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    • 专利摘要:
    PROCESS FOR TREATING BIOMASS. A process for the treatment of biomass with a relatively high water and salt content, such as agricultural or forest waste, comprises: (a) the mechanical pre-treatment of wet biomass; (b) extracting the pre-treated biomass with water at a temperature between 40 and 160 ° C at a pressure that keeps the water substantially liquid; (c) the dehydration of the heated biomass for the production of a dehydrated biomass and an aqueous effluent; (d) optionally, heating the dehydrated biomass to a temperature above 160 ° C; (e) drying, before or after step (d), and compacting the heat-treated biomass. The treated biomass can be used as a solid fuel. The aqueous effluent is subjected to an anaerobic treatment for the production of biogas / or alcohols.
    公开号:BR112014026412B1
    申请号:R112014026412-0
    申请日:2013-04-18
    公开日:2020-11-24
    发明作者:Jan Remmert Pels；Constantinos Krokos
    申请人:Stichting Energieonderzoek Centrum Nederland；
    IPC主号:
    专利说明:

    [0001] [001] The invention relates to a process for the thermal treatment of biomass, especially fibrous biomass, for the removal of salts and other undesirable components, and to make it suitable as a solid fuel. HISTORIC
    [0002] [002] Roasting is known to be a useful process for converting low-cost biomass, such as agricultural waste and the like, into high-grade fuels. In a roasting process, the biomass is heated to moderately high temperatures, typically from 200 to 320 ° C, without the addition of oxygen, which results in the removal of most of the residual water and a smooth disintegration of the woody constituents of the biomass. , which produces a fraction of gas, the so-called "tor-gas", which comprises water vapor, carbon dioxide and small organic molecules, and a compactable solid product that can be processed into a solid fuel, for example, as a coal substitute.
    [0003] [003] As an example, WO 2005/056723 describes a roasting process in which the biomass is roasted between 200 and 320 ° C, and the gas produced by the roasting is cooled in order to condense impurities and combustible material.
    [0004] [004] Document NL 1029909 describes a pressurized roasting process in which the water remains in a liquid state during heat treatment. This hydrothermal treatment leads to the roasting of biomass and the release of salts that can be removed by mechanical means. However, if the hydrothermal treatment is carried out in a single step with dehydration afterwards, the temperature must be relatively high, in order to create the desired characteristics of the fuel, for example, 190 ° C for grass or up to 210 ° C for cane and straw. At this temperature, water-soluble phenols and other undesirable by-products are formed from decomposition. The pressed effluent then contains components that are not digestible and may even be toxic.
    [0005] [005] EP2206688 describes a hydrothermal process for the carbonization of biomass between 190 and 230 ° C and between 10 and 30 bar for 1 to 5 hours, followed by the separation between the liquid and the solid resulting from a wet oxidation treatment of liquid. The purpose of heat treatment is the chemical conversion of biomass.
    [0006] [006] WO 2010/112230 discloses a method for hydrothermal carbonization of biomass which involves a pressurized wet pretreatment at 90 ° C and subsequent carbonization, for example, between 190 and 220 ° C and about 20 bar, followed by drying.
    [0007] [007] The present invention aims to provide a process for the treatment of biomass that has one or more, preferably all, the following advantages:
    [0008] [008] - biomass with relatively high water content can be dehydrated and processed;
    [0009] [009] - the aqueous fraction of the wet biomass is fermentable (anaerobically) to a high degree;
    [0010] [010] - the dehydrated biomass is converted into a useful solid fuel substitute with a high caloric value;
    [0011] [011] - the ash content, in particular the salt content of the resulting biomass, is low and meets current and future standards for solid fuels;
    [0012] [012] - any residual effluents can be discarded or reused without environmental disadvantages;
    [0013] [013] - the general process can be performed without the need for a power input. SUMMARY OF THE INVENTION
    [0014] [014] The invention provides a process for the thermal treatment of biomass that results in a solid that can be used as a fuel, as well as a product of gaseous or liquid fermentation in the form of biogas (methane) or alcohols. It has also surprisingly been discovered that an aqueous extract that results from the process of the invention can be fed directly to an anaerobic treatment, without impairing anaerobic digestion in any way. The process, therefore, still results in a fully anaerobic digestible effluent that does not contain unwanted (thermal) degradation by-products. In addition, efficient dehydration and high levels of salt removal, as well as product roasting, can be achieved. The process is a hydrothermal chemical treatment that does not impose limitations on the raw material due to biology or the link to seasonal availability. Biogas can be produced by digesting liquid effluents, and can be used on site for the generation of heat and possibly electricity, but it can also be improved to the quality of natural gas and used as green gas elsewhere. Essentially, no waste should be discarded. The output is biogas, heat, energy, solid fuel and an effluent that can be disposed of.
    [0015] [015] As in the case of dry roasting, an energy densification of the biomass is obtained in combination with a better grinding capacity and water resistance. The process can be fully integrated with heat. An overall energy efficiency of 60 to 70% for fuel production can be achieved. The process can be carried out autonomously, that is, without the entry of heat from another party. However, it can also be integrated with various forms of wastewater treatment, with great synergy in digestion and production of heat and green energy, or optimized for external heat sources, when available. Due to the possibility of carrying out the process autonomously, it is possible to have a decentralized production of high quality solid fuel from bulky low quality biomass. The ideal size of a decentralized unit depends on local conditions.
