METHODS FOR PRODUCING A HYDROLYZED OR PRE-TREATED LIGNOCELLULOSIC RAW MATERIAL

专利摘要:
method for heating a raw material. the present invention provides a method for producing a hydrolyzed or pretreated lignocellulosic feedstock. the method comprises feeding the lignocellulosic feedstock into a plug forming device and forming a plug of feedstock therein. the plug or segments thereof are fed into an elongated chamber comprising steam adding means for direct addition of steam and a rotary shaft mounted co-axially within the chamber having one or more disintegration elements mounted thereon. particles of disintegrated raw material are produced in the elongated chamber by the disintegrating elements. the disintegrated raw material particles are heated by contact with the steam introduced through the steam addition means. the disintegrated feedstock particles are then treated in a reactor to produce the hydrolyzed or pretreated lignocellulosic feedstock. Also provided are methods of reducing erosion on equipment by maintaining the consistency of discharge from the plug forming device below 35% by weight.
公开号:BR112014006621B1
申请号:R112014006621-3
申请日:2012-09-19
公开日:2021-08-10
发明作者:Torbjorn van der Meulen；Stephen A. Rowland
申请人:Iogen Energy Corporation；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The present invention provides an improved process to heat a raw material before it enters a downstream reactor. The present invention further provides an improved process for processing lignocellulosic feedstock while reducing erosion on process equipment. BACKGROUND OF THE INVENTION
[002] There is growing interest in the production of ethanol fuel or other fermentation products from lignocellulosic raw materials such as, for example, wheat straw, corn silage, and forage grass. One advantage of using these raw materials is that they are widely available and can be obtained at low cost. In addition, lignocellulosic feedstocks are typically burned or landfilled, and then using them for ethanol production offers an attractive alternative to disposal costs. Another advantage of these raw materials is that a by-product of the conversion process, known as lignin, can be used as fuel to supply energy for the process instead of fossil fuels. Several studies have concluded that when the entire production and consumption cycle takes into account the use of ethanol produced from cellulose, it generates greenhouse gases close to zero.
[003] A process to produce a fermentation product, such as ethanol, from lignocellulosic raw materials is carried out by a pre-treatment followed by enzymatic hydrolysis of cellulose to glucose. Pretreatment often breaks down the fiber structure to make it accessible to cellulase enzymes. The pretreatment can be carried out so that a high degree of xylan hydrolysis and only a small amount of cellulose to glucose conversion takes place. Cellulose is hydrolyzed to glucose in a subsequent step using cellulase enzymes. Other pretreatment processes, such as certain alkaline pretreatments, do not hydrolyze or result in limited hydrolysis of xylan. Furthermore, it is possible to hydrolyze both xylan and cellulose using a more severe chemical treatment, such as concentrated acid hydrolysis.
[004] Regardless of the method to produce fermentable sugar, the addition of water to the new raw material to form a suspension is often performed to facilitate the transport and mechanical handling of the cellulosic raw material. The suspension consists of pieces or particles of lignocellulosic raw material in water. Raw material suspensions can be more easily pumped when they have a consistency of about 1 and about 10% by weight of dry undissolved solids.
[005] However, for lignocellulosic conversion processes to be economical, it would be desirable for them to operate at a lower water content. Processing raw material with low water content has several advantages at various stages of the process, one of which is reductions in equipment size, which in turn reduce the investment cost. Other benefits of low water content include reduced energy consumption including reductions in pumping, heating, cooling and evaporation costs. In addition, water usage costs can be reduced, which is especially beneficial in arid climates where water is at a premium.
[006] One stage of the process that particularly benefits from low water levels is pre-treatment or other stages that need to treat the raw material. During these treatments, the amount of energy required to heat the raw material suspension, upstream of the reactor, or within the reactor itself, is a direct function of the total mass of the raw material suspension, including the water added for transporting the feedstock. Operating a pre-treatment or hydrolysis process with low water levels can reduce the energy needed for heating. Various methods are known for heating raw material including indirect heating methods such as heating jackets, adding heated water to a chamber as disclosed in Canadian patent application No. 2,638,152 or adding steam to the reactor (US Patent No. 5,338,366).
[007] One method to reduce the water content and the consequent energy requirements for heating is to dehydrate the fresh raw material suspension and form a compacted raw material buffer before carrying out the pretreatment or hydrolysis in a reactor to downstream (see co-pending and co-titled WO 2010/022511, which is incorporated herein by reference). Raw material plugs can be produced by various devices such as plug feeder screw and pressurized screw presses. Often, the water content of the raw material is reduced so that the solids content is high enough for plug formation to occur. Dehydration can take place within a tampon forming device or tampon formation and dehydration can be performed in separate parts of the equipment. Alternatively, it is possible to eliminate dehydration upstream of plug formation if the solids content of the raw material already has a desired high consistency.
[008] The plug that is formed can prove to be difficult to heat prior to its entry into the downstream reactor. Often the plug discharges in large segments, which can be 7.62 to 12.7 cm in diameter or larger. Such large segments prevent the rapid penetration of steam into the fibrous material and result in uneven temperature distributions. The inventors recognized that unequal temperature distributions in the buffer, or segments of it, can result in overcooking or undercooking of the feedstock in the downstream reactor. Overcooking in the reactor can result in raw material degradation, while undercooking can result in low xylose yield and difficulty in hydrolyzing cellulose.
[009] Another problem that arises during processes that use high consistency material is that the equipment tends to erosion. Erosion damage to the plug-forming device or other equipment exposed to the suspension of high-consistency raw material can be costly as it requires frequent repair or a potentially even more costly replacement of equipment. The inventor recognized that erosion damage to equipment could be particularly problematic with lignocellulosic feedstocks that contain relatively high levels of ash, such as cultivated crops, sugar processing or agricultural residues. Sugarcane straw and bagasse, which are currently of interest for second generation biofuel production, often contain quite significant amounts of ash. Although ash can be removed by washing or leaching, such steps are often undesirable as they increase the use of water in the process.
[0010] Thus, there is a need in the art for an improved process for heating a raw material buffer, or segments thereof, prior to entering a downstream reactor. There is also a need in the art for an improved process for reducing equipment erosion when operating processes that involve plugging a material from non-ligneous lignocellulosic raw materials. SUMMARY OF THE INVENTION
[0011] Disclosed here are processes for overcoming or ameliorating problems, or providing useful alternatives to known processes that form a material buffer from lignocellulosic raw materials prior to pretreatment or hydrolysis.
[0012] According to certain embodiments of the invention, the present invention can overcome the difficulties in heating a raw material before it enters a downstream reactor. In particular, by ensuring that a plug of raw material or segments thereof are disintegrated into particles in a heating chamber comprising disintegration elements, a larger specific surface area can be obtained. As a consequence, faster penetration of steam into the fibrous material and more uniform temperature distributions can be obtained before pre-treatment or hydrolysis of the raw material. By contacting the particles with steam in this way, overcooking or undercooking of the feedstock in the downstream reactor can potentially be reduced, which, in turn, can improve xylose yield and cellulose hydrolysis.
[0013] According to a first aspect of the invention, there is provided a method for producing a hydrolyzed or pretreated lignocellulosic feedstock comprising: feeding a lignocellulosic feedstock to a plug forming device and forming a plug of material. press on this one; feeding the plug or segments thereof into an elongated chamber having at least a portion thereof which is cylindrical and to which it is preferably horizontally oriented or essentially horizontally oriented, the chamber having steam adding means for direct steam addition and a rotating shaft mounted thereon having one or more disintegrating elements disposed therein; produce particles of raw material disintegrated in the elongated chamber by the disintegration elements; heating the disintegrated raw material particles by contacting the particles with steam introduced through the steam addition means, wherein the operating pressure in the chamber is at least about 90 psia (0.62 MPa); and then pre-treating or hydrolyzing the disintegrated feedstock particles in a reactor to produce the hydrolyzed or pretreated lignocellulosic feedstock.
[0014] According to a second aspect of the invention, there is provided a method as described above, wherein the disintegrating elements are arranged on the axis so as to sweep the inner surface of at least one region of the chamber. The disintegrating elements can continuously axially sweep the inner surface of at least one region of the chamber.
[0015] According to a third aspect of the invention, there is provided a method, as described above, in which the disintegrating elements are oriented in the direction of movement of the raw material through the heating chamber in order to facilitate the transport of the material. - press through the heating chamber.
[0016] According to an embodiment of any of the foregoing aspects of the invention, the lignocellulosic raw material is fed to a dehydration device to produce a dehydrated raw material and the dehydrated raw material is then fed to the dewatering device. buffer formation. In another embodiment of the invention, the raw material is pressurized and then fed to the dehydrating device and the raw material pressure at the inlet of the dehydrating device is greater than about 45 psia (0.31 MPa).
[0017] The disintegrating elements for disintegrating the raw material may comprise a cutting helix, feeder ribbon, toothed drill, blades, bars, paddles, handles, arms or a combination thereof. According to an embodiment of the invention, the disintegrating elements are located on the axis at least in the middle region of the chamber. The shaft region in the inlet section of the chamber may comprise a feeder tape, a cutting helix or a toothed drill.
[0018] The disintegration elements may project out of the axis and can be configured such that the outer edges of the disintegration elements on the rotating axis describe one or more circles that are concentric or essentially concentric with respect to the inner surface of the chamber.
[0019] According to another embodiment of the invention, the speed of the outer edge of the disintegrating element which is closest to the inner surface of the chamber is about 200 m/min to about 1000 m/min. In another embodiment of the invention, the speed of the outer edge of the disintegrating element which is closest to the inner surface of the chamber is about 450 m/min to about 800 m/min.
[0020] In another embodiment of the invention, the distance between the inner surface of the chamber and the outer edge of the disintegrating element that is closest to the inner surface is less than 10% of the inner diameter of the chamber.
[0021] In another embodiment of the invention, the steam addition means comprises inlets for direct steam injection arranged along the length of the chamber. Preferably, the chamber does not contain an indirect heating jacket.
