostic Systems No.:

288130) from 250 uL freezer stocks. The culture was incubated overnight in a shaker incubator at 37 °C and 150-200rpm.

[00209] Fermentation to produce the lactic acid was conducted in a bioreactor equipped with stirring paddle, heating mantel, stirring impellors, pH monitoring probes and temperature monitoring thermocouples.

[00210] The production medium for an experiment used 11 L of saccharified biomass, 22g of yeast extract, 1.6 mL of antifoam AFE-0010. The media was heated to 70 °C for 1 hour and then cooled to 37 °C. The pH of the media was raised to 6.5 using 12.5N NaOH solution. The media was then inoculated with 1 % (110 mL) of the Lactobacillus rhamnosus. Fermentation was allowed to proceed at 37 °C while the solution was stirred at 200 rpm and the pH maintained above 6.5. Glucose was completely consumed by 48 hours. The product is L-lactic acid as the sodium salt. Xylose produced during saccharification was not consumed; it was essentially unconverted during this step.

Biomass Produced D-lactic acid and Xylose Stream with Lactobacillus coryniformis

[00211] Saccharified biomass made utilizing similar steps as described above was used as the sugar source to produce an L-lactic acid xylose stream.

[00212] The glucose to D-Lactic acid fermenting organism Lactobacillus coryniformis subspecies torquens B-4390 was grown in 25 mL of MRS medium (BD Diagnostic Systems No.: 288130) from 250 μL· freezer stocks. The culture was incubated overnight at 37 °C without agitation.

[00213] The production medium for an experiment used 644 mL of saccharified biomass, 5 g/L of tryptone, and 100 μL· of antifoam AFE-0010. The media was heated to

70 °C for 1 hour and then cooled to 37 °C. The pH was raised to 6.5 using 12.5N NaOH solution and maintained thereafter using the same base solution. The media was inoculated with 1% of the B-4390 and the fermentation wall allowed to proceed at 37 °C while the media was stirred at 200 rpm and the pH maintained at about 6.5. Glucose consumption was complete in 144 hours. The product is D-lactic acid as the sodium salt. Xylose produced during saccharification was not consumed; it was essentially unconverted during this step.

[00214]

Processing of Sodium Lactate solution

[00215] Both the D-lactic acid and L-lactic acid derived sodium lactate were decolorized as described here. Fermentations were run repeatedly to provide larger quantities of material and facilitate the decolorization.

[00216] Thirty liters of fermentation medium containing sodium lactate prepared by fermentation as described above were centrifuged at 4200 rpm for 60 minutes. The supernatant was filtered through a 0.22 micron cartridge filter producing 26.5 L of filtrate. Nineteen liters of the filtrate were percolated through a column containing 2.7 L of a highly porous styrenic polymeric bead type resin, Mitsubishi Diaion SP-700, at a flow rate of 1.5 BV/h. The first 1.5 L of eluate are discarded and the rest of the medium and an additional 1.5 L of water are eluted and pooled. The remaining portion of the medium was decolorized in a similar manner resulting in 7.5 L of pale colored solution. The two batches of decolorized material were pooled and stored in the cold if not used immediately.

Desalination Electrodialvsis of decolorized Lactate solution

[00217] The decolorized medium prepared as described above was subjected to electro dialysis using a desalination membrane.

[00218] The a reservoir of the Electrodialysis apparatus was charged with the decolorized sodium lactate medium and the Concentrate reservoir of the apparatus was charged with 4 L of deionized water. Electrodialysis was continued for 5 hours using a voltage of 40 V and a maximum current of 5 A.

[00219] This procedure produced a concentrated lactate stream with a typical concentration of around 66 g/L (starting at 38 g/L) and a concentrated xylose stream with a typical conductivity of 5 μ8 :ιη (starting 34 μ8 :ιη).

Bipolar Membrane Dielectrodialysis

[00220] The liquid in the stream in sodium lactate produced as described above can be subjected to a second electro dialysis using a bipolar membrane to produce a lactic acid solution and a sodium hydroxide solution. The procedure that can be followed is described here.

[00221] Sodium lactate (1.6 L) solution prepared by desalination electrodialysis is added to the Diluate reservoir. Deionized water (1 L) is added to each reservoir for the lactic acid and sodium hydroxide streams. The electrodialysis is carried out using a 4- chamber electro dialysis cell fitted with a bipolar membrane stack. The voltage is set to 23 V and the maximum current is set to 6.7 A. The dialysis can be carried out for 5 hours or until the conductivity of the dilute stream is < 5 % of its starting value. [00222] This procedure produced a concentrated lactate stream with a typical concentration of around 66 g/L (starting at 38 g/L) and a xylose stream with a typical conductivity of 5 μ8 :ιη (starting 34 μ8 :ιη) and concentration of 30g/L . The lactate stream is typically 96% lactic acid to 4 % xylose after the bipolar membrane dialysis. The xylose stream is typically 93 % xylose to 7 % lactic acid after the bipolar membrane dialysis.

