KR20190128503A - De-Ash in Biomass at Low-Temperature, Manufacturing Method and System of Fuel Production and Generation Connected with Reverse Electrodialysis - Google Patents

Abstract

The present invention relates to a production and power generation system of a boiler fuel obtained by removing an ash inducing component from fuel. More specifically, the present invention relates to a production and power generation system of an ash inducing component-removed fuel within a biomass of a low temperature condition connected with a RED (reverse electrodialysis) power generation apparatus, which removes, through physical and chemical methods, the ash inducing component having adverse effects such occurrence of fouling, slagging, high temperature corrosion, clinker or the like on a heating surface of a reactor wall surface, a heat exchanger or the like during operation of a boiler from a plant biomass, a wood-based biomass, or an algae biomass; allows a solid component to be used as solid fuel in single firing or multi fuel firing after the removal process; performs a water treatment process on liquid components including the ash inducing component by using methods including acid treatment, alkali treatment, hydrothermal treatment, membrane filtration, ion exchange, agglomeration, adsorption and centrifugation; and applies RED to dehydrated water including ionic components discharged after performing the water treatment process. The present invention can effectively and easily extract and separate an ash inducing component from plant or woody biomass.

Description

De-Ash in Biomass at Low-Temperature, Manufacturing Method and System of Fuel Production and Generation Connected with Reverse Electrodialysis}

The present invention relates to a fuel production and power generation system that removes ash-induced components in biomass under low temperature conditions in connection with RED, and more specifically, fouling, slag in 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 gingham, high temperature corrosion, and clinker formation, are removed by physical and chemical methods, and after removal, the solid phase components are used for burning or mixing with solid fuel. Liquid components containing components are ash-induced in biomass under low temperature conditions linked with RED applied by the method of water treatment using methods including acid treatment, alkali, hot water treatment, membrane filtration, ion exchange, flocculation, adsorption, and centrifugation. It relates to a fuel production and power generation system from which components are removed.

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 carbon dioxide emissions compared to conventional fossil fuels such as petroleum and coal, which can cope with global warming and climate change. Because it is an energy source.

With the depletion of fossil fuels and the reduction of greenhouse gases in response to the international agreement on climate change, the total amount of power generated by power generation companies (duties of supply mandates) with power generation facilities (excluding renewable energy facilities) of more than 500MW. Renewable Portfolio Standard (RPS) was introduced, which requires a certain percentage of the supply to be made by using renewable energy.For those who do not meet this mandatory supply, the reason for failure 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 power generation company produced and supplied electricity by using renewable energy facilities in order to supply and receive renewable energy, the supply manger can purchase the renewable energy supply certificate to cover the mandatory supply. Renewable Energy Certificate (REC) is applied to multiply the weight of renewable energy based on MWh supplied from the equipment 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 greenhouse gas emission reduction.

As a result, large coal-fired power plants have integrated coalification combined cycle (IGCC) and ultra-supercritical (Ultra) systems to link and improve power plants to reduce CO2 emissions. 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 is lowered 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 mixing is different, so that multi-stage combustion occurs in the existing power plant designed with coal as a target material, causing problems in the operation of the facility.

In addition, there is a problem in that clinker or fouling occurs by an inorganic component including a metal component included 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 cohesion between oil-based biomass and coal surface, coal and biomass each retain their existing combustion characteristics, resulting in different combustion characteristics. Therefore, when applied to the 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, 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 combustion furnaces, respectively. Ash agglomeration, and the like.

It is expected to wear due to the high temperature chlorine corrosion of the power plant tube, the change caused by the flow rate caused by the coke tube clogging phenomenon, the tube wear caused by the flow yarn of the fluidized bed combustor, and the 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, the worsening of these processes leads to the suspension of operations, which leads to enormous 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.

