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    • 专利摘要:
    METHOD FOR PROCESSING A BIOMASS CONTAINING LIGNOCELLULOSIS A method for processing a biomass (for example, straw) containing lignocellulose is disclosed such that cellulose and hemicellulose become accessible for further processing, usually by decomposition, without requiring dissolution of biomass in expensive water power. The method includes repeated compressions of the biomass in a reciprocating piston press where non-compacted biomass is continuously fed into a tubular reaction chamber in which the biomass is compressed to produce a steam explosion and auto-hydrolysis under simultaneous displacements of compressed biomass through the reaction chamber. After compression, liquid cattle manure, residual water sludge, etc. can be added to the biomass. in a biogas plant for further processing of biogas.
    公开号:BR112014025372B1
    申请号:R112014025372-2
    申请日:2013-04-10
    公开日:2021-01-12
    发明作者:Torben Andreas Bonde
    申请人:Kinetic Biofuel A/S；
    IPC主号:
    专利说明:

    Field of the Invention
    The present invention relates to a method for processing a biomass (for example, straw) containing lignocellulose, so that cellulose and hemicellulose are accessible for further processing, usually by decomposition, which is preferably an enzymatic decomposition. more specifically, the invention relates to the method in which processed lignocellulose is used for the production of biofuels, 10 such as, for example, ethanol, butanol, hydrogen, methanol and biogas. Biomass can be, for example, straw, biomass can be, for example, straw.
    The invention arose in relation to the treatment of straw. At various points in the invention, therefore, it is explained with reference to straw, but by these explanations it is understood that the corresponding advantages are achieved by other types of biomass that contain lignocellulose. Fundamentals of the Invention
    First generation bioethanol is produced mainly based on cereals such as wheat and corn, as well as sugar cane. This is due to the fact that corn and sugarcane contain readily accessible carbohydrates such as starch, which can be converted to sugar in a simple way, and which is subsequently fermented in ethanol.
    However, this production has been criticized for converting good food into energy, in addition to not being sustainable. Therefore, for some years, the research was done using crop residues from the production of 25 foods for the production of biofuels, in particular bioethanol. Research has mainly focused on converting straw and wood chips into bioethanol. This type of ethanol is labeled as second generation bioethanol or cellulosic ethanol.
    Biomass, such as wheat straw and straw from other maize and crops of 30 maize and wood, basically consist of cellulose, hemicellulose and lignin, which is why it is collectively called lignocellulose.
    Cellulose is a linear homogeneous polymer of up to 15,000 glucose units linked together by β-1,4-glycoside bonds. Hemicellulose is, however, a heterogeneous branched polymer, with a length of up to 200 units, which can consist of, for example, arabinose, xylose, galactose, mannose and glucose.
    Lignin is a network formed by the polymerization of monomers p-coumaryl alcohol, coniferyl alcohol and synaphyl alcohol. The complex network of lignin encapsulates and contributes to cellulose and hemicellulose together. The cell wall structure of the plant is therefore strengthened and protected against decomposition in nature, for example, by attacks by fungi or insects. In general, lignocellulose contains about 35-50% cellulose, 20-30% hemicellulose and 15-30% lignin.
    However, there are major differences in the content of various plants and the composition of hemicellulose and lignin is very dependent on the species. In general, wood contains more lignin and less hemicellulose than straw, and where straw hemicellulose consists mainly of arabinose and xylose, in conifers it contains mainly mannose and only a small amount of xylose.
    The use of lignocellulose as a substrate for various fermentation processes presupposes a previous decomposition of cellulose and hemicellulose in their respective monomers. The first step in this process is a thermochemical treatment of lignocellulose by which lignin is released and hemicellulose and cellulose are partially dissolved are more accessible to enzymes.
    Enzymes for the decomposition of lignocellulose can be divided into two main groups: cellulases and hemicellulases. The last stage of cellulose decomposition is the cleavage of cellobiose into two glucose molecules by the enzyme β-glucosidase. The more heterogeneous structure of hemicelluloses means that a greater number of different enzymes is needed to break them down completely into sugar molecules. An example of this mixture of complex enzymes is Novozyme Cellic.CTec3 which contains different cellulases and hemicellulars, as well as other hydrolytic enzymes. 5 As mentioned, the first step in the use of lignocellulose is pre-treatment and, normally, thermochemical pre-treatment. The steam explosion is part of this wide range of different thermochemical pretreatment methods. This process is combined with the addition of water and catalysts like acids and bases or gases like oxygen and 10 sulfur dioxide.
    The pre-treatment of biomasses such as straw and wood chips to make fluid biofuels, especially ethanol, has been subject to a very comprehensive research effort, and the huge amount of scientific literature is therefore available in this area. 15 In recent years, dominant biochemical methods have been described.
    In this instrument, a comprehensive presentation of these works will not be made, however, it is observed that several groups point to self-hydrolysis as the preferred technology because it is not based on chemicals, because the formation of inhibitors is modest and because the biomass 20 with a relatively high dry matter content can be processed. It is also preferred by most authors over wet oxidation in which oxygen is added to the process.
    Self-hydrolysis has several different names, but it is often called thermal hydrolysis, vaporization or vapor explosion 25 regardless of whether the explosion part is not necessarily an advantage for the hydrolysis or comminution of the material. The method delimits the "hot liquid water treatment", depending on the amount of water and wet oxidation if oxygen is part of the process.
    In addition, the scientific literature points to the use of various chemicals and catalysts or the hydrolysis of lignocellulose, including weak and strong acids, bases and various gases such as SO2, CO2, O2l NH3, H2O2, O3. To this is added the application of enzymes, being carried out industrially or as biological pre-treatment.
    The technical installations used for these thermochemical pre-treatments of biomasses containing lignocellulose have been carried out in only a few examples.
    The best known device is the staketech hydrolizer from SunOpta which is used in the first commercial plant for the production of bioethanol based on straw. This machine has a horizontal reaction chamber with a helical conveyor that moves the straw forward under high pressure and temperature, allowing it to explode in an associated expansion vessel at frequent intervals, that is, at intervals of a few seconds. The operating temperature and pressure are 190-210 ° C and 15-20 bars, respectively.
