KR101695702B1 - MODIFICATION METHOD FOR LOW RANK COAL USING 2nd GENERATION BIOMASS COMPRISED OF HEXOSE - Google Patents
MODIFICATION METHOD FOR LOW RANK COAL USING 2nd GENERATION BIOMASS COMPRISED OF HEXOSE Download PDFInfo
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- KR101695702B1 KR101695702B1 KR1020150097722A KR20150097722A KR101695702B1 KR 101695702 B1 KR101695702 B1 KR 101695702B1 KR 1020150097722 A KR1020150097722 A KR 1020150097722A KR 20150097722 A KR20150097722 A KR 20150097722A KR 101695702 B1 KR101695702 B1 KR 101695702B1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/02—Treating solid fuels to improve their combustion by chemical means
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
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Abstract
The present invention relates to a method for upgrading a low grade coal using biomass, and more particularly, to a method for improving the quality of a low grade coal using biomass, The present invention relates to a system and a method for improving the quality of low grade coal by using a biomass having high water resistance and impregnating, coating and heat-treating solid phase components including lignin.
Description
The present invention relates to a method for upgrading a low grade coal using biomass, and more particularly, to a method for improving the quality of a low grade coal using biomass, The present invention relates to a system and a method for improving the quality of low grade coal by using a biomass having high water resistance and impregnating, coating and heat-treating solid phase components including lignin.
Interest in coal as an energy source is rising again due to rising oil prices and distrust of nuclear energy stability. However, since coal generates the largest amount of carbon dioxide in fossil fuels, it is a weak source of competitiveness considering the global warming problem.
As a result, the use of renewable energy is one of the issues that are currently being addressed globally as an energy source. This means that the emission of carbon dioxide is reduced compared to conventional fossil fuels such as petroleum and coal, Because it is an energy source.
However, in Korea, when new or renewable energy sources such as solar or wind power are used for power generation or heating, the use and distribution of new fossil fuels are limited due to differences in generation cost compared to fossil fuels. However, As renewable energy mandatory quota system began to be discussed with the depletion of greenhouse gas (GHG) emissions in response to the International Convention on Climate Change Convention, the Renewable Portfolio Standard (RPS) was introduced in 2012, It is a burden to the present.
As a result, power generators are attempting to reduce the generation of carbon dioxide in coal, and to try to reduce the total gasification combined cycle (IGCC) and bio-mass.
However, IGCC can not use existing coal-fired power generation facilities, and it requires huge construction cost of about 1.3 trillion KRW per unit. In addition, Carbon Capture and Storage (CCS) As an additional technology to install, the economic burden is very large.
In the case of biomass coexistence, the power generation efficiency is lowered due to combustion of biomass having a relatively low calorific value as compared with coal. That is, 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 between the oil-based biomass and the coal surface, coal and biomass retain their existing combustion characteristics, resulting in different combustion characteristics. Therefore, when this is applied to a power plant, oxygen is preferentially consumed excessively due to the low-temperature combustion pattern of the oil in the front part of the burner, which eventually inhibits the combustion of coal, thereby increasing the amount of unburned carbon and decreasing power generation efficiency .
Meanwhile, a number of known documents for addressing the above problems are as follows.
Korean Patent Publication No. 2007-0091168 discloses a method for producing a biomass which is characterized in that a high dry matter content in combination with a type of blending that depends on the law of gravity to ensure that the enzymatic hydrolysis adds mechanical force (primary shear force and bursting force) Lt; RTI ID = 0.0 > lysing < / RTI > and saccharification of polysaccharide containing biomass.
Korean Patent Laid-Open Publication No. 2012-0077991 discloses a reaction tank in which a pulverized cellulose-based biomass sample, an acid or an alkali solution and carbon dioxide are injected into the inside thereof and the reaction is carried out under high temperature and high pressure; A separation tank installed at a lower end of the reaction tank and maintained in a low-temperature and low-pressure condition; A fine nozzle installed between the reaction tank and the separation tank and capable of separating the carbohydrate by spraying the reaction product of high temperature and high pressure generated in the reaction tank into the separation tank at low temperature and low pressure; A pretreatment apparatus for producing a substrate for ethanol fermentation from a lignocellulosic biomass is disclosed.
Korean Patent No. 10-1171922 discloses a method for manufacturing and treating carbohydrate-containing materials to change their structure, and a product made from structurally modified materials, for example, a lower molecular weight and / The present invention provides cellulose and / or lignocellulosic materials having crystallinity and is more readily used by various microorganisms to produce useful products such as hydrogen, alcohols such as ethanol or butanol, organic acids such as organic acids, hydrocarbons, (E. G., Protein) or any mixture thereof. ≪ / RTI >
Japanese Patent Application Laid-Open No. 2011-205933 discloses a method for producing a glycosylated solution using an enzyme from a biomass. In the reaction solvent in which a hydrophobic organic solvent is present, biomass, And an enzyme are added to the reaction mixture to stir the polysaccharide in the biomass into hydrogels of a lower molecular weight, and in a final stage of the decomposition step, an extraction step of adding an aqueous solvent in a reaction solvent to extract a saccharide having a lower molecular weight than the one having been decomposed into an aqueous solvent, and a recovery step of recovering the saccharide extracted in the aqueous solvent as a saccharified liquid Thereby producing a saccharified liquid.
