KR101879862B1 - De-Ash in Biomass at Low-Temperature, Manufacturing Method and System of Fuel Production thereof - Google Patents

Abstract

The present invention relates to a fuel production system for boilers, from which ash-inducible components are removed from fuel. More specifically, the present invention relates to a fuel production system for boilers, from which ash-inducible components are removed. To this end, the ash-inducible components, causing adverse effects such as fouling, slagging, high temperature corrosion, and cracker generation on a surface of a reactor such as reactor walls and heat exchangers, are removed via physicochemical methods from herbaceous, woody, and algal biomass upon an operation of the boiler. After the removal, solid components are applied to firing or co-firing as solid fuel. Liquid components containing the ash-inducible component are subjected to water treatment using a method including acid treatment, alkali treatment, hydrothermal treatment, membrane filtration, ion exchange, flocculation, adsorption, and centrifugation.

Description

Technical Field [0001] The present invention relates to a fuel production system that removes ash-induced components in a low-temperature biomass,

The present invention relates to a fuel production system in which ash-induced components in a biomass at low temperature are removed. More particularly, the present invention relates to a fuel production system that removes ash-induced components from biomass at low temperature, The solid phase component is used as a solid fuel for burning or burning. The solid phase component is removed by physical and chemical methods, and the liquid phase containing the ash-induced component The present invention relates to a fuel production system that removes ash derived components from low temperature biomass by applying water treatment using a method including acid treatment, alkali treatment, hydrothermal treatment, membrane filtration, ion exchange, flocculation, adsorption and centrifugation will be.

The energy source that generates the largest amount of carbon dioxide and which is not competitive with global warming is an energy source based on fossil fuel. 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.

In Korea, with the depletion of fossil fuels and the reduction of greenhouse gas (GHG) emissions in response to the international treaty, the United Nations Framework Convention on Climate Change, the number of generators (Renewable Portfolio Standard (RPS)), which mandates that renewable energy should be supplied at a rate of more than a certain percentage of the supply certificate, The penalties were imposed so that penalties could be imposed in consideration of the number of reasons and defaults.

As a result, it is a certificate certifying that the power generation company has produced and supplied electricity using new and renewable energy facilities in order to receive the new and renewable energy. The supply obligator purchases the new and renewable energy supply certificate (REC) Renewable Energy Certificate (REC) that multiplies the new and renewable energy amount of MWh supplied from the facility subject to the supply certificate by the weight, It is reviewed by the government every three years in consideration of the impact on technological development and industrial revitalization, cost of development, availability potential, and effect on GHG emission reduction.

Therefore, in order to achieve the share of renewable energy supply in large-scale coal-fired power generation companies, IGCC (Integrated Gasification Combined Cycle) and Ultra (Clean Coal Technology, CCT) and biomass fuels (Supercritical, USC) technologies, CO ₂ capture and storage technologies, etc. However, there are many areas that need to be overcome to solve fundamental problems. It is a fact that exists.

Particularly, in the case of biomass coexistence, there is a problem that the power generation efficiency is lowered by burning biomass having a relatively low calorific value as compared with coal.

In addition, since combustion characteristics of biomass and coal injected for confluence are different, multi-stage combustion occurs in existing power plant designed for coal as a raw material, causing problems in facility operation.

Also, there is a problem that clinker or fouling occurs due to an inorganic component including a metal component contained in the biomass. In order to solve these problems, in the previous research, a technique of applying fuel mixed with oil-based biomass to coal was developed. In the case of fuel simply mixed with coal and oil-based biomass, the surface of the coal is generally coated with oil or partially impregnated with oil 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 .

The typical aggregation phenomena of ash in the biomass is caused by slagging, clinker, fouling, and fluidized bed combustion in the pulverized coal combustion furnace, As well as agglomeration.

It is expected that the superheater tube of the power plant will be abraded by high temperature chlorine, the abrasion caused by the flow velocity change due to the condenser tube clogging, the tube wear due to the fluidized bed of the fluidized bed combustor and the mechanical wear of the chute blower, KCl (melting temperature 776 ℃) is a viscous material that is well adhered and is known to accelerate corrosion by chlorine reaction when potassium and chlorine form KCl through chemical bonding in the combustion process.

Such a phenomenon in the furnace not only becomes a major cause of the decrease in the efficiency of the process, but ultimately, if such a phenomenon becomes severe, the operation must be stopped, thereby causing a great economic loss. The coagulation phenomena of ash is generally influenced by ash composition, temperature, particle size, gas atmosphere, operating conditions, etc. Especially, when a part of ash is melted at high temperature, such phenomenon accelerates.

Meanwhile, a number of known documents for addressing the above problems are as follows.

