Biomass fractionation device and method

Abstract

A biomass fractionation device and method are disclosed in the present disclosure. The device comprises: a biomass supply unit; a biomass mixing unit into which biomass supplied from the biomass supply unit is introduced; a solvent supply unit for supplying a solvent to the biomass mixing unit; a biomass fractionation unit in which the biomass mixed with the solvent in the biomass mixing unit is transferred and cellulose, hemicellulose and lignin are fractionated; a solid collection unit for collecting solid fractions introduced from the biomass fractionation unit; and a liquid collection unit for collecting liquid fractions introduced from the biomass fractionation unit.

Description

Biomass fractionation apparatus and method

[0001] [Cross-reference of related applications]

[0002] This application claims priority to Korean Patent Application No. 10-2024-0186100 filed on December 13, 2024, the entire contents of which are incorporated by reference into this application.

[0003] [Explanation of government-supported research and development]

[0004] This research was conducted at the Korea Institute of Science and Technology under the management of the National Research Foundation of Korea, which is under the Ministry of Science and ICT. The research project name is Korea Institute of Science and Technology Research Operation Expense Support (Major Project Expense), and the research task title is Development of Source Technology for Electro Super Cellulose Composite Materials (Project Unique Number: 2710034017, Project Number: 2E33200).

[0005] The present disclosure discloses a biomass fractionation apparatus and method.

[0006] To address climate change and sustain civilization, it is necessary to utilize biomass, particularly lignocellulose containing lignin, as a carbon-neutral alternative to petroleum that can avoid conflicts with food sources.

[0007] Lignocellulose is primarily composed of cellulose, hemicellulose, and lignin. Cellulose is a linear polymer with glucose as its monomer, while hemicellulose is a heterogeneous branched polymer of pentoses and hexoses. Lignin is an amorphous, highly branched polymer of phenylpropane units that accounts for approximately 35 wt% (on a dry basis) of biomass. However, most bioethanol production plants and pulp and paper mills focus only on utilizing the cellulose and hemicellulose portions, which are easily convertible. To date, biorefineries utilizing lignocellulose have been established based on corn or plant / animal oils; consequently, biorefineries utilizing lignocellulose have not been industrialized due to economic feasibility issues.

[0008] In order to increase the value of conventional lignin, there have been attempts to produce sustainable aviation fuel, phenols, etc., by fractionating lignin that maintains reactivity (aryl-ether interlink) followed by subsequent demolition and deoxygenation. However, since there were many difficulties in continuously supplying solid raw materials to reactors under relatively high temperature, high pressure, and corrosive conditions, only batch processes have been proposed.

[0009] In one aspect, the present disclosure aims to provide a biomass fractionation device capable of continuous operation.

[0010] In another aspect, the present disclosure aims to provide a biomass fractionation method capable of producing reactive lignin using the biomass fractionation apparatus.

[0011] In one aspect, the present disclosure provides a biomass fractionation apparatus comprising: a biomass supply unit; a biomass mixing unit formed at the bottom of the biomass supply unit and into which biomass supplied from the biomass supply unit is introduced; a solvent supply unit formed separately from the biomass supply unit and into which a solvent is supplied to the biomass mixing unit; a biomass fractionation unit formed at the bottom of the biomass mixing unit and into which cellulose, hemicellulose, and lignin are fractionated by transferring the biomass mixed with the solvent in the biomass mixing unit; a solid collection unit formed at the bottom of the biomass fractionation unit and into which a solid fraction is introduced from the biomass fractionation unit; and a liquid collection unit formed connected to the solid collection unit and into which a liquid fraction is introduced from the biomass fractionation unit, wherein the biomass is supplied to the biomass mixing unit at atmospheric pressure, and then, after a pressure increase through the solvent introduced from the solvent supply unit, is transferred from the biomass mixing unit to the biomass fractionation unit by a free-fall method.

[0012] In an exemplary embodiment, the biomass mixing unit may include a first solvent supply control means for controlling the supply of solvent introduced from a solvent supply unit; a pressure release control means for lowering the pressure within the biomass mixing unit; and a biomass transfer control means for controlling the transfer of the biomass mixed with the solvent to a biomass fractionation unit.

[0013] In an exemplary embodiment, the biomass fractionation unit may comprise: a solvent supply means for a constant flow; an extrusion means for transporting, crushing, and fractionating biomass mixed with the solvent in a horizontal direction; a heating means formed horizontally with respect to the extrusion means and controlling the temperature of the extrusion means; a fraction travel direction changing means formed at the rear of the extrusion means and changing the travel direction of the fraction; and a fraction transport control means for transporting the fraction, whose travel direction has been changed by the fraction travel direction changing means, to a solid collection unit at the bottom by a free fall method.

[0014] In an exemplary embodiment, the solid movement speed and the liquid movement speed within the device are different, and the solid movement may be controlled by the supply amount of biomass and / or the rotational speed of the extrusion means, and the liquid movement may be controlled by the flow rate and / or flow velocity of the solvent supplied through the constant solvent supply means.

[0015] In an exemplary embodiment, the fraction may be carried out at 10 to 30 bar and 150 to 200 ℃.

[0016] In an exemplary embodiment, the extrusion means may be a screw extruder.

[0017] In an exemplary embodiment, the biomass fractionation unit may further include a driving means for driving the extrusion means; and a shaft sealing means for sealing the extrusion means.

