WO2019240306A1 - Appareil pour mélange homogène et injection continue de lignine et de solvant, système de décomposition de lignine utilisant un fluide supercritique comprenant celui-ci et son procédé de fonctionnement - Google Patents

Appareil pour mélange homogène et injection continue de lignine et de solvant, système de décomposition de lignine utilisant un fluide supercritique comprenant celui-ci et son procédé de fonctionnement Download PDF

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Publication number
WO2019240306A1
WO2019240306A1 PCT/KR2018/006645 KR2018006645W WO2019240306A1 WO 2019240306 A1 WO2019240306 A1 WO 2019240306A1 KR 2018006645 W KR2018006645 W KR 2018006645W WO 2019240306 A1 WO2019240306 A1 WO 2019240306A1
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raw material
lignin
reaction
fluid
liquefaction
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PCT/KR2018/006645
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English (en)
Korean (ko)
Inventor
이인구
양제복
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한국에너지기술연구원
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Priority to PCT/KR2018/006645 priority Critical patent/WO2019240306A1/fr
Publication of WO2019240306A1 publication Critical patent/WO2019240306A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G1/00—Lignin; Lignin derivatives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • the present invention relates to an apparatus for uniformly mixing lignin and a solvent and continuously introducing the lignin and a solvent into a liquefaction reaction unit, a lignin decomposition system using the supercritical fluid including the same, and a method of operating the same.
  • Lignin along with cellulose and hemi-cellulose, is a major component of woody biomass. Lignin is produced as a by-product separated from cellulose and the like during pulp production and ethanol production from woody biomass. In the past, separated lignin was burned and used as a process energy source. Recently, lignin is liquefied to manufacture high value-added phenolic raw materials or liquid fuels. As such, continuous process development is required to mass produce high value added liquids from lignin.
  • Rapid pyrolysis technology is a technology that converts a low molecular weight material by applying heat to a material composed of a polymer such as lignin, and the reaction temperature is lower than combustion or gasification and has an advantage of operating at normal pressure.
  • rapid pyrolysis there is a problem in that the yield of liquid substance is low.
  • lignin has a property of being easily separated and precipitated with a liquid such as ethanol or water much faster than sawdust.
  • the present inventors have been trying to develop a continuous reaction apparatus that can be used for the production of high-value liquid substances by the liquefaction reaction using lignin and subcritical fluid or supercritical fluid, and solvents such as lignin and ethanol (liquefaction reaction conditions Subcritical fluid or supercritical fluid) in a uniformly mixed feeder for supplying continuously to the reactor of the next stage and the lignin decomposition system comprising the same to complete the present invention.
  • solvents such as lignin and ethanol (liquefaction reaction conditions Subcritical fluid or supercritical fluid) in a uniformly mixed feeder for supplying continuously to the reactor of the next stage and the lignin decomposition system comprising the same to complete the present invention.
  • Patent Document 1 Republic of Korea Patent Publication 10-2009-0030967
  • Another object of the present invention is to provide a lignin decomposition system using a supercritical fluid including a raw material supply part, a liquefaction reaction part and a catalytic reaction part including the supply device.
  • Another object of the present invention to provide a method for operating a lignin decomposition system using a supercritical fluid.
  • a raw material receiving unit receiving and receiving a mixture of lignin and a solvent as raw materials;
  • a partition wall which is movable while distinguishing a raw material container and a fluid container;
  • a cylinder including a fluid receiving portion capable of receiving a fluid capable of applying pressure to the partition wall;
  • a supply device to the liquefaction reactor of the raw material mixture comprising a discharge portion disposed in a portion of the raw material receiving portion for discharging the raw material stirred by the stirring means.
  • a raw material supply unit including the supply device
  • the present invention provides a lignin decomposition system using a supercritical fluid filled with a supercritical fluid and including a catalytic reaction part receiving a reaction product generated in the liquefaction reaction part and performing a catalytic reaction.
  • step 1 Supplying lignin and a solvent to a raw material receiving portion of the feeder (step 1);
  • It provides a method of using the above feeder comprising the step of applying a pressure to the partition wall and the lignin and solvent mixture mixed in the step 2 into the liquefaction reaction unit through the outlet (step 3).
  • step 1 Supplying a raw material which is a mixture of lignin and a solvent to a feeder of the lignin decomposition system (step 1);
  • step 2 Filling the liquefaction reaction unit and the catalyst reaction unit with a supercritical fluid solvent and setting the reaction pressure and the reaction temperature (step 2); And
  • It provides a method of operating the decomposition system including the step (step 3) of supplying the raw material to the reaction unit using a partition of the supply device and performing a liquefaction reaction and a catalytic reaction.
  • Feeding device for uniform mixing and continuous dosing of lignin and the solvent according to the present invention can be uniformly mixed with the mixture through a stirrer having a horizontal or vertical blade (blade), it can be added to the reaction section of the rear stage .
  • a stirrer having a horizontal or vertical blade (blade)
  • it is possible to prevent the separation of lignin and liquid more effectively by specifying the discharge pipe at a certain value, and evenly mixed into the reaction part for the post-stage process by applying a pressure to the mixture by adding a fluid to the upper part of the partition after partitioning the partition. It is effective to continuously add the mixture.
