KR20200025425A - 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 with ash-producing components removed from fuel. More specifically, the present invention relates to a fuel production system for a boiler with ash-producing components removed. To this end, the ash-producing components causing adverse effects on the heating surfaces of wall surfaces of reactors, heat exchangers, etc. such as fouling, slagging, high temperature corrosion, and clinker production during operation of the boiling from herbaceous, lignocellulosic, and algal biomass are removed via physicochemical methods. After the removal, solid components are applied to the burning or mixing as a solid fuel, and liquid components containing ash-producing components are subjected to water treatment using methods including acid treatment, alkali treatment, hot water treatment, membrane filtration, ion exchange, aggregation, 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-induced components in low-temperature biomass associated with ESS, and more specifically, fouling, slagging, and boiler operation from herbal, wood, and algae biomass. The ash-induced components that cause adverse effects on the reactor walls, heat exchangers, etc., such as high-temperature corrosion and clinker formation, are removed through physical and chemical methods, and after removal, the solid phase components are used for burning or mixing with solid fuels. Containing liquid components include ash-induced components in biomass at low temperature conditions in connection with ESS applying the method of water treatment using methods including acid treatment, alkali, hot water treatment, membrane filtration, ion exchange, flocculation, adsorption, and centrifugation. To a removed fuel production system.

Energy sources that generate the most carbon dioxide and are inadequate for global warming are energy sources based on fossil fuels. Therefore, among the issues currently being issued globally as energy sources, the use and dissemination of new and renewable energy is possible, which reduces CO2 emissions compared to fossil fuels such as petroleum and coal, which can cope with global warming and climate change. Because it is an energy source.

With the depletion of fossil fuels and the reduction of greenhouse gases in response to the international treaty, the climate change convention, the total generation volume for power generation companies (suppliers) with power generation facilities (excluding renewable energy facilities) of a certain size (500MW) is emerging. The Renewable Portfolio Standard (RPS) was introduced, which requires a certain percentage of the supply to be made by using renewable energy.In case of non-compliance, the reason for non-compliance is within 150% of the average transaction price of the supply certificate. The government has enacted a law to impose penalties, taking into account the number of non-compliances.

Accordingly, the certificate of proof that the electricity generation company produced and supplied electricity by using renewable energy facilities in order to supply and receive renewable energy, the supplying obligee can purchase the renewable energy supply certificate to satisfy the mandatory supply. Renewable Energy Certificate (REC) is given to multiply the weight of renewable energy based on MWh supplied from the facilities subject to the supply certificate. The weight of each renewable energy is based on environment, technology development and industry. The government finances and reviews it every three years, taking into account the effects on vitalization, cost of power generation, potential losses, and GHG emission reduction.

As a result, large coal-fired power plants have integrated integrated gasification combined cycle (IGCC) and ultra-supercritical (Ultra) systems to link and improve power plants to reduce CO2 emissions from coal in order to achieve this renewable energy supply. While attempting to clean coal technology (CCT) such as supercritical (USC) technology, CO ₂ capture and storage technology, and bio-mass mixing, there are many areas that need to be overcome to solve fundamental problems. It exists.

In particular, in the case of biomass mixing, there is a problem in that power generation efficiency decreases as the biomass of a relatively low calorific value is burned compared to coal.

In addition, the combustion characteristics of the biomass and coal input for the mixing is different, causing the multi-stage combustion in the existing power plant designed as coal as a raw material causes problems in the operation of the facility.

In addition, there is also a problem that clinker or fouling occurs by the inorganic component including a metal component contained in the biomass. In order to solve this problem, a technique for applying a fuel in which oil-based biomass is mixed with coal has been developed. In the case of a fuel that is simply a mixture of coal and oil-based biomass, the surface of the coal is generally coated with oil or some oil is impregnated into the pores. However, due to the low surface tension of the oil itself and the lack of bonding force between the oil-based biomass and the coal surface, the coal and biomass retain their existing combustion characteristics, resulting in different combustion characteristics. Therefore, when applied to a power plant, oxygen is preferentially consumed excessively due to the low temperature combustion pattern of oil in the front of the burner, which eventually inhibits the combustion of coal, thereby increasing the amount of unburned carbon and decreasing power generation efficiency. .

In addition, the representative flocculation of ash in biomass is found in slag, clinker, fouling and fluidized bed combustor, which are mainly generated in the radiant and convective transfer surfaces of pulverized coal combustor, respectively. Ash agglomeration, and the like.

It is expected to wear due to high temperature chlorine corrosion of the power plant tube, change caused by the flow rate caused by the coagulation tube clogging phenomenon, tube wear caused by the flow sand of the fluidized bed combustor, and mechanical wear of the chute blower. When potassium and chlorine form KCl through chemical bonding during the combustion process, KCl (melting temperature 776 ℃) is known to be highly viscous and accelerates corrosion by chlorine reaction.

The occurrence of these phenomena in the furnace is not only a major factor in reducing the efficiency of the process, but ultimately, when such phenomena intensify, operations must be shut down, resulting in huge economic losses. Agglomeration of ash is generally affected by ash composition, temperature, particle size, gas atmosphere, operating conditions, etc. Particularly, when a part of the ash is melted at a high temperature, this phenomenon is accelerated.

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

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

In Japanese Patent Laid-Open No. Hei 11-240902, after extracting the water-soluble hemicellulose from the raw material including the water-soluble hemicellulose into the aqueous medium at 80 or more and 140 or less under conditions of pH 2 to 7, the extract is 1.5 times. The manufacturing method of water-soluble hemicellulose is disclosed which concentrates as mentioned above and removes an insoluble substance next.