[0018] In an exemplary embodiment, the solid collection unit may include: a solid fraction discharge control means for controlling the discharge of a solid fraction; a solid fraction collection container formed in connection with the solid fraction discharge control means for collecting the discharged solid fraction; and a liquid fraction transfer control means for controlling the transfer of a liquid fraction to a liquid collection unit.

[0019] In an exemplary embodiment, the solid collection unit may further include a second solvent supply control means for pressure correction.

[0020] In an exemplary embodiment, the liquid collection unit may include: a filter means for filtering a liquid fraction introduced through the liquid fraction transfer control means; a liquid fraction discharge control means for controlling the discharge of the liquid fraction filtered by the filter means; a liquid fraction collection container formed in connection with the liquid fraction discharge control means for collecting the discharged liquid fraction; and a bypass means formed separately from the liquid fraction discharge control means and capable of transferring the filtered liquid fraction to the liquid fraction collection container.

[0021] In an exemplary embodiment, the temperature of the biomass fractionation section may be 150 to 200 ℃ and the temperature of the liquid collection section may be 50 ℃ or lower.

[0022] In an exemplary embodiment, the device may separate reactive lignin from biomass.

[0023] In an exemplary embodiment, the reactive lignin may include β-O-4 ether bonds.

[0024] In an exemplary embodiment, the reactive lignin may contain at least 20% of the total number of β-O-4 ether bonds based on the total number of β-O-4 ether bonds contained in the raw biomass prior to the fractionation reaction.

[0025] In an exemplary embodiment, the solvent may include an alcohol having 1 to 6 carbon atoms.

[0026] In an exemplary embodiment, the solvent may be an aqueous solution having an alcohol concentration of 5 to 95 volume%.

[0027] In an exemplary embodiment, the device may be capable of continuous operation.

[0028] In another aspect, the present disclosure provides a biomass fractionation method using the biomass fractionation apparatus.

[0029] In one aspect, the technology disclosed in this disclosure has the effect of providing a biomass fractionation device capable of continuous operation.

[0030] The above device separates the paths for solid biomass supply and high-temperature solvent supply to prevent biomass accumulation, and is equipped with a biomass supply section, a biomass mixing section, and a biomass fractionation section as a vertical structure so that biomass immersed in the solvent reaches the biomass fractionation section by free fall. By moving the biomass through an extrusion means and optimizing the retention time within the fractionation section by controlling the rotation speed, temperature, and / or supply amount, it has the effect of maximizing the yield of reactive lignin.

[0031] The biomass fractionation apparatus according to the present disclosure has the effect of enabling effective refinement of herbaceous and lignocellulosic biomass into fractions of cellulose, hemicellulose, and lignin.

[0032] Lignin obtained through conventional harsh fractionation processes such as high temperature and high pressure has a form with very low reactivity due to an irreversible decomposition process in which β-O-4 ether bonds are broken and additional condensation reactions occur. On the other hand, the biomass fractionation device according to the present disclosure has the effect of enabling the fractionation and separation of lignin with excellent reactivity that retains a large amount of β-O-4 ether bonds.

[0033] In another aspect, the technology disclosed in this disclosure has the effect of providing a biomass fractionation method using the biomass fractionation device.

[0034] Figure 1 shows a biomass fractionation flowchart according to one embodiment.

[0035] FIG. 2 shows a schematic diagram of a biomass fractionation device according to one embodiment.

[0036] Figure 3 shows the fraction yield of Quercus serrata and the fraction amount of each component according to the ethanol concentration according to one embodiment.

[0037] Figure 4 shows the results of component analysis of the solid fraction and liquid fraction after fractionation of Mongolian oak using an aqueous ethanol solution with a concentration of 50 volume% according to one embodiment.

[0038] The present disclosure will be described in detail below.

[0039] The terms used herein are merely for describing specific embodiments and are not intended to limit the disclosure. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “comprising” or “having” are intended to indicate the presence of the features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0040] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by those skilled in the art to which this disclosure pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and should not be interpreted in an ideal or overly formal sense unless explicitly defined herein.

[0041] In one aspect, the present disclosure provides a biomass fractionation apparatus.

[0042] FIG. 1 shows a biomass fractionation flowchart according to one embodiment, and FIG. 2 shows a schematic diagram of a biomass fractionation apparatus according to one embodiment.

[0043] The device comprises: a biomass supply unit (2); a biomass mixing unit (5) formed at the bottom of the biomass supply unit and into which biomass supplied from the biomass supply unit is introduced; a solvent supply unit (1) formed separately from the biomass supply unit and into which a solvent is supplied to the biomass mixing unit; a biomass fractionation unit (6) formed at the bottom of the biomass mixing unit and into which cellulose, hemicellulose, and lignin are fractionated by transferring the biomass mixed with the solvent from the biomass mixing unit; a solid collection unit (7) formed at the bottom of the biomass fractionation unit and into which solid fractions introduced from the biomass fractionation unit are collected; and a liquid collection unit (8) formed connected to the solid collection unit and into which liquid fractions introduced from the biomass fractionation unit are collected.

[0044] The above biomass is supplied to the biomass mixing section (5) at atmospheric pressure, and then, after the pressure is increased through the solvent introduced from the solvent supply section (1), it is transferred from the biomass mixing section (5) to the biomass fractionation section (6) by free fall.

