KR102251160B1 - De-Ash in Biomass at Low-Temperature, Manufacturing Method and System of Fuel Production Connected with Energy Storage System - Google Patents

Abstract

The present invention relates to a fuel production system for a boiler in which ash-causing components are removed from the fuel, and more particularly, fouling, slagging, high temperature corrosion, and clinker generation during boiler operation from herbaceous, woody, and algae biomass. The ash-causing components that adversely affect the heat transfer surface such as the reactor wall, heat exchanger, etc., are removed through physical and chemical methods, and after removal, the solid component is used as solid fuel for burning or mixing, and the liquid component including the ash-causing component is It relates to a fuel production system for boilers in which ash-causing components are removed by applying a method of water treatment using a method including acid treatment, alkali, hydrothermal treatment, membrane filtration, ion exchange, coagulation, adsorption, and centrifugation.

Description

De-Ash in Biomass at Low-Temperature, Manufacturing Method and System of Fuel Production Connected with Energy Storage System}

The present invention relates to a fuel production system that removes ash-causing components in biomass in low temperature conditions linked to ESS, and more particularly, fouling, slagging, and fouling during operation of a boiler from algae biomass. Ash-causing components that adversely affect the reactor wall, heat exchanger, etc., such as high-temperature corrosion and clinker generation, are removed through physical and chemical methods, and after removal, the solid components are used as solid fuel for burning or mixed burning. The liquid component included is an ash-causing component in biomass under low temperature conditions in connection with ESS that applies a method of water treatment using methods including acid treatment, alkali, hot water treatment, membrane filtration, ion exchange, coagulation, adsorption, and centrifugation. It relates to a fuel production system that has been removed.

The most generation of carbon dioxide is the fossil fuel-based energy source, and its competitiveness is weak against global warming. Therefore, the use and supply of new and renewable energy is one of the issues that are currently becoming an energy source worldwide. This is because carbon dioxide emissions are reduced compared to conventional fossil fuels such as petroleum and coal, which can respond to global warming and climate change. Because it is an energy source.

In Korea, with the depletion of fossil fuels and the rise of greenhouse gas reduction in response to the international treaty, the Climate Change Convention, the total amount of power generated by power generation companies (supply obligations) with power generation facilities (excluding renewable energy facilities) of a certain size (500MW) or more. The Renewable Portfolio Standard (RPS), which made it mandatory to supply more than a certain percentage of the company using new and renewable energy, was introduced, and the reason for non-compliance within 150% of the average transaction price of the supply certificate for non-fulfillment of such mandatory supply amount. In consideration of the number of non-compliance, etc., it has been legislated to impose a penalty.

Accordingly, it is a certificate that proves that the power generation business operator has produced and supplied electricity using new and renewable energy facilities in order to be recognized as supplying new and renewable energy, and that the person obligated to supply can cover the mandatory supply by purchasing a new and renewable energy supply certificate. Renewable energy supply certificate (REC) is being given by multiplying the weight of the amount of renewable energy supplied in MWh standards supplied from facilities subject to supply certificate issuance, and the weight of each new and renewable energy source is environmental, technology development, and industry. It is financed by the government and is reviewed every three years in consideration of the effect on activation, generation cost, potential existence, and effect on reduction of greenhouse gas emissions.

Accordingly, large-scale coal-fired power generation companies have integrated gasification combined cycle (IGCC) and ultra-supercritical pressure (IGCC) as a way to connect and improve power plants that reduce the generation of carbon dioxide from coal in order to achieve these new renewable energy supply obligations. Supercritical (USC) technology, _{clean coal technology (CCT) such as CO 2} capture and storage technology, and bio-mass mixing are being attempted, but there are many areas to be improved and overcome in solving the fundamental problem. It exists.

In particular, biomass co-fire has a problem that power generation efficiency decreases as biomass with a relatively low calorific value is burned compared to coal.

In addition, since the combustion characteristics of biomass and coal input for mixed combustion are different, multi-stage combustion occurs in the existing power generation facility designed with coal as a target raw material, causing problems in the operation of the facility.

In addition, there is a problem in that clinker or fouling occurs due to inorganic components including metal components contained in biomass. In order to solve this problem, prior research has developed a technology for applying fuel obtained by mixing oil-based biomass with coal. In the case of a fuel obtained by simply mixing coal and oil-based biomass, the surface of the coal is usually coated with oil or partially impregnated with oil into the pores. However, due to the low surface tension of the oil itself and insufficient bonding strength between the oil-based biomass and the surface of the coal, the coal and biomass each maintain their existing combustion characteristics, resulting in different combustion characteristics. Therefore, if this is applied to a power plant, oxygen is preferentially consumed due to the low-temperature combustion pattern of oil at the front of the burner, and eventually, the amount of unburned carbon increases by inhibiting the combustion of coal, reducing power generation efficiency. .

In addition, representative coagulation phenomena of ash in biomass are slagging, clinker, fouling, and fluidized bed combustion, which are mainly generated in the radiant and convective transfer surfaces of the pulverized coal combustion furnace, respectively. Of ash agglomeration and the like.

High temperature chlorine corrosion of the superheater tube of the power plant, abrasion caused by flow velocity changes due to clogging of the economizer tube, tube wear due to flow sand in the fluidized bed combustor, and mechanical wear of the chute blower are expected. When potassium and chlorine components form KCl through chemical bonding in the combustion process, KCl (melting temperature 776℃) is a viscous material that adheres well and accelerates corrosion due to chlorine reaction.

When such a phenomenon occurs in the combustion furnace, it is not only a major cause of reducing the efficiency of the process, but ultimately, when such a phenomenon intensifies, the operation must be stopped, resulting in enormous economic loss. The agglomeration phenomenon of ash is generally affected by ash composition, temperature, particle size, gas atmosphere, operating conditions, etc. In particular, when some of the ash is melted at high temperatures, such a phenomenon is accelerated.

Meanwhile, a look at a number of known documents to cope with the above problems are as follows.

In Japanese Patent Laid-Open No. 2016-125030, a plant is atomized, the atomized plant is immersed in water at normal pressure, the plant is dehydrated, and the dehydrated plant is used as a fuel, and a solution obtained by dehydration is used. A method of reforming a vegetable biofuel used as a fertilizer is disclosed.

In Japanese Unexamined Patent Application Laid-Open No. 11-240902, extracting water-soluble hemicellulose from raw materials including water-soluble hemicellulose into an aqueous medium is at a temperature of 80 or more and 140 or less, and a pH value of 2 to 7, and then 1.5 times the extract. A method for producing water-soluble hemicellulose, characterized in that the above concentration is performed and then the insoluble substance is removed, is disclosed.

