UA96165C2 - Method of changing a molecular structure of a biomass feedstock - Google Patents

Abstract

The invention relates to a method of changing a molecular structure of a biomass feedstock, wherein the biomass comprises a cellulosic or lignocellulosic material. The method comprises converting a treated biomass feedstock to a product with use of a microorganism comprising yeasts, bacteria or fungi and/or an enzyme comprising a cellulolytic enzyme. The treated biomass feed stock is obtained by pretreatment of biomass feedstock having bulk density less than about 0.5g/cmusing electron beam irradiation of biomass feedstock.

Description

This application claims priority to US Patent No. 60/859911, filed Nov. 17, 2006, US Patent No. 60/875144, filed Dec. 15, 2006, and US Patent No. 60/881891, filed Jan. 23, 2007, the contents of which of each of these applications is incorporated herein by reference.

This invention relates to the processing of biomass and products obtained from it.

Cellulosic and lignocellulosic materials, for example in fibrous form, are obtained, processed and used in large quantities in a number of applications. Often, such materials are used once and then discarded as waste or simply considered as processing waste, or they are, for example, sewage, bagasse, sawdust and dry animal feed.

Various cellulosic and lignocellulosic materials, their use and applications are disclosed in US MoMo patents 7074918, 6448307, 6258876, 6207729, 5973035 and 5952105; and in various patent applications including "Fibrous materials and composites" described in PCT/O52006/010648, filed March 23, 2006, and "Fibrous materials and composites" described in US patent application Me 2007/0045456.

The present invention generally relates to hydrocarbon-containing materials (for example, biomass materials or materials obtained from biomass), methods of obtaining and processing such materials to change their structure, and products obtained from structurally modified materials. Many of the methods disclosed herein can provide, for example, cellulosic and/or lignocellulosic materials that have a reduced molecular weight and/or crystallinity relative to the natural material. Many of the methods provide materials that can be more easily used by a variety of microorganisms to produce useful products such as hydrogen, alcohols (e.g. ethanol or butanol), organic acids (e.g. acetic acid), hydrocarbons, by-products (e.g. proteins ), or mixtures of any of the specified products.

According to one aspect, the present invention is characterized by methods of changing the molecular structure of biomass raw materials, which include the preparation of biomass raw materials by reducing one or more sizes of individual pieces of biomass; pre-treating the biomass feedstock using two or more different pre-treatment methods, each of which alters the molecular structure, wherein the different pre-treatment methods are selected from irradiation, ultrasonic treatment, pyrolysis and oxidation; and processing of prepared and pre-processed biomass raw materials to obtain a product.

In some embodiments, the biomass feedstock is prepared and then pre-treated. Biomass feedstock can also be pre-treated and then prepared.

Reducing one or more sizes of individual pieces of biomass can include, for example, the use of shearing, cutting, or grinding.

In some embodiments, the biomass feedstock is subjected to two or more pretreatment methods at the same or nearly the same time.

Two or more pretreatment methods may include, for example, irradiation and ultrasonic treatment. Irradiation can be, for example, in the form of an electron beam. In certain variants, electron beam irradiation is carried out at a total dose level of 10 Mrad and ultrasonic treatment is carried out at a total energy level of more than 5 MJ/m3. Irradiation may precede sonication, or sonication may precede irradiation, or irradiation and sonication may occur at or near the same time.

Changing the molecular structure of the biomass feedstock may include, for example, changing any one or more characteristics selected from average molecular weight, average crystallinity, specific surface area, degree of polymerization, porosity, branching, grafting, and domain size of the biomass. In some embodiments, changing the molecular structure of the biomass feedstock includes decreasing any one or both characteristics selected from the average molecular weight and average crystallinity of the biomass, or increasing any one or both characteristics selected from the specific surface area and porosity of the biomass.

According to another aspect, the invention is characterized by methods of producing products, such as combustible fuels, which include providing a material comprising a carbohydrate obtained by a method which includes pre-treating a biomass feedstock by any two or more methods selected from irradiation, ultrasonication, pyrolysis and oxidation; and contacting the material with a microorganism that has the ability to convert at least a portion, for example, at least 1 wt.9o, of the material into a product, such as a flammable fuel.

In some embodiments, two or more different pretreatment methods include irradiation and sonication, irradiation and oxidation, irradiation and pyrolysis, sonication and oxidation, sonication and pyrolysis, or oxidation and pyrolysis.

Any method disclosed herein may additionally include, for example, pretreatment of biomass feedstock with steam explosion.

In some embodiments, the method does not include, for example, acid or base hydrolysis of the biomass.

In some embodiments, at least about 70 wt.90% of the biomass is not hydrolyzed, such as at least 95 wt.90% of the biomass. In some embodiments, the biomass is essentially not hydrolyzed at all.

In some embodiments, at least one pretreatment method is applied, for example, to biomass in which less than about 25 wt.95 of the biomass is wetted with a liquid, such as water. In some embodiments, at least one pretreatment method is applied to biomass that is substantially not wetted by a liquid such as water.

Biomass may have, for example, less than about 5 wt.9o of retained water as measured at 25 2C and fifty percent relative humidity.

In some embodiments, at least one pretreatment method may be applied to biomass in which less than about 25 wt.% of the biomass is in a swollen state, wherein the swollen state is characterized by the presence of a volume that is approximately 2.5 95 greater than the volume in the non-swollen state condition In other embodiments, the biomass is mixed with or includes a swelling agent.

In any method disclosed herein, the biomass may be mixed with, for example, a swelling agent or include such an agent, and the biomass may receive a dose of less than about 10 Mrad.

In some embodiments, one of the pretreatment methods is or includes irradiation.

In some embodiments, at least one of the pretreatment methods, such as irradiation, is applied to the biomass feedstock while the biomass feedstock is exposed to air.

Pressure may be used. At least one of the pretreatment methods, such as irradiation, can be used, for example, for biomass under pressure greater than about 2.5 atmospheres, such as greater than or 10 atmospheres.

The method may additionally include oxidation, pyrolysis or steam explosion of biomass.

Examples of biomass feedstocks include paper, paper products, waste paper, wood, particleboard, sawdust, agricultural waste, sewage, silage, grasses, rice husks, bagasse, cotton, jute, hemp, cellulose plant fiber, bamboo, sisal, abaca , straw, corn cobs, corn straw, millet, alfalfa, hay, coconut hair, synthetic cellulose, seaweed, algae or mixtures thereof.

Biomass can be a natural or synthetic material.

Examples of fuels include one or more fuels selected from hydrogen, alcohols, and hydrocarbons. Alcohols may include, for example, ethanol, n-propanol, isopropanol, n-butanol, or mixtures thereof.

A microorganism can be, for example, a bacterium or yeast.

Processing may include fermentation of the material into a product such as combustible fuel.

Irradiation can be performed, for example, using ionizing radiation such as gamma radiation, an electron beam, or ultraviolet C radiation having a wavelength of about 100 to about 280 nm.

Ionizing radiation can include electron beam irradiation.

Irradiation may be administered, for example, at a total dose level of from about 10 to about 150

Mrad, for example, at a dose rate of from about 0.5 to about 10 Mrad/day or from 1 to about 10

Mradi/c.

In some embodiments, the irradiation includes the use of two or more sources of irradiation, such as gamma radiation and an electron beam.

Ultrasonic treatment can be performed, for example, at a frequency of about 15 to about 25 kHz, for example, at a frequency of 18 to 22 kHz.

In some embodiments, the biomass includes a first cellulose having a first number average molecular weight, and the carbohydrate material includes a second cellulose having a second number average molecular weight that is lower than the first number average molecular weight. The second number average molecular weight is lower than the first number average molecular weight, for example by more than about a factor. In some embodiments, the first cellulose has a first crystallinity and the second cellulose has a second crystallinity that is lower than the first crystallinity.

The second crystallinity may be below the first crystallinity by more than about 10 95 .

In some embodiments, the first cellulose may have a first oxidation state and the second cellulose may have a second oxidation state that is higher than the first oxidation state.

Biomass raw material can be obtained, for example, by shifting the fiber of the biomass source to obtain fibrous material. Shifting can be done, for example, with a disk knife. The fibers of the fibrous material may have, for example, an average ratio of length to diameter greater than 5/1. Fibrous material can have, for example, a specific surface according to the BET method of more than 0.25 me/g.

In some embodiments, the carbohydrate may include one or more p-1,4 linkages and have a number average molecular weight of about 3,000 to about 50,000.

The pretreated biomass material may further include, for example, 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, a surfactant substance, mineral or chelating agent.

In some embodiments, the biomass feedstock is pretreated using any three or more methods selected from irradiation, sonication, pyrolysis, and oxidation in any order or at about the same time.

According to another aspect, the invention is characterized by methods of producing a product, such as a combustible fuel, which include providing a material comprising a carbohydrate obtained by pre-treating a biomass feedstock by any one or more methods selected from irradiation, sonication, oxidation, pyrolysis and steam explosion , in which less than approximately 25 wt. 90 of the biomass is in a swollen state, and the swollen state is characterized by the presence of a volume that is approximately 2.5 96 higher than the nominal volume in a non-swollen state; and contacting the material with a microorganism that has the ability to convert at least part, for example, at least 1 wt. 95, material into a product such as flammable fuel.

According to another aspect, the invention is characterized by methods of obtaining a product, such as a combustible fuel, which include providing a material comprising a carbohydrate obtained by pre-treating a biomass feedstock selected from any one or more treatments including irradiation, ultrasonic treatment, oxidation, pyrolysis and a steam explosion in which less than about 25 wt. 90% of biomass is hydrolyzed after pretreatment; and contacting the material with a microorganism that has the ability to convert at least a portion of the material, for example, at least about 1 wt. 95, into a product such as flammable fuel.

According to another aspect, the invention is characterized by methods of obtaining a product, such as a combustible fuel, which include providing a material comprising a carbohydrate obtained by pre-treating a biomass feedstock selected from any one or more treatments including irradiation, ultrasonic treatment, oxidation, pyrolysis and a steam explosion in which less than about 25 wt. 95% of the biomass is in contact with a liquid such as water; and contacting the material with a microorganism that has the ability to convert at least a portion, for example, at least about 1 wt. 95, material into a product such as flammable fuel.

In some embodiments, the methods include selecting two or more different preprocessing methods. Two or more different pretreatment methods may include, for example, irradiation and sonication, irradiation and oxidation, irradiation and pyrolysis, sonication and oxidation, sonication and pyrolysis, or oxidation and pyrolysis. Pretreatment of biomass may optionally include steam explosion.

According to another aspect, the invention features methods of producing a product, such as a combustible fuel, which include providing a material comprising a carbohydrate obtained by pre-treating a sheared biomass feedstock selected from any one or more treatments including irradiation, sonication, oxidation , pyrolysis and steam explosion; and contacting the material with a microorganism that has the ability to convert at least a portion, for example, at least about 1 wt. 9o, material into a product such as flammable fuel.

The sheared biomass may include, for example, discrete fibers having a length-to-diameter ratio (L/L, L/0) greater than about 5/1. The biomass may have, for example, internal fibers, and the biomass can be sheared to the extent that its internal fibers are substantially sheared. For example, biomass is sheared to the extent that it has a bulk density of less than about 0.35 g/cm3.

According to another aspect, the invention is characterized by systems for the processing of biomass raw materials, which include a biomass raw material preparation module designed to reduce the size of biomass pieces; two or more of the following pretreatment modules: an irradiation module positioned to irradiate the biomass; an ultrasonic treatment module placed for the effect of ultrasonic energy on biomass; oxidation module placed for biomass oxidation; pyrolysis module placed for biomass heating; and a biomass transport subsystem designed to move biomass to and between modules within the system for processing. Two or more pretreatment modules are installed sequentially and/or adapted to process a portion of the biomass at approximately the same time. Any system may additionally include, for example, a reactor.

According to another aspect, the invention is characterized by systems comprising a reactor containing pre-treated biomass material comprising a carbohydrate. Pre-treated biomass material is obtained by any method disclosed in this description.

The reactor may also contain, for example, a microorganism in contact with the material, and the microorganism has the ability to convert at least part of the material into a product, such as a flammable fuel. The reactor can have, for example, a total volume greater than about 1000 L, for example greater than 5000 L.

Any system can include, for example, an irradiation module and an ultrasonic processing module.

According to another aspect, the invention is characterized by hydrocarbon materials obtained by a method that includes a pretreatment of the sheared biomass feedstock selected from any one or more treatments including irradiation, ultrasonic treatment, oxidation, pyrolysis, and steam explosion. The pre-treatment can be carried out, for example, by any two or more treatments selected from irradiation, ultrasonic treatment, oxidation, pyrolysis and steam explosion.

According to another aspect, the invention is characterized by hydrocarbon materials obtained by a method that includes pre-treatment of biomass feedstock selected from any two or more treatments including irradiation, ultrasonic treatment, oxidation, pyrolysis and steam explosion.

According to another aspect, the invention features compositions that contain a cellulosic or lignocellulosic material having a peak maximum molecular weight of less than about 25,000 and a crystallinity of less than about 55 95. The cellulosic or lignocellulosic material may, for example, have a porosity greater than about 72 95, a specific surface area by BET is greater than about 0.75 mg/g or a bulk density of less than about 0.5 g/cm3. The composition may additionally include, for example, an enzyme and/or a microbe.

According to another aspect, the invention is characterized by compositions that contain cellulosic or lignocellulosic material including fibers. Cellulosic or lignocellulosic material has a peak maximum molecular weight of about 25,000 and a bulk density of less than about 0.5 g/cm3.

According to another aspect, the invention is characterized by methods of obtaining composite materials, such as composite materials based on fiber and a polymer matrix, which include irradiating a fibrous material that includes a first cellulosic and/or lignocellulosic material having a first molecular weight to obtain a second cellulosic and/or lignocellulosic material or ligocellulosic material having a second molecular weight that is higher than the first molecular weight; and combining the second cellulosic and/or lignocellulosic material with a material such as resin.

According to another aspect, the invention is characterized by methods of obtaining composite materials, such as composite materials based on fiber and polymer matrix, which include combining a material such as a resin with a fibrous material that includes cellulosic and/or lignocellulosic material having a first molecular weight, with the production of a composite material, including a fibrous material and a matrix; and irradiating the composite material to increase the molecular weight of the first cellulosic and/or lignocellulosic material in the matrix, such as the cured binder.

According to another aspect, the invention is characterized by methods of obtaining composite materials, such as composite materials based on fiber and a polymer matrix, which include irradiating a fibrous material that includes a first cellulosic and/or lignocellulosic material having a first molecular weight to obtain a second cellulosic and/or lignocellulosic material or ligocellulosic material having a second molecular weight that is higher than the first molecular weight; combining the second cellulosic and/or lignocellulosic material with a material such as a resin to obtain a composite material; and irradiation of the composite material.

According to another aspect, the invention is characterized by methods of obtaining irradiated wood products, which include providing a wood product that includes a first carbohydrate-containing material having a first molecular weight; and irradiating the wood product to produce an irradiated wood product that includes a second carbohydrate-containing material having a second molecular weight that is higher than the first molecular weight. The methods may additionally include, for example, ultrasonic treatment carried out, for example, before irradiation, after irradiation or simultaneously with irradiation.

Disclosed are methods that include providing a first material that includes cellulose having a first number average molecular weight; irradiating the first material to produce a second material that includes cellulose having a second number average molecular weight that is lower than the first number average molecular weight; and combining the second material with the microorganism. The microorganism uses, for example, enzymes or otherwise converts the second material and in some cases the first material into a useful product, such as a combustible fuel. Flammable fuel may include, for example, one or more products selected from hydrogen, alcohol, organic acid, hydrocarbon, or a mixture of these products.

The preferred product is ethanol or butanol, for example, n-, sec-, or tert-butanol.

In some embodiments, the first material includes cellulosic or lignocellulosic material. For example, the first material may be or may include paper, paper products, wood, wood-like materials, particle board, grasses, rice husks, bagasse, cotton, jute, hemp, plant cellulose fiber, bamboo, sisal, abaca, straw, rods corncobs, algae, seaweed, coconut hair, synthetic cellulose or a mixture of any of these materials.

In preferred embodiments, the first material is in the form of a fibrous material that includes fibers obtained by displacement of the fiber source. Displacement alone can reduce the crystallinity of the fibrous material and can work synergistically with any method technique that can also reduce crystallinity and/or molecular weight. Shifting can be done, for example, with a disk knife. In some embodiments, the fibrous material has an average length to diameter ratio greater than 5/1.

The first and/or second material may have, for example, a BET surface area greater than 0.25 mg/g and/or a porosity greater than about 25 95.

In some embodiments, irradiation is performed with ionizing radiation, such as gamma rays or an electron beam.

In preferred embodiments, the microorganism is a bacterium or a fungus, such as yeast.

In some embodiments, the second number average molecular weight is at least about 25 95 below the first number average molecular weight, e.g., 50 95 below.

Disclosed are methods that include shifting a fiber source to produce a first fibrous material that includes cellulose having a first number average molecular weight; and irradiating the first fibrous material, which includes cellulose having a second number average molecular weight that is lower than the first number average molecular weight. Displacement can work synergistically with irradiation to reduce crystallinity and/or molecular weight.

These methods may additionally include combining the second material with the microorganism.

Disclosed are methods that include irradiating a fiber source, such as paper, that includes cellulose having a first number average molecular weight to produce an irradiated fiber source that includes cellulose having a second number average molecular weight that is less than the first number average molecular weight; and displacement of the irradiated fiber source to produce fibrous material. With respect to pre-irradiated material, it should be noted that the irradiated material may be brittle and more susceptible to "opening" during displacement.

These methods may additionally include combining fibrous material with a microorganism.

Disclosed are methods that include providing a first lignocellulosic material that includes cellulose having a first number average molecular weight; and irradiating the first lignocellulosic material to produce a second lignocellulosic material that includes cellulose having a second number average molecular weight that is lower than the first number average molecular weight.

These methods may additionally include combining the second lignocellulosic material with a microorganism or removing lignin from the second lignocellulosic material to obtain delignified material and subsequent combining the delignified material with a microorganism. The removed lignin can be used, for example, as a substance that improves the technological properties of plastics, or it can be burned to obtain energy.

Disclosed are methods that include providing a first fibrous material that includes cellulose having a first number average molecular weight; densification of the first fibrous material to obtain a densified first fibrous material; and irradiating the compacted first fibrous material to produce a compacted second material that includes cellulose having a second number average molecular weight that is lower than the first number average molecular weight. Densification can work synergistically with irradiation to reduce molecular weight and can also increase productivity in any processing step disclosed herein.

These methods may additionally include combining the second compacted fibrous material with a microorganism or fibrating the second compacted fibrous material to obtain the second fibrous material and then combining the second fibrous material with the microorganism.

An enzyme, such as a fiber-degrading enzyme and/or a swelling agent, may be used to further assist in reducing the molecular weight of the cellulose in any of the methods described herein.

Disclosed methods that include ultrasonic treatment of a first material that includes cellulose having a first number average molecular weight to obtain a second material that includes cellulose having a second number average molecular weight that is lower than the first number average molecular weight; and combining the second material with the microorganism. The microorganism uses, for example, enzymes or otherwise transforms the second material and, in some cases, the first material into a useful product, for example, a combustible fuel. Combustible fuel, for example, may be or may include hydrogen, alcohol, organic acid, hydrocarbon, or a mixture of these products. The preferred product is ethanol or butanol, for example, n-, sec-, or tert-butanol.

In some embodiments, the first material includes cellulosic or lignocellulosic material. For example, the first material may be or may include paper, paper products, wood, wood-like materials, particle board, grasses, rice husks, bagasse, cotton, jute, hemp, plant cellulose fiber, bamboo, sisal, abaca, straw, rods corncobs, algae, seaweed, coconut hair, synthetic cellulose or a mixture of any of these materials.

In preferred embodiments, the first material is in the form of a fibrous material that includes fibers obtained by displacement of the fiber source. Displacement can work, for example, synergistically with sonication to reduce molecular weight and/or crystallinity. Shifting can be done, for example, with a disk knife. In some embodiments, the fibrous material has an average length to diameter ratio greater than 5/1.

The first and/or second material may have, for example, a BET surface area greater than 0.25 mg/g and/or a porosity greater than about 25,905.

In some embodiments, the ultrasonic treatment is performed with sound having a frequency of about 16 to about 100 kHz and/or an intensity of about 30 to about 600 W/cm?.

In preferred embodiments, the microorganism is a bacterium or a fungus, such as yeast.

In some embodiments, the second number average molecular weight is at least about 25,956 below the first number average molecular weight, e.g., below 50,95.

Disclosed are methods that include shifting a fiber source to produce a first fibrous material that includes cellulose having a first number average molecular weight; and sonicating the first fibrous material to obtain a second fibrous material that includes cellulose having a second number average molecular weight that is lower than the first number average molecular weight.

These methods may additionally include combining the second material with the microorganism.

Disclosed are methods that include sonicating a fiber source, such as paper, that includes cellulose having a first number average molecular weight to produce an sonicated fiber source that includes cellulose having a second number average molecular weight that is less than the first number average molecular weight; and displacement of the sonicated fiber source to produce a fibrous material. Regarding the pre-sonicated material, it should be noted that the sonicated material may be brittle and more susceptible to "opening" during shearing.

These methods may additionally include combining fibrous material with a microorganism.

Disclosed are methods that include sonicating a first lignocellulosic material that includes cellulose having a first number average molecular weight to produce a second fibrous material that includes cellulose having a second number average molecular weight that is lower than the first number average molecular weight.

These methods may additionally include combining the second lignocellulosic material with a microorganism or removing lignin from the second lignocellulosic material to obtain delignified material and subsequent combining the delignified material with a microorganism.

Disclosed methods that include ultrasonic treatment of a first fibrous material that includes cellulose having a first number average molecular weight to produce a second fibrous material that includes cellulose having a second number average molecular weight that is lower than the first number average molecular weight; and densifying the second fibrous material to obtain a densified fibrous material.

These methods may additionally include combining the compacted fibrous material with a microorganism or fibrating the compacted fibrous material to obtain a third fibrous material and then combining the third fibrous material with a microorganism.

An enzyme, such as a fiber-degrading enzyme, or a chemical, such as sodium hypochlorite, an acid, a base, or a swelling agent, may be used in any of the methods described herein to further assist in reducing the molecular weight of the cellulose. Enzyme and/or chemical treatment can be performed before, during, or after sonication.

Disclosed are methods that include pyrolyzing a first material that includes cellulose having a first number average molecular weight to produce a second material that includes cellulose having a second number average molecular weight that is lower than the first number average molecular weight; and combining the second material with the microorganism. The microorganism uses, for example, enzymes or otherwise transforms the second material and, in some cases, the first material into a useful product, for example, a combustible fuel. Flammable fuel may include, for example, one or more products selected from hydrogen, alcohol, organic acid, hydrocarbon, or a mixture of these products. The preferred product is ethanol or butanol.

In some embodiments, the first material includes cellulosic or lignocellulosic material. For example, the first material may be or may include paper, paper products, wood, wood-like materials, particle board, grasses, rice husks, bagasse, cotton, jute, hemp, plant cellulose fiber, bamboo, sisal, abaca, straw, rods corncobs, algae, seaweed, coconut hair, synthetic cellulose or a mixture of any of these materials.

In preferred embodiments, the first material is in the form of a fibrous material that includes fibers obtained by displacement of the fiber source. A relatively small cross-section can often be pyrolyzed with great control and efficiency. For example, the shift can be made with a disk knife.

In some embodiments, the fibrous material has an average length to diameter ratio greater than 5/1.

The first or second material can have a BET surface area greater than 0.25 mg/g and/or a porosity greater than about 25 95. High surface areas and/or porosities can increase reaction rates, making the methods more efficient.

In preferred embodiments, the microorganism is a bacterium or a fungus, such as yeast.

In some embodiments, the second number average molecular weight is at least about 25,95 below the first number average molecular weight, e.g., below 50,905.

Disclosed are methods that include shifting a fiber source to produce a first fibrous material that includes cellulose having a first number average molecular weight; and pyrolyzing the first fibrous material to produce a second fibrous material that includes cellulose having a second number average molecular weight that is lower than the first number average molecular weight.

These methods may additionally include combining the second material with the microorganism.

Disclosed are methods that include pyrolyzing a fiber source, such as paper, that includes cellulose having a first number average molecular weight to produce a pyrolyzed fiber source that includes cellulose having a second number average molecular weight that is less than the first number average molecular weight; and displacement of the pyrolyzed fiber source to form a fibrous material. With respect to pre-pyrolyzed material, it should be noted that the pyrolyzed material may be brittle and more susceptible to "opening" during shearing. Displacement of the pyrolyzed material may require less energy and may be more efficient.

These methods may additionally include combining fibrous material with a microorganism.

Methods are disclosed that include pyrolyzing a first lignocellulosic material that includes cellulose having a first number average molecular weight to produce a second lignocellulosic material that includes cellulose having a second number average molecular weight that is lower than the first number average molecular weight.

These methods may additionally include combining the second lignocellulosic material with a microorganism or removing lignin from the second lignocellulosic material to obtain delignified material and subsequent combining the delignified material with a microorganism.

Methods are disclosed that include pyrolyzing a first fibrous material that includes cellulose having a first number average molecular weight to produce a second fibrous material that includes cellulose having a second number average molecular weight that is lower than the first number average molecular weight; and densifying the second fibrous material to obtain a densified fibrous material.

These methods may additionally include combining the compacted fibrous material with a microorganism or fibrating the compacted fibrous material to obtain a third fibrous material and then combining the third fibrous material with a microorganism.

An enzyme, such as a fiber-degrading enzyme, or a chemical, such as sodium hypochlorite or an acid or base, may be used to further assist in reducing the molecular weight of the cellulose in any of the methods described herein. Enzyme treatment and/or chemical treatment can be carried out before, during or after pyrolysis.

In any aspect or embodiment disclosed herein, pyrolysis may include one or more of the following features. Pyrolysis can include heating the first material using a stable heating element, such as a metal thread or metal tape. Heating can be carried out by direct contact between the stable heating element and the first material. Pyrolysis may include heating the first material by induction, for example, using Sitivier-Roiip pyrolysis. Pyrolysis may include heating the first material with radiation, such as infrared radiation. The radiation may be generated by a laser, such as an infrared laser. Pyrolysis may include heating the first material with convective heat. Convective heat can be generated by a flow of heated gas. The heated gas can be maintained at a temperature less than about 12002C, for example, less than 1000, less than 750, less than 600, less than 400, or even less than 3002C. The heated gas can be maintained at a temperature greater than about 2502C. Convective heat can be generated by a hot body surrounding the first material, for example in a furnace. Pyrolysis may include heating the first material with steam at a temperature above about 25,026.

Disclosed are methods that include oxidizing a first material that includes cellulose having a first number average molecular weight and having a first oxygen content to produce a second material that includes cellulose having a second number average molecular weight and having a second oxygen content that is higher than the first content oxygen The second material can be combined with a resin, for example, with a molten thermoplastic resin, to obtain a composite material. A higher level of oxidation while maintaining molecular weight can provide composite materials with exceptional mechanical properties such as increased abrasion resistance, compressive strength, fracture resistance, impact strength, flexural strength, tensile modulus, flexural modulus, and relative elongation at break. The second material may also be combined with any solid and/or liquid substance disclosed herein, or with any solid and/or liquid substance disclosed in any patent application, patent, or publication included into this description by reference.

To further improve dispersibility, the resin may include a component that includes groups capable of forming a hydrogen bond, such as one or more anhydride groups, carboxyl groups, hydroxyl groups, amide groups, amino groups, or a mixture of any of these groups. In some preferred embodiments, the component includes a polymer copolymerized with maleic anhydride and/or grafted to maleic anhydride.

Such materials are available from Yuiropi under the brand name EOZBAVOMOF.

The first material may be or may include, for example, paper, paper products, wood, wood-like materials, chipboard, grasses, rice husks, bagasse, cotton, jute, hemp,

vegetable fiber of cellulose, bamboo, sisal, abaca, straw, corn cobs, coconut hair, synthetic cellulose or mixtures of any of these materials. Other materials that include cellulose are disclosed herein. Additional materials that include cellulose are disclosed in patents, patent applications, and publications incorporated herein by reference.

In some preferred embodiments, the first material is in the form of a fibrous material comprising fibers. Such fibrous materials can, for example, be provided by displacement of the fiber source, for example, displacement of the fiber source using a disk knife. To maximize mechanical properties, it is often desirable, for example, that the fibers of a fibrous material have an average length-to-diameter ratio greater than 5/1. For example, to maximize dispersibility, it is often desirable for the first and/or second material to have a BET surface area greater than 0.25 mg/g and/or a porosity greater than about 25 95.

Oxidation of the materials disclosed herein can be facilitated by a number of methods, including pyrolysis.

For example, the oxidation may involve pyrrole from the first material by heating the first material using a stable heating element, such as a metal filament or metal tape, in an oxidizing environment, such as in the presence of air, an oxygen-enriched inert gas (eg, argon), or in the presence of oxygen itself. . In some preferred methods, heating is carried out by direct contact of a stable heating element and the first material. In other methods, oxidation includes pyrolysis of the first material by heating the first material by induction, for example, using a Sipier-Roipi pyrolyzer, in an oxidizing environment. In other methods, the oxidation includes pyrolysis of the first material by heating the first material with radiation, such as infrared radiation, in an oxidizing environment. In one method, the radiation is generated by an infrared laser. In additional methods, oxidation includes pyrolysis of the first material by heating the first material with convective heat in an oxidizing environment. Convective heat can be generated, for example, by a flow of heated gas. The heated gas can be maintained, for example, at a temperature of less than about 12002C, such as less than 1000, less than 750, less than 600, less than 400, or even less than 3002C. In other methods, convective heat is generated by a hot body surrounding the first material.

In additional methods, the oxidation includes pyrolyzing the first material by heating the first material with steam at a temperature above about 25,026.

Other methods, which include ultrasonic treatment, can also contribute to the oxidation of materials.

Oxidation may include, for example, ultrasonic treatment of the first material in an oxidizing atmosphere.

Ultrasonic treatment can be carried out, for example, during the dispersion of the first material in an aqueous medium. In some preferred embodiments, the ultrasonic treatment is performed using sound having a frequency of about 12 to about 25 kHz.

Oxidation of materials can be carried out by other methods, which include ionizing and/or non-ionizing radiation. Oxidation may include, for example, irradiating the first material with gamma rays in an oxidizing environment and/or irradiating the first material with an electron beam in an oxidizing environment.

To obtain composite materials in some preferred variants, the second number average molecular weight is no more than fifteen percent below the first number average molecular weight. For composite materials, in some embodiments, the second number average molecular weight is substantially the same as the first number average molecular weight.

In some preferred embodiments, the second oxygen content is at least about five percent higher than the first oxygen content, or even more preferably twenty percent higher than the first oxygen content.