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, eluting the fraction mainly composed of hemicellulose in an alkaline aqueous solution, and then purified out of bounds using a membrane and an ion exchange resin. Disclosed is a method for extracting and purifying hemicellulose, which is characterized by the above-mentioned.

In Korean Patent No. 10-0476239, in the preparation of water-soluble and insoluble hemicellulose from rice husk, (1) a step of removing protein from chaff and washing chaff; (2) extracting and filtering the chaff with sodium hydroxide solution at a concentration of 0.5 to 1 M; (3) recovering hemicellulose by precipitation by adding phosphoric acid to the alkaline extraction solution obtained in step (2) to lower the pH of the solution; (4) further washing with phosphate or oxalic acid for the precipitate obtained in step (3) and then decolorizing through oxalate-potassium permanganate treatment; (5) It is possible to selectively separate the water-soluble and insoluble hemicellulose by adjusting the pH of the solution from the decolorized hemicellulose fraction obtained in the above step, but in the recovery of the water-soluble hemicellulose, it is recovered by precipitation by adding phosphoric acid or converted to insoluble by adding calcium. Then recovering; (6) From the rice husks, which consists of a process of obtaining a powder by naturally drying or spray-drying a water-soluble and insoluble hemicellulose obtained through a series of such continuous processes, and then milling and passing a sieve of a suitable size. A method for preparing water-soluble and insoluble hemicellulose is disclosed.

In Korean Patent Publication No. 10-0413384, (i) removing starch and protein from corn husks; (ii) extracting the corn husk from which starch and protein have been removed with an alkaline solution and filtering with a filter cloth; (iii) a step of reacting the alkaline extract obtained in step (ii) by treating cellulase and cellobiase; (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 the step of purifying the filtrate.

Korean Patent Publication No. 10-1457470 discloses a) extracting hemicellulose from biomass; b) precipitating and separating hemicellulose from the hemicellulose extract; And c) introducing the separated hemicellulose into a papermaking process.

Korean Patent Publication No. 10-0982599 discloses a nonaqueous electrolyte secondary battery including a positive electrode composed of an oxide including potassium and manganese.

However, the conventional techniques known to date have applied physicochemical treatments to remove lignin from biomass and extract hemicellulose, which is mainly composed of glucose and xylose, but with drugs such as acids or alkalis. In the case of using, the cost of chemicals increases and the process of recovering the used chemicals is involved, which leads to a complicated process. This was often accompanied. In addition, since the treatment process proceeds at a high temperature of more than 100 ℃ there was a disadvantage that takes a lot of energy costs.

Therefore, in order to promote the utilization and dissemination of renewable energy and to secure the supply stability of biomass fuel, the biomass while maintaining the existing carbon-derived biomass components at the lowest temperature to fundamentally eliminate process problems caused by ash, is maintained. There is an urgent need for the technical development of a fuel production system for ESS-linked boilers that effectively removes and isolates low ash content by selectively removing only ash-induced components in the ash.

Japanese Laid-Open Patent Publication No. 2016-125030 Japanese Patent Laid-Open No. 11-240902 Japanese Patent No. 2688509 Korea 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 has been made in order to solve the above problems, from the herbaceous, wood-based, algae biomass, such as fouling, slagging, high temperature corrosion, clinker generation during boiler operation, reactor wall, heat exchanger, etc. The ash-induced components that cause adverse effects on the heat-transfer surface are removed by physical and chemical methods, and after removal, the solid phase components are used for burning or mixing with solid fuel.The liquid components containing ash-induced components are treated with acid, alkali, and hot water. The present invention provides a fuel production system for a boiler in which ESS is applied to a method of water treatment using a method including membrane filtration, ion exchange, flocculation, adsorption, and centrifugation.

To this end, in the present invention, in the fuel production system to remove the ash-induced components in the biomass of low temperature conditions in conjunction with the ESS, the reaction body 100 for treating with a low-temperature catalyst so that the ash-induced components of the feedstock is separated to the maximum; PH adjusting tank 400 for supplying a low temperature catalyst water to the reaction base; Washing water storage tank 500 for supplying the washing water to the reaction base; A raw material injection device 700 for injecting a raw material into the reaction base; A metal ion separation device 600 for separating metal ions in dehydration discharged from the reaction body; And an ESS 700 for supplying power to the system. Fuel production system to remove the ash-induced components in the biomass of low temperature conditions in conjunction with the ESS.

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

In addition, when the metal ion concentration of the washing liquid is more than a predetermined concentration may be supplied to the metal ion separation device, when less than may be supplied to the wash water storage tank.

In addition, the dehydration liquid containing metal ions that did not pass through the metal ion separation device may be supplied separately from the cation storage tank and the anion storage tank.

In addition, the ESS may be provided with a positive electrode made of an oxide containing a metal ion of the cation storage tank, a negative electrode made of a material capable of occluding and releasing the metal ion, and a nonaqueous electrolyte containing the metal ion.

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

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

In addition, the negative electrode may include carbon capable of occluding 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, in the battery composed of a positive electrode, a negative electrode containing zinc or zinc alloy powder and a gelling agent, and an alkaline electrolytic solution, the ESS uses potassium (VI) acid salt as the active material of the positive electrode and also potassium hydroxide and zinc oxide as electrolyte. It may be an alkaline battery using an alkaline solution containing.

According to the fuel production system removing the ash-induced components in the biomass under low temperature conditions of the present invention, the ash-induced components and the like are effectively and easily extracted and separated from herbaceous or wood-based biomass through low-temperature reaction conditions of catalysts such as acids and alkalis. It is possible to selectively secure raw materials for biomass burning and / or mixing in the boiler.

