EA033687B1 - Processing and transforming biomass to produce alcohols - Google Patents

Abstract

The invention relates to the method for producing one or more alcohols, which comprises saccharification of a cellulosic or lignocellulosic material with obtaining composition of sugars of saccharified biomass containing glucose and xylose; selective fermentation of glucose with obtaining fermented sugars composition containing essentially xylose, whereas xylose concentration in the fermented sugars composition is increased as compared to xylose concentration in sugars composition of the saccharified biomass; obtaining one or more acids from fermented sugars composition; transforming the said one or more acids to one or more esters; and hydrogenation of one or more esters using a catalyst and hydrogen to produce the said one or more alcohols.

Description

This application includes, by reference, a complete description of the following pending patent applications filed March 8, 2013: US Patent Application Nos. 61/774684, 61/774773, 61/774731, 61/774735, 61/774740, 61 / 774744, 61/774746, 61/774750, 61/774752, 61/774754, 61/774775, 61/774780, 61/774761, 61/774723, and 61/793336, filed March 15, 2013.

State of the art

With increasing demand for oil, interest in renewable raw materials for the production of biofuels and biochemical reagents is also growing. The use of lignocellulosic biomass as a raw material for such production processes has been studied since the 1970s. Lignocellulosic biomass is of interest because it is widespread, belongs to renewable resources, is produced domestically and is not used in the food industry.

To date, a large number of potential lignocellulosic raw materials are available, including, in particular, agricultural waste, wood biomass, household waste, oilseeds / oilcake and seaweed. Currently, these materials are either used as animal feed, biohumus materials, fuel for combustion in a facility for the joint production of heat and electric energy, or they are disposed of in landfills. Lignocellulosic biomass contains crystalline cellulose fibrils embedded in a hemicellulosic matrix surrounded by lignin. This provides a compact matrix that is difficult to access for enzymes and other chemical, biochemical and / or biological processes. Cellulosic biomass materials (i.e., the biomass material from which the lignin was removed) are more accessible to enzymes and other conversion processes, but even in this case, natural cellulosic materials often provide a low yield (from theoretical yield) when brought into contact with hydrolysis enzymes. Lignocellulosic biomass has even greater resistance to enzymes. In addition, each type of lignocellulosic biomass has its own specific ratio of cellulose, hemicellulose and lignin.

SUMMARY OF THE INVENTION

In general, the present invention discloses systems, methods and processes for converting biomass raw materials, for example, cellulosic, starch or lignocellulosic materials, into useful primary products, for example, alcohols, acids, esters and sugars. The present invention also discloses equipment, methods and systems for converting said primary products into useful secondary products, for example, for converting esters to alcohols (for example, n-butanol, sec-butanol, isobutanol, tert-butanol, ethanol and mixtures of any of the above alcohols) by hydrogenolysis.

Such a method involves the preparation of one or more acids (e.g., acetic acid, nano-butyric acid, isobutyric acid) from biomass, e.g., saccharified biomass, sugars, e.g., sugar in saccharified biomass, the sugar fraction of saccharified biomass, and converting one or more acids into one or more esters. The method further includes hydrogenating one or more esters with a catalyst and hydrogen to produce one or more products, such as alcohols. Optionally, one or more acids is obtained by fermenting sugars of saccharified biomass. Optionally, saccharified biomass sugars are obtained by saccharification of the cellulosic or lignocellulosic biomass material using one or more enzymes and / or one or more acids, for example, by first applying an acid and then applying one or more enzymes. In addition, this method may further include reducing the resistance of the cellulosic or lignocellulosic material to processing, for example, by irradiating an electron beam, for example, by delivering a radiation dose of 10 to 200 Mrad to the material. Optionally, the catalyst may include a metal, such as Pt, Pd, Re, Os, Ru, Rb, Ni, Co, Mo, W, Zn, Cr, Cu, oxides of these metals, and combinations thereof. During hydrogenation, the hydrogen pressure is from about 5 to 120 atmospheres (from about 0.5 MPa to about 12 MPa) when using a catalyst to produce one or more alcohols. Optionally, the method comprises isolating at least one of the carboxylic acids (e.g., butyric acid) before converting one or more acids to one or more esters (e.g. ethyl butyrate). Optionally, the method can be used to produce esters, including ethyl butyrate, butyl butyrate, hexyl butyrate and octyl butyrate. The alcohol portion of the ester can be obtained by treatment of biomass or by petrochemical processing. Carboxylic acid and alcohol can be reacted by known chemical processes to form an ester.

A process for preparing a product is also contemplated, comprising converting a fermented product of a saccharified treated lignocellulosic material into an ester and producing alcohol by passing the ester over a first catalyst, for example, a catalyst in the presence of hydrogen. The specified method may further include passing the ester over a second catalyst, for example, a catalyst. The first and second catalysts can be different types of catalysts, for example, they can have different compositions (for example, including substrates, such as silicon dioxide and Λ12Θ3). Alternatively, the first and second catalysts may be the same type of catalysts.

The method comprises applying a first hydrogen pressure while passing the ester over the first catalyst and applying a second hydrogen pressure while passing the ester over the second catalyst, wherein the first pressure is at least 0.5 atm (about 50 kPa) higher than the second the method may further include heating the first catalyst to a first temperature while passing the ester over the first catalyst and heating the second catalyst to a second temperature at passing the ester over the second catalyst, wherein the first temperature is at least 10 ° C higher than the second temperature. Alternatively, the temperature of the second reactor may be higher than the temperature of the first reactor and the pressure between the two reactors may be increased. Optionally, the first and second catalysts may include metals, including Pt, Pd, Re, Os, Ru, Rb, Ni, Co, Mo, W, Zn, Cr, Cu, oxides of these metals, and combinations thereof. Optionally, the method may include applying hydrogen pressure with a pressure of from about 5 to 120 atmospheres (from about 0.5 MPa to about 12 MPa). Alternatively, the first and / or second catalyst is classified as a reforming catalyst.

The fermentation product contains carboxylic acid. Optionally, a carboxylic acid may contain from 1 to 20 carbon atoms and from 1 to 5 carboxyl groups (for example, butyric acid, aspartic acid). Optionally, the fermentation product contains alcohol. Optionally, the ester may be, for example, ethyl butyrate, propyl butyrate, butyl butyrate, hexyl butyrate and octyl butyrate, and isomers of the alcohol and carboxyl parts of the ester. That is, butyric acid and butyrates can refer to both the normal (n-) and the iso-isomer. The method may further include fermenting the biomass to produce at least two products, and the conversion involves condensing the products to form an ester. For example, butyric acid and butanol can be converted to butyl butyrate and then, in turn, hydrogenated to give 2 moles of butanol.

The method also includes isolating the fermentation product before converting the product. Optionally, the fermentation product can be brought into contact with the resin and the fermentation product is coupled to the resin. In addition, the fermentation product can be removed from the resin by acidifying the fermentation product and extracting the acidified product with a solvent (eg, alcohol). The specified method includes obtaining the processed lignocellulosic material by irradiating the lignocellulosic material with an electron beam. For example, irradiation can be performed with a dose of about 10 to 150 Mrad.

Next, the treated biomass is subjected to saccharification by bringing the treated biomass into contact with the enzyme. The method may include saccharification, resulting in a mixture containing glucose and xylose, and fermentation, which may include xylose fermentation. In addition, alcohol can form during glucose fermentation (for example, selectively without xylose fermentation), and, optionally, the alcohol can be distilled before xylose fermentation. Optionally, xylose may be added to the saccharified treated material (e.g., xylose in addition to that present in the processed saccharified material).

Also contemplated is a method for producing a product, comprising fermenting a first sugar obtained by saccharizing a treated lignocellulosic material using a first microorganism, and fermenting a second sugar obtained from a saccharified processed lignocellulosic material using a second microorganism. Additionally, optionally, the method may include distilling the fermentation product of the first sugar before fermenting the second sugar. For example, the first sugar may be glucose, and the second sugar may be xylose. The fermentation product of the first sugar is alcohol (e.g., ethanol), and the fermentation product of the second sugar is carboxylic acid (e.g., butyric acid). Optionally, the method may further include adding xylose to the saccharified material. Optionally, the following substances can be added to the saccharified material: acids, bases, buffers, amino acids, vitamins, crude molasses, enhanced environment for clostridia, metal ions, yeast extract, meat extracts, vegetable extracts, peptones, carbon sources, proteins, Fe, Mn, Mg, Na, Cu, Zn, n-aminobenzoic acids, choline, thiamine, albumin, inositol, and combinations thereof. Optionally, the treated lignocellulosic material is obtained by irradiating the lignocellulosic material with an electron beam, for example, at a dose of from about 10 to 200 Mrad.

The specified method further includes the conversion of the product obtained by fermentation of the second sugar into an ester. Optionally, said ester can be hydrogenated to give an alcohol.

The specified method involves extraction of the fermentation product of the second sugar with an alcohol, including n-hexanol, n-octanol, n-decanol, n-dodecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, linoleyl alcohol, isomers of these alcohols and their combinations. Some of the possible advantages of these methods will be considered.

- 2,033,687 below. Some fermentation processes are suppressed by the product, so that the amount of the desired fermentation product that can be obtained can be limited. For example, the fermentation of sugars to produce n-butanol under the action of certain types of Clostridia is often limited to one or two percent, since the alcohol obtained above has an inhibitory effect on this microorganism or is toxic to it. Removing such a small amount of nbutanol from an aqueous spent enzyme broth can be a daunting task. An intermediate in the preparation of n-butanol during fermentation is butyric acid, which is formed in the acid-producing phase of fermentation. Butyric acid is usually less inhibitory or less toxic to Clostridia and, therefore, can accumulate in higher concentrations than butanol, for example, from 4 to 7%. In addition, the isolation of butyric acid from the enzyme broth can be a less difficult task, partly due to its higher molecular weight and partly due to its ionic nature. Butyric acid is a useful product, for example, used in the chemical, food industry, in the production of flavorings, fragrances and in the pharmaceutical industry. In addition, butyric acid can be hydrogenated directly to n-butanol. Alternatively, butyric acid can be esterified, for example to give ethyl butyrate, while the product can be hydrogenated to give n-butanol and ethanol under milder conditions than direct hydrogenation. Along with these advantages, obtaining products, for example, n-butanol, from biomass does not require as many high-energy catalytic steps as are necessary for processing fossil fuels. For example, fossil fuels can have a high concentration of compounds that must be removed before or during cracking, for example, sulfur compounds that must be removed by hydrodesulfurization. When using the described methods for the catalysts (for example, reforming catalysts) used in these processes, a pure biomass-derived raw material is provided, and lower temperatures and pressures can be used.

Thus, specifically, the present invention relates to a method for producing one or more alcohols, which includes:

saccharification of cellulosic or lignocellulosic material to obtain a sugar composition of saccharified biomass containing glucose and xylose;

selective glucose fermentation to produce a fermented sugar composition containing essentially xylose, wherein the xylose concentration in the fermented sugar composition is increased compared to the xylose concentration in the saccharified biomass sugar composition;

obtaining one or more acids from a fermented sugar composition; converting said one or more acids into one or more esters; and hydrogenating one or more esters using a catalyst and hydrogen to produce said one or more alcohols.

In one embodiment of the present invention, said one or more acids include butyric acid or acetic acid.

In another embodiment of the present invention, saccharified biomass sugars are obtained by saccharification of cellulosic or lignocellulosic biomass material using one or more enzymes, one or more acids, and combinations thereof.

In yet another embodiment of the present invention, the proposed method further includes processing the cellulosic or lignocellulosic material by irradiation with an electron beam, where the radiation dose is from 10 to 200 Mrad.

In another embodiment of the present invention, the catalyst includes a metal selected from the group consisting of Pt, Os, Re, Ru, Rb, Ni, Co, Mo, W, Zn, Cr, Cu, oxides of these metals and combinations thereof, and hydrogen is used under pressure from 5 to 120 atm.

In yet another embodiment of the present invention, the proposed method further comprises isolating at least one of the acids before converting said one or more acids into one or more esters, the ester being selected from the group consisting of ethyl butyrate, butyl butyrate, hexyl butyrate and octyl butyrate.

In another embodiment of the present invention, the proposed method further comprises fermenting said biomass to produce at least two fermentation products, said two products being acid and alcohol, which in turn are reacted to form an ester.

Other features and advantages of the present invention will be apparent from the following detailed description and claims.

Description of drawings

The above information will become apparent from the following more specific description of typical embodiments of the present invention, illustrated in the accompanying drawings, where the same reference numbers refer to the same parts in all different images. The drawings are not necessarily drawn to scale, instead, the focus is on illustrating embodiments of the present invention.

FIG. 1 is a diagram illustrating a typical enzymatic hydrolysis of biomass.

FIG. 2 is a flowchart showing processes for preparing sugar solutions from a raw material.

FIG. 3 is a flowchart showing processes for producing sugar solutions from a raw material in a secondary fermentation.

FIG. 4 is a diagram illustrating a reaction scheme for converting sugar to alcohol with ethyl butyrate as an ester.

DETAILED DESCRIPTION OF THE INVENTION

When applying the methods and systems described in this application, cellulosic and / or lignocellulosic raw materials, for example, materials that can be derived from biomass (e.g., plant biomass, animal biomass, paper and household waste biomass) and which are often readily available, but difficult to process, can be turned into useful products. Methods and systems for producing useful primary products, for example, alcohols, acids and sugars, are considered. Also contemplated are methods and systems for converting said primary products into useful secondary products, for example, esters and alcohols (for example, butanol, ethanol, esters and mixtures thereof). Enzymes and biomass-destroying organisms that break down biomass, for example, cellulose, hemicellulose and / or lignin portions of biomass, contain or produce various cellulose-degrading enzymes (cellulases), ligninases, xylanases, hemicellulases or various small biomass-destroying metabolites. In FIG. 1 shows some examples of these biomass-destroying processes. First, the cellulose substrate is hydrolyzed in random places using endoglucanases to form oligomeric intermediates. Further, these intermediates serve as substrates for exothermic cleavage of glucanases, such as cellobiohydrolase, to produce cellobiose from the terminal groups of the cellulose polymer. Cellobiose is a water-soluble 1,4-linked glucose dimer. Finally, cellobiase breaks down cellobiosis to form glucose. In the case of hemicellulose, xylanase (e.g. hemicellulase) acts on this biopolymer and releases xyl oligosaccharides and xylose as possible products.

In FIG. Figure 2 shows the processes for producing sugars and fermentation products from raw materials (e.g., cellulosic or lignocellulosic materials). In the initial step (210), the method includes, optionally, machining the cellulosic and / or lignocellulosic raw material. Before and / or after such processing, the raw material can be processed using another physical processing method (212), for example, by irradiation, sonication, steam explosion, oxidation, pyrolysis, or combinations of these methods, to reduce or further reduce its resistance to processing. A sugar solution, for example, containing glucose, xylose, and combinations thereof, is obtained by saccharification of raw material (214). For example, saccharification can be effectively performed by adding one or more enzymes, for example, cellulases and / or xylanases (211), or by adding one or more enzymes and one or more acids in any order. Sugar solution can be subjected to bioprocessing (216), for example, by using a microorganism to ferment sugars to obtain a primary product, for example, alcohol, carboxylic acid, ketone, hydrogen, and combinations thereof. Optionally, fermentation may include the use of more than one microorganism and includes more than one stage of fermentation, for example, simultaneous or sequential production of one or more products. Optionally, fermentation may be selective for one sugar. The primary product obtained at the bioprocessing stage can be processed by chemical methods (224). For example, a carboxylic acid can be hydrogenated to produce an alcohol, esterified and / or esterified, and then hydrogenated. Hydrogenation may occur in a batch reactor or in a continuous reactor. Optionally, the chemical treatment may include isolating the product, for example, by column extraction, solvent extraction and / or by distillation. If necessary, at different stages of the process, it is possible to perform the steps of measuring the lignin content (218) and setting or adjusting process parameters based on the specified measurement (220), for example, as described in US patent application No. 12/704519, filed February 11, 2011 , the full description of which is incorporated herein by reference.

FIG. 3 is similar to FIG. 2, but has a different naming scheme. After saccharification, the mixture is fermented in step 217 so that only one of the sugars undergoes fermentation to form the first product in the mixture consisting of at least the second (unfermented) sugar and the solids obtained by fermentation. The first product is isolated in step 225 by any of the isolation methods described herein. Optionally, the fermented solids can be separated from at least the second (non-fermented) sugar in step 232. The secondary fermentation process in step 227 will turn the second sugar into a second product, which can be separated in step 230 using any of the isolation methods described

- 4,033,687 herein. Examples of the first and second sugars may be glucose and xylose, respectively, whereby glucose undergoes conversion in the first fermentation step. For example, depending on the fermenting microorganism and / or fermentation conditions, glucose can be converted to ethanol or lactic acid. Alternatively, the first sugar may be xylose, the second sugar may be glucose. In this case, xylose as a fermentation product is the first product.

In FIG. 4 shows an example reaction scheme for the conversion of sugar into alcohol, in particular, butanol. In the first stage, for example, xylose is subjected to fermentation to obtain n-butyric acid. It should be understood that isobutyric acid may also undergo similar reaction schemes. In a second step, butyric acid is contacted with an Amberlite ™ 400 quaternary amine functionalized resin. Butyrate forms bonds with quaternary amine groups and is extracted from the solution in the indicated second step. In a third step, the resin and bound butyrate are contacted with a strong acid, for example, aqueous sulfuric acid, which protonates the butyrate and forms free butyric acid. Then, butyric acid can be extracted with ethanol or another alcohol to obtain butyric acid in an alcohol solution. In a fourth step, butyric acid and ethanol (optionally additional ethanol may be added) are optionally contacted with a catalyst and heated (for example, to a boiling point with vapor condensation of about 80 to 90 ° C. at atmospheric pressure), so that the esterification reaction proceeds with the formation of ethyl butyrate. In a fifth step, ethyl butyrate is hydrogenated to produce butanol and ethanol using hydrogen and a catalyst (e.g., Re / Al ₂ O ₃ ). The hydrogenation step can be performed in any reactor suitable for carrying out hydrogenation processes.

Fermentation can produce carboxylic acid, for example, as described in US APPN 13/177827, filed July 7, 2011, and US APPN 13/668358, filed November 5, 2012, the full description of which is incorporated herein by reference. A carboxylic acid may be, for example, any carboxylic acid containing from 1 to 20 carbon atoms and from 1 to 5 carboxylic acid groups (-CO2H) (for example, from 1 to 10 carbon atoms and from 1 to 4 carboxylic acid groups, from 1 to 5 carbon atoms and 1 to 3 carboxylic acid groups). For example, some carboxylic acids that can be used in the described methods are acetic acid, propionic acid, tartaric acid, malonic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid, maleic acid, gluconic acid, traumatic acid, muconic acid, butyric acid (e.g. n-butyric acid, isobutyric acid), valerianic acid, caproic acid, lauric acid, palmitic acid, stearic acid and peanuts oic acid.