Disclosed are methods that include shifting a fiber source to produce a first fibrous material that includes cellulose having a first number average molecular weight and having a first oxygen content. The first fibrous material is oxidized to produce a second fibrous material that includes cellulose having a second number average molecular weight and having a second oxygen content that is higher than the first oxygen content. The second fibrous material can be used to make composite materials or it can be used for other applications. The second material may be combined, for example, with any solid and/or liquid substance disclosed herein, or with any solid and/or liquid substance disclosed in any patent application, patent or publication , incorporated herein by reference.

If necessary and when obtaining composite materials, the methods may additionally include combining the second fibrous material with a resin, such as a thermoplastic or thermoset resin.

Disclosed are methods that include oxidizing a fiber source that includes cellulose having a first number average molecular weight and having a first oxygen content to produce an oxidized fiber source that includes cellulose having a second number average molecular weight and having a second oxygen content that is higher than the first oxygen content. The oxidized fiber source is then sheared to produce an oxidized fibrous material that includes fibers. The oxidized fibrous material can be used to make composite materials or it can be used for other applications. The second material may be combined, for example, with any solid and/or liquid substance disclosed herein, or with any solid and/or liquid substance disclosed in any patent application, patent or publication , incorporated herein by reference.

Disclosed are methods that include oxidizing a first material that includes cellulose having a first number average molecular weight and having a first oxygen content to produce a second material that includes cellulose having a second number average molecular weight and having a second oxygen content that is higher than the first content oxygen The second fibrous material is compacted to obtain compacted fibrous material.

If necessary, these methods may additionally include combining compacted fibrous material with resin. In a preferred embodiment, the methods additionally include fibrating the densified fibrous material to form a third fibrous material and then combining the third fibrous material with a resin, such as a thermoplastic resin. The densified or third fibrous material may also be combined with any solid and/or liquid substance disclosed herein or with any solid and/or liquid substance disclosed in any patent application, patent or publications incorporated herein by reference.

Methods are disclosed that include converting a first material that includes cellulose having a first number average molecular weight and having a first oxygen content into a second material that includes cellulose having a second number average molecular weight and having a second oxygen content that is higher than the first oxygen content ; and combining the second material with resin to form a composite material. The first and/or second material may be combined, for example, with any solid and/or liquid substance disclosed herein, or with any solid and/or liquid substance disclosed in any patent application , patent or publication incorporated herein by reference.

Disclosed are methods that include oxidizing a first material that includes cellulose having a first number average molecular weight and having a first oxygen content to produce a second material that includes cellulose having a second number average molecular weight that is lower than the first number average molecular weight and has a second oxygen content that is higher than the first oxygen content; and combining the second material with the microorganism. The microorganism can use the second material, for example fermentation, to produce fuels such as hydrogen, alcohols, organic acids and hydrocarbons or mixtures of any of these fuels. In some variants, the first material is also combined.

Methods are disclosed that include converting a first material that includes cellulose having a first number average molecular weight and having a first oxygen content into a second material that includes cellulose having a second number average molecular weight that is lower than the first number average molecular weight and having a second an oxygen content that is higher than the first oxygen content; and combining the second material with a solid and/or liquid substance, for example, with a liquid that includes a microorganism and/or an enzyme. In some cases, the first material is also combined. In some cases, the microorganism uses a second material to produce fuel, such as hydrogen, alcohols, organic acids, and hydrocarbons, or mixtures of any of these fuels. In some variants, the first material can also be used by the microorganism to obtain fuel.

When a microorganism is used, it can be a natural microorganism or an artificially created microorganism. The microorganism can be, for example, a bacterium, such as a cellulose-degrading bacterium, a fungus, such as a yeast, a plant, or a single-celled organism, such as an algae, a protozoa, or a fungus-like single-celled organism, such as a slime mold. When the organisms are compatible, mixtures may be used. Naturally, various microorganisms can produce a number of useful products, such as fuel, by acting on materials, for example, by fermenting materials. For example, alcohols, organic acids, hydrocarbons, hydrogen, proteins or mixtures of any of these materials can be obtained by fermentation or other methods.

Methods are disclosed that include displacement and steam explosion of a fiber source to form a fibrous material; and contacting the fibrous material with the microorganism to produce the product. Examples of useful products include hydrogen, alcohols, organic acids, hydrocarbons, proteins, and combinations thereof. Examples of applicable fiber sources include cellulosic material, lignocellulosic material, and combinations thereof.

Displacement and steam explosion of the fiber source to form the fibrous material can be done in any order. In addition, multiple displacement and/or steam explosion operations can be performed in any order. Shifting can be done, for example, using a disk knife. The fiber source may be cut prior to displacement and/or steam explosion.

In some embodiments, the method includes, for example, shearing the fiber source to form a sheared fiber source and subsequent steam explosion of the sheared fiber source to form a fibrous material. Fibrous material can also be obtained by additional displacement of the fiber source subjected to displacement and steam explosion. It is also possible to shear the fiber source a second time to produce a second sheared fiber source which is then steam exploded to form a fibrous material.

Disclosed are methods that include steam explosion of a fiber source to form a steam-exploded fiber source and subsequent displacement of a steam-exploded fiber source to form a fibrous material. Fibrous material can also be obtained by additional steam explosion of a fiber source subjected to displacement and steam explosion.

Disclosed are methods that include simultaneous displacement and steam explosion of a fiber source to produce a fibrous material.

In some embodiments, the method may include passing the sheared material through one or more sieves, for example, a sieve having an average pore size of 1.59 mm or less (0.0625 inch). Sieving separates material according to size. In one embodiment, the method includes, for example: displacement of the fiber source to obtain a displaced fiber source; passing the displaced fiber source through the first sieve to obtain a screened fiber source; displacement of the screened fiber source to obtain a second displaced fiber source; passing the second biased fiber source through a second sieve having an average pore size smaller than that of the first sieve to obtain a second sieved fiber source; and steam explosion of the second screened fiber source to form a fibrous material. The method may additionally include displacement of the second screened fiber source to obtain a third displaced fiber source and subsequent steam explosion of the third displaced fiber source to obtain a fibrous material.

It is also possible to shear the fiber source and pass it through the sieve at the same time.

The methods may also further include placing the fibrous material in a substantially gas-impermeable material to remove entrapped gas and compact the fibrous material. The essentially gas-tight material may be soluble in water and may take the form of a bag.

Examples of microorganisms that can be used to produce useful products include bacteria, yeast, or combinations thereof. The microorganism can be, for example, a bacterium, such as a cellulose-degrading bacterium, a fungus, such as yeast, a plant, or a single-celled organism, such as algae, protozoa, or a fungus-like single-celled organism, such as slime molds.

Examples of products that can be obtained include mono- and polyhydric C-Cv-alkyl alcohols, monobasic and polybasic carboxylic acids, C1i-Cv-hydrocarbons and their combinations. Specific examples of suitable alcohols include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, and combinations thereof. Specific examples of suitable 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, y-hydroxybutyric acid and their combinations. Examples of suitable hydrocarbons include methane, ethane, propane, pentane, n-hexane and combinations thereof.

Many of these products can be used as fuel.

As used in this description, the term "fibrous material" means a material that includes numerous loose separated and separated fibers. The fibrous material can be obtained, for example, from a source of fiber, which is bleached kraft paper, by shearing, for example, using a disk knife.

As used herein, the term "sieve" means an element capable of screening material according to size. Examples of sieves include a perforated plate, a cylinder or similar element, or a wire mesh, or cloth fabric.

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

Oxygen content is measured by elemental analysis of a sample subjected to pyrolysis in a furnace operating at a temperature of 13002C or higher.

The term "biomass" refers to non-fossilized, i.e. regenerated, organic matter. Different types of biomass include plant biomass (defined below), animal biomass (any animal by-product, animal waste, etc.) and biomass from municipal waste (residential waste and light commercial waste with recycled products such as , from which metal and glass have been removed).

The terms "vegetable biomass" and "lignocellulosic biomass" refer to virtually any organic matter of plant origin (woody or non-woody) suitable for supporting energy. Plant biomass can include, but is not limited to, agricultural crop wastes and residues, such as corn straw, wheat straw, rice straw, sugar cane bagasse, and the like. Plant biomass additionally includes, but is not limited to, trees, woody fuel crops, wood waste and residues, such as softwood residues, cow waste, sawdust, pulp and paper industry waste streams, wood fiber, etc. As another source of plant biomass biomass can be further used for large-scale processing of forage grasses such as millet. In urban areas, the best potential feedstocks for plant biomass include yard waste (eg grass clippings, leaves, tree clippings and brush) and vegetable processing waste. "Ligpocellulosic feedstock" is any type of plant biomass such as, but not limited to, non-woody plant biomass, cultivated crops such as, but not limited to, grasses such as, but not limited to, C4 grasses such as millet , sorghum dgaz5, chaff, tizzapih, reed sedge or combinations thereof, or residues from sugar production, such as bagasse or beet pulp, residues from agricultural production, for example, soybean straw, corn straw, rice straw, rice husk, barley straw, corn cobs , wheat straw, canola straw, rice straw, oat straw, oat hulls, corn fiber, recycled wood pulp fiber, sawdust, hardwoods such as aspen and sawdust, softwood, or a combination thereof.

The ligocellulosic feedstock may additionally include pulp industry waste such as, but not limited to, newsprint, paperboard, 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. In addition, the lignocellulosic feedstock may include fresh lignocellulosic feedstock, partially dried lignocellulosic feedstock, or a combination thereof.

For the purposes of this description, carbohydrates are materials that consist entirely of one or more saccharide units, or materials that include one or more saccharide units. Carbohydrates can be polymeric (for example, the number of units is equal to or greater than 10, 100, 1000, 10000, or 100000), oligomeric (for example, the number of units is equal to or greater than 4.5, 6.7, 8.9, or 10), trimeric, dimeric, or monomeric .

When carbohydrates are formed from more than one repeating unit, the repeating units may be the same or different.

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

Carbohydrates can be part of a supramolecular structure, for example, covalently linked in the structure.

Examples of such materials include lignocellulosic materials such as those found in wood.

Flammable fuel is a product capable of burning in the presence of oxygen. Examples of flammable fuels include ethanol, n-propanol, n-butanol, hydrogen, and mixtures of any two or more of these substances.

As used in this description, the term "swelling agents" means materials that cause visible swelling, for example, an increase in the volume of cellulosic and/or lignocellulosic materials by 2.5 9o compared to the non-swelling state when using such materials in the form of a solution, for example, an aqueous solution. Examples include alkalis such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, acidifying agents such as mineral acids (e.g. sulfuric acid, hydrochloric acid and phosphoric acid), salts such as zinc chloride, calcium carbonate, sodium, benzyltrimethylammonium sulfate, and basic organic amines such as ethylenediamine.

As used herein, the term "sheared material" refers to a material comprising individual fibers in which at least 50 90 of the individual fibers have a length/diameter (L/D) ratio of at least about 5 and have an uncompacted bulk density of less than about 0 ,6 g/cm 3. Displaced material is therefore different from material that is cut, chopped or crushed.

The expression "change in the molecular structure of the biomass raw material" used in this description means a change in the location of the formation of a chemical bond or the conformation of the structure. A change in the molecular structure may include, for example, a change in the supramolecular structure of the material, oxidation of the material, a change in the average molecular weight, a change in the average crystallinity, a change in the specific surface, a change in the degree of polymerization, a change in the porosity, a change in the degree of branching, grafting to other materials, a change in the crystal domain size, or changing the total size of the domain.

Unless otherwise indicated, all technical and scientific terms used in this description have the same meaning as is generally accepted by those skilled in the art to which the present invention belongs. Although similar or equivalent methods and materials to those disclosed herein may be used in the practice or testing of the actual invention, suitable methods and materials are disclosed below. All publications, patent applications, patents and other references mentioned in this description are incorporated by reference in their entirety. In the event of a conflict, this description, including definitions, will control. In addition, the materials, methods and examples are illustrative only and are not intended to be limiting.

Other characteristic differences and advantages of this invention will become apparent from the following detailed description and claims.

Figure 1 is a block diagram illustrating the conversion of biomass into products and by-products.

Figure 2 is a block diagram illustrating the conversion of a fiber source into first and second fiber materials.

Fig. 3 is a sectional view of a disk knife.

Fig.4 is a block diagram illustrating the transformation of a fiber source into first, second and third fibrous materials.

Fig.5 is a block diagram illustrating the compaction of the material.

Fig. b6 is a perspective view of the granulator.

Fig. 7A represents compacted fibrous material in the form of granules.

Fig. 7B is a cross-section of an empty pellet, the center of the cavity of which is located on the line of the center of the pellet.

Fig. 7C is a cross-section of an empty pellet, the center of the cavity of which is outside the line of the center of the pellet.

Fig. 7O is a cross-section of a three-lobed granule.

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

Fig. 9 is a perspective view with a cutout of the gamma irradiator.

Fig. 10 is an enlarged perspective view of area A of Fig. 9.

Fig. 11 is a block diagram illustrating the sequence of pre-treatment of raw materials by electron beam irradiation.

Fig. 12 is a schematic representation of the system for ultrasonic treatment of the technological flow of cellulosic material in a liquid medium.

Fig. 13 is a schematic representation of an ultrasonic installation having two transducers connected in one horn.

Fig.14 is a block diagram illustrating a system for pyrolytic pretreatment of raw materials.

Fig. 15 is a side view in section of the pyrolysis chamber.

Fig. 16 is a side view in section of the pyrolysis chamber.

Fig. 17 is a side view in section of the pyrolyzer chamber, which includes a heated filament. Fig. 18 is a schematic side view in section of the Sipe-Roipi pyrolyzer.

Fig. 19 is a schematic side view in section of the pyrolyzer furnace.

Fig. 20 is a schematic top view in section of the apparatus for laser pyrolysis.

Fig. 21 is a schematic top view in section of a flash pyrolyzer with a tungsten filament.

Fig.22 is a block diagram illustrating a system for pre-treatment of raw materials by oxidation.

Figure 23 is a block diagram illustrating a general scheme of a method for converting a fiber source into a product, for example ethanol.

Fig. 24 is a cross-sectional view of the steam explosion apparatus.

Fig. 25 is a schematic side view in section of a hybrid device that provides processing of raw materials by irradiation with an electron beam and ultrasound.

Fig. 26 is a scanned electron micrograph of an image of a fibrous material obtained from paper with a multilayer coating, at 25 times magnification. The fibrous material was obtained using a disk knife and a 1/8 inch (3.175 mm) screen.

Fig. 27 is a scanned electron micrograph of an image of a fibrous material obtained from bleached paper kraft board, at 25 times magnification. The fibrous material was obtained using a disk knife and a 1/8 inch (3.175 mm) screen.

Figure 28 is a scanned electron micrograph of a fibrous material obtained from bleached kraft paperboard at 25x magnification. The fibrous material was sheared twice using a disc knife and a screen with 1/16 inch (1.588 mm) openings during each shear.

Figure 29 is a scanned electron micrograph of a fibrous material obtained from bleached kraft paperboard at 25x magnification. The fibrous material was sheared three times using a disk knife. A sieve with 1/3 inch (3.175 mm) openings was used during the first shift; the second shift used a 1/16 inch (1.588 mm) screen, and the third shift used a 1/32 inch (0.794 mm) screen.

Fig. 30 is a schematic side view of the apparatus for ultrasonic treatment, while Fig. 31 is a cross-sectional view of the device of Fig. 30.

Fig. 32 is a scanned electron micrograph, at 1000x magnification, of fibrous material obtained by shearing rod millet using a disk knife and then passing the sheared material through a 1/32 inch (0.794 mm) sieve.

Figures 33 and 34 are scanned electron micrographs, at a 1000-fold magnification of the image, of the fibrous material of Figure 32 after irradiation with gamma rays at doses of 10 and 100 Mrad, respectively.

Fig. 35 are scanned electron micrographs, at a 1000-fold magnification of the image, of the fibrous material of Fig. 32 after irradiation with a dose of 10 Mrad and ultrasonic treatment.

Fig. 36 is a scanned electron micrograph, at a 1000-fold magnification of the image, of the fibrous material of Fig. 32 after irradiation with a dose of 100 Mrad and ultrasonic treatment.

Fig. 37 is an infrared spectrum of paper kraft board subjected to displacement with a disk knife.

Fig. 38 is the infrared spectrum of kraft paper Fig. 37 after irradiation with gamma radiation at a dose of 100

Mrad.

Fig. 39 is a schematic representation of the biomass conversion method.

Fig. 40 is a schematic representation of another method of biomass conversion.

Biomass (eg plant biomass, animal biomass and biomass from municipal waste) can be processed into useful products such as fuel. Described below are systems and methods in which cellulosic and/or lignocellulosic materials that are readily available but may be difficult to process, for example by fermentation, can be used, for example, as raw materials. Raw materials are first physically prepared for processing, often by reducing the size of the raw materials. Physically prepared raw materials may be pretreated or processed using one or more treatments selected from irradiation, ultrasonication, oxidation, pyrolysis, and steam explosion. Different pretreatment systems and methods can be used in combinations that include two, three or even four technologies.

In some cases, to provide materials comprising a carbohydrate, such as cellulose, that can be converted by a microorganism into a number of desired products, such as combustible fuels (eg, ethanol, butanol, or hydrogen), a feedstock that may include one or more saccharide units , can be processed in one or more ways disclosed in this description. Other products and by-products that may be produced include, for example, human food, animal feed, pharmaceuticals and nutrients.

A number of examples are presented, the range of equipment in which ranges from an experimental installation in separate pretreatment methods to large-scale installations for biomass processing.

In most cases, any biomass material that is carbohydrates or includes carbohydrates that consist entirely of one or more saccharide units or that include one or more saccharide units can be processed by any of the methods disclosed herein. The biomass material can be, for example, cellulosic or lignocellulosic material.

Said materials may include, for example, paper, paper products, wood, wood-like materials, pressed wood, grasses, rice husks, bagasse, cotton, jute, hemp, vegetable cellulose fiber, bamboo, sisal, abaca, straw, corn cobs, coconut hair, algae, seaweed, synthetic cellulose or mixtures thereof.

Fiber sources include cellulosic fiber sources, including paper and paper products (eg, laminated paper and kraft paper), and ligocellulosic fiber sources, including wood and wood-like materials, such as pressed wood. Other suitable sources of fiber include natural fiber sources such as grasses, rice husks, bagasse, cotton, jute, hemp, vegetable cellulose fiber, bamboo, sisal, abaca, straw, corn cobs, coconut hair; fiber sources with a high content of o-cellulose, for example, cotton; and synthetic fiber sources, such as extruded yarn (oriented yarn or non-oriented yarn). Sources of natural or synthetic fibers can be obtained from scraps of textile materials that have not been used, for example, from residues or scraps, or they can be waste that has been used, for example, pieces (rags). When paper products are used as fiber sources, they may be materials that have not been used, such as scraps of materials that have not been used, or they may be waste that has been used. Apart from raw materials that were not used, raw materials that were used, industrial wastes (e.g. waste from factories) and processing wastes (e.g. waste water from paper recycling) can also be used as fiber sources. The fiber source may also be obtained or extracted from unsuitable human waste (eg sewage), animal or plant waste. Additional sources of fiber are described in MoMo US Pat.

In some embodiments, the carbohydrate is a material or includes a material that has one or more p-1,4 linkages and has a number average molecular weight of 3,000 to 50,000. Such a carbohydrate is cellulose or includes cellulose (I) that is produced from (p -glucose 1) by condensation of p(1--4)-glycosidic bonds. This bond itself is opposite to o(1-54)-glycosidic bonds present in starch and other carbohydrates.

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Mixtures of any of the above materials may also be used.

Fig. 1 shows a system 100 for converting biomass, especially biomass with a significant content of cellulosic and lignocellulosic components, into useful products and by-products. The system 100 includes a subsystem 110 for the preparation of raw materials, a subsystem 114 for preliminary processing, a subsystem 118 for the primary process and a subsystem 122 for further processing. The feedstock preparation subsystem 110 receives the biomass in its raw form, physically prepares the biomass for use as feedstock in subsequent processes (eg, reduces the size of the biomass and homogenizes it), and stores the biomass both in its raw form and in the form of the raw material. Biomass feedstock with a significant content of cellulosic and lignocellulosic components can have a high number average molecular weight and crystallinity, which can make processing the feedstock into useful products (for example, fermentation of the feedstock to produce ethanol) difficult.

Subsystem 114 for preliminary processing receives raw materials from subsystem 110 for preparation of raw materials and prepares raw materials for use in primary production processes, for example, by reducing the average molecular weight and crystallinity of raw materials. Primary process subsystem 118 receives pre-treated raw materials from pre-processing subsystem 114 and produces useful products (eg, ethanol, other alcohols, pharmaceuticals, and/or food products). In some cases, the output from subsystem 113 for the primary process is directly applicable, but in other cases it requires additional processing provided by subsystem 122 for further processing. Subsystem 122 for further processing provides further processing of product streams from subsystem 118 for the primary process that requires it (for example, distillation or denaturation of ethanol), as well as processing of waste streams from other subsystems. In some cases, the by-products of the subsystems 114, 118, 122 may also be directly or indirectly applicable as secondary products and/or in increasing the overall efficiency of the system 100. The downstream subsystem 122 may produce treated water to be recycled for use as process water in other subsystems and/or can produce combustible waste that can be used as fuel for steam boilers producing steam and/or electricity.

The optimal size of biomass conversion plants is influenced by factors that include economic considerations regarding the scale of production and the type and availability of biomass used as feedstock.

An increase in the size of the installation leads to an increase in the savings associated with the processes taking place in the installation. However, increasing the size of the plant also leads to higher costs (for example, transport costs) per unit of raw materials. A study of the analysis of these factors indicates that a suitable biomass conversion plant size can vary from 2000 to 10000 dry tons of feedstock per day depending at least in part on the type of feedstock used. The type of feedstock can also affect facility storage requirements, as facilities designed primarily to process feedstocks whose availability varies seasonally (such as corn straw) require more on-site or off-site feedstock storage. than installations designed for the processing of raw materials, the availability of which is relatively stable (for example, paper waste).

In some cases, the processing methods begin with the physical preparation of the raw material, for example, by reducing the size of the materials used as the raw material, for example, by cutting, grinding, shearing or chopping. In some cases, fluffed raw materials (for example, recycled paper or millet millet) are prepared by displacement or grinding. Sieves and/or magnets may be used to remove material that has not passed through the sieve or unwanted objects such as, for example, pebbles or nails from the feed stream.

Feedstock preparation systems can be configured to produce feedstock streams with specific properties, such as, for example, defined maximum dimensions, defined length-to-width ratios, or defined specific surface areas. As part of obtaining raw materials, it is possible to control (for example, increase) the volumetric weight of the raw materials.

In some embodiments, the material to be processed is in the form of a fibrous material that includes fibers obtained by displacement of the fiber source. Shifting can be done, for example, with a disk knife.

As can be seen, for example, from Fig. 2, the fiber source 210 is sheared, for example, by a disk knife to obtain a first fibrous material 212. The first fibrous material 212 is passed through a first sieve 214 having an average hole size of 1.59 mm or less (1 /16 in., 0.0625 in.), to produce a second fibrous material 216. If desired, the fiber source may be cut prior to shearing, for example by a shredder. When, for example, paper is used as a feedstock, it may first be cut into strips of, for example, 1/4 to 1/2 inch (6.35 mm to 1.27 cm) wide using a shredder, such as a counter-rotating shredder. screw grinder, such as those manufactured by Mypsop (Shisa, 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 knife. A guillotine knife can be used, for example, to cut paper into a sheet, for example, measuring 10 inches (25.40 cm) wide by 12 inches (30.48 cm) long.

In some variants, displacement of the fiber source and passage of the formed first fibrous material through the sieve are carried out simultaneously. Displacement and passing through the sieve can also be carried out periodically.

A disc knife can be used, for example, to simultaneously shift the fiber source and sift the first fibrous material. As can be seen from Fig.3, the disc knife 220 includes a raw material hopper 222, which can be loaded with a crushed fiber source 224 obtained by grinding the fiber source.

The chopped fiber source is sheared between stationary blades 230 and rotating blades 232 to produce a first fibrous material 240. The first fibrous material 240 passes through a screen 242 and the resulting second fibrous material 244 is captured in a hopper 250. To aid in the collection of the second fibrous material, the hopper may be pressurized below nominal atmospheric pressure, for example, at least 10 95 below nominal atmospheric pressure, for example, 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 the hopper below nominal atmospheric pressure.

Displacement can be beneficial for "unfolding" and "squeezing" the fibrous materials, making the cellulose of the materials more susceptible to chain breakage and/or reduced crystallinity. Exposed materials may also be more susceptible to oxidation when exposed to radiation.

The fiber source can be sheared in a dry state, a hydrated state (for example, it can have up to 10 wt. 95 absorption water), or a wet state, for example, it can have from about 10 to about 75 wt. 95 water. The fiber source can even be subjected to displacement during partial or full immersion in a liquid such as water, ethanol, isopropanol.

The fiber source may also be subjected to displacement in a gas atmosphere (eg, a flow or atmosphere of a gas other than air), such as oxygen or nitrogen or water vapor.

Other methods of obtaining fibrous materials include, for example, grinding with a grinding stone, mechanical breaking or tearing, pin grinding or attritor grinding in an air atmosphere.

If necessary, the fibrous material can be divided, for example, continuously or in portions, into fractions according to their length, width, density, type of material or a combination of these characteristics. For example, for the formation of composite materials, it is often desirable to have a relatively narrow distribution of fiber lengths.

The ferrous materials may, for example, be separated from any of the fibrous materials by passing the fibrous material including the ferrous material past a magnet, such as an electromagnet, and then passing the resulting fibrous material through a series of sieves, each of which has holes of different sizes.

Fibrous materials can also be separated, for example, using a high-velocity gas, such as air. With this approach, fibrous materials are separated by pulling out different fractions, which, if necessary, can be characterized photonically. Apparatus for such separation is discussed in the patent

US Mo 6883667, authored by I ipazeu ei ai.

The fibrous materials may be irradiated immediately after receiving them or they may be dried, for example, at a temperature of about 10522 for 4-18 hours to a moisture content of less than about 0.5 95 before use.

If necessary, lignin can be removed from any of the fibrous materials that include lignin. To promote the breakdown of materials comprising cellulose, the material may be treated prior to irradiation with heat, a chemical (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), e.g., 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 (1/128 in, 0.0078125 in), less than 0.18 mm (0.007 in), less 0.13 mm (0.005 in) or even less than 0.10 mm (1/256 in, 0.00390625 in). The sieve is prepared by stacking monofilaments of the appropriate diameter, obtaining the required size of holes.

Monofilaments can be made, for example, of metal, such as stainless steel. As the hole sizes become smaller, the requirements for monofilament structure may increase. For aperture sizes less than 0.40 mm, it may be advantageous to, for example, 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 sheet, for example, a metal sheet, having holes, for example, by cutting into a plate using a laser. In some embodiments, the open surface of the sieve openings is less than 52 90, for example, less than 41 95, less than 36 95, less than 31 95, less than 30 905.

In some embodiments, the second fibrous material is sheared and passed through a first screen or through a screen with different hole sizes.

In some embodiments, the second fibrous material is passed through a second sieve having an average pore size equal to or smaller than the size of the first sieve.

As can be seen from Fig. 4, the third fibrous material 220 can be obtained from the second fibrous material 216 by shifting the second fibrous material 216 and passing the resulting material through the second sieve 222, which has an average hole size smaller than the size of the first sieve 214.

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

The "average fiber width" (i.e. diameter) specified in this description is determined by an optically unordered selection of approximately 5000 fibers. The average fiber lengths are the corrected average mass lengths. BET (Brunauer, Emmett and Teller) specific surfaces are multipoint specific surfaces, and porosities are those determined by mercury porometry.

The average length-to-diameter ratio of the second fibrous material 216 may be, for example, greater than 8/1, for example, greater than 10/1, greater than 15/1, greater than 20/1, greater than 25/1, or greater than 50/1. The average length of the second fibrous material 216 may be, for example, from about 0.5 to 2.5 mm, for example, from about 0.75 to 1.0 mm, and the average width (ie, diameter) of the second fibrous material 216 may be, for example , from about 5 to 50 μm, for example, from about 10 to 30 μm.

In some embodiments, the standard deviation of the length of the second fibrous material 216 is less than 60 905 from the average length of the second fibrous material 216, for example, 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 BET surface area of the second fibrous material is greater than 0.1 mg/g, for example, greater than 0.25, greater than 0.5, greater than 1.0, greater than 1.5, greater than 1.75, greater than 5, 0, more than 10, more than 25, more than 35, more than 50, more than 60, more than 75, more than 100, more than 150, more than 200 or even more than 250 m/h.

The porosity of the second fibrous material 216 may be, for example, greater than 20 95, greater than 25, greater than 35, greater than 50, greater than 60, greater than 70, for example, greater than 80, greater than 85, greater than 90, greater than 92, greater than 94, greater than 95, greater 97.5, more than 99 or even more than 99.5 965,

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 some embodiments, the fibrous material is again sheared and the resulting fibrous material is passed through a second sieve having an average pore size smaller than the size 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, for example, 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 be passed, for example, through the fourth sieve to obtain the fifth material. Such sieving methods can be repeated as many times as necessary to obtain the necessary fibrous material that has the desired properties.

The compacted material may be processed in any of the ways disclosed herein.

A material, for example, a fibrous material having a low bulk weight, can be compacted to a product having a higher bulk weight. For example, a composition of material having a bulk density of 0.05 g/cm3 can be compacted by encapsulating the fibrous material in a relatively gas-tight structure, such as a shell made of polyethylene or a shell made of layers of polyethylene and nylon, which alternating, and subsequent pumping of entrapped gas, for example, air, from the structure. After the air is pumped out of the structure, the fibrous material may have, for example, a bulk density of more than 0.3 g/cm3, for example, 0.5, 0.6, 0.7 or more, for example, 0.85 g/cm3. After compaction, the product may be treated by any of the methods disclosed herein, for example, by irradiation, such as gamma radiation. Such processing can be advantageous when it is desirable to transport the material to another location, for example, to a remote industrial plant, in which the composition of the fibrous material can be added to a solution, for example, to produce ethanol. After "piercing" the substantially gas-tight structure, the densified fibrous material may return to approximately its original bulk density, for example, a bulk density greater than 60

Fo of its original bulk weight, for example, 70,80,85 or more, for example, 95 95 of its original bulk weight. To reduce static electricity in the fibrous material, an antistatic agent may be added to the material.

In some variants, the structure, for example, a shell, is formed from a material that dissolves in a liquid, such as water. For example, the structure can be formed from polyvinyl alcohol so that it dissolves when in contact with a water-based system. Such options provide the possibility of directly adding compacted structures to solutions that include a microorganism without first releasing the contents of the structure, for example, by cutting.

As shown in Figure 5, the biomass material can be combined with any desired additives and binder and then compacted by applying pressure, for example by passing the material through a gap marked between counter-currently rotating pressure rollers, or by passing the material through a granulator. Heating may optionally be used to promote densification of the fibrous material during the application of pressure.