    [0016] [016] Conditions can be manipulated so that P, N and S, as well as other minerals and nutrients - except K - can be dissolved in the effluent or fall behind in the solid phase. The first allows the recovery of nutrients from the processed effluent after digestion. This is of particular interest for those nutrients that cannot be recovered as ash after combustion, in particular N and S. DETAILED DESCRIPTION OF THE INVENTION
    [0017] [017] The invention concerns a hydrothermal treatment of biomass with the objective of converting it into an attractive fuel. The process combines four improvements that are individually interesting: dehydration, salt removal, drying and anaerobic digestion. In the process of the invention, the biomass is treated in liquid water, so that the salts, as defined below, present in the biomass, go into solution. In addition, the structure of the biomass can be altered so that it is easy to dehydrate it mechanically. The process is preferably carried out in combination with the anaerobic digestion of the effluent. This produces enough biogas for power generation to run the process autonomously, if desired.
    [0018] [018] Thus, the invention relates to a process for the treatment of biomass which comprises:
    [0019] [019] (a) the pre-treatment of wet biomass;
    [0020] [020] (b) extraction of pre-treated biomass with water at a temperature between room temperature and 160 ° C (at a pressure that keeps the water substantially liquid);
    [0021] [021] (c) the mechanical dehydration of the extracted biomass for the production of a dehydrated biomass and an aqueous effluent;
    [0022] [022] (g) submitting the aqueous effluent produced in step (c) to an anaerobic treatment while maintaining the aqueous effluent at temperatures below 160 ° C.
    [0023] [023] The process also optionally comprises one or more of the following steps:
    [0024] [024] (d) heating the dehydrated biomass to a temperature above 160 ° C.
    [0025] [025] (e) drying the heated biomass after step (d) comprising evaporating the water, preferably comprising a steam explosion; the drying step can also precede step (d);
    [0026] [026] (f) the processing of heat-treated and optionally dried biomass into a suitable solid as a fuel after, for example, compaction.
    [0027] [027] The invention also relates to a process for the treatment of biomass which comprises:
    [0028] [028] (a) the pre-treatment (mechanical) of wet biomass;
    [0029] [029] (b) the extraction of pre-treated biomass with liquid water at a temperature between room temperature and 160 ° C, especially between room temperature and 100 ° C;
    [0030] [030] (c) the mechanical dehydration of the extracted biomass for the production of a dehydrated biomass and an aqueous effluent;
    [0031] [031] (e) drying the dehydrated biomass;
    [0032] [032] (g) submitting the aqueous effluent to anaerobic fermentation.
    [0033] [033] The raw materials that can be treated with the process of the invention include a wide variety of biomasses: grass, hay, straw, leaves, bamboo, beet root, moss, shavings, garden waste; in short, all organic materials that are dry or wet, salted or leached, silage, half decomposed. Also residues from the food industry and the agrarian sector, for example, beer grains, potato skins, straw, anaerobic digesters can be used. The biggest gain is made for the wet biomass raw material that contains salt, such as ground grass and cane. The water content of the raw material can vary widely, for example, from 10% to 90%, in particular from 30 to 85% by weight, that is, a solids content from 15 to 70% by weight. Even wood can be used, but the advantages of the invention are less applicable because normally the wood has few salts and is dry.
    [0034] [034] Raw materials include volumes of biomass that are currently unused, left to decompose or are composted. Preferably, the biomass is a fibrous biomass derived from a plant material. The fibrous material can form an oilseed bagasse in the dehydration stage. The plant material can be originated, for example, from woody plants, herbaceous, agricultural residues and forest residues, as described above. The process of the invention is particularly useful for treating grasses, reeds and leaves.
    [0035] [035] Non-fibrous biomass such as mud, for example, the bottom of straw fermentation for the production of alcohols or digested for anaerobic digestion, can also be treated with the process of the invention, and may require the use of flocculating materials or adsorbents as an aid to biomass processing. Said flocculants include sludge dehydration polymers, preferably polymers that do not result in ash, that is, constructed only of carbon, oxygen and hydrogen. Most preferably, the polymer auxiliaries are based on biopolymers.
    [0036] [036] Before the heating steps of the process of the invention, the biomass can be pre-treated in step (a). Said pre-treatment can comprise the removal of non-biomass, such as sand, stones, plastic, etc., by sifting or fragmentation, cutting, perforation and / or sweeping, and the like. The pretreatment comprises especially a mechanical pretreatment that may involve the breakdown of the biomass cell structure. This is an important step to allow access to the cellular content of the biomass during the subsequent washing and heating treatments. The mechanical pretreatment preferably comprises trimming, grinding, crushing, or extrusion, using cutters, stone mills, ball mills, extruders, or the like. For non-fibrous materials, such as sludge, no extensive mechanical pretreatment is required.
    [0037] [037] The heating or extraction stage (b) serves to wash the biomass, especially for the extraction of water-soluble materials, such as salts and hydrophilic organic substances. Step (b) can be carried out in different modes. In a preferred embodiment, the heating step is carried out at temperatures of about 100 ° C or higher; a temperature above 160 ° is not desired, as this would lead to an excessive decomposition of plant constituents, which produces phenols, furfural, methanol and other unwanted by-products. Heating above 100 ° C is carried out under superatmospheric pressure, to ensure that water remains largely in the liquid phase, which allows water-soluble material, in particular salts, but also saccharides and others organic components derived from cellulose and hemicellulose materials are not subjected to undesired reactions, and can be extracted from biomass without substantial derivatization. Depending on the process temperature of step (b), a pressure between 1.1 and 15 bar, especially between 1.5 and 10 bar, is applied. The reactor can include a heat exchanger, in which the inlet and outlet flows exchange heat. The inlet flow is heated from room temperature to a level below the reaction temperature. The outflow is cooled from the reaction temperature to about 35 ° C, which is the preferred temperature for digestion in step (g). The reactor also includes a device to raise the temperature of the inlet flow to the desired level. Finally, the reactor allows a space where the solids remain for a desired period of time, from a few seconds to a few hours, preferably from 3 to 60 minutes, more preferably from 10 to 30 minutes.