Japanese Laid-Open Patent Publication No. 2016-125030 discloses a solution obtained by dehydrating a plant by atomizing the plant, dipping 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. 11-240902, after extracting a water-soluble hemicellulose from an raw material including water-soluble hemicellulose into an aqueous medium at a temperature of 80 or more and 140 or less, under a condition 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, water 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 an extract purification method of hemicellulose, characterized in that

Korean Patent Registration No. 10-1557704 discloses a process for producing electricity with only brine and fresh water using RED, and discloses a observable concentration differential power generation experimental apparatus that can confirm that the actual electricity is produced. Doing.

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) 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.

In Korean Patent Publication No. 10-0872358, the sludge dewatering method by two-stage concentrated dehydration includes a first step of introducing wastewater containing sludge into the rotor through the inner space of the main shaft; A second step of rotating the screw shaft positioned in the rotor with a screw to concentrate the sludge and water in the first step by centrifugal force from the wastewater introduced in the first step; A third step of discharging the water separated in the second step through the inner space of the screw shaft and discharging the sludge into the space between the rotor and the wedge wire screen by the action of the concentrated screw; A fourth step of compressing and dehydrating by the rotor together with the wedge wire screen for rotating the sludge discharged in the third step; Disclosed is a dewatering method and apparatus according to the fifth step, wherein the sludge cake compressed and dewatered in the fourth step is discharged through the slide gate valve, and the water discharged to the wedge wire screen is discharged to the drain pipe.

However, in the conventional arts known to date, physicochemical treatment is applied to remove lignin from biomass and extract hemicellulose, which is mainly composed of glucose and xylose, but chemicals such as acid or alkali. In the case of using, the cost of chemicals increases and the process of recovering the used chemicals must be accompanied, which leads to a complicated process. In order to apply the separated components to the target raw materials, high purity and side reactions must be removed as much as possible. 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.

In addition, it is similar to the electrodialysis method in which an anion exchange membrane and a cation exchange membrane are alternately installed between the cathode and the anode, but, like the forward osmosis method, two streams are supplied to the system and two are discharged from the ion exchange membrane into seawater and river water. When filled, the voltage difference is generated by the salinity difference between the two, and electrons are transferred from the cathode to the anode by the movement of ions to produce electricity.Brauns team in Belgium and Hamelers team in the Netherlands are studying biomass dehydration. There is no research applied.

Therefore, in order to promote the utilization and dissemination of renewable energy and to secure supply stability of biomass fuel, biomass while maintaining the existing carbon-derived biomass components at the lowest temperature to fundamentally eliminate process problems caused by ash. There is an urgent need for the development of a fuel production system for boilers in which RED power generators are applied to effectively remove and separate fuel substances with low ash content by selectively removing only ash-induced components in the ash, and applying the RED concept to dehydration containing ionic components. have.

Japanese Laid-Open Patent Publication No. 2016-125030 Japanese Laid-Open Patent Publication No. 11-240902 Japanese Patent No. 2688509 Korean Patent Registration No. 10-1557704 Korean Patent Publication No. 10-0413384 Korean Patent Publication No. 10-0872358

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. Removed ash-induced components in biomass under low temperature conditions by linking RED generator with water treatment and dehydration including ionic components discharged by using methods including membrane filtration, ion exchange, flocculation, adsorption and centrifugation To provide a production and power generation system.

To this end, in the present invention, the reaction base body treated with a low temperature catalyst so as to separate the ash-induced components of the supplied raw material to the maximum; PH adjusting tank for supplying a low temperature catalyst water to the reaction base; Washing water storage tank for supplying the washing water to the reaction base; And a raw material injection device for injecting raw materials into the reaction base, wherein the dehydration flow passage through which the dehydration and / or wash water discharged from the reaction base passes; The dehydration flow path is moved between the cation flow path and the anion flow path through which the flow water flows, the RED generator for generating electricity by the potential difference due to the concentration difference between the dehydration and flow water; Fuel production and power generation systems without components.

