UA111463C2 - Method for sugar production from lignocellulosic biomass - Google Patents

Abstract

Biomass (e.g., plant biomass, animal biomass, and municipal waste biomass) is processed to produce useful products, such as fuels. For example, systems can use feedstock materials, such as cellulosic and/or lignocellulosic materials and/or starchy or sugary materials, to produce ethanol and/or butanol, e.g., by fermentation.

Description

(57) Abstract:

The invention relates to a method of obtaining sugars from lignocellulosic biomass material, in which the biomass is irradiated with an electron beam, the radicals formed in the process of irradiation are quenched by contacting the biomass with gas, and the saccharification of the quenched biomass raw material is carried out using a microorganism.

Description

This invention relates to biomass processing, namely methods and systems for biomass processing.

Technical level

Various carbohydrates, such as cellulosic and lignocellulosic materials, for example in fibrous form, are produced, processed and used in large quantities in a multitude of applications. Often, such materials are used once and then thrown away as waste or simply considered waste, such as sewage, cake, wood sawdust and straw.

The essence of the invention

Biomass can be processed to change its structure at one or more levels.

The processed biomass can then be used, for example, as a source of materials and/or fuel.

Mainly, the invention relates to methods of changing the molecular and/or supramolecular structure of biomass raw materials. As discussed below, in some embodiments, the methods include irradiation and quenching of biomass raw materials. In other embodiments, the methods include irradiation of raw materials, cooling of raw materials and re-irradiation of raw materials.

Carbohydrate-containing materials (eg, biomass materials) or biomass-derived materials, such as starch materials, cellulosic materials, lignocellulosic materials, or biomass materials that are or include significant amounts of low molecular sugar (eg, monosaccharides, disaccharides, or trisaccharides) can be processed. to change their structure, and products can be made from structurally changed materials. For example, many of the methods described herein provide cellulosic and/or lignocellulosic materials that have a lower molecular weight and/or crystallinity relative to the natural material. Many of the methods provide materials that can be more easily utilized by various microorganisms to produce useful products such as hydrogen, alcohols (e.g. ethanol or butanol), organic acids (e.g. acetic acid), hydrocarbons, co-products (e.g. proteins) or any mixtures thereof. Many of the resulting products, such as ethanol or n-

Butanol can be used as a fuel to power cars, trucks, tractors, ships or trains, for example as a fuel for internal combustion engines or as a raw material for a fuel cell. Many of the resulting products can also be used to power aircraft such as jet-powered aircraft or helicopters. In addition, the products described in this description can be used to generate electrical energy, for example, in conventional steam generator installations or in thermal installations.

In one aspect, the invention relates to methods that include quenching a biomass feedstock that is irradiated to ionize the biomass feedstock such that the feedstock has a first level of radicals detectable by an electron spin resonance spectrometer such that the radicals are at a second level. lower than the first level.

In another aspect, the invention relates to methods comprising irradiating the biomass feedstock to ionize the biomass feedstock such that the feedstock has a first level of radicals detectable by an electron spin resonance spectrometer, and quenching the irradiated biomass feedstock such that the radicals in the quenched biomass feedstock were on the second level, lower than the first level."

Some methods additionally include the processing of irradiated and quenched biomass raw materials to obtain a product.

Some embodiments include one or more of the following features.

Quenching may include quenching the radicals to a level that is no longer detectable with an electron spin resonance spectrometer, eg, less than about 1077 spins. Quenching may include applying pressure to the biomass, such as a pressure greater than about 1000 psi. in. (6.89 MPa). Pressure can be applied in conjunction with the application of heat. Quenching may include contacting the biomass with a gas capable of reacting with radicals, such as contacting the biomass with a fluid capable of penetrating the biomass and reacting with radicals. Quenching may also, or alternatively, involve contacting the biomass with an antioxidant. In some cases, the biomass feedstock includes an antioxidant dispersed therein, and quenching includes contacting the antioxidant dispersed in the biomass feedstock with radicals.

In another aspect, the invention relates to a method that includes irradiating biomass raw materials, as obtained by reducing one or more sizes of individual parts of biomass raw materials, using a device containing an accelerator adapted to accelerate particles such as electrons or ions, where the device is capable of processing more than 1000 tons of biomass material per year, for example more than 10,000, 25,000, 50,000, 100,000 or even more than 1,000,000 tons of biomass per year.

In a further aspect, the invention relates to the irradiation of biomass raw materials, for example, with ionizing radiation of electrons or ions, to change the molecular and/or supramolecular structure of the biomass raw materials, cooling the biomass raw materials and then re-irradiating the biomass raw materials. The two radiations applied may be the same or different, for example they may be of the same type, such as electrons in the same level.

The invention also relates to products obtained by such methods and systems for implementing the methods.

Some embodiments of such methods include one or more of the following features.

The biomass feedstock can be cooled to such an extent that after cooling the biomass has a temperature below its initial temperature before irradiation. Cooling the biomass can include contacting the biomass with a fluid medium at a temperature below the initial temperature of the biomass or below the temperature of the biomass after irradiation.

Each irradiation of biomass raw materials can be carried out according to the pneumatic transportation of biomass raw materials in a fluid medium. Radiation can be applied as the biomass feedstock falls under the influence of gravity. For example, biomass may be transported on a first belt conveyor at a first height and enter a second belt conveyor at a second level lower than the first level, wherein the rear edge of the first belt conveyor and the front edge of the second belt conveyor form a gap, and exposure to ionizing radiation may be applied to the biomass feedstock in a fixed gap During the irradiation process, the biomass can be transported past the particle gun and through the charged particle beam. Can biomass feedstock have a bulk density of approximately less than 0.25 g/cm? in the area below and/or above the beam.

In another aspect, the invention relates to methods of changing the molecular structure and/or supramolecular structure of a starchy material or a low molecular weight sugar, such as

From sucrose, in raw biomass, containing at least approximately 10 wt. 95 low molecular sugar. The methods include processing the processed biomass feedstock to obtain a product, and the processed biomass feedstock is obtained by pretreatment of the biomass feedstock using a pretreatment method that changes the molecular structure and/or supramolecular structure of a part of the starch material or low molecular weight sugar selected from radiation exposure, sonication, pyrolysis and oxidation.

In another aspect, the invention relates to methods of processing biomass raw materials, including starch material, to change the molecular structure and/or supramolecular structure of the starch material by at least one method selected from the group consisting of radiation exposure, ultrasound treatment, pyrolysis and oxidation.

Any of the above aspects of the invention in some embodiments may include one or more of the following features.

The method, in addition, may include processing the biomass raw material by one or more other pretreatment methods, where the other pretreatment methods are selected from sonication, pyrolysis, and oxidation.

Radiation exposure can be in the form of an electron beam, which can be used, for example, in a total dosage of about 10 Mrad to about 50 Mrad. Radiation exposure can be ionizing radiation.

Processing may include the manufacture of combustible fuel. In some cases, processing includes converting the irradiated material using a microorganism capable of converting at least about 1 wt. 95 biomass into fuel.

In some embodiments, the processing includes fermentation of the feedstock, either aerobically or anaerobically, to produce a product such as a fuel, such as ethanol. For example, processing may include contacting the raw material with a microorganism capable of converting at least a portion, such as at least about 1 wt. 95, raw materials into a product.

A microorganism can be a natural microorganism or a microorganism obtained by engineering methods. For example, a microorganism can be a bacterium, such as a cellulolytic bacterium, a fungus, such as yeast, a plant, or a single-celled organism, such as algae, protozoa, or a single-celled organism such as a fungus, such as slime mold. When the organisms are compatible, their mixtures can be used.

The product may include one or more of: hydrogen, organic acids, proteins, hydrocarbons, and alcohols, such as ethanol, n-propanol, isopropanol, n-butanol, and mixtures thereof. Other examples of products that can be obtained by the methods described in this description include mono- and polyfunctional C1-C6-alkyl alcohols, mono- and polyfunctional carboxylic acids, C1-C6- hydrocarbons and combinations thereof. Other examples of alcohols include methanol, ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, and combinations thereof. Carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, palmitic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, oleic acid, linoleic acid, glycolic acid, lactic acid , γ-hydroxybutyric acid and their combinations. Hydrocarbons include methane, ethane, propane, pentane, n-hexane and combinations thereof. Many of these products can be used as fuel.

In addition, the method may include the preparation of biomass raw materials by reducing one or more sizes of individual parts of the biomass raw materials.

In some cases, the biomass feedstock has internal fibers, and the biomass feedstock is crushed to such an extent that its internal fibers are substantially exposed. In some cases, the biomass feedstock may include or may consist of individual fibers and/or particles having a maximum size of approximately no more than 0.5 mm.

Biomass feedstock can be obtained and then pre-treated, or pre-treated and then received. The method of pretreatment can be selected, for example, from radiation exposure, such as radiation exposure with a beam of electrons or ions, treatment with ultrasound, pyrolysis and oxidation. In some embodiments, at least one of the pretreatment methods, such as radiation exposure, is performed on the raw biomass while the raw biomass is under the influence of air, nitrogen, oxygen, helium, or argon. In some embodiments, the pretreatment may include pretreatment of the biomass feedstock with steam explosion.

In some embodiments, the biomass is obtained by reducing one or more sizes of individual parts of the biomass, including crushing, wet or dry grinding, slicing, compression, pressing, or combinations of any of these methods. For example, crushing can be done with a cutting device with a rotating knife. Crushing can result in fibers having an average length to diameter ratio greater than 5/1. In some embodiments, the resulting biomass may have a BET surface area greater than 0.25 me/g.

Biomass can be shredded to such an extent that the internal fibers of the biomass are essentially exposed.

Biomass can be crushed to such an extent that it has a bulk density of approximately less than 0.35 g/cm3.

In some embodiments, two or more pretreatment methods may be applied to the biomass feedstock, such as radiation exposure and sonication, radiation exposure and oxidation, radiation exposure and pyrolysis, sonication and oxidation, sonication and pyrolysis, or oxidation and pyrolysis. Two or more processes can be carried out in any order or at about the same time.

In some embodiments, changing the molecular structure and/or changing the supramolecular structure of the biomass, such as cellulosic or lignocellulosic material or low molecular weight sugar or starch material, may include changing one or more of: average molecular weight, average crystallinity, surface area, degree of polymerization, porosity, branching, graft copolymerization, the size of domains or their number, changes in the type or number of chemical functional groups, and changes in molecular weight according to the formula. For example, a change in molecular structure and/or supramolecular structure may include a decrease in either or both of average molecular weight and average crystallinity, or an increase in either or both of surface area and porosity.

BO In some cases, functionalized biomass (biomass in which the number and/or type of functional groups have been changed) is more soluble and more easily utilized by microorganisms compared to non-functionalized biomass. In addition, many of the functionalized materials described herein are less susceptible to oxidation and may have increased long-term environmental stability.

In some embodiments, the implementation of at least one method of pretreatment can be carried out on biomass in which approximately less than 25 wt. 95% of the biomass is in the swollen state, where the swollen state is characterized as having a volume that is more than 2.5 95 greater than the volume in the non-swollen state. In other embodiments, the biomass is mixed and includes a swelling agent. For example, in any method described herein,

the biomass may be mixed or may include a swelling agent, and the radiation dose to the biomass may be approximately less than 10 Mrad.

The pretreated biomass material may further optionally include a buffer such as sodium bicarbonate or ammonium chloride, an electrolyte such as potassium chloride or sodium chloride, a growth factor such as biotin, and/or a base pair such as uracil, surfactant, mineral or chelating agent.

In some cases, pre-treatment is carried out while the raw biomass is under the influence of air, nitrogen, oxygen, helium or argon. The pretreatment can be carried out under pressure, for example under a pressure greater than about 2.5 atmospheres (0.25 MPa).

The methods disclosed herein may further include oxidation of the biomass prior to pretreatment.

Biomass feedstock can include, for example, paper, paper products, paper waste, wood, pressed wood, wood sawdust, agricultural waste, sewage, silage, grasses, rice husk, cake, cotton, jute, hemp, flax, bamboo, sisal, abaca, straw, corncob cores, corn straw, millet, alfalfa, hay, coconut fiber, synthetic cellulose, sea grass, algae and their mixtures. In some cases, biomass may include synthetic material.

In some cases, the biomass may include a carbohydrate that includes one or more DV-1,4 linkages and has a number average molecular weight of about 3,000 to about 50,000.

In some embodiments, the biomass material includes a starch, such as corn starch, wheat starch, potato starch, or rice starch, a starch derivative, or a material that includes starch, such as a food product or crop. For example, the starch material may be arachis, buckwheat, banana, barley, cassava, kudzu, sorrel, sago, sorghum, common house potato, sweet potato, taro, yam, or one or more legumes such as horse beans, lentils, or peas.

In other embodiments, the biomass material is or includes a low molecular weight sugar. For example, biomass materials may include at least about 0.5 wt. 95 low molecular sugar, for example at least about 2, 3, 4, 5, 6, 7, 8, 9,

Co) 10, 12.5, 25, 35, 50, 60, 70, 80, 90 wt, 95 or even at least about 95 wt. 95 low molecular sugar. In some cases, the biomass consists essentially of low molecular weight sugar, for example more than 95 wt. 95, for example 96, 97, 98, 99 wt. 95 or essentially 100 wt. 95 low molecular sugar. Biomass materials that include low molecular weight sugars can be agricultural or food products, such as sugar cane and sugar beet or their extract, such as sugar cane or sugar beet juice. Specific examples of low molecular sugars include cellobiose, lactose, sucrose, glucose and xylose, as well as their derivatives. Processing of low molecular weight sugars by any of the methods described in this description can make the final products more soluble and/or more easily utilized by microorganisms.

In one aspect, the method of converting the intermediate material into a product includes treating the irradiated intermediate product with a microorganism, where the intermediate material is obtained by irradiating the starch material and treating the starch material with an enzyme.

In another aspect, the method of converting the intermediate into a product includes obtaining the intermediate by irradiating the starch material and treating the starch material with an enzyme, and treating the irradiated intermediate with a microorganism.

Another aspect includes a product obtained by one of the above methods.

In one aspect, a biomass feedstock processing system includes an irradiation device adapted to ionize the biomass feedstock such that the feedstock has a first level of radicals detectable by an electron spin resonance spectrometer; and a quencher adapted to quench the ionized biomass feedstock to such an extent that the radicals are at a second level lower than the first level.

In another aspect, the system for processing biomass raw materials includes one or more irradiation devices adapted to irradiate the biomass raw materials with at least two different doses of radiation exposure; and a cooling device adapted to cool the biomass feedstock between doses of radiation exposure.

In some embodiments, the system also includes a biomass feedstock positioned to be ionized by the irradiation device(s).

In any of the methods or systems disclosed in this description, it is possible to apply radiation exposure from a device that is in storage.

The term "fibrous material" as used herein is a material that includes a plurality of loose, discrete and separable fibers. For example, the fibrous material can be obtained from a source of fibers, which is bleached kraft paper, by crushing, for example, using a cutting device with a rotating knife.

The term "sieve", as used herein, means an element capable of sieving material according to size. Examples of sieves include a plate, a cylinder with holes or the like, or a wire sieve or cloth.

The term "pyrolysis", as used in this description, means the destruction of bonds in the material using thermal energy. Pyrolysis can occur when the material in question is in a vacuum or immersed in a gaseous substance such as an oxidizing gas such as air or oxygen or a reducing gas such as hydrogen.

The oxygen content is determined using elemental analysis by pyrolysis of the sample in a furnace operating at 1300 "C or higher.

The term "biomass" refers to any non-fossilized, i.e. renewable, organic material. Different types of biomass include plant biomass (defined below), microbial biomass, animal biomass (any livestock by-product, livestock waste, etc.) and municipal waste biomass (domestic waste and light industrial waste with recyclable materials such as such as discarded metal and glass).

The terms "plant biomass" and "lignocellulosic biomass" refer to virtually any organic material derived from plants (woody or non-woody). Plant biomass may include, but is not limited to, agricultural or food crops (such as sugar cane, sugar beet or corn kernels) or their extract (such as sugar cane and corn starch), agricultural waste and residues such as corn straw, wheat straw, rice straw, sugarcane bagasse, etc. In addition, plant biomass includes, but is not limited to, trees, tree energy crops, wood waste and residues such as softwood chips, bark waste, wood sawdust, waste streams of the paper and pulp industry, wood fiber, etc. In addition, as another source of plant biomass, it is potentially possible to grow fodder grass, such as millet, etc., on a large scale. For urban

Of the areas, the best potential plant biomass feedstocks include horticultural wastes (eg grass clippings, leaves, tree trimmings and windrows) and vegetable processing wastes. "Lignocellulosic feedstock" is any type of plant biomass, such as, but not limited to, non-woody plant biomass, crops such as, but not limited to, grasses, such as, but not limited to, C4 grasses such such as millet, spartina, ryegrass, miscanthus, tricot or combinations thereof, or residues from sugar processing such as cake or beet pulp, agricultural residues such as soybean straw, corn straw, rice straw, rice husk, barley straw, corn cob core, wheat straw, canola straw, oat straw, oat hulls, corn fiber, recycled wood pulp fiber, wood sawdust, hardwood such as aspen wood and sawdust, softwood, or combinations thereof. In addition, lignocellulosic feedstock may include waste cellulosic materials such as, but not limited to, newsprint, cardboard, wood sawdust, and the like.

The lignocellulosic feedstock may include a single type of fiber or, alternatively, the lignocellulosic feedstock may include a mixture of fibers derived from different lignocellulosic feedstocks. Moreover, the lignocellulosic feedstock may contain fresh lignocellulosic feedstock, partially dried lignocellulosic feedstock, fully dried lignocellulosic feedstock, or a combination thereof."

For the purposes of this invention, carbohydrates are materials that consist entirely of one or more saccharide elements or that include one or more saccharide elements. The saccharide elements can be functionalized in the ring region with one or more functional groups, such as carboxylic acid groups, amino groups, nitro groups, nitroso groups, or nitrile groups, and still be considered carbohydrates.

Carbohydrates can be polymeric (e.g., equal to or greater than 10-mer, 100-mer, 1000-mer, 10000-mer, or 100000-mer), oligomeric (e.g., equal to 4-mer, 5-mer, b-mer, 7 -mer, 8-mer, 9-mer or 10-mer or exceeding them), makeup, dimeric or monomeric. When carbohydrates are made of more than one repeating element, all the elements can be the same or different.

Examples of polymeric carbohydrates include cellulose, xylan, pectin, and starch, while examples of dimeric carbohydrates include cellobiose and lactose. Examples of monomeric carbohydrates include glucose and xylose.

Carbohydrates can be part of a supramolecular structure, for example, covalently attached to the structure. Examples of such materials include lignocellulosic materials, such as materials found in wood.

A starch material is a material that is starch or a starch derivative or includes significant amounts of starch or a starch derivative, such as about more than 5 wt. 95 starch or derived starch. For the purposes of this invention, starch is a material that includes amylose, amylopectin or their physical and/or chemical mixture, for example a mixture of amylose and pectin, which is 20:80 or 30:70 by weight. 95. For example, rice, corn and their mixtures are starchy materials. Starch derivatives include, for example, Malto dextrin, acid-modified starch, basic-modified starch, bleached starch, oxidized starch, acetylated starch, acetylated and oxidized starch, phosphate-modified starch, genetically modified starch, and starch that is resistant to cleavage.

For the purposes of this invention, a low molecular weight sugar is a carbohydrate or a derivative thereof having a formula molecular weight (excluding moisture) of about less than 2,000, such as about less than 1,800, about less than 1,600, about less than 1,000, about less than 500 , about less than 350 or about less than 250.

For example, a low molecular sugar can be a monosaccharide, such as glucose or xylose, a disaccharide, such as cellobiose or sucrose, or a trisaccharide.

Combustible fuel is a material capable of burning in the presence of oxygen. Examples of combustible fuels include ethanol, n-propanol, n-butanol, hydrogen, and mixtures of any two or more of them.

Swelling agents, as used herein, are materials that cause visible swelling, such as an increase in the volume of cellulosic and/or lignocellulosic materials relative to an unswollen state of 2.5 95 when such materials are used in solution , such as an aqueous solution. examples of which include alkaline substances such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxides, acidifying substances such as mineral acids (eg sulfuric acid, hydrochloric acid and phosphoric acid), salts such as zinc chloride, calcium carbonate, carbonate sodium, besyltrimethylammonium sulfate, and basic organic amines such as ethylenediamine. A "crushed material" as used herein is a material that includes individual fibers in which at least about 5,095 individual fibers have a length/diameter (MO) ratio of at least about 5, and which have an uncompressed bulk density of about less than 0.6 g/cm3. Thus, shredded material is different from material that is chopped, chopped, or ground.

Changing the molecular structure of biomass raw materials, as used in this description, means changing the location of chemical bonds, for example, the type and number of functional groups or the conformation of the structure. For example, a change in molecular structure may include a change in the supramolecular structure of the material, oxidation of the material, change in average molecular weight, change in average crystallinity, change in surface area, change in degree of polymerization, change in porosity, change in degree of branching, graft copolymerization with other materials, change in crystal domain size, or resizing the entire domain.

This description includes as a reference the full content of international application Mo PCT/OVZ2007/022719, filed on October 26, 2007. The complete disclosures of each of the following US patent applications are incorporated herein by reference: prior US applications Serial Nos. 61/049391; 61/049394; 61/049395; 61/049404; 61/049405; 61/049406; 61/049407; 61/049413; 61/049415 and 61/049419, all of which were filed on April 30, 2008; US Patent Application Serial Nos. 61/073432; 61/073436; 61/073496; 61/073530; 61/073665 and 61/073674, all of which were filed on June 18, 2008; US Provisional Application Serial No. 61/106861, filed Oct. 20, 2008; US Provisional Application Serial Nos. 61/139324 and 61/139453, both filed Dec. 19, 2008, and US Patent Application Serial No. 12/417707; 12/417720; 12/417840; 12/417699; 12/417731; 12/417900; 12/417880; 12/417723; 12/417786 and 12/417904, all filed Apr. 2009.

Unless otherwise defined, all technical and scientific terms used in this description have the same meaning as is commonly understood by those skilled in the art to which the present invention belongs. Although methods and materials similar to or equivalent to the methods or materials may be used in practice or testing of this invention,

described herein, suitable methods and materials are described below. All publications, applications, patent applications, patents and other references cited or attached to this description are incorporated by reference in their entirety. In case of contradiction, you need to be guided by this description. In addition, the materials, methods and examples are illustrative only and are not intended to be limiting. Other features and advantages of the invention will become apparent from the detailed description and claims presented below.

Description of drawings

In fig. 1 presents a block diagram illustrating the conversion of biomass into products and by-products.

In fig. 2 is a block diagram illustrating the conversion of a fiber source into a first and a second fibrous material.

In fig. A cross-sectional view of a cutting device with a rotating knife is presented.

In fig. 4 is a block diagram illustrating the conversion of a fiber source into a first, second, and third fibrous material.

In fig. 5 is a block diagram illustrating the compaction of the material.

In fig. 6 is a perspective view of a pelletizing press.

In fig. 7A shows compacted fibrous material in the form of granules.

In fig. 7B shows a cross-section of hollow granules in which the center of the cavity is on the same line as the center of the granule.

In fig. 7C shows a cross-section of a hollow pellet in which the center of the cavity is offset relative to the center of the pellet.

In fig. 70 shows a cross-section of a three-lobed pellet.

In fig. 8 is a block diagram illustrating the sequence of processing for the processing of raw materials.

In fig. 9 shows a cross-sectional perspective view of a gamma emitter located in a concrete storage.

In fig. 10 presents an enlarged perspective view of the EC area from fig. 9.

In fig. 11 is a block diagram illustrating the preprocessing sequence

From raw materials by irradiation with a beam of electrons.

In fig. 11A shows the schematic preparation of ionized biomass and then oxidized or quenched.

In fig. 118 is a schematic side view of a system for irradiating material with a low bulk density, and in FIG. 11C is a cross-sectional view of the system taken along 110-116.

In fig. 110 shows a schematic cross-sectional view of a system with a fluidized bed for irradiation of material with a low bulk density.

In fig. 11 shows a schematic side view of another system for irradiating material with a low bulk density.

In fig. 12 presents a schematic view of the system for ultrasound treatment of the technological flow of cellulosic material in a liquid medium.

In fig. 13 is a schematic view of an ultrasonic treatment device having two transducers attached to a single horn.

In fig. 14 presents a block diagram illustrating a system for pyrolytic pretreatment of raw materials.

In fig. 15 shows a side cross-sectional view of the pyrolysis chamber.

In fig. 16 is a side cross-sectional view of the pyrolysis chamber.

In fig. 17 is a cross-sectional side view of a pyrolyzer that includes a heated hair.

In fig. 18 shows a schematic cross-sectional view of the side of the pyrolyzer along the Curie point.

Fig. 19 shows a schematic view of the cross-section from the side of the furnace pyrolyzer.

In fig. 20 shows a schematic cross-sectional top view of a laser device for pyrolysis.

In fig. 21 shows a schematic cross-sectional top view of a device for instant pyrolysis with a tungsten hair.

In fig. 22 is a block diagram illustrating a system for oxidative pretreatment of raw materials.

In fig. 23 is a block diagram illustrating a general view of the process of converting a fiber source into a product, such as ethanol.

In fig. 24 shows a cross-sectional view of a steam explosion device.

In fig. 25 shows a schematic cross-sectional view of a hybrid device for electron beam/ultrasound treatment.

In fig. 26 presents a block diagram illustrating the process of dry grinding of corn kernels.

In fig. 27 presents a block diagram illustrating the process of wet grinding of corn kernels.

In fig. 28 is a scanning electron microscope image of fibrous material obtained from laminated paper at 25X magnification. The fibrous material was obtained on a rotary knife cutter using a screen with 1/8 inch (0.32 cm) openings.

In fig. 29 shows a scanning electron microscope image of a fibrous material obtained from bleached kraft paperboard at a magnification of 25X. The fibrous material was obtained on a rotary knife cutter using a screen with 1/8 inch (0.32 cm) openings.

In fig. 30 presents a picture obtained with the help of a scanning electron microscope, a fibrous material obtained from bleached kraft cardboard, at a magnification of 25X. The fibrous material was crushed twice on a rotary knife cutter using a screen with 1/16 inch (0.16 cm) openings for each crushing.

In fig. 31 shows a scanning electron microscope image of a fibrous material obtained from bleached kraft paperboard at 25X magnification. The fibrous material was crushed three times on a cutting device with a rotating knife. A 1/8 inch (0.32 cm) sieve was used during the first crushing; a 1/16 inch (0.16 cm) sieve was used for the second crushing, and a 1/32 inch (0.08 cm) sieve was used for the third crushing.

In fig. 32 is a schematic side view of the ultrasonic treatment device, and FIG. 33 is a cross-sectional view of the processing cell of FIG. 32.

Zo In fig. 34 is a scanning electron microscope image of fibrous material obtained by crushing millet on a rotary knife cutter at 1000X magnification and then passing the crushed material through a 1/32 inch (0.08 cm) screen.

In fig. 35 and 36 present images obtained with the help of a scanning electron microscope, the fibrous material from fig. 34 after exposure to gamma rays at a dose of 10

Mrad and 100 Mrad, respectively, at a magnification of 1000X.

In fig. 37 presents pictures obtained with the help of a scanning electron microscope, the fibrous material from fig. 34 after irradiation with a dose of 10 Mrad and treatment with ultrasound, at a magnification of 1000X.

In fig. 38 presents pictures obtained with the help of a scanning electron microscope, the fibrous material from fig. 34 after irradiation with a dose of 100 Mrad and treatment with ultrasound, at a magnification of 1000X.

In fig. 39 presents the infrared spectrum of kraft cardboard cut on a cutting device with a rotating knife.

In fig. 40 presents the infrared spectrum of the kraft paper from fig. 39 after exposure to gamma radiation at a dose of 100 Mrad.

In fig. 41 presents a schematic view of the biomass conversion process,

In fig. 42 presents a schematic view of another biomass conversion process.

Detailed description

The present invention describes systems and methods in which various biomass materials can be used, such as cellulosic materials, lignocellulosic materials, starch materials, or materials that are or include low molecular weight sugars, such as feedstock materials. Such materials are often readily available, but are difficult to process, for example by fermentation, or may give insufficient yields at low rates. In some cases, the difficulty of processing is a consequence, at least in part, of the inflexibility of the raw material.

The present invention describes processing steps that can reduce this reluctance and thereby facilitate the conversion of the biomass feedstock into the desired product.

In the methods described in the present invention, the raw materials are first physically prepared for processing, often by reducing the size of the raw materials. 60 The physically prepared feedstock can then be pretreated or processed using one or more of: radiation exposure (which in some cases can occur under controlled temperature conditions), sonication, oxidation, pyrolysis, and steam explosion. Different systems and pretreatment methods can use combinations of two, three or even four of these technologies. This description describes other technologies that can be used to enhance processing of raw materials, such as cooling raw materials between irradiation stages and quenching biomass raw materials after irradiation.

Also described in this invention are functionalized materials having the desired types and amounts of functional groups, such as carboxylic acid groups, enol groups, aldehyde groups, ketone groups, nitrile groups, nitro groups, or nitroso groups, which can be obtained using the methods described in this invention . Such functionalized materials can be, for example, more soluble, more easily utilized by different microorganisms, or they can be more stable over a long time, for example, less prone to oxidation.

In some cases, raw materials may include low molecular weight sugars or starchy materials, as discussed in detail herein.

TYPES OF BIOMASS

In general, any biomass material that is or includes carbohydrates consisting entirely of one or more saccharide elements or includes one or more saccharide elements can be processed by any of the methods described herein. For example, the biomass material may be cellulosic or lignocellulosic materials, starchy materials such as corn kernels, rice kernels, or other feedstuffs, or materials that are or include one or more low molecular weight sugars such as sucrose or cellobiose.

For example, such materials may include paper, paper products, wood, related wood materials, pressed wood, grasses, rice husks, cake, cotton, jute, hemp, flax, bamboo, sisal, abaca, straw, corncob cores, coconut fibers, algae, sea grass, synthetic cellulose or any mixture thereof. Suitable materials include the materials listed in the Summary of the Invention section above.

Zo Fiber sources include cellulosic fiber sources, including paper and paper products (eg, laminated paper and kraft paper), and lignocellulosic fiber sources, including wood and wood-related materials, such as pressed wood. Other suitable fiber sources include natural fiber sources such as grasses, rice husks, rice husks, jute, hemp, flax, bamboo, sisal, abaca, straw, corncob cores, coconut fibers; fiber sources with a high α-cellulose content, such as cotton; and synthetic fiber sources such as extruded yarn (oriented yarn or non-oriented yarn). Natural or synthetic sources of fibers can be obtained from scraps of primary textile materials, such as scraps, or they can be used waste, such as rags. When paper products are used as fiber sources, they may be natural materials, such as scraps of virgin materials, or they may be used waste. In addition to primary raw materials, used product waste, industrial (for example, by-products) waste and processing waste (for example, waste water from paper processing) can also be used as sources of fibers. Also, the source of the fibers can be obtained or formed from human waste (eg sewage), animals or plants. Additional sources of fibers are described in US Patent Nos. 6,448,307, 6,258,876, 6,207,729, 5,973,035, and 5,952,105.

Microbial biomass includes biomass that is derived from unicellular organisms (and/or multicellular organisms, naturally occurring or genetically modified, such as organisms from the ocean, lakes, bodies of water, such as salt water or fresh water, or terrestrial organisms, and contains a source carbon (e.g., cellulose).Microbial biomass may include, but is not limited to, e.g., unicellular organisms (e.g., animals (e.g., protozoa such as flagellates, amoebae, ciliates, and spores) and plants (e.g., algae such as alveolobionts , chlorarachniophytes, cryptomonads, euglenids, glaucophytes, haplophytes, red algae, straminopyles, and green algae)), sea grass, plankton (e.g., macroplankton, mesoplankton, microplankton, nanoplankton, picoplankton, and femtoplankton), phytoplankton, bacteria (e.g., gram-positive bacteria, gram-negative bacteria and extremophiles), yeasts and/or their mixtures. In some cases, microbial biomass can be obtained from natural sources, such as the ocean, lakes, bodies of water, such as salt water or fresh water, or from sources on land. Alternatively or additionally, microbial biomass can be obtained from culture systems, such as large-scale dry and wet culture systems.

Animal biomass includes any organic waste material, such as material derived from animal waste or excrement, or material derived from human waste or excrement (eg compost and sewage).

In some embodiments, the carbohydrate is or includes a material that has one or more (8-1,4-linkages) and has a number average molecular weight of about 3,000-50,000.

Such a carbohydrate is or includes cellulose (I), which is formed from B-glucose 1 by condensation of DV-(1--4)-glycosidic bonds. This bond is the opposite of a-(1--4)-glycosidic bonds present in starch and other carbohydrates.

BUT", nat he

WEDNESDAY / DAY is about but ra sia cha ich o o o government

AND

Starch materials

Starch materials include starch itself, such as corn starch, wheat starch, potato starch or rice starch, a starch derivative, or a material that includes starch, such as a food or crop. For example, the starch material may be arachis, buckwheat, banana, barley, cassava, kudzu, sorrel, sago, sorghum, common house potato, sweet potato, taro, yam, or one or more legumes such as horse beans, lentils, or peas. A starchy material is also a mixture of two or more starchy materials. Sources of starch include, for example, wheat, barley, corn and potatoes. In specific embodiments, the starch material is derived from corn. Various corn starches and their derivatives are described in "bot etagsn", Sogp Veijipeg5 Avzosiayop (11th edition, 2006), which is attached to this description in the form of appendix A.

Starch (for example, SAEZH 9005-25-8 and the chemical formula (SeH':oOb5)p) usually contains a mixture of amylose and amylopectin (usually in a ratio of 20:80 or 30:70) and usually exists in

In the form of a homopolymer of repeating elements of anhydroglucose with an α-glycosidic position of glucose on the adjacent starch element through hemiacetal bonds. Starch molecules formed mainly by 1,4-linkages are called amylose, and the 1,6-linkages serve as branching points in branched starch molecules called amylopectin.

Granular structure

Table 1

Granule size of different starches (μm) (SoshPeg counter (Corn with high amylose content | 422 777777111111111111981СсС21С oManiiyukai////77777771111111111111111Ї11111111111182811111117111111111141111

Table 1

The granule size of different starches and the granule size range are also .

Starch type d No. of grains Average size (μm) (μm) (SoshPeg counter

Arrowroot

Sago 15-50

Potatoes 10-70

Canna (Australian arrowroot) 22-85

Plants store starch in specialized organelles called amyloplasts, where it is deposited to form granules. These granules consist of newly synthesized starch layered around the core of the hilum and vary in diameter from 2 to 130 micrometers.

The size and shape of the granule is characteristic of the origin of the plant and serves as a way of identifying the source of a particular starch (Table 1). The structure of a grain granule is crystalline, where the starch molecules are oriented to form radially oriented crystals, giving rise to the phenomenon of birefringence. When a beam of polarized light is directed through a starch granule, the granule is divided by dark lines into four wedge-shaped sectors. This cross-hatching or crossing is characteristic of spherocrystalline structures. About amylose:

N He and not not NECK, Жы pdv --ey, in у Зв жан on KT hai d) Ha and he acha ey i

Figure 2. Representative partial structure of amylose

Amylose molecules consist of separate, mostly undissolved chains of 500-20,000 α-(1,4)-0-glucose units, depending on the source. a(1,4) bonds ensure the formation of a spiral structure. The structural formula of amylose is shown in figure 2, where the number of repeating glucose subunits (n) can be many thousands (usually in the range from 300 to 3000). Amylose starch is more difficult to break down than amylopectin; however, it takes up less space so that it is preferred for storage in plants, Amylose is about 3095 of the stored starch in plants. The digestive enzyme amylase acts on the ends of the starch molecule, breaking it down into sugars.

Amylose molecules participate in the formation of the gel, since the linear chains can be oriented parallel to each other, shifting close enough to each other to form a bond. Perhaps due to the ease with which the amylose molecules move relative to each other in the paste, they do not make a significant contribution to viscosity.

From Amylopectin same. and a Kk nn, GAS

In Hn: y MN Che WHOSE chai ino bnoSh M: che sha she uch na I NN! Sune ; "re HM, what; and . in Zh in ZU Kk. I chan uk ni n

EI day

Figure 3. Representative partial structure of amylopectin

Amylopectin is formed by non-random a-(1,6)-branching of a-(1,4)-0-glucose structure of the amylose type. As can be seen in Figure 3, glucose elements are connected linearly by α-(1,4) bonds. Branching occurs through c(1,6)-bonds, which occur every 24-30 glucose elements, and it is determined with the help of enzymes that split the branched structure. Each amylopectin molecule contains a million or so residues, approximately 5 95 of which form branch points.

Branched amylopectin molecules add viscosity to the paste due to its role in supporting the swollen granule. The side chains and bulky shape of the amylopectin molecules keep them from an orientation close enough to form hydrogen bonds with each other, so they usually do not participate in gel formation.

Source

Plants hydrolyze starch, releasing glucose subunits when energy is needed.

A much larger source of starch is corn (maize), and other commonly used sources are wheat, potatoes, tapioca, and rice.

The relative ratios of amylose and amylopectin and the branching points through the 1,6-bond are determined genetically and are relatively constant for each type of starch. For example, amylo-corn contains more than 50 95 amylase, and "waxy" corn practically does not have it (3 Ob).

Unprocessed starch

Starch obtained by wet grinding corn and then dried is called regular, regular or unmodified corn starch. There are different forms of cornstarch, including finely ground or coarse powders, flakes, grains, or even larger particles. Unmodified starch can be minimally processed by pH correction, mild heat treatment, or the addition of small amounts of chemical reagents or adjuvants before or after drying to optimize parameters. As an example, the enzymatic conversion of starch to sugars can be accelerated by adjusting the starch pH.

Starch is a much more widely used polysaccharide in the human diet. Starch (especially corn starch) is used in the preparation of thickened foods such as sauces. In industry, it is used in the manufacture of glues, paper, fabrics and as a base in the manufacture of confectionery products such as chewing marmalade and jelly beans. Papermaking is the largest non-food application of starch worldwide, using millions of metric tons annually. In an ordinary sheet of copy paper, for example, the starch content can be up to 8 95. Both chemically modified and unmodified starches are used in paper production.

The chemical composition of starch, organic molecules with a high oxygen content, makes starch an excellent product for use as a chemical raw material.

Genetically modified starch

Genetically modified starch, which refers to starch derived from genetically engineered plants, is modified to reduce the need for chemical processing (reducing cost, toxicity or environmentally friendly processes) or to produce new carbohydrates that may not occur naturally in plants harvested in in the form of a crop.

Modification in this sense refers to genetic engineering of plant DNA, but not further processing or processing of starch or starch granules.

Genetically modified starch is of particular interest in the production of biodegradable polymers and non-cellulosic raw materials in the paper industry, as well as in the creation of new food additives. For example, waxy corn was widely studied in the 1950s due to its desirable properties. Waxy corn starch, which is essentially 100 95 amylopectin, yields a paste that is practically clear on cooling, does not set, and when dried in thin films yields a translucent, soluble coating that is often used to thicken a wide variety of prepared foods. food products. Genetic modification of this starch to test for amylose and increase its content could potentially lead to an excellent film-forming material and could be spun into fiber. Research in this field has led to the commercial development of two corn hybrids, one containing approximately 55 95 and the other containing approximately 70 95 amylose, and recently research has produced a starch with 80 95 amylose.

Modified starch

Modified starch is a food additive obtained by processing starch or starch granules, which leads to partial degradation of starch. Modified starch is used as a thickener, stabilizer or emulsifier. In addition to food products, modified starch is also found in pharmaceuticals. Starches are modified for a number of reasons, including to increase their resistance to excessive heat, acids, and freezing, to change their texture, or to lengthen or shorten gelatinization time.

Acid-modified starch

Acid treated starch, which is usually simply called "modified starch", is obtained by treating starch or starch granules with inorganic acids.