Korean Patent Publication No. 10-1195416 discloses a method in which a hydrophilic surface present in a lower carbon is coated with a carbon component of a biomass-derived material to modify the natural carbon component and the artificial carbon component, Hybrid coal having a high heat content and a method for producing the hybrid coal, comprising the steps of: i) kneading a coal with a solution of a biomass-derived material to form a paste, ii) introducing the paste into a carbonization furnace to dry the biomass- A method for producing a hybrid of high calorific value in which a carbonaceous component derived from biomass is coated on a hydrophilic surface of coal, comprising the step of simultaneously performing carbonization, wherein a paste is prepared at room temperature and atmospheric pressure before performing the step (ii) And aging for 5 to 240 hours. ≪ RTI ID = 0.0 > It discloses a method for preparing a coal.
However, in the conventional techniques known so far, lignin is removed from the biomass and drugs or decomposition enzymes are mainly used to extract hemicellulose, which is mainly composed of cellulose and xylose, which are glucose-based, In the case of using a chemical such as an acid or an alkali, not only the drug cost is increased but also the process of recovering the used chemical must be accompanied, which complicates the process. Also, even if a biomass containing the same cellulose has different contents of cellulose, hemicellulose and lignin depending on the kind of the raw material, various degrading enzymes and decomposition conditions must be satisfied during saccharification. As a result, the extraction and separation conditions of the desired substance are not reliable.
Therefore, in order to promote the utilization and diffusion of renewable energy and secure the supply stability of biomass fuels, it is urgently required to develop technologies for high-grade coal of low grade coal utilizing the extraction and separation of biomass- have.
Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in an effort to solve the above-mentioned problems, and an object of the present invention is to provide a method and apparatus for extracting and separating a liquid component containing glucose from herbaceous or woody biomass, The present invention is to provide a system and a method for improving the quality of low grade coal using the biomass having high water resistance while improving the heat generation by impregnating the fine pores of the low grade coal with a coating and heat treatment on the surface.
In the present invention, in the second generation biomass-based coal upgrading system, the biomass derived from lignocellulose is subjected to a high-temperature and high-pressure reaction to convert the liquid component containing xylenes derived from hemicellulose into cellulose, A high-temperature and high-pressure reaction unit (100) for separating the solid phase component and the lignin into a solid phase component including the solid phase component and the lignin; An enzyme
The second-generation biomass refers to lignocellulose-based herbaceous or woody biomass, and is not limited to materials belonging to the biomass. Cellulose, which is a major component of lignocellulose, is a stable polysaccharide in which glucose is linked by β-1,4 bonds. Another major component is a polymer of xylose, which is a pentane. In addition, it is composed of a polymer such as 5-valent arabinose, 6-valent mannose, galactose, glucose, rhamnose, etc. Of a polymer.
Glucan is a generic term for polysaccharides composed of glucose. There are various types of polysaccharides depending on the binding style of D-glucose. They are largely divided into α-glucan and β-glucan by the arrangement of the adduct carbon atoms. The α-glucan includes amylose (α-1,4 bond), amylopectin (α-1,4 and α-1,6 bonds), glycogen (α-1,4 and α-1,6 bonds), bacterial dextran (? -1,6 bond), and the like. Typical examples of? -glucan include cellulose (? -1,4-linked), brown alga laminaran (? -1,3-linked), lichenous lichenan (? -1,3 and? -1,4-linked) have.
The liquid component containing xylan includes xylan (xylan). Glucuronoxylan, arabinoxylan, glucomannan, xyloglucan, and the like may be included. The liquid component containing xylan as the above-described components is not limited, and various components may be separated depending on the components of the biomass to be injected.
The saccharides are not limited to the above-described compounds and can be variously produced depending on the kind of the second generation biomass. Therefore, it is divided into 2, 3, 4, 5, and 6-carbon sugars according to the number of carbon atoms. Glycoaldehyde, Glyceraldehyde, Dihydroxyacetone, , Erythrose, erythrulose, pentose, ribose, arabinose, xylose, ribulose, and Zylurozu as quaternary sugars. xylulose and 6-carbon sugars can be glucose, glucose, fructose, fructose, galactose and mannose.
Examples of the disaccharide to which two monosaccharides are combined may include lactose, lactose, lactose, glucose, maltose, maltose, sugar, sucrose, trehalose, melibiose and cellobiose.
Examples of the small sugars that are sugar-bonded sugars having 2 to 10 molecules include raffinose, melezitose and maltoriose as three saccharides, starchose and schrodose as four saccharides, And oligosaccharides may be galactooligosaccharides, isomaltooligosaccharides, and fructooligosaccharides.
