KR102028451B1 - System for high concentration bio-liquid using 2nd generation biomass - Google Patents

Abstract

The present invention relates to a high concentration of mixed bio-sugar solution, specifically, to a bio-liquid with increased concentration of lignin, and a bio-liquid with increased concentration of xylose and glucose from herbal or wood-based biomass through a high temperature and high pressure reaction unit. In addition, the present invention relates to a system and method for improving the calorific value by impregnating, coating, and heat treating low-grade coal using the same, and at the same time, high-quality coal of low grade using biomass having excellent water resistance.

Description

System for high concentration bio-liquid using 2nd generation biomass

The present invention relates to a high concentration of mixed bio-sugar solution, specifically, to a bio-liquid with increased concentration of lignin, and a bio-liquid with increased concentration of xylose and glucose from herbal or wood-based biomass through a high temperature and high pressure reaction unit. It relates to a device for.

Recently, interest in coal as an energy source is rising again due to rising oil prices and distrust on the stability of nuclear energy. However, coal is the largest source of carbon dioxide among fossil fuels, which makes it a weak energy source in view of global warming.

Therefore, among the issues currently being issued globally as energy sources, the use and dissemination of new and renewable energy is possible, which reduces carbon dioxide emissions compared to conventional fossil fuels such as petroleum and coal, which can cope with global warming and climate change. Because it is an energy source.

However, in Korea, when renewable energy sources such as solar or wind power are used for power generation or heating, the use and dissemination of fossil fuels is limited due to differences in power generation costs compared to fossil fuels. With the depletion and the reduction of greenhouse gases in response to the international convention on climate change, the new renewable energy mandatory quota system has been introduced since 2012, and the Korean Renewable Energy Standard (RPS) was introduced in 2012. It is a situation that acts as a burden to him.

Accordingly, power generation companies are attempting to reduce coal generation of carbon dioxide by using an integrated gasification combined cycle (IGCC) and bio-mass mixing.

However, IGCC cannot use existing coal-fired power generation facilities, requires huge construction costs of about KRW 1.3 trillion per unit, and uses Carbon Capture and Storage (CCS) to process carbon dioxide. As an additional technology, the economic burden is very high.

In addition, in the case of biomass mixing, there is a problem that power generation efficiency is lowered as the biomass of a relatively low calorific value is burned compared to coal. In other words, in the case of a fuel simply mixed with coal and oil-based biomass, the surface of the coal is coated with oil or oil is impregnated into the pores. However, due to the low surface tension of the oil itself and the lack of bonding force between the oil-based biomass and the coal surface, coal and biomass each retain their existing combustion characteristics, resulting in different combustion characteristics. Therefore, when applied to a power plant, oxygen is preferentially consumed excessively due to the low temperature combustion pattern of oil at the front of the burner, which eventually inhibits the combustion of coal, thereby increasing the amount of unburned carbon and decreasing power generation efficiency. .

On the other hand look at a number of known documents to address the above problems are as follows.

Korean Patent Publication No. 2007-0091168 discloses a high dry matter content in combination with a type of mixing that relies on the law of gravity to ensure that enzymatic hydrolysis exerts mechanical forces (primarily shear and rupture forces) on the biomass. A method of liquefying and saccharifying polysaccharide-containing biomass having is disclosed.

Korean Patent Publication No. 2012-0077991 discloses a reaction tank in which a powdered cellulose-based biomass sample, an acid or alkaline solution, and carbon dioxide are added to react under high temperature and high pressure; A separation tank installed at a lower end of the reaction tank and maintained inside at a low temperature and low pressure condition; A fine nozzle installed between the reaction tank and the separation tank to separate carbohydrates by ejecting a high temperature and high pressure reactant generated in the reaction tank at a low temperature and low pressure inside the separation tank; Disclosed is a pretreatment apparatus for producing a substrate for ethanol fermentation from lignocellulosic biomass comprising a.