Sugars from biomass may include one or more sugars. For example, some fermenting microorganisms may consume more than one sugar simultaneously or sequentially. Some fermenting microorganisms prefer one sugar. For example, some microorganisms may prefer fructose fermentation, as described in PCT Patent Application No. PCT / US12 / 71097, filed December 20, 2012, where the United States is indicated as the state in which the applicant intends to obtain the patent and published in English. Optionally, the sugar solution can be processed before any fermentation step. For example, a saccharified solution obtained using the methods described herein can be purified and / or processed by filtration (e.g., including filtering using a rotating vacuum drum), chromatography (e.g., fluidized bed chromatography), electrodialysis , including bipolar electrodialysis, crystallization, and combinations of these methods. Optionally, the treatment may include fermenting one sugar in a mixture of two sugars and removing the fermentation product, wherein the remaining sugar solution is essentially a second sugar that is easier to use, for example, by isolation and / or fermentation (for example, to produce a carboxylic acid). Some typical cleaning and / or processing methods that can be used are described in the pending US patent applications 61/774775, 61/774780 and 61/774761, which are incorporated herein by reference. In some cases, the biomass source can provide a higher amount of essentially only one sugar, for example, some paper products, cotton and other biomass, which is almost entirely a glucose source with a small, if any, xylose content. Other biomass sources can provide mainly xylose and / or lignin.

Some suitable butyrate-producing microorganisms may include C. saccharobutylacetonicum, C. saccharoperbutylacetonicum, C. saccharobutylicum, C. Puniceum, C. beijernckii, C. acetobutylicum, C. acetobutylicum, C. roseum, C. aurantibutyricum, C. felsineum and . tyrobutyricum. It may be appropriate to introduce additives during the fermentation, for example, acids, bases, buffers, amino acids, vitamins, crude molasses, enhanced Clostridia medium (RCM), metal ions, yeast extract, bottoms, meat extracts, vegetable extracts, peptones, carbon sources and proteins. For example, the addition of metal ions Fe, Mn, Mg, Na, Cu, Zn and

- 5,033,687 combinations thereof. Other additives may be useful, for example, p-aminobenzoic acids, choline, inositol, thiamine and albumin. A preferred additive that can be used is still bottoms from the fermented saccharified lignocellulosic or cellulosic material (e.g. biomass). For example, in yeast fermentation of saccharified material described herein, ethanol is obtained, which can be distilled to give a bottom residue. VAT residue containing yeast cells and spent biomass (for example, lignin, unfermented sugars, proteins) can be used as an additive in secondary fermentation.

Optionally, the bottoms can be purified prior to use, for example, by the methods described herein (for example, using rotating vacuum drum filters, fluidized bed chromatography and advanced fluidized bed chromatography, filtration, deposition). The concentration of solids (for example, dissolved and / or suspended solids) may be at least about 5 wt.%, (For example at least about 10 wt.%, At least about 20 wt.%, 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.%, From about 10 to 90 wt.%, from about 20 to 60 wt.%). The bottom residue can be used directly in the distillation or it can be diluted with a solvent (for example, water) and used as at least 5 wt.%, The bottom residue in the solvent (for example, at least 10 wt.%, At least 20 wt.% at least 30 wt.%, at least 40 wt.%, from about 10 to 80 wt.%, from about 10 to 60 wt.%, from about 10 to 50 wt.%, from about 20 to 50 wt. %, from about 20 to 40% by weight). The bottoms additive may be used in combination with another additive described herein and additional sugars (e.g., glucose and / or xylose).

During fermentation, the pH of the fermented medium can be an important parameter from the point of view of controlling the process. Buffer solutions, such as phosphate, sulfate, and acetate buffers, help maintain the desired pH. To maintain and / or change or adjust the pH, it is also possible to add acids and bases (for example, ammonium hydroxide, sodium and potassium hydroxides, acetic acid, sulfuric acid, phosphoric acid, nitric acids) before fermentation, after and during the fermentation process. During fermentation, the optimum pH is from about 2 to 8 (for example, from about 3 to 8, from about 4 to 8, from about 4 to 7). Maintaining the pH above a critical value, for example, above about 3 (for example, above about 3.5, above about 4), by adding a base often improves the fermentation process. Such regulation can be especially important when using acid-producing bacteria, since acidic products can lower the pH during fermentation to values that are toxic to microorganisms. In addition, temperature can be a determining and important parameter in fermentation. Optimally, the temperature is maintained in the range of from about 20 to 50 ° C (for example, from about 20 to 40 ° C, from about 30 to 40 ° C). In some cases, lower or higher temperatures relative to the optimum temperature can be used to stimulate the desired fermentation phase, for example, acid formation, solventogenesis, logarithmic growth phase, sporulation.

For anaerobic microorganisms, it is preferable to carry out fermentation in the absence of oxygen, for example, under a pad of an inert gas such as N ₂ , Ar, He, CO ₂ or mixtures thereof. In addition, the mixture can be continuously sparged with an inert gas passing through the tank or bioreactor during part of the process or the entire fermentation process.

The fermenting or saccharifying microorganism can be immobilized on a substrate. For example, the use of such a process is described in US Pat. The fermentation product can be removed from the fermentable medium by any suitable means. For example, butyric acid and other fermentation products can be removed / purified by adding a base to the fermentation solution, adding acid to the fermentation solution, using extraction, filtration, centrifugation, distillation, cross-flow filtration, membrane filtration, transfer, electrodialysis, adsorption and / or binding to a resin or other solid and combinations of the above methods. Optionally, after purification, if the product is wet, it can be dried, for example, by contacting the product with molecular sieves or other desiccants (e.g. sodium sulfate, magnesium sulfate). An extraction method for organic acids, including the formation of an alkylamine adduct in an aqueous solution, which can then be extracted from the aqueous phase, is described in US patent application No. 12935075, filed March 27, 2009, the full description of which is incorporated herein by reference. According to one preferred embodiment of the invention, organic acids (e.g., butyric acid) can be extracted by adsorption / adduct / bonding to a solid support, for example, a resin support, a solid support and / or a polymer support.

- 6 033687

The fermented product can be extracted directly from the fermentation solution or from a solution that has been distilled. The extracting solvent may be, for example, alcohol, ether, oil (for example, castor oil, coconut oil, palm oil). For example, in the case of extraction of a carboxylic acid (e.g., butyric acid), some particularly useful alcohols are fatty alcohols, for example, containing from 6 to 20 carbon atoms and from 1 to 5 alcohol functional groups (e.g., n-hexanol, n-octanol, n-decanol, n-dodecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, linoleyl alcohol, isomers of the listed alcohols and combinations thereof). Before extraction, the acid can be protonated by treating the solution containing said acid with mineral acid to adjust the pH to about 3 (for example, from about 2 to 4).

The acid can be esterified as described herein to form an ester. In addition, the alcohols listed in this document can be used to esterify the acid obtained by fermentation. The esterification can be performed in an extraction solution. For example, alcohol may be added to the extraction solvent. If the extraction solvent is an alcohol, then said alcohol can be directly used for esterification with or without concentration or dilution of the alcohol. For example, butyric acid obtained by fermenting biomass can be protonated by adding sulfuric acid to the fermented solution. Then, butyric acid can be distilled from the acidified solution. The distillate can then be extracted into alcohol (e.g. n-octanol). An acid catalyst can be added to the extracted acid, and the alcohol and solution are heated to form an ester. Alternatively, the fermented solution can be acidified and then directly extracted with alcohol (e.g., octanol). Further, the mixture can be esterified.

Resins used for the adsorption of organic acids (for example, butyric acid) can be polymers with ion-exchange properties, for example, containing quaternary amine functional groups that are capable of ion exchange with an acidic acid proton. For example, Amberlite ™ IRA 410, Amberlite ™ IRA-67, Amberlite ™ 96, Amberlite ™ XAD-1180M, Amberlite ™ XAD-2, Amberlite ™ 400 and Amberlite ™ IRN150. The solution containing the organic acid can be brought into contact with the ion exchange resin by passing the solution through a packed column (e.g. glass, metal, plastic) with the resin. Optionally, a solution containing an organic acid can be combined with the resin in a vessel (e.g., in batch mode) and mixed (e.g., shake, mix) for several minutes to several hours (e.g. 1 minute to 24 hours, 1 minutes to 12 hours, from 1 minute to 8 hours, from 1 minute to 4 hours, from 1 minute to 1 hour, from 1 hour to 4 hours, from 1 hour to 12 hours). An organic acid depleted solution can be decanted or filtered off from the resin in a batch mode over a period of time sufficient to adsorb / bind at least some organic acid. When using batch separation methods or column separation methods, the amount of butyric acid can be monitored using any suitable method, for example, equilibrium vapor analysis, titration and HPLC. The organic acid adsorption resin can be brought into contact with the fermentation solution during the fermentation process or after completion of the fermentation. For example, the active fermentable medium can be pumped through a column of resin or the specified resin can be added to the fermentation broth. For example, organic acid can be removed from the resin by contacting the resin and the associated organic acid with an acidic solution. For example, the acidic solution may include a mineral acid (e.g. hydrochloric, sulfuric, phosphoric, nitric acid) or the acid may be an organic acid (acetic acid, trifluoroacetic acid). In general, it is preferable to use an acid with a low pK _a , for example, about lower than pK _a butyric acid, for example, with a pK _a less than about 4, less than about 3, less than about 2. The pH of the solution after acidification is optimally from about 1 to 6 (e.g., from about 2 to 5, from about 2 to 4). To facilitate the extraction of the organic acid or organic acid salt from the resin, it may be preferable to use a solvent containing or not containing water. For example, the solvent may be an alcohol (e.g., methanol, ethanol, propanol, butanol or fatty acid alcohols described above), an ether (e.g., diethyl ether, tetrahydrofuran, methyl tert-butyl ether, diisopropyl ether), acetonitrile, acetone , butyl acetate, dimethylformamide, ethyl acetate and combinations thereof. These compounds can be combined in any percentage with water and with each other. A preferred method for removing adsorbed organic acid from a resin packed column is to elute with acidified alcohol (e.g., ethanol and / or methanol with added acid) or an acidified alcohol / water solution (e.g., ethanol / water, methanol / water with added acid) . After acid removal, the resins can be reused, for example, by washing with an excess of acidified solution, followed by washing with water, optionally deionized water.

Acidified eluent / extraction solution obtained by processing a resin containing

- 7 033687 carboxylic acid, can be neutralized by adding a base. As a result of this procedure, a carboxylic acid salt can be obtained. Carboxylic acid salts can be evaporated to dryness and then dried in an oven (for example, at a temperature of 80 to 100 ° C). Further, salts can be used in esterification reactions with optional re-acidification before the reaction. As an alternative to acidification to remove the organic acid from the resin, the acidic proton of the organic acid can be removed by ion exchange with a cation to give an organic acid salt. Some suitable exchange ions include, for example, quaternary ammonium ions, alkali metal ions and alkaline earth metal ions, transition metal ions, and combinations thereof. Thus, the resulting carboxylic acid salt can be further processed as previously described.

The preparation of esters described herein from carboxylic acids can be accomplished by the use of any alcohol, for example, alcohols containing from 1 to 20 carbon atoms and from 1 to 5 alcohol groups (for example, from 1 to 10 carbon atoms and from 1 to 4 alcohol groups, from 1 to 10 carbon atoms and from 1 to 2 alcohol groups). Some typical alcohols are methanol, ethanol, propanol, n-butanol, n-hexanol, n-octanol, n-decanol, n-dodecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, linoleyl alcohol, diols (e.g., ethylene glycol), triols (e.g., glycerin), polyols, isomers of these compounds, and combinations thereof. The esterification can be performed with an excess of alcohol, for example, with a molar ratio of from about 1 to 50, with or without a diluent. The esterification reaction can be performed at temperatures from about 80 to 300 ° C (for example, from about 80 to 200 ° C, from about 80 to 150 ° C) and at pressures from about 1 to 30 atmospheres (from about 0 to about 3 MPa) (for example, from about 1 to 20 atm (from about 0.1 MPa to about 2 MPa), from about 1 to 10 atm (from about 0.1 MPa to about 1 MPa)). In some embodiments of the invention, the alcohol used includes alcohol obtained by fermentation of saccharified lignocellulosic or cellulosic raw materials, for example, ethanol and / or butanol can be used as described herein. In addition, alcohol can be obtained from other renewable sources of sugar and using other methods, for example, these sources may include starch and sugars obtained from corn kernels, sugarcane, fruits, legumes and / or beets. Ethanol and butanol are particularly suitable alcohols that can be obtained by the method described herein. In addition, alcohol can be obtained from sources of hydrocarbon. The esterification reaction can be facilitated by the use of a catalyst, for example, an acid catalyst. The acid catalyst may be homogeneous or heterogeneous. Some suitable homogeneous acid catalysts include sulfuric, phosphoric, nitric, hydrochloric and trifluoroacetic acid. Heterogeneous acid catalysts include resins or functionalized polymers, for example, sulfonated polystyrene resins. Acids can be solid catalysts, for example, such as zeolites, sulfonated carbons, alumina, clays, aluminosilicates, heteropoly acids, silicon dioxide, and combinations thereof. Dehydrating agents, for example, molecular sieves, can be used along with the catalysts or after esterification to remove water formed during the esterification. Other methods can be used to remove water, for example, distillation using a low boiling azeotrope with toluene. An acid (e.g., butyric acid) can be esterified while it is bonded to a resin used to adsorb organic acids. The ester can then be extracted into a solvent, for example, the solvents described previously, to remove protonated acid from the resin.

Optionally, esters can be obtained using a microorganism. For example, Staphylococci can be combined with carboxylic acids (e.g., butyric acid) and alcohols (e.g., ethyl alcohol) to produce ethyl butyrate. Other carboxylic acids, alcohols, and combinations of microorganisms may also be used. Other esters that can be formed from acids and alcohols derived from sugars by microorganisms (e.g. S. cerevisiae) include isoamyl acetate, ethyl caproate, ethyl caprylate, ethyl caproate, phenylethyl acetate, ethyl laurate, ethyl myristate and ethyl palmitate.

The ester can be separated from excess alcohol, unreacted acid and impurities in any suitable way. For example, distillation, chromatography, and filtration may be used. If there is any excess acid, it can also be removed by passing over / through the ion exchange material, for example, as described previously. In addition, the ester can simply be used in the form of a mixture, mainly with an excess of alcohol, for example, as direct fuel or fuel additive, for example, distributed into reformers, to obtain high-octane fuel and / or fuel additive. Other uses in the form of a mixture in the chemical, food industry, flavoring and flavoring industries, and the pharmaceutical industry are obvious to those skilled in the art.

Organic acids obtained by the methods described herein can be directly hydrogenated to form an alcohol. However, direct hydrogenation requires very high pressures, often with rapid deactivation of the catalysts. Etherification is preferred

- 8 033687, since it allows the use of milder conditions for hydrogenolysis. For example, direct hydrogenation may require pressures above 100 atm (approximately 10 MPa), temperatures above 300 ° C, and catalyst lifetimes of only a few hours before these catalysts need to be regenerated or replaced. Hydrogenolysis of esters can be performed at temperatures from about 100 to 300 ° C (for example, from 120 to 250 ° C, from 150 to 300 ° C), hydrogen pressures less than about 120 atm (about 12 MPa) (for example, from about 5 to 120 atm (from about 0.5 MPa to about 12 MPa), from about 5 to 60 atm (from about 0.5 MPa to about 6 MPa)), while the functioning of the catalysts can continue for at least an hour (for example, at least two hours, at least 5 hours, at least 8 hours, at least 16 hours, more than one day, two days, week, month, od) before it will need to be regenerated or replaced.

Important parameters that must be taken into account in the process of hydrogenolysis of the ester are the degree of conversion and selectivity for the products. The degree of conversion can be expressed as the percentage of the interacting product (for example, the original product / final product x100%). In addition, the degree of conversion can be expressed as the rate of consumption of the starting material (e.g., ester). Selectivity is a measure of the amount of the desired product that is obtained compared to undesirable products (e.g., by-products, decomposition products). Selectivity can be expressed as a percentage, for example, as a percentage of purity, or as the rate of formation of the desired product relative to the rate of formation of unwanted products (or as the rate of formation of the desired product relative to the rate of consumption of the starting product). Some undesired products may be partial reduction products, oligomers and / or thermal decomposition products. Although this is not always the case, it is often found that there is an inverse relationship between conversion rates and selectivity, so it is sometimes difficult to quickly complete the reaction with high selectivity. Catalysts are used in hydrogenolysis. Catalysts may include metals Pd, Pt, Os, Ru, Rb, Re, Ir, Rh, Ni, Co, Mo, W, Cu, Zn, Cr, oxides of these metals and combinations thereof. In some cases, accelerator or moderator substances are added / combined, including Cr, Mn, Pb, Zn, Cd, Ag, Ba, Ca, Mg, Sn, Ni, Co, U, As, and Ge and the oxides of these metals and their combinations. One or more catalyst and one or more accelerator can be combined in any concentration and in any ratio. Accelerators increase the productivity of the catalyst, for example, by increasing the degree of conversion and selectivity. The catalysts and accelerators can be used in the form of bulk catalysts (for example, not located on the substrate). Bulk catalysts can be obtained in forms that increase surface area and allow reactants to flow over their surface. For example, in the form of: cotton wool, sieves, gratings, wire, perforated solid with channels, sponges, balls and / or powder. When used, the catalysts and accelerators can be mixed in volume, for example, powders of one or more catalysts and powders of one or more accelerators can be combined / mixed. Accelerated metals or metals can be predominantly adsorbed on the substrate and / or form chemical bonds with the substrate. The substrate may be, for example, alumina, silica, aluminosilicates, clays, zeolites (e.g. USY and beta zeolite) or other inorganic materials. The supported catalysts typically contain from about 0.1 to 10 wt.%, Each metal (for example, from 0.1 to 1 wt.%), Although higher amounts can be used. One or more metals and one or more accelerators can be combined with one or more substrates in all combinations. These supported catalysts can be prepared in any convenient form. The catalysts can be homogeneous catalysts, for example, tris (triphenylphosphine) rhodium (I) chloride and similar catalysts, while the metal forms complexes with a stabilizing ligand (s) (for example, amines, phosphines, alcohols, ethers, ketones, carboxylates, acetylacetones optionally bis, tri or tetrakis chelate ligands, combinations thereof). The catalyst may be an analog on a polymer substrate of a homogeneous catalyst, for example, in which the ligands are attached to the polymer, for example, functionalized polystyrenes, while the functional groups are the ligands mentioned above.

Catalysts on a substrate can be obtained by any suitable means, for example, using a method for impregnation by moisture capacity, a precipitation method during decomposition, a self-assembly method in solution and / or by vapor deposition / decomposition. For example, when applying the method of impregnation by moisture capacity, the desired metal precursor can be dissolved or suspended in a solvent volume similar to the pore volume of the substrate, wherein said precursor is combined with the substrate. The catalyst can be activated. Activation may include removing the solvent in vacuo, calcining, for example, in the presence of oxygen, nitrogen, hydrogen or other gases, in any order and repeatedly. The catalysts can be added before the use of the accelerator, together with the accelerator, after the use of the accelerator or by combinations of the stages of addition. The catalysts on the substrate can be obtained in the form of balls or extruded in the form of rods and other shapes. Often, these catalysts are combined with binders (e.g., inert ceramic

- 9 033687 material, porous binders). Some catalysts, conditions, equipment, and systems that can be used herein for hydrogenolysis and esterification are described in: Catalysis of Organic Reactions published by John R. Sowa, Jr., CRC Press (2005); Catalytic Naphtha Reforming Second Edition, Revised and Expanded by George J. Antos and Abdullah M. Aitani, Marcel Dekker (2005), chapters 6, 8 and 9; and Steam reforming catalysts Natural gas, associated gas and LPG Johnson Matthey, pp. 1-15; For example, for the hydrogenolysis of ethyl butyrate, bi- and tri-metal catalysts on a SnRu and SnRePt substrate can be used.

