UA119058C2 - PROCESSING OF ION BEAM MATERIALS - Google Patents

Abstract

The invention relates to the processing of materials under the action of ion beams. A method of obtaining a fermentation product, which includes: processing of lignocellulosic material to change the molecular structure of the material by subjecting the specified material to an ion beam, where the change in molecular structure is a decrease in the molecular weight of the material; and fermenting the treated lignocellulosic material by contacting said material with an enzyme and / or microorganism; wherein the ion beam consists of two or more different types of ions, and where the material is first exposed to carbon ions and oxygen ions for decomposition of lignin and then exposed to protons, helium ions and / or electrons for decomposition of cellulose and / or hemicellulose.

Description

Biomass, particularly biomass-based waste, and hydrocarbon-bearing materials such as oil sands, oil shale, tar sands, bitumen and coal are widely available.

It is advisable to obtain fuel such as ethanol from biomass and hydrocarbon-containing material.

Biomass and hydrocarbon-containing material can be processed to change their structure at one or more levels. The recycled materials can then be used as a source of modified materials and/or fuel.

In most versions of the implementation of this application, the publication Maitsyga is used! ERogse "m

Spitiwig In the ways of publishing Maishiga! Rogse "m Spetivig uses the controlled application of physical forces, such as particle beams, gravity, light, and the like, and the manipulation of them, to create the intended structural and chemical molecular change.

Methods of changing the molecular and/or supramolecular structure of a material, for example, any biomass material, may include radiation treatment of the material. In particular, the radiation may include particles, particularly charged particles (eg, accelerated charged particles). Charged particles include ions such as positively charged ions such as protons, carbon or oxygen ions. Radiation can be used in an amount sufficient to change the molecular structure and/or supramolecular structure of the material.

Radiation can also be used to obtain one or more products from the material. The material may in some cases include carbohydrates or materials that include carbohydrates, such as cellulosic materials, lignocellulosic materials, starchy materials, or mixtures of any biomass materials.

Particles with a charge different from the charge of electrons and/or particles heavier than electrons can be used for irradiation. For example, protons, helium nuclei, argon ions, silicon ions, neon ions, carbon ions, phosphorus ions, oxygen ions, or nitrogen ions can be used to modify the structure of the biomass, such as reducing the molecular weight or increasing the molecular weight of the biomass. In some implementations, heavier particles can cause higher degrees of chain destruction compared to electrons or photons. In addition, in some cases, positively charged particles can cause relatively large degrees of chain destruction due to their acidity. In certain cases, negatively charged

Zo particles can stimulate the appearance of relatively large degrees of chain destruction due to their alkalinity.

Accordingly, in one aspect, a feature of the invention is a method of changing the molecular structure of a material, such as a biomass material or a hydrocarbon-containing material, as a result of obtaining an ion beam characterized by a first energy distribution of ions having a full width at half maximum m; adjusting the energies of at least some of the ions to obtain a second energy distribution of the ions in the ion beam, which has a full width at half maximum greater than the mu value; and impacting the material with a regulated ion beam. The energies of at least some of the ions can be adjusted based on, for example, the thickness of the material.

In another aspect, a feature of the invention is a method of changing the molecular structure of a material, for example, a biomass material or a hydrocarbon-containing material, as a result of obtaining an ion beam characterized by an ion energy distribution having a full width at half maximum m; the direction of the ion beam to pass through the scattering element, configured to increase the full width at half maximum of the ion energy distribution to a value greater than the mu value; and impacting the material with an ion beam after passing the ion beam through the scattering element.

In yet another aspect, a feature of the invention is a method of changing the molecular structure of a material, for example a biomass material or a hydrocarbon-containing material, as a result of obtaining an ion beam characterized by a distribution of ion energies, while the distribution has the most probable energy E; filtering the ion beam to remove from the ion beam at least some of the ions having an energy lower than the E value; and impacting the material with a filtered ion beam.

In one additional aspect, a feature of the invention is a method of changing the molecular structure of a material, for example a biomass material or a hydrocarbon-containing material, as a result of obtaining an ion beam characterized by the distribution of ion energies; regulation of ion energy distribution based on the expected ion dose profile in the material; and impacting the material with a regulated ion beam.

A feature of the invention is also a method of changing the molecular structure of a material, for example a biomass material or a hydrocarbon-containing material, as a result of receiving an ion beam, which has a distribution of ion energies; adjustment of ion energy distribution based on the full width at half maximum (FWHM) of the Bragg peak of the expected ion dose profile in the material; and impacting the material with a regulated ion beam, wherein the regulation includes increasing the value of the PSHIM to reduce the difference between the thickness of the biomass material and the value of the PSHPM.

In some cases, after adjustment, the difference between the material thickness and the PSHPM value is 0.01 cm or less.

In yet another aspect, the feature of the invention is a method of changing the molecular structure of the material as a result of receiving the first ion beam from the ion source, while the first ion beam is characterized by the first average energy of the ions; impacting the material with the first ion beam; adjustment of the ion source to obtain a second ion beam characterized by a second average ion energy that differs from the first average ion energy; and impacting the material with a second ion beam.

In some cases, the method additionally includes repeating the adjustment and impact to impact the material with a plurality of ion beams characterized by different average ion energies. The composition of the first and second ion beams can be identical.

In one additional aspect, a feature of the invention is a method of changing the molecular structure of a material as a result of: receiving a first ion beam from an ion source, while the first ion beam characterized by the first average ion energy corresponds to the first position of the Bragg peak on the expected ion dose profile in the material; impacting the material with the first ion beam; adjusting the ion source to obtain a second ion beam characterized by a second average ion energy and corresponding to a second Bragg peak position that is different from the first position; and impacting the material with a second ion beam.

In some cases, the method additionally includes repeating the regulation and exposure to impact the material with a plurality of ion beams corresponding to different positions of the Bragg peak. The composition of the first and second ion beams can be identical.

In yet another aspect, a feature of the invention is a method of changing the molecular structure

From the material as a result of receiving an ion beam from an ion source, while the ion beam includes a first type of ions and a second type of ions, which is different from the first type of ions; and impacting the material with an ion beam.

For example, the first type of ions may include hydrogen ions and the second type of ions may include carbon ions, or the first type of ions may include hydrogen ions and the second type of ions may include oxygen ions, or the first and second types of ions may include at least one type that is selected from protons and hydride ions. In some cases, each ion type selected from the first and second is characterized by ion energies in the range from 0.01 MeV to 10 MeV.

In another aspect, a feature of the invention is a method of changing the molecular structure of the material as a result of receiving an ion beam, characterized on the surface of the material by a divergence angle of 10 degrees or more, for example, 20 degrees or more; and effecting the biomass material with an ion beam.

In yet another aspect, the feature of the invention is a method of changing the molecular structure of the material as a result of adjusting the ion source to obtain an ion beam characterized by an average ion current and average ion energy; and irradiating the material with an ion beam, where the ion source is regulated based on the expected ion dose profile in the material, and where each part of the material receives a radiation dose in the range of 0.01 Mrad to 50 Mrad, for example, from 0 ,1 Mrad to 20 Mrad.

In yet another aspect, changing the molecular structure of the material includes obtaining an ion beam characterized by a first ion energy distribution that exhibits a full width at half maximum of the MU, adjusting the energies of at least some of the ions based on the thickness of the hydrocarbon-containing material to obtain a second ion beam energy distribution, showing a full width at half maximum greater than the MU value, and impacting the hydrocarbon-bearing material with a tuned ion beam. The hydrocarbon-bearing material may be selected from the group consisting of oil sands, oil shale, tar sands, bitumen, and coal.

In yet another aspect, changing the molecular structure of the material includes obtaining an ion beam characterized by a first ion beam energy distribution exhibiting a full width at half maximum of Y, adjusting the energies of at least some of the ions to obtain a second ion beam ion energy distribution exhibiting a full width at half of the maximum, greater than the MU value, and impacting the material with a regulated ion beam.

In some cases, the material is a biomass material, a non-biomass material, or any combination thereof. For example, the material can be hydrocarbon-bearing material such as oil sands, oil shale, tar sands, bitumen, coal and other mixtures of hydrocarbon and non-hydrocarbon material.

In some cases, the method additionally includes impacting the material with a plurality of electrons or ultrasonic energy followed by impact with an ion beam.

Some embodiments of any of the above aspects of the invention may include one or more of the following features. Adjusting the energies of at least some of the ions may include adjustment based on the thickness of the material exposed to the ion beam. In some cases, adjusting the energies of at least some of the ions may include adjusting based on the expected ion dose profile in the material. The adjustment may also include increasing the full width at half maximum of the Bragg peak of the expected ion dose profile in the material, sufficient to reduce the difference between the material thickness and the full width at half maximum of the Bragg peak. After adjustment, the difference between the material thickness and the full width at half maximum of the Bragg peak can be 0.01 centimeters or less.

The full width at half maximum for the second distribution may be greater than the mu value by a factor of 2.0 or more, for example by a factor of 4.0 or more. Regulating the energies of at least some of the ions may include directing the ions to pass through a scattering element, such as a hemispherical analyzer. In some cases, the adjusted ion beam before falling on the material passes through a fluid medium, for example, through air under a pressure equal to 0.5 atmospheres or more. An ion beam may include two or more different types of ions, such as hydrogen ions and carbon ions or hydrogen ions and oxygen ions. (The ion beam may include at least one type selected from protons and hydride ions. The average energy of the ions in the ion beam may range from 0.01 MeV to 10 MeV.

Changing the molecular structure of a material, such as a biomass-based process feedstock or a hydrocarbon-containing material, as used herein

Zo means a change in the composition of chemical bonds, such as in connection with the type and number of functional groups or the conformation of the structure. For example, changing the molecular structure may include changing the supramolecular structure of the material, oxidation of the material, changing the average molecular weight, changing the average degree of crystallinity, changing the specific surface area, changing the degree of polymerization, changing the porosity, changing the degree of branching, grafting onto other materials, changing the size of crystalline domains or resizing full domains.

Biomass or hydrocarbon-containing material can be exposed to radiation, such as an ion beam, such as a beam corresponding to one or more configurations described herein. The beam and duration of exposure can be chosen to change the molecular structure of the material. The material can be treated before and/or after exposure. The exposed material can be used in a wide range of applications, including fermentation and the production of composite materials.

In addition, the systems and devices for radiation treatment of materials described herein are features. One example system includes a reservoir for biomass, a device that conducts a particle beam, for example, as described herein, and a transport device for moving the biomass away from the reservoir. to the device that conducts the particle beam.

Embodiments may include one or more of any of the features described herein.