Korean Patent No. 10-1171922 relates to methods of making and processing carbohydrate-containing materials to change their structure, and to products made from structurally changed materials, for example lower molecular weight and / or lower than natural materials. It provides cellulose and / or lignocellulosic material with crystallinity and is more readily used by various microorganisms to provide useful products such as hydrogen, alcohols (eg ethanol or butanol), organic acids (eg organic acids), hydrocarbons, by-products ( For example, a system for providing a material capable of producing a protein) or any mixture thereof is disclosed.

In Japanese Patent Laid-Open No. 2011-205933, a method of producing a saccharified solution using an enzyme from biomass, and of a reaction solvent in which a hydrophobic organic solvent is present, biomass And by adding and stirring an enzyme, a reaction step of hydrolyzing the polysaccharides in the biomass to lower molecular sugars, and more preferably the reaction solvent in the final stage of the decomposition step. and an extraction step of adding an aqueous solvent in a reaction solvent, extracting a lower molecular weight sugar into an aqueous solvent than the one decomposed, and a recovery step of recovering the sugar extracted in the aqueous solvent as a saccharification liquid. Disclosed is a production method for producing saccharified solution.

In Korean Patent Publication No. 10-1195416, the hydrophilic surface of low coal is coated with a carbon component of a biomass-derived material to be modified, thereby resorbing moisture even after drying. A hybrid high calorific value hybrid coal and a method for producing the same, i) kneading coal with a solution of a biomass-derived material to form a paste, ii) putting the paste into a carbonization furnace to dry the biomass-derived material and A method of manufacturing a high calorific value hybrid coal coated with a biomass-derived carbon component on a hydrophilic surface of coal, comprising simultaneously performing carbonization, wherein the paste is prepared at a normal temperature and atmospheric pressure before the step (ii). High calorific value hybrid further comprising the step of aging for 5 to 240 hours It discloses a method for preparing a coal.

However, the conventional techniques known so far use medicaments or degrading enzymes to remove lignin from biomass and extract hemicellulose, which is mainly composed of glucose (glucose) and xylose, In the case of using a chemical such as an acid or an alkali, there is a problem that the process is complicated because the cost of the chemical increases and the process of recovering the used chemical must be accompanied. In addition, even if the biomass containing the same cellulose is different in the content of cellulose, hemicellulose and lignin, depending on the type of raw material, various degradation enzymes and degradation conditions must be satisfied when saccharifying. This results in a cause for which the extraction and separation conditions of the desired substance are not reliable.

Therefore, in order to promote the use and dissemination of renewable energy and to secure the supply stability of biomass fuel, it is urgently required to develop technology for the high quality of low grade coal by effectively extracting and separating biomass-derived materials and using them. have.

Korean Laid-Open Patent No. 2007-0091168 Korean Laid-Open Patent No. 2012-0077991 Korea Patent Registration No. 10-1171922 Japanese Laid-Open Patent No. 2011-205933 Korean Patent Publication No. 10-1195416

The present invention is to solve the above problems, through a plurality of high-temperature high-pressure reaction unit from a herbal or wood-based biomass bio-sugar containing a high concentration of lignin and a bio-sugar containing a high concentration of xylose and glucose An object of the present invention is to provide a mixed biosugar liquid high concentration system.

