Processing biomass
Abstract
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Term
2.6 yearsto projected expiry
Projected expiry 28 April 2029, counted from filing; an application has no term until it is granted.
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1 claim: 1 independent, 0 dependent
- 1PATENT RESERVATIONS:ZASTRZEŻENIA PATENTOWE: 1. The method of producing nutrient material, which consists of: 1. Metoda wytwarzania materiału odżywczego, która polega na: changing the molecular structure of polysaccharides in biomass containing polysaccharides in the form of cellulose by exposing the biomass to an electron beam emitted by an electron beam irradiation device with a minimum power of 1 kW and a maximum of 500 kW to produce nutrient material with nutrient availability exceeding the availability of biomass nutrients this method does not involve the use of a micro-organism. zmianie struktury molekularnej polisacharydów w biomasie zawierającej polisacharydy w postaci celulozy poprzez poddanie biomasy działaniu wiązki elektronów emitowanej przez urządzenie do napromieniania wiązką elektronów o mocy minimalnej 1 kW i maksymalnej 500 kW w celu wyprodukowania materiału odżywczego o dostępności składników pokarmowych przekraczającej dostępność składników pokarmowych biomasy, przy czym metoda taka nie obejmuje użycia mikroorganizmu. 2. The method indicated in Claim 1 further comprising feeding the nutrient material to animals, in particular humans or crop plants. 2. Metoda wskazana w Zastrzeżeniu 1 obejmująca w dalszej części podawanie materiału odżywczego zwierzętom, a w szczególności ludziom, lub roślinom uprawnym. 3. The method indicated in Claim 1 or Claim 2 consisting in the further use of the nutrient material in agriculture, in particular in hydroponic solution or in aquaculture. 3. Metoda wskazana w Zastrzeżeniu 1 lub Zastrzeżeniu 2 polegająca w dalszej części na wykorzystaniu materiału odżywczego w rolnictwie, w szczególności w roztworze hydroponicznym, lub w akwakulturze. 4. The method indicated in Claim 1, wherein the biomass is irradiated with an electron beam using a dose rate of 1 Mrad / s to 10 Mrad / s. 4. Metoda wskazana w Zastrzeżeniu 1, w której biomasa jest napromieniana wiązką elektronów z zastosowaniem mocy dawki od 1 Mrad/s do 10 Mrad/s. 5. The method indicated in Claim 1, wherein the biomass comprises lignocellulosic material. 5. Metoda wskazana w Zastrzeżeniu 1, w której biomasa obejmuje materiał lignocelulozowy. 6. The method indicated in Claim 1, in which the biomass is selected from the group consisting of grasses, rice hulls, sugar cane pomace, jute, hemp, flax, bamboo, sisal, manila bananas, straw, corn cobs, corn straw, alfalfa, hay , coconut hair, seaweed, and mixtures of these ingredients. 6. Metoda wskazana w Zastrzeżeniu 1, w której biomasa jest wybierana z grupy składającej się z traw, łusek ryżowych, wytłoków z trzciny cukrowej, juty, konopi, lnu, bambusa, sizalu, bananów manilskich, słomy, kolb kukurydzy, słomy kukurydzianej, lucerny, siana, włosów kokosowych, wodorostów oraz mieszanin tych składników. 7. The method indicated in Claim 6, in which the biomass comprises corn cobs or corn straw. 7. Metoda wskazana w Zastrzeżeniu 6, w której biomasa obejmuje kolby kukurydzy lub słomę kukurydzianą. 8. The method indicated in Claim 1, wherein the biomass receives a radiation dose of at least 2.5 Mrad. 8. Metoda wskazana w Zastrzeżeniu 1, w której biomasa otrzymuje dawkę promieniowania na poziomie co najmniej 2,5 Mrad. 9. The method indicated in Claim 1, wherein the biomass receives a radiation dose of at least 5.0 Mrad. 9. Metoda wskazana w Zastrzeżeniu 1, w której biomasa otrzymuje dawkę promieniowania na poziomie co najmniej 5,0 Mrad. 10. The method indicated in Claim 1, wherein the availability of nutrients is determined by providing the same amount of nutrient and biomass to at least two different groups of at least one animal, and determining the loss of at least one nutrient in the faeces for a specified period of time. 10. Metoda wskazana w Zastrzeżeniu 1, w której dostępność składników odżywczych jest oznaczana poprzez podanie jednakowej ilości materiału odżywczego oraz biomasy co najmniej dwóm różnym grupom składającym się z co najmniej jednego zwierzęcia i oznaczanie strat co najmniej jednego ze składników odżywczych w odchodach przez określony okres czasu. 11. The method indicated in Claim 1, in which the material is further processed to increase material sterility and / or remove, deactivate and / or neutralize materials that may be present in the biomass. 11. Metoda wskazana w Zastrzeżeniu 1, w której materiał jest dodatkowo przetwarzany w celu zwiększenia sterylności materiału i/lub usunięcia, dezaktywacji i/lub neutralizacji materiałów, które mogą być obecne w biomasie. 12. The method indicated in Claim 1, in which the material is compacted to increase its bulk density. 12. Metoda wskazana w Zastrzeżeniu 1, w której materiał zostaje zagęszczony w celu zwiększenia jego gęstości nasypowej. 13. The method indicated in Claim 1, in which the material is solid. 13. Metoda wskazana w Zastrzeżeniu 1, w której materiał ma postać stałą. 14. The method indicated in Claim 13, wherein the solid form is in the form of a powder, tablet, mineral block, granulate, biscuit or a mixture of unprocessed and processed material. 14. Metoda wskazana w Zastrzeżeniu 13, w której postać stała ma formę proszku, tabletki, bloku mineralnego, granulatu, suchara lub mieszaniny nieprzetworzonego i przetworzonego materiału. 100 100 BIOMASA BIOMASS 100 100 SIDE SIDE. SIDE UBOCZNE UBOCZNE Fig.1 RYS.1 LYNX. 2 RYS. 2 222 222 220 \ \ 220 \ \ SOURCE ZRODŁO PODCIŚNIENIA VACUUM LYNX. 3 RYS. 3 252 252 FIRST TWO PIERWSZE DRUGIE SITO SITO SITO SITO LYNX. 4 RYS. 4 Fig.5 RYS.5 300 300 360 360 LYNX. 6 RYS. 6 370 370 LYNX. 7A RYS. 7A LYNX. 7C RYS. 7C LYNX. 7B RYS. 7B LYNX. 7D RYS. 7D OBROBKA TREATMENT Μη, Μη, OXIDATION UTLENIANIA Mru mru This. To. This, To, LYNX. 8 RYS. 8 LYNX. 10 RYS. 10 3000 3000 LYNX. 11 RYS. 11 OXIDATION UTLENIANIE OBROBKI WSTĘPNEJ PRELIMINARY PROCESSING HO ^ o biomass A CONNECTING GUIDELINES DEACTIVATION Q HO^o biomasAZAwierająca RODNIKI DEZAKTYWACJA Q Q Q LYNX. 12 RYS. 12 11109 11109 LYNX. 11B RYS. 11B LYNX. 11E RYS. 11E LYNX. 11D RYS. 11D CN CN CN CN CN CN 1250 1250 ABOUT O CN CN CN CN LYNX. 12 RYS. 12 GENERATOR GENERATOR SPRZĘGAJĄCY coupling GENERATOR GENERATOR Ύ Ύ LYNX. 13 RYS. 13 353 353 Rozpuszczalniki solvents LYNX. 16 RYS. 16 GAS (EC) GAZ (WE) GAS (WY) GAZ(WY) LYNX. 17 RYS. 17 1820 1820 LYNX. 18 RYS. 18 130 130 LYNX. 19 RYS. 19 142 142 LYNX. twenty RYS. 20 LYNX. 21 RYS. 21 LYNX. 22 processing RYS. 22 przetwarzanie 5140 j 5140 j lyophilized ł LIOFILIZOWANE DROŻDŻE, BAKTERIE YEAST, BACTERIA AND / OR ENZYM τ Ψ I/LUB ENZYM τ Ψ OPCJONALNE ODWRACALN OPTIONAL REVERSIBLE INCREASE DENSITY ZWIĘKSZENIE GĘSTOŚCI NASYPOWEJ bulk CELULAZY cellulase 414 414 OPCJONALNE OPTIONAL PRZEWAPNOWAN PRZEWAPNOWAN IE HYDROLIZA IE HYDROLYSIS ENZYMATIC ENZYMATYCZNA TRANSPORT AND / OR TRANSPORT I/LUB PRZECHOWYWANIE STORAGE 412 412 CUKRY SUGARS FERMENTABLES FERMENTUJĄCE E. coli E.COLi K011 K011 FERMENTACJA FERMENTATION 450 450 LYNX. 23 RYS. 23 ΔΆΔ ΔΆΔ OPENING TO THE ATMOSPHERE UJŚCIE DO ATMOSFERY LYNX. 24 RYS. 24 2500 2500 2510 2510 LYNX. 25 RYS. 25 Χ25 1 mm Χ25 1 mm LYNX. 26 RYS. 26 Χ25 1 mm Χ25 1 mm LYNX. 27 RYS. 27 Χ25 Χ25 1mm 1mm LYNX. 29 RYS. 29 LYNX. thirty RYS. 30 512 512 LYNX. 31 RYS. 31 LYNX. 32 RYS. 32 LYNX. 33 RYS. 33 LYNX. 35 RYS. 35 ................. 4271 'SEI ................. 4271' SEI LYNX. 36 RYS. 36 Przepuszczalność % Transmittance% Liczby falowe (cm-1) Wave numbers (cm-1) LYNX. 37 RYS. 37 Przepuszczalność % Transmittance% Liczby falowe (cm-1) Wave numbers (cm-1) LYNX. 38 RYS. 38 ELECTRICITY ELEKTRYCZNOŚĆ Fig.39 RYS.39 118 118 OBRÓBKA WSTĘPNA PRELIMINARY PROCESSING 114 114 PREPARED PRZYGOTOWANY RAW MATERIAL irradiation SUROWIEC napromienianie PROCES PROCESS WATER WODA BASIC PODSTAWOWY LYNX. 40 RYS. 40 8000 8000 LYNX. 41 RYS. 41 LYNX. 42 RYS. 42 8532 8532 8534 8534 8508 8508 8516 8516 8518 8518 8520 8520 8514 8514 8504 8504 8502 8502 8526 8526 8530 8530 8528 8528 8506 8506 8510 8510 8512 8512 LYNX. 43A RYS. 43A LYNX. 43B RYS. 43B PRODUCTS PRODUKTY LYNX. 44 RYS. 44 LYNX. 45 RYS. 45 BIOMASA BIOMASS INTRODUCTION PROCESSING OBROBKA WSTĘI KROZDRABNIANIE / CUT) KROZDRABNIANIE/CIĘCIE) PRODUKT1 Product1 PRODUCT 2 PRODUKT 2 PROCESSING PRZETWARZANIE PRODUCT 3 " PRODUKT 3" LYNX. 46 RYS. 46
720 paragraphs in 15 sections, as filed
TECHNICAL FIELD
The present invention relates to a method of producing nutritional material.
INFORMATION ABOUT THE PRESENT TECHNOLOGY
Biomass is a widely available material. This applies in particular to biomass waste. Obtaining biomass products would therefore be very useful.
SUMMARY
The present invention relates to a method for producing nutrient material consisting in changing the molecular structure of polysaccharides in biomass containing cellulose polysaccharides by exposing the biomass to an electron beam emitted by an electron beam irradiation device with a minimum power of 1 kW and a maximum of 500 kW to produce nutrient material with component availability nutrients exceeding the availability of biomass nutrients, this method does not include the use of a microorganism.
In one aspect, the present invention includes methods of producing nutritional materials for animals (e.g., humans and animals, including, but not limited to, farm, domestic, zoo animals, etc.), plants (e.g., agricultural plants, cereals or plants) aquatic plants, including, but not limited to, plants grown in hydroponic solutions or in aquaculture) and aquatic organisms (e.g. fish, crustaceans, molluscs, etc.).
These methods include obtaining initial material containing biomass (e.g. plant biomass, animal biomass and biomass from municipal waste) with the content of polysaccharides in the form of cellulose. Then, the molecular structure of the polysaccharides contained in the starting material is modulated (e.g. increase, decrease or behavior) to produce secondary material with higher nutrient availability (e.g. proteins, carbohydrates, fats, vitamins and / or minerals) than for the starting material. These methods can optionally include administering the secondary material to animals (including humans).
In some embodiments, materials useful in supporting and stimulating the growth of aquatic organisms (e.g., aquaculture) and / or plants and trees (e.g., agriculture, hydroponics, and forestry) can be produced using the methods described herein.
For some implementations, biomass can be selected from the group consisting of paper, paper products, paper waste, wood, chipboard, sawdust, agricultural waste, sewage, silage, grasses, rice hulls, sugar cane pomace, cotton, jute, hemp, flax, bamboo, sisal, manila bananas, straw, corn cobs, corn straw, cane, alfalfa, hay, coconut hair, seaweed, algae and mixtures of these ingredients. In some cases, the biomass has internal fibers and has been cut in such a way that these fibers are highly exposed and / or the BET surface area of the biomass exceeds about 0.25 m / g and its bulk density is less than about 0.5 g / m.
Mixtures prepared using the methods described herein may contain saccharide units linked into a molecular chain in which from about 1 in every 2 units to about 1 in every 250 saccharide units forms a carboxylic acid group or an ester or salt of the carboxylic acid, and such a mixture is useful for ingestion in the form of a nutritional material.
For some implementations, the composition has many such chains. In some cases, from about 1 in every 5 to about 1 in every 250 saccharide units of each chain forms a carboxylic acid group or an ester or salt of the carboxylic acid. This applies in particular from about 1 in every 8 to about 1 in every 100 saccharide units or from about 1 in every 10 to about 1 in every 50 saccharide units of each chain that form a carboxylic acid group or an ester or salt of the carboxylic acid. Each chain may contain from about 10 to about 200 saccharide units. Each chain contains cellulose and may contain saccharide units containing groups selected from the group consisting of the following groups: nitroso, nitro and nitrile. Saccharide units may contain 5- or 6-carbon saccharide units. The average molecular weight of the composition in relation to PEG standards is from 1,000 to 1,000,000, usually below 10,000.
The term "suitability for consumption as a nutritional material" means that, under the intended conditions, the mixture is not toxic to the living organisms to which it is administered, and provides them with specific nutritional values, i.e. energy and / or nutrients.
In some embodiments, the raw biomass is pretreated. In some examples, the methods described in this paper may include pretreatment to reduce at least one of the dimensions of individual biomass fragments. Pre-treatment by reducing at least one of the dimensions of individual biomass fragments may include, for example, shearing, cutting, crushing, breaking or abrasion.
Pressure can be used for all methods described in this paper. For example, at least one of the methods of treatment (e.g. irradiation) of biomass may be carried out at a pressure exceeding about 2.5 atmospheres, for example greater than 5 or 10 atmospheres.
Biomass (also called "raw biomass" or "raw material") may include cellulosic or lignocellulosic materials, such as paper, paper products, paper waste, wood, chipboard, sawdust, agricultural waste, sewage, silage, grass, rice husk, pomace from sugar cane, cotton, jute, hemp, flax, bamboo, sisal, manila bananas, straw, corn cobs, corn straw, cane, alfalfa, hay, coconut hair, cassava, synthetic cellulosic materials and / or mixtures of these ingredients.
In some cases, the biomass may contain organic waste, such as animal or human waste or manure (e.g. manure and sewage). In some cases, the biomass may contain any combination of these components. Other materials included in the biomass have been described in this study. In addition, other cellulose-containing materials are described in patents, patent applications and publications referenced herein. In some cases, the biomass may be in e.g. diluted, dried and frozen form.
In some cases, the biomass may or may contain natural or synthetic material.
Irradiation is carried out using ionizing radiation, in this case electron beams.
Ionizing radiation is in the form of an electron beam. An exemplary total radiation dose may be between about 10 Mrad and about 150 Mrad with a daily dose of between about 0.5 to about 10 Mrad or a dose rate of about 1 Mrad / s to about 10
Mrad / s. In some embodiments, irradiation involves the use of at least two radiation sources, such as gamma rays and an electron beam.
Biomass (e.g. biomass raw materials) can be pre-cut to obtain fibrous material. For example, a rotary cutter can be used for cutting. An exemplary average length to diameter ratio (L / D) of fibers of the fibrous material may exceed 5/1. An exemplary BET surface area of fibrous material may be, for example, 0.25 m<sup>2</sup>/ g (0.3 m<sup>2</sup>/ g, 0.35 m<sup>2</sup>/ g, 0.4 m<sup>2</sup>/ g, 0.5 m<sup>2</sup>/ g, 1 m<sup>2</sup>/ g, 1.5 m<sup>2</sup>/ g, 2 m<sup>2</sup>/ g, 3 m<sup>2</sup>/ g, 10 m<sup>2</sup>/ g, 25 m<sup>2</sup>/ g or over 25 m<sup>2</sup>/ G).
In some examples, the pretreated biomass material may contain a buffer solution such as sodium bicarbonate or ammonium chloride, an electrolyte such as potassium chloride or sodium chloride, a growth factor such as biotin and / or a base pair, e.g. uracil, a surfactant , minerals or chelating agent.
The term "fibrous material" in this study will mean a number of loose, separate fibers. The fibrous material can be prepared, for example, from bleached Kraft paper fibers by cutting (e.g. using a rotary cutter).
The term "screen" in this study will mean an element capable of screening material by size. Examples of sieves include perforated sheet, a drum or similar, or wire mesh or fabric.
Swelling agents will be understood here as materials that cause pronounced swelling, e.g.
A 2.5% increase in volume relative to the volume of non-swollen biomass materials after using such materials in the form of a solution, for example, an aqueous solution. Examples include basic substances such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxides, acidifying agents such as mineral acids (e.g. sulfuric acid, hydrochloric acid and phosphoric acid), salts such as zinc chloride, calcium carbonate, sodium carbonate, benzyltrimethylammonium sulfate, and basic organic amines such as ethylenediamine.
In some embodiments of the methods described herein, no chemicals such as swelling agents are added to the biomass, which means that the biomass is not exposed to such substances prior to irradiation. For example, basic substances such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxides, acidifying agents such as mineral acids (e.g. sulfuric acid, hydrochloric acid and phosphoric acid), salts such as zinc chloride, calcium carbonate, sodium carbonate, benzyltrimethylammonium sulfate or basic organic amines such as ethylenediamine. In some cases, no additional water is added. For example, prior to processing, the biomass may contain less than 0.5 percent by weight of added chemicals, e.g., less than 0.4, 0.25, 0.15, or 0.1 percent by weight of added chemicals. In some cases, prior to irradiation, biomass may only contain trace amounts of added chemicals, e.g., less than 0.05 weight percent. In other cases, the biomass will generally not contain any added chemicals or swelling agents prior to irradiation. Avoiding the use of such chemicals can also be extended to all stages of the process.
The term "edible" will be understood here as being suitable for consumption in the form of food.
"Cut material" will be understood here as a material comprising separate fibers in which at least about 50% of the separate fibers have a length / diameter (L / D) ratio of at least 5 and a bulk density uncompressed by
the material is approximately less than about 0.6 g / cm.
In some embodiments, a change in the molecular structure of the biomass will be understood herein as a change in the distribution of chemical bonds, for example, the type and number of functional groups, or the conformation of the structure. Changing the molecular structure may include, for example, changing the level of material resistance, changing the supramolecular structure of the material, oxidizing the material, changing the average molecular weight, changing the average crystallinity, changing the surface area, changing the degree of polymerization, changing the porosity, changing the degree of branching, transplanting to other materials, changing crystal domain size or change in overall domain size.
Unless otherwise specified, all technical and scientific terms used in this publication have the same meaning as commonly accepted by persons having ordinary knowledge in the field covered by the present invention. Suitable applications and materials used in connection with the present invention are described below. In practice or for testing, however, methods and materials similar or equivalent to those described herein are possible. In the event of inconsistencies, the description presented in this study, together with the terminology used, will prevail. In addition, the materials, methods and examples presented are illustrative only, not restrictive.
The term 'object' will be used in this specification to refer to animals, humans or non-human organisms. This concept will refer to, among others to birds, reptiles, fish, plants, amphibians and mammals, e.g. humans, other primates, pigs, rodents such as mice and rats, rabbits, guinea pigs, hamsters, cows, horses, cats, dogs, sheep and goats.
In each of the methods described here, irradiation can be carried out using a device available in stock.
Other features and advantages of the present invention will be set forth in the following detailed description and in the claims.
DESCRIPTION OF THE DRAWINGS
LYNX. 1 is a block diagram illustrating the conversion of biomass into products and by-products.
LYNX. 2 is a block diagram illustrating the conversion of fiber sources into first and second fibrous material.
LYNX. 3 shows a cross-sectional view of a rotary cutter.
LYNX. 4 is a block diagram illustrating the conversion of fiber sources into second and third fibrous material.
LYNX. 5 is a block diagram illustrating material compaction.
LYNX. 6 is a space view of a granulate mill.
LYNX. 7A shows a dense granular fibrous material.
LYNX. 7B shows a cross-section of a granulated grain with a hollow, where the hollow is centered.
LYNX. 7C shows a cross-section of a granulated grain with a hollow, where the hollow is not centered.
LYNX. 7D shows a cross-section of a three-arm granulate grain.
LYNX. 8 is a block diagram illustrating the processing sequence for processing the raw material.
LYNX. 9 is a spatial view of the vertical cross-section of the gamma irradiation apparatus enclosed in a concrete bunker.
LYNX. 10 shows an enlarged spatial view of the R area in FIG. 9.
LYNX. 11 is a block diagram illustrating the sequence of raw material pretreatment by electron beam irradiation.
LYNX. 11A shows a diagram of biomass that is ionized and then oxidized and deactivated.
LYNX. 11B shows a schematic side view of a system for irradiating low bulk density material, while FIG. 11C shows a cross section of the system along axis 11C-11C.
LYNX. 11D is a schematic cross-sectional view of a fluidized bed system for irradiating low bulk density material.
LYNX. 11E is a schematic side view of another system for irradiating material with a low bulk density.
LYNX. 12 shows a schematic view of the system for sonication of a process stream of cellulosic material in a liquid medium.
LYNX. 13 shows a schematic view of an ultrasonic homogenizer equipped with two transducers connected to one generator.
LYNX. 14 is a block diagram illustrating a raw material pyrolytic pretreatment system.
LYNX. 15 is a cross-sectional side view of the pyrolysis chamber.
LYNX. 16 is a cross-sectional side view of the pyrolysis chamber.
LYNX. 17 shows a cross-sectional side view of a filament pyrolyzer.
LYNX. 18 is a cross-sectional side view of the Curie point pyrrolyser.
LYNX. 19 is a cross-sectional side view of the furnace pyrolyzer.
LYNX. 20 is a cross-sectional top view of the laser pyrolyser.
LYNX. 21 is a cross-sectional top view of a tungsten filament pyrolyzer.