[0022] Preheating or hydrolysis may comprise the addition of chemical to the disintegrated raw material particles. The chemical is typically acidic or alkaline.
[0023] The present invention also provides an improved process for reducing erosion in equipment when processing a high consistency material from non-ligneous lignocellulosic raw materials. As discussed, non-wood raw materials often contain relatively high levels of ash compared to woody biomass and thus processes using these raw materials are more prone to erosion damage to equipment, particularly equipment exposed to high consistency material such as tampon forming devices. The inventor recognized that the impact of erosion damage on equipment when processing such raw materials could be particularly seen when material consistency is high. This is in contrast to woody materials such as wood chips and pulp that contain relatively low levels of ash. Processes described in the literature that use wood chips or pulp as a raw material to produce ethanol can typically operate at a higher consistency in the plug forming device.
[0024] Therefore, by operating at a lower consistency than that which is more prevalent in pulp and paper processes, erosion damage can be reduced, thus resulting in operational cost and investment savings. The consistency is controlled at the outlet of the plug forming device so that it remains below the consistency threshold value of 35% by weight of dry undissolved solids, but above 20% by weight to maintain low water conditions.
Thus, according to another aspect of the invention, there is provided a method for producing a hydrolyzed or pretreated lignocellulosic feedstock comprising: (i) feeding the lignocellulosic feedstock in the form of a suspension to a forming device of the plug and form a raw material plug therein, wherein the plug or segments thereof exiting the plug forming device has a dry undissolved solids content of between about 20% by weight and about 35% by weight ; (ii) pre-treating the lignocellulosic feedstock after step (i) to produce a pretreated lignocellulosic feedstock having a dry undissolved solids content of between about 15% by weight and about 30% by weight; (iii) enzymatically hydrolyzing the pretreated lignocellulosic feedstock to produce a solution comprising at least glucose; and (iv) fermenting at least the glucose to produce an alcohol, wherein the lignocellulosic feedstock is selected from cultivated crops, sugar processing residues and agricultural residues having an ash content greater than 0.5% (w/ for).
[0026] As demonstrated here, the method described above was effective in producing a cellulosic substrate from which high yields of glucose could be recovered, while at the same time reducing erosion. In some embodiments of the invention, at least 70% of the cellulose in the pretreated lignocellulosic feedstock is converted to glucose. Preferably at least 80% or at least 90% of the cellulose in the pretreated lignocellulosic feedstock is converted to glucose.
[0027] The present invention also provides an improved method for producing a hydrolyzed or pretreated lignocellulosic feedstock comprising a step of immersing the feedstock in an aqueous solution. The immersed raw material can have a dry undissolved solids content of between about 1% by weight to about 12% by weight. Preferably, the immersion is carried out using an aqueous solution comprising an acidic or alkaline pretreatment chemical. A benefit of soaking the raw material prior to pretreatment is that it can ensure uniform wetting of the biomass, which in turn helps to achieve uniform cooking in subsequent pretreatment or hydrolysis. The immersed raw material is subsequently fed to a plug forming device to form a plug of material and the plug or segments thereof exiting the plug forming device outlet has a dry undissolved solids content not exceeding 35 % by weight, thus reducing erosion on the equipment.
[0028] Thereby, according to another aspect of the invention, there is provided a method for producing a hydrolyzed or pretreated lignocellulosic feedstock comprising: (i) immersing a lignocellulosic feedstock with an aqueous solution to produce a material - immersed lignocellulosic feedstock, wherein said lignocellulosic feedstock does not primarily contain wood chips or pulp; (ii) feeding the immersed lignocellulosic raw material to a plug forming device and forming a plug of raw material therein, wherein the plug or segments thereof exiting the plug forming device have a non-dry solids content. dissolved between about 20% by weight and about 35% by weight; (iii) disintegrating the plug and segments thereof to produce disintegrated raw material particles and heating the disintegrated raw material particles; and then (iv) preheating or hydrolyzing the disintegrated feedstock particles in a reactor to produce the hydrolyzed or pretreated lignocellulosic feedstock.
[0029] According to an embodiment of the invention, the immersed raw material is partially dehydrated in a dewatering device before being fed to the plug-forming device. Partial dehydration can alternatively be carried out within the tampon forming device itself.
[0030] Preferably, the lignocellulosic raw material is sugarcane bagasse or sugarcane straw. Sugarcane bagasse or straw have been found to contain high levels of ash. In one embodiment of the invention, the lignocellulosic feedstock has an ash content between about 1.5% and about 15% (w/w). According to another embodiment of the invention, the lignocellulosic raw material is sugarcane bagasse or sugarcane straw having an ash content between about 1.5% and about 15% (w/ p) or between 1.5% and about 12% (w/w).
[0031] In some embodiments of the invention, at least 70% of the cellulose in the pretreated lignocellulosic feedstock is converted to glucose. Preferably at least 80% or at least 90% of the cellulose in the pretreated lignocellulosic feedstock is converted to glucose.
[0032] Without being limiting, by carrying out the above methods that result in reduced erosion of the process equipment, the use of a washing or leaching step can be reduced or even avoided together. This reduces water usage. However, it may be advantageous to remove a certain portion of the ash from the lignocellulosic feedstock for further erosion reduction or for other reasons. Thus, according to some embodiments of the invention, the lignocellulosic raw material is not leached or washed before step (i) in order to remove more than 50% by weight of the ash.
[0033] According to another aspect of the invention, there is provided a lignocellulosic feedstock composition comprising: (i) disintegrated lignocellulosic feedstock particles; (ii) about 15 to about 35% by weight of undissolved solids, wherein the undissolved solids comprise between about 20 and about 60% by weight of cellulose and between about 10 and about 30% by weight of xylan; and (iii) an organic or mineral acid, wherein the pH of the raw material composition is between about 0.5 and about 4.5. The temperature of the composition can be between about 100°C and about 280°C.
[0034] According to another embodiment of the invention, the lignocellulosic raw material particles are derived from sugarcane bagasse or straw. According to another embodiment of the invention, the lignocellulosic feedstock composition comprises about 15% by weight to about 30% by weight of dry undissolved solids, or between about 20% by weight to about 30% by weight. weight of undissolved dry solids.
[0035] Already according to another aspect of the invention, there is provided a lignocellulosic feedstock composition comprising: particles of disintegrated lignocellulosic feedstock; (ii) about 15 to about 30% by weight of dry undissolved solids, wherein the dry undissolved solids comprise between about 20 and about 60% by weight of cellulose and between about 10 and about 30% by weight of xylan; and (iii) a mineral acid, in which the raw material particles are not primarily derived from wood chips or pulp, and in which the pH of the raw material composition is between about 0.5 and about 3, 5. The temperature of the composition can be between about 100°C and about 280°C.
[0036] Also provided is a method comprising pre-treating the prior lignocellulosic feedstock composition. The present invention also provides a pretreated lignocellulosic feedstock composition, wherein at least 70%, more preferably 80% or 90% of the cellulose in the pretreated lignocellulosic feedstock, in a percentage by weight, can be converted to glucose, as measured by hydrolyzing with cellulase enzymes from Trichoderma reesei, where the pretreated lignocellulosic feedstock originates from sugarcane bagasse or sugarcane straw. The method for determining the digestibility of the cellulase pretreated lignocellulosic feedstock is presented in Example 4. BRIEF DESCRIPTION OF THE DRAWINGS
[0037] In the attached drawings,
[0038] Figure 1 is a flowchart of a method according to an embodiment of the invention;
[0039] Figure 2 is a cross section of a toothed drill used in a heating chamber according to an embodiment of the invention; and
[0040] Figure 3 is a graph showing the consistency of dry undissolved solids (% by weight) of a pretreated raw material suspension produced according to the method of the invention measured over a one month period of operation . DETAILED DESCRIPTION OF THE INVENTION
[0041] The following description is of a preferred embodiment by way of example only and without limitation to the combination of features necessary to carry out the invention in effect. The titles given are not intended to limit the various embodiments of the invention. Terms such as "comprises", "comprising", "comprises", "includes", "including" and "includes" are not intended to be limiting. Furthermore, the use of the singular includes the plural, and “or” means “and/or”, unless otherwise stated. Unless otherwise defined herein, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Raw material and raw material size reduction
[0042] The raw material for the method is a lignocellulosic material. By the term "lignocellulosic feedstock" means any type of plant biomass such as, but not limited to, plant biomass, including cultivated crops, such as, but not limited to grams, for example, but not limited to C4 grams, such as forage grass, esparto, ryegrass, eulalia, reed, or a combination thereof, sugar processing residues, for example, but not limited to bagasse, such as sugarcane bagasse, beet pulp, or a combination thereof, agricultural residues, for example, but not limited to, soybean straw, corn straw, rice straw, sugar cane straw, rice husks, barley straw, corn cobs, wheat straw, canola straw, oat straw, oat husks, corn fiber, or a combination thereof, forest biomass, for example, but not limited to, recycled wood pulp fiber, sawdust, hardwood, by example, beech, softwood, or a combination thereof. Furthermore, the lignocellulosic feedstock may comprise lignocellulosic waste material or forest waste materials such as, but not limited to, newsprint, cardboard and the like. Lignocellulosic feedstock can comprise one kind of fiber or alternatively, lignocellulosic feedstock can comprise a mixture of fibers originating from different lignocellulosic feedstocks. In addition, the lignocellulosic feedstock may comprise fresh lignocellulosic feedstock, partially dry lignocellulosic feedstock, completely dry lignocellulosic feedstock, or a combination thereof. In addition, new lignocellulosic feedstock varieties can be produced from any of those listed above by plant crossing or genetic engineering.
[0043] Preferably, the lignocellulosic raw material is sugarcane bagasse or sugarcane straw. As would be noted by those skilled in the art, sugarcane straw includes the tops and leaves of the sugarcane.
[0044] Lignocellulosic raw materials comprise cellulose in an amount greater than about 20%, more preferably greater than about 30%, more preferably greater than about 40% (w/w). For example, the lignocellulosic material can comprise from about 20% to about 50% (w/w) of cellulose, or any amount in between. Such raw materials comprise hemicellulose, including xylan, arabinan, mannan and galactan. Furthermore, the lignocellulosic feedstock comprises lignin in an amount greater than about 10%, more typically in an amount greater than about 15% (w/w). The lignocellulosic raw material may comprise small amounts of sucrose, fructose and starch.