    [0038] [038] In this pressurized embodiment of the heating step (b), the biomass preferably has a water content between 60 and 95% by weight, more preferably between 70 and 90% by weight. In other words, the dry matter content of the biomass material introduced in step (b) is preferably between 5 and 40% by weight, more preferably between 10 and 30% by weight.
    [0039] [039] As an alternative embodiment of step (b), the biomass is heated only moderately, to room temperature (arbitrarily chosen as 20 ° C) or higher, preferably 40 ° C or higher. A temperature above 100 ° C is not particularly advantageous in this mode, but can be chosen, as long as the system is closed and pressurized, in order to avoid excessive water evaporation. Heating and extraction in this embodiment can be carried out by contacting the biomass, preferably with a water content of 60 to 95% by weight, although initial levels of, for example, 40% or even 15% of water may be possible in several steps with an aqueous liquid, for example, by immersion or spraying, with the collection of the drained water and with the use of the drained water in the previous contact step, that is, in a countercurrent mode. In this way, maximum extraction efficiency is coupled with a minimal need for contact with water. The preferred temperature for this embodiment is between 40 and 100 ° C, and most preferred between 60 and 95 ° C.
    [0040] [040] Advantageously, the multiple phases are arranged in such a way that the quality of the extraction water increases with the progress of the phases, with relatively low quality water used in a first phase and relatively high quality water used in a later stage or the last stage. Here, "low quality" and "high quality" refer mainly to temperature and dissolved matter (solutes): the higher the temperature or the lower the level of solutes, the higher the quality. In a suitable embodiment, the eluate (extract) from a later stage of the multiple extraction stages (b) is used in a first stage, and the condensed steam with a relatively high temperature and a low level of solutes ("without salt") , in particular less than 100 ppm of solutes (salts), which results from the evaporation of water in step (e) is used as liquid water in a last phase of the extraction step (b). Likewise, the water that results from the dehydration of the biomass extracted in step (c) can be used in a last phase or in the penultimate phase of the extraction step (b).
    [0041] [041] The equipment suitable for this moderate temperature realization comprises multi-phase extraction units, or the like. A particularly useful example of equipment in this alternative is a belt press washer in which the biomass is transported horizontally in a mesh. The liquid water is sprayed evenly over the biomass from above. Below the mesh, a vacuum drains the liquid effluent. Spraying or diving (immersion) can be done only with clean water, and all effluents can be collected at one outlet. To use less fresh water, the effluent can be collected in separate sections in which the effluent from one section is sprayed in the previous section, thus creating an advantageous countercurrent washing.
    [0042] [042] In this embodiment, the material resulting from the pretreatment step (a), in particular from a cutter or an extruder, is fed to a belt press washer. The preferred dry solids content for entering a belt press washer or similar apparatus is between 15 and 70% by weight, more preferably between 20 and 50% by weight. The treatment in step (b) (for example, the belt press washer) can be done with between 2 and 8 times the amount of water for dry solids, preferably 3 to 6 times per wash cycle. This water includes the water already present in the incoming biomass. Multiple washes can be done with the corresponding largest amount of water, but preferably through the reuse of spent water from a downstream washing step in the previous step. Depending on the type of biomass used, between 10 and 40% by weight of the dry solids content are extracted, leaving between 60 and 90%, in particular between 65 and 80% of the dry solids yield of the solid fraction. Alternatively, based on the total flow (water and dry solids together), the weight ratio of liquid effluent input to biomass is preferably between 1.5 and 3.
    [0043] [043] After the heating and extraction step (b), the excess water is removed from the biomass by mechanical means. Preferably, the biomass is dehydrated in step (c) by pressing, for example, with the use of a piston press, or a screw press equipped with perforations to drain the water that is pressed out of the biomass. Other suitable equipment comprises a chamber filter press, a decanter or a pneumatic press. The pressures applied in step (c) can vary from 20 to 1000 bar, preferably from 40 to 800 bar, more preferably from 100 to 700 bar. The pressing temperature is not very critical, although it may be advantageous to use a temperature below 100 ° C, for example, between 60 and 100 ° C to facilitate handling. The equipment, time, pressure and temperature of step (c) are chosen to achieve substantial dehydration, for a residual water content of less than 50%, preferably 40% or less, more preferably 35% or less. Thus, the dehydrated biomass produced in step (c) preferably has a water content between 40 and 20% by weight, more preferably between 35 and 25% by weight. It is conceivable that the bagasse is rehydrated and then pressed repeatedly, in order to remove even more salts, but it is better to carry out an additional washing in the extraction phase (b), because there the biomass structure is more accessible.
    [0044] [044] The dehydrated biomass resulting from step (c) can then be heat treated, in order to partially decompose the resulting plant material, which includes cellulose and comparable material. This can be done in a relatively wet process, that is, with a water content between, say, 40 and 20% by weight, or in a relatively dry process, that is, with a water content below 20% by weight . Both process variants are within the scope of the present invention, and are referred to below as roasting. Both process variants can be carried out at temperatures above 160 ° C and in the substantial absence of oxygen, that is, without air being introduced in the process step. Alternatively, the dehydrated biomass can be dried directly, for example, by means of steam drying, or fed to a roasting unit in which it is heat treated at temperatures between 200 and 350 ° C, as described, for example, in WO 2007/078199.
