KR102297595B1 - Lignin Decomposition System Using Supercritical Fluid and Its Operation Method - Google Patents

Abstract

a raw material supply unit for supplying a raw material that is a mixture of lignin and a solvent; and 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; as a lignin decomposition system using a supercritical fluid, the solvent is ethanol and water A lignin degradation system is provided which is mixed in a weight ratio of 4:8 to 8:2. The lignin decomposition system and its manufacturing method provided in one aspect of the present invention can continuously inject lignin into a high-pressure liquefaction reactor, and are liquefied in a specially designed reactor to smoothly separate liquid products and solid residues, and maximize the liquid-phase yield. It works.

Description

Lignin Decomposition System Using Supercritical Fluid and Its Operation Method

The present invention relates to a system for decomposing lignin using a supercritical fluid and a method for operating the same.

Lignin is a major component of lignocellulosic biomass along with cellulose and hemi-cellulose. Lignin is produced as a by-product after being separated from cellulose and the like during the production of pulp or ethanol from lignocellulosic biomass. In the past, the separated lignin was burned and used as a process energy source, but recently, technologies for liquefying lignin to manufacture high value-added phenolic raw materials or liquid fuels have been developed. As such, continuous process development is required to mass-produce liquid high-value-added substances from lignin.

The simplest continuous process is rapid pyrolysis. The rapid pyrolysis technology converts a material composed of a polymer such as lignin into a low-molecular material by applying heat to it. However, in the case of rapid pyrolysis, there is a problem in that the yield of the liquid material is low.

On the other hand, recent studies have revealed that liquefaction of lignin in subcritical water or supercritical fluid (eg, supercritical ethanol) can produce a high yield of liquid phenolic substances, and research on this is being actively conducted (Patent Document) One). In this process, the reaction proceeds at a lower temperature than rapid pyrolysis, but there is a difficulty that a high reaction pressure of 100 atmospheres or more is required. it is impossible to do

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

For this reason, most of the papers published to date dealt with the liquefaction of lignin in a batch reactor. However, this is not suitable for commercialization of the liquefaction technology of lignin. Therefore, in order to develop a continuous reaction device that produces liquid high-value-added substances by subcritical or supercritical fluid liquefaction of lignin, above all else, a system that continuously injects lignin development is needed.

Republic of Korea Patent Publication 10-2009-0030967

It is an object of the present invention to provide a continuous reactor for liquefying lignin and a method for operating the same. More specifically, it is intended to provide specific operating conditions for a continuous reactor for liquefying lignin.

In one aspect of the present invention to achieve the above object

a raw material supply unit for supplying a raw material that is a mixture of lignin and a solvent; and

A lignin decomposition system using a supercritical fluid comprising a; a liquefaction reaction unit filled with a supercritical fluid and receiving a stirred raw material discharged from the raw material supply unit to perform a liquefaction reaction,

The solvent is provided with a lignin decomposition system in which ethanol and water are mixed in a weight ratio of 4:6 to 8:2.

In addition, in another aspect of the present invention

a raw material supply unit for supplying a raw material that is a mixture of lignin and a solvent; and a liquefaction reaction unit filled with a supercritical fluid and receiving a stirred raw material discharged from the raw material supply unit to perform a liquefaction reaction;

supplying a raw material that is a mixture of lignin and a solvent from the raw material supply unit (step 1);

setting the reaction pressure and reaction temperature after filling the liquefaction reaction unit with a solvent for a supercritical fluid (step 2); and

After setting the pressure of the raw material supply unit to be the same as the reaction pressure of the reaction unit, supplying the raw material to the reaction unit to perform a liquefaction reaction (step 3),

The solvent is provided as a method of operating a lignin decomposition system in which ethanol and water are mixed in a weight ratio of 4:6 to 8:2.

In addition, in another aspect of the present invention

There is provided a lignin degradation method performed by the lignin degradation system.

In addition, in another aspect of the present invention

A phenolic compound prepared by the lignin decomposition method is provided.

Furthermore, in another aspect of the present invention

A liquid fuel produced by the lignin decomposition method is provided.

The lignin decomposition system and its manufacturing method provided in one aspect of the present invention can continuously inject lignin into a high-pressure liquefaction reactor, and are liquefied in a specially designed reactor to smoothly separate liquid products and solid residues, and maximize the liquid-phase yield. It works.

1 is an image showing a process of pre-treating a lignin sample in an embodiment of the present invention,
Figure 2 shows a schematic diagram and a photograph of a lignin degradation system used in an embodiment of the present invention,
Figure 3 shows a process flow diagram of the lignin input, liquefaction, product separation process in an embodiment of the present invention,
4 is a graph showing the liquefaction operation result of lignin in an experimental example of the present invention;
5 is an image showing the room temperature mixing degree of lignin according to the ethanol:water weight ratio of the solvent according to an experimental example of the present invention;
6 shows the results of GC-MS analysis of liquid fuel obtained in an experimental example of the present invention;
7 is a graph showing the concentration of lignin liquefied product gas according to the ethanol:water weight ratio of the solvent in an experimental example of the present invention;
8 is a graph showing the concentration of lignin liquefied product gas according to the reaction temperature in another experimental example of the present invention;
9 shows the results of GS-MS analysis by lignin concentration of liquid fuel obtained in another experimental example of the present invention;
10 shows the results of GC-MS analysis of liquid fuel obtained in another experimental example of the present invention;
11 is a schematic diagram showing a specific example of a lignin degradation system used in an embodiment of the present invention.

In addition, all terms in this specification that are not specifically defined may be used in a meaning that is understandable to all those of ordinary skill in the art to which the present invention belongs.

However, it should be understood that the present invention is not intended to be limited only to the specific embodiments to be described below, and includes all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

Accordingly, there may be other equivalents and modifications to the embodiments described herein, and the embodiments presented herein are only the most preferred embodiments.

In one aspect of the invention

a raw material supply unit for supplying a raw material that is a mixture of lignin and a solvent; and

A lignin decomposition system using a supercritical fluid comprising a; a liquefaction reaction unit filled with a supercritical fluid and receiving a stirred raw material discharged from the raw material supply unit to perform a liquefaction reaction,

The solvent is provided with a lignin decomposition system in which ethanol and water are mixed in a weight ratio of 4:6 to 8:2.