In Japanese Patent No. 2688509, bran is washed with water to remove water-soluble substances, then treated with an alkaline aqueous solution of 0.1~0.4 to elute the main divisions from hemicellulose in an alkaline aqueous solution, and then purified outside the limit and using a membrane and an ion exchange resin in order. Disclosed is a method for extracting and purifying hemicellulose, characterized in that:

In Korean Patent No. 10-0476239, in preparing water-soluble and insoluble hemicellulose from rice husk, (1) removing proteins from rice husk and washing the rice husk; (2) extracting rice husk with a sodium hydroxide solution having a concentration of 0.5 to 1M and filtering; (3) adding phosphoric acid to the alkali extraction solution obtained in step (2) to lower the pH of the solution to recover hemicellulose as precipitation; (4) a process of decolorizing the precipitate obtained in step (3) by additional washing with phosphoric acid or oxalic acid, followed by treatment with oxalate-potassium permanganate; (5) It is possible to selectively separate water-soluble and insoluble hemicellulose from the decolorized hemicellulose fraction obtained in the above step by adjusting the pH of the solution.However, in recovering the water-soluble hemicellulose, phosphoric acid is added to recover it as precipitation or calcium is added to convert it into insoluble. The next recovery process; (6) The water-soluble and insoluble hemicellulose obtained through such a series of continuous processes is naturally dried or spray-dried to obtain powder, and then milled and passed through a sieve of an appropriate size to obtain fine powder. Disclosed is a method for producing water-soluble and insoluble hemicellulose.

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

In Korean Patent Publication No. 10-1457470, a) extracting hemicellulose from biomass; b) separating and separating hemicellulose from the hemicellulose extract; And c) injecting the separated hemicellulose into a papermaking process; and a paper manufacturing method with improved drying strength is disclosed.

Korean Patent Publication No. 10-0982599 discloses a non-aqueous electrolyte secondary battery including an anode composed of an oxide including potassium and manganese.

However, in the conventional techniques known so far, a physicochemical treatment was applied to remove lignin from biomass and to extract cellulose, which is mainly composed of glucose, and hemicellulose, which is mainly composed of xylose. In the case of using, there is a problem that the process is complicated because the chemical cost increases as well as the process of recovering the used chemicals has to be accompanied.In order to apply the separated components to the target raw materials, the purity is high and side-reactants must be removed as much as possible. This was often accompanied by this. In addition, since the treatment process is performed at a high temperature of 100° C. or higher, there is a disadvantage in that energy cost is high.

Therefore, in order to promote the use and supply of new and renewable energy, and to secure the supply stability of biomass fuel, biomass is maintained as much as possible while preserving existing carbon-derived biomass components under low temperature conditions to fundamentally exclude process problems caused by ash. There is an urgent need to develop a technology for a fuel production system for boilers connected with ESS that effectively extracts and separates fuel materials with a low ash content by selectively removing only the ash-causing components in it.

Japanese Unexamined Patent Publication No. 2016-125030 Japanese Patent Application Laid-Open No. Hei 11-240902 Japanese Patent No. 2688509 Korean Patent Registration No. 10-0476239 Korean Patent Publication No. 10-0413384 Korean Patent Publication No. 10-1457470 Korean Patent Publication No. 10-0982599

The present invention is an invention conceived to solve the above problems, such as fouling, slagging, high temperature corrosion, clinker generation, etc. during boiler operation from herbaceous, woody, algae biomass, etc. Ash-causing components that cause adverse effects on the heat transfer surface are removed through physical and chemical methods, and after removal, the solid components are used as solid fuel for burning or mixed burning, and liquid components including ash-inducing components are treated with acid, alkali, and hot water. , Membrane filtration, ion exchange, coagulation, adsorption, and centrifugation.

To this end, in the present invention, in the fuel production system in which the ash-inducing component in the biomass in low temperature conditions linked to the ESS is removed, the reaction base body 100 is treated with a low-temperature catalyst so that the ash-inducing component of the supplied raw material is maximally separated; A pH adjusting tank 400 for supplying low-temperature catalyst water to the reaction body; A washing water storage tank 500 for supplying washing water to the reaction body; A raw material injection device 700 for injecting raw materials into the reaction base body; A metal ion separation device 600 for separating metal ions in the dehydration discharged from the reaction body; And an ESS (700) supplying power to the system. It may include a fuel production system that removes ash-causing components in biomass under low temperature conditions in connection with ESS including.

In addition, when the dehydration liquid that has passed through the metal ion separation device is less than a predetermined metal ion concentration, it may be supplied to the pH adjustment tank.

In addition, when the metal ion concentration of the washing liquid is higher than a predetermined concentration, it may be supplied to the metal ion separating device, and when it is less than the metal ion concentration, it may be supplied to the washing water storage tank.

In addition, the dehydration liquid containing metal ions that have not passed through the metal ion separation device may be separated and supplied into a cation storage tank and an anion storage tank.

In addition, the ESS may include a positive electrode made of an oxide containing metal ions in a cation storage tank, a negative electrode made of a material capable of storing and releasing the metal ions, and a non-aqueous electrolyte containing the metal ions.

In addition, the metal ion may be any one or two or more of alkali and alkaline earth metals.

In addition, the positive electrode may include KxMnO2+y (0<x<1, -0.1<y<0.1).

In addition, the negative electrode may contain carbon capable of storing and releasing potassium.

In addition, the ESS is a carbon material capable of occluding and releasing potassium,

It may be a potassium ion capacitor having a negative electrode for a potassium ion secondary battery or a negative electrode for a potassium ion capacitor containing a binder containing polycarboxylic acid and/or a salt thereof.

In addition, the ESS uses iron (VI) acid salt as an active material of the positive electrode in a battery comprising a positive electrode, a negative electrode containing zinc or zinc alloy powder and a gelling agent, and an alkaline electrolyte, and potassium hydroxide and zinc oxide as the electrolyte. It may be an alkaline battery using an alkali solution it contains.

According to the fuel production system in which the ash-causing component in the biomass under low temperature conditions of the present invention is removed, the ash-inducing component is effectively and easily extracted and separated from the herbaceous or lignocellulosic biomass through the low-temperature reaction conditions of a catalyst such as acid or alkali. It is possible to selectively secure raw materials for biomass burning and/or mixed burning in the boiler.

In addition, in the present invention, by treating acid and alkali under low temperature conditions, the wastewater treatment process is simplified and contributes to cost reduction, and the elution of carbon-based components such as cellulose, hemicellulose, and lignin can be excluded as much as possible.

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

In addition, the liquid component (sugar containing most of xylose) is a separate source, which is an important cause of mixing only biomass of less than 3.5wt% into the existing power plant through a hybrid coal process that is carbonized after impregnation with low-grade coal, which is a previously secured technology. There is an effect of not having a biomass pulverizing device and using an existing coal pulverizing facility.

In addition, since cellulose, hemicellulose, and lignin from biomass from which ash-causing components are removed are used to produce molding fuel and anti-carbon fuel, it is expected from ash caused by biomass after combustion and gasification in fluidized bed and pulverized combustion furnace and gasifier. There is an effect that can fundamentally exclude the problem of clinker fouling and high temperature corrosion.

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

In addition, there is an effect of reducing fuel NOx generated during combustion by removing the nitrogen component in the fuel component.

In addition, it is possible to increase energy efficiency and economic efficiency in wastewater treatment by configuring an ESS system in which a secondary battery and a supercapacitor are connected using metal ions generated as side reactants.