In addition, the acid and alkali treatment in the low temperature conditions in the invention contributes to simplifying and reducing the waste water treatment process, and has the effect of maximizing the dissolution of carbon-based components such as cellulose, hemicellulose, lignin.

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

In addition, the liquid component (sugar mainly containing xylose) is an important cause of mixing and mixing only the biomass of 3.5 wt% or less into the existing power plant through a hybrid coal process in which carbon is impregnated after being impregnated with low-grade coal, which is a conventional technology. There is an effect that the existing coal atomization equipment can be used without the biomass atomization device.

In addition, since the production of molded fuel and semi-carbonized fuel using cellulose, hemicellulose, and lignin of biomass from which ash-induced components have been removed, it is expected from the ash resulting from biomass after combustion and gasification in fluidized bed and micronized combustion furnace and gasifier. There is an effect that can fundamentally exclude the problems of clinker fouling and high temperature corrosion.

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

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

In addition, an ESS system in which secondary batteries and supercapacitors using metal ions generated as side reactions are formed may be configured to increase energy efficiency and economic efficiency due to wastewater treatment.

1 is a flow chart showing a fuel production system for a boiler removes the ash-induced components linked to the ESS according to an embodiment of the present invention.
Figure 2 shows the changes in the components of the raw material before and after the fuel production system for the boiler remove the ash-induced components linked to the ESS according to an embodiment of the present invention.
Figure 3 shows the change in the mineral component of the raw material before and after the fuel production system for the boiler to remove the ash-induced components linked to the ESS according to an embodiment of the present invention.
Figure 4 shows the ash removal rate according to the pH change in the alkaline liquid treatment conditions of the fuel production system for the boiler remove the ash-induced components linked to the ESS according to an embodiment of the present invention.
Figure 5 shows the ash removal rate according to the temperature change in the alkaline liquid treatment conditions of the fuel production system for the boiler to remove the ash-induced components linked to the ESS according to an embodiment of the present invention.
Figure 6 shows the ash removal rate according to the change of residence time in the alkaline liquid treatment conditions of the fuel production system for the boiler remove the ash-induced components linked to the ESS according to an embodiment of the present invention.
Figure 7 shows the ash removal rate according to the pH change in the acidic liquid treatment conditions of the fuel production system for boilers removed ash-induced components linked to the ESS according to an embodiment of the present invention.
Figure 8 shows the ash removal rate according to the temperature change in the acidic liquid treatment conditions of the fuel production system for the boiler to remove the ash-induced components linked to the ESS according to an embodiment of the present invention.
Figure 9 shows the ash removal rate according to the change of residence time in the acid solution treatment conditions of the boiler fuel production system to remove the ash-induced components linked to the ESS according to an embodiment of the present invention.
FIG. 10 shows biomass SEM photographs before and after the fuel production system for a boiler from which ash-induced components are linked to ESS according to an embodiment of the present invention.
11 is a graph showing the remaining amount of biomass combustible carbon compound powder according to an embodiment of the present invention.
12 is an operation flowchart of a fuel production system for a boiler removes ash-induced components linked to the ESS according to an embodiment of the present invention.
13 is a photograph comparing the electrical conductivity of the metal ion separated dehydration generated in the fuel production system for the boiler to remove the ash-induced components linked to the ESS according to an embodiment of the present invention and 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 in which ash-induced components are removed in connection with a dehydration washing process according to an embodiment of the present invention.
15 is a cation concentration result of the mixed bio solution discharged from the dehydration unit of the fuel production system for the boiler removing the ash-induced components associated with the dehydration washing process according to an embodiment of the present invention through the cation exchange resin column; to be.
16 is an anion concentration result of the mixed bio solution discharged from the dehydration unit of the fuel production system for the boiler removing the ash-induced components linked to the dehydration washing process according to an embodiment of the present invention passes through the anion exchange resin column to be.

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

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

In addition, the raw material may be biomass. As the biomass raw material, wood based and herbal based may be used. The wood system includes wood blocks, wood chips, logs, tree branches, wood chips, deciduous trees, woodcuts, sawdust, lignin, xylan, lignocellulose, palm trees, palm kernel shell (PKS), palm fibres, and empty fruit bunches (EFB). , FFB (fresh fruit bunches), palm leaves, palm mill residues, etc. can be used. Herbs include corn stalks, rice straw, sorghum, sugar cane, grains (rice, sorghum, coffee, etc.), husks, beets, vargas, millet, artichoke, molasses, flax, hemp, horses, cotton stalks, tobacco stems, Biomass such as starch corn, potato, cassava, wheat, barley, rye wheat, other starch processed residues, fruit avocados, jatropha and their processed residues may be used.

Algae may be used as a biomass raw material. Green algae, Cyanobacteria, Diatoms, Diatoms, Red algae, Chlorella, Spirulina, Dunaliella, Porphyridium, Phaeodactylum may be used as the algae.

Hereinafter, with reference to the accompanying drawings will be described in detail a fuel production system removing the ash-induced components in the biomass of low temperature conditions in conjunction with the ESS according to the present invention.

1 is a flow chart showing a fuel production system removing the ash-induced components in the biomass of low temperature conditions in conjunction with the ESS according to an embodiment of the present invention.

A reaction base 100 for treating with a low temperature catalyst so as to separate ash-induced components of the supplied raw materials to the maximum; PH adjusting tank 400 for supplying a low temperature catalyst water to the reaction base; Washing water storage tank 500 for supplying the washing water to the reaction base; It may be a fuel production system removing the ash-induced components in the biomass of low temperature conditions in conjunction with the ESS including a; raw material injection device 700 for injecting the raw material to the reaction base.

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

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

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

If it is out of the above conditions, a thermal insulation effect cannot be obtained.