Japanese Laid-Open Patent Application No. 2016-125030 discloses a method for preparing a plant by atomizing a plant, immersing the plant into an atmospheric pressure water, dehydrating the plant immersed in atmospheric pressure water, A method of modifying a plant biofuel used as a fertilizer is disclosed.

Japanese Patent Application Laid-Open No. 11-240902 discloses a method of extracting water from a raw material containing water-soluble hemicellulose at a temperature of 80 or more and 140 or less at a pH of 2 to 7 for extracting water-soluble hemicellulose into an aqueous medium, , And then removing the insoluble matter. The method of producing water-soluble hemicellulose according to claim 1,

In Japanese Patent No. 2688509, the bran is washed with water to remove the water-soluble substance, and then treated with an aqueous alkali solution of 0.1 to 0.4. The fraction mainly composed of hemicellulose is eluted into the aqueous alkali solution. And extracting and purifying hemicellulose.

Korean Patent No. 10-0476239 discloses a process for preparing water soluble and insoluble hemicellulose from rice hulls, comprising the steps of (1) removing protein from rice hulls and washing rice hulls; (2) extracting the rice hulls with a sodium hydroxide solution having a concentration of 0.5 to 1 M and filtering the same; (3) adding phosphoric acid to the alkali extraction solution obtained in step (2) to lower the pH of the solution to recover hemicellulose by precipitation; (4) a step in which the precipitate obtained in step (3) is further washed with phosphoric acid or oxalic acid and then decolorized by treatment with oxalate-potassium permanganate; (5) Separation of water-soluble and insoluble hemicelluloses is possible through pH control of the solution from the decolorized hemicellulose fraction obtained in the above step. In the recovery of water-soluble hemicellulose, phosphoric acid is recovered by precipitation or added with calcium to be insoluble The next recovering step; (6) A process for producing fine powder from a rice husk comprising a step of obtaining a powder by natural drying or spray drying the water-soluble and insoluble hemicellulose obtained through a series of such continuous processes, and then milling and passing the fine- Discloses a process for preparing water-soluble and insoluble hemicellulose.

Korean Patent Publication No. 10-0413384 discloses a process for removing (i) starch and protein from a corn husk; (ii) a step of extracting the corn husk from which the starch and protein have been removed with an alkaline solution and filtering with a filter cloth; (iii) treating the alkali extract obtained in step (ii) with cellulase and cellobiase to react; (iv) a step of treating the enzyme reaction solution obtained in step (iii) with an adsorbent to obtain a filtrate through membrane filtration; and (v) purifying the filtrate. The present invention also provides a method for producing a water-soluble dietary fiber.

Korean Patent Publication No. 10-1457470 discloses a process for extracting hemicellulose from a biomass; b) precipitating and separating hemicellulose from the hemicellulose extract; And c) introducing the separated hemicellulose into a papermaking process, wherein the a) extracting step comprises the steps of: adding NaOH to the bran biomass at 135-160 for 70-180 minutes; To 25% of the total weight of the extract, the extraction ratio is 1: 8 to 1:16. In the step b), acetone is mixed with the hemicellulose extract to precipitate and separate hemicellulose. In the step c), the separated hemicellulose Characterized in that a polydicyanediamide electrolyte having a molecular weight of 300,000 to 700,000 and a cationic charge density of 3 to 7 meq / g using dicyandiamide as a fixing agent is used as a fixing agent for fixing in paper. A paper manufacturing method is disclosed.

However, in the prior arts known to date, lignin is removed from biomass and physicochemical treatment is applied to extract hemicellulose, which is a main component of cellulose and xylose, which glucose is a main component, but a drug such as acid or alkali There is a problem in that the process is complicated because it involves a process of recovering used chemicals as well as an increase in the cost of the medicament. In order to apply the separated ingredients to a desired raw material, In many cases. In addition, since the treatment process proceeds at a high temperature of 100 캜 or more, it is disadvantageous in that a high energy cost is required.

Therefore, in order to promote the utilization and diffusion of new and renewable energy and secure the supply stability of the biomass fuel, it is necessary to maintain the existing carbon-derived biomass component at a low temperature to fundamentally exclude process problems caused by ash, There is a desperate need to develop a technique for producing a fuel production system for a boiler by effectively extracting and separating fuel materials having a low ash content and selectively using only the ash-induced components in the boiler.