1 is a flowchart showing a fuel production system for a boiler from which ash-causing components are removed in connection with an ESS according to an embodiment of the present invention.
FIG. 2 is a diagram showing a change in components of raw materials before and after the fuel production system for a boiler from which ash-causing components linked to ESS according to an embodiment of the present invention are removed.
FIG. 3 is a diagram illustrating changes in mineral components of raw materials before and after the fuel production system for a boiler from which ash-causing components are removed according to an embodiment of the present invention.
4 shows the ash removal rate according to the pH change in the alkaline liquid treatment condition of the fuel production system for a boiler from which ash-causing components are removed according to an embodiment of the present invention.
FIG. 5 shows an ash removal rate according to temperature change in an alkali liquid treatment condition of a fuel production system for a boiler from which ash-causing components are removed according to an embodiment of the present invention.
6 shows an ash removal rate according to a change in residence time in an alkali liquid treatment condition of a fuel production system for a boiler from which ash-causing components are removed according to an embodiment of the present invention.
7 shows an ash removal rate according to a pH change in an acidic liquid treatment condition of a fuel production system for a boiler from which ash-causing components are removed according to an embodiment of the present invention.
8 shows the ash removal rate according to the temperature change in the acidic liquid treatment condition of the fuel production system for a boiler from which ash-causing components are removed according to an embodiment of the present invention.
9 shows an ash removal rate according to a change in residence time in an acidic liquid treatment condition of a fuel production system for a boiler from which ash-causing components are removed according to an embodiment of the present invention.
FIG. 10 shows SEM pictures of biomass before and after the fuel production system for a boiler from which ash-causing components linked to ESS according to an embodiment of the present invention are removed.
11 is a graph showing the residual amount of biomass combustible carbon compound powder according to an embodiment of the present invention.
12 is a flowchart illustrating an operation of a fuel production system for a boiler from which ash-causing components are removed in connection with an ESS according to an embodiment of the present invention.
FIG. 13 is a photograph comparing the electrical conductivity of dewatered metal ions generated in the fuel production system for a boiler from which ash-causing components are removed in connection with the ESS according to an embodiment of the present invention with distilled water.
14 is a residence time of a solution in a column according to a pumping speed of a fuel production system for a boiler from which ash-causing components are removed in connection with a dehydration washing process according to an embodiment of the present invention.
15 is a result of cation concentration over time when the mixed bio solution discharged from the dehydration unit of the fuel production system for a boiler from which ash-causing components are removed in connection with the dehydration washing process according to an embodiment of the present invention passes through the cation exchange resin column. to be.
FIG. 16 is a result of anion concentration over time when a mixed bio solution discharged from a dehydration unit of a fuel production system for a boiler from which ash-causing components are removed in connection with a dehydration washing process according to an embodiment of the present invention passes through an anion exchange resin column. to be.

The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is. Therefore, since the embodiments described in this specification are only the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention, there are various equivalents and modified examples that can replace them at the time of the present application. It should be understood that you can.

In addition, the fuel used in the present invention means any one or more selected from low-grade coal recognized in the art, such as peat, lignite, sub-bituminous coal, bituminous coal, or anthracite coal.

In addition, the raw material may be biomass. Wood-based and herbal-based may be used as the biomass raw material. As for the wood system, wood blocks, wood chips, logs, tree branches, wood chips, fallen leaves, wooden boards, sawdust, lignin, xylan, lignocellulosic, palm trees, PKS (palm kernel shell), palm fiber, EFB (empty fruit bunches) , FFB (fresh fruit bunches), palm leaves, palm milling dregs, etc. can be used. Herbal systems include corn stalks, rice straw, sorghum stalks, sugar cane stalks, grains (rice, sorghum, coffee, etc.), husks, sugar beet leaves, bagasse, millet, artichoke, molasses, flax, hemp, sheep, cotton stalks, tobacco stalks, Biomass such as starch-based corn, potato, cassava, wheat, barley, lye, other starch-based processed residues, fruit avocados, jatropha, and processed residues thereof may be used.

Algae can be used as a raw material for biomass. As algae, green algae, cyanobacteria, diatom, red algae, Chlorella, Spirulina, Dunaliella, Porphyridium, Phaeodactylum, and the like may be used.

Hereinafter, with reference to the accompanying drawings, a fuel production system in which ash-causing components in biomass in a low-temperature condition linked to an ESS according to the present invention are removed will be described in detail.

1 is a flow chart showing a fuel production system in which ash-causing components in biomass are removed under low temperature conditions in connection with an ESS according to an embodiment of the present invention.

A reaction base body 100 for treating with a low-temperature catalyst so that the ash-causing component of the supplied raw material is maximally separated; A pH adjusting tank 400 for supplying low-temperature catalyst water to the reaction body; A washing water storage tank 500 for supplying washing water to the reaction body; And a raw material injection device 700 for injecting raw materials into the reaction base body. It may be a fuel production system that removes ash-causing components in the biomass under low temperature conditions that are linked to the ESS.

The reactor body may include a reactor insulating material 101; The insulating material is not limited to the material as long as it can have a heat insulating effect.

The reactor insulating material may be any one or two or more of glass wool, rubber foam, PE foam, Perlite, and urethane.

Preferably, it may be a Hiplex of 0.05 [g/cm ³ ] and 0.035 [W/m·k]. More preferably, it may be 0.05 [g/cm ³ ], 0.035 [W/m·k], a mass ratio absorption rate of 3% or less, ^{and a Hiplex of 5 to 10 [ng/m 2} ·s·Pa].

If it is out of the above conditions, the warming effect cannot be obtained.

The low-temperature catalyst may be supplied independently or mixed with water.

The catalyst may be supplied to the warming catalyst water inlet 110.

The washing water may flow into the washing water inlet 120. The washing water may be mixed and supplied to the catalyst.

The reaction base body may include a reaction heater 130 for temperature control. It is obvious that the reaction heating unit is not limited in shape as long as it can control the temperature of the reaction base body. The reaction increaser may have a temperature increase rate of 1 to 5°C/min.

If it is out of the above conditions, the effect of increasing the temperature cannot be obtained.

Additionally, a vent for maintaining the internal pressure condition of the reaction base body may be performed through the vent part 140.

It may include a high-pressure gas generator 150 to maintain the pressure condition of the reaction body.

The high-pressure gas generated through the high-pressure gas generator may be provided with a first high-pressure gas injection part for supplying to the dehydration pressure part, and a second high-pressure gas injection part may be formed in the reaction base body.

The high-pressure gas condition may be 1 to 5 m ³ /min * 1 to 10Kg/cm ² . Exceeding the above conditions, sufficient pressure conditions cannot be obtained.

The high-pressure gas supplied to the second high-pressure gas injection unit also has an effect for aeration. The high-pressure gas may be any one or two or more of air, oxygen, nitrogen, and helium.

After the metal ion removal reaction, dehydration and washing process of the fuel, it may be discharged through a solid fuel discharge unit for discharging the fuel.

The pH adjustment tank is a device for supplying a catalyst for supply to the reaction body. The pH adjustment tank may include a treated water supply unit 210 for supplying water for mixing with the catalyst. A catalyst storage tank 430 for supplying a catalyst to the pH adjustment tank may be formed, and the catalyst may be supplied to the pH adjustment tank. The catalyst supply unit 420 may be formed. An organic acid storage tank 440 for forming an organic acid from the dehydration and/or washing water of the raw material may be additionally formed. The organic acid storage tank may be generated through over-reaction with one or two or more catalysts of cellulose, hemicellulose, and lignin separated from the raw material. The pH adjusting tank may be provided with a stirrer 401 for internal catalyst mixing characteristics. The stirrer may be stirred and rotated at 100 to 500 rpm, preferably 350 rpm, when the capacity of the pH adjusting tank is 100 L. The pH adjustment tank may include a temperature riser 403 for temperature control. It is obvious that the shape of the heater is not limited as long as the heater can control the temperature of the reaction body. The reaction increaser may have a temperature increase rate of 1 to 5°C/min.

