Hydrothermal treatment of biomass

Abstract

The present invention relates to an improved method for the treatment of biomass, comprising the steps of: (a) exposing biomass to hydrothermal treatment in a hydrothermal reactor by immersing the biomass in a treatment liquid, wherein the waste liquid discharged from step (b) or (c) is used as the treatment liquid; (b) discharging the liquid from the reactor through a liquid outlet to obtain a solution and simultaneously or subsequently introducing another wash liquid into the reactor, wherein the wash liquid is preheated to at least 30°C below the operating temperature of step (a) before being introduced into the reactor; and (c) discharging the reactor to obtain washed hydrothermally treated biomass and waste liquid, wherein at least one of steps (a) and (b) is carried out at a temperature in the range of 100 to 250°C.

Description

FIELD OF THEINVENTION

[0001]

[0001] The present invention relates to a method for treating biomass, in particular fibrous biomass, to remove salts and other unwanted components, and to the solid fuel obtained by said method.

[0002]

[0002] Torrefaction is a useful process for converting cheap, low-value biomass, such as agricultural waste, into premium fuels. In the torrefaction process, biomass is heated to moderately high temperatures, typically 200-320°C, without added oxygen, resulting in the removal of most of the residual water and gentle decomposition of the biomass elements to produce a gaseous fraction, so-called "tall gas," which contains water vapor, carbon dioxide, small organic molecules, and compressible solid products that can be processed into solid fuels, for example as a coal substitute.

[0003]

[0003] As an example, WO 2005 / 056723 describes a torrefaction process, in which biomass is torrefied at 200-320°C and the gases produced by the torrefaction are cooled so as to condense impurities and combustible materials. Dutch patent 1029909 describes a pressure torrefaction process, in which water remains in liquid state during the thermal treatment. This hydrothermal treatment causes torrefaction of the biomass and liberation of salts, which are dissolved in water and can be removed by mechanical means. However, if the hydrothermal treatment is carried out in a single step with subsequent dehydration, the temperature must be relatively high to produce the desired fuel properties, for example 190°C for grass, or even 210°C for reeds and straw. At this temperature, water-soluble phenols and other undesired by-products are formed from the decomposition. The expressed waste liquid then contains components that are not easily digested and can even be toxic. EP 2206688 describes a hydrothermal process for carbonizing biomass at 190-230°C and 10-30 bar for 1-5 hours, followed by separation of the resulting solid-liquid by a wet oxidation treatment of the liquid. The aim of the thermal treatment is the chemical conversion of the biomass.

[0004]

[0004] The applicant has developed a hydrothermal torrefaction process, as described in WO 2013 / 162355, which is called Torwash™. Torwash allows the torrefaction of biomass with high salinity, as the salts are effectively removed during Torwash. Such biomass could not be effectively treated by conventional torrefaction methods. Torwash as described in WO 2013 / 162355 requires the use of fresh water in a first step (pre-wash below 160°C) and a later step (hydrothermal treatment above 160°C). WO 2019 / 059768 describes a method comprising a torrefaction step, in which a mixture of biomass and POME is heated at a temperature and high pressure between 100 and 400°C, followed by a post-wash step. The pressure during torrefaction can typically be in the range of 4 to 50 bar. The wash step may be carried out at a temperature in the range of 10 to 50°C at a pressure in the range of 1 to 1.5 bar. Washing may be carried out in countercurrent mode to minimize the amount of water required.

[0005]

[0005] WO 2015 / 091861 describes a method for reducing unwanted inorganic components in cellulosic biomass by washing the biomass with water at a temperature of 120-150°C at a pressure high enough to maintain the water in the liquid phase. The solid cellulosic biomass material can be washed in a countercurrent manner. The cellulosic biomass material may contain lignin. It is further explained that the washed solid biomass may be subsequently dried and / or torrefied. WO 2014 / 122163 describes the problem of heat recovery in thermal biomass processing and proposes using pressure loss to generate steam, which is then used to release its heat to a heat exchanger by condensation. In particular, WO 2014 / 122163 describes a method for preparing fuel from biomass by subjecting the biomass to a thermal treatment at a temperature of 150-300°C in a reactor pressurized with steam and air, the final pressure of the thermal treatment being released. At least a portion of the pressure in the reactor is suddenly released, thereby releasing the reaction gases from the reactor to a pressure release tank. The gases then flow to a heat exchanger where they are condensed and release their heat. Summary of the Invention

[0006]

[0006] The inventors have surprisingly found that the hydrothermal treatment (Torwash process) can be efficiently combined with the post-washing step under the same conditions, i.e., high temperature and pressure, thereby improving the efficiency of the washing of the biomass. High removal rates of potassium and chlorides can be achieved and the resulting solids meet the requirements of fuel pellets in terms of ash content and heating value / calorie value. Furthermore, the lignin can be largely removed from the biomass. Another advantage is that the washing effluent of the post-washing step can be recycled and reused in the hydrothermal treatment step, and the effluent of the hydrothermal treatment step is removed at high temperature so that it can transfer its latent heat to the incoming liquid water in the heat exchanger, which makes the whole process more energy efficient.

[0007] The present invention therefore relates to a method for the treatment of biomass, comprising the steps of: (a) subjecting biomass to hydrothermal treatment in a hydrothermal reactor by immersing the biomass in a treatment liquid, wherein the waste liquid discharged from step (b) or (c) is used as the treatment liquid; (b) discharging said liquid from the reactor through a liquid outlet to obtain a solution, and simultaneously or subsequently introducing another wash liquid into the reactor, the wash liquid being preheated to at least 30° C. below the operating temperature of step (a) before being introduced into the reactor; (c) discharging the reactor to obtain a washed hydrothermally treated biomass and a waste liquor. wherein at least one of steps (a) and (b) is carried out at a temperature in the range of 100 to 250° C.

[0008]