Catalysts can be used for hydrogenolysis in a batch mode. For example, an ester is combined, often with a solvent, in a vessel (e.g., a Parr ™ reactor). The specified vessel can be sparged with hydrogen and / or create an increased pressure in it using hydrogen. Such vessels can be equipped with heating devices (for example, heating jackets) and mixers (for example, blades, impellers). Catalysts can also be used in a fluidized bed reactor. These reactors, along with hydrogen and ester, require a high gas flow rate, for example, an inert gas (for example, nitrogen, He, Ar). The catalyst is fluidized by the rapid flow of gases through the reactor. One or more catalysts may be used sequentially or in combination (e.g., mixed together). A circulation reactor can be used since it is a variant of the design of a batch reactor except that the liquid in the vessel recirculates outside the reactor. In sequential use, the catalysts can be used under various reaction conditions, for example, at different temperatures, pressures (for example, hydrogen pressures) and / or different mixing conditions (for example, at different mixing speeds). These combinations allow, for example, to optimize the throughput and the total degree of conversion / selectivity.

Optionally, the catalysts are used in fixed bed flow reactors (for example, a flow reactor, a carrier layer reactor, an irrigation layer reactor). These reactors are made in the form of a column filled with catalysts (for example, a bulk catalyst or a catalyst on a substrate) through which reactants (for example, esters and hydrogen) pass. The column can be heated, for example, using a heating jacket, into which a liquid coolant (for example, water, high pressure water, oil) is supplied, steam, electric heating devices are placed (for example, by resistive heating), or using any other means of heating. Columns can also be configured to withstand high pressures, for example at least about 50 psi (about 345 kPa), at least about 100 psi (about 689 kPa), at least about 150 psi (about 1034 kPa), at least at least about 200 psi (about 1379 kPa), at least about 300 psi (about 2068 kPa), at least about 500 psi (about 3447 kPa). The columns can also be equipped with safety equipment, for example, pressure relief valves, and devices for shutting off high-temperature processes (for example, devices for shutting off the flow, ventilation). Optionally, to pass one reagent stream, two or more fixed bed reactors can be used sequentially (for example, up to 20, up to 10, 2 to 5, 3 to 10, 1 to 3 reactors). In some optional configurations, some of the reactors have a workaround, for example, for use as backup equipment. Having backup equipment is especially useful for avoiding downtime when one or more of the flow reactors is not operating within the range of acceptable parameters, for example, if the catalysts in the reactor are deactivated. Another advantage of using sequential reactors is that such reactors can be loaded with various catalysts, for example, having different selectivity and conversion rates, in order to achieve optimal performance and overall degree of conversion / selectivity. Columns can also work under various conditions, for example, at different flow rates, pressures and temperatures. For example, you can use two or more columns in which the temperature difference can be from about 0 to 10 ° C (for example, from about 10 to 200 ° C, from about 50 to 200 ° C, from about 50 to 150 ° C, approximately 50 to 100 ° C). Additionally or alternatively, the pressure difference (eg, hydrogen pressure) when using at least one column may be from about 0 to 5 atm (from 0 to about 0.5 MPa,) (for example, from about 5 to 50 atm (from about 0.5 MPa to 5 MPa), from about 10 to 50 atm (from about 1 MPa to about 5 MPa), from about 30 and 50 atm (from about 3 MPa to about 5 MPa)).

As described, hydrogenolysis catalysts can be reused / regenerated. For example, catalysts are often oxidized by heating to a high temperature in an oxidizing environment (for example, in the presence of oxygen), for example, from about 200 to 800 ° C (for example, from 400 to 600 ° C). After purging with an inert gas (for example, nitrogen, argon, helium), the catalysts are reduced at high temperature, for example, from about 200 to 800 ° C. The reducing agent may be, for example, hydrogen gas, which is directed to flow over the catalyst.

Hydrogen used in the described processes can be supplied by biogas, for example, generated during anaerobic digestion of biomass, for example, processed biomass described in

- 10,033,687 herein. Before its use for hydrogenation, hydrogen can be purified. Contaminants such as carbon monoxide should be removed. Other hydrogen sources include placing a hydrogenolysis reactor system adjacent to a hydrogen source containing a pipeline and a steam reformer of methane, natural gas, or the like.

When using the catalysts, it is possible to provide an overall selectivity of greater than about 90% (for example, greater than 95%, greater than 98%, greater than 99%). Total conversion rates are above 80% (for example, more than about 90%, more than about 95%, more than about 99%).

Alcohols obtained by hydrogenolysis can be separated, for example, by distillation, if the boiling point varies sufficiently. For example, the hydrogenolysis product of ethyl butyrate, ethanol and butanol can be separated by distillation. Recoverable ethanol can be reused in the esterification. The mixture of alcohols can even be used without separation, for example, as direct fuel or fuel additive. Other applications as a mixture or purified separated products applicable in the chemical, food industry, in the production of flavors and fragrances, and in the pharmaceutical industry will be apparent to one skilled in the art. In the case of some esters, for example, butyl butyrate, the hydrogenolysis product is butanol, and a separation scheme can be used to remove impurities.

Radiation treatment

The raw material can be processed by electron bombardment to modify its structure in order to reduce the resistance of the material to processing. Such processing allows, for example, to lower 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.

In general, electron bombardment by an electron beam is preferable because it provides very high throughput. Electron beam accelerators can be purchased, for example, from IBA, Belgium and NHV Corporation, Japan.

Electron bombardment can be carried out using an electron beam device whose nominal energy is less than 10 MeV, for example, less than 7 MeV, less than 5 MeV or less than 2 MeV, for example, from about 0.5 to 4 MeV, from about 0.6 to about 3 MeV, from about 0.5 to 1.5 MeV, from about 0.8 to 1.8 MeV, or from about 0.7 to 1 MeV. According to other embodiments of the invention, the nominal energy is from about 500 to 800 keV.

The electron beam can have a relatively high total power (the combined power of the beam of all accelerating heads, or, when using several accelerators, all accelerators and all heads), for example, at least 25 kW, for example, at least 30, 40, 50, 60 , 65, 70, 80, 100, 125 or 150 kW. In some cases, the power is even 500 kW, 750 kW, or even 1000 kW or more. In some cases, the power of the electron beam is 1200 kW or more, for example, 1400, 1600, 1800, or even 3000 kW.

This high total beam power is usually achieved by using several accelerating heads. For example, an electron beam device may include two, four or more accelerating heads. The use of several heads, each of which has a relatively low beam power, prevents an excessive increase in the temperature of the material, thereby preventing combustion of the material, and also increases the uniformity of the dose passing through the thickness of the material layer.

In General, it is preferable that the layer of biomass material has a relatively uniform thickness. In some embodiments, the thickness is less than about 1 inch (2.54 cm) (for example, less than about 0.75 inches (1.905 cm), less than about 0.5 inches (1.27 cm), less than about 0.25 inches (0.635 cm), less than about 0.1 inch (0.254 cm), from about 0.1 (0.254 cm) to 1 inch (2.54 cm), from about 0.2 (0.508 cm) to 0.3 inch ( 0.762 cm)).

According to other embodiments of the invention, it is desirable to cool the material during and between the training of the material by electron bombardment. For example, the material can be cooled during transportation, for example, using a screw extruder, a vibratory conveyor or other transport equipment. For example, refrigeration during transportation is described in provisional applications for US patent No. 61/774735, and 61/774752, the full description of which is incorporated herein by reference.

To reduce the energy required for the process of reducing the resistance to processing, it is desirable to process the material as quickly as possible. In general, it is preferable to perform processing at a radiation dose rate greater than about 0.25 Mrad per second, for example, greater than about 0.5, 0.75, 1, 1.5, 2, 5, 7, 10, 12, 15 or even more than about 20 Mrad per second, for example, from about 0.25 to 2 Mrad per second. Higher dose rates allow for a higher throughput of a given (e.g., required) dose. Higher dose rates generally require higher linear rates to avoid thermal decomposition of the material. According to one embodiment of the invention, the accelerator is set to 3 MeV, a beam current of 50 mA and a linear velocity of 24 feet / minute (731.52 cm / minute), for a sample thickness of about 20 mm (for example, crushed material from a corncob with bulk density of 0.5 g / cm ³ ).

- 11 033687

Electron bombardment is carried out until the material receives a total dose of at least 0.1 Mrad, 0.25 Mrad, 1 Mrad, 5 Mrad, for example, at least 10, 20, 30 or at least 40 Mrad. According to some embodiments of the invention, the treatment is carried out until the material receives a dose of from about 10 Mrad to about 50 Mrad, for example, from about 20 Mrad to about 40 Mrad or from about 25 Mrad to about 30 Mrad. In other embodiments, a total dose of 25 to 35 Mrad is preferred, ideally applied for a couple of seconds, for example, at 5 Mrad / cycle, with each cycle continuing for about one second. The use of a dose greater than 7 to 8 Mrad / cycle can in some cases cause thermal decomposition of the starting material. Before irradiation, after or during it, cooling can be used. For example, you can use the methods, systems and equipment for cooling described in the following applications: provisional application for US patent No. 61/774735 and provisional application for US patent No. 61/774754, the full description of which is incorporated herein by reference.

Using several heads, as described above, the material can be processed in several cycles, for example, in two cycles at a dose of 10 to 20 Mrad / cycle, for example, from 12 to 18 Mrad / cycle, separated by several seconds of cooling, or in three cycles at dose from 7 to 12 Mrad / cycle, for example, from 5 to 20 Mrad / cycle, from 10 to 40 Mrad / cycle, from 9 to 11 Mrad / cycle. As described herein, treating a material with several relatively low doses is usually better than one high dose, prevents overheating of the material, and also increases the uniformity of the dose passing through the thickness of the material. According to other embodiments of the invention, the material is mixed or otherwise mixed during or after each cycle and then leveled again before the next cycle to obtain a uniform layer to further increase uniformity during processing. Electrons are accelerated, for example, to a speed of more than 75 percent relative to the speed of light, for example, more than 85, 90, 95 or 99 percent relative to the speed of light.

Any treatment described in this application is carried out using lignocellulosic material that remains dry as purchased, or which has been dried, for example, using heat and / or reduced pressure. For example, cellulosic and / or lignocellulosic material contains less than about 25 wt.%, Retained water, measured at 25 ° C and at a relative humidity of fifty percent (for example, 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. 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.%, less than about 0.5 wt.%, less about 15 wt.%). Two or more electron sources are used, such as two or more ionizing sources. For example, samples can be processed, in any order, using an electron beam, followed by gamma radiation and UV irradiation with wavelengths from about 100 nm to about 280 ni. In some embodiments, the samples are processed using three sources of ionizing radiation, such as an electron beam, gamma radiation, and high energy UV radiation. Biomass is moved through the treatment area, where it can be bombarded with electrons.

It may be preferable to repeat the treatment in order to more thoroughly reduce the resistance to biomass processing and / or to further modify the biomass. In particular, the technological parameters can be adjusted after the first (for example, second, third, fourth or more) cycle depending on the resistance of the material to processing. Preferably, a conveyor may be used that comprises a circular system in which biomass is transported several times through the various processes described above. For multiple processing of biomass (for example, 2, 3, 4 or more times), several processing devices (for example, electron beam generators) are used. A single electron beam generator can be the source of several beams (for example, 2, 3, 4 or more beams) that can be used to process biomass.

Conveyors (e.g. vibration conveyor) can be made from corrosion resistant materials. In the manufacture of conveyors, structural materials may be used that include stainless steel (e.g., 304, 316 stainless steel, HASTELLOY® alloys, and INCONEL® alloys). For example, corrosion-resistant HASTELLOY® alloys from Hynes (Kokomo, Indiana, USA), such as HASTELLOY® B-3® alloy, HASTELLOY® HYBRID-BC1® alloy, HASTELLOY® C-4 alloy, HASTELLOY® C22® 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 .

Vibratory conveyors may have non-adhesive release coatings, for example, TEFLON ™ (Dupont, Delaware, USA). Vibratory conveyors can also have anti-corrosion coatings. For example, coatings supplied by Metal Coatings Corp (Houston, Texas, USA) and other coatings, such as fluoropolymer coating, XYLAN® coating, molybdenum disulfide coating, epoxy-phenolic coating, black metal phosphate coating

- 12,033,687 tall, high-gloss polyurethane topcoat for epoxy resin, inorganic zinc, polytetrafluoroethylene coating, PPS / RITON (PPS / RYTON®) coating, fluorinated ethylene-propylene coating, PVDF / DICOR (PVDF / DYKOR®) coating, eSTAPE / XYTAL / XYTAL / ECTFE / HALAR®) and ceramic epoxy coating. These coatings can improve resistance to process gases (eg, ozone), chemical corrosion, pitting, abrasion and oxidation.

Efficiency when changing the molecular / supermolecular structure and / or reducing the resistance to processing carbohydrate-containing biomass depends on the applied electron energy and the dose received, while the exposure time depends on the power and dose. Optionally, the dose rate and total dose are adjusted so as not to destroy (e.g., char or burn) the biomass material. For example, carbohydrates should not be damaged during processing so that they can be released from the biomass intact, for example, in the form of monomeric sugars.

Processing (using any electron source or combination of sources) is carried out until the material receives a dose of at least about 0.05 Mrad, for example, 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. According to another embodiment, the processing is carried out until the material receives a dose of 0.1 to 100 Mrad, 1 to 200, 5 to 200, 10 to 200, 5 to 150, 50 to 150 Mrad, 5 to 100 , from 5 to 50, from 5 to 40, from 10 to 50, from 10 to 75, from 15 to 50, from 20 to 35 Mrad.

Opaque materials for radiation

Also considered is the processing of the material in a chamber and / or hopper designed using radiation-opaque materials. Opaque materials for radiation are selected so as to be able to protect components from high-energy (short-wave) x-rays that can penetrate many materials. One of the important factors in the design of a casing that shields radiation is the attenuation length of the materials used, which will determine the required thickness of a particular material, mixture of materials or layered structure. The attenuation length is the penetration depth at which the radiation decreases by about 1 / e (e = Euler's number) times with respect to the incident radiation. Although virtually all materials are opaque to irradiation at a sufficient thickness, materials with a high percentage (e.g. density) of elements having a high Z (atomic number) have a shorter radiation attenuation length, and thus, using such materials, you can use thinner and lighter shielding. Examples of high Z materials used in radiation protection are tantalum and lead. Another important parameter in radiation protection is half the distance, which is the thickness of a particular material, which will reduce the intensity of gamma rays by 50%. As an example, for X-ray radiation with an energy of 0.1 MeV, half the thickness is approximately 15.1 mm for concrete, approximately 0.27 mm for lead, while with an X-ray energy of 1 MeV, half the thickness for concrete is approximately 44.45 mm and for lead is approximately 7.9 mm. Opaque to radiation materials can be materials that are thick or thin, provided that they can reduce the radiation passing through them towards the other side of the material. Thus, if it is necessary for a particular casing to have a low wall thickness, for example, to ensure light weight or due to size limitations, the selected material must have a sufficient Z value and / or a decay length such that half its length is less than or equal to the required wall thickness casing. In some cases, the radiation-opaque material may be a laminate, for example, containing a layer of a material with a higher Z value to provide effective shielding and a layer of a material with a lower Z value to provide other properties (for example, structural integrity, strength at shock, etc.). In some cases, the laminate may be a laminate selected according to the Z value, for example, including a laminate in which the layers provide a Z gradient in the range from successively arranged elements with a high Z value to elements with a lower Z value. In some cases, opaque radiation materials can be overlapping blocks, for example, lead and / or concrete blocks can be supplied by NELCO Worldwide (Burlington, Massachusetts), and cameras with variable con configuration as described in provisional patent application US No. 61/774744.

A material opaque to radiation can reduce radiation passing through a structure (e.g., wall, door, ceiling, casing, a number of these structures or combinations thereof) made of said material by 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 m Herere about 97%, at least about 98%, at least about 99%, at least about 99.9%, at least about 99.99%, at least about

- 13 033687

99.999%) compared with incident radiation. Therefore, a casing made of a material which is opaque to radiation can reduce the effect on the equipment / system / components by the same amount. Opaque materials for radiation may include stainless steel, metals with Z values above 25 (for example, lead, iron), concrete, waste rock, sand, and combinations thereof. Opaque to radiation materials may include a barrier layer in the direction of incident radiation, comprising at least about 1 mm (for example, 5 mm, 10 mm, 5 cm, 10 cm, 100 cm, 1 m, 10 m).

Radiation sources

The type of radiation determines the types of radiation sources used, as well as radiating devices and auxiliary equipment. The methods, systems and equipment described in this application, for example, for processing materials by radiation, can use the sources described in this application, as well as any other suitable source.

Sources of gamma radiation include radioactive nuclei, as isotopes of cobalt, calcium, technetium, chromium, gallium, indium, iodine, iron, krypton, samarium, selenium, sodium, thallium and xenon.

X-ray sources include electron beam collisions with metal targets, such as tungsten or molybdenum, or alloys, or compact light sources, such as those commercially available from Lyncean.

Alpha particles are identical to the nucleus of a helium atom and are formed during alpha decay of various radioactive nuclei, such as isotopes of bismuth, polonium, astatine, radon, France, radium, some actinides, such as actinium, thorium, uranium, neptunium, curium, californium, americium and plutonium.

UV sources include deuterium or cadmium lamps.

Sources of infrared radiation include ceramic lamps with sapphire, zinc or selenide windows.

Microwave sources include klystrons, Slevin-type radio frequency sources, or atomic-beam sources using gaseous hydrogen, oxygen, or nitrogen.

Accelerators used to accelerate particles (e.g., electrons or ions) can be direct current (e.g., electrostatic direct current or electrodynamic direct current), radio frequency linear, magnetic induction linear or continuous radiation. For example, in the methods described herein, various irradiation devices can be used, including electric field ionization sources, electrostatic ion separators, electric field ionization generators, thermionic emission sources, microwave radiation sources, recirculation or static accelerators, dynamic linear Accelerators, Van de Graaff accelerators, Cockroft Walton accelerators (e.g. PELLETRON® accelerators), LINACS, Dynamitrons (e.g. DINAMIT accelerators RON (DYNAMITRON®)), cyclotrons, synchrotrons, betatrons, transformer type accelerators, microtrons, plasma generators, cascade accelerators and folded tandem accelerators. For example, cyclotron-type accelerators such as the RHODOTRON® system can be purchased from IBA, Belgium, while DCI accelerators such as DYNAMITRON® can be purchased from RDI, now IBA Industrial. Other suitable accelerator systems include, for example: ICT transformer type DC systems available from Nissin High Voltage, Japan; S-band LINAC accelerators, which can be purchased at L3-PSD (USA), Linac Systems (France), Mevex (Canada) and Mitsubishi Heavy Industries (Japan); L-band LINAC accelerators, which can be purchased from Iotron Industries (Canada); and ILU-based accelerators, which can be purchased at Budker Laboratory (Russia). Ions and ion accelerators reviewed by 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, March 18-20, 2006, Iwata, Y. et al., Altemating-Phase-Focused 1H-DTL for Heavy-Ion Medical Accelerators Proceedings of EPAC 2006, Edinburgh, Scotland) and Leaner, CM et al., Status of the Superconducting ECR Ion Heavy Venus Proceedings of EPAC 2000, Vienna, Austria. Some particle accelerators and their use are described, for example, Medoff in US patent No. 7931784, the full description of which is incorporated herein by reference.

