阅读说明：本技术 结合脱水洗涤工艺的低温条件下去除生物质内产灰成分的燃料生产系统 (Fuel production system for removing ash-producing components in biomass under low-temperature condition combined with dehydration washing process ) 是由 崔荣燦 金正根 李动昱 崔钟元 朴世埈 南宫煊 李泳周 朴柱炯 宋奎涉 于 2018-04-06 设计创作，主要内容包括：本发明涉及用于从燃料中去除产灰成分的锅炉用燃料生产系统,更具体涉及从草本类、木质类、藻类生物质中,通过物理、化学方法来去除在锅炉运行时对反应器壁面、热交换器等传热面引起结垢、结渣、高温腐蚀、炉渣的产生等不良影响的产灰成分,将去除后的固相成分作为固体燃料应用于单燃或者共燃中,并且对含有产灰成分的液相成分应用了利用包括酸处理、碱处理、热水处理、膜过滤、离子交换、凝聚、吸附、离心分离的方法来进行水处理的去除产灰成分的锅炉用燃料生产系统。(The present invention relates to a fuel production system for a boiler for removing ash-producing components from fuel, and more particularly, to a fuel production system for a boiler for removing ash-producing components from herbaceous, woody, and algal biomass by physically and chemically removing ash-producing components that cause adverse effects such as scaling, slagging, high-temperature corrosion, and slag generation on heat transfer surfaces such as reactor wall surfaces and heat exchangers during boiler operation, applying the removed solid-phase components as solid fuel to single combustion or co-combustion, and applying water treatment using methods including acid treatment, alkali treatment, hot water treatment, membrane filtration, ion exchange, coagulation, adsorption, and centrifugal separation to liquid-phase components containing the ash-producing components.)

1. A fuel production system for removing ash-producing components in biomass in combination with a low-temperature condition of a dehydration washing process, comprising:

a reactor body (100) for treating the supplied raw material with a low-temperature catalyst so as to maximally separate an ash-producing component from the raw material;

a pH adjustment tank (400) for supplying a low-temperature catalyst liquid to the reactor body;

a washing water storage tank (500) for supplying washing water to the reactor body; and

a raw material injection device (700) for injecting raw material into the reactor body.

2. The fuel production system for removing ash components in biomass in combination with low temperature conditions of a dehydration washing process according to claim 1,

the reactor body includes:

a dehydration press (200) for pressing the raw material after the reaction;

a transfer press (300) for transferring the pressurized raw material.

3. The fuel production system for removing ash components in biomass in combination with low temperature conditions of a dehydration washing process according to claim 2,

comprises a metal ion separation device (600), wherein the metal ion separation device (600) is used for separating metal ions in the dehydration liquid discharged from the reactor body.

4. The fuel production system for removing ash components in biomass in combination with low temperature conditions of dehydration washing process according to claim 3,

when the supplied low-temperature catalyst liquid and/or the supplied washing water meet the specified reaction conditions with the raw material, the reactor body is subjected to gas explosion stirring operation.

5. The fuel production system for removing ash components in biomass in combination with low temperature conditions of dehydration washing process according to claim 3,

when the reaction completion conditions are satisfied, the reactor body performs primary dehydration for separating the raw material and the dehydration solution by the dehydration press.

6. The fuel production system for removing ash components in biomass in combination with low temperature conditions of dehydration washing process according to claim 5,

and carrying out aeration stirring washing on the raw material from which the dehydration liquid is separated.

7. The fuel production system for removing ash components in biomass in combination with low temperature conditions of dehydration washing process according to claim 6,

performing a secondary dehydration for separating the washed raw material and the washing liquid.

8. The fuel production system for removing ash components in biomass in combination with low temperature conditions of dehydration washing process according to claim 5,

when the dehydrated liquid having passed through the metal ion separation device is at a predetermined metal ion concentration or less, the dehydrated liquid is supplied to the pH adjustment tank.

9. The fuel production system for removing ash components in biomass in combination with low temperature conditions of dehydration washing process according to claim 7,

the washing water is supplied to the metal ion separation device when the metal ion concentration of the washing water is equal to or higher than a predetermined concentration, and is supplied to the washing water storage tank when the metal ion concentration of the washing water is lower than the predetermined concentration.

10. The fuel production system for removing ash components in biomass in combination with low temperature conditions of dehydration washing process according to claim 4,

the mass ratio of the low-temperature catalyst liquid and/or the washing water supplied to the reactor body to the raw material is 1.05: 1 to 10: 1.

11. the fuel production system for removing ash components in biomass in combination with low temperature conditions of dehydration washing process according to claim 3,

the metal ion separation device separates an ion component by using an ion exchange resin and/or a membrane.

