BRPI0914292B1 - METHOD OF CHANGING MOLECULAR STRUCTURE OF A CELLULOSIC OR LIGNOCELLULOSE MATERIAL - Google Patents

Description

Report of the Invention Patent for "METHOD OF CHANGING A MOLECULAR STRUCTURE OF A CELLULOSIC OR LIGNOCELLULOSTIC MATERIAL".

Background The present invention relates to biomass, particularly biomass residues, and hydrocarbon-containing materials, such as oil sands, oil shale, oil sands, bitumen and coal, are widely available. It would be useful to derive materials and fuel, such as ethanol, from biomass and hydrocarbon-containing material.

Summary Biomass and hydrocarbon-containing material can be processed to alter its structure on one or more levels. Processed materials can then be used as a source of altered and / or combustible materials.

Many modalities of this application use Natural Force® Che-mistry (NFC). Natural Force® Chemistry methods use the controlled application and manipulation of physical forces, such as particle beams, gravity, light, etc., to create the intended structural and chemical molecular change. Methods for changing a molecular and / or supramolecular structure of a material, for example, any biomass material, may include treating the material with radiation. In particular, radiation may include particles, particularly charged particles (e.g., accelerated charged particles). Charged particles include ions, such as positively charged ions, such as protons, carbon or oxygen ions. Radiation may be applied in an amount sufficient to change the molecular structure and / or supramolecular structure of the material. Radiation may also be applied to produce one or more products from the material. The material in some cases may include carbohydrates or materials including carbohydrates, for example cellulosic materials, lignocellulosic materials, starch rich materials, or mixtures of any biomass materials.

Particles having a different charge of electrons and / or particles heavier than electrons may 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 biomass, for example. -example for breaking molecular weight or increasing molecular weight of biomass. In some embodiments, heavier particles may induce greater amounts of chain fission compared to electrons or photons. Moreover, in some cases positively charged particles can induce relatively large amounts of chain fission because of their acidity. On occasion, negatively charged particles can induce relatively large amounts of chain fission because of their alkalinity.

Thus, in one aspect, the invention features a method of changing a molecular structure of a material, for example a biomass material or a hydrocarbon-containing material, by producing an ion beam comprising a first ion energy distribution having a full width at half height of w; adjusting the energies of at least some of the ions to produce a second ion energy distribution in the ion beam having a full width at half height of more than w; and expose the material to the adjusted ion beam. The energies of at least some of the ions can be adjusted based on, for example, a thickness of the material.

In another aspect, the invention features a method of changing a molecular structure of a material, for example a biomass material or a hydrocarbon-containing material, by producing an ion beam comprising an ion energy distribution having a full width at half height of w; directing the ion beam to traverse a scattering element configured to increase the full width at half height of the ion energy distribution to a value greater than w; and exposing the material to the ion beam after the ion beam has passed through the scattering element.

Also in another aspect, the invention features a method of changing a molecular structure of a material, for example a biomass material or a hydrocarbon-containing material, by producing an ion beam having an ion energy distribution at distribution having a more likely energy E; filter the ion beam to remove at least some ions having an energy less than E from the ion beam; and expose the material to the filtered ion beam.

In a further aspect, the invention features a method of changing a molecular structure of a material, for example a biomass material or a hydrocarbon-containing material, by producing an ion beam having an ion energy distribution; adjust the ion energy distribution based on an expected ion dose profile in the material; and expose the material to the adjusted ion beam. The invention also features a method of changing a molecular structure of a material, for example a biomass material or a hydrocarbon-containing material, by producing an ion beam having an ion energy distribution; adjusting the ion energy distribution based on a full width at half height (FWHM) of a Bragg peak of an expected ion dose profile in the material; and exposing the material to the adjusted ion beam, wherein the adjustment comprises increasing the FWHM to reduce a difference between a biomass material thickness and the FWHM.

In some cases, following adjustment, the difference between material thickness and FWHM is 0.01 cm or less.

Also in another aspect, the invention features a method of changing a molecular structure of a material by producing a first ion beam from an ion source, the first ion beam having a first average ion energy; expose the material to the first beam of ions; adjusting the ion source to produce a second ion beam having a second average ion energy different from the first average ion energy; and exposing the material to the second beam of ions.

In some cases, the method further includes repeat adjustment and exposure to expose the material to a plurality of ion beams having different average ion energies. The composition of the first and second ion beams may be the same.

In a further aspect, the invention features a method of changing the molecular structure of a material by producing a first ion beam from an ion source, the first ion beam having a first average ion energy corresponding to a first position of a Bragg peak in an expected ion dose profile of the material; expose the material to the first beam of ions; adjusting the ion source to produce a second ion beam having a second average ion energy corresponding to a second Bragg peak position different from the first position; and exposing the material to the second beam of ions.

In some cases, the method further includes repeat adjustment and exposure to expose the material to a plurality of ion beams corresponding to different positions of the Bragg peak. The composition of the first and second ion beams may be the same.

Also in another aspect, the invention features a method of changing a molecular structure of a material by producing an ion beam from an ion source, the ion beam comprising a first type of ion and a second type of different ion. of the first type of ions; and expose the material to the ion beam.

For example, the first type of ions may comprise hydrogen ions and the second type of ions may comprise carbon ions, or the first type of ions may comprise hydrogen ions, and the second type of ions may comprise oxygen ions, or The first and second types of ions may comprise at least one of proton and hydride ions. In some cases each of the first and second ion types has ion energies between 0.01 MeV and 10 MeV.

In another aspect, the invention features a method of changing a molecular structure of a material by producing an ion beam having a divergence angle of 10 degrees or more, for example 20 degrees or more, on a surface of the material; and exposing the biomass material to the ion beam.

Also in another aspect, the invention features a method of changing a molecular structure of a material by adjusting an ion source to produce an ion beam having an average ion current and an average ion energy; and exposing the material to the ion beam, wherein the ion source is adjusted based on an expected ion dose profile in the material and each part of the material receives a radiation dose between 0.01 Mrad and 50 Mrad, for example, between 0.1 Mrad and 20 Mrad as a result of ion beam exposure.

In another aspect, changing a molecular structure of a material includes producing an ion beam including a first ion energy distribution having a full width at half height of W, adjusting the energies of at least some of the ions based on a thickness. of a hydrocarbon-containing material to produce a second ion energy distribution in the ion beam having a full width at half height of more than w, and exposing the hydrocarbon-containing material to the adjusted ion beam. The hydrocarbon-containing material may be selected from the group consisting of oil sands, oil shale, oil sands, bitumen and coal.

In another aspect, changing a molecular structure of a material includes producing an ion beam including a first ion energy distribution having a full width at half height of W, adjusting the energies of at least some of the ions to produce a second distribution. of ion energies in the ion beam having a full width at half height of more than w, and exposing the material to the adjusted ion beam.

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

In some cases, the method further includes exposing the material to a plurality of electrons or to ultrasonic energy following exposure to the ion beam.

Some implementations of any of the aforementioned 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 adjusting based on a 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 an expected ion dose profile in the material. Adjusting may also include increasing a full width at half height of a Bragg peak from an expected ion dose profile in the material sufficiently to reduce a difference between a material thickness and the full width at half height of the Bragg peak. Following adjustment, the difference between the material thickness and the total width at half height of the Bragg peak may be 0.01 cm or less. The total width at half height of the second distribution may be greater than w by a factor of 2.0 or more, for example by a factor of 4.0 or more. Adjusting the energies of at least some of the ions may include directing the ions to traverse a scattering element, for example a hemispheric analyzer. In some cases, the adjusted ion beam passes through a fluid before it is incident on the material, for example through air at a pressure of 0.5 atmosphere or more. The ion beam may include two or more different types of ions, for example hydrogen ions and carbon ions or hydrogen ions and oxygen ions. The ion beam may include at least one of proton and hydride ions. The average ion energy in the ion beam can be between 0.01 MeV and 10 MeV.

Changing a molecular structure of a material such as a biomass feedstock or a hydrocarbon-containing material as used herein means changing the chemical bonding arrangement, such as the type and amount of functional groups or conformation of the structure. For example, the change in molecular structure may include changing the supramolecular structure of the material, oxidizing the material, changing an average molecular weight, changing an average crystallinity, changing a surface area, changing a degree of polymerization, changing a porosity, change a degree of shunt, graft into other materials, change a crystalline domain size, or change a total domain size.

Biomass or hydrocarbon-containing material may be exposed to radiation, for example an ion beam, for example a beam according to one or more of the embodiments described herein. The beam and duration of exposure may be chosen such that the molecular structure of the material is altered. Material may be treated before and / or after exposure. The exposed material may be used in a variety of applications including fermentation and the production of composite materials.

Systems and devices for treating radiation materials as disclosed herein are also characterized. An exemplary system includes a biomass reservoir, a particle beam producing device, for example as described herein, and a transport device for moving biomass from the reservoir to the particle beam producing device.

Implementations may include one or more of any of the features described in this document. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. While methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, this descriptive report, including definitions, will control. Furthermore, the materials, methods and examples are illustrative only and not intended to be limiting.