[0045] Unlike the conventional method of slurrying biomass using a solvent and then supplying it using a pump, the present disclosure supplies solid biomass and a liquid solvent through separate supply units and transports the biomass by free fall, thereby preventing bridge formation (biomass accumulation) that occurs during the high-pressure transport process of solid biomass. In addition, the present disclosure has the effect of eliminating the need for drying, hydration, and fiberization processes of the biomass.

[0046] In an exemplary embodiment, the biomass mixing section (5) may include: a first solvent supply control means (5-1) for controlling the supply of solvent introduced from a solvent supply section; a pressure release control means (5-2) for lowering the pressure within the biomass mixing section; and a biomass transfer control means (5-3) for controlling the transfer of the biomass mixed with the solvent to a biomass fractionation section.

[0047] In an exemplary embodiment, the solvent supply unit (1) may supply solvent to the biomass mixing unit (5) through the first solvent supply control means (5-1).

[0048] In an exemplary embodiment, the solvent supply unit (1) may supply a heated solvent to the biomass mixing unit (5) through the first solvent supply control means (5-1).

[0049] In an exemplary embodiment, the solvent supply unit (1) may supply a heated solvent to the biomass mixing unit (5) via a pump (3) and a preheating device (4).

[0050] In an exemplary embodiment, the biomass supply unit (2) may supply biomass to the biomass mixing unit (5) through a biomass supply control means (2-1).

[0051] In an exemplary embodiment, the biomass supply control means (2-1) may be a ball valve.

[0052] In an exemplary embodiment, the first solvent supply control means (5-1) acts as a pressure switching valve and may be an inlet valve. The first solvent supply control means can perform the function of pressure correction by increasing the pressure within the biomass mixing section (5) through solvent supply by a pump.

[0053] In an exemplary embodiment, the pressure release control means (5-2) acts as a pressure switching valve and may be a pressure releasing drain valve.

[0054] In an exemplary embodiment, the biomass transfer control means (5-3) may be a ball valve.

[0055] In an exemplary embodiment, the supply and transfer of the biomass may be achieved by a biomass supply control means (2-1), a first solvent supply control means (5-1), a pressure release control means (5-2), and a biomass transfer control means (5-3).

[0056] In an exemplary embodiment, the biomass may be supplied from the biomass supply unit (2) to the biomass mixing unit (5) by opening the pressure release control means (5-2) while the biomass supply control means (2-1), the first solvent supply control means (5-1), and the biomass transport control means (5-3) are closed, thereby lowering the internal pressure of the biomass mixing unit (5), and then opening the biomass supply control means (2-1).

[0057] In an exemplary embodiment, after biomass is supplied from the biomass supply unit, the first solvent supply control means (5-1) is opened to increase pressure through solvent injection while the biomass supply control means (2-1), pressure release control means (5-2), and biomass transfer control means (5-3) are closed, and then the first solvent supply control means (5-1) is closed and the biomass transfer control means (5-3) is opened to transfer the biomass mixed with the solvent from the biomass mixing unit (5) to the biomass fractionation unit (6) by free fall. That is, the transfer from the biomass mixing unit (5) to the biomass fractionation unit (6) may be a vertical transfer. At this time, the solvent may be continuously supplied through the constant solvent supply means (6-1) after passing through the pump and the preheating device.

[0058] In an exemplary embodiment, the biomass fractionation unit (6) may comprise: a solvent supply means (6-1) for a constant solvent supply; an extrusion means (6-4) for transporting, crushing, and fractionating biomass mixed with the solvent in a horizontal direction; a heating means (6-5) formed horizontally with respect to the extrusion means and controlling the temperature of the extrusion means; a fraction travel direction changing means (6-6) formed at the rear of the extrusion means and changing the travel direction of the fraction; and a fraction transport control means (6-7) for transporting the fraction, whose travel direction has been changed by the fraction travel direction changing means, to a solid collection unit at the bottom in a free-fall manner.

[0059] In an exemplary embodiment, the biomass fractionation unit (6) may further include a driving means (6-2) for driving the extrusion means; and a shaft sealing means (6-3) for sealing the extrusion means.

[0060] In an exemplary embodiment, the constant solvent supply means (6-1) supplies a continuously heated solvent and may be an inlet valve. The constant solvent supply means (6-1) may perform the function of pressure correction by continuously supplying a heated solvent by a pump.

[0061] In an exemplary embodiment, the above-mentioned solvent supply means (6-1) may supply heated solvent to the biomass fractionation unit (6).

[0062] In an exemplary embodiment, the above-mentioned solvent supply means (6-1) may supply heated solvent to the biomass fractionation unit (6) via a pump and a preheating device.

[0063] In an exemplary embodiment, the driving means (6-2) may be a motor.

[0064] In an exemplary embodiment, the shaft sealing means (6-3) may be a V-shape series seal, which is a sealing means capable of withstanding a high temperature and high pressure solution environment. For example, the sealing means may be composed of a series of V-shape rings made of high-temperature resistant plastic (e.g., PEEK), and the surrounding housing may preferably have a jacket installed for cooling so that cooling water can flow through it.

[0065] In an exemplary embodiment, the extrusion means (6-4) may be a screw extruder. Biomass transported by free fall is transported horizontally by the extrusion means under a high temperature and high pressure solution environment.

[0066] In an exemplary embodiment, the retention time of the biomass in the high-temperature and high-pressure biomass fractionation section can be optimized by controlling the rotational speed of the screw extruder and the biomass feed rate. Accordingly, the yield of reactive lignin can be maximized.