To this end, in the present invention, in the mixed biosugar solution high concentration system using the second generation biomass, the second generation biomass and the base solution are added, and the solid phase component including xylan and glucan is included through high temperature and high pressure reaction. A first high temperature high pressure reaction unit separating the bio sugar solution; Bio-sugar solution containing lignin separated from the second generation biomass and the first high temperature and high pressure reaction unit is input to separate the solid component, including xylan and glucan, and the biosugar solution with increased concentration of lignin through high temperature and high pressure reaction. 2 high temperature high pressure reaction unit; Bio sugar solution with increased concentration of lignin separated from the second generation biomass and the second high temperature and high pressure reaction unit is introduced into the solid sugar component including xylan and glucan and the bio sugar solution with higher concentration of lignin through high temperature and high pressure reaction. Separating the third high temperature high pressure unit; A fourth high temperature and high pressure reaction unit generating a bio-sugar solution containing xylose and glucose through a high temperature and high pressure reaction by inputting a solid phase component and an acidic solution including xylan and glucan separated from the first high temperature and high pressure reaction unit; Bio-sugar solution containing xylan and glucan separated from the second high temperature and high pressure reaction unit and xylose and glucose generated from the fourth high temperature and high pressure reaction unit are added to the xylose and glucose through high temperature and high pressure reaction. A fifth high temperature high pressure reaction unit generating a bio-sugar solution with an increased concentration of; A solid component including xylan and glucan separated from the third high temperature high pressure reaction unit and a biosugar solution having an increased concentration of xylose and glucose generated from the fifth high temperature high pressure reaction unit are added to the xylose through high temperature and high pressure reaction. And a sixth high temperature high pressure reaction unit for generating a bio sugar solution having an increased concentration of glucose. 2.

The present invention can effectively and easily extract and separate the bio-sugar solution containing xylose and glucose from herbal or wood-based biomass through high temperature and high pressure reaction conditions, replacing the existing chemicals such as acid or alkali. The concentration of sugar solution is increased.

1 is a block diagram of a mixed bio-sugar high concentration system using a second generation biomass according to the present invention.
Figure 2 is a flow chart showing a high concentration of mixed bio-sugar solution using the second generation biomass according to the present invention.
Figure 3 is a graph showing the concentration of bio sugar solution containing lignin and bio sugar solution containing xylose and glucose according to the number of high temperature and high pressure reaction.
Figure 4 is a graph showing the concentration of the bio-sugar solution containing lignin and the bio-sugar solution containing xylose and glucose according to the reaction temperature.
Figure 5 is a graph showing the concentration of the bio-sugar solution containing lignin and the bio-sugar solution containing xylose and glucose according to the reaction time.

The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention. Therefore, the exemplary embodiments described herein are merely exemplary embodiments of the present invention, and do not represent all of the technical ideas of the present disclosure, and thus, various equivalents and modifications may be substituted for them at the time of the present application. It should be understood that it can.

Hereinafter, with reference to the accompanying drawings will be described in detail a high-grade method of low grade coal using a biomass according to the present invention.

1 is a block diagram of a mixed bio-sugar high concentration system using a second generation biomass according to the present invention.

A first high temperature and high pressure reaction unit as shown in FIG. 1; A second high temperature high pressure reaction unit; A third high temperature high pressure reaction unit; A fourth high temperature high pressure reaction unit; A fifth high temperature high pressure reaction unit; The sixth high temperature high pressure reaction unit.

Here, the HCK manufacturing unit for producing a high calorific value coal by using the mixed bio-sugar liquid produced by the mixed bio-sugar liquid high concentration system may be further included.

The HCK manufacturing unit is designed by the present inventors prior to this invention, and is described in detail in Korean Patent No. 10-1709328, Korean Patent No. 10-1695702, and Korean Patent No. 10-14164920.

Figure 2 is a flow chart showing a high concentration of mixed bio-sugar solution using the second generation biomass according to the present invention.

The second generation biomass refers to lignocellulosic based herbal, woody biomass, and is not limited as long as it belongs to the biomass. Cellulose, a major component of lignocellulosic cellulose, is a polysaccharide with a stable structure in which glucose is connected by β-1,4 bonds. It is composed of a polymer of xylose, another pentose, and other major components, and in addition, arabose, pentose, mannose, galactose, glucose, and rhamnose. And polymers).

The bioliquid concentration method using the second generation biomass according to the present invention starts from physically treating the biomass. The physical treatment method of the biomass is not limited to the method as long as it can achieve the purpose of increasing the surface area while reducing the size of the biomass such as crushing, shearing and cutting. The apparatus for performing the physical treatment method of the biomass may be a mill, a mixer, a screw extruder, a rotary knife cutter, but is not limited thereto.