    [0045] [045] In the optional step (d), the oilseed cake resulting from step (c) is heat treated. This treatment affects the structure of the biomass even more, so that characteristics comparable to those of roasted biomass are obtained. There is no substantial washing of the biomass and, therefore, the by-products formed as a result of the high temperature decomposition reactions, which are not digestible, remain trapped in the bagasse.
    [0046] [046] In the relatively wet roasting stage (d), the water content of the initial biomass can be the water content that results directly from the mechanical dehydration stage (c), that is, preferably from 20 to 40% by weight. The roasting temperature in this embodiment is between 160 and 250 ° C, preferably between 180 and 230 ° C, and more preferably between 190 and 220 ° C. The pressure is sufficient to keep the water in a liquid state, that is, typically between 10 and 50 bar, preferably between 15 and 25 bar. Conventional pressure vessels with the necessary inlets and outlets can be used for the wet (closed) roasting step, for example, in document NL1029909. At the end of step (d), the pressure is released so that the vapor evaporates. This steam can be used in other parts of the heating process, or it can be condensed to be used as extraction water in step (b). In addition, the residual heat that results from the heating step (d) can be used for heating. The organic components present in the steam end up in the effluent that goes to the digester. It is possible to release steam gradually or in the form of a steam explosion. The latter may result in further product breakdown.
    [0047] [047] The "wet" roasting step (d) is followed by a drying step (e) in which the water is largely removed by evaporation, preferably with the use of a steam explosion. If necessary, another drying step is used, which leads to a final dry matter content of 85 to 95% by weight.
    [0048] [048] In the relatively dry roasting step, the dehydrated biomass produced in step (c) is first dried to a water content between 20 and 5% by weight before being subjected to the heating step (d). Roasting is then carried out at conventional roasting temperatures, between 200 and 320 ° C, preferably between 230 and 300 ° C, or even at pyrolysis temperatures of 300 to 600 ° C, preferably from 320 to 500 ° C. The gas produced during roasting can escape and can still be treated, for example, by cooling and condensing the volatilized material (see, for example, WO 2005/056723 and NL 2005716).
    [0049] [049] Instead of the heating (roasting) step (d) described above, the dehydrated biomass resulting from step (c), for example, dehydrated to a water content of 20 to 60%, for example, about 50 %, can be dried in a more conventional manner, for example, with the use of steam drying with steam of, for example, 140 to 190 ° C. The spent steam from steam drying at a lower temperature, for example, between 105 and 120 ° C, can be reused by reheating, and partially condensed to be used as an extraction liquid in step (b), as described above. The dry solid from the drying step can still be dried, if desired, and / or further processed mechanically to result in a pelletized or otherwise compacted or molded powder as described below, to produce a solid that can be used as a solid fuel.
    [0050] [050] The result of the process of the invention is a low salt content. In the thermal conversion of biomass, salts are undesirable components. In particular, alkali metals (Na, K, etc.) and halogens (Cl, Br, etc.) can cause serious problems in combustion systems and also in gasification. Alkali metals can result in ash with low melting points, which results in slag and scale, as well as agglomeration of ash and bedding materials. Halides are a corrosion hazard. As used here, "salts" are defined as the sum of alkali metals and halides. Whenever "salt removal" is discussed, this means the removal of alkali metals and halides. Of these two elements, K and Cl are the most abundant in biomass, therefore, salts in biomass are well represented by (among others) potassium (K) and chlorine (Cl).
    [0051] [051] It should be noted that other elements of salt formation are also removed, for example, alkaline earth metals (Mg, Ca, etc.), although their removal rate may be lower than that of alkali metals and of halogens. The same applies to sulfate (SO4), phosphate (PO4), and transition metals (Fe, Zn, etc.) · Removing them from biomass is considered beneficial, but less urgent, because - at the levels typically found in biomass - they cause less problems to thermal conversion systems. Even silicon (Si) and aluminum (Al) are partially removed by the present process. These elements are present in the biomass as oxides. They can be part of biomass, but also as clay or sand. In thermal conversion systems, they are mostly inert, and are not considered problematic at the levels normally found in biomass.
    [0052] [052] Just as an indication, the following examples can be given for the rate of removal of elements of formation of grass salts in the present process:
    [0053] [053] - Na, K, Cl and Br:> 95%, especially> 98%
    [0054] [054] - Mg: about 85%
    [0055] [055] - Ca: about 60%
    [0056] [056] - P and S: about 70% (as phosphate, sulfate and several other components)
    [0057] [057] - Zn: about 20%
    [0058] [058] - Fe: about 5%
    [0059] [059] - Si: about 15%
    [0060] [060] - Al: <5%.
    [0061] [061] The standards for biomass fuels include maximum levels of chlorine (Cl). According to DINplus and ENplus-Al standards widely used for clean biomass fuel pellets, the maximum level of Cl is 200 mg / kg (dry basis). The other ENplus standards (A2 and B), the Swedish industrial standard SS187120 and the US PIF standards define 300 mg / kg (dry basis) as the limit. European industry standards for co-incineration pellets currently (2012) in development - have maximum levels of 300, 500 or 1000 mg / kg (dry basis) of three pellet qualities. The standards do not yet include maximum potassium levels. This is due to the fact that they are based on wood as a raw material that has a low level of potassium, which does not cause problems. Since the standards will be developed for fuels from agricultural waste with high levels of potassium in the raw material, a limit for potassium can be expected. For the time being, a maximum potassium content of 500 mg / kg (dry basis) can be considered as a target for good fuel quality. These and other requirements are more stringent and can be achieved using the process of the invention. In fact, it is the melting behavior of fuel residues that must be controlled, and this behavior depends on several elements that include silicon and its interaction, rather than the quantities of elements such as potassium. However, the levels of alkali metals and halogens have been found to be a good criterion for acceptable fuel characteristics.