The main reaction that occurs during acid treatment is the hydrolysis of glycosidic bonds in starch molecules. Acid modification reduces the length of the starch chain, but essentially does not change the configuration of the molecule. In this method, the starch-water suspension is shaken, subjected to mild treatment with diluted mineral acid at elevated temperatures,

But below the gelatinization temperature of starch. When the desired viscosity is reached, the acid is neutralized with sodium carbonate and the starch is filtered, washed and dried.

Oxidized corn starch

Another way to reduce viscosity is oxidation. Despite the fact that such oxidizing agents as chlorine, hydrogen peroxide, and potassium permanganate can be used, oxidized starches obtained by the method of wet grinding are almost always produced using sodium hypochlorite as an oxidizing agent. Aqueous suspensions of starch when shaken are treated with dilute sodium hypochlorite containing a small excess of sodium hydroxide (MZ0O11) and heated to 120" (49°C). When the desired viscosity is reached, the oxidized starch suspension is treated with a reducing agent such as sodium bisulfite to remove excess hypochlorite, pH is adjusted and starch is filtered, washed and, finally, dried.

Treatment of starch with an oxidizing agent randomly converts hydroxyl groups into carboxyl or carbonyl groups, which leads to the cleavage of the adjacent glycosidic bond. Oxidized starches are used in unleavened dough and in breading, as they stick to meat quite well.

Dextrins

Dextrins are a group of low molecular weight carbohydrates obtained by dry heating or burning unmodified starch with or without an acid or alkaline catalyst. In other methods of dextrinization, a fluidized bed is used, where unmodified starch is placed in a reactor and suspended or "fluidized" in a stream of heated air. Then the starch is acidified and heated to obtain the required final product. In the process of dextrinization, the granule is not destroyed, but the integrity of the granule is violated. When dextrins are suspended in water and heated, the granules swell and separate into layers, which are eventually released and dispersed. Dextrins are mixtures of linear α-(1,4)-linked polymers of O-glucose starting with an α-(1,6) bond. Industrial products are usually produced by acid hydrolysis of potato starch.

Dextrins are water-soluble solids from white to light yellow that are optically active. During analysis, dextrins can be detected with iodine solution, which gives a red color.

There are three main types of dextrins: white, yellow and British gum. White dextrins are white in color and have reduced viscosity and solubility in cold water in the range from 5 to more than 90 95. White dextrins are used to make very soft gels. Yellow dextrins (made with less acid, higher temperatures, and longer) are yellow in color and have higher water solubility. Yellow dextrins are used to make pastes with a high content of solid particles, which are very sticky and, when applied in the form of thin films, dry quickly. Finally, British gums are obtained by adding a small amount of acid to very dry starch, or without adding it, and then firing it at a gradually increasing temperature. gels to viscous liquids.

Cyclodextrins

Cyclodextrins are non-reducing cyclic oligosaccharides of glucose, which are formed during the degradation of starch catalyzed by cyclomaltodextringlucanotransferase. Three common cyclodextrins have b, 7 or 8 ХО-glucopyranosyl residues (c-, DV- and y-cyclodextrins, respectively), linked by α-1,4-glycosidic bonds (Figure 4). All three cyclodextrins have similar structures (bond lengths and orientations), except for the structural need to accommodate different amounts of glucose residues. They are unlimited cup-shaped molecules (truncated cone), held together by hydrogen bonds between 3-OH and 2-

OH groups around the outer edge. Cyclodextrins are used for encapsulation with the purpose of controlled release of flavors, masking of unpleasant odors and tastes, stabilization of emulsions, increase of foaming capacity and control or masking of color.

Starch derivatives (cross-linked and stabilized) - Starch can be chemically converted into a derivative in the primary and secondary hydroxyl positions, which gives properties different from those found in the original starch. Presumably, this occurs as a result of the destruction of hydrogen bonds. Two types of derivatives are produced commercially: cross-linked/inhibited and stabilized. Cross-linked starches, which are sometimes called inhibited starches, are obtained by the reaction of hydroxyl

From groups on two different molecules in a granule with a bifunctional agent, such reagents as phosphorus oxychloride or sodium trimetaphosphate can be used as cross-linking agents. Very small amounts of these agents can have a pronounced effect on the characteristics of the paste.

Starch can be stabilized against gel formation using multifunctional reagents. These reagents react with the hydroxyl groups on the starch, introducing substituent groups that interfere with the effects of hydrogen bonding, thereby increasing its water miscibility or viscosity, or giving the starch molecule a positive charge. Reagents used to stabilize starch by breaking hydrogen bonds include ethylene oxide to produce hydroxyethyl starch, acetic anhydride to produce starch acetates, succinic anhydride to produce starch succinates, monosodium orthophosphate or sodium tripolyphosphate to produce starch phosphates, and propylene oxide to produce hydroxypropyl starches . Reagents that impart a positive charge to the starch molecule include tertiary or quaternary amines to produce cationic starches.

Pregelatinized starch

Suspensions of many starches and starch derivatives can be gelatinized and dried to produce a wide variety of pregelatinized starches. This is done in a single-drum dryer using application rollers. The starch suspension is heated for its gelatinization, immediately dried and ground to the desired granule parameters. Pre-gelatinized starch is used to thicken instant desserts such as puddings, allowing the food to thicken when cold water or milk is added. Similarly, granules of cheese sauce (such as in macaroni and cheese or lasagna) or granules of gravy can be thickened in boiling water without forming lumps. Commercial pizza toppings containing modified starches thicken when heated in the oven, keeping them on top, and then become runny when cooled.

Bleached starches

Bleaching by very mild oxidation is carried out using sodium hypochlorite, sodium chlorite, hydrogen peroxide, potassium permanganate, peracetic acid or ammonium persulfate with sulfur dioxide. The interaction with the starch molecules should be very small so that there are no changes in the physical properties of the starch or its solution, except for the color. Theoretically, a small amount of aldehyde or carboxyl groups is formed. Only trace amounts of sodium chloride, sodium sulfate, or sodium acetate remain in the final product. The bleached starch is isolated on continuous filters or centrifuges using large amounts of water to remove trace amounts of inorganic salts formed from the bleach, dried and packaged.

Low molecular weight sugars

Biomass materials that include low molecular sugars can include, for example, at least about 0.5 wt. 9; low molecular weight sugar, for example at least approximately 2, 3.4, 5.6, 7, 8, 9, 10, 12.5, 25, 35, 50, 60, 70, 80, 90 wt. 95 or even at least approximately 95 wt. 95 low molecular sugar. In some cases, the biomass essentially consists of low molecular sugar, for example, more than 95 wt. 95, for example, 96, 97, 98, 99 wt. 95 or essentially 100 wt. 95 low molecular sugar.

Biomass materials that include low molecular sugars can be agricultural products or food products, such as sugar cane or sugar beet, or their extract, such as sugar cane juice or sugar beet juice. Biomass materials that include low molecular weight sugars can be essentially pure extracts, such as unrefined or crystallized table sugar (sucrose). Low molecular weight sugars include sugar derivatives. For example, low molecular weight sugars can be oligomeric (eg, equal to or greater than 4-mer, 5-mer, b6-mer, 7-mer, 8-mer, 9-mer, or 10-mer), trimeric, dimeric, or monomeric. When carbohydrates are formed by more than one repeating element, all the repeating elements can be the same or different.

Specific examples of low molecular sugars include cellobiose, lactose, sucrose, glucose and xylose, as well as their derivatives. In some cases, sugar derivatives dissolve more quickly in solution or are utilized by microbes to produce a useful material such as ethanol or butanol. A few of these sugars and sugar derivatives are presented below. t no a he and that schu more - i she i i p i How to be Saint shop r sn you T Gayukosa I KU

N N s: i naya or Shchi i

Eat here

K-MA5 and x gr-monoacid sucrose n 1

Meketogluconate chnodota

IN

"there is mo CHK, rys ЧИ dok х r : H ne How to E and

Sho a dl z. and 7 no and en

IY; ate dk vai y b p i

Y y chen Gaknkurovak as fashionable. wow

I am not acid! i ema KI k b-movochnelota sucrose JHE Ha

Fructose

Z h and sni aa sy still un and ku | H ts 10 Sucrose sugar

Ethanol from low molecular weight sugars

More than half of the world's ethanol production is produced from sugars or sugar by-products, with Brazil clearly the world leader. Currently, there is no commercial ethanol production from sugar cane or sugar beet in the US, where 97.95 percent of ethanol is produced from corn.

Technologically, the method of producing ethanol from sugar is simpler than converting corn into ethanol. Converting corn to ethanol requires additional preparation (wet milling) and the use of enzymes, while converting sugar requires only a yeast fermentation process. The energy requirement for converting sugar into ethanol is about two times less than for corn. However, technology and direct energy costs are only one of several factors that determine the feasibility of ethanol production. Other factors include relative cost of production (including raw materials), conversion rates, proximity to process equipment, alternative prices and government policies, equipment design, and processing costs. Since it has been shown in other countries that the production of ethanol from sugar can be economically feasible and other new raw materials are being searched for, in

Interest in the production of ethanol from sugar has increased in the United States. In response to the growing interest in sugar and ethanol, the OBOA published a research report in July 2006 entitled: "Pe Esopotis

Eeaziriyu oi E(Pooi! Rhodisiip iot 5idag ip She Opiei 5iaiev", which is incorporated herein by reference in its entirety. The report shows that at current market prices for ethanol, converting sugar cane, sugar beet and molasses to ethanol can be profitable (see Table 1).

Table 1

Current market prices for ethanol

I'm waiting and waiting; Gcheme o; ovo grinding) (Syracucrovatrostinoid /-:/ 71151240 | 5 | 092 (Raw sugar beet.////////777777711111111111111115 11235 | 5 | 077

Melyas?i //////77777777111111111111111111111111111111118 117127 | 5 1 036 (Unrefined sugar? 77777111 51 348 | 5 | 036 (Refined sugar? -: 11175 | 397 | 5 | 036 x Per gallon (3.8 L). ""Does not include shipping costs.

Sugar beet

Sugar beets are an annual crop grown in 11 states in a variety of climates, from the hot climates of the Imperial Valley in California to the cooler climates of Montana and North Dakota. Sugar beet by-products include beet pulp, which can be sold for animal feed, and molasses, which can also be sold for animal feed or further processed to extract more sugar.

Zo Sugar beet processing equipment converts raw sugar beet directly into refined sugar in a one-step process While the area under sugar beet cultivation has declined slightly since the 1990s, sugar production has actually increased due to investments in new processing equipment, the introduction of new technologies, improved crop varieties and enhanced technologies for extracting sugar from molasses. Sugar beet is very bulky and relatively expensive to transport, and it must be processed fairly quickly before the sucrose breaks down. Thus, all sugar beet processing enterprises are located in the growing regions.

Cane

Sugarcane is a perennial tropical crop grown in four states: Florida, Hawaii, Louisiana, and Texas. Byproducts of sugar cane processing include molasses and cake, the fibrous material that remains after sugar cane is pressed to make sugar. Cake is often burned as fuel to increase the capacity of sugarcane mills. Sugar cane is first processed into unrefined sugar in mills near the cane fields. Like beets, cane is bulky and relatively expensive to transport, and must be processed as quickly as possible.

to minimize the destruction of sucrose. The raw sugar is then transported to a refinery to produce refined sugar.

Over the last decade, sugar beet has reached a higher share in sugar production

POWER, currently accounting for 58.8 95 of the national production of Sugar, while the share of sugar cane has decreased to 41.2 Ob.

Molasses

The most widely used sugar for ethanol fermentation is cane molasses, which contains approximately 35-40 wt. 95 sucrose, 15-20 wt. 95 invert sugars, such as glucose and fructose, and 28-35 wt. 965 non-sugar solids. Molasses (syrup) is collected as a by-product of cane sugar production. Molasses is diluted to a soft mass containing approximately 1020 wt. 95 sugar. After bringing the pH of the soft mass to approximately 4-5 with the help of mineral acid, yeast is inoculated into it, and fermentation is carried out in aseptic conditions at 20-32 "C for approximately 1-3 days. Then from the fermented wort, which, as a rule, , contains approximately 6-10 wt. 95 ethanol, the product is extracted in the purification department of the plant.

Ethanol production (using a sucrose conversion factor of 141 gallons (533.7 L) per ton) is calculated for sugar cane, sugar beet, and white molasses.

Cane:

Raw sugar extraction rate 12.24 95, plus 41.6 lb (0.0189 tons) of sucrose from molasses - 235.0 pounds (0.1066 tons) of sucrose from raw sugar and 41.6 pounds 1 ton (0.0189 tons ) sucrose from molasses, sugar cane - 276.6 pounds (0.1383 tons) of sucrose, cane - 19.5 gallons (73.8 L) of ethanol, or 0.051 tons of sugar cane per gallon (3.8 L) of ethanol produced.

Sugar beet:

Refined sugar extraction level 15.58 95, plus 40.0 lb (0.0181 tons) beet molasses sucrose 1 ton - 311.6 pounds (0.1411 tons) sugar refined sugar sucrose and 40.0 pounds (0. 0181 tons) of sucrose from beet molasses, beets - 351.6 pounds (0.1758 tons) of sucrose, t 24.8 gallons (94 liters) of ethanol, or 0.040 tons of sugar beet per gallon (3.8 L) of ethanol produced

Molasses: 49.2 95 total sugars as sucrose 1 ton - 984 lb (0.492 tons) sucrose, molasses - 69.4 gallons (262.3 L) ethanol or 28.8 lb (0.0131 kg) molasses per gallon (3 .8 L) of ethanol produced, or 2.45 gallons (9.3 L) of molasses per gallon (3.8 L) of ethanol produced (using the conversion of 1.0 gallon (3.8 L) of molasses - 11.74 pounds per mass (5.3

KG).

Unrefined sugar: 96.0 95 total sugars as sucrose 1 ton - 1,920 lb (0.96 tons) of sucrose, unrefined - 135.4 gallons (512.5 L) of ethanol or 14.77 lb (6.7 kg) of unrefined sugar of sugar per gallon (3.8 L) of ethanol produced.

Refined beet sugar: 100.0 95 total sugars as sucrose 1 ton - 2,000 lb (1.0 ton) sucrose refined - 141.0 gallons (533.7 L) ethanol or 14.18 lb (6.4 kg) refined of sugar sugar per gallon (3.8 L) of ethanol produced.

The results of this study have several important implications for ethanol production from sugarcane crops in the United States. First, with existing fermentation technology, corn is currently the cheapest feedstock available for use in ethanol production in the United States. Second, given current and projected future market prices for sugar and ethanol, it is clear that sugar production is the most appropriate use of sugar cane or sugar beet. Third, the conversion of cellulosic biomass to ethanol provides the potential for the use of a wide variety of different types of raw materials in the production of ethanol.

This description presents systems and methods in which these low-molecular-weight compounds can be used for ethanol production more quickly and more cost-effectively.

Mixtures of any of the biomass materials described herein can be used to produce the products described herein, such as ethanol. For example, mixtures of cellulosic materials and starch materials can be used to make any product described herein.

BIOMASS PROCESSING SYSTEMS

In fig. 1 presents a system for converting biomass 100, in particular biomass with significant amounts of cellulosic and lignocellulosic components and/or starch components, into useful products and by-products. System 100 includes feedstock preparation subsystem 110, pretreatment subsystem 114, primary processing subsystem 118, and further processing subsystem 122. Feedstock preparation subsystem 110 is fed raw biomass and physically prepared for use as feedstock. for further processes (for example, size reduction and homogenization of biomass), and is stored both in raw form and in the form of raw materials. Biomass feedstocks with significant amounts of cellulosic and/or lignocellulosic components or starch components may have a high average molecular weight and crystallinity, which may complicate the processing of the feedstock into useful products (for example, fermentation of the feedstock to produce ethanol). For example, in other systems, acids, bases and enzymes are used for the processing of cellulosic, lignocellulosic or starchy raw materials. As described herein, in some embodiments, such treatment is unnecessary or required only in small or catalytic amounts.

The raw material from the raw material preparation subsystem 110 is fed into the pre-processing subsystem 114 and in it the raw material is prepared for use in the main production processes, for example, by reducing the average molecular weight and crystallinity of the raw material. From the pre-processing subsystem 114, the pre-treated raw materials are fed to the main processing subsystem 118 and useful products (eg, ethanol, other alcohols, pharmaceuticals and/or food) are produced in it. In some cases, the product of the primary processing subsystem 118 is usable directly, but in other cases it requires additional processing performed by the downstream processing subsystem 122. The downstream processing subsystem 122 provides further processing of the product stream from the primary processing system 118 that is required for it (for example, distillation and denaturation of ethanol), as well as processing of waste streams from other subsystems. In some cases, the co-products of subsystems 114, 118, 122 may also be directly or indirectly useful as secondary products and/or to increase the overall efficiency of system 100. For example, downstream processing subsystem 122 may produce treated water for recirculation as process water in other subsystems and/or it can produce combustible waste that can be used as fuel for boilers that generate steam and/or electricity.

The optimal size of a biomass conversion plant is influenced by factors that include economies of scale and the type and availability of biomass used as feedstock. Increasing plant size tends to increase the economies of scale associated with the processes in the plant. However, increasing plant size also tends to increase costs (such as transportation costs) per unit of raw material.

Studies that analyze these factors indicate that acceptable plant size for biomass conversion can range from 1,000 to 10,000 or more dry tons per day, depending, at least in part, on the type of feedstock used. The type of feedstock can also affect storage requirements at the facility, where facilities designed primarily to process feedstocks whose availability varies seasonally (eg, corn straw) require more on-site than off-site storage of the feedstock in compared to installations designed for the processing of raw materials, the availability of which is relatively constant (for example, waste paper),

CALLISTHENICS

In some cases, the processing methods begin with physical preparation of the raw materials, such as reducing the size of the raw materials, for example, by slicing, grinding, crushing, ball milling, contact roller processing, or chopping. In some cases, the material can be reduced to particles using a hammer mill, disc mill, or stone crusher. In some cases, loose raw materials (such as recycled paper, starch materials, or millet) are prepared by crushing or cutting. Sieves and/or magnets can be used to remove very large objects or unwanted objects, such as stones or nails, from the raw material stream.

Systems for the preparation of raw material can be adapted to produce streams of raw materials with specific characteristics, for example, specific maximum dimensions, specific ratios of length to width, or specific ratios of surface areas. As part of the preparation of the raw material, it is possible to adjust the bulk density of the raw material (for example, increase or decrease it).

Size reduction

In some embodiments, the material to be recycled is in the form of a fibrous material that includes fibers obtained by crushing a fiber source. For example, crushing can be done using a cutting device with a rotating knife.

For example, and referring to fig. 2, the fiber source 210 is crushed, for example in a rotary knife cutter, to produce a first fibrous material 212. The first fibrous material 212 is passed through a first screen 214 having an average hole size of 1.59 mm or less (1/16 inch, 0 .0625 inch), to produce a second fibrous material 216. If desired, the fiber source may be ground prior to crushing, such as by means of a shredder. For example, when paper is used as the fiber source, the paper may first be shredded into strips with a width of, for example, 1/4 to 1/2 inch (0.64 to 1.28 cm) using a shredding device, such as a shredder with counter-rotating screws such as the device manufactured. Myp5op (Lisa, M.U.). As an alternative to shredding, the size of the paper can be reduced by cutting it to the desired size using a guillotine cutter. For example, a guillotine cutter can be used to cut paper into sheets that are, for example, 10 inches (25.4 cm) wide and 12 inches (30.5 cm) long.

In some embodiments, crushing the fiber source and passing the resulting first fibrous material through the first sieve are performed simultaneously. Crushing and passing can also be carried out sequentially, for example, in a batch process.

For example, a cutting device with a rotating knife can be used to simultaneously crush the fiber source and screen the first fibrous material. Referring to fig. 3, the rotary knife cutting device 220 includes a hopper 222 into which the chopped fiber source 224 obtained by grinding the fiber source can be placed. Shredded

From the source, the fiber is crushed between stationary blades 230 and rotating blades 232, producing a first fibrous material 240. The first fibrous material 240 is passed through a sieve 242, and the resulting second fibrous material 244 is collected in a basket 250. To facilitate the collection of the second fibrous material, the basket may have pressure below nominal atmospheric pressure, such as at least 10 95 below nominal atmospheric pressure, such as at least 25 95 below nominal atmospheric pressure, at least 50 95 below nominal atmospheric pressure, or at least 75 95 below nominal atmospheric pressure. In some embodiments, a vacuum source 252 is used to maintain basket pressure below nominal atmospheric pressure.

Crushing can be advantageous to "open", "stress" or even reduce the molecular weight of fibrous materials, making the cellulose of the materials more susceptible to chain separation and/or reduced crystallinity. Exposed materials may also be more sensitive to oxidation when exposed to radiation.

The fiber source can be crushed in a dry state, in a hydrated state, for example, with the presence of up to 10 wt. 95 of absorbed water, or in the wet state, for example, with the presence of about 10 95 to about 75 wt. 95 water. The fiber source can be crushed even when partially or fully immersed in a liquid such as water, ethanol, or isopropanol.

The fiber source can also be crushed in a gas (such as a stream or atmosphere of a gas other than air), such as oxygen or nitrogen or steam.

Other methods of obtaining fibrous materials include, for example, mill grinding, mechanical fluffing or tearing, rod mill grinding, ball mill grinding, contact roll processing, or air grinding.

If desired, the fibrous materials can be separated, for example continuously or in batches, into fractions according to their length, width, density, type of material, or some combination of these characteristics.

For example, ferrous metals can be separated from any fibrous material by passing the fibrous material, which includes the ferrous metal, past a magnet, such as an electromagnet, and then passing the resulting fibrous material through a series of sieves, each sieve having holes of a distinct size.

Fibrous materials can also be separated, for example, using a 60 high-velocity gas such as air. In this approach, fibrous materials are separated by removing different fractions, which, if desired, can be subjected to photon characterization. Such a device for separation is considered, for example, in the I page of the AI., in the US patent No. 6883667.

The fibrous materials to be processed may have a low moisture content, for example less than about 7.5, 5, 3, 2.5, 2, 1.5, 1 or 0.5 wt. 95. This material can be irradiated with a beam of particles such as electrons and protons. Irradiation can be carried out directly after the preparation of the material or after a stage of reducing the moisture content, for example, drying at about 105 "C for 4-18 hours, so that the moisture content before use is, for example, about less than 0.5 95.

If desired, the lignin can be removed from fibrous materials that include lignin. Also, to facilitate degradation of materials that include cellulose, the material may be treated prior to irradiation with heat, a chemical reagent (eg, a mineral acid, a base, or a strong oxidizing agent such as sodium hypochlorite), and/or an enzyme.

In some embodiments, the average opening size of the first screen is less than 0.79 mm (1/32 inch, 0.03125 inch), such as less than 0.51 mm (1/50 inch, 0.02000 inch), less than 0.40 mm (1/64 in, 0.015625 in), less than 0.23 mm (0.009 in), less than 0.20 mm (1128 in, 0.0078125 in), less than 0.18 mm (0.007 in), less than 0, 13 mm (0.005 in) or even less than 0.10 mm (1/256 in, 0.00390625 in). The sieve is made by interweaving monofilament, which has the appropriate diameter to obtain the desired hole size. For example, monofilaments can be made of metal such as stainless steel. As the size of the holes decreases, the structural requirements for the monofilament increase. For example, for hole sizes less than 0.40 mm, it may be preferable to fabricate monofilament screens made from a material other than stainless steel, such as titanium, titanium alloys, amorphous metals, nickel, tungsten, rhodium, rhenium, ceramics or glass. In some embodiments, the sieve is made from a plate, such as a metal plate, having holes, for example, cut into the plate using a laser. In some embodiments, the area of the holes in the sieve is less than 52 95, for example less than 41 95, less than 36 95, less than Ж1 95, less than 30 95.

In some embodiments, the second fibrous material is crushed and passed through a first sieve or sieve with a different size. In some embodiments, the second fibrous material is passed through a second sieve having an average mesh size equal to or

From less than the size of the holes of the first sieve.

Referring to Fig. 4, a third fibrous material 220 can be obtained from a second fibrous material 216 by crushing the second fibrous material 216 and passing the resulting material through a second sieve 222 having an average pore size smaller than that of the first sieve 214.

Typically, the fibers of fibrous materials can have a relatively high average length to diameter ratio (eg, greater than 20 to 1), even if they have been subjected to crushing more than once. In addition, the fibers of the fibrous materials described herein may have a relatively narrow length distribution and/or length-to-diameter ratio.

As used herein, the average fiber width (ie, diameter) is determined optically by randomly selecting approximately 5,000 fibers. Average fiber length is length-weighted adjusted lengths. The surface area of VET (Vgypaceg, Ettei and

TeiPeg) is a multipoint surface area, and porosity is a quantity determined by mercury porometry.

The average length-to-diameter ratio of the second fibrous material 14 may, for example, exceed 8/1, 10/1, 15/1, 20/1, 25/1 or even 50/11. The average length of the second fibrous material 14 may be, for example, about 0.5 to 2.5 mm, such as about 0.75 to 1.0 mm, and the average width (ie, diameter) of the second fibrous material 14 may be, for example, from about 5 to 50 µm, for example from about 10 to 30

MKM.

In some embodiments, the standard deviation of the length of the second fibrous material 14 is less than 60 95 from the average length of the second fibrous material 14, such as less than 50 95 from the average length, less than 40 95 from the average length, less than 25 95 from the average length, less than 10 95 from the average length, less than 5 95 of the average length or even less than 1 95 of the average length.

In some embodiments, the VET surface area of the second fibrous material is greater than 0.1 m-/g, such as greater than 0.25 mg/g, greater than 0.5 m-/g, greater than 1.0 mg/g, greater than 1.5 m -/g, exceeds 1.75 m-/g, exceeds 5.0 m-/g, exceeds 10 m-/g, exceeds 25 mg/g, exceeds 35 m-/g, exceeds 50 mg/g, exceeds 60 mg/g, greater than 75 mg/g, greater than 60,100 mg/g, greater than 150 mg/g, greater than 200 mg/g or even greater than 250 mg/g. The porosity of the second fibrous material 14 may, for example, exceed 20 95, exceed 25 95, exceed 35 95, exceed 50 95, exceed 60 95, exceed 70 95, for example exceed 80956, exceed 85905, exceed 9095, exceed 92 95, exceed 94 95 , exceed 95 95, exceed 97.5 95, exceed 99 95, or even exceed 99.5 95.

In some embodiments, the ratio of the average length-to-diameter ratio of the first fibrous material to the average length-to-diameter ratio of the second fibrous material is, for example, less than 1.5, for example, less than 1.4, less than 1.25, less than 1.1, less than 1.075, less than 1.05, less than 1.025, or even essentially equal to 1.

In specific embodiments, the second fibrous material is crushed again, and the resulting fibrous material is passed through a second sieve having an average pore size smaller than that of the first sieve to produce a third fibrous material. In such cases, the ratio of the average length-to-diameter ratio of the second fibrous material to the average length-to-diameter ratio of the third fibrous material may be, for example, less than 1.5, such as less than 1.4, less than 1.25, or even less than 1.1.

In some embodiments, the third fibrous material is passed through a third sieve to produce a fourth fibrous material. The fourth fibrous material can, for example, be passed through the fourth sieve to obtain the fifth material. Similar sieving processes can be repeated as many times as desired to obtain the desired fibrous material having the desired properties.

Consolidation

Any of the methods disclosed herein may process compacted materials, or any material disclosed herein, such as any fibrous material described herein, may be processed by any one or more of the methods disclosed herein, and then compact as disclosed herein.

A material such as a fibrous material having a low bulk density can be compacted into a product having a higher bulk density. For example, a composition of material having a bulk density of 0.05 g/cm can be compacted by isolating the fibrous material in a relatively gas-tight structure, such as a bag made of polyethylene,

From or a bag made of alternating layers of polyethylene and nylon, with subsequent removal from the structure of the gas contained in it, such as air. After the air is removed from the structure, the fibrous material may have, for example, a bulk density greater than 0.3 g/cm3, such as 0.5, 0.6, 0.7 g/cm3 or greater, such as 0.85 g/cm3 . After compaction, the product may be processed by any of the methods disclosed herein, such as irradiation, such as gamma radiation. This can be advantageous when it is desired to transport the material to another location, such as a remote manufacturing facility, where the fibrous material composition can be added to a solution, for example, to produce ethanol. After piercing the substantially gas-impermeable structure, the densified fibrous material may be returned to substantially its original bulk density, such as greater than 60 95 of its original bulk density, such as 70, 80, 85 95 or greater, such as 95 95 of its original volume density. To reduce static electricity in the fibrous material, a means that removes static charges can be added to the material.

In some embodiments, the structure, such as a bag, is made of a material that dissolves in a liquid, such as water. For example, the structure can be made of polyvinyl alcohol so that it dissolves when in contact with an aqueous system. Such variants of implementation allow adding compacted structures directly into solutions that include a microorganism, without primary release of the contents of the structure, for example, by cutting.

Referring to fig. 5, the biomass material can be combined with any desired additives and binder, and then compacted by applying pressure, such as by passing the material through a certain gap between counter-rotating pressure rollers or by passing the material through a pelletizing press. During the application of pressure, heating may optionally be applied to facilitate compaction of the fibrous material. The compacted material can then be irradiated.

In some embodiments, the material before compaction has a bulk density of less than 0.25 g/cm3, such as 0.20, 0.15, 0.10, 0.05 g/cm3 or less, such as 0.025 g/cm3. The bulk density is determined using ABTM 018958. Briefly, the method includes filling a measuring cylinder with a known volume of the sample and determining the mass of the sample. The bulk density is calculated by dividing the mass of the sample in grams by the known volume of the cylinder in cubic centimeters.

Preferred binders include binders that are water-soluble because they swell when exposed to water or that have a glass transition temperature of less than 25°C as determined by differential scanning calorimetry. By water-soluble binders is meant binders having a solubility in water of at least about 0.05 wt. 95. By water-swellable binders is meant binders whose volume increases by more than 0.5 95 under the influence of water.

In some embodiments, binders that are water-soluble or water-swellable include functional groups that are capable of forming a bond, such as a hydrogen bond, with the fibers of a fibrous material, such as a cellulose fibrous material. For example, a functional group can be a carboxylic acid group, a carboxylate group, a carbonyl group, such as an aldehyde or a ketone, a sulfonic acid group, a sulfonate group, a phosphoric acid group, a phosphate group, an amide group, an amino group, a hydroxyl group, such as an alcohol, and combinations thereof. groups, for example, a carboxylic acid group and a hydroxyl group. Specific examples of monomers include glycerol, glyoxal, ascorbic acid, urea, glycine, pentaerythritol, monosaccharide or disaccharide, citric acid and tartaric acid. Suitable saccharides include glucose, sucrose, lactose, ribose, fructose, mannose, arabinose and erythrose. Examples of polymers include polyglycols, polyoxyethylene, polycarboxylic acids, polyamides, polyamines and polysulfonic acids, polysulfonates. Specific examples of polymers include polypropylene glycol (PPO), polyethylene glycol (PES), polyoxyethylene, such as POI MOHF copolymers of ethylene oxide and propylene oxide, polyacrylic acid (PAA), polyacrylamide, polypeptides, polyethyleneimine, polyvinylpyridine, poly(sodium-4-styrenesulfonate) and poly (2-acrylamidomethyl-1-propanesulfonic acid).

In some embodiments, the binder comprises a polymer that has a glass transition temperature of less than 25°C. Examples of such polymers include thermoplastic elastomers (TPEs). Examples of TPEs include polyester block amides, such as polyester block amides available commercially under the name REVAHF), polyester elastomers such as polyester elastomers available under the trade name NUTREIG FU, and styrenic block copolymers such as block copolymers available under the trade name KKATOMF). Other suitable polymers having a glass transition temperature of less than 25 "C , include copolymers of ethylene and vinyl acetate (EMA), polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymers, and copolymers of ethylene and alpha-olefins, such as 1-octene, such as copolymers available under the trade name EMOACEF. In some embodiments, for example, when the material is pulped paper with a multilayer coating, the material is compacted without adding a special polymer with a low glass transition temperature.

In a specific embodiment, the binder is lignin, for example natural or synthetically modified lignin.

A suitable amount of binder added to the material, calculated on a dry weight basis, is, for example, from about 0.01 95 to about 50 95, for example 0.03, 0.05, 0.1, 0, 25, 0.5, 1.0, 5, 10 95 or more, for example 25 95, based on the total mass of compacted material. The binder can be added to the material in the form of an undiluted pure liquid, in the form of a liquid in which the binder is dissolved, in the form of a dry powder of the binder, or in the form of granules of the binder.

Compacted fibrous material can be made in a pelletizing press.

Referring to fig. 6, the pelletizing press 300 has a hopper 301 for holding uncompacted material 310, which includes carbohydrate-containing materials such as cellulose. The container is connected to an auger 312 which is driven by a variable speed motor 314 so that the uncompacted material can be transported to the mixing device 320, in which the uncompacted material is mixed by blades 322 which are rotated by the motor 330 of the mixing device. Other ingredients, such as any additives and/or fillers described herein, may be added through inlet 332. If desired, heat may be added while the fibrous material is in the mixing device. After mixing, the material is removed from the mixing device through the sleeve 340 to another auger 342. The sleeve, controlled by the drive mechanism 344, ensures the smooth passage of material from the mixing device to the auger. The screw rotates under the action of motor 346 and controls the supply of fibrous material to the die assembly with rollers 350. Specifically, the material is fed into a hollow cylindrical die 352 that rotates about a horizontal axis and has radial holes 250. The die 352 rotates about an axis under the action of motor 360, which includes a power meter that indicates the total energy consumed by the engine.

Compacted material 370, for example in the form of pellets, falls from the chute 372 and is collected and 60 processed, for example, by irradiation.

It is convenient that after compaction the material has the form of granules or chips that take different shapes. Then the pellets can be irradiated. In some embodiments, the granules or chips are cylindrical in shape, for example having a maximum transverse dimension of, for example, 1 mm or more, for example 2, 3, 5, 8, 10, 15 mm or more, for example 25 mm. Other convenient forms include pellets or chips that are plate-shaped, for example having a thickness of 1 mm or more, for example 2, 3, 5, 8, 10 mm or more, for example 25 mm; width, for example, 5 mm or more, for example 10, 15, 25, 30 mm or more, for example 50 mm; and a length of 5 mm or more, for example 10, 15, 25, 30 mm or more, for example 50 mm.

Next, referring to fig. 7A-70, the pellets can be made to have a cavity inside. As shown, the cavity may be located substantially in line with the center of the pellet (Fig. 78) or it may be offset from the center of the pellet (Fig. 7C),

Making the pellet hollow inside can increase the dissolution rate in the liquid after irradiation.

Next, referring to fig. 7O, the granule may have, for example, a cross-sectional shape that is multilobed, such as three-lobed as shown, or four-lobed, five-lobed, six-lobed or ten-lobed. Making granules with this transverse shape can also increase the dissolution rate in the solution after irradiation. Alternatively, the compacted material may have any other desired shape, for example the compacted material may be in the form of a plate, cylinder or briquette.

Examples

In one example, half-gallon (1.9 L) juice cartons made of white kraft paperboard having a bulk density of 20 lb/ft (0.32 g/cm3) can be used as raw materials. The paperboard can be folded flat and then fed into a shredder to produce a confetti-like material that is 0.1 inch (0.25 cm) to 0.5 inch (1.27 cm) wide, 0. 25 inches (0.63 cm) to 1 inch (2.54 cm) and a thickness equivalent to the thickness of the parent material (approximately 0.075 inches (0.19 cm)). The confetti-like material can be fed into a cutting device with a rotating knife that crushes the confetti-like fragments, breaking the fragments and releasing the fibrous material.

In some cases, multiple shredder-to-shredder systems

Zo can be located with consistent performance. In one embodiment, two shredder-shredder systems can be arranged in series, where the product of the first shredder is fed as input to the second shredder. In another embodiment, the three shredder-shredder systems can be arranged in series, where the product of the first shredder is fed as input to the second shredder and the product of the second shredder is fed as input to the third shredder. It is expected that multiple passes through the shredder-shredder systems can reduce the particle size and increase the total surface area in the feed stream.

In another example, the fibrous material obtained by shredding and shredding juice cartons can be processed to increase its bulk density. In some cases, the fibrous material can be sprayed with water or diluted mother liquor

ROGMOH M UUBK M10 (polyoxyethylene) prepared in water. The wetted fibrous material can then be processed in a granulation press operating at room temperature.

A granulation press can increase the volume density of the source material flow by more than one order of magnitude.

PRE-PROCESSING

Physically prepared raw materials can be pre-processed for use in main production methods, for example, by reducing the average molecular weight and crystallinity of the raw materials and/or increasing the surface area and/or porosity of the raw materials. In some embodiments, the cellulosic and/or lignocellulosic material includes a first cellulose having a first number average molecular weight, and the resulting carbohydrate includes a second cellulose having a second number average molecular weight lower than the first number average molecular weight. For example, the second number average molecular weight is lower than the first number average molecular weight by about more than twenty-five percent, for example, it can be 2x, 3x, 5x, 7x, 10x, 25x, and even 100x less.

In some embodiments, the first cellulose has a first crystallinity and the second cellulose has a second crystallinity lower than the first crystallinity, for example by about two, three. five, ten, fifteen or twenty-five percent.

In some embodiments, the first cellulose has a first oxidation level and the second cellulose has a second oxidation level that exceeds the first oxidation level, for example, by two, three, four, five, ten, or twenty-five percent.

Pretreatment methods may include one or more of irradiation, sonication, oxidation, pyrolysis, and steam explosion. Different pretreatment systems can be used, combining two, three, or even four of these technologies.

Combined pretreatment

In some embodiments, the biomass can be processed using two or more of any methods described herein, such as two, three, four or more of radiation exposure, sonication (or any other destruction method described herein , such as treatment with a rotor-stator destruction device), oxidation, pyrolysis and steam explosion either before, in between or after the preparation of raw materials as described in this document. The methods can be applied to biomass in any order or simultaneously. For example, a carbohydrate can be obtained by applying radiation, sonication, oxidation, pyrolysis, and optionally steam explosion to cellulosic and/or lignocellulosic material (in any order or simultaneously).

The resulting carbohydrate-containing material can then be subjected to conversion by one or more microorganisms, such as bacteria, yeast or mixtures of yeast and bacteria, to a number of desired products as described herein. Complex methods can provide materials that can be more easily utilized by various microorganisms due to lower molecular weight, lower crystallinity and/or higher solubility.

Complex methods can provide synergy and can reduce the total required energy costs, compared to any single method.

For example, in some embodiments, a feedstock is provided that includes a carbohydrate obtained by a method that includes irradiation and sonication, irradiation and oxidation, irradiation and pyrolysis, or irradiation and steam explosion (in any order or simultaneously) of cellulosic and/or lignocellulosic material. . Then the provided raw material can be brought into contact with a microorganism that has the ability to convert at least a part, for example at least about 1 wt. 95, raw materials for a product, such as burned fuel.

From the Pre-processing Conditions

In some embodiments, the method does not include hydrolysis of the cellulosic and/or lignocellulosic material, in particular, with an acid, such as a mineral acid such as hydrochloric or sulfuric acid, an enzyme, or a base. If desired, a portion of the raw material may or may not include hydrolyzed material. For example, in some embodiments, at least about 70 wt. All of the raw materials are non-hydrolyzed material, for example at least 95 wt. 95% of the raw material is non-hydrolyzed material.

In some embodiments, substantially all of the raw material is non-hydrolyzed material.

For example, you can avoid treatment with alkali.

Any feedstock or any reactor or fermenter loaded with the feedstock may include a buffer such as sodium bicarbonate, ammonium chloride or Ti; an electrolyte such as potassium chloride, sodium chloride or calcium chloride; a growth factor 50 such as biotin and/or a base pair such as uracil or its equivalent; a surfactant, such as TiepFb or polyethylene glycol; a mineral such as calcium, chromium, copper, iodine, iron, selenium or zinc; or a chelating agent such as ethylenediamine, ethylenediaminetetraacetic acid (EOTA) (or a salt form thereof, such as sodium or potassium EOTA) or dimercaprol.