  • 1 is a schematic diagram showing a feeding device of a raw material mixture to a liquefaction reactor
  • FIG. 2 is a schematic diagram showing a lignin decomposition system using a supercritical fluid
  • FIG. 3 is a photograph of an acrylic reactor equipped with a horizontal blade stirrer
  • FIG. 4 is a table showing the results of mixing experiments of lignin and ethanol in an acrylic reactor equipped with a horizontal blade stirrer;
  • FIG. 6 is a table showing the results of mixing experiments of lignin and ethanol in an acrylic reactor equipped with a vertical blade stirrer;
  • FIG. 7 is a photograph and a table showing the results of mixing experiments of lignin and ethanol in an acrylic reactor equipped with a vertical cross blade stirrer;
  • FIG. 8 is a photograph showing an acrylic reactor equipped with a cross blade stirrer and having a 3/8 inch inside of the outlet conduit;
  • FIG. 9 is a table showing the results of mixing experiments with lignin and ethanol according to pipeline improvement in an acrylic reactor equipped with a cross blade stirrer;
  • FIG. 13 is a graph showing temperature and pressure versus lignin digestion system operating time
  • FIG. 15 is a graph of the analysis of gaseous products resulting from the operation of the lignin decomposition system
  • FIG. 16 is a graph showing temperature and pressure versus lignin decomposition system operating time of a lignin slurry mixture at a concentration of 5 wt%;
  • 17 is a table showing the color change and conditions of the liquid product produced due to the lignin decomposition system operation of the lignin slurry mixture of 5 wt% concentration;
  • FIG. 18 is a graph showing the results of GC-MS analysis of a liquid product obtained from the liquefaction of a lignin decomposition system of a lignin slurry mixture at a concentration of 5 wt%;
  • 19 is a graph showing the composition of a gas product obtained from the liquefaction of a lignin decomposition system of a lignin slurry mixture at a concentration of 5 wt%;
  • 20 is a graph showing temperature and pressure versus lignin decomposition system operating time of a lignin slurry mixture at a concentration of 25 wt%;
  • FIG. 21 is a table showing the color change and conditions of the liquid product produced due to the lignin decomposition system operation of the lignin slurry mixture at 25 wt% concentration;
  • FIG. 22 is a graph showing the results of GC-MS analysis of a liquid product obtained from the liquefaction of a lignin decomposition system of a lignin slurry mixture at a concentration of 25 wt%;
  • FIG. 23 is a graph showing the composition of a gas product obtained from the liquefaction of a lignin decomposition system of a lignin slurry mixture at a concentration of 25 wt%.
  • the present invention is a.
  • a raw material accommodating part 111 receiving and receiving a mixture of lignin and a solvent as raw materials;
  • a partition wall 112 that is movable while separating the raw material accommodating part and the fluid accommodating part 113;
  • a cylinder 110 including a fluid accommodating part 113 capable of accommodating a fluid capable of applying pressure to the partition wall;
  • FIG. 1 An example of the supply device 100 according to the present invention is shown through a schematic diagram of FIG.
  • the supply apparatus includes a cylinder 110, the cylinder includes a raw material receiving portion 111 for receiving and receiving a mixture of lignin and a solvent as a raw material; A partition wall 112 that is movable while separating the raw material accommodating part and the fluid accommodating part 113; And a fluid accommodating part capable of accommodating a fluid capable of applying pressure to the partition wall.
  • the supply device 100 is a raw material storage tank 140 for mixing and storing the lignin and the solvent; It may include an atmospheric pressure pump 141 for transferring the raw material to the raw material receiving portion.
  • the raw material storage tank is a storage tank for uniformly mixing and storing the lignin and the solvent for the supercritical fluid at a constant weight ratio, and may transfer the mixed raw material of the uniformly mixed lignin and the solvent to the raw material accommodating part 111. Preparation and storage of the mixed raw material of the lignin and the solvent may be stirred at a stirring speed of 200 rpm to 1,000 rpm, preferably 300 rpm or more at room temperature and normal pressure.
  • the raw material reservoir is preferably maintained in agitation in order to maintain a uniform mixed state of the mixed raw material of the lignin and the solvent.
  • the raw material storage tank may include a stirring means capable of performing the stirring.
  • the supply device 100 includes a fluid reservoir 150 for storing the fluid; And it may include a high pressure pump 151 for supplying the fluid to the fluid receiving portion.
  • the fluid is a substance present as a liquid at room temperature and a pressure of 400 bar or less, and may be water, ethanol, methanol, or the like. Fluid transported from the fluid reservoir to the fluid receiving unit 113 through the high pressure pump serves to transport the mixed raw material of the raw material receiving unit 111 to the reaction unit that can be installed at the rear end by pushing the partition 112 downward. .
  • the fluid and the raw material are preferably not mixed with each other in a completely blocked state by the partition wall.