The biomass pulverized to the appropriate size is transferred to a high temperature and high pressure reactor with warmed steam or hot water, and the reactor is operated to maintain a predetermined temperature, pressure and reaction time. The biomass particles supplied to the high temperature and high pressure reactors are damaged by high pressure and temperature.

As shown in FIG. 2, the second generation biomass is introduced into the base solution and the first high temperature and high pressure reaction unit, and separated into a solid sugar component including xylan and glucan and a biosugar solution including lignin through a high temperature and high pressure reaction.

 Since cellulose and hemicellulose are soluble in acid while lignin is soluble in alkali, the second generation biomass in the first high temperature and high pressure reaction unit is separated into a bio liquid containing lignin and a solid component including xylan and glucan.

Glucan (glucan) is a generic term for polysaccharide composed of glucose, and there are various types according to the binding mode of D-glucose, and it is largely divided into α-glucan and β-glucan by the arrangement of sub-carbon atoms. α-glucan contains amylose (α-1,4 bond), amylopectin (α-1,4 and α-1,6 bond), glycogen (α-1,4 and α-1,6 bond), bacterial dextran (α-1,6 bond) and the like. Representatives of β-glucan include cellulose (β-1,4 bond), laminaran of brown algae (β-1,3 bond), lichenan (β-1,3 and β-1,4 bond) of lichens, etc. have.

Xylan-containing components include xylan. Glucuronoxylan, arabinoxylan, glucomannan, xyloglucan, and the like. Components containing xylan as the above-described components are not limited, and various components may be separated according to the components of the biomass to be introduced.

The bio-sugar solution containing lignin separated from the first high temperature and high pressure reaction unit is added to the second high temperature and high pressure reaction unit together with the second generation biomass, and the concentration of the solid phase component and lignin including xylan and glucan is increased through the high temperature and high pressure reaction. Separated into increased biosugars.

Here, the bio-sugar solution in which the concentration of the lignin separated from the second high temperature high pressure reaction unit is increased is introduced into the third high temperature high pressure reaction unit together with the second generation biomass, and the solid phase component including xylan and glucan through high temperature and high pressure reaction. It is separated into biosugars, where the concentration of lignin is further increased.

The solid component including xylan and glucan separated from the first high temperature and high pressure reaction unit is introduced into the fourth high temperature and high pressure reaction unit together with an acidic solution to generate a biosugar solution containing xylose and glucose through high temperature and high pressure reaction, The bio-sugar solution containing xylose and glucose generated from the fourth high temperature high pressure reaction unit is introduced into the fifth high temperature high pressure reaction unit together with the solid phase component including xylan and glucan separated from the second high temperature high pressure reaction unit. The high pressure reaction produces biosugars with increased concentrations of xylose and glucose.

Here, the bio-sugar solution with increased concentrations of xylose and glucose generated from the fifth high temperature high pressure reaction unit may be added to the solid phase component and the sixth high temperature high pressure reaction unit including xylan and glucan separated from the third high temperature high pressure reaction unit. Injected into a high temperature and high pressure reaction to produce a bio-sugar solution with a higher concentration of xylose and glucose.

Herein, the bio-liquid containing lignin is added to the second high temperature high pressure reaction unit to increase the concentration, and the lignin bio-liquid whose concentration is increased may be added to the third high temperature high pressure reaction unit to further increase the concentration.

The solid component including xylan and glucan separated from the first high temperature high pressure reaction unit is introduced into the fourth high temperature high pressure reaction unit together with an acidic solution to generate a bio liquid containing xylose and glucose, and the xylose and glucose The containing bio-liquid is added to the fifth high-temperature high-pressure reaction unit together with the solid phase component including xylan and glucan separated from the second high-temperature high-pressure reaction unit to generate a bio-liquid containing xylose and glucose having increased concentration.