Electrons can be obtained using 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 due to its thermionic emission and accelerated due to the accelerating potential. An electron gun generates electrons, which are then accelerated by a large potential difference (for example, more than about 500 thousand, more than about 1 million, more than about 2 million, more than about 5 million, more than about 6 million, more than about 7 million, more than about 8 million , more than about 9 million or even more than 10 million volts) and then they are scanned magnetically in the XY plane, where the electrons are first accelerated in the Z direction down the accelerator tube and released through the window from the foil. Electron beam scanning can be used

- 14 033687 to increase the irradiation surface when irradiating materials, for example, biomass moved through a scanning beam. Scanning electron beams also allows you to evenly distribute the heat load on the window and helps to reduce the destruction of the foil window due to local heating under the influence of the electron beam. The destruction of the foil window causes a significant downtime due to subsequent necessary repairs and the restart of the electron gun. An electron beam can be used as a radiation source. The advantages of an electron beam are high dose rates (for example, 1, 5, or even 10 Mrad per second), high throughput, equipment with less sealing and less insulation. Electron beams can also have a high electrical efficiency (for example, 80%), which allows less energy to be used relative to other irradiation methods, which can lead to lower operating costs and lower greenhouse gas emissions corresponding to the lower amount of energy used. Electron beams can be obtained, for example, using electrostatic generators, cascade generators, transformer generators, low-energy accelerators with a scanning system, low-energy accelerators with a linear cathode, linear accelerators and pulse accelerators.

Electrons can also be more effective in terms of causing changes in the molecular structure of carbohydrate-containing materials, for example, through a chain splitting mechanism. In addition, electrons with energies from 0.5 to 10 MeV can penetrate materials with a low density, such as biomass materials described in this application, for example, materials with a bulk density of less than 0.5 g / cm and a depth of 0.3 up to 10 cm. Electrons as a source of ionizing radiation can be used, for example, for relatively thin stacks, layers or substrates of materials, for example, with a thickness of less than about 0.5 inches (1.27 cm), for example, less than about 0.4 inches (1.016 cm), 0.3 inch (0.762 cm), 0.25 inch (0.635 cm) or less than about 0.1 inch (0.254 cm). According to some embodiments of the invention, the energy of each electron from the electron beam is from about 0.3 MeV to about 2.0 MeV (million electron volts), for example, from about 0.5 MeV to about 1.5 MeV or from about 0, 7 MeV to about 1.25 MeV. Methods of irradiating the materials are described in the publication of US patent application 2012/0100577 A1, filed October 18, 2011, the full description of which is incorporated herein by reference.

Electron beam irradiation devices can be purchased or designed. For example, components or components, such as inductors, capacitors, housings, power supplies, cables, wiring, voltage-controlled systems, voltage-controlled elements, insulation material, microcontrollers and cooling equipment, can be purchased and mounted to provide a device. Optionally, the serial device can be modified and / or adapted. For example, devices and components can be purchased from any of the commercial sources described herein, including Ion Beam Applications (Louvain-la-Neuve, Belgium), Wasik Associates Inc. (Drakat, Massachusetts), NHV Corporation (Japan), the Titan Corporation (San Diego, California), Vivirad High Voltage Corp (Billerika, Massachusetts) and / or Budker Laboratories (Russia). Typical electron energies may be 0.5 MeV, 1 MeV, 2 MeV, 4.5 MeV, 7.5 MeV or 10 MeV. The power of a typical device for electron beam irradiation 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 mid-energy illuminators NHV EPS-500 (for example, with an accelerator voltage of 500 kV and a beam current of 65, 100 or 150 mA), EPS-800 (for example, with an accelerator voltage of 800 kV and a beam current of 65 or 100 mA) or EPS-1000 (for example, with an accelerator voltage of 1000 kV and a beam current of 65 or 100 mA). In addition, you can use accelerators from the NHV series with high energy, such as EPS-1500 (for example, with an accelerator voltage of 1500 kV and a beam current of 65 mA), EPS-2000 (for example, with an accelerator voltage of 2000 kV and a beam current of 50 mA) , EPS-3000 (for example, with an accelerator voltage of 3000 kV and a beam current of 50 mA) and EPS-5000 (for example, 5000 and a beam current of 30 mA).

The choice of the optimal solution when considering the technical characteristics of the power of the device for electron beam irradiation includes the cost of operation, capital costs, depreciation costs and dimensions of the device. The choice of the optimal solution when considering the levels of the exposure dose of electron-beam irradiation can be based on energy costs and concern for the environment, safety and health. Typically, generators are placed in a chamber, for example, of lead or concrete, especially when using x-ray radiation that is generated in the process. Choosing the optimal solution when considering electron energies includes the cost of energy.

Using a device for electron beam irradiation, you can create either a stationary beam or a scanning beam. A scanning beam may be preferred due to the long scan length and high scanning speeds, since these properties effectively replace the large width of the stationary beam. In addition, the available sweep widths are 0.5 m, 1 m, 2 m or more. A scanning beam is preferred according to most embodiments of the invention described herein because of the wider width of the scan and

- 15 033687 reduced likelihood of local heating and window breaks.

Electronic gun-windows

The extraction system for an electron accelerator may comprise two foil windows. Foil windows are described in international patent application No. PCT / US2013 / 064332, filed October 10, 2013, the full description of which is incorporated herein by reference. The cooling gas in the extraction system with two foil windows may be a purge gas or a mixture, for example, air, or pure gas. In one embodiment, the gas is an inert gas such as nitrogen, argon, helium and / or carbon dioxide. It is preferable to use a gas rather than a liquid, since energy losses in the electron beam are minimized. Mixtures of pure gas may also be used, either pre-mixed or mixed in-line before entering the windows or the space between the windows. The cooling gas can be cooled, for example, by a heat exchange system (e.g., a refrigerator) and / or by evaporation from condensed gas (e.g., liquid nitrogen, liquid helium).

When using the housing, the conveyor placed in the housing can also be purged with an inert gas to maintain an atmosphere with a low oxygen level. Maintaining low oxygen levels avoids the formation of ozone, which in some cases is undesirable due to its reactivity and toxic nature. For example, oxygen may be less than about 20% (for example, 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%). The purge can be carried out using an inert gas, including, but not limited to, using nitrogen, argon, helium or carbon dioxide. These gases may come, for example, by evaporation of a liquid source (e.g., liquid nitrogen or helium), may be obtained or released from air in situ, or may come from tanks. Inert gas can be recycled and any amount of residual oxygen can be removed using a catalyst, such as a layer of copper catalyst. According to an alternative embodiment of the invention, combinations of purging, recycling, and removing oxygen can be performed to maintain low oxygen levels.

The casing can also be purged with a reactive gas that can interact with biomass. Such interaction can be carried out before the irradiation process, during or after it. The reactive gas may include, but is not limited to, nitrous oxide, ammonia, oxygen, ozone, hydrocarbons, aromatics, amides, peroxides, azides, halides, oxyhalides, phosphides, phosphines, arsines, sulfides, thiols, boranes and / or hydrides. The reactive gas can be activated in the casing, for example, by irradiation (for example, using an electron beam, UV irradiation, microwave irradiation, heating, IR irradiation), so that it reacts with biomass. Biomass itself can be activated, for example, by irradiation. The biomass is preferably activated by an electron beam to produce radicals, which then interact with an activated or inactive reactive gas, for example, by combining or quenching the radicals.

The purge gases supplied to the 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 evaporated from compressed gas, such as liquid nitrogen, or sublimated from solid carbon dioxide. As an alternative example, the gas may be cooled using a refrigerator, or part or all of the conveyor may be cooled.

Heat and throughput during irradiation treatment

In inelastic collisions in biomass, several processes can occur during the interaction of electrons from an electron beam with matter. For example, ionization of a material, chain splitting of polymers in a material, crosslinking of polymers in a material, oxidation of a material, generation of x-rays (bremsstrahlung) and vibrational excitation of molecules (e.g. generation of phonons). Without being associated with a particular mechanism, a decrease in resistance to processing may be due to several of these inelastic collision effects, for example, ionization, polymer chain splitting, oxidation, and phonon generation. Some of these effects (for example, in particular, the generation of x-rays) require shielding and technical barriers, for example, the conclusion of the irradiation processes in a concrete chamber (or a chamber from another material opaque to radiation). Another irradiation effect, vibrational excitation, is equivalent to heating a sample. Heating the sample by irradiation can help reduce the resistance to processing, but overheating can destroy the material, as will be described below.

The adiabatic increase in temperature (ΔΤ) as a result of absorption of ionizing radiation is described by the equation: \ T = D / Cp. where D is the average dose in KGy, Cp is the heat capacity in J / g ° C and ΔΤ is the temperature change in ° C. The heat capacity of a typical dry biomass material will be about 2. Wet biomass will have a higher heat capacity depending on the amount of water, since the heat capacity of the water is very high (4.19 J / g ° C). Metals have much lower heat capacities, for example, the heat capacity of stainless

- 16,033,687 steel 304 is 0.5 J / g ° C. The temperature change due to the instantaneous absorption of radiation by biomass and stainless steel for different doses of radiation is shown below. Calculated temperature increase for biomass and stainless steel

Dose (Mrad) Estimated biomass ΔΤ (° C) Steel ΔΤ (° C) 10 fifty 200 fifty 250, decomposition 1000 100 500 decomposition 2000 150 750 decomposition 3000 200 1000 decomposition 4000

High temperatures can destroy and / or modify biopolymers in biomass so that polymers (e.g. cellulose) are not suitable for further processing. Exposed to high temperatures biomass can become dark, sticky and emit odors indicating decomposition. Stickiness can even complicate the transport of material. Smells can be unpleasant and create a safety problem. In fact, it was found that in the described processes it is advisable to maintain biomass at a temperature below about 200 ° C (for example, 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, from about 60 ° C to 180 ° C, from about 60 ° C to 160 ° C, from about 60 ° C to 150 ° C, from about 60 ° C to 140 ° C, from about 60 ° C to 130 ° C, from about 60 ° C to 120 ° C, from about 80 ° C to 180 ° C, from about 100 ° C to 180 ° C, from about 120 ° C to 180 ° C, from about 140 ° C to 180 ° C, from about 160 ° C up to 180 ° C, from about 100 ° C to 140 ° C, from about 80 ° C to 120 ° C). It was found that for the described processes (for example, to reduce the resistance to processing), irradiation with a dose above about 10 Mrad is necessary. In addition, high throughput is required so that irradiation does not become a bottleneck in biomass processing. Processing obeys the dose rate equation: M = FP / D x time, where M represents the mass of the irradiated material (kg), F represents the fraction of the power that is absorbed (dimensionless quantity), P represents the radiation power (kW = voltage in MeV x current in mA), time represents the processing time (s) and D represents the absorbed dose (KGy). In a typical process in which the fraction of absorbed power is fixed, the radiation power remains constant and a certain dose is needed, the throughput (for example, M, processed biomass) can be increased by increasing the exposure time. However, increasing the irradiation time without the possibility of cooling the material can lead to excessive heating, as illustrated by the calculations shown above. Since biomass has a low thermal conductivity (less than about 0.1 W m ^-1 K ^-1 ), heat dissipation is slow, unlike, for example, metals (more than about 10 W m ^-1 K ^-1 ), which can dissipate energy quickly, provided that there is a heat sink for energy transfer.

Electron guns - beam absorbers

In some embodiments, systems and methods include a beam absorber (eg, a shutter). For example, a beam absorber can be used to quickly stop or reduce irradiation of a material without turning off the power of the electron beam device. Alternatively, the beam absorber can be used when connecting the power of the electron beam, for example, the beam absorber can stop the electron beam until the beam current reaches the desired level. The beam absorber can be placed between the first foil window and the second foil window. For example, the beam absorber can be installed so that it is movable, that is, so that it can be moved along the path of the beam and removed from the specified path. You can even use partial beam overlap, for example, to control the dose of radiation. The beam absorber can be installed on the floor, on a biomass conveyor, attached to a wall, to a radiating device (for example, to a scanning bell) or to any supporting structure. The beam absorber is preferably fixed relative to the scanning bell so that the beam can be effectively controlled by the beam absorber. The beam absorber may contain a hinge, rail, wheels, slots, or other means that allow it to function when moving into and out of the beam. The beam absorber can be made of any material that will trap at least 5% of the electrons, for example, 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.

The beam absorber can be made of metal, including, but not limited to, stainless steel, lead, iron, molybdenum, silver, gold, titanium, aluminum, tin or alloys of the above metals, or laminates (laminated materials) made using specified metals (for example, a ceramic material with a metal coating, a polymer with a metal coating, a composite material with a metal coating, multilayer metal

- 17,033,687 materials).

The beam absorber can be cooled, for example, using a cooling fluid, such as an aqueous solution or gas. The beam absorber may be partially or completely hollow, for example, contain cavities. The interior of the beam absorber can be used for coolants and gases. The beam absorber can have any shape, including flat, curved, round, oval, square, rectangular, beveled and wedge-shaped. The beam absorber can have perforations, which allows some electrons to pass through them, thereby regulating (for example, decreasing) the radiation levels over the entire window area or in certain areas of the window. The beam absorber may be a network made, for example, of fibers or wire. To control exposure, multiple beam absorbers can be used, jointly or independently. The beam absorber can be adjusted remotely, for example, using a radio signal, or rigidly mounted in the engine to move the beam to different positions.

Biomass materials

Lignocellulosic materials include, but are not limited to, wood, pressed wood, wood waste (e.g., sawdust, aspen wood, wood shavings), herbs (e.g., millet rod-shaped, Chinese reed, spartina, double-reed-shaped), grain waste (e.g. rice husk, oat husk, wheat straw, barley husk), agricultural waste (e.g. silage, canola straw, wheat straw, barley straw, oat straw, rice straw, jute, hemp, flax, bamboo, sisal, abacus, corncobs , ukuruznuyu straw, soybean straw, corn fiber, alfalfa, hay, scalp coconut), waste from the processing of sugar (e.g., bagasse, beet pulp, bagasse agave), algae, seaweed, manure, sewage and mixtures of any of these substances.

In some cases, the lignocellulosic material includes corn cobs. Crushed or crushed by a hammer corn cobs can be distributed as a layer of relatively uniform thickness for irradiation and after irradiation they can be easily dispersed in a medium for further processing. In some cases, an entire corn plant is used to facilitate harvesting and collection, including corn stalks, corn kernels, and in some cases even the root system of the plant.

Mostly, additional nutrients are not required (except for a nitrogen source, for example, urea or ammonia) during the fermentation of corn cobs or cellulosic or lignocellulosic materials containing significant amounts of corn cobs. In addition, corn cobs, before and after grinding, are easier to transport and disperse, and they are less likely to form explosive mixtures in air compared to other cellulosic or lignocellulosic materials such as hay and grass.

Pulp materials include, for example, paper, paper products, paper waste, paper pulp, pigment paper, coated paper, coated paper, filler paper, magazines, printed matter (e.g. books, catalogs, reference books, labels, calendars, greeting cards , brochures, brochures, newsprint), printer paper, polymer coated paper, cards, paperboard, paperboard, high α-cellulose materials such as cotton wool, and mixtures of any of these materials. For example, paper products described in US Patent Application No. 13 / 396,365 (Magazine Feedstocks Medoff et al., Filed February 14, 2012), the entire disclosure of which is incorporated herein by reference.

Cellulosic materials may also include lignocellulosic materials that have been partially or fully delignified. In some cases, other biomass materials can be used, for example, starch materials. Starch materials include starch itself, for example, corn starch, wheat starch, potato starch or rice starch, a starch derivative, or a starch containing material such as an edible food product or crop. For example, starchy material may be edible arachacha, buckwheat, banana, barley, cassava, kudzu, sour, sago, sorghum, ordinary homemade potatoes, sweet potatoes, taro, yams or one or more kinds of legumes such as horse beans, lentils or peas. Mixtures of any two or more starch materials are also starch materials. In addition, mixtures of starch, cellulosic and / or lignocellulosic materials can be used. For example, the biomass can be an entire plant, part of a plant, or different parts of a plant, for example, wheat, cotton, corn, rice, or tree. Starch materials can be processed using any of the methods described in this application. Microbial materials include, but are not limited to, any natural or genetically modified microorganism or organism that contains or is capable of providing a source of carbohydrates (e.g. cellulose), e.g. protests, e.g. animal protests (e.g. protozoa, such as flagellates, amoeboid protozoa , ciliates and sporozoans) and plant protests (e.g. algae, such as alveolar, chloroarachnophytic, cryptomonadic, euglenides, glaucophytic, hap

- 18,033,687 tophitic, red algae, stranopilophytes and green algae). Other examples include algae, plankton (e.g., macroplankton, mesoplankton, microplankton, nanoplankton, picoplankton and femtoplankton), phytoplankton, bacteria (e.g. gram-positive bacteria, gram-negative bacteria and extremophiles), yeast and / or mixtures thereof. In some cases, microbial biomass can be obtained from natural sources, such as the ocean, lakes, water bodies, such as salt water or fresh water, or on land. Alternatively or in addition, microbial biomass can be obtained from cell culture systems, for example, large-scale systems of dry and wet cultivation and fermentation.

The same biomass materials, such as cellulosic, starch and lignocellulosic starting materials, can be obtained from transgenic microorganisms and plants that have been modified relative to the wild-type variety. Such modifications can be carried out, for example, through repeated stages of selection and breeding to obtain the desired characteristics in the plant. In addition, these plants could contain, in comparison with the wild-type variety, deleted, modified, with suppressed expression and / or added genetic material. For example, genetically modified plants can be obtained using recombinant DNA technologies in which genetic modifications include the introduction or modification of specific genes from parental varieties, or, for example, by applying transgenic dilution in which a specific gene or genes from another plant species are introduced into the plant and / or bacteria. Another way of creating genetic variation is realized through mutational breeding, in which new alleles are artificially created from endogenous genes. Artificial genes can be created in many ways, including treating a plant or seed, for example, using chemical mutagens (for example, using alkylating agents, epoxides, alkaloids, peroxides, formaldehyde), radiation (for example, X-rays, gamma radiation, neutrons, beta particles, alpha particles, protons, deuterons, UV radiation) and heat stroke or using another external load and subsequent selection methods. Other methods for producing modified genes are implemented using reduced precision PCR and rearrangement in DNA, followed by insertion of the necessary modified DNA into the desired plant or seed. Methods for introducing the desired genetic variation into a seed or plant include, for example, the use of a bacterial carrier, ballistic transfection, precipitation of calcium phosphate, electroporation, gene splicing, suppression of gene expression, lipofection, microinjection and the use of viral carriers. Additional genetically modified materials have been described in US patent application No. 13/396369, filed February 14, 2012, the full description of which is incorporated herein by reference.