  • the raw material storage tank 140 may include a supply line in communication with the raw material receiving portion 111, the supply line includes one or more valves for controlling the supply flow rate.
  • the valve may be, for example, a first valve 142.
  • the feed line is preferably kept horizontally to minimize the space between the raw material reservoir and the raw material receiving portion to prevent separation of the lignin and the solvent.
  • the fluid includes water, but any fluid that can apply pressure to the partition wall 112 can be used without limitation.
  • the cylinder 110 is divided into an upper chamber 10 and a lower chamber 20, wherein the upper chamber and the lower chamber are detachable from each other, and the supply device 100 includes a portion where the upper chamber and the lower chamber are detachable. It includes a high pressure cover 114 to maintain the pressure of the upper chamber. At this time, the detachment of the upper chamber and the lower chamber is preferably achieved through a screw type.
  • the high pressure cover 114 serves to fix the upper chamber 10 (upper layer) in a high pressure state, and when the high pressure cover is released, the upper chamber can be separated from the lower chamber 20, and the upper chamber is In a detached state, the partition wall 112 in the cylinder may be removed or replaced.
  • the upper chamber 10 has a fluid injection conduit 115 formed at the center of the upper end, through which the fluid capable of applying pressure to the partition wall 112 is injected into the fluid receiving part 113.
  • the inner diameter range of the fluid injection pipe is not particularly limited but may be preferably in the range of 3/4 inch (0.75 inch) to 1.5 inch.
  • the valve is mounted on the fluid injection line under high pressure to control the fluid input amount. There is a problem that is difficult to do.
  • an air discharge pipe 116 is formed at an upper portion of the upper chamber 10, and when the pressure is generated while the raw material is supplied to the raw material accommodating part 111 through the pipe, the partition 112 is pushed upward. I can raise it.
  • the air discharge line may be connected to the fluid reservoir 150.
  • Supply apparatus 100 includes a stirring means 120, the stirring means is provided in the raw material accommodating portion 111 to agitate the raw material.
  • the diameter of a portion of the raw material accommodating part in which the stirring means is located is smaller than the diameter of the partition so that the partition wall 112 cannot contact the stirring means 120. As the jaw is formed, the partition cannot contact the stirring means.
  • the stirring means 120 comprises a stirrer, the stirrer comprising a horizontal blade or a vertical blade, preferably a vertical blade.
  • the stirrer may be oriented blades in a straight or cross shape.
  • the stirring speed of the stirring means 120 may be 200 rpm to 1000 rpm, may be 300 rpm or more. If the stirring speed is less than 200 rpm there may be a problem that the mixture is not sufficiently stirred, there is a problem that unnecessary energy is required if it exceeds 1000 rpm.
  • the supply device 100 includes a discharge unit 130 and is disposed in a portion of the raw material receiving unit 111 to discharge the raw material stirred by the stirring means 120.
  • the discharge unit 130 may be disposed on the bottom or side of the raw material receiving portion 111, preferably may be disposed on the bottom.
  • the discharge unit 130 may have an inner diameter of 3/8 inch to 1 inch range.
  • the discharge unit 130 may include a single valve in the same way as the supply line to control the input amount of the lignin and the solvent mixture passing through the discharge unit.
  • the solvent is ethanol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, pentanol, hexanol, cyclopentanol, cyclohexanol, 2-methylcyclopentanol, hydroxyketone, cyclic ketone, acetone, Propane, butanone, pentanone, hexanone, 2-methyl-cyclopentanone, ethylene glycol, 1,3-propanediol, propylene glycol, butanediol, pentanediol, hexanediol, methylglyoxal, butanedione (butanedione), pentanedione, diketohexane, hydroxyaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal, formic acid, acetic acid, Propi
  • the solvent may be a supercritical fluid or a subcritical fluid.
  • a supercritical fluid for example, when lignin is liquefied using subcritical water or supercritical ethanol, it is possible to produce a high yield of liquid phenolic material.
  • Raw material supply unit 200 including the supply device 100;
  • a liquefaction reaction unit 300 filled with a fluid in a supercritical state and receiving a stirred raw material discharged from the raw material supply unit 200 to perform a liquefaction reaction;
  • the lignin decomposition system 1000 using the supercritical fluid according to the present invention includes a raw material supply part 200 including the supply device 100 as described above.
  • the raw material mixture containing lignin When the raw material mixture containing lignin is introduced into the reaction part 300 of the rear stage using the feeder 100, separation of the lignin and the liquid may be prevented, and thus the raw material mixed uniformly may be continuously added.
  • the supply device 100 may apply pressure to the raw material accommodating part 111 by using the fluid and the partition wall 112 supplied to the fluid accommodating part 113, and the high pressure condition when supplying the raw material through the applied pressure Can be formed.
  • the raw material may be supplied at the same pressure (eg, 200 bar to 400 bar pressure conditions) as that of the liquefaction reaction unit 300 and the catalytic reaction unit 400 at the rear stage.
  • the lignin decomposition system 1000 using the supercritical fluid according to the present invention includes a liquefaction reaction unit 300, and the liquefaction reaction unit is filled with a fluid in a supercritical state and supplies the stirred raw material discharged from the raw material supply unit. Take and perform the liquefaction reaction.