[0045] The lignocellulosic feedstock is typically subjected to size reduction by methods including, but not limited to, milling, crushing, agitating, shredding, compressing/expanding, or other types of mechanical action. Size reduction by mechanical action can be performed by any type of equipment adapted for the purpose, for example, but not limited to size reduction devices, selected from the group consisting of hammer mills, tube crushers, roller presses, refiners and Hydra-pulpers (hydra-mills). Raw material can be reduced to particles having a length of about 0.15 to about 20.32 cm, or any amount in between. The length of the reduced particles can also be such that at least about 90% by weight of the particles have a length less than about 12.7 cm or even less; for example, at least about 90% by weight of the particles can be less than about 10.16, about 7.62, about 5.08 cm, about 2.54, or about 1.27 cm in length. . Washing can be performed to remove sand, gravel and other external particles as they can cause damage to downstream equipment. It will be understood that the lignocellulosic feedstock need not undergo size reduction, for example, if the particle size of the feedstock is already between 1.27 to 20.32 cm.
[0046] For the purposes of this report, the particle size of the raw material is determined by image analysis using techniques known to those skilled in the art. An example of a suitable image analysis technique is revealed in Igathinathane (sieveless particle size analysis of particulate materials through computer screen, Computers and Electronics in Agriculture, 2009, 66:147-158, the content of which is here incorporated by reference), which reports particle size analyzes of several different hammer milled raw materials. The measurement can be an average length by weight or volume. Raw material consistency
[0047] Before feeding the lignocellulosic raw material to the plug forming device, the amount of undissolved solids in the lignocellulosic raw material can be adjusted to a desired consistency. The lignocellulosic feedstock may have a dry undissolved solids consistency of between about 1% by weight and about 40% by weight or between 4% by weight and about 20% by weight, upon entering the plug forming device. and all proportions in between. The percentage of dry undissolved solids in the lignocellulosic feedstock can be determined at the inlet of a plug forming device. Desired consistency is determined by factors such as pumpability, piping requirements and other practical considerations.
[0048] The consistency (also referred to as dry undissolved solids or "UDS") of the lignocellulosic feedstock is determined by filtering and washing a sample to remove undissolved solids and then drying the sample at a temperature and for a period of time that are sufficient to remove water from the suspension sample or wet material, but do not result in thermal degradation of the raw material solids. After dewatering, or drying, the dry solids are weighed and the weight of water in the suspension sample or wet material is the difference between the weight of the suspension sample or wet solids and the weight of the dry solids. The amount of dry undissolved solids (UDS) in an aqueous suspension is referred to as the consistency of the suspension. Consistency is expressed as the weight of dry solids in a suspension weight, for example, as a ratio on a weight basis (weight:weight), or as a percentage on a weight basis, for example, % (w/w ), also described herein as % by weight. The method for determining consistency is shown in Example 1.
[0049] Before feeding the lignocellulosic raw material to the plug forming device, the raw material must be immersed in an aqueous solution including water, or a solution comprising pretreatment chemical. A benefit of soaking the raw material prior to pretreatment with a solution comprising a pretreatment chemical is that it can ensure a uniform impregnation of the biomass with the pretreatment chemical, which in turn , it helps to obtain an even cooking in the subsequent pre-treatment. Uniform impregnation ensures that some material is not overcooked and degraded due to the high localized concentration of the pretreatment chemical, while other material is not undercooked, resulting in low xylose yield and difficult cellulose hydrolysis. Undercooking or overcooking of the lignocellulosic feedstock can be particularly problematic when pretreatment is conducted under medium to high solids consistency, as the non-uniformity of pretreatment chemical concentration and temperature is more pronounced. Dehydration
[0050] The raw material can be dehydrated to increase the consistency of the undissolved solids within a desired range prior to buffer formation. However, it should be understood that dehydration may not be necessary if the consistency of the raw material is already at a desired level when it is fed to the plug forming device. Dehydration can involve the removal of water under raw material pressure, or at atmospheric pressure, as discussed below.
[0051] A plug forming device can be configured to dehydrate the raw material, although separate respective devices for dewatering and plug forming can be employed. Without being limiting, a plug forming device incorporating a dewatering section suitable for use in the invention may be a pressurized screw press or a plug feed screw as described in co-titled and co-pending WO 2010/022511 , which is incorporated herein by reference. Expressed water from the lignocellulosic raw material by the dehydration step can be reused in the process, such as to suspend and/or immerse the new raw material.
[0052] There are a variety of known devices that can be used to dehydrate the raw material prior to plug formation. Examples include drainage agents, filtration devices, sieves, screw presses, extruders or a combination thereof.
[0053] If the raw material is subjected to dehydration under pressure, the pressure increase may be caused by one or more high pressure pumps. The pump or other feed device increases the pressure of the raw material before dehydration, for example, to about 45 psia (0.31 MPa) to about 900 psia (6.21 MPa), or about 70 psia ( 0.48 MPa) to about 800 psia (5.52 MPa) or about 140 psia (0.97 MPa) to about 800 psia (5.52 MPa). Pressure can be measured with a pressure sensor located at a raw material inlet port on a dewatering device or a plug forming device that also dehydrates the raw material. Alternatively, the raw material subjected to dehydration may be at atmospheric pressure or at a pressure below about 45 psia (0.31 MPa).
[0054] There may be an optional raw material pre-draining step in order to drain the aqueous solution of the raw material suspension at atmospheric pressure or greater. This pre-drained raw material suspension can then be subjected to further dehydration. Cap forming devices
[0055] The formation of the plug can be considered an integration of lignocellulosic particles into a compacted mass referred to herein as a plug. Plug forming devices form a plug that acts as a seal between areas of different pressure. In embodiments of the invention, the plug seals against higher pressure in a device downstream of the plug. However, it should be understood that the pressure may be greater at the inlet of the plug forming device.
[0056] As previously mentioned, the plug forming device can dehydrate the raw material, or this function can be performed by an upstream dewatering device. Plug-forming devices that dehydrate may comprise a housing or shell with openings through which water can pass. The plug forming device can be operated at atmospheric pressure or below pressure.
[0057] Without being limiting, the plug forming device can be a plug feed screw, a pressurized screw press, a coaxial piston feed screw or a modular screw device.
The lignocellulosic feedstock buffer may have a weight ratio of water to dry undissolved solids of lignocellulosic feedstock from about 0.5:1 (67% by weight UDS) to about 5:1 (17% by weight UDS), or about 1:1 (50% by weight UDS) to about 4:1 (20% by weight UDS), or about 1.5:1 (40% in weight of UDS) to about 4:1 (20% by weight of UDS), or about 1.5:1 (40% by weight of UDS) to about 3.5:1 (22% by weight of UDS ), and all proportions between them. The weight ratio of water to dry undissolved solids of lignocellulosic feedstock or the % by weight of UDS in the lignocellulosic feedstock buffer or segments thereof can be determined by the method described in example 1. Lignocellulosic feedstock is a non-ligneous feedstock, the dry undissolved solids content of the lignocellulosic feedstock buffer is below 35% by weight. As discussed, operating below a dry undissolved solid content of 35% by weight, the process equipment is less prone to erode due to ash present in such raw materials. According to some embodiments of the invention, the dry undissolved solids content of the lignocellulosic feedstock buffer is between 20% by weight and 35% by weight, between 20% by weight and 32% by weight, between 22% by weight and 32% by weight or between 22% by weight and 30% by weight.
[0059] The non-wood raw material can be a cultivated crop, a sugar processing residue or an agricultural residue. The non-wood raw material will contain more than 0.5% by weight ash (w/w), or more typically greater than 1% by weight ash (w/w). Ash includes, but is not limited to, silica, and potassium, calcium, and sodium salts. Salts can exist as carbonate, phosphate, chloride or other common salt forms. Magnesium and other minerals may be present as well depending on the source of the raw material. In some embodiments of the invention, the ash content of the non-ligneous lignocellulosic feedstock is between about 0.5% by weight and about 18% by weight, between about 1% by weight and about 17% by weight. between about 15% by weight and about 15% by weight or between about 15% by weight and about 10% by weight. Ash content is measured as described in example 2 and is determined in relation to the oven-dried weight of a raw material sample. Disintegration and steam contact
[0060] After plug formation, the lignocellulosic feedstock is fed to an elongated downstream chamber, also referred to herein as a "high shear heating chamber" or a "heating chamber", in which the raw material is disintegrated into particles by the disintegrating elements as it is transported through them. Typically, the heating chamber is horizontally oriented or essentially horizontally oriented. The disintegrated particles are heated by direct contact with the steam, which allows an efficient heat transfer.
[0061] At least a portion of the heating chamber is cylindrical. For example, at least one median region of the chamber may be cylindrical and the entry and exit regions of the chamber may be of a different shape, although chambers that are cylindrical along with their full axial lengths are preferred. It is to be understood that the term "cylindrical" includes frusto-conical or other shapes that are substantially cylindrical.
[0062] The plug or its segments do not need to be fed directly into the heating chamber. Any of a variety of known devices can be positioned between the plug forming device and the heating chamber. Without being limiting, examples of such devices include mechanical restraint devices, restraint devices, scrapers and conveyors. It should be understood that the plug can break into segments as it is discharged from the plug forming device, or in other devices positioned downstream of the plug forming device, or as it is fed into the heating chamber.
[0063] The chamber comprises a steam addition means for direct addition of steam and a rotary shaft mounted generally co-axially within the chamber comprising one or more disintegration elements projecting outwardly from the shaft. Advantageously, it has been found that effective disintegration of a plug or plug segments can be achieved using disintegration elements which impart energy to the plug or plug segments in a shear action. As discussed below, operating parameters can be selected as needed for optimal raw material disintegration.
[0064] As used herein, the term "disintegration elements" refers to members arranged on the shaft that carries the raw material plug or its segments through the chamber and which provides sufficient shear to the raw material, thus producing particles of raw material disintegrated when the shaft rotates at a suitable speed. The disintegrating elements may comprise a cutting helix, a feeder ribbon, a toothed drill, blades, bars, paddles, handles, arms or a combination thereof. It should be understood that the disintegrating elements can vary in length.
[0065] Disintegration involves turning the plug or its segments into disintegrated particles. By disintegrated particles, we mean that, in the heating chamber, a bundle of fibers originating from the plug are broken down into their constituent particles, or that the bundles are substantially reduced in size in the high-shear heating chamber. Without being limiting, if wheat straw is used, the bundles can be smaller than about 10 mm, or preferably smaller than about 5 mm in their minimum dimensions.