Hereinafter, the lignin degradation system provided in one aspect of the present invention will be described in detail for each configuration.

First, the lignin decomposition system provided in one aspect of the present invention includes a raw material supply unit.

The raw material supply unit supplies a raw material that is a mixture of lignin and a solvent.

The solvent may be a mixture of ethanol and water in a weight ratio of 4:6 to 8:2. Preferably 4.5:5.5 to 7.8:2.2, more preferably 4.8:5.2 to 7.3:2.7.

From the standpoint of the solid product to be produced later, the weight ratio of ethanol and water may be preferably 6.5:3.5 to 7:5:2.5, and also preferably 4.5:5.5 to 5.5:4.5.

From the standpoint of a liquid product to be produced later, the weight ratio of ethanol and water may be preferably 5.5:4.5 to 7:5:3.5, and preferably 5.5:4.5 to 6.5:5.5.

From the standpoint of a gaseous product to be produced later, the weight ratio of ethanol and water may be preferably 4:6 to 6.5:4.5, and preferably 4.5:5.5 to 5.5:4.5.

Among them, the condition in which the liquid product is maximized may be particularly preferable.

When the weight ratio of ethanol and water is less than 4:6 or exceeds 8:2, there may be a problem in that it is difficult to introduce the lignin residue into the liquefaction reaction unit.

The raw material supply unit includes a cylinder, and the cylinder includes a raw material receiving unit for receiving and receiving a mixture of lignin and a solvent as a raw material; The partition wall may include a movable partition wall and a fluid accommodation part capable of accommodating a fluid capable of applying pressure to the partition wall while separating the raw material receiving part and the fluid receiving part.

In addition, the raw material supply unit is a raw material storage tank for mixing and storing the lignin and the solvent; It may include an atmospheric pump for transferring the raw material to the raw material receiving unit. The raw material storage tank is a storage tank that uniformly mixes and stores lignin and a solvent for a supercritical fluid in a constant weight ratio, and may transfer the uniformly mixed raw material of the lignin and the solvent to the raw material receiving unit. The 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 pressure. The raw material storage tank preferably maintains agitation in order to maintain a uniform mixing state of the mixed raw material of lignin and solvent. The raw material storage tank may include a stirring means capable of performing stirring.

Furthermore, the raw material supply unit includes a fluid storage tank for storing the fluid; and a high-pressure pump for supplying the fluid to the fluid accommodating part. The fluid is a material that exists as a liquid at room temperature and a pressure of 400 bar or less, and may be water, ethanol, methanol, or the like. The fluid transferred from the fluid storage tank to the fluid accommodating part through the high-pressure pump serves to transport the mixed raw material of the raw material accommodating part to the reaction part which can be installed at the rear end by pushing the partition wall downward. Preferably, the fluid and the raw material are not mixed with each other in a state in which they are completely blocked by the partition wall.

In this case, the raw material storage tank may include a supply line communicating with the raw material receiving unit, the supply line may include one or more valves for controlling the supply flow rate. The valve may be, for example, a first valve. In addition, it is preferable that the supply line minimizes the space between the raw material storage tank and the raw material receiving part in order to prevent separation of the lignin and the solvent, and is maintained horizontally. Furthermore, the fluid includes water, but any fluid capable of applying pressure to the partition wall may be used without limitation.

The cylinder is divided into an upper chamber and a lower chamber, the upper chamber and the lower chamber are detachable from each other, and the raw material supply unit includes a portion where the upper chamber and the lower chamber are detachably attached. can At this time, it is preferable that the attachment and detachment of the upper chamber and the lower chamber is achieved through a screw type.

Here, the high-pressure cover serves to fix the upper chamber in a high-pressure state, and when the high-pressure cover is released, the upper chamber can be separated from the lower chamber, and the partition wall inside the cylinder is removed or replaced while the upper chamber is separated. can do.

In the upper chamber, a fluid injection pipe is formed in the upper center of the upper chamber, and a fluid capable of applying pressure to the barrier rib may be injected into the fluid receiving part through this pipe pipe. In this case, the inner diameter range of the fluid injection pipe is not particularly limited, but may preferably be 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 part. There is a problem that is difficult to do.

In addition, a pipe for discharging air is formed in the upper part of the upper chamber, and when a pressure is generated while the raw material is supplied to the raw material receiving part through this pipe, the bulkhead can be pushed upward. At this time, the air discharge pipe may be connected to the fluid storage tank.

The raw material supply unit may include a stirring unit, and the stirring unit may be provided in the raw material receiving unit to stir the raw material.

It is preferable that the 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 so that the partition wall cannot come into contact with the stirring means so that the jaws are formed. As the jaws are formed, the septum cannot contact the stirring means.

The stirring means may include a stirrer, and the stirrer may include a horizontal blade or a vertical blade, preferably a vertical blade. When a vertical blade is used, the content of lignin in the lignin and solvent mixture discharged to the discharge part represents 99% or more of the initial lignin content supplied to the mixture receiving part, so that the mixture is uniformly mixed. At this time, the agitator blades may be oriented in a straight or cross shape.

In addition, the stirring speed of the stirring means may be 200 rpm to 1000 rpm, 300 rpm or more. When the stirring speed is less than 200 rpm, there may be a problem that the mixture is not sufficiently stirred, and when it exceeds 1000 rpm, there is a problem that unnecessary energy is required.

The raw material supply unit may include a discharge unit, and may be disposed in a portion of the raw material receiving unit to discharge the raw material stirred by the stirring means.

The discharge unit may be disposed at the lower end or side of the raw material receiving unit, preferably at the lower end.

In addition, the discharge portion may have an inner diameter of 3/8 inch or more.

At this time, when the inner diameter of the discharge part is less than 3/8 inch, separation of lignin and solvent may occur, causing the lignin to adhere to and accumulate on the pipe wall, and only the solvent may pass through the pipe.

Furthermore, the discharge unit may include a single valve in the same manner as in the supply line to control the input amount of the lignin and solvent mixture passing through the discharge unit.

In the mixture of lignin and solvent, 5 wt% to 40 wt% of lignin may be included, and preferably 10 wt% to 30 wt%.

When the content of lignin in the mixture exceeds 40 wt%, it is difficult to input to the liquefaction reaction unit, and there is a problem that the yield of the liquid product may be reduced.