If it is out of the above conditions, the effect of increasing the temperature cannot be obtained.

The pH adjustment tank may include a heat insulating material 402; The insulating material is not limited to the material as long as it can have a heat insulating effect.

The insulating material may be any one or two or more of glass wool, rubber foam, PE foam, Perlite, and urethane.

Preferably, it may be a Hiplex of 0.05 [g/cm ³ ] and 0.035 [W/m·k]. More preferably, it may be 0.05 [g/cm ³ ], 0.035 [W/m·k], a mass ratio absorption rate of 3% or less, ^{and a Hiplex of 5 to 10 [ng/m 2} ·s·Pa].

If it is out of the above conditions, the warming effect cannot be obtained.

A treated water supply unit 410 for additionally supplying water to the pH adjustment tank may be formed.

A heated catalyst water discharge unit 460 for supplying the catalyst to the reaction body may be formed.

A pH adjusting tank drain part 470 for discharging the excess generated catalyst water may be formed.

A washing water supply unit 510 for supplying water to the washing water storage tank may be formed. A secondary dewatering supply unit 520 for supplying the washing water discharged through washing from the reaction body to the washing water storage tank may be formed. A washing water discharge unit 530 for supplying the washing water generated in the washing water storage tank to the reaction body may be formed. A washing water drain part 540 for discharging excess washing water in the washing water storage tank may be formed.

In the reaction body, the pH adjustment tank, and the washing water storage tank, a water level measuring gauge capable of checking the liquid level may be additionally formed.

The raw material inflow device comprises: a pulverizing unit for forming the biomass into a raw material having a predetermined size; A hopper for storing the raw material; It may include; a raw material supply feeder for quantitatively supplying the raw material stored in the hopper to the rear end.

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

Preferably, silver grass, EFB (Empty Fruit Bunches), kenaf, cornstalk, rice husk, may be any one of two or more.

The predetermined size may be 500 mm or less.

Preferably, it may be 10 μm to 300 mm or less.

More preferably, it may be 20mm to 50mm or less.

If the particle size is exceeded, the grinding cost may be excessively required, or the removal efficiency of the ash-causing component may be lowered.

The crushing unit may perform crushing and/or grinding. The crushing unit may use one or more of the physical properties of compression, impact, friction, shear, and bending, and the method is not limited as long as it can achieve the purpose of increasing the surface area while reducing the size of the biomass such as cutting.

The crushing unit includes a jaw crusher, a gyretory crusher, a roll crusher, an edge runner, a hammer crusher, a ball mill, and a jet mill. mill) or a disk crusher.

The raw material supply feeder is not particularly limited as long as it is a device capable of quantitatively supplying the raw material to the rear end. Preferably, there is a screw feeder and a lock hopper.

The ash-causing component is physically and chemically attached to the surface of the reactor wall, heat exchanger, and exhaust gas treatment facility after the reaction among inorganic components included in the biomass used in the combustion reaction to generate fouling, slagging, corrosion, and clinker. It refers to the ash-causing component that causes the back.

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

Preferably, it may be sodium, potassium, or chlorine.

The temperature of the injected water for the hot water treatment of the predetermined temperature may be 30 ℃ to 500 ℃. Preferably, it may be from 120°C to 300°C, and more preferably from 30°C to 99°C. The temperature of the low-temperature catalyst water for the hot water treatment at the predetermined temperature may be 40°C to 60°C.

If the temperature condition is out of the above, the ash-causing component is not sufficiently separated from the raw material. The temperature condition may be changed depending on the raw material.

The time for the feedstock to stay in the reaction body may be 10 minutes to 10 hours. Preferably, the residence time may be 20 minutes to 2 hours, more preferably the residence time may be 30 minutes to 1 hour. If the residence time is exceeded, the ash-causing component is not sufficiently separated from the raw material.

The residence time condition may be changed depending on the raw material.

In the fuel treatment apparatus, the fuel may be carbonized or semi-carbonized through the hydrothermal treatment at the predetermined temperature.

As the fuel is carbonized or semi-carbonized, the calorific value per unit fuel may increase.

The calorific value of the carbonized or semi-carbonized fuel may be 3,500 kcal/kg to 4,500 kcal/kg based on the low-level calorific value.

Out of the above temperature and time conditions, the efficiency of the removal component decreases or the process cost is high.

The amount of low-temperature catalyst input per unit feedstock varies depending on the type of biomass, and may be defined as BTW (Biomass to Water, kg/kg). It may be preferably 0.02 to 0.5, and more preferably 0.11 to 0.18 (based on silver grass, wood pellets, cornstalk 1kg/6kg).

When the BTW ratio is out of the above, the separation efficiency of the inducing component decreases.

Water, an acidic solution, or a basic solution may be injected into the front or rear end of the reaction body for controlling the separation efficiency.

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 co-firing condition may be 1wt% to 50wt% compared to the existing fossil fuel. Preferably, it may be 3wt% to 40wt%, more preferably 5wt% to 30wt%.

The ash-causing component may be included in the liquid component discharged from the reaction body.

The liquid component may be an aqueous solution containing a small amount of organic compounds and ash-causing components. The organic compound may have carbon, hydrogen, nitrogen, oxygen, and sulfur components as major constituents. Preferably, the liquid component may include hemicellulose, organic acids, furfural, 5-hydroxymethylfufural (5-HMF), and inorganic substances.

The solid component discharged from the reaction body may include a combustible component from which the ash-causing component is separated.

The combustible component may be an organic compound. The combustible component may have carbon, hydrogen, nitrogen, oxygen, and sulfur components as major constituents. The combustible component is characterized in that the carbon fraction in carbon, hydrogen, nitrogen, oxygen, and sulfur of the raw material per unit mass increases, and the hydrogen, nitrogen, oxygen, and sulfur components decrease.

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

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

The optimum pH condition of the liquid component may be 3.

The pH of the liquid component is technically characterized in 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-hydroxy-butanoic acid, and 2-butenoic acid.

_{In addition, acetic acid (C 2} H ₄ O ₂ ), formic acid (HCOOH), propanoic acid (CH ₃ CH ₂ COOH), 4-hydroxy-butanoic acid, 2-butenoic acid solutions are used to improve the reactivity of the ash-causing component separation unit. Any one or more of acid, sulfuric acid (H2SO4), hydrochloric acid (HCl), nitric acid (HNO3), phosphoric acid (H3PO4), peracetic acid (C2H4O3), acetic acid (CH3COOH), and oxalic acid (C2H2O4) may be additionally added.

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

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

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

The aqueous solution having a low pH obtained by separating the organic compound from the liquid component may include recycling to the reaction body.

In order to remove organic compounds from the liquid component, at least one of centrifugation, aggregation, adsorption, filtration membranes, and ion exchange resins may be applied.