  • the liquefaction reactor 300 is a liquefaction reactor 310 for receiving a raw material discharged from the raw material supply unit 200 including the supply device 100 to perform a liquefaction reaction and to separate the solid product generated in the liquefaction reactor It comprises a solid product separator 320.
  • the liquefaction reaction unit 300 may include a heater, and a heater 311 may be formed on an outer circumferential surface of the liquefaction reactor 310.
  • the liquefaction reaction unit 300 may include a filter 330 between the liquefaction reactor 310 and the solid phase product separator 320, in a specific example by installing a filter at the bottom of the liquefaction reactor liquid phase product It can be separated from the product and gaseous product.
  • the raw material input tube 350 connected to the lower end of the supply device 100 passes.
  • the raw material input tube may preferably have an inner diameter of 0.5 cm or more, and may be 0.5 cm to 5 cm.
  • the raw material input tube is installed vertically from the bottom of the feeder to the top of the solid phase product separator to prevent the high concentration of lignin contained in the raw material from being separated from the valve or line with a solvent for supercritical fluid such as ethanol.
  • the raw material is heated while passing through the liquefaction reactor, the solvent is converted into a supercritical fluid and the liquefaction of lignin proceeds.
  • the preheating and liquefaction of the raw material is indirectly performed using a heater installed outside the liquefaction reactor, and the heater may be an electric furnace or a combustion furnace.
  • the liquefaction reactor may maintain the reaction temperature and the reaction pressure, the reaction temperature may be at least 300 °C, preferably at least 350 °C, 350 °C to 500 °C, the reaction pressure is 200 bar or more, 200 bar to By keeping it as high as possible in the 400 bar range, the solvent in the feed material (eg ethanol) can reach the supercritical state and the lignin can react with the supercritical fluid to maximize liquefaction.
  • the solvent in the feed material eg ethanol
  • the liquefaction reaction unit 300 may include a valve 340 on the top of the liquefaction reactor 310, the valve may be connected to the external environment.
  • the supercritical fluid is filled inside the liquefaction reactor, but generally the supercritical fluid is not filled inside the reactor.
  • the liquefaction reactor of the lignin decomposition system 1000 according to the present invention forms a valve on the upper portion, the valve in the supercritical fluid can be opened to fill the supercritical fluid to the top of the reactor.
  • the solid product separator 320 also includes a heater, and a heater 321 may be formed on the outer circumferential surface of the solid product separator.
  • the solid product separator may also include a discharge valve 322 disposed below the solid product separator for discharging the solid product separated from the liquefaction reactor 310. While passing through the liquefaction reactor, the solvent contained in the raw material becomes a supercritical fluid and the liquefaction of lignin proceeds. The result is a liquid product, a gaseous product and a solid product.
  • the solid product separator is operated at the same pressure as the liquefaction reactor at a temperature of about 300 °C, preferably in the temperature range of 200 °C to 400 °C, pressure range of 200 bar to 400 bar and precipitates the solid product by gravity And from gaseous products.
  • the liquid product and the gaseous product are heated to about 350 ° C. while passing through the upper liquefaction reactor and introduced into the catalytic reaction unit 400.
  • the solids are discharged within a range that does not affect the reaction conditions by using a high temperature and high pressure valve at the bottom.
  • the lignin decomposition system 1000 using the supercritical fluid according to the present invention includes a catalytic reaction part 400, and the catalytic reaction part is filled with a fluid in a supercritical state, and the reaction occurring in the liquefaction reaction part 300.
  • the product is supplied to carry out the catalytic reaction.
  • the catalytic reaction unit 400 may include a catalytic reactor 410 and a heater 411 filled with a solid catalyst.
  • the catalyst decomposes a supercritical fluid to generate reducible radicals such as hydrogen, which are highly reactive therefrom, and promotes a deoxygenation reaction which removes oxygen from the oxidized organic compounds of the generated radicals and liquid products. Play a role.
  • the catalyst may preferably be a catalyst well dispersed and supported on a metal having activity in the reaction, such as nickel, on a well-developed mesopore.
  • the catalyst is molded and filled to have an appropriate particle size at a level that does not interfere with the flow of supercritical fluids and products.
  • a heater which is an electric furnace or a combustion furnace, is installed outside the catalytic reactor to maintain the temperature of the catalyst in the catalytic reactor at least 300 ° C or more, preferably in the range of 300 ° C to 500 ° C and 300 ° C to 350 ° C, and the reaction pressure is 200 bar It maintains the same pressure as the liquefaction reactor 310 and the solid phase product separator 320 in the range from to 400 bar.
  • the decomposition system 1000 is a supercritical fluid solvent reservoir 500 for storing a solvent for the supercritical fluid; And it may include a high pressure pump 510 for supplying the solvent to the reactor.
  • the solvent storage tank for the supercritical fluid is a storage tank of an organic solvent which serves as a supercritical fluid at reaction temperature and reaction pressure conditions, and the high pressure pump is a liquid phase reactor for liquefying the organic solvent in the solvent storage tank for the supercritical fluid. 320), the catalytic reactor 410 and the like to serve as a unit.
