WO2019240306A1 - Apparatus for homogeneous mixing and continuous injecting of lignin and solvent, lignin decomposition system using supercritical fluid comprising the same, and operating method thereof - Google Patents

Abstract

The present invention provides an apparatus for feeding a raw material mixture to a liquefaction reactor, comprising: a raw material receiving unit for receiving a mixture of lignin and a solvent supplied as a raw material; a partition wall which can move while separating the raw material receiving unit from a fluid receiving unit; a cylinder including the fluid receiving unit capable of receiving a fluid that is capable of applying pressure to the partition wall; a stirring means, provided in the raw material receiving unit, for stirring the raw material; and a discharging unit, disposed in a portion of the raw material receiving unit, for discharging the raw material stirred by the stirring means. According to the present invention, a feeding apparatus for homogeneously mixing and continuously injecting the mixture of lignin and a solvent can mix a mixture homogeneously by means of a stirrer having horizontal or vertical blades, and maintain the mixture to be injected into a reaction unit at a post stage. In addition, it is possible to more effectively prevent separation between the lignin and a liquid by specifying a pipe in the discharging unit to a certain value. After the raw material and a fluid are separated by means of the partition wall, the fluid is injected into the top of the partition wall such that a pressure is applied to the mixture, thereby allowing the homogeneously mixed mixture to be continuously injected into the reaction unit for a post-stage process.

Description

Apparatus for homogeneous mixing and continuous dosing of lignin and solvent, lignin decomposition system using supercritical fluid comprising the same and method of operation thereof

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.

The simplest continuous process is rapid pyrolysis. 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. However, in case of rapid pyrolysis, there is a problem in that the yield of liquid substance is low.

On the other hand, recent studies have shown that liquefaction of lignin in subcritical water or supercritical fluids (e.g. supercritical ethanol) can produce high yields of liquid phenolic materials, and studies on this have been actively conducted. One). In this process, although the reaction proceeds at a lower temperature than rapid pyrolysis, it requires a high reaction pressure of 100 atm or higher. At such a high pressure, lignin raw material is continuously introduced into the supercritical fluid reactor using a screw device commonly used in the rapid pyrolysis process. It is impossible to do.

In addition, lignin has a property of being easily separated and precipitated with a liquid such as ethanol or water much faster than sawdust.

Therefore, in order to develop a continuous reactor for producing a liquid high value-added material by the subcritical or supercritical fluid liquefaction of lignin, the development of a system for continuously injecting lignin is necessary.

Accordingly, 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.

<Preceding technical literature>

(Patent Document 1) Republic of Korea Patent Publication 10-2009-0030967

It is an object of the present invention to provide a feeder of a lignin and solvent mixture to a liquefaction reactor.

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.

It is a further object of the present invention to provide a method of using a feeder of a lignin and a solvent mixture to a liquefaction reactor.

Another object of the present invention to provide a method for operating a lignin decomposition system using a supercritical fluid.

In order to achieve the above object, the present invention

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;

Stirring means provided in the raw material accommodating portion to stir the raw materials; And

Provided is 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.

In addition, the present invention

A raw material supply unit including the supply device;

A liquefaction reaction unit filled with a fluid in a supercritical state and receiving a stirred raw material discharged from the raw material supply unit to perform a liquefaction reaction; And

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.

Furthermore, the present invention

Supplying lignin and a solvent to a raw material receiving portion of the feeder (step 1);

Mixing the lignin and the solvent supplied to the raw material accommodating part with stirring means (step 2); And

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).

Furthermore, the present invention

Supplying a raw material which is a mixture of lignin and a solvent to a feeder of the lignin decomposition system (step 1);

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 . In addition, 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;

2 is a schematic diagram showing a lignin decomposition system using a supercritical fluid;

3 is a photograph of an acrylic reactor equipped with a horizontal blade stirrer;

4 is a table showing the results of mixing experiments of lignin and ethanol in an acrylic reactor equipped with a horizontal blade stirrer;

5 is a photograph showing an acrylic reactor equipped with a vertical blade stirrer;

6 is a table showing the results of mixing experiments of lignin and ethanol in an acrylic reactor equipped with a vertical blade stirrer;

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.