    [0062] [062] This means that, for the present process, a target for the salts defined as the sum of the K and Cl content can be a maximum of 700 mg / kg (dry basis) for the highest quality of the fuel. Second-grade fuels can contain up to 1500 mg / kg (dry basis). A third fuel quality may have a limit of 3,000 mg / kg (dry basis).
    [0063] [063] The present process is capable of producing material derived from biomass with relatively high initial salt contents, reaching high standards for fuels derived from biomass in terms of chlorine, potassium and other elements of salt formation. High temperature washing is not necessary to remove this salt.
    [0064] [064] Thus, in the present process, the content of alkali metals and / or halogens in the biomass is reduced by at least 80% by weight, preferably by at least 90% by weight, on a dry weight basis, between step (a ) and step (d), while a reduction of at least 95% by weight, or even at least 98% by weight is possible and most preferred. In absolute terms, the treated biomass resulting from step (d) has a chloride content of less than 500 mg / kg, and / or a chloride content of less than 500 mg / kg, on a dry weight basis.
    [0065] [065] After the heating (extraction) and drying steps of the present process, it may be advantageous to compact the heated dehydrated biomass, in order to produce a solid material suitable for use as fuel in one step (f). The solid material can be used directly as a fuel, for example, in the form of down or bagasse with approximately 75% dry matter content, for example, in fluidized bed combustion or in a grid feeder. In many cases, another post-treatment is desired, which includes (among others):
    [0066] [066] i) Drying: necessary for almost all cases where the material is not used directly. The biomass treated by the present process is significantly more resistant to biological degradation, but it is still possible for microorganisms to feed on it.
    [0067] [067] ii) Grinding: the material is transformed into a powder that can be used in combustion or pulverized fuel gasification (PF), for example, co-incineration in power plants.
    [0068] [068] iii) Densification: the material is densified, for example, by compression to pellets or briquettes, which improves logistics. Generally, no binder is necessary, since the heat treatment is such that the lignin, often present in biomass, retains its binding capabilities, although the use of a binder is also possible.
    [0069] [069] Since the temperature in step (d) is typically low enough to prevent the lignin from decomposing significantly, no added binders are needed for densification, and the pellets become water-repellent. Thermal drying in the post-treatment is an attractive possibility, because it prevents the formation of a liquid effluent. Indigestible or toxic by-products are solid and do not go to the digester. The amount of heat for drying is relatively small. A bagasse with 65% dry matter can have 75% dry matter content after the steam explosion, which is close to 85 to 90% of what is necessary for an effective pelletization.
    [0070] [070] Using biogas combustion energy, the process of the invention can be carried out without heat input. By choosing the correct process configuration and equipment, it is possible to recover the heat from both steps (b) and (d). When a gas engine is used, energy can also be generated for the operation of the equipment, while sufficient residual heat is still available. However, there are a number of ways to integrate heat treatment with other processes. The combination with wastewater treatment is of particular interest.
    [0071] [071] When, after mechanical dehydration in step (c), the water remains in the solids, this leads to the entry of additional heat to step (d). However, this additional heat is released after step (d) in the form of steam which is fully used for heating or extraction in the rest of the process. Thus, heating the additional moisture need not be a loss. In addition, water is useful in step (d) in different ways, for example, as a lubricant.
    [0072] [072] Combinations of various forms of post-treatment are possible, in no particular order. A preferred combination would be drying from 10 to 15% of the moisture, followed by pelletizing. The post-treatment can be done on site or in a different place, for example, grinding the pellets of the power plant. The exact choice in relation to post-treatment depends on local conditions and the user-defined specifications of the fuel product. These local conditions may include, but are not limited to, logistics (transport and storage), legislation, economics and existing facilities.
    [0073] [073] In a step (g), the aqueous effluent produced in step (c) is subjected to an anaerobic treatment. The effluent is rich in dissolved materials, such as salts and organic materials, which includes the products of the decomposition of hemicellulose, and is digestible, because in the previous step (b), the temperature remained below the level at which the undesirable by-products that are formed are not anaerobically digestible or have a negative influence on digestion (toxicity). In particular, the temperature was kept below 160 ° C. The anaerobic treatment of step (g) results in the production of biogas, through the action of hydrolytic, acidogenic and acetogenic bacteria and methanogenic arteries. Biogas can be used for heating steps (b) and / or (d), or for the production of electric energy, and / or in the production of bio-alcohols.
    [0074] [074] Anaerobic treatment can be carried out in a conventional reactor or, for example, in an Upflow Anaerobic Sludge Blanket (UASB) reactor, using an anaerobic culture of commercial anaerobic digestion, or fermentation as a starting sludge. The temperatures used in the anaerobic reactor are typical for mesophilic microorganisms, that is, between 15 and 55 ° C, preferably between 30 and 45 ° C. The reactor has a means for collecting biogas at the top that can be used for heating purposes or for generating electricity. If necessary, anaerobic treatment can be followed by an aerobic post-treatment. However, said post-treatment can be dispensed with for most types of biomass and for most effluent quality requirements. The biogas from the digester can be used on site to generate heat and, possibly, energy. Biogas contains enough energy to provide the energy for the process to function.