Japanese Laid-Open Patent Application No. 2016-125030 Japanese Patent Application Laid-Open No. 11-240902 Japanese Patent No. 2688509 Korean Patent No. 10-0476239 Korean Patent Publication No. 10-0413384 Korean Patent Publication No. 10-1457470

DISCLOSURE OF THE INVENTION The present invention has been devised in order to solve the above-mentioned problems, and it is an object of the present invention to provide a process for producing a fermentation product, which comprises a reactor wall, a heat exchanger, and the like such as fogging, slagging, The ash-induced components, which cause adverse effects on the heat transfer surface, are removed by physical and chemical methods, and the solid phase components are used for burning or firing with solid fuel. The liquid components including ash derived components are treated with acid, alkali, The present invention is to provide a fuel production system for a boiler in which a batch inducing component to which water treatment is applied using a method including membrane filtration, ion exchange, flocculation, adsorption, and centrifugation is eliminated.

To this end, the present invention comprises a grinding unit 100 for forming a biomass into a raw material of a predetermined size; A hopper 200 for storing the raw material; A raw material supply feeder 210 for supplying the raw material stored in the hopper to a downstream end in a fixed amount; And a first separation unit (300) for treating the feedstock fed from the feeder feeder with a low temperature alkali and / or acidic liquid so that the ash-induced components of the feedstock are separated at the maximum, Fuel production system.

The apparatus may further include a second separation unit (400) for treating the raw material processed in the first separation unit with a low temperature alkali and / or acidic liquid.

And an ion separation unit (500) for separating ion components of the low temperature alkali and / or acidic waste liquid discharged from the first separation unit and the second separation unit.

Further, the low-temperature condition in the first separation unit and the second separation unit may be less than 100 for excluding the latent heat loss of evaporation of water.

The low temperature condition in the first separation unit and the second separation unit may be 40 to 80 to exclude the latent heat loss of evaporation of water.

The acidic liquid supplied to the first separation unit and the second separation unit may be an organic acid generated through soaking of biomass.

The alkali solution supplied to the first separation unit and the second separation unit may be 1 wt% of sodium hydroxide.

The acidic liquid supplied to the first separation unit and the second separation unit may be 50 wt% acetic acid.

The reaction time of the first separation unit or the second separation unit may be 1 minute to 5 hours.

The acidic liquid supplied to the first separation unit and the second separation unit may have an acid to water mass ratio of 15 to 4.

In addition, the wastewater treatment unit can separate ion components using an ion exchange resin and / or a membrane.

Further, it may include a water treatment unit for satisfying predetermined treatment conditions for supplying the treatment liquid supplied through the first separation unit and / or the second separation unit to the wastewater treatment unit.

Further, the basic or acidic waste liquid from which the ion component is separated in the wastewater treatment unit can be recycled to the first separation unit and / or the second separation unit.

The biomass may have a particle diameter of 10 to 10 mm.

Further, a discharge unit may further be included at the downstream end of the wastewater treatment unit.

According to the fuel production system in which the ash-induced components in the biomass of the present invention are removed at a low temperature, the ash-induced components can be efficiently and easily separated from the herbaceous or woody biomass through the low temperature reaction conditions of the catalyst such as acid or alkali It is possible to selectively secure raw materials for biomass burning and / or confluence in the boiler.

Further, in the invention, acid and alkali treatment at a low temperature condition contributes to simplification of the wastewater treatment process and cost reduction, and it is possible to eliminate the elution of carbon-based components such as cellulose, hemicellulose and lignin as much as possible.

In addition, it is possible to effectively remove the clinker, fouling and alkali corrosion problems that may occur during the operation of the combustion system when the ash-generating components such as alkaline and alkaline earth metals and halogen elements contained in the biomass are effectively removed and applied to the power generation fuel .

In addition, the above-mentioned liquid component (sugar in which xylose is mostly contained) is separated from the existing power plant by an amount of less than 3.5 wt% of biomass through the hybrid coal process, It is possible to use an existing coal undifferentiation facility without a biomass subdivision device.

It is also expected that ash due to biomass after combustion and gasification in fluidized bed and undifferentiated combustion furnaces and gasification furnaces is produced using the cellulose, hemicellulose and lignin of the biomass from which ash derived components have been removed, The problem of clinker fouling and high-temperature corrosion can be eliminated.

In addition, there is an effect that the treated water can be recycled by effectively separating the ash-induced components in the liquid component of the biomass by applying an ion exchange resin and / or a membrane filtering process.

Further, by removing the nitrogen component in the fuel component, there is an effect of reducing the amount of Fuel NOx generated during combustion.