    The Atlas Stord hydrolyzer for feather hydrolysis uses a different principle, called piston flow, where the reaction chamber is a vertical chamber with a valve at the bottom that opens and closes every few seconds. The overpressure in the reaction chamber will therefore cause the hydrolyzed feathers to explode in an expansion vessel. The reaction chamber, therefore, does not have a stem passage. The operating temperature and pressure are 160-210 ° C and 6-10 bars, respectively.
    Finally, Villavicencio (1987) published an invention for the thermochemical treatment of fibers by means of several reaction chambers. The biomass is supplied by helical conveyors, which also act as back pressure valves, for the first reaction chamber.
    The elements most common to all techniques are 1) heat that is supplied from an external heat source, especially through hot water or steam; 2) water that in liquid or vapor form is added to the process, so that the dry matter content is at most 30-40% in the reaction chamber and normally 10%; 3) water or steam that is added as a necessary prerequisite for treatment at high temperatures at the level of 160-220 C.
    The operational mode of the technique indicates and, as the name "steam explosion" indicates, to be a mechanical decomposition of the biomass fibers by a steam explosion caused by a sudden pressure drop of, for example, 20 bars at atmospheric pressure . The state of the water, for example, at 200 ° C, under pressure is liquid, but when the pressure drops sharply at atmospheric pressure, part of the water is transformed into steam, that is, the water occurs in all parts of the plant fibers as well . When this water explodes in the cellulose fibers, the biomass is mechanically torn. The tearing action contributes to making parts of the lignocellulose component of cellulose and hemicellulose accessible to other processing, for example, by enzymatic decomposition.
    The conventional steam explosion is often carried out at temperatures ranging from 160 to 220 ° C and pressures corresponding to 0.60-4.83 MPa. Processing time varies from a few seconds to several minutes before the material is exposed to atmospheric pressure through explosive decompression. The process causes the decomposition of hemicellulose and the transformation of lignin due to the high temperature. Hemicellulose is decomposed by acetic acid and other organic acids formed during treatment, that is, through so-called self-hydrolysis. Lignin is not decomposed to the same degree, but is redistributed on the fiber surfaces as a result of fusion and depolymerization / repolymerization reactions.
    In addition to these chemical effects, the steam explosion also has a purely physical or mechanical effect as the material explodes and breaks up, thereby increasing the accessible surface.
    The procedure is implemented, as mentioned, by adding water to the biomass, in liquid or vapor form, or a combination of the two, and heating the mixture. High temperatures are reached by heating with hot water or steam.
    The highest concentration of dry matter reached by these systems is about 30 to 40%, usually much lower, requiring large technical installations due to the amount of water and the bulky structure of the biomass. Even a bale of compressed straw has a density of around 150 kg / m 3, which is not much.
    A crucial challenge for the technique is the large amount of water and energy used for pretreatment and the large installations required for pressure vessels, valves, pipes, helical conveyors, etc.
    This also implies substantial disadvantages for biogas plants since the large addition of water with the straw overloads the hydraulic capacity of the biogas plant, and that energy consumption reduces the production of liquid energy and the cost efficiency.
    Biofuel can also be supplied in the form of biogas. Until now, biomass, preferably in the form of straw, has not been used for the production of biogas. It is not known to use straw for the production of biogas. 20 It is only known that that straw is part of the biogas plants since the straw is used as a bedding material in animal production and that the resulting animal manure is degassed.
    In fact, it is quite surprising that straw is not used for biogas. Taking into account the fact that manure from livestock, that is, cattle manure and pig liquid manure, is fluid with a dry matter content of between 4 and 8%, there is room for additional dry matter in the biogas plant. , especially straw.
    Straw is a difficult material to handle. It is very abrasive, very hydrophobic and has a very low density, that is, less than 100 kg / m 3. 30 The handling of straw in any connection and, especially, in biogas plants, therefore, requires a special technique.
    In addition, straw consists predominantly of cellulosic fibers which are crystalline polymers of (1-4) -β-D-glucose. Hemicellulose is part of it, which is correspondingly an amorphous and partially crystalline polymer consisting of (1-4) -β-xylose. Hemicellulose is part of the fibers and cell walls. Lignin, a third essential component of straw, is a polymer of phenol. Hemicellulose, as well as lignin, protects cellulose from "weather and wind" and, in this context, from decomposition by enzymes and microorganisms.
    In order to efficiently use the straw in a biogas plant, it is therefore necessary to pre-treat the straw in order to open the straw fibers and allow the parts of the lignocellulose component to be accessible for decomposition. As mentioned above, this will be the necessary and energy-consuming use of bulky plants. Object of the Invention
    The object of the present invention indicates a method for the processing of a biomass (for example, straw) containing lignocellulose, so that cellulose and hemicellulose become accessible for enzymatic decomposition, in particular, with the intention of making biofuels as , for example, ethanol and biogas. Description of the Invention
    According to the present invention, this is achieved by a method that is peculiar in that it includes steps for: - repeated biomass compressions in an alternating piston press, where the loose biomass is continuously fed into a piston chamber in front of a piston which moves the loose biomass in a tubular reaction chamber where the biomass is compressed, to produce an explosion of mechanically induced water vapor and self-hydrolysis in a simultaneous displacement of the compacted biomass through the reaction chamber.
    An efficient method is therefore achieved by the present invention to establish a first stage of the process of using lignocellulose as a substrate for various processes, since the explosion of water by the mechanically induced vapor explosion causes the cellulose fibers to be torn mechanically . This tearing action allows the components of cellulose lignocellulose and hemicellulose to be accessible for further enzymatic decomposition for their respective monomers.
    The continuous feeding of the biomass and a simultaneous displacement of the compressed biomass to and from the reaction chamber allow a continuous process in a plant in which there is only the need for a processing unit with a very restricted volume. A piston press with a capacity of 1 ton of biomass per hour can therefore be less than 3 cubic meters in size. Another development for larger machines can further optimize this relationship.
    As the piston travel acts on the biomass with a pressure between 500 and 3000 bars, in particular between 1000 and 2500 bars. The biomass is then compressed to 500-1000 kg / m3 and is directly impacted mechanically. At the same time, the piston kinetic energy is deposited in the straw as heat.