LYNX. 22 is a block diagram illustrating a raw material pre-oxidation system.
LYNX. 23 is a block diagram illustrating the overall process of converting fiber sources into a product, e.g., ethanol.
LYNX. 24 is a cross-sectional view of the steam explosion apparatus.
LYNX. 25 is a cross-sectional side view of a hybrid device for electron beam sonication / irradiation.
LYNX. 26 is a scanning electron microscope image of a fibrous material obtained from laminated paper at a magnification of 25x. The fibrous material was obtained using a rotary cutter using a 1/8 inch screen.
LYNX. 27 is a scanning electron microscope image showing fibrous material obtained from bleached Kraft cardboard at 25x magnification. The fibrous material was obtained using a rotary cutter using a 1/8 inch screen.
LYNX. 28 is a scanning electron microscope image showing fibrous material obtained from bleached Kraft cardboard at 25x magnification. The fibrous material was cut twice using a rotary cutter using a 1/16 inch screen during each cutting cycle.
LYNX. 29 is a scanning electron microscope image showing fibrous material obtained from bleached Kraft cardboard at 25x magnification. The fibrous material was cut three times using a rotary cutter. During the first cut, a 1/8 inch screen was used, during the second cut, a 1/16 inch screen was used, and during the third cut, a 1/32 inch screen was used.
LYNX. 30 is a schematic side view of the sonication apparatus, while FIG. 31 is a cross-sectional view through the processing chamber of the apparatus shown in FIG. thirty.
LYNX. 32 is a scanning electron microscope image at 1000x magnification showing fibrous material formed by cutting a cane using a rotary cutter, and then passing the cut material through a 1/32 inch screen.
LYNX. 33 and 34 are images from a scanning electron microscope at 1000x magnification showing the fibrous material shown in FIG. 32 after irradiation with gamma rays at a dose of 10 Mrad and 100 Mrad, respectively.
LYNX. 35 are images from a scanning electron microscope at 1000x magnification showing the fibrous material presented in FIG 32 after irradiation with a dose of 10 Mrad and sonication.
LYNX. 36 are images from a scanning electron microscope at 1000x magnification showing the fibrous material shown in FIG 32 after irradiation with a dose of 100 Mrad and sonication.
LYNX. 37 shows the infrared spectrum of kraft paper cut with a rotary cutter.
LYNX. 38 shows the infrared spectrum of Kraft paper presented in FIG. 37 after irradiation with gamma rays at a dose of 100 Mrad.
LYNX. 39 is a schematic diagram of the biomass conversion process.
LYNX. 40 is a diagram of another biomass conversion process.
LYNX. 41 is a diagram of a portable automotive biomass processing installation.
LYNX. 42 is a diagram of a portable railway biomass processing installation.
LYNX. 43A and 43B are diagrams illustrating processing steps to produce basic and by-products from biomass (A) and to produce products using a biochemical reacting step.
LYNX. 44 is a diagram illustrating a fermentation process based on variable volume batches.
LYNX. 45 is a diagram illustrating a fermentation process based on constant volume batches.
LYNX. 46 is a diagram illustrating the processing steps required to manufacture products 1, 2 and 3. An asterisk indicates optional steps. The black arrow indicates the possibility of performing the optional compaction step.
DETAILED DESCRIPTION
Biomass (e.g. plant biomass, animal biomass and municipal waste biomass) can be processed using the methods described here to obtain useful food products.
In the systems and processes described below, the raw materials may be various biomass cellulosic or lignocellulosic materials.
The present invention is at least in part based on the observation that the methods described herein can be used to convert biomass into non-energy components and materials. Such materials and ingredients are foods (e.g., fit for human and / or animal consumption).
BIOMASS TYPES
In principle, any biomass material that is a carbohydrate consisting of at least one saccharide unit or containing at least one saccharide unit, or which contains such carbohydrate can be processed using the methods described herein. In this study, it will be assumed that the biomass contains cellulosic and lignocellulosic materials. The biomass material may be, for example, cellulosic or lignocellulosic materials, such as corn grains or other feeds.
Such materials include, for example, paper, paper products, wood, wood-based materials, chipboards, grasses, rice husk, sugar cane pomace, cotton, jute, hemp, flax, bamboo, sisal, manila bananas, straw, corn cobs, coconut hair, algae, seaweed (e.g. large seaweed), water hyacinths, cassava, coffee beans, coffee grounds (used), cotton, synthetic celluloses or mixtures of these ingredients.
Fiber sources are sources of cellulose fibers, such as paper and paper products (e.g., laminated paper and kraft paper), and sources of lignocellulosic fibers, such as wood and wood-based materials, e.g. chipboard. Other useful sources of fiber are natural sources such as grasses, rice husk, sugar cane pomace, cotton, jute, hemp, flax, bamboo, sisal, manila bananas, straw, corn cobs, coconut hair, as well as sources of high fiber content alphacelluloses, such as cotton, and synthetic fiber sources, such as extruded (pre-oriented or non-oriented) yarns. Natural or synthetic fiber sources can be obtained from primary textile waste materials, e.g. debris, or from post-consumer waste, such as used clothing. Paper products used as fiber sources may be primary materials, e.g. primary waste materials, or post-consumer waste. In addition to primary raw materials, fiber sources can also be post-consumer, industrial (e.g. waste) and technological waste (e.g. waste water generated during paper processing). Fiber sources can be obtained or recovered from human (e.g. sewage), animal or plant waste. Additional fiber sources have been described in the prior art, see, for example, US Patent Nos. 6,448,307, 6,258,876, 6,207,729, 5,973,035 and 5,952,105.
Biomass may include, for example, renewable organic matter, such as plant biomass, animal biomass (e.g. animal by-products, animal waste, etc.) and municipal waste biomass, as well as any combination of these biomass materials.
Plant biomass and lignocellulosic biomass include organic (wood or non-wood) matter derived from plants, in particular matter that is available at a constant level. Examples include harvest residues and waste such as corn straw, wheat straw, rice straw, sugar cane pomace, etc. Plant biomass includes, among others residues and wastes from trees, energy woody plants and wood, such as residues from logging of conifers, waste bark, sawdust, waste streams of the pulp and paper industry, wood fibers, etc. In addition, cultivated grasses such as reeds can provide an additional source of biomass large-scale plant culture. In urban areas, plant raw biomass is also household waste (e.g. grass clippings, leaves, felled tree branches and brushwood) and waste generated during vegetable processing.
In some embodiments, the biomass may contain lignocellulosic raw materials, which may include plant biomass, including non-wood derived biomass, cultivated cereals, such as grasses, for example C4 grasses, such as cane, sparta, ryegrass, Miscanthus, reed canary or combinations thereof, or sugar processing residues, such as sugar cane pomace or beet pulp, or agricultural residues, for example soy straw, corn straw, rice grass, rice husk, barley straw, corn cobs, wheat straw, rape straw, rice straw, oat straw, oat husk, corn fiber, fibers recovered from wood pulp, sawdust, deciduous wood, for example aspen wood and sawdust, softwood and combinations of these raw materials. In addition, lignocellulosic raw materials include cellulosic waste materials, such as waste paper, cardboard, sawdust, etc. Lignocellulosic raw materials may consist of one type of fiber or a mixture of fibers derived from different lignocellulosic raw materials. In addition, lignocellulosic raw materials may consist of fresh lignocellulosic raw materials, partially dried lignocellulosic raw materials, completely dried lignocellulosic raw materials or a combination of these raw materials.
Animal biomass includes any organic waste material, such as waste material from animals or their faeces, or human waste material or human faeces (e.g. manure or sewage).
In some embodiments, the carbohydrate is a material or comprises a material having at least one β-1,4 bond and having a number average molecular weight between about 3000 and 50,000. Such a carbohydrate is cellulose or comprises cellulose (I) obtained from (β-glucose 1 ) by condensation of 3- (1 ^ 4) glycosidic bonds. This combination contrasts with the combination characteristic of α- (Ι> 4) glycosidic bonds found in starch and other carbohydrates.
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AND
Combinations (e.g., a single biomass material, product and / or by-product produced by the methods described in this study, or a combination of such materials or products) described in this study, biomass materials can be used to make any of the products described herein.
BIOMASS PROCESSING SYSTEMS
LYNX. 1 shows a system 100 for converting biomass, in particular biomass with a high content of cellulosic and lignocellulosic components into useful basic and by-products. System 100 includes batch production subsystem 110, pretreatment subsystem 114, basic processing subsystem 118 and final processing subsystem 122. Biomass in raw form is introduced into the feed subsystem 110, where it is physically produced to form the raw material used in subsequent processes (e.g. by reducing the size and homogenization of biomass) and stored both in raw form and in raw material form.
The raw material biomass containing cellulosic and / or lignocellulosic components of large size may have high average molecular weight and crystallinity, which may impede the processing of the raw material into useful products. For this reason, raw biomass treatment is useful, for example, using the treatment methods described in this paper. As described herein, in some embodiments, biomass treatment does not use acids or bases for biomass processing, or uses such agents in small or catalytic amounts.
The pretreatment subsystem 114 receives raw biomass from the batch production subsystem 110 and prepares the feedstock for use in major production processes by, for example, reducing the average molecular weight and crystallinity of the feedstock. Primary processing subsystem 118 receives the processed raw material from pre-treatment subsystem 114 and produces useful products (e.g. feed products). In some cases, the output from the basic processing subsystem 118 is directly useful, but in other cases it requires further processing by the post-processing subsystem 122. The post-processing subsystem 122 provides further processing of product streams originating from the primary processing system 118 and requiring such treatment and processing of the streams wastes from other subsystems. In some cases, by-products of subsystems 114, 118, 122 may also be useful directly or indirectly as secondary products and / or increase the overall performance of the system 100. The post-processing subsystem 122 may, for example, produce treated water for reuse as water technology in other subsystems and / or combustible waste that can be used as fuel for steam boilers and / or for producing electricity.
The optimal size of a biomass conversion plant depends on factors such as economies of scale and the type and availability of raw biomass. Increasing the size of the installation allows increasing the economies of scale associated with plant processing. However, increasing the size of the installation may involve an increase in costs (e.g. transport costs) per unit of raw material. Research to analyze these factors suggests that the right size of the biomass conversion plant ranges from 100 to over 1000 (e.g., 10,000) tons of dry raw material per day, depending (at least in part) on the type of raw material used. The type of raw biomass also affects the installation's requirements for storage, where for installations mainly intended for processing raw material with seasonal availability (e.g. corn straw) requires more resources for storing raw material on and off the plant than in the case of installations intended for processing raw material with relatively constant availability (e.g. waste paper).
PRELIMINARY BIOMASS PROCESSING
In some cases, the processing methods used at the pretreatment stage start with the production of biomass, for example, reducing the size of raw biomass raw materials by cutting, abrasion, crushing, breaking, shearing or chopping. In some embodiments, methods (e.g., mechanical methods) are used to reduce the size and / or dimensions of individual biomass elements. In some cases, the raw material in loose form (e.g. waste paper or cane) is subjected to pre-treatment consisting of cutting or shredding. Using sieves and / or magnets, you can remove too large or unwanted objects such as stones or nails from the batch stream.
Batch pretreatment systems can be configured to produce batch streams with specific characteristics, such as specific maximum sizes, specific length-width ratios, or specific surface area proportions. As part of the pre-treatment of the charge, you can control the bulk density of the raw materials (e.g. increase density).
Size reduction
In some embodiments, the biomass is in the form of a fibrous material containing fibers obtained in the biomass cutting process. For example, a rotary cutter can be used for cutting.
Source biomass fibers 210 can be cut, for example, as in FIG. 2, using a rotary cutter to obtain the first fibrous material 212. The first fibrous material 212 is forced through a first screen 214 with an average hole size of 1.59 mm or smaller (1/16 inch, 0.0625 inch) to obtain second fibrous material 216. If necessary, the fiber source can be shredded, e.g. with a chopper, before cutting. If the source material is, for example, paper, then it will first be cut into strips with an exemplary width of 1/4 to 1/2 inches using a shredder, such as a counter-rotating screw shredder manufactured, for example, by Munson (Utica, New York). Instead of shredding, the paper size can also be reduced by cutting to the right size with a guillotine shear. Guillotine shears can be used, for example, to cut paper into 10 inch by 12 inch sheets.
In some embodiments, cutting the fiber source and forcing the obtained first fibrous material through the first screen occurs simultaneously. Cutting and pressing can also be carried out as a batch process.
For example, a rotary cutter can simultaneously cut fiber sources and screen the first fibrous material. With reference to FIG. The 3 rotary cutter 220 consists of a 222 hopper into which shredded fiber sources 224 produced using standard methods can be loaded. A shredded fiber source is cut between stationary blades 230 and movable blades 232 to obtain a first fibrous material 240. The first fibrous material 240 is forced through a screen 242, and the second fibrous material 244 obtained in this way goes to the basket 250. To aid the accumulation of the second fibrous material, a basket can be pressurized below nominal atmospheric pressure, e.g. at least 10 percent lower than nominal atmospheric pressure, at least 25 percent lower than nominal atmospheric pressure, at least 50 percent lower than nominal pressure atmospheric or at least 75 percent lower than the nominal atmospheric pressure. In some embodiments, a vacuum source 252 is used to maintain the basket pressure below the nominal atmospheric pressure.
Cutting allows the fiber material to "open" and "stretch", making the cellulose contained in the materials more susceptible to chain degradation and / or reduction of crystallinity. Opened materials after irradiation may also be more susceptible to oxidation.
In some embodiments, the cut allows the fiber material to "open" and "stretch", making the cellulose contained in the materials more digestible and better absorbed for ruminants.
The fiber source can be cut in a dry, hydrated state (with absorbed water content up to ten percent by weight) or in a wet state (with water content from about 10 to about 75 percent by weight). The fiber source can be cut even under partial or total immersion in a liquid such as water, ethanol or isopropanol.
The fiber source can also be cut in a gas envelope (such as a stream or atmosphere of a gas other than air), e.g. oxygen or nitrogen, or in a cloud of steam.
Other methods of producing fibrous material include grinding stone grinding, mechanical tearing or tearing, abrasion with mandrel grinders and / or air-milling.
If desired, fibrous materials can be divided, e.g. continuously or in batch, into fractions according to length, width, density, material type or combination of these properties.
For example, magnetic materials can be separated from all fibrous materials by passing the fibrous material containing the magnetic material through a magnet, e.g. an electromagnet, and then by squeezing the resulting fibrous material through a series of screens with different hole sizes.
The fibrous material can also be separated by a high speed gas stream (e.g. air).
In this case, the separation of fibrous materials occurs by transfer of different fractions, which, if desired, can be characterized in a photonic manner. Such a separation device is described in Lindsey et al., US Patent No. 6,883,667.
The fibrous material can be pretreated immediately after manufacture or it can be dried, e.g. at about 105 ° C for 4-18 hours, so that the moisture content before use does not exceed about 0.5%.
If necessary, lignin can be removed from fibrous materials that contain it. To increase the susceptibility of cellulose-containing materials, such material may be subjected to heat or chemical treatment before irradiation (e.g. with a mineral acid, alkali or strong oxidant such as sodium hypochlorite).
In some embodiments, the average opening size of the first screen is less than 0.79 mm (1/32 inch, 0.03125 inch), e.g., less than 0.51 mm (1/50 inch, 0.02000 inch), less than 0.40 mm (1/64 inch, 0.015625 inch), less than 0.23 mm (0.009 inch), less than 0.20 mm (1/128 inch, 0.0078125 inch), less than 0.18 mm (0.007 inch), smaller than 0.13 mm (0.005 inch) or even smaller than 0.10 mm (1/256 inch, 0.00390625 inch). The sieve is made by interlacing individual fibers of appropriate diameter to obtain the desired size of holes. Monofilaments can for example be made of metal, such as stainless steel. The smaller the hole size, the greater the structural requirements for individual screen fibers. For example, in the case of apertures smaller than 0.40 mm, it is preferable to use fibers made of a material other than stainless steel for the sieve, e.g. of titanium, titanium alloys, amorphous metals, nickel, tungsten, rhodium, rhenium, ceramics or glass. In some embodiments, the screen is made of sheet metal, e.g., sheet metal with laser cut holes. In some embodiments, the mesh opening area is less than 52%, e.g., less than 41%, less than 36%, less than 31%, less than 30%.
In some embodiments, the second fibrous material is cut and pressed through the first screen or through a different size screen. In some embodiments, the second fibrous material is forced through a second screen with an average hole size equal to or smaller than the first screen size.
With reference to FIG. 4 from the second fibrous material 216, a third fibrous material 220 can be prepared by shearing the second fibrous material 216 and forcing the material thus obtained through a second screen 222 with an average opening size equal to the opening size of the first screen 214 or smaller.
Generally, the fibers in the fibrous materials may have a relatively large length to diameter ratio (e.g., more than 20 to 1), even if they have been cut more than once. Furthermore, the fibers of the fibrous materials described in this study may have a relatively narrow length distribution and / or length to diameter ratio.
For the purposes of this study, it is assumed that the average fiber widths (e.g. diameters) are optically determined on the basis of about 5,000 randomly selected fibers. Average fiber lengths are corrected weighted lengths. BET surface areas (Brunauer, Emmett and Teller) are surface areas measured by the multipoint method, and porosities are determined by mercury porosimetry.
The average ratio of length to diameter in the second fibrous material 14 may be greater than 5/1, e.g. greater than 8/1, greater than 10/1, greater than 15/1, greater than 20/1, greater than 25/1, or greater than 50/1. The average length of the second fibrous material 14 may be e.g. from about 0.5 mm to 2.5 mm or from about 0.75 mm to 1.0 mm, and the average width (e.g. diameter) of the second fibrous material 14 may be e.g. from about 5 pm to 50 pm or from about 10 pm to 30 pm.
In some embodiments, the standard deviation of the length of the second fiber material 14 is less than 60 percent of the average length of the second fiber material 14, e.g., less than 50 percent of the average length, less than 40 percent of the average length, less than 25 percent of the average length, less than 10 percent medium length, less than 5 percent of average length, and even less than 1 percent of average length.
In some embodiments, the BET surface area of the second fibrous material is greater than 0.1 m<sup>2</sup>/ g, e.g. greater than 0.25 m<sup>2</sup>/ g, greater than 0.5 m<sup>2</sup>/ g, greater than 1.0
2 2 2 2 m / g, greater than 1.5 m / g, greater than 1.75 m / g, greater than 5.0 m / g, greater than 10 m / g,
2 2 2 greater than 25 m / g, greater than 35 m / g, greater than 50 m / g, greater than 60 m / g, larger
2 2 2 than 75 m / g, greater than 100 m / g, greater than 150 m / g, greater than 200 m / g or even greater than 250 m / g. For example, the porosity of the second fibrous material 14 may be greater than 20 percent, greater than 25 percent, greater than 35 percent, greater than 50 percent, greater than 60 percent, greater than 70 percent, greater than 80 percent, greater than 85 percent, greater than 90 percent, greater than 92 percent, greater than 94 percent, greater than 95 percent, greater than 97.5 percent, greater than 99 percent, and even greater than 99.5 percent.
In some embodiments, the ratio of the average length to diameter ratio of the first fibrous material to the average length to diameter ratio of the second fibrous material is, for example, less than 1.5, less than 1.4, less than 1.25, less than 1.1, less than 1.075, less than 1.05, less than 1.025, and even close to 1.
In particular embodiments, the second fibrous material is re-cut, and the fibrous material obtained in this way is forced through a second screen, whose average hole size is smaller than the size of the first screen holes, whereby a third fibrous material is obtained. In such cases, the ratio of average length to diameter ratio of the second fiber material to average ratio of length to diameter of the third fiber material is, for example, less than 1.5, less than 1.4, less than 1.25, and even less than 1.1.
In some embodiments, the third fibrous material is forced through a third screen to obtain a fourth fibrous material. For example, the fourth fibrous material can be forced through a fourth screen to obtain a fifth material. A similar screening process can be repeated any number of times until the desired fibrous material having the desired properties is obtained.
thickening
Compaction will be understood here as increasing the bulk density of the material. Using the methods described in this paper, you can process condensed materials or compact all processed materials.
A material, e.g. a fiber material, with a low bulk density can be compacted to obtain a product with a higher bulk density. For example, a material with a bulk density of 0.05 sts
g / cm<sup>3</sup> can be compacted by placing the fibrous material in a relatively gas-tight structure, e.g. in a polyethylene bag or in a bag made of alternating layers of polyethylene and nylon, and then sucking off the gas, e.g. air, enclosed in this space. After suction of air from such a structure, the bulk density of the fibrous material can be, for example, more than 0.3 g / cm<sup>3</sup>, 0.5 g / cm<sup>3</sup>, 0.6 g / cm<sup>3</sup>, 0.7 g / cm<sup>3</sup> about
or more, e.g. 0.85 g / cm. After concentration, the product can be subjected to pre-treatment by irradiation. This may be advantageous when it is necessary to transport the material to another location, such as a remote manufacturing plant, where fiber material will be added to the solution. After making the hole in a substantially gas-tight structure, the densified fibrous material can return to a bulk density close to its initial value, e.g. to a density of at least 60 percent of the initial bulk density, e.g., 70 percent, 80 percent, 85 percent or more, e.g., 95 percent of the initial bulk density. To reduce the occurrence of static electricity in fibrous material, an antistatic agent can be added to it.
In some embodiments, the structure, e.g., a carrier, such as a bag, is formed of a liquid-soluble material, e.g., water. The structure can be formed, for example, from polyvinyl alcohol, therefore it will dissolve on contact with the aqueous solution.
With reference to FIG. The biomass material can be combined with any desired additives or binders and then compacted by applying pressure, for example by passing the material through the contact area of counter-rotating pressure rollers or by passing the material through a granulate mill. When applying pressure, you can optionally use heat to help thicken the fiber material. The compacted material can then be irradiated.
In some embodiments, before the compaction, the bulk density of the material is less than 0.25 g / cm, e.g. less than or approximately 0.20 g / cm, 0.15 g / cm, 0.10 g / cm, 0.05 g / cm or less, e.g. 0.025 g / cm. Bulk density is determined using the method described in ASTM D1895B. Briefly, this method involves filling a measuring cylinder with a specific volume with a sample and measuring the weight of the sample. The bulk density is calculated by dividing the sample mass in grams by the specific volume of the cylinder in cubic centimeters.
Preference is given to water-soluble, water-swellable or glass transition binders below 25 ° C as determined by differential scanning calorimetry. Water-soluble binders have a solubility of at least about 0.05 percent by weight in water. Water-swellable binders are those whose volume in contact with water increases by more than 0.5 percent.