The compacted material can then be irradiated.

In some embodiments, the material prior to compaction has a bulk density of less than 0.25 g/cm3, such as 0.20, 0.15, 0.10, 0.05, or less, such as 0.025 g/cm3. The volumetric weight is determined using A5TM 018958. The method includes, briefly, filling a measuring cylinder of known volume with a sample and obtaining the mass of the sample. The volumetric weight is calculated by dividing the mass of the sample in grams by the known volume of the cylinder in cubic centimeters.

Preferred binders include water-soluble binders that swell with water or those that have a glass transition temperature of less than 252°C as determined by differential scanning calorimetry. The authors consider water-soluble binders to be binders that have a solubility in water of at least 0.05 wt. 95.

The authors consider water-swellable binders to be binders that, when exposed to water, increase in volume by more than 0.5 95.

In some embodiments, binders that are water-soluble or water-swellable include a functional group capable of forming a bond, for example, a hydrogen bond, with fibers of a fibrous material, for example, a cellulose fibrous material. The functional group can be, for example, a carboxyl group, a carboxylate group, a carbonyl group, for example, 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, for example, an alcohol, and combinations of of these groups, for example, a carboxyl group and a hydroxyl group. Suitable 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, polyethylene oxide, polycarboxylic acids, polyamides, polyamines, and polysulfonates of polysulfonic acids. Some examples of polymers include polypropylene glycol (PPG, PPO), polyethylene glycol (PEG, RES), polyethylene oxide, for example, ROI MOHF, copolymers of ethylene oxide and propylene oxide, polyacrylic acid (PAK, RAA), polyacrylamide, polypeptides, polyethyleneimine, polyvinylpyridine, poly(sodium- 4-styrenesulfonate) and poly(2-acrylamidomethyl-1-propanesulfonic acid).

In some embodiments, the binder includes a polymer having a glass transition temperature of less than 2520. Examples of such polymers include thermoplastic elastomers (TPE, TPE). Examples of TPEs include block copolymers of amides and a simple polyester elastomer, such as those available under the trade name REVAHF, complex polyester elastomers, such as those available under the trade name NUTAEIF, and block copolymers of styrene, such as those available under the trade name KAATOMF. Other suitable polymers having a glass transition temperature of less than 252C include a copolymer of ethylene and vinyl acetate. (SEV, EMA), polyolefins, for example, polyethylene, polypropylene, copolymers of ethylene and propylene and copolymers of ethylene and c-olefins, for example, 1-octene, for example, those available under the trade name EMOSACEF. In some embodiments, for example, when the material is fibrous paper with a multilayer coating, the material is compacted without adding a separate polymer that has a low glass transition temperature.

In a separate 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 matter basis, is, for example, from about 0.01 to about 50 95, for example, 0.03, 0.05, 0.1, 0.25, 0.5, 1.0, 5, 10 or more, for example, 25 95 in terms of the total weight of the compacted material. The binder can be added to the material in the form of an unadulterated pure liquid, in the form of a liquid with a binder dissolved in it, in the form of a dry binder powder, or in the form of binder granules.

Compacted fibrous material can be obtained in a granulator. As can be seen from Fig. b6, the granulator 300 has a raw material hopper 301 for placing uncompacted material 310, which includes carbohydrate-containing materials such as cellulose. The raw material hopper is connected to an auger 312 driven by a variable speed motor 314 so that the uncompacted material can be transported to the conditioner 320, which mixes the uncompacted material with blades 322 rotated by the conditioner motor 330. Other ingredients may be added to inlet 332, such as any of the additives and/or fillers described herein. If necessary, heating may be added when the fibrous material is present in the conditioner. After conditioning, the material flows from the conditioner into the discharge chute 340 and into another auger 342. The discharge chute, which is controlled by the drive 344, ensures the unhindered passage of material from the conditioner to the auger. The screw is rotated by a motor 346 and regulates the supply of fibrous material to the head and rollers 350. The material is fed into a hollow cylindrical head 352, which rotates about a horizontal axis and has radially elongated holes in the head 350. The head 352 is rotated about an axis by a motor 360, which includes a power meter that shows the total power consumed by the engine. Compacted material 370, for example in the form of pellets, falls from chute 372 and is captured and processed, for example by irradiation.

The material after compaction may conveniently be in the form of granules or chips having a plurality of forms.

The pellets can then be irradiated. In some embodiments, the granules or chips are cylindrical in shape and have, for example, a maximum cross-sectional dimension of 1 mm or more, such as 2 mm, 3 mm, 5 mm, 8 mm, 10 mm, 15 mm or more, such as 25 mm. Another suitable form for the manufacture of composite materials includes pellets or chips having a plate-like shape, which has, for example, a thickness of 1 mm or more, for example 2, 3, 5, 8, 10 or more, for example 25 mm; width, for example, 5 mm or more, for example, 10, 15, 25, 30 or more, for example, 50 mm; and a length of 5 mm or more, such as 10, 15, 25, 30 or more, such as 50 mm.

As can be seen from Fig. 7A-70, the granules can be made in such a way that they have a cavity inside.

As shown, the cavity can usually be in line with the center of the pellet (Fig. 7B) or out of line with the center of the pellet (Fig. 7C). Making the pellet hollow inside can increase the dissolution rate in the liquid after irradiation.

As can now be seen from Fig. 7O, the granule can have, for example, a cross-sectional shape that is multilobed, for example, three-lobed, which is shown, five-lobed, six-lobed or ten-lobed.

Making the granules in such transverse shapes can also increase the dissolution rate in the solution after irradiation.

In one example, half-gallon (1.89 L) juice cartons made from unprinted white kraft paperboard having a bulk weight of 20 lb/ft (320.37 kg /m). The cardboard can be bent and flattened and then fed into a shredder to produce confetti-like material that is 0.1 to 0.5 inches (0.254 to 1.27 cm) wide, 0.25 to 1 inch (0.635 to 2.54 cm) and a thickness equivalent to the thickness of the parent material (approximately 0.075 inch (approximately 0.190 cm)). The confetti-like material can be fed to a disk cutter, which shears the confetti-like pieces, tearing them apart and releasing the fibrous material.

In some cases, multiple stacked rows of shredder-slicing machines with product output can be installed in series. In one variant, two stacked rows of shredder-slicing machine can be installed in series with the output of the product from the first cutting machine being fed as input product to the second shredder. In another variant, three stacked rows of chopper-slicing machines can be installed in series with the product output from the first cutting machine, supplied as input product, to the second chopper, and with the product output from the second cutting machine, supplied as input product, to the third chopper. The multiple passes through the shredder-slicing machine rows prevent an increase in reduced particle size and an increase in total surface area in the incoming material stream.

In another example, the fibrous material obtained from pulped and sheared pulp paperboard can be processed to increase its bulk density. In some cases, the fibrous material can be sprayed with water or a diluted mother solution of ROI MOH "M M/5A M10 (polyethylene oxide) obtained in water. The moistened fibrous material can then be processed in a granulator that operates at room temperature. The granulator can increase the volume of capacity weight of the incoming material flow by an order of magnitude.

Physically prepared raw materials can be pre-treated for use in primary production processes, for example, by reducing the average molecular weight and crystallinity of the raw material and/or increasing the specific surface area and/or porosity of the raw material. Pretreatment methods may include one or more treatments selected from irradiation, ultrasonication, oxidation, pyrolysis, and steam explosion. Different pretreatment systems and methods can be used in combinations that include two, three or even four of the above technologies.

In some embodiments, the biomass may be treated using two or more of any of the methods disclosed herein, such as two or more treatments selected from irradiation, sonication, oxidation, pyrolysis, and steam explosion, or with prior, intermediate, or subsequent preparation of raw materials disclosed in this description, or without such. Processing of biomass, for example, cellulosic and/or lignocellulosic material, can be carried out in any order (or simultaneously). In other embodiments, the carbohydrate-containing materials are prepared using three, four, or more of the methods disclosed herein (in any order or simultaneously). The carbohydrate can be prepared, for example, using irradiation, ultrasonication, oxidation, pyrolysis and optionally steam explosion for cellulosic and/or lignocellulosic material (in any order or simultaneously). The resulting carbohydrate-containing material can then be converted by one or more microorganisms, such as bacteria, yeasts, or mixtures of yeasts and bacteria, into a number of desired products presented herein. Numerous processing methods can provide materials that can be more easily used by a number of microorganisms due to their reduced molecular weight, reduced crystallinity and/or increased solubility. Multiple processing methods can provide a synergistic effect and can reduce the overall energy input required compared to a single processing method.

In some embodiments, for example, a carbohydrate-containing feedstock obtained by a method that includes irradiation and ultrasonic treatment (in any order or simultaneously) of cellulosic and/or lignocellulosic material is obtained by a method that includes irradiation and oxidation (in any in which order or simultaneously) cellulosic and/or lignocellulosic material, by a method that includes irradiation and pyrolysis (in any order or simultaneously) of cellulosic and/or lignocellulosic material, or by a method that includes irradiation and steam explosion (in any order or simultaneously) of cellulosic and/or ligpocellulosic material. The resulting raw material can then be contacted with a microorganism capable of converting at least part, for example, at least 1 wt. 9juo, raw materials into a product, such as combustible fuel, as disclosed herein.

In some embodiments, the method does not include hydrolysis of the cellulosic and/or lignocellulosic material, for example, with an acid or a base, for example, a mineral acid such as hydrochloric or sulfuric acid.

If desired, some of the feedstock may include hydrolyzed material or none of the feedstock may include such material. In some embodiments, for example, at least 70 wt. 90% of the raw material is unhydrolyzed material, for example, at least 95 wt. 95 raw materials are non-hydrolyzed material. In some embodiments, substantially all of the starting material is unhydrolyzed material.

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

If irradiation is used, it can be applied to any sample that is dry or moist or even dispersed in a liquid such as water. It can be carried out, for example, irradiation of cellulosic and/or lignocellulosic material, in which at least approximately 25 wt. 95 cellulosic and/or ligpocellulosic material has surfaces wetted by a liquid such as water. In some embodiments, cellulosic and/or lignocellulosic material is irradiated in which essentially no amount of cellulosic and/or lignocellulosic material is moistened with a liquid such as water.

In some embodiments, any processing disclosed herein occurs after the cellulosic and/or lignocellulosic material is dried or is dried, for example, using heat and/or reduced pressure. In some embodiments, the cellulosic and/or lignocellulosic material has, for example, less than about 5 wt. to retained water as measured at 252C and a relative humidity of 50295.

If desired, a specific swelling agent may be used in any method disclosed herein. In some variants, when processing cellulosic and/or lignocellulosic material using irradiation, less than approximately 25 wt. 90 cellulosic and/or lignocellulosic material is in a swollen state, and the swollen state is characterized by the presence of a volume that is approximately 2.5 95 higher than the volume in an unswollen state, for example, by 5.0, 7.5, 10 or 15 95 above the volume in an unswollen state. In some embodiments, when irradiation is used for cellulosic and/or lignocellulosic material, essentially none of the cellulosic and/or lignocellulosic material is in a swollen state.

In some embodiments, when using irradiation, 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.

When irradiation is used in any method, it can be applied while the cellulosic and/or lignocellulosic material is exposed to air, oxygen-enriched air, or even oxygen itself, or blanketed with an inert gas such as nitrogen, argon, or helium. . When maximum oxidation is desired, an oxidizing medium such as air or oxygen is used.

When irradiation is used, it can be applied to biomass, such as cellulosic and/or lignocellulosic material, at pressures greater than about 2.5 atm, for example, greater than 5, 10, 15, 20, or even greater than about 50 atm.

In certain embodiments, the method includes irradiation and sonication, and the irradiation precedes the sonication In other certain embodiments, the sonication precedes the irradiation, or the irradiation and sonication occur simultaneously.

In some embodiments, the method includes irradiation and sonication (in any order or simultaneously) and further includes oxidation, pyrolysis, or steam explosion.

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

In certain embodiments, the ultrasonic treatment can be performed at a frequency of about 15 to about kHz, for example, from about 18 to 22 kHz, using a horn with a power of 1 kW or more, for example, 2, 3, 4, 5, or even 10 kW.

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 that is lower than the first number average molecular weight. The second number average molecular weight is lower than the first number average molecular weight, for example, more than about 25 95, for example, less than 2, 3, 5, 7, 10, 25 or even 100 times.

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

In some embodiments, the first cellulose has a first oxidation state and the second cellulose has a second oxidation state that is higher than the first oxidation state, such as two, three, four, five, ten, or even twenty-five percent higher.

One example of the use of oxidative irradiation pretreatment uses half-gallon (1.89 L) juice cartons made from unprinted white laminated kraft paperboard having a bulk weight of 20 as the starting material. lb/ft? (320.37 kg/m3). The carton is bent and flattened and then fed into three successive stacked rows of disc shredders with product output from the first disc knife fed as input product to the second shredder and product output from the second disc knife fed as product is introduced into the third shredder.

The resulting fibrous material can be sprayed with water and processed in a granulator that operates at room temperature. Compacted granules can be placed in a glass container, which is sealed in an air atmosphere. The pellets in the container are irradiated with gamma radiation for about 3 hours at a radiation dose rate of 1 Mrad/hour to produce an irradiated material in which the cellulose has a lower molecular weight than the source material, which is fibrous kraft paperboard.

One or more sequential processes may be used to process raw materials from a wide variety of sources to extract useful substances from the raw materials and to provide partially degradable organic material that functions as input to subsequent stages and/or processing sequences. irradiation treatments. Irradiation can reduce the molecular weight and/or crystallinity of the raw material. In some embodiments, materials are irradiated using energy deposited in the material, which releases electrons from their atomic orbitals. Irradiation can be provided by: 1) heavy charged particles such as alpha particles, 2) electrons produced, for example, in beta decay or electron beam accelerators, or 3) electromagnetic radiation, such as gamma rays, X-rays, or ultraviolet rays In one variant, radiation generated by radioactive substances can be used to irradiate raw materials. In another variant, electromagnetic radiation obtained, for example, using electron beam emitters, can be used to irradiate raw materials. The doses used depend on the required effect and characteristics of the raw material. High doses of radiation can, for example, break chemical bonds in the components of the raw material, and low doses of radiation can increase the strength of the chemical bond (for example, due to crosslinking) in the components of the raw material.

As can be seen from Fig. 8, in one method the first material 2, which is cellulose or includes cellulose having a first number average molecular weight ("Mm1i"), is irradiated, for example, by treatment with ionizing radiation (for example, in the form of gamma radiation, X-ray , ultraviolet radiation (UV) with a wavelength from 100 to 280 nm, a beam of electrons or other charged particles) to obtain a second material 3, which includes cellulose having a second average molecular weight ("Mkg"), which is lower than the first average molecular weight. The second material (or the first and second materials) may be combined with a microorganism (e.g., a bacterium or yeast) that may utilize the second and/or first material to produce a fuel 5 that is hydrogen, an alcohol (e.g., ethanol or butanol, such as n-, sec- or tert-butanol), an organic acid, a hydrocarbon or mixtures of any of these substances or which includes them.

Since the second material C includes cellulose having a reduced molecular weight relative to the molecular weight of the first material and, in some cases, also reduced crystallinity, the second material is usually one that is more dispersible, swellable and/or soluble in the solution containing the microorganism. These properties make the second material Z more susceptible to chemical, enzymatic and/or biological action relative to the first material 2, which can increase the productivity and/or level of production of the required product, for example, ethanol. Irradiation can also sterilize materials.

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

In some cases, the second material includes cellulose having a crystallinity (Cg) that is lower than the crystallinity (Si) of the cellulose of the first material. For example, (2) may be below (Ci) by more than about 10 95 , such as below by 15, 20, 25, 30 90, 35, 40, or even more than about 50 95 .

In some embodiments, the initial crystallinity (before irradiation) is from about 40 to about 87.5 9o, for example, from about 50 to about 75 95 or from about 60 to about 70 95, and the crystallinity after irradiation is from about 10 to about 50 905, e.g., from about 15 to about 45 95 or from about 20 to about 40 95. However, in some embodiments, such as after intense irradiation, it is possible to have a crystallinity index below 5 90. In some embodiments, the material after irradiation is substantially amorphous

In some embodiments, the starting number average molecular weight (before irradiation) is from about 200,000 to about 3,200,000, e.g., 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, it is possible to have a number average molecular weight of less than about 10,000 or even less than about 5,000.

In some embodiments, the second material may have an oxidation state (72) that is higher than the oxidation state (0) of the first material. A higher degree of oxidation of a material can contribute to its dispersibility, swelling and/or solubility, which further increase the susceptibility of materials to chemical, enzymatic or biological effects. In some variants, to increase the degree of oxidation of the second material relative to the first material, irradiation is carried out in an oxidizing environment, for example, under a blanket of air or oxygen, resulting in a second material that is more oxidized than the first material.

The second material can have, for example, a larger number of hydroxyl groups, aldehyde groups, ketone groups, ester groups or carboxyl groups, which can increase its hydrophilicity.

Any form of radiation ionizes biomass through special interactions determined by the energy of the radiation. Heavy charged particles initially ionize matter by Coulomb scattering; then these interactions generate high-energy electrons that can additionally ionize the substance. Alpha particles are identical to the nucleus of a helium atom and are generated by the alpha decay of various radioactive nuclei such as isotopes of bismuth, polonium, astatine, radon, francium, radium, several actinides such as actinium, thorium, uranium, neptunium, curium, californium, americium and plutonium.

Electrons interact by means of Coulomb scattering and bremsstrahlung generated 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 using thermionic emission.

Electromagnetic radiation interacts through three processes: photoelectric absorption, Compton scattering, and vapor generation. The predominant interaction is determined by the energy of the incident radiation and the atomic number of the material. A summary of the interactions contributing to the absorbed radiation in the cellulosic material can be expressed by the mass absorption coefficient, graphically depicted below as a function of the energy of the incident radiation.

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Energy of incident radiation (MeV)

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

Gamma radiation can be used to irradiate materials. As can be seen from Figures 9 and 10 (enlarged image of area B), the gamma emitter 10 includes sources 408 of gamma radiation, for example, CO pellets, a work table 14 for holding materials to be irradiated, and a storage 16, made, for example, of a plurality of iron plates, all of which are placed in a concrete sealed chamber 20, which includes a labyrinthine path to an entrance 22 behind a lead-lined door 26. The vault 16 includes a plurality of channels 30, for example sixteen or more channels, which allow the passage of gamma radiation sources through storage on their way near the desktop.

In action, the sample to be irradiated is placed on the work table. The irradiator has a configuration that ensures the delivery of the necessary radiation power, and the experimental unit 31 is connected to the automatic adjustment equipment. The operator then leaves the sealed chamber, passing through a labyrinthine path and through a lead-lined door. The operator controls the control panel 32, instructing the computer 33 to move the radiation sources 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 a number of materials in the sample.

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.

Gamma-ray sources include electron beam collisions with metallic targets such as tungsten or molybdenum or alloys, or compact light sources such as those produced commercially

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Sources of ultraviolet radiation include deuterium or cadmium lamps.

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

Microwave sources include klystrons, Slevin-type high-frequency sources, or atomic beam sources that use hydrogen, oxygen, or nitrogen gas.

In some variants, an electron beam is used as a source of irradiation. The electron beam offers advantages that include the ability to use high radiation powers (eg, 1.5 or even 10 Mrad/;s), high performance, smaller volume, and less equipment constraints. Electrons may also be more effective in causing chain breakage. In addition, electrons having energies of 4-10 MeV can have a penetration depth of 5 to 30 mm or more, for example 40 mm.

Electron beams can be generated, for example, by electrostatic generators, cascade generators, transformation generators, low energy accelerators with a scanning system, low energy accelerators with a linear cathode, linear accelerators and pulse accelerators.

As a source of ionizing radiation, electrons may be applicable, e.g., for relatively thin layers of material, e.g., less than 0.5 in. (1.27 cm), e.g., less than 0.4 in. (1.016 cm), 0.3 in. (0.762 cm ), 0.2 inches (0.508 cm) or less than 0.1 inches (0.254 cm). In some embodiments, the energy of each electron in the electron beam is from about 0.3 to about 2.0 MeV (million electron volts), such as from about 0.5 to about 1.5 MeV or from about 0.7 to about 1, 25 MeV.

Fig. 11 shows a technological diagram of the method 3000, which includes various stages in the sequence of pre-treatment of raw materials by irradiation with an electron beam. In the first stage 3010, a load of dry raw materials is received from the raw material source. As discussed above, the dry raw material from the raw material source may be pretreated prior to delivery to the electron beam irradiation device. For example, if the raw material is produced from plant sources, some parts of the plant material may be removed before harvesting the plant material and/or before delivering the plant material by the raw material vehicle. Alternatively, or additionally, the biomass feedstock in optional step 3020 may be subjected to mechanical processing (eg, to reduce the average length of fibers in the feedstock) prior to delivery to the device for electron beam irradiation.

In step 3030, the dry raw material is transferred to a raw material vehicle (eg, a belt conveyor) and distributed across the cross-sectional width of the raw material vehicle approximately uniformly by volume. The distribution can be carried out, for example, manually or by inducing a localized vibrational movement at some point of the vehicle for the raw material before treatment with electron beam irradiation.

In some embodiments, the mixing system introduces a reagent 3045 into the raw material in an optional process 3040 that prepares a slurry. The combination of water with the processed raw material in stage 3040 of mixing creates an aqueous suspension of the raw material, which can be transported, for example, preferably by pumping through a pipeline, rather than using, for example, a belt conveyor.

The next stage 3050 is a loop that finishes subjecting the raw material (in dry form or in suspension form) to electron beam irradiation with one or more (i.e., M) electron beam irradiation devices. A suspension of feedstock is moved through M "streams" of electron beams at stage 3052. The movement may be carried out at a constant speed through the "streams" and there may be a pause between the "streams" or during movement through each "stream", followed by rapid movement to the next "flow". A small portion of the feed slurry is exposed to each stream for a predetermined exposure time in step 3053 .

Devices for electron beam irradiation can be purchased commercially from op Veat Arriisaiopv,

Yi oimaip-Ia-Meime, VeiYidisht, or from Tiap Sogrogayop, Zap Oiedo, SA. Typical energies of electron motion can be 1, 2, 4, 5, 7, 5 or 10 MeV. A typical power of an electron beam irradiation device can be 1, 5, 10, 20, 50, 100 kW, 250 or 500 kW. The efficiency of depolymerization of the suspension of raw materials depends on the used electron energy and the used dose, while the duration of exposure depends on the power and dose. Typical doses can be 1, 5, 10, 20, 50, 100 or 200 kCSU.

Total costs when considering the power specifications of an electron beam device include manufacturing costs, capital costs, depreciation, and installation footprint. Total costs, taking into account dose levels of electron beam exposure, include energy costs and environmental, safety and health concerns. Total costs, taking into account the energy of electron movement, include energy costs; in this case, to maintain the depolymerization of the suspension of the specified raw material, the reduced energy of electron movement can be beneficial (see, for example, Voyspaga, ei ai, SePshose (2006) 13:601-610).

To ensure a more efficient depolymerization process, it may be beneficial to perform double-pass electron beam irradiation. A feedstock vehicle may direct, for example, the feedstock (in dry or slurry form) down and in a direction opposite to its original direction of travel. Double-pass systems can provide processing of thicker feedstock suspensions and can provide more uniform depolymerization throughout the feedstock suspension.

An electron beam irradiation device can generate either a fixed beam or a scanning beam. A scanning beam can be advantageous at long sweep lengths and high scan speeds, and is an effective replacement for a fixed beam with a large width. In addition, available deployment widths of 0.5, 1, 2 m or more are suitable.

To mechanically separate the liquid and solid components of the feedstock slurry in some embodiments, such as at step 3060, it may be necessary to move a portion of the feedstock slurry through an M-number electron beam irradiation device. In such embodiments, the liquid portion of the feedstock slurry is filtered to remove remaining solids and recycled back to the slurry preparation stage 3040. The solid portion of the feedstock slurry is then sent to the next processing stage 3070 via a feedstock vehicle. In other variants, the raw material is stored in the form of a suspension for further processing.

In such embodiments, where exposure is conducted by electromagnetic radiation, the electromagnetic radiation may have, for example, a photon energy (in electron volts) greater than 102 eV, such as greater than 103, 104, 105, 106, or even greater than 107 eV. In some embodiments, the electromagnetic radiation has a photon energy of 107 to 107 eV, such as 105 to 102 eV. Electromagnetic radiation can have, for example, a frequency greater than 1015 Hz, greater than 1017, 1018, 1019, 1029 or even greater than 102! Hz. In some embodiments, the electromagnetic radiation has a frequency from 1018 to 1072 Hz, for example, from 10'Yado102!Hz.

In some embodiments, irradiation (by any radiation source or combination of radiation sources) is carried out until the material receives a dose of at least 0.25 Mrad, for example, at least 1.0, at least 2.5, at least 5.0, or at least 10.0 Mrad. In some embodiments, irradiation is carried out until the material receives a dose of from 1.0 to 6.0 Mrad, for example, from 1.5 to 4.0 Mrad.

In some variants, irradiation is carried out at a dose rate 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, two or more sources of radiation are used, for example, two or more ionizing radiations. The samples may be treated, for example, with an electron beam, subsequent gamma radiation, and UV light having wavelengths from about 100 to about 280 nm in any order. In some embodiments, the samples are treated with three sources of radiation, such as an electron beam, gamma radiation, and energetic UV radiation.

In some embodiments, relatively low doses of radiation can crosslink, graft, or otherwise increase the molecular weight of a carbohydrate-containing material such as cellulosic and/or lignocellulosic material (eg, cellulose). Such a material having an increased molecular weight can be used,

for example, in the manufacture of a composite material that has, for example, improved mechanical properties such as abrasion resistance, compressive strength, fracture resistance, impact strength, flexural strength, tensile modulus, flexural modulus and elongation at break . Such material, which has an increased molecular weight, can be used in the preparation of the composition.

For example, a fibrous material that includes a first cellulosic and/or lignocellulosic material having a first molecular weight can be irradiated in such a way as to produce a second cellulosic and/or lignocellulosic material having a second molecular weight that is higher than the first molecular weight. If, for example, gamma radiation is used as the source of radiation, a dose of from about 1 to about 10 Mrad, for example from about 1.5 to about 7.5 Mrad or from about 2.0 to about 5.0 Mrad, can be applied. After applying a low dose of radiation, the second cellulosic and/or lignocellulosic material can be combined with the resin and transformed into a composite material, for example, by direct pressing, molding or extrusion. The formation of composite materials is described in U 2006/102543 and in previous MoMo patent applications 60/664832, filed on March 24, 2005, 60/688002, filed on June 7, 2005, 60/711057, filed on August 24, 2005, 60/715822, filed September 9, 2005, 60/725674 filed October 12, 2005, 60/726102 filed October 12, 2005 and 60/750205 filed December 13, 2005.

Alternatively, a fibrous material comprising a first cellulosic and/or lignocellulosic material having a first molecular weight may be combined with a resin to form a composite material, and then the composite material may be irradiated with relatively low dose radiation to form a second cellulosic and/or lignocellulosic material. or lignocellulosic material having a second molecular weight that is higher than the first molecular weight. If the source of radiation is used, for example, gamma radiation, a dose of about 1 to about 10 Mrad can be applied. Using this approach increases the molecular weight of the material while it is in the curing binder. In some embodiments, the resin is a crosslinkable resin and crosslinks as such as the molecular weight of the hydrocarbon-containing material increases, resulting in a synergistic effect that maximizes the mechanical properties of the composite material. Such composite materials can have, for example, excellent low-temperature characteristics, for example, a reduced tendency to break and/or crack at low temperatures, for example, at temperatures below 02C, for example, below -10, -20, -40, -50, -60 or even below -1002C, and/or excellent high temperature performance, e.g., the ability to retain their favorable mechanical properties at relatively high temperature, e.g., at temperatures above 1002C, e.g., above 125, 150, 200, 250, 300, 400 or even 5002C. In addition, such composite materials can have excellent chemical resistance, such as resistance to swelling in a solvent such as a hydrocarbon solvent, resistance to aggressive action such as strong acids, strong bases, strong oxidizing agents (such as chlorine or bleaches) or reducing agents (eg active metals such as sodium and potassium).

Alternatively, in another example, the fibrous material, including cellulosic and/or lignocellulosic material, is irradiated and optionally treated with acoustic energy, for example, ultrasound.

One example of irradiation pretreatment uses half-gallon (1.89 L) juice cartons made from unprinted white laminated kraft paperboard having a bulk weight of 20 lb/ foot? (320.37 kg/m3). The carton is bent and flattened and then fed into three successive stacked rows of disc shredders with product output from the first disc knife fed as input product to the second shredder and product output from the second disc knife fed as product is introduced into the third shredder. The resulting fibrous material can then be dewatered and processed in a granulator that operates at room temperature.

Compacted granules can be placed in a glass container, from which the air is pumped out in a high vacuum and then filled with argon gas. The container is sealed in an argon atmosphere. Granules in the tank are irradiated with gamma radiation for about 3 hours at a radiation dose rate of 1 Mrad/hour to produce irradiated material in which cellulose has a lower molecular weight than the original material.

One or more sequential processes may be used to process raw materials from a wide variety of different sources to extract useful substances from the raw materials and to provide partially degradable organic material that functions as input to subsequent stages and/or processing sequences. ultrasonic treatments. Ultrasonic treatment can reduce the molecular weight and/or crystallinity of raw materials.

As can be seen from the figure, in one method, a first material 2, which includes cellulose having a first number average molecular weight ("µm"), is dispersed in a medium such as water and sonicated and/or otherwise cavitated to produce a second material 3 , which includes cellulose having a second number average molecular weight ("Mnmg") that is lower than the first number average molecular weight. The second material (or first and second materials in some embodiments) can be combined with a microorganism (eg, a bacterium or yeast) that can use the second and/or first material to produce a fuel 5 that is hydrogen, alcohol, organic acid, hydrocarbon or mixtures of any of the specified substances or which includes them.

Since the second material includes cellulose having a reduced molecular weight relative to the molecular weight of the first material and, in some cases, also reduced crystallinity, the second material is typically one that is more dispersible, swellable and/or soluble in the solution containing the microorganism, e.g. at a concentration of more than 105 microorganisms/ml. These properties make the second material Z more susceptible to chemical, enzymatic and/or biological effects relative to the first material 2, which can significantly increase the productivity and/or level of production of the required product, for example, ethanol. Ultrasonication can also sterilize materials, but should not be used when microorganisms are expected to be alive.

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

In some cases, the second material includes cellulose having a crystallinity (Cg) that is lower than the crystallinity (Si) of the cellulose of the first material. For example, (/C2) may be below (7C1) by more than about 10 95 , such as 15, 20, 25, 30, 35, 40, or even more than about 50 95 .