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.

10 is a graph showing temperature and pressure versus lignin digestion system operating time;

11 is a graph of the analysis of the liquid product generated by the operation of the lignin decomposition system;

12 is a graph of the analysis of the gaseous products resulting from the operation of the lignin decomposition system;

FIG. 13 is a graph showing temperature and pressure versus lignin digestion system operating time; FIG.

14 is a graph of the analysis of the liquid product generated by the operation of the lignin decomposition system;

FIG. 15 is a graph of the analysis of gaseous products resulting from the operation of the lignin decomposition system; FIG.

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;

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

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;

Stirring means 120 provided in the raw material accommodating part 111 to stir the raw material; And

It is provided to the supply device 100 to the liquefaction reactor of the raw material mixture including a discharge unit 130 is disposed in a portion of the raw material receiving portion 111 for discharging the raw material stirred by the stirring means 120.

At this time, an example of the supply device 100 according to the present invention is shown through a schematic diagram of FIG.

Hereinafter, with reference to the schematic diagram of FIG. 1, the supply apparatus 100 to the liquefaction reactor of the raw material mixture which concerns on this invention is demonstrated in detail.

The supply apparatus according to the present invention 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.

In addition, 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.

Further, 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.

In this case, 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. In addition, 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. Further, 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.

Here, 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. At this time, 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. When the inner diameter is less than 3/4 inch (0.75 inch), it is difficult to inject the fluid into the fluid receiving portion, and when the inner diameter exceeds 1.5 inches, 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.

In addition, 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. In this case, the air discharge line may be connected to the fluid reservoir 150.

Supply apparatus 100 according to the present invention includes a stirring means 120, the stirring means is provided in the raw material accommodating portion 111 to agitate the raw material.

It is preferable that 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. When the vertical blade is used, the content of the lignin in the lignin and the solvent mixture discharged to the discharge unit 130 is equal to or greater than 99% of the initial lignin content supplied to the mixture receiving unit, thereby having an effect of uniform mixing. At this time, the stirrer may be oriented blades in a straight or cross shape.

In addition, 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 according to the present invention 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.

In addition, the discharge unit 130 may have an inner diameter of 3/8 inch to 1 inch range.

At this time, when the inner diameter of the outlet 130 is less than 3/8 inch, separation of lignin and solvent occurs, so that lignin is attached to the pipe wall and accumulated, and only the solvent passes through the pipe. If it exceeds 1 inch there is a problem that it is difficult to control the high temperature, high pressure in the connection portion with the liquefaction reactor 310 is connected to the rear end of the discharge.

Furthermore, 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.

On the other hand, 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, Propionic acid, butanoic acid, pentanic acid, hexanoic acid, lactic acid, glycerol, furan, tetrahydrofuran, dihydrofuran, 2-furan methanol, 2-methyl-tetrahydrofuran, 2,5 -Dimethyl-tet Hydrofuran, 2-ethyl-tetrahydrofuran, 2-methylfuran, 2,5-dimethylfuran, 2-ethylfuran, hydroxymethylfurfural, 3-hydroxytetrahydrofuran, tetrahydro-3- Furanol, 5-hydroxymethyl-2 (5H) -furanone, dihydro-5- (hydroxymethyl) -2 (3H) -furanone, tetrahydro-2-furoic acid, dihydro-5- ( Hydroxymethyl) -2 (3H) -furanone, tetrahydrofurfuryl alcohol, 1- (2-furyl) ethanol, hydroxymethyltetrahydrofurfural, etc. Can be.

More specifically, the solvent may be a supercritical fluid or a subcritical 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.

In addition, the present invention

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; And

A lignin decomposition system 1000 using a supercritical fluid filled with a fluid in a supercritical state and including a catalytic reaction part 400 which receives a reaction product generated from the liquefaction reaction part 300 and performs a catalytic reaction to provide.

At this time, an example of the lignin decomposition system 1000 according to the present invention is shown through the schematic diagram of FIGS.