The lignin may be concentrated sulfuric acid hydrolysis (CSAH) lignin.

The strong acid hydrolyzed lignin has the advantage of being cheaper than Kraft lignin.

Strong acid hydrolyzed lignin is a by-product generated in the bioalcohol production process and has a higher molecular weight and fewer functional groups on the surface than Kraft lignin generated in the pulp production process, making it relatively difficult to put into a liquefaction reactor.

However, in the present invention, the strong acid hydrolyzed lignin can be used by presenting the operating conditions for introducing the strong acid hydrolyzed lignin to the high-pressure liquefaction reactor. In addition, the present invention can suggest optimal liquefaction reaction conditions because strong acid hydrolyzed lignin is difficult to liquefy compared to Kraft lignin.

Next, the lignin decomposition system provided in one aspect of the present invention includes a liquefaction reaction unit.

The liquefaction reaction unit may be filled with a supercritical fluid, and may receive a stirred raw material discharged from the raw material supply unit to perform a liquefaction reaction.

The liquefaction reaction unit may include a liquefaction reactor that receives the raw material discharged from the raw material supply unit and performs a liquefaction reaction, and a solid product separator that separates a solid product generated in the liquefaction reactor.

The liquefaction reaction unit may include a heater, and the heater may be formed on the outer peripheral surface of the liquefaction reactor.

In this case, the liquefaction reaction unit may include a filter between the liquefaction reactor and the solid product separator, and as a specific example, a filter may be installed at the bottom of the liquefaction reactor to separate the solid product from the liquid product and the gaseous product. A tube for inputting the raw material connected to the lower end of the raw material supply unit may pass inside the liquefaction reactor. The tube for inputting the raw material may have an inner diameter of preferably 0.5 cm or more, and may be 0.5 cm to 5 cm. The raw material input tube is installed vertically from the lower end of the raw material supply unit to the upper end of the solid product separator to prevent the high concentration of lignin contained in the raw material from being separated from the solvent for supercritical fluid, such as ethanol, in a valve or line. The raw material is heated while passing through the liquefaction reactor, the solvent is converted to a supercritical fluid, and the liquefaction reaction of lignin may proceed. The preheating and liquefaction reaction 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 reaction pressure, the reaction temperature may be at least 300 ℃ or more, preferably 350 ℃ or more, 350 to 500 ℃, the reaction pressure is 200 bar or more, 200 bar to By maintaining it as high as possible in the range of 400 bar, the solvent (ethanol and water) in the input raw material can reach the supercritical state, and the lignin can react with the supercritical fluid to liquefy as much as possible.

In addition, the liquefaction reaction unit may include a valve at the top of the liquefaction reactor, the valve may be connected to the external environment. The supercritical fluid is filled inside the liquefaction reactor, but in general, the supercritical fluid is not fully filled in the reactor. Accordingly, in the liquefaction reactor of the lignin decomposition system according to the present invention, a valve is formed in the upper part, so that the supercritical fluid can be filled up to the uppermost part of the reactor by opening the valve when filling the supercritical fluid.

Furthermore, the solid product separator may also include a heater, and the heater may be formed on an outer peripheral surface of the solid product separator. In addition, the solid product separator may include a discharge valve disposed at the bottom of the solid product separator for discharging the separated solid product from the liquefaction reactor. As it passes through the liquefaction reactor, the solvent contained in the raw material becomes a supercritical fluid, and the liquefaction reaction of lignin may proceed. 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 a temperature range of 200° C. to 400° C., and in a pressure range of 200 bar to 400 bar, and precipitates the solid product by gravity to obtain a liquid product. and from the gaseous product. The liquid product and the gaseous product may be heated to about 350° C. while passing through the upper liquefaction reactor to be introduced into the catalyst reaction unit. When a certain amount of solid products are accumulated, the solids can be discharged in a range that does not affect the reaction conditions by using the high-temperature and high-pressure valves at the bottom.

The lignin decomposition system provided in one aspect of the present invention may further include a catalytic reaction unit.

The catalytic reaction unit may be filled with a fluid in a supercritical state, and may be supplied with a reaction product generated in the liquefaction reaction unit to perform a catalytic reaction.

The catalyst reaction unit may include a catalyst reactor and a heater filled with a solid catalyst. The catalyst decomposes the supercritical fluid to generate a reducing radical such as hydrogen with good reactivity therefrom, and promotes a deoxidation reaction that removes oxygen from the generated radical and the oxidized organic compound of the liquid product by reacting it. can play a role The catalyst may be a catalyst in which a metal having activity in the reaction, such as nickel, is well dispersed and supported on a support in which mesopores are well developed. The catalyst may be filled and molded to have an appropriate particle size at a level that does not interfere with the flow of the supercritical fluid and the product. 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 higher, preferably in the range of 300°C to 500°C, and 300°C to 350°C, and the reaction pressure is 200 bar It is possible to maintain the same pressure as the liquefaction reactor and the solid product separator in the range of to 400 bar.

The lignin decomposition system provided in one aspect of the present invention may further include a solvent storage tank for supercritical fluid for storing the solvent for the supercritical fluid, and a high-pressure pump for supplying the solvent to the reactor. The solvent storage tank for the supercritical fluid is a storage tank of an organic solvent serving as a supercritical fluid at reaction temperature and reaction pressure conditions, and the high pressure pump transfers the organic solvent in the solvent storage tank for the supercritical fluid to a liquefaction reactor, a solid product separator, a catalytic reactor, etc. It can serve as input to the same unit devices.

At the initial stage of operation of the lignin decomposition system, it is introduced into a liquefaction reactor, a solid product separator, a catalytic reactor, etc. installed at the bottom of the raw material supply unit to maintain the supercritical fluid state of the unit device under the reaction temperature and reaction pressure conditions. In addition, when dilution of the mixed raw material containing lignin is required, it may be added during the liquefaction reaction operation to control the input concentration of lignin.

In addition, the lignin decomposition system may further include a heat exchanger located at the rear end of the catalyst reaction unit to cool the reaction product formed in the catalyst reaction unit. The heat exchanger may serve to cool the reaction product generated in the catalyst reaction unit from the reaction temperature to room temperature. The pressure may range from 200 bar to 400 bar, the same pressure range as the liquefaction reactor, the solid product separator, the catalytic reactor.