1 is a flowchart showing a fuel production system for a boiler in which ash-induced components are removed according to an embodiment of the present invention.
FIG. 2 is a graph showing changes in the composition of raw materials before and after the boiler fuel production system in which the ash-induced components are removed according to an embodiment of the present invention.
FIG. 3 is a graph showing changes in mineral components of raw materials before and after the boiler fuel production system in which the ash-induced components are removed according to an embodiment of the present invention.
FIG. 4 is a graph showing the ash removal rate according to the pH change in the alkaline solution treatment condition of the fuel production system for a boiler in which the ash-induced component is removed according to an embodiment of the present invention.
FIG. 5 is a graph illustrating the ash removal rate according to the temperature change in the alkaline solution treatment condition of the fuel production system for a boiler in which the ash-induced component is removed according to an embodiment of the present invention.
FIG. 6 is a graph illustrating the ash removal rate of the fuel production system for a boiler from which the ash-induced components have been removed according to an embodiment of the present invention, according to the change of the residence time under the alkaline solution treatment condition.
FIG. 7 is a graph showing the ash removal rate according to the pH change in the acidic liquid treatment condition of the fuel production system for a boiler in which the ash-induced component is removed according to an embodiment of the present invention.
8 is a graph showing the ash removal rate according to the temperature change in the acidic liquid treatment condition of the fuel production system for a boiler in which the ash-induced component is removed according to an embodiment of the present invention.
9 is a graph showing the ash removal rate of the fuel production system for a boiler from which the ash-induced components are removed according to an embodiment of the present invention, according to the change of the residence time under the acidic solution treatment condition.
FIG. 10 is a photograph of a biomass SEM before and after a fuel production system for a boiler in which ash-induced components are removed according to an embodiment of the present invention.
FIG. 11 is a graph showing a residual amount of carbonaceous compounds capable of burning biomass according to an embodiment of the present invention.

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.

The coal used for the boiler fuel used in the present invention means any one or more selected from peat, lignite, bituminous coal, bituminous coal or anthracite coal, which are recognized in the art.

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.

Algae can be used as biomass feedstock. Green algae, Cyanobacteria, Diatom, Red algae, Chlorella, Spirulina, Dunaliella, Porphyridium, Phaeodactylum can be used as algae.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a composite fuel production system using ashprobiomass according to the present invention will be described in detail with reference to the accompanying drawings.

1 is a flowchart showing a fuel production system for a boiler in which ash-induced components are removed according to an embodiment of the present invention.

A crushing unit (100) for forming the biomass into a raw material of a predetermined size; A hopper 200 for storing the raw material; A raw material supply feeder 210 for supplying the raw material stored in the hopper to a downstream end in a fixed amount; And a first separation unit (300) for treating the feedstock fed from the feeder feeder with a low temperature alkali and / or acidic liquid so that the ash-induced components of the feedstock are separated at the maximum, Fuel production system.

The biomass may be one or more of first generation biomass, second generation biomass, and third generation biomass.

Preferably, it may be a herb, Empty Fruit Bunches (EFB), kenaf, cornstalk, or rice hull.

The predetermined size may be 500 mm or less.

Preferably 10 mu m to 300 mm or less.

More preferably 20 mm to 50 mm or less.

If the particle size is out of the above range, the pulverization cost may be excessively high or the removal efficiency of the ash-induced component may be lowered.

The crushing unit may perform crushing and / or grinding. The crushing unit can use any of physical characteristics such as compression, impact, friction, shearing and bending, and the method is not limited as long as it can achieve the purpose of reducing the size of the biomass such as cutting and enlarging the surface area.

The crushing unit may be a jaw crusher, a gyratory crusher, a roll crusher, an edge runner, a hammer crusher, a ball mill, a jet mill mill, and a disk crusher.

The raw material supply feeder is not particularly limited as long as it can supply the raw material quantitatively to the downstream end. Preferably, there are a screw feeder and a lock hopper.

The ash-induced component is physically and chemically adhered to the surface of the reactor wall, the heat exchanger, and the downstream-end flue gas treating facility of the downstream reaction part among the inorganic components contained in the biomass used in the combustion reaction to generate fouling, slagging, corrosion, And the like.

The ash-generating component may be an alkali, an alkaline earth metal, or a halogen group element.

Preferably, it may be sodium, potassium or chlorine.

The temperature of the injection water for the hydrothermal treatment of the predetermined temperature may be 40 ° C to 500 ° C. Preferably 120 ° C to 300 ° C, and more preferably 180 ° C to 220 ° C. The time for the feedstock to stay in the ash-derived component separation unit may be from 30 minutes to 2 hours.

The fuel can be semi-carbonated through hot water treatment at the predetermined temperature.

As the fuel becomes semi-carbonated, the calorific value per unit fuel can be increased.

The calorific value of the semi-carbonated fuel may be 3,500 kcal / kg to 4,500 kcal / kg on the basis of the low calorific value.

Beyond the above temperature and time conditions, the efficiency of the removed component is low or the process cost is high.

The amount of heat input per unit feedstock varies depending on the type of biomass, and may be defined as BTW (Biomass to Water, kg / kg). Preferably from 0.02 to 0.5, and more preferably from 0.11 to 0.18 (based on weight, wood pellets, 1 kg / 6 kg of corn).