12. The fuel production system for removing ash components in biomass in combination with low temperature conditions of dehydration washing process according to claim 8,

the dehydrated liquid can be supplied to an organic acid storage tank for generating an organic acid before being supplied to the pH adjustment tank.

13. The fuel production system for removing ash components in biomass in combination with low temperature conditions of dehydration washing process according to claim 7,

the feedstock is transferred to a fuel processing apparatus (800) by the transfer press.

14. The fuel production system for removing ash components in biomass in combination with low temperature conditions of dehydration washing process according to claim 8,

the dehydrated liquid containing the metal ions that have failed to pass through the metal ion separation device is separated and supplied to a cation storage tank and an anion storage tank.

15. The fuel production system for removing ash components in biomass in combination with low temperature conditions of dehydration washing process according to claim 7,

the water content of the raw material subjected to the secondary dehydration is less than 15%.

16. The fuel production system for removing ash components in biomass in combination with low temperature conditions of dehydration washing process according to claim 3,

includes an energy storage system (900) that utilizes the separated metal ions.

17. A fuel production system for removing ash-producing components from biomass at low temperatures, comprising:

a pulverization unit (1000) for forming biomass into a raw material of a predetermined size;

a hopper (2000) for storing the raw material;

a raw material feeder (2100) for quantitatively supplying the raw material stored in the hopper to a rear end;

a first separation unit (3000) for treating the raw material supplied from the raw material feeder with a low temperature lye and/or acid liquid in order to separate the ash-producing components from the raw material to the maximum extent.

18. The fuel production system for removing ash-producing components from biomass under cryogenic conditions according to claim 17,

comprises a second separation unit (4000), wherein the second separation unit (4000) treats the raw material treated by the first separation unit by using low-temperature alkali liquor and/or acid solution.

19. The fuel production system for removing ash-producing components from biomass under cryogenic conditions according to claim 18,

the device comprises an ion separation unit (5000), and the ion separation unit (5000) is used for separating the ion components of the low-temperature alkaline waste liquid and/or the low-temperature acidic waste liquid discharged from the first separation unit and the second separation unit.

20. The fuel production system for removing ash-producing components from biomass under cryogenic conditions according to claim 18,

the low temperature conditions of the first and second separation units are below 100 in order to eliminate the latent heat of vaporization loss of water.

21. The fuel production system for removing ash-producing components from biomass under cryogenic conditions according to claim 18,

the low temperature conditions of the first and second separation units are 40 to 80 in order to eliminate the latent heat of vaporization loss of water.

22. The fuel production system for removing ash-producing components from biomass under cryogenic conditions according to claim 17,

the acidic solution supplied to the first and second separation units uses organic acids generated by a separate biomass soaking (solaking) process.

23. The fuel production system for removing ash-producing components from biomass under the low-temperature condition according to claim 17 or 18,

the lye supplied to the first and second separation units was 1% by weight sodium hydroxide.

24. The fuel production system for removing ash-producing components from biomass under the low-temperature condition according to claim 17 or 18,

the acidic liquid supplied to the first and second separation units was 50 wt% acetic acid.

25. The fuel production system for removing ash-producing components from biomass under the low-temperature condition according to claim 17 or 18,

the reaction time of the first separation unit and the second separation unit is 1 minute to 5 hours.

26. The fuel production system for removing ash-producing components from biomass under the low-temperature condition according to claim 17 or 18,

the acid to water mass ratio in the acidic liquid supplied to the first and second separation units is 15 to 4.

27. The fuel production system for removing ash-producing components from biomass under cryogenic conditions according to claim 19,

the wastewater treatment unit utilizes ion exchange resins and/or membranes to separate ionic components.

28. The fuel production system for removing ash-producing components from biomass under cryogenic conditions according to claim 19,

comprises a water treatment unit for satisfying a prescribed treatment condition so as to supply the treatment liquid supplied by the first separation unit and/or the second separation unit to the wastewater treatment unit.

29. The fuel production system for removing ash-producing components from biomass under cryogenic conditions according to claim 27,

the alkaline or acidic waste liquid from which the ionic component is separated in the wastewater treatment unit is recycled to the first separation unit and/or the second separation unit.

30. The fuel production system for removing ash-producing components from biomass under cryogenic conditions according to claim 17,

the particle size of the biomass is 10 mu m-10 mm.

31. The fuel production system for removing ash-producing components from biomass under cryogenic conditions according to claim 29,

the rear end of the wastewater treatment unit further comprises a discharge unit.