    [0075] [075] Alternatively, anaerobic fermentation can be carried out to convert the decomposition products into ethanol or other alcohols, with the use of yeasts capable of converting sugars (for example, cellulose glucose) into alcohols and carbon dioxide. Yeast may have been advantageously designed to be able to convert other sugars (arabinose, xylose) from hemicelluloses to alcohols, as well, for example, by introducing xylose isomerase and / or arabinose converting enzymes into yeast (see , for example, WO 03/062430, WO 2008/041840, WO 2010/074577).
    [0076] [076] The conditions in the heating and extraction stage (b) can be chosen so that almost all the potassium is removed, but the volume of nitrogen and phosphate remains in the solid phase and does not become part of the effluent. This can be done by selecting a relatively low washing temperature, for example, below 100 ° C, in particular between 40 and 80 ° C, or by adjusting the pH. This can be advantageous when the effluent is discharged into surface water or on the ground, where K and the carbonaceous compound are acceptable, but the presence of N and P is undesirable. An example of this situation is the use of invasive plant species as raw material and the return of the effluent to the plant biotope, in which renewed growth is not desired. DESCRIPTION OF THE DRAWING
    [0077] [077] The attached figure shows an embodiment of the process of the invention with the use of multi-phase extraction and anaerobic treatment of the extract.
    [0078] [078] With reference to the Figure, the biomass is introduced through line 1 in a mechanical pretreatment device 2, in particular a cutter. The cut material is fed through line 3 to the extraction device 4. The device 4 comprises several extraction compartments 5, 6, 7 and 8. Other compartments can be added, if desired. The biomass is transported through the extraction device using conveyor belts 9 and 10. Instead of them, there may be a single belt or more than two belts. The extraction liquid is sprayed on the biomass using the sprayers 22, 23, 24, 25 and 26, while any other number of sprayers can be used, if desired. The spent liquid (extract) is discarded from the extraction compartments 5, 6, 7 and 8 through lines 15, 16, 17 and 18, respectively.
    [0079] [079] The extracts are partially fed to an anaerobic reactor 33 through a heat exchanger 31 and feed line 32 and partially reused as extraction liquids 21. Anaerobic reactor 33 can be a UASB reactor inoculated with the appropriate anaerobic bacteria . Biogas is collected through line 35, and the liquid effluent that possibly contains the alcohols produced by anaerobic bacteria is discharged through line 34.
    [0080] [080] In the figure, the first extract 15 is totally fed to the anaerobic treatment, while the last extracts 17 and 18 are totally reused as extraction liquid. The intermediate extract 16 is divided between the feed of the anaerobic reactor and the extraction liquid through the distributor 12 and lines 13 and 14, respectively. However, other divisions may also be suitable. Fresh water from an external source can be used as a supplementary extraction liquid fed through line 11, and after combining with a partial extract from 13 to line 19 and extracts 17 and 18, the combined extraction water is fed sprays 22-25 through pump 20 and line 21. As an alternative, it is possible that extract 18 is fed to sprayer 26, and / or that extracts 17 and 18 are fed only to sprays 23-25, with sprayer 22 fed by extract 16.
    [0081] [081] The solid that was extracted in the extraction device 4 is dehydrated by the press 41, and the resulting water is collected in compartment 8. The dehydrated biomass is transported through line 42 to the steam dryer 43. Steam is introduced through the line 46 and spent steam is discharged through 45, and can be reused after reheating through 44, and is partially fed to condenser 49 through line 48. The dry biomass is discarded from dryer 43 through transmission medium 47, and then processed. The condensed steam in condenser 49 passes through line 50, to be used as an extraction liquid, for example, through the sprayer 26. EXAMPLES
    [0082] [082] In all the examples below, grass was used as a raw material in the form of hay. EXAMPLE 1: PRE-TREATMENT IN THE EXTRUDER
    [0083] [083] The hay (dry matter content of about 30%) was extruded in an extruder with a capacity of 150 kg of hay per hour. The result was the extruded material, in which the cell structure was broken due to stress in the extruder. The hay was fed at room temperature, since the extruded hay is as hot as 100 ° C. To illustrate the extrusion effect, the extruded hay can be submerged in water and does not float, unlike the raw material. The chloride content was 11,000 mg / kg, and the potassium content was 15,000 mg / kg, both on a dry basis. EXAMPLE 2: WASHING AT 60 ° C
    [0084] [084] The extruded hay of Example 1 was washed in an industrial washing machine. A quantity of 5 kg of extruded hay was washed with approximately 32 liters of water. The hay was placed in a mesh bag with 100 μm holes. The water temperature was maintained at 60 ° C, and the duration of the wash was 1 hour. At the end of the wash cycle, the hay was centrifuged, so that the free water was removed. The driving force in the centrifuge is equivalent to using vacuum in a belt press washer. The result of washing was about 11 kg of wet hay with a dry matter content of 33% by weight. About 25.5 liters of pre-wash liquid were produced, with a solids content of 4.9%. As a result, about 25% of the dry mass of the extruded hay is present in the prewash effluent, partly in dissolved form, partly as fine suspended particles. The washed hay has a dry matter content of 32% by weight. The washed hay has a chloride content of 3,500 mg / kg, and a potassium content of 590 mg / kg, both on a dry basis. In comparison to the original material, this is a 68% removal of chloride and a 61% removal of potassium. EXAMPLE 3: WASHING AT 60 AND 160 ° C FOLLOWED BY PRESSING