[0008] The invention further relates to a system for carrying out the method according to the invention and to a solid fuel obtainable by the method according to the invention, where the solid fuel corresponds to or can be obtained from washed hydrothermally treated biomass. [List of preferred embodiments] 1. A method for the treatment of biomass, comprising: (a) subjecting biomass to hydrothermal treatment in a hydrothermal reactor by immersing the biomass in a treatment liquid, wherein the waste liquid discharged from step (b) or (c) is used as the treatment liquid; (b) discharging said liquid from the reactor through a liquid outlet to obtain a solution, and simultaneously or subsequently introducing another wash liquid into the reactor, the wash liquid being preheated to at least 30° C. below the operating temperature of step (a) before being introduced into the reactor; (c) discharging the reactor to obtain a washed hydrothermally treated biomass and a waste liquor. wherein at least one of steps (a) and (b) is carried out at a temperature in the range of 100 to 250°C. 2. Step (b) (b1) a first washing step, comprising introducing a first washing liquid into the reactor and simultaneously and / or subsequently discharging the first washing liquid from the reactor via a liquid outlet to obtain a solution; (b2) optionally, one or more intermediate wash steps, in which further wash liquid is introduced into the reactor and simultaneously discharged from the reactor via a liquid outlet to obtain intermediate wash waste liquid; (b3) a final wash step, in which a final wash liquid is introduced into the reactor and simultaneously discharged from the reactor through a liquid outlet to obtain a final wash waste liquid; 2. The method of embodiment 1, wherein each washing liquid is preheated to the operating temperature of step (a) before being introduced into the reactor. 3. The method of embodiment 2, wherein step (b2) comprises 0 to 10 intermediate washing steps. 4. The method according to embodiment 2 or 3, carried out in a hydrothermal treatment plant, in which at least two hydrothermal reactors run the process in parallel, and one or more of the intermediate wash effluent and the final wash effluent from the first reactor are used as wash effluent in one or more of the first wash step or intermediate wash steps in the second reactor, preferably with the temperature of the wash effluent kept above 150°C. 5. The method according to any one of the preceding embodiments, wherein the waste liquid discharged from step (c) is used as the treatment liquid in step (a). 6. The method according to any one of the preceding embodiments, wherein in step (c) the washed biomass after discharge is subjected to steam explosion or controlled pressure release by reducing the pressure. 7. The method of any one of the preceding embodiments, wherein the temperature of the effluent from step (c), typically in the form of steam, is used to heat the treatment liquid prior to step (a), preferably in a heat exchanger or by direct injection into the treatment liquid. 8. The method according to any one of the preceding embodiments, wherein the liquid to solid (L / S) ratio during the treatment in step (a) is in the range of 2-25, preferably in the range of 15-20. 9. The method of any one of embodiments 1-8, wherein the biomass comprises fibrous lignocellulosic biomass of woody or herbaceous origin, i.e., hardwood, softwood, and wood including wood obtained from pruning or chopping wood, straw, bamboo, or mixtures thereof, preferably the biomass is a fibrous biomass selected from sugarcane harvest residue (SHR), empty fruit bunch (EFB), discarded fresh fruit bunch (FFB), mesocarp, coconut fiber, and pericarp. 10. The method of any one of the preceding embodiments, further comprising treating the washed hydrothermally treated biomass into solid fuel pellets, preferably by one or more of dewatering, drying, and pelletizing. 11. The method of any one of the preceding embodiments, wherein the solution obtained in step (a) is used to preheat the wash liquid in step (b), preferably in step (b3), preferably in a heat exchanger, and / or the solution obtained in step (a) is kept at a temperature above 140°C until it is cooled to below 100°C in a lignin collection vessel, causing the lignin to precipitate from the solution. 12. A solid biomass-derived fuel obtainable by the method according to any one of embodiments 1 to 11. 13. A solution obtainable by the method according to any one of embodiments 1 to 12, in particular by step (b1). 14. An installation for the hydrothermal treatment of biomass comprising at least two hydrothermal reactors, a reactor sequence of (a) a first hydrothermal reactor and (b) a second hydrothermal reactor, All reactors operated in parallel (1) a reactor interior for containing an aqueous biomass mixture; (2) an inlet for receiving biomass; (3) an inlet for receiving a treatment or cleaning liquid; (4) heating means, preferably in the form of an inlet for receiving steam; (5) an outlet for discharging a solution or waste liquid; (6) an outlet for discharging the torrefied biomass; (7) Outlet for releasing process gas Equipped with The installation, wherein the outlet (5) of reactor (a) is fluidly connected to the inlet (3) of reactor (b) and the outlet (5) of the last reactor in the sequence is fluidly connected to the inlet (3) of reactor (a). 15. The installation according to embodiment 14, wherein the outlet (5) is provided with a valve capable of closing the fluid connection with the inlet (3) and opening the fluid connection with the lignin collecting vessel.

[0009]

[0009] The present invention relates to a method for the treatment of biomass and to a system (reactor) for carrying out the treatment. Everything defined herein for the method according to the invention applies equally to the system according to the invention and vice versa.

[0010] method In a first aspect, the present invention provides a method for the treatment of biomass, comprising the steps of: (a) subjecting biomass to hydrothermal treatment in a hydrothermal reactor by immersing the biomass in a treatment liquid, wherein the waste liquid discharged from step (b) or (c) is used as the treatment liquid; (b) discharging said liquid from the reactor through a liquid outlet to obtain a solution, and simultaneously or subsequently introducing into the reactor a separate wash liquid, the wash liquid being preheated to at least 10° C. below the operating temperature of step (a) before being introduced into the reactor; (c) discharging the reactor to obtain a washed hydrothermally treated biomass and a waste liquor. wherein at least one of steps (a) and (b) is carried out at a temperature in the range of 100 to 250° C.

[0011]

[0011] In one embodiment, step (b) is carried out directly after step (a), without substantially modifying the torrefied biomass. In one embodiment, step (c) is carried out directly after step (b). The method can also be described as directed to the production of a solid fuel, which is obtained in step (c) as a washed hydrothermally treated biomass material, optionally after further washing and processing steps as defined below. The inventors have found that the solid fuel obtained by the method according to the invention can be more easily dewatered by mechanical pressing, and as a result, the product of the conventional drying torrefaction process can be more easily pelletized. The solid fuel obtained by the method according to the invention also contains non-soluble or non-leachable salts, which improve its suitability as a solid fuel, resulting in less fouling of the furnace.

[0012] The present invention further relates to a solid fuel obtainable by the method according to the invention. The solid fuel according to the invention is preferably characterized in that its total ash content comprises a high level of silicates and a low level of halides and alkali metals compared to untreated biomass. The solid fuel according to the invention is typically in the form of pellets.

[0013] The present invention further relates to an extract obtainable by the process according to the invention, in particular the effluent of step (b1). The extract obtained from the leaching with water at high temperature according to the invention contains organic and inorganic components which are poorly soluble below 100°C, but which are readily soluble in water at the process temperatures defined below, preferably in the range of 150-250°C. This extract is also referred to as a solution in the context of the present invention. The extract according to the invention has improved compatibility with digestion and generation of beneficial compounds.

[0014]

[0014] While any type of biomass feedstock could be used, in one embodiment the method is carried out with biomass that would benefit from Torwash over standard (dry) torrefaction, including biomass with high salt content, such as high potassium and / or chloride content. The benefits are greatest when the biomass is fibrous in nature and requires substantial amounts of water for removal of dissolution of salts. Thus, in a preferred embodiment, the biomass is a fibrous lignocellulosic biomass of woody or herbaceous origin. This biomass may be wood, including hardwoods, softwoods, and wood obtained from pruning or chopping trees. Biomass of herbaceous origin may include grass, straw, hay, straw, leaves, bamboo, sugar beet heads, moss, grass clippings, yard waste, residues from the food industry (e.g., sugarcane harvest residue (SHR), empty fruit bunches (EFB), discarded fresh fruit bunches (FFB), coconut fiber, mesocarp, olive kernels, rice husks). The method is particularly advantageous for fibrous biomass, as post-cleaning of the torrefied biomass provides the most optimal results. In a particularly preferred embodiment, the biomass is fibrous biomass, preferably selected from hardwood, softwood, and wood, including wood obtained from pruning or chopping wood, straw, bamboo, or mixtures thereof, preferably the biomass is selected from SHR, EFB, FFB, mesocarp, coconut fiber, bamboo, hardwood, softwood, and wood, including wood obtained from pruning or chopping wood, most preferably the biomass is selected from SHR, EFB, FFB, mesocarp, coconut fiber, and bamboo.

[0015]

[0015] Before being subjected to step (a), the biomass may be pre-treated. Such pre-treatment may include the removal of non-biomass materials such as sand, stones, plastics, etc. by sieving or otherwise chopping, cutting, chopping and / or screening, etc. Pre-treatment may include mechanical pre-treatment, which may involve breaking down the structure of the biomass into small particles, e.g., 0.1-10 cm in diameter. Mechanical pre-treatment preferably includes chopping, crushing, grinding or extrusion, e.g., using a chopper, millstone, ball mill, extruder, etc.

