WO2019212067A1

WO2019212067A1 - Method for continuous hydrolysis of herbaceous biomass

Info

Publication number: WO2019212067A1
Application number: PCT/KR2018/005009
Authority: WO
Inventors: 이영규; 조상현; 탁건태; 김희정; 임홍규
Original assignee: (주)웰크론한텍
Priority date: 2018-04-30
Filing date: 2018-04-30
Publication date: 2019-11-07

Abstract

The present invention relates to a method for continuous hydrolysis of biomass comprising continuously performing the steps of: adding pulverized biomass and a liquid catalyst to a storage vessel to fill the storage vessel with the pulverized biomass and the liquid catalyst; transferring, to a high-pressure reactor, a mixture of the liquid catalyst and the pulverized biomass in the storage vessel and hydrolysing same; and separating solids and a liquid phase which are in the hydrolysis products obtained in the hydrolysis step, the liquid phase containing the liquid catalyst and a biomass extract.

Description

Continuous Hydrolysis Method of Herbal Biomass

The present invention relates to a method for continuous hydrolysis of herbal biomass.

In general, biofuel produced by the biochemical conversion process of biomass is a high value-added transportation fuel such as bioethanol and butanol. Bioethanol production powerhouses represented by the United States and Brazil mostly produce bioethanol from starch biomass such as corn and sugarcane, which are represented by first-generation biomass. Recently, many side effects have been presented in the process of using edible starch biomass as a raw material for the production of bioalcohol for transportation, and more than 70% of cellulose-based biomass (2nd generation biomass) composed of carbohydrates is proposed as an alternative raw material. It is becoming. Unlike starch-based biomass, cellulose biomass is composed of most cellulose and is surrounded by a phenolic substance called lignin. Therefore, in order to effectively produce biofuels, a hydrolysis process that removes these obstacles is required.

Herbal biomass hydrolysis processes can be performed in reactors at high temperatures and pressures in the presence of liquids. Examples of hydrolysis methods are base catalysis methods using ammonia, alkali-peracetic acid, alkaline hydrogen peroxide, alkali solvents, lime, lime under oxygen pressure, sodium hydroxide, autohydrolysis, hydrothermal, hydrothermal-pH neutral, steam, etc. Non-catalytic method using, sulfuric acid, hydrochloric acid, peracetic acid, phosphoric acid, acid catalyzed method using dilute acid or dilute acid, using solvent such as organic solvent, chemical method using hydrogen peroxide, wet oxidation, etc. have.

In order to extract the active ingredient by hydrolyzing the herbal biomass, generally, the biomass is pulverized finely and a catalyst is added to the hydrolysis reaction in a high temperature reactor. When the liquid phase catalyst is used for the hydrolysis reaction, a high pressure closed reactor is required due to the characteristics of the catalyst, and the amount of the catalyst needs to be minimized in order to reduce the process cost.

In general, when the process is a pure liquid phase, it is possible to apply a process using a continuous high pressure reactor, because the inlet and outlet of the reactor may be filled with liquid as a process product and airtightness may be maintained. However, if the process is a solid, it is not easy to implement a continuous high pressure reactor. In this case, a large amount of solids is present in the pipe, which is a conveying passage of the process, and as a result, the gas between the high pressure portion flows back to the low pressure portion due to the gap between the solids and it is difficult to maintain the pressure inside the high pressure reactor at a high pressure. It is impossible to transfer the biomass into the reactor. This makes it difficult to continuously feed biomass pulverized into the high pressure reactor, or to implement a continuous process to continuously discharge the treated solids in the high pressure reactor. For this reason, in the biomass hydrolysis process, it is common to apply a batch process in which the biomass pulverized product and the catalyst are introduced into the reactor in the open state at normal pressure, the reactor is closed, and then pressurized.

However, if it is possible to continuously feed herbal biomass and catalyst into the reactor, separate solids and liquid phases from the reaction product, recycle the liquid phase containing the catalyst, and continuously discharge the separated solids, the catalyst may be reused. Of course, since a large amount of biomass can be processed in a short time, cost reduction and productivity improvement can be expected.

Therefore, it is necessary to present a herbaceous biomass continuous hydrolysis method capable of continuously introducing a herbaceous biomass into a high temperature and high pressure reactor and continuously discharging the completed solids out of the reactor.

SUMMARY OF THE INVENTION An object of the present invention is to provide a herbal biomass continuous hydrolysis method capable of continuously introducing herbal biomass into a high temperature and high pressure reactor and continuously discharging the solids from which the reaction is completed to the outside of the reactor.