[0067] In the present disclosure, the extrusion means acts only on the transport of the slurried biomass, so there is no pressure burden, which has the effect of not affecting the biomass particles. In addition, the present disclosure uses an aqueous organic solvent solution rather than a basic solution, and through continuous operation that minimizes the retention time in the high-temperature section of the biomass fractionation section, it has the effect of maintaining the reactivity of lignin to the maximum.

[0068] In an exemplary embodiment, the size of the solid fraction particles discharged by crushing and fractionation in the extrusion means may be reduced to about 50% of the original size.

[0069] In an exemplary embodiment, the scale can be scaled up according to the scale of the extrusion means.

[0070] In an exemplary embodiment, the heating means (6-5) may be a heater.

[0071] In an exemplary embodiment, the fraction travel direction changing means (6-6) may be a guiding brush. The fraction travel direction changing means changes the travel direction of the fraction to transport the fraction conveyed by the extrusion means to a solid collection unit in a free-fall manner.

[0072] In an exemplary embodiment, the fraction transfer control means (6-7) may be a ball valve. The fraction refers to a material after a fractionation reaction that has passed through an extrusion means, and the fraction is transferred to a solid collection unit through the fraction transfer control means.

[0073] In an exemplary embodiment, the solid movement speed and the liquid movement speed within the device may be different, and the solid movement may be controlled by the supply amount of biomass and / or the rotational speed of the extrusion means, and the liquid movement may be controlled by the flow rate and / or flow velocity of the solvent supplied through the constant solvent supply means. The biomass fractionation device of the present disclosure may control the retention time of the liquid and solid in the high-temperature portion, i.e., the biomass fractionation portion, respectively, to secure reactive lignin. Specifically, the biomass fractionation device may control the retention time of the liquid in the biomass fractionation portion to be shorter. Thus, by making the retention times of the solid biomass and the liquid solvent in the biomass fractionation portion different, the fractionated lignin is prevented from remaining in a high-temperature state, thereby preventing the condensation of the fractionated lignin and maximizing the yield of reactive lignin.

[0074] In an exemplary embodiment, the temperature of the biomass fractionation unit (6) may be 150 to 200°C.

[0075] In an exemplary embodiment, the fraction may be carried out at 10 to 30 bar and 150 to 200 ℃.

[0076] In an exemplary embodiment, the biomass supply unit (2), biomass mixing unit (5) and biomass fractionation unit (6) may be formed sequentially as vertical structures.

[0077] In an exemplary embodiment, the solid collection unit (7) may include: a solid fraction discharge control means (7-2) for controlling the discharge of a solid fraction; a solid fraction collection container (7-4) formed in connection with the solid fraction discharge control means for collecting the discharged solid fraction; and a liquid fraction transfer control means (7-3) for controlling the transfer of a liquid fraction to a liquid collection unit.

[0078] In an exemplary embodiment, the solid collection unit (7) may further include a second solvent supply control means (7-1) for pressure correction.

[0079] In an exemplary embodiment, the second solvent supply control means (7-1) may be an inlet valve. The second solvent supply control means may perform the function of pressure correction through solvent supply by a pump.

[0080] In an exemplary embodiment, the second solvent supply control means (7-1) may supply heated solvent to the solid collection unit (7).

[0081] In an exemplary embodiment, the second solvent supply control means (7-1) may supply heated solvent to a solid collection unit (7) via a pump and a preheating device.

[0082] In an exemplary embodiment, the solid fraction discharge control means (7-2) may be a ball valve.

[0083] In an exemplary embodiment, the liquid fraction transfer control means (7-3) may be a ball valve.

[0084] In an exemplary embodiment, the solid fraction can be moved to a solid fraction collection container (7-4) by opening the solid fraction discharge control means (7-2) while the fraction transfer control means (6-7), the second solvent supply control means (7-1), and the liquid fraction transfer control means (7-3) are closed. For example, the solid fraction is moved in a free-fall manner to a solid collection unit (7) through the fraction transfer control means (6-7) and the direction of travel of the solid fraction is changed through the fraction travel direction changing means (6-6), and the solid fraction is also moved in a free-fall manner to an external solid fraction collection container (7-4) and stored.

[0085] In an exemplary embodiment, to increase pressure, the fraction transfer control means (6-7), solid fraction discharge control means (7-2), and liquid fraction transfer control means (7-3) are closed, and then a solvent is supplied through the second solvent supply control means (7-1) to increase pressure. When the system pressure is reached, the second solvent supply control means (7-1) is closed and the fraction transfer control means (6-7) and the liquid fraction transfer control means (7-3) are opened to maintain continuous operation.

[0086] In an exemplary embodiment, the temperature of the solid collection unit (7) may be air-cooled and lower than the temperature of the biomass fractionation unit (6).

[0087] In an exemplary embodiment, the temperature of the solid collection unit (7) may be 150°C or lower, or less than 150°C, for example, 60 to 100°C.

[0088] In an exemplary embodiment, the liquid collection unit (8) may include: a filter means (8-1) for filtering a liquid fraction introduced through the liquid fraction transfer control means; a liquid fraction discharge control means (8-2) for controlling the discharge of the liquid fraction filtered by the filter means; a liquid fraction collection container (8-4) formed in connection with the liquid fraction discharge control means for collecting the discharged liquid fraction; and a bypass means (8-3) formed separately from the liquid fraction discharge control means and capable of transferring the filtered liquid fraction to the liquid fraction collection container.