Hereinafter, referring to the schematic diagrams of FIGS. 1 to 3, the lignin decomposition system 1000 using the supercritical fluid according to the present invention will be described in detail.

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.

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.

In addition, 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. Through this, 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.

At this time, 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. Inside the liquefaction reactor, 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 ℃, preferably at least 350 ℃, 350 ℃ to 500 ℃, 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.

In addition, 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. Thus, 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.

Furthermore, 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 ℃, preferably in the temperature range of 200 ℃ to 400 ℃, 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. When a certain amount of solid products accumulate, 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.

In addition, 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.

In the initial stage of operation of the decomposition system 1000, 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. In addition, when 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.

In addition, 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.

Further, the cracking system 1000 includes a back-pressure regulator 700 that constantly controls the pressure in the cracking system. As a specific example, 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.

In addition, 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.

In this case, 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.

Furthermore, the decomposition system 1000 may include a control unit for monitoring and controlling temperature and pressure. The apparatus for temperature control and monitoring of the liquefaction reactor 310, the solid-phase product separator 320, the catalytic reactor 410. In addition, by installing 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.

In addition, 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. For example, when agitation is sufficiently completed in one feeder and a uniform raw material is injected into the liquefaction reactor, at the same time, the other feeder may prepare a uniformly stirred raw material by stirring the raw material. At the time when all the raw materials in the feeder injecting the stirred raw material into the liquefaction reactor are injected, 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.

Furthermore, the present invention

Supplying lignin and a solvent to the raw material accommodating part 111 of the supply device 100 (step 1);

Mixing the lignin and the solvent supplied to the raw material accommodating part 111 with the stirring means 120 (step 2); And

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). .

Hereinafter, a method of using the supply device 100 to the liquefaction reaction unit of the lignin and the solvent mixture according to the present invention will be described in detail for each step.

First, in the method of using the feeder 100 according to the present invention, step 1 is a step of supplying lignin and a solvent to the raw material receiving portion 111 of the feeder.

In the step 1, 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.

Next, in the method of using the feeder 100 according to the present invention, 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 descent of the ground bulkhead stops.

When the pressure applied by the fluid in the upper part of the partition wall 112 and the pressure of the mixture at the lower part of the partition wall are equal, that is, when the lowering of the partition wall is stopped, 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. Through this, the feed rate can be adjusted to the liquefaction reactor, and when the partition reaches the jaw formed so that the partition cannot pass through the stirring means 120, the input of the lignin and the solvent mixture through the discharge unit 130 is stopped. do.

Furthermore, the present invention

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);

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

Setting the pressure of the raw material accommodating part 111 to be equal to the reaction pressure of the reaction part using the partition 112 of the supply device 100, and then supplying the raw material to the reaction part to perform the liquefaction and catalytic reactions (step It provides a method of operating the decomposition system 1000 comprising a).

Hereinafter, with reference to the schematic diagram of Figure 2, the operation method of the decomposition system 1000 according to the present invention will be described in detail for each step.

First, in the operating method of the decomposition system 1000 according to the present invention, 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.

In 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.

In this case, 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. At this time, it is preferable that the third valve 117 and the fifth valve 119 are completely closed, and the fourth valve 118 is left open. When pressure is generated while the raw material is supplied to the raw material accommodating part, the partition wall 112 is pushed upward. At this time, air may be discharged out through the fourth valve 118 at the upper end of the cylinder. When a certain amount of the mixed raw material of lignin and the solvent is filled in the raw material receiving portion, the feeding is stopped and the first valve is completely closed.

In addition, 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.

Next, in the operating method of the decomposition system 1000 according to the present invention, 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.

As a specific example, 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. 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. When the solvent exits the gas-liquid separator, use a back-pressure regulator to raise the pressure of the device through which the solvent passes to equal reaction pressure. The solvent is not discharged from the gas-liquid separator until the pressure rises to the reaction pressure, and is discharged again when the reaction pressure is reached. At this time, the reaction pressure is maintained at 1 bar to 2 bar lower than the pressure of the supply device 100 performing high pressure maintenance and raw material stirring. Using a high pressure pump at a reaction pressure, the temperature of the supercritical fluid is continuously added to the reactor while the temperature is raised to the reaction temperature. It is desirable for the temperatures of the liquefaction reactor, solid product separator, catalytic reactor, etc. to reach the target temperature and remain stable.