[0066] Tip speed of the disintegrating elements is selected to cause the raw material to disintegrate and is generally greater than that used in known mixing conveyors in other industries. The tip speed of the disintegrating elements can be between about 200 m/min and about 1000 m/min, or between about 450 and about 800 m/min or any range in between. The shear action is generally a function of the shape of the disintegration elements, the number of the disintegration elements (if more than one disintegration element is used) and tip velocity. These parameters can be adjusted as needed to obtain a desired shear rate.
[0067] In some embodiments of the invention, the disintegration elements are located on the axis in at least a median region thereof. The inlet region of the shaft may comprise means for feeding and transporting the plug, or segments thereof, to the middle region of the shaft where more aggressive disintegration of the raw material may occur. The shaft exit region may comprise means for transporting the plug to the chamber exit.
[0068] In other embodiments of the invention, the disintegration elements are located in the input and/or output region of the shaft. According to these modalities, the elements of the input and/or output regions of the axis not only transport the raw material, but also disintegrate the raw material. In some embodiments of the invention the shaft entry region comprises a feeder tape, a cutting helix or toothed drill. This configuration can improve performance capacity and minimize blockage upstream of the heating chamber.
[0069] Some or all of the disintegration elements can be oriented in the direction of movement of the raw material through the heating chamber so as to facilitate the transport of the raw material through it. That is, a disintegration element can be mounted on the shaft at an angle adjusted from a line drawn across the heating chamber. Such a configuration can reduce the raw material residence time distribution, which, in turn, minimizes overheating or underheating of the raw material. For example, disintegration elements can be mounted on the axis at an angle that is adjusted between 0° and about 45° from a line drawn across the axis. For example, the disintegration elements can be mounted on the shaft at an angle that is adjusted between 1° and about 45° from a line drawn across the axis, or on an axis that is adjusted between 5° and 30° from a line drawn to the axis.
[0070] The steam addition means may comprise one or more inlet for direct steam injection. The introduction of steam along the length of the chamber at injection points spaced apart allows for more uniform heating of the raw material particles. Steam can be introduced through raw material inlets, inlets arranged along the length of the chamber, or a combination of these. Additionally, chemical used for pretreatment or hydrolysis can be introduced into the heating chamber.
[0071] The operating pressure and temperature of the heating chamber will typically comprise the pressure and temperature of the downstream reactor. Chamber operating pressure can be at least about 90 psia (0.62 MPa). Examples of operating pressures include between about 90 (0.62 MPa) and about 680 psia (4.69 MPa).
[0072] The temperature of the heating chamber will be greater than about 100°C. Examples of temperature ranges include between about 100°C and about 280°C, or between about 160°C and about 260°C.
[0073] In some embodiments of the invention, the disintegration elements project out of the axis and are configured so that their outer edges describe one or more circles that are concentric or essentially concentric with respect to the inner surface of the chamber. By the term “essentially concentric”, it means that the eccentricity of one or more circles described by the outer margins is less than that of about 10% of the diameter of the heating chamber.
[0074] According to an embodiment of the invention, the distance between the inner surface of the chamber and the outer edge of the disintegrating element that is closest to the inner surface (also referred to as "clearance") is less than about 10% of the inner diameter of the chamber. As mentioned previously, the lengths of the disintegrating elements can vary. Consequently, clearance is measured at the outer edge of the disintegrating element which is closest to the inner surface of the chamber. In some embodiments of the invention, clearance is between about 25% and about 8%, or between about 2.5% and about 6% of the inner diameter of the chamber.
[0075] The disintegration elements are arranged on the axis so as to sweep the inner surface of at least one region of the chamber. By sweeping the inner surface of the chamber in at least a region thereof, the disintegrating elements can reduce or remove scale formation, including lignin deposits that can reduce the transport and mixing capacity of the heating chamber.
[0076] By the term "sweep", it means that the distance between the inner surface of the chamber and the outer edge of the disintegrating element that is closest to the inner surface is less than 5% of the inner diameter of the chamber. By using such a clearance, a scale formation can be removed from the inner surface of the chamber or the formation can be reduced. Examples of suitable clearance ranges for scanning include about 1.0% to about 5.0%, about 1.5% to about 4.5%, or about 2.0% to about 4.0 %.
[0077] Furthermore, if separate disintegration elements are mounted on the axis, for example blades, bars, paddles, handles, arms, the spacing between adjacent elements can be chosen so as to eliminate stagnant areas of the surfaces on. the inner surface of the chamber between adjacent disintegration elements where organic deposits accumulate on the inner surface of the chamber. For example, the disintegration elements can overlap to provide continuous axial scanning over at least one region of the chamber, thus reducing or eliminating stagnant zones.
[0078] The present invention also relates to a lignocellulosic feedstock composition comprising: (i) disintegrated lignocellulosic feedstock particles; (ii) about 15 to about 35% by weight of dry undissolved solids, wherein the dry undissolved solids comprise between about 20 and about 60% by weight of cellulose and between about 10 and about 30% of xylan; and (iii) a mineral or organic acid, in which the raw material particles are not primarily derived from wood chips or pulp, and in which the pH of the raw material composition is between about 0.5 and about 4.5.
[0079] By the phrase "does not contain primarily", it means that the raw material composition does not contain more than about 50% by weight of raw material particles from wood chips or pulp, preferably less than 40, 30 , 20 or 10% by weight. In some embodiments of the invention, the raw material composition does not primarily contain forest biomass.
[0080] According to some embodiments of the invention, the undissolved dry solids content is 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 , 31, 32, 33, 34 or 35% by weight. The range of dry undissolved solids in the feedstock composition can include numerical limits of any of these values. In accordance with other embodiments of the invention, the dry undissolved solids content is between about 20 and about 32% by weight or between about 18 and about 28% by weight.
[0081] According to other embodiments of the invention, the pH of the raw material composition is 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4, 0 or 4.5. The pH range of the raw material composition can include numerical limits of any of these values. In accordance with other embodiments of the invention, the pH is between about 0.5 and about 3.5 or between about 0.5 and about 3.0. The mineral acid can be sulfuric acid, sulfurous acid, hydrochloric acid, phosphoric acid or a combination thereof. Without being limiting, the acid can be sulfuric acid. The organic acid can be acetic acid.
Undissolved solids may contain 20, 25, 30, 35, 40, 45, 50, 55 or 60% by weight of cellulose. The range of cellulose content in undissolved solids can include numerical limits of any of these values. According to other embodiments of the invention, the cellulose content in the undissolved solids can be between about 30 and about 60% by weight.
[0083] Undissolved solids can contain 10, 15, 20, 25 or 30% by weight of xylan. The range of xylan content in undissolved solids can include numerical limits of any of these values. According to other embodiments of the invention, the xylan content in undissolved solids can be between about 15 and about 30% by weight.
[0084] The temperature of the composition can be between about 100°C, 120°C, 140°C, 160°C, 180°C, 190°C, 200°C, 220°C, 240°C, 260° C or 280°C. The temperature range can include numerical limits on any of these values. According to other embodiments of the invention, the temperature range is between 160°C and 280°C. Pre-treatment and hydrolysis
[0085] After increasing the temperature of the disintegrated raw material particles in the heating chamber, they are pretreated or hydrolyzed.
[0086] The term "pre-treatment" or "pre-treat" means a process in which the lignocellulosic raw material is reacted under conditions that disrupt the fiber structure and that increase the susceptibility or accessibility of cellulose in cellulosic fibers to subsequent enzymatic or chemical conversion steps. A portion of the xylan in the lignocellulosic feedstock can be hydrolyzed to xylose and other hydrolysis products in a pretreatment process, although pretreatment processes that do not hydrolyze xylan are also included by the invention. In embodiments of the invention, the amount of xylan hydrolyzed to xylose is greater than about 50, about 60%, about 70%, about 80% or about 90% by weight.
[0087] The term "pre-treated raw material" means a raw material that has been subjected to pre-treatment so that the cellulose contained in the cellulosic fibers has a greater susceptibility or accessibility to subsequent enzymatic or processing steps. chemical conversion. The pre-treated raw material contains cellulose that was present in the raw material before pre-treatment. In some embodiments, at least a portion of xylan contained in the lignocellulosic feedstock is hydrolyzed to produce at least xylose in a pretreatment.
[0088] The terms of pretreatment or hydrolysis are not intended to be limited to the particular treatment methods disclosed herein. That is, they may or may not include the use of chemicals (eg, hydrothermal pretreatment) and the pretreatment or hydrolysis may be a multi-step or one-step process that produces fermentable sugar or prepares matter - press for subsequent conversion to fermentable sugar. All or a portion of the polysaccharides contained in the raw material can be converted to monomeric or oligomeric sugars, or a combination thereof, during pretreatment or hydrolysis. If chemical is used during pretreatment or hydrolysis, it may include organic solvents, oxidizing agents, or inorganic acids or bases. Lignin may or may not be removed during pretreatment or hydrolysis.
[0089] According to an embodiment of the invention, at least a portion of polysaccharides contained in the lignocellulosic raw material is hydrolyzed to produce one or more monosaccharides.
[0090] Several types of reactors can be used to pre-treat or hydrolyze the raw material including two or more reactors, arranged in series or parallel.
[0091] According to an embodiment of the invention, the reactor is a vertical reactor, which can be a vertical reactor either an upward flow or a downward flow. In another embodiment of the invention, the reactor is a horizontal or inclined reactor. The reactor may be equipped with an internal mechanism, such as a screw, a conveyor and a scraper or similar mechanism, for transporting the same lignocellulosic feedstock therethrough and/or to assist in the discharge of the reactor.
[0092] The chemical for the pretreatment or hydrolysis of the raw material can be added to the raw material during an immersion process carried out before dehydration, before buffer formation, in the heating chamber, in the forming device of the buffer, in the reactor, or a combination thereof.
[0093] The pressure in the reactor is between about 90 psia (0.62 MPa) and about 680 psia (4.69 MPa) and any pressure in between. The pressure in the reactor can be measured with one or more pressure sensors. If one or more reactors are configured so that there are different pressure levels inside each one, the pressure at the place where the raw material enters the first reactor is considered here to be the reactor pressure.
[0094] In some embodiments of the invention, the lignocellulosic raw material is treated in the reactor under acidic conditions. For acidic conditions, a suitable pH is from about 0 to about 3.5 or about 0.2 to about 3 or about 0.5 to about 3, and all pH values in between.