Unless otherwise defined, all technical and scientific terms used in this document have the same meanings as the ordinary technique understood by a person skilled in the relevant field to which the present invention belongs. Although methods and materials similar to or equivalent to those described herein may be used in practice or testing of this invention, acceptable methods and materials are described below. All publications, patent applications, patents, and other cited documents referenced herein are hereby incorporated by reference in their entirety. In case of conflict, this description of the invention, including definitions, will prevail. In addition, the materials, methods, and examples are illustrative only and are not intended to be limiting.

This application incorporates in its entirety US Patent No. PCT/O52007/022719, filed Oct. 26, 2007, and US Prior Application No. No. 61/049406, filed Apr. 30, 2008 by reference.

Other features and advantages will become apparent from the detailed description of the invention that follows and from the claims.

Figure 1 is a block diagram of the conversion of biomass into products and associated products.

Figure 2 is a diagram of the dose profiles for ions, electrons and photons in a condensed phase material.

Figure C is a diagram of the ion beam impact system.

Figures 4A and 48 are diagrams of the energy distribution of the ion beam.

Figure 4C is a diagram of the ion dose profiles in the exposed sample.

Figure 5 is a diagram of a scattering element that includes several sub-regions.

Figure b is a diagram of the ion beam impact system, which includes an ion filter.

Figures 7A-C are energy distribution diagrams for unfiltered and filtered ion beams.

Figure 8 is a diagram of three ion dose profiles corresponding to impact on the sample with ion beams having different average energies.

Figure 9A is a plot of the resulting ion dose profile for the exposed sample based on the three ion dose profiles of Figure 8.

Figure 9B is a diagram of three different ion dose profiles corresponding to ion beams characterized by different average energy and ion current.

Figure 9C is a plot of the resulting ion dose profile based on the three ion dose profiles of Figure 98.

Figure 10A is a diagram of three different ion dose profiles corresponding to impacting the sample with beams of three different types of ions.

Figure 10B is a diagram of the resulting ion dose profiles based on the three ion dose profiles of Figure 10A.

Similar position designation symbols on different drawings indicate similar elements.

З Treatment of biomass with radiation is suitable for obtaining fuel and products. In general, biomass material is physically prepared before radiation treatment.

The material can be prepared to make it more uniform, for example to reduce the particle size, to change the water content, to control the viscosity and the like. The material is subjected to radiation treatment to change the molecular and/or supramolecular structure. In addition, the material can be treated in other ways, for example, in the form of treatment with ultrasonic waves, oxidation, pyrolysis and treatment with steam. The resulting material can be stored or used in a wide variety of ways.

One application is fermentation to produce a combustible product such as alcohol. Microorganisms can be combined with the resulting material and optionally other ingredients. The combination is subjected to fermentation and the product is extracted.

For example, alcohols can be extracted as a result of distillation.

In some embodiments, large-scale radiation is used, for example, for a batch of at least 50 kg, 100 kg, or 500 kg. Processing can also be carried out in a continuous or semi-continuous mode, for example, for material that moves under the radiation beam, for example, when processing at least 100, 500, 1000, 5000 or 20000 kg per hour.

A wide range of biomass materials can be used as a primary material.

Examples of biomass include plant biomass, animal biomass, and municipal waste biomass. Biomass also includes process feedstock materials such as cellulosic and/or lignocellulosic materials.

Often, biomass is a material that includes a carbohydrate such as cellulose. In general, any biomass material that is or includes carbohydrates formed exclusively from one or more saccharide units, or that includes one or more saccharide units, can be processed by any of the methods described herein. links For example, the biomass material can be cellulosic or lignocellulosic materials or starchy materials such as corn kernels, rice kernels or other food products.

Additional examples of biomass materials include paper, paper products, wood, wood-related materials, wood chipboard, grasses, rice bran, bagasse,

cotton, jute, yarn, flax, bamboo, sisal, abaca, straw, corn cobs, rice bran, coconut husk, seaweed, sea grass, cotton, synthetic cellulose or mixtures of any of the data. Other examples are described in document M/O 2008/073186, submitted on October 26, 2007, and in document ). 5. Zegia! Mo. 12/429,045, filed Apr. 23, 2009.

Different biomass materials are often readily available, but - unless pre-treated - can sometimes be difficult to process, for example through fermentation, or can lead to sub-optimal yields at low rates. In the methods described herein, process feedstock materials may first be physically prepared for processing, often by reducing the size of the process's primary feedstock materials. Physically prepared raw materials of the process can be subjected to preliminary treatment or processing using one or more options selected from radiation treatment, ultrasonic wave treatment, oxidation, pyrolysis and water vapor treatment. Various systems and pretreatment methods can be used in combinations of two, three or even four of these technologies.

Combinations of different pretreatment methods are generally described, for example, in document UMO 2008/073186.

In some cases, to produce materials that include a carbohydrate, such as cellulose, that can be converted by a microorganism into several desired products, such as combustible fuels (eg, ethanol, butanol, or hydrogen), a process feedstock that includes one or more saccharide units , may be processed in any one or more of a plurality of ways. Other products and related products that can be obtained include, for example, human food products, animal food products, pharmaceuticals and nutraceuticals. Examples of other products are described in the documents

TSO.5. Zegia! Mo5. 12/417,900, 12/417,707, 12/417,720 and 12/417,731, all of which filed Apr. 2009.

In the case of biomass that is or includes a carbohydrate, it may include, for example, material that contains one or more VD-1,4 linkages and has a number average molecular weight in the range of about 3,000 to 50,000. Such a carbohydrate is by yourself or

Zo includes cellulose (1), which is made from (B-glucose 1) as a result of the condensation of DV(1-24)-glycosidic bonds. This link contrasts with the link for α(1-24)-glycosidic bonds present in starch and other carbohydrates.

Starchy materials include starch itself, such as corn starch, wheat starch, potato starch, or rice starch, a starch derivative, or a material that includes starch, such as an edible food product or starch.

For example, the starchy material may be sorghum, buckwheat, banana, barley, cassava, kudzu, sorghum, sago, sorghum, potato, sweet potato, taro, yam, or one or more legumes such as forage beans, lentils, or pea. Starchy materials are also mixtures of any one or more starchy materials. In specific implementation options, the starchy material is produced from corn.

Various corn starches and derivatives are described in the publication "Sogp eiagsy", Sogp Keipege5

Avv5osiyop (111th Eaiyop, 2006).

Biomass materials that include low molecular sugars can, for example, include at least about 0.595 wt. low molecular sugar, for example, at least about 2, 3, 4, 5.6, 7, 8, 9, 10, 12.5, 25, 35, 50, 60, 70, 80, 90 or even at least about 95 95 wt. low molecular weight sugar. In some cases, the biomass is formed essentially from low molecular weight sugar, for example, by more than 95 95 wt. since 96, 97, 98, 99 or essentially 100 95 wt., from low molecular weight sugar.

Biomass materials that include low molecular weight sugars can be agricultural or food products, such as sugar cane and sugar beet, or an extract thereof, such as sugar cane juice or sugar beet juice.

Biomass materials that include low molecular weight sugars can be essentially pure extracts such as raw sugar or crystallized table sugar (sucrose).

Low molecular weight sugars include derived sugars. For example, low molecular weight sugars can be oligomeric (eg, equal to or greater than 4-dimensional, 5-dimensional, 6-dimensional, 7-dimensional, 8-dimensional, 9-dimensional, or 10-dimensional), trimeric, dimeric, or monomeric.

When carbohydrates are formed from more than one repeating unit, each repeating unit may be identical or different.

Specific examples of low molecular sugars include cellobiose, lactose, sucrose, 60 glucose and xylose, together with their derivatives. In some cases, derived sugars dissolve more quickly in solution or are used by microbes to produce a useful material such as ethanol or butanol.

Combinations of any of the biomass materials described herein (e.g., combinations of any biomass materials, components, products, and /or related products formed using the methods described in this document).

For example, mixtures of cellulosic materials and starchy materials can be used to obtain products.

Fuels and other products (for example, ethanol, bioethanol, other alcohols and other combustible hydrocarbons), obtained by the methods described in this document, can be mixed with other hydrocarbon-containing substances. For example, ethanol produced using any of the methods described herein can be blended with gasoline to produce "gasohol," which can be used as a combustible fuel in a wide variety of applications, including communications with car engines.

Biomass processing methods

Figure 1 shows a system 100 for converting biomass, in particular biomass that largely contains cellulosic and lignocellulosic components and/or starchy components, into acceptable products and related products. System 100 includes process feedstock preparation subsystem 110, pretreatment subsystem 114, main process subsystem 118, and further processing subsystem 122. Process feedstock preparation subsystem 110 receives biomass in its primary form, physically prepares biomass for use as process feedstock in processes, located further down the process stream, (for example, reduces the size and homogenizes biomass) and preserves biomass both in its primary form and in the form of raw materials of the process.

Biomass that largely contains cellulosic and/or lignocellulosic components or starchy components can be characterized by high average molecular weight and degree of crystallinity, which are modified by using one or more pre-treatments to facilitate the use of the material.

The pre-processing subsystem 114 receives the process raw materials from the subsystem

From the preparation of the raw materials of the process 110 and prepares the raw materials of the process for use in the main production methods, for example, due to the reduction of the average molecular weight and the degree of crystallinity of the raw materials of the process and/or the increase of the specific surface area and/or the porosity of the raw materials of the process. In some cases, the pretreated biomass material is characterized by a low moisture content, for example, less than about 7.5, 5, 3, 2.5, 2, 1.5, 1, or 0.5 95 wt. Reducing the amount of moisture can be achieved, for example, as a result of drying the biomass material. Pretreatment methods can avoid the use of aggressive chemical reagents, such as strong acids and bases.

Main process subsystem 118 receives pretreated process feedstock from pretreatment subsystem 114 and produces useful products (eg, ethanol, other alcohols, pharmaceuticals, and/or food). Basic production methods usually include methods such as fermentation (for example, using microorganisms such as yeast and/or bacteria), chemical treatment (for example, hydrolysis) and gasification.

In some cases, the produced product of the main process subsystem 118 is acceptable for immediate use, but in other cases, the produced product requires additional processing carried out in the further processing subsystem 122. The further processing subsystem 122 provides additional processing of product streams from the main process system 118 (for example , in the form of ethanol distillation and denaturation), as well as processing for waste streams from other subsystems. In some cases, the combined products of the subsystems 114, 118, 122 may also be suitable for direct or indirect use as secondary products and/or in terms of increasing the overall efficiency of the system 100. For example, the downstream processing subsystem 122 may allow obtaining purified water that is sent for recycling for use as process water in other subsystems, and/or may allow for incineration waste that can be used as fuel for boilers producing steam and/or electricity. In general, further processing steps may include one or more steps such as distillation to separate other components, wastewater treatment (eg, sieving, organic averaging, sludge conversion), mechanical separation, and/or waste incineration. 60 Ion beam systems for biomass pretreatment

Ion beam pretreatment (for example, exposure to ions) for biomass can be a particularly effective, economical, and highly productive method of treatment.