If the BTW ratio is exceeded, the separation efficiency of the induced component becomes low.

Acid, or basic solution for controlling the separation efficiency may be injected into the front end or the rear end of the first separation unit and / or the second separation unit.

The water may be hot water, hot water, or steam.

The acidic solution may be any one or two or more of acetic acid, nitric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid, and formic acid.

The blending condition may be 1 wt% to 50 wt% of the conventional fossil fuel. , Preferably from 3 wt% to 40 wt%, and more preferably from 5 wt% to 30 wt%.

The ash-induced component may be contained in the liquid component discharged from the separation unit.

The liquid component may be an aqueous solution containing a small amount of organic compound and ash-generating component. The organic compound may include carbon, hydrogen, nitrogen, oxygen, and sulfur. Preferably, the liquid component may comprise hemicellulose, organic acid, furfural, 5-hydroxymethylfufural (5-HMF) and inorganic.

The solid phase component discharged from the separation unit may include a combustible component in which the ash-induced component is separated.

The combustible component may be an organic compound. The combustible component may include carbon, hydrogen, nitrogen, oxygen, and sulfur. The combustible component is characterized in that the carbon fraction of carbon, hydrogen, nitrogen, oxygen and sulfur of the raw material per unit mass is increased and the hydrogen, nitrogen, oxygen and sulfur components are decreased.

The pH of the liquid component may be 6 or less.

More preferably, the pH may be 2.5 to 4 or less.

The pH of the liquid component has a technical feature that the pH is lowered by the organic acid in the raw material. Examples of the organic acid include acetic acid, formic acid, propanoic acid, 4-hydroxybutanoic acid, and 2-butenoic acid.

In order to improve the reactivity of the ash-induced component separation unit, acetic acid (C ₂ H ₄ O ₂ ), formic acid (HCOOH), propanoic acid (CH ₃ CH ₂ COOH), 4-hydroxybutanoic acid, at least one of sulfuric acid (H2SO4), hydrochloric acid (HCl), nitric acid (HNO3), phosphoric acid (H3PO4), peracetic acid (C2H4O3), acetic acid (CH3COOH) and oxalic acid (C2H2O4).

The added amount of the acid solution may be 10 wt% or more based on the total input heat amount.

The pH by adding the acid solution may preferably be 4 or less.

More preferably, the pH may be 2.5 to 4 or less.

The aqueous solution having a low pH, from which the organic compound is separated from the liquid component, may be recycled to the first separation unit and / or the second separation unit.

In order to remove the organic compound from the liquid component, at least one of centrifugal separation, flocculation, adsorption, filtration membrane and ion exchange resin may be applied.

The raw material may be supplied to a first separation unit which is treated with an alkali and / or an acidic solution before being fed to the second separation unit.

The pretreatment solid-phase component generated in the first separation unit is supplied to the second separation unit, and the first separation unit liquid-phase component can be separated and discharged.

The first separation unit solid phase component may be an organic compound. The combustible component may include carbon, hydrogen, nitrogen, oxygen, and sulfur. The combustible component is characterized in that the carbon fraction of carbon, hydrogen, nitrogen, oxygen and sulfur of the raw material per unit mass is increased and the hydrogen, nitrogen, oxygen and sulfur components are decreased.

The first separation unit liquid phase component may be an aqueous solution containing a small amount of an organic compound and an inorganic substance. The organic compound may include carbon, hydrogen, nitrogen, oxygen, and sulfur. Preferably, the organic compound may be lignin. Preferably, the inorganic material may include at least one of Al, Si, P, Ca, Ti, Mn, and Fe.

And a molded fuel unit for producing the molded fuel by applying the solid phase component.

And may further include a membrane filter unit for ion component separation of the liquid component.

The membrane filter unit may be any one or more of a micro filter, an ultrafilter, a nanofilter, and a reverse osmosis membrane. In addition, water, an acidic solution, and a basic solution can be injected to the front or rear end of the membrane filter unit for pH and concentration control. In addition, the solid component in the liquid component can be separated by using one or more methods such as evaporation, centrifugation, precipitation, precipitation, coagulation, and adsorption at the front end or the rear end of the membrane filter unit. Hemicellulose in the liquid component can be separated and used as dietary fiber.

One or two units of a cleaning unit and a moisture removal unit for cleaning may be added to the rear end of the first separation unit or the second separation unit.

Or a fuel produced in a fuel production system in which the ash-generating component for biomass burning and / or confluence in the boiler is removed.

In addition, the biomass refers to lignocellulose-based herbaceous and woody biomass, and the material belonging to the biomass is not limited. It is also apparent that first- or third-generation biomass is also applicable. 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.