In some embodiments, water-soluble or swellable binders containing a functional group capable of forming a bond, e.g., a hydrogen bond, with the fibers of a fibrous material, e.g., a cellulosic fibrous material. The functional group may be, for example, a carboxylic acid group, a carboxyl group, a carbonyl group, e.g. aldehyde or ketone, sulfonic acid group, sulfonic group, phosphoric acid group, phosphate group, amide group, amino group, hydroxyl group, e.g. alcohol, and also a combination of these groups, e.g. carboxylic acid group and hydroxyl group. Among specific examples of monomers, glycerin, glyoxal, ascorbic acid, urea, glycine, pentaerythritol, monosaccharides or disaccharides, citric acid and tartaric acid can be mentioned. Useful saccharides include glucose, sucrose, lactose, ribose, fructose, mannose, arabinose and erythrosis. Examples of polymers include polyglycols, polyethylene oxide, polycarboxylic acids, polyamides, polyamines, and polysulfonic acid polysulfonates. Specific examples of polymers include polypropylene glycol (PPG), polyethylene glycol (PEG), polyethylene oxide, e.g. POLYOX®, copolymers of ethylene oxide and propylene oxide, polyacrylic acid (PAA), polyacrylamide, polypeptides, polyethyleneimine, polyvinylpyridine, poly (sodium 4-styrene sulfonate) and poly (2-acrylamido-methyl-1-propylsulfonic acid).
In some embodiments, the binder comprises a polymer with a glass transition temperature below 25 ° C. Examples of such polymers are thermoplastic elastomers (TPE). Examples of TPE elastomers may be block polyetheramides available, for example, under the trade name PEBAX®, polyester elastomers available, for example, under the trade name HYTREL®, and styrene block copolymers available, for example, under the trade name KRATON®. Other suitable polymers with a glass transition temperature below 25 ° C are ethylene vinyl acetate copolymer (EVA), polyolefins such as polyethylene, polypropylene, ethylene and propylene copolymers, as well as ethylene and alpha olefin copolymers, e.g. 1-octene, available for example under the trade name ENGAGE®. In some embodiments, for example, when the material is fibrous laminated paper, the material is compacted without adding a separate low glass transition temperature polymer.
In specific embodiments, the binder is lignin, for example, natural or synthetically modified lignin.
The appropriate amount of binder added to the material is calculated based on the weight of the dry material and is, for example, from about 0.01 percent to about 50 percent of the total weight of the compacted material, e.g. 0.03 percent, 0.05 percent, 0.1 percent, 0.25 percent, 0.5 percent, 1.0 percent, 5 percent, 10 percent or more, e.g. 25 percent of the total weight of compacted material. The binder can be added to the material in the form of a clean liquid, liquid binder solution, dry powder or granules.
The compacted fibrous material can be prepared in a granulate mill. With reference to FIG. 6 granulate mill 300 is equipped with a 301 chute, in which there is a non-concentrated material 310 consisting of carbohydrate-containing materials such as cellulose. The chute is connected to a screw conveyor 312 driven by a variable speed motor 314, which is responsible for transporting the non-concentrated material to the conditioner 320, in which the non-concentrated material is mixed using blades 322 propelled by a conditioner motor 330. Other components, e.g. any additives and / or fillers described in this study may be added through inlet 332. If necessary, the fiber material in the conditioner can be heated. After conditioning, the material passes from the conditioner through the chute 340 to the next screw feeder 342. The chute controlled by the actuator 344 allows the free flow of material from the conditioner to the screw feeder. The auger feed is rotated by a motor 346 and controls the feeding of fibrous material to the roll assembly with the mold 350. The material is introduced into a hollow cylindrical mold 352 which rotates around a horizontal axis and has radially propagating molding holes 250. The mold 352 is moved around the axis by means of a 360 motor that is equipped with a power meter that indicates the total power consumption of the engine . The compacted material 370, for example in the form of granules, falls through the gutter 372, after which it is captured and processed, for example by irradiation.
After compaction, the material can have a convenient form of granules or sawdust of various shapes. The granulate can then be irradiated. In some embodiments, the granules or sawdust have a cylindrical shape, e.g., with a maximum transverse dimension of 1 mm or more, e.g. 2 mm, 3 mm, 5 mm, 8 mm, 10 mm, 15 mm or more, e.g. 25 mm . Other convenient shapes include granules or sawdust in discs 1 mm thick or larger, e.g. 2 mm, 3 mm, 5 mm, 8 mm, 10 mm or more, e.g. 25 mm and with a width e.g. 5 mm or larger, e.g. 10 mm, 15 mm, 25 mm, 30 mm or larger, e.g. 50 mm; and a length of 5 mm or more, e.g. 10 mm, 15 mm, 25 mm, 30 mm or more, e.g. 50 mm.
With reference to FIG. 7A-7D granules can be hollow inside. As shown, the hollow may be centered relative to the granule (FIG. 7B) or non-centered relative to the granule (FIG. 7C). The use of a hollow in granules may increase the rate of its dissolution in the liquid after irradiation.
With reference to FIG. 7D the cross-sectional shape of the granules can be a multi-armed figure, e.g. a three-armed (as in the drawing), four-armed, five-armed, six-armed or ten-armed. The production of granules with such a cross-sectional shape also increases the dissolution speed in the solution after irradiation.
The compacted material may also have any other form, for example mats, rolls or bales.
Examples of compaction
In the first example, the raw material will be juice cartons with a capacity of half o
gallon made of unprinted white Kraft cardboard with a bulk density of 20 lb / ft<sup>3</sup>. Cartons can be flattened and then fed to a crusher to produce confetti-like material from 0.1 inch to 0.5 inch wide and 0.25 inch to 1 inch long and with a thickness equivalent to that of the starting material (about 0.075 inches). Confetti-like material can be fed to a rotary cutter, which will cut confetti-like fragments, tearing them and releasing fibrous material.
In some cases, series of machines consisting of shredders and cutters can be used. In one embodiment, the two chopper modules connected to the cutter can be arranged in a row so that the outlet of the first cutter will be simultaneously an inlet to the second chopper. In another embodiment, the three shredder modules connected to the slicer can be arranged in a row so that the outlet of the first slicer is simultaneously the inlet to the second shredder and the outlet of the second slicer is the inlet to the third shredder. It is envisaged to use multiple passages through shredders and cutters to achieve smaller particle sizes and increase overall surface area within the batch stream.
In another example, the fibrous material produced at the stage of grinding and cutting juice cartons can be treated to increase bulk density. In some cases, the fibrous material can be sprayed with water or a prepared dilute solution of POLYOX ™ WSR N10 (polyethylene oxide) dissolved in water. The wetted fibrous material can then be treated with a granulate mill at room temperature. The granulation mill can increase the bulk density of the feed stream by more than an order of magnitude.
In some embodiments, the processing does not include hydrolyzing biomass, e.g., an acid or base, e.g., a mineral acid, such as hydrochloric acid or sulfuric acid.
If necessary, only part of the biomass may contain hydrolysed material or the biomass may not contain it at all. For example, in some embodiments, at least seventy percent by weight of the biomass is non-hydrolyzed material, e.g., at least 95 percent by weight of the raw material is non-hydrolyzed material. In some embodiments, substantially all of the biomass is non-hydrolysed material. In some embodiments, 100% of the biomass is non-hydrolysed material.
Any raw material or any reactor or fermenter with a raw material charge may contain a buffer solution such as sodium bicarbonate, ammonium chloride or Tris; an electrolyte such as potassium chloride, sodium chloride or calcium chloride; growth factor such as biotin and / or base pair, e.g. uracil or its equivalent; a surface active agent such as Tween® or polyethylene glycol; a mineral such as calcium, chromium, copper, iodine, iron, selenium or zinc; or a chelating agent such as ethylenediamine, ethylenediamine tetraacetic acid (EDTA) (or a salt thereof, e.g. sodium edetate or potassium edetate) or dimercaprol.
If irradiation is used for or during treatment, it can be used on a dry or wet sample, or even dissolved in a liquid such as water. For example, biomass material of which less than about 25 percent by weight has a surface moistened with a liquid, such as water, can be irradiated. In some embodiments, the biomass material is irradiated, wherein substantially no part is wetted with a liquid such as water.
In some embodiments, all of the processing forms described herein are taken on dry biomass material that has been provided or dried in such form, for example, by heat and / or vacuum. In some embodiments, the biomass material contains less than about five percent by weight of retained water when measured at 25 ° C and a relative humidity of fifty percent.
If necessary, a bulking agent can be used in each of the processes described in this study. In some embodiments, when processing biomass material using radiation, less than about 25 percent by weight of the biomass material is swollen, wherein the swelling state is taken to be a volume of more than about 2.5 percent greater than the swelling state, e.g. more than 5.0, 7.5, 10 or 15 percent greater than the volume in the swollen state. In some embodiments, when the biomass material is exposed to radiation, substantially no part of it is swollen.
In certain embodiments, when radiation is used, the biomass material comprises a swelling agent, and the swollen biomass material receives a dose of less than about 10 Mrad.
The radiation used for processing can be given when the biomass is exposed to air, air with a higher oxygen content or even oxygen itself or is surrounded by an inert gas such as nitrogen, argon or helium. When maximum oxidation is required, an oxygenating environment such as air or oxygen is used.
The radiation used can be used for biomass at a pressure above about 2.5 atmospheres, e.g. above 5, 10, 15, 20, and even above about 50 atmospheres. Irradiation may increase the biomass susceptibility to dissolution, swelling or dispersion in the solvent.
When the process involves radiation, an electron beam is used for irradiation. In some embodiments, irradiation involves the use of at least two radiation sources, such as gamma rays and an electron beam, which can be administered in any order or simultaneously.
irradiation
At least one irradiation sequence can be used to process biomass from a variety of sources to extract substances useful from the raw material and to produce partially degraded organic material that will serve as a feedstock at subsequent processing stages and / or in subsequent sequences. Irradiation can reduce the resistance, molecular weight and / or crystallinity of the raw material.
Radiation is produced by electron accelerators. The doses used depend on the desired effect and the particular raw material. For example, high doses of radiation can break the chemical bonds of raw materials, and low doses of radiation can increase the number of chemical bonds (e.g., through cross bonds) among the raw materials.
With reference to FIG. 8, in one method, the first cellulose material 2 or containing cellulose with a first average number molecular weight (tMn1) is irradiated, e.g. by providing an electron beam, to obtain a second material 3 containing cellulose with a second average number molecular weight ( tMn2) less than the first number average molecular weight. The second material (or the first and second materials) can be combined with microorganisms (e.g. bacteria or yeast) that can use the second and / or first material to produce product 5, but this is not the embodiment of the invention.
The second material 3 contains cellulose with reduced resistance, has a lower molecular weight compared to the first material and in some cases reduced crystallinity, therefore the second material is generally more susceptible to dispersion, swelling and / or more soluble in a solution containing microorganisms. This makes the second material 3 more susceptible to chemical, enzymatic and / or biological attacks (e.g. carried out by microorganisms) than the first material 2, which can significantly improve the rate of production and / or the level of production of the desired product, e.g. ethanol. Radiation can also be used to sterilize materials.
In some embodiments, the second number average molecular weight (Mn2) is lower than the first number average molecular weight (Mn2)<sup>T</sup>Mn1) by more than about 10 percent, e.g. 15, 20, 25, 30, 35, 40, 50 percent, 60 percent, and even more than about 75 percent.
An electron beam
In the present invention, the electron beam serves as a source of radiation. The advantages of the electron beam are high dose rates (e.g. 1, 5 and even 10 Mrad per second), high throughput and lower requirements for the security devices used.
Electrons can also provide greater efficiency in causing chain breakdowns. In addition, the electron penetration depth with 4-10 MeV energies can be from 5 to 30 mm or more, e.g. 40 mm.
Electron beams can be produced, e.g., by means of electrostatic machines, cascade generators, transformer generators, low energy accelerators with a scanning system, low energy accelerators with a linear cathode, linear accelerators and impulse accelerators. Electrons that are a source of ionizing radiation can be useful, for example, for relatively thin piles of material, with a thickness less than, for example, 0.5 inches, e.g. less than 0.4 inch, 0.3 inch, 0.2 inch or 0.1 inch. In some embodiments, the energy of each electron in the electron beam is from about 0.3 MeV to about 2.0 MeV (million electron volts), e.g. from about 0.5 MeV to about 1.5 MeV or from about 0.7 MeV to about 1.25 MeV.
LYNX. 11 is a flow diagram of a 3000 process that includes various stages of a raw material pretreatment sequence by electron beam irradiation. In the first step 3010, the dry raw material is fed from the source. According to the above considerations, the dry raw material derived from the source may be pre-processed before being delivered to electron beam irradiation equipment. For example, if the raw material originates from plant sources, certain parts of the material can be removed prior to harvesting the plant material and / or before it is delivered by means of the raw material transport device. As an alternative or complementary solution, as in optional step 3020, the raw biomass can be subjected to mechanical processing (e.g. to reduce the average fiber length of the raw material) before it is delivered to electron beam irradiation devices.
At step 3030, the dry raw material is transferred to the raw material handling device (e.g., conveyor belt) and distributed approximately evenly across the entire width of the raw material transporting device. This can be done, for example, manually or by inducing vibration at a specific point in the raw material transport device before processing by electron beam irradiation.
In some embodiments, the mixing system incorporates chemical 3045 into the feedstock as part of an optional 3040 process that produces a slurry. By combining water with the processed raw material at mixing stage 3040, an aqueous raw material slurry is obtained, for which the pipeline will be a better transport channel than, for example, a conveyor belt.
The next stage 3050 involves a loop consisting of exposure of the raw material (in dry or suspended form) to electron beam radiation emitted from one or more (N) electron beam irradiation devices.
The raw material slurry passes through each of the "showers" A electron beams at stage 3052. Movement at such a transition can be at a constant speed of passage through and between showers or between individual showers may be followed by a pause, followed by a sudden transition to the next shower. A small portion of the raw material suspension is exposed to each shower for some pre-determined exposure time at step 3053.
Electron beam irradiation equipment can be purchased commercially from Ion Beam Applications, Louvain-la-Neuve in Belgium or Titan Corporation, San Diego, California. Typical electron energies can be 1 MeV, 2 MeV, 4.5 MeV, 7.5 MeV or 10 MeV. The power of typical electron beam irradiation devices can be 1 kW, 5 kW, 10 kW, 20 kW, 50 kW, 100 kW, 250 kW or 500 kW. The depolymerization efficiency of the raw material suspension depends on the electron energy and dose used, while the exposure time depends on the strength and dose. Typical doses may be 1 kGy, 5 kGy, 10 kGy, 20 kGy, 50 kGy, 100 kGy or 200 kGy.
When choosing the power specifications of electron beam irradiation devices, a compromise solution should be selected that takes into account service costs, capital costs, depreciation and space requirements. When choosing the exposure doses for electron beam irradiation, a compromise solution should be chosen that takes into account energy costs, as well as environmental, safety and health (OHS) issues. The compromise solution for the selection of electron energy should take into account energy costs. In this case, lower electron energy may be beneficial for stimulating depolymerization of a particular raw material suspension (see, for example, Bouchard, et al., Cellulose (2006) 13: 601-610).
It may be beneficial to provide a double pass by electron beam irradiation to improve the efficiency of the depolymerization process. For example, the raw material handling device may direct the raw material (in dry or slurry form) in a direction opposite to the initial direction of transport under the initial transport channel. Two-track systems enable the processing of thicker layers of raw material suspensions and ensure greater homogeneity of depolymerization over the entire thickness of the raw material slurry.
An electron beam irradiation device can produce a solid beam or a scanning beam. Scanning beam can be beneficial at large spans and high scanning speeds, because such a configuration will effectively replace fixed beams of large width. In addition, beam spans of 0.5 m, 1 m, 2 m or more are available. One of the relevant devices is shown in Example 22.
After transporting a portion of the raw material slurry through N electron beam irradiation equipment in some embodiments, as in step 3060, it may be necessary to mechanically separate the liquid and solid constituents of the raw material slurry. In such embodiments, the liquid portion of the raw material slurry is filtered to recover residual solids and recovered for the 3040 slurry preparation step. The solid part of the raw material slurry is then transferred to the next 3070 processing stage via a raw material transporting device. In other embodiments, the raw material is kept in suspension for further processing.
doses
In some embodiments, the irradiation (using any radiation source or combination of sources) is performed until the material receives a dose of at least 0.25 Mrad, e.g. at least 1.0 Mrad, at least 2.5 Mrad, at least 5.0 Mrad or at least 10.0 Mrad. In some embodiments, the irradiation is performed until the material receives a dose between 1.0 Mrad and 6.0 Mrad, e.g., between 1.5 Mrad and 4.0 Mrad.
In some embodiments, the irradiation is performed at a dose rate between 5.0 and 1500.0 kilorades / hour, e.g. between 10.0 and 750.0 kilorades / hour or between 50.0 and 350.0 kilorades per hour.
In some embodiments, at least two radiation sources are used, e.g., at least two ionizing radiation. For example, samples can be irradiated in any order with an electron beam, followed by gamma rays and light
UV wavelengths from about 100 nm to about 280 nm. In some embodiments, the samples are exposed to three ionizing radiation sources, such as an electron beam, gamma radiation, and energetic UV radiation.
Deactivation and controlled functionalization of biomass
After irradiation with an electron beam, all the hydrocarbon-containing mixtures or materials described in this study become ionized, i.e. they contain radicals at levels detectable using an electron spin resonance spectrometer. The current limit of detection of radicals is about 1014 spins at room temperature. After ionization, the ionized biomass material can be deactivated to reduce the level of radicals in the ionized biomass, e.g. to such a level at which the radicals will no longer be detectable by means of an electron spin resonance spectrometer. Radicals can be deactivated, for example, by exposing the biomass to sufficient pressure and / or using a liquid in gas or liquid form, which in contact with the ionized biomass will react with the radicals (deactivating the radicals). The use of a gas or liquid at least as a factor supporting the deactivation of radicals can be used to functionalize the ionized biomass with the desired amount and types of functional groups, such as carboxylic acid groups, enol groups, aldehyde groups, nitrogen groups, nitrile groups, amino groups, alkylamino groups, alkyl groups , chloroalkyl groups or chlorofluoroalkyl groups. In some cases, such deactivation may improve the stability of some ionized materials. Inactivation can, for example, improve the resistance of biomass to oxidation. Functionalization through deactivation can also improve the solubility of the biomass described in this study and its thermal stability, which in turn can improve the use of material by various microorganisms.
LYNX. 11A illustrates the change in the molecular and / or supramolecular structure of raw biomass after electrons have penetrated into the raw biomass and generated the first level of radicals. As seen in FIG. 11A, if the ionized biomass remains in the atmosphere, it will be oxidized to the extent that it can produce carboxylic acid groups by reaction with atmospheric oxygen. For some materials, this oxidation is desirable because it helps to further reduce the molecular weight of the carbohydrate-containing biomass, and oxidative groups, e.g. a carboxylic acid group, may in some cases promote solubility. However, due to the fact that radicals may "live" for some time after irradiation, e.g. for more than 1 day, 5 days, 30 days, 3 months, 6 months and even more than 1 year, the properties of materials may change over time, which in some cases may be undesirable. The detection of radicals in irradiated samples using ESR spectroscopy and the viability of radicals in such samples are discussed by Bartolotta et al., Physics in Medicine and Biology, 46 (2001), 461-471 and Bartolotta et al., Radiation Protection Dosimetry, Vol. 84, No. 14, pp. 293-296 (1999). As shown in FIG. 11A, the ionized biomass can be deactivated to functionalize and / or stabilize the ionized biomass. At any stage, when, for example, the material is "live" (contains a significant amount of reactive intermediates such as radicals), "partially live" or completely inactivated, the processed biomass can be converted into a product, e.g. food.
In some embodiments, the deactivation includes exposing the biomass to pressure, e.g., by mechanically deforming the biomass, e.g., by mechanically compressing the biomass in one, two or three dimensions, or by increasing the pressure of the liquid in which the biomass is immersed, e.g., by isostatic pressing. In such cases, the mere deformation of the material means that the radicals, which are often trapped in the crystal domains, are close enough that they can change combinations or react with another group. In some cases, the increase in pressure is accompanied by the use of a heat source, for example, supplying an amount of heat that causes the biomass temperature to rise above a melting or softening point for the biomass component, such as cellulose. Heat can improve molecular mobility in polymeric materials, which can be helpful in deactivating radicals. When deactivated under pressure, the pressure may be higher than about 1000 psi, e.g., higher than about 1250 psi, 1450 psi, 3625 psi, 5075 psi, 7250 psi, 10,000 psi, and even higher than 15,000 psi.
In some embodiments, the deactivation consists of contacting the biomass with a liquid or gaseous liquid, for example a gas that reacts with radicals such as acetylene or a mixture of acetylene in nitrogen, ethylene, chlorinated ethylenes or chlorofluoroethylenes, propylene or mixtures of these gases. In other specific embodiments, the deactivation consists in contacting the biomass with a liquid, e.g. a liquid which is soluble in biomass or at least able to penetrate the biomass and reacts with radicals, e.g. belonging to dienes, such as 1,5-cyclooctadiene. In some specific embodiments, deactivation involves contact of the biomass with an antioxidant such as vitamin E. If desired, raw biomass may contain the antioxidant dispersed therein, and deactivation may occur by contact of the antioxidant dispersed in the raw biomass with radicals. Combinations of these and other deactivating materials may be used.
It is possible to use other deactivation methods. For example, any method for deactivating 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, can be used, for example, to deactivate each ionized biomass material described herein. In addition, any deactivating agent (referred to in Muratoglu's "sensitizing agent" as mentioned above) and / or any antioxidant described in each of Muratoglu's above may be used to deactivate each ionized biomass material.
In some embodiments, after deactivation, each of the inactivated ionizing materials described herein may be further processed by at least one radiation, such as ionizing or non-ionizing radiation, sonication, pyrolysis and oxidation to provide additional change in molecular and / or supramolecular structure.
Particle irradiation in fluids
In some cases, cellulosic or lignocellulosic materials may be irradiated with a particle beam in the presence of at least one additional fluid (e.g., gas and / or liquid). Irradiation of the material with a particle beam in the presence of at least one additional fluid can increase processing efficiency.
In some embodiments, the material is irradiated with a particle beam in the presence of a fluid such as air. Particles introduced into accelerated motion by means of at least one of the types indicated in this study (or another type of accelerator) are led out of the accelerator through the exit port (e.g. a thin membrane, such as metal foil), then pass through the volume of space occupied by the liquid and go to the material. In addition to interacting directly with the material, some particles produce additional chemicals by interacting with fluid particles (e.g., ions and / or radicals formed from various air components, such as ozone and nitrogen oxides). These manufactured chemicals can also interact with the material and initiate a variety of different chemical bond breaking reactions. For example, any oxidant produced can oxidize the material, which can lead to molecular weight reduction.
In certain embodiments, additional fluids can be selectively introduced into the particle path prior to irradiation of the material. As mentioned above, the reactions between the beam particles and the particles of introduced fluids can result in the formation of additional chemicals that will react with the material and support the functionalization of the material and / or selectively change specific properties of the material. At least one additional fluid can be directed to the beam path using, for example, a power cord. The direction and flow rate of introduced fluids can be selected based on the desired indicator and / or direction of exposure to control the efficiency of the entire treatment process, including the effects resulting from both particle beam irradiation and the effects resulting from the interaction of substances produced dynamically from the introduced fluid from material. In addition to air, fluids such as oxygen, nitrogen, at least one inert gas, at least one halogen and hydrogen can be introduced into the ion beam.