Furthermore, the lignin digestion system may further include a back-pressure regulator for constantly controlling the pressure in the digestion system. As a specific example, the back-pressure controller may serve to constantly control the pressures of the raw material receiving part of the cylinder of the raw material supply part, the liquefaction reactor, the solid product separator, the catalytic reactor, and the heat exchanger. The back pressure controller may be located at the rear end of the catalytic reactor, more preferably at the rear end of the heat exchanger, and when the reaction product passes through the back pressure controller, the pressure may be reduced to normal pressure.

In addition, the lignin decomposition system may further include a gas-liquid separator positioned at the rear end of the catalyst reaction unit to separate the reaction product into a gas phase and a liquid phase. The gas-liquid separator serves to separate the product at room temperature and atmospheric pressure into a gas phase and a 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 lignin decomposition system may include a gas flow rate meter for measuring the flow rate of the gaseous product in real time. The gas flow rate meter may be connected to the gas-liquid separator to measure the flow rate of the gaseous product, and a wet test meter may be used as a specific example.

Furthermore, the lignin decomposition system may further include a control unit for monitoring and controlling the temperature and pressure. It is a device for temperature control and monitoring of the liquefaction reactor, the solid product separator, and the catalytic reactor. In addition, all unit devices including the raw material supply unit and a pressure gauge are installed at the front and rear ends of the device to monitor the pressure change, so that it can be utilized as information necessary for the operation of the decomposition system.

In addition, the lignin decomposition system may include a raw material supply unit such that a plurality of raw material supply units are connected in parallel to the liquefaction reaction unit, and as the plurality of raw material supply units are provided, the stirred raw material may be continuously supplied to the liquefaction reactor. For example, when stirring is sufficiently completed in one raw material supply unit and a uniform raw material is injected into the liquefaction reactor, the raw material is stirred in the other raw material supply unit at the same time to prepare a uniformly stirred raw material. When all of the raw materials in the raw material supply unit for injecting the stirred raw material into the liquefaction reactor are injected, the stirred raw material from the raw material supply part preparing the uniformly stirred raw material is injected into the liquefaction reactor to perform continuous supply.

In another aspect of the invention,

a raw material supply unit for supplying a raw material that is a mixture of lignin and a solvent; and a liquefaction reaction unit filled with a supercritical fluid and receiving a stirred raw material discharged from the raw material supply unit to perform a liquefaction reaction;

supplying a raw material that is a mixture of lignin and a solvent from the raw material supply unit (step 1);

setting the reaction pressure and reaction temperature after filling the liquefaction reaction unit with a solvent for a supercritical fluid (step 2); and

After setting the pressure of the raw material supply unit to be the same as the reaction pressure of the reaction unit, supplying the raw material to the reaction unit to perform a liquefaction reaction (step 3),

The solvent is provided as a method of operating a lignin decomposition system in which ethanol and water are mixed in a weight ratio of 4:6 to 8:2.

A method of operating a lignin decomposition system provided in another aspect of the present invention includes: a raw material supply unit for supplying a raw material that is a mixture of lignin and a solvent; and a liquefaction reaction unit filled with a supercritical fluid and receiving a stirred raw material discharged from the raw material supply unit to perform a liquefaction reaction; is an operating method for a lignin decomposition system using a supercritical fluid comprising a.

As the contents of the lignin degradation system have been described above, the description will not be repeated.

Hereinafter, the operation method of the lignin decomposition system provided in another aspect of the present invention will be described in detail for each step.

First, the operating method of the lignin decomposition system provided in another aspect of the present invention includes supplying a raw material that is a mixture of lignin and a solvent from the raw material supply unit (step 1).

In one embodiment, the step 1 comprises the steps of supplying lignin (lignin) and a solvent to the raw material receiving part of the raw material supply unit; mixing the lignin and the solvent supplied to the raw material receiving unit by a stirring means; and injecting the mixed lignin and solvent mixture into the liquefaction reaction unit through the discharge unit by applying pressure to the partition wall.

In the step of supplying the lignin and the solvent to the raw material receiving part of the raw material supply part, the raw material lignin and the solvent may be independently or mixedly supplied to the raw material receiving part in a state in which the valve of the discharge part is completely closed.

The steps of mixing the lignin and solvent supplied to the raw material receiving unit by a stirring means and applying pressure to the partition wall to introduce the mixed lignin and solvent mixture into the liquefaction reaction unit through the discharge unit include the lignin and solvent supplied to the raw material receiving unit. The mixture may be mixed by a stirring means, and pressure may be applied to the partition wall to introduce the mixed lignin and solvent mixture into the liquefaction reaction unit through the discharge unit. After the raw material is stirred by a stirring means provided in the raw material receiving unit, a fluid pressure is applied to the partition wall in the cylinder, and the mixed lignin and solvent mixture may be introduced into the liquefaction reaction unit through the discharge unit.

The mixing time through a stirrer, which is a stirring means, may vary depending on the size of the raw material supply part and is not particularly limited, but may be stirred for 5 to 30 minutes, preferably 7 to 20 minutes, and more preferably Preferably, it may be stirred for 8 to 15 minutes, and most preferably, it may be stirred for 10 minutes.

Fluid is fed until the lowering of the partition wall stops, and if the fluid is continuously supplied to the upper part of the partition wall, the partition wall descends until the pressure between the lignin and solvent mixture and the pressure of the fluid become the same. descent stops.

When the pressure applied by the fluid at the upper part of the bulkhead and the pressure of the mixture at the lower part of the bulkhead are equal, that is, in the state where the drop of the bulkhead stops, the valve of the outlet is opened and the fluid is continuously supplied again to the main surface of the mixture supplied to the liquefaction reactor. The amount is equal to the amount of fluid injected. Through this, it is possible to control the feed rate to the liquefaction reactor, and when the partition reaches a jaw formed at a position where the stirring means is provided so that the partition cannot pass, the input of the lignin and solvent mixture through the discharge part is stopped.

The solvent may be a mixture of ethanol and water in a weight ratio of 4:6 to 8:2. Preferably 4.5:5.5 to 7.8:2.2, more preferably 4.8:5.2 to 7.3:2.7.