When radiation exposure is used, it can be applied to any sample that is dry or wet, or even dispersed in a liquid such as water. For example, irradiation can be carried out on cellulosic and/or lignocellulosic material in which approximately less than 25 wt. 95 cellulosic and/or lignocellulosic material has a surface wetted by a liquid such as water. In some embodiments, the irradiation is performed on a cellulosic and/or lignocellulosic material in which the cellulosic and/or lignocellulosic material is substantially unwetted by a liquid such as water.

In some embodiments, any processing described herein is performed on cellulosic and/or lignocellulosic material that remains dry as received or after drying the material, for example, using heat and/or reduced pressure. For example, in some embodiments, the cellulosic and/or lignocellulosic material has approximately less than 5 wt. 95 of retained water, measured at 25 "C and at a relative humidity of fifty percent.

- The raw material can be processed to have a low moisture content, for example less than about 7.5, 5, 3, 2.5, 2, 1.5, 1 or 0.5 wt. 95, This material can be irradiated with a beam of particles or protons. Irradiation can be carried out immediately after the preparation of the material or after the stage of reducing the moisture content, for example drying at approximately 105 C for 4-18 hours.

If desired, in any method described herein, a swelling agent as defined herein may be used. In some embodiments, when cellulosic and/or lignocellulosic material is processed using radiation exposure, approximately less than 25 wt. 95 cellulosic and/or lignocellulosic material is in a swollen state, where the swollen state is characterized as having a volume that is more than 2.5 95 greater than the volume in an unswollen state, for example, more than 5.0, 7.5, 10 51 or 15 95 exceeds the volume in the unswollen state. In specific embodiments, when radiation exposure is used, the cellulosic and/or lignocellulosic material includes a swelling agent, and the swollen cellulosic and/or lignocellulosic material receives a dose of less than about 10 Mrad. In other embodiments, when radiation exposure is applied to the cellulosic and/or lignocellulosic material, the cellulosic and/or lignocellulosic material is essentially not in a swollen state.

In some embodiments, no chemical reagents, such as swelling agents, are added to the biomass prior to irradiation. For example, in some of these embodiments, no alkaline substances (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonium hydroxide), acidifiers (such as mineral acids (for example, sulfuric acid, hydrochloric acid) are added before irradiation or other processing and phosphoric acid)), salts such as zinc chloride, calcium carbonate, sodium carbonate, benzyltrimethylammonium sulfate, or basic organic amines such as ethylenediamine. In some cases, no additional water is added. For example, biomass before processing may have less than 0.5 wt. 95 added chemical reagents, for example less than 0.4, 0.25, 0.15 or 0.1 wt. 95 added chemical reagents. In some cases, the biomass has no more than trace amounts, such as less than 0.05 wt. 96, added chemical reagents before irradiation. In other cases, the biomass prior to irradiation has essentially no added chemical reagents or swelling agents. The use of such chemical reagents, which can be avoided, can also be extended to processing, for example, during the whole time before fermentation or during the whole time.

When radiation exposure is used in any method, it can be applied by simultaneously exposing the cellulosic and/or lignocellulosic material to air, oxygen-enriched air, or even oxygen itself, or it can be in an inert gas atmosphere such as nitrogen, argon, or helium. When maximum oxidation is desired, an oxidizing atmosphere such as air or oxygen is used. The distance from the source of radiation exposure can also be optimized to maximize the formation of an active gas such as ozone and/or nitrogen oxides.

When radiation exposure is used, it can be applied to biomass, such as cellulosic and/or lignocellulosic material, at pressures greater than about 2.5 atmospheres (253 kPa), such as greater than 5 (506 kPa), 10 (1012 kPa), 15 (1518 kPa), 20 (2036 kPa) or even about more than 50 atmospheres (5060 kPa).

When the method includes radiation exposure, the exposure may be performed using ionizing radiation such as gamma rays, X-rays, energetic ultraviolet radiation such as ultraviolet C radiation having a wavelength of about 100 nm to about 280 nm, a particle beam such as as a beam of electrons, slow neutrons or alpha particles. In some embodiments, the implementation of irradiation includes two or more sources of radiation exposure, such as gamma rays and an electron beam, which can be applied in any order or simultaneously.

Any method of processing presented in this description can be used at pressures above or below the normal atmospheric pressure of the Earth. For example, any process that uses radiation exposure, sonication, oxidation, pyrolysis, steam explosion, or combinations of any of these methods to produce materials that include a hydrocarbon can be carried out at high pressures, which can increase reaction rates. For example, any process or combination of processes can be carried out at a pressure greater than about normal atmospheric pressure, such as at a pressure greater than about 25 MPa, such as greater than 50, 75, 100, 150, 200, 250, 350, 500, 750, 1000 MPa or higher than 1500 MPa.

Radiation treatment

For the processing of raw materials from a wide variety of different sources, one or more processing sequences can be used to extract useful substances from the raw materials and to obtain partially degraded organic material that serves as an input stream in further processing stages and/or sequences. Irradiation can reduce the molecular weight and/or crystallinity of raw materials. In some embodiments, materials are irradiated using energy stored in the material, which releases an electron from its atomic orbit. Radiation exposure can be provided by 1) heavy charged particles such as alpha particles or protons, 2) electrons produced, for example, in beta decay or in electron beam accelerators, or 3) electromagnetic radiation such as gamma rays, X-rays or ultraviolet rays. In one approach, radiation generated by radioactive substances can be used to irradiate raw materials. In some embodiments, any combination of (1)-(3) can be used in any order or simultaneously. In another approach, electromagnetic radiation (for example, generated using electron beam sources) can be used to irradiate raw materials. The doses used depend on the desired effect and the specific raw material. For example, high doses of radiation exposure can destroy chemical bonds in the components of the raw material, and low doses of radiation exposure can increase the formation of chemical bonds (eg, cross-linking) in the components of the raw material. In some cases where chain separation is desired and/or functionalization of polymer chains is desired, particles heavier than electrons can be used, such as protons, a group of helium nuclei, argon ions, silicon ions, neon ions, carbon ions, phosphorus ions, oxygen ions, or nitrogen ions. When ring-opening chain separation is desired, positively charged particles can be used for enhanced ring-opening due to their Lewis acid properties.

For example, when oxygen-containing functional groups are desired, irradiation in the presence of oxygen or even irradiation with oxygen ions can be carried out. For example, when nitrogen-containing functional groups are desired, irradiation in the presence of nitrogen or even irradiation with nitrogen ions can be performed.

With reference to fig. 8, in one method, the first material 2, which is or includes cellulose having a first number average molecular weight ("Mmi") is irradiated, for example by treatment with ionizing radiation (e.g., in the form of gamma radiation, X-ray radiation, ultraviolet (UV) light from 100 nm to 280 nm, a beam of electrons or other charged particles), to obtain a second material 3, which includes cellulose having a second number average molecular weight ("Mmg") lower than the first number average molecular weight. The second material (or the first and second materials) can be mixed with a microorganism (e.g., bacteria or yeast) that can utilize the second and/or the first material to produce a product, such as fuel 5, which is or includes hydrogen, an alcohol (e.g., ethanol or butanol, such as n-, sec-, or tert-butanol), an organic acid, a hydrocarbon, or any mixture thereof.

Since the second material C has cellulose having a reduced molecular weight relative to the first material and, in some cases, also reduced crystallinity, the second material is generally more dispersible, swellable and/or soluble in the solution containing the microorganism. These properties make the second material C more susceptible to chemical, enzymatic and/or biological action relative to the first material 2, which can significantly increase the production rate or level of production of a desired product, such as ethanol. Radiation exposure can also sterilize materials.

In some embodiments, the second number average molecular weight ("Mg") is lower than the first number average molecular weight ("Mmi) by about more than 10 95,

BO for example 15, 20, 25, 30, 35, 40, 50, 60 95 or even about more than 75 95.

In some cases, the second material contains cellulose that has a crystallinity (Cg) that is lower than the crystallinity (Si) of the cellulose of the first material. For example, (Cg) may be lower than (Si) by about more than 10 95 , such as 15, 20, 25, 30, 35, 40 95 , or even by about more than 50 95 .

In some embodiments, the initial crystallinity index (before irradiation) is from about 40 95 to about 87.5 95, such as from about 50 95 to about 75 95 or from about 60 95 to about 70 95, and the crystallinity index after irradiation is from about 10 95 to about 50 95, such as about 15 95 to about 45 95 or about 20 95 to about 40 95. However, in some embodiments, such as after extensive irradiation, the crystallinity index may be less than 5 95. In some embodiments implementation of the material after irradiation is essentially amorphous.

In some embodiments, the starting number average molecular weight (before irradiation) is from about 200,000 to about 3,200,000, such as from about 250,000 to about 1,000,000 or from about 250,000 to about 700,000, and the number average molecular weight after irradiation is from about 50,000 to about 200,000, e.g. from about 60,000 to about 150,000 or from about 70,000 to about 125,000. However, in some embodiments, such as after extensive irradiation, the number average molecular weight may be less than about 10,000 or even less than about 5,000. In some embodiments, the second material may have a level oxidation (102), which exceeds the oxidation level (7101) of the first material. A higher level of oxidation of a material can contribute to its ability to disperse, swell and/or dissolve, further increasing the susceptibility of the material to chemical, enzymatic or biological attack. In some embodiments, to increase the oxidation level of the second material relative to the first material, irradiation is performed in an oxidizing atmosphere, such as air or oxygen, producing a second material that is more oxidized than the first material. For example, the second material may have more hydroxyl groups, aldehyde groups, ketone groups, ester groups, or carboxylic acid groups that may increase its hydrophilicity.

Ionizing radiation

Each form of radiation ionizes biomass through specific interactions determined by the energy of the radiation. Heavy charged particles mainly ionize matter through Coulomb scattering; moreover, these interactions generate energetic electrons that can further ionize matter. Alpha particles are identical to the nucleus of a helium atom and are produced by the alpha decay of various radioactive nuclei such as isotopes of bismuth, polonium, astatine, radon, francium, radium, several actinoids such as actinium, thorium, uranium, neptunium, curium, californium, americium and plutonium.

When particles are used, they can be neutral (uncharged), positively charged, or negatively charged. When they are charged, charged particles can carry a positive or negative charge, or multiple charges, such as one, two, three, or even four or more charges. In cases where chain separation is desired, positively charged particles may be desirable, in part due to their acidic nature. When particles are used, the particles may have the mass of the rest electron or a greater mass, such as 500, 1000, 1500, or 2000 or more times the mass of the rest electron. For example, the particles can have a mass of from about 1 atomic unit to about 150 atomic units, such as from about 1 atomic unit to about 50 atomic units, or from about 1 to about 25, such as 1, 2, 3, 4, 5, 10, 12 or 15, atomic units. Accelerators used for particle acceleration can be US-electrostatic, US-electrodynamic, AVE-linear, linear with magnetic induction or continuous. For example, cyclotron accelerators are available from IVA, Belgium, such as the KpodoigopF system, and UOS-type accelerators are available from VO, currently IVA Ipadivigia!, such as OupatigopF). Ions and ion accelerators are considered in Ipigodisiogu Mysieag Rnuzisv, Keppeiip 5. Ktgape, dopp U/ieeu b 5opv, Ips. (1988), Kivio

RgeeiJies, RIKA B 6 (1997) 4, 177-206, a copy of which is attached to this description in the form of Appendix B,

Spy, Mat T., "Omegmiyem oi Gidp-op Veat Tnegaru", Soishtriv-ONio, ISVO-IAEA Meeiipa, 18-20

Magsp 2006, a copy of which is attached to this description in the form of an appendix C, Imaia, U. ei ai., "Apetaiipd-Rnpaze-Rosized 1H-OTI og Neamu-Iop Medisa! AsseiIegayugv", Rgoseedipud5 oi ERAS 2006, Ediprigai, Zsoyapa, copy which is added to this description in the form of appendix 0, and I epeg,

S.M. ей ай., "ав ой Ше Зирегсопайсійпяа ЕСА Iop boshgse Mepyv", Rgoseyedipa5 ой ERAS 2000,

Mieppa, A!tsvipa, a copy of which is attached to this description in the form of Appendix E.

Electrons interact by means of Coulomb scattering and inhibition of radiation caused by changes in the speed of electrons. Electrons can be generated by radioactive nuclei that undergo beta decay, such as isotopes of iodine, cesium, technetium, and iridium. Alternatively, an electron gun can be used as a source of electrons through thermionic emission.

Electromagnetic radiation acts through three processes: photoelectric absorption, Compton scattering, and vapor formation.

The predominant effect is determined by the energy of the incident radiation and the atomic number of the material. The sum of the interactions leading to the absorption of radiation in the cellulosic material can be expressed using the mass absorption coefficient.

Electromagnetic radiation is divided into gamma rays, X-rays, ultraviolet rays, infrared rays, microwaves or radio waves, depending on the wavelength.

For example, gamma radiation can be used to irradiate materials.

Referring to fig. 9 and 10 (enlarged view of region I), the gamma emitter 10 includes sources of gamma radiation 408, such as CO tablets, a work table 14 for holding the materials to be irradiated, and a storage device 16, for example, made of a plurality of iron plates, all of which are in a concrete-shielded chamber (storage) 20, which includes a labyrinthine entrance 22 behind a leaded door 26. The accumulator 16 includes a plurality of channels 30, such as sixteen or more channels, that allow the gamma radiation sources to pass through the accumulator near desktop

In the process of work, the sample to be irradiated is placed on the work table.

The irradiator is adapted to deliver the desired dose level and to be connected to the experimental unit 31 by control equipment. The operator then leaves the protective chamber, passing through the entrance in the form of a labyrinth and through a leaded door. The operator of the control panel 32 issues a command to the computer 33 to bring the sources of radiation radiation 12 into the working position using the cylinder 36 connected to the hydraulic pump 40. Gamma radiation has the advantage of a significant depth of penetration into various sample materials. Sources of gamma rays include radioactive nuclei such as isotopes of cobalt, calcium, technetium, chromium, gallium, indium, iodine, iron, krypton, samarium, selenium, sodium, thallium, and xenon.

X-ray sources include electron beam collisions with metal targets such as tungsten or molybdenum or alloys, or compact light sources such as commercially produced I upseap light sources.

Sources of ultraviolet radiation include deuterium or cadmium lamps.

Infrared radiation sources include ceramic lamps with a sapphire, zinc, or selenide window.

Zo Microwave sources include klystrons, Ziemip KE-type sources, or atomic beam sources that use gaseous hydrogen, oxygen, or nitrogen.

Various other irradiation devices may be used in the methods disclosed herein, including field ionization sources, electrostatic ion separators, field ionization generators, thermionic emission sources, ultrahigh frequency discharge ion sources, recirculation or static accelerators, dynamic linear accelerators, accelerators Van de Graafia and bent tandem accelerators. Such devices are disclosed, for example, in US Patent Application Serial No. 61/073665, the full contents of which are incorporated herein by reference.

Electron beam

In some embodiments, an electron beam is used as a source of radiation. The electron beam has the advantage of high dose levels (eg 1, 5 or even 10 Mrad per second), high performance, less protective insulation and less isolation equipment. Electron beams can also have an electrical efficiency of up to 80 95, providing low energy use, which can lead to low process cost and low greenhouse gas emissions, corresponding to low energy consumption. Electrons can also be more efficient at providing chain separation. In addition, electrons having an energy of 4-10 MeV can have a penetration depth of 5 to 30 mm or more, for example 40 mm. In materials with a low bulk density, such as many of the materials disclosed herein, such as materials having a bulk density of less than about 0.5 g/cm3, electrons having energies in the range of 4- 10

MeV, can penetrate 4-8 inches (10-20 cm) or even more.

Electron beams can be generated, for example, using electrostatic generators, cascade generators, transformer generators, low-energy scanning accelerators, low-energy linear cathode accelerators, linear accelerators, and pulse accelerators. Electrons may be suitable as a source of ionizing radiation, e.g., for relatively thin stacks of material, e.g., less than about 0.5 in. (1.27 cm), e.g., less than 0.4 in. (1.02 cm), 0.3 in. (0.76 cm), 0.2 in (0.51 cm), or less than 0.1 in (0.25 cm). In some embodiments, the energy of each electron in the electron beam is from about 0.3 MeV to about 2.0 MeV (megaelectronvolts), such as from about 0.5 MeV to about 1.5

MeV or from about 0.7 MeV to about 1.25 MeV.

In fig. 11 presents a basic technological scheme 3000, which includes various stages in the sequence of preliminary processing of raw materials with an electron beam. In the first stage 3010, the dry raw material is fed from the feedstock source. As discussed above, the dry feedstock from the feedstock source may be preprocessed prior to delivery to the electron beam devices. For example, if the raw material is derived from plant sources, certain parts of the plant material may be removed prior to harvesting the plant material and/or prior to delivering the plant material using a raw material transport device. Alternatively or additionally, as reflected in optional stage 3020, the biomass feedstock can be subjected to mechanical processing (eg, to reduce the average fiber length in the feedstock) prior to delivery to the electron beam irradiation devices.

In step 3030, the dry raw material is moved to a raw material transport device (eg, a conveyor belt) and is distributed along the transverse length of the raw material transport device approximately uniformly in volume. This can be done, for example, manually or by inducing a localized vibrational motion at some point of the device for transporting raw materials before processing by means of electron beam irradiation.

In some embodiments, the mixing system supplies a chemical reagent 3045 to the raw material in an optional process 3040 in which a slurry is formed. Combining water with processed raw materials in the mixing stage 3040 results in an aqueous suspension of raw materials that can be transported, for example, through a system of pipes, rather than using, for example, a conveyor belt. The next stage 3050 is a cycle that includes exposure to the raw material (in dry form or in the form of a suspension) of electron beam irradiation from one or more (for example, M) electron beam irradiation devices. The suspension of feedstock is moved through each of the M "streams" of electron beams at stage 3052. Movement through or between the streams may occur at a constant rate, or there may be a pause during passage through each stream, followed by rapid movement to the next stream. At step 3053, a small portion of the feedstock slurry is exposed to each stream for some time

From the given exposure time.

Electron beam irradiation devices can be purchased commercially from Op Veat

Arrisaiopv, I ochmaiip-Ia-Mayme, Belgium, or She Tiiap Sogrohaiop, Diego, SA. The specific electron energy can be 1, 2, 4.5, 7.5 or 10 MeV. The specific power of the electron beam irradiation device can be 1, 5, 10, 20, 50, 100, 250 or 500 kW.

The efficiency of depolymerization of the raw material suspension depends on the used electron energy and the applied dose, while the exposure time depends on the power and dose.

Specific doses can be 1, 5, 10, 20, 50, 100 or 200 kGy.

When choosing the optimal power characteristics of the device for electron beam irradiation, operating costs, capital costs, depreciation costs and the area of the device are taken into account. When choosing the optimal levels of the exposure dose of electron beam irradiation, energy consumption and environmental, safety and health (EN) issues are taken into account. As a rule, generators are contained in storage, for example, made of lead or concrete. When choosing the optimal electron energy, energy consumption is taken into account; in this case, a lower electron energy may be preferable from the point of view of promoting the depolymerization of any suspension of raw materials (see, for example, Voshispnaga, ei a!., SePshiove (2006) 13: 601-610).

To ensure a more efficient depolymerization process, it may be preferable to conduct irradiation with an electron beam with a double pass. For example, a raw material transport device can direct the raw material (in dry form or in slurry form) down and in a reverse direction relative to its original direction of transport. Dual-pass systems can handle thicker stock slurries and can provide more uniform depolymerization through the thickness of the stock slurry.

An electron beam irradiation device can generate either a fixed beam or a scanning beam. A scanning beam with long scan sweep lengths and high scan speeds may be preferred, as this can effectively replace a large fixed beam width. In addition, sweep lengths of 0.5, 1.2 m or more are available.

After transporting a portion of the raw material suspension through M devices for electron beam irradiation, in some embodiments it may be necessary, as in step 3060, to mechanically separate the liquid and solid components of the raw material suspension. In these embodiments, residual solid particles are filtered from the liquid portion of the raw material suspension and because are returned to the slurry preparation stage 3040. Then, the solid part of the raw material slurry is moved to the next processing stage 3070 using a raw material transport device. In other embodiments, the raw material is maintained in the form of a suspension for further processing.

Beams of heavy ion particles

Particles heavier than electrons can be used to irradiate carbohydrates or materials that include carbohydrates, such as cellulosic materials, lignocellulosic materials, starchy materials, or mixtures of any of these and other materials described herein. For example, protons, a group of helium nuclei, argon ions, silicon ions, neon ions, carbon ions, phosphorus ions, oxygen ions or nitrogen ions can be used. In some embodiments, particles heavier than electrons can induce higher levels of chain separation. In some cases, positively charged particles can induce higher levels of chain separation than negatively charged particles due to their acidity.

Heavier beams can be generated, for example, using linear accelerators or cyclotrons. In some embodiments, the energy of each particle in the beam is from about 1.0 MeV/atomic unit to about 6000 MeV/atomic unit, such as from about 3 MeV/atomic unit to about 4800 MeV/atomic unit or from about 10 MeV/atomic unit up to approximately 1000 MeV/atomic unit.

Electromagnetic radiation

In embodiments in which exposure is performed using electromagnetic radiation, the electromagnetic radiation may have, for example, an energy per photon (in electron volts) greater than 102 eV, such as greater than 103, 107, 105, 105 eV, or even greater than 107 eV. In some embodiments, the electromagnetic radiation has an energy per photon of 107 to 107 eV, such as 105 to 106 eV. Electromagnetic radiation can have a frequency, for example, greater than 1015 Hu, more than 1077, 1018, 109, 1020 Hu, or even more than 102! Hz. In some embodiments, the electromagnetic radiation has a frequency of 108 to 1022 Hz, such as 10" to 102! Hz.

Doses

In some variants, the implementation of irradiation (with any source of radiation

from radiation or a combination of sources) is carried out until the material receives a dose of at least 0.05 Mrad, for example at least 0.1, 0.25, 1.0, 2.5, 5.0 or 10.0 Mrad. In some embodiments, the irradiation is carried out until the material receives a dose of at least 1.0 to 6.0 Mrad, such as 1.5 to 4.0 Mrad. In other embodiments, the irradiation is performed at a dose of from about 0.1 Mrad to about 10 Mrad, such as from about 0.25 Mrad to about 9 Mrad, from about 0.5 Mrad to about 7.5 Mrad, or from about 0.75 Mrad to about 5 Mrad.

In some embodiments, the irradiation is carried out at a dose level of 5.0 to 1500.0 kilorads/hour, for example, from 10.0 to 750.0 kilorads/hour or from 50.0 to 350.0 kilorads/hour.

In some embodiments, the implementation uses two or more sources of radiation, such as two or more sources of ionizing radiation. For example, samples can be treated in any order with an electron beam followed by gamma radiation and UV radiation having wavelengths from about 100 nm to about 280 nm. In some embodiments, samples are treated with three sources of ionizing radiation, such as an electron beam, gamma radiation, and energy

UV radiation.

In one example, half-gallon (1.9 L) juice cartons made of white kraft paperboard having a bulk density of 20 lb/ft (0.32 g/cm3) can be used as raw materials. The paperboard can be folded flat and then fed into a sequence of three shredder - shredder systems arranged in series, where the product of the first shredder is fed as input to the second shredder and the product of the second shredder is fed as input in the third device for grinding. The fibrous material obtained in the shredder-shredder system can be sprayed with water and processed using a pellet press operating at room temperature. Compacted granules can be placed in a glass ampoule, from which the air is pumped out under high vacuum and then refilled with argon gas. The ampoule is sealed in an argon atmosphere. Alternatively, in another example, the ampoule is sealed in an air atmosphere. Granules in the ampoule are irradiated with gamma radiation for about 3 hours at a dose level of about 1 Mrad per hour, producing irradiated material in which the cellulose has a lower molecular weight of 60 than the original material.

Zo

Additives to enhance molecular weight reduction during irradiation

In some embodiments, various materials, such as solids or liquids, can be added to the biomass prior to irradiation to enhance molecular weight reduction.

In cases where a liquid is used, the liquid may be in contact with the external surfaces of the biomass and/or the liquid may be in the interior of the biomass, eg the liquid may be poured into the biomass.

For example, the material may be a neutral weak base such as alanine, ammonia, an ammonia/water mixture, such as 25% ammonia in water, water, methylamine, dimethylamine, trimethylamine, pyridine, or an anionic base such as an acetic acid salt (e.g., sodium acetate), sodium carbonate, sodium bicarbonate, or a salt of the hydrogen sulfide ion (e.g., sodium hydrosulfide).

Alternatively, the material may be a neutral weak acid such as formic acid, acetic acid, trichloroacetic acid, water, hydrosulfide, or a cationic acid such as an ammonium salt.

Extinction and controlled functionalization of biomass

After treatment with one or more types of ionizing radiation, such as photon radiation (for example, X-rays and gamma rays), exposure to an electron beam, or particles heavier than electrons that are positively or negatively charged (for example, protons or carbon ions), any of hydrocarbon-containing materials or mixtures described in this description become ionized; that is, they include radicals at levels detectable by an electron spin resonance spectrometer. The current limit of radical detection is approximately 1077 spins at room temperature. After ionization, any biomass material that is ionized can be quenched to reduce the level of radicals in the ionized biomass, for example, such that the radicals are no longer detectable by an electron spin resonance spectrometer. For example, radicals can be quenched by applying sufficient pressure to the biomass and/or using a fluid medium in contact with the ionized biomass, such as a gas or liquid, which reacts (quenches) with the radicals. The application of a gas or liquid to at least contribute to radical quenching can be used to functionalize the ionized biomass with the desired amount and type of functional groups, such as

From the group of carboxylic acids, enol groups, aldehyde groups, nitro groups, nitrile groups, amino groups, alkylamino groups, alkyl groups, chloroalkyl groups or chlorofluoroalkyl groups. In some cases, such quenching can increase the stability of some of the ionized biomass materials. For example, quenching can increase the resistance of biomass to oxidation. Functionalization by quenching can also increase the solubility of any biomass described herein, can increase its thermal stability, and can increase the utilization of the material by various microorganisms. For example, the functional groups provided to the biomass material by quenching can act as receptor sites for binding by microorganisms, for example to enhance the hydrolysis of cellulose by various microorganisms.

In fig. 11A illustrates changing the molecular and/or supramolecular structure of the biomass feedstock by pre-treating the biomass feedstock with ionizing radiation, such as electrons or ions with energy sufficient to ionize the feedstock, to provide a first level of radicals. As shown in fig. 11A, if the ionized biomass remains in the atmosphere, it oxidizes, for example, to the extent that carboxylic acid groups are formed by reaction with atmospheric oxygen. In some cases, for some materials, such oxidation is desirable because it can further reduce the molecular weight of the carbohydrate-containing biomass, and oxidizing groups, such as carboxylic acid groups, can in some cases be beneficial for solubility and utilization by the microorganism. However, since the radicals can "live" for some time after exposure, such as more than 1 day, 5 days, 3 days, 3 months, 2 months, or even more than 1 year, the properties of the material can continue to change over time, which, in some cases, may be undesirable.

The detection of radicals in irradiated samples using electron spin resonance spectroscopy and the life time of radicals in such samples are considered in Vapoioia ei ai., in Rpuvisv ip

Meadisipe apa Vioiodu, 46 (2001), 461-471 and Vapoiiotsa ei a!., Nadianop Rgoiesiop Rositeigu, Moi. 84,

As. 1-4, pp. 293-296 (1999), which are attached to this description in the form of Appendix E and Appendix C, respectively. As shown in fig. 11A, the ionized biomass can be quenched to functionalize and/or stabilize the ionized biomass. At any point in time, such as when the material is "live", "partially live" or fully decomposed, the pre-treated biomass can be converted into a product such as a fuel, food or composite material.

In some embodiments, quenching includes applying pressure to the biomass, for example by mechanically deforming the biomass, such as by direct mechanical compression of the biomass in one, two, or three dimensions, or by applying pressure to a fluid medium in which the biomass is immersed, such as isostatic pressing. In such cases, the deformation of the material itself yields radicals that are often trapped in crystalline domains close enough for the radicals to recombine or react with another group. In some cases, the pressure is applied together with the application of heating, such as an amount of heat sufficient to raise the temperature of the biomass to a level above the melting point or to the softening temperature of a biomass component such as lignin, cellulose, or hemicellulose. Heating can increase the mobility of molecules in the polymer material, which can help quench radicals. When pressure is used for extinguishing, the pressure may exceed 1000 psi. in. (6.9 MPa), for example to exceed approximately 1250 lb/sq. in. (8.6 MPa), 1450 lb/sq. in. (10 MPa), 3625 lb/sq. in. (25.2 MPa), 5075 lb/sq. in. (35 MPa), 7250 lb/sq. in. (50 MPa), 10,000 psi. in. (69 MPa) or even more than 15,000 psi. inch (103.4

MPa).

In some embodiments, quenching includes contacting the biomass with a fluid medium, such as a liquid or gas, such as a gas capable of reacting with radicals, such as acetylene or a mixture of acetylene in nitrogen, ethylene, chlorinated ethylenes or chlorofluoroethylenes, propylene, or mixtures of these gases. In other specific embodiments, quenching includes contacting the biomass with a liquid, such as a liquid soluble in the biomass or at least capable of penetrating the biomass and reacting with radicals such as a diene such as 1,5-cyclooctadiene. In some specific embodiments, quenching includes contacting the biomass with an antioxidant such as vitamin E. If desired, the biomass feedstock may include an antioxidant dispersed therein, and the quenching may occur by contacting the antioxidant dispersed in the biomass feedstock with radicals.

Other extinguishing methods are possible. For example, to quench any ionized material described in this document, any method of quenching radicals in polymeric materials described in Mygadiya et al., US Patent Application Publication No. 2008/0067724 and Mygadiya et al., US Pat. Mo. 7166650, which are attached as Appendix H and Appendix I, respectively. Moreover, any quenching agent described as a "sensitizing agent" in the Migaiodish disclosures above, or any antioxidant described in any of refs., can be used to quench any ionized biomass material.

Mithagudiya.

Functionalization can be enhanced using heavy charged ions, such as any of the heavier ions described herein. For example, if it is desired to increase oxidation, charged oxygen ions can be used for irradiation. If nitrogen functional groups are desired, nitrogen ions or anions that include nitrogen can be used.

Similarly, if sulfur or phosphorus groups are desired, sulfur or phosphorus ions can be used for irradiation.

In some embodiments, after quenching, any of the quenched ionized materials described herein can be further treated with one or more of radiation exposure, such as ionizing or non-ionizing radiation, sonication, pyrolysis, and oxidation to further alter the molecular and/or supramolecular structures.

Particle beam irradiation in fluid media

In some cases, cellulosic or lignocellulosic materials can be subjected to particle beam irradiation in the presence of one or more additional fluid media (eg, gases and/or liquids). The effect on the material of a beam of particles in the presence of one or more additional fluid media can increase the efficiency of processing.

In some embodiments, the material is irradiated with a beam of particles in the presence of a fluid medium, such as air. Particles accelerated in one or more of the types of accelerators disclosed herein (or in another type of accelerator) exit the accelerator through an outlet (e.g., a thin membrane such as a metal foil), pass through a volume of space occupied by the fluid medium, and then fall on the material. In addition to the direct processing of the material, some of the particles form additional chemical particles by interaction with the particles of the fluid medium (for example, ions and/or radicals generated by various components of the air, such as ozone and nitrogen oxides). These formed chemical particles can also react with the material and can act as initiators of various chemical bond breaking reactions in the material. For example, any oxidizing agent formed can oxidize the material, which can lead to a decrease in molecular weight.

In certain embodiments, additional fluids can be selectively applied to the path of the particle beam before the beam hits the material. As discussed above, reactions between the particles of the beam and the particles of the supplied fluids can form additional chemical particles that react with the material and can contribute to the functionalization of the material and/or otherwise selectively change certain properties of the material. One or more additional fluids can be directed into the path of the beam, for example, from a downpipe. The direction and flow rate of the supplied fluid(s) can be selected according to the desired power or direction of irradiation to control the overall processing efficiency, including both effects resulting from particle processing and effects resulting from the interaction of dynamically generated particles with of the given fluid medium with the material. In addition to air, illustrative fluids that can be supplied to the ion beam include oxygen, nitrogen, one or more noble gases, one or more halogens, and hydrogen.

Irradiation of biomass materials with low bulk density and cooling of irradiated biomass

In the process of treating biomass materials with ionizing radiation, especially at high dose levels, such as levels greater than 0.15 Mrad per second, for example 0.25, 0.35, 0.5, 0.75 Mrad/s or even more than 1 Mrad/ c, biomass materials can store significant amounts of heat, so that the temperature of biomass materials increases. While elevated temperatures may be preferred in some embodiments, such as when a higher reaction rate is desired, it is preferred to control the heating of the biomass to maintain control over ionizing radiation-initiated chemical reactions such as cross-linking, chain scission, and/or or graft copolymerization, for example, to maintain process control. Low bulk density materials, such as materials having a bulk density of less than about 0.4 g/cm3, such as about less than 0.35, 0.25 g/cm3, or about less than 0.15 g /cm3, especially when combined with materials that have thin cross-sections, such as fibers that have small cross-sectional dimensions, are generally easier to cool. In addition, photons and particles can mainly penetrate deeper into or through materials of relatively low bulk density, which can enable the processing of larger volumes of materials at higher speeds and can enable the application of photons and particles , which have lower energies, such as 0.25, 0.5, 0.75 or 1.0 MeV, which can reduce shielding requirements for safety. Many of the biomass materials described herein can be processed in one or more of the systems shown in FIG. 118, 11C, 110 and 11E, which are described below. The presented systems allow the application to biomass material with a low bulk density of one or more types of ionizing radiation, such as relativistic electrons or electrons in combination with X-rays, at high dose levels, for example at a level greater than 1.0, 1.5, 2 .5 Mrad/s or even more than 5.0 Mrad/s, and then give the opportunity to cool the biomass before applying radiation exposure for the second, third, fourth, fifth, sixth, seventh, eighth, ninth, or even tenth time.

For example, in one method of altering the molecular and/or supramolecular structure of the biomass feedstock, the biomass is pretreated at a first temperature with ionizing radiation, such as photons, electrons, or ions (eg, singly or multiply charged cations or anions), for a sufficient time and/or at a sufficient dose, to raise the temperature of the raw biomass to the second temperature, which exceeds the first temperature. The pretreated biomass is then cooled to a third temperature below the second temperature. Finally, if desired, the cooled biomass can be treated one or more times with radiation, such as ionizing radiation. If desired, the biomass can be cooled after and/or during each irradiation treatment.

The biomass feedstock can be physically prepared as discussed above, for example, by reducing the size of one or more individual fragments of the biomass feedstock so that the feedstock can be processed more efficiently, such as being more easily cooled and/or more permeable to ionizing radiation.

In some embodiments, ionizing radiation is applied at a total dose of less than 25 Mrad or less than 10 Mrad, such as less than 5 Mrad or less than 2.5 Mrad, and at a rate greater than 0.25 Mrad per second, such as greater than 0.5, 0.75 or more than 1.0 Mradi/s, before biomass cooling.

Pre-treatment of biomass raw materials with ionizing radiation can be carried out by pneumatically transporting the biomass raw materials into a fluid medium, such as a gas such as nitrogen or air. To facilitate molecular weight reduction and/or functionalization of materials, the gas may be saturated with any swelling agent 60 described herein and/or steam. For example, you can use acidic steam. To facilitate molecular weight reduction, water can be acidified with an organic acid such as formic or acetic acid or a mineral acid such as sulfuric or hydrochloric acid.

Pre-treatment of biomass raw materials with ionizing radiation can be carried out as the biomass raw materials fall under the influence of gravity. This process can effectively reduce the bulk density of the biomass feedstock as it is processed, and it can help cool the feedstock. For example, biomass can be transported from a first conveyor belt at a first height above ground level, and then it can enter a second belt at a second level above ground level, which is lower than the first level. For example, in some embodiments, the trailing edge of the first strip and the leading edge of the second strip form a gap.

Preferably, ionizing radiation, such as a beam of electrons, protons, or other ions, can be applied to the gap region to prevent damage to the biomass transport system.

Cooling the biomass may include contacting the biomass with a fluid medium, such as a gas at a temperature below the first or second temperature, such as nitrogen gas at about 77K (-196C). Even water can be used, such as water at a temperature below nominal room temperature (for example, 25 "C).

It is often preferred that the biomass feedstock has internal fibers and prior to exposure to ionizing radiation, the biomass feedstock is shredded to such an extent that its internal fibers are essentially exposed. This crushing can provide material with a low bulk density that has small cross-sectional dimensions, which can contribute to molecular weight reduction and/or biomass functionalization. For example, in some embodiments, the biomass is or includes individual fibers and/or particles having a maximum size of about no more than 0.5 mm, such as about no more than 0.25 mm, about no more than 0.1 mm, or approximately no more than 0.05 mm.

In some embodiments, the biomass feedstock to which ionizing radiation is applied has a bulk density of less than about 0.35 g/cm3, such as about less than about 0.3, 0.25, 0.20 g/cm" or about less than 0.15 g/cmu, during the application of ionizing radiation In such embodiments, the biomass feedstock may be cooled, and then ionizing radiation may be applied to the cooled biomass.

In some preferred embodiments, the biomass feedstock is or includes individual fibers and/or particles having a maximum size of about no more than about 0.5 mm, such as about no more than about 0.25 mm, about no more than about 0.1 mm, about no more than 0.05 mm or about no more than 0.025 mm.

In fig. 118 and 11C show the acquisition, processing, transportation of the fibrous material and the device for irradiation 1170 (shielding not illustrated in the figures). In operation, a sheet of paper 1173, such as fragments of a bleached sheet of kraft paper, is fed from a roller 1172 and delivered to a device 1174, such as a rotary knife cutter. The sheet 1173 is converted into a fibrous material 1112 and delivered to the fiber loading area 1180 by means of a conveyor 1178. If desired, the fibers of the fibrous material can be separated, for example by screening, into fractions having different 1/0 ratios. In some embodiments, fibrous material 1112, typically of low bulk density and preferably of thin cross-section, is continuously delivered to zone 1180; in other embodiments, the fibrous material is delivered in batches.

A fan 1182 in the loop 1184 is located adjacent to the fiber loading area 1180 and is capable of moving a fluid medium, such as air, at a speed and volume sufficient to pneumatically circulate the fibrous material 1112 in the direction indicated by arrow 1188 through the loop 1184.

In some embodiments, the air velocity passing through the loop is sufficient to homogeneously disperse and transport the fibrous material throughout the loop 1184. In some embodiments, the flow rate exceeds 2500 ft/min (760 m/min), such as 5000 ft/min (1520 m/min, ), 6,000 ft/min (1,800 m/min) or greater, such as 7,500 ft/min (2,300 m/min) or 8,500 ft/min (2,600 m/min).

The loaded fibrous material 1112 passing through the loop passes through an application zone 1190, which forms part of the loop 1184. Here, any desired additives described herein, such as a liquid such as water, which may be acidifying or alkalizing, are introduced. In operation in application zone 1190, an additive such as liquid solution 1196 is applied to the circulating fibrous material through nozzles 98, 99, and 11100. When the liquid is applied, the nozzles form a misted spray or aerosol that affects the fibers as the fibers pass 60 near the nozzles. . Valve 11102 controls the flow of fluid to the respective nozzles 1198, 1199, and 11100. After the desired amount of additive is added, valve 11102 closes.

In some embodiments, the application zone 1190 is two feet (0.6 m) or greater in length, such as 125 feet (38 m), 150 feet (46 m), 250 feet (76 m), or greater, such as 500 feet (152 m ). Longer application zones allow liquid to be applied over a longer period of time as the fibrous material passes through application zone 1190. In some embodiments, the nozzles are spaced, for example, from about three to about four feet (0.9-1.2 m) apart. , along the length of the loop 1184.