The solid component of the raw material discharged after the reaction from the reaction base body may be an organic compound. The combustible component may have carbon, hydrogen, nitrogen, oxygen, and sulfur components as major constituents. The combustible component is characterized in that the carbon fraction in carbon, hydrogen, nitrogen, oxygen, and sulfur of the raw material per unit mass increases, and the hydrogen, nitrogen, oxygen, and sulfur components decrease.

The dehydration and/or washing water component discharged from the reaction body through dehydration and/or washing may be an aqueous solution containing a small amount of organic compounds and inorganic substances. The organic compound may have carbon, hydrogen, nitrogen, oxygen, and sulfur components as major constituents. Preferably, the organic compound may be lignin. Preferably, the inorganic material may include any one or more of Al, Si, P, Ca, Ti, Mn, and Fe.

The fuel processing device may further include a molding fuel unit for manufacturing molding fuel by applying the solid component.

It may further include a membrane filter unit to separate the ionic component of the liquid component.

The membrane filter unit may be any one or two or more of a micro filter, an ultra filter, a nano filter, and a reverse osmosis membrane. In addition, water, acidic solution, and basic solution for pH and concentration control may be injected into the front or rear end of the membrane filter unit. In addition, the solid component in the liquid component may be separated by any one or more of moisture evaporation, centrifugation, precipitation, precipitation, aggregation, and adsorption at the front or rear end of the membrane filter unit. The hemicellulose in the liquid component can be purified and separated and used as a substitute for dietary fiber.

The reaction body may be dehydrated and/or washed.

It may be a fuel produced in a fuel production system in which an ash-causing component for biomass burning and/or mixed burning in the boiler is removed.

In addition, the biomass refers to lignocellulosic-based herbal or woody biomass, and any material belonging to the biomass is not limited. In addition, it is obvious that the 1st generation or 3rd generation biomass can also be applied. Cellulose, a major component of lignocellulosic, is a polysaccharide with a stable structure in which glucose is linked by β-1,4 bonds. It is composed of a polymer of xylose, another major component, and in addition, arabinose, a pentose, mannose, a hexasaccharide, galactose, glucose, and rhamnose It is composed of a polymer.

Glucan is a generic term for a polysaccharide composed of glucose, and there are various types according to the binding style between D-glucose, and is largely divided into α-glucan and β-glucan by the arrangement of subtitle carbon atoms. α-glucan includes amylose (α-1,4 binding), amylopectin (α-1,4 and α-1,6 binding), glycogen (α-1,4 and α-1,6 binding), bacterial dextran (α-1,6 bonds) and the like are included. Representative examples of β-glucan include cellulose (β-1,4 bonds), brown algae laminaran (β-1,3 bonds), lichenan (β-1,3 and β-1,4 bonds), etc. have.

The liquid ingredient that contains xylan is xylan. It may include glucuronoxylan, arabinoxylan, glucomannan, and xyloglucan. The liquid component containing xylan as the above-described component is not limited, and various components may be separated according to the component of the biomass to be introduced.

Sugars are not limited to the compounds described above, and can be produced in various ways depending on the type of second-generation biomass. Therefore, it is classified into disaccharides, trisaccharides, tetrasaccharides, pentose sugars, and hexasaccharides according to the number of carbon atoms, and as disaccharides, glycoaldehyde (Glycoaldehyde), as trisaccharides, glyceraldehyde (Glyceraldehyde), dihydroxyacetone (Dihydroxyacetone). , Erythrose, erythrulose as a quaternary sugar, ribose, arabinose as a pentose, xylose, ribulose, and xylulose (xylulose), hexose, glucose, glycose (glucose), fructose, fructose (fructose), galactose (galactose), there may be mannose (mannose).

A combination of two monosaccharides Disaccharides may include lactose, lactose, lactose, malt sugar, maltose, maltose, sugar, sucrose, trehalose, melibiose, and cellobiose.

Small saccharides, which are sugars with 2 to 10 molecules of sugar combined, are trisaccharides such as raffinose, melezitose, and maltoriose, and as tetrasaccharides, stachiose and schrodose. There may be galactooligosaccharide, isomaltooligosaccharide, and fructooligosaccharide as oligosaccharides.

Polysaccharides are simple polysaccharides, pentosan in which pentoses are combined, and may include xylan and araban.

Hexanoic acid condensed with hexasaccharides is a polymer of starch, starch, and glucose, which is amylose, dextrin, glycogen, cellulose, fructan, and galactan. There may be (galactan), mannan, etc.

Complex polysaccharides may include agar, alginic acid, carrageenan, chitin, hemicellulose, pectin, and the like.

Acids participating in the reaction include sulfuric acid (H ₂ SO ₄ ), hydrochloric acid (HCl), nitric acid (HNO ₃ ), phosphoric acid (H ₃ PO ₄ ), peracetic 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 described acid, and any acid that decomposes hemicellulose and cellulose may include sodium hydroxide, calcium hydroxide, and urea as a base participating in the reaction. The base is not limited to the described base, and any base that enhances reaction characteristics may be used.

The ionic liquid participating in the reaction is an imidazolium-based compound, 1-ethylacrylate-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium Chloride (1-buthyl- 3-methylimidazolium chloride), 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluoro Phosphate (1-butyl-3-methylimidazolium hexafluoro phosphate), 1-butyl-3-methylimidazolium trifluoromethanesulfonate (1-butyl-3-methylimidazolium trifluoromethanesulfonate), 1-ethyl-3-methylimidazolium Acetate (1-ethyl-3-methylimidazolium acetate), 1-benzyl-3-methylimidazoliumchloride, 1,3-dimethylimidazolium methyl sulfate (1,3-dimethylimidazoliummethyl sulfate), 1-butyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium acetate, etc., ethylmethylimidazolium chloride ([EMIM]Cl), ethylmethylimida Jolium bromine ([EMIM]Br), ethylmethylimidazolium iodine ([EMIM]I), 1-ethyl-3-methyl imidazolium, 1-ethyl imidazolium nitrate, 1-ethyl imida Zolium bromide, 1-ethyl-3-methyl imidazolium chloride, 1-ethyl-imidazolium chloride, 1,2,3-trimethyl imidazolium methyl sulfate, 1-methyl imidazolium chloride, 1-butyl-3 -Methyl imidazolium, 1-butyl-3-methyl imidazolium tetrachloroaluminate, 1-ethyl-3-methyl imidazolium tetrachloroaluminate, 1-ethyl-3-methyl imidazolium hydrogensulfate, 1-butyl-3-methyl imi Dazolium hydrogensulfate, methylimidazolium chloride, 1-ethyl-3-methyl imidazolium acetate, 1-butyl-3-methyl imidazolium acetate, Tris-2 (hydroxy ethyl) methylammonium methylsulfate, 1 -Ethyl-3-methyl imidazolium ethylsulfate, 1-ethyl-3-methyl imidazolium methanesulfonate, methyl-tri-n-butylammonium methylsulfate, 1-butyl-3-methyl imidazolium chloride, 1 -Ethyl-3-methyl imidazolium chloride, 1-ethyl-3-methyl imidazolium thiocyanate, 1-butyl-3-methyl imidazolium thiocyanate, 1-butyl-3-methylimidazolium chloride , 1-butyl-3-methylimidazolium nitrate, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimida Zolium chloride, 1-ethyl-3-methylimidazolium nitrate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ali-3-methyl Imidazolium chloride, 1-ali-3-methylimidazolium nitrate, 1-ali-3-methylimidazolium acetate, and 1-ali-3-methylimidazolium tetrafluoroborate. The ionic liquid is not limited to the described ionic liquid, and any one that enhances reaction characteristics may be used.