[0095] The acids added to adjust the acidic conditions in the reactor can be sulfuric acid, sulfurous acid, hydrochloric acid, phosphoric acid or a combination thereof. The addition of sulfurous acid includes the addition of sulfur dioxide, sulfur dioxide plus water or sulfurous acid. Organic acids can also be used, alone or in combination with a mineral acid.
[0096] The alkali added to adjust the alkaline conditions in the reaction zone can be ammonia, ammonium hydroxide, potassium hydroxide, sodium hydroxide or any combination thereof.
[0097] The proper temperature and reaction time in the reactor will depend on a number of variables, including the pH in the reactor and the degree, if any, to which hydrolysis of the polysaccharides is desired.
[0098] Without being limiting, the pre-treatment of lignocellulosic raw material can occur under acidic or alkaline conditions. In an acid pretreatment process, according to examples of embodiments of the invention, the time in the pretreatment reactor may be from about 10 seconds to about 20 minutes or about 10 seconds to about 600 seconds, or about 10 seconds to about 180 seconds and anytime in between. The temperature can be from about 150°C to about 280°C and any temperature in between. The pH for the pretreatment can be between about 0.5 and about 3, or between about 1.0 and about 2.0.
[0099] In an alkaline pretreatment process, the time in the reactor is about 1 minute to about 120 minutes, or about 2 minutes to about 60 minutes and all times in between, and at a suitable temperature from about 20°C to about 220°C or about 120°C to about 220°C and all temperatures in between.
[00100] Fiber expansion with ammonia (AFEX), which is an alkaline pretreatment method, may produce few or no monosaccharides. Therefore, if an AFEX treatment is employed in the reaction zone, the hydrolyzate produced from the reaction zone may not produce any monosaccharides.
[00101] According to the AFEX process, cellulosic biomass is contacted with ammonia or ammonium hydroxide, which is typically concentrated, in a pressure vessel. Contact is maintained long enough to allow the ammonia or ammonium hydroxide to swell (ie decrystallize) the cellulose fibers. The pressure is then quickly reduced, which allows the ammonia to heat up or boil and explode the cellulose fiber structure. The heated ammonia can then be recovered according to known processes. The AFEX process can be run at about 20°C to about 150°C or at about 20°C to about 100°C and all temperatures in between. The duration of this pretreatment can be from about 1 minute to about 20 minutes, or any time in between.
[00102] Pretreatment with dilute ammonia uses more dilute solutions of ammonia or ammonium hydroxide than AFEX. Such a pretreatment process may or may not produce any monosaccharides. The pretreatment with dilute ammonia can be conducted at a temperature of from about 100°C to about 150°C or any temperature in between. The duration of such a pretreatment can be from about 1 minute to about 20 minutes, or any time in between.
[00103] When sodium hydroxide or potassium hydroxide are used in the pretreatment, the temperature may be from about 100°C to about 140°C, or any temperature in between, the duration of the pretreatment it can be from about 15 minutes to about 120 minutes, or any time in between, and the pH can be from about pH 11 to about 13, or any pH value in between.
[00104] Alternatively, an acidic or alkaline hydrolysis process can be operated under conditions severe enough to hydrolyze the cellulose to glucose and other products.
Acid hydrolysis that is severe enough to hydrolyze xylan and cellulose can be carried out for about 10 seconds to about 20 minutes, or any time in between. The temperature can be between about 180°C and about 260°C, or any temperature in between. The pH can be between 0 and about 1 or any pH in between.
[00106] Alkaline hydrolysis that is severe enough to hydrolyze xylan and cellulose can be carried out at about 125°C to about 260°C, or about 135°C to about 260°C, or about 125°C to about 180°C, or any temperature in between, for about 30 minutes to about 120 minutes, or any time in between and about pH 13 to about 14, or any pH in between.
[00107] The pretreated or hydrolyzed raw material can be discharged to a discharge device such as a threaded weir, a swept-hole weir, a rotary weir, a piston type weir and the like. Two or more reactors, arranged in series or in parallel, can be used.
[00108] The pretreated or hydrolyzed raw material leaving the reaction zone can be depressurized and cooled rapidly, for example, to between about 30°C and about 100°C. In one embodiment of the invention, the pressure is reduced to about atmospheric. Cooling and depressurization can be carried out by one or more flash containers.
[00109] The dry undissolved solids of the pretreated feedstock suspension can be between about 15% and about 30% by weight or between about 15% and about 25% by weight. Enzymatic hydrolysis and fermentation
[00110] If the pretreated or hydrolyzed raw material leaving the reactor contains cellulose, it can be subjected to cellulose hydrolysis with cellulase enzymes. By the term "cellulase enzymes", "cellulases", or "enzymes", it is meant that the enzymes catalyze the hydrolysis of cellulose to products such as glucose, cellobiose, and other cello-oligosaccharides. Cellulase is a generic term denoting a multi-enzyme mixture composed of exo-cellobiohydrolases (CBH), endoglucanases (EG) and β-glucosidases (βG) that can be produced by a variety of plants and microorganisms. The process of the present invention can be carried out with any type of cellulase enzymes, regardless of their sources.
[00111] Optionally, before enzymatic hydrolysis, the sugars resulting from the pre-treatment are separated from the components of the non-hydrolyzed raw material in the pre-treated raw material suspension. Means which allow separation to be carried out include, but are not limited to, filtration, centrifugation, washing or other known processes for removing fiber solids or suspended solids. The aqueous sugar stream can then be concentrated, for example, by evaporation, with membranes, or the like. Any solid traces are usually removed by microfiltration.
[00112] In one embodiment, the aqueous sugar stream separated from the fiber solids is fermented to produce a sugar alcohol by a yeast or bacteria. Sugar alcohol can be selected from xylitol, arbitol, erythritol, mannitol and galactitol. Preferably the sugar alcohol is xylitol. Alternatively, the sugar is converted to an alcohol, such as ethanol or butanol, by fermentation with a naturally-occurring or recombinant bacteria or fungus. It is to be understood that the invention is not limited to the particular chemistry that can be produced from fermentable sugar or the particular method employed to produce the same.
[00113] In general, a temperature in the range of about 45°C to about 55°C, or any temperature in between, is adequate for most cellulase enzymes, but the temperature may be higher for thermophilic cellulase enzymes . The dosage of cellulase enzyme is chosen to achieve a sufficiently high level of cellulose conversion. For example, a suitable dosage of cellulase can be about 5.0 to about 100.0 filter paper units (FPU or IU) per gram of cellulose, or any amount in between. FPU is a standard measure known to those skilled in the art and is defined and measured according to Ghose (1987, Pure and Appl. Chem. 59:257-268). The β-glucosidase dosage level can be from about 5 to about 400 β-glucosidase units per gram of cellulose, or any amount in between, or from about 35 to about 100 β-units. glucosidase per gram of cellulose, or any amount in between. The β-glycosidase unit is also measured according to the Ghose method (supra).
[00114] The enzymatic hydrolysis of cellulose continues for about 24 hours to about 250 hours, or any amount of time in between, depending on the degree of conversion desired. The suspension so produced is an aqueous solution comprising glucose, xylose, other sugars, lignin and other suspended and unconverted solids. Other sugars that can be produced in the reaction zone can also be present in the aqueous solution. Sugars are readily separated from suspended solids and can be further processed as needed, for example, but not limited to, fermentation to produce fermentation products, including, but not limited to ethanol or butanol by yeast or bacteria. If ethanol is produced, fermentation can be carried out with a yeast, including but not limited to Saccharomyces cerevisiae.
[00115] Dissolved sugars that undergo fermentation may include not only glucose released during the hydrolysis of cellulose, but also sugars derived from a pre-treatment, ie, xylose, glucose, arabinose, mannose, galactose, or a combination of the same. These sugars can be fermented together with glucose produced by hydrolysis of cellulose, or they can be fed to a separate fermentation. In one embodiment of the invention, such sugars are converted to ethanol, along with glucose from cellulose hydrolysis, by a Saccharomyces cerevisiae yeast strain, having the ability to convert glucose and xylose to ethanol. The strain of Saccharomyces cerevisiae can be genetically modified so that it is capable of producing this valuable by-product (see, for example, US Patent No. 5,789,210, which is hereby incorporated by reference), although some strains of Saccharomyces have been reported to cerevisiae are naturally capable of converting xylose to ethanol. EXAMPLES Example 1: Determination of the concentration of undissolved solids in a lignocellulosic feedstock suspension
[00116] The determination of the content of dry undissolved solids (UDS) in a suspension is carried out as follows.
[00117] A fixed amount of suspension is dispensed into a heavy plastic dish and the weight of the suspension is accurately recorded using an analytical balance. A circular, 1.6 mM filter paper, sized appropriately for a Buchner funnel, is placed in an aluminum weighing can and the combined weight of the can and filter paper is recorded. After transferring the pre-weighed filter paper to the Buchner funnel, the pre-weighed suspension is passed through the filter paper to isolate solids. Small volumes of deionized water are used to ensure that solids are quantitatively transferred from the weighing pan to the Buchner funnel. The solids are then washed with excess deionized water, after which the washed sample and filter paper are transferred to the pre-weighed aluminum can. Care must be taken to ensure that solids are quantitatively transferred. After drying the aluminum can in an oven at 105°C overnight, the contents are accurately weighed and the UDS is quantified by determining, as a percentage or ratio, the number of grams of dry solids per gram of suspension. Example 2: Determination of ash content of lignocellulosic raw material
[00118] The amount of ash is expressed as the percentage of residue remaining after dry oxidation at 575°C according to Technical Report NREL NREL/TP-510-42622, January 2008, which is incorporated herein by reference. Results are reported for a sample oven dried at 105°C (dryed overnight).
[00119] In order to determine the ash content, a crucible is first heated without any sample in a muffle oven for 4 hours at 575°C ± 25°C, cooled and then weighed. After heating, the crucible is cooled and then dried to a constant weight, which is defined as less than a ± 3 mg change in crucible weight in one hour of crucible reheating to 575°C ± 25° Ç.
[00120] The analyzed sample is an oven dried species at 105°C. The weight of the oven dried sample is recorded after drying at 105°C overnight in an oven and this weight is referred to as "oven dry weight" or "ODW". Weighed and dried sample is placed in the crucible and incinerated to constant weight in a muffle furnace set at 575 ± 25°C. The crucible and ash are subsequently weighed for incineration and the ash percentage is determined on an ODW basis. Ash is quantified by determining, as a percentage, the number of grams of soda ash per gram of oven dried sample. Example 3: Raw material dehydration, plug formation, plug disintegration and pre-treatment system
[00121] The following describes a system for the production of a pre-treated raw material according to embodiments of the invention.