Irradiation of low bulk density biomass materials and cooling of irradiated biomass
When irradiating biomass materials using ionizing radiation, especially at high dose rates, e.g. dose rates exceeding 0.15 Mrad per second, e.g. 0.25 Mrad / s, 0.35 Mrad / s, 0.5 Mrad / s , 0.75 Mrad / s, and even 1 Mrad / s, biomass materials accumulate significant amounts of heat so that the temperature of the biomass materials rises. Although in some embodiments, higher temperatures may be preferred, e.g. when it is desired to increase the reaction rate, it is preferable to control the heat of the biomass to maintain control over chemical reactions initiated by ionizing radiation, such as cross-linking, chain disintegration and / or transplantation, e.g. to maintain control over the process. Materials with low bulk density, i.e.
those whose bulk density is less than about 0.4 g / cm, e.g. less than about 0.35, o
0.25 or less than about 0.15 g / cm<sup>3</sup>, especially when combined with materials with small cross-sections, such as fibers with a small cross-section, are easier to cool. In addition, photons and particles generally penetrate deeper into materials with a relatively low bulk density and penetrate better through them, which allows the processing of larger amounts of materials at a higher speed and allows the use of photons and particles with lower energies, e.g. 0.25 MeV, 0.5 MeV, 0.75 MeV or 1.0 MeV, which reduces the requirements for safety guards. Many of the biomass materials described in this paper can be processed in at least one of the systems presented in FIG. 11B, 11C, 11D and 11E and described below. The presented systems allow irradiation of low bulk density biomass materials with at least one type of ionizing radiation, e.g. relativistic electrons or electrons in combination with X-rays, using high dose rates for example at levels exceeding 1.0, 1.5, 2.5 Mrad / s, and even about 5.0 Mrad / s, and then allow the biomass to be cooled before giving the second, third, fourth, fifth, sixth, seventh, eighth, ninth and even tenth radiation dose.
For example, in one method of changing the molecular and / or supramolecular structure of raw biomass, the biomass at the first temperature is exposed to ionizing radiation by electron irradiation for a sufficient time and / or at a sufficient dose to increase the temperature of the raw biomass to a second temperature higher than the first temperature. Then the biomass after pre-treatment is cooled to a temperature lower than the second temperature. Finally, if necessary, the cooled biomass can be irradiated at least once, e.g. using ionizing radiation. If desired, cooling of the biomass can be carried out after each radiation treatment and / or during each such treatment.
In some embodiments, the raw biomass is cooled until the biomass reaches a third temperature lower than the first temperature.
Irradiation of raw biomass with ionizing radiation can take place, for example, during pneumatic transfer of raw biomass in a fluid such as gas, e.g. nitrogen or air. This process will be described in more detail below. To assist in molecular weight reduction and / or functionalization of materials, the gas can be saturated with any of the swelling agents described herein and / or with steam. For example, acidified water vapor can be used for this purpose. To help reduce molecular weight, water can be acidified with an organic acid, such as formic acid or acetic acid, or a mineral acid, such as sulfuric acid or hydrochloric acid.
Irradiation of the raw biomass with ionizing radiation can take place, for example, during the fall of the raw biomass under the influence of gravity, as described below. This procedure effectively reduces the bulk density of the raw biomass during processing and promotes the cooling of the raw biomass. For example, the biomass can be conveyed on a first belt at a certain height above the ground and then captured by a second belt at a second level above the ground below the first level. In some embodiments, the rear edge of the first tape and the front edge of the second tape define a gap. The advantage of this solution is that the ionizing radiation of the electron beam can be applied at the gap, avoiding damage to the biomass conveyor system.
In the methods described herein, cooling of the biomass may involve contact of the biomass with a fluid, such as a gas, at a temperature lower than the first and second temperatures, for example with nitrogen gas at 77 K or similar. You can even use water, e.g. water with a temperature lower than the rated room temperature (e.g. 25 degrees Celsius).
Raw biomass can be irradiated at the first temperature using ionizing radiation for a sufficiently long time and / or using a sufficiently high dose, e.g. from about 1 second to about 10 seconds at a dose rate of from about 0.5 Mrad / s to about 5 Mrad / s to increase the raw biomass temperature to a second temperature, higher than the first temperature. After applying the radiation, the biomass can be cooled to a temperature lower than the second temperature.
In some embodiments, the method of changing the molecular and / or supramolecular structure of raw biomass optionally comprises pretreatment of raw biomass to reduce at least one of the dimensions of individual raw biomass fragments and the use of ionizing radiation in the form of electrons directed to the raw biomass. In such embodiments, β-treated feed biomass is fed with ionizing radiation
ionizing radiation has a bulk density of less than about 0.35 g / cm β
an example less than about 0.3, 0.25, 0.20 or less than about 0.15 g / cm. In such embodiments, the raw biomass can be cooled and then the chilled biomass treated with ionizing radiation. In some favorable embodiments, the raw biomass consists of discrete fibers and / or particles, or comprises discrete fibers and / or particles with a maximum dimension not exceeding about 0.5 mm, e.g. not exceeding approximately 0.25 mm, 0.1 mm, 0.05 mm or 0.025 mm.
At this point, reference is made to FIG. 11B and 11C, which shows a device for producing, processing, transferring and irradiating biomass material 1170 (covers are not shown in the drawings). During the working cycle, a sheet of 1173 paper, e.g., a sheet of bleached Kraft recycled paper, is fed from a roll 1172 and delivered to a 1174 fiberizer, such as a rotary cutter. Sheet 1173 is processed into fibrous material 1112 and delivered to the fiber loading zone 1180 by means of a conveyor 1178. If desired, fibrous material fibers can be separated, e.g. by screening, into fractions with different length-diameter ratios. In some embodiments, fibrous material 1112 with a substantially low bulk density and appropriately thin sections is fed into zone 1180 continuously, and in other embodiments, it is fed in batch. Blower 1182 in loop 1184 is positioned adjacent to the fiber loading zone 1180 and is used to displace fluid medium, e.g. air, at a speed and in an amount sufficient to provide pneumatically forced circulation of fibrous material 1112 through loop 1184 in the direction of arrow 1188.
In some embodiments, the velocity of air flowing in the loop is sufficient to ensure uniform dispersion and transport of fibrous material throughout the 1184 loop. In some embodiments, the flow velocity exceeds 2500 feet per minute, e.g., 5000 feet per minute, 6000 feet per minute or more, e.g., 7500 feet per minute or 8500 feet per minute.
Aerated fibrous material 1112 circulating in the loop passes through the application zone 1190, which is part of the loop 1184. All desired additives described in this study, such as liquid, for example acidified water or water-based base, are used here. In operation, application zone 1190 supplies an additive, such as liquid solution 1196, to the circulating fibrous material by means of nozzles 98, 99 and 11100. After applying the liquid, the nozzles spray a liquid or mist that hits the fibers passing near the nozzles. Valve 11102 is responsible for controlling the flow of liquid to individual nozzles 1198, 1199 and 11100. After applying the desired amount of additive, valve 11102 closes.
In some embodiments, application zone 1190 is two to one hundred feet or more, e.g., 125 feet, 150 feet, 250 feet or more, e.g., 500 feet. Longer application zones allow application for extended periods of time as the fibrous material passes through application zone 1190. In some embodiments, the nozzles are spaced along the entire length of the 1184 loop at intervals of about three to about four feet.
As the fibrous material passes through loop 1184 and through the section of loop 11107 where the irradiation takes place and which contains a generator 11109 generating ionizing radiation, this radiation is applied to the fibrous material (the figure does not show the shields).
As the irradiated fibrous material circulates in the 1184 loop, it is cooled by the action of gases, such as air, which circulates in the loop at high speeds, and is bathed in reactive gases, such as ozone and / or nitrogen oxides, produced by ionizing radiation to circulating gases such as air. After passing through the section 11107 where the irradiation takes place, the coolant in the form of a liquid (e.g. water) or gas (e.g. liquid nitrogen at 77 K) can be injected into loop 1184 to assist in the cooling of fibrous material. If desired, this process can be repeated many times, e.g. 2, 3, 4, 5, 6, 7, 8, 9, 10 or more times, e.g. 15 times to provide the desired dose to the fiber material. Although, as shown, the longer generator axis runs in the flow direction, in some implementations the longer generator axis runs transversely to the flow direction. In some implementations, an electron beam is used as the main source of ionizing radiation, and X-rays are a secondary source of ionizing radiation. X-rays can be produced using a metal disk, such as the tantalum disk 11111, located on the inside of the loop 1184 that electrons will collide with, causing x-ray emissions.
Once the desired dose has been delivered to the fibrous material, the fibrous material can be withdrawn from loop 1184 via separator 11112, which is connected to loop 1184 by means of section 11114 and gate valve 11116. After opening gate valve 11116, the air supply valve to loop 1184 is also opened to compensate for losses associated with the discharge of air through separator 11112.
At this point, reference is particularly made to FIG. 11D showing a fluidized bed device for irradiation of fibers 11121 with shields. The fibrous material immersed in a fluid such as gas, e.g. compressed air, is introduced into the enclosed closed tank 11123 via pipeline 11125 and into the enclosed fluidized bed 11127. Contra-flow streams 11131 of fluid, such as gas, and laterally flowing streams of fluid 11133, such as gas, which may be the same as counter-current, or other fluid, combine to cause agitation in the bed. When the fibrous material is passed through a section of the fluidized bed, ionizing radiation is applied to the bed. For example, three electron beams generated by Rhodotron® 11135, 11136 and 11137 generators can be used as shown. The advantage of this solution is that each beam can penetrate into the fluidized bed to a different depth and / or each beam can emit electrons with different energy, e.g. 1, 3 and 5 MeV. As the irradiated fibrous material is passed through the system, it is cooled by the action of gases, such as air, which circulates in the system at high speeds, and is bathed in reactive gases, such as ozone and / or nitrogen oxides, produced by radiation ionizing to circulating gases such as air. If necessary, the process can be repeated the desired number of times until the fibrous material receives the appropriate dose. The fluidized bed is illustrated in such a way that its longitudinal axis is arranged horizontally relative to the substrate, while in other implementations the longitudinal axis of the bed is perpendicular to the substrate, so that the fibrous material falls under the influence of gravity.
At this point, reference is particularly made to FIG. 11E showing another device for irradiation and transport of fibrous material 11140 without covers. Fibrous material 11144 is fed from the basket 11142 to the first conveyor 11150 located at the first level above the ground, and then the material is transferred to the second conveyor 11152 located at a level lower than the first conveyor. The rear edge 11160 of the first conveyor and the front edge 11161 of the second conveyor 11152 define a distance S. The distance S may be, for example, from 4 to about 24 inches. The momentum of the material 11144 is sufficient to ensure free fall under the influence of gravity, and then capture it by the second conveyor 11152 without falling material into the gap. The free-falling material is exposed to ionizing radiation. This arrangement can be advantageous in the sense that there is less risk of damage to the conveyor system by ionizing radiation, since the system has no direct contact with it.
After passing through the section in which the irradiation takes place, the cooling fluid in the form of a liquid (e.g. water) or gas (e.g. liquid nitrogen at a temperature of 77 K) can be applied to the material to assist in the cooling process of the fibrous material. If desired, this process can be repeated many times, e.g. 2, 3, 4, 5, 6, 7, 8, 9, 10 or more times, e.g. 15 times to provide the desired dose to the fiber material. Although, as shown, the longer axis of the generator runs transversely to the material flow direction, other beam distributions are also possible. In some implementations, an electron beam is used as the main source of ionizing radiation, and X-rays are a secondary source of ionizing radiation. X-rays can be produced by means of a metal disk, made e.g. from tantalum, placed in a gap on the other side of the material, so that the electrons passing through the material hit the shield, producing x-rays.
In the first example, pretreatment by irradiation with oxidation will be used, and the raw material will be juice cartons with a capacity of half a gallon made of unprinted laminated white Kraft cardboard with a bulk density of 20 o
lb / ft<sup>3</sup>. Cartons are squeezed flat and then fed into a sequence of three modules composed of a shredder and a slicer arranged in a row, so that the outlet of the first slicer is at the same time the inlet to the second shredder, and the outlet of the second slicer - the inlet to the third shredder. The fibrous material obtained in this way can be sprayed with water and processed with a granulate mill at room temperature. The concentrated granulate can be placed in an airtight glass capsule in an atmosphere of air. The granules in the capsule are irradiated with gamma radiation for about 3 hours at a dose rate of about 1 Mrad per hour to obtain irradiated material containing cellulose with a lower molecular weight than in the starting material, i.e. kraft fibrous paper.
Combinations of devices for irradiation, sonication and oxidation
In some embodiments, it may be beneficial to combine at least two separate devices for irradiation, sonication, pyrolysis and / or oxidation into a single hybrid device. With such a hybrid device, many processes can be carried out directly or even simultaneously, which increases the efficiency of pre-treatment and provides potential savings.
In this way, for example, electron beam irradiation and sonication processes can be treated. Each of these processes allows you to effectively reduce the average molecular weight of cellulosic material by at least an order of magnitude or by several orders of magnitude when used in series.
Both the irradiation process and the sonication process can be carried out using a hybrid device for electron beam generation and sonication presented in FIG. 25. The 2500 electron beam sonication / irradiation device is shown above a shallow puddle (depth ~ 3-5 cm) of a suspension of cellulosic material dispersed in a 2550 aqueous oxidizing agent such as hydrogen peroxide or urea peroxide. The 2500 hybrid device is equipped with a 2510 energy source that powers both the 2540 electron beam generation device and 2530 sonication generators.
The 2540 electron beam generating device produces electron beams that pass through the 2545 electron beam reticle, entering a slurry 2550 containing cellulosic material. The electron beam viewfinder may be in the form of a scanner that guides a beam with a maximum span of about 6 feet in a direction approximately parallel to the surface of the 2550 suspension.
On both sides of the 2540 electron beam generation device there are 2530 sonication generators that transfer energy in the form of ultrasonic waves to the 2550 suspension. The 2530 sonication generators are terminated with a removable end piece 2535 that contacts the 2550 suspension.
2530 sonication generators are at risk of damage due to prolonged exposure to electron beam radiation. Therefore, the generators can be protected with a standard 2520 shield made of, for example, lead or a heavy metal alloy, such as Lipowitz alloy, which is resistant to electron beam radiation. However, precautions should be taken so that the presence of the shield does not adversely affect the ultrasonic energy. The demountable end pieces 2535 are made of the same material and connected to the generators 2530. Their purpose is to ensure contact with the cellulosic material 2550 and it is anticipated that they will be damaged. Accordingly, the demountable end pieces 2535 have been designed so that they can be easily replaced.
Another benefit associated with the simultaneous process of electron beam irradiation and ultrasound treatment is the fact that the effects obtained as a result are complementary. In the case of electron beam irradiation alone, an insufficient dose may cause cross-linking of some polymers contained in the cellulosic material, which will reduce the efficiency of the entire depolymerization process. The simultaneous use of electron beam irradiation and sonication also allows the use of lower doses of electron beam irradiation and / or ultrasound than when these processes are used separately.
The electron beam generating device can also be combined with at least one high-frequency rotor-stator device that can be an alternative to devices generating ultrasonic energy and perform a similar function.
Further combinations of devices are also possible. For example, a device for the production of ionizing radiation that produces gamma radiation emitted, e.g., by isotope granules<sup>60</sup>What, can be combined with an electron beam source and an ultrasonic wave source.
The radiation devices for the pretreatment of biomass discussed above can also be combined with at least one device for performing at least one pyrolysis sequence. This combination can also increase performance. However, caution should be exercised because the requirements for some irradiation and pyrolysis processes may conflict. For example, ultrasonic devices may require immersion of the raw material in a liquid oxidant. On the other hand, as previously mentioned, a specific moisture content in a sample of the raw material may be beneficial from a pyrolysis point of view. In this case, new systems automatically measure, monitor and regulate specific moisture content. In addition, some or all of the devices listed above, in particular the pyrolysis device, may be combined with the oxidation device in the manner described above.
PRODUCTS / BY-PRODUCTS
In some embodiments, the present invention provides materials prepared using the methods described herein. In some cases, such materials can be used in the absence of materials added to the biomass before or after processing, e.g. materials that do not occur naturally in biomass. In such cases, the materials will contain naturally occurring materials, e.g. from biomass. As an alternative or complementary solution, materials prepared using the methods described in this study can be combined with other natural and / or synthetic materials, e.g. materials that do not occur naturally in biomass.
By using the methods described in this paper, the availability of at least one of the components contained in biomass (e.g. unprocessed and / or partially processed biomass) can be increased. Components with increased availability can be obtained more easily (e.g. extracted and / or isolated), easier to use and / or they can be better absorbed by animals (e.g. digested or absorbed by animals). Components with increased availability include, for example, components that naturally occur in biomass and / or components that are manufactured using the methods described in this study (e.g., cross-linking substances or low molecular weight substances). Such components can increase the value of biomass. For example, low molecular weight substances are better hydrolysed in the stomach than unprocessed biomass. Therefore, biomass containing readily available low molecular weight substances can be used as a more valuable food source, e.g. for animals or insects or in agriculture, aquaculture, fish farming, aquatic plants, seaweed and algae.
In some embodiments, biomass sterilization can be performed using methods described herein to provide materials suitable for human and / or human consumption (e.g., by ingestion or implantation), insects, or for use in agriculture, aquaculture, e.g., farming fish, aquatic plants, seaweed and algae. In some embodiments, irradiation of the cellulosic material will provide sterilization of the biomass, making it suitable for human and / or animal consumption (e.g., by ingestion or implantation). Irradiated cellulose can also be used in other products or by-products.
In some embodiments, biomass can be processed into consumable material (e.g., ingested or implanted) for humans and / or animals using the methods described herein. Such materials should be essentially free of infectious materials (e.g. pathogenic and / or non-pathogenic materials), toxins and / or other materials (e.g. bacterial spores, fungal spores, insects and larvae) that may be harmful to humans and / or animals . Using already known methods and / or methods described in this study, it is possible to remove, deactivate and / or neutralize infectious material (e.g. pathogenic and / or non-pathogenic) and / or toxins which may be harmful to humans and / or animals or which are generally undesirable in material intended for humans and / or animals. By means of such methods, it is possible, for example, to remove, deactivate and / or neutralize infectious material that may be present in biomass. Such materials include, for example, pathogenic and non-pathogenic bacteria, viruses, fungi, parasites and prions (e.g., infectious proteins). In some cases, toxins, e.g. bacterial and plant toxins, can be removed, deactivated and / or neutralized using the methods described in this paper. As an alternative or complementary solution, using the methods described in this paper, you can remove, deactivate and / or neutralize materials that may be present in biomass and are not necessarily harmful, but may be undesirable in material intended for humans and / or animals or for use in agriculture or aquaculture. Examples of such materials include bacterial spores, fungal spores, insects and larvae.
In some embodiments, the methods and by-products described herein and biochemical reacting products in demanding environments can be produced by the methods described herein. Such environments may include spatially limited environments and / or environments where extreme conditions occur, for example very high or low temperatures, high radiation, high pollution and / or limited access of oxygen or sunlight. In some embodiments, such environments may include, but are not limited to, spacecraft, space stations (e.g. extraterrestrial locations), submarines (e.g. nuclear submarines) and other naval vessels, barges or platforms designed to be at sea for extended periods of time, underwater locations (e.g. civil and / or military facilities underwater), desert environments, polar environments, environments with subzero temperatures (e.g. permafrost areas), environments at high altitudes (e.g. with limited oxygen content and / or extreme temperatures) and remote locations (e.g. self-sufficient and independent areas).
foods
The methods allow to prepare material with higher nutritional value (e.g. higher energy value - e.g. food energy better available in the digestion process - and / or the availability of nutrients) during digestion by animals compared to native material or unprocessed biomass. Such methods do not necessarily increase the total amount of energy or nutrients present in a certain amount (e.g. by mass) of a specific type of processed biomass compared to the same amount and type of raw biomass. However, using the methods described in this study, you can increase the nutritional value (e.g. availability of energy and / or at least one of the nutrients) in a specific amount (e.g. mass) of a specific type of processed biomass compared to the same amount and type of raw biomass.
Increasing the availability of food energy of a particular type of biomass may enable an increase in metabolismable energy intake (MEI) of such biomass. Methods for measuring energy in food are known in the industry. Metabolic energy intake (MEI) is calculated by multiplying the number of kilocalories or kilojoules contained in food by 85%. In some embodiments, the metabolic energy consumption of biomass can be increased by the methods described herein.
Methods for comparing metabolic energy intake (MEI) of processed and unprocessed biomass may involve, for example, feeding the same amounts of processed or unprocessed biomass to at least two different groups of animals and measuring the growth response.
The availability of nutrients can be assessed by performing a digestion test. Protocols for performing digestion tests are known in the industry. Total nutrient levels can, for example, be determined in processed and / or unprocessed biomass. Equal quantities of processed or unprocessed biomass may be given to at least two different groups of at least one animal species. Then, the loss of at least one of the nutrients in the faeces is determined for a defined period of time. Increased availability of nutrients is defined as smaller amounts of at least one of the nutrients in animal faeces. Alternatively or additionally, the availability of nutrients can be assessed by measuring and comparing the level of at least one nutrient in the blood of animals fed with processed and unprocessed biomass.
In some embodiments, the nutritional value of biomass can be increased by improving the digestibility of at least one source of food energy, carbohydrates, sugars, proteins, fats (saturated, monounsaturated and polyunsaturated), cholesterol, fiber, vitamins (e.g. vitamins A, E, C, B6, B12, carotene, thiamine, riboflavin and niacin), minerals (e.g. calcium, phosphorus, magnesium, iron, zinc, copper, potassium, selenium and sodium) and oils during animal digestion of biomass.
Basically, the methods described in this paper can be selected and / or optimized for the chosen method or combination of methods leading to obtaining the most soluble, absorbable and / or digestible material e.g. with the desired availability of nutrients (e.g. higher availability of nutrients - e.g. proteins, amino acids, carbohydrates, minerals, vitamins, lipids and or oils - than in unprocessed native material), which can be used as food for humans and / or animals. Biomass materials are available and cheap, therefore materials obtained by such methods will provide economical food and reduce the amount of waste.
In some embodiments, the materials and methods described in this study can be used in the production of feed, e.g., agricultural feed and feed suitable for consumption by mammals, birds and / or fish. Such animals include farm animals, pets, zoo animals, laboratory animals and / or humans.
In some embodiments, materials produced using the methods described herein for food (e.g., for humans and / or animals) may be further processed, e.g., hydrolyzed. Hydrolysis methods are known in the art and include, for example, the use of acids and / or bases to reduce the molecular weight of saccharides.