In addition, the RED generator may include a cation exchange membrane formed between the cation flow path and the dehydration flow path and an anion exchange membrane formed between the anion flow path and the dehydration flow path.

The dewatering flow path and the front end of the RED generator may include a filter unit for removing particulate matter in the dewatering.

In addition, a cation electrode spaced apart from the cation exchange membrane may be disposed and an anion electrode spaced apart from the anion exchange membrane.

In addition, the dehydration supplied to the dehydration passage and the flow water supplied to the cation passage and the anion passage may be alternately supplied.

In addition, the dehydration supplied through the dehydration passage may be dehydration including the ash-derived component in the biomass.

In addition, the dehydration flow path and the flow water flow path may be formed by two or more flow path pairs, and the dehydration and flow water may be supplied in parallel, respectively.

In addition, the dehydration flow path and the flow water flow path may be formed by two or more flow path pairs, and the dehydration and flow water may be supplied in series, respectively.

In addition, the dehydration flow path and the flow water flow path may be formed by two or more flow path pairs, and the dehydration and flow water may be supplied in a honey comb structure, respectively.

In addition, dehydration and the flow water supplied to the RED power generation device may be supplied in a counterflow or parallel flow.

In addition, the mass ratio of the low temperature catalyst water and / or the wash water and the raw material supplied to the reaction base may be 1.05: 1 to 10: 1.

In addition, a metal ion separation device for separating the metal ions in the dewatered and / or flowing water discharged from the RED power generation device; may include.

In addition, the metal ion for use as a secondary battery material can be used.

According to the fuel production and power generation system removing the ash-induced components in the biomass under low temperature conditions in connection with the RED of the present invention, ash-induced components and the like are extracted from herbal or wood-based biomass through low-temperature reaction conditions of catalysts such as acids and alkalis. Effective and easy extraction and separation allows the selective acquisition of 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 present invention contributes to the simplification and cost reduction of the wastewater 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 and alkaline earth metals and halogen group elements included in the biomass, it can effectively reduce the clinker, fouling and alkali corrosion problems that may occur during operation of the combustion system when applied to the power generation fuel. .

In addition, the liquid component (sugar mainly containing xylose) is an important cause of mixing and mixing only less than 3.5wt% of biomass into an 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 can use the existing coal atomization equipment 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, there is an effect that can be produced by applying the RED using the concentration difference between the ion component and the flow water in the dewatering.

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

1 is a flow chart illustrating a fuel production system for a boiler removes ash-induced components linked to RED according to an embodiment of the present invention.
Figure 2 shows the changes in the composition of the raw material before and after the fuel production system for boilers removed ash-induced components linked to the dehydration washing process 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 remove the ash-induced components linked to the dehydration washing process 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 dehydration washing process 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 remove the ash-induced components linked to the dehydration washing process 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 boilers removed ash-induced components linked to the dehydration washing process 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 the boiler remove the ash-induced components linked to the dehydration washing process 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 remove the ash-induced components linked to the dehydration washing process according to an embodiment of the present invention.
Figure 9 shows the ash removal rate according to the residence time change in the acid solution treatment conditions of the boiler fuel production system to remove the ash-induced components linked to the dehydration washing process according to an embodiment of the present invention.
Figure 10 shows a biomass SEM picture before and after the fuel production system for boilers removed ash-induced components linked to the dehydration washing process 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 a flowchart illustrating an operation 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.
FIG. 13 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.
14 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 linked to the dehydration washing process according to an embodiment of the present invention through the cation exchange resin column; to be.
15 is an anion concentration result of the mixed bio solution discharged from the dehydration unit of the fuel production system for the boiler remove the ash-induced components linked to the dehydration washing process according to an embodiment of the present invention through the anion exchange resin column to be.
FIG. 16 illustrates BTW with a low temperature catalyst added per unit feedstock according to an embodiment of the present invention.
17 shows a conceptual diagram of a RED-linked fuel production and power generation system according to an embodiment of the present invention.
18 is a diagram illustrating a RED configuration of a RED-linked fuel production and power generation system according to an embodiment of the present invention.