[0016]

[0016] In another embodiment, the method according to the invention is ideally suited to replace a steam distillation process, where the biomass is stripped of volatile components, especially those that are water insoluble, such as oils, terpenes or fragrances. This is particularly advantageous in the production of D-limonene from orange peel, where the steam stripped biomass is considered a waste stream. Subjecting orange peel to the method according to the invention allows the production of D-limonene, simultaneously converting the treated biomass into a valuable product. Also, the heat and pressure of the steam stripped biomass can be utilized in step (a) of the method according to the invention, which further improves the energy efficiency of the entire process.

[0017] Step (a)

[0017] Step (a) of the method according to the invention is a standard hydrothermal treatment step as known to the skilled person, for example from WO 2013 / 162355. This hydrothermal treatment already results in the desired desalination to a large extent. Ash, especially halides and alkali metals, need to be removed from the solid fuel to avoid corrosion, slagging, fouling and agglomeration problems. Of the relevant ions, potassium and chloride are the most abundant in biomass, therefore the salts in biomass are well represented, but not limited to, by K and Cl.

[0018] During step (a), the solid phase (biomass) and the treatment liquid are contacted, typically by immersing the biomass in the treatment liquid, which is heated to a temperature in the range of 100-250°C before being introduced into the reactor. Step (a) may also be called "torrefaction" or "wet torrefaction". The mixture of biomass and treatment liquid is treated at high temperature to obtain a hydrothermally treated material. The mixture may take the form of, for example, a suspension or solids submerged in the liquid. The best results are obtained by submerging the biomass in the hot treatment liquid, as this allows short treatment times with the minimum amount of liquid required per amount of solids. The solid phase is formed by the biomass and includes any attached liquid.

[0019] The treatment liquid comprises the waste liquid discharged from step (b) or (c) and is preheated before being added to the biomass. Such preheating advantageously takes the form of keeping the waste liquid at the temperature, and preferably the pressure, that it will have when discharged from the reactor. Any additional heat can be introduced into the reactor using steam, which may be discharged downstream in the process or any other heat source. In one embodiment, the treatment liquid comprises at least 50 wt% of the waste liquid discharged from step (b) or (c), preferably at least 80 wt% of the waste liquid discharged from step (b) or (c), more preferably at least 90 wt% or at least 95 wt% of the waste liquid discharged from step (b) or (c). In one embodiment, the treatment liquid is (i.e. consists of) the waste liquid discharged from step (b) or (c). If step (b) comprises more than one washing step, as further defined below, the treatment liquid preferably comprises the waste liquid from step (b) that is not the first washing step of step (b). If step (b) comprises only one washing step, it is preferred that the treatment liquid comprises the waste liquid from step (c). In another embodiment, the treatment liquid comprises a combination of various waste liquids obtained from the method. The treatment liquid can also be combined with another water source, such as tap water, fresh water, rain water, or other aqueous liquids.

[0020] The inventors have surprisingly found that the use of the effluent discharged from step (b) or (c) as treatment liquid in the hydrothermal treatment step (step (a)) prevents the removal of ions such as potassium and chloride, as well as organic compounds from the biomass. Even if these ions are contained in the effluent in reduced amounts, the solid fuel obtained is depleted in these ions compared to the incoming biomass, as would be the case if fresh water were used. In fact, any remaining K- and Cl-containing species in the solid obtained in step (a) are contained in the liquid remaining in the solid matrix after discharge and are thus easily removed in step (b). Therefore, furnace corrosion and similar problems are not at hand when burning the solid fuel obtained by the method according to the invention.

[0021]

[0021] The liquid to solid (L / S) ratio in the mixture subjected to step (a) is preferably in the range of 2 to 25, more preferably in the range of 15 to 20. These L / S ratios take into account the solids present in the liquid phase (which are classified as solids) and the liquids in the solid phase (which are classified as liquids). Excellent results have been obtained with L / S ratios in the range of 15 to 20, preferably when the solids are fully submerged. At these high L / S ratios, salts could be effectively removed from the biomass. Complete immersion of the biomass in the treatment liquid, although preferred, is not absolutely necessary. Typically, the biomass protruding from the treatment liquid at the beginning of step (a) will quickly disintegrate and sink.

[0022] At least one of steps (a) and (b) is carried out at a temperature in the range of 100-250°C, also referred to as the "roasting temperature". In one embodiment, at least step (a) is carried out at a temperature of at least 100°C, preferably in the range of 100-250°C. In one embodiment, at least step (b) is carried out at a temperature of at least 100°C, preferably in the range of 100-250°C. Preferably, at least (b) is carried out at the roasting temperature, and most preferably both steps (a) and (b) are carried out within that temperature range. In one embodiment, the temperature during step (a) and all washing steps (b) is kept substantially constant, identified herein as the "roasting temperature". Thus, the method according to this embodiment is advantageous in that it is not necessary to raise or lower the temperature of the liquid, which is beneficial in terms of energy consumption. In an alternative embodiment, step (a) is carried out at a temperature lower than the roasting temperature and step (b) is carried out at the roasting temperature. The method according to this embodiment effectively improves the digestibility of the solution discharged from the (first) step (b) compared to the solution discharged when step (a) is carried out at torrefaction temperatures.

[0023]

[0023] To ensure that the biomass is fully treated, at least one of steps (a) and (b) is carried out at a torrefaction temperature in the range of 100-250°C, preferably in the range of 120-230°C. Preferably, both steps (a) and (b) are carried out within this temperature range. At this temperature, torrefaction is carried out. During the hydrothermal treatment or wet torrefaction at this temperature, various reactions take place in the biomass, such as opening of the fibrous structure of the biomass and hydrolysis of hemicellulose. If step (a) is carried out at a relatively low temperature, such as below 160°C, and step (b) is carried out at a high temperature, such as above 175°C, the decomposition compounds of the hemicellulose hydrolysis are largely removed during the discharge at the beginning of step (b) before the hotter washing liquid is introduced. Therefore, these decomposition compounds are removed from the reactor without being subjected to the high temperatures of step (b), which is beneficial for their digestibility. Therefore, also the solution of the hydrothermal treatment is further improved in terms of compatibility with digestion and compounds of value generated. The inventors have found that at such relatively low temperatures, the fibrous structure of the biomass is already sufficiently opened to allow the extraction of organic compounds. At higher temperatures in step (b), the torrefaction reaction takes place further and the structure of the biomass becomes more brittle and more easily compressible, which is desirable for the production of solid fuel from the treated biomass. The inventors have found that in this particular embodiment, the optimal temperature for torrefaction in step (a) in the context of the present invention is in the range of 130-160°C, most preferably about 140°C. Such a temperature provides sufficient opening of the biomass structure to remove salts by washing, while at the same time maintaining a solid structure with sufficient structural integrity from which water can be removed to obtain the solid fuel. In this embodiment, it is preferred that step (b) is carried out at a temperature of 175-250°C, most preferably about 190°C.

[0024]

[0024] When step (b) is carried out at a roasting temperature as defined above, then step (a) may be carried out at a temperature ranging from ambient temperature (about 15°C) to 160°C. Step (a) therefore serves as a pre-wash step where salts and other extractables are washed away prior to the actual roasting.