In some embodiments, materials prepared using methods described herein for food (e.g., for humans and / or animals) may be further processed to increase material sterility and / or remove, deactivate and / or neutralize materials that may be found in biomass, e.g. infectious materials (e.g. pathogenic and / or non-pathogenic materials), toxins and / or other materials (e.g. bacterial spores, fungal spores, insects and larvae). In general, the methods described in this paper can be selected and optimized to obtain an optimal rate of removal, deactivation and / or neutralization of materials that may be undesirable.
feed
Annually, over 600 million tonnes of feed are produced worldwide with an annual growth rate of around 2%. The agricultural industry is one of the largest feed consumers, and farmers in the United States spend over $ 20 billion a year on livestock feed. Other feed consumers include, for example, pet owners, zoos and laboratories keeping animals for research purposes.
Feed should meet or exceed specific requirements for a given animal species, for example to ensure or improve animal health of a particular type or species, ensure animal growth (e.g. tissue growth) and / or promote food production. Improved feeds (e.g. more soluble, absorbable and / or digestible) allow the same effects to be achieved with less feed and / or at a lower cost.
The raw materials currently used in commercially available ready feeds include feed grains (e.g. corn, soybean, sorghum, oats and barley). The feed industry is the largest buyer of corn, feed grains and soybean meal in the United States. However, due to the rising prices of feed grains, such as corn, there is a need for cheaper solutions. The most commonly available feed material is biomass, e.g. cellulosic material. In some embodiments, the methods described herein increase the availability of nutrients in any of such materials, for example to provide or improve animal health of a particular type or species, ensure animal growth (e.g., tissue growth), and / or promote production food. Low availability of nutrients in commonly used feed materials (e.g. hay and grass) is attributed largely to the high content of cellulose, hemicellulose and lignin in such material. Unlike people who are unable to digest cellulose, herbivores, e.g. ruminants, can at least partially digest cellulose in a process called chewing. However, this process is inefficient and requires multiple regurgitation. For example, ruminants only digest about 30-50 percent cellulose and hemicellulose. By using the methods described herein, the availability of nutrients or the nutritional value of each of these materials is increased, for example to ensure or improve animal health of a particular type or species, ensure animal growth (e.g., tissue growth), and / or promote food production. The methods described in this study allow you to reduce the amount of food used, reduce their cost and / or reduce the amount of waste.
In general, increasing the availability of animal feed nutrients allows you to reduce the amount of food fed to animals to achieve a specific energy value. Hence, the animal will require less feed, which will make it more economical.
Various techniques have been tried with limited success to increase the availability of nutrients in feed raw materials. Among these techniques, the use of enzymes, such as cellulosic enzymes, used to break down cellulosic material into shorter chain oligosaccharides that were more easily digestible can be mentioned. Although this technique is used in Europe and Australia, in practice it is expensive and not widely used in developing countries. Other techniques include: straw removal to prevent leaf loss, deaeration, physical treatment of the material (e.g., compression of cellulose material, reduction of particle size, and fine abrasion), chemical treatment and overfeeding. In addition, feed materials consisting largely of cellulose material are often supplemented with nutrient systems (e.g. premixtures). Such nutrient systems are typically designed to meet the nutritional requirements of the target animals. Although animals receive the required nutrients, such systems do not ensure the efficient use of cellulosic material.
The methods described in this study allow improving the availability of nutrients or the nutritional value of biomass (e.g. by modification, i.e. increasing, decreasing or maintaining biomass solubility and / or changing the structure, e.g. by functionalization, native materials and / or by changing, e.g. lowering, molecular weight and / or crystallinity) as described above, allowing for more valuable feed materials. In some embodiments, the methods described herein can increase the availability of biomass nutrients by breaking down cellulosic material (e.g., cellulose) into saccharides and / or shorter chain monosaccharides. By increasing the availability of nutrients in biomass, these methods will produce more efficient feed material that can be used to ensure or improve animal health of a particular type or species, ensure animal growth (e.g. tissue growth), and / or promote food production.
In some embodiments, useful animal feed material may contain partially processed biomass, e.g. biomass, which has been chopped using the methods described herein. Such partially processed biomass can be better hydrolysed in the stomach of the animal.
In some embodiments, biomass can be processed to obtain the materials described herein using the methods described herein. These materials may include, inter alia, polysaccharides with a length exceeding 1000 saccharide units or equal to about 1000 saccharide units, about 800-900 saccharide units, about 700-800 saccharide units, about 600-700 saccharide units, about 500-600 saccharide units, about 400-500 saccharide units, about 300-400 saccharide units, about 200-300 saccharide units, about 100-200 saccharide units, 100, 90, 80, 70, 60, 50, 45, 40, 35,
30, 25, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2 and 1 of the saccharide unit.
In some embodiments, these methods result in disaccharides (e.g., sucrose, lactose, maltose, trehalose, and cellobiose). In some embodiments, these methods result in monosaccharides (e.g., glucose (dextrose), fructose, galactose, xylose and ribose). These shorter molecular chains are better absorbed by animals, which increases the availability of biomass nutrients. Therefore, the methods and materials described in this study can be used as feed materials or in the production of feed materials.
In some embodiments, the materials described in this study can be used as agricultural feed and / or feed suitable for consumption by mammals, birds and / or fish. As an alternative or complementary solution, raw materials for use as animal feed or its component can be processed using the methods described in this paper.
Materials that can be successfully processed using the methods described in this study include cellulosic and lignocellulosic materials, e.g. agricultural products, cereals, grasses, plants and / or feed cereals, including plant material (e.g. fodder plants such as alfalfa meal, hay, bermuda grass hay, bison grass, corn stalks and soybean hay), cereals (e.g. barley, maize - including organic and genetically modified maize - oats, rice, sorghum and wheat), vegetable protein products (e.g. rapeseed meal, cakes and cottonseed meal, safflower meal and feed and soybean meal - including organic and genetically modified soybeans), processed cereal by-products (e.g. distillery products, dried cereals, corn gluten, sorghum germ fritters and flour, nut shells and wheat bran), fruit and fruit by-products (e.g. dried citrus pulp, apple pomace and pectin pulp), molasses (e.g. beet, citrus, starch and reed molasses), almond shells, ground shells, buckwheat hulls, legumes and leguminum by-products and other by-products. Other raw materials may include alfalfa, barley, commonfoot, brassica (e.g. kale, cabbage (rapeseed), swede and turnip), clover (e.g. Swedish clover, red clover, underground clover and white clover), grass (e.g. ryegrass, fescue, grass) bermudzka, stokłosa, heather grass, meadow grass, cocksfoot grass, ryegrass, timothy grass), maize (common), millet, barley, sorghum and soybean. In some embodiments, the raw material may be animal waste (e.g. waste of ruminants) or human.
In some embodiments, the feed material only includes materials produced using methods described in this study. Alternatively or additionally, the feed material contains additional raw materials (including raw materials that have not been processed using the methods described in this study) and additives. Such feed materials should be formulated to meet the specific requirements of the target animals, for example to ensure or improve animal health of a particular type or species, to ensure animal growth (e.g. tissue growth) and / or to promote food production. In some cases, the composition of a feed material may be selected to meet the nutritional requirements of the target animal at the lowest cost ('lowest cost principle'). The methods for determining the composition of the feed and the principle of selection according to the lowest cost are well known to those skilled in the art (see for example Pesti and Miller,
Animal Feed Formulation: Economic and Computer Applications (Plant and Animal Science), Springer Publishing, February 28, 1993 and liveinformatics.com web address).
Additional raw materials and additives that can be successfully combined with the material produced by using the methods described in this study, include, among others animal products (e.g. meat meal, meat meal fertilizer, meat and bone meal, poultry meal, animal by-product meal, dried animal blood, blood meal, feather meal, egg shell meal, hydrolysed whole chicken carcases, hydrolyzed whole carcasses and bone marrow ), animal waste, basic and by-products of marine origin (e.g. krill, fish parts and fish meal, fish leftover meal, crab parts and crab meal, shrimp parts and shrimp meal, fish oil, liver and fish gland meal and other fish by-products), dairy products (e.g. dried milk) cow, casein, whey products and dried cheese), fats and oils (e.g. animal fat, vegetable fat or vegetable oil and hydrolyzed fats), restaurant waste (e.g. food leftovers from restaurants, bakeries and cafes) and contaminated / changed food processed to destroy pathogens.
Other additives include antibiotics (e.g. tetracyclines, macrolides, fluoroquinolones and streptogramins), fragrances, excretions, drug by-products (e.g. mycelium and fermentation products), minerals and trace elements (e.g. bone carbon, calcium carbonate, rock Cretaceous, iron salts, magnesium salts, oyster flour meal and sulfates), protein minerals (e.g. protein selenium and chromium), vitamins (e.g. vitamin A, vitamin D, vitamin B12, niacin and betaine), prebiotics (e.g. mannan oligosaccharides (MOS), fructooligosaccharides and mixed oligo-dextran), flavors (e.g. aloe gel concentrate, ginger, Capsicum and Italian fennel), acid acetic, sulfuric acid, aluminum salts, dextrans, glycerin, beeswax, sorbitol, riboflavin, preservatives (e.g. butylated hydroxyanisole and sodium bisulfite), nutraceuticals (e.g. herbal and botanical products), amino acids, protected proteins, urea, molasses, fatty acids (e.g. acetic, propionic and butyric acid) and metabolic modifiers (e.g. somatotropins and adrenergic antagonists). In some cases, materials produced using the methods described in this study can be combined or incorporated into urea molasses mineral block (UMMB).
Feeds prepared using the materials described in this study may be digestible, e.g. for target animals. In some cases, the feed may be in a solid form. Alternatively or additionally, the feed may be in liquid form, e.g. the feed may be in the form of a suspension or solution based on a suitable solvent. Examples of forms include solid forms, such as powders, tablets, mineral blocks, granules, rusks and mixtures of unprocessed raw material (e.g. grass) and processed material using the methods described in this study.
In some embodiments, the materials described in this study may be incorporated into feed (e.g., by mixing) by a farmer, e.g., for local use and / or small-scale distribution. In such cases, the materials described in this study may be delivered to the farmer in a packaged form, e.g. in a form suitable for inclusion in feed. As an alternative or complementary solution, the materials described in this study can be incorporated into feed (e.g. by mixing) by the feed producer, e.g. for large-scale distribution. In such cases, the materials described in this study may be delivered to the feed manufacturer in a form suitable for inclusion in the feed. As an alternative or complementary solution, the materials described in this study can be prepared from the raw material at the place where the feed is prepared.
In some embodiments, the materials described in this study can be distributed separately and fed to animals in the absence of additional raw materials and / or additives.
In some embodiments, the materials will require final processing before being used as food. As an alternative or complementary solution, the materials can be wiped off to fine particles with a stainless steel grinder to obtain a flour-like substance.
Typically, biomass-based feeds are only fed to ruminants that are capable of at least partially digesting cellulose. The present invention makes it possible to obtain materials in which the cellulosic material has been broken down into shorter sugar chains, which is why it can be successfully used as animal feed that is not able to digest cellulose. Therefore, feed prepared using the materials and methods described in this study can be successfully fed to animals, including breeding animals, zoo animals, laboratory animals and / or pets. Feeds can also be used in agriculture and aquaculture. In addition, due to the greater availability of nutrients in feed prepared using the materials described in this study, the animal needs less feed to obtain the same amount of energy, which reduces the overall cost of feed. Alternatively, animals will be able to receive more energy, resulting in increased growth rates, tissue growth, milk production and egg production.
In some embodiments, the materials described in this study can be successfully administered to ruminants (e.g., cattle, goats, sheep, horses, elks, bison, deer, camels, alpacas, llamas, giraffes, yaks, domestic buffaloes, wildebeests and antelopes), poultry , pigs, wild boars, birds, cats, dogs and fish.
In some embodiments, the grain decoction with solutes can be converted into a valuable by-product of the distillation and dehydration process. After completing the distillation and dehydration process, the grain decoction with solutes can be dried to improve the storage and transportability of the material. The distillation dried cereal (obtained in this way) dried distillers grains, DDG) with soluble substances are characterized by low starch content, high fat, protein, fiber and phosphorus content. Therefore, among other things, for this reason DDG can be a valuable source of food for animals (e.g. as a food source for dairy cattle). DDG can then be combined with nutritional supplements to meet specific dietary requirements of specific animal categories (e.g., balancing digestible lysine and phosphorus in pig diets). As an alternative or complementary solution, biomass processed using the methods described in this study can be combined with DDG. The ratio of processed biomass and DDG can be optimized for the needs of the target animals.
Human foods
As indicated above, people are generally less able to digest cellulose and cellulosic material. Biomass is a widely available material, but using it as human food would be a new solution. However, for biomass material (e.g. cellulose containing material) to be useful as human food, it would be necessary to increase the availability of nutrients in biomass by (1) increasing the solubility of biomass, (2) changing the structure (e.g. functionalization) of native materials, (3) change (e.g. reduction) of molecular weight and / or crystallinity relative to native material and / or (4) the breakdown of cellulosic material into smaller sugars, e.g. sugars with a length exceeding 1000 saccharide units or equal to about 1000 saccharide units, about 800-900 saccharide units, about 700- 800 saccharide units, about 600-700 saccharide units, about 500-600 saccharide units, about 400-500 saccharide units, about 300-400 saccharide units, about 200-300 saccharide units, about 100-200 saccharide units, 100, 90, 80, 70, 60, 50, 45, 40, 35, 30, 25, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2 and 1 saccharide unit. Such materials will have an increased availability of nutrients (as described above), e.g. in humans, and will be useful as human food. In principle, a food that is useful to humans should, for example, provide useful and available energy and sources of nutrients for humans to, for example, maintain or improve their health, and / or promote growth (e.g., tissue growth). The methods described in this paper can be used to produce such foods that are useful to humans, for example from biomass-based material.
In some embodiments, the materials will need to be processed before being used as food. As an alternative or complementary solution, the materials can be wiped off to fine particles with a stainless steel grinder to obtain a flour-like substance.
Such foods include energy supplements (e.g. powders and liquids). As an alternative or complementary solution, the materials described in this study can be combined with basic foods to increase the nutritional value of such foods. The foods described in this study can be combined with, for example, low energy foods to increase the amount of energy in the food.
As an alternative or complementary solution, the materials described in this study can be used to sweeten food, e.g. as a sweetener, and a valuable nutrient. In such cases, it may be desirable to obtain at least one specific type of sugars (e.g., monosaccharides, disaccharides, oligosaccharides and / or polysaccharides) from materials e.g. by isolating at least one such type from it. Sugar isolation methods are known in the industry.
In some embodiments, the materials described in this study can be used as cheap materials for food production. For example, these materials can be delivered to the bakery for use in bread and / or confectionery and to food producers who can use it as a filler, e.g. to increase the volume and / or nutritional value of food.
In some embodiments, the materials can serve as a source of dietary fiber for humans. In these cases, methods for breaking down cellulolytic material will be configured to provide an incomplete reduction in molecular weight, for example, so that the resulting materials will contain some cellulose and / or longer polysaccharide chains that are not easily absorbed by humans. Such materials can be administered to humans in solid (e.g. tablets or granules) or liquid (e.g. solution, gel, colloid or suspension).
In some embodiments, the materials described in this study can be administered to humans alone or in combination with a second human food. Such foods include breads, dairy products, meat, fish, cereals, fruit, vegetables, beans (e.g. soy) and gums. In some embodiments, the materials described in this study can be combined with proteins, fats, carbohydrates, minerals, pharmaceutical products and vitamins.
Biochemical reacting products
As described above, using the methods described in this paper, biomass can be processed to obtain / produce feed (e.g. for animals, including aquatic) and / or human food. As shown in FIG. 43A in general, these methods rely on biomass processing, e.g., changing (e.g., reducing) the biomass resistance level to obtain products, e.g., directly derived from biomass and / or to produce products consisting of such materials.
As an alternative or complementary solution, the methods described in this study can be used to process the first material (e.g. biomass), e.g. to change (e.g. reduce) the biomass resistance level to obtain a second material that can be a substrate for additional processes to for example, to produce materials and products present (e.g. essentially present) or dominant in the first material. In some embodiments, additional processes may include biochemical reacting as shown in FIG. 43B. Further examples of such methods are described below.
Hydroponics
In some embodiments, the first material (e.g., biomass) can be processed by methods described herein for, e.g., to change (e.g., lower) the biomass resistance level to obtain a second material for use in hydroponics. Hydroponics is a method of growing plants using mineral nutrient solutions, without soil. Plants can grow with roots immersed only in a solution of mineral nutrients (solution culture) or in an inert medium (inert culture), such as perlite, gravel or mineral wool. The three main types of solution cultures are static culture, continuous solution culture and aeroponics. Materials formed using the processes disclosed in this study may be used alone or in combination with macronutrients such as potassium nitrate, calcium nitrate, potassium phosphate and magnesium sulfate to produce a hydroponic solution. To provide the necessary elements, various micronutrients such as Fe (iron), Mn (manganese), Cu (copper), Zn (zinc), B (boron), Cl (chlorine) and Ni (nickel) can be added. Chelating agents can be added to increase iron solubility. Various hydroponic solutions can be used to improve growth conditions during the plant's life cycle.
aquaculture
In some embodiments, the first material (e.g., biomass) can be processed by methods described herein for, e.g., to change (e.g., lower) the biomass resistance level to obtain a second material for use in aquaculture. For example, the second material may be used to feed or otherwise maintain aquatic species. Aquaculture is the cultivation of freshwater and saltwater organisms such as molluscs, crustaceans and aquatic plants. Unlike fish farming, aquaculture, also known as aquaculture, is about cultivating aquatic populations under controlled conditions. Mariculture refers to aquaculture practiced in marine environments. Specific types of aquaculture include algae cultures (production of sea dwarfs / seaweed and other algae), fish, shrimps and oyster farms in aquaculture, and pearl farms.
Aquaponics integrates fish and plant breeding using symbiotic cultivation of aquatic plants and animals in a circulating environment.
Food production
In some embodiments, the products described in this study can be used as food products or as an ingredient in the manufacture of food products (e.g., solid or liquid food products). In some embodiments, the food products may be used alone or in combination. In some embodiments, the food products can be combined with textured materials (e.g., wheat proteins). In some embodiments, the food products disclosed in this study may be produced as an alternative to meat (see, for example, Quom® manufactured by Marlow Foods in the UK). In some embodiments, the food products disclosed in this study may be combined with other proteins, protein sources or foods such as mucoproteins, textured plant proteins, tofu, tempeh, miso, soy products and / or wheat proteins.
In some embodiments, each of the primary and by-products described herein may be combined with flavors and / or dyes, e.g., high-quality chemical flavors and flavors.
Process water
Gray water, e.g. municipal gray water, or black water may be used to perform all processes disclosed in this study that require the use of water. In some embodiments, gray or black water is sterilized before use. Sterilization can be carried out by any desired technique, e.g. irradiation, steam treatment or chemical sterilization.
EXAMPLES
The examples presented below are for illustration only and do not limit the knowledge contained in this disclosure.
Reference example 1 - Preparation of fibrous material from laminated paper
A 1,500-pound pallet of juice cartons with a capacity of half a gallon made of unprinted laminated Kraft oo cardboard has been obtained from International Paper.
bulk density 20 lb / ft. Each carton was folded flat and then passed through a 3 HP Flinch Baugh shredder at an approximate speed of 15 to 20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between the rotating and fixed blades was set to 0.10 inch. The shredder product resembled confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long and with a thickness equivalent to that of the starting material (about 0.075 inches).
Confetti-like material was fed to a Munson rotary cutter, model SC30. The SC30 model is equipped with four rotary blades, four fixed blades and a 1/8 inch sieve at the outlet. The distance between rotary and stationary blades was approximately 0.020 inches. A rotary cutter cut fragments reminiscent of confetti to the edges of blades, tearing them apart and releasing fibrous material at a speed of about one pound per hour. The fibrous material had a BET surface area of 0.9748 m / g +/- 0.0167 m / g, porosity at 89.0437 percent, and bulk density (at 0.53 psi) of 0.1260 g / ml. The average fiber length was 1.141 mm and the average fiber width was 0.027 mm, which gives an average length to diameter ratio (L / D) of 42: 1. In FIG. 26 is a scanning electron microscope image showing fibrous material at 25x magnification.
Reference example 2 - Preparation of fibrous material from bleached Kraft cardboard
A 1,500-pound pallet of fresh bleached white o was obtained from International Paper
Kraft cardboard with a bulk density of 30 lb / ft. The material was folded flat and then passed through a 3 HP Flinch Baugh shredder at an approximate speed of 15 to 20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between the rotating and fixed blades was set to 0.10 inch. The shredder product resembled confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long and with a thickness equivalent to that of the starting material (about 0.075 inches). Confetti-like material was fed to a Munson rotary cutter, model SC30. The outlet screen had 1/8 inch openings.
The distance between rotary and stationary blades was approximately 0.020 inches. A rotary cutter cut confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The fibrous material had a BET surface area of 1.1316 m / g +/- 0.0103 m / g, porosity at 88.3285 percent and a bulk density (at 0.53 psi) of 0.1497 g / ml. The average fiber length was 1.063 mm and the average fiber width was 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1. In FIG. 27 is a scanning electron microscope image showing fibrous material at 25x magnification.
Reference example 3 - Preparation of double cut fiber material from bleached Kraft cardboard
A 1,500-pound pallet of fresh bleached white o was obtained from International Paper
Kraft cardboard with a bulk density of 30 lb / ft. The material was folded flat and then passed through a 3 HP Flinch Baugh shredder at an approximate speed of 15 to 20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between the rotating and fixed blades was set to 0.10 inch. The output from the shredder resembled confetti (as above). Confetti-like material was fed to a Munson rotary cutter, model SC30. The outlet screen had 1/16 inch openings. The distance between rotary and stationary blades was approximately 0.020 inches. A rotary cutter cut confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The resulting material from the first cut again underwent a process with the configuration identical to that described above. The resulting fibrous material had a BET surface area of 1.4408 m / g +/- 0.0156 m / g, porosity at 90.8998 percent, and bulk density (at 0.53 psi) 0.12898 g / ml. The average fiber length was 0.891 mm and the average fiber width was 0.026 mm, which gives an average length to diameter ratio (L / D) of 34: 1. In FIG. 28 is a scanning electron microscope image showing fibrous material at 25x magnification.
Reference example 4 - Preparation of triple cut fibrous material from bleached Kraft cardboard
A 1,500-pound pallet of fresh bleached white o was obtained from International Paper
Kraft cardboard with a bulk density of 30 lb / ft. The material was folded flat and then passed through a 3 HP Flinch Baugh shredder at an approximate speed of 15 to 20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between the rotating and fixed blades was set to 0.10 inch. The output from the shredder resembled confetti (as above). Confetti-like material was fed to a Munson rotary cutter, model SC30. The outlet screen had 1/8 inch openings. The distance between rotary and stationary blades was approximately 0.020 inches. The rotary cutter cut the material with a structure resembling confetti on the edges of knives. The resulting material from the first cut was re-cut while maintaining the same configuration, while the screen was replaced with a sieve with 1/16 inch openings. This material has been cut. The resulting material from the second cut was re-cut while maintaining the same configuration, while the screen was replaced with a 1/32 inch screen. This material has been cut. The resulting fibrous material had a BET surface area of 1.6897 m / g + / 0.0155 m / g, porosity at 87.7163 percent, and bulk density (at 0.53 psi) 0.1448 g / ml. The average fiber length was 0.824 mm and the average fiber width was 0.0262 mm, which gives an average length to diameter ratio (L / D) of 32: 1. In FIG. 29 is a scanning electron microscope image showing fibrous material at 25x magnification.