Examples of the polysaccharides include pentosan, which is a simple polysaccharide with pentoses attached thereto, and may include xylan and araban.
Hexoxanes condensed with 6-valent sugars include starch, starch, polymers of glucose such as amylose, dextrin, glycogen, cellulose, fructan, galactan galactan, mannan, and the like.
Composite polysaccharides may include agar, alginic acid, carrageenan, chitin, hemicellulose, pectin, and the like.
In addition, a compound such as furfural can be produced through the recycle unit while the liquid component including glucose participates in the high-temperature high-pressure reaction.
A predetermined amount of the liquid component containing glucose attributable to the cellulose is recycled to the high-temperature and high-pressure reaction unit to concentrate the liquid component containing glucose due to cellulose, in a recycle unit, The charging ratio of the liquid component including glucose injected into the high-temperature high-pressure reaction unit through the recycle unit among the solid-phase components including the glucan may be more than 0.001 and less than 1. Preferably from 0.01 or more to 0.3 or less, more preferably from 0.05 or more to 0.2 or less.
If the amount is lower than the above-mentioned charging ratio, the concentration effect of the liquid component containing glucose is low, and if it is higher than the above-mentioned charging ratio, energy to be added for the concentration effect will increase.
Also, a spraying generating
The concentration of the spraying solution is determined by a solid phase component containing glucan due to cellulose separated from the high temperature and high pressure reaction unit, a liquid component containing glucan due to cellulose concentrated through the recycle unit, And the liquid component containing the produced glucose contains a certain amount of water in one or two or more liquid components.
The concentration is expressed as a solution ratio of the liquid component to be added to the total spraying solution, and may be more than 0 and less than 1. Preferably from 0.3 or more to 0.95 or less, and more preferably from 0.5 or more to 0.9 or less.
If the solution ratio is lower than the above-mentioned range, there is a disadvantage in that the amount of water is large and thus the process ratio is large, and when it is higher than the solution ratio, viscosity conditions for spraying and the like are difficult.
Also, a
The spray solution is sprayed onto the coal while rotating coal having an average particle size of less than 4 mm among the coarsely pulverized coals using the spray solution generated through the spraying generating unit to granulate the coal while impregnating or coating the coal. A coal granulating unit (700) for increasing the size of the coal; May be further included.
The coal pretreatment unit or the coal granulation unit may be operated independently or simultaneously depending on whether or not the coal satisfies the average grain size condition.
A
Further, a coal grain processing unit (900) for performing grain size treatment of coal in accordance with a predetermined reaction condition of a reactor in which the heat-treated coal is charged into a reaction material; May be further included.
The reactor may be a pulverized coal boiler, a fluidized bed boiler, a grate boiler, or the like. The gasifier may be a fixed bed gasifier, a fluidized bed gasifier, a classifying bed gasifier, or a reactor to which a steel coke oven or a PCI coal is applied It is possible. The reactor to be charged with the reactant is not limited to the above-mentioned reactor, and applicable reactors can be applied to all of them satisfying the granular conditions charged according to the use of the reactor.
The high-temperature and high-pressure reaction is carried out in a high-temperature and high-pressure reaction unit, and is characterized by extracting and separating a solid phase component containing glucan and a solid phase component containing lignin due to cellulose under a temperature condition of 30 ° C. to 300 ° C. .
In the high-temperature and high-pressure reaction unit, the temperature condition may be 30 to 300 ° C. Preferably 100 to 250 ° C, and more preferably 150 to 220 ° C. When the temperature is lower than this temperature, the decomposition rate of the biomass is lowered. If the temperature is higher than this temperature condition, the decomposition efficiency is lowered depending on the process cost and the like.
The high-temperature and high-pressure reaction is carried out in a high-temperature and high-pressure reaction unit, and is characterized by extracting and separating a solid phase component containing glucan and a solid phase component containing lignin due to cellulose under a pressure condition of 0.4 to 90 bar .
The pressure condition in the high temperature and high pressure reaction unit may be 0.4 or more and 90 bar or less. Preferably from 1 to 41 bar, and more preferably from 4.8 to 23.3 bar. When the pressure is lower than the pressure, the decomposition rate of the biomass is lowered, and when the pressure is higher than the pressure, the decomposition efficiency is lowered depending on the process cost.
Also, the high-temperature and high-pressure reaction is carried out in a high-temperature and high-pressure reaction unit, and the reaction time is from 1 minute to 4 hours or less, thereby extracting and separating the solid phase component containing glucan and the solid phase component containing lignin due to cellulose .
The reaction time in the high-temperature high-pressure reaction unit means the reaction time from the steady state of the reactor after reaching the target temperature. The reaction time may be more than 1 minute and not more than 4 hours. Preferably 5 minutes or more to 2 hours or less, and more preferably 10 minutes or more to 30 minutes or less.
If the reaction time is less than the above reaction time, the decomposition effect of the input biomass is lowered. If the reaction time is longer than the reaction time, the energy consumption for decomposing effect of the input biomass is increased, and the process cost is increased.