    The formation of heat in the biomass occurs primarily due to the friction between the biomass and the walls of the reaction chamber and the internal friction in the biomass. The formation of heat causes a strong heating of the walls of the reaction chamber and a lower heating of the biomass. The walls are usually heated between 110 and 200 ° C, the biomass between 60 and 170 ° C, although locally the temperature is above 200 ° C. Compression in the reaction chamber causes many local steam explosions to occur.
    Since this water is under pressure, it remains in a liquid state until the piston retracts before a new piston stroke. In the retraction, the water explodes and the biomass is impacted by a steam explosion. This is repeated several times until the compressed biomass advances to the compression chamber and the piston stroke no longer has any influence on that biomass.
    The action of heat and the explosion of steam causes a certain self-hydrolysis of biomass, which means that steam at high temperature partially dissolves lignocellulose by a hydrolytic process. Self-hydrolysis generates organic acids that reduce the pH to 4-6, usually pH 5.
    The process is distinguished by its great energy savings, and there is no need to heat large amounts of water.
    In short, it can be said that steam explosion is a technique with several cooperating effects: high temperature effect (that is, formation of organic acids, melting of lignin); effect of self-hydrolysis (hemicellulose and lignin are partially decomposed by acetic acid activity); and the effect of mechanical tearing.
    A mechanical press is designed as an eccentric press. Mechanical presses include a constant rotary movement mechanism converting a rotary movement into an alternating movement of a piston by means of an eccentric. The piston has two extreme positions. In one position, the face of the piston press is located in a piston chamber, also called a pre-compression chamber, the material being pre-treated, especially by compression in a briquette, and in the other extreme position the face of the piston press is located at the entrance of an open conical nozzle on the side of the pre-compression chamber. On the way between one end and the other, the piston pushes the material from the chamber in front of it to the nozzle. The compacted and pre-treated parts of the material for each piston stroke or in concrete situations have formed bio-briquettes, are continuously pushed out by the nozzle outlet. Mechanical presses operate at much higher pressures than hydraulic presses as a pressure of at least 800 bar is achieved. In a bio-briquette made in a hydraulic press the connection of biological material is primarily mechanical and secondarily by adhesion, whereas the connection of biological material in a bio-briquette made in a mechanical press is primarily by adhesion and secondarily mechanical. The present invention is used within the technical area of mechanical briquette pressing machines, since it concerns the production of high-capacity bio-briquettes or the pre-treatment of biological material.
    Alternating mechanical briquette pressing machines, mainly wooden or other biological briquettes 10 usable as fabric, MDF sawdust, vegetable fibers, straw, hemp, bark, paper, cardboard, coal dust, household waste, cattle manure or mud, are known. Briquettes can be used mainly for burning in solid fuel ovens for, for example, heating the domestic space. The material is typically a waste product from the timber industry in the form of sawdust or shavings.
    The material should have a moisture content of 5% to 20%, usually 6% to 16%. We are talking here about the percentage by weight. The material is compressed in the mold under great pressure and consequent high temperature. The biological material contains cells that, among others, include water, cellulose and lignin. The purpose of the compressions is to activate the lignin which, after cooling, provides the connection of the material (the bio-briquette). During application as a pretreatment and the possible addition of organic acid, this is the basis for extracting lignin and thus exposing the cellulose and hemicellulose fibers for further processing. The increase in pressure in the biological material produces an increase in the temperature in the cells, causing the water in the cell to be transformed into steam by an explosion of steam through which the cell wall is destroyed and the lignin is released. The steam explosions start at a pressure of about 400 to 500 bar and continue as long as the pressure increases to a maximum value of more than 30 2000 bar. If the humidity falls below 6%, there is usually not enough moisture in the material to produce enough steam explosions for a bond to occur. If the humidity rises above 16%, the steam bursts usually become so strong that the process fragments the briquettes, and they are thrown out of the machine or back into the system. This can be advantageous as a pretreatment and pretreatment like this is desired instead of forming a real briquette.
    As explained above, a more complete decomposition of the cells forming the briquette in a mechanical briquette press is achieved due to the higher pressure. The amount of lignin released for subsequent binding of the bio-briquette is substantially greater.
    The biological material leaves the briquette press as a continuous rod. Each stroke of the piston adds, so to speak, a biomass "disk" for the execution of the material, and fracture surfaces are formed between each disk. Mechanical presses are generally used in large installations of around 200 kg / hour and up to about 2500 kg / hour. In a mechanical press, the desired back pressure can therefore only be adjusted by fitting a nozzle with a different taper or with a variable compression nozzle. Due to the fact that the mechanical press is driven by electric motors and not by a hydraulic motor, there is only a small loss of energy in the machine, and the relationship between production and energy consumption is therefore ideal. The life cycle of a mechanical press is considerably longer than that of a hydraulic press.
    It is possible to present the invention as a decentralized solution, which means that the compression for briquette formation is carried out in a single location and that the briquettes are stored and later transported to a decomposition facility, such as a biogas plant or a bioethanol plant.
    Because of the invention, it is possible to compact high-density biomass, supply heat by mechanical kinetic energy, to avoid adding water and to use the natural water content of about 5% to 20% and, normally, 6% to 16% of a biomass for repeated steam explosions. The process thus becomes rational so that the biomass is treated exclusively at high temperatures - and not a large amount of water - and that this occurs in very small reaction chambers.
    The compression of wood and straw is known to press these materials into briquettes or pellets for further combustion. However, it is not known how to optimize mechanical compression for application as a mechanically induced vapor explosion of biomass so that cellulose and hemicellulose are accessible for enzymatic decomposition before fermentation in ethanol or other biofuels.
    By the present invention, a very high specific density of straw between 800 and 1200 kg / m3 is achieved, generally an apparent density between 500 and 600 kg / m3, considerably reducing the size of the reaction chamber (due to the high specific density) and the need for possible transportation to a central processing plant (due to the high density). One of the special advantages achieved by the present invention is, therefore, a compact reaction chamber. Only a few liters of the reactor volume are used, that is, less than 50 liters and usually about 10 liters, as opposed to the several cubic meters that are common in other systems (5-10 m3 or more).
    The addition of water is avoided and biomass, for example, in the form of straw, is treated, therefore, in its natural water content of 5% to 20%, usually between 6% and 16%. This substantially reduces the energy requirement since the thermal capacity of the water is approximately 4.2 J / gK, whereas the thermal capacity of dry straw and wood is approximately 1.2 J / gK. A normal addition of water 10 times the straw weight by thermo-chemical pretreatment therefore increases energy consumption by about 40 times in the direct process.