This application incorporates herein by reference the total contents of International Application No. PCT / US2007 / 022719, filed October 26, 2007, and U.S. Provisional Application No. 61 / 049,406, filed April 30, 2008.

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

DESCRIPTION OF THE DRAWINGS Figure 1 is a block diagram illustrating conversion of bi-mass into products and co-products. Figure 2 is a schematic diagram showing dose profiles for ions, electrons and photons in a condensed phase material. Figure 3 is a schematic diagram of an ion beam exposure system.

Figures 4A and 4B are schematic diagrams showing ion beam energy distributions. Figure 4C is a schematic diagram showing ion dose profiles in an exposed sample. Figure 5 is a schematic diagram of a spacer element including multiple subregions. Figure 6 is a schematic diagram of an ion beam exposure system including an ion filter.

Figures 7A-7C are schematic diagrams showing energy distributions for unfiltered and filtered ion beams. Figure 8 is a schematic diagram showing three ion dose profiles corresponding to exposure of a sample to ion beams having different mean energies. Figure 9A is a schematic diagram showing a liquid ion dose profile for an exposed sample based on the three ion dose profiles of Figure 8. Figure 9B is a schematic diagram showing three different ion dose profiles corresponding to the beams. of average energy ions and current of different ions. Figure 9C is a schematic diagram showing a liquid ion dose profile based on the three ion dose profiles of Figure 9B. Figure 10A is a schematic diagram showing three different ion dose profiles corresponding to exposure of a sample to beams of three different types of ions. Figure 10B is a schematic diagram showing a liquid ion dose profile based on the three ion dose profiles of Figure 10A. Equal reference numbers in the various drawings indicate like elements.

Detailed Description Treating biomass with radiation is useful for producing fuel and products. Generally biomass material is physically prepared prior to radiation treatment. The material may be prepared to become more uniform, for example to reduce particle size, to change water content, to control viscosity and so on. The material is treated with radiation to alter the molecular and / or supramolecular structure. Furthermore, the material may be treated in other ways, for example with sonication, oxidation, pyrolysis and vapor explosion. The resulting material may be stored or used in a variety of ways.

One application is fermentation to produce a combustible product such as an alcohol. Microorganisms may be combined with the resulting material and optionally with other ingredients. The combination is fermented and product is recovered. For example, alcohols may be recovered by distillation.

In some embodiments, radiation is applied on a large scale, for example to a batch of at least 50 kg, 100 kg or 500 kg. The treatment may also be applied in a continuous or semi-continuous mode, for example to material moving under a beam of radiation, for example to process at least 100, 500, 1,000, 5,000 or 20,000 kg / hr. .

A variety of biomass materials can be used as a starting material. Examples of biomass include plant biomass, animal biomass and urban waste biomass. Biomass also includes raw materials such as cellulosic and / or lignocellulosic materials.

Often, biomass is material that includes a carbohydrate, such as cellulose. Generally, any biomass material that is or includes carbohydrates composed entirely of one or more saccharide units or including one or more saccharide units may be processed by any of the methods described herein. For example, biomass materials may be cellulosic or ligocellulosic materials, or starch-rich materials such as corn kernels, rice kernels or other foods.

Additional examples of biomass materials include paper, paper products, wood, wood related materials, particle board, grass, rice husks, bagasse, cotton, jute, hemp, flax, bamboo, sisal, Philippine banana, straw, corn cobs, rice husks, coconut hair, seaweed, seagrass, cotton, synthetic celluloses, or mixtures of any of these. Still other examples are described in WO 2008/073186, filed October 26, 2007 and U.S. Series 12 / 429,045, filed April 23, 2009. Various biomass materials are frequently and readily available, but, unless pretreated, can sometimes be difficult to process, for example by fermentation, or can give ideal byproducts at a slow rate. In the methods described herein, raw materials may first be physically prepared for processing, often by downsizing raw materials. Physically prepared raw material may be pretreated or processed using one or more of radiation, sonication, oxidation, pyrolysis and vapor explosion. The various pretreatment systems and methods can be used in combinations of two, three or even four of these technologies. Combinations of various pretreatment methods generally are described in WO 2008/073186, for example.

In some cases, to provide materials that include a carbohydrate, such as cellulose, which can be converted by a microorganism into several desirable products, such as fuels (eg, ethanol, butanol or hydrogen), raw materials that include one or more. saccharide units may be treated by any or more of the multiple processes. Other products and co-products that may be produced include, for example, human food, animal food, pharmaceutical and nutraceutical products. Examples of other products are described in U.S. Series No. 12 / 417,900, 12 / 417,707, 12 / 417,720 and 12 / 417,731, all of which were filed on April 3, 2009.

Where biomass is or includes a carbohydrate it may include, for example, a material having one or more β-1,4-bonds and having a number average molecular weight of between about 3,000 and 50,000. A carbohydrate such as this is or includes cellulose (I), which is derived from (β-glucose 1) by condensation of β (1 -> - 4) -glycoside bonds. This bond in itself contrasts with that for the (1-> 4) glycosidic bonds present in starch and other carbohydrates.

Starch-rich materials include starch itself, for example 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 an agricultural crop. . For example, the starch-rich material may be baroa potatoes, buckwheat, bananas, barley, cassava, grapes, sago, sorghum, potatoes of regular domestic life, sweet potatoes, yams, or one or more beans, such as broad beans. , lentils or peas. Mixtures of any one or more starch rich materials are also starch rich materials. In particular embodiments, the starch rich material is derived from corn. Various starches and corn derivatives are described in "With Starch", With Refiners Association (Eleventh Edition, 2006).

Biomass materials that include low molecular weight sugars, for example, may include at least about 0.5% by weight of low molecular weight 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% by weight of low molecular weight sugar. In some cases, biomass is composed substantially of low molecular weight sugar, for example, more than 95 wt%, such as 96, 97, 98, 99 or substantially 100 wt% of low molecular weight sugar.

Biomass materials that include low molecular weight sugars may be agricultural products or food products such as sugar cane and sugar beets or an extraction thereof, for example sugar cane juice or sugar beet juice. sugar. Biomass materials that include low molecular weight sugars may be substantially pure extractions, such as raw or crystallized table sugar (sucrose). Low molecular weight sugars include sugar derivatives. For example, low molecular weight sugars may be oligomeric (e.g., equal to or greater than 4-mer, 5-mer, 6-mer, 7-mer, 8-mer, 9-mer or 10-mer ), trimeric, dimeric or monomeric. When carbohydrates are formed from more than one repeating unit, each repeating unit may be the same or different.

Specific examples of low molecular weight sugars include cellobiose, lactose, sucrose, glucose and xylose, together with their derivatives. In some cases, sugar derivatives are dissolved faster in solution or used by microbes to provide useful material such as ethanol or butanol.

Combinations of any biomass materials described herein (for example, combinations of any biomass materials, components, products, and / or co-products generated using the methods described herein) may be used to manufacture any of the products described herein, such as as ethanol. For example, mixtures of cellulosic and starch-rich materials may be used to make products.

Fuels and other products (eg, ethanol, bioethanol, other alcohols and other combustible hydrocarbons) produced by the methods disclosed herein may be mixed with another hydrocarbon-containing species. For example, ethanol produced using any of the methods disclosed herein may be mixed with gasoline to produce "alconafta", which may be used as fuel in a wide variety of applications, including car engines.

Biomass Treatment Processes Figure 1 shows a system 100 for converting biomass, particularly biomass with significant cellulosic and lignocellulosic components and / or starch-rich components, into useful products and co-products. System 100 includes a feed preparation subsystem 110, a pretreatment subsystem 114, a primary process subsystem 118, and a postprocessing subsystem 122. Feed preparation subsystem 110 receives raw biomass, prepares physically biomass for use as raw material through downstream processes (eg, reduces size and homogenizes biomass), and stores biomass in both its raw and raw material forms.

Biomass with significant cellulosic and / or ligocellulosic components, or starch rich components, may have a high average molecular weight and crystallinity that may be modified by one or more pretreatments to facilitate use of the material. Pretreatment subsystem 114 receives feedstock from feed preparation subsystem 110 and prepares feedstock for use in primary production processes, for example by reducing the average molecular weight and crystallinity of feedstock and / or increase the surface area and / or porosity of the raw material. In some cases, the pretreated biomass material has a low moisture content, for example, less than about 7.5, 5, 3, 2.5, 2, 1.5, 1, or 0.5%. of water by weight. Moisture reduction can be achieved, for example, by drying biomass material. Pretreatment processes can avoid the use of adverse chemicals such as acids and strong bases. Primary process subsystem 118 receives pre-treated raw material from pretreatment subsystem 114 and produces useful products (e.g., ethanol, other alcohols, pharmaceuticals and / or food products). Primary production processes typically include processes such as fermentation (e.g. using microorganisms such as yeast and / or bacteria), chemical treatment (e.g. hydrolysis) and gasification.