As the fibrous material passes through loop 1184 and through the radiating portion 11107 of the loop, which includes horn 11109 for delivering ionizing radiation, the fibrous material is exposed to ionizing radiation (shielding not shown).

As the irradiated fibrous material moves through the loop 1184, it is cooled by gases, such as air, circulating through the loop at high speeds. The material is surrounded by reactive gases, such as ozone and/or nitrogen oxides, which are produced by the action of ionizing radiation on circulating gases such as air. After passing through the irradiating portion 11107, a cooling fluid such as a liquid (eg, water) or a gas such as nitrogen at 77K may be introduced into the loop 1184 to help cool the fibrous material. If desired, this process can be repeated more than once, for example 2, 3, 4, 5, 6, 7, 8, 9, 10 times or more, for example 15 times, to deliver the desired dose to the fibrous material. While the long axis of the horn is shown to be along the direction of flow, in some embodiments, the long axis of the horn is transverse to the direction of flow. In some embodiments, an electron beam is used as the primary source of ionizing radiation, and X-rays are used as a secondary source of ionizing radiation. X-rays can be generated by having a metal target, such as tantalum target 11111, on the inside of loop 1184, so that when electrons reach the target, X-rays are emitted.

After the desired dose has been delivered to the fibrous material, the fibrous material can be removed from loop 1184 via separator 11112, which is selectively coupled to loop 1184

With sectional 11114 and shut-off valve 11116. When valve 11116 opens, another valve also opens, allowing air to enter loop 1184 , replacing the air exiting separator 11112 .

In fig. 110 presents a device for irradiating fibrous material 11121 in a fluidized bed with shielding. Fibrous material in a fluid medium, such as a gas, such as compressed air, is delivered to the shielded protective jacket 11123 through the conduit 11125 and to the fluidized bed shielded portion 11127. Counterflows 11131 of the fluid, such as gas, and crossflows 11133 of the fluid, such as gas, which may be the same as or different from the oncoming gas, combine to cause turbulence in a portion of the bed. Ionizing radiation is applied in part of the fluidized bed as the fibrous material is transported through part of the bed. For example, as shown, it is possible to use three electron beams from three KpodoihopF devices 11135, 11136 and 11137. Preferably, each beam can penetrate the fluidized bed to a different depth and/or each beam can emit electrons with different energies, such as 1.3 and 5 MeV. As the irradiated fibrous material passes through the system, it is cooled by gases, such as air, circulating through the system at high velocities, and it is surrounded by reactive gases, such as ozone and/or nitrogen oxides, produced by the action of ionizing radiation on the circulating gases. , such as air. If desired, the process can be repeated as many times as desired until the fibrous material receives the desired dose. Although the fluidized bed is illustrated with its long axis horizontal to the ground, in other embodiments the long axis is perpendicular to the ground so that the fibrous material is subject to gravity.

In fig. 11E shows another method of transporting fibrous material and an irradiation device 11140 without shielding. The fibrous material 11144 is delivered from the basket 11142 to the first conveyor 11150 at the first level above the ground, and then the material is transferred to the second conveyor 11152 at a lower height than the first conveyor. The rear edge 11160 of the first conveyor and the front edge 11161 of the second conveyor 11152 define a gap of a distance of 5.

For example, the distance 5 can be from 4 inches (0.1 m) to about 24 inches (0.6 m).

The material 11144 has sufficient momentum to free fall under the influence of gravity and then to enter the second conveyor 11152 without falling into the gap. In the process of free fall, ionizing radiation is applied to the material. This arrangement may be advantageous in that ionizing radiation is less likely to damage the transport system, since the transport system is not in direct contact with radiation exposure.

After passing the material through the radiating part, a cooling fluid such as a liquid (eg water) or a gas such as liquid nitrogen at 77K may be applied to the material to aid in cooling the fibrous material. If desired, this process can be repeated more than once, for example 2, 3, 4, 5, 6, 7, 8, 9, 10 times or more, for example 15 times, to deliver the desired dose to the fibrous material.

Although, as shown, the long axis of the horn is transverse to the direction of the material flow, a different arrangement of the beams is possible. In some embodiments, an electron beam is used as the primary source of ionizing radiation, and X-rays are used as a secondary source of ionizing radiation. X-rays can be generated by having a metal target, such as a tantalum target, on the inside of the loop, so that when the electrons reach the target, X-rays are emitted.

Ultrasound treatment and other methods of biomass destruction

To process raw materials from a wide variety of different sources, to extract useful substances from the raw materials and to provide partially degraded organic material that serves as an input stream, one or more series of sonications can be used for further processing stages and/or sequences. Sonication may reduce the molecular weight and/or crystallinity of feedstocks such as one or more of any of the biomass materials described herein, such as one or more carbohydrate sources such as cellulosic or lignocellulosic materials or starchy materials.

Referring again to FIG. 8, in one method, a first material 2 that includes cellulose having a first number average molecular weight ("Mmi") is dispersed in a medium such as water and sonicated or otherwise cavitated to produce a second material 3 that includes cellulose , having a second number average molecular weight ("Mmg") lower than the first number average molecular weight. The second material (or in certain embodiments, the first and second materials) can be mixed with the microorganism (e.g.

With a bacterium or yeast), which can dispose of the second and/or the first material, producing fuel 5, which includes hydrogen, alcohol, organic acid, hydrocarbon or any mixtures thereof.

Since the second material C comprises cellulose having a reduced molecular weight relative to the first material and, in some cases, also reduced crystallinity, the second material is generally more dispersible, swellable and/or soluble in the solution containing the microorganism, for example greater than 105 microorganisms/ml. These properties make the second material C more susceptible to chemical, enzymatic and/or microbial attack relative to the first material 2, which can significantly increase the production rate and/or production level of the desired product, such as ethanol. Sonication can also sterilize materials, but should not be used as long as the microorganisms are expected to be alive.

In some embodiments, the second number average molecular weight ("Mg") is lower than the first number average molecular weight ("Mmi) by about more than 10 95, such as 15, 20, 25, 30, 35, 40, 50, 60 95 or even about more than 75 95.

In some cases, the second material contains cellulose having a crystallinity ("Cg") that is lower than the crystallinity (Si) of the cellulose of the first material. For example, (7C2) may be lower than (C) by about more than 10 95 such as 15, 20, 25, 30, 35, 40 95 or even approximately more than 50 95.

In some embodiments, the initial crystallinity index (before sonication) is from about 40 95 to about 87.5 95, such as from about 50 95

BO to about 75 95 or from about 60 956 to about 70 9b5 and the crystallinity index after irradiation is from about 10 95 to about 50 95, such as from about 15 95 to about 4595 or from about 2095 to about 4095. However, in certain embodiments implementation, such as after extensive irradiation, the crystallinity index may be less than 5 95. In some embodiments, the material after irradiation is essentially amorphous.

In some embodiments, the initial number average molecular weight (before sonication) is from about 200,000 to about 3,200,000, such as from about 250,000 to about 1,000,000 or from about 250,000 to about 700,000, and the number average molecular weight after irradiation is from about 50,000 to about 200,000, for example from about 60000 to about 150000 or from about 60 70000 to about 125000. However, in some embodiments, for example after

Due to extensive irradiation, the number average molecular weight may be less than about 10,000 or even less than about 5,000.

In some embodiments, the second material may have an oxidation level (702) greater than the oxidation level (7101) of the first material. A higher level of oxidation of a material can contribute to its ability to disperse, swell and/or dissolve, further increasing the susceptibility of materials to chemical, enzymatic or microbial attack. In some embodiments, to increase the oxidation level of the second material relative to the first material, the irradiation is carried out in an oxidizing atmosphere, producing a second material that is more oxidized than the first material. For example, the second material may have more hydroxyl groups, aldehyde groups, ketone groups, ester groups, or carboxylic acid groups that may increase its hydrophilicity.

In some embodiments, the sonication medium is an aqueous medium. If desired, the medium may include an oxidizing agent such as a peroxide (eg, hydrogen peroxide), a dispersing agent, and/or a buffer. Examples of dispersing agents include ionic dispersing agents, such as sodium lauryl sulfate, and nonionic dispersing agents, such as poly(ethylene glycol).

In other embodiments, the sonication medium is non-aqueous.

For example, sonication can be carried out in a hydrocarbon such as toluene or heptane, in an ether such as diethyl ether or tetrahydrofuran, or even in a liquefied gas such as argon, xenon or nitrogen.

Without being bound by any particular theory, it is believed that sonication destroys the bonds in the cellulose by creating bubbles in the medium containing the cellulose that grow and then collapse. In the process of bubble collapse, which can occur for less than a nanosecond, the implosive force raises the local temperature in the bubble to about 5100 K (in some cases, even higher; see, e.g., BiwiisK ei ai., Mayte 434, 52-55) and creates pressures from several hundred atmospheres to more than 1000 atmospheres or more. It is these high temperatures and pressure that destroy bonds. In addition, without being bound by any particular theory, it is believed that the reduced crystallinity is a consequence, at least in part, of the extremely high cooling rates during bubble collapse, which can exceed approximately 10"K/second. High cooling rates generally do not allow the cellulose to organize and crystallize, resulting in materials that have reduced crystallinity. Ultrasonic systems and ultrasonic chemistry are considered, for example, in ОЙ ей ай., in US patent Mo 5766764; Vobep5, US patent Mo 5828156; Mazop, Spetivigu mypy OPgavoshpa,

Eizemiyei, Okhtoga, (1990); ZyviiskK (yeayog), Oigazotsypa: iv Spetisai, Rpuzisa! apa Viioodisa! ePesiv,

MSN, M/eipneit, (1988); Riise, "Sctepi Tgtepav ip Bopospetivzigu" Nowa! Bosieiu oi Spetivig,

Satgidde, (1992); ZiviisK eyi ai, App. German Maiveg. All together. 29, 295, (1999); Life Science, Mayte 353, 414 (1991); Niieg eyi a), Rnuvz. Wow And hey. 69, 1182 (1992); Waibeg yei ai, Mate, 352, 414 (1991); ByviiskK ei ai, U. At. Spent boss, 108, 5641 (1986); Tapd eyi a. Snet Sott., 2119 (2000); The map is

Aduapsea Maieg., 12, 1137 (2000); I apdats ei ai, 9. oi Saia|uviv, 201, 22 (2001); ReiKkaz vii a), Snet.

Sott., 988 (2001); Mikpepko eyi a), Apdem. Spent Ipieg. Ed. (Ossetbreg 2001); 5 Naiyi eiyi ai., 9. Rpuv.

Speth B 103, 3358 (1999); Amimi yei ai, U. Ateg. Spent 5 people 121, 4196 (1999); and Amimi vi ai, U. Ateg.

Spent 5 people 122, 4331 (2000).

Systems for ultrasound treatment

In fig. 12 shows a general system in which a flow of cellulosic material 1210 is mixed with a flow of water 1212 in a container 1214 to form a process flow 1216.

First pump 1218 pumps process stream 1216 out of vessel 1214 toward flow cell 1224. Ultrasonic transducer 1226 delivers ultrasonic energy to process stream 1216 as process stream passes through flow cell 1224. Second pump 1230 pumps process stream 1216 out of flow cell 1224 into direction of further processing.

The container 1214 includes a first receiver 1232 and a second receiver 1234, in hydraulic communication with the volume 1236. A conveyor (not shown) delivers a stream of cellulosic material 1210 into the container 1214 through the first receiver 1232. The water stream 1212 enters the container 1214 through the second receiver 1234. In some embodiments, the water flow 1212 enters the volume 1236 along a tangential line, which causes the flow to swirl in the volume 1236. In certain embodiments, the cellulosic material flow 1210 and the water flow 1212 may be fed into the volume 1236 along opposite axes to increased mixing in the volume.

Valve 1238 controls the flow of water stream 1212 through second receiver 1232 to obtain a desired ratio of cellulosic material to water (eg, approximately 10 95 bo of cellulosic material, weight to volume). For example, 2000 tons/day of cellulosic material can be combined with 1 million to 1.5 million gallons/day (3800-5700 m3/day), such as 1.25 million gallons/day (4700 m3/day), of water.

Mixing of the cellulosic material and water in the container 1214 is controlled by the size of the volume 1236 and the flow rates of the cellulosic material and water into the volume. In some embodiments, the volume 1236 is sized to provide minimal residence time for the cellulosic material and water during mixing. For example, when 2,000 tons/day of cellulosic material and 1.25 million gallons/day (4,700 m3/day) of water flow through vessel 1214, the volume 1236 may be approximately 32,000 gallons (120 m3) to achieve the minimum mixing residence time. which is about 15 minutes.

The container 1214 includes a mixer 1240 in hydraulic communication with the volume 1236. The mixer 1240 mixes the contents of the volume 1236, completely dispersing the cellulosic material in the water of the volume.

For example, the mixer 1240 may be a rotating blade located in the container 1214. In some embodiments, the mixer 1240 disperses cellulosic material in water essentially homogeneously.

In addition, the vessel 1214 includes an outlet 1242 in hydraulic communication with the volume 1236 and the process flow 1216. The mixture of cellulosic material and water in the volume 1236 flows out of the vessel 1214 through the outlet 1242. The outlet 1242 is located near the bottom of the vessel 1214 to provide ejection under by gravity of the mixture of cellulosic material and water from the container 1214 into the process stream 1216. The first pump 1218 (for example, any of several pumps with a vortex impeller manufactured by Ebv5so Rytr5 4 Sopigoiv, 05 Apdeiyev,

Saijogia) moves the contents of the process stream 1216 toward the flow cell 1224. In some embodiments, the first pump 1218 agitates the contents of the process stream 1216 so that the mixture of cellulosic material and water is substantially homogeneous at the inlet 1220 of the flow cell 1224. For example, the first pump 1218 agitates the process stream 1216 creating a turbulent flow along the process stream between the first pump and the inlet 1220 of the flow cell 1224 .

The flow cell 1224 includes a reactor volume 1244 in hydraulic communication with an inlet 1220 and an outlet 1222. In some embodiments, the reactor volume 1244 is a stainless steel tube capable of withstanding elevated pressure (eg, 10 bar). Additionally or

Alternatively, the reactor volume 1244 includes a rectangular cross-section.

In addition, the flow cell 1224 includes a heat exchanger 1246 in thermal contact with at least a portion of the reactor volume 1244. A cooling fluid 1248 (e.g., water) flows into the heat exchanger 1246 and absorbs the heat generated during the sonication of the process stream 1216 in the reactor volume. 1244. In some embodiments, the flow rate and/or temperature of the cooling fluid 1248 in the heat exchanger 1246 is controlled to maintain an approximately constant temperature in the reactor volume 1244. In some embodiments, the temperature of the reactor volume 1244 is maintained at 20-50 C, for example 25, 30, 35, 40 or 45 76s.

Additionally or alternatively, heat transferred to cooling fluid 1248 from reactor volume 1244 may be used in other parts of the overall process.

The transition compartment 1226 provides hydraulic communication between the reactor volume 1244 and the booster 1250 connected (eg, mechanically connected using a flange) to the ultrasonic transducer 1226. For example, the transition compartment 1226 may include a flange and an O-ring system positioned so , to create a vacuum-tight connection between the reactor volume 1244 and the booster 1250. In some embodiments, the ultrasonic transducer 1226 is a high-power ultrasonic transducer manufactured by NieuwsNpeg ShPgazopisw oi Tej, Germany.

In operation, generator 1252 delivers electricity to ultrasonic transducer 1252. Ultrasonic transducer 1226 includes a piezoelectric element that converts electrical energy into sound in the ultrasonic range. In some embodiments, materials are sonicated using sound having a frequency of about 16 kHz to about 110 kHz, such as from about 18 kHz to about 75 kHz or from about 20 kHz to about 40 kHz (for example, sound having a frequency of 20 to 40 kHz). In some embodiments, the sonication is performed, for example, at a frequency of about 15 kHz to about 25 kHz, such as about 18 to 22 kHz. In specific embodiments, sonication can be performed using a horn of 1 kW or more, such as 2, 3, 4, 5 kW, or even 10 kW.

Then the ultrasonic energy is delivered to the working environment through the booster 1248.

Ultrasonic energy passing through the booster 1248 in the reactor volume 1244 creates a 60 series of compressions and decompressions of the process stream 1216 with an intensity sufficient to cause cavitation of the process stream 1216. The cavitation disaggregates the cellulosic material dispersed in the process stream 1216. Cavitation also results in production of free radicals in the water of process stream 1216. These free radicals act to further destroy cellulosic material in process stream 1216.

Typically, an ultrasonic energy ranging from 5 to 4000

MJ/m", for example 10, 25, 50, 100, 250, 500, 750, 1000, 2000 or 3000 MJ/m3. After exposure to ultrasonic energy in the reactor volume 1244, the process stream 1216 exits the flow cell 1224 through the outlet channel 1222, Second pump 1230 moves process stream 1216 for further processing (eg, any of several vortex impeller pumps manufactured by Evzso Ritrz and Sopigo!v, I o5 Apdeiyev, Sa pogpia).

Although certain embodiments have been described, other embodiments are possible. As an example, although process flow 1216 has been described as a single flow path, other schemes are possible. For example, in some embodiments, process flow 1216 includes multiple parallel flow paths (eg, with a flow rate of 10 gallons/min (38 L/min)). Additionally or alternatively, a plurality of parallel flow paths of process flow 1216 flow in separate flow cells and are sonicated in parallel (eg, using a plurality of 16 kW ultrasonic transducers).

As another example, although one ultrasonic transducer 1226 has been described as being coupled to a flow cell 1224, other schemes are possible. In some embodiments, a plurality of ultrasonic transducers 1226 are located in the flow cell 1224 (for example, ten ultrasonic transducers may be located in the flow cell 1224). In some embodiments, the sound waves generated by the plurality of ultrasonic transducers 1226 are time-adjusted (eg, synchronized to be out of phase with each other) to enhance the cavitation effect on the process stream 1216 .

As another example, although a single flow cell 1224 has been described, other designs are possible. In some embodiments, the second pump 1230 moves the process stream into a second flow cell where the second booster and ultrasonic transducer are further sonicated

From technological stream 1216.

As another example, although reactor volume 1244 has been described as a closed volume, in certain embodiments, reactor volume 1244 is open to ambient conditions. In such embodiments, the ultrasonic pretreatment can be performed substantially simultaneously with other pretreatment methods. For example, ultrasonic energy can be applied to the process stream 1216 in the reactor volume 1244 simultaneously with the supply of electron beams to the process stream 1216.

As another example, although a streaming method is described, other schemes are possible. In some embodiments, the sonication can be performed in a cyclic manner. For example, a volume may be filled with a 10 95 (weight by volume) mixture of cellulosic material in water and exposed to sound at an intensity of from about 50 W/cmg to about 600 W/cm- eg from about 75 W/cm? up to about 300 W/cm? or from about 95 W/cm? to about 200

W/cm7. Additionally or alternatively, the bulk mixture may be sonicated for about 1 hour to about 24 hours, such as about 1.5 hours to about 12 hours or about 2 hours to about 10 hours. In certain embodiments, the material is sonicated for a predetermined period of time and then allowed to settle for a second predetermined period of time before being sonicated again.

Further referring to fig. 13, in some embodiments, two electroacoustic transducers are mechanically coupled to one horn. As shown, a pair of piezoelectric transducers 60 and 62 are connected to the slotted rectangular horn 64 by respective intermediate connecting horns 70 and 72, the latter of which are also known as auxiliary horns.

The mechanical vibration provided by the transducers responding to the high-frequency electrical energy applied to them is transmitted to the corresponding coupling horns, which can be designed to provide mechanical amplification, for example, with a ratio of 1 to 1.2. Horns are provided with appropriate mounting flanges 74 and 76 to support the transducer and horn system in a stationary housing.

The vibration transmitted from the transducers through the connecting or auxiliary horns is transmitted to the input surface 78 of the horn and is transmitted through the horn to the opposite output surface 80, which during operation is in forced contact with the workpiece 60 (not shown), until which uses vibration.

High-frequency electrical energy provided by the power source 82 is supplied to each of the converters electrically connected in parallel through the compensating transformer 84 and corresponding series-coupled capacitors 86 and 90, with one capacitor connected in series by electrical connection to each of the converters. The compensating transformer is also known as "raishShp", which means "balancing device". The compensating transformer includes a magnetic core 92 and a pair of identical coils 94 and 96, also called the primary coil and the secondary coil, respectively.

In some embodiments, the transducers include commercially available piezoelectric transducers, such as the 105 or 502 models, each designed to operate at 20 kHz and a maximum power of 3 kW. The potential difference when turning on the power to ensure the maximum dynamic amplitude on the output surface of the converter is 930 rms volts. The electrical current through the converter can vary from zero to 3.5 amps, depending on the load resistance. At 930 rms volts, the output swing is about 20 micrometers. The maximum deviation of the final voltage for the same dynamic amplitude can therefore be 186 volts. Such a deviation in voltage can lead to large stray currents between the converters. Balancing device 430 provides a balanced condition by providing equal current through the converters, thus eliminating the possibility of stray currents. The wire size in the coil must be selected for the maximum load current specified above, and the maximum potential difference occurring at the input of the coil is 93 volts.

Although the ultrasonic transducer 1226 is described as including one or more piezoelectric active elements for generating ultrasonic energy, other schemes are possible. In some embodiments, the implementation of the ultrasonic transducer 1226 includes active elements made of other types of magnetostrictive material (eg, ferrous metals).

The design and operation of such a high-power ultrasonic transducer is considered

Napsep et al., in US patent 6,624,539. In some embodiments, the ultrasonic energy is transferred to the process flow 16 using an electro-hydraulic system.

Although the ultrasonic transducer 1226 is described as utilizing the electromagnetic response of magnetostrictive materials to produce ultrasonic energy, other schemes are possible. In some embodiments, acoustic energy in the form of an intense shock wave using an underwater discharge can be applied to the process flow 16. In some embodiments, ultrasonic energy is transferred to the process stream 16 through a thermodynamic system. For example, high energy density acoustic waves can be generated by applying a potential across an enclosed volume of electrolyte, thereby heating the enclosed volume and causing a pressure increase that is further transmitted through the sound propagating medium (eg, process flow 1216). The scheme and operation of such a thermo-hydraulic converter is discussed by Naitaptp Yei A!., in US patent 6383152.

In some embodiments, a high-frequency rotor-stator device is used.

This type of device generates high shear microcavitation forces that can disintegrate biomass upon contact with such forces. Two types of commercially available high-frequency rotor-stator dispersing devices are Zirgaiop "m devices manufactured by Kgirr Ipdivigieitesnpik CitrN and supplied to the Roit-Oiimeg market

Reshivzsniapa StrnN oi Soppesiisitsi, and Rrizrah "M devices, which are manufactured and supplied to the market of IKa-UUogkv, Ips. oi Sipsippaiyi, Opio. The operation of such a microcavitation device is considered

Zishayi, in US patent Mo 5370999.

In another biomass degradation method, microwave or radio wave energy is applied to treated or untreated biomass material, such as lignocellulosic material, so that the water in the biomass material is vaporized, but the biomass material as a whole undergoes little cumulative heating. For example, a frequency of about 10 MHz to about 300,000 MHz can be applied to the biomass material. In some cases, the microwave or radio wave energy is applied in short pulses, such as having a duration of less than 0.1 second, such as less than 0.05 second, less than 0.03 second, less than 0.01 second, or even less than, for example, 0.005 second. Without being bound by any particular theory, it is believed that when microwave or radio wave energy is applied in this way, water is vaporized from the biomass material with explosive force that destroys the lignin and "exfoliates" it from the cellulose. At the same time, since the application of such energy does not heat the base material, the lignin tries to reattach to the cellulose, which can block access to the cellulose, for example, by an enzyme or a microorganism. Many of the properties of lignin are described by Sapeg Boch in theses entitled "SNetisaii apa TnegtaiY

Spagasiyegigayop oi Tngye Ipaiviya! Gidpip apa Tneig Soitezropaipu Eviegv (Mau 2006, OpimegzPu oi

Idano).

In another method of breaking down biomass, treated (eg, using any treatment method described herein) or untreated biomass material is exposed to a hot compressed fluid such as water. In this method, the biomass is placed in a high-pressure vessel containing a fluid medium such as water at an elevated temperature, for example above 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170 "C or above 180 "C. The pressurized container is placed in a pressurized gas atmosphere, such as argon, nitrogen, or air, then agitated, for example, by a two-bladed turbine propeller for a period of time, such as 10 minutes, 20 minutes, 30 minutes, 45 minutes, 60 minutes, or 90 minutes. In some embodiments, the pressure is from about 500 psi. inch long (3.5 MPa) to 2000 lb/sq. inch long (13.8 MPa), for example from about 650 lb/sq. in. H.D., (4.5 MPa) to approximately 1,500 psi. inch long (10.3 MPa) or from about 700 lb/sq. inch long (4.8 MPa) to approximately 1,200 lb/sq. inch long (8.3 MPa). In some embodiments, the temperature is 5 or 10°C above the glass transition temperature for lignin. Without being bound by any particular theory, it is believed that when the temperature exceeds the glass transition temperature of lignin, the conditions in the high-pressure vessel cause the lignin to "exfoliate" from cellulose, making the cellulose more susceptible to degradation, for example by an enzyme.

In another method of biomass destruction, treated, for example irradiated, or untreated biomass material is delivered into a gap defined by two counter-rotating pinch rollers, which may optionally be heated. The pressure in the gap can be adjusted depending on the amount of biomass material fed into the gap and the distance between the pressure rollers. In some embodiments, the gap pressure may exceed 1000 psi. inch (6.9 MPa) per linear inch (2.5 cm), for example, exceeds 2,500 psi, inch (17.2 MPa), exceeds 5,000 psi. in. (34.4 MPa), exceeds 7,500 psi. inch (51.7

MPa), exceeds 10,000 lb/kV. in. (68.9 MPa) or even exceeds 15,000 psi. inch (103.4 MPa) per linear inch (2.5 cm). In some embodiments, the pressure rollers operate at elevated temperatures, such as above 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170 "C or above 180 "C. In some embodiments, the rollers operate at a temperature above the glass transition temperature of lignin. Without being bound by any particular theory, it is believed that the pressure and heat in the gap can break down any lignin in the biomass material, making the cellulose more open and accessible to the enzyme.

Pyrolysis

One or more pyrolysis processing sequences can be used to process raw materials from a wide variety of different sources to extract useful substances from the raw materials and to obtain partially degraded organic material that serves as an input stream for further processing stages and/or sequences.

Referring again to FIG. 8, in one method, a first material 2 that includes cellulose having a first number average molecular weight ("Mmi") is pyrolyzed, for example by heating the first material in a tube furnace, to produce a second material 3 that includes cellulose having a second number average molecular weight ("Mkg") ("Mkg"), lower than the first number average molecular weight. The second material (or in certain embodiments, the first and second materials) is mixed with a microorganism (eg, a bacterium or yeast) that can dispose of the second and/or the first material, producing fuel 5, which includes hydrogen, an alcohol (for example, ethanol or butanol, such as n-, sec-, or tert-butanol), an organic acid, a hydrocarbon, or any mixture thereof.

Because the second material has cellulose having a reduced molecular weight relative to the first material and, in some cases, also reduced crystallinity, the second material is generally more dispersible, swellable and/or soluble in a solution containing a microorganism, such as greater than 105 microorganism / ml. These properties make the second material C more susceptible to chemical, enzymatic and/or microbial attack relative to the first material 2, which can significantly increase the production rate and/or production level of the desired product, such as ethanol. Pyrolysis can also sterilize the first and second materials.

In some embodiments, the second number average molecular weight ("Mg") is lower than the first number average molecular weight ("Mm:") by about more than 10 95 , such as 15, 20, 25, 30, 35, 40, 50, 60 95 or even about more than 75 95.

In some cases, the second material contains cellulose having a crystallinity (Cg) that is lower than the crystallinity (Si) of the cellulose of the first material. For example, (7C2) may be lower than (Ci) by about more than 10 95 , such as 15, 20, 25, 30, 35, 40 95 , or even by about more than 50 95 .

In some embodiments, the initial crystallinity index (before pyrolysis) is from about 40 95 to about 87.5 95, such as from about 50 95 to about 75 95 or from about 60 95 to about 70 95, and the crystallinity index after irradiation is from about 10 95 to about 50 95, for example from about 15 95 to about 45 95 or from about 20 95 to about 40 95. However, in certain embodiments, for example after extensive pyrolysis, the crystallinity index may be less than 5 9". In some embodiments, the material after pyrolysis is essentially amorphous.

In some embodiments, the starting number average molecular weight (before pyrolysis) is from about 200,000 to about 3,200,000, such as from about 250,000 to about 1,000,000 or from about 250,000 to about 700,000, and the number average molecular weight after pyrolysis is from about 50,000 to about 200,000, e.g. from about 60,000 to about 150,000 or from about 70,000 to about 125,000. However, in some embodiments, such as after extensive pyrolysis, the number average molecular weight may be less than about 10,000 or even less than about 5,000.

In some embodiments, the second material may have an oxidation level (702) greater than the oxidation level (101) of the first material. A higher level of oxidation of a material can contribute to its ability to disperse, swell and/or dissolve, further increasing the susceptibility of materials to chemical, enzymatic or microbial attack. In some embodiments, to increase the level of oxidation of the second material relative to the first material, pyrolysis is carried out in an oxidizing atmosphere, producing a second material that is more oxidized than the first material. For example, the second material may have more hydroxyl groups, aldehyde groups, ketone groups, ester groups, or carboxylic acid groups that may increase its hydrophilicity.

In some embodiments, the pyrolysis of materials is continuous. In other embodiments

The material is subjected to pyrolysis for a predetermined period of time and then allowed to cool for a second predetermined period of time before pyrolysis again.

Systems for pyrolysis

In fig. 14 presents a flow chart 6000, which includes various stages of a pyrolytic system for pre-treatment of raw materials. In the first stage 6010, dry raw material is supplied from the source of raw material.

As described above, the dry raw material from the feedstock source may be preprocessed prior to delivery to the pyrolysis chamber. For example, if the raw material is obtained from plant sources, certain parts of the plant material may be removed before harvesting the plant material and/or before delivering the plant material to the raw material transport device. Alternatively or additionally, the biomass feedstock can be subjected to mechanical processing 6020 (eg, to reduce the average fiber length in the feedstock) prior to delivery to the pyrolysis chamber.

After mechanical processing, the raw material undergoes the moisture correction stage 6030. The nature of the moisture correction stage depends on the moisture content in the mechanically processed raw material. As a rule, pyrolysis of raw materials occurs most efficiently when the moisture content of the raw materials is from about 10 95 to about 30 95 (eg, from 15 to 25 95) by weight of the raw materials.

If the moisture content in the raw material exceeds approximately 40 wt.9U5, the excessive heat load provided by the water content in the raw material increases the energy consumption in the subsequent stages of pyrolysis. In some embodiments, if the raw material has a moisture content exceeding 30 wt. 95, it is possible to mix with it the drier material of raw material 6220, which has a low moisture content, obtaining a mixed raw material at stage 6030 with an average moisture content that is within the limits indicated above. In certain embodiments, raw materials with a high moisture content can simply be dried by distributing the raw material on a moving conveyor that cycles the raw material through an in-line heating element.

The heating element evaporates part of the water present in the raw material.

In some embodiments, if the feedstock from stage 6020 has a moisture content that is very low (eg, lower than about 10 wt. 95 ), the mechanically processed feedstock can be combined with feedstock material 6230 with a higher moisture content, such as bottoms waste water Alternatively or additionally, to increase the moisture content, water 6240 can be added to the dry raw material 60 of stage 6020.

At stage 6040, the raw material, now with its moisture content adjusted to be within acceptable limits, can be preheated in an optional preheat stage 6040. The preheat stage 6040 can be used to raise the temperature of the raw material to 75-150" C in preparation for subsequent pyrolysis of the feedstock Depending on the nature of the feedstock and the specific design of the pyrolysis chamber, preheating the feedstock can ensure that the heat distribution in the feedstock remains more uniform during pyrolysis and can reduce the heat load on the pyrolysis chamber.

The feedstock is then transported to a pyrolysis chamber to undergo pyrolysis in step 6050. In some embodiments, feedstock transport is aided by the addition of one or more compressed gases 6210 to the feedstock stream. The gases create a pressure gradient in the feedstock transport channel, moving the feedstock into the pyrolysis chamber ( and even through a pyrolysis chamber). In certain variants, the implementation of the transportation of raw materials occurs mechanically; namely, the raw material is transported to the pyrolysis chamber by a conveying system that includes a conveyor, such as a screw conveyor.

It is also possible to add other gases 6210 to the raw material before the pyrolysis chamber. In some embodiments, for example, one or more catalytic gases may be added to the feedstock to promote decomposition of the feedstock in the pyrolysis process. In certain embodiments, one or more absorbers can be added to the feedstock to trap volatile materials released during pyrolysis. For example, various sulfur-based compounds such as sulfides may be released during pyrolysis, and an agent such as hydrogen gas may be added to the feedstock to ensure desulfurization of the pyrolysis products. Hydrogen combines with sulfides to form gaseous hydrogen sulfide, which can be removed from pyrolyzed raw materials.

Pyrolysis of the feedstock in the chamber may include heating the feedstock to relatively high temperatures to ensure partial decomposition of the feedstock. Typically, the feedstock is heated to a temperature in the range of 150 to 1100°C. The temperature to which the feedstock is heated depends on a number of factors, including feedstock composition, average feedstock particle size, moisture content, and desired pyrolysis products. For many types of biomass feedstocks use, for example, pyrolysis temperatures from 300 to 550 "С.

The residence time of the raw materials in the pyrolysis chamber usually depends on a number of factors, including the pyrolysis temperature, the composition of the raw materials, the average particle size of the raw materials, the moisture content, and the desired pyrolysis products. In some embodiments, the feedstock materials are pyrolyzed at a temperature slightly above the decomposition temperature of the material in an inert atmosphere, such as about 2°C above to about 10°C above the decomposition temperature or about 3°C above to about 7°C above decomposition temperature. In such embodiments, the material is typically held at this temperature for more than 0.5 hours, such as more than 1.0 hours or about more than 2.0 hours. In other embodiments, the materials are pyrolyzed at a temperature significantly above the decomposition temperature of the material in an inert atmosphere, such as from about 75°C above to about 175°C above the decomposition temperature, or from about 85°C above to about 150°C C above the decomposition temperature. In such embodiments, the material is typically held at this temperature for less than 0.5 hour, such as less than 20 minutes, less than 10 minutes, less than 5 minutes, or less than 2 minutes. In other embodiments, the materials are pyrolyzed at an extreme temperature, such as about 200°C above to about 500°C above the decomposition temperature of the material in an inert environment or about 250°C above to about 400°C above the decomposition temperature. In such embodiments, the material is typically held at this temperature for less than 1 minute, such as less than 30 seconds, 15 seconds, 10 seconds, 5 seconds, 1 second, or less than 500 ms. Such implementation options are usually called instant pyrolysis.

In some embodiments, the feedstock in the chamber is heated relatively quickly to the selected pyrolysis temperature. For example, the chamber can be designed to heat the raw material at a rate of 500 to 11,000 "S/s, for example, from 500 to 1,000 "S/s.

Turbulent flow of the feed material in the pyrolysis chamber is usually preferred because it provides relatively efficient heat transfer of the feed material from the heating subsystem. Turbulent flow can be achieved, for example, by driving the feed material through the chamber using one or more carrier gases 6210 that are pumped. As a rule, the carrier gases are relatively inert with respect to the raw material, even at high temperatures in the pyrolysis chamber. Illustrative carrier gases include, for example, nitrogen, argon, methane, carbon monoxide and carbon dioxide. Alternatively or additionally, mechanical transport systems such as screw conveyors can transport the raw material and circulate it in the pyrolysis chamber, creating a turbulent flow of the raw material.

In some variants, the pyrolysis of raw materials takes place essentially in the absence of oxygen and other reactive gases. Oxygen can be removed from the pyrolysis chamber by periodically purging the chamber with high-pressure nitrogen (eg, nitrogen pressure of 2 bar or more).

After purging the chamber, the gas mixture present in the chamber for pyrolysis (for example, in the process of pyrolysis of raw materials) may include less than 4 mol. 956 oxygen (for example, less than 1 mol. 95 oxygen and even less than 0.5 mol. 95 oxygen). The absence of oxygen ensures the absence of ignition of raw materials at elevated pyrolysis temperatures.

In certain embodiments, relatively small amounts of oxygen can be supplied to the raw material and be present in the pyrolysis process. This method is called oxidative pyrolysis. As a rule, oxidative pyrolysis proceeds in several stages of heating. For example, in the first stage of heating, the raw material is heated in the presence of oxygen to ensure partial oxidation of the raw material. This stage uses up the available oxygen in the pyrolysis chamber. Then, in the subsequent stages of heating, the temperature of the raw material is further increased. However, due to the consumption of all the oxygen in the chamber, ignition of the raw material does not occur, but pyrolytic decomposition of the raw material occurs without ignition (for example, with the formation of hydrocarbon products). As a rule, the process of heating raw materials in a pyrolysis chamber to initiate decomposition is endothermic. However, in oxidative pyrolysis, the formation of carbon dioxide by oxidation of raw materials is an exothermic process. The heat released during the formation of carbon dioxide can contribute to further heating stages during pyrolysis, thereby reducing the heat load provided by the raw material.

In some embodiments, the pyrolysis takes place in an inert environment, for example, when the raw materials are surrounded by argon or gaseous nitrogen. In certain embodiments, pyrolysis may occur in an oxidizing environment, such as air or argon enriched air. In some embodiments, pyrolysis can occur in reducing ambient conditions, for example, when the raw materials are surrounded by gaseous hydrogen. Various chemicals such as oxidizing agents, reducing agents, acids, or bases can be added to the material prior to or during the pyrolysis process to promote pyrolysis. For example, you can add sulfuric acid

Co) or you can add peroxide (for example, benzoyl peroxide).

As discussed above, a number of different processing conditions can be used, depending on factors such as feedstock composition and desired pyrolysis products. For example, for a cellulosic feedstock material, relatively mild pyrolysis conditions can be used, including flash pyrolysis temperatures of 375 to 450°C, and residence times of less than 1 second. As another example, for an organic solid waste material such as sludge of waste water, they usually use instant pyrolysis temperatures from 500 to 650 °C, with a residence time of 0.5 to 3 seconds. As a rule, many parameters of the pyrolysis process, including residence time, pyrolysis temperature, raw material turbulence, moisture content, composition of raw materials, composition of pyrolysis products, and total composition of gases, can be regulated automatically by a system of regulators and an automated control system.

After the pyrolysis stage 6050, the pyrolysis products pass through the quenching stage 6250 to reduce the temperature of the products before further processing. Typically, the quench stage 6250 includes spraying the pyrolysis products with streams of cooling water 6260. The cooling water also forms a slurry that includes solid undissolved material and various dissolved products. Also in the product stream there is a mixture that includes various gases, including gaseous products, carrier gases and other types of process gases.

The flow of products is transported through the gas line installed in the line to the gas separator, which performs the gas separation stage 6060, at which gaseous products and other gases are separated from the suspension formed during quenching of pyrolysis products. The separated mixture of gases is optionally sent to the fan 6130, which increases the pressure of the gas by blowing the mixture with air.

The gas mixture may be subjected to a filtration step 6140 in which the gas mixture is passed through one or more filters (eg, activated carbon filters) to remove particulates and other impurities. In the next stage 6150, the filtered gas can be compressed and stored until use. Alternatively, the filtered gas may be subjected to further processing steps 6160 .

For example, in some embodiments, the filtered gas may be subjected to condensation to separate various gaseous compounds from the gas mixture. Various compounds may include, for example, various hydrocarbon products (eg, alcohols, alkanes, alkenes, alkynes, ethers) formed in the pyrolysis process. In certain embodiments, filtered gas containing a mixture of hydrocarbon components may be combined with vapor gas 6170 (e.g.,

a mixture of water vapor and oxygen) and subjected to the cracking process to reduce the molecular weight of hydrocarbon components.