    If appropriate in a given process, lignin can be extracted, after the mechanical steam explosion, but then at temperatures below 100 ° C and, usually, around 50 ° C to 80 ° C. Lignin can be extracted by water or by acids or bases according to known prescriptions for the extraction of lignin. Here, generally organic acids such as lactic acid, citric acid or acetic acid are applied, which can possibly be added before pressing and contribute to hydrolysis, as well as to the lignin extraction.
    The straw is impacted with greater mechanical intensity since it is directly impacted by the piston strokes under compression and also by repeated steam explosions. This provides better accessibility for enzymes during the subsequent enzymatic reaction such as liquefaction and saccharification before ethanol fermentation and, consequently, less need for enzyme addition.
    There are several commercial enzymes for cellulose / hemicellulose liquefaction and saccharification. It is estimated that consumption can be reduced to below 50% and normally to 20% of normal consumption by conventional thermochemically processed straw.
    The thermal treatment of biomass is adapted so that it is carried out at temperatures ranging from 40 C to 240 ° C, preferably with measurable temperatures, usually between 60 ° C to 170 ° C and especially in the range between 60 ° C and 120 C. The processing time can be adjusted between 1 and 30 min and particularly between 1 and 5 min. As only the straw is heated and processed in a compact reactor chamber, there is no practical limit for heat treatment depending on temperature and time. Treatment can be optimized without being limited by these considerations. When more time is required for heat treatment, including hydrolysis, the nozzle is extended to an isolated helical conveyor duct that allows a holding time of 1-2 hours or more. Typically, there may be a need for complementary heat treatment and hydrolysis for one hour at 90 ° C.
    The straw reaches a capacity to increase water absorption. It seems that straw can absorb between 2 and 15 times its own weight in water and, normally, between 5 and 10 times its own weight.
    The straw becomes directly miscible with water and enzymes. The addition of surfactants is usually not necessary to improve the mixture with water and the action of enzymes.
    Significant dissolution of lignins is achieved due to the heat and the presence of oxygen during the process. The partial pressure of oxygen in the water is about 2 x 10'5 atmospheres (1 atm = 101.325 kPa); the partial pressure of oxygen in the atmosphere is about 2 x 10'1; the partial pressure is therefore 104 times greater in the atmosphere than in oxygen-saturated water. Oxygen is therefore added by wet oxidation under pressure, ie 5-20 atm, usually 10 atm, but there is still limited access for the reaction of oxygen with lignin due to the addition of large amounts of water to the process. During the mechanical steam explosion the straw and the ambient atmosphere with about 20% oxygen are subject to a maximum pressure of 2000 to 2500 bars. Oxygen is therefore much more reactive than during conventional wet oxidation, and lignin is therefore destroyed to a greater extent.
    In addition, the straw can be impregnated with gases and / or bases or acids, cf. the aforementioned thermochemical methods for pretreating lignocellulose prior to introduction into the piston chamber. This can occur in a mixer or a free-fall mixer.
    Finally, enzymes and water can be added after treatment using a nozzle that sprays the mixture over all the dry straw in a free-fall mixer. Enzymes and water will therefore be distributed evenly throughout the straw, and the new water-specific absorption capacity of the straw will distribute, in particular, moisture and enzymes to all parts of the straw.
    Enzyme-moistened straw can now be liquefied (hydrolyzed) and supplied to a membrane-enzyme reactor where cellulose and hemicellulose are finally saccharified in oligo sugar - and monomers. In the reactor, the associated membranes will retain lignin and other unconverted substances while the sugars pass to alcoholic fermentation. In other configurations, it may be an advantage to ferment the total mixture of lignin, sugar etc. the so-called "whole paste" - and separate after fermentation and distillation. This depends specifically on the amount of lignin in the biomass.
    The new technical means for use in the steam explosion of biomass, preferably straw, include a piston. This will be mounted on a hand crank to establish the reciprocating movement that moves straw from the loose biomass from a piston chamber to the reaction chamber. The latter is formed, preferably, by an open duct with a funnel-shaped nozzle, where the biomass is compressed at a pressure between 500 and 3000 bar, especially between 1000 and 1500 bar.
    Back pressure is established by means of biomass (straw), which is accumulated and compressed in the reaction chamber and which moves through a compression chamber in a compacted form and by the friction between the biomass and the chamber wall.
    The length of the reaction chamber and its insulation are adapted according to the need, depending on the duration of the temperature action. The chamber has a heating jacket so that the temperature can be adjusted according to the need.
    It is preferable that the biomass (the straw) can be cut a few centimeters from the straw length. In addition, it is preferable that a cleaning of the biomass of stones and sand and other foreign bodies is carried out before compression.
    The press has thermometers and manometers as needed.
    The temperature in the straw is regulated by the force of the piston stroke, cooling of the reaction chamber and isolation of the reaction chamber.
    The finished and compressed straw can be disintegrated later, appearing again as cut straw, although much softer now. However, straw completely changed its nature after treatment and became water-absorbent, among others. Straw can absorb between 2 and 15 times its own weight, specifically 5 to 10 times its own weight.
    Thus, it is possible to add enzymes and water simultaneously, for example, by means of spray nozzles, in a free-fall mixer or other type of mixer. Thus, water and enzymes are distributed equally in the straw.
    It is also possible to add straw in compressed form and directly to a bioreactor, thermoreactor, chemical reactor, thermochemical reactor or other type of reactor. In addition, it is possible to add straw to cattle liquid manure, residual water sludge, etc. before a biogas process, in which the straw will then be converted into biogas reactors into biogas with maximum yield.
    Method, according to the invention, can be used in pre-treatment of straw for use in the production of biogas. A typical biogas plant that degasifies 100,000 tons of liquid cattle manure and distributes the gas to a decentralized thermoelectric plant can - with the proper technique - without more substantial investments in the biogas plant itself use, for example, 10,000 tons of straw annually also. Therefore, biogas production will increase from about 2.5 mm3 of liquid cattle manure with about 4 m3 of straw to 6.5 m3 in total annually. The method offers the possibility of a substantial increase in the production of biogas in the existing plants.