In some cases, output from primary process subsystem 118 is directly useful, but in other cases the output requires additional processing provided by postprocessing subsystem 122. Postprocessing subsystem 122 provides additional processing to produce flows from primary process system 118 (eg ethanol distillation and denaturation) as well as treatment for waste streams from other subsystems. In some cases, co-products from subsystems 114, 118, 122 may also be directly or indirectly useful as by-products and / or in increasing the overall efficiency of system 100. For example, post-processing subsystem 122 may produce water. treated to be recycled for use as process water in other subsystems and / or may produce flammable waste that may be used as fuel for boilers producing steam and / or electricity. In general, post-processing steps may include one or more steps such as distillation to separate different components, wastewater treatment (e.g., filtration, organic equalization, sludge conversion), mechanical separation and / or residue combustion.

Ion Beam Systems for Biomass Pretreatment Ion beam pretreatment (eg exposure to ions) of biomass can be a particularly efficient, economical and high throughput treatment method. Ion beam pretreatment generally includes exposing biomass (mechanically processed or unprocessed) to one or more different types of ions generated from one or more ion sources. Ions can be accelerated in accelerator systems that are coupled to ion sources, and can produce ions with varying energies and speeds. Typically, in ion-based pretreatment, ions are not accelerated to sufficient energies to cause large amounts of X-ray radiation to be produced. Thus, bending and protection requirements for ion sources can be considerably relaxed from 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 may be performed on cellulosic and / or lignocellulosic material in which less than about 25% by weight of cellulosic and / or lignocellulosic material has surfaces wet with a liquid such as water. In some embodiments, ion beam irradiation is performed on cellulosic and / or lignocellulosic material in which substantially none of the cellulosic and / or lignocellulosic material is wetted with a liquid such as water.

When ion beam irradiation is used, it can be applied while cellulosic and / or lignocellulosic material is exposed to air, oxygen enriched air, or even oxygen itself, or covered by an inert gas such as nitrogen, argon, or helium. When oxidation of biomass material is desired, an oxidation environment is used, such as air or oxygen, and the properties of the ion beam source can be adjusted to induce reactive gas formation, eg ozone formation and / or nitrogen oxides. These reactive gases react with biomass material, either alone or together with incident ions, to cause material degradation. As an example, when biomass ion beam exposure is used, the biomass may be exposed to ions under a pressure of one or more gases of more than about 2.5 atmospheres, such as more than 5, 10, 15, 20 or even more than about 50 atmospheres. Ions that are incident on biomass material typically scatter and ionize parts of the biomass through Coulomb scattering. The interaction between ions and biomass can also produce energetic electrons (eg secondary electrons) that can interact additionally with biomass (eg causing additional ionization). ions may be positively charged or negatively charged, and may withstand a single positive or negative charge, or multiple charges, for example, one, two, three or even four or more charges. In cases where chain splitting is desired, positively charged particles may be desirable, in part, because of their acidic nature.

Ions to which biomass material is exposed may have the mass of an electron at rest, or greater, for example, 500, 1,000, 1,500, or 2,000 or more, for example, 10,000 or even 100,000 times the mass of an electron. in rest. For example, ions may have a mass 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, for example. , 1, 2, 3, 4, 5, 10, 12, or 15 atomic units. Exemplary ions and ion accelerators are discussed in Introductory Nuclear Physics, Kenneth S. Krane, John Wiley & Sons, Inc. (1988), Krs-to Prelec, FIZIKA B 6 (1997) 4, 177-206, Chu, William T , "OverView of Light-Beam Therapy", Columbus-Ohio, ICRU-IAEA Meeting, March 18-20, 2006, Iwata, Y. et al., "Alternating-Phase-Focused IH-DTL for Heavy-lon Medical Accelerators ", EPAC 2006 Proceedings, Edinburgh, Scotland, and Leitner, CM and others," Status of the Superconducting ECR Lon Source Venus ", EPAC 2000 Proceedings, Vienna, Austria.

A wide variety of different types of ions can be used to pretreat 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 embodiments, ions may induce greater amounts of chain fission than an equivalent dose of electrons. In some cases, positively charged ions may induce greater amounts of chain fission and / or other processes than negatively charged ions because of their acidity. Alternatively, in certain embodiments, depending on the nature of biomass, negatively charged ions may be more effective than positively charged ions in inducing chain fission and / or other processes because of their alkaline nature.

Following generation and / or acceleration, the average ion energy in an ion beam may be from about 1.0 MeV / atomic unit to about 6,000 MeV / atomic unit, for example from about 3 MeV / atomic unit. about 4,800 MeV / atomic unit, or about 10 MeV / atomic unit to about 1,000 MeV / atomic unit.

In general, many different types of ions can be used to radiate 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, and / 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 radiate biomass materials may include more than one different type of ion. For example, ion beams may include mixtures of two or more (for example, three, four, five, six or more) different types of ions. Exemplary mixtures may include carbon and proton ions, carbon and oxygen ions, nitrogen and proton ions, and iron and proton ions. More generally, mixtures of any of the ions discussed herein (or any other ions) may be used to form ion beams that are used to radiate biomass. In particular, relatively light and relatively heavier ion mixtures may be used in a single ion beam, where each of the different ion types has different effectiveness in radiating different types of biomass materials.

In some embodiments, ion beams to radiate biomass materials include positively charged ions. Positively charged ions can include, for example, positively charged hydrogen ions (eg protons), noble gas ions (eg helium, neon, argon), carbon ions, nitrogen ions, oxygen ions, atoms. silicon, phosphorus ions and metal ions such as sodium ions, calcium ions and / or iron ions. Without wishing to be bound by any theory, it is believed that such positively charged ions behave chemically as acidic Lewis components when exposed to biomass materials, initiating and sustaining reactions such as cationic ring and chain opening fission reactions in an acidic and / or oxidative environment.

In certain embodiments, ion beams to radiate biomass materials include negatively charged ions. Negatively charged ions may include, for example, negatively charged hydrogen ions (eg hydride ions), and negatively charged ions from various relatively electronegative nuclei (eg oxygen ions, nitrogen ions, carbon ions, carbon ions). silicon and phosphorus ions). Without wishing to be bound by any theory, it is believed that such negatively charged ions behave chemically as Lewis base components when exposed to biomass materials, causing cationic chain and ring opening fission reactions in a basic environment and / or of reduction.

In some embodiments, beams for radiating biomass materials may include neutral atoms. For example, any one or more of hydrogen atoms, helium atoms, carbon atoms, nitrogen atoms, oxygen atoms, neon atoms, silicon atoms, phosphorus atoms, argon atoms, and iron atoms may be included. in beams that are used for irradiation of biomass materials. In general, mixtures of any two or more of the types of atoms indicated above (e.g., three or more, four or more, or even more) may be present in the beams. The previous discussion has focused on ion beams that include mononuclear ions and / or neutral particles (eg, atomic ions and neutral atoms). Typically, such particles are the most energy-efficient to generate, and parent particles from which these species are generated may be available in abundant supply. However, in some embodiments, beams for radiating biomass materials may include one or more types of ions or neutral particles that are pollutants, for example including multiple nuclei, and even including two or more different types of nuclei. For example, ion beams may include positive and / or negative ions and / or neutral particles formed from species such as N2, 02, H2, CH4, and other molecular species. Ion beams may also include ions and / or neutral particles formed from heavier species that include even more nuclei, such as various hydrocarbon-based species and / or various inorganic species, including coordinating compounds of various metals.

In certain embodiments, ion beams used to radiate biomass materials include separately charged ions such as one or more of H +, H ", He +, Ne +, Ar +, C +, C ', 0+, O', N +, IST, Si + , Si ', P +, P', Na +, Ca +, Fe +, Rh +, lr +, Pt +, Re +, Ru + and Os + In some embodiments, ion beams may include multiplied charged ions such as one or more of C2 +, C3 +, C4 + , N3 +, N5 +, N3 ', 02+, O2', 022 ', Si2 +, Si4 +, Si2' and Si4 'In general, ion beams may also include more complex polynuclear ions that support multiple positive or negative charges. In some embodiments, because of the polynuclear ion structure, the positive or negative charges can be effectively distributed over substantially the total ion structure In some embodiments, the positive or negative charges may be somewhat localized over parts of the ion structure, for example. cause of the electronic structures of ions. In general, ion beams used to irradiate Delaying biomass materials may include ions - both positive and / or negative - from any of the molecular species disclosed herein, and ions generally may include one or multiple charges. Ion beams can also include other types of positively and / or negatively charged ions supporting one or multiple charges. Ions and ion beams can be generated using a wide variety of methods. For example, hydrogen ions (eg, both protons and hydride ions) may be generated by hydrogen gas field ionization and / or by thermal heating of hydrogen gas. Noble gas ions can be generated by field ionization. Carbon, oxygen, and nitrogen ions can be generated by field ionization, and can be separated from each other (when they are cogenerated) by a hemispherical analyzer. Heavier ions such as sodium and iron may be produced by thermionic emission from a suitable target material. Suitable methods for generating ion beams are disclosed, for example, in U.S. Provisional Applications No. 61 / 049,406 and 61 / 073,665 and U.S. Serial No. 12 / 417,699.

A wide variety of particle beam accelerators can be used to accelerate ions before exposing biomass material to ions. For example, suitable particle beam accelerators include Dynamitron® accelerators, Rhodotron® accelerators, static accelerators, dynamic linear accelerators (eg LINACs), van de Graaff accelerators, and folded tandem Pelletron accelerators. These and other suitable accelerators are discussed, for example, in U.S. Provisional Applications No. 61 / 049,406 and 61 / 073,665, and in U.S. Serial No. 12 / 417,699.