[00223] Other than in the examples herein, or unless otherwise expressly specified, all of the numerical ranges, amounts, values and percentages, such as those for amounts of materials, elemental contents, times and temperatures of reaction, ratios of amounts, and others, in the following portion of the specification and attached claims may be read as if prefaced by the word "about" even though the term "about" may not expressly appear with the value, amount, or range. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the embodiments. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[00224] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains error necessarily resulting from the standard deviation found in its underlying respective testing measurements. Furthermore, when numerical ranges are set forth herein, these ranges are inclusive of the recited range end points (e.g., end points may be used). When percentages by weight are used herein, the numerical values reported are relative to the total weight.

[00225] Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10. The terms "one," "a," or "an" as used herein are intended to include "at least one" or "one or more," unless otherwise indicated. [00226] Any patent, publication, or other disclosure material, in whole or in part, that is said to be incorporated by reference herein is incorporated herein only to the extent that the incorporated material does not conflict with existing definitions, statements, or other disclosure material set forth in this disclosure. As such, and to the extent necessary, the disclosure as explicitly set forth herein supersedes any conflicting material incorporated herein by reference. Any material, or portion thereof, that is said to be incorporated by reference herein, but which conflicts with existing definitions, 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.

[00227] While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.

APPENDIX

Electrodialysis Cell Unit

PCCell ED 64 0 02

Technical Data

s.de

www.pccell.de

Version: Jan 06

Table of Contents

1 . General 2

2. Function.. 3

3. Cell and Parts 5

4. Technical Data 8

5. Application Examples 10

6. Maintenance and Replacement 11

7. Application areas , 12

8. General Remarks / Safety................... ..... 13

9. Warranty 13

10. Further Information / Contact Address ... 14

1. General

The electrodialysis cell unit PCCell ED 64 is used in laboratory electrodialysis processes to remove ions from one solution (diluate). The ions are collected in another solution (concentrate). The electrodialysis unit PCCell ED 64-2 allows to carry out different types of experiments for a variety of applications, to examine the characteristics of ion exchange membranes in use. It is concepted as an easy- to- manage laboratory cell.

2

2. Function

The electrodialysis unit PCCell ED64-2 consists of an anode chamber, a cathode chamber and a membrane stack between them. With this constitution, a variety of experiments, like desalination, can be processed.

Concentrate

Fig. 1 : Functional setup of an ED stack. Salts are removed in cells called "Diluate" and are collected in the Concentrate. Beside this, the electrodes need a solution, the Catholyte and the Anolyte.

To run a standard ED, the membrane stack consists of n (typically 5, 10, 50 or even 100) cell pairs, which are formed by n+ 1 cation exchange membranes, n anion exchange membranes and 2 n spacers.

At the shown polarity (Fig. 1 ), one of the cell systems is the diluate and the other one is the concentrate. If the polarity is changed, the function of the cell system changes accordingly.

3

A complete ED System fs set up by this ED Cell in combination with an ED pump unit, e.g. PCCell B-ED 1 and the external solvent tanks build (Fig. 2).

Fig. 2: A complete ED setup: it consists of the stack (upper dotted rectangle), the ED pump unit (middle) and the external electrolyte containers (below).

Please remark in this context, that the ED cell is only one part of the complete system and will work properly only in combination with the other parts.

4

3. Cell and Parts

The PCCell ED 64 consists of several parts. They are described as follows:

Fig. 3: PCCell ED 64 setup and functional parts

# Description Art No.

1 ,2 Electrode end plates

3, 4, 5 Membrane stack

4 Screw set

Fig. 5: PCCell ED 64 0 02 Membrane size. Size given is in mm. Dotted square area in the middle of the membrane is the active membrane area of the cell.