The technical problem of the present invention as described above is solved by the following means.

(1) adding biomass pulverized product and liquid catalyst to the storage tank to fill the storage tank with biomass pulverized product and liquid catalyst, (2) mixing the mixture of biomass pulverized product and liquid catalyst in the storage tank to a high pressure reactor A biomass continuous hydrolysis method comprising the step of performing a decomposition reaction and (3) separating the liquid phase in the hydrolysis reaction product obtained in the step (2) from a solid.

According to the present invention there is provided a method of continuous hydrolysis of herbal biomass.

In the present invention, the herbal or wood-based biomass is mixed with the excess liquid catalyst to be transferred to a high pressure reactor to ensure fluidity and airtightness in the subsequent process flow, and to maintain the temperature and pressure inside the high pressure reactor at a constant level It is possible to continuously carry out the hydrolysis process of the biomass by preventing the reactants in the reactor from flowing back into the reservoir, thereby allowing the introduction and discharge of the biomass continuously.

In addition, in the present invention, by separating the solids and the liquid catalyst and the liquid containing the extract liquid from the reaction product generated in the high pressure reactor, and by transporting the separated liquid to the reservoir configured to reuse the liquid catalyst, the catalyst usage is minimized, the high pressure reactor The energy of the reaction product was recovered by recovering the heat.

1 is a process diagram briefly showing a biomass continuous hydrolysis method according to an embodiment of the present invention.

The first aspect of the invention

(1) a step of filling the reservoir with the biomass pulverized product and the liquid catalyst by injecting the biomass pulverized product and the liquid catalyst into the reservoir;

(2) transferring the mixture of the biomass pulverized product and the liquid catalyst in a storage tank to a high pressure reactor for hydrolysis reaction, and

(3) A step of separating the liquid phase in the hydrolysis reaction product obtained in the step (2) from a solid

It relates to a biomass continuous hydrolysis method comprising continuously performing the.

In the present invention, in the step (1), the biomass pulverized product and the liquid catalyst are added to the reservoir to fill the reservoir with the biomass pulverized product and the liquid catalyst. At this time, the added liquid catalyst is excessively more than the biomass pulverized product, preferably 5 times or more, and most preferably added so that the weight of the liquid catalyst is 5 to 20 times the weight of the biomass pulverized product.

In the step (1), the biomass pulverized product introduced into the storage tank may be previously mixed with the liquid catalyst during the pulverization of the biomass. In this case, the liquid catalyst may be mixed at a weight of 1 to 5 times the weight of the biomass introduced into the grinder, but this pre-mixing is not essential to the present invention.

In the present invention, the liquid catalyst is added in excess to the solid biomass pulverized product in the storage tank as described above to ensure the fluidity of the mixture transferred from the storage tank to the high pressure reactor, that is, the mixture of the liquid catalyst and the biomass pulverized product. The reservoir is filled with liquid phase, which prevents backflow of reactants in the high pressure reactor.

In the present invention, the biomass is a herbaceous biomass or wood-based biomass, and examples thereof include, but are not limited to, cornstalks, dense, crests, giant moss and eucalyptus trees.

In the step (2), the mixture of the biomass pulverized product and the liquid catalyst in the storage tank is transferred to a high pressure reactor for hydrolysis reaction. At this time, the temperature inside the high pressure reactor is a temperature suitable for the hydrolysis reaction of the herbal biomass pulverization, that is, a temperature suitable for extracting the lignin contained in the biomass at a high rate by activating the catalyst, preferably 80 to 200 ° C. Most preferably, it is maintained at 120-180 degreeC.

The liquid catalyst may be an aqueous ethanol solution or ammonia water. Preferably the concentration of the ethanol aqueous solution is 20 to 70% by weight, the concentration of the ammonia water is 10 to 50% by weight.

When using an aqueous ethanol solution as the liquid catalyst, the pressure inside the reactor is preferably maintained at 5 to 40 atmospheres. On the other hand, when ammonia water is used as the liquid catalyst, the pressure of the reactor is preferably maintained at 10 to 60 atmospheres. The pressure inside the high pressure reactor depends on the vapor pressure of the liquid phase catalyst depending on the temperature inside the reactor. Therefore, the pressure inside the reactor is selected in consideration of the vapor pressure according to the selected temperature range. For example, when the reactor internal temperature is maintained at 150 ° C, it is appropriate to maintain the pressure at 10 atmospheres or more for the ethanol aqueous solution and the pressure at 40 atmospheres or more for the aqueous ammonia in consideration of the vapor pressure of the liquid catalyst.