    [0085] [085] An amount of hay washed from Example 2 was subjected to another wash at 160 ° C. Fresh water was added to 4.5 kg of washed hay (1.5 kg of dry matter), so that the hay was submerged in about 14 liters of water. The washing was carried out in a 20 liter autoclave. The contents were heated to a temperature of 160 ° C and kept in this condition for 10 minutes, then the autoclave was cooled. The effect is that about 20% of the solids passed into the solution, forming a fluid paste with 92% by weight of moisture. A batch of about 10 liters of slurry was pressed into a bagasse in a horizontal uni-axial press at 533 bar, so that almost all of the liquid was expelled. The resulting bagasse had a dry matter content of about 65% by weight. The bagasse had a chloride content of 350 mg / kg, and a potassium content of 750 mg / kg, both on a dry basis. In comparison to the original material, this is a 97% removal of chloride and a 95% removal of potassium. EXAMPLE 4: PRE-WASH REPEATED AT 90 ° C FOLLOWED BY PRESSING
    [0086] [086] The extruded hay of Example 1 was also washed at 90 ° C. In three cycles, a quantity of 5.0 kg of hay was washed at 90 ° C in three cycles of 1 hour, 15 minutes and 15 minutes, respectively, in which, after each washing cycle, the effluent was removed by means of centrifugation. . After the first cycle, the Cl content was 3400 mg / kg, and after the second and third cycles it was still reduced to 910 and 350 mg / kg, respectively. The potassium content was 5500, 2200 and 1000 mg / kg after each cycle, respectively. After centrifugation, the hay has a dry matter content of 31% by weight, but it can be pressed into a bagasse with a dry matter content of 59% by weight. This implies another reduction in the chlorine content to 110 mg / kg, and the potassium content to 310 mg / kg. In comparison to the original material, this is a 99% removal of chloride and a 98% removal of potassium. The entire content of Cl and K is on a dry basis. EXAMPLE 5: PRE-WASH REPEATED AT 90 ° C, 160 ° C FOLLOWED BY PRESSING
    [0087] [087] A quantity of washed hay from Example 4 (without pressing) was subjected to another wash at 160 ° C, following the same procedure as in Example 3. The resulting bagasse had a dry matter content of 53% by weight, a content chloride content of 120 mg / kg and a potassium content of 200 mg / kg, both on a dry basis. In comparison to the original material, this is a 99% chloride removal and a 99% potassium removal. The entire content of Cl and K is on a dry basis. EXAMPLE 6: HEAT TREATMENT OF HAY WASHED AT 190 ° C WITHOUT DEHYDRATION
    [0088] [088] The washed hay from Example 4 was subjected to wet roasting conditions. The input material had a dry matter content of 59%, a chlorine content of 110 mg / kg, and a potassium content of 310 mg / kg. A quantity of 50 g was placed in a 100 ml autoclave and heated at 190 ° C for 30 minutes. After heat treatment, the autoclave was cooled to 100 ° C, and then opened to allow evaporation until the material reached room temperature. The outlet material had a dry matter content of 73%, a chlorine content of 120 mg / kg, and a potassium content of 330 mg / kg. The resulting material lost about 5% by weight of dry matter due to the formation of CO2 and small amounts of other volatile components.
    [0089] [089] For comparison purposes, hay was washed at 60 ° C, hydrothermal treatment in a single step at 190 ° C in a large amount of water, and subjected to mechanical dehydration of the resulting slurry in a press. The final product of this material had a dry matter content of 64% by weight, a chloride content of 130 mg / kg and a potassium content of 330 mg / kg. Both resulting materials were practically identical, not only in Cl and K content, but also in grinding capacity and density when compressed. EXAMPLE 7: GRINDING CAPACITY
    [0090] [090] Two marcs were prepared. A bagasse was made by washing, heat treatment and pressing, following the procedures described in Example 2. The other bagasse was prepared in exactly the same way, but by means of heat treatment at 190 ° C. Both bagasse was ground in a laboratory scale Retch cutter using a 500 micron screen. This size results in a powder with a size distribution suitable for combustion of pulverized fuel. The specific energy consumption for grinding bagasse made from heat-treated material at 160 and 190 ° C was 476 and 221 kJ / kg, respectively. For comparison, a third milling was done using extruded hay, prepared as described in Example 4 and dried. The specific energy consumption of this material was 561 kJ / kg. It was concluded that heat treatment at 160 ° C results in about 15% less energy needed to spray hay, but that another heat treatment at 190 ° C has a substantial impact and reduces the lower energy requirements for fence grinding 60%. EXAMPLE 8: DIGESTION
    [0091] [091] The effluents from Example 2 and a mixture of effluents from Example 2 and Example 3 were tested for anaerobic digestibility in a laboratory-scale UASB reactor inoculated with bacteria from a regular wastewater treatment plant. There was no significant difference in the biogas yield per unit of organic matter between the two tests. The efficiency of converting organic material into biogas based on components containing carbon in the effluent ranged between 80 and 90%. The high conversion efficiency indicates that the water-soluble part of the original biomass is almost completely transformed into an energy carrier. Only a small part of the original energy content of biomass is lost.
    [0092] [092] When the effluent from Example 2 was mixed with the effluent from the heat treatment similar to that described in Example 3, but carried out at 190 ° C, a difference was observed. The conversion efficiency based on the carbon-containing components in the effluent decreased from 80 to 90% to 70 to 80%. No effluent toxicity was observed in any of the digestion experiments. Similar results were found for the anaerobic digestion of effluents from the treatment of other biomasses, such as fresh grass, beet leaves and cane. By increasing the treatment temperature from 150 ° C to 230 ° C, the efficiency of converting organic matter in the effluent to biogas under anaerobic conditions decreased from 80 to 90% to 50 to 60%.