In some embodiments, the pyrolysis chamber includes heat sources that burn hydrocarbon gases such as methane, propane, and/or butane, heating the feedstock. A portion of the separated gases 6270 may be recirculated in the pyrolysis chamber for combustion, generating process heat to support the pyrolysis process.

In certain embodiments, process heat can be supplied to the pyrolysis chamber, which can be used to increase the temperature of the raw materials. For example, irradiating raw materials with radiation (eg, gamma radiation, electron beam irradiation, or other types of radiation exposure) can heat raw materials to relatively high temperatures. Heated raw materials can be cooled by a heat exchange system that removes some of the excess heat from the irradiated raw materials. The heat exchange system can be adapted to transport part of the thermal energy into the pyrolysis chamber to heat (or preheat) the raw material, thereby reducing the energy consumption of the pyrolysis process.

A suspension containing liquid and solid pyrolysis products may be subjected to an optional dehydration step 6070, in which excess water may be removed from the suspension by processes such as mechanical compression and evaporation. Excess water 6280 may be filtered and then recycled for further use in quenching pyrolysis decomposition products in stage 6250.

The dewatered slurry then passes through a mechanical separation stage 6080, in which the solid product material 6110 is separated from the liquid product material 6090 by means of a series of fine filters with increasing degrees of purification. In step 6100, the liquid product material 6090 may be further condensed (eg, by evaporation) to remove waste water 6190 and purified by methods such as extraction. Extraction may include the addition of one or more organic solvents 6180, for example, to separate products such as oils from products such as alcohols. Suitable organic solvents include, for example, various hydrocarbons and halogenated hydrocarbons. The purified liquid products 6200 can then be subjected to further stages of processing. Waste water 6190

The CO can be filtered, if necessary, and recycled for further use in quenching pyrolysis decomposition products in stage 6250.

After separation in step 6080, solid product material 6110 is optionally subjected to a drying step 6120, which may include evaporation of water. The solid material 6110 can then be saved for further use or it can be subjected to further stages of processing, depending on the situation.

The parameters of the pyrolysis process discussed above are illustrative. As a rule, the values of these parameters can vary widely, depending on the nature of the raw materials and the desired products.

Moreover, a wide variety of pyrolysis methods can be used, including the use of heat sources such as hydrocarbon flames and/or furnaces, infrared lasers, microwave heaters, induction heaters, resistive heaters, and other heating devices and configurations.

A wide variety of different pyrolysis chambers can be used to decompose raw materials. In some embodiments, for example, pyrrole from the raw material may include heating the material using a resistive heating element, such as a metal hair or metal tape. Heating can occur through direct contact between the resistive heating element and the material.

In certain embodiments, the pyrolysis may include heating the material by induction, for example, using a Curie point pyrolyzer. In some embodiments, pyrolysis may include heating the material by applying radiation, such as infrared radiation. Radiation can be generated by a laser, such as an infrared laser.

In certain embodiments, pyrolysis may include heating the material with convective heat. Convective heat can be generated by a flowing stream of heated gas.

The heated gas may be maintained at a temperature less than about 1200 "C, for example less than about 1000 "C, less than 750 "C, less than 600 "C, less than 400 "C, or even less than 300 C. The heated gas may be maintained at a temperature greater than about 250 "6.

Convective heat can be generated by a heated body surrounding the first material, for example, as in a furnace.

In some embodiments, pyrolysis may include heating the material with steam at a temperature greater than about 250°C.

The embodiment of the chamber for pyrolysis is shown in Fig. 15. The chamber 6500 includes an insulated chamber wall 6510 with a vent 6600 for exhaust gases, a plurality of furnaces 6520 that generate heat for the pyrolysis process, a transport channel 6530 for transporting raw materials through the chamber 6500, a screw conveyor 6590 for transporting raw materials through the channel 6530 in a turbulent flow and a quenching system 6540, which includes a screw conveyor 6610 for transporting pyrolysis products, water nozzles 6550 for spraying the pyrolysis products with cooling water, and a gas separator for separating gaseous products 6580 from a slurry 6570 containing solid and liquid products.

Another embodiment of the chamber for pyrolysis is shown in fig. 16. The chamber 6700 includes an insulated chamber wall 6710, a feed channel 6720, an inclined inner wall of the chamber 6730, furnaces 6740 that generate heat for the pyrolysis process, a vent 6750 for waste gases, and a gas separator 6760 for separating gaseous products 6770 from liquid and of solids 6780. Chamber 6700 is adapted to rotate in the direction shown by arrow 6790 to ensure proper mixing and turbulent flow of raw materials in the chamber.

The next embodiment of the chamber for pyrolysis is shown in fig. 17. Filament pyrolyzer 1712 includes a sample holder 1713 with a resistive heating element 1714 in the form of a wire wound around an open space defined by the sample holder 1713.

Optionally, the heated element may rotate about an axis 1715 (as indicated by arrow 1716 ) to rotate the material, which includes cellulosic material, in the sample holder 1713 .

The space 1718 defined by the enclosure 1719 is maintained at a temperature above room temperature, for example from 200 to 250 "C. In a typical application, a carrier gas, such as an inert gas or an oxidizing or reducing gas, moves transversely through the sample holder 1713, in which while the resistive heating element rotates and heats up to the desired temperature, for example 325 "C. After an appropriate period of time, such as 5 to 10 minutes, the pyrolyzed material is removed from the sample holder. The system presented in fig. 17, can be scaled and made continuous. For example, instead of a wire, a screw conveyor can be used as a heating element. Material can continuously enter the sample holder, coming into contact with the heated screw, which pyrolyzes the material. IN

At the same time, the screw can push pyrolyzed material out of the sample holder, allowing new non-pyrolyzed material to enter.

Another embodiment of the chamber for pyrolysis is shown in fig. 18, which shows a Curie point pyrolyzer 1820 that includes a sample chamber 1821 containing a ferromagnetic foil 1822. The sample chamber 1821 is surrounded by a radio frequency coil 1823.

Space 1824, defined by enclosure 1825, is maintained at a temperature above room temperature, such as 200 to 250 °C. In a typical application, the carrier gas moves transversely through sample holder 1821 while foil 1822 is inductively heated by an applied radio frequency field for pyrolysis of the material at the desired temperature.

Another embodiment of the chamber for pyrolysis is shown in fig. 19. Furnace pyrolyzer 130 includes a movable sample holder 131 and a furnace 132. In a typical application, the sample is lowered (as indicated by arrow 137) into the heating zone 135 of the furnace 132 while the carrier gas fills the jacket 136 and moves transversely through the holder of sample 131. The sample is heated to the desired temperature for the desired period of time to obtain the pyrolyzed product.

The pyrolyzed product is removed from the pyrolyzer by lifting the sample holder (as indicated by arrow 134).

In certain embodiments, as shown in FIG. 20, the cellulosic target 140 can be pyrolyzed by treating the target contained in the vacuum chamber 141 with laser radiation, such as radiation having a wavelength of about 225 nm to about 1500 nm. For example, the target can be destroyed at 266 nm, using the fourth harmonic wave of the Ma-mAs laser (Zresiga RNuvzis5, YASA170, Zap dose, Saiy). The optical configuration shown allows the practically monochromatic light 143 generated by the laser 142 to be directed using mirrors 144 and 145 to the target after passing through the lens 146 in the vacuum chamber 141. As a rule, the pressure in the vacuum chamber is maintained at a level of less than 105 mm Hg. In some embodiments, the implementation uses infrared radiation, for example, radiation from a Ma-MasS laser, which is 1.06 micrometers. In such embodiments, an infrared-sensitive dye can be mixed with the cellulosic material to produce a cellulosic target. The infrared dye can increase the heating of the cellulosic material. Laser destruction is described by Viapspei-Ripspeg. in US patent Mo 5942649.

Referring to FIG. 21, in some embodiments, the cellulosic material may be subjected to flash pyrolysis by coating a tungsten filament 150, such as a 5 to 25 mm tungsten filament, with the desired cellulosic material while the material is contained in a vacuum chamber 151. To provide pyrolysis , a current is passed through the hair that causes rapid heating of the hair for a desired period of time. As a rule, the heating is continued for a few seconds, and then the hair is allowed to cool down. In some embodiments, the heating is carried out several times to ensure the desired degree of pyrolysis.

In certain embodiments, the carbohydrate-containing biomass material may be heated in the absence of oxygen in a fluidized bed reactor. If desired, the carbohydrate-containing biomass may have relatively thin cross-sections and may include any of the fibrous materials described herein for efficient heat transfer. The material can be heated by heat transfer from hot metal or ceramic, such as glass, pellets or sand in a reactor, and the resulting pyrolyzed liquid or oil can be transported to a central treatment plant to produce combustible fuels or other useful products.

In some embodiments, irradiating the biomass material, such as with a beam of particles such as electrons, prior to pyrolysis can lower the pyrolysis temperature, providing less energy consumption in the pyrolysis process.

Oxidation

One or more oxidative processing sequences can be used to process raw materials from a wide variety of different sources to extract useful substances from the raw materials and to obtain partially degraded organic material that serves as an input stream for further stages and/or processing sequences.

Referring again to FIG. 8, in one method, the first material 2, which includes cellulose having a first number average molecular weight ("Mm:i) and having a first oxygen content (70), is subjected to oxidation, for example, by heating the first material in a tube furnace in a stream of air or enriched with air oxygen, to obtain a second material 3, which includes cellulose having a second number average molecular weight ("Mig) and having a second oxygen content (702) lower than the first oxygen content (701). The second material (or in certain embodiments

The first and second materials can, for example, be mixed with a resin, such as a molten thermoplastic resin, or with a microorganism, to obtain a composite 4 having the desired mechanical properties, or a fuel 5.

Such materials can also be combined with a solid and/or liquid. For example, a liquid can be in the form of a solution, and a solid can be in the form of particles. The liquid and/or solid may include a microorganism, such as a bacterium and/or an enzyme.

For example, a bacterium and/or an enzyme can act on cellulosic or lignocellulosic material to produce a fuel such as ethanol or a by-product such as protein. Fuel and co-products are described in RIVNO MATENIAI 5 AMO SOMROBITE5, О55М11/453951, submitted on June 15, 2006. The full content of each of the above applications is incorporated herein by reference.

In some embodiments, the second number average molecular weight is no more than 97 units below the first number average molecular weight, such as no more than 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 30 , 20, 12.5, 10.0, 7.5, 5.0, 4.0, 3.0, 2.5, 2.0 95 or not more than 1.095 below the first number average molecular weight. The amount of molecular weight reduction depends on the application.

In some embodiments, in which the materials are used to produce a fuel or coproduct, the starting number average molecular weight (before oxidation) is from about 200,000 to about 3,200,000, such as from about 250,000 to about 1,000,000 or from about 250,000 to about 700,000, and the number average molecular weight

The BW after pyrolysis is from about 50,000 to about 200,000, such as from about 60,000 to about 150,000 or from about 70,000 to about 125,000. However, in some embodiments, such as after extensive oxidation, the number average molecular weight may be less than about 10,000 or even less than about than 5000.

In some embodiments, the second oxygen content is at least about five percent greater than the first oxygen content, such as greater than 7.5, 10.0, 12.5, 15.0, or 17.5 95. In some preferred embodiments, the second oxygen content of oxygen is at least about 20.0 956 greater than the oxygen content of the first material. The oxygen content is measured by elemental analysis by pyrolysis of the sample in a furnace operating at 1300 C or higher. A suitable device for elemental analysis is the analyzer 1еСО СНМ5-932 3 furnace for high-temperature pyrolysis MTE-900.

In some embodiments, the oxidation of the first material 200 does not significantly change the crystallinity of the cellulose. However, in some cases, for example after excessive oxidation, the second material has a cellulose having a crystallinity (Cg) lower than the crystallinity (Si) of the cellulose of the first material. For example, (Cg) may be lower than (7Ci) by about more than 5 95 , such as 10, 15, 20 95 , or even 25 95 . This may be desirable to increase the solubility of the materials in a liquid, such as a liquid that includes a bacterium and/or enzyme.

In some embodiments, the initial crystallinity index (before oxidation) is from about 40 95 to about 87.5 95, such as from about 50 95 to about 75 95 or from about 60 9o to about 7095, and the crystallinity index after oxidation is from about 30 95 to about 75.0 95, such as from about 35.0 95 to about 70.0 9 or from about 37.59o to about 65.095. However, in certain embodiments, such as after extensive oxidation, the crystallinity index may be less than 5 95.

In some embodiments, the material is essentially amorphous after oxidation.

Without being bound by any particular theory, it is believed that oxidation increases the number of hydrogen-bonding groups on the cellulose, such as hydroxyl groups, aldehyde groups, ketone groups, carboxylic acid groups, or anhydride groups, which can increase its dispersibility and/or its solubility (for example, in liquid). To further enhance the dispersibility in the resin, the resin may include a component that includes hydrogen-bonding groups, such as one or more anhydride groups, carboxylic acid groups, hydroxyl groups, amide groups, amino groups, or a mixture of any of these groups. In some preferred embodiments, the component includes a polymer that is copolymerized with maleic anhydride and/or has grafted maleic anhydride. Such materials are available from Europe under the trade name EOBAVOMOF).

As a rule, the oxidation of the first material 200 occurs in an oxidizing environment.

For example, oxidation can be achieved by pyrolysis in an oxidizing medium, or it can be facilitated by pyrolysis in an oxidizing medium such as air or argon enriched air. Various chemicals, such as oxidizing agents, acids, or bases, may be added to the material prior to or during oxidation to promote oxidation.

For example, peroxide (for example, benzoyl peroxide) can be added before oxidation.

Oxidation systems

Fig. 22 shows a technological scheme 5000, which includes various stages in the system of oxidative pretreatment of raw materials. In the first stage 5010, dry raw material is fed from the feedstock source. The feedstock source may include, for example, a platform or storage container that is connected to the combined oxidation reactor via a conveyor belt or other feedstock transport device.

As described above, the dry feedstock from the feedstock source may be preprocessed prior to delivery to the oxidation reactor. For example, if the raw material is derived from plant sources, certain parts of the plant material may be removed before harvesting the plant material and/or before delivering the plant material to the raw material transport device. Alternatively or additionally, the biomass feedstock can be subjected to mechanical processing (for example, to reduce the average fiber length in the feedstock) before delivery to the reactor for oxidation.

After the mechanical processing 5020, the raw material 5030 is transported to a mixing system that supplies water 5150 to the raw material in the process of mechanical mixing.

The combination of water with the processed raw material at the stage of mixing 5040 leads to an aqueous suspension 5050 of the raw material, which can then be treated with one or more oxidizers.

As a rule, one liter of water is added to the mixture for every 0.02 to 1.0 kg of dry raw materials.

The ratio of raw materials and water in the mixture depends on the source of raw materials and specific oxidizers used further in the process in general. For example, in conventional industrial lignocellulosic biomass processing sequences, aqueous suspension 5050 feedstock includes from about 0.5 kg to about 1.0 kg of dry biomass per liter of water.

In some embodiments, also at the stage of mixing raw materials 5040, one or more fiber-protecting additives 5170 may be added to the raw material suspension. Fiber-protecting additives can be used, for example, if the desired product of the processing of lignocellulosic raw materials includes cellulose fibers. illustrative fiber-protecting additives include magnesium compounds such as magnesium hydroxide. Concentrations of fiber-protecting additives in suspension 5050 raw materials can be, for example, from 0.1 to 0.4 95 dry mass of raw biomass.

In certain embodiments, the aqueous suspension 5050 of the raw material can be subjected to optional extraction 5180 with an organic solvent to remove water-insoluble substances from the suspension. For example, extraction of slurry 5050 with one or more organic solvents results in a purified slurry and organic waste stream 5210, which includes water-insoluble materials such as fats, oils, and other nonpolar hydrocarbon-based substances. Suitable solvents for carrying out the extraction of suspension 5050 include, for example, various alcohols, hydrocarbons and halogenated hydrocarbons.

In some embodiments, the aqueous suspension 5050 of the raw material can be subjected to an optional heat treatment 5190 to further prepare the raw material for oxidation.

An example of heat treatment includes heating a suspension of raw materials in the presence of compressed steam. In fibrous biomass raw materials, the compressed steam causes the fibers to swell, exposing a large part of the fiber surfaces to the aqueous solvent and oxidants that are fed in further stages of processing.

In certain embodiments, the aqueous slurry of raw material 5050 can be optionally treated with basic substances 5200. Treatment with one or more basic substances can facilitate the separation of lignin from cellulose in the lignocellulosic biomass feedstock, thereby improving further oxidation of the raw material. Illustrative basic substances include hydroxides of alkali and alkaline earth metals, such as sodium hydroxide, potassium hydroxide and calcium hydroxide. As a rule, a plurality of basic substances can be used, usually in concentrations of about 0.01 95 to about 0.5 95 of the dry weight of the raw material.

Aqueous slurry 5050 of feedstock is transported (eg, through an in-line piping system) to a chamber, which may be a pre-oxidative processing chamber or an oxidation reactor. At the stage of preliminary oxidation processing 5060, one or more oxidizing agents 5160 are added to the liquid suspension 5050 to form an oxidizing medium. In some embodiments, for example, oxidizing agents 5160 may include hydrogen peroxide. Hydrogen peroxide can be added to suspension 5050 as an aqueous solution and in ratios ranging from 3 to 30-35 wt. 95 suspensions 5050. Hydrogen peroxide has

It has a number of advantages as an oxidizer. For example, an aqueous solution of hydrogen peroxide is relatively inexpensive, relatively chemically stable, and not particularly harmful relative to other oxidizing agents (and thus does not require burdensome storage procedures and expensive protective equipment). Moreover, hydrogen peroxide decomposes with the formation of water in the process of oxidation of raw materials, so that the treatment of the waste stream is relatively simple and inexpensive.

In certain embodiments, the oxidizing agents 5160 may include oxygen (eg, oxygen gas) either alone or in combination with hydrogen peroxide. Oxygen gas can bubble the 5050 slurry in ratios ranging from 0.5 to 10 wt. 95 of slurry 5050. Alternatively or additionally, gaseous oxygen may also be fed into the aqueous phase in equilibrium with slurry 5050 (eg, a steam head above slurry 5050). Oxygen gas can be supplied to either the pre-oxidative processing chamber or the oxidation reactor (or both), depending on the configuration of the oxidative processing system. As a rule, for example, the partial pressure of oxygen in the vapor above the suspension 5050 exceeds the atmospheric pressure of oxygen and is in the range from 0.5 to 35 bar, depending on the nature of the raw material.

Oxygen gas can be supplied in its pure form or can be mixed with one or more carrier gases. For example, in some embodiments, high-pressure air provides oxygen in water vapor. In certain embodiments, gaseous oxygen can be continuously provided in the vapor phase to ensure that during the processing of raw materials, the concentration of oxygen in the vapor remains within certain predetermined limits. In some embodiments, gaseous oxygen may first be supplied in sufficient concentration to oxidize the feedstock, and then the feedstock may be transported to a closed, pressurized vessel (eg, an oxidation reactor) for processing.

In certain embodiments, the oxidants 5160 may include generated oxygen (eg, oxygen radicals). As a rule, the generated oxygen is produced, if necessary, in the oxidation reactor or in a chamber in hydraulic communication with the oxidation reactor by means of one or more decomposition reactions. For example, in some embodiments, the generated oxygen can be formed during the interaction between MO and O2 in a mixture of gases or in solution. In certain embodiments, the generated oxygen may be produced during the decomposition of the NOSI in solution. Other methods by which the generated oxygen can be produced include electrochemical generation, for example in an electrolyte solution.

As a rule, the oxygen formed is an effective oxidant due to the relatively high reactivity of oxygen radicals. However, the oxygen produced can also be a relatively selective oxidant. For example, when lignocellulosic raw materials are treated with generated oxygen, the selective oxidation of lignin with respect to other components of raw materials, such as cellulose, takes place. As a result, the oxidation of raw materials by the generated oxygen provides a method of selective removal of the lignin fraction from certain types of raw materials. As a rule, in order to achieve effective oxidation, concentrations of the generated oxygen from about 0.5 95 to about 5 95 of the dry weight of the raw material are used.

Without regard to theory, it is believed that the generated oxygen reacts with the lignocellulosic raw material by at least two different mechanisms. In the first mechanism, the generated oxygen undergoes a reaction of attachment to lignin, leading to partial oxidation of lignin, which solubilizes lignin in an aqueous solution. As a result, solubilized lignin can be removed from the rest of the raw material by washing. In the second mechanism, the oxygen formed breaks the butane crosslinks and/or opens the aromatic rings that are connected through the butane crosslinks. As a result, the solubility of the aqueous solution of lignin increases, contributing to the separation of the lignin fraction from the rest of the raw material by washing.

In some embodiments, the oxidizing agents 5160 include ozone (Oz). The use of ozone can introduce some conditions for the handling of chemical reagents in the sequence of oxidative processing. When heated excessively, an aqueous solution of ozone can rapidly decompose, with potentially adverse consequences for both the people operating the system and the system equipment. Thus, ozone, as a rule, is formed in a thermally insulated container with thickened walls, separate from the container containing the suspension of raw materials, and transported to it at the appropriate stage of the method.

Without being bound by theory, it is believed that ozone decomposes into oxygen and oxygen radicals, and that the oxygen radicals (for example, oxygen formed) are responsible for the oxidizing properties of ozone, as described above. Ozone, as a rule, preferentially oxidizes the lignin fraction in lignocellulosic materials, leaving the cellulose fraction relatively unaffected.

Conditions for the oxidation of biomass raw materials based on ozone, as a rule, depend on the nature of the biomass. For example, for cellulosic and/or lignocellulosic raw materials, effective oxidation of raw materials is ensured by ozone concentrations from 0.1 to 20 g/m of dry raw materials. As a rule, the water content in the 5050 suspension is from 10 to 80 wt. 95 (for example, from 40 to 60 wt. 95). In the ozone-based oxidation process, the temperature of the 5050 slurry can be maintained between 0 and 100 °C to avoid extensive ozone decomposition.

In some embodiments, the slurry 5050 feedstock may be treated with an aqueous alkaline solution that includes one or more alkali or alkaline earth metal hydroxides, such as sodium hydroxide, potassium hydroxide, and calcium hydroxide, and may then be treated with ozone-containing gas in an oxidation reactor. It was found that this process significantly increases the decomposition of biomass in suspension 5050. As a rule, for example, the concentration of hydroxide ions in an alkaline solution is from 0.001 to 10 wt. 9o suspension 5050. After wetting the raw material by contact with an alkaline solution, ozone-containing gas is fed into the reactor for oxidation, where it contacts the raw material and oxidizes it.

Oxidizers 5160 may also include other substances. In some embodiments, for example, halogen-based oxidants such as chlorine and oxychloride substances (eg, hypochlorite) can be added to slurry 5050. In certain embodiments, nitrogen-containing oxidants can be added to the suspension 5050. Illustrative nitrogen-containing oxidizing agents include, for example, MO and MO." Nitrogen-containing substances in suspension 5050 can also combine with oxygen, creating additional oxidants. For example, both MO and MO' combine with oxygen in the 5050 suspension to form nitrate compounds that are effective oxidizing agents for biomass feedstocks. Halogen- and nitrogen-based oxidants can, in some embodiments, provide bleaching of biomass raw materials, depending on the nature of the raw materials. Bleaching may be desirable for certain biomass-derived products that are extracted in further processing stages.

Other oxidizing agents may include, for example, various peroxyacids, peroxyacetic acids, persulfates, percarbonates, permanganates, osmium tetroxide, and chromium oxides.

After the stage of preliminary oxidation processing 5060, the slurry 5050 of the raw material is oxidized in the stage 5070. If the oxidants 5160 are added to the slurry 5050 in the reactor for oxidation, then the oxidation proceeds in the same reactor. Alternatively, if oxidizing agents 5160 60 are added to slurry 5050 in the pretreatment chamber, then slurry 5050 5O0 is transported to the reactor for oxidation through a piping system connecting them. After entering the oxidation reactor, the oxidation of the biomass feedstock continues under a controlled set of ambient conditions. As a rule, for example, an oxidation reactor is a cylindrical container that is closed from the external environment and is under pressure. Both cyclic and continuous operation are possible, although environmental conditions are generally easier to control in flow-through cyclic processing operations.

Oxidation of suspension 5050 raw materials, as a rule, takes place in a reactor for oxidation at elevated temperatures. For example, the temperature of the slurry 5050 in the oxidation reactor is generally maintained above 100 "C, for example in the range of 120 to 240 "C. For many types of biomass feedstock, oxidation is particularly effective if the temperature of the 5050 slurry is maintained between 150 and 220 C. The 5050 slurry can be heated using various heat transfer devices. For example, in some embodiments, the oxidation reactor contacts a heating bath that includes oil or molten salts. In certain embodiments, a series of heat exchange tubes surround and contact the oxidation reactor, and the circulation of hot fluid in the tubes heats the slurry 5050 in the reactor. Other heating devices that can be used to heat the suspension 5050 include, for example, resistive heating elements, induction heaters, and microwave sources.

The residence time of the feedstock suspension 5050 in the feedstock oxidation reactor can be varied if desired. As a rule, the 5050 suspension is in the reactor during oxidation from 1 minute to 60 minutes. For a relatively soft biomass material such as lignocellulosic material, the residence time in the reactor for oxidation can be from 5 minutes to 30 minutes, for example, at a reactor oxygen pressure of 3 to 12 bar and a slurry temperature of 160 to 210 °C . However, for other types of feedstock, the residence time in the oxidation reactor can be longer, for example up to 48 hours. To determine the appropriate residence time of the 5050 suspension in the oxidation reactor, aliquots of the suspension can be withdrawn from the reactor at certain time intervals and analyzed to determine the concentrations of specific products of interest, such as complex saccharides Information on the increase in concentrations of certain products in suspension 5050 as a function of time can be used to determine residence times for specific classes of feedstock material.

In some embodiments, in the process of oxidation of the suspension of 5050 raw materials, it is possible to correct the pH of the suspension by adding one or more chemicals to the oxidation reactor. For example, in certain embodiments, oxidation occurs more efficiently in the pH range of approximately 9-11. To maintain the pH in this range, such substances as alkali and alkaline earth metal hydroxides, carbonates, ammonia and buffer solutions can be fed into the reactor for oxidation.

In the oxidation process, circulation of the slurry 5050 may be important to ensure sufficient contact between the oxidizing agents 5160 and the feedstock. Circulation of the suspension can be achieved using different methods. For example, in some embodiments, the oxidation reactor may be equipped with a mechanical stirring device that includes impeller blades or a bladed wheel. In certain embodiments, the oxidation reactor may be a loop reactor in which the aqueous solvent in which the feedstock is suspended is simultaneously drained from the bottom of the reactor and recirculated to the top of the reactor by pumping, thereby ensuring that the slurry is continuously mixed repeatedly and does not stagnate in reactors

After the oxidation of the raw material is complete, the slurry is transported to the separation device where the mechanical separation stage 5080 proceeds. As a rule, the mechanical separation stage 5080 includes one or more fine filtration stages with an increasing degree of purification of the slurry for mechanical separation of solid and liquid components.

The liquid phase 5090 is separated from the solid phase 5100 and the two phases are then processed independently. The solid phase 5100 may optionally be subjected to a drying step 5120, for example, in a drying device. The drying step 5120 may include, for example, mechanically distributing the solid material on the drying surface and evaporating water from the solid phase 5100 by gently heating the solid material. After the drying step 5120 (or, alternatively, without the drying step 5120 ), the solid phase 5100 is transported for further processing steps 5140 .

The liquid phase 5090 may optionally be subjected to a drying step 5110 to reduce the concentration of water in the liquid phase. In some embodiments, for example, the drying step 5110 may include evaporation and/or distillation, and/or extraction of water from the liquid phase 5090 by gently heating the liquid. Alternatively or additionally, one or more chemical dewatering reagents may be used to remove water from the liquid phase of bo 5090. After the drying step 5110 (or, alternatively, without the drying step 5110), the liquid phase 5090 is transported for further processing steps 5130, which may include various chemical and biological processing steps, such as chemical and/or enzymatic hydrolysis.

The drying stage 5110 produces a waste stream 5220, an aqueous solution that includes dissolved chemicals such as acids and bases in relatively low concentrations. Treatment of the waste stream 5220 may include, for example, pH neutralization with one or more mineral acids or bases. Depending on the concentration of dissolved salts in the waste stream 5220, the solution may undergo partial deionization (eg, by passing the waste stream through an ion exchange system). The waste stream, which includes primarily water, may then be recirculated into the overall process (eg, as water 5150 ), may be diverted to another process, or may be discarded.

Typically, in the case of lignocellulosic biomass feedstock, after the separation step 5070, the liquid phase 5090 includes a variety of soluble poly- and oligosaccharides, which can then be separated and/or reduced to shorter chain length saccharides by further processing steps.

The solid phase 5100, as a rule, includes mainly cellulose, for example, with smaller amounts of hemicellulose and lignin products.

In some embodiments, the oxidation can be carried out at an elevated temperature in a reactor, such as a pyrolysis chamber. For example, referring again to FIG. 17, feed materials may be oxidized in a filament pyrolyzer 1712. In typical use, an oxidizing carrier gas, such as air or an air/argon mixture, is moved transversely through the sample holder 1713 while the resistive heating element is rotated and heated to a desired temperature , such as 325 °C. After an appropriate period of time, such as 5 to 10 minutes, the oxidized material is removed from the sample holder.

The system presented in fig. 17, can be scaled and made continuous. For example, instead of a wire, a screw conveyor can be used as a heating element.

Material can continuously enter the sample holder, impinging on the heated screw, which pyrolyzes the material. At the same time, the screw can push oxidized material out of the sample holder, allowing new unoxidized material to enter.

The raw materials can also be oxidized in any of the pyrolysis systems presented

From in fig. 18-20 and described above in the section "Systems for pyrolysis".

Referring again to FIG. 21, raw materials can be rapidly oxidized by coating the tungsten filament 150, along with an oxidizing agent such as peroxide, with a desired cellulosic material while the material is in a vacuum chamber 151. To provide oxidation, a current is passed through the filament which causes the filament to rapidly heat up. during the desired period of time. As a rule, heating is continued for several seconds, and then the hair is allowed to cool. In some embodiments, the heating is carried out several times to ensure the desired degree of oxidation.

Referring again to FIG. 12, in some embodiments, raw materials can be oxidized using sound and/or cavitation. Typically, to achieve oxidation, materials are sonicated in an oxidizing medium, such as water saturated with oxygen or another chemical oxidizer, such as hydrogen peroxide.

Referring again to FIG. 9 and 10, in certain embodiments, ionizing radiation is used to promote oxidation of raw materials. Typically, to achieve oxidation, materials are irradiated in an oxidizing medium, such as air or oxygen. For example, gamma radiation or electron beam irradiation can be used to irradiate materials.

Other ways

Steam explosion can be used alone without any of the methods described in this document, or in combination with any one or more of the methods described in this document.

In fig. 23 shows a general view of the entire process of converting a fiber source or raw material 400 into a product 450, such as ethanol, by a method that includes crushing and steam explosion to obtain a fibrous material 401, which is then hydrolyzed and converted, for example, fermented, to form a product. The fiber source can be converted into fibrous material 401 in a number of possible ways, including at least one crushing method and at least one steam explosion method.

For example, one embodiment involves crushing the fiber source, followed by an optional screening step(s) and an optional additional crushing step(s) to produce a comminuted fiber source 402, which may then be subjected to a steam explosion to form a fibrous material 401. After the steam explosion process optionally includes a fiber extraction process to remove liquids or "solution" 404 formed during the steam explosion process. The material formed after the steam explosion of the fragmented fiber source may be further fragmented in an optional additional crushing stage(s) and/or an optional screening stage(s).

In another method, the fibrous material 401 is first steam-exploded to form a steam-exploded fiber source 410. The resulting steam-exploded fiber source is then subjected to an optional fiber extraction process to remove liquids or solution. The resulting steam-exploded fiber source can then be subjected to crushing to produce a fibrous material. The steam-exploded fiber source may also be subjected to one or more additional sieving steps and/or one or more optional additional crushing steps. The method of crushing and steam explosion of the fiber source to obtain crushed and steam-exploded fibrous material is further discussed below.

Prior to crushing or steam explosion, the fiber source may be cut into fragments or strips of confetti-like material. Crushing processes occur on the material in a dry state (eg, having less than 0.25 wt. 95 of absorbed water), in a hydrated state, or even when the material is partially or completely submerged in a liquid such as water or isopropanol. Also, the method may optionally include stages of drying the output stream after steam explosion or crushing to provide additional stages of dry crushing or steam explosion. The stages of crushing, sieving and steam explosion can be carried out in the presence or absence of various chemical solutions.

In the steam explosion method, the fiber source or the fragmented fiber source is contacted with steam under high pressure, and the steam diffuses into the structures of the fiber source (eg, lignocellulosic structures). The steam is then condensed at high pressure, thereby "wetting" the fiber source. Moisture in the fiber source can hydrolyze any acetyl groups in the fiber source (eg, acetyl groups in hemicellulose fractions) to form organic acids such as acetic and uronic acids. Acids, in turn, can catalyze the depolymerization of hemicellulose, the release of xylan and limited amounts of glucan. Then, when the pressure is released, the "soaked" fiber source (or crushed source

From fiber, etc.) "explodes". The condensed moisture evaporates instantly due to the sudden pressure drop, and the expansion of the water vapor exerts a shear force on the fiber source (or shredded fiber source, etc.). Sufficient shear force leads to mechanical destruction of the internal structures (for example, lignocellulosic structures) of the fiber source.

The shredded and steam-exploded fibrous material is then converted into a useful product such as ethanol. In some embodiments, the fibrous material is converted into fuel. One way to convert fibrous material into fuel is through hydrolysis to produce fermentable sugars 412, which are then fermented to produce a product. You can also use other methods of converting fibrous materials into fuel.

In some embodiments, prior to mixing with the microorganism, the shredded and steam-exploded fibrous material 401 is sterilized to kill any competing microorganisms that may be present on the fibrous material. For example, the fibrous material can be sterilized by exposing the fibrous material to radiation such as infrared radiation, ultraviolet radiation, or ionizing radiation such as gamma radiation. Microorganisms can also be destroyed using chemical sterilants such as bleach (for example, sodium hypochlorite), chlorhexidine, or ethylene oxide.

One of the methods of hydrolysis of shredded and steam-exploded fibrous material is the use of cellulases. Cellulases are a group of enzymes that act synergistically to hydrolyze cellulose. You can also use the commercially available enzyme complex AssayPegazeF 1000, which contains a complex of enzymes that break down lignocellulosic biomass into fermentable sugars.

According to current understanding, cellulase components include endoglucanases, exoglucanases (cellobiohydrolases) and β-glucosidases (cellobiases). Synergism between cellulase components exists when hydrolysis by a combination of two or more components exceeds the sum of the types of activity exhibited by individual components. The generally accepted mechanism of action of the cellulase system (in particular, the system of T. Iopdibgaspiasht) on crystalline cellulose is that endoglucanase hydrolyzes internal (B-1,4-glycosidic bonds of amorphous regions, thereby increasing the number of exposed non-reducing ends. Then exoglucanases cleave cellobiose elements from non-reducing ends, which, in turn, are hydrolyzed by B-

glucosidases to individual glucose elements. There are several configurations of both endo- and exoglucanases, distinguished by their stereospecificity. As a rule, the synergistic effect of components in different configurations is necessary for optimal hydrolysis of cellulose. However, cellulases are more prone to hydrolyze the amorphous regions of cellulose. There is a linear relationship between crystallinity and hydrolysis rates, with higher crystallinity indices corresponding to slower enzyme hydrolysis rates. Amorphous regions of cellulose are hydrolyzed at twice the rate of crystalline regions. Hydrolysis of shredded and steam-exploded fibrous material can be carried out using any method of biomass hydrolysis.

Steam explosion of biomass sometimes leads to the formation of by-products, such as toxic substances, which are inhibitory to the activity of microbes and enzymes. Thus, the method of converting shredded and steam-exploded fibrous material into fuel may optionally include a liming stage prior to fermentation to precipitate some of the toxic substances. For example, the pH of shredded and steam-exploded fibrous material can be raised to a pH above 10 by adding calcium hydroxide (Ca(OH)»2), followed by a step of lowering the pH to about 5 by adding Na5Ox. The calcified fibrous material can then be used in this form without removing the sediment. As shown in fig. 23, an optional liming stage is carried out immediately before the hydrolysis stage of the shredded and steam-exploded fibrous material, but it is also envisaged to carry out the liming stage after the hydrolysis stage and before the fermentation stage.

In fig. 24 shows an example of a steam explosion device 460. The steam explosion device 460 includes a reaction chamber 462 into which a fiber source and/or fibrous material is placed through a fiber source inlet 464. The reaction chamber is closed by closing the fiber source inlet valve 465. In addition, the reaction chamber includes an inlet for compressed steam 466, which includes a steam valve 467. In addition, the reaction chamber includes an outlet for depressurization of the explosion 468, which includes an outlet valve 469, which is connected to the cyclone 470 through a connecting pipe 472 When the reaction chamber contains a fiber source and/or a crushed fiber source and

Zo is closed by shut-off valves 465, 467 and 469, steam is supplied to the reaction chamber 462 by opening the steam inlet valve 467, which allows the steam to exit through the steam inlet 466. After the reaction chamber reaches a predetermined temperature, which may take approximately 20-60 seconds, the dwell time begins. The reaction chamber is held at the desired temperature for the desired holding time, which is typically about 10 seconds to 5 minutes. At the end of the holding period, the outlet valve opens, allowing the blast pressure to be released. The depressurization process moves the contents of the reaction chamber 462 from the depressurization outlet 468, through the connecting pipe 472, into the cyclone 470. The steam-exploded fiber source or fibrous material then exits the cyclone in slurry form into a collection basket 474, while most of the residual steam exits the cyclone to the atmosphere through vent 476. In addition, the steam explosion device includes a purge outlet 478 with a purge outlet valve 479 connected to a connecting pipe 472.

The purge outlet valve 479 is closed in the process of using the steam explosion device 460 in the steam explosion, but open in the process of flushing the reaction chamber 462.

The set temperature of the reaction chamber 462 is preferably from 180 to 240 "C or from 200 to 220 "C. The holding time is preferably from 10 seconds to 30 minutes, or from 30 seconds to 10 minutes, or from 1 minute to 5 minutes.

Since the steam explosion process results in a deposit in the form of a steam-exploded fibrous material, the steam-exploded fibrous material may not necessarily be subjected to a fiber drawing process where a "solution" is separated from the steam-exploded fibrous material. This fiber extraction step is desirable because it enables further crushing and/or screening processes and can provide conversion of the fibrous material to fuel. The fiber separation process is carried out using a mesh fabric to separate the fibers from the solution. In addition, drying processes can also be included to obtain a fibrous material or a steam-exploded fiber source for further processing.

Combination of devices for irradiation, pyrolysis, sonication and/or oxidation.

In some embodiments, it may be preferable to combine two or more separate devices for irradiation, sonication, pyrolysis and/or oxidation into a single hybrid device. With the use of such a hybrid device, several processes can be carried out sequentially or even simultaneously, which has the advantage of increasing the productivity of pre-treatment and potential cost savings.

For example, the processes of electron beam irradiation and ultrasound treatment are considered.

Each individual process is effective in reducing the average molecular weight of the cellulosic material by an order of magnitude or more, and several orders of magnitude when performed sequentially.

Both irradiation and sonication processes can be applied using a hybrid electron beam/sonication device, as illustrated in FIG. 25. A hybrid electron beam/ultrasound treatment device 2500 is shown above an empty bath (3-5 cm deep) for a suspension of cellulosic material 2550 dispersed in an aqueous oxidizing medium such as hydrogen peroxide or carbamide peroxide. The hybrid device 2500 has a power source 2510 that powers both the electron beam emitter 2540 and the sonication horns 2530 .

Electron beam emitter 2540 generates electron beams that pass through electron beam targeting device 2545 to impinge on slurry 2550 containing cellulosic material. The electron beam targeting device may be a scanner that transmits the beam over a range of up to about b feet in a direction approximately parallel to the surface of the slurry 2550 .