4. Technical Data

Stack

Membrane size 110 x 110 mm

Active membrane area 64 cm ²

Membrane spacing electrode - membrane: ca. 1 mm over cells: 0,5 mm

Number of membranes Maximum 25 cell pairs Current Connectors 4 mm banana plugs

Processing length 80 mm

Medium Contacting Materials End plate materials

Cellframe polypropylene

Tubes polyethylene

Electrodes Titane, Pt/lr coating

Sp acer options

1 available mensions and Weight (ca)

width 165 mm

depth 150 mm

height 190 mm

weight 2.5 kg

Electrical Connecting data

Hydraulical Connecting data

ED 64

Type connectors for 8 mm id tubes

Flow through electrode circuits: nominal150 I / h

Nominal flow through concentrate 4-8 I / h

and diluat per single cell (10 cell pairs result in 40-80 I / h Flux through concentrate or diluate)

Max. pressure transmembrane pressure has to be kept zero:

Never pump only one of the diluate / concentrate circuits alone! pressure drop over cell Max. 0,5 bar

5. Application [Examples

The PCCell ED 64 is intended to be driven in a batch process. Process length and nominal flowthrough are given above.

Figure 7 shows an example of a batch desalination (conductivity of diluate against time). The effect of a single pass desalination at the start and stop time result in a conductivity jump. It depends on the current, flowing and other factors. The plot shows, that it is - more ore less - proportional to the current.

68 tnS cm ~» 64 mS cm:

power-on conductivity drop

(single pass salt removal)

ED 247 d (LF Dil)

E

n

E

0 50 mS cm --> 1.0 mS cm

power-off conductivity raise

(last pass sart removal disabled) υ Starting current 10 A

Current at stopping time: 1.6 A

Experimental Time

Fig. 6: A batch desalination of aqueous NaCl, about 14 I / m2.

Figure 6 shows the salt (calculated as NaCl) removal in dependence of the current at theoretical current efficiency (ce) and at 85% ce. With the PCCell ED 200 you can expect for sodium chloride ce's in the range between 90 and 95 %. It depends on current denity, concentration and other factors. The amount is given per cell pair. A 25 cell pair- unit will make 25 times of this.

10

50 Current Efficiency

_ 100 %

/ . 85%

ϋ

ro

10 15 20

Amperage

Fig. 7: Transport rate of one ED cell pair in dependence of the Amperage.

6. Application areas

Desalination of salt water

Stabilisation of wine

Whey demineralisation

Pharmaceutical application

Pickling bath recycling

11

7. General Remarks / Safety

By running an electrodialysis with this cell unit, concentrated acids and bases, which are corrosive, may be produced. Adequate protective measures have to be taken. At the electrodes, explosive gases and aerosol may be produced. Also in this case, appropriate protection has to be ensured. The cell has to be run in a tank large enough to collect any liquids passing out of the system.

8. Further Information / Contact Address

For further information, visit our web site www.electrodialysis.info. In case of any technical questions, please contact

PCCell GmbH

Dr. Patrick Altmeier

Phone: ++49- (0)6806/603730

Fax: ++49- (0)6806/603731 email: pccell@electrodialysis.de

Note:

The information in this handling instructions is presented in good faith, and all recommendations or suggestions are made without guarantee. The products are intended for use by persons having technical skill, at their own discretion and risk. PCCell is not responsible for any risks or liabilities which may result from the use of it's products.

12 GE o er G i:er

Water & Process Technologies

with Electrodialysis

Author: Robert P. Allison water recovery is important for resource conservation and cost control.

Reprinted from Proceedings of 1993 ^' AWWA Membrane Conference, by permission. Baltimore; MD

August, 1993. Sou res of EDR asie a tsf

Note: GE Water s Process Technologies purchased The source water feed to an EDR system is divided Ionics in 2005. into three streams as shown in Figure 1 The largest flow is the dilute feed which passes through the

Introduction stacks once and exits as desalted product. The second stream; termed concentrate makeup, is fed

For many membrane desalination Users, the need to a concentrate stream being recirculated to achieve ¹ maximum water recovery is a prime through the stacks. At the exit from the stacks priority. For some, source water is limited, allocated there is an overflow to waste. The concentrate or otherwise regulated. It is now recognized that makeup flow rate controls the average number of withdrawals from many aquifers exceed the retimes the concentrate is recirculated, and therecharge with resulting drops in water tables, land fore, is the main means of controlling recovery in subsistence and saltwater intrusion in coastal an EDR system The third stream is electrode comareas. Surface supplies can also be limited, as was partment flush water, which on most systems so clearly evident during the recent California is 1% of the dilute flow. Normally this water drought. For users who purchase. their feedwater, is directed to. waste after it passes through the costs are rising and can represent a substantia stacks, but it can be used as a portion of the portion of their total treated water cost. concentrate makeup water to further improve

Concentrate disposal is also getting more expenwater recovery.

sive and complicated as regulations intended to

preserve the quality of water supplies and the

environment become more strict. Permits for surface discharge can be difficult to impossible to get.