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

In addition, the fuel used in the present invention means any one or more selected from 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. Woods include wood blocks, wood chips, logs, tree branches, wood chips, leaves, 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. may 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 corn, potatoes, cassava, wheat, barley, lymil, other starch-based processed residues, fruit avocados, jatropha, and processed residues thereof, 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 dehydration washing process according to the present invention.

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

Reaction base 100 for treating with a low temperature catalyst so as to separate the ash-induced components of the supplied raw material 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 linked to the dehydration washing process including a; and a raw material injection device 700 for injecting the raw material to the reaction base.

The reactor body may include a reactor heat insulating material (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], 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 main body may include a reaction warmer 130 for temperature control. It is obvious that the type of the reaction warmer is not limited as long as it 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 condition is exceeded, a temperature increase effect cannot be obtained.

Additionally, the vent for maintaining the internal pressure condition of the reaction base may be performed 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 be formed with a first high-pressure gas injection unit for supplying to the dehydration place, and a second high-pressure gas injection unit may be formed at 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 adjustment 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 adjusting 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 condition is exceeded, a temperature increase effect cannot be obtained.

The pH adjustment 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], 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.

A treatment water supply unit 410 may be formed to additionally supply water to the pH adjustment tank.

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

A 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 part 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 washing 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 silver 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, bending, and can be used 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, a disk crusher may be any one.

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 component is 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-induced component 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 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 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 condition 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.

FIG. 16 illustrates BTW with a low temperature catalyst added per unit feedstock according to an embodiment of the present invention.

The amount of cold catalyst added per unit feedstock depends on the type of biomass and may be defined as BTW (Biomass to Water, kg / kg). Preferably, for each biomass, silver grass is 0.05 to 0.2, preferably 0.11 to 0.13, more preferably 0.125, kenaf is 0.05 to 0.2, preferably 0.14 to 0.18, more preferably 0.1667, corn cob 0.05 to 0.2, preferably 0.11 to 0.13, more preferably 0.125, Napier glass is 0.05 to 0.2, preferably 0.14 to 0.18, more preferably 0.1667, EFB is 0.1 to 0.4, preferably 0.15 to 0.25 , More preferably 0.2, PKS is 0.3 to 0.9, preferably 0.45 to 0.75, more preferably 0.6667, the cashew nut shell is 0.3 to 0.9, preferably 0.45 to 0.75, more preferably 0.5, coffee husk 0.2 to 0.6, preferably 0.35 to 0.45, more preferably 0.4, wood pellets are 0.05 to 0.2, preferably 0.14 to 0.18, more preferably 0.1667, pine is 0.1 to 0.4, preferably Crab can be from 0.15 to 0.25, more preferably 0.2, woody byproducts can be from 0.1 to 0.4, preferably from 0.15 to 0.25, more preferably from 0.2, very preferably up to ± 10% for each biomass May be acceptable.

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 acidic 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 body.

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 an inorganic substance.

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 combustible component may be composed of carbon, hydrogen, nitrogen, oxygen, sulfur components 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 component decreases.

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. The organic acid may include acetic acid, formic acid, levulinic acid, 5-HMF, furfural, propanoic acid, 4-hydroxy-butanoic acid, 2-butenoic acid, and the like. The organic acid may be in the form of one or more mixed with each other. Preferably, the concentration of the organic acid to maintain pH 3.11 may be 10 wt% of formic acid, 43.81 wt% of acetic acid, 4.58 wt% of levulinic acid, 0.91 wt% of 5-HMF, and 40.04 wt% of furfural. More preferably, the concentration of the corresponding organic acid comprises a form mixed with water to maintain pH 3.11.

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

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

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

In order to remove the organic compound in the liquid component, any one or more of centrifugation, aggregation, adsorption, filtration membrane, ion exchange resin may be applied.