Next, in the operating method of the decomposition system 1000 according to the present invention, 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.

In 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.

As a specific example, 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. At this time, 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. Thereafter, while continuously supplying the raw materials using the high pressure pump 151 and the supply device 100 to the reaction unit, a supercritical fluid liquefaction operation of lignin is performed.

In addition, 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. In addition, 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. In the liquefaction conditions, 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: In addition, the reaction pressure may be controlled through the after pressure controller 700 and the reaction temperature may be controlled through the temperature controller.

<Description of the code>

Feeder: 100 cylinder: 110

Raw material receptacle: 111 bulkhead: 112

Fluid reservoir: 113 High pressure cover: 114

Pipe for fluid injection: 115 Pipe for air discharge: 116

Stirring means: 120 outlet: 130

Raw material storage: 140 atmospheric pressure pump: 141

First valve: 142 Fluid reservoir: 150

Raw material supply part: 200 Liquefaction reaction part: 300

Liquefaction Reactor: 310 Solid Phase Product Separator: 320

Discharge Valve: 322 Filter: 330

VALVE: 340 TUBE: 350

Catalytic Reactor: 400 Catalytic Reactor: 410

Solvent reservoir for supercritical fluids: 500

Heat Exchanger: 600 After Pressure Controller: 700

Gas-liquid separator: 800

Hereinafter, the present invention will be described in detail by Examples and Experimental Examples.

However, the following Examples and Experimental Examples are only illustrative of the present invention, the present invention is not limited by the following Examples and Experimental Examples.

< Experimental Example  1> Experimental mixing of lignin and ethanol in an acrylic reactor equipped with a horizontal blade stirrer

1-1. Experiment method

In this experiment, lignin and ethanol were used as by-products generated by strong acid hydrolysis of wood.

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.

1-2. Experiment result

In the experiment using a horizontal stirrer, as shown in FIG. 4, 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.

< Experimental Example  2> Experimental mixing of lignin and ethanol in an acrylic reactor equipped with a vertical blade stirrer

2-1. Experiment method

As shown in Figure 5, the stirrer was converted to a vertical type and the experiment was carried out in the same manner as the experimental method of Experimental Example 1. However, the initial lignin mixing rate was increased to 30 wt%.

2-2. Experiment result

As shown in FIG. 6, the mixing occurred well enough that it was difficult to visually confirm phase separation under all conditions. The lignin content of the samples from the four harvesting ports was similar at 23-27 wt%, but lower than that of the undiluted 30 wt%. This shows that there is a significant difference in the mixing ratio of lignin and ethanol according to the blade shape of the stirrer, and the mixing rate is significantly increased when the vertical blade is used than when the horizontal blade is used. Confirmed.

< Experimental Example  3> Experimental Mixing of Lignin and Ethanol in Acrylic Reactor Equipped with a Cross Vertical Blade Stirrer

3-1. Experiment method

Since it was confirmed that the stirrer equipped with a vertical blade was effective for lignin and ethanol mixing, the stirrer equipped with a cross blade was manufactured and used as shown in FIG. The experiment was carried out in the same manner as 1.

3-2. Experiment result

As shown in FIG. 7, 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.

< Experimental Example  4> Experimental Study of Lignin and Ethanol Mixtures with Improved Pipe in Acrylic Reactor with Cross Blade Agitator

4-1. Experiment method

From the result that the lignin content is constant according to the height of the sampling port, the stirring effect is good, but it is judged that the sampling channel may not have been normally performed because the sampling port pipe is narrow, and the channel pipe is improved to the outer diameter of 3/8 inch (inch). As shown in FIG. 8, the experiment was performed in the same manner as in Experiment 1.

4-2. Experiment result

As shown in FIG. 9, there was almost no difference in the lignin concentration according to the height of the reactor, and the lignin content of all the sample collection ports was 29.5 wt% or more and about 99% of the initial lignin content of 30 wt%.