In some embodiments, the initial crystallinity (before sonication) is from about 40 to about 87.5 90, such as from about 50 to about 75 90 or from about 60 to about 70 95, and the crystallinity after sonication is from about 10 to about 9o, e.g., from about 15 to about 45 95 or from about 20 to about 40 95. However, in some embodiments, such as after intensive sonication, it is possible to have a crystallinity index below 5,905.

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

In some embodiments, the starting 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 sonication is from about 50,000 to about 200,000 , for example, from about 60,000 to about 150,000 or from about 70,000 to about 125,000. However, in some embodiments, such as after intensive sonication, a number average molecular weight of less than about 10,000 or even less than about 5,000 can be achieved.

In some embodiments, the second material may have an oxidation state (72) that is higher than the oxidation state (0) of the first material. A higher degree of oxidation of a material can contribute to its dispersibility, swelling and/or solubility, which further increase the susceptibility of materials to chemical, enzymatic or biological effects. In some variants, to increase the degree of oxidation of the second material relative to the first material, ultrasonic treatment is performed in an oxidizing environment, resulting in a second material that is more oxidized than the first material. The second material can have, for example, a larger number of hydroxyl groups, aldehyde groups, ketone groups, ester groups or carboxyl groups, which can increase its hydrophilicity.

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

In other embodiments, the sonication medium is non-aqueous. Ultrasonic treatment can, for example, 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 wishing to be bound by any particular theory, the authors suggest that sonication disrupts the bonds in the cellulose by creating bubbles in the medium containing the cellulose, which grow and then rapidly explode. During a bubble explosion, which can occur for less than one nanosecond, the force of the inwardly directed explosion raises the local temperature inside the bubbles to about 5100 K (in some cases even higher; see, for example, ZyzwiisK ei ai., Maishge 434,52-54) and generates pressures from a few hundred atmospheres to over 1000 atmospheres or more. It is these high temperatures and pressures that break bonds. Furthermore, without wishing to be bound by any particular theory, the authors suggest that the reduced crystallinity increases at least in part as a result of extremely high cooling rates during bubble bursting, which can be greater than about 10! K/s. High cooling rates usually do not allow cellulose to organize and crystallize, resulting in materials with reduced crystallinity. Ultrasonic systems and ultrasonic chemistry are discussed, for example, in ОЙ ей яй., 0О.5.Raiepi Mo.5766764; Noretgiv, 0.5.Raiepi Mo.5828156; Mazop, Spetivigu m/yp Shgavoshpa,

Eiwemieg, Ohio, (1990); Biviisk (eaiog), OpKgazoypa:iv Spetisai, Rpuzisa! apa Viioodisa! EMPesiv, MSN, M/eipNneit, (1988); Rgise, "Sctepi Tgepav ip bBoposPpetivighu" Wow! Bosieiu oi Spetivigu, Satbgidde, (1992); Biviisk ei ai.,

App. Nem. Maieg. 5si. 29,295, (1999); Biviisk ei aYi. Maishge 353,414 (1991); NiMPeg eyi ai., Rpuz.Nem.I ei. 69,1182 (1992);

Vateg ei ai. Maishte, 352,414 (1991); ZiziisK ei ai, U. At.Spet.zos, 108,5641 (1986); Tapo ei ai, Spet.Sott, 2119 (2000); UUapd ei aI.Admapsey Maieg, 12,1137 (2000); Iapdats yei ai, 9U. oi Saiyaiuvii, 201.22 (2001); Reikiav ei ai,

Spet.Sott, 988 (2001); Mikiepko ei AII, Apdezh.SNet.Ipieg.Ed. (December 2001); Zpayii eyii ai, U. Rpuz.Spet B 103,3358 (1999); Amimi yei ai, U. Ateg. Spet. 5os. 121, 4196 (1999); and Amimi eyi ai, U. Ateg.Spet.5bos.122,4331 (2000).

Figure 12 shows a general system in which a cellulosic material stream 1210 is mixed with a water stream 1212 in a tank 1214 to form a process stream 1216. A first pump 1218 draws the process stream 1216 from the tank 1214 and into a flow cell 1224. An ultrasonic transducer 1226 transmits ultrasonic energy into the process flow 1216 flowing into the flow cell 1224. The second pump 1230 draws the process flow 1216 from the flow cell 1224 for further processing.

Reservoir 1214 includes a first inlet 1232 and a second inlet 1234 for fluid communication with volume 1236. A conveyor (not shown) delivers a stream of cellulosic material 1210 to reservoir 1214 through first inlet 1232. Water stream 1212 enters reservoir 1214 through second inlet 1234. In some embodiments, the water flow 1212 enters the volume 1236 along a tangent line creating a swirling flow in the volume 1236. In some embodiments, the cellulosic material flow 1210 and the water flow 1 Fig.39 is a schematic representation of the biomass conversion method. 1212 are introduced into the volume 1236 along opposite axes to enhance mixing in the volume.

The valve 1238 regulates the flow of the water stream 1212 through the second inlet 1232 to obtain the desired ratio of cellulosic material to water (eg, approximately 10 vol. 95 cellulosic material). May be,

for example, 2000 tons/day of cellulosic material is combined with water taken at 1 million to 1.5 million gallons/day (3.785 million to 5.6775 million L/day), for example 1.25 million gallons/day (4.73 million L/day).

The mixing of the cellulosic material and water in the tank 1214 is regulated 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 adjusted to the required size to ensure a minimum mixing time of the cellulosic material and water. For example, when 2,000 tons/day of cellulosic material and 1.25 million gallons/day (4.73 million L/day) of water flow through tank 1214, to obtain a minimum mixing time of approximately 15 minutes, volume 1236 may be approximately 32,000 gallons (approximately 121,120 L).

The tank 1214 includes a mixer 1240 for fluid communication with the volume 1236. The mixer 1240 mixes the contents of the volume 1236 with the dispersion of cellulosic material throughout the volume of water. The mixer 1240 may be, for example, a rotating blade placed in the tank 1214. In some embodiments, the mixer 1240 substantially uniformly disperses the cellulosic material in the water.

Reservoir 1214 further includes an outlet 1242 for fluid communication with volume 1236 and process stream 1216. A mixture of cellulosic material and water in volume 1236 flows out of reservoir 1214 through outlet 1242. Outlet 1242 is located near the bottom of tank 1214, which enables the mixture of cellulosic material and water to flow out of the tank 1214 by gravity under the influence of gravity and enter the process flow 1216.

A first pump 1218 (e.g., any of several submersible centrifugal vortex pumps manufactured by Ev5so Richards 4 Sopigoii5, Los Angeles, CA) 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 flow 1216 so that at the entrance 1220 of the flow cell 1224 the mixture of cellulosic material and water is essentially homogeneous. The first pump 1218 mixes, for example, the process stream 1216 , creating a turbulent flow that continues to exist with the process stream between the first pump and the inlet 1220 of the flow cell 1224 .

Flow cell 1224 includes a reaction volume 1244 for fluid communication with inlet 1220 and outlet 1222. In some embodiments, reaction volume 1244 is a stainless steel tube capable of withstanding elevated pressures (eg, 10 bar). Additionally or alternatively, the reaction volume 1244 includes a rectangular cross-section.

The flow cell 1224 further includes a heat exchanger 1246 that is connected to at least a portion of the reaction volume 1244. A cooling fluid 1248 (eg, water) enters the heat exchanger 1246 and absorbs the heat generated during the sonication of the process stream 1216 in the reaction volume 1244. In some embodiments, the flow rate of the coolant 1248 into the heat exchanger 1246 is regulated to maintain an approximately constant temperature in the reaction volume 1244. Additionally or alternatively, the temperature of the coolant 1248 flowing into the heat exchanger 1246 is regulated to maintain the reaction volume 1244 of approximately constant temperature. In some embodiments, the temperature of the reaction volume 1244 is maintained at a value between 20 and 50°C, for example, at a value of 25, 30, 35, 40, or 4520. Additionally or alternatively, heat transferred from the reaction volume 1244 to the coolant 1248 may to be used in other parts of the method.

Adapter section 1226 creates fluid communication between reaction volume 1244 and booster 1250 connected (eg, mechanically connected using a flange) to ultrasonic transducer 1226 .

The adapter section 1226 may include, for example, a flange and an O-ring assembly installed to create a sealed connection between the reaction volume 1244 and the booster 1250. In some embodiments, the ultrasonic transducer 1226 is a high-power ultrasonic transducer manufactured by the company NieI5speg

Shppgasopisz oi Teyom, Germany.

In operation, generator 1252 supplies 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, the materials are sonicated using sound that has a frequency of about 16 to about 110 kHz, such as about 18 to about 75 kHz or about 20 to about 40 kHz (e.g., sound that has a frequency of about 20 to about 40 kHz).

Then the ultrasonic energy is fed to the working medium through the booster 1248.

Ultrasonic energy entering through the booster 1248 into the reaction volume 1244 creates a series of pressures and differences in the process stream 1216 with an intensity sufficient to create cavitation in the process stream 1216. The cavitation disaggregates the cellulosic material dispersed in the process stream 1216. The cavitation also generates free radicals in the water of process stream 1216. Such free radicals contribute to the additional breakdown of cellulosic material in process stream 1216.

For a process stream 1216 flowing at a rate of about 0.2 m3/s (about 3200 gal/min), ultrasonic energies between 5 and 4000 MJ/m3 are typically used, for example 10, 25, 50, 100, 250, 500 , 750, 1000, 2000 or 3000 MJ/m3. After exposure to ultrasonic energy in the reaction volume 1244, the process stream 1216 flows out of the flow cell 1224 through the outlet 1222. A second pump 1230 moves the process stream 1216 to the next processing (for example, any of several submerged centrifugal vortex pumps manufactured by Ezzso Rytrzh 4 Sopigoiv5, Los Angeles, California).

Although some options are described, other options are also possible.

Although process flow 1216 is described as a single-path flow, by way of example, other variations are possible. In some embodiments, for example, process stream 1216 includes streams with multiple parallel paths (flowing, for example, at a rate of 10 gallons/min (37.85 L/min)). Additionally or alternatively, streams with a plurality of parallel process flow paths 1216 flow into separate flow cells and are sonicated in parallel (eg, using a plurality of 16 kW ultrasonic transducers).

Although one ultrasonic transducer 1226 is described as the ultrasonic transducer connected to the flow cell 1224, as another example, other options are also possible. In some embodiments, a plurality of ultrasonic transducers 1226 (eg, ten ultrasonic transducers) are placed in the flow cell 1224 . In some embodiments, the sound waves generated by each of the plurality of ultrasonic transducers 1226 (eg, synchronized with each other out of phase) are timed to enhance cavitation acting on the process flow 1216 .

Although one flow cell 1224 is described, other variations are possible as another example. In some embodiments, the second pump 1230 moves the process stream into a second flow cell in which the second booster and ultrasonic transducer further assist in the sonication of the process stream 1216 .

Although the reaction volume 1244 is described as a closed volume, as yet another example, the reaction volume 1244 in some embodiments is open to the environment. In such embodiments, pre-sonication can be performed essentially simultaneously with other pre-treatment methods. For example, ultrasonic energy can be used for the process stream 1216 in the reaction volume 1244 at the time when electron beams are simultaneously introduced into the process stream 1216.

Although the described flow is in a continuous process, as another example, other options are possible. In some embodiments, ultrasonic treatment may be performed periodically. The volume can be filled, for example, 10 volumes. 95 mixture of cellulosic material in water and exposed to sound at an intensity of about 50 to about 600

W/cm?, for example from about 75 to about 300 W/cm2 or from about 95 to about 200 W/cm".

Additionally or alternatively, the mixture in the volume may be sonicated for a time of from about 1 to about 24 hours, for example, from about 1.5 to about 12 hours or from about 2 to about 10 hours. In some embodiments, the material is sonicated for a predetermined time and then allowed to stand for a second predetermined time before re-sonication.

As can be seen from Fig. 13, in some versions, two electroacoustic transducers are mechanically connected into one horn. As shown, a pair of piezoelectric transducers 60 and 62 are connected to horn 64 with rectangular openings by respective intermediate connecting horns 70 and 72, the latter of which are known as booster horns.

The mechanical vibrations provided by transducers sensitive to high-frequency electrical energy are transmitted to appropriate coupling horns, which may be constructed to provide a mechanical magnification such as a ratio of 1 to 1.2. Horns are equipped with matching mounting flanges 74 and 76 to support the transducer and horn assembly in the stationary housing.

Vibrations transmitted from the transducers through connecting or booster horns connected to the input surface 78 of the horn inlet are transmitted through the horn to the opposite output surface 80, which during operation is in forced engagement with the workpiece (not shown). to which vibrations are applied.

The high-frequency electrical energy provided by the power source 82 is supplied to each of the converters electrically connected in parallel through a balancing transformer 84 and corresponding series-connected capacitors 86 and 90, one capacitor being electrically connected in series to each of converters. Balancing transformer is also known as "Braishp", which means "balancing element". Balancing transformer includes a magnetic core 92 and a pair of identical windings 94 and 96, also called primary and secondary windings, respectively.

In some embodiments, the transducers include commercially available piezoelectric transducers, such as Vgapzop Opgavzopisia Sogrogayop model 105 or 502 transducers, each designed to operate at 20 kHz and a maximum power rating of 3 kW. The boosting voltage to ensure the maximum dynamic deviation on the output surface of the converter is 930 volts (rms).

The current flow through the converter can vary between 0 and 3.5 amps depending on the total load resistance. At an rms voltage of 930 volts, the movement at the output is approximately 20 microns.

The maximum voltage difference across the terminals for the same dynamic amplitude can therefore be 186 volts. Such a voltage difference can cause significant circulating currents flowing between the converters.

Balancing element 430 guarantees a balanced state by ensuring that the same current flows through the converters, thus eliminating the possibility of circulating currents. The wire size of the windings should be selected for the full load current specified above, and the maximum voltage appearing in parallel with the input of the winding is 93 volts.

As an alternative to the use of ultrasonic energy, high-frequency rotor-stator devices can be used. This type of device provides high shear forces of microcavitation, which can disintegrate biomass upon contact with such forces. Two commercially available high-frequency rotor-stator dispersion devices are Zyrgayup "M" devices, manufactured by Kgyrr Ipaivipespecpic Sith and sold

Boit-Oiimeg Oetsizspiapa Str oi Soppesiisii, and Oizrah "M devices, manufactured and sold by IKka-UMogkv, Ips.oi Sipsippaiii,

OpPio. The operation of the specified microcavitation device is discussed in Section 5, US Patent No. 5370999.

Although the ultrasonic transducer 1226 is described as including one or more piezoelectric active elements that generate ultrasonic energy, other options are also possible. In some embodiments, the ultrasonic transducer 1226 includes active elements made of other types of magnetostrictive materials (eg, ferrous metals). The design and operation of such a high-power ultrasonic transducer is discussed in Napzep et al., US Pat. No. 6,624,539. In some embodiments, the ultrasonic energy is transferred to the process stream 1216 through an electro-hydraulic system.

Although the ultrasonic transducer 1226 is described as using the electromagnetic property of the magnetostrictive material to generate ultrasonic energy, other options are also possible. In some embodiments, the acoustic energy in the form of an intense shock wave can be directly used for the process flow 1216 using a submerged spark. In some embodiments, ultrasonic energy is transferred to process stream 1216 via a thermohydraulic system. For example, acoustic waves with a high energy density can be produced by applying a force across a closed volume of electrolyte, resulting in increased heating of the closed volume and pressure, which is further transferred to the sound propagation medium (eg, process flow 1216). The design and operation of such a thermo-hydraulic converter is discussed in Naitapatp et al., US Pat. No. 6,383,152.

One or more sequential processes may be used to process raw materials from a wide variety of different sources to extract useful substances from the raw materials and to provide partially degradable organic material that functions as input to subsequent stages and/or processing sequences. pyrolysis treatment.

As follows from the general diagram in Fig. 8, the first material 2, which includes cellulose having a first number average molecular weight ("Mmi"), is pyrolyzed, for example, by heating the first material in a tube furnace, to obtain the second material 3, which includes cellulose, having a second number average molecular weight (Mmg) that is lower than the first number average molecular weight.The second material (or the first and second materials in some embodiments) is combined with a microorganism (eg, a bacterium or yeast) that can utilize the second and/or the first material, with the production of fuel 5, which is or includes hydrogen, an alcohol (for example, ethanol or butanol, such as n-, sec- or tert-butanol), an organic acid, a hydrocarbon, or mixtures of any of these substances.

Since the second material includes cellulose having a reduced molecular weight relative to such first material and, in some cases, also reduced crystallinity, the second material is usually one that is more dispersible, swellable and/or soluble in the solution containing the microorganism, for example when concentration of more than 109 microorganisms/ml. These properties make the second material Z more susceptible to chemical, enzymatic and/or biological effects relative to the first material 2, which can significantly increase the productivity and/or level of production of the required product, for example, ethanol. Pyrolysis can also sterilize the first and second materials.

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

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

In some embodiments, the initial crystallinity (prior to pyrolysis) is from about 40 to about 87.5 9o, such as from about 50 to about 75 95 or from about 60 to about 70 95, and the crystallinity after pyrolysis is from about 10 to about 50 95, for example, from about 15 to about 45 95 or from about 20 to about 40 95. However, in some embodiments, such as after extensive pyrolysis, it is possible to have a crystallinity index below 5 95. 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, e.g., 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, it is possible to have a number average molecular weight of less than about 10,000 or even less than about 5,000.

In some embodiments, the second material can have an oxidation state (702) that is higher than the oxidation state (TO) of the first material. A higher degree of oxidation of the material can contribute to its dispersibility, swelling and/or solubility, which further increase the susceptibility of the materials to chemical, enzymatic or biological effects. In some variants, to increase the degree of oxidation of the second material relative to the first material, pyrolysis is carried out in an oxidizing environment, resulting in a second material that is more oxidized than the first material. The second material can have, for example, a larger number of hydroxyl groups, aldehyde groups, ketone groups, ester groups or carboxyl groups, which can increase its hydrophilicity.

In some embodiments, pyrolysis of materials is continuous. In other embodiments, the material is pyrolyzed for a predetermined time and then allowed to cool for a second predetermined time prior to subsequent pyrolysis.

Fig.14 shows a technological diagram 6000 of the method, which includes various stages in the pyrolytic system of pre-treatment of raw materials.

As indicated above, the dry feedstock from the feedstock source may be pretreated prior to delivery to the pyrolysis chamber. For example, if the raw material is produced from plant material, some parts of the plant material may be removed before the plant material is harvested and/or before the plant material is delivered by the raw material vehicle. Alternatively or additionally, the biomass feedstock may 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 is subjected to stage 6030 of moisture content correction. The nature of the moisture content adjustment stage depends on the moisture content of the mechanically processed raw material. Usually, the pyrolysis of raw materials occurs most efficiently when the moisture content of the raw materials is from about 10 to about 30 wt. 905 (for example, from 15 to 25 wt. 95). If the moisture content of the raw material is more than 40 wt. 9o, the additional thermal overload, which is present due to the water content in the raw material, will increase the energy consumption in the subsequent stages of pyrolysis.

If in some versions the raw material has a moisture content greater than approximately 30 wt. 95, a dry feedstock 6220 having a low moisture content may be mixed to produce a feedstock mixture at stage 6030 having an average moisture content within the above range. In some embodiments, feedstock with a high moisture content can simply be dried by dispersing the feedstock material onto a moving conveyor that continuously moves the feedstock into an in-line heating device.

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

If, in some embodiments, the feedstock from stage 6020 has a moisture content that is too low (eg, below about 10 wt. 95), the mechanically treated feedstock may be combined with wetted feedstock material 6230 that has an increased moisture content, such as slurry waste water Alternatively or additionally, water 6240 may be added to the dry feedstock from stage 6020 to increase its moisture content.

At step 6040, the raw material - now with its moisture content within acceptable limits - can be preheated in an optional preheat step 6040. The preheating stage 6040 can be used to increase the temperature of the raw material to values from 75 to 1502C in preparation of the raw material for subsequent pyrolysis of the raw material. Depending on the origin of the raw material and the features of the design of the pyrolysis chamber, preheating the raw material can ensure that there is a more even distribution of heat in the raw material during pyrolysis and can reduce the thermal load on the pyrolysis chamber.

The feedstock is then transported to the pyrolysis chamber to be pyrolyzed in step 6050. In some embodiments, feedstock transport is aided by the addition of one or more compressed gases to the feedstock stream 6210. The gases create a pressure gradient in the transport conduit for the feedstock, advancing the feedstock into the pyrolysis chamber (and even through the pyrolysis chamber). In some versions, the movement of raw materials occurs mechanically; that is, a vehicle including a conveyor, such as a screw conveyor, moves the raw material into the pyrolysis chamber.

Other gases 6210 may also be added to the feedstock prior to being fed into the pyrolysis chamber. In some embodiments, one or more catalytic gases may be added to the feedstock to aid decomposition of the feedstock during pyrolysis, for example. In some embodiments, one or more absorbers may be added to the feedstock to trap volatile components released during pyrolysis. For example, various sulfur-containing compounds such as sulfides may be released during pyrolysis, and a reagent such as hydrogen gas may be added to the feedstock to cause desulfurization of the pyrolysis products. Hydrogen combines with sulfides to form hydrogen sulfide gas, 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 cause partial decomposition of the feedstock. Usually, the raw material is heated to a temperature in the range from 150 to 11102С. The temperature to which the raw material is heated depends on a number of factors, including the composition of the raw material, the average size of the raw material particles, the moisture content and the required pyrolysis products. For many types of biomass raw materials, for example, pyrolysis temperatures from 300 to 55020 are used.

The residence time of the raw material in the pyrolysis chamber usually depends on a number of factors, including the pyrolysis temperature, the composition of the raw material, the average size of the raw material particles, the moisture content and the required pyrolysis products. In some embodiments, the feed materials are pyrolyzed at a temperature slightly above the decomposition temperature of the material in an inert atmosphere, for example, from about 2 above to about 1026 above the decomposition temperature or from about 3° above to about 72° above the decomposition temperature. In such embodiments, the material is usually maintained at the specified temperature for more than 0.5 hours, for example, more than 1.0 or more than about 2 hours. In other embodiments, the materials are pyrolyzed at a temperature significantly above the decomposition temperature of the material in an inert atmosphere, for example, from about 75°C to about 175°C above the decomposition temperature, or from about 85°C to about 1502°C above the decomposition temperature. In such embodiments, the material is usually maintained at the specified temperature for less than 0.5 hour, for example, less than 20, less than 10, less than 5, or less than 2 minutes. In additional embodiments, the materials are pyrolyzed at an extremely high temperature, such as from about 200 to about 500°C above the decomposition temperature of the material in an inert atmosphere or from about 250 to about 4002°C above the decomposition temperature. In such embodiments, the material is typically maintained at the specified temperature for less than 1 minute, for example, less than 30, less than 15, less than 10, less than 5, less than 1 second, or less than 500 msec. Such options are usually classified as flash pyrolysis.

In some embodiments, the feedstock is heated relatively quickly to the selected pyrolysis temperature in the chamber.

For example, the chamber may have a design designed to heat the raw material at a rate of 500 to 110002C/s. Typical heating rates of the raw materials obtained from biomass are, for example, from 500 to 110002C/s.

In a pyrolysis chamber, a turbulent flow of feedstock material is usually advantageous, as it ensures relatively efficient heat transfer to the feedstock material from the heating subsystem. Turbulent flow can be achieved by blowing the feed material through the chamber using, for example, one or more injected carrier gases 6210. The carrier gases are typically relatively inert to the feed material, even at high temperatures in the pyrolysis chamber. Typical 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 and circulate the feedstock into the pyrolysis chamber to create a turbulent flow of the feedstock.

In some variants, the pyrolysis of the raw material takes place essentially in the absence of oxygen and other chemically active gases. Oxygen can be removed from the pyrolysis chamber by periodically blowing the chamber with high-pressure nitrogen (for example, at nitrogen pressures of 2 bar or more). After purging the chamber, the gas mixture present in the pyrolysis chamber (for example, during the pyrolysis of the raw material) may include less than 4 moles. 9o oxygen (for example, less than 1 and even less than 0.5 mol. 90 oxygen). The absence of oxygen ensures the absence of ignition of the raw material at elevated pyrolysis temperatures.

In some variants, relatively small amounts of oxygen may be introduced into the feedstock and present during pyrolysis. This method refers to oxidative pyrolysis. Oxidative pyrolysis usually occurs in numerous stages of heating. For example, in the first stage of heating, the raw material is heated in the presence of oxygen to cause partial oxidation of the raw material. At this stage, the available oxygen in the pyrolysis chamber is consumed. Then, in the following stages of heating, the temperature of the raw material is additionally increased. However, after the consumption of all the oxygen available in the chamber, combustion of the raw material does not occur, and pyrolytic decomposition of the raw material (for example, with the generation of hydrocarbon products) occurs without combustion. The process of heating the raw materials in the pyrolysis chamber with the initiation of decomposition is usually endothermic. However, in oxidative pyrolysis, the formation of carbon dioxide by the oxidation of raw materials is an exothermic process. The heat released from the process of carbon dioxide formation can contribute to additional heating stages of pyrolysis, as a result of which the heat load on the raw material is reduced.

In some embodiments, pyrolysis occurs in an inert environment, for example, during processing of raw materials in an atmosphere of gaseous argon or nitrogen. In some embodiments, pyrolysis may occur in an oxidizing environment, such as air or argon-enriched air. In some embodiments, pyrolysis may occur in a reducing environment, for example, during the treatment of feedstock materials in hydrogen gas.

Various chemical reagents such as oxidizing agents, reducing agents, acids, or bases may be added to the material to promote pyrolysis, prior to, or during pyrolysis. For example, sulfuric acid or a peroxide (eg, benzoyl peroxide) may be added.

As noted above, depending on factors such as the composition of the raw material and the desired pyrolysis products, a variety of different processing conditions can be used. For example, relatively mild pyrolysis conditions can be used for cellulosic feedstock material, which include flash pyrolysis temperatures of 375 to 45020 and chamber residence times of less than 1 second. As another example, for organic solid waste materials such as sewage sludge, flash pyrolysis temperatures of 500 to 6502 and chamber residence times of 0.5 to 3 seconds are commonly used. Many of the parameters of the pyrolysis process, including the residence time in the pyrolysis chamber, pyrolysis temperature, turbulence of the raw material, moisture content, composition of the raw material, composition of pyrolysis products, and composition of additive gases, can be regulated automatically by a system of regulators and an automatic control system.

After the pyrolysis stage 6050, the pyrolysis products are subjected to a quenching stage 6250 to reduce the temperature of the products before further processing. Typically, quenching stage 6250 includes irrigation of the pyrolysis products with streams of cooling water 6260. The cooling water also forms a slurry that includes solid undissolved product material and various dissolved products. The product stream also contains a mixture containing various gases, which include gaseous products, carrier gases, and other types of process gases.

The product stream is transported through a pipeline on the line to a gas separator, which performs gas separation stage 6060, in which gaseous products and other gases are separated from the suspension formed by quenching pyrolysis products. The separated gas mixture is optionally sent to the gas blower 6130, which increases the gas pressure by blowing air into the mixture. The gas mixture may be subjected to a filtration stage 6140 in which the gas mixture passes through one or more filters (eg, through activated carbon filters) to remove macro particles and other impurities. In the next stage 6150, the filtered gas can be compressed and stored for later use. Alternatively, the filtered gas may be subjected to further processing steps 6160. For example, in some embodiments, the filtered gas may be condensed to separate the various gaseous compounds in the gas mixture. Different compounds may include, for example, different hydrocarbon products (eg, alcohols, alkanes, alkenes, alkynes, ethers) obtained during pyrolysis. In certain embodiments, filtered gas containing a mixture of hydrocarbon components may be combined with superheated steam 6170 (eg, a mixture of water vapor and oxygen) and subjected to a cracking process to reduce the molecular weight of the hydrocarbon components.

In some embodiments, the pyrolysis chamber includes heating sources that burn hydrocarbon gases such as methane, propane, and/or butane to heat the feedstock. Part 6270 of the separated gases can be recirculated to the pyrolysis chamber for combustion with the generation of process heat to support the pyrolysis process.

In some embodiments, the pyrolysis chamber can receive process heat that can be used to increase the temperature of the raw materials. For example, irradiating raw materials with radiation (eg, gamma radiation, electron beam radiation, or other types of radiation) can heat the raw materials to relatively high temperatures. Heated raw materials can be cooled by a heat exchange system that removes excess heat from irradiated raw materials. The heat exchange system can have a configuration that ensures the transfer of some part of the thermal energy to the pyrolysis chamber for heating (or preheating) the raw material, as a result of which the energy costs for the pyrolysis process are reduced.

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 that include, for example, mechanical pressing and evaporation. Excess water 6280 can be filtered off and then recycled for further use in tempering the pyrolysis decomposition products in step 6250.

The dewatered slurry is then subjected to a mechanical separation stage 6080 in which the solid product material 6110 is separated from the liquid product material 6090 by a group of fine filters. In step 6100, the liquid product material 6090 may then be condensed (eg, by evaporation) to remove wastewater 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. Purified liquid products 6200 may then be subjected to further processing steps. Effluent 6190 may, if necessary, be filtered and recirculated for further use in tempering the pyrolysis products of stage 6250.

After separation in step 6080, the 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 stored for subsequent use or subjected to further suitable processing steps.

The above process parameters are illustrative. The values of the specified parameters can vary widely depending on the nature of the raw materials and required products. In addition, a wide variety of different pyrolysis methods can be used, which include the use of heating 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, pyrolysis of the feedstock may include, for example, heating the material using a resistive heating element, such as a metal filament or metal tape. Heating can be done by direct contact between the resistive heating element and the material.

In some embodiments, pyrolysis may include heating the material by induction, for example, using a Sipier-Roipi pyrolyzer. In some embodiments, pyrolysis may include heating the material using radiation, such as infrared radiation. The radiation may be generated by a laser, such as an infrared laser.

In some embodiments, pyrolysis may include heating the material with convective heat. Convective heat can be generated by a flow of heated gas. The heated gas can be maintained at a temperature of less than about 12002C, for example, less than 1000, less than 750, less than 600, less than 400, or even less than 3002C. The heated gas can be maintained at a temperature greater than about 250 20. Convective heat can be generated by a hot body that surrounds the first material, such as a furnace.

In some embodiments, pyrolysis may include heating the material with steam at a temperature above about 25,026.

A variant of the pyrolysis chamber is shown in Fig. 15. Chamber 6500 includes walls 6510 of an insulated chamber with an outlet 6600 for waste gases, a plurality of burners 6520 that generate heat for the pyrolysis process, a transport pipeline 6530 for transporting feedstock into chamber 6500, screw conveyors 6590 for advancing feedstock through pipeline 6530 in turbulent flow, and hardening system 6540, which includes a screw conveyor 6610 for advancing pyrolysis products, water ejectors 6550 for irrigation of pyrolysis products with cooling water, and a gas separator for separating gaseous products 6580 from suspension 6570, which contains solid and liquid products.