The low temperature catalyst can be supplied independently or in admixture with water.

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

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

The reaction base may include a reaction warmer 130 for temperature control. It is obvious that the shape of the reaction warmer is not limited as long as the reaction warmer can control the temperature of the reaction body. The reaction warmer may have a temperature increase rate of 1 to 5 ℃ / min.

If the above conditions are exceeded, a temperature increase effect cannot be obtained.

Additionally, the vent may be performed to maintain the internal pressure condition of the reaction base through the vent 140.

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

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

The high pressure gas conditions may be 1 to 5 m ³ / min * 1 to 10 Kg / cm ² . Outside of 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 may be discharged through a solid fuel discharge unit for discharging the fuel.

The pH adjusting tank is a device for supplying a catalyst for supplying the reaction base. The pH adjusting tank may include a treatment water supply unit 210 for supplying water for mixing with the catalyst. A catalyst storage tank 430 may be formed to supply the catalyst to the pH adjusting tank, and the catalyst may be supplied to the pH adjusting tank. Catalyst supply unit 420 may be formed. An organic acid storage tank 440 for forming an organic acid from dehydration and / or wash water of the raw material may be further formed. The organic acid storage tank may be generated through overreaction with any one or two or more catalysts of cellulose, hemicellulose, lignin separated from the raw material. The pH adjusting tank may be formed with a stirrer 401 for the internal catalyst mixing characteristics. The stirrer may be rotated by stirring at 100 to 500rpm, when the capacity of the pH adjustment tank is 100L, preferably 350rpm. The pH adjustment tank may include a temperature increaser 403 for temperature control. If the temperature increaser can control the temperature of the reaction body is obvious that the form of the temperature increaser is not limited. The reaction warmer may have a temperature increase rate of 1 to 5 ℃ / min.

If the above conditions are exceeded, a temperature increase effect cannot be obtained.

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

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

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

If it is out of the above conditions, a thermal insulation effect cannot be obtained.

Treatment water supply unit 410 for supplying additional water to the pH adjustment tank may be formed.

A warm catalyst water discharge part 460 for supplying the catalyst to the reaction base may be formed.

PH adjusting tank drain portion 470 for discharging the excess 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 dehydration supply unit 520 may be formed in the washing water storage tank to supply the washing water discharged through the washing from the reaction body. A washing water discharge unit 530 may be formed to supply the washing water generated in the washing water storage tank to the reaction body. A washing water drain unit 540 for discharging excess washing water of the washing water storage tank may be formed.

The reaction body, the pH adjustment tank, the wash water storage tank may be further formed with a level gauge to check the liquid level.

The raw material inlet device is a grinding unit for forming the biomass into a raw material of 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, it may be two or more of any one of pampas grass, EFB (Empty Fruit Bunches), kenaf, corn stalk, rice husk, wild boar.

The predetermined size may be 500 mm or less.

Preferably it may be less than 10μm to 300mm.

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

If it is out of the particle size, the grinding cost is excessively consumed, or the removal efficiency of the ash-induced components may be lowered.

The grinding unit may perform crushing and / or grinding. The grinding unit may use any one or more of physical properties such as compression, impact, friction, shear 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 widening the surface area.

The crushing unit is a jaw crusher, a gyre crusher, a roll crusher, an edge runner, a hammer crusher, a ball mill, 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 supplying the raw material quantitatively at the rear end. Preferably there is a screw feeder, a lock hopper.

The ash-induced components are physically and chemically attached to the surface of the reactor wall, the heat exchanger, and the exhaust gas treatment equipment at the rear stage of the reaction among the inorganic components included in the biomass used in the combustion reaction to generate fouling, slagging, corrosion, and clinker. It means a ash-inducing ingredient causing the back.

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

Preferably sodium, potassium, chlorine.

The temperature of the injection water for the hydrothermal treatment of the predetermined temperature may be 30 ℃ to 500 ℃. Preferably it may be 120 ° C to 300 ° C and more preferably 30 ° C to 99 ° C. The temperature of the low temperature catalyst water for the hydrothermal treatment of the predetermined temperature may be 40 ℃ to 60 ℃.

If the temperature is out of the condition, the ash-inducing component is not sufficiently separated in the raw material. The temperature conditions may vary depending on the raw material.

The residence time of the feedstock 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-inducing component is not sufficiently separated in the raw material.

The retention time condition may vary depending on the raw material.

The fuel treatment device may be carbonized or semi-carbonized through the hydrothermal treatment of 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 calorific value.

Outside the temperature and time conditions, the efficiency of the removal component is lowered or the process cost is high.

The amount of cryocatalyst introduced per unit feedstock depends on the type of biomass and may be defined as BTW (Biomass to Water, kg / kg). It may be preferably from 0.02 to 0.5, more preferably from 0.11 to 0.18 (pampung, wood pellets, corn cobs 1 kg / 6 kg).

When it is out of the BTW ratio, the separation efficiency of the trigger component is lowered.

Water, acidic solution and basic solution for controlling separation efficiency may be injected at the front or rear end of the reaction base.

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

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

The mixing 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-inducing component may be included in the liquid component discharged from the reaction base.

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

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

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

PH of the liquid component may be 6 or less.

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

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

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-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, sulfuric acid (H2SO4), hydrochloric acid (HCl), nitric acid (HNO3), phosphoric acid (H3PO4), peracetic acid (C2H4O3), acetic acid (CH3COOH), oxalic acid (C2H2O4) may be further added.

The addition amount of the acid solution may be 10wt% or more relative to the total amount of hot water input.

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

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

A low pH aqueous solution from which the organic compound is separated from the liquid component may include recycling to the reaction base.