In addition, the high-temperature and high-pressure reaction unit may include a liquid phase component containing xylan caused by the hemicellulose, a solid phase component containing glucan due to cellulose, and a solid phase component containing lignin in the high- And a re-evaporator unit (120) for re-evaporating the water containing the liquid component and the steam discharged together with the solid-phase component discharged through the lock hopper unit to the high-temperature and high-pressure reaction unit 130); May be further included.
Further, a solid phase containing a liquid component containing xylan caused by hemicellulose separated and interlocked with the rear end of the re-evaporation unit and a glucan derived from cellulose
And a
Further, the reheating
Further, the granulating unit is characterized in that it is carried out in a drum type, a kiln type, a disk type granulator or a briquetting production facility.
Further, a coarse crushing
Further, a
Further, the enzyme saccharification reaction unit is characterized in that any one or two or more of enzymes, acids, alkalis and ionic liquids are introduced.
Examples of enzymes involved in the degradation of hemicellulose include enzymes such as Endo-1,4-β-D-xylanases, exo-1,4-β-D-xylosidases, endo-1,4- L-arabinofuranosidases, α-galactosidases, and ferulic acid esterase. Endo-glucanase (EG), cellobiogydrase (CBH), and β-mannosidase ), β-glucosidase (BGL), and the like. The enzyme is not limited to the enzymes described, and any enzymes capable of decomposing hemicellulose and cellulose may be used.
The acid participating in the reaction are sulfuric acid (H 2 SO 4), hydrochloric acid (HCl), nitric acid (HNO 3), phosphoric acid (H 3 PO 4), and acetic acid (C 2 H 4 O 3) , oxalic acid (C 2 H 2 O 4 ), and the like. The acid is not limited to the acid described, and any acid which decomposes hemicellulose and cellulose can be used.
The bases involved in the reaction include sodium hydroxide, calcium hydroxide, urea, and the like. The base is not limited to the base described, and any base that promotes the reaction characteristics can be used.
Examples of the ionic liquid participating in the reaction include imidazolium compounds such as 1-ethyl acrylate-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, Butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium chloride, 1-butyl- Butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium 1-ethyl-3-methylimidazolium acetate, 1-benzyl-3-methylimidazoliumchloride, 1,3-dimethylimidazoliummethylsulfate, sulfate, 1-butyl-3-methylimidazolium chloride, 1- Ethylimidazolium bromide ([EMIM] Br), ethylmethylimidazolium acetate, and the like, and ethylmethylimidazolium chloride ([EMIM] Cl) Ethyl imidazolium bromide, 1-ethyl-3-methyl imidazolium chloride, 1-ethyl imidazolium bromide, 1-ethyl imidazolium iodide, Ethyl-imidazolium chloride, 1,2,3-trimethyl imidazolium methyl sulfate, 1-methyl imidazolium chloride, 1-butyl-3-methyl imidazolium, Ethyl-3-methyl imidazolium hydrogensulfate, 1-butyl-3-methyl imidazolium hydrogensulfate, methylimidazole 1-ethyl-3-methyl imidazolium acetate, 1-butyl-3- Ethyl-3-methyl imidazolium methanesulfonate, methyl-tri- methyl-imidazolium acetate, tris-2- butyl-3-methyl imidazolium chloride, 1-ethyl-3-methyl imidazolium chloride, 1-ethyl-3-methyl imidazolium thiocyanate, 1-butyl- Methylimidazolium nitrate, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium chloride, Methylimidazolium nitrate, 1-ethyl-3-methylimidazolium acetate, 1- (2-methylimidazolium) acetate, 1- Ethyl-3-methylimidazolium tetrafluoroborate, 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methyl Imidazolium nitrate, 1-methyl-3-Ali are imidazolium acetate, 1-methyl-3-Ali may be a borate as imidazolium tetra flow. The ionic liquid is not limited to the ionic liquid described above, and any ionic liquid can be used as long as it improves the reaction characteristics.
The amount of one or more of the enzyme, acid, alkali, and ionic liquid introduced into the reaction unit may not be supplied depending on the reaction conditions.
In order to solve this problem, in a method for upgrading coal using a second-generation biomass, a biomass derived from lignocellulose is subjected to a high-temperature and high-pressure reaction to convert the liquid component containing xylenes derived from hemicellulose into cellulose, A high-temperature and high-pressure reaction step of separating into a solid phase component including the solid phase component and lignin; An enzyme saccharification reaction step of performing enzymatic saccharification of a predetermined amount among the solid phase components including glucan due to the cellulose; A solid phase component including glucose and a solid phase component including lignin and a solid phase component including glucan due to cellulose produced through the high-temperature and high-pressure reaction step and a solid phase component including lignin produced through the enzyme saccharification reaction step A solid-liquid separation step of separating the liquid component containing glucose; And a recycling step of recycling a liquid component containing a predetermined amount of glucose separated in the solid-liquid separation step to a high-temperature and high-pressure reaction step; The present invention can provide a method for upgrading coal using second generation biomass.