Discharge to sewers and deepwells.can substantially increase costs. "Zero Liquid _. Disch rge" facilities, where all liquid wastes are purified for reuse,

can have very high costs. Figure i: EDR Flow Diagram

Electrodialysis Reversal (EDR) is a desalination A small amount of the dilute stream water flow is process where salts are passed through the memtransferred to the concentrate stream as it passes branes ¹ instead of water as in reverse osmosis (RO). through the stack. First, water is transferred The process is fundamentally different from RO through the membrane with the passage of ions; and has its own distinct -capabilities and limitations This "water-transfer" amounts to 0:15% to 0,45% of on water recovery. The capabilities of the EDR the dilute flow per 1000 ppm img/Ll of salts process are helping many municipal and industria removed. Membranes with -the best resistance to users, in desalinatio :applications, where high internal scale formation tend to have water trans- fer near the higher value. Internal leakage also Table 1: Suffolk, VA EDR Unit Flow Summary occurs between the dilute stream and the concentrate stream which is approximately 0.25% to

0.50% per stage. The concentrate stream is normally operated about 1 psi lower in pressure than

the dilute stream so that this leakage will be from

the dilute stream to the concentrate stream. Water

transfer and cross leakage do not reduce water

recovery. These flows are calculated as part of the

concentrate makeup flow in the plant design. The

actual controlled concentrate makeup flow is

reduced proportionately.

The periodic reversal of the DC power polarity A 5 mgd EDR plant located on Grand Canary Island interchanges the solutions in the individual spacoperates on a 5,000 to 7,000 ppm (mg/l) feedwater ers. Spacers carrying the dilute flow in negative at 85% water recovery. Table 2 shows the unit flow polarity carry concentrate in the positive polarity. summary. The Controlled Concentrate makeup flow Automatic inlet and outlet diversion valves direct is approximately 1/2 of the total waste. The ultithe dilute and concentrate flows to the correct mate water recovery capability based on flows of spacers for each polarity. this plant is only 91.8%. The higher TDS increases

While the concentrate is being flushed out during water transfer and the additional stages increase reversal, poor quality product is produced. This is cross leakage.

diverted to waste by a conductivity-controlled EDR Unit Flo Summary automatic valve. By timing the operation of the

automatic diversion valves and the DC polarity

reversal of each stack to the flow through the system, high conductivity product is produced for only

36 seconds. This phased polarity reversal occurs

every 15 to 30 minutes. The high conductivity or

"off specification" product from the "phased reversal" represents 2% to 4% waste. This waste is high

TDS concentrate and cannot be recycled to the

feed or concentrate makeup.

Some Exam les

The water recovery of this plant is really limited by

The highest water recovery EDR plant in operation two additional physical factors. The first is a pheis the 3.76 mgd (14,233 mVday) facility operated by nomenon called "shorting". Figure 2 shows how the City of Suffolk, VA. The plant has three stages leakage currents can travel sideways through the and achieves 94% water recovery. Table 1 shows a membranes and pass down a concentrate maniflow summary for one of the three EDR units brofold hole. If the concentration is sufficiently conken down to show where the waste is generated. ductive, the current passing through the The units have no continuous chemical feeds. A membrane to the manifold hole can create enough 14.9 gpm (55 Ipm! concentrate makeup flow is heat to soften the spacer material and cause it to used to control calcium carbonate scaling potendeform. This limitation can be overcome by a varitial in the concentrate. If the units did not ety of means which increase costs. The second require this controlled concentrate makeup flow, limit is imposed by membrane current efficiency waste could be reduced to 43,1 gpm giving an properties. Figure 3 shows the DC power consumpultimate recovery capability of 95.3%. tion and membrane current efficiency vs. water recovery for an EDR unit desalting 2,000 ppm (mg/l) NaCI solution to 334 ppm (mg/l). Membrane efficiency is related to the difference in normality between the dilute and concentrate streams. As water recovery is increased, the concentrate nornately exposes membrane surfaces and the water mality Increases and current efficiency drops, raisflow paths to concentrate with a tendency to preing power consumption: cipitate scale and desalted water which tends to dissolve scale. This allows the process to operate with supersaturated concentrate streams up: to specific limits without chemical additions to prevent scale formation. If chemicals are added to the concentrate, higher levels of supersaturation can be achieved.

Calcium Carbonate

The design limit for CaC<¾ without antiscalants is an Langelier Saturation Index (LSI) of +1.8. Actual scale precipitation starts at an LSI near +2,2. This

Figure 2: EDR Stack Shorting

limit is sufficiently high that few EDR units need any chemical additions to prevent CaC03 scaling from high concentrate LSI. Where chemical addition is used, acid or carbon dioxide addition to the concentrate is employed.