Another version of the pyrolysis chamber is shown in Fig. 16. The chamber 6700 includes the walls 6710 of the insulated chamber, a pipeline for supplying raw materials 6720, an inclined inner wall 6730 of the chamber, burners 6740 that generate heat for the pyrolysis process, an opening 6750 for waste gases, and a gas separator 6760 for separating gaseous products 6770 from liquid and solid products 6780 .Chamber 6700 has a configuration designed to rotate in the direction shown by the arrow, which provides adequate mixing and turbulent flow of feedstock in the chamber.

An additional version of the pyrolysis chamber is shown in Fig. 17. The filament pyrolyzer 1712 includes a sample holder 1713 with a resistive heating element 1714 in the form of a wire coil in an open space designated by the sample holder 1713 . The heating element may optionally rotate about the axis 1715 (as shown by the arrow 1716) for felting the material, including cellulosic material in the holder 1713 of the sample. The space 1718, marked by the enclosure 1719, is maintained at a temperature above room temperature, for example, from 200 to 2502C. In a typical use, a carrier gas, such as an inert gas or an oxidizing or reducing gas, crosses the sample holder 1713 while the resistive heating element rotates and heats to a desired temperature, such as 3252C. After an appropriate time, for example, after a period of 5 to 10 minutes, the pyrolyzed material is poured from the sample holder. The system shown in Fig. 17 can be reduced to a certain scale and made continuous. More preferred use as a heating element instead of a screw wire. The material can continuously fall into the sample holder, hitting the heated screw, which pyrolyzes the material. At the same time, the screw can push the pyrolyzed material out of the sample holder, allowing fresh non-pyrolyzed material to enter.

Another variant of the pyrolysis chamber is shown in Fig. 18, which is characterized by a Sipe-Roipi pyrolyzer 1820, which includes a sample chamber 1821 containing a ferromagnetic foil 1822. Surrounding the sample chamber 1821 is an inductor 1823 for heating with a high frequency current. Space 1824, defined by enclosure 1825, is maintained at a temperature above room temperature, e.g., 200 to 250 20. In typical use, a carrier gas traverses sample chamber 1821 while foil 1822 is inductively heated by an applied high-frequency electromagnetic field to pyrolyze the material at the required temperature

An additional version of the pyrolysis chamber is shown in Fig. 19. The pyrolysis furnace 130 includes a movable sample holder 131 and a furnace 132. In typical use, the sample is lowered (as shown by arrow 137) into the hot zone 135 of the furnace 132 as the carrier gas fills the jacket 136 and crosses the sample holder 131. The sample is heated to the required temperature for the desired time to obtain a pyrolyzed product. The pyrolyzed product is removed from the pyrolyzer by lifting the sample holder (as shown by arrow 134).

In some embodiments shown in FIG. 20, the cellulose target 140 may be pyrolyzed by treating the target, which is placed in the vacuum chamber 141, with laser light, for example, light having a wavelength of about 225 to about 1500 nm. The target can be, for example, destroyed at 266 nm using the fourth harmonic of the Ma-zhAsS;i laser (Zresiga RNuvziskh, 24СА170, Zap Tsdovze, California). The optical configuration shown provides the ability to direct nearly monochromatic light 143 generated by laser 142 using mirrors 144 and 145 onto a target in vacuum chamber 141 after passing through lenses 146 .

The normal pressure in the vacuum chamber is maintained at a value less than approximately 1092 mm Na. In some variants, infrared radiation is used, for example, radiation of 1.06 microns from a Ma-ZhaaS laser. In such variants, the infrared sensitive dye can be combined with cellulosic material to form a cellulosic target. The infrared dye can enhance the heating of the cellulosic material. Laser destruction is described in Ripsnig et al., US Patent No. 5,942,649.

As shown in FIG. 21, in some embodiments, the cellulosic material may be subjected to flash pyrolysis by coating the cellulosic material with a tungsten filament 150, such as a 5 to mil tungsten filament, while the material is placed in the vacuum chamber 151. To affect the pyrolysis, a current is passed through the filament, which causes rapid heating of the filament for the required time. Usually, the heating is continued for seconds, after which the thread is given the opportunity to cool down. In some variants, heating is carried out several times to obtain the required degree of pyrolysis.

In some embodiments, the hydrocarbon-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 disclosed herein for efficient heat transfer. The material can be heated by the transfer of heat from hot metal or ceramics, for example, from glass chips or sand in the reactor and the resulting pyrolysis liquid or oil can be transported to a refinery to produce combustible fuels or other useful products.

One or more sequential oxidation processes can be used to obtain raw materials from a wide variety of different sources in order to extract useful substances from the raw materials and to obtain partially degraded organic material that functions as input material for subsequent stages and/or processing sequences. processing

As can be seen from the figure, the first material 2, which includes cellulose having a first number average molecular weight ("Mmi") and having a first oxygen content (701), is oxidized, for example, by heating the first material in a tubular furnace in a stream of air or air enriched with oxygen , to obtain the second material 3, which includes cellulose having a second average molecular weight ("Mkig") and having a second oxygen content (7Og) that is higher than the first oxygen content (701). The second material (or the first and second materials in defined variants) can be combined, for example, with a resin, such as a molten thermoplastic resin, or a microorganism to obtain a composite material 4 that has the required mechanical properties, or a fuel 5. Providing a higher oxidation level can improve the dispersibility of the oxidized material in the resin and can also strengthen the bond at the interface between the oxidized material and the resin. Improved dispersibility and/or interface bonding (in some cases in combination with molecular weight retention) can provide composite materials with exceptional mechanical properties such as improved abrasion resistance, compressive strength, fracture resistance, impact toughness, bending resistance, tensile modulus, flexural modulus and elongation at break.

Such materials can also be combined with a solid and/or liquid. The liquid can be, for example, in the form of a solution, and the solid can be, for example, in the form of macroparticles. The liquid and/or solid may include a microorganism, for example, a bacterium and/or an enzyme. The bacterium and/or enzyme can act, for example, on cellulosic and/or lignocellulosic material to produce a fuel such as ethanol or a by-product such as protein. Fuel and by-products are described in RIVVOSHO MATENVIA! 5 AMO

SOMROBITE5, О55М11/453951, submitted on June 15, 2006. The entire 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 95 below the first number average molecular weight, e.g., 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 or not more than 1.0 95 below the first number average molecular weight. The amount of molecular weight reduction will depend on the application. In some preferred embodiments providing composite materials, the second number average molecular weight is, for example, substantially the same as the first number average molecular weight. In other applications, for example in the production of ethanol or other fuel or by-product, a higher amount of molecular weight reduction is usually preferred.

For example, in some embodiments providing a composite material, the initial 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 after oxidation is from about 175,000 to about 3,000,000, such as from about 200,000 to about 750,000 or from about 225,000 to about 600,000.

The resins used can be thermosetting resins or thermoplastics. Examples of thermoplastic resins include solid and elastomeric thermoplastics. Solid thermoplastics include polyolefins (eg, copolymers of polyethylene, polypropylene, or polyolefin), polyesters (eg, polyethylene terephthalate), polyamides (eg, nylon b, 6/12, or 66/10), and polyethyleneimines. Examples of elastomeric thermoplastic resins include elastomeric copolymers of styrene (eg, copolymers of styrene, ethylene, and butylene), polyamide elastomers (eg, copolymers of plain polyester and polyamide), and copolymers of ethylene and vinyl acetate.

In some embodiments, lignin is used, for example, any lignin that is generated in any of the methods disclosed herein.

In some embodiments, the thermoplastic resin has a melt flow rate of 10 to 60 g/10 minutes, such as 20 to 50 g/10 minutes or 30 to 45 g/10 minutes, as measured using A5TM1238. In some embodiments, compatible blends of any of the above thermoplastic resins may be used.

In some embodiments, the thermoplastic resin has a polydispersity index (PP, ROT), i.e., the ratio of weight average molecular weight to number average molecular weight, greater than 1.5, for example, greater than 2.0, greater than 2.5, greater than 5.0, greater than 7.5 or even more than 10.0.

In certain variants, polyolefins or mixtures of polyolefins are used as thermoplastic resin.

Examples of thermosetting resins include natural rubber, butadiene rubber, and polyurethanes.

In some embodiments, in which the materials are used to produce a fuel or byproduct, the original 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 weight after oxidation is from about 50,000 to about 200,000, for example 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, it is possible to have a number average molecular weight of less than about 10,000 or even less than about 5,000.

In some embodiments, the second oxygen content is at least about five percent higher than the first oxygen content, e.g., higher than 7.5 95 , higher than 10.0 95 , higher than 12.5 956 , higher than 15.0 95 , or higher than 17.5 95. In some preferred embodiments, the second oxygen content is at least about 20.0 95 higher than the oxygen content of the first material. Oxygen content is measured by elemental analysis of a sample subjected to pyrolysis in a furnace operating at 13002C or higher. A suitable elemental analyzer is a GESO SNM5-932 analyzer with a MUTE-900 high-temperature pyrolysis furnace.

In some embodiments, the oxidation of the first material 200 does not lead to a significant change in the crystallinity of the cellulose. However, in some cases, for example, after intensive oxidation, 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, (Cg) may be lower than (7Si) by more than about 5 95, such as 10, 15, 20, or even 25 95. This difference may be desirable when optimizing the elastic properties and fatigue strength of composite materials. A decrease in crystallinity can, for example, increase the relative elongation at break or can increase the impact strength of a composite material. This difference may also be desirable to increase the solubility of the materials in a liquid, for example, in a liquid containing a bacterium and/or an enzyme.

In some embodiments, the initial crystallinity (before oxidation) is from about 40 to about 87.5 95, such as from about 50 to about 75 95 or from about 60 to about 70 90, and the crystallinity after oxidation is from about 30 to about 75.0 95, for example, from about 35.0 to about 70.0 95 or from about 37.5 to about 65.0 95. However, in certain embodiments, for example, after extensive oxidation, it is possible to have a crystallinity index below 5 95. In some embodiments, the material is essentially amorphous after oxidation.

Without wishing to be bound by any theory, the authors believe that oxidation increases the number of groups in cellulose capable of forming hydrogen bonds, such as hydroxyl groups, aldehyde groups, keto groups, carboxyl groups or anhydride groups, which can increase its dispersibility and/or its solubility (for example, in liquid). To further increase dispersibility in the resin, the resin may include a component that contains groups capable of forming hydrogen bonds, such as one or more anhydride groups, carboxyl groups, hydroxyl groups, amide groups, amino groups, or a mixture of any of these groups. In some preferred embodiments, the component includes a polymer copolymerized with maleic anhydride and/or grafted thereto. Such materials are available from Yuiropi under the trade name EOBAVOMOF).

Oxidation of the first material 200 usually occurs in an oxidizing environment. For example, oxidation can be carried out in an oxidizing environment, for example in air or in air enriched with argon, or it can promote pyrolysis in said environment. Various chemical reagents, such as oxidizing agents, acids, or bases, may be added to the material prior to or during oxidation to promote oxidation. For example, a peroxide (eg, benzoyl peroxide) may be added before oxidation.

Fig. 22 shows a technological diagram of the method 5000, which includes various stages in the system of preliminary oxidative treatment of raw materials. In the first stage, 5010 receive a load of dry raw material from the raw material source. The source of raw materials can include, for example, a layer of raw materials from a warehouse or from a container that is connected to the oxidation reactor on the line by a belt conveyor or other means of transport for raw materials.

As mentioned above, the dry raw material from the raw material source may be pretreated before delivery to the oxidation reactor. For example, if the raw material is obtained from plant sources, some parts of the plant material may be removed before harvesting the plant material and/or before delivering the plant material by means of a raw material vehicle. Alternatively or additionally, the biomass feedstock may be mechanically treated (for example, to reduce the average length of fibers in the feedstock) prior to delivery to the oxidation reactor.

After mechanical processing 5020, the raw material 5030 is transported to the mixing system, which introduces water 5150 into the raw material in the process of mechanical mixing. The combination of water with the processed raw material in the mixing stage 5040 creates an aqueous suspension 5050 of the raw material, which can then be treated with one or more oxidizing agents.

Usually, one liter of water is added to the mixture for every 0.02-1.0 kg of dry raw material. The ratio of raw materials to water in the mixture depends on the source of raw materials and the type of oxidizing agents used in subsequent processing of the method. For example, in typical industrial sequential treatments of lignocellulosic biomass, the aqueous slurry of feedstock 5050 contains from about 0.5 to about 1.0 kg of dry biomass per liter of water.

In some embodiments, one or more fiber protection additives 5170 may also be added to the feed stock slurry in the mixing step 5040. Fiber protection additives help reduce the breakdown of certain types of biomass fibers (eg, cellulosic fibers) during oxidation of the feed stock. Fiber protection additives can be used, for example, if the required product from the processing of lignocellulosic raw materials includes cellulose fibers. Typical fiber protection 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 in terms of dry biomass raw materials.

In some embodiments, the aqueous suspension 5050 of the raw material may 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 yields a purified slurry and organic waste stream 5210 containing water-insoluble materials such as fats, oils, and other nonpolar hydrocarbon-containing substances. Suitable solvents for extraction from suspension 5050 include, for example, various alcohols, hydrocarbons and halogenated hydrocarbons.

In some variants, the aqueous suspension 5050 of the raw material can be optionally subjected to heat treatment 5190 for additional preparation of 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, compressed steam promotes the swelling of the fiber, exposing most of the fiber surfaces to the action of the aqueous solvent and oxidizing agents that are introduced in subsequent processing stages.

In certain variants, the aqueous suspension 5050 of the raw material can be subjected to optional treatment with basic substances 5200. Treatment with one or more basic substances can contribute to the separation of lignin from cellulose in the lignocellulosic biomass raw material, thus contributing to the increase of further oxidation of the raw material. Typical basic substances include alkali and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide. A plurality of the basic substances can usually be used at concentrations from about 0.01 to about 0.5 96 on a dry basis.

An aqueous slurry of feedstock 5050 is transported (eg, by an in-line piping system) to a chamber, which may be an oxidation pretreatment chamber or an oxidation reactor. At the stage 5060 of pretreatment by oxidation, one or more oxidizing agents 5160 are added to the suspension 5050 of the raw material to form an oxidizing medium. In some embodiments, oxidizing agents 5160 may include, for example, hydrogen peroxide. Hydrogen peroxide can be added to suspension 5050 in the form of an aqueous solution and in proportions ranging from 3 to 30-35 wt. 95 based on the mass of suspension 5050. Hydrogen peroxide as an oxidizer has a number of advantages. An aqueous solution of hydrogen peroxide is, for example, relatively inexpensive, relatively chemically stable, especially safe compared to other oxidizing agents (and therefore does not require burdensome methods of handling and expensive safe equipment). In addition, hydrogen peroxide decomposes during the oxidation of raw materials to form water, so the waste stream is relatively directly purified and inexpensive.

In some embodiments, oxidizing agents 5160 may include oxygen (eg, oxygen gas) either alone or in combination with hydrogen peroxide. Oxygen gas can be bubbled into the 5050 suspension in proportions ranging from 0.5 to 10 wt. 9o relative to the mass of the suspension 5050. Alternatively or additionally, oxygen gas may also be introduced into the gaseous phase in equilibrium with the suspension 5050 (eg, in the vapor fraction above the suspension 5050). Depending on the configuration of the oxidation treatment system, oxygen gas can be introduced into either the oxidation pretreatment chamber or the oxidation reactor (or both). Usually, the partial pressure of oxygen in the vapor phase above suspension 5050 is higher, for example, than the external pressure of oxygen and is, depending on the nature of the raw material, in the range from 0.5 to 35 bar.

Oxygen gas can be introduced 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 the vapor phase. In some embodiments, oxygen gas may be continuously supplied to the vapor phase so that the oxygen concentration in the vapor phase remains within defined predetermined limits during feedstock processing. In some embodiments, oxygen gas may be introduced first in concentrations sufficient to oxidize the feedstock, and then the feedstock may be transported to a closed high-pressure apparatus (eg, an oxidation reactor) for processing.

In certain embodiments, oxidants 5160 may include oxygen released in the process (eg, oxygen radicals). Usually, the necessary oxygen released in the process is obtained in an oxidation reactor or in a chamber in liquid communication with the oxidation reactor by one or more decomposition reactions. In some variants, the oxygen released in the process can be obtained, for example, from the interaction between MO and Ог2 in a gas mixture or in a solution. In certain variants, the oxygen released in the process can be obtained as a result of the decomposition of the CARRIER in the solution. Other ways in which the oxygen released in the process can be obtained include, for example, electrochemical generation in an electrolyte solution.

The oxygen released in the process is an effective oxidizer, due to the relatively high chemical activity of oxygen radicals. However, the oxygen released in the process can also be a relatively selective oxidant.

For example, during the treatment of lignocellulosic raw materials with oxygen released in the process, there is a better selective oxidation of lignin, rather than other components of the raw materials, such as cellulose. As a result of oxidation of raw materials with oxygen released in the process, it provides a method of selective removal of the lignin fraction present in certain types of raw materials. Usually, for effective oxidation, the concentration of oxygen released in the process is from about 0.5 to about 5 95 in terms of dry raw materials.

Without wishing to be bound by theory, the authors believe that the oxygen released in the process interacts with the ligocellulosic feedstock according to at least two different mechanisms. According to the first mechanism, the oxygen released in the process undergoes an addition reaction with lignin, which leads to incomplete oxidation of lignin, which solubilizes lignin in an aqueous solution. As a result, solubilized lignin can be removed from another part of the raw material by washing. According to the second mechanism, the oxygen released in the process breaks butane cross-links and/or opens aromatic rings connected by butane cross-links. As a result, the solubility of lignin in an aqueous solution increases, and the lignin fraction can be separated from the remaining raw materials by washing.

In some embodiments, oxidants 5160 include ozone (Oz). The use of ozone may introduce several considerations in the handling of the chemical reagent in the oxidation treatment sequence. If the heating is too vigorous, the aqueous ozone solution can significantly decompose, potentially causing adverse effects to both the operators operating the system and the system equipment. Accordingly, ozone is usually generated in a thermally insulated thick-walled vessel, which is separate from the reactor, which contains a suspension of raw materials, and is transported to it at the appropriate stage of the method.

Without wishing to be bound by theory, the authors believe that ozone decomposes into oxygen and oxygen radicals and that oxygen radicals (eg, oxygen released in the process) are responsible for the oxidizing properties of ozone in the above mode of action. Ozone usually preferentially oxidizes the lignin fraction in lignocellulosic materials, leaving the cellulose fraction relatively intact.

The conditions for the oxidation of biomass raw materials with an ozone-based oxidizer usually depend on the nature of the biomass. For example, for cellulosic and/or lignocellulosic raw materials, ozone concentrations from 0.1 to 20 g/m3 of dry raw materials will ensure effective oxidation of the raw materials. The usual water content in suspension 5050 is from 10 to 80 wt. 95 (for example, from 40 to 60 wt. 95). During oxidation with an ozone-based oxidizer, the temperature of the 5050 slurry can be maintained in the range of 0 to 1002C to prevent significant ozone decomposition.

In some embodiments, the suspension of feedstock 5050 may be treated with an aqueous alkaline solution containing one or more hydroxides of alkali and alkaline earth metals, such as sodium hydroxide, potassium hydroxide, and calcium hydroxide, and then treated with ozone-containing gas in an oxidation reactor. It was observed that this method significantly increases the degree of decomposition of biomass in suspension 5050. Usually, the concentration of hydroxide ions in an alkaline solution is, for example, from 0.001 to 10 wt. 95 relative to the mass of suspension 5050. After moistening the raw material by contact with an alkaline solution, the ozone-containing gas is introduced into the oxidation reactor, where it contacts the raw material and oxidizes it.

Oxidizers 5160 may also include other substances. In some embodiments, the suspension 5050 may be introduced, for example, halogen-based oxidants, such as chlorine, and oxygen chloride-containing compounds (eg, hypochlorite). In certain variants, nitrogen-containing oxidants may be introduced into suspension 5050. Typical examples of nitrogen-containing oxidizing agents include, for example, MO and MO. Nitrogen-containing reagents can also be combined in suspension 5050 with oxygen to obtain additional oxidants. For example, both "MO" and "MO" combine in suspension 5050 with oxygen to form nitrate compounds, which are effective oxidizers of biomass raw materials. Halogen- and nitrogen-containing oxidants can, in some variants, cause, depending on the nature of the raw material, bleaching of biomass raw materials. Bleaching may be desirable for some products made from biomass that is extracted in subsequent processing steps.

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

After the stage of pretreatment 5060 by oxidation, the suspension 5050 of the raw material is oxidized at stage 5070. If oxidizing agents 5160 were added to the suspension 5050 in the oxidation reactor, then the oxidation takes place in the same reactor. Alternatively, if oxidizing agents 5160 were added to the slurry 5050 in the pretreatment chamber, then the slurry 5050 is transported to the oxidation reactor via an in-line piping system. At the same time, the oxidation of biomass raw materials takes place in the oxidation reactor under a controlled set of environmental conditions. Usually, the oxidation reactor is, for example, a cylindrical vessel, closed to the outside environment and sealed. Both batch and continuous reactor operation are possible, although ambient conditions are usually easier to control on-line in batch processing processes.

Oxidation of suspension 5050 raw material usually occurs at elevated temperatures in the oxidation reactor. The temperature of the suspension 5050 in the oxidation reactor is usually maintained, for example, at a value above 1002C, for example, in the range from 120 to 2402C. For many types of biomass feedstocks, oxidation is particularly effective if the temperature of the slurry 5050 is maintained at a value between 150 and 22026. The slurry 5050 can be heated using a variety of heat transfer devices. In some embodiments, the oxidation reactor contacts, for example, a heating bath containing oil or molten salts. In certain embodiments, the oxidation reactor is surrounded by a series of heat exchange tubes in contact with the oxidation reactor, and the circulation of hot fluid within 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 heating and microwave sources.

The residence time of the suspension 5050 raw material in the oxidation reactor for processing the raw material can be varied as desired. Typically, the 5050 slurry is oxidized in the reactor for 1 to 60 minutes. For a relatively soft biomass material, such as lignocellulosic material, the residence time in the oxidation reactor can be from 5 to 30 minutes, for example, at an oxygen pressure in the reactor from 3 to 12 bar and at a suspension temperature from 160 to 2102C. However, for other types of raw materials, the residence time in the oxidation reactor can be longer, for example, up to 48 hours. To determine the appropriate residence time of the slurry 5050 in the oxidation reactor, aliquots of the slurry may be withdrawn from the reactor at specified time intervals and analyzed to determine concentrations of products of interest, such as complex saccharides.

Information on the increase in concentrations of some products in suspension 5050 in the form of a function of time can be used to determine the time of finding special classes of raw materials.

In some variants, during the oxidation of the suspension of 5050 raw materials, the pH of the suspension can be adjusted by introducing one or more chemical reagents into the oxidation reactor. In certain embodiments, oxidation occurs, for example, most efficiently at a pH in the range of approximately 9-11. To maintain the pH in the specified range, substances such as hydroxides of alkali and alkaline earth metals, carbonates, ammonia and alkaline buffer solutions can be introduced into the oxidation reactor.

Circulation of the slurry 5050 may be important to ensure sufficient contact between the oxidizers 5160 and the feedstock during oxidation. Circulation of the slurry may be achieved using a variety of techniques. In some embodiments, the oxidation reactor may be equipped with, for example, mechanical stirring equipment that includes impeller blades or an impeller. In certain embodiments, the oxidation reactor can be a circulating reactor, where 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 continuous re-mixing and no stagnation in the reactor.

After the oxidation of the raw material is complete, the suspension is transported to a separation device, in which stage 5080 of mechanical separation takes place. Typically, stage 5080 of mechanical separation includes one or more stages of fine filtration of the suspension to mechanically separate solid and liquid components.

The liquid phase 5090 is separated from the solid phase 5100 and the two phases are then treated independently. The solid phase 5100 can optionally be subjected to a drying step 5120, for example, in a dryer. The drying stage 5120 may include, for example, mechanically dispersing the solid material onto the drying surface and evaporating water from the solid phase 5100 by gently heating the solid material. After the drying stage 5120 (or, alternatively, without being subjected to the drying stage 5120), the solid phase 5100 is transported to the additional processing stage 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, the drying step 5110 may include, for example, 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 desiccants may be used to remove water from the liquid phase 5090. After the drying step 5110 (or, alternatively, without being subjected to the drying step 5110), the liquid phase 5090 is transported to the additional processing step 5130, which may include a number of chemical and biological processing steps, such as chemical and/or enzymatic hydrolysis.

The drying stage 5110 creates a waste stream 5220 which is an aqueous solution that may contain dissolved chemical reagents such as acids and bases at 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 be partially deionized (eg, by passing the waste stream through an ion exchange system). The waste stream, containing mainly water, can then be recirculated back into the complete process (eg, as water 5150 ), diverted to another process, or drained.

Typically, after the separation step 5080 of the lignocellulosic biomass feedstock, the liquid phase 5090 contains a variety of soluble poly- and oligosaccharides, which can then be separated and/or reduced to smaller chain saccharides in subsequent processing steps. The solid phase 5100 usually contains mainly cellulose, for example, with small amounts of products produced from hemicellulose and lignin.

In some embodiments, the oxidation can be carried out at an elevated temperature in a reactor, such as a pyrolysis chamber. As again follows from Fig.17, the raw materials can be oxidized in the pyrolyzer 1712 with a filament. In typical use, an oxidizing carrier gas, such as air or an air/argon mixture, is supplied to the sample holder 1713 while the resistive heating element is rotating and heated to a desired temperature, such as 3252C. After an appropriate time, for example, after a time period of 5 to 10 minutes, the oxidized material is poured from the sample holder. The system shown in Fig. 17 can be reduced to a certain scale and made continuous. As a heating element instead of a wire, it is preferable to use an auger screw. The material can continuously fall into the sample holder, striking the heated screw, which pyrolyzes the material. At the same time, the screw can push oxidized material out of the sample holder, allowing fresh, unoxidized material to enter.

As again follows from Fig.18, raw materials can be oxidized in the 1820 Sipe-Roipi pyrolyzer.

In a typical use, an oxidizing carrier gas is introduced into the sample chamber 1821 while the foil 1822 is inductively heated by an applied high frequency electromagnetic field to oxidize the material at the desired temperature.

As again follows from Fig.19, the raw materials can be oxidized in the furnace 130 for pyrolysis. In typical use, the sample is lowered (as shown by arrow 137) into the hot zone 135 of the furnace 132 while the carrier gas fills the jacket 136 and enters the sample holder 131. The sample is heated to the required temperature for the desired time to obtain an oxidized product. The oxidized product is removed from the pyrolyzer by lifting the sample holder (as shown by arrow 134).

As again shown in Fig. 20, the raw materials can be oxidized together with an oxidizing agent such as peroxide to form a cellulosic target 140 and treatment of the target, which is placed in the vacuum chamber 141, with laser light, for example, light having a wavelength of about 225 to about 1600 nm. The optical configuration shown provides the ability to direct the monochromatic light 143 generated by the laser 142, using mirrors 144 and 145, to the target in the vacuum chamber 141 after passing through the lenses 146.

The normal pressure in the vacuum chamber is maintained at a value of less than approximately 109 mm Na. In some variants, infrared radiation is used, for example, radiation of 1.06 microns from a Ma-ZhaaS laser. In such variants, the infrared sensitive dye can be combined with cellulosic material to form a cellulosic target. The infrared dye can enhance the heating of the cellulosic material. Laser processing of polymers is described by Viapspei-Rippspeg and a). in US patent Me 5942649.

As again shown in Figure 21, the feedstock materials can be rapidly oxidized, along with an oxidizing agent such as peroxide, by placing a tungsten filament 150 over the desired cellulosic material while the material is placed in a vacuum chamber 151. To effect oxidation through the filament pass a current that causes rapid heating of the thread for the required time. Usually, the heating is continued for seconds, after which the thread is given the opportunity to cool down. In some variants, heating is carried out several times to obtain the required degree of oxidation.

As again follows from Fig. 12, in some variants the raw materials can be oxidized with the help of sound and/or cavitation. Usually, to carry out oxidation, materials are treated with ultrasound in an oxidizing medium, such as water saturated with oxygen or another chemical oxidizer, such as hydrogen peroxide.

As again follows from Fig. 9 and 10, in some versions, ionizing radiation is used to promote the oxidation of raw materials. Usually, to carry out oxidation, materials are irradiated in an oxidizing environment, such as air or oxygen. For example, gamma radiation and/or electron beam irradiation can be used to irradiate materials.

Steam explosion can be used by itself, without using any of the methods disclosed in this description, or in combination with each of the methods disclosed in this description.

Fig.23 shows a general flow diagram of the complete process of converting a fiber source 400 into a product 450, such as ethanol, in a manner that includes displacement and steam explosion to obtain a fibrous material 401, which is then hydrolyzed and converted, for example, fermented, to obtain a product. The fiber source may be converted into fibrous material 401 by a number of possible methods, including at least one displacement method and at least one steam explosion method.

One choice includes, for example, displacement of the fiber source, followed by an optional scattering step(s) and an optional displacement step to produce a displaced fiber source 402, which may then be subjected to a steam explosion with the production of fibrous material 401. The steam explosion process is optionally followed by a fiber extraction process to remove liquids or "lye" 404 formed as a result of the steam explosion process. The material produced by the steam explosion biased fiber source may be additionally biased in an optional additional biasing stage(s) and/or an optional scattering stage(s).

In another method, the fibrous material 401 is first subjected to a steam explosion to obtain a steam-exploded source 401 fiber. The steam blasted fiber source is then subjected to an optional fiber drawing process to remove liquids or alkali. The steam-blasted fiber source can then be sheared to produce a fibrous material. The vapor-exploded fiber source may also be subjected to one or more optional scattering stages and/or one or more optional additional displacement stages. The method of shearing and steam explosion of the fiber source to obtain sheared and steam exploded fibrous material will be further discussed below.

The fiber source may be cut prior to shearing or steam blasting into pieces or ribbons of confetti material. Displacement processes can occur in the dry (eg, having less than 0.25 wt. 90 absorption water), hydrated state of the material, or even while the material is partially or fully immersed in a liquid such as water or isopropanol. The method may also optimally include stages of drying the product after steam explosion or displacement to ensure additional stages of displacement or steam explosion of the dry product. The stages of displacement, dispersion and steam explosion can occur in the presence of various chemical solutions or without their presence.

In the steam explosion process, a fiber source or a displaced fiber source is contacted with water vapor at high pressure, and the water vapor diffuses into the fiber source structures (eg, lignocellulosic structures). The water vapor is then condensed under high pressure, causing the fiber source to "wet". 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, releasing xylan and limited amounts of glucan. The "wetted" fiber source (or sheared fiber source, etc.) then "explodes" when the pressure is released. The condensed moisture evaporates instantly due to the rapid pressure drop, and the expansion of the water vapor affects the shear force applied to the fiber source (or a fiber source subjected to shear, etc.). Sufficient shear force causes mechanical rupture of the internal structures (for example, lignocellulosic structures) of the fiber source.