Ion beam pretreatment generally involves exposing the biomass (treated or not to mechanical processing) with one or more different types of ions generated in one or more ion sources. (They can be accelerated in accelerator systems that are coupled to ion sources and can produce ions of variable energies and velocities. Usually, ion-based preprocessing does not accelerate the ions to energies sufficient to induce significant levels of X-ray radiation Accordingly, the doming and shielding requirements for ion sources can be greatly reduced compared to similar requirements for electron sources.

When ion beam radiation is used, it can be applied to any sample that is dry or wet or even dispersed in a liquid such as water.

For example, ion beam irradiation can be performed on a cellulosic (and/or lignocellulosic) material in which the surfaces wetted by a liquid, such as water, have less than about 25 95 wt. of cellulosic and/or lignocellulosic material. bundle is carried out for cellulosic and/or lignocellulosic material in which no cellulosic and/or lignocellulosic material is wetted with a liquid such as water.

In the case of using ion beam irradiation, it can be applied with simultaneous exposure to cellulosic and/or lignocellulosic material with air, oxygen-enriched air, or even oxygen itself, or in an inert gas atmosphere such as nitrogen, argon, or helium. If oxidation of the biomass material is desired, an oxidizing medium, such as in the case of air or oxygen, will be used, and the properties of the ion beam source can be adjusted to promote the formation of a reactive gas such as ozone and/or nitrogen oxides. These reactive gases react with the biomass material, individually or together with the falling ions, which causes the decomposition of the material. In one example, when ion beam exposure to biomass is used, the ions may impact the biomass under pressure conditions of one or more gases greater than about 2.5 atmospheres, such as greater than 5, 10, 15, 20, or even

More than about 50 atmospheres.

Ions that fall on the biomass material usually scatter on parts of the biomass and ionize them by the Coulomb scattering mechanism. The interaction between ions and biomass can also lead to the production of high-energy electrons (for example, secondary electrons), which can additionally interact with biomass (for example, causing additional ionization). Ions can be positively charged or negatively charged and can have a single positive or negative charge or can be multi-charged, such as singly, doubly, tri- or even quadruplely charged or more. In cases where it is desirable to undergo chain destruction, positively charged particles may be desirable, partly due to their acidic nature.

The ions impinging on the biomass material may have a rest electron mass or may exceed the rest electron mass by, for example, 500, 1000, 1500, or 2000 times or more, such as 10,000 or even 100,000 times. For example, ions can have a mass in the range of about 1 atomic unit to about 150 atomic units, for example, from about 1 atomic unit to about 50 atomic units. or from about 1 to about 25, such as 1, 2, 3, 4, 5, 10, 12, or 15 a.o.m. Examples of ions and ion accelerators are discussed in the publications of Ipigodisiogu Misieag Rpuzis5, Keppeip 5. Kgape, dhopp Umieu 5 5opv,

Ips. (1988).

TNnegaru", Soimtriv-ONio, ISVO-IAEA Meeviipo, 18-20 Magsy 2006, Imaia, U. eyi ai., "APegaiiipd-

Rpaze-Rosyzei IN-OTI. oh Neamu-Iop of Medes! Asseiegayogv5", Rgoseyedipo5 oi ERAS 2006, Ediprigon,

Zsoptsapoa and Iepeg, S. M. ei ai., "Zgayi5 oi She Z!yregsopdisiipd ESEA Iop boshse Mepyv", Rgoseyedipa5

OGERAS 2000, Mieppa, A!yvipa.

A wide range of different types of ions can be used for pretreatment of biomass material. For example, protons, helium nuclei, argon ions, silicon ions, neon ions, carbon ions, phosphorus ions, oxygen ions or nitrogen ions can be used. In some variants of the implementation of idsn can lead to the appearance of higher degrees of destruction of the chain in comparison with what takes place for an equivalent dose of electrons. In some cases, positively charged ions can lead to the appearance of higher degrees of chain destruction and/or degrees of passage of other processes in comparison with what is the case for negatively charged ions, due to their acidity. In an alternative case, depending on the nature of the biomass, in certain variants of implementation, which more effectively lead to the destruction of the chain and/or other processes, there may be negatively charged ions in comparison with what is the case for positively charged ions, due to their alkaline nature.

After generation and/or acceleration, the average energy of the ions in the ion beam may range from about 1.0 MeV/atomic unit to about 6000 MeV/atomic unit, for example, from about 3 MeV/atomic unit to about 4800 MeV/atomic unit or from about 10 MeV/atomic unit to about 1000 MeV/atomic unit.

In general, a variety of different types of ions can be used to irradiate biomass materials. For example, in some embodiments, ion beams may include relatively light ions, such as protons and/or helium ions. In certain embodiments, ion beams may include moderately heavier ions, such as carbon ions, nitrogen ions, oxygen ions, or neon ions. In some embodiments, ion beams may include even heavier ions, such as argon ions, silicon ions, phosphorus ions, sodium ions, calcium ions, and/or iron ions.

In certain embodiments, ion beams used to irradiate biomass materials may include more than one type of ion that is different. For example, ion beams may include mixtures of two or more (eg, three, four, five, six or more) different types of ions. Examples of mixtures may include carbon ions and protons, carbon ions and oxygen ions, nitrogen ions and protons, and iron ions and protons. More generally, mixtures of any of the ions discussed herein (or any other ions) can be used to produce ion beams used to irradiate biomass.

In particular, in one ion beam, mixtures of relatively light and relatively heavier ions can be used, where each of the different types of ions is characterized by excellent efficiency when irradiating different types of biomass materials.

In some implementations, ion beams for irradiation of biomass materials include positively charged ions. Positively charged ions may include, for example, positively charged hydrogen ions (eg, protons), noble gas ions (eg, helium, neon, argon), carbon ions, nitrogen ions, oxygen ions, silicon atoms, phosphorus ions, and metal ions such as as sodium ions, calcium ions and/or iron ions. As you can imagine without wanting to be bound by any theory, such positively charged ions when exerting influence on materials

Biomasses exhibit a chemical behavior similar to that of Lewis acid fragments, initiating and supporting the passage of reactions, such as cationic ring-opening and chain-breaking destruction reactions, in an acidic and/or oxidizing environment.

In certain implementation options, ion beams for irradiation of biomass materials include negatively charged ions. Negatively charged ions may include, for example, negatively charged hydrogen ions (eg, hydride ions) and negatively charged ions of various relatively electronegative nuclei (eg, oxygen ions, nitrogen ions, carbon ions, silicon ions, and phosphorus ions). As one can imagine without being bound by any theory, such negatively charged ions, upon impacting biomass materials, exhibit a chemical behavior similar to that of Lewis base fragments, causing the passage of anionic destruction reactions with cycle opening and chain breaking, mainly and/ or a reducing environment.

In some implementations, beams for irradiating biomass materials may include neutral atoms. For example, beams used to irradiate biomass materials may include any one or more types of atoms selected from hydrogen atoms, helium atoms, carbon atoms, nitrogen atoms, oxygen atoms, neon atoms, silicon atoms, phosphorus atoms , argon atoms and iron atoms. In general, mixtures of any two or more of the above types of atoms (eg, three or more, four or more, or even more) may be present in the bundles.

The previous discussion focused on ion beams, which include mononuclear ions and/or neutral particles (eg, atomic ions and neutral atoms). Of course, such particles are the easiest - from the point of view of energy - to generate, and the parent particles from which these particles are generated can be available in excessive quantities. However, in some embodiments, beams for irradiating biomass materials may include one or more types of ions or neutral particles that are multinuclear, for example, that include multiple nuclei and that even include two or more different types of nuclei. For example, ion beams may include positive and/or negative ions and/or neutral particles formed from particles such as Me», O», H»

SnNae and other molecular particles. Ion beams may also include ions and/or neutral particles formed from heavier particles that include even more nuclei, such as various hydrocarbon-based particles and/or various inorganic particles, including coordination compounds of various metals.

In certain embodiments, ion beams used to irradiate biomass materials include singly charged ions, such as one or more types of ions selected from

NU, NU, Ne", Met, Ag, C, C, 0, 0, M, M, Bi, ZI, Re, R-, Ma", Sa", Ee", VN", I, RE, Ve" , You: and 05. In some embodiments, the ion beams may include multi-charged ions, such as one or more types of ions selected from Ce, Xx, SYA, Mk, Mox, MU, 02, 02-, Og2-, Big» , Bi, 5i2- and 5I-. In general, ion beams can also include more complex polynuclear ions that are multi-charged, being positively or negatively charged. In certain embodiments, due to the polynuclear ion structure, positive or negative charges can be effectively distributed over essentially the entire ion structure. In some implementations, due to the electronic structures of ions, positive or negative charges can be localized to some extent on parts of the ion structure. In general, ion beams used to irradiate biomass materials can include ions - either positive or negative - for any of the molecular particles described herein, and in general the ions can be singly or multi-charged. ion beams may also include other types of ions, positively and/or negatively charged and singly or multi-charged.

Ions and ion beams can be generated using a wide variety of methods.

For example, hydrogen ions (eg, both protons and hydride ions) can be generated by field ionization of hydrogen gas and/or by thermal heating of hydrogen gas. Noble gas ions can be generated as a result of field ionization. Carbon, oxygen and nitrogen ions can be generated as a result of field ionization and can be separated from each other (in the case of their joint generation) when using a hemispherical analyzer. Heavier ions, such as in the case of sodium and iron, can be produced by thermionic emission from an acceptable target material. Acceptable methods of generating ion beams are described, for example, in the previous applications of the US MoMo 61/049406 and 61/073665 and in the document Sh. 5. Zegia! Mo. 1 2/417,699.

A wide range of different particle beam accelerators can be used to accelerate the ions prior to ion impact on the biomass material. For example, acceptable particle beam accelerators include Oupatigop accelerators, Kpoadoigop accelerators),

These are static accelerators, dynamic linear accelerators (for example, GIMAS), Van de Graaf accelerators, and folded tandem Riegehop accelerators. These and other acceptable accelerators are discussed, for example, in US MoM prior applications 61/049406 and 61/073665 and in

U. 5. Sepia! Mo. 12/417,699.

In some implementation options, combinations of two or more different types of accelerators can be used to produce ion beams that ARE acceptable for biomass processing.

For example, a pleated tandem accelerator can be used in combination with a linear accelerator, a CPP accelerator, a UOupatigope accelerator, a static accelerator, or any other type of accelerator that produces ion beams.