In some embodiments, combinations of two or more of the various types of accelerators may be used to produce ion beams that are suitable for treating biomass. For example, a folded tandem accelerator may be used in combination with a linear accelerator, a Rhodotron® accelerator, a Dynamitron® accelerator, a static accelerator, or any other type of accelerator to produce ion beams. Accelerators can be used in series, with the output ion beam of one type of throttle directed into another type of throttle for additional acceleration. Alternatively, multiple accelerators may be used in parallel to generate multiple ion beams for biomass treatment. In certain embodiments, multiple accelerators of the same type may be used in parallel and / or series to generate accelerated ion beams.

In some embodiments, multiple similar and / or different accelerators may be used to generate ion beams having different compositions. For example, a first accelerator can be used to generate one type of ion beam, while a second accelerator can be used to generate a second type of ion beam. Each of the two ion beams can then be further accelerated on another accelerator, or can be used to treat biomass.

Additionally, in certain embodiments, a single accelerator may be used to generate multiple ion beams to treat biomass. For example, any of the accelerators discussed in this document (and other types of accelerators alike) can be modified to produce multiple output ion beams by subdividing an initial ion current introduced into the accelerator from an ion source. Alternatively, or in addition, any ion beam produced by any of the accelerators disclosed herein may include only a single type of ion, or multiple different types of ions.

In general, where multiple different accelerators are used to produce one or more biomass treatment ion beams, the multiple different accelerators may be positioned in any order relative to each other. This allows for great flexibility in producing one or more ion beams, each having carefully selected properties to treat biomass (for example, to treat different components in biomass).

The ion accelerators disclosed herein may also be used in combination with any of the other biomass treatment steps. For example, in some embodiments, electrons and ions may be used in combination to treat biomass. Electrons and ions may be produced and / or accelerated separately, and used to treat biomass sequentially (in any order) and / or simultaneously. In certain embodiments, electron and ion beams can be produced in a common accelerator and used to treat biomass. Certain ion accelerators can be configured to produce electron beams as an alternative, or in addition to ion beams. For example, Dynamitron® accelerators, Rhodotron® accelerators, and LINACs can be configured to produce electron beams for biomass treatment.

In addition, ion-beam biomass pretreatment may be combined with other biomass pretreatment methods such as sonication, pyrolysis, oxidation, vapor explosion and / or irradiation with other forms of radiation (eg electrons, gamma radiation, X-rays, ultraviolet radiation). In general, other pretreatment methods such as sonication-based pretreatment may occur before, during or after ion-based biomass pretreatment.

Exposure Conditions and Properties of Ion Beams In general, when a condensed medium is exposed to a beam of charged particles, the charged particles penetrate the medium and settle within the medium at a depth distribution below the surface over which the particles They are incidents. It has generally been observed (see, for example, Figure 1 in Prelec (infra, 1997)) that the dose distribution for ions includes a significantly sharp maximum (Bragg peak), and that ions exhibit significantly less scatter. laterally than other particles such as electrons and neutrons and other forms of electromagnetic radiation such as X-rays. In this way, because of the relatively well controlled dose profile of accelerated ions, they operate relatively efficiently to alter the structure of biomass material. Furthermore, as is apparent from Prelec's Figure 6 (infra, 1997), heavier ions (such as carbon ions) even have sharper dose profiles than lighter ions such as protons, and thus the effectiveness The relative relative weight of these ions in the treatment of biomass material is even higher than for lighter ions.

In some embodiments, the average energy of the accelerated ions that are incident on biomass material is 1 MeV / u or more (e.g. 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15 , 20, 30, 50, 100, 300, 500, 600, 800, or even 1,000 MeV / u or more).

In certain embodiments, the average energy of accelerated ions is 10 MeV or more (e.g., 20, 30, 50, 100, 200, 300, 400, 500, 600, 800, 1,000, 2,000, 3,000, 4,000, or even 5,000 MeV or more).

In certain embodiments, an average rate of accelerated ions is 0.0005 c or more (e.g. 0.005 c or more, 0.05 c or more, 0.1 c or more, 0.2 c or more, 0, 3 c or more, 0.4 c or more, 0.5 c or more, 0.6 c or more, 0.7 c or more, 0.8 c or more, 0.9 c or more), where c represents the speed of light in a vacuum. In general, for a given acceleration potential, lighter ions are accelerated to higher speeds than heavier ions. For example, for a given acceleration potential, a maximum velocity of a hydrogen ion may be approximately 0.05 c, while a maximum velocity of a carbon ion may be approximately 0.0005 c. These values are exemplary only; The velocity of accelerated ions depends on the applied acceleration potential, the mode of operation of the accelerator, the number of passes through the acceleration field, and other such parameters.

In some embodiments, an average ion stream of accelerated ions is 105 particles / s or more (e.g., 106, 107, 108, 109, 101 °, 1011, 1012, 1013, 1014, 1015, or even 1016 particles / s). I'm more).

In some embodiments, a radiation dose delivered to biomass material from an ion beam is 5 Mrad or more (e.g. 10, 15, 20, 30, 40, 50, 60, 80, or even 100 Mrad or more).

When a sample is exposed to an ion beam, energy is deposited into the sample according to an ion dose profile (also sometimes referred to as a depth dose distribution). Figure 2 shows a schematic diagram of 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, plotted as a function of depth below a sample surface that is exposed to the ion beam on the horizontal axis. Figure 2 also includes, for comparative purposes, a 2020 electron dose profile, a gamma radiation dose profile 2030 and an x-ray dose profile 2040.

As shown in Figure 2, both gamma radiation and X-ray radiation (and in addition, other types of electromagnetic radiation) are strongly absorbed in a region adjacent to the sample surface, resulting in the highest energy doses being deposited near the surface of the sample. sample. Gamma radiation and X-ray dose profiles 2030 and 2040 decrease approximately exponentially from the sample surface as progressively fewer photons are able to penetrate deeper into the sample to be absorbed. The 2020 electron dose profile shows a developmental effect whereby, because of Compton's electron penetration capacity, the deposited energy dose increases near the exposed surface of the sample to a maximum deposited dose at a depth of penetration typically about 3-4 cm in condensed media. Then the relative dose of deposited energy decreases relatively rapidly with distance increasing below the sample surface.

Ion beams, by contrast, typically have dose profiles that are sometimes described as inverse with respect to electron and photon dose profiles. As shown in Figure 2, the ion dose profile 2010 includes a region 2012 in which a relatively constant energy dose is applied to the sample. Next, the 2010 ion dose profile includes a region 2014 referred to as the Bragg peak, which corresponds to a portion of the sample in which a comparatively larger fraction of the ion beam energy is deposited, followed by a region 2016 in the region. which a much smaller energy dose is deposited. The Bragg peak, which has a full width at half height (FWHM) of δ, ensures that the ion dose profile differs significantly from the electron and photon dose profiles of various wavelengths. As a result, exposing materials such as biomass materials to ion beams can produce effects that are different from the effects produced by photon and electron beams.

Typically, the Bragg 2014 peak width δ depends on a number of factors, including the nature of the sample, the type of ions, and the average ion energy. An important factor influencing the width δ of the Bragg 2014 peak is the energy distribution in the incident ion beam. In general, the narrower the energy distribution in the incident ion beam, the narrower the width δ of the Bragg 2014 peak. As an example, the Bragg 2014 peak typically has a width of about 3 mm or less for a distribution. ion energies that have an FWHM of 1 keV or less. The width δ of the Bragg 2014 peak can also be much smaller than 3 mm under these conditions, for example 2.5 mm or less, 2.0 mm or less, 1.5 mm or less, 1.0 mm or less. . The position of the Bragg 2014 peak, indicated by γ in figure 2, depends on several factors including the average incident beam energy. In general, for higher average ion beam energies, the Bragg 2014 peak will shift to greater depths in Figure 2, because higher energy ions have the ability to penetrate deeper into a material before most of the kinetic energy of ions be lost through scattering events. Various properties of one or more incident ion beams can be adjusted to expose samples (eg biomass materials) to ion beam radiation, which may result in depolymerization and other chain fission reactions in the samples. by reducing the molecular weight of the samples in a predictable and controlled manner. Figure 3 shows a schematic diagram of a 2100 ion beam exposure system. The 2100 system includes a 2110 ion source that generates a 2150 ion beam. The 2120 optics (including, for example, lenses, apertures, baffles) and / or other electrostatic and / or magnetic elements to adjust the ion beam 2150) direct the ion beam 2150 to be incident on sample 2130, which has a thickness h in a direction normal to the surface 2135 of sample 2130. In addition to directing the 2150 ion beam, the 2120 optics may be used to control various properties of the 2150 ion beam, including collimation and focusing of the 2150 ion beam. The 2130 sample typically includes, for example, one or more of several types of ion beam. biomass materials that are discussed in this document. The 2100 system also includes a 2190 electronic controller in electrical communication with the various system components (and with other components not shown in figure 3). The 2190 electronic controller can control and / or adjust any of the system parameters described herein, either entirely automatically or in response to input from a human operator. Figure 3 also shows the ion dose profile resulting from exposure of sample 2130 to the 2150 ion beam. The 2160 position of the Bragg peak within sample 2130 depends on the average energy of the 2150 ion beam, the nature of the ions in the ion beam 2150, the material from which the 2130 sample is formed, and other factors.