A spraying step of generating a spraying solution having a predetermined concentration using a liquid component containing glucose and / or a solid component containing lignin separated through the solid-liquid separation step; . ≪ / RTI >
A
The spray solution is sprayed onto the coal while the coal having an average particle size of less than 4 mm among the coarsely pulverized coals is spun using the spray solution generated through the spraying step to impregnate or coat the coal with granulation, Lt; RTI ID = 0.0 > granulation < / RTI >
The coal pretreatment step or the coal granulating step may be operated independently or simultaneously depending on the presence or absence of the inflow of coal meeting the average grain size condition.
Further, the method may further include a heat treatment step of drying and heat-treating the coal produced through the coal pretreatment step or the coal granulation step.
Further, the method may further include a step of performing a grain size treatment of coal in accordance with a predetermined condition of a reactor into which the heat-treated coal is charged as a reactant.
Also, the high-temperature and high-pressure reaction is performed in a high-temperature and high-pressure reaction step, and is characterized by extracting and separating a solid phase component containing glucan and a solid phase component containing lignin due to cellulose at 180 to 200 ° C.
Also, the high-temperature and high-pressure reaction is performed in a high-temperature and high-pressure reaction step, and is characterized by extracting and separating solid-phase components including glucan and lignin due to cellulose under the condition of 0.4 to 90 bar.
Also, the high-temperature and high-pressure reaction is performed in a high-temperature and high-pressure reaction step, and the reaction is performed for 10 minutes to 4 hours to extract and separate solid phase components containing glucan and lignin-containing solid phase components derived from cellulose.
In addition, in the high-temperature and high-pressure reaction step, the liquid phase component containing xylan caused by the hemicellulose, the solid phase component including glucan due to cellulose and the solid phase component including lignin are discharged in a high- And a re-evaporating unit for re-evaporating the liquid containing the discharged liquid component and the solid component together with the steam discharged through the lock hopper unit to the high-temperature and high-pressure reaction unit.
Further, a
Further, the reheating
The granulating step is also characterized in that it is carried out in a drum type, a kiln type, a disk type granulator or a briquetting production facility.
Further, it may further comprise a coarse grinding step of grinding raw coal to produce the coarsely pulverized coal.
Further, a biomass pretreatment step for reducing the size of the second generation biomass may be further included at the upstream of the high-temperature high-pressure reaction step.
Further, the enzyme saccharification reaction step is characterized in that any one or two or more of enzymes, acids, alkalis and ionic liquids are added.
According to the method for upgrading low-grade coal using the biomass of the present invention, glucose can be effectively and easily extracted from an herbaceous or woody biomass through high-temperature and high-pressure reaction conditions without using an additional chemical such as acid or alkali There is an effect that can be done.
In addition, it is possible to prevent the moisture from being re-adsorbed by impregnating, drying and carbonizing the low-grade coal with the liquid component containing the obtained glucose and / or the solid component including lignin, thereby enabling the supply of coal having a high calorific value High-grade coal of low grade is possible.
1 is a flowchart illustrating a method for upgrading a low grade coal using the biomass according to the present invention.
FIG. 2 is a conceptual diagram for upgrading low grade coal using a solution containing glucose from the biomass according to the present invention.
Figure 3 is a diagram of a high grade coal grade system using biomass according to the present invention.
FIG. 4 is a diagram of a high-temperature high-pressure reaction unit of a high-grade coal-grade upgrading system using biomass according to the present invention.
FIG. 5 is a diagram illustrating an embodiment of a high-grade coal grade system using biomass according to the present invention.
6 is a diagram illustrating an embodiment of a system for upgrading a low grade coal using the biomass according to the present invention.
FIG. 7 is a graph showing the results of weight change of the xylan with temperature according to the present invention in order to confirm the application of high grade of low grade coal using the biomass.
FIG. 8 is a graph showing the result of weight change according to the temperature of a sample during simple heat treatment mixing for comparison with high-grade application of low grade coal using the biomass according to the present invention.
FIG. 9 is a graph showing a result of weight change of a sample to which a high-grade coal using a biomass according to the present invention is applied.
The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention. Therefore, the embodiments described herein are merely the most preferred embodiments of the present invention and are not intended to represent all of the technical ideas of the present invention, so that there are various equivalents and modifications that can be substituted at the time of the present application It should be understood.
Further, the coal used in the present invention means at least one selected from among low grade coal recognized in the art such as peat, lignite, bituminous coal, bituminous coal or anthracite coal.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for upgrading low grade coal using biomass according to the present invention will be described in detail with reference to the accompanying drawings.
1 is a flowchart illustrating a method for upgrading a low grade coal using the biomass according to the present invention.
Referring to FIG. 1, a method for upgrading a low grade coal using the biomass according to the present invention starts from physically treating the biomass. The physical treatment of biomass is not limited as long as it can achieve the purpose of reducing the size of the biomass, such as crushing, shearing, cutting, and increasing the surface area.