[0089] In an exemplary embodiment, the filter means (8-1) may be a sintered metal filter formed by a metal particle sintering method.

[0090] In an exemplary embodiment, the liquid fraction discharge control means (8-2) may be a relief valve or a back pressure regulator. Liquid discharge through the liquid fraction discharge control means can maintain a constant system pressure within the device.

[0091] In an exemplary embodiment, the bypass means (8-3) may be a bypass valve.

[0092] In an exemplary embodiment, the liquid fraction introduced into the liquid collection unit (8) through the liquid fraction transfer control means (7-3) can pass through the filter means (8-1) and be discharged outside the atmospheric pressure through the liquid fraction discharge control means (8-2).

[0093] In an exemplary embodiment, the flow rate of the liquid fraction can be controlled via a pump (not shown). For example, the liquid flow rate within the device can be controlled by a pump to optimize the retention time within the high-temperature and high-pressure biomass fractionation section for improving the fractionation yield of lignin and securing reactive lignin.

[0094] In an exemplary embodiment, the liquid collection unit (8) is relatively lower than the system temperature within the device, which has the effect of maintaining the reactivity of the lignin to the maximum extent.

[0095] In an exemplary embodiment, the temperature of the liquid collection unit (8) may be a low temperature of 50°C or lower, for example, room temperature to 40°C. The biomass fractionation device of the present disclosure can reduce the residence time of the solvent in the high-temperature section compared to a conventional batch fractionation device, and thereby has the effect of separating reactive lignin from biomass with a high yield.

[0096] In an exemplary embodiment, the constant solvent supply means may continuously supply solvent, and the first solvent supply control means and the second solvent supply control means may supply solvent only when pressure correction is required.

[0097] In an exemplary embodiment, the system pressure within the device can be maintained by a liquid fraction discharge control means.

[0098] In an exemplary embodiment, the system temperature within the device can be maintained by a preheated and supplied solvent and a heating means.

[0099] In an exemplary embodiment, the biomass may be woody or herbaceous.

[0100] In an exemplary embodiment, the biomass may be lignocellulose.

[0101] In an exemplary embodiment, the biomass may have a size smaller than the inner diameter of the pipe through which the biomass is transported and the pitch of the extrusion means.

[0102] In an exemplary embodiment, the device may be capable of continuous collection of solid fractions and liquid fractions.

[0103] In an exemplary embodiment, the solid fraction may include cellulose.

[0104] In an exemplary embodiment, the solid fraction may contain cellulose in an amount of 60% or more, 65% or more, or 70% or more based on the total weight of the solid fraction, and 80% or less, 75% or less, or 70% or less.

[0105] In an exemplary embodiment, the liquid fraction may comprise hemicellulose and lignin.

[0106] In an exemplary embodiment, the liquid fraction may contain 25 wt% or more, 26 wt% or more, 27 wt% or more, 28 wt% or more, 29 wt% or more, or 30 wt% or more, and 45 wt% or less, 40 wt% or less, 35 wt% or less, or 30 wt% or less, based on the total weight of the liquid fraction.

[0107] In an exemplary embodiment, the liquid fraction may contain lignin in an amount of 30% or more by weight, 35% or more by weight, 40% or more by weight, or 45% or more by weight, and 60% or less by weight, 55% or less by weight, or 50% or less by weight, based on the total weight of the liquid fraction.

[0108] Lignin is a copolymer of three phenylpropane monomers. Although the bonding patterns of these monomers vary, β-aryl ether (β-O-4) bonds are the most common, accounting for 46–60%.

[0109] In an exemplary embodiment, the device may separate reactive lignin from biomass.

[0110] In an exemplary embodiment, the reactive lignin may include β-O-4 ether bonds.

[0111] In an exemplary embodiment, the reactive lignin may comprise 20% or more, or 20% to 80%, of the total number of β-O-4 ether bonds contained in the raw biomass prior to the fractionation reaction. In another exemplary embodiment, the reactive lignin may comprise 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, or 75% or more, and 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, or 25% or less of β-O-4 ether bonds based on the total number of β-O-4 ether bonds contained in the raw biomass prior to the fractionation reaction.

[0112] In an exemplary embodiment, the solvent supplied by the device may have a boiling point lower than that of water.

[0113] In an exemplary embodiment, the solvent supplied by the device may include an alcohol having 1 to 6 carbon atoms.

[0114] In an exemplary embodiment, the solvent may include ethanol.

[0115] In an exemplary embodiment, the solvent may be an aqueous solution having an alcohol concentration of 5 to 95 volume%. In another exemplary embodiment, the solvent is 5 volume% or more, 10 volume% or more, 15 volume% or more, 20 volume% or more, 25 volume% or more, 30 volume% or more, 35 volume% or more, 40 volume% or more, 45 volume% or more, 50 volume% or more, 55 volume% or more, 60 volume% or more, 65 volume% or more, 70 volume% or more, 75 volume% or more, 80 volume% or more, 85 volume% or more, or 90 volume% or more, and 95 volume% or less, 90 volume% or less, 85 volume% or less, 80 volume% or less, 75 volume% or less, 70 volume% or less, 65 volume% or less, 60 volume% or less, 55 volume% or less, 50 volume% or less, 45 volume% or less, 40 volume% or less, 35 volume% or less, 30 volume% or less, 25 volume% or less, 20 It may be an aqueous solution having an alcohol concentration of 15 volume% or less, 10 volume% or less, or 10 volume% or less.