Accelerators can be used in series by directing the output ion beams from one type of accelerator to the input of another type of accelerator for additional acceleration. Alternatively, several accelerators can be used in parallel to generate several ion beams during biomass processing. In certain implementation options, several accelerators of the same type can be used in parallel and/or in series to generate accelerated ion beams.

In some implementation options, several similar and/or different accelerators can be used to generate ion beams having different compositions. For example, the first accelerator can be used to generate one type of ion beam, while the second accelerator can be used to generate a second type of ion beam. After that, each of the two ion beams can be further accelerated in another accelerator or can be used for biomass processing.

In addition, in certain implementation options, one accelerator can be used to generate several ion beams during biomass processing. For example, any of the accelerators discussed herein (as well as other types of accelerators) can be modified to produce multiple output ion beams by splitting the primary ion current introduced into the accelerator from the ion source. Alternatively or additionally, any ion beams obtained using any of the accelerators described herein may include only one type of ion or several different types of ions.

In the general case, when using several different accelerators to obtain one or more ion beams 60 in biomass processing, several different accelerators can be arranged in any order relative to each other. This provides great flexibility in obtaining one or more ion beams, each of which has properties carefully selected for biomass processing (for example, for processing different components in biomass).

The ion accelerators described herein can also be used in combination with any other biomass processing steps. For example, in some implementation options for processing biomass, electrons and ions can be used in combination.

Electrons and ions can be obtained and/or accelerated separately and used to process biomass sequentially (in any order) and/or simultaneously. In certain implementation options, electron and ion beams can be obtained in the same accelerator and used for biomass processing. Certain ion accelerators can be configured to produce electron beams as an alternative to, or in addition to, ion beams. For example, to obtain electron beams during the processing of biomass, accelerators BOupatiihopF), accelerators Kpodoihop and I IMAS can be configured.

In addition, ion beam pretreatment of biomass can be combined with other biomass pretreatment methods, such as ultrasonic treatment, pyrolysis, oxidation, steam treatment, and/or irradiation with other forms of radiation (e.g., electrons, gamma rays, X-rays). radiation, ultraviolet radiation). In general, other pretreatment methods, such as pretreatment based on the use of ultrasonic waves, can be carried out before, during or after the pretreatment of biomass based on the use of ions.

Exposure conditions and properties of ion beams

In the general case, when the condensed medium is affected by a beam of charged particles, the charged particles penetrate into the medium and are absorbed in the medium with a depth distribution below the surface on which the particles fall. In general, according to observations (see, for example, figure 1 in Rges (see below, 1997)), the dose distribution for ions includes a much narrower maximum (peak

Bragg), and the ions show much less side scattering compared to what has

It is the place for other particles, such as electrons and neutrons, and other forms of electromagnetic radiation, such as X-rays. Accordingly, due to the relatively well-controlled dose profile of the accelerated ions, they are relatively effective in terms of changing the structure of the biomass material. Furthermore, as is evident from Fig. 6 of Rgeies (see below, 1997), heavier ions (such as carbon ions) are characterized by even narrower dose profiles compared to lighter ions such as as protons, and thus the relative efficiency of these heavier ions in processing biomass material is even greater than that of lighter ions.

In some implementations, the average energy of the accelerated ions falling on the biomass material is 1 MeV/ae or more (for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 20, 30 , 50, 100, 300, 500, 600, 800 or even 1000 MeV/aeem and more).

In certain embodiments, the average energy of the accelerated ions is 10 MeV or greater (eg, 20, 30, 50, 100, 200, 300, 400, 500, 600, 800, 1000, 2000, 3000, 4000, or even 5000

MeV and more).

In certain embodiments, the average speed of the accelerated ions is 0.0005 s or more (for example, 0.005 s or more, 0.05 s or more, 0.1 s or more, 0.2 s or more, 0.3 s or more, 0 .4 s or more, 0.5 s or more, 0.6 s or more, 0.7 s or more, 0.8 s or more, 0.9 s or more), where s is the speed of light in a vacuum U in general, for a given acceleration potential, lighter ions are accelerated to higher velocities compared to heavier ions. For example, for a given acceleration potential, the maximum velocity of a hydrogen ion may be approximately 0.05 s, while the maximum velocity of a carbon ion may be approximately 0.0005 s. These values are examples only; the speed of accelerated ions depends on the applied acceleration potential, the operating mode of the accelerator, the number of passes through the accelerating field, and other such parameters.

In some embodiments, the average ion current of accelerated ions is 105 particles/second or more (eg, 109, 107, 108, 109, 1010, 1011, 1012, 1015, 1014, 1015 or even 1015 particles/second or more).

In slow implementations, the radiation dose delivered to the biomass material by the ion beam is 5 Mrad or more (for example, 10, 15, 20, 30, 40, 50, 60, 80 or 60 even 100 Mrad or more).

When a sample is exposed to an ion beam, the energy in the sample will be absorbed according to the ion dose profile (also sometimes called the depth dose distribution).

Figure 2 shows a schematic diagram illustrating a representative ion dose profile 2010 for a condensed phase biomass sample. The vertical axis of the ion dose profile 2010 in Figure 2 shows the relative ion dose to graphically represent its dependence on the depth shown on the horizontal axis below the surface of the sample affected by the ion beams. Figure 2 also turns off electron dose profile 2020, gamma dose profile 2030, and x-ray dose profile 2040 for comparative purposes.

As shown in Figure 2, both gamma rays and X-rays (and, in addition, other types of electromagnetic radiation) are strongly absorbed in the region adjacent to the sample surface, resulting in the highest energy doses being absorbed near the sample surface. The gamma and X-ray dose profiles 2030 and 2040 decrease approximately exponentially from the surface of the sample, as successively fewer photons have the ability to penetrate deeper for absorption in the sample.

The 2020 electron dose profile demonstrates a ramp-up effect in which, due to the penetrating power of Compton electrons, the absorbed energy dose increases around the exposed sample surface to the maximum absorbed dose at the penetration depth, which is typically about 3-4 cm in condensed media. After that, the relative dose of absorbed energy decreases relatively quickly with increasing distance below the surface of the sample.

In contrast, ion beams are usually characterized by dose profiles that are sometimes described as the inverse of electron and photon dose profiles. As shown in Figure 2, the ion dose profile 2010 includes a region 2012 in which the sample is exposed to a relatively constant energy dose. Thereafter, the ion dose profile 2010 includes a region 2014 called a peak

Bragg, which corresponds to the part of the sample in which a relatively larger fraction of the energy of the ion beams is absorbed, followed by the region 2016, in which a much smaller dose of energy is absorbed. Peak

Bragg, which is characterized by the full width at half maximum (FWMF) b, provides a significant difference in the dose profile for ions from the dose profiles for electrons and photons of different wavelengths. As a result of impacting materials such as biomass materials,

With an ion beam can lead to the appearance of effects that differ from the effects created by photons and electron beams.

Of course, the width of the b Bragg peak 2014 depends on several factors, including the nature of the sample, the type of ions, and the average energy of the ions. One important factor that affects the width of the 2014 Bragg peak b is the distribution of energies in the incident ion beams. In general, the narrower the energy distribution in the incident ion beams, the narrower the width b of the 2014 Bragg peak. In one example, for an ion energy distribution characterized by a PSPM value of 1 keV or less, the 2014 Bragg peak typically has a width of which is approximately 3 mm and less. The width of Bragg peak 2014 in these conditions can also be much smaller than 3 mm, for example, equal to 2.5 mm and less, 2.0 mm and less, 1.5 mm and less, 1.0 mm and less.

The position of the 2014 Bragg peak, denoted by the symbol y in Figure 2, depends on several factors, including the average energy of the incident ion beams. In general, for higher average ion beam energies, the 2014 Bragg peaks in Figure 2 will shift to greater depths, as ions with higher energies have the ability to penetrate deeper into the material before most of the kinetic energy of the ions is lost due to scattering phenomenon.

Various properties of one or more incident ion beams can be adjusted in order to affect samples (for example, biomass materials) with ion beam radiation, which can lead to depolymerization and other chain destruction reactions in the samples, which reduce the molecular weight of the samples in a predictable and controlled manner .

Figure C shows a schematic diagram explaining an ion beam exposure system 2100. System 2100 includes an ion source 2110 that generates ion beams 2150. Optical elements 2120 (including, for example, lenses, apertures, deflectors, and/or other electrostatic and or magnetic elements for adjusting the ion beams 2150) guide the ion beams 2150, ensuring that it falls on the sample 2130, which has a thickness and in a direction normal to the surface 2135 of the sample 2130. In addition to directing the ion beam 2150, the optical elements 2120 can be used to control various properties of the ion beam 2150, including collimation and focusing of the ion beam 2150. The sample 2130 typically includes, for example, one or more of the different types of biomass materials discussed herein. System 2100 also includes an electronic controller 2190 that is in electrical communication with various system components (and other components not shown in Figure 3). The electronic controller 2190 can controllably maintain and/or adjust any of the system parameters described herein, either fully automatically or in response to input from a human operator.

Figure C also shows the ion dose profile that results from exposing the sample 2130 to the ion beam 2150. The position 2160 of the Bragg peak in the sample 2130 depends on the average energy of the ion beam 2150, the nature of the ions in the ion beam 2150, and the material from which the sample 2130 is made. , and other factors.

In many applications of ion beams, such as ion therapy for radical tumor removal, the relatively small width of the b Bragg peak 2014 is advantageous, as it allows for fairly fine targeting of specific tissues in the patient undergoing therapy and helps reduce damage from exposure to adjacent benign tissues.

However, when impacting biomass materials, such as sample 2130, with ion beam 2150, the relatively small width of the b Bragg peak 2014 may limit performance. Of course, for example, the thickness y of the sample 2130 is greater than the width b of the Bragg peak 2014. In some embodiments, the value of y may be significantly larger compared to the value of b (eg, large by a factor of 5 or more or 10 or more, or 20 or more, or 50 or more, or 100 or more, or even more).

To increase the thickness of the sample 2130 for which the selected dose can be delivered during a specific time interval, the energy distribution of the ion beam 2150 can be adjusted. Various methods can be used to adjust the energy distribution of the ion beam 2150. One such method is to use one or more removable scattering elements 2170 located in the path of the ion beam 2150, as shown in Figure 3. The scattering element 2170 may be, for example, a thin membrane made of a metal-based material such as tungsten, tantalum, copper, and/or a polymer-based material such as polymer I isyef).

Before passing through the scattering element 2170, the ion beam 2150 is characterized by the energy distribution width m shown in Figure 4A. When the ion beam 2150 passes through the element(s) 2170, at least some of the ions in

From the ion beam 2150 will be affected by scattering phenomena on the atoms in the element (elements) 2170 with the transfer of part of the kinetic energy of the ions to the atoms of the element (elements) 2170. As a result, the energy distribution for the ion beam 2150 widens to a width B, greater than the value of mu, as shown in Figure 48. In particular, as a result of scattering on the element(s) 2170, the energy distribution of the ion beams 2150 acquires a broadened low-energy tail.