It was confirmed that the pipeline effect of the sample port was due to the lignin being entangled and attached to the pipe wall while passing through the narrow 1 / 4-inch channel tube and separated from the ethanol.

< Experimental Example  5> Confirmation of decomposition system performance using ethanol

5-1. Experiment method

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.

First, in an experiment using a catalyst, 4 g of Mg-Ni-Mo / AC catalyst was put into a catalytic reactor and the reactor was fastened. The catalyst was prepared by supporting an aqueous solution in which Ni, Mo, and Mg precursors were dissolved in activated charcoal (AC) by an incipient wetness method.

Thereafter, 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. In a stable pressure state, 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. 50 g (5 wt%) or 250 g (25 wt%) of lignin and 950 g or 750 g of ethanol were added to a raw material container in a syringe-type cylinder and mixed at a constant speed (> 300 rpm) using an agitator. After the pressure leak test was performed by raising the cylinder to 300 bar, ethanol in the fluid reservoir was introduced into the fluid receiving portion above the partition wall using a high pressure pump. When the ethanol is added to the upper part of the partition wall and the pressure increases, a pressure difference occurs with the lower part of the reactant. The 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. At the end of the reaction, 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.

5-2. Experiment result

One) Treatment flow rate  Impact Analysis

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.

Driving time (minutes)	Liquefied layer temperature (℃)	Catalyst bed temperature (℃)	Pressure (bar)	Ethanol Flow Rate (g / min)	Product flow rate (g / min)
30	353	302	348.5	0.8	0.7
60	350	301	348.9	1.5	1.4
90	348	304	347.9	2.2	2.1
120	347	308	348.1	3.1	2.9
150	349	307	349.2	3.9	3.7

As shown in Table 1, 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.

2) Operation time effect analysis

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.

As shown in Figure 10, it can be seen that the temperature and pressure are kept constant during the operation period.

As shown in FIG. 11 and FIG. 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.

3) Catalyst Impact Analysis

In the catalyst effect experiment, 4 g of Mg-Ni-Mo / AC catalyst was charged to the catalyst layer and ethanol was continuously added to investigate the reactor temperature of 350 ° C. and the pressure of 300 bar. Operation was carried out for 4 hours under conditions of WHSV (reactant mass flow rate (g / h) / catalyst weight (g)) 35.6 h ⁻¹ . 13 illustrates changes in temperature and pressure over time.

In addition, the liquid and gas product compositions obtained in the ethanol continuous dosing experiment performed with the catalyst charged are shown in FIGS. 14 and 15.

As shown in FIG. 13, the reactor temperature and pressure remained generally constant during the catalyst influence experiment.

In addition, as shown in FIG. 14 and FIG. 15, it can be seen that 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). In addition to propanoic acid ethyl ester and acitic acid propyl ester, 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. In particular, 1,1-diethoxy ethane is produced from dehydration and dehydrogenation of ethanol, and acetaldehyde is produced from dehydrogenation of ethanol. These results indicate that the Mg-Ni-Mo / AC catalyst promotes the dehydration and dehydrogenation of ethanol.

In addition, high carbon alcohols such as 1-butanol and 1-hexanol were produced on the catalyst, which is interpreted as alkali metals such as Mg promoted the Gurbet reaction and ethanol coupling occurred. The amount of gas produced was 94 ml / min, which was about 30 times higher than that of the noncatalyst. The gaseous products were mostly hydrogen, and in addition to CH ₄ , CO, CO ₂ and paraffinic or olefin based lower hydrocarbons. In particular, the content of methane on the catalyst was increased compared to the noncatalytic case, indicating that the reforming capacity was promoted on the nickel-based catalyst. In conclusion, it can be said that the Mg-Ni-Mo / AC catalyst activates the reaction of producing active hydrogen from the decomposition of ethanol.