The sheared and steam-exploded fibrous material is then converted into a useful product such as ethanol. In some cases, the fibrous material is converted into fuel. One way to convert fibrous material into fuel is through hydrolysis, which provides fermentable sugars 412, which are then fermented to produce a product. Other known and unknown ways of converting fibrous materials into fuel can also be used.

In some embodiments, prior to combining with the microorganism, the sheared and steam exploded fibrous material 401 is sterilized to kill competing microorganisms that may be present in the fibrous material.

The fibrous material can be sterilized, for example, by exposing the fibrous material to radiation such as infrared radiation, ultraviolet radiation, or ionizing radiation such as gamma radiation. Microorganisms can also be killed using chemical sterilizers such as bleaches (eg, sodium hypochlorite), chlorhexidine, or ethylene oxide.

One method of hydrolysis of sheared and steam-exploded fibrous material involves the use of cellulases. Cellulases are a group of enzymes that act synergistically on the hydrolysis of cellulose. Commercially available AssePegaze "m 1000, containing a complex of enzymes that restores lignocellulosic biomass to fermentable sugars, can also be used.

According to the generally accepted understanding, the components of cellulose include endoglucanases, exoglucanases (cellobiohydrolases) and β-glucosidases (cellobiases). Synergism between cellulose components exists when hydrolysis by a combination of two or more components exceeds the sum of activities expressed by individual components. In most cases, the acceptable mechanism of action of the cellulase system (especially T. Iopdiogaspiasht) on crystalline cellulose is as follows: endoglucanase hydrolyzes the internal pD-1,4-glycosidic bonds of amorphous regions, thus increasing the number of available non-regenerating ends. Then, exoglucanases cleave cellobiose links from the non-reducing ends, which in turn are hydrolyzed to individual glucose links by p-glucosidases. There are several configurations of both endo- and exoglucanases that differ in stereospecificity.

Of course, the synergistic effect of components in different configurations is necessary for optimal hydrolysis of cellulose.

However, celluloses are more prone to hydrolysis of amorphous areas of cellulose. There is a linear relationship between crystallinity and hydrolysis rates, as a result of which higher indicators of crystallinity correspond to lower rates of enzymatic hydrolysis. Amorphous areas of cellulose are hydrolyzed at a rate that is twice the rate of hydrolysis of crystalline areas. Hydrolysis of fibrous material subjected to displacement and steam explosion can be carried out by any method of hydrolysis of biomass.

The steam explosion of biomass sometimes causes the formation of by-products, for example, toxic substances that suppress microbial and enzymatic activities. Therefore, the method of converting the fibrous material subjected to displacement and steam explosion into fuel may not necessarily include a stage of excessive liming before fermentation, intended for the precipitation of some toxic substances. For example, the pH of a fibrous material subjected to displacement and steam explosion can be increased to a value that exceeds pH 10 by adding calcium hydroxide (Ca(OH)»g), after which a stage of lowering the pH to about 5 is carried out by adding Nebo.

The overcalcified fibrous material can then be used as such without removing the sediments. As shown in Fig.23, an optional stage of excessive liming occurs just before the stage of hydrolysis of the sheared and steam-exploded fibrous material, but it is also envisaged to carry out the stage of excessive liming after the stage of hydrolysis and before the stage of fermentation.

Fig. 24 depicts an example of apparatus 460 for a steam explosion. Apparatus 460 for steam explosion includes a reaction chamber 462 into which a source of fiber and/or fibrous material is placed through an inlet 464 for the source of fiber. The reaction chamber is sealed by closing the fiber source inlet with a valve 465. The reaction chamber further includes a compressed vapor inlet 466 that includes a steam valve 467. The reaction chamber further includes a flash pressure relief outlet 468 that includes an outlet valve 469 connected to cycle 470 connecting pipe 472. After filling the reaction chamber with the fiber source and/or displaced fiber source and sealing by closing the valves 465, 467 and 469, water vapor is supplied to the reaction chamber 462 by opening the steam valve 467 of the inlet, which provides the possibility of water vapor entering through inlet 466 for steam. After the camera reaches the set temperature, which can happen within 20-60 seconds, the exposure time begins.

The reaction temperature is maintained at the desired temperature for the required holding time, which typically ranges from about 10 seconds to 5 minutes. At the end of the holding time, the exhaust valve is opened, thereby allowing the flash pressure to be released. The flash pressure relief process advances the contents of the reaction chamber 462 from the flash pressure relief outlet 468 through the connection tube 472 into the cyclone 470. The steam-exploded source of fiber or fibrous material then exits the cyclone in pulp form and enters the receiving hopper 474, then as most of the remaining water vapor exits the cyclone to the atmosphere via valve 476. The steam explosion apparatus further includes a purge outlet 478 with a purge valve 479 connected to a connecting pipe 472. The purge valve 479 for the wash is closed when using the steam explosion apparatus 460, but is open during the wash of the reaction chamber 462. The set temperature of the reaction chamber 462 is preferably from 180 to 240°C or from 200 to 2202°C. The holding time is preferably from seconds to 30 minutes, or from 30 seconds to 10 minutes, or from 1 to 5 minutes.

Since the steam explosion process results in a pulp of exploded fibrous material, the exploded fibrous material may optionally be subjected to a fiber drawing process in which the "lye" is separated from the exploded fibrous material. The fiber drawing step is useful because it allows for additional shearing and/or scattering processes and can provide an opportunity to convert the fibrous material into fuel. The fiber extraction process takes place using a fabric mesh designed to separate the fibers from the lye. Additional drying processes may also be included to obtain fibrous material or steam-exploded fibrous material for further processing.

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

In some embodiments, it may be advantageous to combine two or more separate devices for irradiation, ultrasonic treatment, pyrolysis and/or oxidation into a single hybrid installation. In such a hybrid installation, multiple processes can be performed sequentially or even simultaneously, with benefits that include increased pretreatment productivity and potential cost reductions.

The authors propose to consider, for example, the processes of electron beam irradiation and ultrasonic treatment. Each process is individually effective in reducing the average molecular weight of the cellulosic material by an order of magnitude or more and by several orders of magnitude when the processes are carried out sequentially.

Irradiation and ultrasonic treatment processes can be performed using the hybrid electron beam/ultrasound device shown in Fig.25. A hybrid electron beam/ultrasound device 2500 is shown above a shallow pool (approximately 3-5 cm deep) containing a pulp of cellulosic material 2550 dispersed in an aqueous medium of an oxidizing agent such as hydrogen peroxide or carbamide peroxide. The hybrid installation 2500 has a power source 2510 that powers both the electron beam emitter 2540 and the horn 2530 of the ultrasound device.

Electron beam emitter 2540 generates electron beams that pass through electron beam sighting device 2545 to impact pulp 2550 that contains cellulosic material. The aiming device for the electron beam may be a scanner that sweeps the beam up to about 6 feet (1.8288 m) in a direction approximately parallel to the surface of the pulp 2550 .

On each side of the electron beam emitter 2540 are ultrasonic horns 2530 that deliver ultrasound wave energy into the pulp 2550. The ultrasonic horns 2530 terminate in a detachable end piece 2535 that contacts the pulp 2550.

The 2530 ultrasonic horns are potentially susceptible to damage from long-term residual exposure to electron beam radiation. Therefore, the horn can be protected by a standard shield 2520 made, for example, of lead or an alloy containing a heavy metal, such as Lipovich alloy, which is impervious to electron beam radiation. However, precautions should be taken to ensure that the ultrasound energy is not affected by the presence of the screen. Detachable end pieces 2535 made of the same material and attached to the mouthpieces 2530 are used in contact with the cellulosic material 2550 and are expected to be damaged. Accordingly, the 2535's detachable end pieces are designed to be easily replaceable.

An additional benefit from such simultaneous presence of an electron beam and an ultrasonic process is to obtain additional results. When irradiated only with an electron beam, an insufficient dose can lead to the crosslinking of some polymers in the cellulosic material, which reduces the efficiency of the complete depolymerization process. Reduced doses of electron beam irradiation and/or ultrasound irradiation can also be used to achieve a similar degree of depolymerization, which is achieved using electron beam irradiation and ultrasound treatment separately.

The electron beam irradiation device can also be combined with one or more high-frequency rotor-stator devices, which can be used as an alternative to ultrasonic energy devices and perform a similar function.

Additional device combinations are also possible. The device for ionizing radiation, which generates gamma radiation emitted, for example, from 99Co granules, can be combined, for example, with an electron beam source and/or a source of ultrasonic energy. In this case, the shielding requirements may be more stringent.

The above-mentioned irradiation devices used for pretreatment of biomass can also be combined with one or more devices that perform one or more sequential pyrolysis treatments.

Such a combination can again give a benefit, which is increased productivity. However, caution should be exercised, as some methods of irradiation and pyrolysis may have conflicting requirements. For example, ultrasonic irradiation devices may require the raw material to be immersed in a liquid oxidizing medium. On the other hand, as previously indicated, it may be beneficial for a sample of the feedstock to be pyrolyzed to have a defined moisture content. In this case, the new systems automatically measure and register the determined moisture content and adjust it. In addition, some or all of the above devices, especially pyrolysis devices, can be combined with the oxidation devices discussed earlier.

In most cases, different microorganisms can produce a number of useful products, such as fuel, by acting, for example fermentation, on pre-treated biomass materials. For example, alcohols, organic acids, hydrocarbons, hydrogen, proteins or mixtures of any of these products can be obtained by fermentation or other methods.

A microorganism can be a natural microorganism or an artificially created microorganism. The microorganism can be, for example, a bacterium, such as a cellulose-degrading bacterium, a fungus, such as a yeast, a plant, or a single-celled organism, such as an algae, a protozoa, or a fungus-like single-celled organism, such as a slime mold. When organisms are compatible, mixtures of organisms may be used.

One or more enzymes, such as a fiber-degrading enzyme, may be used to promote the breakdown of materials comprising cellulose. In some embodiments, materials comprising cellulose are first treated with an enzyme, for example, by combining the material and the enzyme in an aqueous solution.

Then the material can be combined with the microorganism. In other embodiments, materials including cellulose, one or more enzymes, and a microorganism are combined together, for example, by combining in an aqueous solution.

To promote the breakdown of materials that include cellulose, the materials after exposure to heat can be treated with a chemical product (eg, a mineral acid, a base, or a strong oxidizer, eg, sodium hypochlorite) and/or an enzyme.

During fermentation, the sugars released as a result of cellulolytic hydrolysis or the saccharification stage are fermented, for example, into ethanol by a fermenting microorganism such as yeast. Suitable fermentative microorganisms have the ability to convert carbohydrates such as glucose, xylose, arabinose, mannose, galactose, oligosaccharides or polysaccharides into fermentation products.

Microorganisms that cause enzymatic processes include strains of the genus Zasspgotusez z5r., for example,

Zasspgotusev segemiviaye (baker's yeast), Zasspagotusevz aiviaysiv, Zassopagotusez tsmagpt; genus

Kisuhegotusev, for example, types of Kipuuegotusev5 taghiapiv, Kipumegotusez Igadiyiiv; genus Sapaida, for example, species

Sapaida reecidogihorisaii and Sapaida rgazvisae, genus Siamigroga, e.g. ip Naparook op Vioeipapo!:Rgodisip apa

Oii2ganop, UUutap, S.E., unit, Tauiog 5 Egapsiv, MMazpipdiyup, OS, 179-212.

Commercially available yeasts include, for example, Nei biakzh/ ezaite ESHShapo! Ney (available from Wei

Log in, BOTH), RAGIF (available from Riezsptappya Ueavi, subdivision Vygte Ryyr Bora Ips., I5A),

ZMCREABZTANTF (available from AShesp), SENT Z5TVAAMOF (available from Se bigapa AV, bmedep) and REEVMOI! F (available from OBM BresiaNev).

Bacteria that can ferment biomass into ethanol and other products include, for example, 7utotopav5 tobi and Sioziaite Sheptoseisht (RpPiirrii5, 1996, see above). Ievspipe ei ai. (Ipiegpayopa! docsygpa! oi

Zuzietaiiys apa EmoiIshiopagu Misgobioodu 2002,52,1155-1160), anaerobic, mesophilic bacteria, isolated from the forest soil, capable of decomposing cellulose, Siovilasht rpuyuheptepiapz" zr.pou., which transforms cellulose into ethanol.

Fermentation of biomass to ethanol and other products can be carried out using specific types of thermophilic or genetically engineered microorganisms, such as the species Tpeppoapaiegobasieh, which includes T. taiNgapii, and yeast species such as Rispia zresieh. An example of a strain of T. taiPgapia is AZMA, described in boppe-

Napze ei ai. (Arriiei Misgobioiodu apa VioiespppoIodu 1993,38,537-541) or Apipdega!. (Agop. Misgobio!. 1997, 168, 114-119).

Yeast and bacteria can be used for fermentation or transformation 7Khutotopav. The optimal pH level for yeast is about 4 to 5, while the optimal pH level for 2utopahs is about 5 to 6. Typical fermentation times are about 24 to 96 hours at temperatures ranging from 26 to 40°C, however, with thermophilic microorganisms elevated temperatures prevail.

Enzymes that are capable of breaking down biomass, such as cellulose, into lower molecular weight carbohydrate materials, such as glucose, during saccharification are referred to as cellulose-degrading enzymes or cellulases. Such enzymes can be a complex of enzymes acting synergistically to break down crystalline cellulose. Examples of enzymes that break down cellulose include endoglucanases, cellobiohydrolases, and cellobiases (p-glucosidases). The cellulosic substrate is first hydrolyzed by endoglucanases at randomly selected locations with the production of oligomeric intermediates.

The resulting intermediates are then substrates for exocleaving glucanases, such as cellobiohydrolase, involved in the production of cellobiose from the ends of the cellulose polymer. Cellobiose is a water-soluble dimer of glucose linked by a p-1,4 bond. Finally, cellobiase breaks down cellobiose to yield glucose.

Cellulase is capable of breaking down biomass and can be of fungal or bacterial origin. Suitable enzymes include cellulases from the genera Vasiy5, Reepdotopav, Nitisoia, Eryzapcyt, Tneiamia, Astgetopyt,

Spguzovzrogisht and Tpispodepta and include species of Nyptisoia, Sorgipi5, Tpieiamia, Eryzagpit, Museiorpipoga,

Astgetopisht, Serpaiuzrogpt, 5suiiiiSht, RepisshShiit or Azregoyiz (see, e.g., EP 458162), especially produced by a strain selected from the species Nitisoia ipzoJep5 (reclassified as 5suiiiidint (Sheptorpisht, see, e.g., US Patent 4,435,307), Sorgiproyts zapeguis5 Museiiornipoga (pegptorpiia, Megiriishv didapiveiv, Tniieiamia (egpeviivv, Asgetopisht v5r., Asgetopisht regvisipit, Asgetopisht asgtetopisht, Asgetopiit

Bgaspurepisht, Asgtetopisht aispgotovrogyt, Asgetopisht obsiamayit, Asgetopisht ripkepopiaye, Asgetopisht gozeodgizent, Asgetopisht ipsoiogayit and Asgetopisht igait; переважно з видів Нитісоіїа іпзоїєпе Ю5М 1800,Ризайцт охузрогит О5М 2672,МусеїйорпїШога (Шептпорпіа СВ5 117.65,Серпаіозропййт 5р.АУМ- 202,Асгетопішт в5р.Св5 478.94,Асгетопішт в5р.СВв5 265.95,Асгетопішт регзісіпит СВ 169.65,Астгетопійт асгетопішт АНИ 9519,Сернаювзрогішт 5р .Св5 535.71,Асгтетопішт ргаспурепішт СВ5 866.73,Астгетопійт діспготозрогпит СВ5 683.73,Астетопішт обсіамайшт СВ5 311.74 Астетопішт ріпкепопіає СВ5 157.70,Астетопіт гозеодгізент СВ5 134.56, Астетопішт іпсоіогашт СВ5 146.62 і Астгетопішт Пгайшт СВ5 299.70Н. Ферменти, що розщеплюють целюлозу, можуть бути також одержані з Spguzozrogt, mainly strain Spguzozrogpyt

InsKkpozhepze. Additionally, Tispodepta (especially Tispodetpta migide, Tgispodegta geezvi and

Thyspodepta Copidia), alkalophilic Vasiyl5 (see, for example, US Pat. No. 3,844,890 and EP4,58162) and

Zneriotusez (see, for example, EP 458162).

Anaerobic bacteria capable of decomposing cellulose were also isolated from the soil, for example, new cellulolytic species

Sioziypast, Siovygait rnuyuheptepiape 5r.pou. (see.

Emoishiopagu Misgobioiodu (2002), 52,1155-1160).

Can also be used cellulosic enzymes that use recombinant technology (see, for example, UUO2007/071818 and MMO2006/110891).

The cellulolytic enzymes used can be produced by fermentation of the above microbial strains in a nutrient medium containing suitable sources of carbon and nitrogen and inorganic salts, using methods known in the field (see, for example, Veppei, M. and Ga Zyge, GI. (ed.5. ), Moge Sepe

Mapirshaiiopv ip Rypdi, Asadetis Rgez5, SA1991). Suitable media are available from commercial suppliers or can be obtained according to published compositions (eg, in the catalogs of the American type culture collection). Temperature ranges and other conditions suitable for the growth and production of cellulose are known in the art (see, e.g., Vaieu, .E. and Ollie, O.E., Viospetisa!

Sotrapu, Moscow State University, 1986).

Processing of cellulose with cellulase is usually carried out at temperatures from 30 to 652C. Cellulases are active in the pH range from about 3 to 7. The saccharification stage can last up to 120 hours.

The dosage of the cellulase enzyme ensures the achievement of a sufficiently high level of cellulose conversion.

The appropriate dose of cellulose is usually from 5 to 50 units of filter paper (ERI or I)) per gram of cellulose. ERI is a standard measure that is defined and measured according to Stpose (1987, Ryge apa

Arri. Spet. 59:257-268).

In addition to the use of pyrolysis for the pretreatment of raw materials, pyrolysis can also be used for the treatment of pretreated raw materials in order to extract useful materials. A form of pyrolysis, known as gasification, can be particularly used to generate fuel gases, along with other various gaseous, liquid and solid products. To carry out gasification, pre-treated raw materials are introduced into the pyrolysis chamber and heated to a high temperature, usually up to 7002C or more.

The temperature used depends on a number of factors, which include the nature of the raw material and the required products.

Oxygen (for example, in the form of pure oxygen gas and/or in the form of air) and steam (for example, superheated steam) are also added to the pyrolysis chamber to promote gasification. These compounds interact with the carbon-containing raw material in a multistage reaction with the generation of a gas mixture called synthesis gas (or "syngas"). During gasification, an essentially limited amount of oxygen is introduced into the pyrolysis chamber, which enables some part of the raw material to burn with the formation of carbon monoxide and generate process heat.

The heat of the process can then be used to promote a second reaction that converts the additional feedstock into hydrogen and carbon monoxide.

In the first stage of the general reaction, heating the feed material gives a charred product, which can include a wide variety of different hydrocarbon-based products. Some volatile substances (for example, some gaseous hydrocarbon substances) can be obtained, which leads to a decrease in the total mass of the raw material. Then, in the second stage of the reaction, some part of the volatile substances obtained in the first stage interacts with oxygen in a combustion reaction with the production of both carbon monoxide and carbon dioxide. The combustion reaction releases heat, which promotes the third stage of the reaction. In the third stage, carbon dioxide and water vapor (for example, water) interact with the charred product generated in the first stage, with the formation of carbon monoxide and hydrogen gas. Carbon monoxide can also react with water vapor in a water gas shift reaction to form carbon dioxide and additional hydrogen gas.

Gasification can be used, for example, as a primary process for the direct generation of products from pre-processed raw materials for their further transportation and/or sale. Alternatively or additionally, gasification can be used as an auxiliary fuel generation method for the overall processing system. The hydrogen-enriched synthesis gas generated in the gasification process can be burned, for example, to produce electricity and/or process heat that can be directed for use elsewhere in the processing system. As a result, the overall processing system can be at least partially self-sustaining. A number of other products may also be produced during and/or after gasification, which include pyrolysis oils and hydrocarbon-based gaseous substances; they can, if necessary, be separated and stored or transported.

A variety of different pyrolysis chambers are suitable for gasification of pretreated raw materials, which include the pyrolysis chambers disclosed herein. Fluidized bed reaction systems, in which pretreated raw materials are fluidized in steam and/or oxygen/air mixtures, particularly provide relatively high productivity and direct product extraction. The solid char remaining after gasification in a fluidized bed system (or in other pyrolysis chambers) can be burned to generate additional process heat intended to promote subsequent gasification reactions.

After fermentation, the resulting liquids can be distilled using, for example, a "fermentation column" to separate the ethanol and other alcohols from most of the remaining water and solids. The steam leaving the fermentation column can contain 35 wt. 90% of ethanol, and it is fed into the rectification column. A mixture of near-azeotropic (92.5 90) ethanol and water from the distillation column can be purified to obtain pure (99.5 95) ethanol using molecular sieves in the vapor phase. The residues from the bottom of the fermentation column can be sent to the first body of the three-body evaporator. A fractional condenser of hot irrigation of the distillation column may provide heat for said first housing. After the first case, the solid particles can be separated using a centrifuge and dried in a drum dryer.

Part (25 95) of the flow flowing out of the centrifuge can be recirculated for fermentation and the other part is directed to the second or third bodies of the evaporator. Most of the condensate of the evaporator can be returned to the process in the form of completely clean condensate, a small portion of which is separated and sent to wastewater treatment to prevent the accumulation of low-boiling compounds.

Wastewater treatment is used to minimize plant leachate requirements by treating process water for reuse in the plant. Wastewater treatment can also produce fuels (such as sludge and biogas) that can be used to increase the overall efficiency of the ethanol production process. As detailed below, sludge and biogas can be used, for example, to produce steam and electricity, which can be used in various production methods.

The wastewater is first pumped through a screen (such as a grate screen) to remove large particles, which are collected in a hopper. In some versions, large particles are directed to an earth mound. Additionally or alternatively, large particles are burned to produce steam and/or electricity, as described in more detail below. The distance between the rods in a grate screen is usually between 1/4 inch (0.635 cm) and 1 inch (2.54 cm) (eg 1/2 inch (1.27 cm)).

The wastewater then flows into the equalization tank, in which the organic concentration of the wastewater is equalized during the retention time. In most cases, the retention time is from 8 to 36 hours (for example, 24 hours). A mixer is placed in the tank to mix the contents of the tank. In some embodiments, a plurality of mixers located throughout the tank are used to mix the contents of the tank. In certain embodiments, the mixer substantially mixes the contents of the equalization tank so that conditions (eg, wastewater concentration and temperature) throughout the tank are the same.

The first pump pumps water from the expansion tank into the liquid-liquid heat exchanger. The heat exchanger is controlled (for example, by controlling the flow rate of the liquid into the heat exchanger) so that the wastewater leaving the heat exchanger is at the temperature required for anaerobic treatment. The desired temperature for anaerobic treatment can be, for example, from 40 to 6020.

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

A nutrient solution containing nitrogen and phosphorus is dosed into each anaerobic reactor containing wastewater.

The feed solution interacts with the sludge in an anaerobic reactor to produce biogas, which may contain 50-90% methane and have a calorific value of approximately 12,000 British thermal units (or Vish) per pound (approximately 27,912 kJ/kg). Biogas leaves each anaerobic reactor through a gas outlet pipe and flows into a collector, in which multiple biogas streams are combined into a single stream. The compressor moves the biogas stream to a steam boiler or internal combustion engine, as detailed below. In some embodiments, the compressor also moves the single biogas stream to the desulfurization catalyst. Additionally or alternatively, a compressor can move a single stream of biogas into a sump.

A second pump moves the anaerobic stream that flows out of the anaerobic reactors into one or more aerobic reactors (eg, activated sludge reactors). An aerator is placed in each aerobic reactor to mix the anaerobic effluent, sludge, and oxygen (eg, oxygen contained in air). In each aerobic reactor, the oxidation of cellular material in the anaerobic effluent produces carbon dioxide, water, and ammonia.

The aerobic flow that flows out is moved (for example, by gravity) to a separation device, in which the sludge is separated from the treated water. A portion of the sludge is returned to one or more aerobic reactors to create an increased concentration of sludge in the aerobic reactors, thereby facilitating the aerobic breakdown of cellular material in the wastewater. The conveyor removes excess sludge from the separation device. As detailed below, excess sludge is used as fuel to generate steam and/or electricity.

The treated water is pumped from the separation device into the sump. Solid particles dispersed in the treated water settle to the bottom of the sump and are then removed. After settling, the treated water is pumped from the sump to a fine filter to remove additional solids remaining in the water. In some variants, one or more methods of physical and chemical separation are used for additional purification of treated water. Treated water can be pumped, for example, into a carbon adsorption reactor. As another example, treated water can be pumped into a reverse osmosis reactor.

The production of alcohol from biomass can lead to various by-product streams used to generate steam and electricity used in different parts of the plant. Water vapor generated from the combustion of the byproduct streams can be used in the distillation process. As another example, electricity generated from the combustion of byproduct streams can be used to power electron beam generators and ultrasonic transducers used in pretreatment.

By-products used to generate steam and electricity are produced from a number of sources throughout the process. For example, anaerobic "digestion" of wastewater produces biogas with a high methane content and a small amount of biomass waste (sludge). In another example, solid particles after distillation (for example, unconverted lignin, cellulose and hemicellulose remaining after pretreatment and primary processes) can be used as fuel.

Biogas is diverted to an internal combustion engine connected to an electric generator to produce electricity. Biogas can be used, for example, as a fuel source for a natural gas spark ignition engine. 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 may be configured for cogeneration. The heat of exhaust gases from internal combustion engines can be used, for example, to provide hot water or steam in the plant.

Sludge and solid particles after distillation are burned to heat the water that flows into the heat exchanger. In some versions, the water flowing into the heat exchanger is evaporated and superheated to produce water vapor. In certain variants, water vapor is used in the pretreatment reactor and in heat exchange in the processes of distillation and evaporation. Additionally or alternatively, the steam expands and drives a multi-stage steam turbine connected to an electric generator. The steam leaving the steam turbine is condensed using cooling water and returned to the heat exchanger to reheat the steam. In some variants, the rate of water flow into the heat exchanger is regulated to obtain a target current output from a steam turbine connected to an electric generator. For example, water may be added to the heat exchanger to allow the steam turbine to operate at above-limit conditions (for example, the turbine rotates fast enough to spin an electric generator).

Although certain options are disclosed, other options are possible.

As an example, although the biogas is described as directed to an internal combustion engine coupled to an electric generator, in some 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 sludge and solids after distillation, in certain embodiments, all of the byproducts may be burned together with steam.

The obtained alcohols can be a monohydric alcohol, for example, ethanol, or a polyhydric alcohol, for example, ethylene glycol or glycerin. Examples of alcohols that can be used include methanol, ethanol, propanol, isopropanol, butanol, for example n-, sec- or tert-butanol, ethylene glycol, propylene glycol, 1,4-butanediol, glycerin or mixtures of these alcohols.

Each of the alcohols obtained in the installation has commercial value as an industrial raw material. Ethanol can be used, for example, in the production of varnishes and perfumes. As another example, methanol can be used as a solvent used as a component of car windshield wiper fluid. As yet another example, butanol can be used in plasticizers, resins, varnishes, and brake fluids.

The bioethanol produced in the plant has value as an ingredient used in the food industry and in the production of beverages. For example, the ethanol produced in the plant can be purified to alcohol for food purposes and used as the main ingredient in alcoholic beverages.

The bioethanol produced in the plant is also of commercial importance as a transport fuel. The use of ethanol as a transportation fuel can be accomplished with relatively low capital costs for spark ignition engine manufacturers and owners (eg, changes in injection timing, excess air ratio, and fuel injection system components). Many car manufacturers usually offer vehicles capable of running on ethanol/gasoline mixtures containing up to 85 vol. 9% of ethanol

(for example, standard equipment on Spemu Tapoe 4x4).

The bioethanol produced in the plant can be used as motor fuel to improve environmental protection and increase savings outside the location of the plant. For example, ethanol produced in this facility and used as fuel can reduce greenhouse gas emissions from man-made sources (for example, transport sources). As another example, the ethanol obtained in this plant and used as a motor fuel can also replace the consumption of refined gasoline from oil.

Bioethanol has a higher octane number than conventional gasoline and can therefore be used to improve the performance (for example, to provide a higher compression ratio) of spark ignition engines. For example, small amounts (eg 10 vol. 95) of ethanol can be mixed with gasoline and will act as an octane booster for fuels used in spark ignition engines. As another example, increased amounts (eg, 85 vol. 90) of ethanol can be blended with gasoline to further increase the octane number of the fuel and replace the increased volumes of gasoline.

Bioethanol strategies are discussed, for example, by OiRagao in doshitgpa! ой Oshiook g Viotav5 ESHPapo! Rhodisiop apa

Oetapa (EIA Rogesavziv), 2002; 5Ppeeeipap ip Vioiespppoiodu Rgodgez5, 15:8179, 1999; Mapyip ip Epgute Misgorez

Thesppoiodu, 31:274,2002:Sgeeg ip VioSusie, 61-65,ArpI2005;Yupa ip Misgobioyudu apa Moiesshiag Vioiodu VNemiemuv, 66:3,506-577,2002;Tsipodaani eyi a. in US patent Me 4292406; and VePatu in US Pat. No. 4,094,742.

The resulting organic acids 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-oxybutyric acid or mixtures of these acids.

In some embodiments, all or part of the fermentation process may be interrupted prior to complete conversion of the cellulosic material to ethanol. Fermentation intermediates include high concentrations of sugars and carbohydrates. These fermentation intermediates can be used in the preparation of food for human or animal consumption. In some embodiments, pretreatment of the cellulosic material with irradiation will provide sterile fermentation intermediates (eg, suitable for human consumption). In some embodiments, the fermentation intermediates require further processing before consumption as a food product. For example, a drying chamber may be used to remove moisture from the fermentation intermediates in order to facilitate the storage, handling and shelf life of the product.

Additionally or alternatively, fermentation intermediates can be ground in a stainless steel laboratory mill to produce a dusty substance consisting of finely divided particles.

The grains and solubles of the distillation apparatus can be converted into a valuable by-product of the distillation-dehydration process. After the distillation-dehydration process, the grains and solutes of the distillation apparatus can be dried to improve the ability to preserve and manipulate the material.

The obtained dried grains and soluble substances of the distillation apparatus (0005) contain little starch, a lot of fat, a lot of protein, a lot of fiber and a lot of phosphorus. Ora5 may be valuable, for example, as a source of animal feed (eg, as a source of feed for dairy cattle). OO can then be combined with food additives to meet the special dietary requirements of certain categories of animals (for example, balancing digestible lysine and phosphorus for the food ration of pigs).