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)} , acetic acid (CH ₃ COOH), oxalic acid (C ₂ H ₂ O ₄ ), and the like. The acid is not limited to the acid described above, and any acid which decomposes hemicellulose and cellulose may be used. Examples of the base 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 injected into the first separation unit and / or the second separation unit may not be injected depending on the reaction conditions.

Also, a compound such as furfural can be generated through the unit while the solid phase component participates in a high-temperature high-pressure reaction.

The fuel from which the ash-induced component is removed can be used in a fluidized bed, a grate, an undifferentiated boiler, a gasifier, and the like. In the course of combustion and gasification, clogging of clinker fouling caused by inorganic components including metal elements, It is possible to eliminate the root cause of the corrosion caused by the metal.

The apparatus may further include a second separation unit (400) for treating the raw material processed in the first separation unit with a low temperature alkali and / or acidic liquid.

And an ion separation unit (500) for separating ion components of the low temperature alkali and / or acidic waste liquid discharged from the first separation unit and the second separation unit.

Further, the low-temperature condition in the first separation unit and the second separation unit may be less than 100 for excluding the latent heat loss of evaporation of water.

The low temperature condition in the first separation unit and the second separation unit may be 40 to 80 to exclude the latent heat loss of evaporation of water.

The low temperature condition of the first separation unit or the second separation unit may be 60 minutes.

The low temperature condition of the first separation unit or the second separation unit may be 60 minutes.

The acidic liquid supplied to the first separation unit and the second separation unit may be an organic acid generated through soaking of biomass.

The alkali solution supplied to the first separation unit and the second separation unit may be 1 wt% of sodium hydroxide.

The acidic liquid supplied to the first separation unit and the second separation unit may be 50 wt% acetic acid.

The reaction time of the first separation unit or the second separation unit may be 1 minute to 5 hours. The reaction time may be preferably from 5 minutes to 2 hours, more preferably from 8 minutes to 1 hour. If the reaction time is lower than the reaction time, the removal efficiency of the ash-induced components in the biomass is lowered. If the reaction time is longer than the reaction time, the cellulose, hemicellulose and lignin components in the biomass are eluted and the calorific value of the biomass fuel is lowered.

The reaction time in the alkaline solution treatment of the first separation unit or the second separation unit may be 30 minutes.

The reaction time in the acidic solution treatment of the first separation unit or the second separation unit may be one hour.

The acidic liquid supplied to the first separation unit and the second separation unit may have an acid to water mass ratio of 15 to 4. The mass ratio of the acid groups may be preferably 12 to 6, and more preferably 10 to 8. If the mass ratio of the acid component is out of the range, it takes a lot of cost to recover the acid component from the rear end separator.

The wastewater treatment unit is not particularly limited as long as the ion component can be separated using the ion exchange resin, the ion exchange membrane and / or the membrane, and the ions contained in the wastewater can be removed and separated. The ion-exchange resin as an example is ^{Ba 2 +, Pb 2 +,} Sr 2 +, Ca 2 +, Ni 2 +, Cd 2+, Cu 2 +, Zn 2 +, Tl +, Ag +, Cs +, Rb + , K ⁺ , NH4 ⁺ , Na ⁺ , Li ⁺ , or a cation exchange resin capable of selectively separating two or more cations.

In addition, the ion exchange resin is ^{_{Citrate, SO 4 2-, Oxalate,}} I -, NO 3 -, CrO 4 2 -, Br -, SCN -, Cl -, Formate, Acetate, F -, OH - or any one of 2 Or an anion exchange resin capable of selectively separating the above-mentioned anions.

Here, the anion exchange resin and the cation exchange resin preferably use a strongly acidic cation exchange resin or a strong basic anion exchange resin so that they can be used in a wide pH range.

The membrane may be any one or more of a nanofiltration membrane and a reverse osmosis membrane capable of separating cation and / or anion substances contained in wastewater.

On the other hand, the wastewater discharged from the first separation unit and / or the second separation unit may contain various particulate matter including ash-induced components, and these materials may deteriorate the ion exchange ability of the cation exchange resin or the anion exchange resin , And furthermore, the pores between the ion exchange resins are closed. In addition, when a cation or anion using a nanofiltration membrane or a reverse osmosis membrane is to be removed, it is preferable to provide an appropriate pretreatment unit since the above-mentioned particulate matter may cause a sharp decrease in the permeation performance.

For example, the pretreatment unit may introduce an aggregation and / or precipitation process, or may be supplied to an ion exchange resin, a nanofiltration membrane, or a reverse osmosis membrane after previously removing particulate matter with an ultrafiltration membrane or a microfiltration membrane having relatively large pores.

Further, the basic or acidic waste liquid from which the ion component is separated in the wastewater treatment unit can be recycled to the first separation unit and / or the second separation unit.