4) 5 wt%  Reaction Analysis of Lignin Slurry Mixtures

5 wt% of lignin and 95 wt% of ethanol were added to the cylinder raw material receiving unit, mixed with a stirrer, and added to the reactor to conduct a liquefaction experiment. The reaction conditions are liquefied bed temperature 350 ℃, Mg-Ni-Mo / AC catalyst bed temperature 350 ℃, 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	97.2%
Weather products	2.6%
Solid product	0.1%
Sum	100%

As shown in Table 2, in the case of continuous reactor experiments, the yield of the liquid product was high and the yield of the solid product was low as compared to the batch reactor experiment.

In addition, after completion of the lignin liquefaction experiment, the inside of the cylinder, the input line, and the inside of the reactor were visually observed. There was no lignin and ethanol mixture around the stirrer and only a small amount of lignin remained inside the cylinder. The cylinder outlet and the reactor input line were not observed at all due to plugging of lignin, and thus, it was judged that the reactor injection of lignin proceeded stably. The used catalyst was collected, dried at 105 ° C. for 12 hours, and weighed to 4.03 g. The weight increased slightly by the formation of carbon during the reaction.

19 shows the results of GC-MS analysis of the liquid product obtained from the lignin 5 wt% liquefaction. Liquid products were classified into N-compounds, phenols, aromatics, acids, esters, aldehydes, ketones, alcohols, ethers, hydrocarbons, and others. In particular, 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.

In the WHSV of 244.7 h ^-1 , a large amount of other substances were included. As WHSV decreased, the area% of other substances decreased drastically. This is interpreted as being converted to other groups of substances by the deoxygenation of other substances containing a large amount of oxygen and the hydrogenation of supercritical ethanol. As WHSV decreased, the phenols group increased. In particular, alkyl phenols increased by ring-alkylation reaction on Mg-Ni-Mo / AC catalyst under supercritical ethanol conditions. As WHSV decreased, alcohols tended to increase. In particular, in WHSV 36.8h- ¹ , not only linear high carbon alcohols but also benzeneethanols such as benzeneethanol, 2-methyl-benzenemethanol, and 2-Naphthalenol were identified.

18 and 19 show the gas product composition obtained from the continuous liquefaction of 5 wt% lignin. As WHSV decreased, CO selectivity increased and CO ₂ selectivity decreased. It can be seen that as the WHSV decreases, the decarbonylation reaction is intensified and the decarboxylation reaction is relatively weakened. In addition, the hydrogen concentration decreased as the WHSV decreased from 244.7 h ⁻¹ to 61.2 h ⁻¹ . On the other hand, hydrogen selectivity increased as WHSV decreased from 61.2 h ⁻¹ to 36.8 h ⁻¹ . As the WHSV decreased, the methane selectivity tended to increase. This shows that the cracking reaction on the Mg-Ni-Mo / AC catalyst was enhanced. Also, as the WHSV decreased, the selectivity of C ₂ paraffins and olefins decreased and the selectivity of C ₃ paraffins and olefins increased.

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). As WHSV decreased, the carbon and hydrogen contents increased and the oxygen contents tended to decrease. In particular, oxygen content of 17.6 wt% in WHSV 36.8 h- ¹ was reduced by 57.5% compared to 41.5 wt% of lignin. As the oxygen content decreased, the high calorific value increased. In particular, the high calorific value (HHV) of WHSV 36.8 h ^-1 was 33.33 MJ / kg, which was 62.6% higher than that of 20.50 MJ / kg of lignin.

WHSV (h-1)	Elemental Composition (wt%)					O / C (mol / mol)	H / C (mol / mol)	HHVa (MJ / kg)
	C	H	O	N	S
Lignin	52.8	5.3	41.5	0.4	0.0	0.59	1.20	20.50
244.7	63.8	6.8	29.2	0.1	0.1	0.34	1.28	27.31
122.3	69.2	7.5	22.7	0.5	0.1	0.25	1.29	30.60
61.2	71.4	7.5	20.5	0.5	0.1	0.21	1.26	31.69
36.8	73.7	8.0	17.6	0.6	0.1	0.18	1.30	33.33

5) 25 wt%  Reaction Analysis of Lignin Slurry Mixtures

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.

20 shows the change in reaction temperature and reaction pressure as the operation time elapses.