[0025] In a particularly preferred embodiment, step (a) is carried out at a torrefaction temperature in the range of 100-250°C, preferably in the range of 120-230°C. The temperature at which step (a) is carried out is also referred to as the operating temperature. The hydrothermal reactor preferably comprises a heating means for heating the reactor to the operating temperature. Preferably, steam is used to heat the reactor to the operating temperature. This may be done by introducing steam into the reactor, which will increase the temperature and pressure of the reactor. Alternatively, the treatment liquid may be heated by steam prior to introduction into the reactor, such as in a heat exchanger, or steam may be injected into the treatment liquid prior to introduction into the reactor. The introduced steam may condense in the reactor and become part of the treatment liquid, taking into account the increasing pressure. Steam may also be used to preheat the treatment liquid prior to introduction into the reactor, such that the reactor is heated by the introduction of hot treatment liquid. The most energy efficient use of steam is to inject it directly into the reactor, which is thus the preferred method of heating the reactor. In a preferred embodiment, the steam originates from the process off-gas, preferably from the present process. For example, when pressure is released, steam is generated in step (c). Advantageously, this steam is taken and used to heat the reactor in step (a). This may be a second reactor operating in parallel, or the same reactor, when a new batch of biomass is introduced into the reactor for another cycle of the process.

[0026]

[0026] Steps (a) and (b) are typically carried out at high pressure to keep the liquid phase liquid. Typical pressures are slightly higher than the vapor pressure at the operating temperature, typically in the range of 4 to 50 bar, preferably 12 to 25 bar. The duration of both steps (a) and (b) typically ranges from 5 minutes to 5 hours, preferably 10 minutes to 2 hours, more preferably 15 minutes to 1 hour.

[0027] Step (a) results in a liquid phase, called solution or torrefaction solution, and a solid phase, called treated (torrefaction) biomass or material. At the end of step (a), both these phases are still contained in the reactor. The treated biomass is kept in the reactor and subjected to step (b) (in case of multiple steps (b) it is subjected to step (b1)), while the solution is discharged from the reactor and disposed of as waste, to be used as deemed suitable. The solution obtained in the process according to the invention is characterized by a relatively high amount of lignin. Since some lignin is fully soluble in hot water, but easily precipitates when the water cools, it is preferred that the solution is led to the lignin collecting vessel and kept at an elevated temperature until it arrives there. The solution is preferably kept at at least 100° C., more preferably at least 140° C. or at least 150° C., most preferably at the torrefaction temperature, until it is discharged in the lignin collecting vessel. Thus, the lignin is not precipitated prior to the lignin collection vessel, which avoids fouling of the system with precipitated lignin. As a result, the lignin is separated from the solution in a controlled manner, allowing its further application. The solution may be used, if deemed suitable, optionally after precipitation of the lignin. A possible application of the solution is the production of biogas by digestion, typically anaerobic digestion. The biogas thus obtained can be advantageously used, for example, to heat the reactor by generating steam. Thus, a further improvement in the cost-effectiveness and the renewability of the entire process is achieved. Alternatively, the solution may be used to obtain bio-based chemicals and products. The invention also relates to the solution obtained in step (b), preferably in step (b1), which is particularly suitable for digestion and generating valuable compounds.

[0028]

[0028] Step (a) also typically provides a gaseous product, which comprises decomposition products of the biomass and possibly of the organic matter present in the treatment liquid. The gaseous product comprises mainly H2O, and often also CO2, and possibly one or more of CO, H2, methane, methanol, formic acid, and acetic acid. This gaseous product can be used where deemed suitable, for example in the production of biogas (bio-SNG). In one embodiment, the gaseous product of step (a) is subjected to condensation of at least the water present. The condensation product is a salt-free liquid that can be used as a water source in step (a) of the method according to the invention or in steam generation.

[0029] Step (b) At the end of step (a), the reactor containing the biomass being treated is drained in step (b). Draining refers to the removal of the liquid phase (solution) from the reactor, which may be done for example by opening a valve at the bottom, by decanting the reactor or by removing the liquid through a dip tube. During step (b), a wash liquid is also introduced into the reactor. The introduction of the wash liquid may be done simultaneously with the draining, such wash liquid replacing the solution obtained in step (a). Such replacement processes for emptying and filling the reactor are known in the art. Alternatively, the reactor may be drained first, and optionally after a short period of agitation (e.g. stirring or shaking the reactor contents), typically 5 to 15 minutes, and then filled with wash liquid. The wash liquid is typically introduced through the same inlet as the treatment liquid of step (a).

[0030] In step (b), the torrefied solid product resulting from step (a) is washed, also referred to as post-washing. Even if step (b) is carried out at the torrefaction temperature, some torrefaction is carried out during step (b). This is particularly true if step (a) is carried out at a relatively low temperature, e.g. below 160°C, and step (b) is carried out at the torrefaction temperature. In such a case, it is particularly preferred that step (b) comprises at least two washing steps, at least the first washing step should be carried out at the torrefaction temperature. In the conventional torrefaction and Torwash process, the biomass is washed before being subjected to the torrefaction step (i.e., "pre-washing") to remove ions and other extractives from the biomass as much as possible. The presence of ions such as chlorine and potassium in the final solid fuel causes undesirable furnace slagging, fouling, clumping, and corrosion. These ions need to be removed from the biomass to avoid such problems. However, it was found that removing ions before step (a) is not very efficient, since the treatment liquid may contain salts such as chloride, potassium, and sodium. The inventors found that a post-washing step, in which the treated biomass is washed at high temperatures, provided optimal results when the wash waste liquid is used as the treatment liquid in step (a) and fresh water is used in step (b), or in the case of multiple steps with a final washing step in step (b). The inventors further found that a greater proportion of undesirable elements present in the biomass can be removed by the post-washing step compared to the pre-washing step. Without being bound by theory, it is believed that prior to the heat treatment in step (a), some of the Cl, K, and other undesirable ions are bound or embedded in the structural matrix of the biomass and cannot be washed away, and the heat treatment in step (a) liberates these ions, so that substantially all soluble Cl and K can be washed away. However, the resulting solids may be brittle and easily broken, so that post-washing may not be usable for dry torrefied biomass or biomass that has been subjected to Torwash, as this may result in breakage or shattering of the torrefied biomass.Since post-washing typically uses filters to store the solids and to pass the liquid, small pieces that break off from the solids can pass through these filters and contaminate the liquid flow or cause filter clogging. Despite these disadvantages of post-washing, the inventors have successfully performed a post-washing step on torrefied SHR, which did not cause any breakage of the torrefied material due to its tough, robust nature. Filtration of the washed solids does not cause any significant breakage of the solids, so that contamination of the liquid flow with solid branch debris and clogging of the filters is not observed. Furthermore, due to the high fiber content of SHR, even after Torwash the torrefied solids preserve their open structure, so that the washing liquid has optimal contact with the solids, ions are effectively removed, and at the same time the structure of the torrefied materials is not significantly compromised, so that they can be further treated as a normal torrefied manufactured solid fuel. For that reason, it is preferred that the biomass subjected to step (a) of the method according to the invention is a woody or fibrous biomass, as defined above.

[0031] Importantly, the washing liquid introduced in step (b) is preheated to at least 30°C below the operating torrefaction temperature, preferably at least 10°C below the operating torrefaction temperature. Typically, step (a) is carried out at a torrefaction temperature in the range of 100-250°C, such as 150-250°C, preferably in the range of 120-230°C, and the temperature of the washing liquid introduced in step (b) is at least 90°C, preferably at least 110°C, and step (a) is carried out at a temperature at least 30°C below the actual temperature. Thus, the reactor remains hot throughout the process and energy losses are minimized. In a preferred embodiment, the temperature of the washing liquid is at least the operating torrefaction temperature, more preferably at least 10°C above the operating torrefaction temperature.