One or more of centrifugal separation, agglomeration, adsorption, filtration membrane, and ion exchange resin may be applied to remove the organic compound in the liquid component.

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

The dehydration and / or wash water component discharged through dehydration and / or washing in the reaction base 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 as main components. Preferably the organic compound may be lignin. Preferably, the inorganic material may include any one or more of Al, Si, P, Ca, Ti, Mn, Fe.

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

A membrane filter unit may be further included 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, it is possible to inject water, acidic solution, basic solution for pH, concentration control to the front or rear of the membrane filter unit. In addition, the solid component in the liquid component may be separated by any one or more methods of water evaporation, centrifugation, precipitation, precipitation, aggregation, and adsorption at the front or rear end of the membrane filter unit. Hemicellulose in the liquid component can be used as a substitute for dietary fiber by purification.

The reaction base may be dewatered and / or washed.

The fuel may be a fuel produced in a fuel production system in which ash-induced components for biomass burning and / or mixing in the boiler are removed.

In addition, the biomass means a lignocellulosic based herbal, woody biomass, and if the material belonging to the biomass is not limited. It is obvious that the first generation or third generation biomass can also be applied. Cellulose, the main component of lignocellulosic cellulose, is a polysaccharide with a stable structure in which glucose is connected by β-1,4 bonds. It is composed of polymers of xylose, another pentose, and other major components, and arabose, pentose, mannose, galactose, glucose, and rhamnose. It consists of a polymer of.

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

Liquid components containing xylan include xylan. Glucuronoxylan, arabinoxylan, glucomannan, xyloglucan, and the like. The liquid component including xylan is not limited to the above-described components, and various components may be separated according to the components of the biomass to be added.

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, depending on the carbon number, it is classified into saccharides, saccharides, pentoses, pentoses, pentoses, and saccharides. , Erythrose, erythrulose as tetrasaccharide, ribose, arabinose, xylose, ribulose and zirurose as ethanol (xylulose), hexose may be glucose, glucose, fructose, fructose, galactose, mannose.

Combined Two Monosaccharides Disaccharides can include lactose, lactose, lactose, maltose, maltose, maltose, sugar, sucrose, trehalose, melibiose, and cellobiose.

Small sugars, which are sugars of 2 to 10 molecules combined, are trisaccharides as raffinose, melezitose and maltoriose, and tetrasaccharides as starch and strodose. And oligosaccharides may include galactooligosaccharides, isomaltooligosaccharides and fructooligosaccharides.

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

Hexanes condensed with hexose include starch, starch and glucose polymers of 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 acid described, and any base that participates in the reaction may be sodium hydroxide, calcium hydroxide, urea, etc., as long as any acid decomposes hemicellulose and cellulose. The base is not limited to the base described, and any base may be used as long as it enhances the reaction characteristics.

The ionic liquid participating in the reaction is an imidazolium compound, 1-ethylacrylate-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride Phosphate (1-butyl-3-methylimidazolium hexafluoro phosphate), 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium 1-ethyl-3-methylimidazolium acetate, 1-benzyl-3-methylimidazolium chloride, 1,3-dimethylimidazolium methyl sulfate sulfate), 1-butyl-3-methylimidazolium chloride, 1- Yl-3-methylimidazolium acetate and the like, and ethylmethylimidazolium chloride ([EMIM] Cl), ethylmethylimidazolium bromine ([EMIM] Br), ethylmethylimidazolium Iodine ([EMIM] I), 1-ethyl-3-methyl imidazolium, 1-ethyl imidazolium nitrate, 1-ethyl imidazolium 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 tetra Chloroaluminate, 1-ethyl-3-methyl imidazolium tetrachloroaluminate, 1-ethyl-3-methyl imidazolium hydrogensulfate, 1-butyl-3-methyl imidazolium hydrogensulfate, methylimida Zolium chloride, 1-ethyl-3-methyl imidazolium acetate, 1-butyl-3-meth Tyl imidazolium acetate, Tris-2 (hydroxy ethyl) methylammonium methyl sulfate, 1-ethyl-3-methyl imidazolium ethyl sulfate, 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-methylimidazolium chloride, 1-ethyl-3-methylimidazolium nitrate, 1-ethyl-3-methylimidazolium acetate, 1- Ethyl-3-methylimidazoliumtetrafluoroborate, 1-ali-3-methylimidazolium chloride, 1-ali-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, and any ionic liquid can be used as long as it enhances the reaction characteristics.

The amount of one or two or more of enzymes, acids, alkalis and ionic liquids introduced into the reaction base may not be added depending on the reaction conditions.

In addition, a compound such as furfural may be produced while the solid phase participates in the high temperature and high pressure reaction through the reaction base.

The pressure condition of the reaction base may be 1 ~ 20atm, preferably 1 ~ 10atm. The reaction base may be changed in pressure conditions depending on the raw material.

Outside the above pressure conditions, metal ions in the appropriate raw materials cannot be separated.

These ash-induced fuels can be used in fluidized beds, grates, micronized boilers and gasifiers, and clogging and alkali-based fouling, such as clinker fouling due to inorganic components, including metal elements in the fuel during combustion and gasification. Corrosion caused by metals can be ruled out.

In addition, the metal ion separation device 600 for separating the low-temperature alkali and / or acidic dehydration metal ion component discharged from the reaction base; may include.