In many ion beam applications, such as ion therapy for tumor eradication, the relatively small width δ of the Bragg 2014 peak is advantageous because it allows reasonably thin targeting to particular tissues within a patient undergoing therapy, and helps reduce damage because of exposure to nearby benign tissues.

However, when exposing biomass materials such as sample 2130 to the 2150 ion beam, the relatively small width δ of the Bragg 2014 peak may restrict yield. Typically, for example, the thickness h of sample 2130 is larger than the width δ of the Bragg 2014 peak. In some embodiments, h may be substantially greater than δ (for example, larger 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 a sample thickness 2130 at which a selected dose can be delivered over a particular time interval, the energy distribution of the 2150 ion beam can be adjusted. Various methods can be used to adjust the energy distribution of the 2150 ion beam. A method such as this is to employ one or more 2170 removable scattering elements positioned in the path of the 2150 ion beam as shown in Figure 3. spreading element 2170 may be, for example, a thin membrane formed of a metal material such as tungsten, tantalum, copper and / or a polymer based material such as Lucite® polymer.

Prior to traversing the spreading element 2170 the ion beam 2150 has a power distribution of width w shown in Figure 4A. When the 2150 ion beam crosses the 2170 element (s), at least some of the ions in the 2150 ion beam undergo scattering events with atoms in the 2170 element (s) transferring a portion of their kinetic energy. to the atoms of element (s) 2170. As a result, the energy distribution of ion beam 2150 is enlarged to a width b greater than w, as shown in Figure 4B. In particular, the energy distribution of the 2150 ion beam achieves a broader low-energy rear as a result of scattering in the element (s) 2170. Figure 4C shows the widening effect of the ion energy distribution of the 2150 ion beam in the ion dose profiles in the 2130 sample. The 2140a ion dose profile is produced by exposing the 2130 sample to the 2150 ion beam having the ion energy distribution shown in Figure 4A. The 2140a ion dose profile includes a relatively narrow Bragg peak. As a result, the region of sample 2130 in which a relatively high dose is deposited is small. In contrast, by widening the ion energy distribution of the 2150 ion beam to produce the distribution shown in Figure 4B, the ion dose profile 2140b is obtained in sample 2130 after exposing the sample to the extended ion energy distribution. As the dose profile 2140b shows, by widening the ion energy distribution, the region of sample 2130 in which a relatively high dose is deposited is increased relative to the ion dose profile 2140a. By increasing the region of sample 2130 exposed to a relatively high dose, the efficiency of the exposure process can be improved.

In certain embodiments, the width b of the extended power distribution may be greater than w by a factor of 1.1 or more (e.g. 1.2, 1.3, 1.4, 1.5, 1.7, 2.0, 2.5, 3.0, 3.5, 4.0, 5.0, or even 10.0 or more).

Typically, the ion dose profile in sample 2130 produced by exposing the sample to the extended ion energy distribution shown in Figure 4B has a Bragg peak having a full width at half height (FWHM) of ε. As a result of widening the ion energy distribution, ε may be greater than δ by a factor of 1.1 or more (for example, 1.2 or more, 1.3 or more, 1.5 or more, 1, 7 or 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 more).

For the 2130 thickness h sample, after extending the ion energy distribution of the 2150 ion beam and exposing the sample to the ion beam, a ratio of ε / h may be 1 x 10 "6 or more (for example, 1 x 10 "5.5 x 10" 5, 1 x 10 "*, 5 x 10" *, 1 x 10'3, 5 x 10'3, 0.01, 0.05, 0.08, 0, 1, or even 0.5 or more).

In certain embodiments, sample 2130 includes a plurality of particles (e.g., approximately spherical particles, and / or fibers, and / or filaments, and / or other particle types). In general, the particles have a different size distribution with an average particle size r. The ion energy distribution of the 2150 ion beam can be adjusted (eg by flaring) based on the average particle size r of sample 2130 to improve the efficiency of sample-based treatment of sample 2130. For example, the ion beam 2150 may be adjusted such that a ratio of ε / r is 0.001 or more (e.g. 0.005 or more, 0.01 or more, 0.05 or more, 0.1 or more, 0.5 or 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, 1,000 or more, or more).

In some embodiments, a scattering element 2170 may include multiple different scattering subelements that are configured to extend the distribution of ion energies in the 2150 ion beam by different amounts. For example, Figure 5 shows a multiple sub-element spreading element 2170 including sub-elements 2170a-e. Each of the 2170a-e subelements extends the distribution of ion energies in the 2150 ion beam to a different extent. During operation of the 2100 system, the electronic controller 2190 may be configured to select an appropriate subelement of the scattering element 2170 based on information such as sample thickness h, 2130, ion type in the 2150 ion beam, and ion energy. average on the 2150 ion beam. Selection of an appropriate subelement can be done in fully automated mode, or based at least in part on input from a human operator. Selecting an appropriate subelement is done by translating the scattering element 2170 in the direction shown by arrow 2175 to position a selected subelement in the path of the 2150 ion beam.

In certain embodiments, other devices may be used in addition to or as an alternative to the spreading element (s) 2170. For example, in some embodiments, combinations of electric and or magnetic fields produced by ion optics may be used to extend the ion energy distribution of the 2150 ion beam. The 2150 ion beam may traverse a first configured field. to spatially disperse ions in the ion beam. Then spatially dispersed ions can traverse a second field that is well-located spatially, and which selectively delays only a portion of spatially dispersed ions. The ions then traverse a third field that spatially reassembles all the ions in a collimated beam, which is then directed to the surface of the 2130 sample. Typically, the optical ion elements used to generate the fields that adjust the energy distribution of ions controlled by the electronic controller 2190. By selectively applying spatially located fields, a high degree of control over the modified ion energy distribution is possible, including the generation of ion energy distributions having complicated profiles (eg multiple lobes). ). For example, in some embodiments, by applying a localized field that accelerates a portion of the spatially dispersed ion distribution, the ion energy distribution shown in Figure 4A may be enlarged on the high energy side of the maximum distribution. Information used by the electronic controller 2190 to adjust the ion energy distribution of the 2150 ion beam may include the thickness h of sample 2130 as discussed above. In some embodiments, the 2190 electronic controller may use information regarding the expected ion dose profile in the 2130 sample to adjust the ion energy distribution of the 2150 ion beam. Information regarding the expected ion dose profile may be obtained. from a database including, for example, ion dose profile measurements obtained from literature sources and / or calibration experiments performed on representative samples of the material from which the 2130 sample is formed. Alternatively, or in addition, information about the expected ion dose profile can be determined from a mathematical model of ion interactions in the 2130 sample (eg, an ion scattering model).

In certain embodiments, information regarding the expected ion dose profile may include information regarding the Bragg peak FWHM in the expected ion dose profile. The Bragg peak FWHM can be determined from measurements of ion dose profiles and / or from one or more mathematical models of ion scattering in the sample. Adjustments of the ion energy distribution of the 2150 ion beam can be performed to reduce a difference between the 21h sample thickness h and the Bragg peak FWHM. In some embodiments, for example, a difference between h and the full width at half height of the Bragg peak is 20 cm or less (e.g. 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 or less, or even zero).

In some embodiments, the ion beam exposure system may adjust the ion energy distribution in the 2150 ion beam in other modes. For example, the ion beam exposure system can be configured to filter the ion beam by removing ions from the 2150 ion beam that have energies below a selected energy threshold and / or above a selected energy threshold. Figure 6 shows an ion beam exposure system 2200 including an ion filter 2210 discussed in more detail below. The other 2200 system components are similar to the 2100 system components, and will not be discussed further. Figure 7A shows an ion energy distribution corresponding to the 2150 ion beam produced by the 2110 ion source. The 2150 ion beam, with an energy distribution as shown in Figure 7A, enters the ion filter 2210 where the distribution The energy of the 2150 ion beam is adjusted by filtering certain ions from the ion beam. For example, in some embodiments, the 2210 ion filter may be configured to remove ions from the 2150 ion beam having an energy lower than a selected energy threshold. In Figure 7A, the selected energy threshold is the E0 position of the peak in the ion energy distribution, although more generally any energy threshold can be selected. By removing all ions (or even exactly a large fraction of them) having an energy less than E0, the ion energy distribution for ion beam 2150 is as shown in Figure 7B.

In contrast, in some embodiments, the 2210 ion filter may be configured to remove ions from the 2150 ion beam that have an energy greater than a selected energy threshold (when the 2210 ion filter is implemented as a hemispherical analyzer, for example). ). For example, the selected energy threshold may correspond to the peak E0 position in the ion energy distribution, although more generally any energy threshold may be selected. By removing all ions (or even a large fraction of them) from the 2150 ion beam having an energy greater than E0, the ion energy distribution for the 2150 ion beam is as shown in Figure 7C.