[0032]

[0032] The preheating of the washing liquid can be carried out in any manner known in the art. In a particularly energy-efficient embodiment of the process according to the invention, the washing liquid originates from the process itself, for example from the same process carried out in parallel in a separate reactor. This embodiment is described in more detail below.

[0033] Step (b) is carried out at an elevated temperature, preferably in the same temperature range as defined in step (a). As the skilled person will appreciate, the temperature may vary throughout step (b), especially if there are multiple washing steps as defined below. The introduction of the washing liquid at an elevated temperature ensures that the reactor containing the biomass is kept at a sufficiently high temperature that no significant drop in temperature is observed during the period between the introduction of the washing liquid and its discharge. As is common in the art, it is preferred that the hydrothermal reactor is thermally insulated to avoid heat loss from inside the reactor.

[0034]

[0034] The washing of step (b) lasts for a duration also referred to as the washing time, defined as the end of the introduction of the washing liquid to the beginning of the discharge of the same liquid. Thus, when step (b) comprises several washing steps, each step has a washing time. This washing time is preferably in the range of 1 minute to 2 hours, preferably in the range of 2 minutes to 1 hour, most preferably 5 to 30 minutes. Step (b) is preferably carried out at approximately the same pressure at which step (a) is carried out, such as within 10% of the pressure of step (a).

[0035]

[0035] Although step (b) is typically referred to as a washing step, it can be foreseen in the context of the present invention that some torrefaction reactions also take place during step (b). This is particularly true if step (a) is carried out as a pre-washing step, but it can also be the case if step (a) is already an actual hydrothermal treatment step. Washing step (b) comprises at least one washing step, which may be repeated one or more times. The last of such a series of washing steps is referred to as the final washing step, i.e. the final washing step before the biomass is discharged from the reactor. Step (b) may also comprise more than one washing step, in which case the first washing step carried out directly after step (a) is referred to as the first washing step. And one or more intermediate washing steps may be carried out before the final washing step is carried out. If more than one washing step is carried out, the washing liquid of each step should be preheated, as defined above.

[0036] Thus, in a preferred embodiment, step (b) comprises: (b1) a first washing step, comprising introducing a first washing liquid into the reactor and simultaneously and / or subsequently discharging the first washing liquid from the reactor via a liquid outlet to obtain a solution; (b2) optionally, one or more intermediate wash steps, in which further wash liquid is introduced into the reactor and simultaneously discharged from the reactor via a liquid outlet to obtain intermediate wash waste liquid; (b3) a final washing step, in which a final washing liquid is introduced into the reactor and simultaneously discharged from the reactor through a liquid outlet to obtain a final washing waste liquid; Includes.

[0037]

[0037] Preferably, step (b2) of the method according to the present embodiment comprises 0 to 10 intermediate washing steps, more preferably 0 to 5 intermediate washing steps, most preferably 1 to 2 intermediate washing steps.

[0038] Each of the washing steps results in a liquid effluent. The liquid output of the first washing step is a liquid formed during step (a) and referred to as solution. Each subsequent washing step provides a washing effluent, the effluent of an intermediate washing step referred to as intermediate washing effluent and the effluent of the final washing step referred to as final washing effluent.

[0039] It is particularly preferred that the wash effluent from an intermediate or final wash step is used as wash effluent in the first or intermediate wash step, thus performing a stepwise liquid flow from countercurrent to solids flow. This is possible if the effluent is stored in a buffer or if two or more reactors perform the process according to the invention in parallel, but out of phase. To perform a non-buffered operation, the number of parallel reactors must be at least equal to the number of repetitions in step (b), preferably at least equal to the number of wash steps during step (b) plus one. In a preferred embodiment, the further wash effluent used in any of steps (b2) is the effluent from a downstream wash step in a countercurrent manner.

[0040]

[0040] The washing liquids used in the process of the present invention are all aqueous, i.e., they contain water, and preferably water is the only liquid. The inventors have found that only the final washing step, which in some embodiments is the only washing step, should be performed with clean water, while the washing waste liquid is suitable for any further upstream washing steps, while maintaining optimal desalination. Thus, the final washing liquid must be substantially free of the ions that are the object of removal, such as potassium and chloride. Thus, in one embodiment, the water used in step (b3) is substantially free of ions of alkali metals (Li, Na, K, etc.) and ions of halides (Cl, Br, etc.). In a preferred embodiment, fresh water is used as the final washing liquid, such as rainwater, surface water, tap water, or reverse osmosis water. The content of alkali metal ions and halides is sufficiently low in these water sources that they can be used as the final washing liquid to achieve the benefits of the present invention, particularly the details of the resulting solid fuel. Preferably, the content of each of these ions is kept individually below 150 mg / L, most preferably below 90 mg / L. Notably, the relatively small amount of final wash liquid is the only fresh water required in the method according to the invention, and thus is perfectly suitable to be carried out in areas where fresh water is scarce. In fact, the amount of biomass that can be removed from the ions with this small amount of fresh water is unprecedented in the art.

[0041] Step (c) At the end of step (b), the reactor containing the biomass being treated is discharged in step (c). Discharge refers to the removal of the liquid phase (solution) from the reactor and can be done for example by opening a valve at the bottom or by decanting the reactor. During step (c), an effluent is obtained but no further liquid is introduced into the reactor. The effluent from step (c) can thus be called the final wash effluent. The discharge of step (c) is thus without replenishment.

[0042]

[0042] Typically, step (c) is carried out in two stages, a first stage where the liquid effluent is discharged from the reactor, and a second stage where the treated biomass is removed from the reactor. The treated biomass may be obtained by opening the reactor, which releases the pressure. This pressure release may take any form. In one embodiment, the pressure is released instantaneously and the biomass is subjected to a steam explosion step. For pressure release, at least a portion of the remaining water in the reactor is evaporated into steam causing a sudden expansion of the biomass structure. Alternatively, the pressure is released gradually or controlled. After the biomass is obtained from the reactor, where some expansion of the biomass structure may occur, although to a lesser extent than when steam explosion is performed, it is advantageously further processed into a solid fuel. Such further processing is known in the art and may include dewatering, drying, milling, and granulation. Dewatering can be accomplished by any method known in the art, such as centrifugation, filtration, and / or mechanical dewatering. Such separation of liquid and solid product may be enhanced by, for example, pressing, squeezing or centrifuging the solid material using a porous mould to drive out any remaining liquid inside the solid material. Typically, a centrifuge is used. After discharge of step (c), the moisture content of the solid material is typically in the range of 50-90%, such as 65-80%, which could be reduced to about 50% by a dewatering step. Depending on the moisture content of the resulting solid material, further drying may be beneficial. Granulation of the resulting solid, which may include milling, provides fuel pellets that are easy to store and transport. Drying and pelletizing the washed solid in the context of a hydrothermal treatment process is well known in the art. In a preferred embodiment, pelletizing is carried out at a temperature in the range of 70-150°C, preferably in the range of 100-140°C. It has been found that pelletizing at such temperatures improves cohesion within the solid fuel pellets according to the invention.

[0043] In addition to the liquid effluent and the treated biomass, step (c) produces steam, which is advantageously used elsewhere in the process. Preferably, the steam obtained in step (c) is used in step (a) as a heat source or compressed to a liquid. During steam generation, light organic components such as methanol and furfural may also evaporate from the reactor and thus be entrained in the vapor stream. These components are compressed together with the vapor and are removed from the biomass to a greater extent than the heavier organic components. Without being bound by theory, it is believed that the removal of light organic components from the biomass during step (c) leads to less odor evaporation from the biomass and thus from the final solid fuel.