[00122] Referring to Figure 1, a lignocellulosic feedstock suspension having a consistency of about 1% to about 10% (w/w), preferably about 3% to about 5% (w/w ) in the suspension line 102 is pumped by means of the pump 104, through the feed line 106 in the pressurized dewatering screw press indicated by the general reference numeral 108. The pressurized dewatering screw press 108 comprises a solid shell 105 having a raw material inlet port 112 and a pressing port 114. In the feed line 106 it feeds lignocellulosic raw material into the dewatering screw press 108 through the raw material inlet port 112 at a pressure of, for example , about 70 psia (0.48 MPa) and about 900 psia (6.21 MPa). Pressure can be determined by measuring pressure with a pressure sensor located at the raw material inlet port 112.
[00123] The screen 116 is disposed within the shell 105 to provide an outer space 118 between the screen and the inner circumference of the shell 105. A thread 120 is concentrically and rotatably mounted within the screen 116. The helices 122 of the thread 120 are generally of constant outside diameter and connected to a screw axis with a core diameter that increases from the inlet end 124 to the outlet end 126 of the pressurized dewatering screw press 108.
[00124] Water and other liquids, including dissolved solids, which were expressed from the lignocellulosic raw material suspension are withdrawn into space 118, which serves as a collection chamber for the withdrawn water. Space 118 is connected via press port 114 to a turbine 132 which draws withdrawn water through a press line 130. The withdrawn, or press, water can then be sent to a water suspension constitution system. press return (not shown), via line 134.
[00125] The partially dehydrated lignocellulosic feedstock exits the dewatering zone and cap-forming zone of screw press 108 at outlet end 126. The ratio of water to dry lignocellulosic feedstock solids in the material. partially dehydrated lignocellulosic raw material can be in the range of from about 1.5:1 (67% by weight UDS) to about 4:1 (20% by weight UDS) exiting the dewatering and tampon-forming zone. The weight ratio of water to dry solids of lignocellulosic feedstock in the dehydrated lignocellulosic feedstock or the percentage of dry undissolved solids is determined by taking a sample of the feedstock from, for example, the outlet end 126 of the screw press, and determining the proportion by weight or % by weight of UDS in the sample by the method described in Example 1 above. More preferably, the consistency of the raw material plug or segments thereof at the outlet should not exceed 35% by weight of UDS, in order to reduce erosion in the screw press 108.
[00126] The outlet end 126 of the pressurized screw press 108 is operatively connected to a plug zone 136. A plug of partially dehydrated lignocellulosic raw material is forced through the plug zone 136 and is discharged into the plug outlet 137. Also there may be a restriction device (not shown) at the buffer output 137.
[00127] A steam inlet port 138 and/or ports 138A are provided by a source of steam through steam inlet line 139. The partially dehydrated raw material plug which contains water in the range of about 0 .5 to about 5 times the weight of the dry raw material solids is fed to a high shear heating chamber 140 via a feed chamber 141.
[00128] In the high shear heating chamber 140, the raw material plug or segments thereof are disintegrated into particles, which are heated by direct contact with the steam through the steam introduced through line 139 and/or ports 138A. Steam can also be introduced into the heating chamber body 140. As mentioned earlier, the plug can break into segments as it is discharged from the pressurized screw press 108, or as it is fed into other positioned devices downstream of the screw press 108.
[00129] The heating chamber 140 is a horizontally oriented, cylindrical device having a concentric, rotatable axis 142 mounted co-axially within the chamber. The concentric shaft 142 comprises a plurality of disintegration elements 143 mounted in its medial region and which design radially derived therefrom. Some disintegrating elements comprise a distal end 144 that is "T-shaped" for sweeping the inner surface of chamber 140, as described below. The shaft entry region 142 comprises an entry drill 145 for transporting the plug, or segments thereof, to the medial region of the chamber. In addition, an exit drill 146, with opposite orientation, is provided in an exit zone of shaft 142 for the discharge of disintegrated and heated raw material produced in heating chamber 140 in a pretreatment reactor 152.
[00130] Shearing action is imparted to the raw material plug or its segments, in the heating chamber 140 by a plurality of disintegrating elements 143. The speed of the shaft end is such that the raw material segments are disintegrated and it is typically within a range of between 450 m/min to about 800 m/min, in order to achieve optimal disintegration. The extent of the shear action is largely a function of the number and shape of the disintegrating elements times the tip speed. During disintegration, the raw material plug or segments of it are broken down into small particles.
[00131] Each blast element is configured so that the clearance between the inner surface of chamber 140 and the distal outer edge of the distal "T-shaped" end 144 of each blast element is less than 4 percent of the inner diameter of chamber 140. Such a clearance allows disintegration elements 143 to sweep the inner surface of chamber 140.
[00132] Furthermore, the disintegration elements 143 are arranged on the axis 142 so that there is no continuous axial sweep of the inner surface of the chamber 140. According to this embodiment of the invention, the end portions of each disintegration element "T-shaped" overlaps the corresponding end portions of an adjacent T-shaped element. This allows the area swept by each T-shaped element to overlap the area swept by an adjacent T-shaped element so that there are no stagnation zones for organic deposits that accumulate on the inner surface of the chamber.
[00133] According to another embodiment of the invention, the disintegration elements are "Y-shaped". In addition, a combination of "Y-shaped" and "T-shaped" disintegration elements can be arranged on the axis.
The drill 145 for transporting the plug, or segments thereof, in the medial region of the chamber 140 may be a toothed drill. Cross sections of various drill configurations suitable for use in the invention are shown in Figure 2. The provision of such a drill in the entry region facilitates transport of the plug, or segments thereof, through the heating chamber 140. A toothed drill works to disintegrate the raw material plug or segments as it enters the heating chamber.
[00135] The disintegrated and heated raw material is discharged from the heating chamber 140 to the pre-treatment reactor 152, which comprises a cylindrical vessel, horizontally oriented, in which a screw conveyor 154 having propellers 156 is mounted. of pretreatment 152 operates at a pressure of about 90 psia (0.62 MPa) to about 680 psia (4.69 MPa), a pH of about 0.5 to about 3.0 and a temperature of about 160°C to about 260°C. The lignocellulosic raw material is treated in the reactor for a time of about 10 to about 600 seconds. The desired pH in reactor 152 can be achieved by adding acid to the lignocellulosic feedstock prior to entry to the pressurized screw press.
[00136] A discharge device 158 discharges the pre-treated raw material from the pre-treatment reactor 152. Subsequently, the pre-treated raw material is directed into a flash tank or tanks (not shown) for cooling. la before enzymatic hydrolysis. Example 4: Production of a pre-treated raw material with improved enzymatic digestibility of cellulase, while reducing equipment erosion
[00137] The method described in this example involves immersing a lignocellulosic feedstock in an acidic aqueous solution of low consistency and subsequently dehydrating the immersed feedstock suspension with a pressurized screw press to a consistency of undissolved solids 28% by weight. The plug segments exiting the screw press were disintegrated in a heating chamber and further pretreated at high temperature and pressure.
[00138] By keeping the UDS not greater than 28% by weight in the screw press plug zone, excessive wear in the screw press is avoided. The highest consistency of UDS occurs in the buffer zone of the pressurized screw press and thus it is at this stage that consistency is controlled to reduce erosion. The subsequent pretreatment results in a raw material suspension of 20% by weight of UDS. The results below demonstrate that the pretreatment was effective in producing a pretreated feedstock suspension from which a high yield of glucose could be recovered under low water conditions.
[00139] Wheat straw was subjected to particle size reduction and immersed in an acidic solution with a pH of 1.4. Wheat straw has been reported to contain an ash content of 3.1% silica and 4.9% non-silicon salts. (See co-owned US Patent No. 7,754,457).
[00140] Referring to Figure 1, the immersed raw material suspension was pumped by means of a pump 104 through the feed line 106 to the pressurized dewatering screw press indicated by general reference number 108. The screw press Pressurized dehydration device 108 is operated so that the plug segments exiting the device have a UDS of 28% by weight. As discussed, by operating at this consistency of dry solids, erosion in the screw press due to the ash content of the raw material can be reduced.
[00141] The plug segments are fed into a high-shear heating chamber 140 via a feed chamber 141. In the high-shear heating chamber 140, the plug segments exiting the device are disintegrated into particles. Raw material particles are heated by direct steam contact through steam introduced through line 139 and/or 138A ports.
[00142] The disintegrated and heated raw material is discharged from the heating chamber 140 to a pre-treatment reactor. The pretreatment is carried out at a pH, temperature and time set forth in co-owned US Patent No. 7,754,457, which is incorporated herein by reference.
[00143] The dry undissolved solids content of the pretreated raw material was measured over an operating period of one month. The results are shown in Figure 3. The figure shows that, during the period of time in which the measurements were taken, there were no large deviations in the solids concentration of the pre-treated raw material. This shows that the process can be operated at constant consistency over an extended period of time.
[00144] A sample of the pretreated raw material was also tested for its ability to be hydrolyzed by cellulase enzymes to produce glucose. Using the methods described here for producing a pre-treated raw material, a high production of glucose can be achieved.
[00145] In this example, the pretreated raw material was hydrolyzed using cellulase enzymes secreted by Trichoderma reesei. Cellulase was produced by submerged liquid culture fermentation of the P1380H Iogen Energy strain using methods described in US 2010/0304438, which is incorporated herein by reference. The filtered fermentation broth was desalted using Biospin® columns (Bio-Rad) following the manufacturer's protocol. The total protein concentration of the desalinated enzyme was tested using a BCA kit (Sigma-Aldrich®) with the bovine serum albumin control (Sigma-Aldrich®).
[00146] The cellulose from the pretreated wheat straw was hydrolyzed in a batch reaction, using the cellulolytic enzyme systems obtained as described above. Pretreated wheat straw was hydrolyzed with 30 mg of cellulase per gram of cellulose in reactions at 50°C and pH 5.0, with orbital agitation at 250 rpm, in a total reaction volume of 50 ml. After 165 hours, an aliquot was removed from the reaction; the reaction was well mixed during sampling to ensure homogeneity of solids and liquids in the sample. The reaction was stopped on the aliquot sample by incubating it in a heated block at 100°C for 5 minutes.
[00147] The liquid fraction of the inactivated sample was analyzed for glucose concentration to determine the extent of cellulose conversion. Glucose concentration was determined using a coupled enzymatic assay based on glucose oxidase and horseradish peroxidase, using methods known in the art. (See Trinder, 1969, Ann. Clin. Biochem., 6:24-27, which is incorporated herein by reference). The amount of glucose equivalents present in the cellulose at the start of the reaction was determined in an acid hydrolysis separated from the pretreated cellulose to glucose, using methods known to those skilled in the art. The conversion calculation included correction terms for the effect of glucose on solution density and the volume exclusion effect of non-hydrolyzable lignin present in the reaction.
[00148] The calculated conversion of cellulose into the pretreated feedstock was 90%, which indicates that the pretreatment was effective in producing a cellulosic substrate from which glucose production can be recovered.