Figure 4C demonstrates the effect of broadening the ion energy distribution of the ion beam 2150 on the ion dose profile in the sample 2130. The ion dose profile 2140a is obtained as a result of impacting the sample 2130 with the ion beam 2150, characterized by the ion energy distribution shown in Figure 4A. The ion dose profile of 2140a includes a relatively narrow peak

Bragg. As a result, the region of sample 2130 in which a relatively large dose is absorbed is small. In contrast, as a result of the broadening of the ion energy distribution of the ion beam 2150 to obtain the distribution shown in Figure 4B, in the sample 2130 after impacting the sample using the broadening of the ion energy distribution, the ion dose profile 2140r is obtained. As demonstrated by the dose profile 2140B0, due to the broadening of the ion energy distribution, the region of the sample 2130 in which a relatively high dose is absorbed increases compared to what is the case for the ion dose profile 2140a. As a result of increasing the area of the sample 2130 exposed to a relatively large dose, the performance of the exposure method can be improved.

In certain embodiments, the width B of the broadened energy distribution may be greater than the value of mu by a factor equal to 1.1 or more (for example, 1.2, 1.3, 1.4, 1.5, 1.7, 2.0, 2.5,

BO 3.0, 3.5, 4.0, 5.0 or even 10.0 or more).

Typically, the ion dose profile in sample 2130 resulting from exposure to the sample using the broadened ion energy distribution shown in Figure 4B includes a Bragg peak characterized by full width at half maximum (FMF).

Due to the broadening of the ion energy distribution, the value of ε can be greater than the value of b by a factor of 1.1 or more (for example, 1.2 or more, 1.3 or more, 1.5 or more, 1.7 and more, 2.0 or more, 2.5 or more, 3.0 or more, 4.0 or more, 5.0 or more, 6.0 or more, 7.0 or more, 10.0 or more) .

For sample 2130 with a thickness of P, after broadening the energy distribution of ions of ion beams 2150 and impacting the sample with an ion beam, the ratio е/п can be 1x1055 or more

(for example, 1x107, 5x10-5, 1x10-5, 5x10-7, 1x10-3, Bx103, 0.01, 0.05, 0.08, 0.1 or even 0.5 or more).

In certain embodiments, the sample 2130 includes a plurality of particles (eg, approximately spherical particles and/or fibers, and/or elementary fibers, and/or other types of particles). In general, particles are characterized by different size distributions with an average particle size g. To improve the efficiency of ion-based sample processing 2130, the ion energy distribution of ion beams 2150 can be adjusted (eg, due to broadening) based on the average particle size g of the sample 2130.

For example, the ion beam 2150 can be adjusted such that the y/g ratio is 0.001 or greater (eg, 0.005 or greater, 0.01 or greater, 0.05 or greater, 0.1 or greater, 0.5 and more, 1.0 or more, 1.5 or more, 2.0 or more, 2.5 or more, 3.0 or more, 3.5 or more, 4.0 or more, 5.0 or more, 6.0 or more, 8.0 or more, 10 or more, 50 or more, 100 or more, 500 or more, 1000 or more or even more).

In some embodiments, the scattering element 2170 may include several different scattering sub-elements, which are configured to broaden the distribution of ion energies in the ion beam 2150 to different degrees. For example, Figure 5 shows a scattering element consisting of a plurality of sub-elements 2170, which includes sub-elements 2170a-e. Each of the sub-elements 2170a-e widens the distribution of ion energies in the ion beam 2150 to an excellent degree.

During operation of the system 2100, the electronic controller 2190 may be configured to select an appropriate sub-element of the scattering element 2170 based on information such as the thickness P of the sample 2130, the type of ions in the ion beam 2150, and the average energy of the ions in the ion beam 2150. Selection of the appropriate sub-element may be made in fully automatic mode or may be based at least partially on input from a human operator. The selection of the appropriate sub-element is done by moving the scattering element 2170 in the direction shown by the arrow 2175 to position the selected sub-element in the path of the ion beam 2150.

In certain implementations, other devices can be used in addition to the scattering element(s) 2170 or as an alternative to it. For example, in some implementation options, to broaden the energy distribution of the ions of the ion beam 2150, there may be

Combinations of electric and/or magnetic fields created by ion-optical elements are used. The ion beam 2150 may pass through a first field configured to spatially disperse ions in the ion beam. After that, the spatially dispersed ions can pass through the second field, which is well localized in space, and which selectively traps only a part of the spatially dispersed ions. The ions can then pass through a third field that re-collects all the ions in space into a collimated beam that is then directed onto the sample surface 2130. Typically, the ion optics used to generate the fields that control the ion energy distribution are controlled by an electronic controller 2190 As a result of the selective application of spatially localized fields, a high degree of control of the modified ion energy distribution can be provided, including the generation of ion energy distributions characterized by complicated profiles (for example, in a multi-petal configuration). For example, in some embodiments, due to the application of a localized field that accelerates part of the spatially dispersed ion distribution, the ion energy distribution shown in Figure 4A can be broadened on the high-energy side of the maximum of the distribution.

The information used by the electronic controller 2190 to adjust the ion energy distribution of the ion beam 2150 may include the thickness PP of the sample 2130, as discussed previously. In some embodiments, to adjust the ion energy distribution of the ion beam 2150, the electronic controller 2190 can use information about the expected ion dose profile in the sample 2130. The information about the expected ion dose profile can be obtained, for example, from a database that includes the results of changes in ion dose profiles , established based on literature sources and/or calibration experiments performed on representative samples of the material from which sample 2130 is obtained. Alternatively or additionally, information regarding the expected ion dose profile may be determined based on a mathematical model of ion interactions in sample 2130 (e.g., ion scattering models).

In certain implementation options, the information regarding the expected ion dose profile may include information regarding the value of the Bragg peak PSHPM in the expected ion dose profile.

The value of the PSPM of the Bragg peak can be determined based on the results of measurements of ion dose profiles and/or based on one or more mathematical models of ion scattering in the sample. Adjustment of the ion energy distribution of the ion beam 2150 can be carried out to reduce the difference between the thickness Pp of the sample 2130 and the PSIM value of the Bragg peak. In some embodiments, for example, the difference between the value of y and the full width at half maximum of the Bragg peak is 20 cm or less (eg, 18, 16, 14. 12, 10.8.6 cm, 5, 4, 3.2, 1,0.5,0.1,0.05,0.01, 0.001, 0.0001 or even 0.00001 cm and less or even zero).

In some implementations, the ion beam impact system can regulate the distribution of ion energies in the ion beam 2150 in a different way. For example, the ion beam exposure system may be configured to filter the ion beam by removing from the ion beams 2150 ions having energies less than a selected energy threshold and/or greater than a selected energy threshold. Figure 6 shows an ion beam exposure system 2200 that includes an ion filter 2210, which is discussed in more detail below. Other components of system 2200 are similar to those of system 2100 and will not be discussed further.

Figure 7A shows the ion energy distribution corresponding to the ion beam 2150 obtained from the ion source 2110. The ion beam 2150, characterized by the energy distribution shown in Figure 7A, enters the ion filter 2210, where the energy distribution of the ion beam 2150 is adjusted due to filtering from the ion a beam of certain ions. For example, in some embodiments, the ion filter 2210 may be configured to remove from the ion beam 2150 ions that have an energy lower than a selected energy threshold. On the figure

AND the selected energy threshold represents the position of Eo at the peak in the ion energy distribution despite the possibility of choosing any energy threshold in the more general case.

As a result of filtering out all (or even just a large fraction) of ions having an energy less than the Eo value, the ion energy distribution for the ion beam 2150 will be that shown in Figure 7B.

In contrast, in some implementations, the ion filter 2210 can be configured to remove from the ion beams 2150 ions that have an energy greater than the selected energy threshold (in the case of implementing the ion filter 2210, for example, in the form of a hemispherical analyzer). For example, the selected energy threshold may correspond to the position of Es at the peak in the ion energy distribution, despite the possibility of choosing any energy threshold in the more general case. As a result of removing from the ion beam 2150 all (or even a large fraction) of the ions having an energy greater than the Eo value, the ion energy distribution for the ion beam 2150 will be that shown in Figure 7.

In certain implementations, the sample 2130 may be directly exposed to the filtered ion beam 2150. As a result of filtering the ion beam, for example, to achieve a narrower ion energy distribution, the ion dose profile in the sample 2130 after exposure to the sample will be narrower compared to had 6th place otherwise in the absence of filtering of the ion beams 2150. As a result, the width of the Bragg peak in the sample 2130 will be smaller compared to the width of the Bragg peak for the unfiltered ion beam.

As a result of the impact on the sample 2130 when using a narrower energy distribution of incident ions, improved control of the position of the ion beams 2150 can be achieved; this level of control of exposure to Iysna may be acceptable for use in exposure to various types of sample materials that require careful handling.

Alternatively, the filtered ion beam may then be passed through one or more scattering elements and/or one or more other devices to increase the width of the ion energy distribution. This two-stage approach to modifying the ion energy distribution—a first filtering stage followed by a second broadening stage—can be used to obtain ion energy distributions that are specifically designed for specific applications (e.g., specific to certain types of ions and/or certain materials and/or certain pre-treatment conditions), which may be impossible to achieve when using a simpler one-stage method of broadening the energy distribution.

In one example, by first filtering the ion beam 2150 and then passing the filtered ion beam through one or more scattering elements 2170 , the shape of the ion energy distribution can be made more Gaussian compared to what would otherwise be possible using only the scattering stage instead of the two-stage technique.

The ion filter 2210 may include one or more devices from a wide variety of different devices for removing ions from the ion beam 2150. For example, in some embodiments, the ion filter 2210 includes a hemispherical analyzer and an aperture filter.

The hemispherical analyzer includes a magnetic field source that disperses the ions of the bo 2150 ion beam according to their kinetic energies. After that, on the path of the dispersed ion beam

2150 place an aperture filter to ensure passage through the aperture of only ions characterized by a specific range of energies.

In certain implementations, other devices may be used to filter the ion beam 2150. For example, absorbing elements (eg, elements configured to absorb incident ions having energies less than a selected energy threshold) may be used to filter the ion beam 2150 . Acceptable absorbent elements include, for example, metal foil.

In some implementations, the ion beam 2150 (and, in particular, the Bragg peak in the expected ion dose profile obtained according to the impact on the sample 2130 with the ion beam 2150) may be scanned over the sample 2130 to deliver selected doses of radiation to different parts of the sample. In general, the position of the Bragg peak in the sample 2130 can be selected by adjusting the average energy of the ion beam 2150 (the average energy of the ion beam 2150 usually corresponds to a maximum in the ion energy distribution). The ion source 2110 under the control of the electronic controller 2190 can adjust the average energy of the ion beam 2150 due to a change in the pulling voltage applied to accelerate the ions in the ion source.