The biomass may have a particle diameter of 10 to 10 mm.

Further, a discharge unit may further be included at the downstream end of the wastewater treatment unit.

It is clear that the wastewater treatment unit may include ion exchange resins, separation membranes, flocculation, adsorption, and the like. The ionic materials removed from the sanitary wastewater treatment unit may be further buried or incinerated through a consignment treatment or the like, and the treated water from which these substances have been removed may be discharged to the water system (river, river, etc.). The discharge unit may be a pump.

(Example)

The biomass source sample is dried in an oven at 105 ° C to remove moisture. Water is added to a portion of the dried sample (eg EFB) to maintain the viscosity below 5000 cP. In the case of EFB, the above condition is 1: 3 by weight ratio of EFB to water. 1 wt% of NaOH is added to the aqueous solution. The process solution is added to the reactor and maintained at 60 ° C for 10 minutes. The stirrer is stirred at rpm 10-1000. The reaction temperature is 60 ° C at a rate of 2 ° C per minute and the reaction time is 40 minutes.

 After the reaction, the treatment liquid is subjected to solid-liquid separation using a 1-μm filter. The recovered solid is dried in an oven at 105 ° C. The ratio of 1wt% of sample recovered from the oven to 3wt% of acetic acid aqueous solution (ratio of acetic acid to treatment solution is 1: 1) is stirred.

The treatment liquid is placed in the reactor and maintained at 60 DEG C for 10 minutes. Through this process, Na ions contained in the treatment liquid are removed as acetic acid in the reactor.

The reaction liquid in which the reaction is terminated is subjected to solid-liquid separation with a 1-μm filter. The residue is washed with distilled water.

Finally, the dried biomass is dried in an oven at 105 ° C to remove the metal component, which is the ash-induced component in the biomass.

FIG. 2 is a graph showing changes in the composition of raw materials before and after the boiler fuel production system in which the ash-induced components are removed according to an embodiment of the present invention.

The biomass considered as a raw material includes herbaceous tree, neck tree, and algae. Among them, FIG. 2 shows the result of analysis of fuel characteristics using herbaceous biomass such as herbaceous, cornstalks and woody pine trees. The biomass from which the ash-induced components were removed through this process showed a removal efficiency of 77-97% or more on a dry basis and an average improvement of about 10% in calorific value. In addition, it can be seen that the numerical values of the fuel NOx generating material and SOx producing materials N and S of the fuel itself are reduced by about 80%. It can be improved through the pretreatment process which shows the low calorific value of the biomass fuel as compared with the coal and the ash effect.

FIG. 3 is a graph showing changes in mineral components of raw materials before and after the boiler fuel production system in which the ash-induced components are removed according to an embodiment of the present invention.

FIG. 3 shows the ash characteristics of the fuel from which the ash-induced component has been removed. K ₂ O, which has the lowest melting point at 349 ° C, has a removal efficiency of over 99%, and Na ₂ O with a melting point of 1,132 ° C has a removal efficiency of 95%. By eliminating the ash-induced components, it is possible to prevent generation of slagging, fouling, and clinker generated in the boiler tube or wall in advance, and to maintain stable boiler operation rate. (Less than 70% utilization rate for general biomass boiler)

FIG. 4 is a graph showing the ash removal rate according to the pH change in the alkaline solution treatment condition of the fuel production system for a boiler in which the ash-induced component is removed according to an embodiment of the present invention.

4 is a graph showing the ash extraction rate in the alkaline region and the recovery rate of ALB as a combustible material. The fuel that is removed from the ash-induced components in the biomass to be developed in this patent is characterized in that only the ash-induced components are removed while maintaining the combustible substance as the solid substance as much as possible. In the region above pH 13.4, the removal efficiency of ash-induced components is decreased and the yield of ALB is also decreased. Therefore, batch extraction should be performed in the range of pH 13.3 ~ 13.4 which is the most maximizing condition.

FIG. 5 is a graph illustrating the ash removal rate according to the temperature change in the alkaline solution treatment condition of the fuel production system for a boiler in which the ash-induced component is removed according to an embodiment of the present invention.

FIG. 5 shows the influence of temperature under a pH 13.4 condition based on the experimental results of FIG. As the temperature increases, the ash extraction rate increases, and the most maximized value can be seen in the 80 ℃ range. However, since the yield of ALB as a combustible material is low, the appropriate temperature range is 55 ~ 65 ℃ where the ash extraction rate and combustible material recovery rate are good.

FIG. 6 is a graph illustrating the ash removal rate of the fuel production system for a boiler from which the ash-induced components have been removed according to an embodiment of the present invention, according to the change of the residence time under the alkaline solution treatment condition.