    The full effect of the mechanical steam explosion includes mechanical compression, heat treatment, steam explosion, oxidation and self-hydrolysis.
    The method according to the invention can, for example, be carried out in the manner described on the basis of straw, but which can be used in a similar manner in other biomasses containing lignocellulose.
    Before the mechanical steam explosion, the process begins by feeding the cut and dry straw, dry sawdust or similar lignocellulose into a piston chamber. A piston in a crank moves the loose straw in a tubular reaction chamber. The piston moves back and forth by the crank and moves the new straw into the reaction chamber at each stroke. The compressed straw is pushed through the duct by the renewed feeding of the straw and its compression.
    The straw can be impregnated with gases, acids or bases as needed, before being introduced into the piston chamber. Self-hydrolysis can be intensified and the pH can be further reduced in the treated material, ie pH between 1 and 4, usually pH 2. Alternatively, the base can be added and then a basic hydrolysis is performed in addition to the effects mechanically induced.
    The compacted straw can be disintegrated at a later time and then opens up for the addition of water and enzymes in a free-fall mixer or other type of mixer.
    The treated straw is supplied to a biogas process, a bioethanol process or another fermentation process or process for the production of biofuel, organic acids or other organic biological products such as paper, industrial chemicals, fodder or other material.
    Commercially available mechanical components can be used for the invention, including lines for handling straw in the form of large bales, including mats, tearing, comminution to a desired particle size through hammer mills, separation of stones, sand and other contaminants before the mechanical steam explosion.
    Commercial briquette presses can therefore also be used after modification in order to present process parameters that are necessary to induce the steam explosion in straw and similar biomass.
    After the mechanical steam explosion, the material can adapt to the production of bioethanol, biogas or another form of biofuel; it will normally be bioethanol. In bioethanol production, there are, in principle, two systems that use the material directly in the ethanol process or that use a lignin extraction before the ethanol process.
    Finally, the fact that the treatment results in the compression of the high density material can be used in several ways. Firstly, a further treatment can take place in a thermochemical or other reactor and in high density since the straw is compressed and, even so, it can be introduced in the reactor (such as, for example, a bioreactor). However, it can also be used so that biomass, for example straw, can be collected locally and treated at decentralized processing stations and places where it is stored compressed before being transported to a central processing plant, for example. example, a bioethanol plant.
    Thus, the local treatment includes the collection, for example, of straw in quantities of 10,000 to 50,000 tons similar, treating in a straw handling line, pressing etc., as described by the invention and making the weighing, recording and control before local storage.
    It is observed that the treatment and the compression are used for a total logistic solution for collection in the magnitude 0.5 to 1 m of tons of straw or more for a central bioethanol plant.
    In addition, acid, base or gases are added as catalysts in the treatment and at the same time as antimicrobial agents during storage. Therefore, it prevents the biomass from being attacked by microorganisms during storage - the biomass is simply preserved. At the same time cleaning, registration and quality control are carried out by means of the total pre-treatment, they are stored in relation to type and quality.
    According to a special modality, the method, according to the invention, is peculiar so that, after leaving the reaction chamber, the biomass moves directly to a reactor selected from an enzyme reactor, a thermal chemical reactor, a thermal reactor, a chemical reactor, a biological reactor or a different reactor.
    According to a special modality, the method, according to the invention, is peculiar so that, after leaving the reaction chamber, the biomass is stored locally and that further processing is carried out in a central plant. 10 According to an even more special modality, there is an indication of a method for making fodder, such as forage for cattle. This occurs through the ensiling of straw, which is treated by the mechanically induced steam explosion. This makes it possible to ensilage the straw, independently or by mixing hay, corn or another crop for ensilement. This improves the nutritional value of straw and mixed silages, including increased dry matter content, protein content and overall digestibility of the silage.
    According to an even more special modality, there is an indication of a method for the treatment of biomass in the form of wood chips 20 for pulp or other fiber product in which the mechanically induced steam explosion constitutes an interrupted pre-treatment . This pretreatment occurs before a conventional thermochemical treatment (KRAFT) in sodium hydroxide (NaOH) and sodium sulfide (Na2S). This implies that conventional treatment can be carried out with less consumption of water, chemicals and energy in a smaller volume, and that, therefore, it is carried out in a more profitable way. Description of the Figures
    In the following, the invention will be explained in more detail, with reference to the drawing attached to the document: Fig. 1 schematically shows the design of a piston press to be used in the establishment of a mechanical steam explosion in a biomass; Fig. 2 shows a diagram to illustrate various modalities of a method according to the invention; Fig. 3 shows a diagram to illustrate a principle in the use of the mechanical steam explosion as a technique for simultaneous pretreatment and straw feeding in a biogas reactor, alternatively, direct or indirect feeding for thermal, chemical, thermochemical or other; Fig. 4 shows a diagram to illustrate a principle in the use of the mechanical steam explosion as a pre-treatment of straw before a bioethanol process and the most important principles in the bioethanol process, and in which lignin is extracted in a enzyme reactor; Fig. 5 shows a diagram to illustrate a principle in the use of the mechanical steam explosion as a pre-treatment of straw before a bioethanol process and the most important principles in the bioethanol process, in which the lignin is removed by a pressing action; Fig. 6 shows a diagram to illustrate a principle in the integration of the mechanically induced steam explosion in a bioethanol process containing a typical thermochemical or other for pretreatment reactor; Fig. 7 schematically shows a biogas plant where a piston press is used to establish the mechanical steam explosion in a biomass as a pre-treatment of the biomass before introduction into a bioreactor; Fig. 8 shows a diagram to illustrate a principle in the integration of mechanically induced steam explosion in a method for the production of fodder, such as, forage for cattle; and Fig. 9 shows a diagram to illustrate a principle in the integration of mechanically induced steam explosion in a method for treating biomass in the form of wood chips for pulp or other fiber product prior to a conventional thermochemical treatment.