Any of the methods described in this application can be implemented using mixtures of any biomass materials described in this application.

Obtaining biomass material - mechanical processing

The biomass may be in dry form, for example, contain less than about 35% moisture (for example, 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 supplied in a wet state, for example, in the form of a wet solid, sludge or suspension containing at least about 10 wt.%, A solid phase (for example, at least about 20 wt.%, At least about 30 wt. wt.%, at least about 40 wt.%, at least about 50 wt.%, at least about 60 wt.%, at least about 70 wt.%).

In the described methods, materials with a low bulk density can be used, for example, cellulosic or lignocellulosic raw materials that have been pretreated with physical methods to provide a bulk density of less than about 0.75 g / cm ³ , for example, 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, for example, about 0.025 g / cm ³ . Bulk density is determined using ASTM D1895B. In short, the method includes filling a measuring cylinder of known volume with a sample and measuring the mass of the sample. Bulk density is calculated by dividing the mass of the sample in grams by the known cylinder volume in cubic centimeters. If necessary, materials with a low bulk density can be densified, for example, by the methods described by Medoff in US Pat.

In some cases, pretreatment involves screening the biomass material. Screening can be done through a mesh or perforated plate with the desired hole size, for example, less than about 6.35 mm (1/4 inch, 0.25 inch), (for example, less than about 3.18 mm (1/8 inch, 0.125 inch ), less than about 1.59 mm (1/16 inch, 0.0625 inch), less than about 0.79 mm (1/32 inch, 0.03125 inch), for example, 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 inches), less than about 0.18 mm (0.007 inches), less than about 0.13 mm (0.005 inches), or even less approximately 0.10 mm (1/256 in., 0.00390625 in.)). In one configuration, the required biomass falls through the perforations

- 19 033687 or a sieve and thus a biomass with a size larger than the perforations or sieve is not exposed. Such larger materials can be reprocessed, for example, by grinding, or they can simply be removed from the treatment. In another configuration, a material that is larger than the perforations is irradiated and the smaller material is removed by sieving or reused. In this kind of configuration, the conveyor itself (for example, a part of the conveyor) can be perforated or made using a mesh. For example, according to one particular embodiment of the invention, the biomass material may be wet, while the perforations or mesh allow water to flow out of the biomass before irradiation.

The sieving of the material can also be carried out manually, for example, using an operator or a mechanical device (for example, an automatic machine equipped with a color, reflective or other sensor) that removes unwanted material. Screening can also be carried out by magnetic screening, with the magnet placed near the transported material, and the magnetic material is removed by magnetic action.

Possible pretreatment may include heating the material. For example, a portion of the conveyor may pass through a heating zone. A heating zone can be created, for example, by means of infrared radiation, microwaves, combustion (for example, gas, coal, oil, biomass), resistive heating and / or inductive coils. Heat can be applied from at least one side or more than one side, heating can be continuous or batch, and only part of the material or all of the material can be heated. For example, a portion of the conveying chute can be heated with a heating jacket. Heating can be carried out, for example, with the aim of drying the material. In the case of drying the material, said drying can be facilitated, with or without heating, by moving gas (e.g., air, oxygen, nitrogen, He, CO ₂ , argon) over the biomass and / or through the biomass during transportation.

In some cases, pretreatment may include cooling the material. The cooling of the material is described by Medoff in US Pat. No. 7,900,857, the disclosure of which is incorporated herein by reference. For example, cooling can be accomplished by supplying a cooling fluid, for example, water (for example, with glycerin) or nitrogen (for example, liquid nitrogen) to the bottom of the conveying trough. According to an alternative embodiment of the invention, a cooling gas, for example, cooled nitrogen, can be blown over the biomass material or under a conveying system.

Another possible pre-treatment method may include adding material to the biomass. Additional material can be added, for example, by irrigation, spraying and / or pouring material into the biomass during its transportation. Materials that can be added include, for example, metals, ceramic materials and / or ions, as described in US Patent Application Publication 2010/0105119 A1 (filed October 26, 2009) and US Patent Application Publication 2010/0159569 A1 (filed December 16, 2009), the full description of which is incorporated herein by reference. Possible materials that can be added include acids and bases. Other materials that can be added are oxidizing agents (e.g., peroxides, chlorates), polymers, polymerizable monomers (e.g., containing unsaturated bonds), water, catalysts, enzymes and / or organisms. The material can be added, for example, in pure form, in the form of a solution in a solvent (eg, water or an organic solvent) and / or in the form of a solution. In some cases, the solvent is volatile and can be prepared for evaporation, for example, by heating and / or blowing gas, as described previously. The added material may form a uniform coating on the biomass or be a homogeneous mixture of different components (for example, biomass and additional material). The added material can modulate the subsequent stage of irradiation by increasing the efficiency of the irradiation, damping the irradiation, or changing the effect of the irradiation (for example, from electron beams to x-ray radiation or heating). The specified method may not affect the exposure, but may be applicable for subsequent sequential processing. Added material can help in transporting the material, for example, by reducing dust levels.

Biomass can be sent to a conveyor (for example, vibratory conveyors used in the chambers described in this application) using a belt conveyor, pneumatic conveyor, screw conveyor, hopper, pipe, manually or through a combination of the above devices. Biomass can, for example, be dumped, poured and / or placed on a conveyor by any of these methods. For example, the material is delivered to the conveyor using a enclosed material distribution system that helps maintain a low oxygen atmosphere and / or control dust and fine particles. Small particles of biomass and dust suspended or suspended in air are undesirable because they can create an explosion hazard or damage the foil of the electron gun window (when using such a device for processing material).

The material may be leveled to form a uniform thickness of from about 0.0312 (about 0.7925 mm) to 5 inches (about 127 mm) (e.g., from about 0.0625 (about

- 20 033687

1.5875 mm) to 2,000 inches (approximately 50.8 mm), from approximately 0.125 (approximately 3.175 mm) to 1 inch (approximately 25.7 mm), from approximately 0.125 (approximately 3.175 mm) to 0.5 inches (approximately 12.7 mm), from about 0.3 (about 7.62 mm) to 0.9 inches (about 22.86 mm), from about 0.2 (about 5.08 mm) to 0.5 inches (about 12.7 mm), from about 0.25 (about 6.35 mm) to 1 inch (about 25.4 mm), from about 0.25 (about 6.35 mm) to 0.5 inches (about 12, 7 mm). In general, it is preferable to transport the material through an electron beam as quickly as possible to maximize throughput. For example, the material can be mixed at speeds of at least 1 ft / min (about 0.305 m / min), for example at least 2 ft / min (about 0.610 m / min), at least 3 ft / min (about 0.914 m / min), at least 4 ft / min (about 1.219 m / min), at least 5 ft / min (about 1.524 m / min), at least 10 ft / min (about 3.048 m / min) at least 15 ft / min (about 4.572 m / min), 20 (about 6.093 m / min), 25 (about 7.62 m / min), 30 (about 9.144 m / min), 35 (about 10.668 m / min), 40 (about 12.192 m / min), 45 (about 13.716 m / min), 50 ft / min (about 15.24 m / min). The transport speed is related to the beam current, for example, in the case of biomass with a thickness of 1/4 inch (about 0.635 cm) and 100 mA, to ensure a sufficient dose of radiation, the conveyor can move at a speed of about 20 feet / min (about 6.096 m / min), The 50 mA conveyor can travel at a speed of approximately 10 ft / min (approximately 3.048 m / min) to provide approximately the same dose.

After moving the material through the irradiation zone, additional preliminary processing can be carried out. A possible additional pretreatment may, for example, be a process described in relation to pretreatment treatment. For example, biomass can be processed by sieving, heating, cooling and / or combining with additives. Exclusively during preliminary irradiation, radical quenching, for example, quenching of radicals by adding fluids or gases (e.g. oxygen, nitrous oxide, ammonia, liquids), when applying pressure, heat and / or adding radical scavengers, can take place. For example, biomass can be transported from a conveyor enclosed in a casing and exposed to gas (for example, oxygen), while the biomass is quenched to form carboxylated groups. According to one embodiment of the invention, the biomass is exposed to a reactive gas or liquid during irradiation. Extinguishing the biomass that has been irradiated is described by Medoff in US Pat. No. 8,083,906, the entire disclosure of which is incorporated herein by reference.

If necessary, along with irradiation, one or more machining methods can be used to further reduce the resistance to processing of carbohydrate-containing material. These methods can be applied before irradiation, during and / or after it.

In some cases, machining may include initial preparation of the feedstock immediately after receipt, for example, reducing the size of the materials, for example, by grinding, for example, cutting, crushing, shear, spraying or chopping. For example, in some cases, friable feedstocks (e.g., recycled paper, starchy materials, or rod millet) are prepared by shearing or shredding. Mechanical processing allows to reduce the bulk density of the carbohydrate-containing material, increase the surface area of the carbohydrate-containing material and / or reduce one or more sizes of the carbohydrate-containing material.

Alternatively or in addition, the starting material can be processed by another processing method, such as chemical processing methods, for example, using acid (HCl, H ₂ SO ₄ , H ₃ PO ₄ ), a base (for example, KOH and NaOH) chemical oxidizing agent (e.g. peroxides, chlorates, ozone), radiation, steam explosion, pyrolysis, sonication, oxidation, chemical treatment. These processing methods can be implemented in any order and in any sequence and combinations. For example, the starting material can first be physically processed using one or more processing methods, for example, by chemical treatment, including in combination with acid hydrolysis (for example, when using HCl, H ₂ SO ₄ , H ₃ PO ₄ ), irradiation , sonication, oxidation, pyrolysis or steam explosion, and then machined. Such a sequence may be preferable since materials processed by one or more other processing methods, for example, by irradiation or pyrolysis, are usually more fragile and, therefore, it may be easier to further modify the structure of the material during machining. As another example, the starting material can be passed through ionizing radiation using a conveyor, as described in this application, and then machined. Chemical treatment allows you to remove some or all of the lignin (for example, during chemical pulping) and allows you to partially or completely hydrolyze the material. These methods can also be used with pre-hydrolyzed material. In addition, these methods can be used with material that has not been previously hydrolyzed. These methods can be used with mixtures of hydrolyzed and non-hydrolyzed materials, for example, mixtures containing about 50% or more non-hydrolyzed material, about 60% or more non-hydrolyzed material, about 70% or more non-hydrolyzed material, about 80% or more non-hydrolyzed material or even 90% or more non-hydrolyzed material.

Along with the reduction in size that can be performed first and / or later during processing, machining may also be preferable from the point of view of opening, tension, breaking or loosening of carbohydrate-containing materials, obtaining cellulose from materials more susceptible to chain cleavage and / or destruction of the crystal structure during physical processing.

Methods for machining a carbohydrate-containing material include, for example, grinding or crushing. Grinding can be performed using, for example, a hammer mill, ball mill, colloid mill, conical or cone mill, disk mill, runner mill, Wiley mill, grain mill or other mill. Crushing can be carried out using, for example, a cutting mill / impact mill. Some typical grinders include mill grinders, pin grinders, coffee grinders, and burrs. Crushing or grinding can be achieved, for example, using a reciprocating pin or other element, as is the case in a pin mill. Other mechanical processing methods include mechanical slitting or tearing, other methods in which the fibers exert pressure, and crushing by abrasion by air. Suitable machining methods further include any other method that continues to disrupt the internal structure of the material that was initiated by previous processing steps.

Systems for the mechanical preparation of raw materials can be configured to produce streams with specific characteristics, such as, for example, specific maximum dimensions, specific ratios of length to width, or specific ratios of surface areas. Physical preparation allows you to increase the reaction rate, improve the movement of the material on the conveyor, improve the irradiation profile of the material, improve the uniformity of the irradiation of the material or reduce the required processing time by disclosing the materials and converting them into more accessible materials for processes and / or reagents, such as reagents in solution. Bulk density of the feedstock can be controlled (for example, increase). In some cases, it may be desirable to obtain a material with a low bulk density, for example, by densifying the material (for example, sealing can make it easier and less expensive to transport the material to another location) and then returning the material to a state with a lower bulk density (for example, after transportation). The material can be densified, for example, from less than about 0.2 g / cm. cube to more than about 0.9 g / cm. cube (for example, less than about 0.3 to more than about 0.5 g / cm3, less than about 0.3 to more than about 0.9 g / cm3, less than about 0.5 to more than about 0.9 g / cm3, less than about 0.3 to more than about 0.8 g / cm3, less than about 0.2 to more than about 0.5 g / cm3). For example, material can be densified using the methods and equipment described by Medoff in US Pat. No. 7,932,065 and International Publication No. WO 2008/073186 (which was filed October 26, 2007, published in English and where as the state in which the applicant intends to obtain Patent, United States), full descriptions of which are incorporated herein by reference. The densified materials can be processed by any of the methods described in this application, or any material processed using any of the methods described in this application can subsequently be densified.

The material to be processed is in the form of a fibrous material containing fibers obtained by applying shear to a fiber source. For example, the specified application of shear forces can be performed using a rotary knife-shaped tool.

For example, to a fiber source, for example, which is difficult to decompose or which had lower levels of resistance to processing, shear forces can be applied, for example, in a rotary knife-shaped tool, to obtain the first fibrous material. The first fibrous material is passed through a first sieve, for example, with an average hole size of 1.59 mm or less (1/16 inch, 0.0625 inch), and a second fibrous material is obtained. If necessary, the fiber source can be cut before shearing, for example, using a shredder. For example, when using paper as a source of fibers, paper can first be cut into strips that, for example, have a width of 1/4 (about 0.635 cm) to 1/2 inch (about 1.27 cm) using a shredder, for example Oscillating rotary screw shredder, such as shredders manufactured by Munson (Utica, NY). As an alternative to shredding, paper size can be reduced by cutting to size using a guillotine cutting machine. For example, a guillotine cutting machine can be used to cut paper into sheets, for example, 10 inches wide (about 25.4 cm) and 12 inches long (about 30.5 cm).

The application of shear forces to the fiber source and transmission of the obtained first fibrous material through the first sieve is performed simultaneously. Shearing and transmitting can also be done in a batch process.

For example, a rotary knife-shaped tool can be used to simultaneously cut a fiber source and sift the first fibrous material. The rotary knife-shaped tool contains a hopper that can be loaded with fiber source scraps obtained by cutting the specified source.

Alternatively, before saccharification and / or fermentation, the feedstock is processed physically. Physical processing methods may include one or more of any of the methods described herein, such as machining, chemical treatment, irradiation, sonication, oxidation, pyrolysis, or steam explosion. Processing methods can be used with a combination of two, three, four or even all of the described technologies (in any order). When applying more than one processing method, these methods can be applied simultaneously or at different times. In addition, you can use other methods that change the molecular structure of the feedstock based on biomass, individually or in combination with the methods described in this application.

The mechanical processing methods that can be used and the characteristics of the mechanically processed carbohydrate-containing materials are described in more detail in the publication of US patent application 2012/0100577 A1, filed October 18, 2011, a full description of which is hereby incorporated by reference.

Sonication, pyrolysis, oxidation, steam explosion

If necessary, instead of or along with irradiation, one or more methods selected from sonication, pyrolysis, oxidation methods or steam explosion methods can be used to reduce or further reduce the resistance of the carbohydrate-containing material to the treatment. For example, these methods can be applied before irradiation, during and / or after it. Such methods are described in detail by Medoff in US patent No. 7932065, the full description of which is incorporated herein by reference.

The use of processed biomass material

Using the described methods, the biomass starting material (for example, plant biomass, animal biomass, paper and biomass from household waste) can be used as a starting material for useful intermediates and products, such as organic acids, salts of organic acids, anhydrides, esters organic acids and fuel, for example, fuel for internal combustion engines or feedstock for fuel cells. Systems and processes are described in which cellulosic and / or lignocellulosic materials that are readily available but often difficult to process, such as household waste streams and waste paper streams such as newsprint streams, kraft paper, can be used as feedstock. corrugated paper or mixtures thereof.

To convert the feed into a form that can be easily processed, glucan or xylan-containing cellulose in the feed can be hydrolyzed to produce low molecular weight carbohydrates such as sugars using a saccharifying agent, such as an enzyme or an acid, a process called saccharification. Then, low molecular weight carbohydrates can be used, for example, in an existing manufacturing facility, such as a single-cell protein manufacturing facility, an enzyme manufacturing facility, or a fuel manufacturing facility, such as an ethanol manufacturing facility. The feedstock can be hydrolyzed using an enzyme, for example, by combining materials and an enzyme in a solvent, for example, in an aqueous solution.

Alternatively, the enzymes can come from organisms that decompose biomass, such as the cellulosic and / or lignin portions of the biomass, contain or produce various cellulose-degrading enzymes (cellulases), ligninases, or various biomass-destroying metabolites with small molecules. These enzymes can be a complex of enzymes that act synergistically and decompose crystalline cellulose or lignin portions of biomass. Examples of fiber-degrading enzymes include: endoglucanases, cellobiohydrolases and cellobiases (beta-glucosidases). During saccharification, the cellulosic substrate can first be hydrolyzed with endoglucanases in random places to give oligomeric intermediates. Further, these intermediates become substrates for exothermic cleavage of glucanases, such as cellobiohydrolase, to produce cellobiose from the terminal groups of the cellulose polymer. Cellobiose is a water-soluble 1,4-linked glucose dimer. Finally, cellobiase breaks down cellobiose to produce glucose. The effectiveness (e.g., hydrolysis time and / or completeness of hydrolysis) of such a process depends on the resistance to processing the cellulosic material.

Intermediates and Products

Using the processes described, biomass material can be converted into one or more products, such as energy, fuels, food, and materials. Specific product examples 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, since ethanol, n -propanol, isobutanol, sec-butanol, tert-butanol or n-23 033687 butanol), hydrated or water-containing alcohols (for example, containing more than 10%, 20%, 30% or even more than 40% water), biodiesel, organic acids, hydrocarbons (e.g. methane, ethane, propane, isobutene, pentane, n-hexane, biodiesel, bio-gasoline and mixtures thereof), by-products (e.g. proteins, such as fiber-degrading proteins (enzymes) or unicellular proteins) and mixtures of any of these compounds in any combination or relative concentration, and possibly in combination with any additives (e.g. fuel additives). Other examples include carboxylic acids, carboxylic acid salts, a mixture of carboxylic acids and carboxylic acid salts and carboxylic acid esters (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, glycerin, sorbitol, threitol, arabitol, ribitol, mannitol, dulcite, fusitol, iditol, isomalt , maltitol, lactitol, xylitol and other polyols) and methyl or ethyl esters of any of the listed alcohols. Other products include methyl acrylate, methyl methacrylate D- or L-lactic acid, citric acid, formic acid, acetic acid, propionic acid, butyric acid, succinic acid, valerianic acid, caproic acid, 3hydroxypropionic acid, palmitic acid, stearic acid, stearic acid, stearic acid malonic acid, glutaric acid, oleic acid, linolenic acid, glycolic acid, gamma-hydroxybutyric acid and mixtures thereof, salts of any of the listed acids, mixtures of any acids and their corresponding salting salts.