权利要求:
Claims (11)
[0001]
1. A method for producing a hydrolyzed or pretreated lignocellulosic feedstock, characterized in that it comprises: (i) feeding a lignocellulosic feedstock to a plug forming device and forming a plug from the feedstock; (ii) feeding the plug or segments thereof into an elongated heating chamber having at least a portion thereof which is cylindrical, said elongated heating chamber having steam adding means for direct addition of steam and a rotatable shaft mounted on the it has one or more disintegration elements disposed therein, said disintegration elements projecting outside the axis and configured such that the outer edges of the disintegration elements on the rotatable axis, when in use, describe one or more circles that are concentric or essentially concentric with respect to the inner surface of the chamber and axially continuously sweeps the inner surface of at least one region of the chamber; (iii) producing disintegrated raw material particles in said elongated heating chamber by said disintegrating elements; (iv) heating the disintegrated raw material particles by contacting the particles with steam introduced through said steam addition means, wherein the operating pressure in the chamber is at least 0.62 MPa (90 psia); and thereafter (v) pre-treating or hydrolyzing the disintegrated raw material particles in a reactor to produce the hydrolyzed or pre-treated lignocellulosic raw material.
[0002]
2. Method according to claim 1, characterized in that the lignocellulosic raw material is in the form of a suspension and is fed to a dehydration device to produce a dehydrated raw material and, in which the raw material dehydrated is then fed to the plug forming device.
[0003]
3. Method according to claim 1, characterized in that the raw material is pressurized and then fed to a combined plug-forming and dehydration device and in which the pressure of the raw material at the input of the device is greater that 0.31 MPa (45 psia).
[0004]
4. Method according to any one of claims 1 to 3, characterized in that the means for adding steam comprise inlets for direct steam injection arranged along the length of the chamber.
[0005]
5. Method according to any one of claims 1 to 4, characterized in that the elongated heating chamber does not contain an indirect heating jacket.
[0006]
6. Method according to any one of claims 1 to 5, characterized in that the pre-treatment or hydrolysis comprises the addition of chemical to the disintegrated raw material particles.
[0007]
7. Method according to claim 6, characterized in that the chemical is acidic or alkaline.
[0008]
8. Method according to any one of claims 1 to 7, characterized in that the distance between the inner surface of the elongated heating chamber and the outer edge of the disintegration element which is closer to the inner surface of said chamber is smaller than 10% of the inner diameter of the chamber.
[0009]
9. Method according to any one of claims 1 to 8, characterized in that the speed of the outer edge of the disintegration element which is closest to the inner surface of the elongated heating chamber is 200 m/min to 1000 m /min.
[0010]
10. Method according to claim 9, characterized in that the speed is from 450 m/min to 800 m/min.
[0011]
11. A method for producing a hydrolyzed or pretreated lignocellulosic feedstock, characterized in that it comprises: (i) feeding a lignocellulosic feedstock to a plug forming device and forming a plug of feedstock therein; (ii) feeding the plug or segments thereof from a plug forming device into an elongated heating chamber having at least a portion thereof which is cylindrical, said elongated heating chamber having steam adding means for the addition steam jet and a rotatable shaft mounted thereon having one or more disintegration elements disposed thereon, wherein the disintegration elements are disposed on said shaft so as to sweep the inner surface of at least one region of the elongated heating chamber , said disintegration elements projecting outwards from the axis and configured such that the outer edges of the disintegration elements on the rotatable axis, when in use, describe one or more circles that are concentric or essentially concentric with respect to the inner surface of the chamber and sweep axially continuously the inner surface of at least one region of the chamber; (iii) producing disintegrated raw material particles in said elongated heating chamber by said disintegrating elements; (iv) heating the disintegrated raw material by contacting the particles with steam introduced through said steam adding means, wherein the operating pressure in the chamber is at least 0.62 MPa (90 psia); and then (v) preheating or hydrolyzing the disintegrated feedstock particles in a pretreatment reactor to produce the hydrolyzed or pretreated lignocellulosic feedstock.