The device for performing the physical treatment of the biomass may be a mill, a mixer, a screw extruder, a rotary knife cutter, but is not limited thereto.
On the other hand, as biomass raw materials, woody plants and herbaceous plants can be used. Woody lines include wood blocks, wood chips, logs, tree branches, wood crumbs, leaves, wood boards, sawdust, lignin, xylenes, lignocellulosic, palm trees, palm kernel shells, palm fiber, empty fruit bunches (EFB) , Fresh fruit bunches (FFB), palm leaves, coconut crumbs, and the like. Herbal products include corn stover, straw straw, canteen, sugar cane, grain (rice, millet, coffee, etc.) husks, candy leaves, bagasse, millet, artichoke, molasses, flax, hemp, Biomass such as starchy maize, potato, cassava, wheat, barley, lime, other starch-based remnants, fruit-bearing avocados, jatropha and their processing residues can be used.
The pulverized biomass is transferred to the high-temperature high-pressure reactor together 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 reactor are destroyed by high pressure and temperature, and are separated into a liquid phase containing hemicellulose, a solid phase containing cellulose and lignin.
Among the components separated from the high-temperature high-pressure reactor, the liquid phase containing hemicellulose is finally subjected to saccharification to obtain xylose. On the other hand, the obtained sugar is not particularly limited as long as it can be obtained from hemicellulose, but it may be preferably Arabinose or Xylose.
Here, the high-temperature and high-pressure reactor is operated at a temperature of 160 to 200 ° C, 9 to 11 bar, and 2 to 3 hours so as to separate the supplied biomass particles into a solid phase containing hemicellulose and a cellulose- . If the temperature range, the pressure range, or the reaction time is out of the above range, the recovery rate of the finally obtained glucose may be lowered, or the reaction time may become too long or the operation cost may increase.
On the other hand, conventional known techniques for separating and extracting glucose and xylose from biomass include a physical pretreatment process for crushing and crushing raw materials to a proper size, a chemical pretreatment process using chemicals such as acids and alkalis, And xylose and glucose have been separated and extracted through processes. However, in the present invention, by conducting a high-temperature high-pressure reaction under optimized conditions without using chemicals such as acids or alkalis after the physical pretreatment process, glucose can be effectively extracted and separated, and the recovery rate of glucose can be increased And these configurations and effects can be said to be the main features of the present invention.
In addition, since cellulose and hemicellulose are soluble in acid, lignin is soluble in alkali, and therefore, acid or alkali is pre-treated at a high temperature with a solvent. However, hemicellulose, which is a major component of xylose, has a weak heat characteristic, and when a long time treatment is performed at a high temperature, a part of hemicellulose is changed into a fermentation inhibiting substance to cause not only xylose loss but also fermentation inhibition problem. It is possible to prevent the loss of the xylose and the fermentation degradation problem in advance.
It is a matter of course that the solid matter containing xylose, glucose and lignin separated and discharged from the high-temperature high-pressure reactor of the present invention can be recovered separately and then used as a raw material for bioethanol through saccharification, fermentation and purification.
The structure of the high-temperature high-pressure reactor will be described with reference to FIG. 1 attached hereto.
The high-temperature high-pressure reactor of the present invention comprises a crushed biomass feeder for storing crushed biomass and supplying the crushed biomass to a high-temperature high-pressure reactor, a high-temperature high-pressure reactor for receiving the crushed biomass, And a solid-liquid separator for separating the effluent to be separated into a liquid phase containing hemicellulose and a solid phase containing cellulose or the like. The liquid phase separated in the solid-liquid separation unit may be subjected to a separate saccharification process to obtain xylose.
Referring to a process of obtaining a hemicellulose-containing liquid phase using the high-temperature high-pressure reaction unit shown in FIG. 4, the pulverized biomass is first stored in a storage tank and then supplied to a first storage tank by a transfer conveyor. In addition, hot water is supplied to the primary storage tank through a separate transfer line to soften the biomass structure.
The biomass mixed with hot water is injected through an opening formed in one side of the high-temperature high-
The structure including the openings can be any device capable of maintaining the temperature and pressure of the high-temperature high-pressure reactor, and can be preferably a lock hopper unit. After completion of the reaction for a predetermined time, the reactants are discharged from the discharge port formed on the other side of the high-temperature high-pressure reactor and stored in the second storage tank. Here, the reactant to be stored in the second reservoir is a mixture of a liquid phase component and a solid phase component. After the liquid phase component and the solid phase phase are separated through the phase separation unit, a liquid phase component containing glucose is obtained through a separate saccharification process can do. There may also be a re-evaporator unit that re-evaporates the moisture contained in the second reservoir and recycles it to the high temperature, high pressure reactor.
On the other hand, as the raw material of coal, any one or more selected from peat, lignite, bituminous coal, bituminous coal, or low grade coal including anthracite coal may be used, and the surface of the raw coal is formed with a plurality of pores It contains moisture. Although not shown in the drawings, a storage tank for storing raw coal, a crushing and sorting device for raw coal may be further included.