The above pretreatment methods can be used for plants with healing properties. In some embodiments, ultrasonic treatment can stimulate the bioactivity and/or bioavailability of medicinal plant components with healing properties. Additionally or alternatively, irradiation stimulates the bioactivity and/or bioavailability of medicinal plant components with healing properties. Treatment with ultrasound and irradiation can be combined, for example, in the preliminary treatment of willow bark to stimulate the production of salicin.

In some embodiments, fermentation intermediates (eg, products that include high concentrations of sugars and carbohydrates) can be supplemented to create nutritional supplements. Fermentation intermediates can be supplemented with, for example, calcium to create a dietary supplement that provides energy and helps increase or maintain bone strength.

As noted above, lignin-containing residues from primary and pretreatment processes have value as high/medium energy fuels and can be used to generate power and steam for use in plant processes. However, such lignin residues are a new type of fuel solids and have low requirements outside the plant, and the cost of drying them for further transportation only reduces their potential value. In some cases, gasification of lignin residues can turn them into a high-value product at low costs.

Cell matter, furfural, and acetic acid have been identified as potential byproducts of biomass-to-fuel equipment. The cellular intermediate may be of value but may require extensive purification. Markets for furfural and acetic acid are in place, although it is unlikely that they are large enough to consume the output of a fully commercialized lignocellulosic ethanol industry.

The following examples are intended to illustrate and not to limit the ideas of this specification.

Example 1 - Production of fibrous material from laminated paper 1500 lb (680.39 kg) of empty half gallon (1.89 L) juice cartons made from unprinted laminated white kraft paperboard, which has a density of 20 lb/ft? (320.37 kg/m3), received from the company Ipiegpaiopai! Rare Each box was bent and flattened and then fed into a Z pr Riipspy Vacdp shredder at a rate of approximately 15-20 pounds/hour (6.80-9.07 kg/hour).

The shredder was equipped with two 12-inch (30.48-cm) rotating blades, two non-rotating blades, and a 0.30-inch (0.76 cm) discharge screen. The gap between the rotating and non-rotating blades was adjusted to 0.10 inches (0.254 cm). The product from the shredder was confetti-like, 0.1 inch (0.254 cm) to 0.5 inch (1.27 cm) wide, 0.25 inch (0.635 cm) to 1 inch (2.54 cm) long ) and a thickness equivalent to that of the parent material (approximately 0.075 inch (approximately 0.190 cm)).

The confetti-like material was fed into a Munson Model 50630 disc knife. The Model 50630 is equipped with four rotating blades, four non-rotating blades, and a discharge screen having an opening size of 1/8 inch (3.175 mm). The gap between the rotating and non-rotating blades was set to approximately 0.020 inch (0.5 mm). The disc knife moved across the confetti-like pieces with knife blades, tearing them apart and releasing the fibrous material at a rate of about 1 lb/hour (0.453 kg/hour).

The fibrous material had a BET surface area of 0.9748-0.0167 mg/g, a porosity of 89.0437 965 and a bulk density (at 0.53 lb/in: (0.373 kg/cm2)) 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 L/D ratio of 42:11. A scanned electron micrograph of the fibrous material is shown in Fig. 26 at a 25-fold magnification.

Example 2 - Preparation of Fibrous Material from Bleached Kraft Paper 1500 lb (680.39 kg) of clean bleached white kraft paperboard having a bulk density of 30 lb/ft3 (480.55 kg/m3) was obtained from Ipiegpaiopa ! Rare The material was bent and flattened and then fed into a C Nr RBiIipsp Wacodp shredder at a rate of approximately 15-20 pounds/hour (6.80-9.07 kg/hour). The shredder was supplied with two 12-inch (30.48-cm) rotating blades, two non-rotating blades, and a 0.30-inch (0.76 cm) discharge screen. The gap between the rotating and non-rotating blades was adjusted to 0.10 inches (0.254 cm). The product from the shredder was confetti-like, 0.1 inch (0.254 cm) to 0.5 inch (1.27 cm) wide, 0.25 inch (0.635 cm) to 1 inch (2.54 cm) long ) |and a thickness equivalent to the thickness of the parent material (approximately 0.075 inch (approximately 0.190 cm)).

The confetti-like material was fed into a Munson Model 52630 disc knife. The discharge screen had an opening size of 1/8 inch (3.175 mm). The gap between the rotating and non-rotating blades was set to approximately 0.020 inch (0.5 mm). The disc knife moved across the confetti pieces, releasing the fibrous material at a rate of approximately 1 lb/hr (0.453 kg/hr). The fibrous material had a BET surface area of 1.1316-0.0103 m2/g, a porosity of 88.3285 95 and a bulk density (at 0.53 lb/in? (0.373 kg/cm?)) 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 D/D ratio of 43:1. A scanned electron micrograph of the fibrous material is shown in Fig. 27 at a 25-fold magnification.

Example C - Preparation of Double Sheared Bleached Kraft Paperboard 1500 lb (680.39 kg) discharge of clean bleached white kraft paperboard having a bulk density of 30 lb/ft3 (480.55 kg/m3) was obtained from the company Ipiegpayopa! Rare The material was bent and flattened and then fed into a C Nr RBiIipsp Vacdp shredder at a rate of approximately 15-20 lb/hr (6.80-9.07 kg/hr). The shredder was supplied with two 12-inch (30.48-cm) rotating blades, two non-rotating blades, and a 0.30-inch (0.76 cm) discharge screen. The gap between the rotating and non-rotating blades was adjusted to 0.10 inches (0.254 cm). The product from the shredder was similar to the confetti (which is listed above). The confetti-like material was fed into a Mason disc knife model 52630. The discharge screen had an opening size of 1/16 inch (1.588 mm). The gap between the rotating and non-rotating blades was set to approximately 0.020 inch (0.50 mm). The disc knife moved the confetti-like pieces across, releasing the fibrous material at a rate of approximately 1 lb/hr (0.453 kg/hr). The material obtained as a result of the first displacement was fed back into the same above-mentioned installation and subjected to displacement again. The resulting fibrous material had a BET surface area of 1.4408-40.0156 mg/g, a porosity of 90.8998 95 and a bulk density (at 0.53 lb/in? (0.373 kg/cm?)) of 0.1298 g/ml The average fiber length was 0.891 mm and the average fiber width was 0.026 mm, giving an average L/D ratio of 34:11. A scanned electron micrograph of the fibrous material is shown in Fig. 28 at a 25-fold magnification.

Example 4 - Preparation of Tri-Sheared Bleached Kraft Fiberboard A 1500 lb (680.39 kg) discharge of clean bleached white kraft paperboard having a bulk density of 30 lb/ft3 (480.55 kg/m) was obtained from the company Ipiegpayopa! Rare The material was bent and flattened and then fed into a C Nr RBiIipsp Vacdp shredder at a rate of approximately 15-20 lb/hr (6.80-9.07 kg/hr). The shredder was supplied with two 12-inch (30.48-cm) rotating blades, two non-rotating blades, and a 0.30-inch (0.76 cm) discharge screen. The gap between the rotating and non-rotating blades was adjusted to 0.10 inches (0.254 cm). The product from the shredder was similar to the confetti (which is listed above). The confetti-like material was fed into a Munson Model 52630 disc knife. The discharge screen had a 1/3 inch (3.175 mm) hole size. The gap between the rotating and non-rotating blades was set to approximately 0.020 inch (0.50 mm). The disk knife moved across the confetti-like pieces with the knife blades.

The resulting material from the first shift was fed back to the same plant as above and the screen was replaced with a 1/16 inch (1.588 mm) screen. The specified material was subjected to displacement. The resulting material from the second shift was fed back into the same above plant and the screen was replaced with a 1/32 inch (0.794 mm) screen. The specified material was subjected to displacement. The resulting fibrous material had a BET surface area of 1.6897--0.0155 m2/g, a porosity of 87.7163 95 and a bulk density (at 0.53 lb/in? (0.373 kg/cm?7 ) ) 0.1448 g/ml. The average fiber length was 0.824 mm and the average fiber width was 0.0262 mm, giving an average L/D ratio of 32:11. A scanned electron micrograph of the fibrous material is shown in Fig. 29 at a 25-fold magnification.

Example 5 - Production of compacted fibrous material from bleached kraft paperboard without adding a binder

The fibrous material was prepared according to Example 2. For every 10 pounds (4.535 kg) of fibrous material, approximately 1 pound (0.4536 kg) of water was sprayed. The fibrous material was densified using a Siligoria Reilly Miii 1100 (granulator) operating at 752°C. Did you get pellets that have a bulk density in the range of about 7 lbs/ft? (112.13 kg/m3) to about 15 lb/ft3 (240.28 kg/m3).

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

Fibrous material was obtained according to example 2.

Received 2 wt. 95 initial solution of ROI MOH M MU5A M10 (polyethylene oxide) in water.

For every 10 pounds (4.535 kg) of fibrous material, approximately 1 pound (0.4536 kg) of water was sprayed.

The fibrous material was densified using a Saijopia Reiyi Mi 1100 (granulator) operating at 7526. Pellets having bulk weights ranging from about 15 lb/ft? (240.28 kg/mu) to about 40 lb/ft? (640.74 kg/m).

Example 7 - Reduction of the molecular weight of cellulose in fibrous kraft paper by gamma irradiation 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 container with a maximum volume of 250 ml. Air was pumped out of the glass vessel under high vacuum (107 mm Na) for 30 minutes and then filled with argon gas. The container was sealed in an argon atmosphere. The pellets in the container were irradiated with gamma radiation for about 3 hours at a dose rate of about 1 Mrad/goodin to produce irradiated material in which the cellulose had a molecular weight lower than the molecular weight of the fibrous starting kraft material.

Example 8 - Reduction of the molecular mass of cellulose in fibrous kraft paper by gamma irradiation with 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 container with a maximum volume of 250 ml. The glass container was sealed in an air atmosphere. The pellets in the tank were irradiated with gamma radiation for about 3 hours at a dose rate of about 1 Mrad/hour to produce irradiated material in which the cellulose had a molecular weight lower than the molecular weight of the fibrous starting kraft material.

Example 9 - Method for determining the molecular weight of cellulosic and lignocellulosic materials by gel permeation chromatography

The cellulosic and ligpocellulosic material for analysis was processed according to Example 4. Sample materials present in the following tables include Kraft paper (P), wheat straw (M/5), alfalfa (A), and millet (5021). The number "132" of the IO sample refers to the particle size of the material after shearing and using a 1/32 inch (0.794 mm) mesh screen. The number after the dash refers to the radiation dose (Mrad) and the "05" refers to the ultrasound treatment. For example, the sample of IU "RI132-10" belongs to kraft paper, which was subjected to a shift to obtain a particle size of 132 mesh and irradiated with a dose of 10 Mrad.

Table 1

Peak average molecular weight of irradiated kraft paper

RAZ2 77777 17171717171717171017171717171711 1717111 None | 32853-210006

Kraft paper

RIZAOV 17777770 17771711 yes | zoeBnNoiZ "Low doses of radiation appear to increase the molecular weight of some materials" The dose rate is 1 Mrad/hour g2 Ultrasound treatment with a frequency of 20 kHz for 30 minutes using a horn with a power of 10008 W in conditions of recirculation of material dispersed in water

Table 2

Peak average molecular weight of irradiated materials

Zrazokir | Mapika | DozaieMrad) | Ultrasound SrednyaMMesSKO 1 11117177111110111111111171111 None | sllotaltnyvtei0O

Mig 2 11117177711110111111171171111111« 1111117 lvolvvbnivitoi0

A132 а1111711111ек1111111ек11111111гавни0 2 11117177711110111111171171111111« 11111171 5Б736оз83693 Sh

Za132 "Coalescence of peaks after treatment "Low doses of radiation appear to increase the molecular weight of some materials "The dose rate is 1 Mrad/hour 2Ultrasound treatment at a frequency of 20 kHz for 30 minutes using a horn with a power of 10008 W under conditions of recirculation of material dispersed in water

Gel permeation chromatography (SPC, GPC) was used to determine the molecular weight distribution of polymers. During GPC analysis, a polymer sample solution is passed through a column filled with a porous gel that traps small molecules. The sample was separated based on molecular size, with larger molecules eluting faster than smaller molecules. The retention time of each component was most often detected using refractive index (H1, PZ), evaporative light scattering (E! 5, BSR) or ultraviolet light (UV) and compared to a calibrated curve. Then the obtained data were used to calculate the molecular mass distribution of the sample.

For the characterization of synthetic polymers, the distribution of molecular weights is more preferable than a single molecular weight. Statistical averages are used to characterize such a distribution.

The most well-known values in this case are "number average molecular weight" (Ma) and "weight average molecular weight" (Mu).

We are similar to the standard arithmetic value associated with a group of numbers. When applying this term to polymers, M refers to the average molecular weight of the molecules in the polymer. We calculate by assigning the same number of values to each molecule regardless of its individual molecular weight.

The average value We calculate according to the following formula, in which M; is the number of molecules with a molar mass equal to Mi:

In MM; 2.1 mind 1

Mu is another statistical descriptor of the molecular weight distribution, which is more heavily weighted in the distribution on larger molecules than on smaller molecules. The formula below shows the statistical calculation of the weight average molecular weight:

UM" 2.1 that UM; 1

The index of polydispersity or PZ is defined as the Mu/My ratio. The more SW, the wider or more scattered the distribution. The lowest value that the PW can have is 1. In this case, the sample is monodisperse; that is, all polymer molecules have the same molecular weight distribution.

Peak molecular weight (Me) is another descriptor determined by the molecular weight distribution method. It means the molecular weight that is most predominant in the distribution. The specified value also contributes to the molecular mass distribution.

Most GPC measurements are performed relative to another polymer standard. The accuracy of the results depends on how closely the characteristics of the analyzed polymer correspond to the characteristics of the used standard. The expected error in reproducibility between different series of determinations calibrated separately is approximately 5-10 95 and is characteristic of the limited precision of GPC determinations. Therefore, GIPC results are most useful when comparing the molecular weight distributions of different samples during the same series of determinations.

Lignocellulosic samples must be prepared prior to GIPC analysis. First, a saturated solution (8.4 wt. 95) of lithium chloride (LIS!) in dimethylacetamide (OMAs) was prepared. About 100 mg of the sample was added to about 10 g of freshly prepared saturated solution of GIICI/OMAs and the mixture was heated to about 150-17022 with stirring for 1 hour. The resulting solutions, in most cases, had a color from light to dark yellow. The temperature of the solutions was reduced to about 1002 and heated for an additional 2 hours. The temperature of the solutions was then reduced to about 502C and the sample solution was heated for about 48 to 60 hours. It should be noted that samples irradiated at 100 Mrad were more easily solubilized compared to their untreated copies. In addition, the sheared samples (numbered 132) had slightly lower average molecular weights compared to the unsheared samples.

The obtained sample solutions were diluted in a ratio of 1:11 using OMas as a solvent and filtered through an RTEE filter with a hole size of 0.45 μm. Filtered sample solutions were then analyzed

GOH. The maximum average molecular weight (Me) values of the samples determined by gel permeation chromatography (GPC) are summarized in Tables 1 and 2. Each sample was prepared in duplicate and each sample preparation was analyzed twice (two injections) for a total of four injections. To construct a calibrated molecular mass curve with a scale from approximately 580 to 750,000 daltons, standards RUTA and PO1B polystyrene of EagazisSai were used.

Table C

GPC analysis conditions

Magegz APapse

Device: аРС2гОООРИДе! torus.

Micah-V ee DEC

Columns (3): 1omM-mMv-148-84710M-

Mv-174-129 "10.5 965 PISI in OMas (1.0

The temperature of

Example 10 - Determination of crystallinity of irradiated material by 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 X-rays is registered and information about the crystal structure of the irradiated sample is obtained.

The characteristic "print" formed provides the possibility of identifying the crystalline compounds present in the sample. Using whole-sample fit analysis (NiemeI purification), quantitative analyzes of samples containing more than one crystalline compound can be performed.

Table 4

DRP data including domain size and 9o crystallinity

Each sample was placed in a zero background holder and placed in a diffractometer RPYiYurz RM/1800 using Cy irradiation. Then scans were performed in the range from 5 to 502 s with a step size of 0.052 and a counting time of every 2 hours.

After obtaining the diffraction pattern, the phases were identified using the powder diffraction file published by the International Diffraction Data Center. In all samples, the identified crystalline phase was cellulose-ia, which has a triclinic structure.

A distinctive feature of the 20 samples is the peak width, which is attributed to the size of the crystallite domain. The experimental peak width was used to calculate the domain size and percent crystallinity presented in Table 4.

The percentage content of crystallinity (Xe 9o) was determined as the ratio of the crystalline surface to the total surface under the X-ray diffraction peaks

Hob x10095

IA Residential Complex Ar) where:

Ac is a section of the crystalline phase;

Aga is a section of the amorphous phase;

Xe represents the percentage of crystallinity.

To determine the percentage of crystallinity of each sample, it is necessary to first subtract the amount of the amorphous phase. This can be done by identifying the area of each diffraction pattern that can be attributed to the crystalline phase (represented by the sharper peaks) and to the non-crystalline phase (represented by the broad maxima below the pattern and centered at 22 and 382).

A systematic method was used to minimize the error in these calculations due to wide crystal peaks and high background intensity. First, they tried it on and then removed the linear background. Second, two Gaussian peaks centered at 22 and 382 with widths of each 10-122 were consistent with maxima below the crystalline peaks. Thirdly, the area under the two broad Gaussian peaks and the other part of the diffraction pattern were determined. | finally, the percentage content of 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 determined by X-ray diffraction (XRD) are presented in Table 4.

Example 11 - Porometric analysis of irradiated materials

Mercury pore size and pore volume analysis (Table 5) is based on forcing mercury (a non-wetting liquid) into a porous structure at controlled pressures. Since mercury does not wet most substances and will not spontaneously penetrate the pores due to capillary action, it should be pressed into the voids of the sample by applying external pressure. The pressure required to fill voids is inversely proportional to the pore size. Only a small amount of force or pressure is needed to fill large voids, while much more pressure is needed to fill very small pore voids.

Table 5

Size and volume distribution of pores determined by mercury porometry

General -- Average y- Volumetric weight ; General Average - Average |at a pressure of 0.50| Pretended -

Sample IO volume pore surface |pore diameter (in pore diameter pore diameter | lb/in? skeletal Porosity implementation! (mg/g) 0 | volume) (μm) | (and surfaces) | /du/d) (μm). | (0.035 kg/sme) density (g/l). 02) (mol/g) (μm) g/ml

The Autopore 9520 can reach a maximum pressure of 414 MPa or 60,000 psi? (4218.6 kg/cm?). There are four low pressure stations for sampling and macroporosity data collection at pressures ranging from 0.2 to 50 psi (0.014 to 3.515 kg/cm2). There are two high-pressure chambers that collect data at pressures from 25 psi to 60,000 psi (1.757 to 4218.6 kg/cm). The sample is placed in a cup-shaped device called a penetrometer, which is connected to a glass capillary column with a metal coating. As mercury enters the voids of the sample and around it, it lowers the capillary column. The loss of mercury from the capillary column leads to a change in electrical capacity. The change in capacity during the experiment is converted into the volume of mercury using the knowledge of the column volume of the used penetrometer. A variety of penetrometers with various cup and capillary sizes are available to accommodate a large number of sample sizes and configurations.

Table 6 below identifies some of the main parameters calculated for each sample.

Table 6

Definition of parameters

7 blown into the ocean, the porosity of the sample and the volume of the compressed sample allow for cylindrical pores " at a fill pressure of typically 0.5 psi? (0.03516 kg/cm?

And the pressure, of course, is 60,000 psi (4,218.6 kg/cm?).

Example 12 - Granulometric analysis of irradiated materials

The method of particle selection by fractions by static light scattering is based on Mie's theory (which includes the Egashppoieg theory). Mie theory predicts the relationship between intensity and angle as a function of the size of the spherical scattering particles, provided that the other system variables are known and held at constant values. Such variables include the wavelength of the incident light and the relative index of refraction of the sample material. The application of Mieje's theory provides detailed information about the grain size composition. Table 7 shows the particle sizes using median diameter, average diameter and modal diameter as parameters.

Table 7

Particle size determined by laser light scattering (dry sample dispersion)

Particle size was determined by laser light scattering (dry sample dispersion) using Maimet

Mawiegwige g2000 under the following conditions:

Feed speed: 35 bo

Dispersant pressure: 4 bar

Optical model: (2,610,1,0001st), 1,000

The appropriate amount of the sample was introduced onto the vibrating tray. The feed rate and air pressure were adjusted to values that ensure proper dispersion of the particles. The key element is the choice of air pressure that will break up the agglomerates, but will not affect the integrity of the sample. The amount of sample required varies depending on the particle size. In most cases, fine-grained samples require less material than coarse-grained samples.

Example 13 - Analysis of the specific surface of irradiated materials

The specific surface of each sample was analyzed using the system for accelerated determination of the specific surface and porometry Misgotegiyys5 ABAR 2420. The samples were prepared by degassing at 402C for 16 hours. Then the free space (both warm and cold) with helium was calculated and after that the vacuum was again created in the tube with the sample by removing the helium. Data collection began after the specified second pumpdown and included the determination of target pressures that control the amount of gas dosed per sample. At each target pressure, the amount of adsorbed gas and the actual pressure were determined and recorded. The pressure inside the sample tube was measured by a pressure sensor. Additional gas dosing was continued until the target pressure was reached and equalization was ensured. The amount of adsorbed gas was determined by summing up the numerous doses applied to the sample. The pressure and amount determine the gas adsorption isotherm and are used to calculate a number of parameters, which include the specific surface according to the BET method (table 8).

Table 8

A brief summary of the specific surface area determined by gas adsorption

Specific surface of one point Specific surface by method

The BET model for isotherms is a widely used theory for calculating 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 densely packed layer of krypton. To determine the total surface area, the capacity of the monolayer is increased by the cross-sectional area of the gas molecule under study. The specific surface is the surface area of a sample aliquot divided by the mass of the sample.

Example 14 - Determination of the length of fibers of irradiated materials

Fiber length distribution studies were conducted three times on the presented samples using the system

Tesprar Mogri I VO1. The average length and width are presented in Table 9.

Table 9

Length and width data of lignocellulosic fiber

Statistically

Average Average weight adjusted Width

Sample IU arithmetic (mm) length in length mass average (micrometers) (μm) (mm) length in length

MM

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

The rod-shaped millet was subjected to displacement according to example 4. The rod-shaped millet was treated only with ultrasound or gamma ray irradiation with a dose of 10 or 100 Mrad and then subjected to ultrasonic treatment. The obtained materials corresponded to (3132-BA (unirradiated), y132-10-BA (10 Mrad and ultrasonic treatment) and 2132-100-BA (100 Mrad and ultrasonic treatment), as presented in Table 1. Ultrasonic treatment was performed for each sample during 30 minutes using 20 kHz ultrasound from a 1000 W horn under recirculation conditions.Each sample was dispersed in water at a concentration of 0.10 g/mL.

Figures 30 and 31 show the equipment used for ultrasonic treatment. The apparatus 500 includes a transducer 502 connected to a booster 504 that communicates with a mouthpiece 506 made of titanium or a titanium alloy. The horn, which has a seal 510 made of MITOMO around its perimeter on its working side, forms a seal impermeable to the fluid of the working cell 508. The working side of the horn is immersed in a liquid, such as water, which disperses the sample to be sonicated. The pressure in the cell is recorded by the pressure sensor 512.

During the operation, each sample is moved by the pump 517 from the reservoir 516 into the working cell and subjected to ultrasonic treatment. After ultrasonic treatment, the sample is captured in reservoir 520. The process can be reversed, and the contents of reservoir 520 can be directed into the working cell and captured in reservoir 516. This method can be repeated multiple times until the desired level of sample processing is achieved.

Example 16 - Scanning electron micrographs of non-irradiated rod millet compared to irradiated and irradiated and sonicated rod millet

Rod millet samples for scanning electron micrographs were placed on carbon tape and coated with gold sputtering (70 seconds). The images were obtained using an emission electron scanning microscope UEOI 6500.

Fig.32 is a scanned electron micrograph of fibrous material obtained by shearing millet rod in a disc knife and subsequently passing the sheared material through a 1/32 inch (0.794 mm) sieve at 1000x magnification.

Fig. 33 and 34 are scanned electron micrographs of the fibrous material of Fig. 32 after irradiation with gamma rays at a dose of 10 and 100 Mrad, respectively, at a 1000-fold magnification of the image.

Fig. 35 are scanned electron micrographs of the fibrous material of Fig. 32 after irradiation with a dose of 10

Mrad and ultrasonic processing at a 1000-fold image magnification.

Fig. 36 are scanned electron micrographs of the fibrous material of Fig. 32 after irradiation with a dose of 100 Mrad and ultrasonic treatment at a 1000-fold magnification of the image.

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

ET-IA analysis was performed on the MisoieItrasi400 device. The results show that the samples presented in Table 1 are compatible with cellulose-based material.

Fig. 37 is an infrared spectrum of the paper kraft cardboard subjected to displacement according to the method of example 4, while Fig. 38 is an infrared spectrum of the kraft paper of Fig. 37 after irradiation with gamma radiation at a dose of 100 Mrad. The irradiated sample shows an additional peak in region A (centered at about 1730 cm"), which is not found in the spectrum of the unirradiated material.

Example 18 - Pretreatment with a combination that includes electron beam and ultrasonic treatment

Millet was used as the raw material, which was subjected to displacement with a disk knife

Munson with the production of fibrous material. The fibrous material was then uniformly distributed on an open tray made of tin having an area greater than about 500 in? (3225.8 cm"). The fibrous material was distributed so that it had a depth of approximately 1-2 inches (2.54-5.08 cm) in the open tray.

Fibrous material can be distributed in plastic bags at reduced radiation doses (below 10

Mrad) and left uncovered on a metal tray at higher radiation doses.

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

The device for ultrasonic processing includes a transducer connected to a booster that communicates with a horn made of titanium or a titanium alloy. The horn, which has a seal made of MITOMF around its perimeter on its working side, forms a seal that is impermeable to the liquid of the working cell. The working side of the horn is immersed in a liquid, such as water, in which the irradiated fibrous material is subjected to ultrasonic treatment. The pressure in the cell is recorded by a pressure sensor. During the operation, each sample is moved by a pump into the working cell and subjected to ultrasonic treatment.

To prepare the irradiated fibrous material for ultrasonic treatment, the irradiated fibrous material is removed from a container (eg, plastic bags) and dispersed in water at a concentration of approximately 0.10 g/ml. Ultrasonic treatment is carried out for each sample for 30 minutes using ultrasound with a frequency of 20 kHz from a horn with a power of 1000 W in recirculation conditions. After ultrasonic treatment, the irradiated fibrous material is collected in a tank. This process can be repeated many times until the desired level of processing is achieved, based on the control of structural changes in the millet. Again, some irradiated samples are maintained under the same conditions as the other samples but not sonicated and serve as controls. In addition, some samples that were not irradiated are subjected to ultrasonic treatment, and they again serve as controls. Thus, some control samples are not treated, some are only irradiated, and some are only subjected to ultrasonic treatment.

Example 19 - Microbial testing of pre-treated biomass

Individual lignocellulosic materials, pretreated as described herein, were analyzed for toxicity to common strains of yeast and bacteria used in biofuel production at the fermentation stage in ethanol production. To determine the viability of the processing process, sugar content and compatibility with cellulosic enzymes were additionally checked. Testing of pre-treated materials was carried out in two phases as follows.

Y. Toxicity and sugar content

The toxicity of pre-treated herbs and paper was measured in the yeasts Zasspagotuses segemisiae (wine yeast) and Risnia viirii (ATOS66278), as well as in the bacteria 72utotopaz torbiiis (ATOS31821) and Siozilaiit (pegtosePIit (ATSS31924). To determine the optimal cultivation time and sample selection, growth studies were carried out with each of the organisms.

Then each raw material was incubated in two repetitions with 5. segemiviae, R. zviri, 2. tobii and s.

Iegptoseiisht in a standard microbiological environment for each organism. UM broth was used for two yeast strains 5. segemiviae and R. viriyv. VM medium was used for 72. tobiosis, and for C.

ShegptoseYit used medium CM.4. For comparison, we used a positive control sample with added pure sugar, which does not contain the original raw material. During the incubation, five samples were taken within a 12-hour time period after 0, 3, 6, 9 and 12 hours and analyzed for viability (determination of the number of 2.thorbia by seeding on Petri dishes and determination of the number of 5.segemiviae by direct counting) and concentration ethanol.

The sugar content of the raw material was measured using high-performance liquid chromatography (HPLC), supplied either with a Zpodeh"m 5ROZ810 sugar measuring device or a Viogaa Atipeh? NRH-87R column. Each raw material (approximately 5 g) was mixed with reverse osmosis water (RO , 00) for 1 hour. The liquid portion of the mixture was removed and analyzed for the content of glucose, galactose, xylose, mannose, arabinose, and cellobiose. The analysis was carried out according to the protocol for determining structural carbohydrates and lignin in biomass

of the National Bioenergy Center.

II. Compatibility with cellulose

The starting material was tested in two replicates with the commercially available AssayIegazeM 1000, which contains a complex of enzymes that restore lignocellulosic biomass to fermentable sugars. Two different cellulose preparations, TPispodegta geesei and AzregoiPsh5 podshapv, at the recommended temperature and concentration in an Erlenmeyer flask. Flasks incubated with moderate circular shaking at 200 rpm for 12 hours. During this time period, samples were taken every three hours, i.e., after 0, 3, 6, 9, and 12 hours, to determine the concentration of reducing sugars (Nore and Oeap, Vioyesi .)., 1974,144:403) in the liquid part of the flask.

Example 20 - Production of alcohol using pretreatment that includes irradiation and ultrasonic treatment

The optimal size of biomass conversion plants is influenced by factors that include economies of scale, type and availability of biomass used as feedstock. An increase in the size of the installation leads to an increase in the savings associated with the processes that take place in the installation. However, increasing the size of the plant also leads to higher costs (for example, transport costs) per unit of biomass feedstock. Analysis of the study of these factors suggests that the appropriate size of biomass conversion units can be in the range of 2,000 to 10,000 tons of dry biomass feedstock per day. The installation mentioned below is designed to process 2,000 tons of dry biomass raw materials per day.

Fig. 39 shows a schematic method of biomass conversion in a system that has a configuration intended for the processing of rod millet. The raw material preparation subsystem processes the biomass raw material with the removal of foreign objects and provides sequentially sized particles for further processing. The pretreatment subsystem changes the molecular structure (for example, reduces the average molecular weight and crystallinity) of biomass raw materials by irradiating the biomass raw materials, mixing the irradiated biomass raw materials with water to form a suspension, and applying ultrasonic energy to the suspension. Irradiation and ultrasonic treatment transform cellulosic and lignocellulosic components of raw biomass into materials capable of fermentation. The subsystem for the primary process ferments glucose and others present after pretreatment of low-mass sugars to form alcohols.