[0044] Step (c) may be carried out at a starting temperature in the same temperature range as defined in step (a). Preferably, step (c) starts at a temperature at the upper end of this range, such as 200-250°C, more preferably 210-230°C. In a particular advantageous embodiment, step (c) is carried out at a temperature at least 20°C higher than the operating temperature of step (a). In a further particular advantageous embodiment, steps (a) and (b) are carried out at approximately the same temperature, while step (c) is carried out at a temperature at least 20°C higher. Most preferably, the temperature at which step (c) is carried out is 20-50°C higher. During step (c), the temperature typically decreases, especially when pressure is released from the reactor. Evaporation of water reduces the temperature in the reactor. Step (c) typically ends at a temperature of around 100°C.

[0045] Obtained fuel

[0045] The present invention further relates to a solid fuel obtainable or obtained by the method according to the invention. The solid fuel according to the invention typically has a pellet form. The obtained solid fuel has excellent properties as a fuel pellet and can replace coal in power generation in the same way as white wood pellets can, but they are made from less valuable biomass feedstock. The method according to the invention allows for a washing step at high temperatures to remove a larger amount of lignin from the incoming biomass. At the same time, a large amount of ash, including chlorides and potassium, is removed from the biomass.

[0046]

[0046] The solid fuel according to the invention is based on biomass. In other words, it is derived from biomass. Preferred embodiments of the biomass are defined above and include biomass with a high ash content and / or biomass that is fibrous in nature. In a particularly preferred embodiment, the biomass is fibrous biomass, preferably selected from hardwoods, softwoods, and wood, including wood obtained from pruning or chopping wood, straw, bamboo, or mixtures thereof, preferably the biomass is selected from SHR, EFB, FFB, mesocarp, coconut fiber, bamboo, hardwood, softwood, wood, including wood obtained from pruning or chopping wood, most preferably the biomass is selected from SHR, EFB, FFB, mesocarp, coconut fiber, and bamboo.

[0047]

[0047] In a preferred embodiment, the solid fuel is characterized by an ash content of 1-15 wt%, preferably 5-10 wt% (dry weight). In particular, the chloride content is preferably in the range of 2-50 mg, more preferably 10-40 mg per kg of solid fuel. Similarly, the potassium content is preferably in the range of 50-500 mg, more preferably 200-400 mg per kg of solid fuel.

[0048]

[0048] The total ash content of the solid fuel according to the invention may be reduced compared to the total ash content of the incoming biomass, but this is not necessarily the case. In any case, the solid fuel according to the invention has a more beneficial ash composition compared to conventional solid fuel pellets obtained by torrefaction or steam explosion. In one embodiment, the more beneficial ash composition is defined by a reduction in the content of halides and alkali metals, typically represented by chloride and potassium, compared to their contents in the incoming biomass. Those skilled in the art can easily determine the chloride and potassium of the biomass and of the solid fuel, and can determine the level of reduction of these ions. Thus, the solid fuel is preferably 5-95% lower in ash than in the biomass from which the solid fuel originates (on a dry weight basis). In particular, the potassium content is preferably 50-99.9% lower, preferably 75-99% lower, and most preferably 90-98% lower than the potassium content in the biomass from which the solid fuel originates (on a dry weight basis). Similarly, the chloride content is preferably 50-99.9% lower, preferably 90-99.5% lower, and most preferably 95-99% lower than the chloride content in the biomass from which the solid fuel is derived (on a dry weight basis). Other ash, which typically has a higher melting point, such as silicates, is removed to a lesser extent from the biomass. Because the lower melting ash is removed to a greater extent, the solid fuel according to the invention has a lower chance of furnace fouling.

[0049] The silicon content (determined as SiO2) in the total ash may increase from about 50 wt% to 60-95 wt%, preferably 75-90 wt%, in the treated biomass, which indicates a larger proportion of the ash being formed by highly melting non-leachable salts such as silicates. The presence of those salts does not hinder the suitability of the product as a solid fuel, since they do not cause furnace fouling. On the other hand, the chlorine content in the total ash may be reduced from about 3 wt% to as low as 0.001-1 wt%, preferably 0.01-0.1 wt%, in the treated biomass. Similarly, the potassium content in the total ash may be reduced from about 9 wt% to as low as 0.01-2 wt%, preferably 0.05-1 wt%, in the treated biomass. The reduction in chlorine and potassium indicates a significantly reduced amount of low melting, easily soluble ash in the solid fuel. These ashes usually increase furnace fouling when solid fuels are burned.

[0050] Thus, in a preferred embodiment, the silicon content (determined as SiO2) of the solid fuel according to the invention relative to the total ash content is in the range of 60-95 wt%, preferably 75-90 wt%. In a further preferred embodiment, the chloride content of the solid fuel according to the invention relative to the total ash content is in the range of 0.001-1 wt%, preferably 0.01-0.1 wt%, and the potassium content of the solid fuel according to the invention relative to the total ash content is in the range of 0.01-2 wt%, preferably 0.05-1 wt%. These preferred ranges typically relate to a total ash content in the solid fuel in the range of 1-15 wt%, preferably 5-10 wt%, based on dry weight.

[0051] The solid fuel has excellent properties. For example, it has a calorific value in the range of 20-30 MJ, preferably in the range of 21-25 MJ per kg of solid fuel. Taking into account the open structure of the biomass and the decomposition of hemicellulose, the solid fuel is more brittle and breaks down easily compared to conventional pellets obtained by torrefaction. On the other hand, they are hard enough to be able to handle them properly, for example during packaging and transportation. The solid fuel according to the invention is generally harder than conventional fuel pellets obtained by torrefaction. Furthermore, the inventors have found that the stickiness of the solid fuel upon heating in the range of 150-300°C is reduced compared to fuel pellets obtained by steam explosion. Furthermore, the solid fuel according to the invention has better water resistance than the solid fuel obtained by conventional torrefaction and Torwash processes, meaning that they are less prone to disintegrate into pulp when wet. The solid fuel according to the invention retain their solid shape for a few days in a humid environment, whereas conventional solid fuel pellets obtained by dry torrefaction, Torwash, or steam explosion typically disintegrate very quickly. The inventors have further found that the solid fuel obtained by the method according to the invention exhibits a significantly reduced unpleasant odor. In particular, step (c) of the method according to the invention ensures that sufficient light organic compounds are removed from the treated biomass and that the odors normally caused by these light organic compounds are significantly reduced.

[0052] equipment

[0052] The present invention further relates to an installation for the hydrothermal treatment of biomass, designed in particular for the embodiment of the method according to the invention, in which two or more reactors operate in parallel. Thus, in its simplest construction, the hydrothermal treatment installation according to the invention comprises (a) a first hydrothermal reactor and (b) a second hydrothermal reactor, both reactors operating in parallel but out of phase.

[0053] Both the first and second hydrothermal reactors contain: (1) a reactor interior for containing an aqueous biomass mixture; (2) an inlet for receiving biomass; (3) an inlet for receiving a treatment or cleaning liquid; (4) heating means; (5) an outlet for discharging a solution or waste liquid; (6) an outlet for discharging the torrefied biomass; (7) An outlet for releasing process gases.