  • the liquefaction reactor 310, the solid-phase product separator 320, the catalytic reactor 410, etc. installed at the lower end of the supply device 100 are put into the unit apparatus under reaction temperature and reaction pressure conditions. Maintains supercritical fluid status.
  • dilution of the mixed raw material containing lignin may be required during the liquefaction reaction operation, it may also serve to adjust the concentration of lignin.
  • the decomposition system 1000 includes a heat exchanger 600 positioned at the rear end of the catalytic reaction unit 400 to cool the reaction product formed in the catalytic reaction unit.
  • the heat exchanger serves to cool the reaction product generated in the catalytic reaction unit from the reaction temperature to room temperature.
  • the pressure may be in the same pressure range as the liquefaction reactor 310, the solid phase product separator 320, the catalytic reactor 410 in the range of 200 bar to 400 bar.
  • the cracking system 1000 includes a back-pressure regulator 700 that constantly controls the pressure in the cracking system.
  • the after-pressure controller is a raw material receiving portion 111, liquefaction reactor 310, solid state product separator 320, catalytic reactor 410, heat exchanger 600 of the cylinder 100 of the feeder 100 It serves to control the pressure constantly.
  • the after pressure controller may be located after the catalytic reactor, more preferably after the heat exchanger, and the reaction product is depressurized to atmospheric pressure as it passes through the after pressure controller.
  • the decomposition system 1000 includes a gas-liquid separator 800 located at the rear end of the catalytic reaction unit 400 to separate the reaction product into gas phase and liquid phase.
  • the gas-liquid separator serves to separate the product at room temperature and pressure into the gas phase and the liquid phase.
  • the gaseous product is discharged to the top of the gas-liquid separator, and the liquid product is obtained from the bottom of the gas-liquid separator.
  • the decomposition system 1000 may include a gas flow rate meter 810 for measuring the production flow rate of the gaseous product in real time.
  • the gas flow rate meter may be connected to a gas-liquid separator to measure a production flow rate of the gaseous product, and as a specific example, a wet test meter may be used.
  • the decomposition system 1000 may include a control unit for monitoring and controlling temperature and pressure.
  • a pressure gauge at the front and rear ends of all the unit devices, including the supply device 100, by monitoring the pressure change can be utilized as information necessary for the operation of the decomposition system.
  • the decomposition system 1000 may include a feeder such that the plurality of feeders 100 are connected in parallel to the liquefaction reaction unit 300, and the raw material stirred by the liquefaction reactor as the plurality of feeders are provided. Can be fed continuously.
  • the other feeder may prepare a uniformly stirred raw material by stirring the raw material.
  • the agitated raw material may be injected into the liquefaction reactor from the feeder, which prepares the uniformly stirred raw material, to perform continuous feeding.
  • step 1 Supplying lignin and a solvent to the raw material accommodating part 111 of the supply device 100 (step 1);
  • It provides a method of using the supply device 100 comprising applying a pressure to the partition wall 112 and injecting the lignin and solvent mixture mixed in the step 2 into the liquefaction reaction unit through the discharge unit 130 (step 3). .
  • step 1 is a step of supplying lignin and a solvent to the raw material receiving portion 111 of the feeder.
  • the lignin and the solvent which are the raw materials, may be supplied to the raw material accommodating part 111 independently or in a mixed state while the valve of the discharge part 130 is completely closed.
  • step 2 and step 3 the lignin and the solvent supplied to the raw material accommodating portion 111 is mixed with the stirring means 120, partition (! 12) is added to the liquefaction reaction unit 300 through the discharge unit 130 by adding a pressure to the lignin and solvent mixture mixed in step 2 above.
  • Steps 2 and 3 are a mixture of the lignin and solvent mixture by stirring the raw material with the stirring means 120 provided in the raw material receiving portion 111, and then applying a pressure to the partition 112 in the cylinder 110 with a fluid To the liquefaction reaction unit 300 through the discharge unit 130.
  • Mixing time through the stirrer which is the stirring means 120 may vary depending on the size of the supply device 100 and is not particularly limited but may be stirred for 5 to 30 minutes, preferably for 7 to 20 minutes May be stirred, more preferably 8 minutes to 15 minutes, and most preferably 10 minutes.
  • the fluid is introduced until the lowering of the partition 112 stops, and if the fluid is continuously supplied to the upper part of the partition wall, the partition wall is lowered until the pressure between the lignin and the solvent mixture is equal to the pressure of the fluid, and the pressure is the same.
  • the valve of the outlet 130 is opened and the fluid is continuously supplied again.
  • the amount of the mixture supplied to the liquefaction reactor 310 is equal to the amount of fluid introduced.
  • step 1 Supplying a raw material which is a mixture of lignin and a solvent to a supply device 100 of the lignin decomposition system 1000 (step 1);
  • step 2 Filling the liquefaction reaction unit 300 and the catalytic reaction unit 400 with a supercritical fluid solvent and setting the reaction pressure and the reaction temperature (step 2); And
  • step It provides a method of operating the decomposition system 1000 comprising a).