From the standpoint of the solid product to be produced later, the weight ratio of ethanol and water may be preferably 6.5:3.5 to 7:5:2.5, and also preferably 4.5:5.5 to 5.5:4.5.

From the standpoint of a liquid product to be produced later, the weight ratio of ethanol and water may be preferably 5.5:4.5 to 7:5:3.5, and preferably 5.5:4.5 to 6.5:5.5.

From the standpoint of a gaseous product to be produced later, the weight ratio of ethanol and water may be preferably 4:6 to 6.5:4.5, and preferably 4.5:5.5 to 5.5:4.5.

Among them, the condition in which the liquid product is maximized may be particularly preferable.

When the weight ratio of ethanol and water is less than 4:6 or exceeds 8:2, there may be a problem in that it is difficult to introduce the lignin residue into the liquefaction reaction unit.

In the mixture of lignin and solvent, 5 wt% to 40 wt% of lignin may be included, and preferably 10 wt% to 30 wt%.

When the content of lignin in the mixture exceeds 40 wt%, it is difficult to input to the liquefaction reaction unit, and there is a problem that the yield of the liquid product may be reduced.

In one embodiment, a mixture of lignin and supercritical fluid solvent (ethanol and water) of a desired concentration is added to the raw material storage unit at normal pressure and mixed by a stirring means to prepare and store the mixture, and then use the atmospheric pump and the first valve to store the mixture in the cylinder. It is fed into the raw material receiving part. At this time, it is preferable that the third valve and the fifth valve are completely closed, and the fourth valve is left open. When the pressure is generated while the raw material is supplied to the raw material receiving part, the partition wall is pushed upward. At this time, air may be discharged to the outside through the fourth valve at the top of the cylinder. When a predetermined amount of the mixed raw material of lignin and solvent is filled in the raw material receiving part, the input is stopped and the first valve is completely closed.

In addition, the fourth valve is also completely closed and the third valve is opened to inject the fluid in the fluid storage tank into the fluid receiving unit using a high-pressure pump. If the fluid is continuously added, the pressure in the cylinder increases because the first valve, the fourth valve, and the fifth valve are closed. The internal pressure of the cylinder may be maintained at about 1 bar to 2 bar higher than the reaction pressure. The fluid is introduced into the fluid receiving part using a high-pressure pump until the internal pressure of the cylinder is maintained 1 bar to 2 bar higher than the reaction pressure, and the input is stopped when the target pressure is reached.

Next, the operating method of the lignin decomposition system provided in another aspect of the present invention includes the step of setting the reaction pressure and reaction temperature to the reaction pressure and reaction temperature after filling the liquefaction reaction unit with a solvent for a supercritical fluid.

The above step is a step of forming the reactors in a supercritical fluid state before the decomposition reaction of lignin, and after filling the liquefaction reaction part, which is the reaction part, with a solvent for the supercritical fluid, supercritical conditions are set.

In one embodiment, the step is performed in a state in which the fifth valve 119 connected to the discharge part of the raw material supply part is closed, and the second valve connected to the solvent storage tank for the supercritical fluid and the high pressure pump is opened, and the solvent for the supercritical fluid ( ethanol and water) from the reservoir into the liquefaction reactor. The solvent introduced into the catalytic reactor passes through a solid-phase product separator, a catalytic reactor, a heat exchanger, and a back-pressure controller, and comes out to a gas-liquid separator. The solvent is continuously added through the high-pressure pump until it is confirmed that the solvent comes out of the gas-liquid separator. When the solvent comes out of the gas-liquid separator, the pressure of the devices through which the solvent passes is raised to the reaction pressure by using a back-pressure regulator. 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 1 bar to 2 bar lower than the pressure of the raw material supply part performing high pressure maintenance and raw material stirring. At the reaction pressure, using a high-pressure pump, the solvent for the supercritical fluid is continuously introduced into the reaction apparatus, and the temperature is raised to the reaction temperature. It is desirable to ensure that the temperature of the liquefaction reactor, the solid product separator, the catalytic reactor, etc. reaches the target temperature and is stably maintained.

The reaction temperature may be 300 °C to 500 °C.

In terms of the hard product to be produced later, it may be preferably 330 °C to 500 °C, and 360 °C to 500 °C.

In terms of a liquid product to be produced later, it may preferably be 300°C to 380°C.

In terms of a gaseous product to be produced later, it may be preferably 330 °C to 500 °C, and 360 °C to 500 °C.

When the reaction temperature is less than 300° C., the decomposition rate of strong acid hydrolyzed lignin is significantly lowered, and thus there is a problem in that the yield of the liquid product is lowered.

Next, the lignin decomposition system operating method provided in another aspect of the present invention sets the pressure of the raw material supply part to be the same as the reaction pressure of the reaction part, and then supplies the raw material to the reaction part to perform the liquefaction reaction (step 3). include

In the above step, the feed flow rate of the raw material may be 8 g/min to 15 g/min. Higher feedstock flow rates may increase solid product content, decrease liquid product, and increase gaseous product.

When the feed flow rate of the raw material is less than 8 g/min, the residence time of the liquid product in the reactor is prolonged, and unwanted secondary reactions such as polymerization may occur, and economic efficiency may be deteriorated due to the low throughput. On the other hand, if the feed rate of the raw material exceeds 15 g / min, the reactor residence time of the raw material is too low to supply sufficient time necessary for liquefaction, there may be a problem in that the yield of the liquefied product is lowered.

In step 3, the mixed raw material prepared in step 1 is supplied into the reaction unit prepared in step 2 to perform a decomposition reaction of lignin.

In one embodiment, the step may be performed by opening the fifth valve and simultaneously injecting the solvent into the fluid receiving part of the cylinder using a high-pressure pump to introduce the mixed raw material into the liquefaction reactor. At this time, almost simultaneously, the injection of the solvent for the supercritical fluid through the high-pressure pump is stopped and the second valve is completely closed. Thereafter, the supercritical fluid continuous liquefaction operation of lignin is performed while continuing the input of the raw material into the reaction unit using the high-pressure pump and the raw material supply unit.

In addition, the lignin decomposition system operating method provided in another aspect of the present invention may further include a heat exchanger in which the decomposition system is located at the rear end of the catalytic reaction unit to cool the reaction product formed in the catalytic reaction unit, through which the reaction product is heated. It may further include the step of cooling.