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

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

In addition, the metal ion separation apparatus is not particularly limited as long as it can separate the ionic components using an ion exchange resin, an ion exchange membrane, and / or a membrane, and can remove and separate the ions contained in the dehydration. For example, the ion exchange resin may include Ba ²⁺ , Pb ²⁺ , Sr ²⁺ , Ca ²⁺ , Ni ²⁺ , Cd ²⁺ , Cu ²⁺ , Zn ²⁺ , Tl ⁺ , Ag ⁺ , Cs ⁺ , Rb ⁺ It may be a cation exchange resin capable of selectively separating any one or two or more cations of K ⁺ , NH 4 ⁺ , Na ⁺ , Li ⁺ .

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 that can selectively separate the above anions.

Here, it is preferable to use a strong acid cation exchange resin or a strong base 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 form a plurality of cation and anion exchange module in parallel. The ion exchange module can be operated in part or in whole. 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 may be formed that may be stored before the dehydration discharged from the reaction body is supplied to the metal ion separation device.

(Metal Ion Separation Experiment)

For the experiment of separating metal ions in dehydration, glass wool is placed under a column (diameter 5 cm, length 24 cm, volume 471 cm 3) to prevent resin leakage, and a predetermined amount of ion exchange resin (cation exchange resin 402 g, 346g) of anion exchange resin), and then filled with glass wool again.

The mother solution was pumped to a column at a rate of 50rpm, 30rpm, 10rpm, the solution was passed through the column, and the solution was sampled. After a certain time, a certain amount of the sampled solution was taken to analyze the concentration of each ion.

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

The concentration change of K +, Na +, Mg 2 + cations with time when the mixed bio solution discharged from the dehydration unit is passed through the cation exchange resin column is shown in FIG. 15. The mixed bio solution discharged from the dehydration unit shows the change in concentration of K +, Na + and Mg2 + cations over time passing through the cation exchange resin column, and for K + ions, the concentration is 6.474 ppm after 3 minutes at the initial 457.092 ppm concentration. Was decreased sharply, and after 9 minutes, it was 6.833ppm and gradually decreased, and it was 5.809ppm at 55 minutes. In the case of Mg2 + ion, the concentration rapidly decreased to 1.636ppm after 3 minutes at the initial concentration of 57.114ppm, 0.454ppm after 9 minutes, and gradually decreased to 0.079ppm at 55min. In the case of Na + ions, the concentration rapidly increased to 180.224ppm after 3 minutes at the initial concentration of 32.687ppm, 139.157ppm after 9 minutes, and showed a constant value after 75.739ppm at 22 minutes. K + and Mg 2 + ions can be seen that most of the ions are removed after 3 minutes through the cation exchange resin column.

The separation result according to the time of anion considering the solution residence time in the column according to the pumping speed is shown in Figure 16. The metal ion concentration of the dehydration liquid discharged from the metal ion separator was analyzed by ICP.

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

On the other hand, the ionized water discharged from the metal ion separation device may contain a variety of particulate matter, including ash-induced components, these materials reduce the ion exchange capacity of the cation exchange resin or anion exchange resin, and also between the ion exchange resin Close the voids. In addition, when it is desired to remove a cation or anion using a nanofiltration membrane or a reverse osmosis membrane, the permeation performance may be drastically reduced due to the above-mentioned particulate matter.

For example, the pretreatment unit may introduce a coagulation and / or precipitation process or may remove the particulate matter in advance with a relatively large pore ultrafiltration membrane or microfiltration membrane, and then supply the ion exchange resin, nanofiltration membrane, or reverse osmosis membrane.

In addition, dehydration from which the ionic component is separated in the metal ion separation device may be recycled to the reaction base.

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

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

Obviously, the wastewater treatment unit may include ion exchange resins, separators, flocculation, adsorption, and the like. Ionic materials removed from the harvested wastewater treatment unit are buried or incinerated by consignment treatment, and the treated water from which these substances have been removed may further include a discharge unit for discharging to the water system (river, river, etc.). The discharge unit may be a pump.

(Catalyst Reaction Example)

The biomass feedstock is dried in an oven at 105 ° C. to remove moisture. A portion of the dried sample (eg EFB) is added with water to maintain a viscosity of 5000 cP or less. The conditions are for EFB, the weight ratio of EFB to water is one to three. 1 wt% of NaOH is added to the aqueous solution. Place the treatment solution in the reactor and hold at 60 ° C for 10 minutes. The stirrer is stirred at 10 to 1000 rpm. The reaction time is 60 minutes at 60 ℃ temperature conditions 2 ℃ per minute.

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

The treatment liquid is placed in the reactor and maintained at 60 ° C. for 10 minutes. Na ions contained in the treatment solution through the above process to remove acetic acid in the reactor.

The treatment solution in which the reaction is completed is separated into a solid solution by a 1um filter. The residue is washed with distilled water.

Finally, the biomass is removed by drying in an oven at 105 ℃ to remove the gasoline-induced components in the biomass in which the ash-induced components in the biomass is removed.

The separated metal ions may be applied to secondary batteries and supercapacitors.

Preferably, it is possible to configure the ESS system using the separated metal ions in conjunction with the fuel production system removing the ash-induced components in the biomass under low temperature conditions in conjunction with the ESS.

The metal ions may be alkali, alkaline earth metal ions, preferably lithium, sodium, potassium, more preferably potassium.

Figure 2 shows the changes in the components of the raw material before and after the fuel production system for the boiler remove the ash-induced components according to an embodiment of the present invention.

Biomass under consideration as a raw material is herbaceous, woody, algae (Algae), etc. Among them, Fig. 2 shows the results of the fuel characteristics analysis using herbal biomass, silver grass, corn stalk and woody pine. Biomass from the ash-induced components removed through this process showed removal efficiency over 77 ~ 97% on a dry basis, and averaged about 10% calorific value. In addition, it can be seen that the values of N and S, which are fuel NOx and SOx generating materials of the fuel itself, are reduced by about 80%. This pretreatment process can improve the low calorific value and the ash effect of biomass fuel compared to coal.