  • step 1 is a step of supplying a raw material which is a mixture of lignin and a solvent to the supply device 100 of the lignin decomposition system.
  • step 1 the raw material, which is a mixture of lignin and a solvent, is supplied to the supply device 100 of the decomposition system, and more specifically, to the raw material receiving part 111 inside the cylinder 110 of the supply device.
  • the raw material supplied in step 1 may be a mixture of lignin and a solvent mixed in the raw material storage unit 140.
  • a lignin and a supercritical fluid solvent (for example, ethanol, etc.) of a desired concentration are added to the raw material storage unit at atmospheric pressure, and mixed by stirring.
  • the mixture is prepared and stored, and the atmospheric pressure pump 141 and the first valve are prepared.
  • 142 is used to feed into the raw material accommodating portion 111 of the cylinder 110.
  • the third valve 117 and the fifth valve 119 are completely closed, and the fourth valve 118 is left open.
  • air may be discharged out through the fourth valve 118 at the upper end of the cylinder.
  • the fourth valve 118 is also completely closed and the third valve 117 is opened to inject the fluid in the fluid reservoir 150 into the fluid receiving part 113 using the high pressure pump 151. If the fluid is continuously added, the pressure in the cylinder 100 increases because the first valve 142, the fourth valve 118, and the fifth valve 119 are closed. The pressure inside the cylinder can be maintained at about 1 bar to 2 bar higher than the reaction pressure. The fluid is introduced into the fluid receiving portion using a high pressure pump until the pressure inside the cylinder is maintained at about 1 bar to 2 bar higher than the reaction pressure, and stops when the target pressure is reached.
  • step 2 is to set the reaction pressure and reaction temperature after filling the liquefaction reaction unit 300 and the catalyst reaction unit 400 with a supercritical fluid solvent Step.
  • Step 2 is a step of forming the reaction apparatus in a supercritical fluid state before the decomposition reaction of lignin, the supercritical conditions after filling the liquefaction reaction unit 300 and the catalytic reaction unit 400, the reaction unit with a supercritical fluid solvent is set do.
  • the step 2 is the second valve connected to the solvent reservoir 500 and the high pressure pump 510 for the supercritical fluid in a state in which the fifth valve 119 connected to the outlet 130 of the supply device 100 is closed. 511 is opened and a supercritical fluid solvent (for example, ethanol, etc.) is introduced into the liquefaction reactor 310 using a high pressure pump.
  • a supercritical fluid solvent for example, ethanol, etc.
  • the solvent introduced into the catalytic reactor passes through the solid phase product separator 320, the catalytic reactor 410, the heat exchanger 600, and the back pressure controller 700, and exits the gas-liquid separator 800. Continue to feed through the high pressure pump until it is confirmed that the solvent exits the gas-liquid separator.
  • step 3 uses the partition 112 of the supply device 100 to make the pressure of the raw material accommodating part 111 equal to the reaction pressure of the reaction part. After setting, the raw material is supplied to the reaction unit to perform a liquefaction reaction and a catalytic reaction.
  • step 3 the mixed raw material prepared in step 1 is supplied into the reaction unit prepared in step 2 to perform the decomposition reaction of lignin.
  • the step 3 is to open the fifth valve 119 and at the same time using a high pressure pump 151 to inject a solvent into the fluid receiving portion 113 of the cylinder 100 to the mixed raw material to the liquefaction reactor 310 Can be put in.
  • the solvent input for the supercritical fluid through the high pressure pump 510 is stopped at the same time and the second valve 511 is completely closed.
  • a supercritical fluid liquefaction operation of lignin is performed.
  • the decomposition system 1000 includes a heat exchanger 600 positioned at the rear end of the catalytic reaction unit 400 to cool the reaction product formed in the catalytic reaction unit, and further comprising the step of cooling the reaction product (step 4). It may include.
  • the product passed through the catalytic reactor 410 is separated into a gaseous phase and a liquid phase through cooling and pressure reduction processes, and the gaseous phase is measured in real time with a gas flow meter.
  • a gas sample is placed between the gas-liquid separator 800 and the gas flow rate meter to collect a gas sample and use it for composition analysis.
  • the liquid product is collected from the bottom of the gas-liquid separator for a certain period of time and used for analysis of generation amount and fuel characteristics.
  • the input flow rate is performed while changing the flow rate of the high pressure pump 151 connected to the fluid reservoir 150, and the lignin concentration control is performed and the flow rate change of the high pressure pump 510 connected to the solvent reservoir 500 for the supercritical fluid. This can be done via:
  • the reaction pressure may be controlled through the after pressure controller 700 and the reaction temperature may be controlled through the temperature controller.