Figure 8 is a schematic diagram illustrating the possibility of performing a Bragg peak pattern sweep of the ion dose profile in the sample 2130. In a first step, the ion impact system 2100 is configured to produce a first ion beam having a selected average ion energy corresponding to a particular extraction voltage. , applied to the ion source 2110. If the sample 2130 is exposed to the first ion beam in the sample, an ion dose profile of 2010a will result if the Bragg peak has a position of 2230a. After exposure, the pulling voltage in the ion source 2110 is adjusted to produce a second ion beam having a distinct average ion energy. If the sample 2130 is exposed to the second ion beam in the sample, the result will be an ion dose profile of 20100. As a result of the subsequent repetition of the adjustment of the pulling voltage in the ion source 2110 to obtain additional beams having excellent average ion energies (and therefore characterized by excellent ion dose profiles, for example, with an ion dose profile of 2010sb), and impacting the sample with 2130 additional beams, a peak sweep can be carried out

From the Bragg of the ion dose profile across the sample 2130, for example, in the direction shown by the arrow 2220. However, in a more general case, as a result of changing the pulling voltage in the ion source 2110, the position of the Bragg peak in the sample 2130 can be selected in a desired manner, which ensures the delivery of high doses to selected areas of sample 2130 in any sequence.

In the general case, other properties of the ion beam 2150 can be adjusted in addition to or as an alternative to adjusting the average energy of the ions in the ion beam. For example, in some implementations, the divergence angle of the ion beam 2150 can be adjusted to control the ion dose profile in the sample 2130 surface of the sample 2130. In the general case, as a result of increasing the divergence angle of the ion beam 2150 on the surface of the sample 2130, the full width at half maximum of the Bragg peak in the sample 2130 can be increased. Thus, in certain implementation options, due to the adjustment of the divergence angle of the ion beams, the average energy of the ion beam can be preserved, but the ion dose profile in the material - including the position of the Bragg peak - can be changed.

The angle of divergence can be adjusted in automatic mode or when using the electronic controller 2190 under the control of the operator. Typically, optical elements 2120 include one or more ion beam control elements, such as quadrupole and/or octupole deflectors. As a result of adjusting the potentials applied to the various electrodes of such deflectors, the angle of divergence (and the angle of incidence) of the ion beam 2150 on the surface of the sample 2130 can be adjusted.

In some implementations - in contrast to other fields of application of ion beams, such as surgery - it may be advantageous to use ion beams characterized by relatively large divergence angles, which provides peak coverage

Bragg, positioned in the sample 2130, an acceptable fraction of the thickness of the sample 2130. For example, in certain implementation options, the sample 2130 can be exposed to an ion beam characterized by a divergence angle equal to 2 degrees or more (for example, 5, 10, 15, 20 , 30, 40 or even 50 degrees or more).

In some implementations, both the ion beam current in the ion beam 2150 and the average energy of the ions in the ion beam 2150 can be adjusted to deliver a relatively constant dose depending on the thickness Pp of the sample 2130. For example, in the case of exposure to the sample 2130 according to sequential profiles ion dose 2010a, 201060 and 2010c in figure 8 because the resulting ion dose profile in sample 2130 will correspond to the sum of profiles 2010a-c, which is shown in figure UA. Based on the resulting ion dose profile of Figure 9A, it is apparent that certain areas of sample 2130 receive higher resulting doses compared to other areas of sample 2130.

Differences in the resulting dose can be reduced by adjusting the ion beam current in the ion beam 2150 in conjunction with adjustments to the average ion energy. The ion beam current can be adjusted in the ion source 2110 under the control of the electronic controller 2190. For example, to reduce the difference in the resulting dose delivered to the sample 2130 in the case of performing a Bragg peak sweep on the sample 2130 in the direction indicated by the arrow 2220 in Figure 8, the ion beam current of the beam can be successively reduced for each successive decrease in the energy of the ion beam. As profiles 2010a, Figure 98 shows, respectively, three ion dose profiles, each corresponding to a successive decrease in both the average ion energy and ion current in ion beam 2150. The resulting ion dose profile in sample 2130, which is the result data of three consecutive exposures, shown in figure 9C. The resulting ion dose profile shows significantly reduced variation with position in sample 2130 compared to the resulting ion dose profile of Figure 9A.

As a result of careful management of the average energy and ion current of the ion beam 2150, variations in the resulting relative ion dose across the thickness of the sample 2130 after impacting the sample with the ion beam 2150 can be relatively small. For example, the difference between the maximum resulting relative ion dose and the minimum resulting relative ion dose in sample 2130 after multiple exposures to ion beam 2150 may be 0.2 or less (eg, 0.15, 0.1, 0.05, 0.04, 0.03, 0.02, 0.01 or even 0.005 and less).

As a result of controlling the average energy and ion current of the ion beam 2150, each part of the exposed sample after several exposures to the ion beam can receive a resulting dose in the range of 0.001 Mrad to 100 Mrad (for example, from 0.005 Mrad to 50

Mrad, from 0.01 Mrad to 50 Mrad, from 0.05 Mrad to 30 Mrad, from 0.1 Mrad to 20 Mrad, from 0.5

Mrad to 20 Mrad or from 1 Mrad to 10 Mrad).

In some embodiments, sample 2130 may be exposed to different types of ions.

The sample 2130 may be sequentially exposed to only one type of ion at a time, or exposure to the sample 2130 may include exposing the sample 2130 to one or more ion beams that include two or more different types of ions. Different types of ions produce different ion dose profiles in the exposed material, and as a result of impacting the sample with different types of ions, a specific resulting ion dose profile can be realized in the sample. Figure 10A shows a schematic diagram illustrating three different ion dose profiles 201094 resulting from exposing sample 2130 to three different types of ions.

Ion dose profiles 2010d-i can be obtained by sequentially exposing the sample to each of the different types of ions or by simultaneously exposing the sample to two or even all three different types of ions. The resulting ion dose profile in sample 2130 resulting from exposure to three different types of ions is shown in Figure 108. The variation in the resulting ion dose profile with sample thickness is reduced compared to that of any one of the individual profiles. ion dose shown in figure 10A.

In some embodiments, different types of ions may include ions of different atomic composition.

For example, various types of ions may include protons, carbon ions, oxygen ions, hydride ions, nitrogen ions, chlorine ions, fluorine ions, argon ions, neon ions, krypton ions, and various types of metal ions such as sodium ions, calcium ions, and lithium In general, any of these different types of ions can be used to process the sample 2130, and each will create a distinct ion dose profile in the sample. In certain embodiments, ions may be generated from commonly available gases such as air. When air is used as a source gas, a variety of different types of ions can be generated. Various distinct types of ions may be separated from each other prior to exposure to sample 2130, or sample 2130 may be exposed to several different types of ions generated from a source gas such as air.

In some embodiments, different types of ions may include ions having different charges.

For example, different types of ions may include different positive and/or negative ions. In addition, different types of ions may include ions that are singly and/or multi-charged. In general, positive and negative ions of the same chemical particles can lead to different ion dose profiles in a specific sample, and ions of the same chemical particles that have different charge values can lead to different ion dose profiles in a specific sample (for example, they are single-charged, double-charged, triple-charged, because they are four-charged). By exposing a sample to several different types of ions, a change in the sample can be carefully and selectively controlled, such as sample destruction (eg, depolymerization, chain destruction, and/or molecular weight reduction), functionalization, or other structural change.

In some implementation options, the ion beam exposure system can adjust the composition of the ion beam based on the sample material. For example, certain types of sample, such as cellulosic biomass, include a high concentration of hydroxyl moieties. Accordingly, the effective penetration depth of certain types of ions - in particular, protons - into such materials can be significantly greater than what would otherwise be expected based on ion energy alone. Jumping of a proton from one active center to another and other similar movements of atoms can significantly increase the mobility of such ions in the sample, which effectively increases the penetration depth of incident ions. In addition, the increased mobility of ions in the sample can lead to a broadening of the Bragg peak. The ion beam exposure system can be configured to select specific types of ions to impact certain samples, taking into account the chemical and structural characteristics of the sample. In addition, the ion beam impact system can be configured to account for the expected interactions between the ion beam and the material when determining ways to modify other parameters of the ion beam, such as the distribution of ion energies in it.

One important aspect of the ion beam systems and methods described herein is that the systems and methods described make it possible to ionize biomass in the presence of one or more additional fluid media (eg, gases and/or liquids). . Of course, for example, when impacting the material with an ion beam, the impact is exerted in a low-pressure environment, such as in the case of a vacuum chamber.

A reduced pressure environment is used to reduce or prevent contamination of exposed material, as well as to reduce or prevent ion beam scattering by gas molecules. Unfortunately, however, impacting materials with an ion beam in closed environments, such as a vacuum chamber, significantly limits the potential productivity of large-scale materials processing.

As should be understood, in the systems and methods described herein, exposure to biomass with an ion beam in the presence of one or more additional fluids can increase the efficiency of biomass processing. In addition, impacting biomass with an ion beam in an open environment (eg, in air at normal atmospheric pressure) provides a much higher yield compared to what would otherwise be possible in a reduced pressure environment.

As discussed earlier, in some embodiments, the biomass is exposed to an ion beam in the presence of a fluid medium, such as air. Ions accelerated in any one or more types of accelerators described herein (or another type of accelerator) exit the accelerator through an outlet (eg, a thin membrane such as a metal foil), pass through a volume of space, occupied by the fluid medium, and after that ensure their fall on the biomass material. In addition to the direct processing of biomass, some of the ions generate additional chemical particles as a result of interaction with particles of the fluid medium (for example, ions and/or radicals generated from various air components). These generated chemical particles can also interact with biomass and can act as initiators for a wide range of different chemical bond destruction reactions in biomass (for example, depolymerization and other chain destruction reactions).

In certain implementation options, additional fluids can be selectively introduced along the path of the ion beam before the ion beam falls on the biomass. As discussed earlier, reactions between ions and particles of the injected fluids can generate additional chemical particles that react with the biomass and can contribute to reducing the molecular weight of the biomass and/or otherwise selectively changing certain properties of the biomass. One or more additional fluids can be sent to the path of the ion beam, for example, from a feeding tube. The direction (i.e., vector of the fluid medium) and flow rate of the fluid medium(s) injected may be selected according to the desired degree and/or direction of effect in terms of managing the efficiency of the overall biomass treatment, including as effects resulting from the treatment that is based on the use of ions, as well as the effects caused by the interaction between dynamically generated particles from the introduced fluid medium and biomass. In addition to air, examples of fluids that may be introduced into the ion beam include oxygen, nitrogen, one or more noble gases, one or more halogens, and hydrogen.