The solid phase component of the raw material discharged after the reaction from the reaction base may be an organic compound. The combustible component may be composed of carbon, hydrogen, nitrogen, oxygen, sulfur components 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 component decreases.

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 apparatus 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 components 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 ends of the membrane filter unit. Hemicellulose in the liquid component can be used as a substitute for dietary fiber by purification.

It may further include a filter unit for removing the particulate matter in the dehydration.

The filter unit may be composed of one or more of a nonwoven fabric, glass fiber, micro filter, ultra filter, nano filter.

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 refers to herbal, wood-based biomass based on lignocellulosic, and is not limited if the material belongs to the biomass. It is also apparent that the first generation or third generation biomass can also be applied.

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 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, 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-methylimidazolium tetrafluoroborate, 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 one 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 ~ 150atm, preferably 1 ~ 100atm may be more preferably 1 ~ 50atm. The reaction base may be changed in pressure conditions depending on the raw material.

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

Such ash-induced fuels can be used in fluidized beds, grates, micronized boilers and gasifiers, and blockages such as clinker fouling due to inorganic components including metal elements in the fuel during combustion and gasification, and alkali systems. 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 the 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 is 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 capable of selectively separating 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.

The membrane may be any one or two or more of a nanofiltration membrane, a reverse osmosis membrane capable of separating the cation and / or anionic substances contained in the dehydration.

(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, Fill with 346g) of anion exchange resin and fill it with glass wool again.

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

The residence time of the solution in the column according to the pumping speed is shown in Figure 13. 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. 14. The mixed bio solution discharged from the dehydration unit shows the change in concentration of K ⁺ , Na ⁺ and Mg ²⁺ cations over time passing through the cation exchange resin column, and for K ⁺ ions, 3 minutes at the initial concentration of 457.092 ppm The concentration sharply decreased to 6.474ppm afterwards, and after 6.8 minutes, it showed 6.833ppm and gradually decreased to 55809ppm at 55min. In the case of Mg ²⁺ ion, the concentration sharply decreased to 1.636ppm after 3 minutes at the initial concentration of 57.114ppm, followed by 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. It can be seen that K ⁺ and Mg ²⁺ ions are removed most of the ions after 3 minutes through the cation exchange resin column.

The separation results according to the time of anion considering the solution residence time in the column according to the pumping speed are shown in Figure 15. The metal ion concentration of the dehydration liquid discharged from the metal ion separator was analyzed by ICP.

Cl ^- if of the ion, the concentration was in a concentration of 3 minutes after the initial 183.18ppm 1051.60ppm rapidly decreased, showing 169.07ppm after 9 minutes, and showed an almost constant value of 22 minutes after 147.85ppm Cl ^- anion is an anion exchange 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 ⁻ ions for about 1 hour in the anion exchange resin was 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 1000 mm. Preferably it may be 10 μm to 100 mm, more preferably 10 μm to 10 mm. Deviation from the above conditions may reduce the efficiency of metal ion separation in the raw material.

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

It is apparent that the wastewater treatment unit may include an ion exchange resin, a separator, agglomeration, adsorption, and the like. Ionic materials removed and removed from the harvested wastewater treatment unit may be landfilled or incinerated through 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 (e.g., 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 liquid 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 treated 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 acetic acid aqueous solution (the ratio of the treatment solution and acetic acid is 1: 1).

The treatment solution 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, fuel cells, and supercapacitors.

Preferably, the ESS (Energy Storage System) system using the separated metal ions in conjunction with a fuel production system in which ash-induced components are removed from the biomass under low temperature conditions in connection with a dehydration washing process may be configured.

The ESS system may be any one or more of secondary batteries, fuel cells, supercapacitors, and flow batteries.

Preferably it may be a power generation device using the potential difference of the ion solution.

More preferably, it may be a RED generator.