Figure 3 shows the change in the mineral component of the raw material before and after the fuel production system for the boiler remove the ash-induced components according to an embodiment of the present invention.

3 shows the ash characteristics of the fuel from which ash-induced components have been removed. K ₂ O, which has the lowest melting point of 349 ° C, has a removal efficiency of over 99%, and Na ₂ O having a melting point of 1,132 ° C has a removal efficiency of 95%. As such, by removing the ash-causing component, it is possible to block generation substances such as slagging, fouling, and clinker generated in the boiler tube or wall in advance, and maintain a stable boiler operation rate. (Less than 70% utilization rate for typical biomass burner boilers)

Figure 4 shows the ash removal rate according to the pH change in the alkaline liquid treatment conditions of the fuel production system for the boiler from which ash-induced components are removed according to an embodiment of the present invention.

4 is a graph showing the ash extraction rate and the recovery rate of the flammable material ALB in the alkaline region. Fuel to remove the ash-induced components in the biomass to be developed in this patent is characterized in that to remove only the ash-induced components while maintaining the flammable material as a solid material to the maximum. In the region above pH 13.4, the removal efficiency of ash-induced components decreases and the yield of ALB decreases. Therefore, ash extraction should be made in the pH 13.3 ~ 13.4 region, which is the most maximal condition.

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

FIG. 5 considers the influence of temperature under the pH 13.4 condition based on the experimental results of FIG. 4. As the temperature increases, the ash extraction rate generally increases, and the maximum value can be seen in the 80 ℃ range. However, since the yield of ALB, which is a combustible material, is low, a suitable temperature range is 55-65 ° C. where the ash extraction rate and the flammability recovery rate are good.

Figure 6 shows the ash removal rate according to the change in residence time in the alkaline liquid treatment conditions of the fuel production system for boilers removed ash ash component according to an embodiment of the present invention.

Figure 6 considers the effect of residence time in the region of pH 13.4, temperature 60 ℃. The extraction rate of ash is maximized under the influence of residence time of 10 minutes, and it can be seen that similar performance is maintained over time. Since the recovery rate gradually decreases with time, the residence time in the alkaline region is a meaningless condition for more than 10 minutes.

Figure 7 shows the ash removal rate according to the pH change in the acid solution treatment conditions of the fuel production system for boilers removed ash induction component according to an embodiment of the present invention.

7 is a graph showing the ash extraction rate and the recovery rate of the flammable material ALB in the acidic region. Fuel to remove the ash-induced components in the biomass to be developed in this patent is characterized in that to remove only the ash-induced components while maintaining the flammable material as a solid material to the maximum. As the pH is increased to 1.7, the removal efficiency of ash-induced components increases, but when it is more than 1.8, it tends to decrease again. As a result, ash extraction should be performed at the pH of 1.7 to 1.8, the most maximal condition.

Figure 8 shows the ash removal rate according to the temperature change in the acidic liquid treatment conditions of the fuel production system for boilers removed ash ash component according to an embodiment of the present invention.

FIG. 8 considers the influence of temperature under the pH 1.76 condition based on the experimental results of FIG. 7. As the temperature increases, the ash extraction rate increases, but the ash extraction rate decreases at a temperature higher than 60 ° C. Thus, the optimum temperature conditions may be said to be an appropriate range of 50 ~ 60 ℃ region.

Figure 9 shows the ash removal rate according to the change in residence time in the acid solution treatment conditions of the fuel production system for boilers removed ash firing components according to an embodiment of the present invention.

Figure 9 considers the effect of residence time in the region of pH 1.76, temperature 60 ℃. The extraction rate of ash is maximized under the influence of residence time of 10 minutes, and it can be seen that similar performance is maintained over time. Since the recovery rate gradually decreases with time, the residence time in the acidic region is a meaningless condition for more than 10 minutes.

Figure 10 shows a biomass SEM picture before and after the fuel production system for boilers removed ash ash component according to an embodiment of the present invention.

FIG. 10 compares the surface structure of the untreated raw sample (mistake) and that of the silver sample from which ash-induced components were 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 ash-induced components are removed, the surface shape of the clean state can be seen. It can be said that this process configuration is most appropriate to selectively remove only mineral components without causing structural change of the sample itself.

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

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

12 is an operation sequence of a fuel production system removing ash-induced components in biomass under low temperature conditions in conjunction with ESS.

Operation procedure of the reactor body 1. The dehydration transfer device to the lower portion of the reaction body is raised to the reaction body under a hydraulic condition of 80 ~ 160 kg / cm2. 2. The raw material which is biomass is then supplied to the reaction base through the raw material injection device. 3. The low temperature catalyst water is then supplied through the pH adjustment tank. In this case, the mass ratio of the catalyst water / biomass at low temperature may be 1 to 10. 4. Since air is supplied to the reaction base through the high pressure gas generator, aeration agitation may be performed. The air pressure may be an air flow rate of 0.1 ~ 1 m3 / min in 3 ~ 5 kg / cm2. 5. The biomass may be filtered through the high pressure gas generator through a predetermined time after a predetermined reaction time. The air pressure may be an air flow rate of 0.5 to 2 m3 / min to 3 to 5 kg / cm2. 6. After the press of the dehydrating device can move to the reaction body under the hydraulic conditions of 80 ~ 160 kg / cm2. Thereafter, dehydration is performed by performing pressurization while introducing high pressure air through the high pressure gas generator to proceed with dehydration. 7. The pressurized press moves to the top to finish dehydration.