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同族专利:

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公开号 | 公开日

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CA2848935A1|2013-03-28|

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BR112014006621A2|2017-04-04|

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EP2758589A1|2014-07-30|

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CN103906876A|2014-07-02|

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US20130071903A1|2013-03-21|

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EP2758589A4|2015-08-26|

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CA2848935C|2020-09-15|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

SE7604167L|1976-04-08|1977-10-09|Reinhall Rolf Bertil|DEVICE FOR TREATMENT OF LIGNOCELLULOSE-CONTAINING MATERIAL IN A PRESSURE REACTION VESSEL|

---

ES8201627A1|1980-02-23|1981-12-16|Reitter Franz Johann|Process and apparatus for continuous hydrolysis of cellulosic plant materials for obtaining sugars.|

---

SE506803C2|1996-07-25|1998-02-16|Cellwood Machinery Ab|Method and plant for bleaching recycled pulp|

---

US6176176B1|1998-04-30|2001-01-23|Board Of Trustees Operating Michigan State University|Apparatus for treating cellulosic materials|

---

JP2003119679A|2001-10-17|2003-04-23|Aikawa Iron Works Co Ltd|Apparatus for heating pulp|

---

AU2003281334A1|2002-07-02|2004-01-23|Andritz, Inc.|Solvent pulping of biomass|

---

WO2010013324A1|2008-07-30|2010-02-04|株式会社 ケー・イー・エム|Method of treating substance containing lignocellulose or cellulose|

---

US8328947B2|2008-08-29|2012-12-11|Iogen Energy Corporation|Method for low water hydrolysis or pretreatment of polysaccharides in a lignocellulosic feedstock|

---

US8691050B2|2008-11-21|2014-04-08|Børge Holm Christensen|Methods and devices for continuous transfer of particulate and/or fibrous material between two zones with different temperatures and pressures|

---

CA2673134A1|2009-07-17|2011-01-17|Murray J. Burke|Method and apparatus for the heat treatment of a cellulosic feedstock upstream of hydrolysis|GB2488918B|2010-06-26|2014-03-05|Virdia Ltd|Sugar mixtures and methods for production and use thereof|

---

IL206678D0|2010-06-28|2010-12-30|Hcl Cleantech Ltd|A method for the production of fermentable sugars|

---

IL207329D0|2010-08-01|2010-12-30|Robert Jansen|A method for refining a recycle extractant and for processing a lignocellulosic material and for the production of a carbohydrate composition|

---

IL207945D0|2010-09-02|2010-12-30|Robert Jansen|Method for the production of carbohydrates|

---

GB2524906B8|2011-04-07|2016-12-07|Virdia Ltd|Lignocellulose conversion processes and products|

---

WO2013055785A1|2011-10-10|2013-04-18|Virdia Ltd|Sugar compositions|

---

AU2013256049B2|2012-05-03|2017-02-16|Virdia, Inc.|Methods for treating lignocellulosic materials|

---

US9493851B2|2012-05-03|2016-11-15|Virdia, Inc.|Methods for treating lignocellulosic materials|

---

US9115214B2|2012-09-24|2015-08-25|Abengoa Bioenergy New Technologies, Llc|Methods for controlling pretreatment of biomass|

---

CN103809633B|2012-11-01|2017-02-22|中国石油集团东北炼化工程有限公司吉林设计院|Temperature and humidity measurement control system for straw fiber pretreatment stage|

---

CA2941083C|2014-03-21|2020-07-28|Iogen Energy Corporation|Method for processing a cellulosic feedstock at high consistency|

---

WO2016094594A1|2014-12-09|2016-06-16|Sweetwater Energy, Inc.|Rapid pretreatment|

---

US11078548B2|2015-01-07|2021-08-03|Virdia, Llc|Method for producing xylitol by fermentation|

---

WO2016145527A1|2015-03-16|2016-09-22|Iogen Corporation|Process comprising acid pretreatment and enzymatic hydrolysis|

---

WO2017100907A1|2015-12-18|2017-06-22|Iogen Corporation|Sulfur dioxide and/or sulfurous acid pretreatment|

---

US10995314B2|2015-03-16|2021-05-04|Iogen Corporation|Sulfur dioxide and/or sulfurous acid pretreatment with sulfur dioxide recovery|

---

US10513714B2|2015-03-16|2019-12-24|Iogen Corporation|Lignocellulosic conversion process comprising sulfur dioxide and/or sulfurous acid pretreatment|

---

KR20180012254A|2015-04-10|2018-02-05|코멧 바이오리파이닝 인코포레이티드|Methods and compositions for the treatment of cellulosic biomass and products produced thereby|

---

WO2017088061A1|2015-11-25|2017-06-01|Iogen Energy Corporation|System and method for cooling pretreated biomass|

---

CA3012218A1|2016-02-10|2017-08-17|Iogen Corporation|Pretreatment of lignocellulosic biomass with sulfur dioxide and/or sulfurous acid|

---

RU2710554C1|2016-02-19|2019-12-27|Интерконтинентал Грейт Брендс Ллк|Methods for formation of multiple valuable streams from biomass sources|

---

SE541727C2|2017-11-27|2019-12-03|Valmet Oy|System and method for treating biomass material|

---

CN207828156U|2017-12-06|2018-09-07|易高环保能源研究院有限公司|The device refined sugar using lignocellulose raw material continuous hydrolysis|

---

EP3790409A4|2018-05-10|2021-07-21|Comet Biorefining Inc.|Compositions comprising glucose and hemicellulose and their use|

---

US11118017B2|2019-11-13|2021-09-14|American Process International LLC|Process for the production of bioproducts from lignocellulosic material|

法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-01-12| B25G| Requested change of headquarter approved|Owner name: IOGEN ENERGY CORPORATION (CA) |

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2021-03-16| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-06-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/09/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161536805P| true| 2011-09-20|2011-09-20|

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US61/536.805|2011-09-20|

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PCT/CA2012/050647|WO2013040702A1|2011-09-20|2012-09-19|Method for heating a feedstock|

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