In particular, aliphatic hydrocarbons such as hexane and an aqueous solvent such as pure water, fresh water, brackish water, brine, or a mixed medium of alcohol and water as the flowing water; Aromatic hydrocarbons such as benzene, toluene, xylene and methylnaphthalene; Heterocyclic compounds such as quinoline and pyridine; ketones such as acetone, methyl ethyl ketone and cyclohexanone; Esters such as methyl acetate and methyl acrylate; Amines such as diethylenetriamine and N, N-dimethylaminopropylamine; Ethers such as diethyl ether, propylene oxide and tetrahydrofuran (THF): amides such as N-methylpyrrolidone (NMP), dimethylformamide and dimethylacetamide; It is possible to use one or more selected from organic solvents such as aprotic polar solvents such as hexamethylphosphalamide and dimethyl sulfoxide.

The fluid is a water-soluble electrolyte solution such as NaCl, H ₂ SO ₄ , HCl, NaOH, KOH, Na ₂ NO ₃ , Propylene Carbonate (PC), Diethyl Carbonate (DEC), Tetrahydrofuran (Tetrahydrofuran) And an organic electrolyte solution such as THF).

The cation electrode and the anion electrode, the cation exchange membrane and the anion exchange membrane may be any of those that have been used in the conventional fluidized bed electrode system (battery, storage battery, etc.), and those skilled in the art It can be selected according to the purpose of use and conditions.

In the RED generator, a space formed between a cation electrode and an anion electrode is divided by a cation exchange membrane and an anion exchange membrane. That is, the power generation apparatus includes a cation flow path between the cation exchange membrane and the cation electrode, an anion flow path between the anion exchange membrane and the anion electrode, and a dehydration flow path between the cation exchange membrane and the anion exchange membrane.

In addition, the RED generator is connected to a measuring instrument for measuring electrical energy, it is possible to measure the potential difference generated in the ion generator cell of the RED generator by the current concentration difference.

Therefore, if the RED generator is sent to a relatively high concentration of dehydration and a relatively low concentration of flow water, cations and anions are moved through the cation exchange membrane and the anion exchange membrane to the cation electrode and the anion electrode, respectively, through which the low concentration fluid flows. However, the potential difference is caused by the transferred cations and anions.

On the contrary, when the RED generator has a relatively low concentration of dehydration and a relatively high concentration of flowing water, cations and anions are moved from the high concentration cation channel and the anion channel to the absorbent side through the cation exchange membrane and the anion exchange membrane, respectively. As a result, a potential difference occurs.

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 boilers removed ash component according to an embodiment of the present invention.

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

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 ℃, has a removal efficiency of more than 99%, and Na ₂ O having a melting point of 1,132 ℃ has a removal efficiency of 95%. As such, by removing the ash-inducing 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 boilers removed ash ash component 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. 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 region of pH 13.3 ~ 13.4, 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 fuel production system for boilers removed ash ash component according to an embodiment of the present invention.

FIG. 5 considers the influence of temperature in a 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 of 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 over 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 acidic liquid treatment conditions of the fuel production system for boilers removed ash ash 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. 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. Therefore, ash extraction should be made in the pH 1.7 to 1.8 range, which is 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 it can be seen that 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 induction component according to an embodiment of the present invention.

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 the boiler remove the ash-induced components according to an embodiment of the present invention.

FIG. 10 compares the surface structure changes of SEM samples of untreated raw samples (pampulae) and pampas grass samples from which ash-induced components are removed. 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.

FIG. 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 the fuel production system removing the ash-induced components in the biomass of low temperature conditions associated with the dehydration washing process.

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. Thereafter, 2. The biomass raw material is 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. The press of the dehydration device can be moved to the reaction base under 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. After the washing water from the wash water storage tank may be added to the reaction base to wash the biomass. 9. After the process of 4. to 7. may be repeated. 10. After the dehydration and transfer device moves down, the biomass raw material may be discharged and transferred to the fuel processor 800 through the fuel transfer device 810.