In certain embodiments, sample 2130 may be exposed directly to a filtered ion beam 2150. By filtering the ion beam to achieve a narrower ion energy distribution, for example, the ion dose profile in sample 2130 is more following the sample exposure than it would otherwise have been without filtering the 2150 ion beam. As a result, the Bragg peak width in the 2130 sample is smaller than the Bragg peak width for a unfiltered ions. By exposing the 2130 sample to a narrower distribution of incident ion energies, finer control over the position of the 2150 ion beam can be achieved; This level of ion exposure control can be useful when exposing various types of delicate sample materials.

Alternatively, the filtered ion beam may then be passed through one or more scattering elements and / or other devices to increase the width of the ion energy distribution. This two-step approach to modifying ion energy distribution - a first filtration step followed by a second widening step - can be used to produce ion energy distributions that are tailored for specific applications (for example, specific for certain types of ions and / or certain materials and / or certain pretreatment conditions) that cannot be achieved using a simpler one-step power distribution extension procedure.

As an example, by first filtering the 2150 ion beam and then passing the filtered ion beam through one or more 2170 spacing elements, the shape of the ion energy distribution can be made more Gaussian than would be possible. otherwise using only one spreading step instead of the two-step procedure. The ion filter 2210 may include one or more of a variety of different devices for removing ions from the 2150 ion beam. For example, in some embodiments, the 2210 ion filter includes a hemispherical analyzer and aperture filter. The hemispherical analyzer includes a magnetic field source that disperses the ions of the 2150 ion beam according to their kinetic energies. The aperture filter is then positioned in the path of the scattered ion beam 2150 to allow only ions having a specific range of energies to pass through the aperture.

In certain embodiments, other devices may be used to filter the 2150 ion beam. For example, absorption elements (e.g., elements configured to absorb incident ions having energies less than a selected energy threshold) may be used to filter the beam. 2150. Suitable absorption elements include thin metal blades, for example.

In some embodiments, the 2150 ion beam (and in particular the Bragg peak at an expected ion dose profile produced following exposure of the 2130 sample to the 2150 ion beam) may be shifted through the 2130 sample to deliver doses of radiation selected for various parts of the sample. In general, the Bragg peak position in sample 2130 can be selected by adjusting the average energy of the 2150 ion beam (the average energy of the 2150 ion beam typically corresponds to the maximum in the ion energy distribution). The 2110 ion source, under the control of the 2190 electronic controller, can adjust the average energy of the 2150 ion beam by changing an applied extraction voltage to accelerate ions in the ion source. Figure 8 is a schematic diagram showing how the Bragg peak of an ion dose profile in sample 2130 can be shifted across the sample. As a first step, the 2100 ion exposure system is configured to produce a first ion beam with a selected average ion energy corresponding to a particular extraction voltage applied to the 2110 ion source. When the 2130 sample is exposed to the first ion beam, the 2010a ion dose profile results in the sample, with the Bragg peak at position 2230a. Following exposure, the extraction voltage at ion source 2110 is adjusted to produce a second ion beam with a different average ion energy. When the 2130 sample is exposed to the second ion beam, the 2010b ion dose profile results in the sample. By further repeating the extraction voltage adjustment at the 2110 ion source to produce additional beams with different average ion energies (and therefore different ion dose profiles, eg the 2010c ion dose profile), and expose sample 2130 to additional beams, the Bragg peak of the ion dose profile can be shifted across sample 2130 in the direction shown by arrow 2220, for example. More generally, however, by changing the extraction voltage at ion source 2110, the Bragg peak position in sample 2130 can be selected as desired, allowing large doses to be delivered to selected regions of sample 2130 in any sequence. .

In general, in addition to these other properties of the 2150 ion beam can also be adjusted, or as an alternative to this, adjusting the average ion energy of the ion beam. For example, in some embodiments, the divergence angle of the ion beam 2150 on the sample surface 2130 may be adjusted to control the ion dose profile in the 2130 sample. Generally, by increasing the divergence angle of the ion beam 2150 ions on the surface of sample 2130, the total width at half height of the Bragg peak in sample 2130 can be increased. Thus, in certain embodiments, the average ion beam energy may be maintained, but the ion dose profile in the material, including the Bragg peak position, may be changed by adjusting the divergence angle of the ion beam. The divergence angle may be adjusted automatically or by operator control by the electronic controller 2190. Typically 2120 optical elements include one or more ion beam steering elements such as quadripolar and / or octopolar deflectors. By adjusting potentials applied to the various electrodes of such deflectors, the divergence angle (and incidence angle) of the 2150 ion beam on the sample surface 2130 can be adjusted.

In some embodiments, unlike in other ion beam applications such as surgical intervention, it may be advantageous to use ion beams with relatively large divergence angles to ensure that the Bragg peak positioned on sample 2130 covers an adequate fraction of the thickness. For example, in certain embodiments, sample 2130 may be exposed to an ion beam having a divergence angle of 2 degrees or more (e.g. 5, 10, 15, 20, 30, 40, or even 50 degrees or more).

In some embodiments, both an ion beam current of the 2150 ion beam and the average ion energy of the 2150 ion beam may be adjusted to deliver a relatively constant dose as a function of the thickness h of sample 2130. For example, if sample 2130 is exposed according to sequential ion dose profiles 2010a, 2010b and 2010c in figure 8, the net ion dose profile in sample 2130 corresponds to the sum of profiles 2010a-c which is shown in figure 9A . Based on the net ion dose profile of Figure 9A, it is apparent that certain regions of sample 2130 receive more liquid doses than other regions of sample 2130.

Differences in net doses can be reduced by adjusting the ion beam current of the 2150 ion beam along with average ion energy adjustments. The ion beam current can be adjusted at the ion source 2110 under the control of the 2190 electronic controller. For example, to reduce the difference in net dose delivered to sample 2130 when the Bragg peak is displaced through sample 2130. In the direction indicated by arrow 2220 in Figure 8, the ion beam current may be reduced successively for each successive reduction in ion beam energy. Three ion dose profiles, each corresponding to successive decreases in both the average ion energy and ion current in the 2150 ion beam, are shown as 2010d-f profiles, respectively, in Figure 9B. The net ion dose profile in sample 2130 resulting from these three sequential exposures is shown in Figure 9C. The liquid ion dose profile shows significantly reduced variation as a function of position in sample 2130 relative to the liquid ion dose profile of Figure 9A.

By carefully controlling the average energy and ion current of the 2150 ion beam, variations in the net relative ion dose across the sample thickness 2130 following exposure of the sample to the 2150 ion beam may be relatively small. For example, a difference between a maximum net relative ion dose and a minimum net relative ion dose in sample 2130 following multiple exposures to the 2150 ion beam may be 0.2 or less (e.g. 0.15, 0, 1, 0.05, 0.04, 0.03, 0.02, 0.01, or even 0.005 or less).

By controlling the average energy and ion current of the 2150 ion beam, each portion of the exposed sample can receive a net dose between 0.001 Mrad and 100 Mrad following multiple ion beam exposures (for example, between 0.005 Mrad and 50 Mrad, between 0.01 Mrad and 50 Mrad, between 0.05 Mrad and 30 Mrad, between 0.1 Mrad and 20 Mrad, between 0.5 Mrad and 20 Mrad, or between 1 Mrad and 10 Mrad).

In some embodiments, sample 2130 may be exposed to different types of ions. Sample 2130 may be sequentially exposed to only one type of ion at a time, or exposure of sample 2130 may include exposing 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 an exposed material, and by exposing a sample to different types of ions, a particular liquid ion dose profile in the sample can be realized. Figure 10A shows a schematic diagram of the three different 201 Og-i ion dose profiles resulting from exposing a 2130 sample to three different types of ions. 201 Og-i ion dose profiles can be produced by sequential exposure of the sample to each of the different ion types, or by concurrent exposure of the sample to two or even all three different types of ions. The liquid ion dose profile in sample 2130 resulting from exposure to the three different types of ions is shown in figure 10B. Variations in the liquid ion dose profile as a function of sample thickness are reduced relative to any of the individual ion dose profiles shown in Figure 10A.

In some embodiments, different types of ions may include ions of different atomic composition. For example, different 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 ions. Generally, any of these different types of ions can be used to treat sample 2130, and each will produce a different ion dose profile in one sample. In certain embodiments, ions may be generated from commonly available gases such as air. When air is used as a source gas, many different types of ions can be generated. The various different types of ions may be separated from each other prior to exposing sample 2130, or sample 2130 may be exposed to multiple 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 several positive and / or negative ions. Additionally, different types of ions may include ions having a single charge and / or multiple charges. In general, positive and negative ions of the same chemical species may produce different ion dose profiles in a particular sample, and ions of the same chemical species that have different charge magnitudes (eg, single charged, double charged, triple charged, fourfold) can produce different ion dose profiles in a particular sample. By exposing a sample to multiple different types of ions, change in the sample, for example, sample disruption (eg, depolymerization, chain scission and / or molecular weight reduction), functionalization, or other structural change, can be controlled. carefully and selectively.