Here, the temperature conditions in the first, second, third high temperature high pressure reaction unit may be 30 or more to 300 ° C or less. Preferably it may be 100 to 250 ℃ or less, more preferably 200 or more to 220 ℃ or less. If lower than this temperature condition, the decomposition rate of biomass will be low, and if it is higher than this temperature condition, the decomposition efficiency will be lowered according to the process cost.

In the fourth, fifth and sixth high temperature and high pressure reaction units, the temperature conditions may be 30 or more and 300 ° C. or less. Preferably it may be 100 or more to 250 ° C or less, more preferably 150 or more to 180 ° C or less. If it is higher than this temperature condition, the concentration of bio sugar solution containing xylose and glucose is lowered by overreaction.

In addition, the high temperature and high pressure reaction is carried out in a high temperature and high pressure reaction unit, characterized in that carried out under 0.4 to more than 90 bar conditions.

Pressure conditions in the high temperature and high pressure reaction unit may be more than 0.4 to less than 90 bar. Preferably it may be 1 to 41 bar or less, more preferably 4.8 to 23.3 bar or less. If the pressure is lower than this pressure, the decomposition rate of the biomass is lowered. If the pressure is higher than this pressure, the efficiency of decomposition is lowered due to the process cost.

In addition, the high temperature and high pressure reaction is carried out in a high temperature and high pressure reaction unit, the reaction time is characterized in that the reaction in more than 1 minute to 4 hours or less.

The reaction time may be more than 1 minute and less than 4 hours. Preferably from 5 minutes to 2 hours or less, more preferably from 10 minutes to 30 minutes or less.

In the high temperature and high pressure reaction unit, the reaction time means a reaction time from the steady state of the reactor after reaching the target temperature.

If less than the reaction time, the degradation effect of the input biomass is lowered, if larger than the reaction time, the energy consumption required for the decomposition effect of the input biomass is large, the process cost is high.

<Example 1>

As shown in FIG. 3, the biosaccharide liquid including lignin and the bio sugar liquid including xylose and glucose are increased in concentration as the number of high temperature and high pressure reactions increases.

<Example 2>

As shown in Figure 4, in the case of the lignin solution concentration increases as the treatment temperature increases, but in the case of bio sugar liquid containing xylose and glucose when the treatment at a temperature higher than 170 degrees, the concentration of the sugar solution due to overreaction Will be lowered.

<Example 3>

As shown in FIG. 5, in the case of the bio sugar solution including lignin and the bio sugar solution including xylose and glucose, loss of sugar occurs due to overreaction when the residence time exceeds 30 minutes. Thus, the maximum reaction time is 30 minutes to act as a limit time.

Although the present invention has been described with reference to the accompanying drawings, it is merely one example of various embodiments including the gist of the present invention, which can be easily implemented by those skilled in the art. It is clear that the present invention is not limited to the above-described embodiment only.

Therefore, the protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the scope equivalent to the change, substitution, substitution, etc. within the scope not departing from the gist of the present invention shall be the right of the present invention. It will be included in the scope.

In addition, some of the components of the drawings are intended to more clearly describe the configuration, and it is clear that the exaggerated or reduced size is provided.

10: first high temperature high pressure reaction unit
20: second high temperature high pressure reaction unit
30: third high temperature high pressure reaction unit
40: fourth high temperature high pressure reaction unit
50: fifth high temperature high pressure reaction unit
60: sixth high temperature high pressure reaction unit
70: HCK manufacturing unit

Claims (5)