On either side of the electron beam emitter 2540 are sonication horns 2530 that deliver ultrasonic wave energy to the slurry 2550,

The sonication horns 2530 terminate in a removable nozzle 2535 that contacts the slurry 2550 .

The 2530 sonication horns are at risk of damage due to prolonged residual exposure to electron beam exposure. Thus, the horns may be protected by a standard shield 2520, for example, made of lead or an alloy containing a heavy metal, such as Lipovich metal, which is impermeable to electron beam radiation. However, precautions must be taken to ensure that the presence of the screen does not affect the ultrasonic energy. Detachable tips 2535, which are constructed from that

Made of the same material as the horns 2530 and attached to the horns 2530, contact the cellulosic material 2550 during processing and are expected to be damaged. As such, the 2535's removable tips are designed to be easily replaceable.

Another advantage of this simultaneous electron beam and ultrasound treatment process is that these two processes have complementary results. In the case of irradiation with an electron beam separately, an insufficient dose can lead to cross-linking of some of the polymers in the cellulosic material, which reduces the efficiency of the depolymerization process in general. Also, lower doses of electron beam irradiation and/or ultrasound irradiation can be used to achieve a degree of depolymerization similar to that achieved using electron beam irradiation and sonication separately. The electron beam device can also be combined with one or more of the high frequency rotor-stator devices that can be used as an alternative to sonication devices.

Other device combinations are also possible. For example, a device for irradiation with ionizing radiation, which generates gamma radiation emitted, for example, from tablets 6v0bo, can be combined with a source of electron beams and/or a source of ultrasonic waves. In this case, shielding requirements may be more stringent.

The radiation irradiation devices for biomass pretreatment discussed above can also be combined with one or more devices that perform one or more pyrolysis processing sequences. Such a combination can also have a high performance advantage. However, caution is necessary, as there may be conflicting requirements between some radiation exposure methods and pyrolysis. For example, sonication devices may require the raw material to be immersed in a liquid oxidizing medium. On the other hand, as discussed above, it may be preferable for a feedstock sample to be pyrolyzed to have a specific moisture content. In this case, new systems automatically measure and monitor specific moisture content and regulate it.

In addition, some or all of the above devices, especially the pyrolysis device, can be combined with the oxidation device as discussed above.

BASIC METHODS

Fermentation

Generally, different microorganisms can produce a number of useful products, such as fuel, by acting on pre-treated biomass material, for example by fermenting it. For example, alcohols, organic acids, hydrocarbons, hydrogen, proteins, or mixtures of any of these materials can be produced by fermentation or other processes.

A microorganism can be a natural microorganism or an engineered microorganism. For example, a microorganism can be a bacterium, such as a cellulolytic bacterium, a fungus, such as a yeast, a plant, or a single-celled organism, such as an algae, protozoa, or a single-celled organism similar to a fungus, such as a slime mold. When organisms are compatible, mixtures of organisms can be used.

One or more enzymes, such as a cellulolytic enzyme, can be used to promote the breakdown of materials that include cellulose. In some embodiments, materials that include cellulose are first treated with an enzyme, for example, by combining the material and the enzyme in an aqueous solution. This material can then be combined with a microorganism. In other embodiments, the combination of materials, which include cellulose, one or more enzymes and a microorganism, is carried out simultaneously, for example, by combining in an aqueous solution.

Also, to promote the destruction of materials that include cellulose, the materials after irradiation can be treated with heat, a chemical reagent (eg, a mineral acid, a base, or a strong oxidizing agent such as sodium hypochlorite), and/or an enzyme.

In the fermentation process, the sugars released at the stage of cellulolytic hydrolysis or saccharification are fermented, for example, into ethanol by a fermenting microorganism such as yeast. Suitable fermenting microorganisms are capable of converting carbohydrates such as glucose, xylose, arabinose, mannose, galactose, oligosaccharides or polysaccharides into fermentation products. Fermenting microorganisms include strains of the genus Zasspgotusez 5yr. example

Zasspgotusev segemiziae (baker's yeast), Zasspagotusez aiviaysyv, Zasspagotusev imagit; genus Kinuuhegotusev, for example species Kipsuulegotusev taghiapiv, Kipulegotusez Igadiyiv; genus Sapaid, for example Sapaida rzecydoihorisaii5 and Sapaida Bgazzisae, Rispia v5iiryiz (a relative of Sapaida 5Neaiae), genus Siamigroga, for example species Siamizroga Ish5pyapiae and Siamisgroga oripiae, genus Rasnuzoiep, for example species Raspuzoiep iapporpiyy5, genus Vgeiappotuse5, e.g.

From siaizepia (Riyridie, S.R., 1996, SeyYshiovze Biosopmegviop iesppoiodo, NaparookK op VioyeiNapo!:

Rgodisip apa Shiii2ganyop, MMutap, SE, ey., Tauog b Egapsi5, MMazpipdiop, OS, 179-212). In specific embodiments, for example, when xylose is present, Risnpia virii5 (ATOS 66278) is used for fermentation.

Commercially available yeasts include, for example, Kea 5iagv/ezaite ESHShapoi Kea (available from New York/ezaite, USA)

RPiyir Rosa Ins., USA), ZOREKZT AKT (available from AIShesi, currently the 1st stage), CEVT

ZTKAMOF (available from Sei 5igapa AV, Sweden) and REKMOI F (available from OM bZresiatsiiev).

Bacteria that can ferment biomass into ethanol and other products include, for example, 7utotopav toria and Siovigidiitis (Sheptoseiisht (RNiirriadov, 1996, above). -1160) isolated anaerobic, mesophilic, cellulolytic bacteria from the forest soil, Siovigidiit rpuiyuieeptepiapvy 5r. pou., which convert cellulose into ethanol.

Fermentation of biomass to ethanol and other products can be carried out using certain types of thermophilic or genetically engineered microorganisms, such as species

Tpeptoapayehorasiei, including T. thaiiPgapii and yeast species such as Rispia species. An example of a strain of T. taintapi is AZM4, described by Boppe-Napbep eyi a). in Arriiei Mistorioodu apa

VioyespppoYiodu 1993, 38, 537-541 or AnNhipa ei a). in Agsy. MisgobioI. 1997, 168, 114-119. Other genetically engineered microorganisms are discussed in US Pat. No. 7,192,772.

Yeast and 7utotopap bacteria can be used for fermentation or conversion.

The optimal pH for yeast is about pH 4 to pH 5, while the optimal pH for 7utopahs is about pH 5 to pH 6. The usual fermentation time is about 24 to 96 hours at temperatures in the range of 26 to 40 "C , however, thermophilic microorganisms prefer higher temperatures.

Enzymes that break down biomass such as cellulose into lower molecular weight carbohydrate materials such as glucose in the saccharification process are called cellulolytic enzymes or cellulases. These enzymes can be a complex of enzymes that act synergistically, degrading crystalline cellulose. Examples of cellulolytic enzymes include: endoglucanases, cellobiohydrolases, and cellobiases (β-glucosidases).

The cellulosic substrate is initially hydrolyzed by endoglucanases in random regions, producing oligomeric intermediates. In the future, such intermediate compounds are substrates for exocleaving glucanases, such as cellobiohydrolase, with the formation of cellobiose, which is cleaved from the ends of the cellulose polymer. Cellobiose is a water-soluble, p-1,4-bonded dimer of glucose. Finally, cellobiase breaks down cellobiose to form glucose.

Cellulase is able to degrade biomass and can be of fungal or bacterial origin. Suitable enzymes include cellulases from the genera Vasii5, Rzendotopav, Nitisoia,

Eizagisht, TppieYamia, Asgetopisht, Spguzozorogisht and Tgispodepgta, and include species of Nyptisoia,

Soriipib5, Tniviamia, Ryvagsht, Museiorpiyoga, Astetopisht, SerNaiIozrogisht, Zsuiaiiidiyt,

Repisiysht or AzregudyShie5 (see, for example, EP 458162), especially cellulases produced by strains selected from the species Nyptisoia ipsoiep5 (reclassified as 5Bsugaridiyt

ISheptorpishyt, see, for example, US patent Mo 4435307), Sorgipi5 sipegei5, Ryzagisht ohuzrogyt,

Museiiorpiyoga Iegthornpiia, Megirishv5 adidapiei5, Tniieiamia iegtevigiv, Astetopiit 5r., Astetopiit reguisipit, Astetopisht astetopisht, Asgtetopisht Brgaspurepiit, Astetopisht aispgotozrogyt,

Asgetopisht obsiamayt, Asgetopisht ripKepyopiae, Asgetopisht go5eodgizeit, Asgetopisht ipsoiogaisht and Asgetopisht yiigaisht; mainly from the species Nitisoia ipboyep5 OM 1800, Rizagiit ohuzrogyt OM 2672, Museiiorpiipoga IShepthornpia SV5 117.65, Serpaiosrogisht 5r. AUM-202,

Astetopisht 5 years SV5 478.94, Astetopisht 5 years. SV5 265.95, Astetopisht regvisipit SV5 169.65,

Asgetopiyt asgetopisht ANA 9519, Sernaiozrogisht v5r. SV5 535.71, Astetopisht Bgaspurepiyt

Sv 866.73, Astetopisht aispgotozrogyt SV5 683.73, Astetopisht orsiamaisht SV5 311.74,

Astetopisht ripkepopiae SV5 157.10, Astetopisht goseodiizesht SV5 134.56, Astetopisht ipsoiogasht SV 146.62 and Asgetopisht iigasht SV5 299.70N. Cellulolytic enzymes can also be obtained from Sphuzozoroghist, preferably the strain of Sphuzozoroghist IssKpou'epze. In addition, Thispodegta can be used (in particular Thispodegta migide, Thispodegta geezei and

Tpispodegta Copidia), the alkalophilic Bacilli (see, for example, US Patent No. 3,844,890 and EP 458,162) and 5igeriotuses (see, for example, EP 458,162). The bacterium, sasspagorpadiv dedgadapv»v, produces a mixture of enzymes capable of degrading a number of cellulosic materials, and it can also be used in this process.

Anaerobic cellulolytic bacteria were also isolated from the soil, for example, new cellulolytic species Siovigidiit, Siovigidiit rpuioitetepiapz zr. d. (see I e5spipe ei. a!., Ipiegpaiopai! uChoshgpai oi

Busietaiiis apa EmoIshiopagu Mistoriiodu (2002), 52, 1155-1160).

It is also possible to use cellulolytic enzymes obtained using recombinant technology (see, for example, UUO 2007/071818 and M/O 2006/110891).

Other enzymes and enzyme compositions that can be used are discussed in published US patent applications MoMo 2006/0008885 and 2006/0068475, and PCT application Mo Mo M/O 2006/128304.

The cellulolytic enzymes used can be obtained by fermentation of the indicated strains of microorganisms on a nutrient medium containing suitable sources of carbon and nitrogen and inorganic salts, using methods known in the field (see, for example,

Veppei, UM. and Gazighe, I. (Edv.), Moge Sepe Mapirshiayopv ip Rypdi, Asadetis Rgev55, SA 1991).

Suitable media are available from commercial suppliers and can be obtained according to published formulations (eg, in Ategisap Toure Siyite SoPesiiop catalogs). Temperature ranges and other conditions suitable for the growth and production of cellulase are known in the art (see, for example, Vaieu, U.E., and Ove, O.R., Viospetisa!

VookK Sotrapu, Moscow State University, 1986).

Processing of cellulose with cellulase is usually carried out at temperatures from 30 to 65 s.

Cellulases are active in the pH range from about 3 to 7. The duration of the saccharification stage can be up to 120 hours. The dosage of the cellulase enzyme ensures a fairly high level of cellulose conversion. For example, a suitable cellulase dosage is typically 5.0 to filter paper units (ERI or ME) per gram of cellulose. ERI is a standard measure and is defined and measured according to Spoze (1987, Ryge apa Arri. Snet. 59:257-268). 50 In specific implementation variants, the ASSEGEKABEF 1000 enzyme complex is used as an enzyme system in a dosage of 0.25 ml per gram of substrate. Enzyme complex

ASSAY ECABEF 1000 is a cocktail of many enzymes with many types of activity, mainly exogluconase, endogluconase, hemicellulase and beta-glucosidase. The cocktail has a minimum endogluconase activity of 2500 SMS O/g and a minimum beta-glucosidase activity of 400 pMPOa O/g. The pH of the cocktail is about 4.8 to about 5.2. In other specific embodiments, the enzyme system used is a mixture

SEP PHOSIGABZTF 1.5 and Momolute 188. For example, for each gram of substrate, you can use 0.5 ml of SE OSI ABZTF 1.5I and 0.1 ml of Momolute 188. When higher hemicellulase (xylanase) activity is desired, you can use ORTIMAZ5H m VO.

Portable fermenters can be used as described in the previous patent application

USA Serial No. 60/832735, currently published International Application Mo. MO 2008/011598.

Ethanol fermentation

Ethanol is a product of fermentation. Fermentation is a sequence of reactions that releases energy from organic molecules in the absence of oxygen. In this application of fermentation, energy is generated when sugar is converted into ethanol and carbon dioxide. All food and more than half of industrial ethanol is obtained in this way. The conversion of corn into ethanol by fermentation involves multiple stages. Before fermentation can take place, the starch in the corn must be broken down into simple sugars. This can be achieved, for example, by boiling corn and adding alpha-amylase and glucoamylase enzymes. These enzymes serve as catalysts to accelerate chemical transformations.

After obtaining simple sugar, yeast is added. Yeast are unicellular fungi that feed on sugar and carry out fermentation. As yeast utilizes sugar, they produce alcohol (ethanol) and carbon dioxide. When fermented, ethanol retains most of the energy that was originally in the sugar, which explains why ethanol is an excellent fuel.

The fermentation reaction is represented by a simple equation:

SeNigo6-2SNiIiSnNgOnN2so".

Ethanol can be obtained from a wide variety of available types of raw materials. Fuel ethanol can be produced from crops that contain starch, such as feed grains, food grains such as corn, and tubers such as potatoes and sweet potatoes.

Crops containing sugar, such as sugar beet, sugar cane and sweet sorghum, can also be used to produce ethanol. In addition, by-products of food production such as molasses, cheese whey and cellulosic materials, including grass and wood, as well as agricultural and forestry residues, can be processed into ethanol. As discussed above, these and other types of feedstock can be processed as discussed herein to promote ethanol production.

Conversion of starch materials

In fig. 26 and 27 present block diagrams for the process of dry and wet grinding,

Zo, respectively, and the conversion, such as fermentation, of corn kernels into ethanol and other valuable co-products is illustrated.

Referring in particular to fig. 26, in some embodiments, the dry milling process for converting corn kernels into ethanol, such as anhydrous ethanol that can be used as a fuel, such as automotive or jet fuel, may begin by pretreating the dried corn kernels with any one or more pretreatment methods, disclosed herein, such as radiation exposure, e.g., any one or more types of radiation exposure disclosed herein (e.g., an electron beam in which each electron has an energy of about 5

MeV, or a beam of protons in which the energy of each proton is approximately 3-100 MeV).

After pre-treatment, corn kernels can be ground and/or crushed into powder.

Although one or more of the types of pretreatments disclosed herein may be applied after milling and/or at any time during the dry milling process of FIG. 26, pretreatment prior to grinding and/or crushing may be advantageous because the grains are significantly more brittle after pretreatment and, as a result, may be easier to grind and/or crush, or may require less energy. In some embodiments, the selected pre-treatment in the conversion process can be applied more than once, for example before grinding and then after grinding.

After grinding and/or crushing, the crushed dry grains can optionally be hydrated by adding the crushed material to a container containing water and, optionally, hydrating agents such as surfactants. Optionally, such a reaction vessel may also include one or more enzymes, such as amylase, to promote further breakdown of the starch biomass, or the reaction vessel may contain one or more acids, such as a mineral acid, such as dilute sulfuric acid. If a hydration vessel is used, its contents are poured into a conversion vessel, such as a fermentation vessel, which includes one or more conversion microorganisms, such as one or more species of yeast, bacteria, or a mixture of yeast and/or bacteria. If a hydration tank is not used, the crushed material can be directly loaded into a conversion tank, such as fermentation.

After conversion, the remaining solids are removed and dried to a dry 60 bard (000) while the ethanol is distilled off. In some embodiments, a thermophilic microorganism is used for the conversion, and ethanol is continuously removed by evaporation as it is formed. If desired, the stripped ethanol can be completely dehydrated, for example, by passing aqueous ethanol through a zeolite bed or by distillation with benzene.

Referring in particular to fig. 27, in some embodiments, the wet milling process for converting corn kernels to anhydrous ethanol begins with pretreatment of dried corn kernels with one or more of the types of pretreatments disclosed herein, such as radiation exposure, such as by any one or several types of radiation exposure described in this description (for example, by a beam of electrons in which each electron has an energy of about 5 MeV). After pretreatment, the corn kernels are immersed in dilute sulfuric acid and gently stirred to break down the corn kernels into their components. After soaking, the fiber, oil and germ parts are fractionated and dried, and then combined with the solids remaining after distillation to produce corn gluten feed (CGF). After removing the germs and fibers, in some embodiments, the gluten is separated, resulting in corn gluten meal (COM). The remaining starch can be again (or for the first time) pre-treated with any of the types of pre-treatment disclosed herein, for example to reduce its molecular weight and/or to functionalize the starch so that it is more soluble. In some embodiments, the starch is then placed in a reaction vessel containing water and optionally hydrating agents such as surfactants. Optionally, the reaction vessel may also include one or more enzymes, such as amylase, to promote further breakdown of starch, or the reaction vessel may contain one or more acids, such as a mineral acid, such as dilute sulfuric acid. As shown, saccharification can occur in multiple vessels, and then the contents of the final vessel can be poured into a conversion vessel, such as a fermentation vessel, which includes one or more conversion microorganisms, such as one or more species of yeast or bacteria.

After conversion, ethanol is driven off. In some embodiments, a thermophilic microorganism is used for conversion and ethanol is continuously removed by evaporation as it is formed. If desired, the stripped ethanol can be completely dehydrated, e.g.

By passing aqueous ethanol through a zeolite layer.

Gasification

In addition to the use of pyrolysis for the pretreatment of raw materials, pyrolysis can also be used to process pretreated raw materials to extract useful materials. In particular, a form of pyrolysis known as gasification can be used to produce fuel gases, in addition to various other gaseous, liquid and solid products. For gasification, the pretreated feedstock is fed into a pyrolysis chamber and heated to a high temperature, typically 700°C or higher. The temperature used depends on a number of factors, including the nature of the feedstock and the desired products.

Also, to promote gasification, some amounts of oxygen (for example, in the form of pure gaseous oxygen and/or in the form of air) and steam (for example, superheated steam) are added to the pyrolysis chamber. These compounds react with the carbon-containing feedstock material in a multistage reaction to form a mixture of gases called syngas (or "syngas"). Basically, during gasification, a limited amount of oxygen is supplied to the pyrolysis chamber to ensure the combustion of part of the raw material with the formation of carbon monoxide and the generation of process heat. The process heat can then be used to start a second reaction that converts the additional feedstock into hydrogen and carbon monoxide.

In the first stage of the reaction in general, heating of the feed material results in carbonaceous residues, which may include a wide variety of different hydrocarbon-based compounds. Certain volatiles (such as certain gaseous hydrocarbon materials) may be formed, resulting in a reduction in the total weight of the raw material. Then, in the second stage of the reaction, some of the volatile material formed in the first stage reacts with oxygen in a combustion reaction to produce both carbon monoxide and carbon dioxide. In this combustion reaction, heat is released, which triggers the third stage of the reaction. In the third stage, carbon dioxide and steam (for example, water) react with the carbon residues formed in the first stage, with the formation of carbon monoxide and hydrogen gas. Carbon monoxide can also react with steam in a water vapor conversion reaction, producing carbon dioxide and additional hydrogen gas.

Gasification can be used as a primary process to obtain products 60 directly from pre-treated raw materials, for example, for further transportation and/or sale. Alternatively or additionally, gasification can be used as an auxiliary process to obtain fuel for the entire processing system.

The hydrogen-rich syngas produced in the gasification process can be burned, for example, to generate electricity and/or process heat, which can be used in other parts of the processing system. As a result, the overall recycling system can be at least partially self-sufficient. A number of other products can also be obtained during and/or after gasification, including pyrolytic oils and hydrocarbon-based gaseous substances; they can be separated and stored or transported if desired.

A number of different pyrolysis chambers are suitable for gasification of pretreated feedstocks, including the pyrolysis chambers described herein. In particular, fluidized bed reactor systems, in which pretreated raw materials are subjected to fluidization in oxygen/air vapor, provide relatively high productivity and direct separation of products. The solid carbon residue that remains after gasification in a fluidized bed system (or other pyrolysis chambers) can be burned to generate additional process heat to drive further gasification reactions. Synthesis gas can be converted using the Fischer-Tropsch method, which is a catalyzed chemical reaction in which synthesis gas is converted into liquid alcohols and hydrocarbons. The most common catalysts are based on iron and cobalt, although nickel and ruthenium are also used.

In an alternative process, instead of a chemical catalyst for converting synthesis gas, a biofilm can be used to obtain liquid fuel. This method is described by So5Kaia,

Ips. Any of the biomass materials described in this document can be used in the Co5Kaia method.

In some embodiments, irradiating the biomass material, such as with a beam of particles such as electrons, prior to gasification can lower the gasification temperature, which results in lower energy consumption in the gasification process and can result in less carbon residue and resin formation, leading to increased synthesis yields. gas

FURTHER PROCESSING

Distillation

After fermentation, the obtained fluids can be subjected to distillation using, for example, a "fermentation column" to separate ethanol and other alcohols from most of the water and residual solids. The steam leaving the fermentation column can be, for example, 35 wt. 95 ethanol, and can be fed into the distillation column. A virtually azeotropic mixture (92.5 95) of ethanol and water from the distillation column can be purified to pure (99.5 95) ethanol using vapor phase molecular sieves. The sludge from the fermentation columns can be sent to the first stage of a three-stage evaporator. The reflux condenser can provide the heat for this first stage. After the first stage, the solids can be separated using a centrifuge and dried in a rotary dryer. A portion (25905) of the product from the centrifuge can be reused for fermentation, and the remainder can be sent to the second and third stages of the evaporator. Most of the evaporator condensate can be returned to the process as a fairly clean condensate, where a small portion is separated for waste water treatment to prevent the formation of low-boiling compounds.

Treatment of waste water

Wastewater treatment is used to minimize the need for additional water at the plant by recycling the water for reuse at the plant. Wastewater treatment can also provide fuels (such as sludge and biogas) that can be used to increase the overall efficiency of the ethanol production process.

For example, as described in more detail below, sludge and biogas can be used to generate steam and electricity that can be used in various manufacturing processes.

Waste water is first pumped through a sieve (for example, a grate) to remove large particles that are collected in a waste container. In some embodiments, large particles are sent to landfills. Additionally or alternatively, the large particles are burned to generate steam and/or electricity, as detailed below. Typically, the grid spacing is between 1/4 inch (0.6 cm) and 1 inch (2.5 cm) (eg 1/2 inch (1.3 cm)).

The waste water then flows into an equalization tank, where the concentration of organic compounds in the waste water is balanced during the settling time. As a rule, the settling time is from 8 hours to 36 hours (for example, 24 hours). A mixer for mixing the contents of the container is located in the container. In some embodiments, stirrers located throughout the container are used to mix the contents of the container. In certain embodiments, the agitator essentially agitates the contents of the equilibration vessel so that conditions (eg, wastewater concentration and temperature) are uniform throughout the vessel."

The first pump pumps water from the equalization tank through the liquid-liquid heat exchanger. The heat exchanger is regulated (for example, by controlling the flow rate of the fluid through the heat exchanger) so that the waste water leaving the heat exchanger has the desired temperature for anaerobic treatment. For example, the desired temperature for anaerobic treatment can be from 40 to 60 "С.

After leaving the heat exchanger, the waste water enters one or more anaerobic reactors. In some embodiments, the concentration of sludge in each anaerobic reactor is the same as the total concentration of sludge in the waste water. In other embodiments, the anaerobic reactor has a higher sludge concentration than the total sludge concentration in the waste water.

A nutrient solution containing nitrogen and phosphorus is measured into each anaerobic reactor containing waste water. The feed solution interacts with the bottom in an anaerobic reactor to produce biogas, which can contain 5,095 methane and has a calorific value of approximately 12,000 British thermal units, or Bh, per pound (28,000 kJ/kg). Biogas leaves each anaerobic reactor through a vent and enters the collector, where several streams of biogas are combined into a single stream. The compressor pumps the biogas stream into a steam boiler or internal combustion engine, as described in more detail below. In some embodiments, the compressor also pumps a single stream of biogas through the desulfurization catalyst. Additionally or alternatively, the compressor may pump a single stream of biogas through a sedimentation trap.

The second pump pumps the anaerobic output stream from the anaerobic reactors to one or more aerobic reactors (eg activated sludge rectors). Each aerobic reactor is equipped with an aerator for mixing the anaerobic effluent, the bottom and oxygen (for example, oxygen contained in the air). In each aerobic reactor, the oxidation of cellular material in the anaerobic effluent leads to the production of carbon dioxide, water, and ammonia.

The aerobic outlet stream is moved (for example, by gravity) to a separator, where the sludge is separated from the treated water. A portion of the bottoms is returned to one or more aerobic reactors to create an increased concentration of bottoms in the aerobic reactors, thereby promoting the aerobic destruction of cellular material in the waste water. The conveyor removes excess sediment from the separator. As described in more detail below, excess bottoms are used as fuel to generate steam and/or electricity.

Treated water is pumped from the separator into the sump. Solids dispersed in the treated water settle to the bottom of the sump and are subsequently removed. After the settling period, the treated water is pumped from the settling tank through a fine filter to remove any additional solids remaining in the water. In some embodiments, chlorine is added to the treated water to kill pathogenic bacteria. In some embodiments, one or more methods of physicochemical separation are used for further purification of treated water. For example, treated water can be pumped through a coal absorption reactor. As another example, treated water can be pumped through a reverse osmosis reactor.

In the processes described in this document, when water is used in any of the processes, it may be domestic wastewater, such as municipal wastewater or sewage. In some embodiments, the wastewater or fecal water is sterilized before use. Sterilization can be carried out by any desired method, for example by irradiation, steam or chemical sterilization.

Incineration of waste

The production of alcohol from biomass can lead to the formation of various by-product streams suitable for generating steam and electricity for use in other parts of the plant.

For example, steam generated by burning by-product streams can be used in the distillation process. As another example, electricity generated by burning by-product streams can be used to power electron beam generators and ultrasonic transducers used in pretreatment.

Byproducts used to generate steam and electricity are generated from multiple sources throughout the process. For example, anaerobic digestion of waste water produces biogas with a high methane content and a small amount of waste biomass (scum). As another example, post-distillation solids (eg, unconverted lignin, cellulose and hemicellulose remaining after pretreatment and core processes) can be used as fuel.

Biogas is fed to an internal combustion engine connected to an electric generator to generate electricity. For example, biogas can be used as a fuel source for a natural gas engine with electric ignition. As another example, biogas can be used as a fuel source for a direct injection natural gas engine. As another example, biogas can be used as a fuel source for an internal combustion turbine. Additionally or alternatively, the internal combustion engine can be adapted for a combined configuration to produce electrical and thermal energy.

For example, waste heat from internal combustion engines can be used to provide hot water or steam throughout production.

The residue and solids after distillation are burned to heat the water flowing through the heat exchanger. In some embodiments, the water flowing through the heat exchanger evaporates and is superheated to form steam. In certain embodiments, the steam is used in the reactor for pretreatment and during heat exchange in the processes of distillation and evaporation. Additionally or alternatively, the steam is expanded, powering a multi-stage steam turbine coupled to an electric generator. The steam leaving the steam turbine is condensed with cooling water and returned to the heat exchanger to be reheated to steam. In some embodiments, the rate of flow of water through the heat exchanger is controlled to provide a predetermined production of electricity from a steam turbine coupled to an electric generator. For example, water can be added to the heat exchanger to allow the steam turbine to operate above threshold conditions (for example, the turbine spins fast enough to spin the electric generator).

Although some embodiments have been described, other embodiments are possible.

As an example, although biogas is described as being fed to an internal combustion engine coupled to an electric generator, in certain embodiments the biogas may be passed through a fuel reformer to produce hydrogen. The hydrogen is then converted into electricity using a fuel cell.

As another example, although biogas is described as being burned separately from the bottoms and solids after distillation, in certain embodiments, all waste byproducts may be burned together to produce steam.

PRODUCTS/CO-PRODUCTS

Alcohols

The produced alcohol can be a monohydroxy alcohol, such as ethanol, or a polyhydroxy alcohol, such as ethylene glycol or glycerin. Examples of alcohols that can be produced include methanol, ethanol, propanol, isopropanol, butanol, such as n-, sec-, or tert-butanol, ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, or mixtures of such alcohols.

Each of the alcohols produced at the plant has a commercial value as an industrial raw material. For example, ethanol can be used to make varnishes and perfumes. As another example, methanol can be used as a solvent used as a component in the glass cleaner liquid. As another example, butanol can be used in plasticizers, resins, glazes, and brake fluids.

The bioethanol produced at the plant is valuable as an ingredient used in the food and beverage industry. For example, ethanol produced at the plant can be purified to the level of food grade alcohol and used as the main ingredient in alcoholic beverages.

The bioethanol produced at the plant also has commercial value as a transportation fuel. The use of ethanol as a transportation fuel can be accomplished with relatively little capital investment from manufacturers and owners of electric ignition engines (eg, changing the injection control, fuel-to-air ratio, and fuel injection system components). Many car manufacturers now offer flex-fuel cars capable of running on ethanol/gasoline blends containing up to 85-95% ethanol by volume (for example, standard equipment on the Spnem Taioe 4 x 4).

Bioethanol produced at this facility can be used as engine fuel to improve environmental and economic conditions outside the facility. For example, ethanol produced at this facility and used as a fuel can reduce greenhouse gas emissions from anthropogenic sources (eg, transportation sources). As another example,

ethanol produced at this plant and used as a fuel for engines can also replace the consumed gasoline refined from oil.

Bioethanol has a higher octane number than conventional gasoline, and thus can be used to improve the performance (for example, to provide higher compression ratios) of spark-ignition engines. For example, small amounts (such as 10 vol. 95) of ethanol can be blended with gasoline to act as an octane-enhancing additive to the fuel used in spark-ignition engines. As another example, higher amounts (eg, 85 vol. 95) of ethanol can be mixed with gasoline to further increase the octane number and replace large volumes of gasoline.

Bioethanol strategies are considered, for example, OiRagao v milddai oi OshiokK og Viotav5 ENapo)

Rhodisiyup apa Oetapa (EIIIA Rohesaviv), 2002; ZNeenap in ViotesppoYod Rgodgev5, 15:8179, 1999;

Mapip in Epgut Mystorez5 TesPpoiodu, 31: 274, 2002; Sgeeg in VioSusie, 61-65, Argii 2005; Hupa in

Mistobioodu apa Moiesshiag Vioiodu Nemiem, 66:3, 506-577, 2002; | published in US Pat

MO 4292406; and VePatu, in US Pat. No. 4,094,742.

Organic acids

The organic acids produced may include monocarboxylic acids or polycarboxylic acids. Examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, palmitic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, oleic acid, linoleic acid, glycolic acid, lactic acid acid, γ-hydroxybutyric acid or mixtures of these acids.

Co-products

Lignin residue

As described above, lignin-containing residues from the main and pretreatment processes have value as high/medium energy fuels and can be used to generate power and steam for use in manufacturing processes. However, such lignin residues represent a new type of solid fuel and there is little demand for it outside the plant, and the cost of drying it for transport only reduces its potential value.

In some cases, gasification of lignin residues can turn them into a higher value product with lower costs.

Other co-products

Cell material, furfural, and acetic acid have been identified as potential by-products of biomass-to-fuel equipment. Interstitial cellular material can be valuable, but may require extensive purification. Furfural and acetic acid sales markets

They are relevant, although it is unlikely that they are large enough to absorb the output of a fully commercial lignocellulosic ethanol industry.

EXAMPLES

The following examples are for illustration purposes and are not intended to limit the scope of the present invention.

Example 1 - Production of fibrous material from paper with a multilayer coating

A 1,500 lb (680 kg) slipway of clear half-gallon (1.9 L) juice cartons made of unprinted white kraft paperboard having a bulk density of 20 lb/ft3 (0.32 g/smu), received from Ipiegpayop! Rare Each carton was folded into a flat state and then fed into a Z Pr Nripsi Vacodp shredder at a rate of approximately 15 to 20 pounds per hour (6.8-9.1 kg/hr). The shredder was equipped with two 12-inch (30-cm) rotating blades, two fixed blades, and a 0.30-inch (0.8-cm) discharge screen. The distance between the rotating and fixed blades was set at 0.10 inches (0.25 cm). The material exiting the shredder resembled confetti, 0.1 inch (0.25 cm) to 0.5 inch (1.3 cm) wide, 0.25 inch (0.6 cm) to 1 inch (2.5 cm) and a thickness equivalent to the thickness of the parent material (approximately 0.075 inch (0.2 cm)).

The confetti-like material was fed into a Mipsop Model 5030 Rotary Knife Cutter. The Model 50230 is equipped with four rotating blades, four fixed blades, and a discharge screen having 1/8 inch (0.32 cm) openings. The gap between the rotating and fixed blades was set at approximately 0.020 inch (0.05 cm). A rotating knife cutter crushed the confetti-like fragments with the blade tips, breaking the fragments and releasing the fibrous material at a rate of approximately one pound per hour (454 grams per hour). The fibrous material had a VET surface area of 0.9748520.0167 m/g, a porosity of 89.0437 95 and a bulk density (at 0.53 psi abs. (3.7 kPa)) of 0.1260 g/ Jr. The average fiber length was 1.141 mm and the average fiber width was 0.027 mm, giving an average G/0 of 42:71. A picture obtained with the help of a scanning electron microscope at a magnification of 25X of the fibrous material is shown in Fig. 28.

Example 2 - Production of fibrous material from bleached kraft cardboard.

A slipway weighing 1500 lb (680 kg) of pure bleached kraft paperboard having a bulk density of 30 lb/ft? (0.48 g/smu), received from Ipiegpayop! Rare The material was flattened and then fed into a Z Pr Riipsi Vatsopy shredder at a rate of approximately 15 to 20 pounds per hour (6.8-9.1 kg/hr). The shredder was equipped with two 12-inch (30-cm) rotating blades, two fixed blades, and a 0.30-inch (0.8-cm) discharge screen. The distance between the rotating and fixed blades was set at 0.10 inches (0.25 cm). The material exiting the shredder resembled confetti, 0.1 inch (0.25 cm) to 0.5 inch (1.3 cm) wide, 0.25 inch (0.6 cm) to 1 inch (2.5 cm) and a thickness equivalent to the thickness of the parent material (approximately 0.075 inch (0.2 cm)). The confetti-like material was fed into a Mipbzop rotary knife cutter, Model 5030. The Model 5030 is equipped with four rotary blades, four fixed blades, and a discharge screen having 1/8 inch (0.32 cm) openings. The gap between the rotating and fixed blades was set at approximately 0.020 inch (0.05 cm). A rotating knife cutter crushed the confetti-like fragments with the blade tips, breaking the fragments and releasing the fibrous material at a rate of approximately one pound per hour (454 grams per hour). The fibrous material had a VET surface area of 1.1316240.0103 mg/g, a porosity of 88.3285 95 and a bulk density (at 0.53 psi abs. (3.7 kPa)) of 0.1497 g/ml . The average fiber length was 1.063 mm and the average fiber width was 0.0245 mm, giving an average 1/0 of 43:1. A picture obtained with the help of a scanning electron microscope at a magnification of 25X of the fibrous material is shown in Fig. 29.

Example C - Production of twice-shredded fibrous material from bleached kraft cardboard

A slipway weighing 1500 lb (680 kg) of pure bleached kraft paperboard having a bulk density of 30 lb/ft? (0.48 g/smu), received from Ipiegpayop! Rare The material was flattened and then fed into a Z Pr Riipsi Vatsopy shredder at a rate of approximately 15 to 20 pounds per hour (6.8-9.1 kg/hr). The shredder was equipped with two 12-inch (30-cm) rotating blades, two fixed blades, and a 0.30-inch (0.8-cm) discharge screen. The distance between the rotating and fixed blades was set at 0.10 inches (0.25 cm). The material coming out of the shredder resembled confetti (see above). The candy-like material was fed into a Mipsop model 5230 rotary knife cutter. The discharge screen had 1/16 inch (0.16 cm) openings. The gap between and fixed rotating blades was set at approximately 0.020 inch (0.05 cm). A rotating knife cutter crushed the confetti-like fragments with the blade tips, breaking the fragments and releasing the fibrous material at a rate of approximately one pound per hour (454 grams per hour). The material obtained after the first crushing was again fed into the same plant described above and crushed again.

The resulting fibrous material had a VET surface area of 1.4408 x 20.0156 m/g, a porosity of 90.8998 95 and a bulk density (at 0.53 lb/sq. in. abs. (3.7 kPa)) of 0.1298 g/ Jr. The average fiber length was 0.891 mm and the average fiber width was 0.026 mm, giving an average G/O0 of 3471. A scanning electron microscope image at 25X magnification of the fibrous material is shown in FIG. 30.

Example 4 - Production of three-fold shredded fibrous material from bleached kraft cardboard

A slipway weighing 1500 lb (680 kg) of pure bleached kraft paperboard having a bulk density of 30 lb/ft? (0.48 g/smu), received from Ipiegpayop! Rare The material was flattened and then fed into a Z Pr Riipsi Vatsopy shredder at a rate of approximately 15 to 20 pounds per hour (6.8-9.1 kg/hr). The shredder was equipped with two 12-inch (30-cm) rotating blades, two fixed blades, and a 0.30-inch (0.8-cm) discharge screen. The distance between the rotating and fixed blades was set at 0.10 inches (0.25 cm). The material coming out of the shredder resembled confetti (see above). The candy-like material was fed into a Mipsop rotary knife cutter, model 50230. The discharge screen had 1/8 inch (0.32 cm) openings. The gap between and fixed rotating blades was set at approximately 0.020 inch (0.05 cm). A cutting device with a rotating knife crushed confetti-like bo fragments with the edges of the blades. The material obtained after the first crushing was again fed into the same plant described above, and the screen was replaced with a screen with holes of 1/16 inch (0.16 cm).

The material was crushed. The material obtained after the second crushing was again fed into the same plant described above, and the screen was replaced with a screen with openings of 1/32 inch (0.08 cm). This material was crushed. The resulting fibrous material had a VET surface area of 1.689720.0155 mg/g, a porosity of 87.7163 95 and a bulk density (at 0.53 psi abs. (3.7 kPa)) of 0.1448 g/ Jr.

The average fiber length was 0.824 mm and the average fiber width was 0.0262 mm, giving an average 1/0 of 32:1. A picture obtained with the help of a scanning electron microscope at a magnification of 25X of the fibrous material is shown in Fig. 31.

Example 5 - Preparation of densified fibrous material from bleached kraft paper without the addition of a binder

The fibrous material was prepared according to Example 2. Approximately 1 pound (454 g) of water was sprayed for every 10 pounds (4540 g) of fibrous material. The fibrous material was compacted using a Sioggia Reilly Milli 1100 pellet press operating at 7576. Pellets having bulk densities ranging from about 7 lb/ft3 (0.11 g/cm3) to about 15 lb/ft (0 , 24. g/cm3).

Example 6 - Production of compacted fibrous material from bleached kraft cardboard with a binder

Fibrous material was obtained according to example 2.

The initial solution of ROI MOH "M UUZA M10 (polyoxyethylene) was prepared in water at a concentration of 2 wt. 95.

Approximately 1 pound (454 g) of water was sprayed for every 10 pounds (4540 g) of fibrous material. The fibrous material was compacted using a granulation press

1,100, operating at 75°C. Pellets having a bulk density in the range of about 15 lb/ft (0.24 g/cm3) to about 40 lb/ft (0.64 g/cm3) were obtained. .