Antiscalants can be used as an alternative to acid or C02 addition to the concentrate. A 500,000 gpd EDR unit was operated for seven weeks at a con¬ centrate LSI of +3.0 using a polymer antiscalant

Another EDR unit was operated for 5,000 hours at

Figure 3: Efficiency and Power Consumption vs _. . Water an LSI of +2.7 using sodium hexametaphosphate Recovery antiscalant. This approach has not been adopted in general for three reasons.

Suffolk can achieve 94% water recovery because

the relatively low TDS of the feedwater results in 1. Antiscalants must be dosed at the correct relatively low normality difference between the amounL Too little results in scaling and too dilute and concentrate streams. The Grand Canary much can foul the membranes.

Island plant has a much greater normality differ2. Antiscalant dosages are difficult to monitor: ence and power consumption rises sharply above There is no easy way to test the concentrate 86% water recovery. Anion exchange membranes for correct dosage. With acid or CO2, pH is easare available that have better current efficiency ily monitored.

which improves water recover capability. These 3. The concentrate LSI only needs to be reduced membranes tend to be subject to more internal to + 1.8. The required acid or CO _? dosages are scale formation which can make their use undesiralmost always very small. There is no signifiable on many waters. Cation exchange memcant cost advantage favoring the use of antisbranes have been substantially improved since the calants over acid or CO2.

Canary Islands plant was built in 1985. Long term

testing at this plant show these new membranes Calcium Sulfate

substantially improve current efficiency and

reduce power consumption. They are now stanThe design limit for CaS0 ₄ saturation without andard on all new plants. tiscalant addition is an ion product of 2.25 x Ksp.

The real limit where precipitation starts is near x

Concentrate Scaling limits Ksp. Dell City, Texas has operated a 150,000 gpd

(568 mVday) EDR system since 1975 with the con¬

The water recovery capability of nearly all EDR centrate CaSOs ion product at 3.5 x Ksp without plants is limited by the potential for salts of limited antiscalant addition. The limit cannot be increased solubility to precipitate from the concentrate by acid or C0 ₂ addition, as pH adjustment does not stream as scale. The polarity reversal of EDR alter- increase the solubility of CaSO _¾ . The only way to removal. The first user to encounter BaSC scale increase water recovery is to use antiscalants. has 275,000 gpd (1041 mVday) units. The problem occurs intermittently as the quality of their surface

In 1981 and 1982, the EDR limits of sustained

water supply varies. This user simply added strainoperation at high CaSO* saturations with sodium

ers to the piping before the stacks to catch the hexametaphosphate antiscalant addition were

flakes and has operated this way for over 10 years. explored under an DWRT contract at Roswell, New

Mexico. The final test in this program was operaIt is now known that the threshold point for BaS0 ₄ tion of a 50,000 gpd EDR unit with the concentrate precipitation in EDR is an ion product of 100 x Ksp CaS04 ion product at an average of 12.5 x Ksp for when no antiscalants are used.

over 5,000 operating hours. Inspection of the

The limit with antiscalant addition is currently membranes at the conclusion of the test showed

unknown. Several plants are operating at a BaS0 ₄ the membranes had only small amounts of scale,

ion product of 150 x Ksp and two plants have even though antiscalant addition was lost for four

reached an ion product of 225 x Ksp with a polymer days during the test. Analysis of the membranes at

antiscala nt dosage of 2 to 5 mg l to the concentrate. the conclusion of the test indicated good performance properties. In fact the membranes were used

in another plant after the Roswell test for about Strontium Sulfate

seven years. SrS(¾ scale has not been detected in any EDR

Since the landmark Roswell study, a number of plants. Analyses of concentrate samples from EDR units have operated at high CaS0 saturations many plants show the plants with the highest in the concentrate. In 1988 Sarasota County, Florsupersaturations are operating at an ion product ida installed a mobile 300,000 gpd EDR at its Sorof 4 Ksp. The projected limit is an ion product rento facility to supplement water produced by an about 8 x Ksp without antiscalants.

RO plant operating at 50% water recovery. The water recovery of the EDR plant is only 70%, but the Caidurn Fluoride

CaSOi ion product of the concentrate is CaF ₂ precipitation has never Occurred in an EDR 5.75 x Ksp. Scale formation is prevented by the plant. Plants are operating with ion products addition of 4.3 ppm (mg/l) of a polyacrylate antis500 x Ksp and much higher levels have been encalant to the concentrate. countered in two industrial pilot studies with no

Sarasota County is now constructing a 12 mgd depreci itation. There are no projected limits for satusalination facility scheduled to start operation in ration levels.