The raw coal storage tank is a tank for storing raw coal, and the crushing and sorting unit receives raw coal from the raw coal storage tank and crushes the supplied raw coal. Crushers and sorters sort coal powder from crushed raw coal. For example, the pulverizer and the classifier can classify coal powder having a particle size in the range of 70 to 80 mu m among the pulverized raw coal. On the other hand, the coal powder having a particle size exceeding 80 탆 is continuously pulverized in the pulverizer and sorter.
In the present invention, the pulverizer and the classifier are not necessarily integrally formed. The pulverizer for crushing the raw coal and the classifier for classifying the coal powder in the pulverized raw coal may be separately provided and connected in-line. In this case, the pulverized raw material is supplied to the classifier, which classifies the coal powder among the pulverized raw materials. The classifier can be classified and the remaining crushed raw coal can be supplied to the crusher and crushed again.
Next, a liquid component containing glucose extracted and separated through a high-temperature high-pressure reaction and a saccharification process is sprayed on a pulverized coal powder having an appropriate size to coalesce and coat the liquid component with coal.
Here, the spraying unit is not particularly limited as long as it is an apparatus capable of forming impregnation and coating. The spraying unit may be performed integrally in a single apparatus or may be performed in a separate apparatus step by step. The spraying unit includes a feeder for feeding a liquid component containing glucose extracted and separated from the high-temperature high-pressure reactor, a coal feeder for feeding coal having a predetermined average particle size, a feeder for mixing and stirring the liquid component including glucose, A glucose supply control valve capable of controlling the supply amount of the liquid component including glucose, a coal supply control valve capable of controlling the supply amount of coal, and the like.
The glucose sprayed with glucose is transferred to a dryer. As shown in FIG. 2, the liquid glucose is impregnated into the pores of the coal by the capillary phenomenon inside the dryer, and the remaining feed liquid remains on the surface of the coal.
In the present invention, a known dryer may be used, and there is no particular limitation. Preferably, a drum type, a kiln type or a disk type granulator can be used, and a rotary kiln type dryer is also applicable.
When the drying process as described above is performed, liquid glucose is impregnated into the fine pores of the coal, but since the affinity between the glucose and the coal surface is high, the moisture of the atmosphere is absorbed and the quality of the coal is deteriorated. Additional processes are needed to prevent this. Therefore, a hydrophobic process can be performed so that water is not adsorbed on glucose impregnated with glucose, and the hydrophobic process can be achieved by carbonizing glucose impregnated and dried.
Here, in the carbonization process of the present invention, a known carbonyl group can be used, so that there is no particular limitation, and the heating temperature for carbonization is preferably heated to 180 to 220 캜. More preferably, the carbonization can be carried out at a temperature of 190 ° C to 210 ° C. By this carbonization process, it is possible to prevent the moisture from being adsorbed again to the surface of the coal powder or the fine pores, thereby facilitating the transportation and storage of the coal powder. Also, since the water is less contained, the high- Can be obtained.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying drawings. And it is obvious that such variations and modifications are included in the appended claims.
It is a solid biomass derived from lignocellulose. It is a solid biomass derived from wood block, wood chips, logs, tree branches, wood crumbs, leaves, wood boards, sawdust, lignin, xylenes, lignocellulosic, palm trees, palm kernel shells, , EFB (empty fruit bunches), FFB (fresh fruit bunches, palm leaves, coconut crumbs, etc.), herbaceous cornstalks, rice straw, crockery, sugar cane, cereals, rice, Corn, potato, cassava, wheat, barley, lime, other starch-based residues, fruity grain, sugarcane, sugar beet, bagasse, millet, artichoke, molasses, flax, hemp, Avocado and jatropha were selected and milled into a ball mill to a particle size of more than 0 to 5,500 mu m. After the pulverized sample was injected into the high-temperature high-pressure reactor of Fig. 3, The cellulose was separated into a liquid phase containing cellulose and a solid phase containing cellulose. The solid phase containing cellulose recovered glucose through a separate saccharification process.
Separately, coal was selected from among peat, lignite, bituminous coal, bituminous coal and anthracite coal and then pulverized to prepare low grade coal having a range of 70 to 80 μm and a moisture content of 0 to 50%. The pulverized raw coal and the prepared glucose were mixed, dried and carbonized to obtain the high-grade coal produced by the production method of the present invention.
≪ Example 1 >
In the case of glucose, which is a constituent of cellulose, mass reduction by carbonization occurs generally at about 200 ° C, and carbon produced by carbonization is burned after 400 ° C. In the case of simple blending of glucose and low grade coal extracted from biomass, glucose and low grade coal exhibit independent inherent combustion patterns and do not affect each other 's combustion pattern. However, as shown in FIG. 2, the high-grade coal produced through the process of FIG. 1 is converted into a carbon form through the carbonization process while being impregnated into the pores of the coal, and the coal is fixed while blocking the pores. That is, the two components become one fuel type, and the glucose penetrated into the pore maintains the combustion pattern of the existing low grade coal, or rather promotes and improves the reactivity.