  • Fluid reservoir 113
  • High pressure cover 114
  • Pipe for fluid injection 115 Pipe for air discharge: 116
  • Raw material storage 140 atmospheric pressure pump: 141
  • Raw material supply part 200 Liquefaction reaction part: 300
  • Catalytic Reactor 400 Catalytic Reactor: 410
  • FIG. 3 As shown in FIG. 3, four samples having an internal diameter of 90 mm and a height of 600 mm, having an acrylic mixer reactor equipped with a stirrer at the bottom and having a 1/4 inch pipeline at uniform intervals according to the height. A harvesting port was installed. The four sampling ports are for measuring the mixing rate according to the mixing reactor height. After mixing 25-30 wt% of hydrolyzed lignin in ethanol, it was added to the acrylic reactor, and after sufficient time (about 30 minutes) while stirring at 250 rpm, the valve of the sampling port was slowly opened to collect a sample and lignin by the reactor height. The content was measured. The stirrer used a stirrer with a horizontal blade (blade) as shown in the lower right of FIG.
  • blade horizontal blade
  • the lignin content of all four samples was very low, 6 wt% or less, and the higher the sampling height, the lower the concentration. That is, the mixing of lignin and ethanol did not occur well under such stirring conditions, and most of the lignin was precipitated at the bottom of the reactor.
  • the mixing ratio difference according to the height of the reactor was somewhat improved (particularly, the lignin concentration of sample sampling No. 4) was still different from that of 30 wt% of the lignin concentration of the stock solution.
  • the lignin decomposition system as shown in the schematic diagram in FIG. 2 was configured, and the catalytic reactor was made of Inconel 625 material having an inner diameter of 17.5 mm, a length of 150 mm, and a volume of 35 mL.
  • the deoxidation reaction proceeds while the solid phase cannot pass through the catalyst layer and passes only the liquid and gaseous products.
  • the experimental method is as follows.
  • ethanol was filled with the liquefaction reactor and the catalytic reactor using a high pressure pump, and then boosted to 300 bar using a back pressure controller (BPR) and maintained for 30 minutes to check whether the pressure was leaked.
  • BPR back pressure controller
  • the inside of the reactor was heated up to 350 ° C. using an electric furnace mounted outside the reactor.
  • a cooling device was installed outside the reactor catalyst layer to control the reaction temperature in case of excessive exothermic reaction. Once the reactor temperature reached the target value, the reactor and all tube lines were rechecked for leaks.
  • lignin-ethanol raw material mixture is continuously liquefied and introduced into the catalytic reactor. When the raw material mixture reaches the reactor, a rapid liquefaction of lignin proceeds to produce a first decomposition product.
  • the primary decomposition product passes through the catalyst bed where the deoxygenation reaction proceeds. After passing through the catalyst bed, the product is cooled and decompressed to enter the gas-liquid separator to separate gas and liquid product.
  • the separated gas product was identified in real time using a wet gas meter (wet gas meter). Liquid products were collected for a defined time at the bottom of the gas-liquid separator to determine the weight and rate of production.
  • the heating was stopped and the reactor was cooled down to room temperature. When the temperature inside the reactor reached room temperature, the inside of the reactor was opened to recover the solid product and the catalyst.
  • the solid phase was dried in an atmospheric pressure dryer at 105 ° C. for 12 hours, cooled, and weighed.
  • the liquid product was distilled under reduced pressure in a vacuum distillation apparatus at 60 ° C. to remove ethanol as a solvent, and the remaining material was harvested as a liquefied oil product.
  • the pure ethanol input flow rate was increased to 0.8, 1.5, 2.2, 3.1, and 3.9 g / min, and the reactor was operated to establish the operating conditions for maintaining the reactor temperature and pressure at 350 ° C and 300 bar. No catalyst was used in this experiment. After reaching the target temperature and pressure at each ethanol input flow rate, the product was collected for 30 minutes and then the product was collected and changed to the next flow rate. The results were shown in Table 1 below.
  • the reactor liquefied bed temperature was maintained at 350 ° C. at 3.9 g / min (0.23 kg / h), which is an ethanol input flow rate higher than the initial input flow target 0.1 kg / h flow rate. Since the heating furnaces of the liquefied layer and the catalyst layer are installed and operated independently, the temperature of the catalyst layer can be raised to 300 ° C or more if necessary.
  • the reactor was operated for 4 hours at a ethanol flow rate of 2.37 g / min (0.14 kg / h) in order to confirm that the reactor temperature of 350 ° C. and the pressure of 300 bar were maintained over time.
  • the results are shown in FIG. 10. Liquid and gaseous product samples were collected and analyzed every 1 hour during operation, and the results are shown in FIGS. 11 and 12.
  • the GC-MS analysis showed that the ethanol content was about 79 area% and the acetic acid and propanoic acid were 10 area%, respectively. These results are very different from the experimental results using KOH as a catalyst. On KOH, 90% of ethanol is converted to butanol, hexanol, gas and the like. On the other hand, gas production was very low at an average of 3 ml / min, and the main components were hydrogen and carbon dioxide.
  • the liquid product obtained in the case of the catalyst experiment was composed of a wide variety of organic compounds in comparison with the experiment of 2) (the catalyst-free experiment, see FIG. 12).
  • the liquid product produced various ethers and aldehydes such as 1,1-diethoxy ethane, acetaldehyde, ethyl ether, 1-ethoxy butane and butanoic acid ethyl ester.