Any combination of the above products with each other and / or the above products with other products, while other products can be obtained using the described methods or otherwise, can be packaged together and sold as products. Products can be combined, for example, mixed, mixed, or dissolved together, or can simply be packaged or sold together.

Any of the products or combinations of the products described can be sanitized or sterilized before selling the products, for example, after cleaning or isolation, or even after packaging, to neutralize one or more potentially unwanted contaminants that may be present in the product (s). Such sanitation can be carried out by electron bombardment, for example, with a dose of less than about 20 Mrad, for example, from about 0.1 to 15 Mrad, from about 0.5 to 7 Mrad, or from about 1 to 3 Mrad.

Also, the processes described make it possible to obtain flows of various by-products that can be used to generate steam and electricity for use in other parts of the enterprise (joint production of heat and electricity) or sold on the open market. For example, the steam generated by burning streams of by-products can be used in the distillation process. As another example, electricity generated by burning by-product streams can be used in electron beam generators used in pretreatment.

The by-products used to generate steam and electricity are obtained from several sources throughout the process. For example, anaerobic digestion of wastewater makes it possible to obtain biogas with a high level of methane and a small amount of spent biomass (sludge). As another example, you can use solids obtained after saccharification and / or after distillation (for example, unreacted lignin, cellulose and hemicellulose left over from pre-treatment and primary processes), for example, burning them as fuel.

Other intermediates and products, including food and pharmaceutical products, are described in the publication of US patent application 2010/0124583 A1, owned by Medoff, published May 20, 2010, the full description of which is hereby incorporated by reference.

Products derived from lignin

It is believed that spent biomass (for example, spent lignocellulosic material) obtained as a result of lignocellulosic treatment by the described methods has a high lignin content and, in addition to being used to generate energy by burning in a heat and electricity co-production plant, can be used as other valuable products. For example, lignin can be used as is as a plastic, or its properties can be improved by synthetic methods to produce another plastic. In some cases, lignin can also be converted into lignosulfonates, which can be used as binders, dispersants, emulsifiers or as complexing agents. When used as a binder, lignin or lignosulfonate can, for example, be used in coal briquettes, in ceramic materials, for binding black carbon, for binding fertilizers and herbicides, as a dust suppressor, in the production of plywood and pressed wood, for binding animal feed as a binder for fiberglass, in

- 24 033687 as a binder in mastic for gluing linoleum and as a stabilizer for soils.

As a dispersant, lignin or lignosulfonates can be used, for example, in concrete mixtures, clay and ceramic materials, dyes and pigments, in tanning of leather and in dry plaster.

As an emulsifier, lignin or lignosulfonates can be used, for example, in asphalt, pigments and dyes, pesticides and paraffin emulsions. As a complexing agent, lignin or lignosulfonates can be used, for example, in micronutrient systems, cleaning compositions and water treatment systems, for example, for boiler systems and cooling systems. In the case of energy production, lignin generally has a higher energy content than holocellulose (cellulose and hemicellulose) because it contains more carbon than holocellulose. For example, dry lignin can have an energy content of about 11,000 (about 25.586 MJ / kg) to 12,500 BTUs per pound (about 29,075 MJ / kg) compared to a range from 7,000 (about 16,282 MJ / kg) to 8,000 BTU per pound (about 18,608 MJ / kg) of holocellulose. Essentially, lignin can be compacted and converted into briquettes and pellets used for incineration. For example, lignin can be turned into granules using any method described in this application. To obtain a slower burning granule or briquette, lignin can be crosslinked, for example, using an irradiation dose of from about 0.5 Mrad to 5 Mrad. Crosslinking allows you to get a slower burning form factor. A form factor, such as a granule or briquette, can be converted into synthetic coal or charcoal by pyrolysis in the absence of air, for example, at a temperature of from 400 to 950 ° C. Before pyrolysis, crosslinking of lignin to maintain structural integrity may be desirable.

Combined heat and electric energy production using spent biomass is described in provisional patent application No. 61/774773, filed March 8, 2013, the full description of which is incorporated herein by reference.

Biomass treatment after irradiation

After irradiation, the biomass can be transferred to a saccharification vessel.

Alternatively, the biomass can be heated after irradiation before the saccharification step. A heated medium can be created, for example, by means of infrared radiation, microwaves, combustion (for example, gas, coal, oil, biomass), resistive heating and / or inductive coils. Heat can be applied from at least one side or more than one side, heating can be continuous or batch, and only part of the material or all of the material can be heated. The biomass can be heated to temperatures above 90 ° C in an aqueous liquid that may contain acid or base. For example, an aqueous suspension of biomass can be heated from 90 to 150 ° C, alternatively from 105 to 145 ° C, optionally from 110 to 140 ° C or, optionally, but not necessarily, from 115 to 135 ° C. The time during which the aqueous biomass mixture is maintained at maximum temperature is from 1 to 12 hours, alternatively from 1 to 6 hours, optionally from 1 to 4 hours at maximum temperature. In some cases, the aqueous biomass mixture is acidic and the pH is from 1 to 5, optionally from 1 to 4, or, alternatively, from 2 to 3. In other cases, the aqueous biomass mixture is alkaline and the pH is from 6 to 13 alternatively from 8 to 12, or, optionally, from 8 to 11.

Saccharification

Treated biomass materials can be saccharified, in general, by combining the material and the cellulase enzyme in a liquid medium, for example, an aqueous solution. In some cases, before saccharification, the material is boiled, soaked or boiled in hot water, as described by Medoff and Masterman in the publication of US patent application 2012/0100577 A1, published April 26, 2012, the full description of which is incorporated herein.

The saccharification process can be partially or fully carried out in a tank (for example, in a tank with a volume of at least 4,000, 40,000 or 500,000 l), at a manufacturing plant and / or it can be partially or fully carried out during transportation, for example, in a railway tank, tanker or in a supertanker or ship hold. The time required for complete saccharification will depend on the processing conditions and the carbohydrate-containing material and enzyme used. When saccharification is carried out at a manufacturing plant under controlled conditions, the pulp can be substantially completely converted to sugar, for example glucose, within about 12 to 96 hours. If saccharification is carried out partially or fully during transport, saccharification may take longer.

In General, it is preferable that the contents of the tank during saccharification were mixed, for example, using jet mixing, as described in international patent application No. PCT / US2010 / 035331, filed May 18, 2010, which was published in English as WO 2010/135380 and where the United States is indicated as the state in which the applicant intends to obtain the patent, the full description of which is incorporated herein by reference. The addition of surfactants can increase the rate of saccharification. Examples of surfactants include nonionic surfactants such as Tween® 20 or Tween® 80 polyethylene, glycol surfactants, ionic surfactants, or amphoteric surfactants.

In general, it is preferable that the concentration of the sugar solution obtained by saccharification be relatively high, for example, greater than 40% or greater than 50, 60, 70, 80, 90, or even greater than 95% by weight. Water can be removed, for example, by evaporation, to increase the concentration of the sugar solution. This will reduce the volume being transported and will also inhibit the growth of microbes in the solution.

Alternatively, sugar solutions with lower concentrations can be used, in which case it may be desirable to add an antimicrobial supplement, for example, a broad-spectrum antibiotic, at a low concentration, for example, from 50 to 150 ppm. Other suitable antibiotics include amphotericin B, ampicillin, chloramphenicol, ciprofloxacin, gentamicin, hygromycin B, kanamycin, neomycin, penicillin, puromycin, streptomycin. Antibiotics will inhibit the growth of microorganisms during transportation and storage and can be used at suitable concentrations, for example, from 15 to 1000 ppm by weight, for example, from 25 to 500 ppm or from 50 to 150 ppm. If necessary, an antibiotic can be added, even if the sugar concentration is relatively high. Alternatively, other additives with antimicrobial or preservative properties may be used. Antimicrobial supplement (s) are preferably food additives.

A solution with a relatively high concentration can be obtained by limiting the amount of water added to the carbohydrate-containing material with the enzyme. The concentration can be controlled, for example, by controlling the degree of saccharification. For example, the concentration can be increased by adding more carbohydrate-containing material to the solution. To maintain the level of sugar that forms in the solution, you can add a surfactant, for example, one of the substances described above. In addition, solubility can be increased by increasing the temperature of the solution. For example, the solution can be maintained at a temperature of from 40 to 50 ° C, from 60 to 80 ° C, or even at a higher temperature.

Saccharine agents

Suitable cellulose-degrading enzymes include cellulases derived from species belonging to the genera Bacillus, Coprinus, Myceliophthora, Cephalosporium, Scytalidium, Penicillium, Aspergillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, Triceloma, Cellrum, selected from the species Aspergillus (see, for example, European Patent Publication No. 0 458 162), Humicola insolens (reclassified as Scytalidium thermophilum, see, for example, US Patent No. 4435307), Coprinus cinereus, Fusarium oxysporum, Myceliophthora thermophila, Meripilus, Meripilus , 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. Fiber-degrading enzymes can also be obtained from Chrysosporium, preferably a strain of Chrysosporium lucknowense. Additional strains that can be used include, but are not limited to, Trichoderma (in particular T. viride, T. reesei and T. koningii), alkalophilic Bacillus (see, for example, US patent No. 3844890 and publication of European patent No. 0 458 162) and Streptomyces (see, for example, European Patent Publication No. 0458162). Along with or in combination with enzymes, acids, bases and other chemical compounds (e.g., oxidizing agents) can be used to saccharify lignocellulosic and cellulosic materials. These materials can be used in any combination or sequence (for example, before, after and / or during the addition of the enzyme). For example, strong mineral acids (for example, HCl H ₂ SO ₄ , H ₃ PO ₄ ) and strong bases (for example, NaOH, KOH) can be used.

Sahara

In the processes described, 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., fluid bed chromatography, high pressure chromatography), centrifugation, extraction, any other isolation method known in the art, and combinations thereof.

Hydrogenation and other chemical transformations

Described processes may include hydrogenation. For example, glucose and xylose can be hydrogenated to produce sorbitol and xylitol, respectively. Hydrogenation can be accomplished by using a catalyst (e.g., Pt / gamma-Al ₂ O ₃ , Ru / C, a Raney nickel catalyst or other catalysts known in the art) in combination with H ₂ at high pressure (e.g. from 10 (about 69 kPa) to 12,000 psi (about 82.7 MPa)). You can use other types of chemical conversion of products as a result of the processes described in this application, for example, the production of products derived from organic sugar (e.g. furfural and products derived from furfural). Chemical transformations of sugar-derived products are described in provisional patent application US No. 61/667481, filed July 3, 2012, the description of which is fully incorporated herein by reference.

Fermentation

Zymomonas yeast and bacteria, for example, can be used to ferment or convert sugar (sugars) to alcohol (s). Other microorganisms are described below. The optimum pH for fermentation is from about 4 to 7. For example, the optimal pH for yeast is from about 4 to 5, while the optimal pH for Zymomonas is from about 5 to 6. Typical fermentation times are from about 24 to 168 hours. (for example, from 24 to 96 hours) at a temperature in the range from 20 ° C to 40 ° C (for example, from 26 ° C to 40 ° C), however, thermophilic microorganisms prefer higher temperatures. For example, when using anaerobic organisms, at least part of the fermentation is carried out in the absence of oxygen, for example, in an inert gas atmosphere such as N ₂ , Ar, He, CO ₂ or mixtures thereof. In addition, the mixture can be constantly purged with an inert gas passing through the tank during part or all of the fermentation process. In some cases, an anaerobic condition can be achieved or maintained by the formation of carbon dioxide during the fermentation process, with no additional inert gas required.

Alternatively, all or part of the fermentation process can be interrupted until the complete conversion of low molecular weight sugar into a product (e.g. ethanol). Fermentation intermediates include high concentration sugar and carbohydrates. Sugar and carbohydrates can be isolated using any means known in the art. These fermentation intermediates can be used in the preparation of a food product for human or animal consumption. Additionally or alternatively, the intermediate fermentation products can be pulverized to fine particles in a stainless steel laboratory mill to obtain a flour-like substance. In the fermentation process, jet mixing can be used, and in some cases saccharification and fermentation are carried out in the same tank.

Nutrients for microorganisms can be added during saccharification and / or fermentation, for example, food nutrient packs described in US Patent Application Publication 2012/0052536, filed July 15, 2011, the entire disclosure of which is incorporated herein by reference.

Fermentation includes the methods and products described in international patent application No. PCT / US2012 / 071097 (which was filed on December 20, 2012, published in England as WO 2013/096700 and where the state in which the applicant intends to obtain the patent is indicated United States) and in international patent application No. PCT / US2012 / 071083 (which was filed December 20, 2012, published in England as WO 2013/096693 and where the United States is indicated as the state in which the applicant intends to obtain the patent) , the contents of which are fully included This document is incorporated by reference. Mobile fermenters can be used as described in international patent application No. PCT / US2007 / 074028 (which was filed July 20, 2007, published in English as WO 2008/011598 and where, as the state in which the applicant intends to obtain a patent, United States) and U.S. Published Patent No. 8318453, the entire contents of which are incorporated herein. Similarly, saccharification equipment can be mobile. In addition, saccharification and / or fermentation can be partially or fully carried out during transport.

Fermenting agents

The microorganism (s) used in the fermentation may be natural microorganisms and / or engineered microorganisms. For example, a microorganism can be a bacterium (including, but not limited to, for example, a bacterium that decomposes fiber), a fungus (including, but not limited to, for example, yeast), a plant, protist, for example, protozoa, or mushroom-like protist (including, but not limited to, for example, slime) or seaweed. When organisms are compatible, mixtures of organisms can be used.

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 Saccharomyces spp. (including, but not limited to, S. cerevisiae (baker's yeast), S. distaticus, S. uvarum), genus Kluyveromyces, (including, but not limited to, K. marxianus, K. fragilis), genus Candida (including, but not limited to, C. pseudotropicalis and C. brassicae), Pichia stipitis (a relative of Candida shehatae), Clavispora genus (including, but not limited to, C. lusitaniae and C. opuntiae), genus Pachysolen (including, but not limited to, P. tannophilus), the genus Bretannomyces (including, but not limited to, for example, B. Clausenii (Philippidis, GP, 1996, Cellulose bioconversion technology, in Handbook

- 27,033,687 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 tsukubaensi, yeast species of the genera Zygosaccharomyces, Debaryomyces, Hansenula and Pichia and fungi of the genus dematioid Torula (e.g., T.coral 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.

Some organisms, such as bacteria, yeast and fungi, can be used to ferment products derived from biomass, such as sugars and alcohols, to produce succinic acid and similar products. For example, the organisms can be selected from: Actinobacillus succinogenes, Anaerobiospirillum succiniciproducens, Mannheimia succiniciproducens, Ruminococcus flaverfaciens, Ruminococcus albus, Fibrobacter succinogenes, Bacteroides fragilis, Bacteroides ruminicola, Bacteroides amylophilus, Bacteriodes succinogenes, Mannheimia succiniciproducens, Corynebacterium glutamicum, Aspergillus niger, Aspergillus fumigatus, Byssochlamys nivea, Lentinus degener, Paecilomyces varioti, Penicillium viniferum, Saccharomyces cerevisiae, Enterococcus faecali, Prevotella ruminicolas, Debaryomyces hansenii, Candida catenulata VKM Y-5, C. mycoderma VKM Y-240, C. rugosa VKM Yuga PKigen Y-2443, C. utilis VKM Y-74, C. utilis 766, C. zeylanoides VKM Y-6, C. zeylanoides VKM Y-14, C. zeylanoides VKM Y-2324, C. zeylanoides VKM Y-1543, C zeylanoides VKM Y-2595, C. valida VKM Y-934, Kluyveromyces wickerhamii VKM Y-589, Pichia anomala VKM Y-118, P. besseyi VKM Y-2084, P. media VKM Y-1381, P. guilliermondii HP-4, P. guilliermondii 916, P. inositovora VKM Y-2494, Saccharomyces cerevisiae VKM Y-381, Torulopsis Candida 127, T. Candida 420, Yarrowia lipolytica 12a, Y. lipolytica VKM Y- 47, Y. lipolytica 69, Y. lipolytica VKM Y-57, Y. lipolytica 212, Y. lipolytica 374/4, Y. lipolytica 585, Y. lipolytica 695, Y. lipolytica 704 and mixtures of these organisms.

Many of these microbial strains are publicly available and can be purchased commercially or through repositories such as ATCC (American Cell Culture Collection, Manassas, Virginia, USA), NRRL (Cell Culture Collection Agricultural Research Services, Peoria, Illinois, USA) or DSMZ (Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Braunschweig, Germany) in particular.

Commercially available yeasts include, for example, Red Star® / Lesaffre Ethanol Red (available from Red Star / Lesaffre, USA), FALI® (available from Fleischmann's Yeast Burns Philip Food Inc., United States) SUPERSTART® (Lallemand Biofuels and Distilled Spirits, Canada), EAGLE C6 FUEL ™ or C6 FUEL ™ (available from Lallemand Biofuels and Distilled Spirits, Canada), GERT STRAND (GERT STRAND®) (available from Gert Strand AB, Sweden) and FERMOL (available from DSM Specialties).

Distillation

After fermentation, the resulting liquids can be distilled using, for example, a mash column, to separate ethanol and other alcohols from the main volume of water and the residual solid phase. The steam leaving the brew column may, for example, be 35% by weight ethanol and may be charged to a distillation column. A mixture of almost azeotropic (92.5%) ethanol and water from a distillation column can be purified to obtain pure (99.5%) ethanol using vapor-phase molecular sieves. The still bottoms of the mash column can be sent to the first stage of a three-stage evaporator. A distillation column reflux condenser can provide heat for such a first stage evaporator. After the first stage of the evaporator, the solid can be separated using a centrifuge and dried in a drum dryer. Part (25%) of the centrifuge product can be reused for fermentation, and the remainder sent to the second and third stages of the evaporator. Most of the condensate from the evaporator can be returned to the process in the form of a fairly clean condensate, while a small part is separated and sent to wastewater treatment to prevent the accumulation of low boiling compounds.

Hydrocarbon-containing materials

Using the methods and systems described in this application, it is possible to process hydrocarbon-containing materials. Any described process can be used to process any hydrocarbon-containing material described in this application. It is understood that the hydrocarbon-containing materials used in this application include oil sands, oil shale, tar sands, coal dust, coal slurry, bitumen, various types of coal and other natural and synthetic materials containing both hydrocarbon components and solid matter. 033687 A solid may include rock, sand, clay, stone, sludge, drill cuttings or other solid organic and / or inorganic matter. The term may also include wastes, such as wastes and by-products from drilling, wastes and by-products from oil refining, or other wastes containing hydrocarbon components, such as asphalt roofing tiles and paving, asphalt paving, etc.

Transportation systems

Various transportation systems can be used to transfer biomass materials, for example, as described previously, into the chamber and under the electron beam in the chamber. Typical conveyors are belt conveyors, pneumatic conveyors, screw conveyors, trolleys, trains, trains or trolleys on rails, hoists, frontal loaders, backhoe excavators, cranes, various scrapers and shovels, trolleys and loading devices can be used. For example, vibration conveyors may be used in the various processes described herein. Vibratory conveyors are described in PCT / US2013 / 64289, filed October 10, 2013, the full description of which is incorporated herein by reference.