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: wash 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: cation water storage tank
640: dewatering pump
650: metal ion sensor
700: raw material injection device
800: fuel processor
810: fuel feeder
900: RED generator
901 dehydration / washing liquid
902: dehydration euro
903: Flowing water
904a: cation flow path
904b: anion flow path
905 cation exchange membrane
906: anion exchange membrane
907 cation electrode
908: anion electrode
909: regenerated catalyst water
910 deionized liquid
911: filter unit
912: flow channel
1000: ESS

Claims (13)

Reaction base body treated with a low temperature catalyst so as to separate the ash-induced components of the supplied raw material to the maximum;
PH adjusting tank for supplying a low temperature catalyst water to the reaction base;
Washing water storage tank for supplying the washing water to the reaction base; And
Includes; raw material injection device for injecting the raw material into the reaction base,
A dehydration passage through which dehydration and / or washing water are discharged from the reaction base;
The dehydration flow path is moved between the cation flow path and the anion flow path through which the flow water moves,
And a RED generator for generating electricity with a potential difference due to a difference in concentration between the dehydration and the flow of water. Fuel production and power generation system removing ash-induced components in biomass under low temperature conditions in conjunction with RED.
The method of claim 1,
The RED generator is a fuel production and removal of the ash-induced components in the low-temperature biomass in conjunction with the RED including a cation exchange membrane formed between the cation flow path and the dehydration flow path and an anion exchange membrane formed between the anion flow path and the dehydration flow path and Power generation system.
The method of claim 1,
And a filter unit for removing particulate matter in the dehydration in front of the dehydration flow path and the RED generator. The fuel production and power generation system of removing ash-induced components in biomass under low temperature conditions in conjunction with RED.
The method of claim 2,
A fuel production and power generation system removing ash-induced components in biomass at low temperature in connection with a RED comprising a cation electrode spaced apart from the cation exchange membrane and an anion electrode spaced apart from the anion exchange membrane.
The method of claim 1,
And the dehydration supplied to the dehydration flow path and the flow water supplied to the cation flow path and the anion flow path remove ash ash generation components in biomass under low temperature conditions in connection with RED which may be alternately supplied.
The method of claim 1,
The dehydration supplied through the dehydration flow path is a fuel production and power generation system removing the ash-induced components in the biomass of low-temperature conditions in conjunction with RED, which is a dehydration including the ash-induced components in the biomass.
The method of claim 1,
The dewatering flow path and the flowing water flow path may be formed by two or more flow path pairs, the fuel production and power generation system to remove the ash-induced components in the low-temperature biomass associated with the RED supplied in parallel with the dehydration and the flow water, respectively.
The method of claim 5,
The dewatering flow path and the flowing water flow path may be formed of two or more flow path pairs, the fuel production and power generation system to remove the ash-induced components in the low-temperature biomass associated with the RED supplied in series with the dewatering and the flowing water, respectively.
The method of claim 1,
The dehydration flow path and the flow water flow path may be formed by two or more flow path pairs, and the fuel production and power generation system removing the ash-induced components in the biomass under low temperature conditions in connection with the RED supplied with the dehydration and flow water in a honey comb structure, respectively. .
The method of claim 1,
The dehydration and the flow water supplied to the RED power generation device is a fuel production and power generation system removing the ash-induced components in the biomass of low temperature conditions in connection with the RED supplied in the counter flow or parallel flow.
The method of claim 1,
And a mass ratio of the low temperature catalyst water and / or the wash water and the raw material to be supplied to the reaction base is 1.05: 1 to 10: 1.
The method of claim 1,
And a metal ion separation device for separating metal ions in the dewatered and / or flowed water discharged from the RED generator. The fuel production and power generation system removing ash-induced components in biomass under low temperature conditions in connection with RED.
The method of claim 12,
A fuel production and power generation system that removes ash-induced components in biomass under low temperature conditions in connection with RED using the metal ions for use as secondary battery materials.

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