Reference example 5 - Preparation of compacted fibrous material from bleached Kraft cardboard without the addition of binder
The fibrous material was prepared according to Example 2. About 1 pound of water was sprayed on every 10 pounds of fibrous material. The fibrous material was compacted using a California 1100 granulation mill at 75 ° C.
about
The bulk density of the obtained granulate ranged from about 7 pounds / foot<sup>3</sup> to about 15 sts
lb / ft<sup>3</sup>.
Reference example 6 - Preparation of compacted fibrous material from bleached Kraft cardboard with an adhesive
The fibrous material was prepared according to Example 2.
A 2 percent by weight aqueous solution of POLYOX ™ WSR N10 (polyethylene oxide) was prepared.
About 1 pound of stock solution was sprayed on every 10 pounds of fibrous material. The fibrous material was compacted using a California 1100 granulation mill at 75 ° C. The bulk density of the obtained granulate ranged from about 15 pounds / foot<sup>3</sup> up to about 40 pounds / foot<sup>3</sup>.
Reference Example 7 - Reduction of cellulose molecular weight in kraft fiber paper by gamma irradiation and minimal oxidation
The fibrous material was prepared according to Example 4, and then concentrated according to Example 5.
The concentrated granulate is placed in a glass capsule with a maximum capacity of 250 ml. The glass capsule is vented under high vacuum (10 ~ 5 Tr) for 30 minutes, then filled with argon. The argon containing capsule is sealed. The granules in the capsule are irradiated with gamma radiation for about 3 hours at a dose rate of about 1 Mrad per hour to obtain irradiated material containing cellulose with a lower molecular weight than in the starting material, i.e. kraft fibrous paper.
Reference example 8 - Reduction of cellulose molecular weight in kraft paper by gamma irradiation and maximum oxidation
The fibrous material was prepared according to Example 4, and then concentrated according to Example 5.
The concentrated granulate is placed in a glass capsule with a maximum capacity of 250 ml. The glass capsule containing air is sealed. The granules in the capsule are irradiated with gamma radiation for about 3 hours at a dose rate of about 1 Mrad per hour to obtain irradiated material containing cellulose with a lower molecular weight than in the starting material, i.e. kraft fibrous paper.
Reference example 9 - Methods for determining the molecular weight of cellulosic and lignocellulosic materials by gel permeation chromatography
The cellulosic and lignocellulosic materials for analysis were processed in accordance with Example 4. The material samples presented in the following tables included Kraft paper (P), wheat straw (WS), lucerne (A) and reed (SG). The number "132" in the sample identifier indicates the particle size of the material after shearing and forcing through a 1/32 inch screen. The number after the dash indicates the radiation dose (Mrad), and the designation "US" refers to ultrasonic treatment. For example, the identifier "P132-10" will refer to Kraft paper cut into parts screened through a 132 screen and irradiated with a dose of 10 Mrad.
Table 1. Average peak molecular weight of irradiated Kraft paper
<td>Source</td><td colspan="2">IdentyfikatDawka<sup>1</sup></td><td colspan="2">Ultrasound average</td>
<td>samples</td><td>or</td><td>(Mrad)</td><td></td><td>MC ± bias</td>
<td></td><td>samples</td><td></td><td></td><td>standard.</td>
<td>Paper</td><td>P132</td><td> 0</td><td>No</td><td> 32853 ± 10006</td>
<td>Kraft</td><td>P132-</td><td> 10</td><td></td><td> 61398 ±</td>
<td></td><td> 10</td><td></td><td></td><td> 2468**</td>
<td></td><td>P132-</td><td> 100</td><td></td><td> 8444 ± 580</td>
<td></td><td> 100</td><td></td><td></td><td></td>
<td></td><td>P132-181</td><td> 181</td><td></td><td> 6668 ± 77</td>
<td></td><td>P132-US</td><td> 0</td><td>Yes</td><td> 3095± 1013</td>
** Low radiation doses increase the molecular weight of some materials.
<sup>1</sup>Dose strength = 1 Mrad / hour
30 minutes treatment with ultrasound at 20 kHz, produced with a 1000 W generator under circulating conditions, with material dispersed in water.
Table 2. Average peak molecular weight of irradiated materials
Average MC
Identifier Number Dose<sup>1</sup>
Ultrasounds<sup>2</sup> ± deviation
peak samples (Mrad) standard.
No 1407411 ±
WS132 1 0
175191** “ 39145 ±
3425
<td></td><td> 3</td><td></td><td></td><td> 2886 ± 177</td>
<td>WS132-</td><td></td><td></td><td></td><td> 26040 ±</td>
<td></td><td> 1</td><td> 10</td><td></td><td></td>
<td> 10*</td><td></td><td></td><td></td><td> 3240</td>
<td>WS132-</td><td> 1</td><td> 100</td><td></td><td> 23620 ±</td>
<td> 100*</td><td></td><td></td><td></td><td> 453</td>
<td></td><td></td><td></td><td></td><td> 1604886 ±</td>
<td>A132</td><td> 1</td><td> 0</td><td></td><td> 151701</td>
<td></td><td></td><td></td><td></td><td> 37525 ±</td>
<td></td><td> /</td><td></td><td></td><td> 3751</td>
<td></td><td> 3</td><td></td><td></td><td> 2853 ± 490</td>
<td>A132-10 *</td><td> 1</td><td> 10</td><td></td><td> 50853 ± 1665</td>
<td>A132100 *</td><td> 2 1 2</td><td> 100</td><td></td>
<td>SG132</td><td> 1</td><td> 0</td><td></td>
<td></td><td></td><td></td><td></td>
<td></td><td>L</td><td></td><td></td>
<td></td><td> 3</td><td></td><td></td>
<td>SG13210 *</td><td> 1</td><td> 10</td><td></td>
<td>SG132100 *</td><td> 1</td><td> 100</td><td></td>
<td>US-SG13210</td><td> 1</td><td> 10</td><td>Yes</td>
<td></td><td> 2</td><td></td><td></td>
<td>SG132-</td><td></td><td></td><td></td>
<td>100 US</td><td> 1</td><td> 100</td><td></td>
2461± 17
38291±
2235
2487 ± 15
1557360 ±
83693
42594 ±
4414
3268 ± 249
60888 ±
9131
22345 ±
3797
86086 ±
43518
2247 ± 468
4696 ±
1465 * Peaks combine after treatment ** Low radiation doses increase the molecular weight of some materials. <sup>1</sup>Dose strength = 1 Mrad / hour
30 minutes treatment with ultrasound at 20 kHz, produced with a 1000 W generator under circulating conditions, with material dispersed in water.
Gel permeation chromatography (GPC) allows determining the molecular weight distribution of polymers. During GPC analysis, the polymer sample solution passes through a column filled with fine porous particles capturing the gel. The sample is separated based on the size of the particles, and larger particles are washed away faster than small particles. The retention time of individual components is most often detected using refractive index (RI), laser photodispersion (ELS) or ultraviolet light (UV) and compared with a calibration curve. The resulting data is then used to calculate the molecular weight distribution for the sample.
Synthetic polymers are characterized based on molecular weight distribution rather than on a single molecular weight. Statistical means are used to characterize this distribution. The most common averages of this type are "number average molecular weight" (Mn) and "weight average molecular weight" (Mw). Methods for calculating these values are described in Example 9 in PCT / US / 2007/022719.
The polydispersity index (PI) is defined as the ratio Mw / Mn. The higher the PI value, the wider or more diffuse the distribution. The lowest possible value of PI is 1. It means a monodisperse sample, i.e. a polymer in which all degradation molecules have the same molecular weight.
Peak molecular weight (Mp) is another descriptor defined as a property of molecular weight distribution. It means the dominant molecular mass in the distribution. This value also gives you insight into the molecular weight distribution.
Most GPC measurements are made against various polymer standards. The accuracy of the results depends on the extent to which the characteristics of the polymer being analyzed match those of the standard used. The expected repeatability error between the different series of determinations separately calibrated is approximately 5-10% and is characteristic of the limited precision of GPC determinations. Therefore, GPC analysis results are most useful when comparisons of the molecular weight distributions of different samples are made during the same series of determinations.
Lignocellulose samples had to be prepared before GPC analysis. First, a saturated solution (8.4% by weight) of lithium chloride (LiCl) in dimethyl acetamide (DMAc) was prepared. About 100 mg of each sample was added to about 10 g of a freshly prepared saturated LiCl / DMAc solution, and the mixtures were heated to a temperature of about 150-170 ° C and stirred for 1 hour. The solutions obtained were light yellow to dark yellow in color. The temperature of the solutions was reduced to about 100 ° C and at this temperature they were heated for an additional 2 hours. The temperature of the solutions was then lowered to about 50 ° C and the sample solutions were heated for about 48 to 60 hours. It is noteworthy that samples irradiated with 100 Mrad dissolved more easily than non-irradiated samples. In addition, cut samples (marked with number 132) had slightly lower average molecular weights compared to uncut samples.
The resulting sample solutions were diluted 1: 1 using DMAc as a solvent and passed through a 0.45 pm PTFE filter. The filtered sample solutions were then subjected to GPC analysis. The mean peak molecular weights (Mp) of the samples determined by gel permeation chromatography (GPC) are summarized in Tables 1 and 2 and the analysis conditions are presented in Table 3. Each sample was prepared in two identical copies, and each sample preparation was analyzed in two cycles (using two injections), resulting in a total of four injections per sample. EasiCal PS1A and PS1B polystyrene standards were used to generate a calibration curve for the molecular weight scale from about 580 to 7500.00 Daltons.
Table 3. Conditions for conducting GPC analysis
Instrument: Waters Alliance GPC 2000
PLgel 10μ Mixed-B
Columns (3): Serial numbers: 10M-MB-148-83; 10MMB-148-84; 10M- MB-174-129
Mobile phase (solvent): 0.5% LiCl in DMAc (1.0 ml / min)
Temperature
70 ° C column / detector:
Dispenser temperature: 70 ° C
Sample loop size: 323.5 μΐ
Reference example 10 - Determination of the crystallinity of irradiated material by X-ray diffraction
X-ray diffraction (XRD) is a method that allows irradiation of a crystal sample with mono-energetic X-rays. The interaction of the sample crystal structure with such X-rays is recorded and provides information on the irradiated crystal structure. The resulting characteristic "fingerprint" allows identification of the crystalline compounds found in the sample. Quantitative analysis can be performed on samples containing more than one crystalline compound using the full fit method (Rietveld methods).
Each sample was seated in a zero background holder and placed in a Philips PW1800 diffractometer using Cu radiation. Scanning beams were conducted in the range from 5 ° to 50 ° using a step size of 0.05 ° and a countdown of 2 hours each time.
After obtaining the diffraction patterns, phase identification was made using the Powder Diffraction File diffraction database published by the International Diffraction Data Center (ICDD). In all samples, the crystalline phase identified was cellulose - Ia with a three-cut configuration.
The distinguishing feature among 20 samples is the peak width related to the size of the crystal domain. Based on the experimental peak width, the domain size and percentage of crystallinity were calculated, which are indicated in Table 4.
Table 4. XRD data including domain size and% crystallinity
Identifier Size Crystallinity of domain sample (A)%
P132 55 55
<td>P132-10</td><td> 46</td><td> 58</td>
<td>P132-100</td><td> 50</td><td> 55</td>
<td>P132--181</td><td> 48</td><td> 52</td>
<td>P132-US</td><td> 26</td><td> 40</td>
<td>A132</td><td> 28</td><td> 42</td>
<td>A132-10</td><td> 26</td><td> 40</td>
<td>A132-100</td><td> 28</td><td> 35</td>
<td>WS132</td><td> 30</td><td> 36</td>
<td>WS132-10</td><td> 27</td><td> 37</td>
<td>WS132100</td><td> 30</td><td> 41</td>
<td>SG132</td><td> 29</td><td> 40</td>
<td>SG132-10</td><td> 28</td><td> 38</td>
<td>SG132100</td><td> 28</td><td> 37</td>
<td>SG132-10US</td><td> 25</td><td> 42</td>
<td>US-SG132100</td><td> 21</td><td> 34</td>
The percentage crystallinity (Xc%) is calculated as the ratio of the crystallinity field to the total X-ray diffraction peak area and is 100% x (Ac / (Aa + Ac), where
Ac = crystalline phase field
Aa = amorphous phase field
Xc = percentage crystallinity
To determine the percentage crystallinity for each sample, the size of the amorphous phase had to be determined first. This is done by estimating the field of each diffraction pattern that can be attributed to the crystalline phase (characterized by sharper peaks) and the non-crystalline phase (characterized by broad peaks below the pattern and centered at 22 ° and 38 °).
A systematic approach was used to minimize the error of these calculations due to wide peaks in the crystalline phase and high background intensity. First, a linear background was used and then removed. Secondly, the two peaks on the Gaussian curve centered at 22 ° and 38 ° with widths of 10-12 ° each were fitted to the heights under the crystalline phase peaks. Third, the area under two broad peaks on the Gaussian curve and the rest of the standard were determined. Ultimately, the percentage crystallinity was calculated by dividing the area under the crystal peak by the total intensities (after subtracting the background). Domain size and percentage crystallinity of samples determined by X-ray diffraction (XRD) are shown in Table 4 above.
Reference example 11 - Porosimetric test
Analysis of the pore volume and pore size of mercury (Table 5) was derived from the injection of mercury (non-wetting liquid) into the porous structure under strictly controlled pressures. Mercury does not wet most substances and does not spontaneously enter the pores through capillary transport, so it should be injected into the empty areas of the sample by applying external pressure. The pressure required to fill voids is inversely proportional to the pore size. To fill large spaces, little or little pressure is required, while to fill very small pores, more pressure is needed.
Table 5. Volume and pore size distribution determined by mercury porosimetry
Density
<td colspan="2">Total Total Median</td><td></td><td rowspan="2">Average</td><td colspan="2">heaps of density</td><td></td>
<td></td><td></td><td>Median</td><td></td><td></td><td></td>
<td>volume y</td><td rowspan="2">diameter</td><td></td><td></td><td>and</td><td rowspan="2">(skeleton</td><td>porosity</td>
<td>Identifier</td><td rowspan="2">diameter</td><td>diameter</td><td></td><td rowspan="2">SC</td>
<td>crowded area</td><td>pore</td><td rowspan="2">pore</td><td>at</td><td>wa)</td>
<td>or sample</td><td rowspan="2">(volume)</td><td>pore</td><td rowspan="2"> 0,50</td><td></td><td rowspan="2"> (%)</td>
<td>liquid pores</td><td rowspan="3"><sup>(</sup>p<sup>ole) (</sup>p<sup>m)</sup></td><td></td><td>apparent</td>
<td rowspan="2">(ml / g) (m<sup>2</sup>/ G)</td><td rowspan="2">(Pm)</td><td colspan="2">(4V / A) (pm)</td><td rowspan="2"><sup>(</sup>g<sup>/ Ml)</sup></td><td></td>
<td></td><td>dog</td><td></td>
<td></td><td></td><td></td><td></td><td><sup>(</sup>g<sup>/ Ml)</sup></td><td></td><td></td>
<td>P132</td><td> 6,0594</td><td> 1,228</td><td> 36,2250</td><td> 13,7278</td><td> 19,7415</td><td> 0,1448</td><td> 1,1785</td><td> 87,7163</td>
<td>P132-10</td><td> 5,5436</td><td> 1,211</td><td> 46,3463</td><td> 4,5646</td><td> 18,3106</td><td> 0,1614</td><td> 1,5355</td><td> 89,4875</td>
<td>P132-100</td><td> 5,3985</td><td> 0,998</td><td> 34,5235</td><td> 18,2005</td><td> 21,6422</td><td> 0,1612</td><td> 1,2413</td><td> 87,0151</td>
<td>P132-181</td><td> 3,2866</td><td> 0,868</td><td> 25,3448</td><td> 12,2410</td><td> 15,1509</td><td> 0,2497</td><td> 1,3916</td><td> 82,0577</td>
<td>P132-US</td><td> 6,0005</td><td> 14,787</td><td> 98,3459</td><td> 0,0055</td><td> 1,6231</td><td> 0,1404</td><td> 0,8894</td><td> 84,2199</td>
<td>A132</td><td> 2,0037</td><td> 11,759</td><td> 64,6308</td><td> 0,0113</td><td> 0,6816</td><td> 0,3683</td><td> 1,4058</td><td> 73,7990</td>
<td>A132-10</td><td> 1,9514</td><td> 10,326</td><td> 53,2706</td><td> 0,0105</td><td> 0,7560</td><td> 0,3768</td><td> 1,4231</td><td> 73,5241</td>
<td>A132-100</td><td> 1,9394</td><td> 10,205</td><td> 43,8966</td><td> 0,0118</td><td> 0,7602</td><td> 0,3760</td><td> 1,3889</td><td> 72,9264</td>
<td>SG132</td><td> 2,5267</td><td> 8,265</td><td> 57,6958</td><td> 0,0141</td><td> 1,2229</td><td> 0,3119</td><td> 1,4708</td><td> 78,7961</td>
<td>SG132-10</td><td> 2,1414</td><td> 8,643</td><td> 26,4666</td><td> 0,0103</td><td> 0,9910</td><td> 0,3457</td><td> 1,3315</td><td> 74,0340</td>
<td>SG132-</td><td rowspan="2"> 2,5142</td><td rowspan="2"> 10,766</td><td rowspan="2"> 32,7118</td><td rowspan="2"> 0,0098</td><td rowspan="2"> 0,9342</td><td rowspan="2"> 0,3077</td><td rowspan="2"> 1,3590</td><td rowspan="2"> 77,3593</td>
<td> 100</td>
<td>SG132-10-</td><td rowspan="2"> 4,4043</td><td rowspan="2"> 1,722</td><td rowspan="2"> 71,5734</td><td rowspan="2"> 1,1016</td><td rowspan="2"> 10,2319</td><td rowspan="2"> 0,1930</td><td rowspan="2"> 1,2883</td><td rowspan="2"> 85,0169</td>
<td>US</td>
<td>SG132-</td><td rowspan="2"> 4,9665</td><td rowspan="2"> 7,358</td><td rowspan="2"> 24,8462</td><td rowspan="2"> 0,0089</td><td rowspan="2"> 2,6998</td><td rowspan="2"> 0,1695</td><td rowspan="2"> 1,0731</td><td rowspan="2"> 84,2010</td>
<td>100 US</td>
<td>WS132</td><td> 2,9920</td><td> 5,447</td><td> 76,3675</td><td> 0,0516</td><td> 2,1971</td><td> 0,2773</td><td> 1,6279</td><td> 82,9664</td>
<td>WS132-10</td><td> 3,1138</td><td> 2,901</td><td> 57,4727</td><td> 0,3630</td><td> 4,2940</td><td> 0,2763</td><td> 1,9808</td><td> 86,0484</td>
<td>WSI32-</td><td rowspan="2"> 3,2077</td><td rowspan="2"> 3,114</td><td rowspan="2"> 52,3284</td><td rowspan="2"> 0,2876</td><td rowspan="2"> 4,1199</td><td rowspan="2"> 0,2599</td><td rowspan="2"> 1,5611</td><td rowspan="2"> 83,3538</td>
<td> 100</td>
The AutoPore® 9520 pore density determination device achieves a maximum pressure of 414 MPa or 60,000 psia. Four low-pressure stations are available for sample preparation and macroporous data collection from 0.2 to 50 psia. Two high-pressure chambers are also available for collecting data from 25 psia to 60,000 psia. The sample is placed in a bowl-shaped device called a penetrometer, which is connected to the glass capillary with a metal coating. As mercury penetrates into the hollow areas of the sample and around the sample, its level in the capillary drops. The loss of mercury in the capillary causes a change in the electrical capacity. The change in capacity during the test is converted to the volume of mercury based on the capillary volume of the penetrometer used. Various penetrometers with different vessel (sample) and capillary sizes are available, allowing you to test most sample sizes and configurations. Table 6 below defines the key parameters calculated for each sample.
Table 6. Definition of parameters
Parameter Description
Total volume of mercury introduced into the sample during the test. This value
The total volume may reflect the interstitial filling: the space between the small particles, the porosity of the sample and the volume of the compression space of the sample. Total volume of mercury introduced into the sample
Total pore area: transformed to the value of the field, assuming a cylindrical shape of the pores.
Median pore diameter Size in the 50th percentile of the aggregate plot (volume): volume.
Median pore diameter Size in the 50th percentile of the field cumulative plot. (field):
Total pore volume divided by total pore area (4V / A).
Sample weight divided by bulk volume. The bulk volume is determined at a filling pressure of typically 0.5 psia.
Sample weight divided by sample volume measured at highest pressure, typically 60,000 psia.
(Bulk density / apparent density) x 100%
Average pore diameter:
Bulk density:
Apparent density:
Porosity:
Reference example 12 - Particle size analysis
The technique for determining particle size by static light scattering is based on Mie theory (which also includes Fraunhofer theory). Mie theory predicts the relationship between intensity and angle as a function of the size of spherical scattering particles, provided that other system variables are known and kept constant. These variables are the wavelength of the incident light and the relative refractive index of the sample material. Using Mie theory, you can get detailed information on particle size. Table 7 contains collected data on particle size including median diameter, mean diameter and modal diameter as parameters.
Table 7. Particle size determined by laser scattering (dry sample dispersion)
<td colspan="2">Median Diameter sample ID</td><td rowspan="2">Average diameter fa<sup>m)</sup></td><td rowspan="2">Modal diameter fa<sup>m)</sup></td>
<td></td><td>fa<sup>m)</sup></td>
<td>A132</td><td> 380,695</td><td> 418,778</td><td> 442,258</td>
<td>A132-10</td><td> 321,742</td><td> 366,231</td><td> 410,156</td>
<td>A132-100</td><td> 301,786</td><td> 348,633</td><td> 444,169</td>
<td>SG132</td><td> 369,400</td><td> 411,790</td><td> 455,508</td>
<td>SG132-10</td><td> 278,793</td><td> 325,497</td><td> 426,717</td>
<td>SG132-100</td><td> 242,757</td><td> 298,686</td><td> 390,097</td>
<td>WS132</td><td> 407,335</td><td> 445,618</td><td> 467,978</td>
<td>WS132-10</td><td> 194,237</td><td> 226,604</td><td> 297,941</td>
<td>WS132-I00</td><td> 201,975</td><td> 236,037</td><td> 307,304</td>
The particle size was determined by laser light scattering (dry sample dispersion) using a Malvern Mastersizer 2000 instrument under the following conditions:
Batch Speed: 35%
Pressure in the scattering module: 4 bars
Optical model: (2.610, 1.000i), 1,000
An appropriate size sample was placed on the vibrating tray. Batch speed and air pressure were adjusted to ensure proper particle dispersion. The key component is the selection of air pressure so that the agglomeration breaks down without losing sample integrity. The sample size depends on the particle size. Generally, finer particle samples require less material than large particle samples.