[0116] In an exemplary embodiment, the solvent may be recoverable and recyclable through simple distillation.

[0117] In an exemplary embodiment, the device may be capable of continuous operation.

[0118] In an exemplary embodiment, the device may be a high temperature and high pressure device.

[0119] In an exemplary embodiment, the device may be capable of continuous fractionation of biomass at a high temperature of 150 to 200 ℃ and a high pressure of 10 to 30 bar.

[0120] In an exemplary embodiment, the device has the effect of continuously feeding biomass and continuously fractionating and separating cellulose, hemicellulose, and lignin. Such continuous operation enables the commercialization of a biorefinery with the potential to replace an oil refinery.

[0121] In an exemplary embodiment, the device may be capable of long-term operation.

[0122] In another aspect, the present disclosure provides a biomass fractionation method using the biomass fractionation apparatus.

[0123] In an exemplary embodiment, the method may comprise the steps of: supplying biomass from a biomass supply unit to a biomass mixing unit at atmospheric pressure; supplying a heated solvent from a solvent supply unit to the biomass mixing unit to increase the pressure within the biomass mixing unit; transferring the biomass mixed with the solvent from the biomass mixing unit to a biomass fractionation unit by free fall; fractionating cellulose, hemicellulose, and lignin in the biomass fractionation unit to obtain a fraction; and transferring the fraction to a solid collection unit and then separating the solid fraction containing cellulose and the liquid fraction containing hemicellulose and lignin.

[0124] In an exemplary embodiment, the biomass fractionation method according to the present disclosure is as follows.

[0125] First, with the biomass supply control means (2-1), the first solvent supply control means (5-1), and the biomass transport control means (5-3) closed, the pressure release control means (5-2) is opened to lower the internal pressure of the biomass mixing section (5), and then the biomass supply control means (2-1) is opened to supply biomass from the biomass supply section (2) to the biomass mixing section (5). Afterward, with the biomass supply control means (2-1), the pressure release control means (5-2), and the biomass transport control means (5-3) closed, the first solvent supply control means (5-1) is opened to raise the pressure through solvent injection, and then the first solvent supply control means (5-1) is closed and the biomass transport control means (5-3) is opened to transport the biomass mixed with the solvent from the biomass mixing section (5) to the biomass fractionation section (6) by free fall.

[0126] The biomass reaching the above biomass fractionation unit (6) is transported horizontally through an extrusion means (6-4) formed in a horizontal direction, and is crushed and fractionated by the extrusion means (6-4) in a high temperature and high pressure environment. The residence time of the biomass within the heating section can be controlled by adjusting the rotational speed of the extrusion means and the amount of biomass supplied. In order to transport the fractions transported by the extrusion means (6-4) to the solid collection unit (7) at the bottom in a free-fall manner, the direction of travel is changed by a fraction travel direction changing means (6-6).

[0127] The fraction transferred to the solid collection unit (7) is transferred to the solid fraction collection container (7-4) by opening the solid fraction discharge control means (7-2) while the fraction transfer control means (6-7), the second solvent supply control means (7-1), and the liquid fraction transfer control means (7-3) are closed. To increase pressure, the fraction transfer control means (6-7), the solid fraction discharge control means (7-2), and the liquid fraction transfer control means (7-3) are closed, and then the solvent is supplied through the second solvent supply control means (7-1) to increase pressure. When the system pressure is reached, the second solvent supply control means (7-1) is closed, and the fraction transfer control means (6-7) and the liquid fraction transfer control means (7-3) are opened to maintain continuous operation.

[0128] The liquid fraction introduced into the liquid collection unit (8) through the liquid fraction transfer control means (7-3) passes through the filter means (8-1) and is discharged to the outside at atmospheric pressure through the liquid fraction discharge control means (8-2) and stored in the liquid fraction collection container (8-4). In the above device, the residence time of the liquid within the biomass fractionation unit (6) can be controlled by controlling the flow rate through a pump. Additionally, solid blockage or jamming can be minimized by controlling the system pressure through the liquid fraction discharge control means (8-2).

[0129] In an exemplary embodiment, the separated cellulose pulp can be used as a lignocellulose fiber precursor and a carbon fiber precursor.

[0130] In an exemplary embodiment, the separated cellulose pulp can be applied to a fermentation process of monosaccharides after undergoing a saccharification process.

[0131] In an exemplary embodiment, the separated cellulose pulp can be converted into a monomer for bioplastic synthesis through a chemical cellulose conversion process.

[0132] In an exemplary embodiment, the separated reactive lignin powder can be converted into propyl-, ethyl-, methyl-phenol / cyclohexane through demolecularization and deoxygenation.

[0133] In an exemplary embodiment, the separated reactive lignin powder can be applied as a mixture of SAF (sustainable aviation fuel, bio-aviation fuel) and LOHC (Liquid Organic Hydrogen Carrier) depending on the boiling point.

[0134] In an exemplary embodiment, the separated hemicellulose powder can be applied to a monosaccharide fermentation process after undergoing a saccharification process.

[0135] In an exemplary embodiment, the separated hemicellulose powder can be utilized as a hydrogen donor through liquid-phase modification during the process of demolition and deoxygenation of reactive lignin.

[0136] The present disclosure will be described in more detail below through examples. These examples are solely for illustrating the present disclosure, and it will be obvious to those skilled in the art that the scope of the present disclosure is not to be interpreted as being limited by these examples.

[0137] Example.