From the above results, it is possible to maintain the characteristics of the existing coal only in the case of the high-grade coal manufactured through the manufacturing process of FIG. 1, or to use it as a coal exhibiting further improved reactivity.
As can be seen from FIG. 7, the results of the thermogravimetric test of the heat-treated glucose sample after impregnation and coating with the silica simulating coal showed that in the case of single-component glucose, It can be seen that a plurality of peaks appear at 200 ° C and 400 ° C, and when the pores of the silica are impregnated and coated, they are converted to one peak.
≪ Example 2 >
As shown in FIG. 8, the results of thermogravimetric analysis of the sample mixed with coal and glucose after separate heat treatment showed that the SOCD250 monocomponent coal showed the peak of weight change in the combustion region, and the peak of Glucose250 In the case of glucose, as shown in Fig. 7, a plurality of weight change peaks can be confirmed. As shown in the results of the thermogravimetric analysis of samples in which the content of glucose was changed while the SOCD250 and the glucose of Glucose250 were heat-treated separately, the weight change of coal and glucose did not affect the combustion pattern of each other Independent peaks can be identified.
≪ Example 3 >
As shown in FIG. 9, the results of a sample subjected to a high-grade coal-reforming process in which glucose is impregnated and coated with coal and then subjected to a heat treatment are as follows. The weight change peaks of a single sample of
Although the present invention has been described with reference to the accompanying drawings and embodiments, it is to be understood that the present invention is not limited to the above-described embodiments, but may be modified and changed without departing from the scope and spirit of the invention. It is clear that the present invention is not limited to the above-described embodiments. Accordingly, the scope of protection of the present invention should be construed according to the following claims, and all technical ideas which fall within the scope of equivalence by alteration, substitution, substitution, Range.
In addition, it should be clarified that some configurations of the drawings are intended to explain the configuration more clearly and are provided in an exaggerated or reduced size than the actual configuration.
100: High-temperature and high-pressure reaction unit
110: High temperature and high pressure reactor
120: Lock hopper unit
130: re-evaporation unit
140: phase separation unit
150: reheating unit
200: enzyme saccharification reaction unit
300: solid-liquid separation unit
400: Recycling unit
500: Spraying generating unit
600: Coal pretreatment unit
700: coal granulation unit
800: heat treatment unit
900: Coal grain processing unit
1000: Crushing unit
1100: Biomass pretreatment unit
Claims (40)
Pressure reaction unit 100 for separating the biomass originating from lignocellulose into a solid phase component containing glucan and a solid phase component containing lignin due to cellulose and a liquid phase component containing xylan caused by hemicellulose through a high- );
An enzyme saccharification reaction unit 200 for performing an enzyme saccharification reaction on a predetermined amount among solid phase components including glucan due to the cellulose;
A solid phase component including glucose and a solid phase component including lignin and a solid phase component including glucan due to cellulose produced through the high-temperature and high-pressure reaction unit and a solid phase component including lignin produced through the enzyme saccharification reaction unit A solid-liquid separation unit (300) for separating the liquid component containing glucose;
And a recycle unit (400) for recycling a liquid component containing a predetermined amount of glucose separated from the solid-liquid separation unit to a high-temperature high-pressure reaction unit; / RTI >
A spraying generating unit 500 for generating a predetermined concentration of a spraying solution using a liquid component containing glucose and / or a solid component containing lignin separated through the solid-liquid separation unit; , ≪ / RTI >
The high-temperature and high-pressure reaction unit is a system for upgrading coal using a second-generation biomass in which the reaction is maintained at 160 to 200 ° C, 9 to 11 bar, and 2 to 3 hours.
A high-temperature high-pressure reaction step of separating the lignocellulosic biomass into a solid phase component containing glucan and a solid phase component containing lignin due to cellulose, the liquid phase component containing xylan caused by hemicellulose through a high-temperature high-pressure reaction;
An enzyme saccharification reaction step of performing enzymatic saccharification of a predetermined amount among the solid phase components including glucan due to the cellulose;
A solid phase component including glucose and a solid phase component including lignin and a solid phase component including glucan due to cellulose produced through the high-temperature and high-pressure reaction step and a solid phase component including lignin produced through the enzyme saccharification reaction step A solid-liquid separation step of separating the liquid component containing glucose; And
A recycling step of recycling a liquid component containing a predetermined amount of glucose separated in the solid-liquid separation step to a high-temperature and high-pressure reaction step; / RTI >
A spraying step of generating a spraying solution having a predetermined concentration using a liquid component containing glucose and / or a solid component containing lignin separated through the solid-liquid separation step; , ≪ / RTI >
Wherein the high-temperature and high-pressure reaction step is carried out at a temperature of 160 to 200 ° C, 9 to 11 bar, and 2 to 3 hours, and the second-generation biomass is used.
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