Fig. 6 shows the influence of the residence time in the range of pH 13.4 and temperature 60 캜. The retention time of 10 min showed the maximum extraction rate and the similar performance was maintained over time. The recovery time gradually decreases with time, so the residence time in the alkaline region can be said to be a meaningless time of more than 10 minutes.

FIG. 7 is a graph showing the ash removal rate according to the pH change in the acidic liquid treatment condition of the fuel production system for a boiler in which the ash-induced component is removed according to an embodiment of the present invention.

7 is a graph showing the ash extraction rate in the acidic region and the recovery rate of ALB as a combustible material. The fuel that is removed from the ash-induced components in the biomass to be developed in this patent is characterized in that only the ash-induced components are removed while maintaining the combustible substance as the solid substance as much as possible. As the pH increases to 1.7, the removal efficiency of the ash-induced components increases. However, when the pH is increased above 1.8, the recovery tendency decreases. Therefore, ash extraction should be performed in the range of 1.7-1.8 which is the maximization condition.

8 is a graph showing the ash removal rate according to the temperature change in the acidic liquid treatment condition of the fuel production system for a boiler in which the ash-induced component is removed according to an embodiment of the present invention.

FIG. 8 shows the influence of temperature at pH 1.76 based on the experimental results of FIG. As the temperature increases, the ash extraction rate increases, but the ash extraction rate decreases at temperature above 60 ℃. Therefore, the optimum temperature condition is an appropriate range of 50 to 60 占 폚.

9 is a graph showing the ash removal rate of the fuel production system for a boiler from which the ash-induced components are removed according to an embodiment of the present invention, according to the change of the residence time under the acidic solution treatment condition.

Fig. 9 shows the influence of the residence time in the range of pH 1.76 and temperature 60 캜. The retention time of 10 min showed the maximum extraction rate and the similar performance was maintained over time. Since the recovery rate gradually decreases with time, the residence time in the acidic region can be regarded as a meaningless condition for more than 10 minutes.

FIG. 10 is a photograph of a biomass SEM before and after a fuel production system for a boiler in which ash-induced components are removed according to an embodiment of the present invention.

Figure 10 compares the surface structure changes of untreated raw samples (australia) and ash samples with ash derived components using SEM. In the case of the raw sample, it can be seen that the surface contains a large amount of irregular impurity-type minerals, but in the case of the sample from which the ash-induced component has been removed, a clean surface shape can be seen. The present process configuration is most suitable for selectively removing only mineral components without causing any structural change of the sample itself.

FIG. 11 is a graph showing a residual amount of carbonaceous compounds capable of burning biomass according to an embodiment of the present invention.

11 shows that about 20 wt% of carbon powder remains in the case of the biomass treatment through the pretreatment of the conventional bioethanol process. In the case of acid and / or base treatment according to an embodiment of the present invention, It can be confirmed that at least 80 wt% of carbon powder remains.

100: Crushing unit
200: Hopper
210: feed feeder
300: first separation unit
400: second separation unit
500: wastewater treatment unit

Claims (15)

Forming the biomass into a raw material having a size of 5 to 30 mm by using the crushing unit (100);
Storing the raw material in the hopper 200;
Feeding the raw material stored in the hopper to a feedstock feeder 210 at a later stage;
Acetic acid, acetic acid, and acetic acid are added to hot water at 40 to 60 ° C to maximize the separation of K ⁺ , Na ⁺ , Ca ⁺ , and Cl ^- ions that cause clogging and corrosion by raw materials supplied from the raw material feeder to the boiler. Treating the mixture in a first separation unit (300) with a liquid component, which is a mixture of water, - HF, and furfural,
The pH of the liquid component is 3,
BTW is from 0.125 to 0.25,
The reaction time is 30 minutes.
The ash-induced components in the biomass under low temperature conditions for the power generation fuel are continuously removed Fuel production method.
delete The method according to claim 1,
And a wastewater treatment unit (500) for separating the ion component of the acidic waste liquid discharged from the first separation unit,
The wastewater treatment unit separates ion components using an ion exchange resin or membrane
Wherein the acidic waste liquid from which the ion component is separated from the wastewater treatment unit is recycled to the first separation unit to continuously remove the ash-induced components in the low temperature biomass for the power generation fuel.
delete delete The method according to claim 1,
Wherein the liquid phase component supplied to the first separation unit is an organic acid generated through a soaking process of the biomass. Production method.
delete delete delete The method according to claim 1,
Wherein the acidic liquid supplied to the first separation unit has a mass ratio of acid to water of 15 to 4. 15. The fuel producing method according to claim 13,
delete delete delete delete The method of claim 3,
Wherein the waste water treatment unit further comprises a discharge unit at a downstream end of the waste water treatment unit to continuously remove the ash-induced components in the low temperature biomass for power generation fuel.

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