In some embodiments, the ion beam exposure system may adjust the composition of the ion beam based on the sample material. For example, certain sample types, such as cellulosic biomass, include a high concentration of hydroxyl components. Thus, the effective penetration depth of certain types of ions - particularly protons - in such materials may be considerably greater than would otherwise be expected based on ion energy alone. Proton jumping from location to location and other similar atomic excursions can significantly increase the mobility of such ions in the sample, effectively increasing the penetration depth of incident ions. Additionally, increased ion mobility in the sample may result in a widening of the Bragg peak. The ion beam exposure system can be configured to select particular ion types for exposure of certain samples, considering the chemical and structural features of the sample. Additionally, the ion beam exposure system can be configured to consider the expected interactions between the ion beam and the material while determining how to modify other ion beam parameters such as the distribution of ion energies in it.

An important aspect of the ion beam systems and methods described herein is that the systems and methods described enable exposure of biomass to ions in the presence of one or more additional fluids (e.g. gases and / or liquids). Typically, for example, when a material is exposed to an ion beam, exposure occurs in a reduced pressure environment such as a vacuum chamber. The reduced pressure environment is used to reduce or prevent contamination of the exposed material, as well as to reduce or prevent scattering of the ion beam by gas molecules. However, unfortunately exposing materials to ion beam indoors such as a vacuum chamber greatly restricts the potential throughput for high volume material processing.

In the systems and methods described herein, it has been recognized that exposure of biomass to an ion beam in the presence of one or more additional fluids may increase the efficiency of biomass treatment. Additionally, exposure of biomass to an ion beam in an open environment (eg, air at normal atmospheric pressure) enables much greater yield than would otherwise be possible in a reduced pressure environment.

As discussed earlier, in some embodiments, biomass is exposed to an ion beam in the presence of a fluid such as air. accelerated ions in any one or more of the accelerator types described in this document (or another accelerator type) are coupled outside the accelerator via an exit port (e.g., a thin membrane such as a thin metal blade), they pass through a volume of space occupied by the fluid, and are then incidents in the biomass material. In addition to directly treating biomass, some of the ions generate additional chemical species by interacting with fluid particles (eg ions and / or radicals generated from various air constituents). These generated chemical species can also interact with biomass, and can act as initiators for a variety of different chemical breakage reactions in biomass (eg depolymerization and other chain fission reactions).

In certain embodiments, additional fluids may be selectively introduced into the path of an ion beam before the ion beam is incident on the biomass. As discussed earlier, reactions between the ions and particles of the introduced fluids may generate additional chemical species that react with biomass and may assist in reducing the molecular weight of biomass, and / or selectively alter certain properties of the biomass. biomass. The one or more additional fluids may be directed to the ion beam path from a supply tube, for example. The direction (i.e. fluid vector) and flow rate of the fluid (s) being introduced may be selected according to a desired exposure rate and / or direction to control the efficiency of the total biomass treatment, including both effects that result from ion-based treatment and effects that are due to the interaction of dynamically generated species by the introduced fluid with the biomass. In addition to air, exemplary fluids that can 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 different type of ions may be used to treat biomass. Beams that include multiple different types of ions can be generated by combining two or more different beams, each formed of one type of ion. Alternatively, or in addition, in certain embodiments, ion beams that include multiple different types of ions may be generated by introducing a multi-component supply gas into an ion source and / or accelerator. For example, a multi-component gas such as air can be used to generate an ion beam having different types of ions, including nitrogen ions, oxygen ions, argon ions, carbon ions, and other types of ions. Other multi-component materials (e.g. gases, liquids and solids) may be used to generate ion beams having different compositions. Filter elements (e.g., hemispherical electrostatic filters) may be used to filter certain ionic constituents and / or neutral species to selectively produce an ion beam having a particular composition, which may then be used to treat biomass. By using air as a source to produce ion beams for biomass treatment, the operating costs of a treatment system can be reduced compared to systems that rely on pure materials, for example.

Certain types of biomass materials may be treatable particularly for treatment with multiple different types of ions and / or multiple different processing methods. For example, cellulosic materials typically include crystalline polymeric cellulose chains that are crosslinked by the amorphous hemicellulose fraction. Cellulose and hemicellulose are embedded in an amorphous lignin matrix. Separation of the cellulose fraction from lignin and hemicellulose using conventional methods is difficult and can be energy intensive.

However, cellulosic biomass can be treated with multiple different types of ions to destroy and separate the various components in it for further processing. In particular, the chemical properties of various types of ionic species can be used to process cellulosic biomass (and other types of biomass) to selectively degrade and separate components from it. For example, positively charged ions, and in particular protons, act as acids when exposed to biomass material. Conversely, negatively charged ions, particularly hydride ions, act as bases when exposed to biomass material. As a result, the chemical properties of these species can be used to target specific components of treated biomass.

When treating lignocellulosic biomass, for example, the lignin matrix typically decomposes in the presence of basic reagents. Thus, by first treating cellulosic biomass with basic ions such as hydride (or electron) ions from an ion beam (electron), the lignin fraction may preferably be degraded and separated from the cellulose and hemicellulose fractions. Cellulose is relatively unaffected by such ion treatment as cellulose is typically stable in the presence of basic agents.

In addition to negative ion treatment (or as an alternative to negative ion treatment), lignocellulosic biomass can be treated with one or more basic agents in solution to help separate lignin. For example, treating lignocellulosic biomass with a sodium bicarbonate solution may degrade and / or solubilize lignin, enabling separation of the lignin created and / or suspended from the cellulose and hemicellulose fractions.

Negative ion treatment with an ion beam can also help separate hemicellulose, which is also chemically sensitive to basic reagents. Depending on the particular structure of cellulosic biomass, more than one negative ion treatment may be used (and / or may be required) to effectively separate the hemicellulose fraction from the cellulose fraction. In addition, more than one type of ion may be used to separate hemicellulose. For example, a relatively less basic ion beam such as an oxygen ion beam may be used to treat cellulosic biomass to degrade and / or remove the lignin fraction. Then, a stronger basic ion beam such as a hydride ion beam can be used to degrade and separate hemicellulose from cellulose. The cellulosic fraction remains largely unchanged as a result of exposure to two different types of basic ions.

However, the cellulose fraction decomposes in the presence of acidic agents. Accordingly, an additional processing step may include exposing the cellulose fraction to one or more acidic ions such as protons of an ion beam to help depolymerize and / or degrade the cellulose fraction.

Each of the ion beam pretreatments and methods disclosed in this document may be used in combination with other processing steps. For example, separation steps (including introducing a solvent such as water) may be used to clean particular fractions of cellulosic biomass as they are degraded. Additional chemical agents may be added to help separate the various components. For example, it has been observed that lignin which is separated from the cellulose and hemicellulose fractions may be suspended in a wash solution. However, lignin can readily deposit again from the solution on the cellulose and hemicellulose fractions. To prevent further deposition of lignin, the suspension may be lightly heated to ensure that lignin remains below its glass transition temperature and therefore remains fluid. By keeping lignin below its glass transition temperature, lignin can be more readily removed from cellulosic biomass. In general, heating of the suspension is carefully controlled to prevent thermal degradation of sugars in the cellulosic fraction.

In addition, other treatment steps may be used to remove cellulose and hemicellulose lignin. For example, in certain embodiments, lignocellulosic biomass may first be treated with relatively heavy ions (eg carbon ions, oxygen ions) to degrade lignin, and cellulose and hemicellulose may then be treated with relatively light ions (e.g. protons, helium ions) and / or electrons to cause degradation of cellulose and / or hemicellulose.

In some embodiments, one or more functionalizing agents may be added to the lignin-containing suspension to enhance the solubility of lignin in solution, thereby preventing further deposition on the cellulose and hemicellulose fractions. For example, agents such as ammonia gas and / or various types of alcohols may be used (to introduce amino and hydroxyl / alkoxy groups, respectively) for lignin functionalization.

In certain embodiments, structural agents may be added to the lignin suspension to prevent further deposition of lignin in the cellulose and hemicellulose fractions. Typically, when lignin forms a matrix surrounding cellulose and / or hemicellulose, lignin adopts a heavily folded structure that allows relatively extensive van der Waals interactions with cellulose and hemicellulose. In contrast, when lignin is separated from cellulose and hemicellulose, lignin adopts a more open, unfolded structure. By adding one or more agents that help prevent lignin from folding back into the lignin suspension, re-association of lignin with cellulose and hemicellulose can be prevented, and lignin can be removed more effectively by washing, for example.

In some embodiments, no chemicals, for example no swelling agents, are added to the biomass prior to irradiation. For example, alkaline substances (such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxides), acidifying agents (such as mineral acids (eg sulfuric acid, hydrochloric acid and phosphoric acid)), salts, such as zinc chloride, calcium carbonate, sodium carbonate, benzyltrimethylammonium sulfate, or basic organic amines such as ethylene diamine may or may not be added prior to irradiation or other processing. In some cases no additional water is added. For example, pre-processing biomass may have less than 0.5 wt% of added chemicals, for example less than 0.4, 0.25, 0.15 or 0.1 wt% of added chemicals . In some cases, biomass has no more than one trace, for example, less than 0.05% by weight of added chemicals prior to irradiation. At other times, the pre-irradiation biomass substantially has no chemicals or swelling agents added. Avoidance of the use of such chemicals can also be extended throughout the processing, for example every time before fermentation or at all times.