[0054]

[0054] Here, the outlet (a5) of the reactor (a) is fluidly connected with the inlet (b3) of the reactor (b) to allow one or more wash waste liquids obtained from the reactor (a) to be used as wash liquids in the reactor (b). Hydrothermal reactors or hydrothermal treatment reactors are known in the art and may also be called Torwash reactors. The inventive advantages of the treatment installation according to the invention are mainly based on the connections between the reactors in the reactor sequence forming the installation.

[0055] The reactors in the sequence comprise elements (1) to (7), all as defined above. These elements are well known to those skilled in the art of hydrothermal processing. The heating means (4) are suitable for operating the reactor at the operating temperature of step (a), as defined above. As stated above, this heating means preferably takes the form of an inlet for introducing steam into the reactor. The steam may originate from the process itself, typically from step (c), and / or steam from an external source may be used. This inlet may be fluidly connected with a gas outlet of a reactor, typically another reactor, in the sequence, so that steam is released from the reactor when pressure is released from the reactor, typically at the end of step (c). The reactor may be operated at different temperatures for each step, and for each stage of step (b), depending on the heat load introduced during the various stages of the process. The preferred temperatures are defined above for the process according to the invention.

[0056] In a preferred embodiment, the torrefied biomass discharged from the outlet (6) is further treated in a dewatering device, a milling device, and / or a pelleting device. Preferably, the hydrothermal treatment facility according to the invention comprises at least one of a dewatering device, a milling device, and a pelletizer, preferably at least a dewatering device and a pelletizer, most preferably a dewatering device, a milling device, and a pelletizer. Dewatering devices, milling devices, and pelletizers are known in the technical field of hydrothermal treatment facilities and in the context of solid fuel production. The reactors of the treatment facility may be connected to separate dewatering devices, milling devices, and / or pelletizing devices, respectively, via the outlets (6), or the outlets (6) of the reactors may be connected together to a single dewatering device, milling device, and / or pelletizing device. Thus, in a preferred embodiment, the hydrothermal treatment facility according to the invention comprises at least one dewatering device. Dewatering devices are known in the technical field of hydrothermal treatment plants and in the context of solid fuel production, and any dewatering device is suitable in the context of the present invention. Preferred dewatering devices include centrifuges, filter presses (e.g. belt filter presses), dewatering screws (screw presses or extruders), drum thickeners, and gravity belts. Thus, in a preferred embodiment, the hydrothermal treatment plant according to the present invention comprises at least one milling device. Milling devices are known in the technical field of hydrothermal treatment plants and in the context of solid fuel production, and any milling device is suitable in the context of the present invention. The milling device may also be referred to as a mill capable of milling the torrefied and optionally dewatered biomass. Thus, in a preferred embodiment, the hydrothermal treatment plant according to the present invention comprises at least one pelletizer. Pelletizers are known in the technical field of hydrothermal treatment plants and in the context of solid fuel production, and any pelletizer is suitable in the context of the present invention. The connection between the outlet (6) and the downstream processing equipment described herein is a connection for transporting solids, which typically takes the form of a conveyor belt.

[0057] Each of the reactors in the hydrothermal treatment installation according to the invention is a reactor for hydrothermal treatment. In the reactor (1), both the torrefaction reaction and the washing of the biomass take place. Thus, the hydrothermal treatment installation usually does not include a hydrothermal treatment reactor or a torrefaction reactor upstream of the above defined reactor. At least two reactors of the installation form a reactor sequence, the reactor (a) being the first reactor in the sequence and the reactor (b) being the second reactor in the sequence. The number of reactors in the sequence is not particularly limited, but from a practical point of view there are typically 2 to 12 reactors in the sequence, preferably 3 to 5 reactors. Usually the amount of reactors in the sequence is within one of the amount of washing steps of the method. Thus, if there are three washing steps, the amount of reactors is preferably in the range of 2 to 4. Most preferably, the amount of reactors in the sequence is equal to the amount of washing steps of the method. The last reactor in the sequence is called the last reactor. The second reactor may be the last reactor. The total number of reactors in the installation is typically equal to the amount of washing steps (b) carried out in the process according to the invention plus 1. Thus, if step (b) comprises one first washing step, one intermediate washing step and one final washing step, the installation advantageously comprises four hydrothermal reactors.

[0058]

[0058] The outlet (5) of each reactor is fluidly connected with the inlet (3) of the next reactor in the sequence. Here, the "next reactor" refers to the reactor that is the first one downstream of the present reactor when tracking the liquid flow over time. The first reactor now qualifies as the next reactor to the last reactor in the sequence, resulting in a circular arrangement of reactors. In this way, the outlet (5) of the last reactor is fluidly connected with the inlet (3) of the first reactor, so that the first reactor can also be fed with wash waste from another reactor. If the reactor sequence includes two reactors, the outlet (b5) of reactor (b) is fluidly connected with the inlet (a3) ​​of reactor (a).

[0059] For each reactor, the outlet (5) is also typically fluidly connected with the inlet (3) of the same reactor, allowing the use of one of the washing waste liquids as a treatment liquid in the same reactor. To this end, the outlet (5) is provided with a valve that allows the waste liquid discharged from the reactor to be transferred and directed either to the inlet (3) of the same reactor or to the inlet (3) of the next reactor in the sequence. Similarly, the inlet (3) is provided with a valve that allows the introduction of the waste liquid obtained either from the outlet (5) of the same reactor or from the outlet (5) of the previous reactor in the sequence. Alternatively, the outlet (5) or the inlet (3), or both, take the form of two separate outlets or inlets, one of which is fluidly connected with the same reactor and one of which is fluidly connected with another (previous or next) reactor in the sequence. Preferably, each outlet is configured so that a solution, as defined above, can be discharged from the facility as a (by)product and used wherever deemed suitable. This structure may take the form of a valve or a separate outlet from the reactor. The liquids discharged from all reactors in the installation may be combined before being further processed. Thus, the fluid connections from the outlets (5) through which the waste liquids (solutions) are discharged from the installation may be combined in a single waste stream. After each step in the method, a fully circulated liquid discharge is discharged. If more carousels of reactors are operated in parallel, their final liquid discharges may be combined and discharged in a single discharge stream.

[0060] In a particularly preferred embodiment, the outlet (5) of each reactor is fluidly connected to a lignin collection vessel, preferably a single lignin collection vessel for all reactors in the sequence. The fluid connections of each inlet (3) of the same reactor, the inlet (3) of the next reactor and the outlet (5) to the lignin collection vessel are controlled by one or more valves opening the desired connections at the desired times, as determined by the method defined above. The fluid connections to the lignin collection vessel are configured to keep it at an elevated temperature, as defined above, to avoid precipitation of lignin. Preferably, this fluid connection is kept as short as possible. EXAMPLES

[0061] In this experiment, empty fruit bunches (EFB) were treated according to the present invention. The EFB had a moisture content of 8.9% (as received), an ash content of 7.1 wt% (dry basis), a Cl content of 2200 mg / kg (dry basis) and a K content of 6300 mg / kg (dry basis). One batch of EFB and treatment water was prepared in a 2 L autoclave and consisted of 80.6 g EFB and 1333 g water, such that all the EFB was immersed in the treatment water. The autoclave was closed and heated to 215° C. and the mixture was treated for 30 minutes with continuous stirring. This first step represented the hydrothermal treatment step (a).