[0138] The prepared organic solvent aqueous solution (1) was injected into the biomass mixing section (5) after passing through the pump (3) and the preheating device (4), and the biomass was supplied directly from the biomass supply section (2) to the biomass mixing section (5). The biomass mixing section (5) was capable of pressure control using a valve and an auxiliary pump, so that after the biomass was supplied at atmospheric pressure, the biomass reached the biomass fractionation section (6) by free fall in the pressurized solvent. The biomass that reached the biomass fractionation section (6) along with the solvent was crushed and fractionated while passing through a high-temperature screw extruder. At this time, reactive lignin was selectively fractionated by the organic solvent and water.

[0139] Quercus mongolica was fractionated by continuous operation under high temperature and high pressure conditions of 185 ℃ and 20 bar, and the fractionation yield of Quercus mongolica according to ethanol concentration and the fractionation amount of each component were calculated from the solid fraction and are shown in Figure 3. As a result of the continuous operation fractionation, the fractionation yield of the solid fraction was found to be maintained at approximately 45 to 50 wt% at ethanol concentrations of 25 to 75 volume%. The lignin fractionation amount (i.e., Delignification) reached 85% to 90% of the original amount of lignin contained. Meanwhile, since the hemicellulose retention amount (i.e., Xylan retention) in the solid fraction was 10% to 30%, it was confirmed that the hemicellulose fractionation amount was 70% to 90% of the original amount of hemicellulose contained, and that it was fractionated in the liquid phase along with lignin. It was confirmed that the cellulose retention (i.e., Glucan retention) in the solid fraction was 80% to 90%, with most of it present in the solid pulp, and the cellulose fraction amount was 10% to 20% of the original amount of cellulose contained.

[0140] Lignin reactivity is determined by the remaining amount of β-aryl ether (β-O-4) bonds of Chemical Formula 1 below. HSQC-NMR (DD2 600MHz FT NMR, Agilent Technologies, USA) analysis revealed that 60.69 (MWL) of the β-O-4 ether bonds present in the raw biomass (Korean oak) were present out of 100 aromatics (see Table 1 below). After continuous operation fractionation of the above Korean oak, it was confirmed that the fractions using an aqueous ethanol solution of 25 to 75 volume% contained approximately 19 to 26 β-O-4 ether bonds. Meanwhile, as a comparative example, it was confirmed that approximately 5 β-O-4 ether bonds remained in Kraft lignin (KL), which is generally fractionated with a basic solution.

[0141] [Chemical Formula 1]

[0142]

[0143] [Chemical Formula 2]

[0144]

[0145] [Chemical Formula 3]

[0146]

[0147] MWL a KL b H2OEtOH 25 / H2O 75EtOH 50 / H2O 50EtOH 75 / H2O 25EtOHβ-O-460.694.7610.7519.1920.8425.5627.22β-β8.823.114.415.515.996.386.40β-53.500.510.840.851.191.381.46

[0148] a Milled wood ligin, b kraft lignin

[0149] The components of the solid and liquid fractions of the experimental group using an aqueous organic solvent solution containing 50 volume% ethanol as the solvent during the continuous operation fractionation experiment of the above-mentioned Mongolian oak were analyzed and are shown in Fig. 4. As a result, 49.5 wt% of the solid fraction and 43.7 wt% of the liquid fraction were obtained based on the total weight of the fractions. The solid fraction was in the form of solid pulp, as shown in the top photograph of Fig. 4, and 73.1 wt% of the solid fraction consisted of cellulose. The bottom photograph of Fig. 4 shows the liquid fraction after evaporating the solvent, and 49.7 wt% of the liquid fraction consisted of lignin and 32.7 wt% of hemicellulose.

[0150] In addition, as described above, the Mongolian oak was fractionated by continuous operation, using an aqueous organic solvent solution containing 50 volume% ethanol as the solvent under high temperature and high pressure conditions of 185°C and 10 to 30 bar. The fractionation yield of the Mongolian oak and the fractionation yield of each component were calculated from the liquid fraction and are shown in Table 2. The fractionation yield of the liquid fraction was maintained at 27.0 to 51.0 wt%, and the lignin fractionation yield reached 63% to 95% of the original lignin amount. The hemicellulose fractionation yield was 51.0% to 87.1% of the original hemicellulose amount and was fractionated in the liquid phase along with lignin. The cellulose fractionation yield was 8% to 18% of the original cellulose amount, confirming that 82% to 92% was present in the solid pulp.

[0151] 10 bar 20 bar 30 bar Fractionation yield 27.0 4 3.0 5 1.0 Cellulose fractionation yield 8.0 18.0 11.0 Hemicellulose fractionation yield 5 1.0 7 2.7 8 7.1 Lignin fractionation yield 6 3.0 7 3.0 9 5.0

[0152] Foregoing, specific parts of the present disclosure have been described in detail. It will be apparent to those skilled in the art that such specific descriptions are merely preferred embodiments and do not limit the scope of the present disclosure. Accordingly, the actual scope of the present disclosure is defined by the appended claims and their equivalents.