Vibratory conveyors are especially useful for distributing material across the surface and providing a uniform layer on the surface of the conveyor trough. For example, the feedstock may form a pile of material that may have a height of at least four feet (about 122 cm) (for example, at least about 3 feet (about 91 cm), at least about 2 feet (about 61 cm ), at least about 1 foot (about 30.5 cm), at least about 6 inches (15.24 cm), at least about 5 inches (12.7 cm), at least about 4 inches ( 10.16 cm), at least about 3 inches (7.62 cm), at least about 2 inches (5.08 cm), at least about 1 inch (2.54 cm), at least Here’s about 1/2 inch (1.27 cm)) and a width smaller than the width of the conveyor (for example, 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 allows you to distribute the material in such a way as to cover the entire width of the groove of the conveyor and to ensure uniform thickness, preferably as described above. In some cases, an additional distribution method may be used. For example, a distributor, such as a spreader, drop spreader (e.g., CHRISTY SPREADER ™), or combinations thereof, can be used to distribute (e.g., place, spill, spread, and / or spray) raw material over a large area. In some cases, the distributor can deliver biomass to the vibratory conveyor in the form of a wide rainfall or curtain. In addition, using the second conveyor located higher relative to the first conveyor (for example, the first conveyor is used when irradiating raw material), biomass can be dumped onto the first conveyor, while the second conveyor can have a width that is smaller in the transverse direction relative to the direction of transportation than width of the first conveyor. In particular, if the second conveyor is a vibratory conveyor, the raw material is distributed under the action of the second and first conveyor. According to some possible embodiments of the invention, the second conveyor abuts against an outlet with an oblique cross section (for example, with an oblique section with a ratio of 4: 1), so that the material can be dropped onto the first conveyor in the form of a wide curtain (for example, wider than the width of the second conveyor). The initial area of biomass discharged by means of a distributor (for example, a spreader, gravity spreader, conveyor or cross-sectional vibratory conveyor) may include the entire width of the first vibratory conveyor or may include part of such a width. After falling onto the conveyor, the material is evenly distributed evenly under the vibrations of the conveyor, so that the entire width of the conveyor is preferably covered with a uniform layer of biomass. In some embodiments of the invention, combinations of manifolds may be used. Some methods for distributing feedstocks are described in US Pat. No. 7,153,533, filed July 23, 2002 and published December 26, 2006, the entire disclosure of which is incorporated herein by reference.

In general, it is preferable to transport the material through an electron beam as quickly as possible to maximize throughput. For example, the material can be mixed at speeds of at least 1 ft / min (about 0.31 m / min), for example at least 2 ft / min (about 0.61 m / min), at least 3 ft / min (about 0.91 m / min), at least 4 ft / min (about 1.22 m / min), at least 5 ft / min (about 1.52 m / min), at least 10 ft / min (about 3.05 m / min), at least 15 ft / min (about 4.57 m / min), at least 20 (about 6.09 m / min), at least 25 (about 7.62 m / min), at least 30 (about 9.14 m / min), at least 40 (about 12.19 m / min), at least 5 0 ft / min (about 15.24 m / min), at least 60 ft / min (about 18.29 m / min), at least 70 ft / min (about 21.34 m / min), at least at least 80 ft / min (about 24.38 m / min); at least 90 ft / min (about 27.43 m / min). The transport speed is related to the beam current and a given radiation dose, for example, in the case of biomass with a thickness of 1/4 inch (0.635 cm), distributed across the conveyor width

- 29 033687

5.5 feet (about 1.68 cm), and 100 mA, to ensure a sufficient dose of radiation, the conveyor can move at a speed of about 20 feet / min (about 6.096 m / min), at 50 mA, the conveyor can move at a speed of about 10 feet / min (approximately 3.048 m / min) to provide approximately the same dose.

The speed with which the material can move depends on the shape and weight of the material transported and the processing required. Fluid materials, such as granular materials, are particularly transportable by means of vibrating conveyors. Transportation speeds may, for example, be at least 100 lb / h (about 45 kg / h) (e.g., at least 500 lb / h (about 227 kg / h), at least 1000 lb / h (about 454 kg / h), at least 2,000 lb / h (approximately 907 kg / h), at least 3,000 lb / h (approximately 1361 kg / h), at least 4,000 lb / h (approximately 1814 kg / h), at least 5,000 lb / h (about 2,268 kg / h), at least 10,000 lb / h (about 4,536 kg / h), at least 15,000 lb / h (about 6804 kg / h), or even at least 25,000 pounds / h (approximately 11340 kg / h)). Some typical transport speeds may be from about 1000 (about 454 kg / h) to 10,000 lb / h (about 4536 kg / h), (for example, from about 1000 lb / h (about 454 kg / h) to 8000 lb / h (about 3,629 kg / h), from about 2,000 (about 907 kg / h) to 7,000 lb / h (about 3,175 kg / h), from about 2,000 (about 907 kg / h), to 6,000 lb / h (about 2,722 kg / h), from about 2000 (about 907 kg / h) to 5000 lbs / h (about 2268 kg / h), from about 2000 (about 907 kg / h) to 4500 lb / h (about 2041 kg / h), from about 1,500 (about 680 kg / h) to 5,000 lb / h (about 2268 kg / h), from about 3,000 (about 1361 kg / h) about 7000 lb / h (about 3175 kg / h), from about 3000 (about 1361 kg / h) to 6000 lb / h (about 2722 kg / h), from about 4000 (about 1814 kg / h) to 6000 lb / h (about 2722 kg / h) and from about 4000 (about 1814 kg / h) to 5000 lb / h (about 2268 kg / h)). Typical transport speeds depend on the density of the material. For example, for biomass with a density of about 35 lb / ft (about 0.56 g / cm ³ ) and at a transport speed of about 5000 lb / h (about 2268 kg / h), the material moves at a speed of about 143 ft ³ / h (about 4 m ³ / h), if the material is 1/4 (0.635 cm) thick and the gutter is 5.5 feet (about 168 cm), the material is transported at a speed of about 1250 ft / h (381 m / h) (about 21 ft / min (approximately 6.40 m / min)). Therefore, material transportation speeds can vary greatly. Preferably, for example, a 1/4 thickness biomass layer is transported at speeds from about 5 (about 1.52 m / min) to 100 ft / min (about 30.48 m / min) (for example, from about 5 (about 1.52 m / min) to 100 ft / min (about 30.48 m / min), from about 6 (about 1.82 m / min) to 100 ft / min (about 30.48 m / min), from about 7 ( about

2.13 m / min) to 100 ft / min (about 30.48 m / min), from about 8 (about 2.44 m / min) to 100 ft / min (about 30.48 m / min), about 9 (about 2.74 m / min) to 100 ft / min (about 30.48 m / min), from about 10 (about 3.05 m / min) to 100 ft / min (about 30.48 m / min), from about 11 (about 3.35 m / min) to 100 ft / min (about 30.48 m / min), from about 12 (about 3.66 m / min) to 100 ft / min (about 30 48 m / min), from about 13 (about 3.96 m / min) to 100 ft / min (about 30.48 m / min), from about 14 (about 4.27 m / min) to 100 ft / min (about 30.48 m / min), from about 15 (about 4.57 m / min) to 100 ft / min (about 3 0.48 m / min), from about 20 (about 6.10 m / min) to 100 ft / min (about 30.48 m / min), from about 30 (about 9.14 m / min) to 100 ft / min (about 30.48 m / min), from about 40 (about 12.19 m / min) to 100 ft / min (about 30.48 m / min), from about 2 (about 0.61 m / min ) up to 60 ft / min (about 18.29 m / min), from about 3 (about 0.91 m / min) to 60 ft / min (about 18.29 m / min), from about 5 (about 1, 52 m / min) to 60 ft / min (about 18.29 m / min), from about 6 (about 1.83 m / min) to 60 ft / min (about 18.29 m / min), from about 7 (about 2.13 m / min) to 60 ft / min (about 18.29 m / min), from about 8 (about 2.44 / min) up to 60 ft / min (about 18.29 m / min), from about 9 (about 2.74 m / min) to 60 ft / min (about 18.29 m / min), from about 10 (about 3.05 m / min) up to 60 ft / min (about 18.29 m / min), from about 15 (about 4.57 m / min) to 60 ft / min (about 18.29 m / min), from about 20 (about 6.10 m / min) to 60 ft / min (about 18.29 m / min), from about 30 (about 9.14 m / min) to 60 ft / min (about 18.29 m / min), from about 40 (about 12.19 m / min) to 60 ft / min (about 18.29 m / min), from about 2 (about 0.61 m / min) to 50 ft / min (about 15 24 m / min), from about 3 (about 0.91 m / min) to 50 ft / min (about 15.24 m / min) from about 5 (about 1.52 m / min) to 50 ft / min (about 15.24 m / min), from about 6 (about 1.83 m / min) to 50 ft / min (about 15.24 m / min), from about 7 (about 2.13 m / min) to 50 ft / min (about 15.24 m / min), from about 8 (about 2.44 m / min) to 50 ft / min ( about 15.24 m / min), from about 9 (about 2.74 m / min) to 50 ft / min (about 15.24 m / min), from about 10 (about 3.05 m / min) to 50 ft / min (about 15.24 m / min), from about 15 (about 4.57 m / min) to 50 ft / min (about 15.24 m / min), from about 20 (about 6.10 m / min) to 50 ft / min (about 15.24 m / min), from about 30 (about 9.14 m / min) to 50 ft / min (about 15.24 m / min), from about 40 (about 12.19 m / min) to 50 ft / min (about 15.24 m / min)). It is preferable that the material is transported at a constant speed, for example, to maintain constant irradiation of the material when it is transmitted under an electron beam (for example, under a shower, field).

Described vibratory conveyors may include sieves used for screening and

- 30 033687 sorting materials. Port openings on the side or bottom of the gutters can be used to sort, select or remove specific materials, for example, depending on size or shape. Some conveyors have counterweights to reduce the dynamic forces acting on the support structure. Some vibratory conveyors are made in the form of screw elevators, designed in such a way that they can bend around the surface and / or are designed to drop material from one conveyor to another (for example, on a step, cascade or on a series of steps or stairs). Along with the movement of materials, conveyors can be used, alone or in combination with other equipment or systems, for sieving, selecting, sorting, classifying, distributing, sorting by size, technical control, extraction, removal of metals, freezing, mixing, mixing, orientation , heating, heat treatment, drying, dehydration, cleaning, washing, leaching, quenching, coating, dedusting and / or feeding. Conveyors may also contain coatings (e.g. dustproof coatings), side discharge valves, bottom discharge valves, special gaskets (e.g. anti-stick gaskets, stainless steel, rubber, specialty steel and / or corrugated gaskets), sectional gutters, damping baths, sieves, perforated plates, detectors (e.g. metal detectors), high temperature devices, food devices, heaters, dryers and / or coolers. In addition, the chute can have various shapes, for example, have a flat bottom, a V-shaped bottom, contain a flange at the top, have a curved bottom, have a flat shape with protrusions in any direction, have a tubular shape, a half-pipe shape, have a coating or have any combination of the above forms. In particular, conveyors may be associated with irradiation systems and / or equipment.

Conveyors (e.g. vibration conveyor) can be made from corrosion resistant materials. In the manufacture of conveyors, structural materials may be used that include stainless steel (e.g., 304, 316 stainless steel, HASTELLOY® alloys, and INCONEL® alloys). For example, corrosion-resistant HASTELLOY® 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® ( ULTIMETE).

Vibratory conveyors may have non-adhesive release coatings, for example, TUFFLON ™ (Dupont, Delaware, USA). Vibratory conveyors can also have anti-corrosion coatings. For example, coatings supplied by Metal Coatings Corp (Houston, Texas, USA) and other coatings such as fluoropolymer coating, XYLAN® coating, molybdenum disulfide coating, epoxy-phenolic coating, ferrous metal phosphate coating , polyurethane high gloss topcoat for epoxy resin, inorganic zinc coating, polytetrafluoroethylene coating, PPS / RYTON® coating, fluorinated ethylene propylene coating, PVDF / DYKOR® coating, ESTFE / HALAR (ECTFE / HALAR ) and ceramic epoxy PTFE coating. These coatings can improve resistance to process gases (eg, ozone), chemical corrosion, pitting, abrasion and oxidation. In some cases, along with the transportation systems described herein, one or more other transportation systems can be enclosed. When using a casing, the conveyor placed in the casing can also be purged with an inert gas to maintain an atmosphere with a low oxygen level. Maintaining low oxygen levels avoids the formation of ozone, which in some cases is undesirable due to its reactivity and toxic nature. For example, oxygen may be less than about 20% (for example, 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%). The purge can be carried out using an inert gas, including, but not limited to, using nitrogen, argon, helium or carbon dioxide. These gases may come, for example, by evaporation of a liquid source (e.g., liquid nitrogen or helium), may be obtained or released from air in situ, or may come from tanks. Inert gas can be recycled and any amount of residual oxygen can be removed using a catalyst, such as a layer of copper catalyst. Alternatively, in order to maintain low oxygen levels, combinations of purging, recycling and oxygen removal can be performed. The enclosed conveyor can also be purged using a reactive gas that can interact with biomass. Such a purge can be carried out before, during or after the irradiation process. The reactive gas may include, but is not limited to, nitrous oxide, ammonia, oxygen, ozone, hydrocarbons, aromatics, amides, peroxides, azides, halides, oxyhalides, phosphides, phosphines, arsines, sulfides, thiols, boranes and / or hydrides. The reactive gas can be activated in the casing, for example, by irradiation (for example, using an electron beam, by UV irradiation, microwave irradiation, heating, IR irradiation) so that it interacts with biomass. Biomass itself can be activated, for example, by

- 31 033687 exposure. The biomass is preferably activated by an electron beam to produce radicals, which then interact with an activated or non-activated reactive gas, for example, by means of a radical compound or quenching.

The purge gases supplied to the 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, said gas can be evaporated from compressed gas, such as liquid nitrogen, or sublimated from solid carbon dioxide. As an alternative example, the gas may be cooled with a cooler, or part or all of the conveyor may be cooled.

Other embodiments of the invention

Any material, methods, or processed materials described herein can be used to prepare products and / or intermediates, such as composites, fillers, binders, polymer additives, adsorbents, and controlled release agents. These methods may include compaction, for example, by exposing the materials to pressure and heat. For example, composite materials can be obtained by combining fibrous materials with a resin or polymer. For example, a resin that can be crosslinked by irradiation, such as a thermoplastic resin, can be combined with a fibrous material to form a fibrous material / crosslinkable resin combination. Such materials can, for example, be used as building materials, protective coatings, containers and other structural materials (for example, molded and / or extruded products). The absorbent materials may be, for example, in the form of granules, flakes, fibers and / or sheets. Adsorbents can be used, for example, as bedding for pets, packaging material or in environmental pollution control systems. Controlled release matrices may also be in the form of, for example, granules, flakes, fibers and / or sheets. Matrices for controlled release can, for example, be used for the release of drugs, biocides, fragrances. For example, composite materials, absorbent materials and controlled release agents and their use are described in US No. PCT / US2006 / 010648, filed March 23, 2006, and in US patent No. 8074910, filed November 22, 2011, the full description of which is included in this document by reference.

In some cases, the biomass material is treated at a first level to reduce resistance to processing, for example, using accelerated electrons, to selectively release one or more sugars (e.g. xylose). The biomass can then be processed to a second level to release one or more other sugars (e.g. glucose). In some cases, biomass can be dried between treatments. Processing methods may include the use of chemical and biochemical processing methods for the release of sugars. For example, biomass material can be processed to a level of less than about 20 Mrad (for example, 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 (for example 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%) for xylose release. Xylose, for example, which is released into the solution, can be separated from the solid phase and, optionally, the solid phase washed with a solvent / solution (for example, water and / or acidified water). In some cases, the solid can be dried, for example, in air and / or in vacuum, possibly by heating (for example, at a temperature below about 150 ° C, below about 120 ° C) until the water content is below about 25 wt.%, (below about 20 wt.%, below about 15 wt.%, below about 10 wt.%, below about 5 wt.%). The solid can then be processed at a level of less than about 30 Mrad (for example, 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 completely untreated) and then treat with an enzyme (e.g. cellulase) to release glucose. Glucose (e.g. glucose in solution) can be separated from the remaining solid phase. The solid can then be further processed, for example, used to produce energy / or other products (for example, products derived from lignin).

Examples

Concentrations were determined by HPLC in aqueous dilute and filtered solutions using appropriate standards. Unless otherwise specified, reagents were obtained from Sigma / Aldrich, St. Louis, Missouri, Fisher Scientific, Waltham, Mass. Or from an equivalent reagent supply company.

Saccharification

For saccharification, a cylindrical tank with a diameter of 32 inches (about 81 cm), height 64 inches (about 163 cm), equipped with convex bottoms according to ASME (upper and lower) was used. The tank was also equipped with a 16-inch (about 41 cm) wide blade with hydraulic wings for mixing. Heating was provided by passing hot water through the jacket in the form of

- 32,033,687 loot pipes surrounding the tank.

The tank was loaded with 200 kg of water, 80 kg of biomass and 18 kg of the Duet ™ cellulase enzyme, available from Genencor, Palo Alto, and California. The biomass was the core of the corncob, which was ground with a hammer and sifted through a sieve from 10 to 40 mesh. The biomass was irradiated with an electron beam until a total dose of 35 Mrad was obtained. The pH of the mixture was adjusted and maintained automatically throughout the entire saccharification process at 4.8 using Ca (OH) ₂ . The specified combination was heated to 53 ° C, stirred at a speed of 180 rpm for about 24 hours, after which saccharification was considered complete.

Part of this material was sieved through a 20 mesh sieve and the resulting solution was stored in a bottle with a volume of 8 gallons (approximately 30 L) at 4 ° C.

Fermentation of glucose to produce ethanol

About 400 ml of saccharified material was decanted into a 1 L New Brunswick BioFlow 115 bioreactor. Prior to inoculation, this material was aerated and heated to 30 ° C. The stirring speed was set at 50 rpm. The pH according to the measurements was 5.2, which is acceptable for fermentation, therefore, its value was not regulated. The aeration was stopped and the bioreactor content was inoculated using 5 mg of Thermosacc dry yeast (Lallemand, Inc., Memphis, Tennessee). Fermentation was allowed to proceed for about 24 hours.

After fermentation, the glucose concentration was below the detection limit, the ethanol concentration was approximately 25 g / L and the xylose concentration was 30 g / L.

Getting bottoms

VAT residues were obtained by distillation of ethanol from a fermented material as described above. In addition, solids were removed by centrifugation. The final amount of dissolved solids was from 5 to 10 wt.%. Fine particles were also present in the suspended solid. After distillation, the xylose concentration was approximately 40 g / L.

These residues were designated as vat residues of series A. Similarly, the resulting batch was designated as series R.

Fermentation of xylose to obtain butyric acid

Experiment (A) with bottoms.