  • 1,1-diethoxy ethane is produced from dehydration and dehydrogenation of ethanol
  • acetaldehyde is produced from dehydrogenation of ethanol.
  • reaction conditions are liquefied bed temperature 350 °C, Mg-Ni-Mo / AC catalyst bed temperature 350 °C, reactor pressure 300 bar, reactant stirring speed 400rpm, WHSV 244.7, 122.3, 61.2, 36.8 h -1 .
  • Figure 16 shows the change in reaction temperature and reaction pressure over time. In the experiment, which lasted about two and a half hours, the temperature and pressure remained fairly constant.
  • the temperature of the liquefied layer and the catalyst bed of the reactor can be independently controlled by using a separate heating furnace, so that the temperature of the liquefied layer and the catalyst bed can be raised to 400 ° C. or more if necessary.
  • FIG. 17 shows the color changes and conditions of the liquid product obtained in the separation process of the gas and the liquid product generated from the supercritical ethanol combustion liquefaction of 5 wt% lignin, and the distribution of the liquid, gaseous and solid products is shown in Table 2. Indicated. At lower feed rates, the liquid product had a lighter brown color, which is interpreted as a secondary reaction of the lignin degradation products.
  • Liquid products were classified into N-compounds, phenols, aromatics, acids, esters, aldehydes, ketones, alcohols, ethers, hydrocarbons, and others.
  • other substances include alpha.-d-6,3-Furanos, levoglucosan, ethyl .alpha.-d-glucopyranoside, 1,6-Anhydro-.alpha.-d-galactofuranose, 3-Methylmannoside, Methyl .beta.-d Compounds such as -ribofuranoside d-allose were included.
  • Table 3 shows the results of elemental analysis of the liquid product obtained from the 5 wt% lignin liquefaction and the calculated high calorific value (HHV).
  • HHV high calorific value
  • the liquefaction experiment was carried out by continuously adding 25 wt% of lignin and 75 wt% of ethanol to the reactor while mixing in the cylinder raw material receiving portion.
  • the reaction conditions are reactor temperature 350 ° C., reactor pressure 300 bar, stirring speed 400 rpm, WHSV 244.7, 122.3, 61.2, 36.8 h ⁇ 1 on Mg-Ni-Mo / AC catalyst.
  • the influence of reactant input flow rate on the composition of the liquid product obtained in 25 wt% lignin supercritical ethanol continuous liquefaction is shown in FIG. 22.
  • the liquid product composition was different from that of lignin 5 wt%.
  • aromatic compounds there was a tendency for aromatic compounds to increase as the WHSV decreased. This is interpreted as being converted into an aromatic compound by deoxygenation, hydrogenation, and dehydration of oxygen-containing materials. Phenols also increased until WHSV decreased from 244.7 h -1 to 122.3 h -1 and then decreased to 36.8 h -1 .
  • Table 5 shows the elemental analysis results of the liquid product obtained in the 25 wt% lignin supercritical ethanol continuous liquefaction experiment and the calculated high calorific value (HHV). Overall, oxygen content was lower than that of 5 wt% lignin, and carbon content increased and oxygen content decreased with longer reactor residence time (lower WHSV). The maximum calorific value was 34.78 MJ / kg at WHSV 36.8 h ⁇ 1 .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

La présente invention concerne un appareil d'alimentation d'un mélange de matières premières dans un réacteur de liquéfaction comprenant : une unité de réception de matière première pour recevoir un mélange de lignine et un solvant introduit en tant que matière première ; une paroi de séparation qui peut se déplacer tout en séparant l'unité de réception de matière première d'une unité de réception de fluide ; un cylindre comprenant l'unité de réception de fluide pouvant recevoir un fluide pouvant appliquer une pression à la paroi de séparation ; un moyen d'agitation, disposé dans l'unité de réception de matière première, pour agiter la matière première ; et une unité d'évacuation aménagée dans une partie de l'unité de réception de matière première, pour décharger la matière première agitée par le moyen d'agitation. Selon la présente invention, un appareil d'alimentation pour mélanger de manière homogène et injecter en continu le mélange de lignine et d'un solvant peut mélanger un mélange de manière homogène au moyen d'un agitateur ayant des pales horizontales ou verticales, et maintenir le mélange à injecter dans une unité de réaction à un stade ultérieur. De plus, il est possible de prévenir plus efficacement la séparation entre la lignine et un liquide réglant à une certaine valeur une conduite dans l'unité d'évacuation. Après que la matière première et un fluide sont séparés au moyen de la paroi de séparation, le fluide est injecté dans la partie supérieure de la paroi de séparation de telle sorte qu'une pression est appliquée au mélange, ce qui permet d'injecter en continu le mélange homogène dans l'unité de réaction pour un processus ultérieur.
PCT/KR2018/006645 2018-06-12 2018-06-12 Appareil pour mélange homogène et injection continue de lignine et de solvant, système de décomposition de lignine utilisant un fluide supercritique comprenant celui-ci et son procédé de fonctionnement WO2019240306A1 (fr)

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