21 shows the color change and conditions of the product obtained from the continuous liquefaction of 25 wt% lignin in supercritical ethanol, and the distribution of liquid, gas and solid products is shown in Table 4.

Liquid products	97.2%
Weather products	2.6%
Solid product	0.1%
Sum	100%

Similar to the 5 wt% lignin experiment, the lower the reactant input rate, the lighter the liquid product appeared. In addition, as shown in Table 4, the amount of gas produced was very large in the liquefaction experiment of 25 wt% lignin. This is interpreted as the gasification of the lignin primary decomposition proceeded actively on the catalyst.

After completion of the reaction, the inside of the cylinder, the input line, and the catalyst layer were examined, and almost no lignin and ethanol mixtures were observed around the stirrer. Some lignin was present in the input line between the feeder outlet and the reactor, but line clogging was not expected. The used catalyst was dried at 105 ° C. for 12 hours to obtain 4.28 g as a result of weight measurement. The other solid product was about 54.5 g.

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%. First, 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 . From these results, it can be seen that a constant reactor residence time is required to convert phenol, which is a lignin primary decomposition product, to an aromatic compound by dehydration or hydrogenation. Organic acids were not detected when the WHSV was lower than 122.3 h ⁻¹ (longer residence time). At long reactor residence times, it is interpreted that the organic acid is rapidly converted to another material. On the other hand, as the WHSV decreases, high carbon alcohols tended to decrease, and as a result, the gasification cracking reaction of supercritical ethanol proceeds more actively as the reactor residence time increases.

23 shows the gas phase product composition obtained from the supercritical ethanol continuous liquefaction of 25 wt% lignin. Hydrogen selectivity decreased slightly from WHSV 244.7 h ⁻¹ to 122.3 h ⁻¹ , but then increased rapidly to 36.8 h ⁻¹ . This suggests that the dehydration of supercritical ethanol followed by the gasification proceeds actively at high reactor residence time. As the WHSV decreased, the CO concentration decreased and the CO ₂ concentration increased, indicating that the decarboxylation reaction was more activated than the decarbonylation reaction with longer reactor residence time.

Table 5 below 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 .

WHSV (h-1)	Elemental Composition (wt%)					O / C (mol / mol)	H / C (mol / mol)	HHVa (MJ / kg)
	C	H	O	N	S
Lignin	52.8	5.3	41.5	0.4	0.0	0.59	1.20	20.50
244.7	66.5	7.3	25.5	0.5	0.2	0.28	1.32	29.30
122.3	77.1	7.6	13.9	0.9	0.5	0.14	1.18	34.44
61.2	76.4	7.5	11.6	1.4	3.2	0.11	1.17	34.83
36.8	77.2	7.6	12.8	1.0	1.4	0.12	1.18	34.78

Claims (28)

1. 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;

   Stirring means provided in the raw material accommodating portion to stir the raw materials; And

   And a discharge part disposed in a portion of the raw material accommodating part and discharging the raw material stirred by the stirring means.
2. The method of claim 1,

   And a diameter of a portion of the raw material receiving portion in which the stirring means is located is smaller than the diameter of the partition wall.
3. The method of claim 1,

   The cylinder is divided into an upper chamber and a lower chamber, wherein the upper chamber and the lower chamber is detachable from each other supply apparatus.
4. The method of claim 3,

   The supply apparatus includes a high pressure cover for maintaining the pressure of the upper chamber, including a portion of the upper chamber and the lower chamber detachable.
5. The method of claim 3,

   Supply and detachment of the upper chamber and the lower chamber is achieved through a screw type.
6. The method of claim 3,

   The upper chamber is a supply device is a fluid inlet pipe is formed in the center of the top.
7. The method of claim 1,

   The stirring means comprises a stirrer, the stirrer comprises a horizontal blade or a vertical blade.
8. The method of claim 7, wherein

   The stirrer is a blade orientated feeder in the straight or cross shape.
9. The method of claim 1,

   And the solvent is a supercritical fluid or a subcritical fluid.
10. The method of claim 1,