A first high temperature and high pressure reaction unit apparatus into which a second generation biomass and a base solution are added and separated into a solid sugar component including xylan and glucan and a bio sugar solution including lignin through a high temperature and high pressure reaction;
Bio-sugar solution containing lignin separated from the second generation biomass and the first high-temperature high-pressure reaction unit device is input and separated into solid-phase components including xylan and glucan and bio-sugar solution with increased concentration of lignin through high temperature and high pressure reaction. A second high temperature high pressure reaction unit device;
Bio sugar solution with increased concentration of lignin separated from the second generation biomass and the second high temperature and high pressure reaction unit device was added, and bio sugar solution with higher concentration of lignin and solid phase components including xylan and glucan was added through high temperature and high pressure reaction. A third high temperature high pressure reaction unit device for separating;
A fourth high temperature and high pressure reaction unit device in which a solid component including xylan and glucan separated from the first high temperature and high pressure reaction unit device is input and an acid solution is used to generate a biosugar solution containing xylose and glucose through a high temperature and high pressure reaction;
Bio-sugar solution containing xylan and glucan separated from the second high temperature and high pressure reaction unit device and xylose and glucose generated from the fourth high temperature and high pressure reaction unit device are added and xylose through high temperature and high pressure reaction. And a fifth high temperature hyperpressure unit device for producing a bio-sugar solution with an increased concentration of glucose.
The solid phase component including xylan and glucan separated from the third high temperature high pressure reaction unit device and the bio sugar solution with increased concentration of xylose and glucose generated from the fifth high temperature high pressure reaction unit device are added to each other through a high temperature high pressure reaction. Mixed bio-sugar liquid high concentration system using the second generation biomass, including; a sixth high temperature high-pressure reaction unit apparatus for producing a bio-sugar liquid with an increased concentration of xylose and glucose. The method of claim 1,
The temperature conditions of the first to third high temperature and high pressure reaction unit apparatus is 170 ℃ or more and 220 ° C or less, and the temperature conditions of the fourth to sixth high temperature and high pressure reaction unit apparatus are 150 to 200 ℃. Mixed bio sugar solution high concentration system using the second generation biomass. The method of claim 1,
In the first to sixth high temperature and high pressure reaction unit apparatus, the pressure condition is 0.4 or more and 90 bar or less, and the reaction time is more than 1 minute to 4 hours. . The method of claim 1,
The bio-sugar solution of which the concentration of lignin generated from the third high-temperature hyperpressure unit device is further increased and the bio-sugar solution of which the concentration of xylose and glucose further increased from the sixth high temperature / high pressure reaction unit device are increased. Hybrid coal production unit high concentration system using a second generation biomass, including; a hybrid coal production unit device for producing a hybrid coal. A first high temperature and high pressure reaction step in which a second generation biomass and a base solution are added and separated into a solid sugar component including xylan and glucan and a bio sugar solution including lignin through a high temperature and high pressure reaction;
Bio-sugar solution containing the second generation biomass and the lignin separated from the first high temperature and high pressure reaction step is input to separate the solid component, including xylan and glucan, and the bio-sugar solution with increased concentration of lignin through high temperature and high pressure reaction. 2 high temperature and high pressure reaction step;
Bio sugar solution with increased concentration of lignin separated from the second generation biomass and the second high temperature and high pressure reaction step was added to the biosugar solution with higher concentration of lignin and solid phase components including xylan and glucan through high temperature and high pressure reaction. Separating the third high temperature and high pressure;
A fourth high temperature and high pressure reaction step of generating a bio-sugar solution containing xylose and glucose through a high temperature and high pressure reaction by inputting a solid component including xylan and glucan separated from the first high temperature and high pressure reaction step;
Bio-sugar solution containing xylan and glucan separated from the second high temperature and high pressure reaction step and xylose and glucose generated from the fourth high temperature and high pressure reaction step are added to the xylose and glucose through high temperature and high pressure reaction. A fifth high temperature and high pressure reaction step of producing a bio-sugar solution with an increased concentration of;
The solid component including xylan and glucan separated from the third high temperature and high pressure reaction step and the biosugar solution with increased concentrations of xylose and glucose generated from the fifth high temperature and high pressure reaction step are injected into xylose through high temperature and high pressure reaction. And a sixth high temperature high pressure reaction step of generating a biosugar solution having an increased concentration of glucose. 2.

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