    Detailed Description of the Modalities of the Invention Fig. 1: Illustrates the technical layout and the operation of the mechanical steam explosion of the straw before a biogas process. In Fig. 1 the following reference numbers are used: 11 is a piston chamber; 12 is a piston; 13 is a crank; 14 is loose straw; 15 is a reaction chamber (duct) and 16 is compressed straw. Fig. 2: Illustrates a flow chart for using the invention for the production of bioethanol from straw. Straw 1) is received, shredded and cleaned in a straw handling line before treatment in 2) press and possible complementary hydrolysis before 3) shredding the compressed straw into loose straw. This loose straw can now be sprayed or an appropriate mixture of water and enzymes can be added to perform 4) mixing and liquefaction, also called dedicated hydrolysis. Hydrolytic enzymes are added to the water, and this mixture of water and enzyme is added to the straw, so that the dry matter content is ideal with regard to hydrolysis, as well as the remaining processes in the total production of bioethanol. It is observed that the invention allows to adjust the proportion of dry matter / water / enzyme in an ideal way as the straw is previously treated dry and should not be dehydrated before hydrolysis, for example, because the straw was not pre-treated by explosion at conventional steam in large amounts of water. The liquefaction or dedicated hydrolysis is ideally performed at a temperature ranging from 40 to 80 ° C, usually 50-55 C and at pH 4 to 7, normally pH 5.0 to 5.5. The duration of the dedicated hydrolysis is from 1 to 100 hours, usually 24 to 72 hours, specifically 48 hours. This dedicated hydrolysis can be extended even further by means of a membrane enzyme reactor where the hydrolysis is extended until the complete decomposition of sugar polymers into oligomers and sugar monomers. The temperatures and pH that are ideal for hydrolysis in a membrane reactor are maintained, and an associated membrane allows only the oligomers and monomers of dissolved sugar to pass through the membrane, considering that lignin, unconverted straw and enzymes are retained 5 in the enzyme reactor. The membrane-enzyme system normally consists of screening using a vibrating sieve, rotating sieve or micro sieve for the retention of larger particles in the enzyme reactor, usually particles between 10 and 200 μm (micrometers), preferably 50 to 150 μm and usually below 100 μm. This sieved material now 10 is filtered through a membrane, usually an ultrafiltration membrane (UF-membrane) with a pore size of 10 to 100 nm (nanometers), preferably from 25 to 75 nm and normally around 50 nm. These membranes have a cut-off molecular weight (MWCO) of 5 to 15,000 Dalton and typically around 10,000 Dalton. This membrane allows the sugar to pass while the lignin is retained, constituting a lignin concentrate. In a preferred configuration, UF-filtration is combined with RO-filtration by means of which dissolved sugars are concentrated before fermentation, and where pure, permeated water is recycled to or before the enzyme reactor. The concentrated sugar is supplied to 6) the 20 bioreactor for fermentation in bioethanol, subsequent distillation etc. The process surrounding 5) membrane-enzyme reactor can consist of screening or membrane-UF alone or in combination, and the membrane system can include RO-filtration. The most important advantage associated with the system is that the dissolved sugars - that is, the product of the enzyme's activity - are continuously removed and thus inhibition of the enzyme product is eliminated. In addition, the residence time of the biomass particles in the membrane-enzyme reactor is not linked to the hydraulic residence time, also contributing to a complete hydrolysis of the biomass. Finally, the sugars are concentrated in the RO plant for an ideal concentration of 10 to 30%, usually around 20%, ensuring an ideal concentration of ethanol during fermentation and distillation. Fig. 3. Illustrates a flowchart of straw injection in a biogas reactor, where the straw is shredded and cleaned in a straw handling line before the actual pretreatment in the press. Pre-treated and compressed straw can now be supplied, directly or indirectly, to a biogas reactor, or in the case of that material to a different reactor. Here it is used so that the straw is pre-treated and, therefore, viscous and easily dissolves in the reactor liquid, as well as compressed to a specific high density of 0.5 to 1.5, preferably 0, 8 to 1.2, usually around 1. It is essential that the compacted straw has a high density so that the straw can therefore sink into the liquid in which it is suspended in a short period of time and to be distributed throughout the volume of reactor liquid. Thus, no floating layer or impeding conversion to biogas has been formed. It is also essential that the straw has changed its nature and has become very viscous - that is, absorbent to water - since this property allows the straw to be suspended and distributed throughout the net volume of the reactor. The direct addition can be done by connecting a discharge duct or extension nozzle to the press, directly to the bioreactor, being aware that the compressed straw runs through the extension duct. Here you find a liquid with an overpressure that is proportional to the level of liquid in the reactor, for example, 1 bar or more. However, the compressed straw in the extension duct is then compressed and advances in a large overpressure (up to 2000 bars) that the straw, without the risk of liquid return or leakage of biogas, can be introduced in the bottom of the reactor and therefore, under the liquid surface. It is also possible to supply straw by another helical system where a long inclined or vertical helical conveyor moves the straw to a short inclined feed screw that opens under the liquid surface. Therefore, liquid return and biogas leakage are also prevented. Here, the straw will also sink into the reactor liquid and be suspended in a short period of time. Short time refers to 1 and 120 min, preferably 30 to 90 min and generally less than 1 hour. This is a short period of time compared to the typical hydraulic residence time in a biogas reactor from 10 to 90 days. The straw can also be supplied indirectly to the bioreactor by mixing it in another biomass, usually liquid cattle manure, sludge, residual water and the like, which are suppressed to the biogas reactor by pumping. Often, a receiving reservoir or receiving tank is provided for the 10 liquid biomass at the biogas plant and the straw can be added here from the press, suspended and pumped to the bioreactor with another biomass. Whether pretreatment, compression, storage etc. are carried out at decentralized collection stations prior to transport to the bioenergy plant, the straw will normally be introduced by another helical conveyor or another blocking feeder system. Fig. 4: Illustrates a flowchart for a configuration of the bioethanol process in which lignin is removed after pre-treatment and before fermentation, cf. also Fig. 2 (see here). Fermentation and distillation are ideal, cf. 20 description of Fig. 2, and as the fermentation takes place without substantial amounts of lignin, the fermentation will result in the pure yeast that can be separated from the distillate by centrifugation. The centrifuge concentrate constitutes a fraction of yeast, whereas the rejected water constitutes a fraction of thin liquid with remains of dissolved sugar, yeast cells, lignin, etc. that can be advantageously degassed in a biogas reactor to produce biogas and to condition the liquid before RO-filtration and the manufacture of vinasse (fertilizer K) for fertilizer purposes and pure water for recycling. Examples of the main realists for production flows are shown in the Figure. The input is 100,000 30 tonnes of straw annually or 12.5 t / h in 8000 hours of operation.