The amount of one or two or more of an enzyme, an acid, an alkali, and an ionic liquid added to the reaction body may not be added depending on the reaction conditions.

In addition, a compound such as furfural may be generated while the solid component participates in a high temperature and high pressure reaction through the reaction body.

The pressure condition of the reaction base body may be 1 to 20 atm, preferably 1 to 10 atm. The pressure condition of the reaction body may vary depending on the raw material.

If the above pressure conditions are exceeded, metal ions in an appropriate raw material cannot be separated.

The fuel from which such ash-causing components have been removed can be used in fluidized beds, grates, micronized boilers and gasifiers, and during combustion and gasification processes, clogging such as clinker fouling caused by inorganic components including metal elements in the fuel and alkali-based Corrosion phenomena caused by metal can be excluded from the root.

In addition, it may include a; metal ion separation device 600 for separating the metal ion component of low temperature alkali and / or acid dehydration discharged from the reaction body.

In addition, the low-temperature conditions in the reaction body may be less than 100 ℃ to exclude the loss of latent heat of evaporation of water. The low temperature condition may be 40°C to 80°C to exclude the loss of latent heat of evaporation of water. The low temperature condition may be 60°C.

In addition, the acidic liquid supplied to the reaction body may use an organic acid generated through a separate soaking treatment of biomass.

In addition, the metal ion separation device is not particularly limited as long as it can separate ionic components using an ion exchange resin, an ion exchange membrane and/or a membrane, and can remove and separate ions included in dehydration. As an example, the ion exchange resin 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 ⁺ It may be a cation exchange resin capable of selectively separating any one or 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 It may be an anion exchange resin capable of selectively separating the above anions.

Here, it is preferable to use a strong acidic cation exchange resin or a strong basic anion exchange resin so that the anion exchange resin and the cation exchange resin can be used in a wide pH range.

The metal ion separation device may include a first cation exchange module 601, a first anion exchange module 602, a second cation exchange module 603, and a second anion exchange module 604. The ion exchange module may include a plurality of cation and anion exchange modules in parallel. The ion exchange module may be partially or fully operated. A pump for supplying dehydration to the ion exchange module may be formed.

Dehydration passing through the cation and anion exchange resin of the ion exchange module may be supplied to the pH adjustment tank. The ionic liquid separated from the cation and anion exchange resin may be supplied to the anion water storage tank 620 and the cation water storage tank 630.

A dehydration storage tank 610 in which dewater discharged from the reaction body can be stored before being supplied to the metal ion separation device may be formed.

(Metal ion separation experiment)

For the metal ion separation experiment during dehydration, put glass wool under the column (diameter 5cm, length 24cm, volume 471cm3) to prevent leakage of the resin, and then a certain amount of the target ion exchange resin on it (cation exchange resin 402g, After filling the anion exchange resin (346g), fill it with glass wool again.

The sample solution was pumped to the column at a speed of 50 rpm, 30 rpm, and 10 rpm, and the solution flowing through the column was sampled. After a certain amount of time, the sampled solution was taken and analyzed to measure the concentration of each ion.

The residence time of the solution in the column according to the pumping speed is shown in Fig. 14. The concentration of metal ions in the dehydration liquid discharged from the metal ion separation device was analyzed by ICP.

The change in the concentration of K+, Na+, and Mg2+ cations according to the time that the mixed bio solution discharged from the dehydration unit passes through the cation exchange resin column is shown in FIG. 15. It shows the change in the concentration of K+, Na+, and Mg2+ cations according to the time that the mixed bio solution discharged from the dehydration unit passes through the cation exchange resin column, and in the case of K+ ions, the concentration from the initial concentration of 457.092 ppm to 6.474 ppm after 3 minutes Was rapidly decreased, showed 6.833 ppm after 9 minutes, and gradually decreased to a value of 5.809 ppm at 55 minutes. In the case of Mg2+ ions, the concentration rapidly decreased from the initial concentration of 57.114ppm to 1.636ppm after 3 minutes, 0.454ppm after 9 minutes, and gradually decreased to 0.079ppm at 55 minutes. In the case of Na + ion, the concentration rapidly increased from the initial concentration of 32.687 ppm to 180.224 ppm after 3 minutes, 139.157 ppm after 9 minutes, and 75.739 ppm at 22 minutes, and then almost constant. It can be seen that most of the K+ and Mg2+ ions are removed after 3 minutes passing through the cation exchange resin column.

Figure 16 shows the separation result according to the time of the anion, taking into account the solution residence time in the column according to the pumping speed. The concentration of metal ions in the dehydration liquid discharged from the metal ion separation device was analyzed by ICP.

In the case of Cl-ion, the concentration rapidly decreased from the initial concentration of 1051.60 ppm to 183.18 ppm after 3 minutes, 169.07 ppm after 9 minutes, and 147.85 ppm after 22 minutes. Cl- anion showed an almost constant value. It can be seen that most of the ions are removed after 22 minutes passing through the resin column. In the case of Cl-ion, the adsorption amount rapidly increased from 0 mg/g to 1.26 mg/g after 3 minutes, 1.28 mg/g after 9 minutes, and 1.31 mg/g after 22 minutes. It was found that the adsorption amount of Cl-ion of the anion exchange resin for 1 hour was about 5.0 mg/g.

On the other hand, the ionized water discharged from the metal ion separation device may contain various particulate matter including ash-inducing components, and these substances reduce the ion exchange capacity of the cation exchange resin or the anion exchange resin, and furthermore, Close the void. In addition, when it is desired to remove cations or anions using a nanofiltration membrane or a reverse osmosis membrane, it is preferable to provide an appropriate pretreatment unit because the permeability may be rapidly deteriorated due to the above-described particulate matter.

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

In addition, dehydration from which ionic components are separated in the metal ion separation device may be recycled as the reaction body.

In addition, the biomass may have a particle diameter of 10 μm to 10 mm.

In addition, a discharge unit may be additionally included at the rear end of the metal ion separation device.

It is obvious that the wastewater treatment unit may include an ion exchange resin, a separation membrane, agglomeration, and adsorption. The ionic substances removed and separated from the private wastewater treatment unit are buried or incinerated through consignment treatment, and the treated water from which these substances have been removed may further include a discharge unit that discharges to a water system (river, river, etc.). The discharge unit may be a pump.

(Catalyst reaction example)

The biomass raw material is dried in an oven at 105° C. to remove moisture. Add water to a part of the dried sample (e.g. EFB) to keep the viscosity below 5000cP. For EFB, the above condition is a 1 to 3 weight ratio of EFB to water. 1wt% of NaOH is added to the aqueous solution. Put the treatment solution in the reactor and keep it at 60℃ for 10 minutes. The stirrer is stirred at 10 to 1000 rpm. The reaction time is 40 minutes under the condition of heating at 2°C per minute at 60°C.

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

Put the treatment liquid into the reactor and hold at 60°C for 10 minutes. Through the above process, Na ions contained in the treatment solution are removed from the reactor to acetic acid.