[0062] At the end of the hydrothermal treatment, 1172 g of solution was discharged from the bottom of the autoclave and cooled at the outlet to 80-90 °C to avoid steam. The temperature in the autoclave was reduced to 180 °C. An amount of 1039 g of deionized water was added at a rate of 40 ml / min while maintaining the temperature at 180 °C. The mixture of EFB and water was stirred continuously for 15 minutes. This step represented the washing step (b). At the end of the washing step, 1077 g of washing liquid (waste liquid) was discharged from the bottom of the autoclave and cooled to 100 °C. Finally, an amount of 129 g of washed roasted EFB was recovered from the autoclave with a moisture content of 73% and therefore a dry matter of 27 g. The mass balance of the process was calculated as given in Table 1.

[0063] Roasted EFB has a density of 1075 kg / m at a temperature of 120° C., which is typical of a pelletizer. 3 The mixture is pressed into suitable fuel pellets.

[0064]

[0064] [Table 1]

[0065] The overall solids yield was about 48%: 73.4 g of input solids were recovered as 34.9 g of output solids in the press product. The overall mass balance gives an input of 2452 g and an output of 2378 g, which is 97% of that or a loss of 74 g. Most of the mass loss can be attributed to the evaporation of the discharged hot water. Additionally, some mass loss occurred due to the formation of CO2 in the hydrothermal treatment step (about 10 g) and due to the deposition of lignin in the filter in the bottom discharge tube and in the tube (about 5-10 grams).

[0066]

[0066] Samples of the feedstock, liquid effluent, and solid pressed product were analyzed for chlorine (Cl) and potassium (K) content. The compositions of the initial EFB and the washed roasted pressed product of the EFB are listed in Table 2. The moisture content differs here from above because the samples were further dried before analysis could be performed.

[0067]

[0067] [Table 2]

[0068] The chloride content of the material was reduced from 2200 to 34 mg / kg (dry basis). When taking into account the solid yield, 0.7% of the chlorides remained in the product. Also, the amount of other unwanted elements is substantially reduced. For example, the untreated EFB contained 6300 mg / kg of potassium (K), which was reduced to an amount of only 300 mg / kg of potassium in the pressed product. Furthermore, the heating value of the EFB in the pressed product increased from 19.5 to 21.9 MJ / kg, which represents the amount of heat released during the combustion of a given amount of fuel. The pressed product shows all the properties of an excellent solid fuel. The ash content remained the same. However, the leachable and easily soluble salts content was significantly reduced, and the residual ash forming components are dominated by silicon oxides.

[0069] The overall conclusion is that the process according to the invention results in a solid product as an attractive solid fuel with properties equivalent to clean wood pellets. These biofuel pellets can be used to replace coal in power generation, similar to white wood pellets or black pellets. Furthermore, since the removal of the solution is carried out at higher temperatures and pressures, it is possible to remove lignin from the biomass. Lignin is a highly cross-linked phenolic polymer that acts as a physical barrier that can close the hydrolysis of carbohydrates to produce biochemical products, and thus its removal from the biomass allows the resulting biofuel to be more potent.

Claims

1. A method for the treatment of biomass, comprising: (a) subjecting the biomass to hydrothermal treatment in a hydrothermal reactor by immersing the biomass in a treatment liquid, wherein the waste liquid discharged from step (b) or (c) is used as the treatment liquid; (b) discharging the liquid from the reactor through a liquid outlet to obtain a solution, and simultaneously or subsequently introducing another cleaning liquid into the reactor, wherein the cleaning liquid is preheated to a temperature not lower than 30 °C below the operating temperature of step (a) before being introduced into the reactor; (c) discharging from the reactor to obtain the cleaned hydrothermally treated biomass and waste liquid. The method according to claim 1, wherein at least one of steps (a) and (b) is carried out at a temperature in the range of 100 to 250 °C.

2. Step (b) comprises: (b1) a first cleaning step of introducing a first cleaning liquid into the reactor and discharging from the reactor through the liquid outlet simultaneously and / or subsequently to obtain a solution; (b2) optionally, one or more intermediate cleaning steps of introducing a further cleaning liquid into the reactor and discharging from the reactor through the liquid outlet simultaneously to obtain intermediate cleaning waste liquid; (b3) a final cleaning step of introducing a final cleaning liquid into the reactor and discharging from the reactor through the liquid outlet simultaneously to obtain final cleaning waste liquid. The method according to claim 1, wherein each cleaning liquid is preheated to the operating temperature of step (a) before being introduced into the reactor.

3. The method according to claim 2, wherein step (b2) comprises from 0 to 10 intermediate cleaning steps.

4. The method according to claim 2, which is carried out in a hydrothermal treatment plant, wherein at least two hydrothermal reactors carry out the method in parallel, and one or more of the intermediate cleaning waste liquid and the final cleaning waste liquid from the first reactor are used as the cleaning liquid in one or more of the first cleaning step or the intermediate cleaning step in the second reactor, preferably maintaining the temperature of the cleaning waste liquid above 150 °C.

5. The method according to any one of claims 1 to 4, wherein the waste liquid discharged from step (c) is used as the treatment liquid in step (a).

6. The method according to any one of claims 1 to 4, wherein in step (c), the washed biomass after discharge is subjected to steam explosion or controlled pressure release by reducing the pressure.

7. The method according to any one of claims 1 to 4, wherein the temperature of the waste liquid from step (c) is typically in the form of steam and is used to heat the treatment liquid prior to step (a), preferably in a heat exchanger or by direct injection into the treatment liquid.

8. The method according to any one of claims 1 to 4, wherein the liquid-to-solid (L / S) ratio during the treatment in step (a) is in the range of 2 to 25, preferably in the range of 15 to 20.

9. The biomass comprises fibrous lignocellulosic biomass of wood origin, i.e., wood obtained by cutting or shredding hardwood, softwood, and wood, straw, bamboo, or mixtures thereof, and preferably the biomass is fibrous biomass selected from sugarcane harvest residues (SHR), empty fruit bunches (EFB), discarded fresh fruit bunches (FFB), mesocarp, coconut fiber, and pericarp. The method according to any one of claims 1 to 4.

10. The method according to any one of claims 1 to 4, further comprising treating the washed hydrothermally treated biomass to form solid fuel pellets, preferably by one or more of dehydration, drying, and pelletization.

11. The solution obtained in step (a) is used to preheat the washing liquid in step (b), preferably in step (b3), preferably in a heat exchanger, and / or the solution obtained in step (a) is maintained at a temperature higher than 140 °C until it is cooled to less than 100 °C in a lignin collection container, and lignin precipitates from the solution. The method according to any one of claims 1 to 4.

12. A solid biomass-derived fuel obtainable by the method according to any one of claims 1 to 4.

13. A solution obtainable by the method according to any one of claims 1 to 4, in particular by step (b1).

14. Equipment for the hydrothermal treatment of biomass comprising a reactor sequence of at least two hydrothermal reactors, (a) a first hydrothermal reactor and (b) a second hydrothermal reactor, wherein all reactors operate in parallel, Inside the reactor for containing the aqueous biomass mixture; (2) An inlet for receiving the biomass; (3) An inlet for receiving the treatment liquid or the cleaning liquid; (4) Heating means, preferably in the form of an inlet for receiving steam; (5) An outlet for discharging the solution or the waste liquid; (6) An outlet for discharging the roasted biomass; (7) An outlet for discharging the process gas Comprising, A facility in which the outlet (5) of the reactor (a) is fluidly connected to the inlet (3) of the reactor (b), and the outlet (5) of the final reactor of the sequence is fluidly connected to the inlet (3) of the reactor (a).

15. The facility according to claim 14, wherein the outlet (5) comprises a valve capable of closing the fluid connection with the inlet (3) and opening the fluid connection with the lignin collection container.