    It is assumed that the straw consists of 40% cellulose, 30% hemicellulose, 20% lignin and 10% water. Fig. 5:
    Illustrates a flow chart for a situation in which the biomass contains large amounts of lignin and where, therefore, a specific lignin extraction is inserted after pre-treatment and before fermentation, etc. This lignin extraction has a specific advantage over pre-treated straw, cf. the invention, is dry and hydroscopic and can therefore add a liquid that is optimized with regard to the extraction of lignin. In a preferred configuration, organic acids such as citric acid, lactic acid, acetic acid and similar organic acids are used to extract lignin at 40-120 ° C, preferably 60-100 ° C and usually 80 ° C at a final pH of 1 -6, preferably 2-4 and usually pH 3. It is noted that these acids can be added before the press, cf. the invention, and if so, only water is added after the press for the extraction of the lignin. Therefore, lignin and partially hemicellulose and potassium salts are extracted while pure cellulose fibers are left for further processing. The extraction occurs by adding a mixture of water and organic acid to the treated straw and, after that, the liquid, after some time, undergoes a mechanical pressing in one or two stages. Cellulose fibers remain in the process while the mixture of lignin and acid is supplied to a biogas process where specifically the hemicellulose and dissolved sugars and organic acids are converted into biogas, while the lignin passes through the biogas reactor for concentration subsequent through the UF-membrane. After the UF-membrane, the K salts are concentrated in the RO-membrane while the pure and permeated water is recycled for renewed extraction. The pure cellulose fibers are supplied to the enzyme membrane reactor, cf. Fig. 2, before fermentation and distillation and, finally, centrifugation to produce pure yeast fraction. In the Figure, examples of realistic production figures and material flows are mentioned. The input is 100,000 tons of straw annually or 12.5 t / h in 8000 hours of operation. It is assumed that the straw consists of 40% cellulose, 30% hemicellulose, 20% lignin and 10% water. Fig. 6:
    It illustrates in more detail the so-called "whole paste" process configuration in which there is no separation of lignin after pretreatment, but where the fully pretreated biomass is supplied for fermentation and distillation, and only after distillation is it separated into cells of yeast of the main components, methane through a process of biogas, lignin and vinasse, the vinasse consisting of nutrient salts, in particular potassium, phosphorus and nitrogen. The configuration is initiated by the collection and a first straw treatment by the 1) straw handling line where the straw is torn in lengths from 1 to 20 cm, normally 5 to 10 cm and is cleaned of contaminants through the assisted air cyclone before the hammer mill which further reduces the straw length to 0.1 to 5 cm, usually 1 to 2 cm, before 2) treatment in the mechanical press, cf. invention. In this connection, it is possible and likely that the straw is collected, pre-treated, that the quality is controlled, that it is registered, weighed and stored locally at the decentralized collection stations before transport to a central biogas plant. In the central bioenergetic plant, the compressed straw - in compressed form - is supplied to a 3) thermochemical reactor, where the straw is added water according to the need and is subjected to a complementary hydrolysis by the direct injection of steam, so that the straw is exposed to temperatures between 60 and 220 ° C, usually 120 to 180 ° C and specifically from 140 to 60 ° C, and is incubated for an appropriate time, that is, from 1 to 120 min, usually from 10 to 60 min and specifically 30 to 40 min. The straw is now ready for 4) enzymatic liquefaction, also called dedicated hydrolysis and suitable enzymes are added to the water, and this mixture of enzyme and water is added to the straw, so that the dry matter content is ideal in relation to hydrolysis , as well as the remaining processes in total bioethanol production. It is observed that the invention allows to adjust the proportion of dry matter / water / enzyme in an ideal way as the straw is pre-treated dry and should not be dehydrated before hydrolysis. Correspondingly, it is possible to carry out a complementary pretreatment in the thermochemical reactor with an ideal relationship between water / dry matter and possible catalysts. The liquefaction or dedicated hydrolysis is ideally performed at a temperature ranging from 40 to 80 ° C, usually 50-55 ° C and at pH 4 to 7, normally pH 5.0 to 5.5. The duration of the dedicated hydrolysis is from 1 to 100 hours, usually 24 to 72 hours, specifically 48 hours. Fermentation and distillation 5 occur substantially as SSF fermentation (simultaneous saccharification and fermentation), that is, simultaneous saccharification and fermentation and distillation as vacuum steam distillation, cf. known principles. A special feature, however, is that fermentation is extended to 2 to 14 days, usually 8 to 12 days and specifically 10 days as opposed to the period of 1 to 3 days conventionally operated plants. This is to achieve maximum specific ethanol production while simultaneously considering the lignin content in the entire sludge system. Fermentation takes place at pH and standard temperatures and distillation takes place under standard conditions. During the separation, 6) separation of yeast cells from part of the distillate forms by means of a new technique adapted for this type of distillate containing yeast cells. The distillate is subjected to a "fluctuation of dissolved air", that is, air bubbles that injected and dissolved that lift the yeast to the liquid surface, where it is removed from the liquid and is centrifuged. Therefore, a pure yeast substrate is obtained that can be used as a protein forage. Residual liquid with a dissolved lignin content, residual amounts of sugar, yeast cells and substrate are supplied to a biofilm reactor for biogas production. Lignin generally passes through the biogas reactor, while residual sugar etc. is converted into biogas. After biological degassing, the liquid thus contains a fraction of pure lignin and is suitable for decantation and ultrafiltration for the separation of lignin. Therefore, a fraction of pure lignin is produced. At the same time, UF-filtration allows the separation of dissolved nutrient salts from the residual liquid by means of the final RO-separation (RO: Reverse Osmosis) and evaporation. The RO-separation concentrate consists of vinasse while the permeate is pure water that is recycled for steps 3 and 4. Therefore, the production process is complete and thus bioethanol, yeast substrate, methane, lignin and straw vinasse they are produced from straw. Fig. 7:
    Illustrates a plant, including a container 1, containing a distribution silo and a press of the type shown in Fig. 1, two heat-treating screws 2, a feed unit 3, a first conveyor 4, a bioreactor 5, a unit filler 6 and a second conveyor 7.
    The presented plant that operates in this biomass in the form of cut straw, maximum length of 40 mm, is filled in the filling unit 6.