The treatment liquid after the reaction is completed is solid-liquid separated by a 1 um filter. The residue is washed with distilled water.

Finally, by drying in an oven at 105°C, the biomass in which the ash-causing component in the biomass is removed from the metal component and the gasoline-inducing component in the biomass is discharged.

By applying the separated metal ions, it can be applied to secondary batteries and supercapacitors.

Preferably, it is possible to configure an ESS system using the separated metal ions in connection with a fuel production system in which ash-causing components in biomass in low-temperature conditions linked to ESS are removed.

The metal ion may be an alkali or alkaline earth metal ion, preferably lithium, sodium, potassium, and more preferably potassium.

2 is a view showing a change in the components of raw materials before and after the fuel production system for a boiler from which ash-causing components are removed according to an embodiment of the present invention.

Biomass under consideration as a raw material includes herbaceous, woody, and algae, and FIG. 2 shows the results of fuel characteristics analysis using herbaceous biomass such as silver grass, cornstalk and woody pine. The biomass from which the ash-causing components produced through this process were removed showed a removal efficiency of 77-97% or more on a dry basis, and improved the calorific value of about 10% on average. In addition, it can be seen that the values of N and S, which are fuel NOx generating substances and SOx generating substances of the fuel itself, have been reduced by about 80%. Compared to coal, the low calorific value of biomass fuel or the effect of ash can be improved through this pretreatment process.

3 is a view showing a change in mineral components of raw materials before and after the fuel production system for a boiler from which ash-causing components are removed according to an embodiment of the present invention.

3 shows the ash characteristics of the fuel from which the ash-causing component has been removed. _{In the case of K 2} O, which has the lowest melting point of 349 ℃, the removal efficiency reaches more than 99%, and in _{the case of Na 2} O, which has a melting point of 1,132 ℃, the removal efficiency reaches 95%. By removing the ash-causing components in this way, it is possible to block in advance substances that cause generation such as slagging, fouling, and clinker generated on the boiler tube or wall, and maintain a stable boiler operation rate. (In the case of general biomass burning boiler, operation rate is less than 70%)

4 shows the ash removal rate according to the pH change in the alkaline liquid treatment condition of the fuel production system for a boiler from which ash-causing components are 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, which is a combustible material. The fuel from which the ash-causing component in the biomass to be developed in this patent is removed is characterized by removing only the ash-causing component while maintaining the flammable material, which is a solid material, as much as possible. It can be seen that in the range of pH 13.4 or higher, the removal efficiency of ash-causing components decreases and the yield of ALB decreases. Therefore, ash extraction should be performed in the range of pH 13.3 to 13.4, which is the most maximized condition.

5 shows the ash removal rate according to the temperature change in the alkaline liquid treatment condition of the fuel production system for a boiler from which ash-causing components are removed according to an embodiment of the present invention.

FIG. 5 considers the effect of temperature under the condition of pH 13.4 based on the experimental results of FIG. 4. It can be seen that the ash extraction rate generally increases as the temperature increases, and the most maximized value can be seen in the 80 ℃ range. However, since the yield of ALB, which is a combustible material, is formed at a low yield, a range of 55 to 65°C, which has a good ash extraction rate and a good recovery rate of combustible materials, can be said to be an appropriate temperature range.

6 shows an ash removal rate according to a change in residence time in an alkali liquid treatment condition of a fuel production system for a boiler from which an ash-causing component is removed according to an embodiment of the present invention.

6 shows the effect of the residence time in the region of pH 13.4 and temperature of 60°C. Under the influence of the residence time of 10 minutes, the ash extraction rate is the most maximized, and it can be seen that the similar performance is maintained as the time elapses. In the case of the recovery rate, it gradually decreases over time, so the residence time in the alkaline region is more than 10 minutes, which can be said to be an insignificant condition.

7 shows the ash removal rate according to the pH change in the acidic liquid treatment condition of the fuel production system for a boiler from which ash-causing components are 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, which is a combustible material. The fuel from which the ash-causing component in the biomass to be developed in this patent is removed is characterized by removing only the ash-causing component while maintaining the flammable material, which is a solid material, as much as possible. As the pH increases to 1.7, the removal efficiency of the ash-causing component increases, but when it exceeds 1.8, it tends to decrease again. Therefore, the ash extraction should be performed in the range of pH 1.7 ~ 1.8, which is the most maximizing condition.

8 shows the ash removal rate according to the temperature change in the acidic liquid treatment condition of the fuel production system for a boiler from which ash-causing components are removed according to an embodiment of the present invention.

FIG. 8 considers the effect of temperature under the condition of pH 1.76 based on the experimental results of FIG. 7. As the temperature increases, the ash extraction rate increases, but it can be seen that the ash extraction rate decreases under a temperature condition of 60°C or higher. Accordingly, the optimum temperature condition may be a range of 50 to 60° C. as an appropriate range.

9 shows the ash removal rate according to the change of residence time in the acidic liquid treatment condition of the fuel production system for a boiler from which ash-causing components are removed according to an embodiment of the present invention.

9 considers the effect of the residence time in the range of pH 1.76 and temperature of 60°C. Under the influence of the residence time of 10 minutes, the ash extraction rate is the most maximized, and it can be seen that the similar performance is maintained as the time elapses. In the case of the recovery rate, it gradually decreases over time, so the residence time in the acidic region of 10 minutes or more can be said to be an insignificant condition.

FIG. 10 shows SEM photographs of biomass before and after the fuel production system for a boiler from which ash-causing components have been removed according to an embodiment of the present invention.

FIG. 10 is a comparison of the surface structure changes of the untreated raw sample (Samsa) and the silver grass sample from which the ash-causing component was removed using SEM. In the case of the original sample, it can be seen that the surface contains a large amount of mineral components in the form of irregular impurities, but in the case of the sample from which the ash-causing component is removed, the surface shape in a clean state can be seen. This process configuration can be considered to be the most appropriate to selectively remove only mineral components without causing structural changes of the sample itself.

11 is a graph showing the residual amount of biomass combustible carbon compound powder according to an embodiment of the present invention.

11 shows that in the case of biomass treatment through pretreatment of the existing bioethanol process, only about 20 wt% of carbon content remains, and in the case of acid and/or base treatment according to an embodiment of the present invention, about It can be seen that 80 wt% or more of carbon content remains.

12 is an operation sequence of a fuel production system in which ash-causing components in biomass in low-temperature conditions linked to ESS are removed.

The operating procedure of the reactor main body is as follows: 1. A dehydration transfer device is raised to the reaction main body under a hydraulic condition of 80 to 160 kg/cm2 below the reaction main body. Thereafter, the raw material, which is biomass, is supplied to the reaction body through the raw material injection device. Thereafter, 3. low-temperature catalyst water is supplied through the pH adjustment tank. At this time, the mass ratio of the low-temperature catalyst water/biomass may be 1 to 10. After 4. air is supplied to the reaction body through the high-pressure gas generator to perform aeration and agitation. The air pressure may be an air flow rate of 0.1 to 1 m3/min in 3 to 5 kg/cm2. After 5. After a predetermined reaction time, the biomass may be filtered through the high-pressure gas generator through a predetermined time. The air pressure may be an air flow rate of 0.5 to 2 m3/min at 3 to 5 kg/cm2. After that 6. The press of the dehydration device can move to the reaction body under a hydraulic condition of 80-160 kg/cm2. Thereafter, in order to proceed with dehydration, dehydration is performed by press-pressing while introducing high-pressure air through the high-pressure gas generator. After that, 7. the pressurizing press moves to the top to end the dehydration.