Example 7 - Reduction of the molecular mass of cellulose in fibrous kraft paper by gamma radiation with minimal oxidation

Fibrous material was obtained according to example 4. Fibrous kraft paper was compacted according to example 5.

Compacted granules were placed in a glass ampoule with a maximum capacity of 250 ml. glass

The ampoule was evacuated under high vacuum (107 torr) for 30 minutes and then backfilled with argon gas. The ampoule was sealed in an argon atmosphere. The granules in the ampoule were irradiated with gamma radiation for about 3 hours at a dose level of about 1

Mrad per hour, with the production of irradiated material in which the cellulose had a lower molecular weight than in the source material of fibrous kraft paper.

Example 8 - Reduction of the molecular mass of cellulose in fibrous kraft paper by gamma radiation at maximum oxidation

Fibrous material was obtained according to example 4. Fibrous kraft paper was compacted according to example 5.

Compacted granules were placed in a glass ampoule with a maximum capacity of 250 ml. The glass ampoule was sealed in an air atmosphere. The pellets in the ampoule were irradiated with gamma radiation for about 3 hours at a dose level of about 1 Mrad per hour, producing an irradiated material in which the cellulose had a lower molecular weight than the source material of fibrous kraft paper.

Example 9 - Methods of determining the molecular weight of cellulosic and lignocellulosic materials using gel permeation chromatography

Cellulosic and lignocellulosic materials for analysis were processed according to example 4.

Sample materials presented in the following tables include kraft paper (P), wheat straw (M/5), alfalfa (A), and millet (503). The number "132" in the sample ID refers to the particle size of the material after passing through a 1/32 inch (0.08 cm) sieve. The number after the hyphen refers to the dosage of radiation (Mrad) and "E" refers to ultrasonic treatment. For example, the IU sample "P132-10" refers to kraft paper, which was subjected to crushing to the size of particles of caliber 132 and irradiated with a dose of 10 Mrad.

Table 1

Peak average molecular weight of irradiated kraft paper

Dosage! average

Sample source! W sample (Mrad) Ultrasound! MM standard deviation

Kraft paper RIZ2 77770717 no | з2853510006 79 111111 CUT 17717107 171111 6139ва2468иШО 111111 1 CUTTING 1100/1777 ва4ж80 111111 1 CUTTING 1181/1771 11111111 6668ж1711 1 121711 1 | /70777171717171771717171711 yes | called ""Low doses of radiation appear to increase the molecular weight of some materials.

Dosage level - 1 Mrad/h. 2Treatment for 30 minutes with 20 kHz ultrasound using a 1000 W horn in recirculation conditions where the material is dispersed in water.

Table 2

Peak average molecular weight of irradiated materials

average

IO sample Dosage! Ultrasound? mm tne (Mrad) deviation 1 MYVISA 17711710 17111111no | лота 751910Ш ниІНнН ШЕ Пр ИНА ОО ВЕ СХ ЕЕ ХУ н?"нІЕШНШНЕНИшл ние нин еле До о МуВІЗаЯОМ17111711111о 71117171 26040532407ШГ о МуВІЗатО1 1777177177117100 77771717 236205453..Г-:ЗГЖе 1 АТ32 7 1711711171717771117011111717717171717171717и111111111711116о0488632151701.ЙШЧУЬ ниІНн"Н""Є ЕРИ шили ШЕ БУТ ЭХ НЩІНІІІІІІІІНІНІНИЛІ Шли пи ЕСЕ ST 1 АТ32ОЯ1111111111о 71111111 50853241665 D.-:МЖК ниН;ННІнШоШС6НС They went nin PE S ХЕ u До АТ32О1Я | 7117 Y771lob 17111111 z8vaoizheg3 11211117 111y111111111111gavtn 86132 | 1 ЇЇ ЮюЮЙ0 1 юЮюЮю и 1 1557360ж583693 ЙЩщ РА( 12111111 о5еаняє0 18111711 32685249. о 8візаяої | 7117 Ї7777171-77771717717171717171717и71111111111711111 о вов8вжеі31 о ват3а00ї | 1777100 17777171 22345ж3797 11211117 11111111 (| 5аї32-100-05 | 1 | 10 | юЮр/ли111ИИлсо69651465 4 " The peaks are merged after treatment. ""Low doses of radiation appear to increase the molecular weight of some materials.

Dosage level - 1 Mrad/h. 2Treatment for 30 minutes with 20 kHz ultrasound using a 1000 W horn in recirculation conditions where the material is dispersed in water.

Gel permeation chromatography (GPC) is used to determine the molecular weight distribution of polymers. In CPS analysis, a polymer sample solution is passed through a column filled with a porous gel that traps small molecules. The sample is separated based on molecular size, with larger molecules eluting faster than smaller molecules. The retention time of each component is most often determined using the refractive index (RI). light scattering during evaporation (EB/5) or ultraviolet radiation (UV) and compared with the calibration curve. The resulting data are then used to calculate the molecular weight distribution for the sample.

Molecular weight distribution is used to characterize synthetic polymers instead of individual molecular weight. To characterize such a distribution, statistical averages are used. The most common of these average values are "number average molecular weight" (My) and "weight average molecular weight" (Mu). Methods of calculating these values are described in this field, for example, in example 9 of M/O 2008/073186.

The polydispersity index or RI is defined as the Mu/My ratio. The higher the RI, the wider or more dispersed the distribution. The lowest value that RI can have is 1. It corresponds to a monodisperse sample, that is, a polymer in which all molecules in the distribution have the same molecular weight. The peak value of the molecular weight (Mp) is another descriptive feature defined as the mode of the molecular weight distribution. It means the molecular weight that is most common in the distribution. This value also gives an idea of the molecular weight distribution.

Most of the SPC measurements were performed against various polymer standards. The accuracy of the results depends on how close the characteristics of the analyzed polymer are

Match the characteristics of the used standard. The expected reproducibility error between different series of individually calibrated determinations was approximately 5-10 95 and is typical of the limited precision of CPS determinations. Thus, vRS results are most suitable when comparing the molecular weight distributions of different samples during the same series of determinations.

For lignocellulosic samples, preparation was required before SPC analysis. First, a saturated solution (8.4 wt. 95) of lithium chloride (LI) in dimethylacetamide (DMAC) was prepared.

Approximately 100 mg of each sample was added to approximately 10 g of freshly prepared saturated solution of HYSIIOMAS, and each mixture was heated to approximately 150-170 C with stirring for 1 hour. The obtained solutions had a color mainly from light yellow to dark yellow. The temperature of the solutions was reduced to approximately 100°C and the solutions were heated for an additional 2 hours. The temperature of the solutions was then reduced to approximately 50°C and the solution of each sample was heated for approximately 48 to 60 hours. It should be noted that

The samples irradiated at 100 Mrad were more easily solubilized compared to their untreated counterparts. In addition, the chopped samples (labeled 132) had a slightly lower average molecular weight compared to the uncut samples.

The resulting sample solutions were diluted 1:11 using OMas as a solvent and filtered through a 0.45-μm RTEE filter. Then the filtered solutions of the samples were analyzed using CPS. The peak average molecular weight (Mw) of the samples, as determined by gel permeation chromatography (GPC), is summarized in Tables 1 and 2. Each sample was prepared in duplicate, and each sample preparation was analyzed in two parallels (two injections), total with four injections per sample. To obtain a calibration curve for the molecular weight scale from approximately 580 to 750,000 Daltons, polystyrene standards ROTA and PO1B of EvzisSai were used.

Table C

Terms of analysis of the Fed

Example 10 - Determination of crystallinity of irradiated material using X-ray diffraction

X-ray diffraction (XRD) is a method by which a crystalline sample is irradiated with monoenergetic X-rays. The interaction of the lattice structure of the sample with these X-rays is recorded, and it gives information about the crystalline structure exposed to the radiation. The obtained characteristic "print" allows the identification of crystalline compounds present in the sample. Using pattern matching analysis (She Vieimeii Neiipetepi), it is possible to perform quantitative analyzes of samples containing more than one crystalline compound.

Table 4

HNO data including domain size and 95% crystallinity

Each sample was placed on a zero background holder and placed in a Riyir diffractometer

RM/1800, which uses the radiation of Si. Scans were then performed in the range from 57 to 507 with a step size of 0.05" and a counting time of 2 hours in each case.

After obtaining the diffractograms, the phases were identified using Romjaeg Riygasiup Rije published by Ipiegpaiopa! Sepige tog Ointkasiyop Weight. In all samples, the identified crystalline phase was cellulose - Ia, which has a triclinic structure.

Distinctive features for 20 samples are the peak width, which is related to the size of the crystal domain. The experimental peak width was used to calculate the domain size and percent crystallinity, which are presented in Table 4.

The percentage of crystallinity (He o) is defined as the ratio of the area for the crystalline phase to the total area under the X-ray diffraction peaks

Hoooo- quiet 10086,

Ia that As) where

Ac is the area for the crystalline phase,

Aa is the area for the amorphous phase,

Heh x percentage of crystallinity.

To determine the percent crystallinity of each sample, it was necessary to first determine the amount of amorphous phase. This is done by estimating the area of each diffractogram that can be attributed to the crystalline phase (which is shown by the sharper peaks) and the non-crystalline phase (which is shown by the broad humps below the graph and centered at 22" and 387).

A systematic process was used to minimize error in these calculations due to broad crystal peaks as well as high background intensity. First, they applied

From the linear background and then canceled it. Second, each of the two Gaussian peaks centered at 22" and 38? with a width of 10-12" was aligned with humps below the crystalline peaks. Thirdly, the area under the two broad Gaussian peaks and the other part of the graph was determined. Finally, percent crystallinity was calculated by dividing the area under the crystalline peak by the total intensity (after background subtraction). The domain size and 95 crystallinity of the samples when determined by X-ray diffraction (XRD) are presented in Table 4.

Example 11 - Analysis of irradiated materials by porometry

Mercury analysis of pore size and pore volume (Table 5) is based on passing mercury (a non-wetting liquid) into a porous structure under strictly controlled pressure. Since mercury does not wet most substances and does not penetrate the pores spontaneously due to capillary action, it must be driven into the cavities of the sample using external pressure. The pressure required to fill the cavities is inversely proportional to the pore size. Only a small amount of force or pressure is required to fill large cavities, while much higher pressure is required to fill very small pores.

Table 5

Distribution of the size and volume of pores using mercury porosimetry

General Middle Middle-| Average density

And General "ny "ny | And at 0.50 Imaginary

And the penetration of the sample - |a area) diameter ) diameter | diameter lb./sq. (skeletal Porosity pore pore pore pore pore and bo. ) density (U) volume | (mg/3) | (volume) | (area) | (4B/A) | rim, a (g/ml) (ml/g) (μm) (μm) (μm) (8.45 kPa) (g/ml)

AshoRoge 9520 can reach a maximum pressure of 414 MPa or 60,000 psi. inch abs It has four low pressure stations for sample preparation and macropore data collection at 0.2 psi. inch abs (1.4 kPa) to 50 lb/sq. inch abs (345 kPa). It has two high-pressure chambers that collect data at 25 psi. inch abs (172 kPa) to 60,000 lb/sq. inch abs (414 MPa). The sample was placed in a cup-shaped device called a penetrometer, which is connected to a glass capillary rod with a metal coating. As mercury penetrates the cavities in and around the sample, it moves down the capillary rod. The loss of mercury from the capillary rod leads to a change in capacitance. The change in electrical capacity during the experiment is converted into the volume of mercury, based on the known volume of the rod of the used penetrometer. A variety of penetrometers are available with different bowl (sample) and capillary sizes to accommodate most sample sizes and configurations. Table 6 below identifies the key parameters calculated for each sample.

Table 6

Determination of the parameters of En nCl

The total permeated volume may include interstitial filling between small particles, sample porosity and sample compression volume, total pore area - assuming a cylindrical pore shape

Table 6

Definition of parameters

The mass of the sample divided by the total volume. Full volume

Bulk density is determined at a fill pressure of typically 0.5 lb/sq. inch abs (3.45 kPa)

The mass of the sample divided by the volume of the sample measured at the most

Apparent density at high pressure, as a rule, 60,000 lb./cu. inch abs (414

MPa

Example 12 - Analysis of the particle size of irradiated materials

The method of determining particle size using light scattering is based on theory

Mee (which also covers Fraunhofer's theory). Mie's theory predicts the intensity-angle relationship as a function of the size of the spherical scattering particles, provided that the other system variables are known and held constant. These variables are the wavelength of the incident light and the relative refractive index of the sample material. The application of Mie's theory provides detailed information on particle size. Table 7 summarizes the size of the particles when used as parameters of median diameter, mean diameter and modal diameter.

Table 7

The size of particles during the scattering of laser radiation (dispersion of a dry sample) and (LEK relay end

IO sample diameter Average diameter (μm) (μm) (μm)

Particle size was determined by laser scattering (dry sample dispersion) using Maimet Mazwiegwieg 2000, using the following conditions: feed rate: 35 9, disperser pressure: 4 bar, optical model: (2.610, 1.000), 1.000.

The appropriate amount of the sample was fed to the vibrating tray. The feed rate and air pressure were adjusted to ensure that the particles were properly dispersed.

The key component is choosing an air pressure that breaks up the agglomerates but does not compromise the integrity of the sample. The amount of sample required varies with particle size. As a general rule, samples with fine particles require less material than samples with large particles.

Example 13 - Analysis of the surface area of irradiated materials

The surface area of each sample was analyzed using the Misgotegysv ABAR 2420 Asse|egaied Agea ap Rogoziteiyu Bzuvziet system. The samples were prepared by primary degassing for 16 hours at 40 "C. Next, the free space (both warm and cold) with helium was calculated and then the tube with the sample was vacuumed again to remove helium.

Data collection begins after the second vacuum and consists of setting a set pressure that controls how much gas is dosed into the sample. At each given pressure, the amount of adsorbed gas and the true pressure were determined and recorded. The pressure inside the sample tube was measured using a pressure sensor. Additional doses of gas continued to arrive until the set pressure was reached and equalization was ensured. The amount of adsorbed gas was determined by summing the set of doses for the sample. Pressure and quantity determine the gas adsorption isotherm and are used to calculate a number of parameters, including surface area

VET (table 8).

Table 8

Generalized representation of surface area by gas adsorption

The BET model for isotherms is a widely used theory for calculating the specific surface area. The analysis involves determining the monolayer capacity of the sample surface by calculating the amount needed to cover the entire surface with one close-packed layer of krypton. To determine the total surface area, the capacity of the monolayer is multiplied by the cross-sectional area of the sample gas molecule. The specific surface area is the surface area of a sample aliquot divided by the mass of the sample.

Example 14 - Determination of the length of fibers in irradiated materials Testing of the distribution of fiber lengths was carried out in three parallels on the presented samples using the Tesprar Motgri I VO1 system. The average length and width are presented in Table 9.

Table 9

Generalized presentation of data on the length and width of lignocellulosic fibers

Statistically

Arithmetic Average Length, Adjusted Width

IO sample average value |weighted by length| average length, (micrometers) nen EE, teo Mn

MM

Example 15 - Ultrasonic treatment of irradiated and non-irradiated millet

Millet was crushed according to example 4. Millet was treated only with ultrasound or irradiation with gamma rays at a dose of 10 or 100 Mrad, followed by ultrasound treatment.

The obtained materials correspond to C132-BA (unirradiated), 132-10-82 (10 Mrad and sonication) and y132-100-BA (100 Mrad and sonication), as shown in Table 1.

Ultrasound treatment was carried out for each sample for 30 minutes using ultrasound with a frequency of 20 kHz from a 1000 W horn in recirculation conditions. Each sample was dispersed in water at a concentration of approximately 0.10 g/ml.

In fig. 32 and 33 shows the device used for ultrasonic treatment.

The device 500 includes a transducer 502 connected to a booster 504 connected to a horn 506 made of titanium or a titanium alloy. The horn, which has insulation 510 made of MITOMF) around its perimeter on the processing side, forms a liquid-tight seal with the processing cell 508. The processing side of the horn is immersed in a liquid, such as water, in which the sample to be processed is dispersed. ultrasound treatment.

Cell pressure is monitored using pressure sensor 512. In the operational state, each sample is pushed by pump 517 from container 516 through the processing cell and sonicated. After sonication, the sample is collected in container 520. The process may be reversible in that the contents of container 520 may be sent through the processing cell and collected in container 516. This process may be repeated several times until the desired level of sample processing is achieved. .

Example 16 - Scanning electron microscope images of non-irradiated millet compared to irradiated and irradiated and sonicated millet

Millet samples for scanning electron microscope images were placed on carbon tape and sputter-coated with gold (70 seconds). Images were obtained using a scanning electron microscope with field emission of UEOI. 6500.

In fig. 34 presents a picture obtained with the help of a scanning electron microscope at a magnification of 1000X of fibrous material obtained by crushing millet on a cutting device with a rotating knife and then passing the crushed material through

Using a sieve with 1/32 inch (0.08 cm) openings.

In fig. 35 and 36 show images obtained using a scanning electron microscope at a magnification of 1000X of the fibrous material from fig. 34 after irradiation with gamma rays at a dose of 10 Mrad and 100 Mrad, respectively.

In fig. 37 presents images obtained using a scanning electron microscope at a magnification of 1000X of the fibrous material from fig. 34 after 10 Mrad irradiation and ultrasound treatment.

In fig. 38 presents images obtained using a scanning electron microscope at a magnification of 1000X of the fibrous material from fig. 34 after 100 Mrad irradiation and ultrasound treatment.

Example 17 - Infrared spectrum of irradiated kraft paper compared to non-irradiated kraft paper

ET-IR analysis was performed on a MisoiIetras 400. The results indicate that all the samples presented in Table 1 correspond to cellulose-based material.

In fig. 39 shows the infrared spectrum of kraft cardboard shredded according to example 4, and in fig. 40 presents the infrared spectrum of the kraft hyaper from fig. 39 after exposure to gamma radiation at a dose of 100 Mrad. The irradiated sample exhibits an additional peak in region A (centered at approximately 1730 cm") that is not present in the unirradiated material.

Example 18 - Combination of pretreatment with an electron beam and ultrasound

Millet was used as raw material and crushed with a cutting device with a rotating knife

Mypbzop on fibrous material. The fibrous material was then uniformly distributed on an open tray made of tin with an area of more than 500 in: (12.7 m). The fibrous material was distributed so that it had a thickness of approximately 1-2 inches (2.5-5 cm) in an open tray. The fibrous material can be distributed in plastic bags at lower radiation doses (less than 10 Mrad) and left exposed on a metal tray at higher radiation doses.

Then individual samples of fibrous material were subjected to successive doses of electron beam irradiation to achieve a total dose of 1, 2, 3, 5, 10, 50 and 100 Mrad. Some samples were maintained under the same conditions as other samples but not irradiated to serve as controls. After cooling, the irradiated fibrous material was sent for further processing through an ultrasonic treatment device.

The ultrasonic treatment device includes a transducer connected to a booster connecting a horn made of titanium or a titanium alloy. The horn, which has insulation made of MITOMF around its perimeter on its processing side, forms a liquid-tight seal with the processing cell. The processing side of the horn is immersed in a liquid, such as water, in which the sample to be sonicated is dispersed.

The pressure in the cell is monitored using a pressure sensor. In operation, each sample is pumped from the container through the processing cell and sonicated.

To prepare the irradiated fibrous material for sonication, the irradiated fibrous material was drawn from any container (eg, plastic bags) and dispersed in water at a concentration of approximately 0.10 g/ml. Ultrasound treatment was performed on each sample for 30 minutes using ultrasound with a frequency of 20 kHz from a 1000 W horn in recirculation conditions. After sonication, the irradiated fibrous material is collected in a container. This process can be repeated many times until the desired level of processing is achieved, based on the monitoring of structural changes in the millet. Also, some irradiated samples were kept under the same conditions as the other samples but not sonicated to serve as controls. In addition, some samples that were not irradiated or not treated with ultrasound also act as controls. Thus, some controls are not treated, some are only irradiated, and some are only treated with ultrasound.

Example 19 - Testing of pre-treated biomass using microorganisms

Specific lignocellulosic materials pretreated as described herein are analyzed for toxicity to common strains of yeast and bacteria used in the biofuel industry for the fermentation step of ethanol production. In addition, sugar content and compatibility with cellulase enzymes are investigated to determine the effectiveness of the processing process. Testing of pre-treated materials is carried out in two phases as follows.

Zo I. Toxicity and sugar content

The toxicity of pre-treated herbs and paper raw materials is determined in yeast

Zasspagotuse5 segemisiae (wine yeast) and Risnia viiriy5 (ATSS 66278), as well as in bacteria 7utotopav5 tobi (ATSS 31821) and Sioztiasht Sheptoseiisht (ATSS 51924). For each of the organisms, growth studies are carried out to determine the optimal time of incubation and sampling.

Then, each raw material is incubated, in two parallels, with 5. segemiviae, R. viiriii5, 7. torbiiv and S.

ISheptoseiSht in a standard microbiological environment for each organism. For two yeast strains, Z. segemiviae and R. Biirii5, UM broth is used. VM medium is used for 7 toeorbiums and CMA4 medium is used for S. IshegtosePsht. For comparison, a positive control is used, with the addition of pure sugar, but without raw materials. In the incubation process during the 12-hour period, a total of five samples are obtained at time points 0, 3, 6, 9, and 12 hours and analyzed for viability (counting in cups for 7. torBibii5 and direct counting for 5. segemiviae) and ethanol concentration.

The sugar content in raw materials is determined using high-performance liquid chromatography (HPLC), using a ZpodehF zidag ZPO810 column, or a Viogai column

Atipeh? NRH-87R. Each raw material (approximately 5 g) is mixed with reverse osmosis (RO) water for 1 hour. The liquid part of the mixture is removed and analyzed for the content of glucose, galactose, xylose, mannose, arabinose and cellobiose. The analysis is carried out according to the protocol

Oeieptipaiyop oi 5igisiiga! Sagbopuagaieez apa Gidpip ip Wiotav5 of Mayopai! Vioepegdu Sepivg.

II. Cellulase compatibility

The raw material is tested, in duplicate, using the commercially available enzyme complex AssePegazef 1000, which contains an enzyme complex that reduces lignocellulosic biomass to fermentable sugars, at the recommended temperature and concentration in the vial

EpPepteuieg. Vials are incubated with moderate shaking at approximately 200 rpm for 12 hours. During this period of time, samples are taken every three hours at time points 0, 3, 6, 9 and 12 hours to determine the concentration of reducing sugars (Nore apa Oeap, Wioiesp .4., 1974, 144:403) in the liquid part of the vials.

Example 20 - Production of alcohol using pretreatment in the form of irradiation - ultrasound treatment

The optimal size of biomass conversion plants is influenced by factors including economies of scale and the type and availability of biomass used as feedstock.

Increasing plant size tends to increase the economies of scale associated with manufacturing processes. However, increasing plant size also tends to increase costs (e.g., transportation costs) per unit of biomass feedstock. Studies analyzing these factors indicate that an acceptable biomass conversion plant size can be in the range of 2,000 to 10,000 dry tons of biomass feedstock per day. The installation described below is scaled to process 2,000 tons of dry biomass feedstock per day.

In fig. 41 presents a technological diagram of a biomass conversion system adapted for millet processing. The raw material preparation subsystem processes raw biomass to remove foreign objects and provides particles of constant size for further processing. The pretreatment subsystem changes the molecular structure (eg, reduces the average molecular weight and crystallinity) of the biomass feedstock by irradiating the biomass feedstock, mixing the irradiated biomass feedstock with water to form a slurry, and applying ultrasonic energy to the slurry. Irradiation and ultrasound treatment transform cellulosic and lignocellulosic components of biomass raw materials into fermentable materials. The primary processing subsystem ferments glucose and other low-molecular sugars present after pretreatment to form alcohols.

Example 21 - Processing of table sugar (sucrose) with an electron beam

Sucrose was treated with an electron beam using an arc-shaped accelerator with non-attenuating waves KpodoihopF TT200, which delivers electrons with an energy of 5 MeV at an output power of 80 kW. The table below describes the nominal parameters for T1T200.

Nominal doses (in Mrad) and true doses (in kGy) delivered to the samples are also listed below.

Parameters of Apodoitope TT 200 beams SI11111 nominal (maximum): 10 MeV (10 keV- 250 keV) 300 keV (Energy consumption 77777111 exhausted 11111111

Scanning ruler./////77777771111111111111Ї1111

EE iii ST NN floor 120 cm 25-35 cm from the window

Scan range scan maximum scan length). nominal scan length) o

Dosages delivered to sucrose samples

Total dose (Mrad) Dose that (number associated with IUO | delivered sample) (kKGy) t11111111711111199 "For example, 9.9 kGy was delivered in 11 seconds at a beam current of 5 mA and a linear velocity of 12.9 ft/min. Cooldown time between treatments in dose 1

Mrad was about 2 minutes.

The solubility of sucrose samples treated above 30 Mrad increased, and at 30 Mrad or higher the sucrose visually appeared devoid of crystallinity. Above 70 Mrad, the sucrose was converted into a solid mass of material.

Preparation of source material

The selected level of the given raw material for the enterprise is 2000 tons of dry millet biomass material per day. The specified starting material is chopped and/or crushed millet.

Biomass raw material, in the form of bundles of millet, is delivered to the installation on trucks with trailers. When trucks arrive, they are weighed and unloaded with forklifts. Some bundles are sent to local storage, while others are placed directly on conveyors. From there, the bundles are transported to an automatic unfolding system that cuts through the plastic packaging and/or netting surrounding the bundles. The biomass feedstock is then transported past a magnetic separator to remove foreign metals, after which it is fed into a slicer-shredder system where the material is reduced in size. Finally, the biomass feedstock is transported to the subsystem for pretreatment.

In some cases, the millet bundles are wrapped in plastic netting to ensure that they do not fall apart during transport, and they may also be wrapped in plastic film to protect them from the weather. Ties are either square or round. Bundles are delivered to installations from remote storage on large trucks with trailers.

Since millet is only available seasonally, long-term storage is required to supply the plant with raw material year-round. A long-term storage facility may consist of 400-500 acres of uncovered, clustered bonds in an area (or areas) preferably close to the ethanol production facility. Local short-term storage, equivalent to 72 hours of production, is provided in open areas. Ties and surrounding driveways, as well as transport conveyors are on a concrete slab. Concrete slab

Co.) are used due to the necessary volume of freight traffic to deliver the necessary large amount of biomass raw materials. The concrete slab minimizes the amount of standing water in the storage area, as well as reducing the impact of dirt on the biomass raw materials. Stored material provides short-term supply for weekends, holidays and when normal direct delivery of material for processing is interrupted.

Bundles are unloaded by forklifts and placed directly on conveyors for transporting bundles or on a short-term storage area. Bundles are also removed from short-term storage by forklifts and loaded onto conveyors for bundle transportation.

The bundles are sent to one of two stations for deployment. The unfolded bundles are broken up using a straightening bar and then unloaded onto a conveyor that passes a magnetic separator to remove metal before crushing. A doped iron magnet is provided to capture stray magnetic metal, and a receiving screen removes oversize and foreign material before a plurality of slicer-shredder systems reduce the size of the biomass feedstock to the proper size for pretreatment. Slicing device-crushing device systems include slicing devices and rotary knife cutting devices. Slicing devices reduce the size of the raw biomass raw material and feed the resulting material into cutting devices with a rotating knife. Cutting devices with a rotating knife simultaneously crush raw biomass and sift the resulting material.

In order to limit the total downtime due to necessary maintenance and/or interruptions in the work of the system for the preparation of the raw material, three silo storage hoppers are provided. Each silo can hold approximately 55,000 cubic feet (1,560 m") of biomass feedstock (43 plant hours).

Preliminary processing

The conveyor belt moves the biomass feedstock from the raw material preparation subsystem 110 to the pretreatment subsystem 114. As shown in FIG. 42, in the pre-treatment subsystem 114, biomass raw materials are irradiated using electron beam emitters, mixed with water to form a suspension and exposed to ultrasonic energy. As discussed above, irradiation of biomass raw materials changes the molecular structure (for example, reduces the average molecular weight and crystallinity) of biomass raw materials. Mixing the irradiated biomass raw material into a suspension and applying ultrasonic energy to the suspension further changes the molecular structure of the biomass raw material.

The use of radiation exposure and ultrasound treatment in sequence can have synergistic effects, since the combination of methods apparently provides more significant changes in the molecular structure (for example, reduces the average molecular weight and crystallinity), in

Compared to the changes that can be effectively provided by any of the methods on their own. Without regard to theory, in addition to reducing the polymerization of the biomass feedstock by breaking the intramolecular bonds between the segments of the cellulosic and lignocellulosic components of the biomass feedstock, irradiation can make the overall physical structure of the biomass feedstock more fragile. After mixing the brittle biomass feedstock into a suspension, the application of ultrasonic energy further changes the molecular structure (for example, lowers the average molecular weight and crystallinity) and can also reduce the particle size of the biomass feedstock.

Irradiation with a beam of electrons

A conveyor belt 491 carrying the biomass feedstock to the pretreatment subsystem divides the biomass feedstock into a plurality of feedstock streams (eg, 50 feedstock streams), each of which leads to individual electron beam emitters 492. In this embodiment, the biomass feedstock is irradiated in a dry condition Each stream of source material is transported on a separate conveyor belt to its associated electron beam emitter. Each conveyor belt for irradiation of raw materials can be approximately one meter wide. Before reaching the electron beam emitter, a localized vibration is induced in each conveyor belt to evenly distribute the dry biomass raw material across the width of the conveyor belt.

Electron beam emitter 492 (eg, electron beam irradiators commercially available from Tyap Sogrogayop, Zap Oiedo, CA) is adapted to apply an electron dose of 100 kilogray applied at a power of 300 kW.

Electron beam emitters are devices with a scanning beam with a sector width of 1 meter, corresponding to the width of the conveyor belt. In some embodiments, electron beam emitters with a large fixed beam width are used.

Factors including belt/beam width, desired dose, biomass feedstock density, and applied power govern the number of electron beam emitters required for a plant to process 2,000 tons of dry feedstock per day.

Ultrasound treatment

Before applying ultrasonic energy, the irradiated biomass raw material is mixed with water to obtain a suspension. A separate sonication system may exist for each electron beam source material stream, or multiple electron beam streams may be collected as source material for a single sonication system. In each sonication system, irradiated biomass feedstock is fed into vessel 1214 through first inlet port 1232, and water is fed into vessel 1214 through second inlet port 1234. Appropriate valves (manual or automatic) control biomass feedstock flow and water flow to obtain the desired ratio. raw materials of biomass and water (for example, 10 95 cellulosic material, weight by volume). Each container 1214 includes a stirrer 1240 for mixing the contents of the volume 1236 and dispersing the raw biomass in water.

In each sonication system, the slurry is pumped (eg, using a vortex impeller pump 1218) from the container 1214 and through a flow cell 1224 that includes an ultrasonic transducer 1226. In some embodiments, the pump 1218 is adapted to agitate the slurry 1216, so so that the mixture of biomass feedstock and water is substantially homogeneous in the inlet channel 1220 of the flow cell 1224. For example, the pump 1218 may agitate the slurry 1216, creating a turbulent flow that is maintained throughout the conduit between the first pump and the inlet channel 1220 of the flow cell 1224.

In the flow cell 1224, an ultrasonic transducer 1226 transmits ultrasonic energy to the slurry 1216 as the slurry flows through the flow cell 1224.

The ultrasonic transducer 1226 converts electrical energy into high-frequency mechanical energy (for example, ultrasonic energy), which is then delivered to the suspension through the booster 48. Ultrasonic transducers (for example, from Nivivspeg О5А, Ips. oi Vipzhmosad,

Memu Uegzeu) capable of delivering a constant power of 16 kilowatts are commercially available.

Ultrasonic energy passing through the booster 1248 in the reactor volume 1244 creates a series of compressions and vacuums in the process stream 1216 with an intensity sufficient to cause cavitation in the process stream 1216. The cavitation disaggregates the components of the biomass feedstock, including, for example, cellulosic and lignocellulosic material dispersed in the process stream 1216 (eg, suspensions). Cavitation also leads to the formation of free radicals in process water 1216 (eg, slurry). These free radicals act to further degrade the cellulosic material in process stream 1216. Typically, approximately 250 MJ/m3 of ultrasonic energy is applied to process stream 1216 containing fragments of poplar sawdust. It is possible to other biomass raw materials

Or apply other levels of ultrasonic energy (from about 5 to about 4000 MJ/m3, for example 10, 25, 50, 100, 250, 500, 750, 1000, 2000 or 3000 MJ/m"7). After exposure to ultrasonic energy in the reactor volume 1244, the process flow 1216 leaves the flow cell 24 through the outlet channel 1222.

The flow cell 1224 also includes a heat exchanger 1246 in thermal contact with at least a portion of the reactor volume 1244. A cooling fluid 1248 (e.g., water) enters the heat exchanger 1246 and absorbs the heat generated when the process stream 1216 (e.g., slurry) is irradiated in the reactor chamber. volume 1244. In some embodiments, the flow of cooling fluid 1248 entering the heat exchanger 1246 is controlled to maintain an approximately constant temperature in the reactor volume 1244. Additionally or alternatively, the temperature of the cooling fluid 1248 entering the heat exchanger 1246 is controlled to maintain an approximately constant temperature in reactor volume 1244.

The outlet channel 1242 of the flow cell 1224 is located near the bottom of the container 1214 to induce gravity flow of the process flow 1216 (e.g., slurry) from the container 1214 toward the inlet channel of the second pump 1230, which pumps the process flow 1216 (e.g., slurry) toward the subsystem basic processing.

Sonication systems may include a single flow path (as described above) or multiple parallel flow paths, each associated with an individual sonication element. Multiple sonication elements can also be arranged in series to increase the irradiation energy applied to the slurry.

Basic processing

Before fermentation, a vacuum filter with a rotating drum removes solid particles from the suspension. The liquid from the filter is pumped out in a cooled state before entering the fermenters. The filtered solids pass through the downstream processing subsystem for further processing.

Fermentation tanks are large stainless steel tanks under low pressure, with conical bottoms and slow stirrers. Several containers for the first stage of fermentation can be arranged in series. The temperature in the tanks for the first stage of fermentation is regulated to 30 "C using external heat exchangers. Yeast is added to the tanks for the first stage of fermentation at the beginning of each series of tanks, and they pass through the other tanks located in series. The second stage of fermentation consists of two consecutive continuous fermenters .Both fermenters are continuously agitated by slow mechanical stirrers.Temperature controlled by chilled water in internal heat exchangers with constant recirculation.Recirculation pumps are reciprocating cavity pumps as solids concentration is high.

Gases leaving the fermentation tanks and fermenters are combined and washed in a column with a counterflow of water before being released into the atmosphere.

Off-gases are scrubbed to extract ethanol, not to control emissions into the atmosphere.

Further processing.

Distillation

Distillation and adsorption on molecular sieves are used to extract ethanol from raw fermentation broth and obtain 99.5% ethanol. Distillation is carried out in two columns: the first, called the fermentation column, removes dissolved CO2 and most of the water, and the second concentrates ethanol almost to an azeotropic mixture.

All water from the practically azeotropic mixture is removed by adsorption on vapor phase molecular sieves. Regeneration of adsorption columns requires that the ethanol-water mixture be recycled to the distillation for separation.

Off-gases from fermentation (which contain mainly CO2 but also some ethanol) and off-gas from the fermentation column are cleaned in a water scrubber, which removes almost all the ethanol. The gas leaving the scrubber is fed to the first distillation column together with the fermentation broth.

The sediment after the first distillation contains all unconverted insoluble and dissolved solids. Insoluble solids are dewatered by a pressure filter and sent to the combustion chamber. Liquid from the pressure filter, which is not reused, is concentrated in a multibody evaporator using waste heat from distillation. The concentrated syrup from the evaporator is mixed with the solids sent to the combustor, and the evaporator condensate is used as relatively clean recycle water for processing.

Because the amount of water for distillation that can be recirculated is limited, an evaporator is included in the process. The total amount of water from the pressure filter that is directly recirculated is set at 25 95. This stream contains organic salts such as ammonium acetate or lactate, accumulated fluid components not disposed of by the body, or inorganic compounds in the biomass. Recirculation of very large amounts of this material can lead to levels of ionic strength and osmotic pressure that can be detrimental to the efficiency of the fermenting organism. For water that is not recirculated, the evaporator concentrates the dissolved solids into a syrup that can be sent to the combustion chamber, minimizing the burden on waste water treatment.

Treatment of waste water

The waste water treatment unit treats process water for reuse to reduce the plant's additional water needs. Waste water is first filtered to remove large particles, which are collected in a waste container and sent to a landfill. After filtration, anaerobic digestion and aerobic digestion are performed to break down the organic material in the stream. Anaerobic digestion results in a methane-rich biogas stream that is fed into the combustion chamber. Aerobic digestion results in a relatively clean water stream for reuse in the process, as well as a bottom that is mainly composed of cell mass. The sludge is also burned in the combustion chamber. This sieving/anaerobic digestion/aerobic digestion scheme is standard in today's manufacturing industry

of ethanol, and equipment in the range of 1-5 million gallons per day can be obtained from suppliers as "off-the-shelf" units.

Combustion chamber, steam boiler and turbogenerator

The purpose of the combustion chamber, boiler and turbogenerator system is to burn various by-product streams to generate steam and electricity. For example, some part of lignin, cellulose and hemicellulose remains unconverted during pretreatment and basic processes. Most of the waste water from the process is concentrated into a syrup with a high content of soluble solids. Anaerobic digestion of the remaining waste water leads to the formation of biogas with a high methane content. Aerobic digestion leads to a small amount of waste biomass (bottom). Combustion of these by-product streams to generate steam and electricity provides the plant with energy autonomy, lowers the cost of solid waste disposal, and provides additional revenue through the sale of excess electricity.

Three streams of primary fuel (solids after distillation, biogas and evaporator syrup) are fed into the circulating fluidized bed combustion chamber. A small amount of waste biomass (sludge) after wastewater treatment is also sent to the combustion chamber. The fan supplies air to the combustion chamber. Treated water enters the circuit of the heat exchanger in the combustion chamber and evaporates and is subjected to excessive heating to steam at 510 "С (950 "Р) and 86 atm. (1265 psi or. (8.7 MPa)). Furnace gases from the combustion chamber preheat the air entering the combustion chamber and then pass through a fabric filter to remove particles that are sent to landfill. The gas exits through the chimney.

A multi-stage turbine is used to generate electricity. Steam comes out of the turbine in three different states for injection into the reactor for pretreatment and heat exchange during distillation and evaporation. Other steam is condensed with cooling water and returned to the boiler feedwater system along with condensate from the various heat exchangers in the process. Water from a well is used as additional water to replace the flow used in direct injection.

Other implementation options

A number of variants of implementation of the invention are described. However, it should be understood that various modifications can be made without departing from the essence and scope of the invention. Thus, other implementation options are included in the scope of the invention presented below.