The various ion beam pretreatment methods disclosed herein may be used cooperatively with other pretreatment techniques such as sonication, electron beam irradiation, electromagnetic irradiation, vapor explosion, chemical methods and biological methods. Ion beam techniques provide significant advantages, including the ability to perform ion beam exposure of dry samples, to deliver large doses of radiation to samples in short time periods for high throughput applications, and to exercise relatively precise control over conditions. Exposure

Extinction and Controlled Functionality After treatment with ionizing radiation, the materials described herein become ionized; that is, they include radicals at levels that are detectable with an electron spin resonance spectrometer. The practical limit for detecting radicals is approximately 1014 spins at room temperature. After ionization, any material that has been ionized can be quenched to reduce the level of radicals in the ionized material, for example, such that radicals are no longer detectable with the electron spin resonance spectrometer. For example, radicals may be quenched by applying sufficient pressure to the material and / or by using a fluid in contact with ionized material, such as a gas or liquid, which reacts with (extinguishes) the radicals. The use of a gas or liquid to at least aid in extinction of the radicals also allows the operator to control functionalization of the ionized material with a desired amount and type of functional groups such as carboxylic acid groups, enol groups, aldehyde groups, nitros, nitrile groups, amino groups, amino alkyl groups, alkyl groups, chloroalkyl groups or chlorofluoroalkyl groups. In some cases, such extinction may improve the stability of some of the ionized materials. For example, extinction may improve the material's resistance to oxidation. Extinction functionalization may also improve the solubility of the materials described herein, may improve the thermal stability of a material, and may improve material utilization by various microorganisms. For example, functional groups transmitted to an extinct biomass material may act as receptor sites for attachment by microorganisms, for example, to enhance cellulose hydrolysis by various microorganisms.

Thus, a molecular and / or supramolecular structure of a feedstock may be changed by pretreatment of the feedstock with ionizing radiation, such as with electrons or ions of sufficient energy to ionize the feedstock, to provide a first level of radicals. If an ionized raw material remains in the atmosphere, it will be oxidized, for example, causing carboxylic acid groups to be generated by reacting with atmospheric oxygen. In some cases with some materials such oxidation is desired because it may assist in additional molecular weight disruption, for example of a carbohydrate-containing biomass, and oxidation groups, for example carboxylic acid groups, may be added. useful for solubility and microorganism use. However, since radicals may "live" for some time after irradiation, for example more than 1 day, 5 days, 30 days, 3 months, 6 months or even more than 1 year, material properties may continue to change. over time, which in some cases may be undesirable. Detection of radicals in irradiated samples by electron spin resonance spectroscopy and radical lifetime in such samples is discussed in Bartolotta et al., Physics in in Medicine and Biology, 46 (2001), 461-471 and in Bartolotta et al., Radiation Protection Dosimetry, Vol. 84, Nos. 1-4, pp. 293-296 (1999). The ionized material may be extinguished for its functionality and / or for stabilization. At any point, for example, when the material is "alive", "partially alive" or entirely extinct, the material may be converted into a product, for example a fuel, food or compound.

In some embodiments, quenching includes applying pressure such as mechanically deforming the material, for example by directly compressing the material in one, two or three dimensions, or applying pressure to a fluid in which the material is immersed, for example, isostatic pressing. In such cases, the deformation of the material itself results in radicals, which are often captured in crystalline domains, in sufficient proximity so that the radicals can recombine, or react with another group. In some cases, pressure is applied together with the application of heat, such as a sufficient amount of heat to raise the material temperature above a melting point or softening point of a material component such as lignin, cellulose. or hemicellulose in the case of a biomass material. Heat can improve molecular mobility in the material, which can aid in extinction of radicals. When pressure is used to extinguish, the pressure may be greater than about 6,894.76 kPa (1,000 psi), such as greater than about 8,618.44 kPa (1,250 psi), 9,997.40 kPa (1,450 psi), 24,993, 94 kPa (3,625 psi), 34,990.89 kPa (5,075 psi), 49,986.99 kPa (7,250 psi), 68,947.57 kPa (10,000 psi) or even greater than 103,421.36 kPa (15,000 psi).

In some embodiments, extinction includes contacting the material with a fluid such as a liquid or gas, for example a gas capable of reacting with radicals, such as acetylene or a mixture of acetylene in nitrogen, ethylene, chlorinated ethylene or chlorofluoroethylene, propylene or mixtures of these gases. In other particular embodiments, extinction includes contacting the material, for example biomass, with a liquid, for example a liquid soluble in biomass, or at least capable of penetrating the biomass and reacting with radicals such as a diene such as 1,5-cyclooctadiene. In some specific embodiments, extinction includes contacting the biomass with an antioxidant such as vitamin E. If desired, the feedstock may include an antioxidant dispersed therein, and extinction may arise from contact of the dispersed antioxidant in the feedstock. the radicals.

Other methods for extinction are possible. For example, any method for quenching radicals in polymeric materials described in Muratoglu et al., US Patent Application Publication No. 2008/0067724 and Muratoglu et al., US Patent No. 7,166,650 may be used to quench any described ionized material. in this document. In addition, any extinguishing agent (described as a "sensitizing agent" in the Muratoglu descriptions given above) and / or any antioxidant described in either Muratoglu reference may be used to extinguish any ionized material.

Functionalization can be enhanced by using heavy charged ions such as any of the heavier ions described in this document. For example, if it is desired to enhance oxidation, charged oxygen ions may be used for irradiation. If nitrogen functional groups are desired, nitrogen ions or ions that include nitrogen may be used. Also, if sulfur or phosphorus groups are desired, sulfur or phosphorus ions may be used for irradiation.

In some embodiments, upon extinction any of the extinct materials described herein may be further treated with one or more radiation, such as ionizing or nonionizing radiation, sonication, pyrolysis and oxidation for additional molecular and / or supramolecular structure change.

In particular embodiments, functionalized materials described herein are treated with an acid, base, nucleophile or Lewis acid for additional molecular and / or supramolecular structure change, such as additional molecular weight disruption. 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 a source of hydroxide ions, basic ions such as fluoride ions, or more fragile organic bases such as amines. Even water and sodium bicarbonate, for example, when dissolved in water, can affect change in molecular and / or supramolecular structure, such as additional molecular weight disruption.

Functionalized materials may be used as substrate materials to immobilize microorganisms and / or enzymes during bioprocessing, for example as described in US Provisional Applications Serial No. 61 / 180,032 and 61 / 180,019, the disclosures of which are incorporated. in this document by reference.

Other embodiments are 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-containing materials such as oil sands, oil shale, oil sands, bitumen, coal and other such hydrocarbon mixtures and non-hydrocarbon materials. Many other biomass and non-biomass materials may be processed using the methods described herein including peat, lignin, pre-coal and petrified and / or carbonized materials.

Claims (13)

Method of changing a molecular structure of a cellulosic or lignocellulosic material, characterized in that it comprises: producing an ion beam comprising a first distribution of ion energies having a full width at half height of W; adjusting the energies of at least some of the ions to produce a second ion energy distribution in the ion beam having a full width at half height of more than W; and exposing the cellulosic or lignocellulosic material to the adjusted ion beam, where adjustment is based on a thickness of the cellulosic or lignocellulosic material. Method according to claim 1, characterized in that the total width at half height of the second distribution is greater than W by a factor of 2.0 or more or a factor of 4.0 or more. Method according to claim 1 or 2, characterized in that adjusting the energies of at least some of the ions comprises directing the ions through a scattering element or through a hemispherical analyzer. Method according to any one of claims 1 to 3, characterized in that the beam of adjusted ions passes through a fluid before being incident to the cellulosic or lignocellulosic material. Method according to claim 4, characterized in that the fluid is air at a pressure of 0.5 atmosphere or more. Method according to any one of claims 1 to 5, characterized in that the ion beam comprises two or more different types of ions. Method according to claim 6, characterized in that the two or more different types of ions comprise i) hydrogen ions and carbon ions or ii) hydrogen ions and oxygen ions. Method according to any one of claims 1 to 7, characterized in that the energy adjustment of at least some of the ions is based on an expected ion dose profile in the cellulosic or lignocellulosic material. Method according to claim 8, characterized in that adjusting the energies of at least some of the ions comprises increasing a total width at half height of a Bragg peak of the expected ion dose profile in the material sufficient to reduce a difference between a thickness of the cellulosic or lignocellulosic material and the full width at half height of the Bragg peak. Method according to claim 9, characterized in that, following the adjustment of energies, the difference between the thickness of the cellulosic or lignocellulosic material and the total width at half height of the Bragg peak is 0.01 centimeter. or less. Method according to any one of claims 1 to 10, characterized in that the material comprises lignocellulosic material. Method according to any one of claims 1 to 11, characterized in that the material receives a radiation dose between 0.1 Mrad and 20 Mrad. Method according to any one of claims 1 to 12, characterized in that the lignocellulosic material is first treated with carbon ions or oxygen ions to degrade lignin, and the cellulose and hemicellulose is then treated with protons, ions. helium and / or electrons to degrade cellulose and / or hemicellulose.