Seven 1 L of New Brunswick BioFlow 115 bioreactors were used in this experiment. All seven reactors were initially filled with 200 ml of 3x concentrate in P2 medium (described below) and 72 g of xylose (Danisco, Copenhagen, Delaware). Two of the reactors (BR2 and BR4) were charged with 120 ml of bottom residue obtained as described above (series A). Two reactors (BR6 and BR8) were charged with 240 ml of bottoms (series A). Two reactors (BR18 and BR20) were charged with 360 ml of bottoms (series A). One of the reactors (BR22) was charged with 240 ml of bottoms (series R). All bioreactors were brought to a total volume of 600 ml with deionized water. For example, BR2 contained 200 ml of P2 medium, 120 ml of bottoms from Series A, ~ 72 grams of xylose, and deionized water to bring the volume to 600 ml. The xylose concentration was 72 grams plus ~ 4.8 g of bottoms, resulting in a concentration of approximately 128 g / L. These reactors were sparged with gaseous N ₂ and inoculated with 7% (45 ml) of C. tyrobutyricum (ATCC 25755). Inoculation was grown overnight at 37 ° C in 300 ml of enriched Clostridia medium from 1 ml of frozen strains. Samples were periodically taken from the bioreactors and transferred to GC and HPLC analysis. The fermentation pH was maintained above 6.0 using 3.7 N ammonium hydroxide. In the table. 1 shows the data collected during these experiments.

P2-based medium was prepared as described in US Pat. No. 6,358,717, but as a 3-fold concentrate (3 x), i.e. only 1/3 of the water was used to prepare the solutions. The P2 medium was prepared as follows. The specified medium consisted of the following separately prepared solutions (in grams per 100 ml of distilled water, unless otherwise indicated): 790 ml of distilled water (solution I), 0.5 g K ₂ HPO ₄ , 0.5 g KH ₂ PO ₄ , 2.2 g of CH ₃ COONH ₄ (solution II), 2.0 g of MgSO ₄ -7H ₂ O, 0.1 g of MnSO ₄ -H ₂ O, 0.1 g of NaCl, 0.1 g _of FeSO ₄ -7H ₂ O (solution III) and 100 mg of p-aminobenzoic acid, 100 mg of thiamine, 1 mg of biotin (solution IV). Solutions I and II were sterilized by filtration and then mixed to obtain a buffer solution. Solutions III and IV were sterilized by filtration. Portions (10 and 1 ml) of solutions III and IV, respectively, were added under aseptic conditions to the buffer solution. The final pH of the P2 medium was 6.6.

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Table 1

Try Time (hour) Vat balance Oil acid (g / l) Xylose (g / l) A-br2 17 20% Serie A 8.5 95.1 A-BR4 17 20% Serie A 9.7 93,4 A-BR6 17 40% Serie A 7.9 90,4 A-BR8 17 40% Serie A 4.9 106,4 A-BR18 17 60% Serie A 4.8 94.8 A-BR20 17 60% Serie A 5.5 94.6 A-BR22 17 60% Series R 7.8 115,4 A-br2 24 20% Serie A 15.6 81.4 A-BR4 24 20% Serie A 16.3 79.1 A-BR6 24 40% Serie A 16.3 78.9 A-BR8 24 40% Serie A 8 91.5 A-BR18 24 60% Serie A 9.5 83.8 A-BR20 24 60% Serie A AND 2 81.9 A-BR22 24 60% Series R 12.7 102

A-br2 41 20% Serie A 29.6 40,4 A-BR4 41 20% Serie A 30.8 35.1 A-BR6 41 40% Serie A 31.3 44,4 A-BR8 41 40% Serie A 20.9 55.8 A-BR18 41 60% Serie A 27 54.5 A-BR20 41 60% Serie A 27.6 52,2 A-BR22 41 60% Series R 28.7 60.9 A-br2 48 20% Serie A 34 28.5 A-BR4 48 20% Serie A 36 22.4 A-BR6 48 40% Serie A 34.7 35.7 A-BR8 48 40% Serie A 27.5 44.8 A-BR18 48 60% Serie A 32,7 46.9 A-BR20 48 60% Serie A 33,2 44.6 A-BR22 48 60% Series R 30.8 48.7 A-br2 66 20% Serie A 48 5,6 A-BR4 66 20% Serie A 48.1 0.5 A-BR6 66 40% Serie A 39.1 19.1 A-BR8 66 40% Serie A 36,4 23.1 A-BR18 66 60% Serie A 38.1 28.7 A-BR20 66 60% Serie A 36.1 27.7 A-BR22 66 60% Series R 38.1 25,2 A-br2 72 20% Serie A 43.5 1.8 A-BR4 72 20% Serie A 42.8 Nf A-BR6 72 40% Serie A 41.3 14.9 A-BR8 72 40% Serie A 41 16,4 A-BR18 72 60% Serie A 39.3 23.6 A-BR20 72 60% Serie A 39 23.1 A-BR22 72 60% Series R 48.9 18.2 A-br2 138 20% Serie A 47.4 Nf A-BR4 138 20% Serie A 43,2 Nf A-BR6 138 40% Serie A 49 2.1 A-BR8 138 40% Serie A 46.1 0.5 A-BR18 138 60% Serie A 48,4 3

A-BR20 138 60% Serie A 47.5 3.9 A-BR22 138 60% Series R 47.9 0.7 NF: not detected, below detection limit

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Experiment (B) with bottoms.

Six bioreactors were used in this experiment. In the case of a 600 ml reactor load, two reactors (B-BR2 and B-BR4) filled 72 g of xylose, 5 ppm FeSO ₄ x7H ₂ O and 6 g / L of Fluka brand yeast extract and deionized water added to bring the volume to 600 ml. The other two reactors (BBR6 and B-BR8) filled 72 g of xylose, 5 ppm FeSO ₄ x7H ₂ O, 240 ml of 40% bottoms and deionized water added to bring the volume to 600 ml. One of the reactors (B-BR18) was filled with 72 g of xylose, 200 ml of modified P2 medium supplemented with 240 ml of bottoms, and deionized water added to bring the volume to 600 ml. Another reactor (B-BR20) was filled with 72 g of xylose, 200 ml of modified P2 medium, supplemented (as described above, but not as a 3 × concentrate) with 60 g / l of yeast extract, and deionized water added to bring the volume to 600 ml. All six reactors were sparged with gaseous N2 and then inoculated with 5% (30 ml) C. tyrobutyricum (ATCC 25755). The indicated data are given in table. 2.

Sowing was grown overnight in a modified enriched Clostridia medium containing 10 g peptone, 10 g meat extract, 5 g NaCl, 5 g / l cysteine, 3 g sodium acetate, 5 g anhydrous agar and 5 g xylose per liter. The medium was prepared in 900 ml of deionized water without xylose; 270 ml aliquots were collected in 500 ml vials. The vials were bubbled, autoclaved, and 30 ml of 50 g / l xylose was injected into each vial through a 22 micron filter. Before injection, xylose solution was bubbled with gaseous N2. For a 300 ml vial, 1 ml of the frozen strain was used.

Fermentation pH was maintained above 6.0 using 3.7N NH ₄ OH. Samples were taken periodically and analyzed by GC and HPLC.

table 2

Try Time (hour) Wednesday Butyric acid (g / l) Xylose (g / l) B-BR2 17 6 g / l YE + 5 mg / l FeSO ₄ Nf 94 B-BR4 17 6 g / l YE + 5 mg / l FeSO ₄ Nf 95.4 B-BR6 17 40% DB + 5mg / L FeSO ₄ Nf 117.8 B-BR8 17 40% DB + 5mg / L FeSO ₄ Nf 119.2 B-BR18 17 P2 + 40% DB oh s 104.4 B-BR20 17 P2 + bog / l YE Nf 98.2 B-BR2 24 bg / l YE + 5mg / l FeSO ₄ 0.8 84,4 B-BR4 24 bg / l YE + 5mg / l FeSO ₄ 1,2 83.1 B-BR6 24 40% DB + 5mg / L FeSO ₄ 0.8 113.2 B-BR8 24 40% DB + 5mg / L FeSO ₄ 0.7 OF B-BR18 24 P2 + 40% DB 0.9 101 B-BR20 24 P2 + bog / l YE 1.7 99 B-BR2 41 bg / l YE + 5mg / l FeSO ₄ 5.5 51.9 B-BR4 41 bg / l YE + 5mg / l FeSO ₄ 9.3 48.5 B-BR6 41 40% DB + 5mg / L FeSO ₄ 14.8 88 B-BR8 41 40% DB + 5mg / L FeSO ₄ 14 91.4 B-BR18 41 P2 + 40% DB 7.9 73.7 B-BR20 41 P2 + bog / l YE 32,5 3.8 B-BR2 48 bg / l YE + 5mg / l FeSO ₄ 7.1 44.1 B-BR4 48 bg / l YE + 5mg / l FeSO ₄ AND 41.9 B-BR6 48 40% DB + 5mg / L FeSO ₄ 18.8 77.3 B-BR8 48 40% DB + 5mg / L FeSO ₄ 19,2 81.9 B-BR18 48 P2 + 40% DB 16.8 66,2 B-BR20 48 P2 + bog / l YE 37.1 Nf B-BR2 66 bg / l YE + 5mg / l FeSO ₄ 9.5 31.5 B-BR4 66 bg / l YE + 5mg / l FeSO ₄ 15,2 30.1 B-BR6 66 40% DB + 5mg / L FeSO ₄ 27.4 53.6 B-BR8 66 40% DB + 5mg / L FeSO ₄ 25,2 61 B-BR18 66 P2 + 40% DB 28.7 43.9 B-BR20 66 P2 + bog / l YE 41.3 Nf

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B-BR2 72 bg / l YE + 5mg / l FeSO ₄ 9.5 29th B-BR4 72 bg / l YE + 5mg / l FeSO ₄ 17.8 27.8 B-BR6 72 40% DB + 5mg / L FeSO ₄ 27.6 47.8 B-BR8 72 40% DB + 5mg / L FeSO ₄ 26.7 52,4 B-BR18 72 P2 + 40% DB 30.6 36.5 B-BR20 72 P2 + 60g / l YE 36,2 Nf B-BR2 137 bg / l YE + 5mg / l FeSO ₄ 9.8 19,4 B-BR4 137 bg / l YE + 5mg / l FeSO ₄ 20.6 16.6 B-BR6 137 40% DB + 5mg / L FeSO ₄ 41.9 24.1 B-BR8 137 40% DB + 5mg / L FeSO ₄ 42.6 16.6 B-BR18 137 P2 + 40% DB 40,2 4.3 B-BR20 137 P2 + 60g / l YE 36.3 Nf NF: not detected, below detection limit YE: yeast extract DB: bottoms P2: modified P2 medium

Separation of butyrate with acidic resin.

Amberlite ™ IRA 400 resin (500 g) was washed with water (2 * 500 ml) in a 5 L round bottom flask. Before adding the fermentation broth to the wet resin, excess water was carefully removed with a pipette. An enzymatic broth (2 L) containing 44.7 g / L butyric acid was added, and the resulting mixture was stirred using a magnetic stirrer for 1.5 hours. A small analytical sample was taken and detected by GC analysis of equilibrium vapor, which indicated sample contains 32.5 g / l butyric acid (loss of 27%). The result indicated that 24.5 g of butyric acid was adsorbed on the resin. The supernatant of the solution was discarded and the wet resin was loaded into a glass column with a wire sieve at the bottom to prevent clogging. The enzymatic broth was washed from the resin with a stream of water (2 L) until the eluent became clear. The resin was then transferred to a 2 L round bottom flask containing the armature of a magnetic stir bar, and then treated with 100 ml of 1N HCl, followed by treatment with 8 ml of 6 N HCl. The resulting mixture was stirred for 5 minutes, the pH being 2.5, then the mixture was distilled. A total of five cycles of distillation from flask to flask allowed to obtain from 150 to 250 ml of fractions. Between the distillations, more water and 1 N HCl were added to the resin. Fractions were made basic with 20% aqueous NaOH and concentrated by rotational evaporation. Drying in vacuo at 120 ° C. overnight afforded 16.23 g of a combined crude solid or

14.13 g of sodium butyrate in the sample. For five distillation cycles, this corresponded to a recovery efficiency of 57.7%. Additional distillation cycles will provide a higher degree of recovery.

Butyrate separation using a base resin.

To 400 ml of butyric acid-containing enzyme broth (44.58 g / L) in a 1 L round-bottom flask was added 100 ml of Amberlite ™ IRN 150 wet resin (alkaline component). The resulting mixture was stirred at room temperature for 2 hours and then allowed to stand for 10 minutes. A small analytical sample (1/2 ml) was taken and placed in a flask. Using GC analysis of equilibrium vapor, it was found that this sample contains 24.29 g / l butyric acid (a decrease of 54.49%). The result indicated that 9.72 g of butyric acid was adsorbed on the resin.

The supernatant of the solution was discarded and the remaining broth was removed using a 50 ml pipette. The resin was washed with water (8 * 25 ml) and then treated with a 10% solution of H ₂ SO ₄ in EtOH (50 ml). The resulting mixture was stirred at room temperature for 5 minutes, and then the ethanol solution was removed with a pipette. Next, the resin was washed with EtOH (10 * 25 ml), followed by washing with water (10 * 25 ml). EtOH washings were combined and made basic with 20% NaOH (pH 11) and then concentrated by rotational evaporation. The aqueous washings were treated in a similar manner and both solid fractions were further dried in vacuo at 120 ° C to obtain 6.74 g (72.57% sodium butyrate according to LC analysis) from ethanol and 1.90 g (80.44% sodium butyrate according to LC analysis) from water. The total degree of extraction from the resin was 66.1%.

Conversion of butyrate to ethyl butyrate.

The crude solid mixture containing a total of 8.9 g of sodium butyrate was treated with 50 ml of ethanol in a 250 ml round bottom flask and the resulting mixture was cooled in a water bath and slowly treated with concentrated sulfuric acid (16 g) with stirring using a magnetic anchor mixers. The round bottom flask was equipped with a reflux condenser and

- 36,033,687 the reaction mixture was boiled for 4 hours in an atmosphere of N ₂ . After cooling to room temperature, the reaction mixture was poured into a separatory funnel containing 150 ml of an aqueous solution of Na ₂ HPO ₄ (40 g). The final pH of the solution after stirring was 7. The upper phase was separated and filtered through glass wool to remove a precipitate to give 4.5 ml of ethyl butyrate. The specified sample was combined with other similar samples to obtain approximately 29 g of the crude liquid, which was distilled to obtain 23.6 g (purity 88% according to LC analysis) of ethyl butyrate. The impurities were mainly ethanol (9.2%) and ethyl acetate (2%).

Hydrogenolysis of ethyl butyrate.

Ethyl butyrate (20.8 g, 0.176 mol) in 225 ml dry ethanol was added to 0.5% Re on alumina (8.1 g, reduced) in a 1 L stainless steel autoclave. After purging N2 and evacuating, the resulting mixture was filled with H ₂ at a pressure of 116 psi (approximately 800 kPa) and then stirred at a speed of 600 rpm and heated at 270 ° C for a total of 25.5 hours for 4 days. Each morning, the pressure in the autoclave was released to room temperature and then another H2 (108 to 112 psi) (from about 744 to about 772 kPa) was added. For hydrogenation, pressures in the range of 1400 to 1500 psi (from about 9650 to about 10,340 kPa) were used. A gas chromatographic analysis of equilibrium vapor indicated more than 65% molar conversion of ethyl butyrate with more than 90% selectivity for n-butanol.

Other than those shown in the examples in this application, or unless expressly indicated specifically, all numerical ranges, amounts, quantities and percentages, such as those that express quantities of materials, elementary compositions, reaction times and temperatures, ratios of amounts, and others parameters, in the next part of the description of the invention and the attached claims, it should be understood as if they were preceded by the word approximately, even if the term approximately may not explicitly stand next to the specified value, quantity or pazonom. Accordingly, unless otherwise indicated, the numerical parameters given in the following description of the invention and the attached claims are approximate values, which may vary depending on the desired desired properties, which are intended to be achieved using the present invention. At least not as an attempt to limit the use of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be considered in light of the number of significant digits given and using conventional rounding methods.

Despite the fact that the numerical ranges and parameters defining a wide scope of the invention are approximations, the numerical values given in specific examples are indicated as accurately as possible. However, any numerical value by nature contains an error that necessarily arises as a result of the standard deviation found in the corresponding experimental measurements underlying it. In addition, when numerical ranges are given in this application, these ranges include the endpoints of the given ranges (i.e., endpoints can be used). When applying the percentage by weight in this application, numerical values are given relative to the total weight.

In addition, it should be understood that any numerical range given herein is intended to include all of its sub-ranges. For example, it is understood that a range from 1 to 10 includes all subranges between (and including) a reduced minimum value of 1 and a reduced maximum value of 10, that is, includes a minimum value of 1 or greater than 1 and a maximum value of 10 or less than 10. The term alone and the singular nouns used in this application are meant to include at least one or one or more, unless otherwise indicated.

Any patent, publication or other described material, in whole or in part, which, as indicated, is incorporated into this application by reference, is included in this document only to the extent that the material included does not contradict existing definitions, claims or other disclosing the invention the material described in this application. Essentially and to the extent necessary, the description clearly set forth in this application replaces any contradictory material incorporated herein by reference. Any material or part thereof which, as indicated, is incorporated herein by reference, but which is contrary to existing definitions, statements or other material disclosing the essence of the invention described in this document will be included only to the extent that does not cause a conflict between the specified Included material and existing material disclosing the essence of the invention.

Although the present invention has been shown and described in detail with reference to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and detail are possible without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims (10)

1. A method of producing one or more alcohols, including saccharification of cellulosic or lignocellulosic material to obtain a sugar composition of saccharified biomass containing glucose and xylose; selective glucose fermentation to obtain a fermented sugar composition containing essentially xylose, wherein the xylose concentration in the fermented sugar composition is increased compared to the xylose concentration in the saccharified biomass sugar composition; obtaining one or more acids from a fermented sugar composition; converting said one or more acids into one or more esters and hydrogenating one or more esters using a catalyst and hydrogen to produce said one or more alcohols. 2. The method according to claim 1, characterized in that said one or more acids comprise an butyric acid or acetic acid. 3. The method according to claim 1 or 2, characterized in that the saccharification of cellulosic or lignocellulosic material is carried out using one or more enzymes, one or more acids, or combinations thereof. 4. The method according to any one of claims 1 to 3, further comprising processing the cellulosic or lignocellulosic material by irradiation with an electron beam. 5. The method according to claim 4, characterized in that the radiation dose is from 10 to 200 Mrad. 6. The method according to any one of claims 1 to 5, characterized in that the catalyst comprises a metal selected from the group consisting of Pt, Pd, Os, Re, Ru, Rb, Ni, Co, Mo, W, Zn, Cr, Cu, oxides of the listed metals and their combinations. 7. The method according to claim 6, characterized in that hydrogen is used under pressure from 5 to 120 atm. 8. The method according to any one of claims 1 to 7, further comprising isolating at least one of the acids before converting said one or more acids into one or more esters. 9. The method according to any one of claims 1 to 8, characterized in that the ester is selected from the group consisting of ethyl butyrate, butyl butyrate, hexyl butyrate and octyl butyrate. 10. The method according to any one of claims 1 to 9, characterized in that the acid and alcohol are reacted to form an ester.