Claims (5)

FORMULA OF THE INVENTION 1. A method of obtaining sugars from lignocellulosic biomass material, which includes: irradiation of lignocellulosic biomass with an electron beam at a total dosage of approximately 10 Mrad to approximately 50 Mrad so that the biomass raw material undergoes ionization and acquires the first level of radicals; and then quenching the radicals by contacting the biomass with a radical-reactive gas, wherein the radical-reactive gas is acetylene, a mixture of acetylene in nitrogen, ethylene, chlorinated ethylenes, chlorofluoroethylene, propylene, or a mixture of these gases; and saccharification of extinguished raw biomass using a microorganism. 2. The method according to claim 1, which additionally includes the preparation of biomass raw materials by reducing one or more sizes of individual fragments of biomass raw materials. Q. The method according to claim 2, in which the reduction of one or more sizes of individual fragments of biomass raw materials includes crushing, grinding, slicing, or a combination of these methods. 4. The method according to claim 1, where quenching is carried out to the extent that the level of radicals is no longer detectable using an electron spin resonance spectrometer. 5. The method of claim 1, wherein the level of radicals after quenching is less than about 1077 spins as measured by electron spin resonance at room temperature. 6. The method according to claim 1, where the method additionally includes the processing of biomass raw materials by one or more other methods selected from ultrasound treatment, pyrolysis and oxidation. 7. The method according to claim 1, where the biomass raw material is selected from the group consisting of low molecular sugar, starch, paper, paper products, paper waste, wood, pressed wood, wood sawdust, agricultural waste, sewage, silage, grasses, rice husk . BIOMASS I- Her 0 and 114 118 - 122 PI OTOVKA | PREVIOUS PROCESSING and the main 0 POSTAL OUTPUT - ; PROCESS: NEREROSKA MATEMALU. | . AND PRODUCTS! EDUCATION PRODUCTS Fig. 1 2 -K12 216 and CERTAIN SIEVE sha: shk Her CRUSHING SOURCE | PSRSHNY | DeEUGY VIUOCIST FIBER fibrous 14 MATERIAL. oh MO MATERIAL O (ee n-k Fig. 2 8 who opened his mouth to me! for still vky ii ved v CHI osv olvsy vi Mr z Sud ns 232 224. ХЕ ухлик, ч- ХУ ste vvys . wav i a x - «s for h; E and eta Y; A - my; Vk -ch I sei o; x ! Y ki s de y same tv, Koch s. tk SHY Me Konnov / with Aries; SYA Gaia 2 '230; And R. o o o i same I SA u i Ai i sat tka i SH i on ih U ; i eh 5 ; KO, Z A ha uchi Gi KOD z u Milo ; I and 230 and YOU, E" I DE g I 232 scha " OO Zha Ai and therefore She zh azh y" VAK puti naik. chi - y Y rije A cm 5 oo - IY dichni y Ko tiy viru" y sce Kaya - PE ' la y: ze 15 Mo yaya mk i zhim in, z Х я i y: to 7: y E. how ly U b: eyi, Zo I 7 hm, y ! y y y y y, an Ye SY y НН а С а Щ Чо а ши "5 и "Ah, их Ган у и и -40 их о ДЯ дн ни нник и В ; КИ A '7 и тя, Z rak ky 7, - длгия шч х и ня ;. g y y U kak Yama Ku ikh H y same y . dany zi" "a RY h ke chl y ) Asya Ky "5, y, I "o still RE Ye De, t sho kih b 4 zi ., z, he Fe M Deco MLM MICRO EXPORT I y U shlya 250 242 230 rao-oyao44 U U xx cho x Y ch k yin VACUUM SOURCE 252. fig. With -SHTR? FIRST od SECOND s i i sieve Another sieve SHY 220 CASH SOURCE 34 FRIENDS ZOO EXERCISES FIBER | .1 Fibrous a R FIBROUS FIBROUS MATERIAL To MATERIAL ro MATERIAL Fig. 4 noses ravine SEAL | MATHEMATICS vny, sen VOLUME DENSITY HUSSETINA SUBSTANCE and Fig. 5 00-x 4 iv x s 330 vu Y, b, -322 y Kho le ma zho KZ 3127 | i r I, Za ke Z 465 8. ME zo o Vig. 6 r r t nd i A, din) i" s Zk ki BO a na. Ua ad shih au ai | ke s i a z z Ch ; Uzh i. 5 cha zh . Re y, ek g i ia S ia - 5th stream Fig. 7A Fig. 78 Fig. 7C ho Fig. 70 PROCESSING of the ass nn: pernakyesy COMBINATION WITH PERILLY SECOND DOB NNYAH snnnnnnnn MATERKL U u MATERIAL 0) MICROORGANISMS FUELS OPTIONALLY HARD AND OXIDIZING WITH " t CONDITIONS not Te Te, not what T I That, 0, Fig. 8 I Ж A и тя я я я я я я ня чн чн вык Е вкс са M SIM ох го гы я ' и что Кто ню! i M v vo yam pi 31464 st What kind of son is there? и я De ие зай Шан ХА 5 а Це Шк аж вся о а: Ей Шяе ній і-- І я, Аня А: vo і Ek NI sen; Di : Beat PED be vena i o wn Kn | and and 7; MK you in KE | I'm drowning and VI Kr I: soot! ve, Sya sk ee: still F skob es NI VE te sy sive sko I a i KU lev A Zk M tuya ssh t) Do shi TE . in ia dk iy y -- i Teny Ne skh zh M KO y dyin og A |v vstchoi xx : as kkd Kk y "ak Er a y et v Te y chi B y 5, And not set zay lk y y y ee Ya va y t" ih Y "ai Y She « tuya 36 oz duh Fig. 9 EE Ii YAN Ne VK a; NI Cho a EN tan Kekzhn SHIA SYA ro Dec Reka SN A oS UNCLE NI sec PO o ONE OF THEM day ke DK and pika si Ku 1 oche NYA ef DK kyu DO OO. tuesday Fig. 10 3010 -3020 Neck; '. I nn DISSOLUTION ; (NON-CELLULAR DEVICES FOR MECHANICAL TRANSPORT) 3000000 3045 3045 30000000000000000000000000000000000000000000000000000000000000000000000000000000000. ELECTROVIVAYEI ZM" 3065 3053. r opgovi" Ho. .1 NENNY and LIQUID i-i ' zZ060 sha " ".IVK shi MECHANICAL o nn: SEPARATION into solid material NERMPIZED IN 3070 THE NEXT STAGE OF PROCESSING Fig. 11 pi U oh! sho : OXIDATION in S mov h-- and / in: І ж В A che ! PRE-PROCESSING AND WITH ONY UNIZING AND SAY ME WITH RADIATION AND IN AND BYUMASA THAT INCLUDES GASNINYAO ZK Ko nya yayuMASA RADICALS! 4 fig, 11A 11109 and COOLING UNIT 7; VIDNNA OO 84 ! ! shi PI SHO i mt : She M tn i yaz i | z i -y H 1196 de ya- min I y / ; The same. in xxx and p I | 4 t Be 4 Go ! still out of the silk, ask 98; z y v ro y : і і ka a 1 ke ti me Ve A To? heck, I am! vne NN and I am sleepy 4190 vni 188-- and u182 | Also Ker 1184 pt 400 that 73 - 180; SG) her ; and Y cha au, and 72 chi 178 Fig. 11 GNP and fibrous rock, Y MATERIAL ee | / I to: VAV TSE: SZSH; : - - ts 7 ry ne r Kedy 14125 I Vreneeniky and DY 'yati: ; as well as 16 zi KI ( nmkodie ' shk I as " "elec m Rai yy and AK no 5 o Shery zy z KI fibrous N ! R MZHK ny keV y Z i MATERIALM 1 we ka "hi ! - them I B B) : N y m Y | i i: z ? 1 i ! KA a lan 1) I sht KS UM vyta she she she ro TZ | ii an n u sche | | i y , and y I Х t t е te ! z і - 11733 ! ' 11133 1133 41427 ! fig. 110 digging 11140 r I EX; " eat ! 11145 F 0 REFRIGERATOR; LIQUID : i 11146 11144 И I 4» i / ! and and Dor Z: I know; and ' And k. in E : but 14160 | 11152'; ; 161' eat what! i 5 i i i ' dvntzhnnvshyuoi I dyk nyu fe peso exyue eto zheseek zheseev tovka yakya Z. FSK ChK B ZHY it che rych chto, Z; ЧК ХХЯЯХ che pe chel g chn ie chek ni cht tek tenet nt 1 Fig. 1E 1234 1232 in -4214 tea. Y I 1236 1340 "is 1249 roll 1230-- in Dame (o ; oj Y | re 1246 t tav. 1226 Her with" DETAILS Lata tav that 1226 1250 Fig. 127 vv- VE - 90 60 ssh di i bi pk | CONVERTER dl up to 70 WHAT USHAOE! K-th and CONNECTING THEM and | RUPOR and--y-- 76 tr r, majnvavy: re u z-0-0 EE shenny 0 RUPO? in Fig. 13 DRY GRILL | schishe VO opo Mmekhdpshchnya t 8090 Vora 6220 PROCESSING IN 7 wet regions 65230 raw materials | PREVIOUS 9040 ; ml, HEATING - f685210 v, -v050 ! PYROLYSIS! vI2bO and | 6160 І ный Хе ВВ 0-20 екі і у ВОДА , -e 00 EXTINGUISHING | and PROCESSING Goyan 6050 65130 6140 YATI 9070 suspension Her. ak, Y same 7 Shchi - l FAN and ! led Her - to railroad 8120 in Kn ovo - 61 10 sha ne PRESSING OO MECHANICAL | that IVBODY seam DRYING STORAGE SEPARATION | BALCHOVINN ITS nia Bin shi CONDENSATION CLEANED CLEANING OF MELONS 1. vva I Still in vB'ZO : nie 8100 i | dream | OT VOZCHINNNNKN Go Ya and 9180 Fig. 14 I 6510, in BO LIY | vk same A A 4 CHA Mch shi! b5go) (ego) I o vv5O in d-- t ro: Y x 6540 B Fig. 15 6710 nn an sovuvo 09780 8740 -02- МО 1 втво я 6740 вл 6720 ) 6750 Fig. 16 to MU 1718 Picha he --- at. z - 1716 shi eh ich What What laz 0017e r t s shi Vikh TU Fig. 17 She DT fan 0 INLET GAS 1824 | АНИ that are different in 1821 ЧИ В | o- x1823 tan | rt V nk asked; Pimynyvnyh What is the output of GAS Fig. 18 M VC date t. re ; y - V. ennnnnyutnia r sha - 137 Yanishchishk 131 || IN. I I I V I Yinsch- B. 1 GAS Fig. 19 Y ryn A x | 150 in a stump Because other things are MECHANICAL 9020 and PROCESSING - 51505, ssh ----.. 5030 ше PROCESSED DRY |. water. -th SiVYKA with DEFENDER | WASHING 7, WATER thorn RAW MATERIALS 0 LOBANKA tn and TIM 0005BoBo 0-52 BKSTRAVINYA OR NOMKO OYI vODCHASUETNIYA F; we: knowledge AND DERIVATIVES FROM RAW MATERIALS AND BASIC AGENTS 5180 7 pt 5130 oxidizing process ooporednya OO LNGAGENTY PROCESSING SUSPENAY Glue mianya; raw materials Co. 5110. : -kYadg MY I. sh522o- THERMAL 5160 7 t and panel aopaolanlopainns, and RO PROCESSING rn DRYING, we ! more successful; ShK Y 5070 I! DISTILLATION, KE oOopOocE nn OXIDATION OF SUSCENSION and "Vi 0 EXTRACTION, te TILKHODIV | RAW MATERIALS OF SEPARATION 5190 nyshish Sh o BYU scha vu tv KvDA ANA y and STAGES in 20 7 from the suninion Blyu y, ШЧА 5140 ZOSCHANIY" AND ON y Fig. 22 400 7 402; w honors re , ; TEOBYATKOVE Grozdyovlenk o: HO ZHERELO FROM PROOBLENIA | THE SKY OF THE SKY IS LODDATKOVE. THE SOURCE OF ZOSHOKNA in zi t ts PROSPOVANNIA | from CRUSHING r vashkOon ; i, 404 IT IS MANDATORY AND I ZOK SERE: mine on I INVOLVEMENT OF PAROVNI 1 AROVII HO TIDINA ka and RO pan pKOBOVCHKOVK y t, OPTIONAL their th u INVOLVEMENT ? ADDITIONAL ASSEMBLY background snncnnnni 0 FIBER DEOBLING ; HEALING VOLUME SOURCES: FIBER AND AND g | HER ! CRUSHING and IT NON-FINISHING like ; M. shk I pvospovaniya y le i is: | Y. anv UNOLOKNISTY ; And what, what, and MAJERAI are SHOPPED! IN DEIZHAZHE BACTEVI shi she: and PABOFERMENTY toovant» eat tires M NEOBBLYAKONE. : i " " " i LIMING IS NECESSARY 0 4 o REQUIRED r s HYILATION OF THE VOLUME OF SNESHOPACHA | i ENZYMATIC ! | Then gdz TRANSPORTATION ! STORAGE. 432 HFBeMKNTATED NUCLEAR SSO U OERMENTASHCHYA KO : : PRODUCT y IOO VIALRYKLAD, NOI OO : v Fig. 23 -- 416 - 464 MY 465 or GA 467 i xx 00000000 IPARAZ BOILER M and M 7-48 x "489 4tA 7-49 t AtV Fig. 54 of them are equivalent to 2520 / A | nsh 2 her sha 2520 25zo DY, I ovav KhM 25301 V / z u dyny Proty, cer 25BO PES sho S serny DYU MY fig. 25 DRY GRINDING OF CORN DIA zvhkie WITH POAKE pOOPIBILITY- PRE-PROCESSING IS OPTIONAL | today with JSC NEOBONUZKONE "FKRMENTY SHY Roz? IT IS OPTIONAL! ENZYMES. vena in So» pni VIEROSVEANEM and DISTILTIA N E etno BEH GERDA TANIA ANHYDROUS ETHANOL fig. 26 WET GRINDING: PRE-MAKING. CORN a SOAK WITH o; VYLALEINYA AROLKAT 000 EROZLIZLINA ON OT voleknh sho es ah MY a GLUTEN WITH OPTIONAL shk 5 y . FBVMENTY EpkoBOvyazkOovVE i ROZTISHCHJUNNYA | ! nEoeov Yazhovo PEO-BINDING UM - SACCHARIZATION AND MICROSVSANISM "Y FERMENTATION x ODISTNLIATION Z. Y i " M I UM DEGILRA TATIA | : VEVODNYY " FROM ETHANE fig. 57 vykevkya ZAKO OK o. OO OKO PAK OKO OK OK i o o. s o o: sh o KI o. a svya OK OKH i YAKA MO S AKOO sraka S OH I s o . s o s s o. . o s o. p - a ОХ o PO OVK B kshnia 5 AK s MOU 5 B U o AV o s rok V o OE p- o s o OH OO OKO SANU oh. and. и ООККОКЯ Zhe MZHK UK A VZHK A KK СХ o i U XX o o o: 0 ZAKO OKKO KA PO s VO OO MO Ko Oh a KK KOM Z Z . i, s p y 5 SK BOKOH ZOM EK o UK OKUNYA OK VE ZO X h MK o OA s MNK M sho s o Z s claim 5. OO s s 0 s POM Khx OO. KE UKH OK BIK 5 FW KO o o OO. S. s s o Z. s OO SO OK p. o p KOHH OO 0 o B p MEM OKH shHh s o o o s o. 5 OK СХ OKO KOZAK OK oh KU Uas sna p sho Osa sho KY she OO o: OO MKK SKK MK o 5 TALAZHKKYA MK s o s . s s s 0. OO U OA psh OKO UK UDC S KO OVO OH SKM AK I o. . . . with o o o p po KO ХК OO KOH Okh S i OH COKO s EN OH KOH Me M s gu KU HO OO OO ES ВХ s о o s v OA Okh KOH OO ZO МАК MBO o s M. sho OO ЗХ 5. z p o Z a MO sy pyv Ko 5 RAKI OO KU MO PO h s SU Oh Z s PO is SEC U MY UK ACTA Zh s . in. . s In p. s m sha OVO KK o KO OK s s KOH 5 o U 0 . with o. in CODE OK K VKH KK OKO OKH OM MAE, OKH ZH o. o p. I he and my o 5 OO ODNU s o. o s OO s s s g KO s ZK Ko 5. o o ZNH OO AES KK SKK UC s what o . shcha sho OVO sve KK OH o OO zh OO 5 Kn S NIC 5 s OZ claim 0. OK EN SOKKKYA MK OKU EF UK 5. o OK OO 3. in zhk TO KK KON xx sho Zo s OK OO OH p B MB, KO s poh OO OK OKKO KM MKK o: MOHY MK oh zh OH KNeV s s OH OO what s U Ah Z KV KO OV ke MA V U OO ХK KK OKUNYA M : o what MAY s S s OV o . s s OO Z s o s OK en that On s Z 5 OKO i y 0. ZVU POM more o VH OKO OH MOH zh OAE HE KO BU KO U KY A OV s . . . oh PO ONA eh ooo i o B. o o . o s B o s. at. 0» UK in KO KO s KK PO OKH ee KOH ES OVO OO OMA LE o o. Z B. GOAT what KU OH 5 I OKH ko o o s YAVA s schu VO i x skh B 0. OH KO p S s s: s o s M o 0. Acne o. shh o Oko av JAK ZO B. s s MU ni ZBK i PU KU VK kN SHOCK WITH THE MOUTH FOR KOH AK AH OK KU U nyk YAKA My KD PKEE AV S ZK KAK OA V o o VO KK VU OKH S 5 VK UHA MOU HC OKKO sec i u s s o U ОХ Зх УК Эх OKO mus o o . and. i s i s o Fig. 28 a Z plyu ly po ih a p Pi znav o o i yan AS in s 3 shcha 5 OK, zh NN, Vyk MECKA VY MY Kiya TU KO O ZH ZK zh OO p. oh о с Оу окт, ДИ что EE и вч В с щ ш х ш х п. . s pi m o tic MY KM A a a IVF ki VZHK PTK what. and oh oh mon, I'm with you with you. s MO Mai ss ZA, zhk o KE Bek VE uko yet. 5. p x - o VK OKOM KU ah Zhe 0, EH lo o. with. at. with - . and. i 5 AJ SUK Me I Er o a A ssh Z OKKO AK KEKV that o. se o - s o . s more Z KO more EV yav skh Ohh KK KK ohh OKU PAH y and ke v. . Z. i Oh oh TEO oh Men UK MOH MYH zh sy keV VV Koh S Kh o OO i MUK PBHV N o o o. MKK and: KE sesya i she KE KT I Mi Sa Х . at. OK OO VE SHE tva I Ua o o ZOMKOOO EH SY OO I 5 5 s. and s Kuka V s OK dya o: MNK ZK OO OUN z BYK Okh de s s a My BO 1. Residential complex Koh o. oh oh ke zh her s and s B i s ! U o i o 5 u S On gwe o. 5. OK ke i o o . POH YAN PC PTK KVK ONY s y h hus Z ov S, Z 0 KO ZO Mn p KO KO o i her p zhit s OKO MO 1-5. her Co. S. and BU OKKO S. o. . at. S o B Vo s o. OKU en ikh ya tcha pi IKK KK SAUN Zosh i ya . schi and 1 s OO. . at UK Mu ok r V av SO PUE od idh OKO penya PN ZO Se M X he OK KK OO V p, VKH NK HO pe OK same her. with. KB that Me KKU KO I KK, MUK ON U M y o - . oh and Maybe UVK, SOU KS i SK PO i ZK Don U her a, their b s o still KOH DUH A zhYA Ko KK PK Uh nya SE ZE PK zach Ks schu ee. . . . In Ah My p ah SM o. p o: SKK KU a s OV s o . o MUYA U Zhe Zh Seh s b oo OAE AiH a OO pe so ozh TA shi OO I KU schu u Oh i y. 5. OO s - lak ma ДЖ ХХ zhi KU her JI te MY Kn MK Ki SOKU i pet, KK S M - ! with - with a. oh .- U eko o, Mo a o a DU o ra shyn p OO a iE o o a s OH zh 5, i a - KO . Km Z OO EV OO In Po DOK Kon, I Ba 0 eh shchi OA dOVh san i U ah s s yu o dya s KO VOVK sah VIOOYA KVN" y ry kot ee OO SH I KU KK AV s o . her village Her. s No 55 HU PI VEK I KE I BO ME OGO Pi HE p ok y Zoya i Te OK se OKU MUK OKA On ES Konya OO KOT TEKU SM KN. UM BONUU sya sh KI Te UMH Yae o . s MO and her OO s kV ZY I SOYA Il zh KOHZ OKKO KA ZU OO" o v --- OO HO U ХЖКsya p s ZVoyu ch- OMAN KO PK ih PAK i Me v OO OKO Ko ro u HU ES NK I Kiya Z NYA 5 OK V KO 0. I o - x. sha MO s M I u Be More MO o : ; ; with Fig. 29 OKH o whose UOZ sk KY: Me still. ; KNU A p UVK ZVO PO By 5-5 i p. o Z A KK uzh So AVK SA ZK KK p TANK OKH Ai KV VOK KAK Ka I ON MK Ky DY OKH ch. s v OKOM KI o a I KH KV ka o PI KK I ECO KK i PKEE se o i - he On OV UA PM KU JAK - s i 5 OK e UK U SE OV MU KOH UKVNNNne she o ON U NE UKV OK KV ЖК МХ MA MKM K SOKU shi v M OK a KM MK V VO MO I MO V i same V KK V ov y VOK g. o what ZK YAK AK OK VK sce KU U Ke Okna Me o sh M och" SSLZHYTI OO N KK V. and she is at 6. . I My KO OK KKU WE JH teh DA i lo KOYU ON po OO V ON M Kf. OK o Muki ON p. nn. hers; KE EI I Ky MONO SANY OKA Nnya KU i Z I A KK Z po KK OK what p sh p Ko v u SVU VO A u o younge A KK KK OH KZ x OH yah I ko OKKO Ka E I nia Ko KK вх OKХ at. ZMU OK ZA i MO p VH v Zh OK Nv TI ZU AH V o p.: she KK A ss a sh v o. at. is . NN: st ps MK ak oj KOM o mya VEZHU o Sov Koh i schi po s o ia i Z. i KK Okh x ZO: SE Ko pe PE KE PO ke poh s 0 o V KY Ves okre o i a TI oh MK V Oh M shi Ka oon o Ya MK KK Kiya U i MK o. o o s s. . about o i den i i i MO KYA b MUK M KK AK My Sei U i U OA zi oo o Vk I o eh v pe i We. KO Ok Ko OD eKYA 5 OK KK Ж ТОНЕ КИ оо m MKK OO a EH EN KANYA p or Ki ok EN, p i i o Oi En OKO Ky ni o. Z o oh o A o. 0. and I o s sho o. VAK ON oo she m OK AKVsYA PE v yu i eh o . OK z o ev Ko OK ekeh Kuka OA NI MAK KY Ky, OKU U OO HO TNK I nn SKK Kya and SKK V DY Ko Kiya i MKK ev u o MKK SUBMITTED M Ky M V SOKY p I. KO KE AK LO v i PO is about axes KOH p, sKE VC U UC VU WH se M Sh Ko CHEKA KU U MNK V KVK IK KU KOM TSO i ZHK U MYH KA Pe V Ua V Ky KE Kv se u SO o KE o i DV ky UC VK DAM KK KV Z ВХ СХ С MKK KK: OH MY U AK Se MK AA A K KK FC KK Ky DM ECO OKKO KU OK OK PKU OA p TE oo OO a MAKY OO KO a a o xЯ OO vek KAK MMK Kya o peh i ooo SOM OO i TO, VO IYA o naya OO OO S V Z o o o Ok o ona r r u U AH o UK KK ko KI EH ku MKM KIM m A I POT KN a s 0 po E i. he en i x s pi a i s On oh LOV SE ni POT VN shi mi TV OS M ICT KK Sy SON p. o. s o son OH NN i ZAKO I SV OKH in VZHK and o i ver a 0. ! SNY DK UU oh DU PEKY PIT KK UVO VEK a KON a KK OK p. he KO pev t ; stump with MK KU OVK Kn DEN i HA KUH KI vh i po 5. ky V KK MA ZE KK ZHK V U PKU V, - o v. ish E ZN KK and KHMK, Z I p I s o s nn o A 0 POV nki A p MO i i them OV KK oo ХK Z Uch KONYA UK KU, EK Ta TILA, OO i BOZHYZ KE k ka nn. povi about OKU with z. TO Yes I oh in Ae en: SO VK es ЖХ EK o I o HOW I YUK KOVO KK KK OO . 1. EE Ve No KO pom oh. B I U eV I s Om pi i M So Ov 1 s . 0 0 s VKA of the day MAV EK KK EK v A V OA 0 ve poka KOKO DEC EK Sny ZH KE KY Kn a i pn VA M so o VE Ko Kk UK Po Ya h s her SOVA i VOK KK U PO ICON SK KK i KO LIV KK MYH Ko že Koh Ko z o 5 Eh o s pa OO i MKK Ka I nn m BK i o EK KE OK OA i OKO p NE ih ek Bo OO r UK ; and KO U X i : - Fig. 30 equiv sov zhk. VV U s - Mn v t ozhKH o OO same v: sec pen p - Z 5 ZKU Hu nano RK KK V: A KU VK MOZKU zho EOM V SO o. Gzh Zoya UK -X Okh Zh - Y a, s 3 JAK o o ho Ye shchi For Your UKV i KEKS ih hi U UvIK i KN OKU KIM KK o Aa eh UK SCHI KE I i EE e M KE MAYA B o GK KK A v i Mi Z o KH U Deu M vek Ko E OKH vyh shih s Z v o . p g. B PAK A Kun KN Kv MAK KK, he SPIRIT POM K anno I MO OKO V OO i A ssh I SOKY KO A Ks A You o p. povo y s 5 p, - s o p Z pi KY SO i shk ZK vek i EE 5 Oh ZK UNO i ih Kit I V KAK 35 ah OO V ne PC OO ZK A i KUKY OK ko Sya ZhBK 0. A UK V po i M VO PK Ж VE 5 Ko che OO Kk KY OK VK o Vaya i ON U 0 A VK MK o KK KK A KE A NYA pe ve ve ve 5 o 0-0 p MO i AVK OM Ky B Ж Ж ЖЕ ОВК Dec KUKY KE SO VOK o in Uh p. a PO Po OA i 3 KUN pat u a poki, o ee Ko KOH y; гу Ж KU i Ж 0. . Mr. her m PO i A u V I SIMOH EK KK KAH VE i ХK PEK EK i Xia HM KVK VO Z. s pn KK KE Ol o MO ME Ve OKU schi Kv xx UK KZ EE ak MKK ZK oo i AK GK ki uh be EN AIO VU I EE I she u I OKO M i KK KK so OK Kiya ZYMI Kk Y PTK i Ku Shi still on KK lm KU B 0 EK KY SK o NAMI OV in 1. i : Oh po KO, in U VE Va 5 o o a Te KK KK I KU SEC U Ks Yaya OKKO V KAYE ON nia V MK VK i ke i o p. V EE YE KO uk uya TYSI IMK VK OKO MK SO DK iIya KK B i o KAK I Ky SKU a i OK EE V i POM ХK PNYA . KOH KZ V ONn nia OH DK, A p KE AH UK tu BC: 1. diagonally I MO TAK KK UK m KI I sew her: shk Ou u a ME OK i EK ee o ov Diki I EK se Ve PK, U i p o o i OK V KAK Kn EK US Vo pe V a 0 BITCHES in Y schyh S i, o, in 5 . Kos Kn IC KM Pe OKU M a KK Ku or ns KO MK AK OKU Em INA KK I NK on z AJ, SK V My vi U in PO MAV sa V. p p py i MU VO MM OK Z KI IH OO U UVK My KVK KK MKK KE OO KU in NN Ya. what shzh Oh MON oo V U ZK p s 0. KO Ve 0. Ko o pon MNN HAY TIC i lak o KN PK y: km oi A o OO ven ZK U oo ny MON OM p i M NVK OO zh i OK ZK ON . NN. In the 5th century OKO MO KN SYA a Ov OK KI KK po v ko . BO AK KEKV PO v M X KK MO she p y : o OO 1 fe ON TU I ko AK ON KO . and. o OO i U KN M V KH 5. oh ze M KK PA di UK AK i Gena ME o . Щ S U Vash ХОВ KE ZV ZO KO I KI A nose JE JAK Z u KV 0. KK PO KKya en i a ZO o i Me Knyny KK i I KK KK AK KK OO i KON dn what o she ZKU ZO KK I o KK p Km Ku V is A UK UUVOA UNK II piky MV HM SKK OK SA XX KKD VK Ka PO Ж Ж ВХ MM I OZ OVAKO V SUKI MOm pom o a peya VC MZHK Aa UM OV Kn KK OO SEC Vk 5 і p. z u PE TMMYA MO EV KY Kon veni i DEC I EE, Eh o: o wo POZ TO OK i IN MONACO NOSI KV OK NN s Kk 5 a. PENALTY tet VKA U SKOKKKYA niya UK nya HOW: UK A I KO Z OO o AH nok o. at. and. OBO Ov SD Kv OA I I Kk ov Son I EE . p 3 5 A nya o. p a 5 3 and o 3. 0. Uh KK t Ky OK ShK i Z OH o I -- in V OK i JAK OK o AK g. . - ps a OUN MOH i i OM KAK NK o KV her. g pk u Te OB LIVE AS MAH MK SKZ OVK her o penya OO U M OK uh POV oh i OK o EE S. an to s v. CODEC; p o. yU Kay Co. that her 5 I but . her p OO TOV KO OO METH KM V ХК Ж NEK koh Mo py shiya y she vy i SYA VYSH ZK ON I sy Ko pre te ZK KUKA Hu ZK AOYA OH: yah v what v ; from st. ZAMKY NYM h Fig. Because M that r 5041) od BOV and I r A 12 Fig. 32! vo - z iyi Bov- DID 512 : tA Y roi Sheche g. 45 Yama en Fig. 35 from the east KEKV SNAH and. at. oh oh ; 0 a o Z p xx ik p s 3 i: o "Ku KE OZ Ohh Ko o ohh o o o i y 5 V OO. o S OK o - KY KSO MAH more s OO KO KK OKH ХК С ХХ o x KMU OK OKO OO ok M KO M se V Oh : about her. at. thanks M U, y o o Oh ah M xx ee OO What Mo o. UA Z oh s KOH V o g o s OV WITH their KE M X S: o WHAT IN OURS Ann KA I s o . M t I KO ZO HU OV OH 3 Z S o. c V OK o OZ U c . at. more with KV ve U UK LYA OKH more S Z ZK ZH SOSOK Z a . MOH ho KU M OKH x KO Z NK EH ZK; KY MOU OKH I ZMK p what is OO KOZAK ZO I ON p. . | her o o 5 Ooya o. oh ХХ MV I o o u o 6 . y - she s o . with Z o. oh what oh z o oh y. how are you self-propelled guns in. o U s o s in . p o V sho SMAKU, nya KO Z EK xx o i o o s s: s ia I Tomlovye 33 M OH Z Х Х КН КМ ще ню KK sookh MEN E KO SU xx х Х У что . X Ko SEC MONE ZO OH ZH 5 g o. SK KU Kha sh i Ka XX zh OH U s-i o. . . Z Se OH ve I HK EK HO Oh se OO x sho. 0 SOU KOKO ХХ СО 0 - s х OK o ХSN o КОКО КК Me Te КК я ЯК s z ХО КК о ХХ OKU KU ОО 5 ХК их С 0. хх Ф fo . with 5 o. XX. xx . Me KO o s 5 Z 6 OM yah KO KO V ia de ha MK AK s . : ; » in. o sh o o o s o s Oh Ov o o. 5 s o s. in 0 KK OK 5 ZO from c. o - u 0 o. at. oh 0 sg p KOS C i o o. at. in her about SO OO KK Z . S s o. . pl o s o. o ZV Se SYA shh ET SH So U Kl Z SHO BOTH o o. yes p s NN Sh a EH SKU U Z KOH ZO U KOH SK ZO Okh x shk en 1 o i na: s OV OZ KK I s o VONO, nn o s Po ZHK ZON Ex Ed, 5 o p. . OA and about ig. 35 her advice Asya about sh. PK : rn Ж MKK ХХХ Ksy LK PPO KK OK Ko what pap o v o o v: en A so y, dy ne KOSY NYA a: v OVO v o. Sk in o. y o l o o o VV KM i PC KK OKKO ZK ev V NE oo eh V pe o o o o NN Her, KK v i VB AK KK KV LK SK Kv v en o v: KVU kn p M NK OV OK ya 5 shov ee OO i a ZOV ho OK "o still M 0. uh what ON PO posh Ne Ok ry go kg she ote MAKOM as en ZHK o i Z y shi a p. UVO i ASK OV PC Vk VAK DEek vyk OK KN OKH EB Be Ky VC still oh oh NI SU ON Kn cha sha ON VE oh with B OO o o. om 5. with KS and i M S V that ZKU KO KON . g sho s: o o. za o MOHY o V V XX EOM U KK NYA OM IC Veni KE MK HO PO TAMYA YAKO Po KOKO EV Me UK KAH UNO Ky o A po V sho p s ZK I. s s a B s. what 53. o i SHA KK i V UMO s SO vs p. i o o kos i v A U Me v oon s i i on 2 PO A V im OK ON KK A bo o i ON UK Pe V Vu her shi AY o NAMES IN KK: ho KE oshn ih SE v OO shi I Mr. ON V pi OO I PI KK PAK ECO uniem V I KOH o KO WE KO U 2 0. o. still OO - o. ol s KOVKY ek o A VO OH UK OV On Oh s a OO Ko OH KV a. MONO - OO U AK KK HV Z DKKOK HODA V Pon o s o 3 shcha. sha Se KONYA OO KN i PEK B. 5. s o a s OV VKM M, ZK Z Y I in SOVE OO rt Y DK ov Y sh ХМК or p PI MNN SY p. z 6, p o z OK ON VO KK VO oon BK M Z OK V o oh Oh and ef u a t KO s, o p V MOV po VO. V ev, VOK PC Koh OM Ky DAYS p i B KO V i ZK OO o o uvv PEK 5 z nn p Z a V V MKK ZHEI MK EK KI M zvnnnananN po Vo Ua prkzh A KK oz Kuv Ku KU E o tu Ku in and honor Fig. 36 : : i ES A moh U U a M OK Koh KAK se i ZU Te Uh MK ZO VA M I Zo t g: nn . OK OH KK Kn VK 5 OO i . Oh s o s 5 o o: o o. . VU IN OKO EK KK OO Okh s KO KO KOKO s M p p, oh xx СХ ХХ AKA I MO same UKV OV what EM AK . OO KU o OO Eh OOKOV OH AH i ZO oo ON OV OK A m s s a s 5 I OA o o she . po o o i s o no OH OKH p. M dya PO OH OK V 5 5 o. With and OO with MO. at. at. s o KE OO OKO Zhe OK KL AH o KK o oh OO OK KK OO OO KO SOKOM OK o KK AK MOH OH OKO VAH still in . o o o OO p KKU o z o. ХК ХХ ХУ SU ие Ома UKВ Оу Ж ХХ о о О О о о о о о о. o a a OK A p o U sha OO s o U a OK KK Z I MOM EC MK KOH OKA KO N MOB dk v 5 vs u Ks s v oo M M OM A o V OK s OK OK 3 en. by Ks o KOH with POM o U Okh, MK: and. oh what SH o. at. Ko o. B I o o s I OK i MO g xx p PE 3 A xx yah 5 ЖК NO SN ОХ ЭК ПНО в ЕК КК ZONES ECO M no PT ona scha i Oh sce . : FROM Fr. y g. M. o SHON OKU OV ZHE o I z OO i v m a o KN Y MK OKKO KK KISHKY OK s U Ok o OBO nn PMK OO i OKO EN A OON IDY t KO Oh NV KE ok EH OV OH i what a neck n U 5 S. in 1 V KK OKKO M nn KK t OKKO ON POV KON SK KAK OK KK KE SK AK o. of i» p p on OK OKH MM o KY okon m OKO VO a KK OO KO PK KY ТЕС С SOYA SY o UMO ХК TO V DEMO OK KK OKKO HO o o s s oyu s 0. p. g o. that 5 and p noi o i o. OO o VO VV g ts Z pu vne KE o U zak po o t o. 3. PShya p sho on ME VO EN o s o her. meh her about her I o KOKO Ko HA eye KK I BU He o NN i Ko ME Zhe, . U s PO o KO OKO SA On OK, Mo V V shi o i. Ba U o KE o o Zh o. and 3. I o it Ekh pi p OO i oku KK in vu with right you on PE VENY KN ZK EK KM Z AN V AV she a i a vnsheshny Fig. 37 ME sk K ov YOU WE V V V S spereovsyuvyr I wrote about Ah EK KK don o sho I i - di I she po. V OK kg sho pvh V PP PK oi yin ia ia UP p ia YA On Vo s s s s PIKA Bak o V V Dy ALREADY KK UNO PE V ZV ee ka I V OO p o KO oo o osya i V y OKKO NN UNO 1. A and I s; s o v i y I oh S o s g ESE ov PO i SO OO PEK xx OKH Me od t PETYA va V ON Cody she nn ia Pe s s ket; s VV Pod KK KK VOK MON Os o Shrek NV Kerry o VKM BOM I i p VN a Ver pev eV s i p M V i o v ZO po o i de s OO i o. х KO ek VV SA OK RKK i PE she V OO oven ee Koh A OH KE VA EN KK OK an KO PIV V OO KK i p pya v a I, i OO pa B ECO ed s h i ny o ec v PER RY o o p p. s dv s ve i I MOUTH au Ek s sot i S 0 s o. . in ak Ve OKKO o ON I Ole ikh pev i o an Z M - to Ne u kosha v o. Oka pu v p So er OH I Ko NK ol ky aa MK 0 ns 5. her. o a u V i i OO VOK i VC i ZO VC i MO KK o VE 0 :.- OO in Pe 0. sho p oh IN ME o. TO fs o Ж OK MAYA ON a Ka U We v v KO ZMK ko I them: 5 os p pom me a KI PK KU sh od i ly i a ah I o OO tor U KKU OPO IN oy ne OH Mn NN vyk U ev us I TYA v I PEK OK M she ev A A Dy V oo oo ON Ped o o o o shi KE r. AJ y No p p. p 53 o o. 5. M a i v a V v V OO v V un TOK Nv oct in ek ZOM OKKO KD oo PE s Uk EAVKy ba ov Zh o Z MK i m EK OO KV SV ro o nia MO ny i m VV OK KY nn OO I Mao vk A v en ya i OKKO OSKOKUKK M VK o PI u oo S in POM OH pe o OV i a m et g sha NO pev shu M OO v a VAK i V OVC i she yav dovo in V p vy p p Kom ey Day OVK UNN nn MY pori nn ah i un M y H Ya nn AK ee ShK U y Kt pe you I MO V KV ledles eV s i 0 p. ih 0 . 2 oh her. and with Kn o V o ON i M KK nn VN ve V Zh o o I o o, f: I o o sho p o oves u i, i i g s sho -- s : А. o KE Uk NPP DOES NOT need OK p - sha m still p doshne Fig. 38 95| and Ka with - | and 85 | IS - I. and EE 80 of their Y; t! i Z 5 x | AREA А 70 , о 4000 З500 3000 2500 шЩ 2000 1500 (1 - - rya in WAVE NUMBERS (CM) Fig. 39 cm of walls x 100 ra 2 ; I am ; a a 5 80 x 2 70 1 DE 40 regions x WAVE NUMBERS (CM) Fig. 40 ELECTRICITY, fountains yuzhatyatyanvayazhntitya kt tyu vim. siste tim: NIT TEKI odlninnttstyakktnyaya nannia uhketya acne and WOODENING peisten 3 Z | Sh: I'm YO BO - I! So YVOKNEN and not inhlenkty ninja ATI MK rt inno et zht same usustyanzhnya I: -Z N preparation of SNKOVINY t 7 ": t sho pogerka KeOvKA: to BIECTRICA a ! ELECTENKA OBNVANNA DENaturuvuchny NK rlzlita of exhaust lut Main nin poshi and jump riser zhd shk yus a kozh se already Ж KE oyu in kyu vom kn ko in mash ta oven Ho pbevnemta T.G yaistNyaaya Ye ODEVEATANYU tlu 0 SONNETS 1 prizh lu z : komila , : lizhlya | z VEDENENNI NINU TARA. : pyv navan ( ; no NISHNY: yusyuvni NO sediment TONKA LLC uch VLEKTRNA DeROTSESY. t water -- 4 6 DNU. boiler. No N sh0V SHK MARRA 418 Metkkechkzhyayannunvzheu kn tukkzhtnia of the harvester and o - teOdDALshSHA PERERV Ka.: 22 Fig. 41