1994. Their withdrawals of groundwater are regulated and restricted due to concerns of aquifer Silica

overw ^' ithdrawal and quality degradation. The con¬

Silica in waters below pH 9,5 is essentially nonionic centrate is to be injected into deepwells due to

and is not removed or concentrated by EDR. Tests environmental concern and regulations controlling

Show silica levels are equal in the feed, product surface discharge. They selected EDR for its proven

and brine of operating EDR plants. High water ability to operate at a high CAS(¾ saturation level,

recoveries can be obtained on high silica waters which translates to an 85% water recovery for this plant.

because silica does not limit EDR recovery.

Barium Sulfate The 5 mgd plant on Grand Canary Island is a perfect example of this capability. Th feedwater silica

BaS04 scales started to be encountered in EDR varies from 50 to 60 ppm (mg/l), yet the water plants in the 1980s with the growing trend to recovery is 85%. RO would have a lower operating higher water recoveries: It has now been encouncost on this higher TDS water, but recovery would tered in about ten plants. It precipitates on the have to be much lower. The feedwater is purwalls of the concentrate recirculation piping and in chased at a cost of over US$1 per thousand galthe concentrate pump. It adheres strongly to metlons (per 3.8 m?). The RO cost advantage is lost with als, but breaks off the PVC piping when the scale is the much larger volume of waste required to pre- about .020 inches thick. The flakes then pass to the vent silica scaling.

EDR stacks. Chemical flushes cannot dissolve the

scale. The stacks must be disassembled for conclusion

The maximum water recovery that can be achieved with EDR desalination for any given source water depends on a variety of factors. In most applications the water recovery is limited by the potential for scales to precipitate from the concentrate. EDR has the ability to operate at high supersatu rations of scale-forming salts in the concentrate and is unaffected by silica. This translates to a high water recovery capability. These are the reasons. EDR is meeting the needs of users in many applications where high water recovery is a priority.

Electrodialysis (ED) and Electrodialysis

Reversal (EDR)

Electrodialysis (ED) is an electrochemical process in which ions migrate through ion-selective semipermeable membranes as a result of their attraction to two electrically charged electrodes. ED is able to remove most charged dissolved ions.

1.0 Applicable Contaminants

ED/EDR is an EPA BAT for barium, nitrate and nitrite, selenium, and TDS.

2.0 Description of Technology

Pretreatment Typical operation requires: the addition of a scale inhibitor to prevent scaling and reduce the concentrate LSI below 2.1 in the concentrate stream, residual chlorine concentration of 0.5 rng/L to prevent biological growth, and a cartridge filter (10-20 μιη) prior to the ED/EDR system. Air stripping can also be used prior to ED/EDR in order to remove ¾S [6]. Also, the feed water must be within the limitations of an ED/EDR system (see section 2.2).

Technology Description Electrodialysis is a process that depends on the principal that most dissolved salts are positively or negatively charged and they will migrate to electrodes with a opposite charge [2] . Selective membranes that are able to allow passage of either anions or cations make separation possible [2] . ED uses these membranes in an alternating fashion to create concentrate and product streams.

Electrodialysis 1 A typical ED system includes a membrane stack with a number of cell pairs, each consisting of a cation transfer membrane, a derhineralized flow spacer, an anion transfer membrane, and a concentrate flow spacer. Compartments for the electrodes are at opposite ends of the stack. The electrodes are continually flushed to reduce fouling or scaling.

Recycling the concentrate stream and discharging concentrate to waste, or blowdown, is common and called feed-and-bleed mode [2]. This is necessary because of the fact that there are sharp differences in flow rates between the product and brine streams. Diluate flow is about 10 times the flow of the brine stream; this difference in flows creates pressure imbalances^ requiring concentrate recycle [5].

Membranes are usually made out of cation- or ani on-exchange resins made into sheet form. ED spacers are made out of HDPE, and the electrodes are composed of an inert metal. Membrane selection is based on careful review of raw water characteristics.

Electrodialysis Reversal (EDR) is similar to ED but the polarity of the electrodes is regularly reversed, thereby freeing accumulated ions on the membrane surface. This process minimizes the effect of inorganic scaling and fouling by converting product streams into waste streams [6]. This process requires additional plumbing and electrical controls, but increases membrane life. EDR does not require added chemicals, and eases cleaning as well.

Maintenance ED membranes are durable, can run under a wide range of pH conditions (pH 2 - 1 1), and endure high temperatures during cleaning [4] . They can be removed from the unit and scrubbed if necessary. If operated properly, membranes have an average life of 12 to 15 years [4]. Solids can be flushed out by turning the power off and letting water circulate through the stack. The ED stack must be disassembled, mechanically cleaned, and reassembled at regular intervals. They can also be cleaned using a 5% hydrochloric acid solution [8] .