    The discharge unit is disposed in the lower portion of the raw material receiving unit.
11. The method of claim 1,

    The supply device,

    A raw material storage tank for mixing and storing lignin and a solvent; And an atmospheric pressure pump for transferring the raw material to a raw material accommodating part.
12. The method of claim 1,

    The supply device,

    A fluid reservoir for storing fluid; And a high pressure pump for supplying the fluid to the fluid receiving portion.
13. A raw material supply unit including a supply device according to any one of claims 1 to 12;

    A liquefaction reaction unit filled with a fluid in a supercritical state and receiving a stirred raw material discharged from the raw material supply unit to perform a liquefaction reaction; And

    A lignin decomposition system using a supercritical fluid filled with a fluid in a supercritical state and including a catalytic reaction unit receiving a reaction product generated in the liquefaction reaction unit and performing a catalytic reaction.
14. The method of claim 13,

    The liquefaction reaction unit,

    A liquefaction reactor for receiving a raw material discharged from a discharge part of the supply device and performing a liquefaction reaction; And

    Lignin decomposition system using a supercritical fluid comprising a solid phase product separator for separating the solid product generated in the liquefaction reactor.
15. The method of claim 14,

    The liquefaction reaction unit lignin decomposition system using a supercritical fluid comprising a filter between the liquefaction reactor and the solid phase product separator.
16. The method of claim 14,

    The liquefaction reaction unit lignin decomposition system using a supercritical fluid comprising a valve on the top of the liquefaction reactor.
17. The method of claim 14,

    Wherein the liquefaction reaction unit lignin decomposition system using a supercritical fluid comprising a tube for introducing the raw material into the liquefaction reactor.
18. The method of claim 17,

    The tube is a lignin decomposition system using a supercritical fluid extending from the bottom of the raw material feed through the liquefaction reactor to the solid phase product separator.
19. The method of claim 13,

    The liquefaction reaction unit lignin decomposition system using a supercritical fluid comprising a heating means.
20. The method of claim 13,

    The catalytic reaction unit lignin decomposition system using a supercritical fluid comprising a heater.
21. The method of claim 13,

    The decomposition system,

    A solvent reservoir for the supercritical fluid which stores the solvent for the supercritical fluid; And

    Lignin decomposition system using a supercritical fluid comprising a high pressure pump for supplying the solvent to the reactor.
22. The method of claim 13,

    The decomposition system,

    A lignin decomposition system using a supercritical fluid including a heat exchanger located at a rear end of the catalytic reaction part and cooling a reaction product formed in the catalytic reaction part.
23. The method of claim 13,

    The decomposition system,

    A lignin digestion system using a supercritical fluid that includes a back-pressure regulator that constantly controls the pressure in the digestion system.
24. The method of claim 13,

    The decomposition system,

    A lignin decomposition system using a supercritical fluid, which is located at the rear of the catalytic reaction unit and includes a gas-liquid separator for separating the reaction product into gas and liquid phase.
25. The method of claim 13,

    The decomposition system is a decomposition system in which a plurality of feeders are connected in parallel to the liquefaction reactor.
26. Supplying lignin and a solvent to the raw material receiving portion of the feeder of claim 1 (step 1);

    Mixing the lignin and the solvent supplied to the raw material accommodating part with stirring means (step 2); And

    The method of using the feeder according to claim 1, comprising the step of applying pressure to the partition wall and injecting the lignin and solvent mixture mixed in the step 2 into the liquefaction reaction unit through the discharge unit (step 3).
27. Supplying a raw material which is a mixture of lignin and a solvent to a feeder of the lignin decomposition system of claim 13 (step 1);

    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

    The decomposition system according to claim 13, comprising the step of setting the pressure of the raw material accommodating part to be equal to the reaction pressure of the reaction part by using the partition wall of the feeder, and then supplying the raw material to the reaction part to perform liquefaction and catalytic reaction (step 3). How to operate.
28. The method of claim 27,

    The decomposition system includes a heat exchanger located at the rear end of the catalytic reaction portion to cool the reaction product formed in the catalytic reaction portion,

    Further comprising the step of cooling the reaction product (step 4).

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