    权利要求:
    Claims (21)
    [0001]
    PROCESS FOR TREATING BIOMASS, characterized by understanding: (a) the mechanical pre-treatment of wet biomass; (b) subsequently, washing and extracting the pre-treated biomass with liquid water at a temperature between room temperature and 160 ° C; (c) the mechanical dehydration of the extracted biomass obtained in step (b) for the production of a dehydrated biomass and an aqueous effluent; (d) optionally, heating the dehydrated biomass to a temperature above 160 ° C; (e) drying the dehydrated biomass; (f) optionally, the compaction of dry biomass for the production of a solid material; (g) submitting the aqueous effluent to anaerobic treatment.
    [0002]
    PROCESS according to claim 1, characterized in that step (e) comprises evaporating the water, preferably comprising steam drying.
    [0003]
    PROCESS, according to claim 2, characterized in that, in one step (h), the steam resulting from the evaporation of water in step (e) is condensed, which results in water without salt and used as liquid water in step (b) ).
    [0004]
    PROCESS, according to claim 3, characterized in that, in step (b), the biomass is first extracted with water not derived from step (h) and then with water derived from step (h).
    [0005]
    PROCESS according to any one of claims 1 to 4, characterized in that the dehydrated biomass produced in step (c) and submitted to step (d) or step (e) has a water content between 40 and 20% by weight.
    [0006]
    PROCESS according to any one of claims 1 to 5, characterized in that, in the heating step (d), the dehydrated biomass is heated from 180 to 250 ° C, preferably from 190 to 220 ° C, preferably at a pressure between 15 and 25 bar.
    [0007]
    PROCESS according to either of claims 5 or 6, characterized in that the heated dehydrated biomass is dried in step (e) at a dry matter content of 85 to 95% by weight.
    [0008]
    PROCESS according to any one of claims 1 to 4, characterized in that the dehydrated biomass produced in step (c) is still dried to a water content between 20 and 5% by weight before being subjected to the heating step (d) and be heated in step (d) to a temperature between 250 and 320 ° C.
    [0009]
    PROCESS according to any one of claims 1 to 10, characterized in that the biomass is a fibrous biomass, preferably selected from woody, herbaceous, agricultural residues and forest residues.
    [0010]
    PROCESS, according to claim 9, characterized in that the biomass comprises grasses, reeds and / or leaves.
    [0011]
    PROCESS, according to claim 1, characterized by the pre-treatment (a) comprising extrusion and / or grinding and / or cutting.
    [0012]
    PROCESS according to any one of claims 1 to 11, characterized in that, in step (b), the biomass has a water content between 60 and 95% by weight, preferably between 70 and 90% by weight.
    [0013]
    PROCESS according to any one of claims 1 to 12, characterized in that, in step (b), the biomass is heated from 100 to 160 ° C at a pressure between 1.1 and 15 bar, especially between 1.5 and 10 bar.
    [0014]
    PROCESS according to any one of claims 1 to 13, in particular claims 3 or 4, characterized in that, in step (b), the biomass is heated between 40 and 100 ° C, and preferably comprises the repeated contact between the biomass and water and drainage water from biomass, in a counter-current mode.
    [0015]
    PROCESS according to any one of claims 1 to 14, characterized in that the biomass is dehydrated in step (c) by pressing.
    [0016]
    PROCESS according to claim 15, characterized in that, in step (c), a pressure between 50 and 1000 bar, preferably between 100 and 700 bar, is applied.
    [0017]
    PROCESS according to any one of claims 1 to 16, characterized in that, between step (a) and step (d), the content of alkali metals and / or halogens in the biomass is reduced by at least 90% by weight, preferably at least 95% by weight, on a dry weight basis.
    [0018]
    PROCESS according to any one of claims 1 to 17, characterized by the treated biomass resulting from step (d) having a chloride content of less than 500 mg / kg, and / or a chloride content of less than 500 mg / kg , on a dry weight basis.
    [0019]
    PROCESS according to any one of claims 1 to 18, characterized in that, in step (f), after step (d) or (e), the heated dehydrated biomass is compacted to produce a solid material suitable for use as fuel.
    [0020]
    PROCESS according to any one of claims 1 to 19, characterized in that the anaerobic treatment of step (g) results in the production of biogas that can be used for heating steps (b) and / or (d), or for the production electricity and / or bioalcohol production.
    [0021]
    PROCESS according to any one of claims 1 to 20, characterized by the residual heat or the steam resulting from the heating step (d), (e) or (f) being used for heating in other steps, in particular for the heating step (b).
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    同族专利:
    公开号 | 公开日
    EP2841385A1|2015-03-04|
    NL2008682C2|2013-10-31|
    WO2013162355A1|2013-10-31|
    BR112014026412A2|2017-06-27|
    EP2841385B1|2017-02-22|
    MY170883A|2019-09-11|
    DK2841385T3|2017-04-24|
    PL2841385T3|2017-08-31|
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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]|
    2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-11-24| 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 18/04/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    NL2008682|2012-04-23|
    NL2008682A|NL2008682C2|2012-04-23|2012-04-23|Wet biomass treatment.|
    PCT/NL2013/050281|WO2013162355A1|2012-04-23|2013-04-18|Wet biomass treatment|
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