Waste Disposal The concentrate waste stream, electrode cleaning flows, and residuals from the pretreatment process will be a art of a typical waste stream flow and will require disposal. Common disposal methods include: surface water discharge, evaporation ponds, etc. Spent membranes will also require disposal.

Benefits

• ED and EDR can operate with minimal fouling or sealing, or chemical addition.

• Low pressure requirements.

• ED and EDR facilities are quieter than RQ.

• Long membrane life expectancy.

• Unaffected by non-ionic sealants such as silica ¹ .

• Low chemical usage for pretreatment ¹ .

• Ability to treat feed water with higher SDI, TOC and silica concentrations, and more turbidity than RO ¹ .

• Can operate with up to 0.5 ppm of free chlorine in the feed water to control the biological matter in the feed water. ⁸

Electrodialysis 2 Limitations

• TDS economical up to 8,000 ppm, but often run at waters of 1,200 ppm [6,9]

• pH; 2.0 to 11.0

• TOC : up to 15 mg/L

ppm with spikes up to 15-20 ppm

3.0 Example Treatment Train

The conventional EDR treatment train typically includes raw water pumps, debris screens, rapid mix with addition of an antiscalant, slow mix flocculator, basin or clarifier, gravity filters, EDR membranes, chlorine disinfection, and clearwell storage. Microfiltration (MF) could be used in place of flocculation, sedimentation, and filtration.

Waste Discharge

4.0 Safety and Health Concerns

• Produces hazardous gasses, such as chlorine, hydrogen, ¾S, etc.

• Electrical hazardous

5.0 References

1. Buros, O. K. (2000). The ABCs of Desalting. Topsfield, International Desalination Association, Saline Water Conversion Corporation.

2. American Water Works Association, and American Society of Civil Engineers. Water Treatment Plant Design. Ed. Edward E. Baruth. Fourth ed. New York: McGraw-Hill Handbooks, 2005.

3. General Electric. (2008). "Electrodialysis Reversal (EDR)." Retrieved 9/15/08, from http://'wvw,gewater.;Convproducts/equip;ment/ed edr edi/edr.jsp.

Electrodialysis 3 44.. RReeaahhll,, EE.. RR.. ((22000088)).. ""HHaallff AA CCeennttuurryy ooff DDeessaalliinnaattiioonn wwiitthh EElleeccttroroddiiaallyyssiiss.."" ffrroomm hhtt pp::////wwwwww..eeee iitoto..oeoomm<<pp¾K' eecchhmmccaa3l PPaappeerrss CCttt^st AAmmeeririoeaass//EEftftgglliisshh//TTPP1l0<)3388EENN..pp ddff....

55.. PPeerrrryy,, RRoobbeerrtt HH..,, DDoonn WW.. GGrreeeenn,, aanndd JJaammeess OO.. MMaalloonneeyy.. PPeerrrryy''ss CChheemmiiccaall EEnnggiinneeeerrss HHaannddbbooookk.. SSeevveenntthh eedd.. NNeeww YYoorrkk:: MMccGGrraaww--HHiillll,, 11999977..

66.. BBuurreeaauu ooff RReeccllaammaattiioonn ((22000033)).. DDeessaallttiinngg HHaannddbbooookk ffoorr PPllaannnneerrss.. DDeeppaarrttmmeenntt ooff tthhee IInntteerriioorr.. D Deennvveerr..

77.. TTrruusssseell TTeecchhnnoollooggiieess.. ""DDeessaalliinnaattiioonn TTeecchhnnoollooggiieess"".. PPaassaaddeennaa,, 22000088.. TTrruusssseell

TTeecchhnnoollooggiieess,, 66//1111//22000088.. <<hhtttfpp:://7\wvww..ttirnusssseelllltteecchh..ccoomm //tteecchh ddeessaa.!!iinnaattiiooiiii..aassrr>>>>..

88.. AAlllliissoonn,, RR..PP.. ((22000011)).. ""SSuurrffaaccee aanndd WWaasstteewwaatteerr DDeessaalliinnaatitioonn bbyy EElleeccttrrooddiiaallyyssiiss RReevveerrssaall"" ffrroomm

9.