In one embodiment, the product passing through the catalytic reactor is cooled and depressurized, and separated into a gaseous phase and a liquid phase, and the gaseous phase is measured in real time with a gas flow rate meter. In addition, a sampling port is placed between the gas-liquid separator and the gas flow rate meter to collect gas samples and use them 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 generation and fuel characteristics analysis. In the liquefaction reaction conditions, the input flow rate is performed while changing the flow rate of the high-pressure pump connected to the fluid storage tank, and the lignin concentration control can be performed through the operation and flow rate change of the high-pressure pump connected to the solvent storage tank for supercritical fluid. In addition, the reaction pressure can be controlled through the back pressure controller and the reaction temperature can be controlled through the temperature controller.

In another aspect of the present invention, there is provided a lignin degradation method using a lignin degradation system.

The lignin decomposition method has been described in the lignin decomposition system and the lignin decomposition system operation method, and thus the description will not be repeated.

In another aspect of the present invention, there is provided a phenol-based compound prepared by the lignin decomposition method.

In another aspect of the present invention, a liquid fuel produced by the lignin decomposition method is provided.

That is, lignin can be efficiently decomposed by the lignin decomposition system and the operating method provided in the present invention, and phenolic compounds, liquid fuel, and the like can be produced through this.

Hereinafter, the present invention will be described in more detail through Examples and Experimental Examples. The scope of the present invention is not limited to specific embodiments, and should be construed by the appended claims. In addition, those skilled in the art should understand that many modifications and variations are possible without departing from the scope of the present invention.

<Example>

The lignin sample used in the liquefaction experiment is Concentrated Sulfuric Acid Hydrolysis (CSAH) lignin generated in the demonstration process of G company's biobutanol production, and as a comparative experiment, Kraft prepared from black liquor generated in the M company's pulping process. It was lignin.

The lignin samples were pre-treated in the same order as in FIG. 1 . First, CSAH lignin and Kraft lignin were washed 5 times with distilled water to remove impurities such as inorganic sulfur as much as possible, and then dried at 105°C and atmospheric pressure. After the dried sample was pulverized using a ball mill, only the particle size of 0.25 mm or less was selected and stored at room temperature. The lignin sample was dried at 105° C. and atmospheric pressure for about 10 hours the day before the liquefaction experiment and used as a reactant. Ethanol (purity: 99.5%) was used as the supercritical fluid for the lignin liquefaction reaction.

Fig. 2 shows a lignin decomposition system (continuous supercritical ethanol liquefaction reactor) equipped with a cylinder (high-pressure lignin-ethanol slurry feeder) used for continuous liquefaction experiments of lignin residues. The lignin decomposition system consists of a fluid (ethanol solvent) storage tank and input pump, cylinder (lignin residue slurry feeder), liquefaction reaction unit, product cooling and gas-liquid separator, gas flow meter, controller, data recorder, cooling water supply device, etc. did. The liquefaction reactor has an inner diameter of 100 mm, a length of 250 mm, and a volume of 2,000 mL. A filter device was installed in half of the internal volume of the reactor to prevent the solids generated during the liquefaction of lignin from being discharged to the outside of the reactor along with the liquid product. The filter had an inner diameter of 80 mm, a length of 130 mm, and a volume of 650 mL.

The liquefaction test sequence is as follows. First, a predetermined amount of a pre-prepared lignin and ethanol/water mixture is put into the cylinder lower chamber of the raw material supply part, and then the agitator under the feeder is operated to maintain a homogeneous slurry state. Push the bulkhead up to the slurry surface of the cylinder. Ethanol is injected into the cylinder space above the bulkhead, and the upper head and head cover are installed. With the valve installed between the cylinder and the liquefaction reactor completely closed, water or ethanol is continuously injected into the upper chamber of the slurry feeder piston to pressurize it to the target reaction pressure. Meanwhile, while injecting ethanol into the reactor using another liquid pump, the reaction pressure is pressurized with a back pressure controller (BPR). When the pressure is stably maintained at the target value, the liquefaction reactor is heated to the target reaction temperature by heating the electric furnace using the controller. When the temperature and pressure are stabilized at the target values, the lignin slurry is continuously introduced into the reactor by continuously adding ethanol to the space above the partition wall of the cylinder and moving the partition wall downward. When the reactants in the slurry reach the reactor, the rapid liquefaction reaction of lignin proceeds, and the gaseous and liquid products exiting the reactor are cooled to room temperature while passing through a condenser, and then are reduced to atmospheric pressure while passing through a back pressure controller (BPR). The product at room temperature and normal pressure is separated into a gas phase and a liquid phase in a gas-liquid separator, and the gaseous product is introduced into a wet gas meter to measure the flow rate. Gas-phase product samples were taken at 10-minute intervals with a 10 mL syringe and used for compositional analysis. The liquid product was collected from the lower part of the gas-liquid separator for a certain period of time and used for product flow rate, yield, and fuel characteristics analysis. When the experiment was completed, the amount of lignin was measured by recovering the lignin slurry present in the cylinder. In addition, by dismantling the reactor, solid residues inside the reactor filter were collected and the amount of generation was investigated.

The liquid product was distilled under reduced pressure at 0.2 bar and 80°C to remove ethanol and light components, then liquid-liquid extraction was performed using DCM (dichloromethane) to remove the aqueous phase, and then the oil phase was distilled under reduced pressure at 0.2 bar and 30°C. The DCM solvent was removed to finally produce a liquid fuel. 3 shows a process flow diagram of the liquid fuel manufacturing process in the lignin liquefaction reaction.

Industrial analysis (volatile content, ash, fixed carbon), elemental analysis (C, H, H, S), FT-IR analysis (surface functional groups), ICP analysis (sodium content), thermogravimetry Analysis (pyrolysis properties), oxygen analysis, moisture content, total acid value (TAN), etc. were performed and confirmed. Industrial analysis was performed at the Platform Research Center of the Korea Institute of Energy Research, elemental analysis at the KAIST Analysis Center, ICP analysis at the Chungnam National University Common Lab, and thermogravimetric analysis at the KAIST Analysis Center. The composition analysis of the gaseous product was analyzed using its own gas chromatography (GC/TCD-FID). Elemental analysis including oxygen and sulfur content analysis of liquid product was commissioned by the KAIST Analysis Center and the Korea National Petroleum Institute. The high calorific value (HHV) of the liquid fuel was calculated by a standard method using elemental analysis data.