Reference example 13 - Area analysis
The surface area of each sample was analyzed using the Micromeritics ASAP 2420 accelerated surface area and porosity measurement system. Samples were prepared by degassing at 40 ° C for 16 hours. The free space (hot and cold) is then calculated, and then the sample tube is degassed again to remove helium. Data collection begins after the second degassing and consists in defining target pressures that will allow control of the amount of gas dispensed per sample. The amount of adsorbed gas and specific pressure are determined and recorded at each target pressure. The pressure inside the sample tube is measured with a pressure transducer. Additional gas doses will be administered until the target pressure is reached and equilibrated. The amount of adsorbed gas is determined by adding up the multiple doses given on the sample. Pressure and quantity determine the gas adsorption isotherm and allow the calculation of a number of parameters, including the BET surface area (Table 8).
Table 8. Summary of surface area based on gas adsorption
Sample identifier Measured area Field @ P / Po = (m<sup>2</sup>/ g) p<sup>owierzchn</sup> and BET <sup>(M2 /</sup>g)
<td>PI 32 P132-10</td><td></td><td>0.250387771 1.5253 @ P / Po = 1.0212</td><td> 1,6897 1,2782</td>
<td>P132-100</td><td></td><td>0.239496722 @ P / Po = 1.0338</td><td> 1,2622</td>
<td></td><td>P132-181</td><td>0.240538100 @ P / Po = 0.5102</td><td> 0,6448</td>
<td></td><td>P132-US</td><td>0.239166091 @ P / Po = 1.0983</td><td> 1,6793</td>
<td></td><td></td><td> 0,217359072</td><td></td>
<td></td><td>A132</td><td>@ P / Po = 0.5400</td><td> 0,7614</td>
<td></td><td></td><td> 0,240040610</td><td></td>
<td></td><td>A132-10</td><td>@ P / Po = 0.5383</td><td> 0,7212</td>
<td></td><td>A132-100</td><td>0.211218936 @ P / Po = 0.4258</td><td> 0,5538</td>
<td></td><td>SG132</td><td>0.238791097 @ P / Po = 0.6359 0.237989353</td><td> 0,8350</td>
<td></td><td>SG132-10</td><td>@ P / Po = 0.6794</td><td> 0,8689</td>
0,238576905
SG132- @ P / Po = 0.5518 0.7034
100 0,241960361
SG132-10- @ P / Po = 0.5693 0.7510
US 0.225692889
SG132- @ P / Po = 1.0983 1.4963
100-US 0.225935246
WS132 @ P / Po = 0.6582 0.8663
0,237823664
WS132-10 @ P / Po = 0.6191 0.7912
0,238612476
WS132- @ P / Po = 0.6255 0.8143
100 0,238398832
The BET isotherm model is a widely used theory for calculating the specific surface area. The analysis consists in determining the single-layer surface size of the sample by calculating the size required to cover the entire surface with a single thickened krypton layer. The value of the single-layer surface size is multiplied by the cross-sectional area of the sample gas molecule to determine the total surface area. The specific surface area is the value of the surface area of an aliquot part of the sample divided by the mass of the sample.
Reference example 14 - Determination of fiber length
The fiber length distribution test was carried out in three series on the supplied samples using the Techpap MorFi LB01 system. The values for average length and width are given in Table 9.
Table 9. Summary of data on the length and width of lignocellulosic fibers
Identifier Average Average Average length
Width r arithmetic weighted length (mm) (gm) sample (mm) (mm) corrected
<td>P132-10</td><td> 0,484</td><td> 0,615</td><td> 0,773</td><td> 24,7</td>
<td>P132-</td><td> 0,369</td><td> 0,431</td><td> 0,496</td><td> 23,8</td>
<td> 100</td><td></td><td></td><td></td><td></td>
<td>P132-</td><td> 0,312</td><td> 0,342</td><td> 0,392</td><td> 24,4</td>
<td> 181</td><td></td><td></td><td></td><td></td>
<td>A132-</td><td> 0,332</td><td> 0,423</td><td> 0,650</td><td> 43,2</td>
<td> 10</td><td></td><td></td><td></td><td></td>
<td>A132-</td><td> 0,362</td><td> 0,435</td><td> 0,592</td><td> 29,9</td>
<td> 100</td><td></td><td></td><td></td><td></td>
<td>SG132-</td><td> 0,328</td><td> 0,363</td><td> 0,521</td><td> 44,0</td>
<td> 10</td><td></td><td></td><td></td><td></td>
<td>SG132-</td><td> 0,325</td><td> 0,351</td><td> 0,466</td><td> 43,8</td>
<td> 100</td><td></td><td></td><td></td><td></td>
<td>WS132-</td><td> 0,353</td><td> 0,331</td><td> 0,565</td><td> 44,7</td>
<td> 10</td><td></td><td></td><td></td><td></td>
<td>WS132-</td><td> 0,354</td><td> 0,371</td><td> 0,536</td><td> 45,4</td>
100
Reference example 15 - Ultrasonic treatment of irradiated and non-irradiated cane
The cane was cut according to Example 4. The cane was heated by ultrasound or by gamma irradiation at a dose of 10 Mrad and 100 Mrad and sonication. The obtained materials correspond to the materials with the identifier G132-BR (non-irradiated), G132-10-BR (irradiation with 10 Mrad and the use of sonication) and G132-100-BR (irradiation with the dose of 100 Mrad and the use of sonication), according to the data presented in Table 1 . Sonication for each sample was performed for 30 minutes using 20 kHz ultrasound generated by a 1000 W generator under recirculation conditions. Each sample was dispersed in water at a concentration of about 0.10 g / ml.
LYNX. 30 and 31 show the apparatus used for sonication. The apparatus 500 consists of a 502 converter connected to a 504 booster that communicates with a 506 generator made of titanium or a titanium alloy. The generator has a 510 seal made of VITON® material on the processing side perimeter and is connected to the processing cell 508 using a waterproof seal. The processing side of the generator is immersed in a liquid, such as water, in which the sonicated sample has been dispersed. The cell pressure is monitored by means of a 512 pressure gauge. During operation, each sample is pumped by means of a pump
517 from tank 516 through a processing cell and sonicated. After sonication, the sample is captured in tank 520. The process can be reversed so that the contents of tank 520 can be passed through the processing cell and captured in tank 516. This process can be repeated many times until the desired level of sample processing is achieved.
Reference example 16 - Images of non-irradiated cane from a scanning electron microscope compared to images of irradiated and irradiated and sonicated cane
Cane samples for imaging with a scanning electron microscope were applied to carbon tape and covered with gold dust (for 70 seconds). Images were taken with JEOL 6500 scanning field electron microscope.
LYNX. 32 is a scanning electron microscope image at 1000x magnification showing fibrous material formed by cutting a cane with a rotary cutter and then pushing the cut material through a 1/32 inch screen.
LYNX. 33 and 34 are images from a scanning electron microscope at 1000x magnification showing the fibrous material shown in FIG. 32 after irradiation with gamma rays at a dose of 10 Mrad and 100 Mrad, respectively.
LYNX. 35 are images from a scanning electron microscope at 1000x magnification showing the fibrous material presented in FIG 32 after irradiation with a dose of 10 Mrad and sonication.
LYNX. 36 are images from a scanning electron microscope at 1000x magnification showing the fibrous material shown in FIG 32 after irradiation with a dose of 100 Mrad and sonication.
Reference example 17 - Infrared spectrum of irradiated Kraft paper compared to non-irradiated Kraft paper. Infrared analysis was performed using standard methods using a Nicolet / Impact 400 instrument.
The results indicate that all the samples indicated in Table 1 are consistent with cellulose based material.
LYNX. 37 shows the infrared spectrum of a Kraft cardboard cut according to Example 4, while FIG. 38 shows the infrared spectrum of Kraft paper visible in FIG. 37 after irradiation with gamma rays at a dose of 100 Mrad. An additional peak in area A (centered around 1730 cm) occurs in the irradiated samples<sup>-1</sup>) which is not found for non-irradiated material.
Example 18 - Pre-treatment using a combination of electron beams and sonication
The raw material is cane cut with a Munson rotary cutter into fiber material. The fibrous material is evenly distributed in an open tin tray with an area exceeding about 500 square inches. The fibrous material is unfolded so that its depth in the tray is about 1-2 inches. For lower radiation doses (below 10 Mrad), the fibrous material can be distributed in plastic bags, and for higher radiation doses, leave the material uncovered on a metal tray.
Then individual samples of fibrous material are exposed to successive doses of electron beam radiation until a total dose of 1 Mrad, 2 Mrad, 3 Mrad, 5 Mrad, 10 Mrad, 50 Mrad and 100 Mrad is achieved. Some samples were kept under the same conditions as the others, but they were not irradiated and served as controls. After cooling, the irradiated fibrous material is sent for further processing by means of sonication apparatus.
The sonication apparatus consists of a converter connected to a support device that communicates with a generator made of titanium or a titanium alloy. The generator has a seal made of VITON® material on the processing side perimeter and is connected to the processing cell using a waterproof seal. The processing side of the generator is immersed in a liquid, such as water, in which sonicated fibrous material has been immersed. The pressure in the cell is monitored by a manometer. During operation, each sample is pumped through a processing cell and sonicated.
In order to prepare irradiated fibrous material for sonication, this material is removed from all containers (e.g. plastic bags) and dispersed in water at a concentration of about 0.10 g / ml. Sonication for each sample is performed for 30 minutes using 20 kHz ultrasound generated by a 1000 W generator under recirculation conditions. After sonication, the irradiated fibrous material is captured in the reservoir. This process can be repeated many times until the desired level of processing is recognized by monitoring the structural changes of the cane. Some irradiated samples are kept under the same conditions as the others, but they are not sonicated and serve as controls. In addition, some samples that have not been irradiated are sonicated, also for control purposes. Therefore, some control samples are unprocessed, some are only irradiated and some are only sonicated.
Reference example 19 - Microbiological testing of pre-processed biomass
Certain lignocellulosic materials pretreated in the manner described in this study are subjected to toxicological analysis for common strains of yeast and bacteria used in the biofuel industry at the fermentation stage in ethanol production. In addition, sugar content and compatibility with cellulase enzymes are examined to determine viability in the treatment process. The testing of materials after pre-treatment is carried out in two stages, as described below.
I. Toxicity and sugar content
The toxicity of grasses and raw paper after pre-treatment is measured in the yeast species Saccharomyces cerevisiae (wine yeast) and Pichia stipitis (ATCC 66278), as well as in the bacteria Zymomonas mobilis (ATCC 31821) and Clostridium thermocellum (ATCC 31924). A growth test is performed on each organism to determine the optimal incubation and sampling time.
Then, two parts of each raw material are incubated in the same way with S. cerevisiae, P. stipitis, Z. mobilis and C. thermocellum placed on a standard microbial medium for each microorganism. The standard YM medium is used for two yeast strains S. cerevisiae and P. stipitis. RM medium is used for Z. mobilis bacteria and CM4 medium is used for C. thermocellum bacteria. For comparison, a positive control containing pure sugar without raw material is used. During a 12 hour incubation, a total of five samples are collected, at 0, 3, 6, 9 and 12 hours, which are analyzed for viability (per plate for Z. mobilis and directly for S. cerevisiae) and ethanol concentration.
The sugar content of the raw material is measured by high performance liquid chromatography (HPLC) using a Shodex® sugar SP0810 or Biorad Aminex® HPX-87P column. Each of the raw materials (approximately 5 g) is mixed with reverse osmosis water for 1 hour. The liquid part of the mixture is drained and analyzed for glucose, galactose, xylose, mannose, arabinose and cellobiose. The analysis is carried out according to the procedure for Determination of structural carbohydrates and lignin in biomass made available by the National Bioenergy Center.
II. Compatibility with the cellulase group
Two samples of raw material samples are tested using the commercially available Accellerase® 1000 enzyme complex, which contains a complex of enzymes that reduce lignocellulosic biomass to fermentable sugars, including two different preparations from the cellulase group, Trichoderma reesei and Aspergillus nidulans, at the recommended temperature and recommended concentration in Erlenmeyer flask. The flasks are incubated with moderate shaking at approximately 200 rpm for 12 hours. During this time, samples are taken every three hours at 0, 3, 6, 9 and 12 hours to determine the concentration of reducing sugars (Hope and Dean, Biotech J '1974, 144: 403) in the liquid phase in the flasks.
Reference example 20 - Alcohol production using radiation-ionizing treatment
The optimal size of a biomass conversion plant depends on factors such as economies of scale and the type and availability of raw biomass. Increasing the size of the installation allows you to increase the economies of scale associated with plant processing. However, increasing the size of the installation may involve an increase in costs (e.g. transport costs) per unit of raw biomass. Research to analyze these factors suggests that the right size of biomass conversion plant is an installation with a capacity of 2,000 to 10,000 tons of dried raw biomass per day. The installation described below is adapted to process 2000 tons of dry raw biomass per day.
LYNX. 39 is a flow chart of the technological process of a biomass conversion plant configured for reed processing. The charge production subsystem processes the raw biomass to remove foreign bodies and provide particles of equal size for further processing. The pre-treatment subsystem changes the molecular structure (e.g. reduces the average molecular weight and crystallinity) of raw biomass in the irradiation of raw biomass, mixing irradiated raw biomass with water to form a suspension and subjecting the suspension to ultrasonic energy. As a result of irradiation and sonication, the cellulosic and lignocellulosic components of the raw biomass are transformed into fermenting materials. In the primary processing subsystem, glucose and other low-mass sugars occur as a result of pre-treatment, leading to the formation of alcohols.
Preparation of the charge
The selected designed installation processing is 2000 tons of dry cane biomass per day. The designed feedstock is chopped and / or cut cane.
The plant is supplied with raw material biomass in the form of reed bales. In some cases, reed bales are wrapped in plastic mesh, so that they do not fall apart when carried. They can also be wrapped in plastic foil to protect them from the effects of weather conditions. Bales can be square or round. The bales are delivered to the plant from a warehouse located outside its area on large truck trailers. Arriving trucks are weighed and unloaded with forklifts. Some bales are stored in a local warehouse, while others are taken directly to conveyors.
Reed is only available seasonally, so long storage is required to provide raw material for the plant. The stock for a long period of time will probably consist of 400-500 acres of uncovered rows stacked in bales located in one or many places at a sufficiently close distance from the ethanol plant. The short-term storage at the processing site corresponds to 72 hours of production in the external storage area. Bales, surrounding access roads and transport conveyors will rest on concrete slabs. The use of a concrete slab is necessary due to the amount of road traffic required to supply a large amount of raw biomass. The concrete slab will minimize the amount of standing water in the storage area and reduce the exposure of raw biomass to dirt. The stored material provides short-term access to the raw material on weekends, non-working days or in the event of a break in the normal direct supply of material for processing.
Bales are unloaded using forklifts and placed directly on transport conveyors or in the short-term storage area. From the short-term storage area, bales are picked up with forklifts and loaded onto conveyor belts.
Then the bales pass through one or two unrolling stations. The unfolded bales are broken by means of a spreading bar and unloaded onto a conveyor belt, which passes through a magnetic separator, which allows metal to be removed before cutting. It has a magnet for catching iron particles installed, which allows you to capture fragments made of magnetic metals that have accidentally been found in the material, and the separating sieve allows you to remove too large fragments of material and foreign bodies before passing through the string of shredders and cutters, which reduces biomass raw material to the appropriate size before proceeding with pre-treatment. The shredder and cutter strings consist of shredders and rotary cutters. Shredders reduce the amount of raw biomass and feed the resulting material to rotary cutters. Rotary cutters simultaneously cut raw biomass and screen the obtained material. Finally, the raw biomass is transported on a belt to the pre-treatment subsystem.
The installation is equipped with three storage silos to reduce the overall system downtime due to the required maintenance and / or faults in the equipment included in the batch production subsystem. Each silo can hold approximately 55,000 cubic feet of raw biomass (sufficient for approximately 3 hours of plant operation).
Pretreatment
The belt conveyor transfers raw material biomass from the batch production subsystem 110 to the pretreatment subsystem 114. As shown in FIG. 40 in the pretreatment subsystem 114, the raw biomass is irradiated by means of electron beam generating devices, mixed with water to form a slurry and subjected to ultrasonic energy. As described above, irradiation of the raw biomass changes its molecular structure (e.g. reduces resistance, reduces average molecular weight and crystallinity). Mixing irradiated raw biomass into a suspension, and then subjecting the suspension to ultrasonic energy further changes the molecular structure of the raw biomass. Sequential use of radiation and sonication can have synergistic effects in the sense that a combination of techniques allows greater changes in the molecular structure (e.g. lowering resistance, reducing average molecular weight and crystallinity) than using individual techniques separately. Without being limited to theory, in addition to reducing polymerization of raw biomass by breaking the intramolecular bonds between segments of cellulosic and lignocellulosic components, irradiation can also affect the overall physical structure of the raw biomass, increasing its fragility. After mixing the crumbly raw biomass to form a suspension and applying ultrasonic energy, there are further changes in the molecular structure (e.g. reduction of average molecular weight and crystallinity) and a reduction in the particle size of the raw biomass.
Electron beam irradiation
A conveyor belt 491 transporting raw biomass to the pre-treatment subsystem distributes the raw biomass in several batch streams (e.g. 50 batch streams), each of which leads to a separate device for the production of electron beam 492. In this embodiment, the raw biomass is irradiated. Each batch stream is transferred on a separate conveyor belt to a suitable electron beam generating device. Each conveyor belt with irradiation feedstock can be about one meter wide.
Before reaching the electron beam generating device, the conveyor belt vibrates locally to ensure even distribution of dry raw biomass over the entire width of the belt.
492 electron beam generation equipment (e.g. commercially available electron beam irradiation equipment offered by the Titan Corporation of San Diego, California) is configured for irradiation with an electron dose of 100 kilograms with 300 kW. Equipment for generating electron beams for scanning devices with a beam span of 1 meter, which corresponds to the width of the conveyor belt. In some embodiments, devices are used to produce an electron beam with large, fixed beam widths. The number of electron beam generation devices required for installations processing 2,000 tons of dry raw material per day depends on the width of the tape / beam, the required dose, the density of raw biomass and the power used.
sonication
Before applying ultrasonic energy, the irradiated raw biomass is mixed with water to form a slurry. A separate sonication system can be assigned to each batch stream of electrons, or a batch material from several streams of electrons can be sent to one sonication system.
In each sonication system, irradiated raw biomass is fed to tank 1214 through the first inlet 1232, and water is fed to the tank 1214 through the second inlet 1234. Appropriate valves (manual or automatic) control the flow of raw biomass and water, which allows achieving the desired proportions of raw biomass to water (e.g. 10% cellulose material w / v). Each tank 1214 contains a 1240 stirrer, which disturbs the content of 1236 and allows the distribution of raw biomass in water.
In each sonication system, the suspension is pumped (e.g., using a Vortex 1218 impeller pump) from reservoir 1214 to a flow cell 1224 containing an ultrasonic transducer 1226 and further. In some embodiments, pump 1218 is configured to agitate suspension 1216 so that the mixture of raw biomass and water is relatively homogeneous at inlet 1220 of flow cell 1224. For example, pump 1218 may agitate the slurry 1216 to obtain a turbulent flow that will persist in the pipeline between the first pump and inlet 1220 of flow cell 1224.
In flow cell 1224, the ultrasonic transducer 1226 transmits ultrasonic energy to the slurry 1216 as the slurry flows through the flow cell 1224. The ultrasonic transducer 1226 converts electrical energy into high frequency mechanical energy (e.g., ultrasonic energy), which is then transferred to the slurry via a device booster 48. Ultrasonic transducers are commercially available (e.g., from Hielscher USA, Inc. from Ringwood, New Jersey) capable of delivering 16 kilowatt continuous power.
Ultrasonic energy flowing through the assisting device 1248 in the space of the 1244 reactor generates a series of compressions and dilutions in process stream 1216 with sufficient intensity to cause cavitation in process stream 1216. Under the influence of cavitation, raw material biomass components are ungrouped including, for example, cellulosic and lignocellulosic material dispersed in the technological stream 1216 (e.g. suspension). Cavitation also causes the formation of free radicals in the water of process stream 1216 (e.g. suspension). These free radicals break down the cellulosic material in process stream 1216. Generally, process stream 1216 containing fragments of poplar sawdust is affected by about 250 o
MJ / m ultrasonic energy. Other raw biomass can be influenced by other levels of ultrasonic energy (from about 5 to about 4000 MJ / m3, e.g. 10, 25, 50, 100, 250, 500, 750, 1000, 2000 or 3000). After being subjected to ultrasonic energy in reactor volume 1244, process stream 1216 exits flow cell 1224 through outlet 1222.
Flow cell 1224 also includes a heat exchanger 1246 that conducts heat to at least part of the volume of reactor 1244. Coolant 1248 (e.g., water) flows into heat exchanger 1246 and absorbs heat generated in the sonication process of process stream 1216 (e.g., slurry) in volume reactor 1244. In some embodiments, the flow of coolant 1248 to the heat exchanger 1246 is controlled to maintain a relatively constant temperature in the volume of reactor 1244. As an alternative or complementary solution, the temperature of the fluid 1248 entering the heat exchanger 1246 to maintain a relatively constant temperature in the volume of reactor 1244 can be controlled .
Outlet 1242 of flow cell 1224 is near the bottom of tank 1214 to force gravity flow of process stream 1216 (e.g., slurry) from tank 1214 to the inlet of a second pump 1230 that pumps the process stream 1216 (e.g., slurry) to the main processing subsystem.
Sonication systems can include one flow path (as described above) or multiple parallel flow paths, each of which will be associated with a specific sonication module. Multiple sonication units can also be installed in series to increase the amount of ultrasonic energy emitted into the suspension.
Basic processes
The vacuum rotary drum filter removes solid particles from the slurry before fermentation. The filter liquid is pumped to cool before being pumped into the fermenters. The filtered solids are transferred to the post-processing subsystem for further processing.
Fermentation tanks are large, low-pressure stainless steel vessels with a conical bottom and low-speed mixers. Multiple first-stage fermentation tanks can be arranged in series. The temperature in the first stage fermentation tanks is maintained at 30 degrees Celsius by means of external heat exchangers. Yeast is added to the first of the first level fermentation tanks in each row and transferred to the other tanks in the row.
Second stage fermentation takes place in two continuous fermenters arranged in series. The content of both fermenters is continuously mixed by means of low speed mechanical mixers. The temperature is controlled by means of chilled water in external exchangers with continuous circulation.
Circulation pumps are cavitation pumps due to the high concentration of solid particles.
The gas evaporated from fermentation tanks and fermenters is combined and purified in a counter-current water column before being discharged into the atmosphere. Evaporated gas is purified to recover ethanol, not to regulate emissions into the atmosphere.