In some embodiments, ion beams that include more than one distinct type of ion may be used to treat biomass. As a result of combining two or more different bundles,

each of which is formed by one type of ion, beams can be generated that include several different types of ions. Alternatively or additionally, in certain implementations, ion beams that include a plurality of different types of ions can be generated by introducing a multicomponent feed gas into the ion source and/or accelerator.

For example, a multicomponent gas such as air can be used to generate ion beams that include various types of ions, including nitrogen ions, oxygen ions, argon ions, carbon ions, and other types of ions. Other multicomponent materials (for example, gases, liquids, and solids) can be used to generate ion beams with different compositions. Filter elements (for example, hemispherical electrostatic filters) can be used to filter out certain ionic components and/or neutral particles in order to selectively obtain an ion beam having a specific composition, which can then be used for biomass processing. Due to the use of air as a source for receiving ion beams in the processing of biomass, operating costs for the processing system can be reduced compared to what is the case for systems that, for example, are based on the use of clean materials.

Certain types of biomass materials may prove particularly amenable to processing with multiple different types of ions and/or multiple processing methods. For example, cellulosic materials usually include crystalline polymer cellulose chains that are cross-linked by an amorphous hemicellulose fraction. Cellulose and hemicellulose are incorporated into the amorphous lignin matrix. Separation of the cellulose fraction from lignin and hemicellulose using conventional methods is difficult and may be energy-intensive.

However, cellulosic biomass can be treated with a variety of different types of ions to break down and separate its various components for further processing. In particular, the chemical properties of various types of ionic particles can be used for the processing of cellulosic biomass (and other types of biomass) for the purpose of selective decomposition and separation of its components. For example, positively charged ions - and, in particular, protons - perform the function of acids when they influence the biomass material. On the contrary, negatively charged ions, in particular hydride ions, perform the function of bases when they influence the biomass material. As a result, the chemical properties of these particles can be used for

By targeting specific components of biomass that can be processed.

In the case of processing lignocellulosic biomass, for example, the lignin matrix will usually decompose in the presence of basic chemical reagents. Accordingly, as a result of initial treatment of cellulosic biomass with basic ions, such as hydride ions (or electrons) from an ion (electron) beam, the lignin fraction can be subjected to preferential decomposition and separation from cellulosic and hemicellulosic fractions. Cellulose is relatively unaffected by this treatment with ions, since cellulose is usually stable in the presence of basic additives.

In addition to negative ion treatment (or as an alternative to negative ion treatment), lignocellulosic biomass can be treated with one or more basic additives in solution to promote lignin separation. For example, treatment of lignocellulosic biomass with sodium bicarbonate solution can lead to decomposition and/or solubilization of lignin, which makes it possible to separate solvated and/or suspended lignin from cellulose and hemicellulose fractions.

Treatment with negative ions when using an ion beam can also contribute to the separation of hemicellulose, which is also chemically sensitive to basic chemical reagents. Depending on the specific structure of the cellulosic biomass, more than one negative ion treatment may be used (and/or may be necessary) to effectively separate the hemicellulosic fraction from the cellulosic fraction. In addition, more than one type of ion can be used to separate the hemicellulose. For example, a beam of relatively less basic ions, such as a beam of oxygen ions, can be used to treat cellulosic biomass in order to decompose and/or remove the lignin fraction. After that, an ion beam of stronger bases, such as a hydride ion beam, can be used to decompose and separate the hemicellulose from the cellulose. As a result of exposure to two different types of basic ions, the cellulose fraction remains relatively unchanged.

However, the cellulose fraction decomposes in the presence of acidic additives. Accordingly, an additional processing step may include exposing the cellulosic fraction to one or more acidic ions, such as protons, from an ion beam to promote depolymerization and/or decomposition of the cellulosic fraction.

In each case, the ion beam pretreatments and methods described herein may be used in combination with other processing steps. Example,

separation steps (involving the introduction of a solvent such as water) can be used to elute specific fractions of the cellulosic biomass as it decomposes. Additional chemical additives may be added to aid in the separation of the various components. For example, according to observations, lignin, which is separated from cellulose and hemicellulose fractions, can be suspended in the washing solution. However, lignin can easily redeposit from the solution into cellulose and hemicellulose fractions. To avoid re-precipitation of lignin, the slurry can be gently heated to ensure that the lignin is kept below its glass transition temperature and therefore kept in a fluid state. By keeping lignin below its glass transition temperature, lignin can be more easily washed out of the cellulosic biomass. In general, the heating of the suspension is carefully controlled to avoid thermal decomposition of the sugar in the cellulose fraction.

In addition to this, other processing stages can be used to remove lignin from cellulose and hemicellulose. For example, in certain embodiments, lignocellulosic biomass may first be treated with relatively heavy ions (e.g., carbon ions, oxygen ions) to degrade lignin, and then cellulose and hemicellulose may be treated with relatively light ions (e.g., protons, helium ions). and/or electrons to stimulate the decomposition of cellulose and/or hemicellulose.

In some implementation options, one or more functionalizing additives can be added to the suspension containing lignin to improve the solubility of lignin in the solution and, thereby, create obstacles for its re-precipitation on cellulose and hemicellulose fractions.

For example, additives such as ammonia gas and/or different types of alcohols can be used to functionalize lignin (for carrying amino and hydroxy/alkoxy groups, respectively).

In certain implementation options, structural additives can be added to the lignin suspension to prevent re-precipitation of lignin into cellulose and hemicellulose fractions. Usually, when lignin forms a matrix surrounding cellulose and/or hemicellulose, lignin acquires a strongly folded structure, which ensures the implementation of relatively extensive van der

Waals with cellulose and hemicellulose. In contrast, when lignin is separated from cellulose and hemicellulose, lignin acquires a more open, unfolded structure. Due to the addition of one or more additives to the lignin suspension, which contribute to the prevention

From the reassembly of lignin, the reassociation of lignin with cellulose and hemicellulose can be hindered, and the lignin can be more effectively removed, for example, by washing.

In some implementations, no chemical reagents, such as additives that contribute to swelling, are added to the biomass before irradiation. For example, alkalis (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonium hydroxides), acidifiers (such as mineral acids (such as sulfuric acid, hydrochloric acid, and phosphoric acid) may or may not be added prior to irradiation or other processing. acid)), salts such as zinc chloride, calcium carbonate, sodium carbonate, benzyltrimethylammonium sulfate, or basic organic amines such as ethylenediamine. In some cases, no additional water is added. For example, biomass before processing may contain less than 0.5 95 wt. added chemical reagents, for example, less than 0.4, 0.25, 0.15 or 0.1 95 wt. added chemical reagents. In some cases, the biomass before irradiation contains no more than trace amounts, for example, less than 0.05 95 wt., of added chemical reagents. In other cases, the biomass before irradiation contains essentially no added chemical reagents or additives that promote swelling. The possibility to avoid the use of such chemical reagents can also be extended to the entire processing, for example, for any period of time before fermentation or simply for any period of time.

The various ion beam pretreatment methods described herein can be used in conjunction with other pretreatment techniques such as ultrasonic wave treatment, electron beam irradiation, electromagnetic irradiation, steam treatment, chemical methods, and biological methods. Techniques using ion beams provide significant advantages, including the possibility of impacting dry samples with ion beams, delivering large doses of radiation to samples in short periods of time for high-performance fields of application, and implementing relatively precise control of exposure conditions.

Neutralization of active centers and controlled functionalization

After treatment with ionizing radiation, the materials described in this document become ionized; that is, they contain radicals at content levels that can be detected using an electron paramagnetic resonance spectrometer. The existing practical detection limit for radicals is approximately 107 spins at room temperature. After ionization, any material that has been ionized can be subjected to neutralization of active sites to reduce the level of radicals in the ionized material, for example, such that the radicals can no longer be detected using an electron paramagnetic resonance spectrometer. For example, radicals can be neutralized by adding sufficient pressure to the material and/or by using in contact with the ionized material a fluid such as a gas or liquid that reacts with the radicals (neutralize them). The use of a gas or liquid to at least aid radical neutralization also allows the operator to control the functionalization of the ionized material using the desired amount and type of functional groups, such as carboxylic acid groups, enol groups, aldehyde groups, nitro groups, nitrile groups, amino groups, alkylamino groups, alkyl groups, chloroalkyl groups or chlorofluoroalkyl groups. In some cases, such neutralization of active centers can improve the stability of some ionized materials.

For example, neutralization of active centers can improve the resistance of the material to oxidation.

Functionalization due to neutralization of active sites can also improve the solubility of the materials described herein, can improve the thermal stability of the material, and can improve the degree of utilization of the material by various microorganisms. For example, functional groups introduced into the biomass material due to the neutralization of active centers can function as receptor sites for the attachment of microorganisms, for example, to improve the hydrolysis of cellulose by various microorganisms.

Thus, the molecular and/or supramolecular structure of the raw material of the process can be changed due to the pretreatment of the raw material of the process with ionizing radiation, such as in the case of electrons or ions having energy sufficient to ionize the raw material of the process in order to obtain the first level of radical content. If the ionized raw material of the process is kept in the atmosphere, it will oxidize, which, for example, will cause the formation of carboxylic acid groups due to the reaction with atmospheric oxygen. In some cases, for some materials, such oxidation is desirable because it can contribute to additional reduction in molecular weight, such as carbonaceous biomass, and groups formed during oxidation, such as carboxylic acid groups, can be beneficial in terms of solubility and utilization by microorganisms.

However, due to the ability of radicals to remain "alive" for some period of time after exposure, for example, more than 1 day, 5 days, 30 days, C months, b months, or even more than 1 year, the properties of the material can continue to change during the time that in some cases it may be undesirable. The detection of radicals in irradiated samples using the electron paramagnetic resonance spectroscopy method and the lifetime of radicals in such samples are discussed in the publications Vapoiotsna ei a!., Rpuzis5 ip Medisipe apa Vioiodu, 46 (2001), 461-471 and Vapoioptsa ei ai!., Kadiaiop Rgoiesiop Ooziteigu Moi. 84, Mo5. 1-4 pp. 293-296 (1999).

Ionized material can be subjected to neutralization of active centers for its functionalization and/or stabilization. At any point, for example, when the material is "live", "partially live" or completely neutralized with respect to the active sites, the material can be converted into a product, such as a fuel, a food product or a composite.