<Experimental Example 1> Changes in reaction temperature and reaction pressure according to the lapse of operating time

Changes in reaction temperature and reaction pressure according to the lapse of operating time measured in a liquefaction experiment of lignin (20 wt%) using a lab-scale continuous reactor are shown in FIG. 4 . The temperature was measured inside the reactor filter and outside the filter, and the pressure was measured at the reactor and the raw material supply part. Temperature and pressure were relatively well controlled.

<Experimental Example 2> Evaluation of solvent effect

CSAH lignin, a by-product of the bioalcohol manufacturing process, was mixed with an ethanol solvent and put into the reactor using the raw material supply. couldn't

Accordingly, along with the improvement of the physical properties of CSAH lignin, the effect of mixing water with ethanol as a solvent was investigated. First, as a result of examining the solubility of CSAH lignin according to the solvent mixing ratio at room temperature, as shown in FIG. 5 , the miscibility tends to be relatively high when the water content is 30-50 wt%.

In fact, as a result of adding the lignin slurry in the lab-scale reactor, as shown in Table 1, when the solvent was 100% ethanol and the ethanol:water mixing ratio was 80:20, the lignin slurry could not be added, but the ethanol:water mixing ratio was 70. Lignin input was possible at :30 or higher.

As a result of a continuous liquefaction experiment of CSAH lignin at 350° C., 300 bar, and non-catalyst conditions while varying the amount of water mixed with ethanol, the solid product increased significantly compared to the case of liquefying Kraft lignin in 100% ethanol. It is analyzed that these results are largely due to the molecular structural characteristics of CSAH lignin, which is difficult to depolymerize compared to Kraft lignin.

The yield of the liquid fuel obtained through the separation process of the liquid material was in the range of 28 to 39 wt%. This is lower than the estimated liquefied yield of 55 to 70 wt%, because organic substances were removed during the vacuum evaporation process and the liquid-liquid extraction process. The total acid value (TAN) of the liquid fuel was 0.9-2.3 mg/g, which was much lower than the target value of 30, and the moisture content was slightly higher than the target value of 0.3 in the range of 0.5-1.5 wt%. The high water content is greatly influenced by the addition of water to the solvent.

Solvent composition
(EtOH:H2O)
(wt%) reactant
input flow rate
(g/min) Total liquid product flow rate
(g/min) product yield liquid fuel liquid weather elegance transference number(%) TAN
(mg/g) moisture content
(wt%) 80:20 13.8 Impossible to put in - - - - - - 70:30 13.6 12.4 62.7 7.3 30 38 0.96 0.54 60:40 13.7 11.9 80.4 4.6 15 39 1.84 1.24 50:50 13.7 12.6 68.4 1.6 30 28 2.29 1.37

*Product yield: (product weight)/ total lignin weight x 100

Table 2 shows the results of elemental analysis of the liquid fuel obtained through a series of separation processes of filtering-evaporation-DCM extraction-evaporation of the liquid product obtained in the solvent effect experiment and the calorific value calculated based thereon.

Solvent composition
(EtOH:H2O)
(wt%) Elemental composition (wt%) HHV ^a
(MJ/kg) C H N S O CSAH lignin 58.43 5.67 0.17 0.33 35.40 25.0 70:30 66.34 7.35 0.11 0.19 26.01 29.2 60:40 67.57 7.44 0.12 0.07 24.80 29.8 50:50 63.21 6.86 0.12 0.08 29.73 27.1

^a HHV: Calculated by DIN51900 standard method using elemental composition {HHV = (34xC+1243xH+63xN+193xS-98xO)/100)

As a result of performing GC-MS analysis to investigate major components included in the liquid fuel obtained in the experiment in which the ethanol:water ratio of Table 1 was 70:30, a chromatogram as shown in FIG. 6 was obtained.

As a result of grouping the detected organic compounds by type, phenols accounted for 55 area%, sugar decomposition substances such as furans accounted for 29 area%, and other 16 area%. Since sugar decomposition substances are produced from the degradation of cellulose and hemicellulose, it can be said that they were contained in a significant amount in the CSAH lignin used in the experiment.

As a result of analyzing the composition of the generated gas, as the ratio of water in the solvent increased, as shown in FIG. 7 , the carbon dioxide concentration decreased and the amount of light hydrocarbons such as methane and ethane increased. Hydrogen was detected in very low amounts. From these results, it is determined that the hydrogen production is low or the generated hydrogen is used for the deoxidation reaction.

<Experimental Example 3> Temperature effect evaluation

Table 3 shows the effect of reaction temperature on product yield by liquefaction of lignin in a continuous reactor. It can be seen that the higher the reaction temperature, the higher the yield of the solid residue.

reaction temperature
(℃) reactant
input flow rate
(g/min) total liquid
flow rate
(g/min) Product yield (wt%)
liquid fuel
liquid weather elegance transference number
(%) TAN
(mg/g) moisture content
(wt%) 300 13.8 12.7 74.2 0.8 25 25 1.06 0.97 350 12.6 12.4 62.7 7.3 30 30 0.96 0.54 400 13.7 9.6 54.9 13.1 32 32 1.88 0.68

*Reaction conditions: CSAH lignin 20wt%, ethanol:water ratio = 70:30, liquefaction pressure 300bar, no catalyst

The GC-MS analysis result of the liquid fuel obtained through the separation process of the liquid material liquefied at the reaction temperature of 300° C. is shown in FIG. 8 . Phenols accounted for 56 area%, and sugar decomposed substances such as furan were 23 area% and other 21 area%.

As a result of analyzing the composition of the product gas, as shown in FIG. 8 , the carbon dioxide content was low at a reaction temperature of 350° C. or higher, and the light hydrocarbon content showed a tendency to increase in proportion to an increase in the reaction temperature.