In the present invention, by adjusting the type and concentration of the liquid catalyst, the temperature inside the reactor and the pressure range as described above, the liquid catalyst is prevented from evaporating above the gas / liquid equilibrium state in the high-pressure reactor, through which the Sufficient amount of catalyst is maintained in the liquid phase for the hydrolysis reaction. This ensures that the voids between the biomass grinds are filled with excess liquid catalyst, thereby preventing backflow of the high pressure gas in the reactor in gas / liquid equilibrium out of the reactor through the voids between the biomass grinds.

In one embodiment of the present invention, in the step (2), the mixture of the liquid catalyst and the biomass pulverized product in the reservoir can be passed through a heat exchanger to the high temperature and high pressure reactor. In this case, the mixture of the low temperature biomass and the liquid catalyst transferred from the storage tank can receive heat from the high temperature hydrolysis reaction product discharged from the reactor, thereby achieving a thermal energy saving effect.

In the step (3), the liquid phase in the hydrolysis reaction product obtained in the step (2) is separated from the solid matter. At this time, the separated solid is discharged to the outside of the reactor.

In another embodiment of the present invention, in the step (3), the hydrolysis reaction product obtained in the step (2) is passed through a heat exchanger and cooled to 20 to 60 ℃ to perform a step of separating the liquid and solids It may be. In this case, the heat exchanger may recover heat from the hydrolysis reaction product discharged from the high pressure reactor at a high temperature, where the recovered heat is transferred from the reservoir to the high pressure reactor through the heat exchanger, that is, the liquid catalyst and the biomass. Energy can be saved by allowing it to be absorbed into the mixture of milled products. If necessary, the result of the hydrolysis reaction first cooled by the heat exchanger is further cooled to room temperature or lower.

In another embodiment of the present invention, the method may further include a step (4) of transferring the liquid phase separated in the step (3), that is, the mixture of the liquid catalyst and the biomass extract to a storage tank. As a result, the liquid catalyst recovered from the high pressure reactor can be reused in the storage tank, thereby minimizing the amount of the liquid catalyst added to the storage tank.

Another embodiment of the present invention further includes a step of filtering the liquid phase separated in the step (3) by using a micro filter (MF), an ultrafilter (UF), a nano filter (NF), or the like before returning to a storage tank. You may. In this case, impurities can be filtered out from the liquid phase separated in the step (3), or only the liquid catalyst can be separated and transferred to the storage tank.

Biomass continuous hydrolysis method according to the invention is characterized in that the process of (1) to (3) is carried out continuously. When the step (4) is further performed after the step (3), the steps (1) to (4) are also continuously performed. In the present invention, it is possible to continuously perform the addition of the herbal biomass, the addition of the catalyst, the hydrolysis reaction in the high-pressure reactor, the separation of the liquid and solids from the hydrolysis reaction product, and the discharge of the solids to the outside of the reactor .

The herbal biomass continuous hydrolysis method according to the present invention can be carried out using a device comprising a biomass grinder, a biomass reservoir, a high pressure reactor and a dehydrator.

Such a device may further include a heat exchanger between the reservoir and the high pressure reactor. In this case, the high temperature reaction product generated in the high pressure reactor may be configured to pass through the heat exchanger, whereby the heat retained by the reaction product is recovered to the heat exchanger to cool the reaction product. The heat recovered in the heat exchanger is transferred to the reactants transferred from the reservoir to the high pressure reactor, thereby increasing the temperature of the reactants, thereby reducing the amount of energy to be applied for the hydrolysis reaction in the high pressure reactor. . The heat exchanger may preferably be a spiral heat exchanger. In this case, it is possible to prevent the flow path of the heat exchanger due to solids in the reaction mixture transferred from the reservoir to the heat exchanger or the reaction product transferred from the high pressure reactor to the heat exchanger.

The heat exchanger may be configured as two, and the cooling water may be circulated to the second heat exchanger to further cool the temperature of the reaction product transferred from the high pressure reactor.

In the present invention, a device having a multi-stage centrifugal pump may be used between the reservoir and the heat exchanger, and the pressure required for the hydrolysis reaction in the high pressure reactor may be maintained using the apparatus.

The dehydrator may be in the form of a compactor or a centrifuge, but any form may be used as long as it can separate the solids and the liquid phase from the result of the biomass hydrolysis reaction.

An agitator may be provided inside the reservoir and the high pressure reactor, thereby allowing the liquid catalyst and the biomass pulverized product to be well mixed in the reservoir or improving the efficiency of the hydrolysis reaction in the high pressure reactor.