Post-processing
Distillation
Distillation and adsorption using a molecular sieve are used to recover ethanol from raw fermentation and obtain 99.5% ethanol. The distillation takes place in two columns: the first, called the beer column, in which the dissolved CO2 and most of the water are discharged, and the second, in which the ethanol concentration occurs to a composition similar to the azeotropic mixture.
All water from the azeotrope-like mixture is evaporated by adsorption using a molecular sieve. Regeneration of adsorption columns requires recovery of the ethanol aqueous mixture for distillation.
Fermentation exhausts (consisting mainly of CO2, but also ethanol) and beer column exhausts are moistened in a water scrubber, which allows almost all ethanol to be recovered. The scrubber eluate is fed to the first distillation column along with the fermentation brew.
The first distillation sludge contains all unconverted, insoluble and dissolved solids. Insoluble particles are dewatered using a pressure filter and sent to the combustion system. The unrecovered liquid from the pressure filter is concentrated in a multifunctional evaporator by means of secondary heat from the distillation process. The concentrated syrup from the evaporator is mixed with the solid particles sent to the combustion system, and the evaporated condensate is used as relatively pure water recovered for processing.
The amount of broth that can be recovered is limited, so the process must take into account the use of the evaporator. The total amount of water from the pressure filter that is directly recoverable is 25%. Organic salts, such as ammonium acetate or lactate, soak components not used by the body or inorganic biomass substances reach this stream. Recovery of too much of such material can cause ionic strength and osmotic pressure levels to deteriorate fermenting organism performance. The evaporator has a concentration of undissolved particles in the syrup using unrecovered water. Such syrup can be passed to the combustion system to minimize the load on the wastewater treatment system.
Wastewater treatment
The wastewater treatment section is responsible for treating process water for reuse to reduce the water demand of the installation. Initially, waste water passes through a sieve to remove large particles that are collected in the hopper and directed to the landfill. Sifting is followed by beta fermentation and aerobic fermentation to ferment organic matter in the stream. Anaerobic digestion produces a biogas stream rich in methane, which is sent to the combustion system. Oxygen fermentation produces a stream of relatively clean water for reuse in the process and sludge consisting mainly of cell mass. The sludge is also incinerated in the combustion system. This screening / anaerobic digestion / aerobic digestion scheme is a standard scheme currently used in the alcohol industry, and installations with a capacity range of 1 to 5 million gallons per day can obtain "standard" units from suppliers.
Combustion system, boiler and turbogenerator
The purpose of the subsystem consisting of a combustion plant, boiler and turbogenerator is to burn various by-product streams to produce steam and electricity. This applies, for example, to parts of lignin, cellulose and hemicellulose that have not been converted in the pre-treatment and main treatment process. Most of the process wastewater is concentrated into a syrup with a high content of soluble particles. The anaerobic digestion of the remaining wastewater produces biogas rich in methane. Aerobic fermentation produces a small amount of waste biomass (sludge). Burning these by-product streams to produce steam and electricity enables the plant to be self-sufficient for energy, reduces the cost of solid waste disposal, and creates additional benefits associated with selling excess electricity.
Three main fuel streams (solid waste after distillation, biogas and evaporator syrup) are fed to the circulating fluidized combustion system. A small amount of waste biomass (sludge) from the wastewater treatment plant is also sent to the combustion system. The air is forced into the combustion chamber by means of a fan. Treated water enters the heat exchanger circuit of the combustion system and is evaporated and superheated to 510 ° C (950 ° F) to produce steam at 86 atmospheres (1265 psia). The flue gas from the combustion system preheats the incoming combustion air and then passes through the bag filter to remove particles that are taken to the landfill. The gas is discharged through the chimney.
A multi-stage turbine and generator are used to generate electricity. The steam is withdrawn from the turbine in three different states and injected into the pre-treatment reactor and heat exchanger participating in the distillation and evaporation process. The remaining steam is condensed with the help of cooling water and returns to the installation supplying the boiler with water together with condensate coming from various heat exchangers participating in the process. Treated well water is used to replenish the steam lost by direct injection.
Reference example 21 - Preparation of cane feed
A 1500-pound cane pallet was purchased from the farm and transported to the processing site. The material is passed through a 3 HP Flinch Baugh shredder at an approximate speed of 15 to 20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between rotating and fixed blades is
0.10 inches. The shredder product resembles confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long, and the same thickness as the initial material. Confetti-like material is fed to a Munson rotary cutter, model SC30. The outlet screen has 1/8 inch openings. The distance between rotating and stationary blades is approximately 0.020 inches. A rotary cutter cuts confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The average fiber length is 1.063 mm and the average fiber width is 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1.
These processed samples are concentrated to obtain granules fit for consumption by cows or other farm animals. The granulate is distributed to farms and stored in a storage silo. Cows receive the required daily dose of granules.
Example 22 - Preparation of cane feed
A 1500-pound cane pallet was purchased from the farm and transported to the processing site. The material is passed through a 3 HP Flinch Baugh shredder at an approximate speed of 15 to 20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between rotating and stationary blades is 0.10 inches. The shredder product resembles confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long, and the same thickness as the initial material. Confetti-like material is fed to a Munson rotary cutter, model SC30. The outlet screen has 1/8 inch openings. The distance between rotating and stationary blades is approximately 0.020 inches. A rotary cutter cuts confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The average fiber length is 1.063 mm and the average fiber width is 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1.
The samples are irradiated with an electron beam produced by the Rhodotron® TT200 continuous wave accelerator that supplies 5 MeV electrons at an output of 80 kW. Table 10 describes the parameters used. Table 11 lists the nominal doses used.
Table 10. Rhodotron® TT 200 accelerator parameters
Bundle
Generated beam: Accelerated electrons
Nominal (fixed): 10 MeV (+0 keV-250
Beam energy: keV)
Energy dispersion at 10 MeV: Half width (FWHM) 300 keV
Guaranteed working range from 1 to
Beam power at 10 MeV: 80 kW power consumption
Standby (vacuum <15 kW on and cooling on):
At 50 kW beam power: <210 kW
At 80 kW beam power: <260 kW
Radio signal transmission system
Frequency: 107.5 ± 1 MHz
Thomson TH781
Tetrode Type: Scanning Generator
Nominal scan length (measured at a distance of 25-35 cm from 120 cm of window):
From 30% to 100% of the nominal length
Scan Range:
scan
Nominal scanning frequency (at a maximum length of 100 Hz ± 5% of scanning):
Scan beam uniformity (± 5%)
90% of the nominal scan length)
Table 11. Doses provided for samples Total dose (Mrad)
100
These processed samples are concentrated to obtain granules fit for consumption by cows or other farm animals. The granulate is distributed to farms and stored in a storage silo. Granules are fed to cows and other farm animals.
Reference example 23 - Preparation of alfalfa feed
The 1500-pound alfalfa pallet is passed through a 3 HP Flinch Baugh shredder operating at an approximate speed of 15-20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between rotating and stationary blades is 0.10 inches. The shredder product resembles confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long, and the same thickness as the initial material. Confetti-like material is fed to a Munson rotary cutter, model SC30. The outlet screen has 1/8 inch openings. The distance between rotating and stationary blades is approximately 0.020 inches. A rotary cutter cuts confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The average fiber length is 1.063 mm and the average fiber width is 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1.
These processed samples are concentrated to obtain granules fit for consumption by cows or other farm animals. The granulate is distributed to farms and stored in a storage silo. Such granules are fed to cows and other farm animals.
Example 24 - Preparation of alfalfa feed
The 1500-pound alfalfa pallet is passed through a 3 HP Flinch Baugh shredder operating at an approximate speed of 15-20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between rotating and stationary blades is 0.10 inches. The shredder product resembles confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long, and the same thickness as the initial material. Confetti-like material is fed to a Munson rotary cutter, model SC30. The outlet screen has 1/8 inch openings. The distance between rotating and stationary blades is approximately 0.020 inches. A rotary cutter cuts confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The average fiber length is 1.063 mm and the average fiber width is 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1.
The samples are irradiated with an electron beam generated by the Rhodotron® TT200 continuous wave accelerator providing 5 MeV electrons at an output of 80 kW. Table 10 describes the parameters used. Table 11 lists the nominal doses used.
These processed samples are concentrated to obtain granules fit for consumption by cows or other farm animals. The granulate is distributed to farms and stored in a storage silo. Granules are fed to cows and other farm animals.
Reference example 25 - Preparation of paper feed
The 1,500-pound paper palette is folded flat and passed through a 3 HP Flinch Baugh shredder operating at an approximate speed of 15-20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between rotating and stationary blades is 0.10 inches. The shredder product resembles confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long, and the same thickness as the initial material. Confetti-like material is fed to a Munson rotary cutter, model SC30. The outlet screen has 1/8 inch openings. The distance between rotating and stationary blades is approximately 0.020 inches. A rotary cutter cuts confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The average fiber length is 1.063 mm and the average fiber width is 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1.
These processed samples are concentrated to obtain granules fit for consumption by cows or other farm animals. The granulate is distributed to farms and stored in a storage silo. Such granules are fed to cows and other farm animals.
Example 26 - Preparation of feed from paper
The 1,500-pound paper palette is passed through a 3 HP Flinch Baugh shredder operating at an approximate speed of 15 to 20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between rotating and stationary blades is 0.10 inches. The shredder product resembles confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long, and the same thickness as the initial material. Confetti-like material is fed to a Munson rotary cutter, model SC30. The outlet screen has 1/8 inch openings. The distance between rotating and stationary blades is approximately 0.020 inches. A rotary cutter cuts confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The average fiber length is 1.063 mm and the average fiber width is 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1.
The samples are irradiated with an electron beam generated by the Rhodotron® TT200 continuous wave accelerator providing 5 MeV electrons at an output of 80 kW. Table 10 describes the parameters used. Table 11 lists the nominal doses used.
These processed samples are concentrated to obtain granules fit for consumption by cows or other farm animals. The granulate is distributed to farms and stored in a storage silo. Granules are fed to cows and other farm animals.
Reference example 27 - Preparation of grass feed
The 1,500-pound grass load is passed through a 3 HP Flinch Baugh shredder operating at an approximate speed of 15-20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between rotating and stationary blades is 0.10 inches. The shredder product resembles confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long, and the same thickness as the initial material. Confetti-like material is fed to a Munson rotary cutter, model SC30. The outlet screen has 1/8 inch openings. The distance between rotating and stationary blades is approximately 0.020 inches. A rotary cutter cuts confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The average fiber length is 1.063 mm and the average fiber width is 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1.
Processed samples are concentrated to obtain granules that can be eaten by cows or other farm animals. The granulate is distributed to farms and stored in a storage silo. Such granules are fed to cows and other farm animals.
Example 28 - Preparation of grass feed
The 1,500-pound grass pallet is passed through a 3 HP Flinch Baugh shredder operating at an approximate speed of 15-20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between rotating and stationary blades is 0.10 inches. The shredder product resembles confetti flakes with a width of 0.1 to 0.5 inches and a length of 0.25 inches to 1 inch and a thickness corresponding to the thickness of the starting material. Confetti-like material is fed to a Munson rotary cutter, model SC30. The outlet screen has 1/8 inch openings. The distance between rotating and stationary blades is approximately 0.020 inches. A rotary cutter cuts confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The average fiber length is 1.063 mm and the average fiber width is 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1.
The samples are irradiated with an electron beam generated by the Rhodotron® TT200 continuous wave accelerator providing 5 MeV electrons at an output of 80 kW. Table 10 describes the parameters used. Table 11 lists the nominal doses used.
These processed samples are concentrated to obtain granules that are suitable for consumption by cows and other farm animals. The granulate is distributed to farms and stored in a storage silo. Granules are fed to cows and other farm animals.
Reference example 29 - Preparation of wheat straw feed
The 1,500-pound wheat straw pallet is passed through a 3 HP Flinch Baugh shredder operating at an approximate speed of 15-20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between rotating and stationary blades is 0.10 inches. The shredder product resembles confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long, and the same thickness as the initial material. Confetti-like material is fed to a Munson rotary cutter, model SC30. The outlet screen has 1/8 inch openings. The distance between rotating and stationary blades is approximately 0.020 inches. A rotary cutter cuts confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The average fiber length is 1.063 mm and the average fiber width is 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1.
Processed samples are concentrated to obtain granules that can be eaten by cows or other farm animals. The granulate is distributed to farms and stored in a storage silo. Such granules are fed to cows and other farm animals.
Example 30 - Preparation of wheat straw feed
The 1,500-pound wheat straw pallet is passed through a 3 HP Flinch Baugh shredder operating at an approximate speed of 15-20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between rotating and stationary blades is 0.10 inches. The shredder product resembles confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long, and the same thickness as the initial material. Confetti-like material is fed to a Munson rotary cutter, model SC30. The outlet screen has 1/8 inch openings. The distance between rotating and stationary blades is approximately 0.020 inches. A rotary cutter cuts confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The average fiber length is 1.063 mm and the average fiber width is 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1.
The samples are irradiated with an electron beam generated by the Rhodotron® TT200 continuous wave accelerator providing 5 MeV electrons at an output of 80 kW. Table 10 describes the parameters used. Table 11 lists the nominal doses used.
These processed samples are concentrated to obtain granules fit for consumption by cows or other farm animals. The granulate is distributed to farms and stored in a storage silo. Granules are fed to cows and other farm animals.
Reference example 31 - Preparation of feed from biomass
Palettes containing 1,500 pounds of cane, alfalfa, paper, grass and wheat straw are fed separately into a 3 HP Flinch Baugh shredder operating at an approximate speed of 15 to 20 pounds per hour. The shredder is equipped with two
12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between rotating and stationary blades is 0.10 inches. The shredder product resembles confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long, and the same thickness as the initial material. Confetti-like material is fed to a Munson rotary cutter, model SC30. The outlet screen has 1/8 inch openings. The distance between rotating and stationary blades is approximately 0.020 inches. A rotary cutter cuts confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The average fiber length is 1.063 mm and the average fiber width is 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1.
Processed samples are combined and concentrated to obtain granules that can be consumed by cows or other farm animals. The granulate is distributed to farms and stored in a storage silo. Such granules are fed to cows and other farm animals.
Example 32 - Preparation of feed from biomass
Palettes containing 1,500 pounds of cane, alfalfa, paper, grass and wheat straw are fed separately into a 3 HP Flinch Baugh shredder operating at an approximate speed of 15 to 20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between rotating and stationary blades is 0.10 inches. The shredder product resembles confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long, and the same thickness as the initial material. Confetti-like material is fed to a Munson rotary cutter, model SC30. The outlet screen has 1/8 inch openings. The distance between rotating and stationary blades is approximately 0.020 inches. A rotary cutter cuts confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The average fiber length is 1.063 mm and the average fiber width is 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1.
The samples are irradiated with an electron beam generated by the Rhodotron® TT200 continuous wave accelerator providing 5 MeV electrons at an output of 80 kW. Table 10 describes the parameters used. Table 11 lists the nominal doses used.
Processed samples are combined and concentrated to obtain granules that can be consumed by cows or other farm animals. The granulate is distributed to farms and stored in a storage silo. Such granules are fed to cows and other farm animals.
Reference example 33 - Preparation of feed from biomass
Cane, alfalfa, paper, grass and wheat straw from pallets containing 1500 pounds of raw material are mixed and fed separately into a 3 HP Flinch Baugh shredder operating at an approximate speed of 15 to 20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between rotating and stationary blades is 0.10 inches. The shredder product resembles confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long, and the same thickness as the initial material. Confetti-like material is fed to a Munson rotary cutter, model SC30. The outlet screen has 1/8 inch openings. The distance between rotating and stationary blades is approximately 0.020 inches. A rotary cutter cuts confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The average fiber length is 1.063 mm and the average fiber width is 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1.
Processed samples are concentrated to obtain granules that can be eaten by cows or other farm animals. The granulate is distributed to farms and stored in a storage silo. Such granules are fed to cows and other farm animals.
Example 34 - Preparation of feed from biomass
Cane, alfalfa, paper, grass and wheat straw from pallets containing 1500 pounds of raw material are mixed and fed separately into a 3 HP Flinch Baugh shredder operating at an approximate speed of 15 to 20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between rotating and stationary blades is 0.10 inches. The shredder product resembles confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long, and the same thickness as the initial material. Confetti-like material is fed to a Munson rotary cutter, model SC30. The outlet screen has 1/8 inch openings. The distance between rotating and stationary blades is approximately 0.020 inches. A rotary cutter cuts confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The average fiber length is 1.063 mm and the average fiber width is 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1.
The samples are irradiated with an electron beam generated by the Rhodotron® TT200 continuous wave accelerator providing 5 MeV electrons at an output of 80 kW. Table 10 describes the parameters used. Table 11 lists the nominal doses used.
Processed samples are concentrated to obtain granules that can be eaten by cows or other farm animals. The granulate is distributed to farms and stored in a storage silo. Such granules are fed to cows and other farm animals.
Reference example 35 - Preparation of feed from biomass
Cane, alfalfa, paper, grass and wheat straw from pallets containing 1500 pounds of raw material are mixed and fed separately into a 3 HP Flinch Baugh shredder operating at an approximate speed of 15 to 20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between rotating and stationary blades is 0.10 inches. The shredder product resembles confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long, and the same thickness as the initial material. Confetti-like material is fed to a Munson rotary cutter, model SC30. The outlet screen has 1/8 inch openings. The distance between rotating and stationary blades is approximately 0.020 inches. A rotary cutter cuts confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The average fiber length is 1.063 mm and the average fiber width is 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1.
The processed samples are combined with distillation dried cereals (DDG) to obtain a mixture suitable for consumption by cows and other farm animals. Such mixtures are distributed to farms and stored in a storage silo. Such granules are fed to cows and other farm animals.
Example 36 - Preparation of feed from biomass
Cane, alfalfa, paper, grass and wheat straw from pallets containing 1500 pounds of raw material are mixed and fed separately into a 3 HP Flinch Baugh shredder operating at an approximate speed of 15 to 20 pounds per hour. The shredder is equipped with two 12-inch rotary blades, two stationary rotary blades and a sieve with 0.30 inch openings at the outlet. The distance between rotating and stationary blades is 0.10 inches. The shredder product resembles confetti flakes 0.1 to 0.5 inches wide and 0.25 inches to 1 inches long, and the same thickness as the initial material. Confetti-like material is fed to a Munson rotary cutter, model SC30. The outlet screen has 1/8 inch openings. The distance between rotating and stationary blades is approximately 0.020 inches. A rotary cutter cuts confetti-like fragments, releasing fibrous material at a speed of about one pound per hour. The average fiber length is 1.063 mm and the average fiber width is 0.0245 mm, which gives an average length to diameter ratio (L / D) of 43: 1.
The samples are irradiated with an electron beam generated by the Rhodotron® TT200 continuous wave accelerator providing 5 MeV electrons at an output of 80 kW. Table 10 describes the parameters used. Table 11 lists the nominal doses used.
The processed samples are combined with distillation dried cereals (DDG) to obtain a mixture suitable for consumption by cows and other farm animals. Such mixtures are distributed to farms and stored in a storage silo. Such granules are fed to cows and other farm animals.
Example 37 - Self-sufficient farms
The farmer harvests the cane and sends it for processing to the processing plant. The cane is processed as described in Example 21. The processed material goes to the farmer in the form of granules fed to his cows and other farm animals.
Example 38 - Self-sufficient farms
The farmer harvests the cane and sends it for processing to the processing plant. Cane is processed as described in Example 22. The processed material goes to the farmer in the form of granules fed to his cows and other farm animals.
Example 39 - Self-sufficient farms
The farmer harvests cane crops and processes the material using equipment on the farm. Cane is processed as described in Example 21. The processed material is fed to cows and other farmer's farm animals.
Example 40 - Self-sufficient farms
The farmer harvests cane crops and processes the material using equipment on the farm. Cane is processed as described in the Example
22. The processed material is fed to cows and other farmer's farm animals.
Mobile installations for biomass processing
Stationary biomass processing installations have been described. However, depending on the source of the raw biomass and the products produced from it, it may be beneficial to process biomass in mobile installations that can be located near the source of the raw material and / or near target markets where products made from the raw material will go. In some embodiments, the raw biomass is various grasses, such as reeds. Transporting large amounts of cane from the fields it grows to processing plants hundreds or even thousands of miles away may be unprofitable and expensive (for example, the estimated cost of rail raw material transport is between $ 3.00 and $ 6.00 per tonne for every 500 miles). In addition, some raw cane products can be useful in markets where raw biomass is grown (e.g. as feed for farm animals / ruminants). Re-transporting feed for ruminants through hundreds or thousands of miles to the target market will not be profitable.
Contents15
117 members in 21 offices
Priority claims12
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|---|---|---|---|
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| 7367408 | United States of America | P | |
| 13945308 | United States of America | P | |
| 41790009 | United States of America | A | |
| 09739593 | European Patent Office (EPO) | A | |
| 2009041963 | United States of America | W | |
| EP20090739593 | – | – | – |
| US20080049405P | – | – | – |
| US20080073674P | – | – | – |
| US20080139453P | – | – | – |
| US20090417900 | – | – | – |
| WO2009US41963 | – | – | – |
Members117
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| CA2722560A1 | Canada | A1 | |
| CA3051176A1 | Canada | A1 | |
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| WO2009134746A1 | World Intellectual Property Organization (WIPO) | A1 | |
| WO2009134791A2 | World Intellectual Property Organization (WIPO) | A2 | |
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| WO2009134791A3 | World Intellectual Property Organization (WIPO) | A3 | |
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Numbers
- Publication, DOCDB
- 2276795
- Publication, EPODOC
- PL2276795T
- Application
- 739593
- Application, DOCDB
- 09739593
- Application, EPODOC
- PL20090739593T
Titles2
- English
- PROCESSING BIOMASS
- Polish
- Przetwarzanie biomasy
Classification
- CPC, 44
- A61Q19/00
- C12P13/24
- B01D39/18
- C08H8/00
- C08J3/28
- C08L1/02
- C08L5/14
- C12P13/04
- C12P19/44
- D21C5/005
- D21C9/001
- Y02E50/10
- Y02E50/30
- A23K40/00
- A23K10/12
- A23K10/30
- A23K10/37
- A23K20/163
- A23K50/10
- A23K50/80
- A23L5/36
- A23L7/115
- Y02A40/818
- C13K1/02
- A61K8/9789
- A61P31/04
- Y02P60/87
- C12P13/14
- C12P13/20
- C12P13/222
- C12P13/08
- C12P13/06
- C12P13/12
- C12P13/227
- C12P2201/00
- C12P2203/00
- C12P7/10
- C12P7/16
- C12P7/40
- C12P7/46
- C12P7/56
- C12P19/02
- C12P19/14
- A23V2002/00
- IPC, 15
- C08B15 04
- C08H8 00
- A23K1 14
- A23K10 32
- A23K10 38
- A23L5 30
- A23L7 10
- B01J19 08
- C08B15 06
- C08J3 28
- C08J11 16
- C10L5 44
- C12P19 00
- C13K1 00
- D21C3 02