<Experimental Example 4> Effect of lignin concentration

Table 4 shows the effect of CSAH lignin concentration on product yield by liquefaction of lignin in a continuous reactor. The ethanol:water weight ratio of the solvent was 70:30 and the lignin content was 30 wt%, so there was no difficulty in putting it into the reactor using the slurry feeder.

lignin
density
(wt%) reactant
input flow rate
(g/min) total liquid
flow rate
(g/min) Product yield (wt%) liquid fuel
liquid weather elegance transference number
(%) TAN
(mg/g) moisture content
(wt%) 10 14.1 12.9 85.5 NA 14 35 1.24 0.76 15 13.9 12.6 78.5 NA 21 37 1.76 0.85 20 13.6 12.4 62.7 7.3 30 38 0.96 0.54 25 13.7 12.2 76.2 6.8 17 26 3.87 0.89 30 13.6 12.1 69.0 9.0 22 20 3.18 1.10

At 20 wt% of lignin content, the yield of solid residue was highest at 30 wt%, and lignin content of 30 wt% was 22 wt%.

Table 5 shows the results of elemental analysis of the liquid fuel obtained from the lignin concentration experiment through a series of separation processes of filtering-evaporation-DCM extraction-evaporation of FIG. 3 and the calorific value calculated using it. The effect of lignin concentration on elemental composition and calorific value of liquid fuel was found to be insignificant.

lignin concentration
(wt%) Elemental composition (wt%)
HHV ^a (MJ/kg) C H N S O CSAH lignin 58.43 5.67 0.17 0.33 35.40 25.0 20 66.34 7.35 0.11 0.19 26.01 29.2 25 66.85 7.14 0.11 0.06 25.84 29.4 30 66.80 7.27 0.13 0.16 25.64 29.3

In addition, the GC-MS analysis results of the liquid fuel obtained in the experiment of Table 4 are shown in FIGS. 9 and 6 . In general, as the lignin concentration increased, the phenolic content of the liquid fuel increased and the cellulose or hemicellulose-decomposed substance content tended to decrease.

lignin concentration
(wt%) Organic composition (area%) phenolic Non-lignin-based degradation products etc 10 44 29 27 15 50 30 20 25 52 31 17 30 61 27 12

<Experimental Example 5> Effect of input flow rate

Table 7 shows the effect of the reactant input flow rate on the product yield by liquefaction of lignin in a continuous reactor. As the reactant input flow rate was higher, the solid product content increased, the liquefaction rate decreased, and the gasification rate showed a tendency to increase.

Reactant input flow rate (g/min) Total liquid product flow rate (g/min) Product yield (wt%) liquid fuel liquid weather elegance transference number
(%) TAN
(mg/g) moisture content
(wt%) 10.7 10.7 70.7 7.3 22 23 2.14 0.78 13.6 12.4 56.9 13.1 30 38 0.93 0.54

10 shows the results of GC-MS analysis of the liquid fuel obtained at a reactant input rate of 107 g/min during the experiment of Table 7 in FIG. The phenolic content was 52 and the non-lignin-decomposing material was 28 area%.

Raw material supply: 200 Cylinder: 110
Raw material receiving part: 111 Bulkhead: 112
Fluid receiving part: 113 High pressure cover: 114
Fluid injection pipe: 115 Air exhaust pipe: 116
Stirring means: 120 Discharge part: 130
Raw material storage: 140 Normal pressure pump: 141
1st valve: 142 Fluid reservoir: 150
Liquefaction reaction unit: 300 Liquefaction reactor: 310
Solid Product Separator: 320 Discharge Valve: 322
Filter: 330 Valve: 340
Tube for raw material input: 350 Catalyst reaction unit: 400
Catalytic reactor: 410 Solvent storage tank for supercritical fluid: 500
Heat exchanger: 600 Back pressure controller: 700
Gas-liquid separator: 800

Claims (13)

a raw material supply unit for supplying a raw material that is a mixture of strong acid hydrolyzed lignin and a solvent; and
A lignin decomposition system using a supercritical fluid comprising a; 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,
The liquefaction reaction unit
a liquefaction reactor receiving the raw material discharged from the raw material supply unit and performing a liquefaction reaction;
a solid product separator for separating a solid product generated in the liquefaction reactor;
a filter positioned between the liquefaction reactor and the solid product separator;
a tube for inputting the raw material passing from the lower end of the raw material supply unit into the liquefaction reactor and installed to the upper end of the solid product separator; and
a heater installed outside the liquefaction reactor;
including,
The solvent consists of ethanol and water, and the content of water in the solvent is 30 wt% to 50 wt%.
According to claim 1,
The raw material supplier
a raw material receiving unit for receiving and receiving a mixture of lignin and a solvent as a raw material;
a partition wall that can move while separating the raw material receiving unit and the fluid receiving unit;
a cylinder including a fluid accommodating part capable of accommodating a fluid capable of applying pressure to the partition wall;
agitating means provided in the raw material accommodating part to stir the raw materials; and
a discharge unit disposed in a portion of the raw material receiving unit and discharging the raw material stirred by the stirring means;
Lignin degradation system comprising a.
delete delete delete According to claim 1,
The lignin degradation system, characterized in that the mixture of lignin and solvent comprises 5 wt% to 40 wt% of lignin.
As a method of operating the lignin decomposition system of claim 1,
supplying a raw material that is a mixture of strong acid hydrolyzed lignin and a solvent from the raw material supply unit (step 1);
setting the reaction pressure and reaction temperature after filling the liquefaction reaction unit with a solvent for a supercritical fluid (step 2); and
After setting the pressure of the raw material supply unit to be the same as the reaction pressure of the reaction unit, supplying the raw material to the reaction unit to perform a liquefaction reaction (step 3),
The solvent consists of ethanol and water, and the content of water in the solvent is 30 wt% to 50 wt% of a method of operating a lignin decomposition system.
8. The method of claim 7,
The method of operating a lignin decomposition system, characterized in that the mixture of the lignin and the solvent comprises 5 wt% to 40 wt% of lignin.
8. The method of claim 7,
The reaction temperature is a method of operating a lignin decomposition system, characterized in that 300 ℃ to 500 ℃.
8. The method of claim 7,
The operating method of the lignin decomposition system, characterized in that the raw material supply flow rate in the step of supplying the raw material to the reaction unit is 8 g / min to 15 g / min.
◈Claim 11 was abandoned when paying the registration fee.◈ A lignin degradation method performed by the lignin degradation system of claim 1.
A phenolic compound prepared by the lignin decomposition method of claim 9.
◈Claim 13 was abandoned when paying the registration fee.◈ A liquid fuel produced by the lignin decomposition method of claim 9.

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