In the present invention, it may be preferable to use a further provided with a connection pipe that can be added to the liquid phase separated from the dehydrator in the reservoir. In this case, it is possible to transfer the liquid catalyst used in the hydrolysis reaction in the high pressure reactor to the reservoir for reuse.

In the present invention, a membrane separation device such as a micro filter (MF), an ultra filter (UF), a nano filter (NF), and the like is further used to separate only the liquid catalyst from the liquid phase separated from the dehydrator, that is, a mixture of the liquid catalyst and the biomass extract. It is also possible to transfer the liquid catalyst passed through this apparatus to the reservoir.

In the present invention, a pump for preventing backflow of the gas produced in the high pressure reactor between the reservoir and the high pressure reactor or between the reservoir and the heat exchanger to the storage tank and transferring the mixture of the liquid catalyst and the biomass pulverized product to the high pressure reactor, preferably Can be used further provided with a multi-stage pump. If necessary, it may be desirable to install a pipe connected to the reservoir in the discharge pipe of the pump so that the pressure in the high pressure reactor is maintained without more pressure than necessary in the high pressure reactor.

In the present invention, it may be preferable to further include a pressure sensor or a liquid level sensor for controlling the pressure and water level in the reactor inside the high pressure reactor, to control the pressure and water level inside the high pressure reactor. In addition, a stirrer may be provided inside the high pressure reactor so that the biomass pulverized product and the liquid catalyst can be continuously mixed in the reactor.

In the present invention, a valve is provided between the heat exchanger and the dehydrator, and the valve may be interlocked with a liquid level sensor provided in the high pressure reactor, so that the valve may be used to control the water level inside the high pressure reactor.

In the present invention, a second reservoir, preferably a cyclone-type second reservoir, is additionally installed between the heat exchanger and the dehydrator, if necessary, to prevent the rear end equipment from being damaged by the fast flow solids transferred from the heat exchanger to the reservoir. do. In this case, the reaction product can be transferred from the heat exchanger to the dehydrator by pump or natural flow.

As described above, it will be understood by those skilled in the art that the present invention may be implemented in various modified forms. Therefore, the above-described embodiments are to be understood in all respects as illustrative and not restrictive. The scope of the present invention is shown by the following claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts should be construed as being included in the scope of the present invention. do.

Claims

(1) a step of filling the reservoir with the biomass pulverized product and the liquid catalyst by injecting the biomass pulverized product and the liquid catalyst into the reservoir;

(2) transferring the mixture of the biomass pulverized product and the liquid catalyst in a storage tank to a high pressure reactor for hydrolysis reaction, and

(3) A step of separating the liquid phase and the solid in the hydrolysis reaction product obtained in the step (2)

Biomass continuous hydrolysis method comprising the step of performing continuously.
The method of claim 1, wherein the biomass is herbal based biomass or wood based biomass.
The biomass continuous hydrolysis method according to claim 1, wherein in the step (1), the liquid catalyst is introduced into the reservoir in an amount such that the weight ratio of the liquid catalyst to the biomass pulverized product in the reservoir is 5: 1 to 20: 1. .
The method of claim 1, wherein the internal temperature of the high pressure reactor is 80 to 200 ℃, biomass continuous hydrolysis method.
The biomass continuous hydrolysis method according to claim 4, wherein the liquid catalyst is an aqueous ethanol solution, and the pressure of the reactor is 5 to 60 atmospheres.
The method of claim 5, wherein the concentration of the ethanol aqueous solution is 30 to 70% by weight, biomass continuous hydrolysis method.
The biomass continuous hydrolysis method according to claim 6, wherein the liquid catalyst is ammonia water and the pressure of the reactor is 10 to 60 atmospheres.
The method of claim 7, wherein the concentration of the ammonia water is 10 to 50% by weight, biomass continuous hydrolysis method.
The biomass continuous hydrolysis method according to claim 1, wherein in the step (2), the mixture of the liquid catalyst and the biomass pulverized product in the reservoir is passed through a heat exchanger to a high temperature and high pressure reactor.
The biomass continuous hydrolysis method according to claim 1, wherein in the step (3), the hydrolysis product obtained in the step (2) is passed through a heat exchanger, cooled to 20 to 60 ° C, and the liquid and solids are separated. .
The biomass continuous hydrolysis method according to claim 1, further comprising a step (4) of transferring the liquid phase separated in the step (3) to a storage tank.
The biomass continuous hydrolysis method according to claim 11, wherein step (4) is performed after microfiltration, ultrafiltration, or nanofiltration of the liquid phase separated in step (3).