In some implementations, the neutralization of active centers includes the action of pressure, as a result of mechanical deformation of the material, for example, direct mechanical compression of the material in one, two or three dimensions, or the application of pressure to the fluid medium in which the material is immersed, for example, isostatic pressing. In such cases, it is the deformation of the material that leads to the formation of radicals, which are often trapped in crystal domains in close enough proximity to each other that the radicals can recombine or react with another group. In some cases, the pressure is applied in conjunction with the introduction of heat, such as heat in an amount sufficient to increase the temperature of the material above the melting point or softening temperature of a component of the material, such as lignin, cellulose or hemicellulose in the case of biomass material. Heat can improve molecular mobility in the material, which can help neutralize radicals. If pressure is used to neutralize active sites, the pressure may be greater than about 1000 psi: (6890 kPa), such as greater than about 1250 psi-? (8620 kPa), 1450 psi? (10000 kPa), 3625 psi? (25000 kPa), 5075 psi? (35000 kPa), 7250 psi? (50,000 kPa), 10,000 psi? (68,900 kPa), or even more than 15,000 psi: (103,000 kPa).

In some embodiments, the neutralization of the active sites includes bringing the material into contact with a fluid medium, such as a liquid or a gas, such as a gas capable of reacting with radicals, such as acetylene or a mixture of acetylene with nitrogen, ethylene, chlorinated bo ethylenes or chlorofluoroethylenes, propylene or mixtures of these gases. In other specific embodiments, the neutralization of active sites includes contacting a material, such as biomass, with a liquid, such as a liquid soluble in the biomass or at least capable of penetrating the biomass and reacting with radicals, such as a diene, such as a 1,5- cyclooctadiene. In some specific embodiments, the neutralization of the active sites includes bringing the biomass into contact with an antioxidant such as vitamin E. If desired, the process feedstock may include an antioxidant dispersed therein, and the neutralization of the active sites may result from the inclusion of an antioxidant dispersed in the process feedstock. in contact with radicals.

Other ways of neutralizing active centers are also possible. For example, to neutralize the active sites in any ionized material described in this document, any method of neutralizing radicals in polymeric materials can be used, which is described in the publication of US patent application Mo 2008/0067724 by the authors of Mygaiodia ei ai. and patents

US Mo 7166650 by Mygaodia ei ai... In addition, any active site neutralizer (described in the above descriptions of Mygaodia under the name "sensitizer") and/or any -which antioxidant is described in any reference by the author

Mithagudiya.

Functionalization can be improved by the use of heavy charged ions, such as any of the heavy ions described herein. For example, if it is desirable to improve oxidation, charged oxygen ions can be used for irradiation. If nitrogen-containing functional groups are desired, nitrogen ions or ions that include nitrogen can be used. In the same way, if it is desirable to have sulfur- or phosphorus-containing groups during irradiation, sulfur- or phosphorus-containing ions can be used.

In some embodiments, after the neutralization of the active sites, any of the materials described herein subjected to the neutralization of the active centers may be further treated to further change the molecular and/or supramolecular structure using one or more options selected from radiation treatment. such as ionizing or non-ionizing radiation, treatment with ultrasonic waves,

From pyrolysis and oxidation.

In specific embodiments, the functionalized materials described herein are treated with an acid, base, nucleophile, or Lewis acid to further alter the molecular and/or supramolecular structure, such as further reducing the molecular weight. Examples of acids include organic acids such as acetic acid and mineral acids such as hydrochloric, sulfuric and/or nitric acid. Examples of bases include strong mineral bases such as hydroxide ion source, basic ions such as fluoride ion, or weaker organic bases such as amines. Even water and sodium bicarbonate, for example, when dissolved in water, can provide a change in molecular and/or supramolecular structure, such as an additional decrease in molecular weight.

The functionalized materials can be used as substrate materials for immobilizing microorganisms and/or enzymes in the field of biotechnology, for example, as described in US Patent Application Serial Nos. 61/180032 and 61/180019, the disclosures of which are incorporated herein by reference.

Other implementation options also fall within the scope of the following claims. For example, non-biomass materials and mixtures of biomass materials and non-biomass materials may be processed using the methods described herein.

Examples of non-biomass materials that can be processed include hydrocarbon-bearing materials such as oil sands, oil shale, tar sands, bitumen, coal, and other such mixtures of hydrocarbon and non-hydrocarbon materials. A variety of other biomass and non-biomass materials can be processed using the methods described herein, including peat, lignin, pre-charred coal, and petrified and/or carbonized materials.

Claims (6)

FORMULA OF THE INVENTION 1. The method of obtaining a fermentation product, which includes: processing lignocellulosic material to change the molecular structure of the material by exposing the specified material to the influence of an ion beam, where the change in molecular structure represents a decrease in the molecular weight of the material; and fermentation of the processed lignocellulosic material by bringing the specified material into contact with an enzyme and/or microorganism; wherein the ion beam consists of two or more different types of ions, and where the material is first exposed to carbon ions and oxygen ions to decompose lignin, and then exposed to protons, helium ions and/or electrons to decompose cellulose and/or hemicellulose. 2. The method according to claim 1, which is characterized by the fact that the product is selected from the group consisting of human food products, animal food products, pharmaceuticals and nutraceuticals. 3. The method according to claim 1 or 2, in which the fermentation product is a combustible fuel. 4. The method according to claim 3, which is characterized by the fact that the fuel is selected from the group consisting of alcohols and hydrogen. 5. The method according to claim 1, in which the microorganism is yeast. 6. The method according to any one of claims 1-5, in which the lignocellulosic material is provided in a layer, while the method additionally includes adjusting the technological parameters of the ion beam based on the thickness of the layer. what I K I E ; - sly o Ka a oon dnu i i I IEE RUKA ICONAH and SHIDALEEIAM And seh same Dnnnnyav PU vyk DEKEVDKA IE PyuYEH Z i EP yatttyuttyunintott s s kyu nyny vini E B Ba PED KUN PDM proce KIV Mav EE KIOEUK U Yang. 1 I pocho I: eat- She Z N - still ESH as z chishe y ze he y y i "uva y U sche om chnvyuki y ts syu Shcher rya ze - "espettktse "yade M sche VITAN Ж chn ru se BE zdeseesfessn already g -: E evkn nki vik is y em Te G sche k ; I split -i KE IZ IZ s ka Eya SCHA feny nn ru : В shsh CHE VE Y i i : KI KE i 3 i KU iji ii B: i DE NE ME roya NK I i : x SNY SHU i : Yar oh i E pr. Zh. NM breath EI E and ate kose Y | i: g kchyalkAKAKKK as kKnkknyH nn shi yi yi ka y h NM hu vyh Her y eni Myh y eh I xx ZU i sho ke I had E - VIDEO SMA DOZA z : s : kh «nki KKKA KK nn M BU yi y kh IZ mn to, EN i E yo a tk i | In! | kzhnnn more Z і I And I as Dkszh not yad uyuyuyu yah put muhyu he zhk uk lyumu cafe epoch u me i su i zh yi | as Kelyanyachnk KZ a: xx A and 7 th B. In yuyuyuyuyuyu yus dew and Ba. Wind power plant. "Fig. from their M side I from . Z sh e - Z g-Ya g. and TU z u. хх with Ж Ж ИЗ! J. ho E Kofanov, SE I ; z and x i E :. 5 Ж E KU U ХЕ I s xx E -k х EEG "ng, ZA ho E х их Э 5 х 3 я. and Z high school i V 5 yk Z y y y Х Е KZ xx y 5 "g a I: Ж : KE g. xx KE: e Fig, 8 uh sl. sel 3 VIVEKCHA PEK is and KE persimmon ar VK I VEN AOZEKA that seh in жжижиж tender жиж жижиж жиж жиж жижиж жиж жиж жиж жиж жиж жив жив впсююю kyu yuyukjeukkyuksoyuyuyusyukyus duhuzhzhAzhKAKI MK with how K ak Preheyehya them; Z tr, z i osi z y b, - svi ich E IZ; sya sec 140 En v v V vn nya MK: Ba E e V i E 5 - : E: I I E oi H E i che iz K KZ yah. Z y HU zhu z VAM stand up ET AME TU x for I KA : Z ; X with g E ; Ж E EZ E I I yar Eh Z sudekoi . ju en ach chi Ya a ev es oi Ov POZHVNANKi feoKo Z ven Z fo 1 fan Z y hi ENN ENN TK Fk, 5 Ya. Mn IZ and EYA I: E V o E 14 IZ; і і g dkfososoyusoyeoso E: IZ E: IZ E: IZ zhk hek 00 kutu m h ok her tah IZ ho x g Y SCHO : Nym ka ne EYA Z x 5 u i i E IZ i still SHY DE nin xx i i i ak M i ke koi MON y: tus K- ZU X deya SAME Z KA. Ye IZ KI m IZ ai i sa : shcha 3 i AK DM ААКААЖАКААЙАЖААААААААНАЖВЙKKKKKKKKKKKY V ЖИZ N NK KE NU і Ek OVES і : 1 Kak : 3 і ИЗ ИЗ і И і 5 х ИЗ 3 і ИЗ Chng 5 FG. 5 I eat; : r I with GU E Z ke i 7 de KE NE SYA E SYA KO I sk DU i TE SCHE i ; 3: le x i I x I OA TU x MO x; also E and U with gy V and x with ex. and. i x i E schy fi rmakih U VER HEM Fig. AND IN. her k -oo eko I M what what and her OO i ryeeY i xx Z what B : Oh her h vk RE x Z Po KI I BZ. i U ts xx i Eh z Koossos o ososskyuyusueskekkkkh - sa atekityukya kl ENEVGYA ng. yiv e KU u - z shi z pi 1 : z p m 3 KE i i HU 3 i ne I ka E shchi he I V M OV I I I ISHE: E . Z o Z TIN zm tupu Ku ANI Fig MN, mA TECHN kikimu or og, et ZK Eky NE Ina eya ke i M : KE 5 V Be Z E I: duh i KE VYAOZ, p HUK Y vok : oo Z і : 5.5 X K tuye Z shov E and VU zone KUKY a nyanni a i Z HU s ek: zan y y - K-YA U k. Ga y : skh Vche E ХХ ЖЖ R Ж de Ж HATAH ЖЙ Я КА, KAH КАК КАРАТ Me KO oda mm m AK yar m Z s i IZ i i CHO GI nyka KK KA kyu KAK NK Ky UKH ZHK INC KK KE KAH KK Zh Um Zach sh ia Sm zl CHA me of wo ke eh fe xx xx loh oon yu ОЖ KA yu Her: medi yi yi E nai kh nn KN Sy kh I Z M KI GU paro ti zh zh Ka yi VIDS IAMU u Ku goes KU xx 2 shcha yi u Z Z K; lu with ee and Ki in NAI yam "horn. 8 DENSE SCHEME. Fig. And the beginning, sh-nniny ViNOSna, and I know what the distance is. ZV DNA slot cm «hnu juice DISTANCE B I fic E S TU AN Fig. 10A EV A DOA stitch