Contact Information

This Fact Sheet was produced by the TSC's Water Treatment Engineering Team. Please address any questions or comments to:

Contact; Bob Jurenka

Email: wtprimer(¾usfar. gov

Phone: (303) 445-2254

Web: http;/Avww.usbr.go^

Revision Date: 09/20/10

Electrodialysis 4 Eurodia Industrie bipolar membrane electrodialysis unit for the conversion of sodium acetate into reusable acetic acid and caustic soda:

More than five years of successful operation

(Published in Membrane & Separation Technology News - Mar

In early 2003, Eurodia Industrie commissioned a new bipolar membrane electrodialysis (EDBM) unit at the site of a specialty chemical producer in Germany. Its purpose is to convert a byproduct stream of Sodium Acetate from the production of vitamins into Acetic Acid that can be reused in the process and Sodium Hydroxide to be used in the waste water treatment facility. As a result, the volume of waste (organic load) is significantly reduced and the acid and base values can be recovered. This article will describe the successful operation of this plant over the last three years.

EDBM combines in an electrodialysis stack conventional ion exchange membranes with bipolar membranes to allow the conversion of aqueous salt streams into the acids and bases. Under the action of a DC current, the bipolar membranes effectively split water molecules into H ⁺ and OH ^" ions. These ions combine with the anion and cation of the salt to form the acid and the base. With a three-compartment configuration using anion-exchange, cation-exchange, and bipolar membranes, three loops are circulating in the stacks: acid, base, and salt such as Sodium Chloride. As shown in the schematic below, the two-compartment configuration with bipolar and cation-exchange membranes is used preferably with the salts of weak acids and strong bases, such as Sodium Acetate. Because organic acids are weakly dissociated it is not possible/practical to have a separate acid loop and no anion-exchange membranes are required. In such stacks, the two product streams are an aqueous solution of NaOH (maximum concentration 8w%) and the organic acid mixed with some remaining organic salt for a sufficient conductivity: the higher the salt feed concentration, the higher the conversion rate that can be achieved. More than a dozen EDBM systems are in operation worldwide, mainly for specialty chemicals applications.

At the German plant, the Sodium Acetate stream is fed at an average concentration of 22-23 w% and the acid is produced at a concentration of 18-19 w% (3.2-3.5 M). The NaOH is produced at an average concentration of 6-6.5 w%, sufficient for reuse in the water treatment plant. Since there is also a transport of water from the acid into base loop, the conversion rate is above 90%. The unit processes 1.1 to 1.3 m ³ /hour of feed and converts more than 400 kg/hour of Sodium Acetate.

Since the feed contains low levels of multivalent cations (Ca, Mg, Fe, Cu, etc.), a pretreatment step is required to reduce the total concentration below 1 ppm to avoid precipitation as hydroxides in the stacks: two ion exchange resin columns have been installed for continuous operation. The salt is then converted in two EUR40B-bip EDBM stacks (see picture below), with a total ceil area of 255 m ² (510 m ² of membrane area). The EDBM stacks run in an automatic batch mode with the salt/acid conductivity decreasing from 70 mS/cm to 1 1 .5 mA/cm: when the conductivity reaches such minimum, the acid product is pumped to the storage tank. The overall current efficiency is optimized thanks to proprietary designed spacers.

The EDBM unit has been designed and constructed according to CGMP principles and to customer specifications. Commissioning has been completed within a short time and, since, it has met the needs of the customer and always been in operation when required. The automatic operation is controlled by a PLC. The unit has been installed in a stand-alone building while the overall control room is in an adjacent building. In addition, remote camera monitoring allows that an operator must only be in the building for less than 30 minutes per day. The electric cabinets and rectifiers are located in the same building as the EDBM stacks. A dilute NaOH solution is used as the electrolyte solution and a blower allows the safe venting outside the building of the small amount of hydrogen and oxygen gases that are generated at the electrodes. It is possible to install a modem to allow remote monitoring of plant operation and optimization of operating para

It is worthwhile to note that the performance of the system have continuously exceeded the design and guaranteed parameters: especially for the acid concentration and the acid production rate, as well as the power consumption. While a membrane life of 12,000 hours has been guaranteed, the membranes have run for more than 8,000 hours so far with no sign of deterioration. For a similar application at another site, the bipolar membrane life has exceeded 25,000 hours while the life of the cation-exchange membranes is about 15,000 hours. The DC current is set at 340 A (equivalent to 85 mA/cm ² ) and the average voltage remains at 185 V per half-stack, or less than 1.7 V/ceii. Since ceil maintenance and power consumption are the main operating costs, the economic projections show a payback for the customer of less than two years.

The performance of the EDBM unit demonstrates that, with a good design and the adequate pretreatment, users will have a very successful and trouble-free operation. Of course, this equipment requires the same amount of care as any chemical process step and the plant operators have shown their commitment to the technology. From this experience, it is clear that bipolar membrane electrodialysis can be reliably used in chemical processing with the potential of attractive financial returns.