8. The washing water may be introduced into the reaction body from the washing water storage tank to wash the biomass. Thereafter, the process of 4. to 7. can be repeated. 10. After the dehydration and transfer device moves downward, the biomass raw material may be discharged and transferred to the fuel processor 800 through the fuel transfer device 810. 11. Separation water containing potassium cations may be associated with the ESS. As the positive electrode material binder, polytetrafluoroethylene, polyethylene oxide, polyvinylacetate, polymethacrylate, polyacrylate, polyacrylonitrile, polyvinyl alcohol, styrene-butadiene rubber, carboxymethyl instead of polyvinylidene fluoride At least 1 sort (s) chosen from cellulose etc. can be used.

As the conductive agent for the positive electrode material, other carbon materials such as acetylene black and graphite may be used instead of Ketjenblack. 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 included in the positive electrode material decreases, and a high energy density cannot be obtained.

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

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

The carbon may be applied onto the current collector.

The carbon may be graphite.

The nonaqueous electrolyte may include potassium hexafluorophosphate. The nonaqueous electrolyte may include one or two or more selected from the group consisting of cyclic carbonates, chain carbonates, esters, cyclic ethers, chain ethers, nitriles and amides. .

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

The carbon material may contain graphite.

Examples of the carbon material include particles such as artificial graphite, amorphous carbon materials such as acetylene black, Ketjen black, and furnace black. Among these substances, 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 salts, carboxymethyl cellulose and carboxymethyl cellulose alkali metal salts.

1: deash reactor
100: reaction base
101: reactor insulation
110: warming catalyst inlet
120: washing water inlet
130: reaction warmer
140: vent part
150: high pressure gas generator
151: high pressure gas injection unit
152: high pressure gas injection unit 2
160: solid fuel discharge unit
200: dehydrating pressure device
210: dewatering press
300: dehydration transfer device
310: transfer press
320: second dewatering discharge unit
330: first dewatering discharge unit
340: metal ion sensor
400: pH adjusting tank
401 stirrer
402: insulation
403: a temperature riser
410: treatment water supply unit
420: catalyst supply unit
430 catalyst storage tank
440: organic acid storage tank
450: 1st μ water supply
460: warm catalyst water discharge part
470: pH adjustment tank drain portion
500: washing water storage tank
510: washing water supply unit
520: secondary dewatering supply unit
530: washing water discharge unit
540: washing water drain portion
600: metal ion separator
601: first cation exchange module
602: first negative ion 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 processor
810: fuel feeder
900: ESS

Claims (11)

In a fuel production system that removes ash-induced components in biomass under low temperature conditions linked to ESS,
A reaction base 100 for treating with a low temperature catalyst so as to separate ash-induced components of the supplied raw materials to the maximum;
PH adjusting tank 400 for supplying a low temperature catalyst water to the reaction base;
Washing water storage tank 500 for supplying the washing water to the reaction base;
A raw material injection device 700 for injecting a raw material into the reaction base;
A metal ion separation device 600 for separating metal ions in dehydration discharged from the reaction body; And
An ESS 700 for supplying power to the system; Containing
Fuel production system that removes ash-induced components in low-temperature biomass linked with ESS.
The method of claim 1,
When the dehydration liquid passing through the metal ion separation device is less than a predetermined metal ion concentration, the fuel production system removing the ash-induced components in the biomass of low temperature conditions in conjunction with the ESS supplied to the pH adjustment tank.
The method of claim 1,
When the metal ion concentration of the washing liquid is more than a predetermined concentration is supplied to the metal ion separation device, when less than the fuel production system removing the ash-induced components in the biomass under low temperature conditions in conjunction with the ESS supplied to the wash water storage tank.
The method of claim 1,
Dehydration liquid containing metal ions that did not pass through the metal ion separation device is a fuel production system to remove the ash-induced components in the low-temperature biomass in conjunction with the ESS supplied by separating into a cation storage tank and an anion storage tank.
The method of claim 4, wherein
The ESS is a low temperature biomass in connection with a positive electrode composed of an oxide containing a metal ion of a cation storage tank, a negative electrode composed of a material capable of occluding and releasing the metal ion, and an ESS having a nonaqueous electrolyte containing the metal ion. Fuel production system free of ash-induced components.
The method of claim 5,
The metal ion is a fuel production system removing the ash-induced components in the biomass of low temperature conditions in connection with any one or two or more of alkali, alkaline earth metal.
The method of claim 6,
The metal ion is a fuel production system removing the ash-induced components in the biomass of low temperature conditions in connection with any one or two or more of lithium, sodium, potassium.
The method of claim 5,
The anode includes a KxMnO2 + y (0 <x <1, -0.1 <y <0.1) and the fuel production system to remove the ash-induced components in the biomass of low-temperature conditions in conjunction with the ESS.
The method of claim 5,
The negative electrode is a fuel production system removing the ash-induced components in the biomass of low temperature conditions in conjunction with the ESS containing carbon that can occlude and release potassium.
The method of claim 4, wherein
The ESS is a carbon material capable of occluding and releasing potassium,
Removed ash-induced components in low-temperature biomass in conjunction with ESS, a binder containing polycarboxylic acid and / or a salt thereof, and a potassium ion capacitor containing an anode for a potassium ion secondary battery or a cathode for a potassium ion capacitor. Fuel production system.
The method of claim 4, wherein
The ESS uses a ferric (VI) acid salt as an active material of the positive electrode and a potassium hydroxide and zinc oxide as an electrolyte in a battery composed of a positive electrode, a negative electrode containing zinc or zinc alloy powder and a gelling agent, and an alkaline electrolyte. Fuel production system that removes ash-induced components in biomass under low temperature conditions in connection with ESS, which is an alkaline battery using alkaline solution.

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