    The straw moves through the second conveyor 7 to the distribution silo, which is an integral part of the container 1, and down to the press where a briquetting process is carried out. After the briquetting process, the briquettes move through the discharge duct (also called the extension nozzle) in the reaction chamber of the press towards the heat treatment screws. The heat treatment screws 2 can be adjusted for temperature and passage time. The heat treatment screws have a capacity of 750 to 1200 kg, which normally corresponds to one hour of production.
    The conveyor 4 moves the briquettes to the feed unit 3.
    The feeding unit 3 is adapted to introduce the briquette into a liquid level in the bioreactor in such a way that the gas leakage from the bioreactor 5 does not occur during the feeding of the briquettes.
    Alternatively, the briquettes can be moved by heat treatment screws 2 directly from the piston press at the bottom of the bioreactor 5 below the liquid level. Fig. 8:
    Illustrates a method for the production of forage, for example cattle forage, through the ensiling of treated straw. The mechanically induced steam explosion allows the ensiling of straw, either independently or by mixing cut grass, corn or another crop for ensiling. This improves the nutritional value of straw and mixed silages, by increasing the dry matter content, protein content and general digestibility of the silage. Fig. 9
    Illustrates a method for processing biomass in the form of wood chips in paper pulp or other fiber product where the mechanically induced steam explosion constitutes an interrupted pretreatment prior to conventional thermal chemical processing (KRAFT) in sodium hydroxide (NaOH ) and sodium sulfide (Na2S). This implies that conventional treatment can be carried out with less consumption of water, chemicals and energy in a smaller volume, and that, therefore, it is carried out in a more cost-effective way.
    权利要求:
    Claims (16)
    [0001]
    1. Method of processing a biomass containing lignocellulose such that cellulose and hemicellulose become accessible for further processing, characterized by the fact that the method includes steps of: - repeated compressions of the biomass in a reciprocating piston press, where biomass does not compacted is continuously fed into a piston chamber in front of a piston that moves the non-compacted biomass to a tubular reaction chamber in which the biomass is compressed, and that a pressure of 500 bar (50,000 kPa) to 3000 bar (300,000 kPa ) is applied to the biomass during compression, whereby the kinetic energy of the piston is deposited in the biomass in the form of heat for the production of a mechanically induced steam explosion and self-hydrolysis under simultaneous displacements of compressed biomass through the chamber reaction.
    [0002]
    2. Method, according to claim 1, characterized by the fact that a pressure between 1000 and 2500 bars is applied to the biomass during compression.
    [0003]
    3. Method according to claim 1 or 2, characterized by the fact that the piston press is adapted so that the temperature in at least a first part of the reaction chamber is within the range of 40 oC to 240 oC.
    [0004]
    Method according to any one of claims 1 to 3, characterized by the fact that the biomass is impregnated with gases and / or bases or acids before being introduced into the piston chamber for the pre-processing of lignocellulose.
    [0005]
    Method according to any one of claims 1 to 4, characterized by the fact that enzymes and water are added after compression, and that the compressed biomass is subsequently destroyed.
    [0006]
    6. Method according to any one of claims 1 to 5, characterized in that the compressed biomass is destroyed and disintegrated after leaving the reaction chamber.
    [0007]
    Method according to any one of claims 1 to 6, characterized by the fact that, after leaving the reaction chamber, the biomass is moved to an enzymatic reactor and a subsequent fermentation.
    [0008]
    8. Method according to any one of claims 1 to 7, characterized by the fact that, after compression, the biomass is added to cattle liquid manure, sludge of residual water in a biogas plant.
    [0009]
    9. Method, according to claim 8, characterized by the fact that the biomass is added at a level below a liquid surface in a reactor tank of the biogas plant.
    [0010]
    Method according to any one of claims 1 to 9, characterized in that an additional hydrolysis is carried out after the compressed biomass has left the reaction chamber.
    [0011]
    11. Method according to any one of claims 1 to 10, characterized in that stone, sand and other impurities are removed from the biomass before the biomass is supplied to the piston chamber.
    [0012]
    12. Method according to any one of claims 1 to 11, characterized by the fact that the biomass is straw.
    [0013]
    13. Method according to any one of claims 1 to 4, characterized by the fact that the biomass consists of wood chips and that the biomass, after the mechanically induced steam explosion, is subjected to thermochemical processing (KRAFT) in sodium hydroxide (NaOH) and sodium sulfide (Na2S).
    [0014]
    14. Method according to any one of claims 1 to 13, characterized in that the biomass consists of straw for the production of forage, such as forage for cattle and that the biomass after the induced steam explosion mechanically it is subjected to straw silage.
    [0015]
    15. Method according to any one of claims 1 to 13, characterized in that the biomass, after the mechanically induced steam explosion, is further processed for biofuel.
    [0016]
    16. Method according to claim 15, characterized by the fact that the biofuel is ethanol, butanol, hydrogen, methanol or biogas.
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    同族专利:
    公开号 | 公开日
    CN104271752A|2015-01-07|
    EP3293267A1|2018-03-14|
    BR112014025372A2|2017-07-11|
    DK3293267T3|2019-04-08|
    IN2014MN02086A|2015-08-28|
    EP2836600B1|2018-06-06|
    CN107858386B|2021-08-10|
    US10450386B2|2019-10-22|
    CN104271752B|2018-02-06|
    EP2836600A4|2015-07-22|
    US9714299B2|2017-07-25|
    EA201491801A1|2015-04-30|
    US20170298150A1|2017-10-19|
    US20150147796A1|2015-05-28|
    DK201270180A|2013-10-12|
    PL3293267T3|2019-05-31|
    EP3293267B8|2019-03-13|
    EP2836600A1|2015-02-18|
    DK177818B1|2014-08-11|
    CN107858386A|2018-03-30|
    EP3293267B1|2018-12-12|
    CA2870194A1|2013-10-17|
    WO2013152771A1|2013-10-17|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-03-24| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-12| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 10/04/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DKPA201270180A|DK177818B1|2012-04-11|2012-04-11|Process for treating a biomass with a lignocellulose content|
    DKPA201270180|2012-04-11|
    PCT/DK2013/050097|WO2013152771A1|2012-04-11|2013-04-10|Method for processing a biomass containing lignocellulose|
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