The selected calculation of the consumption of the flow of raw materials entering the installation is 2000 tons per day of dry millet biomass. The selected raw material is crushed and/or sheared millet.

The biomass raw material in the form of stacks of millet rod is delivered by installation on car trailers. After receiving them, they are weighed and unloaded with lifting forks. Some stacks are sent to local storage, while others are transferred directly to conveyors. From the conveyors, the stacks are delivered to an automatic unfolding system that cuts the plastic wrap and/or mesh surrounding the stacks. Then, the raw biomass raw material is sent to a magnetic separation device to remove tramp metal, after which it is introduced into sequentially installed rows of shredder-cutting machine, in which the size of the raw material is reduced. And, finally, the biomass raw material is sent to the subsystem for pre-treatment.

In some cases, piles of rod millet are wrapped with plastic netting to prevent them from falling apart during handling, and they can also be wrapped with plastic wrap to protect the pile from the weather. Stacks are either square or round in shape. Stacks are delivered to the plant from distant warehouses on large truck trailers.

Since millet is only a seasonally available raw material, a warehouse for long-term storage is necessary for a year-round supply of raw materials to the plant. A long-term storage facility would suitably include 400-500 acres of uncovered stacked stack rows on a site (or multiple sites) moderately close to the ethanol production facility. A warehouse for short-term local storage collects raw materials in the amount necessary to receive products within 72 hours outside the storage area. Stacks and the surrounding ways of access to them, as well as transport conveyors, are placed on a concrete slab. A concrete slab is used due to the volume of transport required to deliver large quantities of biomass feedstock. A concrete slab will minimize the amount of standing water in the storage area, as well as reduce exposure of raw materials to dirt. Stored material provides short-term delivery of raw materials for Saturday through Monday, during holidays and when the normal direct delivery of material to the process is interrupted.

Stacks are unloaded with fork lifts and placed directly on stack conveyors or in a short-term storage area. Stacks from short-term storage are also used, which are lifted by lifting forks and loaded onto stack conveyors.

Stacks are moved to one of the packaging deployment systems. Unexpanded stacks are broken up using a spreader bar and then discharged onto a conveyor that passes through a magnetic separator that removes the metal before shredding. An iron magnet is provided to capture random magnetic metal, and the main scraper screen removes the over-sieve top product of coarse grinding and foreign material before being fed to sequential rows of shredder-slicing machines, which grind the raw biomass to the proper size for pre-treatment. The series of shredder-cutting machine includes shredders and disc knives. Shredders reduce the size of the raw biomass raw material and feed the resulting material to disk knives. Disk knives simultaneously move the biomass raw material, and the resulting material is sifted.

In order to limit the downtime of the entire system, caused by the necessary current repairs and/or breakdowns of the equipment of the subsystem for the preparation of raw materials, three silo towers are provided. Each tower can hold approximately 55,000 cubic feet (approximately 1,557 m3) of biomass feedstock (approximately 3 plant hours).

A belt conveyor transports the biomass feedstock from the feedstock preparation subsystem to the pretreatment subsystem 114. As shown in Fig.40, in the subsystem 114 for preliminary treatment, the biomass feedstock is irradiated using electron beam emitters, mixed with water to form a suspension and exposed to ultrasonic energy. As noted above, irradiation of biomass raw materials changes the molecular structure (for example, reduces the number average molecular weight and crystallinity) of biomass raw materials. Mixing of the irradiated biomass raw material in suspension and the influence of ultrasonic energy on the suspension additionally change the molecular structure of the biomass raw material. The sequential use of irradiation and sonication can produce a synergistic effect, in that the combination of methods achieves greater changes in molecular structure (reducing, for example, average molecular weight and crystallinity) than either treatment method used alone. Without wishing to be bound by theory, the authors believe that in addition to reducing the polymerization of biomass raw materials by breaking intramolecular bonds between segments of the cellulosic and lignocellulosic components of the biomass raw materials, irradiation can make the overall physical structure of the biomass raw materials more fragile. After mixing the fragile biomass raw material in suspension, the influence of ultrasonic energy additionally changes the molecular structure (reduces, for example, the average molecular weight and crystallinity) and can also reduce the particle size of the biomass raw material.

A conveyor belt 491 that transports the biomass feedstock to the pretreatment subsystem divides the biomass feedstock into multiple feed streams (eg, 50 feed streams), each of which is directed to separate electron beam emitters 492 . In this version, the raw biomass is irradiated while it is dry. Each stream of raw materials is sent to a separate belt conveyor connected to an electron beam emitter. The width of each conveyor belt with irradiated raw materials can be approximately one meter. Before reaching the electron beam emitter, a localized vibration is induced on each belt conveyor for uniform distribution of dry biomass raw materials across the width of the cross section of the belt conveyor.

The electron beam emitter 492 (eg, electron beam irradiation devices commercially available from Tiap Sogrogayop, Zap Oyedo, CA) is configured to allow an electron dose of 100 kilo-Ssgau applied at 300 kW. The electron beam emitters are scanning beam devices with a penetration width of 1 meter to match the width of the conveyor belt. In some variants, electron beam emitters with a large fixed beam width are used.

Factors including belt/beam width, required dose level, biomass feedstock density, and applied power affect the number of electron beam emitters required to process 2,000 tons of dry feedstock per day in a facility.

Before applying ultrasonic energy, the irradiated raw biomass raw material is mixed with water to form a suspension. A separate system for ultrasonic treatment associated with each stream of raw materials entering the treatment with an electron beam, or with several streams entering the treatment with an electron beam, can be assembled as a whole in the form of a single system for the ultrasonic treatment of raw materials.

In each ultrasonic treatment system, the irradiated biomass feedstock is fed into the tank 1214 through the first inlet port 1232, and water is fed into the tank 1214 through the second inlet port 1234. Appropriate valves (manual or automatic) regulate the biomass feedstock flow and the water flow to obtain the required biomass feedstock ratio. to water (for example, 10 vol. 96 cellulosic material). Each tank 1214 includes a mixer 1240, which mixes the contents of the volume 1236 and disperses the raw biomass in the water.

In each sonication system, the slurry is pumped (eg, using a submersible vortex centrifugal pump 1218) from a reservoir 1214 into a flow cell 1224 and through a flow cell 1224 that includes an ultrasonic transducer 1226. In some embodiments, the pump 1218 is configured to agitate the slurry. 1216 so that the mixture of biomass feedstock and water is essentially homogeneous at the inlet 1220 of the flow cell 1224. The pump 1218 can, for example, stir the slurry 1216 to form a turbulent flow that remains throughout the length of the pipeline between the first pump and the inlet 1220 of the flow cell 1224.

In flow cell 1224, an ultrasonic transducer 1226 transmits ultrasonic energy to slurry 1216 as the slurry flows into flow cell 1224. Ultrasonic transducer 1226 converts electrical energy into high frequency mechanical energy (eg, ultrasonic energy), which is then delivered to the slurry via booster 1248. converters are commercially available (for example, from

Nieivspeg OBA, Ips.oi Vipdmood, Mem Uegzeu) and are able to continuously transmit power equal to 16 kilowatts.

Ultrasonic energy delivered through the booster 1248 to the reaction volume 1244 creates a series of pressures and vacuums in the process stream 1216 with an intensity sufficient to create cavitation in the process stream 1216. Cavitation disaggregates the components of the biomass feedstock, including, for example, cellulosic and ligpocellulosic materials dispersed in process stream 1216 (eg, in suspension). Cavitation also produces free radicals in process water 1216 (for example, in suspension). The free radicals formed act to cause additional breakdown of the cellulosic material in process stream 1216. In most cases, process stream 1216 containing fragments of poplar chips utilizes ultrasonic energy of approximately 250 MJ/m3. Other levels of ultrasonic energy (from about 5 to about 4000 MJ/m3, eg, 10, 25, 50, 100, 250, 500, 750, 1000, 2000, or 3000 MJ/m3) may be used for other biomass feedstocks. After exposure to ultrasonic energy in reaction volume 1244, process stream 1216 exits flow cell 1224 through outlet 1222.

The flow cell 1224 also includes a heat exchanger 1246 that is in thermal communication with at least a portion of the reaction volume 1244. A cooling fluid 1248 (e.g., water) flows into the heat exchanger 1246 and absorbs the heat generated during the ultrasonic treatment of the process stream 1216 (e.g. , suspensions) in the reaction volume 1244. In some variants, to maintain an approximately constant temperature in the reaction volume 1244, the flow of the cooling liquid 1248, which enters the heat exchanger 1246, is regulated.

Additionally or alternatively, to maintain an approximately constant temperature in the reaction volume 1244, the temperature of the coolant 1248 flowing into the heat exchanger 1246 is regulated.

Outlet 1242 of flow cell 1224 is positioned near the bottom of tank 1214 to induce gravity flow of process stream 1216 (e.g., slurry) from tank 1214 toward the inlet of a second pump 1230, which pumps process stream 1216 (e.g., slurry) toward the primary process subsystem .

Ultrasonic treatment systems can include a single flow path (as indicated above) or multiple parallel flow paths, each of which is connected to a separate ultrasonic treatment unit. To increase the amount of energy used for the suspension, a plurality of units for ultrasonic treatment can also be placed in a row.

A drum-type rotary vacuum filter removes solid particles from the suspension before fermentation.

The liquid after filtration is cooled and pumped before entering the fermenters. The filtered solid particles are passed into the after-treatment subsystem for their further processing.

Fermenters are large, low-pressure vessels that are made of stainless steel and have conical agitator bottoms that operate at low speed. Multiple fermenters of the first stage of fermentation can be installed in series. The temperature in the fermenters of the first stage of fermentation is brought up to "C" using external heat exchangers. Yeast is added to the fermenter of the first stage of fermentation, which is located at the head of each row of containers, which passes into other containers installed in a row.

The second stage of fermentation consists of two continuously installed fermenters. In both fermenters, there is continuous mixing with mechanical stirrers at low speed. The temperature in the external heat exchangers is regulated by chilled water with its continuous recirculation. Circulation pumps have a cavity of the progressive type due to the high concentration of solid particles.

Waste gas from tanks and fermenters is combined and washed before being released into the atmosphere in a column with countercurrent water. The exhaust gas is scrubbed more to extract the ethanol than to control the release into the air.

Distillation and molecular sieve adsorption are used to extract ethanol from the mature fermentation liquid and obtain 99.5% ethanol. Distillation is carried out in two columns - the first, called the fermentation column, removes dissolved CO? and most of the water, and the second concentrates ethanol to an almost azeotropic composition.

All water is removed from the almost azeotropic mixture by adsorption of the vapor phase through a molecular sieve. For the regeneration of adsorption columns, it is necessary that the mixture of ethanol and water can be recycled to the distillation for extraction.

The fermentation off-channels (containing mainly CO', as well as some ethanol), as well as the fermentation column off-channel, are washed in a water gas scrubber, extracting almost all the ethanol.

The flow coming out of the gas purifier is sent to the first distillation column together with the fermentation liquid.

The residue from the bottom of the first distillation column contains all unconverted insoluble and dissolved solids. Insoluble solids are dewatered with a pressure filter and sent to the combustion chamber.

The uncirculated liquid from the pressure filter is concentrated in a multi-body evaporator using the waste heat of distillation. The concentrated syrup from the evaporator is mixed with the solids sent to the combustion chamber, and the evaporated condensate is used as relatively clean recycle water that is sent to the process.

Since the amount of distilled water that can be recycled is limited, an evaporator is included in the process. The total amount of water from the pressure filter, which is directly recirculated, is set at 25

Fo. Organic salts such as ammonium acetate or lactate, lock fluid components not used by the body, or inorganic compounds in the biomass in a given stream are exhausted. Recirculation of too much of said material can lead to levels of ionic strength and osmotic pressures that can be dangerous to the fermentative efficiency of the organisms. In non-recirculated water, the evaporator concentrates dissolved solids into a syrup that can be directed to a combustion chamber, minimizing the burden on wastewater treatment.

In the wastewater treatment section, the process water is treated for reuse in order to reduce the requirements for the leachate used in the installation. Wastewater is first screened to remove large particles, which are collected in a bunker and sent to an earthen embankment. After sieving, there is anaerobic digestion and aerobic digestion to evaporate organic substances in the stream.

Anaerobic digestion produces a biogas stream enriched with methane, which is fed into the combustion chamber. Aerobic digestion produces a relatively clean water stream for reuse in the process, as well as a sludge consisting mainly of cell mass. Sludge is also burned in a combustion chamber. The sieving/anaerobic digestion/aerobic digestion scheme presented is standard in ethanol production, and equipment to produce 1-5 million gallons/day (3780000-18900000 L/day) can be obtained commercially in the form of plants that " were in use".

The purpose of the subsystem, which includes a combustion chamber, a steam boiler and a turbogenerator, is to burn streams of various by-products to generate steam and electricity. For example, during pretreatment and primary processes, lignin, cellulose, and hemicellulose remain unconverted.

Most of the wastewater from the process is concentrated to produce a syrup with a high content of soluble solids. Anaerobic digestion of the remaining wastewater produces biogas with a high methane content.

Aerobic digestion produces a small amount of biomass waste (sludge). Combustion of these by-product streams to generate steam and electricity provides the facility with energy self-sufficiency, reduces solid waste disposal costs, and generates additional revenue through the sale of excess electricity.

Three main fuel streams (solids after distillation, biogas and syrup from the evaporator) are fed into the combustion chamber with a circulating fluidized bed. A small amount of biomass waste (sludge) obtained as a result of wastewater treatment is also sent to the combustion chamber. The fan moves air into the combustion chamber. Treated water enters the chain of heat exchangers in the combustion chamber and evaporates and is overheated with the formation of water vapor at 510202 (9502E) and a pressure of 86 atm. (1265 lb/in?). Flue gas from the combustion chamber heats the air entering it, then enters a bag filter to remove macro particles, which are dumped on the earthen mound. The gas is released through the exhaust pipe.

A multi-stage turbine and a generator are used to generate electricity. The steam is extracted from the turbine in three different states for injection into the pretreatment reactor and heat exchange in the distillation and evaporation processes. Other water vapor is condensed using cooling water and returned to the water system that feeds the steam boiler, along with condensate from the various heat exchangers used in the process.

Well-treated water is used as leaching water to replace the water vapor used in the direct injection process.

A number of variants of the invention are disclosed. However, it is clear that various modifications can be made without departing from the spirit and scope of the invention.

In some embodiments, relatively low doses of radiation, optionally combined with acoustic energy, such as ultrasound, are used to crosslink, graft, or otherwise increase the molecular weight of a natural or synthetic hydrocarbon-containing material, such as any of the aforementioned materials in any in any form (e.g., in fibrous form) disclosed herein, e.g., sheared or unsheared cellulosic or lignocellulosic materials such as cellulose. Cross-linking, grafting, or otherwise increasing the molecular weight of a natural or synthetic hydrocarbon-containing material can be accomplished in a controlled and predetermined manner by selecting the type or types of radiation used (e.g., electron beam and ultraviolet radiation or electron beam and gamma radiation) and/or dose or series of doses of radiation used. The obtained material, having an increased molecular weight, can be used in the manufacture of composite materials, such as composite material based on fiber and polymer matrix, which have improved mechanical properties, such as abrasion resistance, compressive strength, fracture resistance, impact toughness , resistance to bending, modulus of elasticity in tension, modulus of elasticity in bending and relative elongation at break. Crosslinking, grafting, or other means of increasing the molecular weight of the selected material can increase the heat resistance of the material relative to the raw material. Increasing the heat resistance of the selected material can provide the possibility of processing it at elevated temperatures without destruction. In addition, treatment of materials with irradiation can sterilize the materials, which can reduce their susceptibility to decomposition and decay, for example, while they are in a composite material. Cross-linking, grafting or otherwise increasing the molecular weight of a natural or synthetic carbohydrate-containing material can be carried out in a controlled and predetermined manner for a particular application to provide optimal properties such as strength, choice of type or types of radiation used and/or dose or doses of radiation used.

By using a combination of radiation, such as low-dose radiation, and acoustic energy, such as sonic or ultrasonic energy, the permeability of the material can be increased and/or energy use can be minimized.

The resin may be thermoplastic, thermoset, elastomer, adhesive, or a mixture of resins specified herein. Suitable resins include any resin or mixture of said resins.

In addition to being used as a resin alone, the high molecular weight material may be combined, mixed, or added to other materials such as metals, metal alloys, ceramics (eg, cement), lignin, elastomers, asphalts, glass, or mixtures of any - any of the specified materials and/or resins. When added to cement, fiber-reinforced cements can be obtained that have improved mechanical properties, such as the above properties, for example, compressive strength and/or fracture resistance.

Crosslinking, grafting, or otherwise increasing the molecular weight of a natural or synthetic hydrocarbon-containing material using irradiation can provide useful materials in many forms and for many uses. The hydrocarbon-containing material can be, for example, in the form of a paper product such as paper, paper pulp or waste water from paper production, chipboard, wood-based adhesive composites such as veneer or plywood, wood materials such as pine, poplar, oak or even balsa. Treatment of paper, chipboard, laminated plastics or timber can improve their mechanical properties such as strength. For example, treatment of pine forest material with irradiation can give a high-strength structural material.

When paper is manufactured using radiation, the radiation can be used at any point in its production. For example, the paper pulp may be irradiated, the preformed pressed fiber blank may be irradiated, or the finished paper itself may be irradiated. In some embodiments, irradiation is used at more than one point during the manufacturing process.

A fibrous material that includes a first cellulosic and/or lignocellulosic material having a first molecular weight can be irradiated, for example, in a manner that provides a second cellulosic and/or lignocellulosic material having a second molecular weight that is higher than the first molecular weight. If the radiation source is, for example, gamma radiation, a dose of from about 0.2 to about 10 Mrad can be used, for example from about 0.5 to about 7.5 Mrad or from about 2.0 to about 5.0 Mrad. If electron beam irradiation is used, a lower dose (relative to gamma radiation) may be used, such as from about 0.1 to about 5 Mrad, for example from about 0.2 to about 3 Mrad or from about 0.25 to about 2 ,5 Mrad. After a relatively low dose of irradiation, the second cellulosic and/or lignocellulosic material can be combined with a material such as a resin and formed into a composite material, for example, by direct compression, injection molding, or extrusion. The formation of composite materials based on fiber and polymer matrix is disclosed in U

2006/102543. After the composite materials are formed, they can be irradiated to further increase the molecular weight of the hydrocarbon-containing material while it is in the composite material.

Alternatively, a fibrous material comprising a first cellulosic and/or lignocellulosic material having a first molecular weight may be combined with a material such as a resin to form a composite material, and then the composite material may be irradiated with a relatively low dose of radiation. to obtain a second cellulosic and/or lignocellulosic material having a second molecular weight that is higher than the first molecular weight. If, for example, gamma radiation is used as the source of radiation, a dose of about 1 to about 10 Mrad can be used. Using this approach increases the molecular weight of the material while it is in a matrix such as a cured binder. In some embodiments, the resin is a crosslinking resin, and as such it crosslinks when the molecular weight of the hydrocarbon-containing material is increased, which can provide a synergistic effect that provides the composite material with maximally improved mechanical properties. Such composite materials can have, for example, excellent low-temperature characteristics, for example, a reduced tendency to fracture and/or cracking at low temperatures, for example, at temperatures below 02C, for example, below -1020, - 2020, -4020, -5020, -602C or even below -1002C, and/or excellent high temperature performance, e.g., the ability to retain their favorable mechanical properties at relatively high temperature, e.g., at temperatures above 1002C, e.g., above 12520, 15020, 20020, 25020, 30020, 4002C or even higher than 50020. In addition, such composite materials can have excellent chemical resistance, for example, resistance to swelling in a solvent, for example, a hydrocarbon solvent, resistance to the aggressive action of chemicals, for example, strong acids, strong bases, strong oxidizing agents (e.g. , chlorine or bleach) or reducing agents (e.g. active metals such as sodium and potassium).

In some embodiments, the resin or other binder material does not crosslink during irradiation. In some embodiments, additional irradiation is used while the carbohydrate-containing material is in the matrix, which results in an additional increase in the molecular weight of the carbohydrate-containing material. In some embodiments, irradiation causes the formation of bonds between the binder and the hydrocarbon-containing material.

In some embodiments, the carbohydrate-containing material is in the form of fibers. In such embodiments, when the fibers are used in a composite material, the fibers may be randomly oriented in the matrix. In other embodiments, the fibers may be substantially oriented, for example, in one, two, three, or four directions.

If necessary, fibers can be continuous or discrete.

Each of the following additives may be added to the fibrous materials, densified fibrous materials, and/or any other materials and composite materials disclosed herein. Additives, for example in the form of a solid, liquid or gas, can be added, for example, to a combination of fibrous material and resin. Additives include fillers such as calcium carbonate, graphite, wollastonite, mica, glass, fiberglass, silica, and talc; inorganic flame retardants such as aluminum oxide trihydrate or magnesium hydroxide; organic flame retardants, such as chlorinated or brominated organic compounds; crushed construction waste; crushed tire rubber; carbon fibers; or metal fibers or powders (e.g. aluminum, stainless steel). These additives may compact, expand, or change electrical, mechanical, or compatibility properties. Other additives include lignin, flavorings, binders, compatibilizers, e.g., maleated polypropylene, process improvers, lubricants, e.g., fluorinated polyethylene, plasticizers, antioxidants, silencers, heat stabilizers, coloring agents, foaming agents, modifying additives , which increase the impact strength, polymers, for example, degradable polymers, photostabilizers, biocides, antistatics, for example, stearates or amines of ethoxylated fatty acids. Suitable antistatic agents include conductive carbon blacks, carbon fibers, metal fillers, cationic compounds such as quaternary ammonium compounds such as M-(3-chloro-2-hydroxypropyl)trimethylammonium chloride, alkanolamides and amines. Typical degradable polymers include polyhydroxy acids, for example, polylactides, polyglycolides and copolymers of lactic acid and glycolic acid, poly(hydroxybutyric acid), poly(hydroxyvaleric acid), polylactide and ε-caprolactone copolymer, polyglycolide and ε-caprolactone copolymer, polycarbonates, poly(amino acids ), poly(hydroxyalkanoates), polyanhydrides, complex polyorthoesters and mixtures of these polymers.

When these additives are included, they may be present in amounts calculated on a dry matter basis from below 1 to above 80 95 based on the total mass of fibrous material. More often, the amounts are in the range of about 0.5 to about 50 wt. 95, for example, they add up to 5, 10, 20, 30 or more, for example, 40 95.

To protect the additives from, for example, heat or moisture during handling, any of the disclosed additives can be encapsulated, for example, spray-dried or microencapsulated.

Fibrous materials, compacted fibrous materials, resins or additives may be colored.

The fibrous material can be colored, for example, before combining with resin and mixing to form composite materials. In some embodiments, such coloring, when desired, may be useful in masking or concealing fibrous material, particularly large agglomerates of fibrous material in molded or extruded parts. These large agglomerates, when present in relatively high concentrations, can be recognized as specks on the surfaces of molded or extruded parts.

The desired fibrous material can be dyed, for example, using an acid dye, a direct dye, or a chemically active dye. These dyes are available from b5resig USA, Keagpu, MO or

Keusiope Apiipe Sogrogaiop, Spisado, IS. Separate examples of dyes include ZRESTKA "M TSONT MES OUM2O,

ZRESTKASIUTM ME OUMASI SOMS200.5RESTKAMU mm KNOOSAMIME 8.5RESTKAMMI lm MEOTAAG VE B,

ZRESTEAMIME"M VEM2OREKRIOKIME, ZRESTEAOSIAO"M VIDSK OV, 5RESTKAMIME"M TOKOTSOYIIZE O and

ZRESTEAMIME M SEM AND MI 200 95, each of which is available from Zresig Buezv.

In some embodiments, colored resin concentrates containing pigments are mixed with dyes. When the resulting mixtures are then mixed with the desired fibrous material, the fibrous material may be dyed ip 5ish during mixing. Color concentrates are available from Siapapi.

It may be beneficial to add a fragrance or flavor to the fibrous materials, densified fibrous materials, or composite materials. For composite materials, the smell and/or appearance of natural wood, such as cedar, may be beneficial. For example, an aroma, such as a natural wood aroma, can be mixed with the resin used to make the composite materials. In some variants, the flavoring agent is mixed directly into the resin in the form of an oil. The oil can be blended into the resin using, for example, a roll mill, such as a Banbury F mixer, or an extruder, such as a twin-screw extruder with counter-current rotating screws. An example of a mixer

Banbury is a mixer Banbury E-zegpie5F, manufactured by RaiteI. An example of a twin-screw extruder is

MESAsotripaegtm M/R 275K50, manufactured by Kgyrr U/egpeg 4. Riiiidegeg. After mixing, the flavored resin can be added to the fibrous material and extruded or pressed. Alternatively, aroma-infused resin master blends are commercially available from Ipiegpayopa! Riamoiz apa Egadgapsez under the trade name RoiuiitmM or from ATP Sotrapu. In some embodiments, the amount of flavoring in the composite material is from about 0.005 to about 10 wt. 95, for example, from about 0.1 to about 5 90 or from 0.25 to about 2.5 95.

Other fragrances with a natural wood scent include evergreen or evergreen redwood.

Other flavors include peppermint, cherry, strawberry, peach, lime, spearmint, cinnamon, anise, cornflower, bergamot, black pepper, camphor, chamomile, citronella, eucalyptus, pine, fir, geranium, ginger, grapefruit ) . In some embodiments, the amount of flavoring in the fibrous material-flavoring combination is from about 0.005 to about 20 wt. 95, for example, from about 0.1 to about 5 95 or from 0.25 to about 2.5 905.

Although fibrous materials such as cellulosic and lignocellulosic fibrous materials are described, other fillers can be used to make composite materials. For example, inorganic fillers such as calcium carbonate (eg, precipitated calcium carbonate or natural calcium carbonate), aragonite clay, orthorhombic clays, liming spar, rhombohedral clays, kaolin clay, bentonite clay, dicalcium phosphate, tricalcium phosphate, calcium pyrophosphate can be used. , insoluble sodium metaphosphate, precipitated calcium carbonate, magnesium orthophosphate, trimagnesium phosphate, hydroxyapatites, synthetic apatites, alumina, silica xerogel, metal aluminosilicate complexes, sodium aluminosilicates, zirconium silicate, silica, or combinations of inorganic additives. The fillers may have, for example, a particle size greater than 1 micron, such as greater than 2.5, 10.25, or even greater than 35 microns.

Nanoscale fillers can be used alone or in combination with fibrous materials of any size and/or shape. Fillers can be, for example, in the form of particles, plates or fibers. Nanoscale clays, silicon-carbon nanotubes, and silicon-carbon nanowires can be used, for example. The filler may have a transverse dimension of less than 1000 nm, for example, less than 900, 800, 750, 600, 500, 350, 300, 250, 200 nm, less than 100 nm, or even less than 50 nm.

In some embodiments, the nanoclay is montmorillonite. Such clays are available from Maposog, Ips. and boshyet Siau rgodisie and are disclosed in US Patent Nos. 6,849,680 and 6,737,464. Before mixing, for example, with a resin or fibrous material, the surface of the clay may be treated. The surface of the clay can be treated, for example, so that the surface has an ionic nature, for example, cationic or anionic.

Aggregated or agglomerated nanoscale fillers or nanoscale fillers assembled into supramolecular structures, such as self-assembled supramolecular structures, may also be used. Aggregate or supramolecular fillers can have an open or closed structure and can have a variety of shapes, such as a cage, tube, or spherical shape.

Accordingly, other options are included in the scope of the following claims.

BIOMASS

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OM and NN ONA n ХК I st y -

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Fig. 26 and the same sya vv Kl ly - pro v KK KA Ky be KNT NERV MV i l re vk vk A Ko vyku le

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MSU Sect i y IY i zhk VTK m ia i Ka i U

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Fig, 27 sotok" fochrnn ak SAN AJ ZNUN den st" nivu st t test vk on nn I o Mykh n Ko Ka i kore p vn ee t i KO I SEC Pope Li

Already eco: MAH FEREVEVIA U ne di KY ee V Pi yai Ky

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NE A Deu Ve U m o KA TI Kulya; Va a VIKY vano but sm nya DY i, Kei A jo I Vo son BU zey J shi

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Fig, 28 in i

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Fig, 29 red and 8 g voE

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Fig. 31

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Fig. 40

Claims (16)

1. A method of changing the molecular structure of biomass raw materials, where biomass includes cellulosic and/or lignocellulosic material, which includes: transformation of processed biomass raw materials into a product using a microorganism, including yeast, bacteria or fungi, 1/or an enzyme, including a cellulolytic enzyme, at the same time, the processed biomass raw material is obtained by processing the biomass raw material having a bulk density of less than approximately 0.5 g/cm", using the irradiation of the biomass material with an electron beam. 2. The method according to claim 1, in which the biomass feedstock has a bulk density of less than about 0.35 g/cm". 3. The method according to claim 1, which additionally includes the preparation of biomass raw materials by physical processing of the raw materials to reduce the volumetric weight of the raw materials. 4. The method according to claim 3, in which the raw material has a bulk weight before preparation greater than about 0.7 g/cm". 5. The method according to claim 3, in which the preparation includes shifting. b. The method according to claim 3, in which the preparation includes reducing the size of the starting material by grinding with a grinding stone, mechanical breaking or tearing, grinding with pins or attritor grinding in an air atmosphere. 7. The method according to item I, in which the processing is carried out under conditions selected to reduce the molecular weight of the biomass raw material. 8. The method according to claim 1, in which the biomass raw material has a specific surface according to the BET method greater than 0.25 m"/g. 9, The method according to item I, in which the biomass raw material has a length-to-diameter ratio that is at least 5. 10. The method according to claim 1, in which the ionizing radiation is used at a total dose level equal to at least about 5 Mrad. 11. The method according to claim 1, in which the treatment is carried out under conditions selected to reduce any one or both characteristics selected from the average molecular weight and average crystallinity of the biomass feedstock, or to increase any one or both characteristics selected from the specific surface and porosity of biomass raw materials. 12. The method according to claim 1, in which the biomass raw material is selected from the group consisting of paper, paper products, paper waste, wood, chipboard, sawdust, agricultural waste, sewage, silage, herbs, rice husk, bagasse, cotton, jute, hemp, vegetable fiber from cellulose, bamboo, sisal, abaca, straw, corn cobs, corn straw, millet, alfalfa, hay, coconut hair, seaweed, algae and mixtures thereof. 13. The method according to claim 1, in which the product includes flammable fuel. 14. The method according to claim 5, in which the biomass raw material has internal fibers and in which the biomass raw material is subjected to displacement, in which its internal fibers are significantly affected. 15. The method according to claim 1, in which the biomass raw material has a porosity greater than 70 90. 16. The method according to item I, which additionally includes carrying out enzymatic hydrolysis of processed biomass raw materials.