[0153] [Explanation of the symbol]

[0154] 1; Solvent supply unit

[0155] 2; Biomass supply unit 2-1; Biomass supply control means

[0156] 3; Pump 4; Preheater

[0157] 5; Biomass mixing section 5-1; First solvent supply control means

[0158] 5-2; Pressure release control means 5-3; Biomass transport control means

[0159] 6; Biomass fractionation unit 6-1; Continuous solvent supply means

[0160] 6-2; Driving means 6-3; Shaft sealing means

[0161] 6-4; extrusion means 6-5; heating means

[0162] 6-6; Means for changing the direction of movement of the fraction 6-7; Means for controlling the transfer of the fraction

[0163] 7; solid collection unit 7-1; second solvent supply control means

[0164] 7-2; means for controlling solid fraction discharge 7-3; means for controlling liquid fraction transfer

[0165] 7-4; Solid fraction collection container

[0166] 8; Liquid collection unit 8-1; Filter means

[0167] 8-2; liquid fraction discharge control means 8-3; bypass means

[0168] 8-4; Liquid fraction collection container

Claims

1. Biomass supply unit; A biomass mixing section formed at the bottom of the above-mentioned biomass supply section, into which biomass supplied from the above-mentioned biomass supply section is introduced; A solvent supply unit formed separately from the biomass supply unit and supplying a solvent to the biomass mixing unit; A biomass fractionation section formed at the bottom of the above biomass mixing section, wherein the biomass mixed with a solvent in the above biomass mixing section is transported to the biomass fractionation section, into which cellulose, hemicellulose, and lignin are fractionated; A solid collection unit formed at the bottom of the biomass fractionation unit and collecting solid fractions flowing in from the biomass fractionation unit; and It includes a liquid collection unit formed in connection with the solid collection unit and collecting liquid fractions flowing in from the biomass fractionation unit, and A biomass fractionation device in which the above biomass is supplied to a biomass mixing section at atmospheric pressure, and then, after a pressure increase through a solvent introduced from a solvent supply section, is transferred from the biomass mixing section to a biomass fractionation section by free fall.

2. In Paragraph 1, The above biomass mixing unit is, A first solvent supply control means for controlling the solvent supply flowing in from a solvent supply unit; Pressure release control means for pressure drop within the biomass mixing section; and A biomass fractionation device comprising a biomass transport control means for controlling the transport of biomass mixed with a solvent to a biomass fractionation unit.

3. In Paragraph 1, The above biomass fractionation unit is, Means for continuous solvent supply; Extrusion means for transporting biomass mixed with a solvent in a horizontal direction and crushing and fractionating it; A heating means formed horizontally with respect to the extrusion means and controlling the temperature of the extrusion means; A fraction travel direction changing means formed at the rear of the extrusion means and changing the fraction travel direction; and A biomass fractionation device comprising a fraction transport control means that transports the fraction, whose direction of travel has been changed by the fraction travel direction changing means, to a solid collection unit at the bottom by a free-fall method.

4. In Paragraph 3, The solid movement speed and liquid movement speed within the above device are different, and The above solid movement is controlled by the supply amount of biomass and / or the rotational speed of the extrusion means, and A biomass fractionation device in which the above liquid movement is controlled by the flow rate and / or flow velocity of the solvent supplied through the above-mentioned solvent supply means.

5. In Paragraph 3, A biomass fractionation apparatus in which the above fractionation is carried out at 10 to 30 bar and 150 to 200 ℃.

6. In Paragraph 3, The above extrusion means is a screw extruder, a biomass fractionation device.

7. In Paragraph 3, The above biomass fractionation unit is, Driving means for driving the above extrusion means; and A biomass fractionation device further comprising a shaft sealing means for sealing the extrusion means.

8. In Paragraph 1, The above solid collection unit is, Solid fraction discharge control means for controlling the discharge of solid fractions; A solid fraction collection container formed in connection with the solid fraction discharge control means and collecting the discharged solid fraction; and A biomass fractionation device comprising a liquid fraction transfer control means for controlling the transfer of a liquid fraction to a liquid collection unit.

9. In Paragraph 8, A biomass fractionation device wherein the above-mentioned solid collection unit further includes a second solvent supply control means for pressure correction.

10. In Paragraph 8, The above liquid collection unit is, Filter means for filtering the liquid fraction introduced through the above liquid fraction transfer control means; Liquid fraction discharge control means for controlling the discharge of a liquid fraction filtered by the above filter means; A liquid fraction collection container formed in connection with the liquid fraction discharge control means and collecting the discharged liquid fraction; and A biomass fractionation device comprising a bypass means formed separately from the liquid fraction discharge control means and capable of transferring the filtered liquid fraction to the liquid fraction collection container.

11. In Paragraph 1, A biomass fractionation device in which the temperature of the biomass fractionation section is 150 to 200 ℃ and the temperature of the liquid collection section is 50 ℃ or lower.

12. In Paragraph 1, The above device is a biomass fractionation device for separating reactive lignin from biomass.

13. In Paragraph 12, A biomass fractionation device in which the above-mentioned reactive lignin contains β-O-4 ether bonds.

14. In Paragraph 12, A biomass fractionation apparatus in which the reactive lignin comprises at least 20% of the total number of β-O-4 ether bonds based on the total number of β-O-4 ether bonds contained in the raw biomass prior to the fractionation reaction.

15. In Paragraph 1, A biomass fractionation apparatus in which the solvent comprises an alcohol having 1 to 6 carbon atoms.

16. In Paragraph 15, A biomass fractionation apparatus in which the solvent is an aqueous solution having an alcohol concentration of 5 to 95 volume%.

17. In Paragraph 1, The above device is a biomass fractionation device capable of continuous operation.

18. A method for biomass fractionation using a biomass fractionation device according to any one of claims 1 to 17.

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