After 8. In order to wash the biomass, washing water may be added from the washing water storage tank to the reaction body. Thereafter, the processes of 4. to 7. above may be repeated. Thereafter, 10. After the dehydration transfer device moves downward, the biomass raw material may be discharged and transferred to the fuel processing device 800 through the fuel transfer device 810. After 11. Separated water containing potassium cation can be linked to ESS. As the cathode material binder, instead of polyvinylidene fluoride, polytetrafluoroethylene, polyethylene oxide, polyvinyl acetate, polymethacrylate, polyacrylate, polyacrylonitrile, polyvinyl alcohol, styrene-butadiene rubber, carboxymethyl At least one selected from cellulose and the like can be used.

As the conductive agent of the positive electrode material, other carbon materials such as acetylene black and graphite can be used instead of ketjen black. In addition, when the addition amount of the conductive agent is small, the conductivity of the positive electrode material cannot be sufficiently improved, while when the addition amount is too large, the proportion of the positive electrode active material contained in the positive electrode material decreases, and high energy density cannot be obtained.

As the positive electrode current collector, foamed aluminum, foamed nickel, or the like can be used in order to improve electronic conductivity.

The negative electrode may include a current collector made of a metal foil.

The carbon may be applied on the current collector.

The carbon may be graphite.

The non-aqueous electrolyte may contain potassium hexafluorophosphate. The non-aqueous electrolyte may include one or two or more selected from the group consisting of cyclic carbonate esters, chain carbonate esters, esters, cyclic ethers, chain ethers, nitriles and amides. .

Examples of the non-aqueous solvent include those composed of cyclic carbonate esters, chain carbonate esters, esters, cyclic ethers, chain ethers, nitriles, amides, etc., and combinations thereof, which are usually used as non-aqueous solvents for batteries. .

The carbon material may contain graphite.

The carbon material may include particles such as artificial graphite, an amorphous carbon material such as acetylene black, Ketjen black, and furnace black. Among these materials, in particular, it may be an amorphous carbon material such as artificial graphite or acetylene black.

The polycarboxylic acid and/or its salt may include at least one selected from the group consisting of polyacrylic acid, polyacrylic acid alkali metal salt, carboxymethylcellulose, and carboxymethylcellulose alkali metal salt.

1: deashing reactor
100: reaction primitive
101: reactor insulation
110: heating catalyst water inlet
120: washing water inlet
130: reaction heater
140: vent part
150: high pressure gas generator
151: high pressure gas first injection unit
152: high pressure gas second injection unit
160: solid fuel discharge unit
200: dehydration pressure device
210: dehydration press
300: dehydration transfer device
310: transfer press
320: second dehydration discharge unit
330: first dehydration discharge unit
340: metal ion sensor
400: pH adjustment tank
401: stirrer
402: insulation
403: heater
410: treated water supply unit
420: catalyst supply unit
430: catalyst storage tank
440: organic acid storage tank
450: 1st μ water supply
460: heating catalyst water discharge unit
470: pH adjustment tank drain part
500: washing water storage tank
510: washing water supply unit
520: secondary dehydration supply unit
530: washing water discharge unit
540: washing water drain portion
600: metal ion separation device
601: first cation exchange module
602: first anion exchange module
603: second cation exchange module
604: second anion exchange module
610: dehydration storage tank
620: anion water storage tank
630: cationic water storage tank
640: dewatering pump
650: metal ion sensor
700: raw material injection device
800: fuel processing device
810: fuel transfer device
900: ESS

Claims (8)

In a fuel treatment system that removes ash-causing components in biomass in low temperature conditions linked to ESS,
A reaction base body 100 for treating with a low-temperature catalyst so that the ash-causing component of the supplied raw material is maximally separated;
A pH adjusting tank 400 for supplying low-temperature catalyst water to the reaction body;
A washing water storage tank 500 for supplying washing water to the reaction body;
A raw material injection device 700 for injecting raw materials into the reaction base body;
A metal ion separation device 600 for separating metal ions in the dehydration discharged from the reaction body; And
An ESS 900 for supplying power to the system; Including,
The ash-causing ingredients are sodium, potassium, and chlorine,
The supplied raw material is biomass,
The low temperature is 40 ℃ to 60 ℃,
The catalyst is an alkaline liquid or an acidic liquid,
The dehydration liquid containing metal ions that has not passed through the metal ion separation device includes an operation sequence that is supplied by being separated into a cation water storage tank and an anion water storage tank,
The ESS is a potassium ion capacitor having a negative electrode for a potassium ion secondary battery or a negative electrode for a potassium ion capacitor containing a carbon material capable of storing and releasing potassium and a binder containing polycarboxylic acid and/or a salt thereof. ,
The ESS is a battery composed of a positive electrode, a negative electrode containing zinc or zinc alloy powder and a gelling agent, and an alkaline electrolyte, using iron (VI) acid salt as an active material of the positive electrode, and containing potassium hydroxide and zinc oxide as an electrolyte. It is an alkaline battery using an alkaline solution,
The separated metal ions are used for the ESS, and the ESS supplies power only to the fuel processing system, thereby connecting the fuel processing system and the ESS.
A fuel treatment system that removes ash-causing components in biomass under low temperature conditions in connection with ESS that only supplies power to the system.
The method of claim 1,
When the dehydration liquid that has passed through the metal ion separation device is less than a predetermined metal ion concentration, a fuel treatment system in which an ash-causing component in a low-temperature condition biomass is removed by linking an ESS including an operation sequence of supplying it to the pH adjusting tank.
The method of claim 1,
When the metal ion concentration of the washing liquid that has passed through the reaction body is higher than a predetermined concentration, it is supplied to the metal ion separation device, and if the concentration is less than that, the ash-inducing component in the biomass in low temperature conditions linked to the ESS including the operating sequence of supplying it to the washing water storage tank. Removed the fuel handling system.
The method of claim 1,
The ESS is a low-temperature biomass in which a positive electrode composed of an oxide containing metal ions in a cation storage tank, a negative electrode composed of a material capable of storing and releasing the metal ions, and an ESS having a non-aqueous electrolyte containing the metal ions are connected. A fuel treatment system that removes ash-causing components.
The method of claim 4,
The metal ion is a fuel treatment system in which an ash-causing component in a biomass in a low-temperature condition is linked to an ESS in which one or two or more of alkali and alkaline earth metals are removed.
The method of claim 5,
The metal ions are any one of lithium, sodium, potassium, or two or more of the fuel treatment system in which the ash-causing component in the biomass in low temperature conditions is linked to each other.
The method of claim 4,
The anode is a fuel treatment system that contains KxMnO2+y (0<x<1, -0.1<y<0.1) and removes ash-causing components in biomass under low temperature conditions linked to ESS.
The method of claim 4,
The anode is a fuel treatment system that removes ash-causing components in biomass under low temperature conditions in connection with an ESS containing carbon capable of storing and releasing potassium.

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