Technical Field

The present invention relates to a fuel production system for a boiler for removing ash-producing components from fuel, and more particularly, to a fuel production system for a boiler, which physically and chemically removes ash-producing components from herbaceous, woody and algal biomass, which have adverse effects such as scaling (fouling), slagging (slagging), high-temperature corrosion, and slag (clinker) on a reactor wall surface, a heat exchanger, and the like during operation of the boiler, applies the removed solid-phase components as solid fuel to single combustion or co-combustion, and applies the ash-producing components in the biomass to liquid-phase components containing the ash-producing components under low-temperature conditions combined with a dehydration washing process using a method including acid treatment, alkali treatment, hot water treatment, membrane filtration, ion exchange, coagulation, adsorption, and centrifugal separation for water treatment.

Background

Fossil fuel-based energy is the main cause of the greatest production of carbon dioxide and is the least competitive energy for global warming issues. Therefore, the utilization and popularization of renewable energy sources become the world focus of energy resources at present. The main reason is that the carbon dioxide emission is reduced compared to the existing fossil fuels such as petroleum and coal, and the energy resource is capable of responding to global warming and climate change.

With the exhaustion of fossil fuels in China and the demand for greenhouse gas emission reduction under the climate change protocol, which is an international treaty, a power plant (supply obligator) having power generation equipment (excluding Renewable energy equipment) of a prescribed size (500MW) or more is established with a Renewable energy obligation system (RPS) for generating power using Renewable energy at a prescribed rate of total power generation, and the law stipulates that fines can be made for the obligation supply amount portion that is not executed, taking account of reasons for non-execution, the number of times of non-execution, and the like, within 150% of the average transaction price of supply certificates.

Accordingly, in order to supply Renewable Energy and obtain certification, as a Certificate for certifying that a power plant produces and supplies electricity using Renewable Energy equipment, a supply obligator may purchase a Renewable Energy supply Certificate as an obligation supply amount, and give the Renewable Energy supply Certificate (REC) to supply MHh-based Renewable Energy electricity to equipment to which the supply Certificate is issued multiplied by a weighted value, and the effect on environment, technical development, and industrial activation, power generation cost, resource potential amount, and greenhouse gas emission reduction, etc. are considered in the weighted value of Renewable Energy, and the government makes a review and review every three years.

Therefore, in order to meet the obligatory proportion of renewable energy supply, large coal-fired power plants have been implemented with Integrated Gasification Combined Cycle (IGCC), Ultra Supercritical (USC) technology, CO, and the like as a scheme for connecting and improving power plants for reducing carbon dioxide emission of coal₂Clean Coal Technology (CCT) such as capture and storage Technology, biomass (bio-mass) co-combustion, and the like, but there are still many problems to be fundamentally solved and portions to be improved.

In particular, when biomass is co-fired, there is a problem that power generation efficiency is reduced by burning biomass having a lower calorific value than that of coal.

Further, since the combustion characteristics of biomass and coal charged for co-combustion are different, multi-stage combustion occurs in a conventional power plant designed using coal as a target raw material, which causes a problem in plant operation.

Further, there is a problem of scaling or slag formation due to metal components contained in inorganic components in the biomass. In order to solve these problems, a development of a mixed fuel technology using a mixed oil biomass in coal has been made in the past. In such a fuel simply mixed with coal and oil biomass, oil is generally coated on the surface of coal or oil is impregnated into pores. But because of the low surface tension of the oil itself and the lack of binding force of the oil biomass and the coal surface, the coal and the oil biomass each maintain inherent combustion characteristics, and as a result, exhibit different combustion characteristics. Therefore, in the case of a power plant, oxygen is consumed in excess in the front end of the combustor due to the low-temperature combustion law of oil, so that the amount of unburnt carbon (unburnt carbon) is increased to hinder the combustion of coal, and the power generation efficiency is lowered.

Typical coagulation phenomena of biomass ash include slag (slagging), slag (clinker), and fouling (fouling) occurring on the radiant surface and convection surface of each furnace in a pulverized coal furnace, and coagulation (agglomeration) of ash in a fluidized bed furnace.

High-temperature chlorine corrosion of a superheated steam pipe of a power plant may occur, abrasion may occur due to a change in flow rate of an economizer pipe plugging phenomenon, pipe abrasion may occur due to flowing sand of a fluidized bed combustor, mechanical abrasion of a soot blower, and if inorganic components of potassium and chlorine in fuel components are chemically combined to generate KCl during combustion, the KCl (melting temperature 776 ℃) is considered to accelerate corrosion due to chlorine reaction and the like because the KCl is a substance having a strong viscosity and is easily stuck.

If such a phenomenon occurs in the combustion furnace, not only is the main cause of the reduction in the process efficiency, but also if such a phenomenon progresses, the operation is eventually stopped, and thus a significant economic loss occurs. The ash agglomeration phenomenon is generally affected by ash (ash) composition, temperature, particle size, gas environment, operating conditions, etc., and particularly, if a portion of the ash is melted at high temperature, the phenomenon is accelerated.

In order to cope with the above problems, a plurality of known documents were investigated as follows.

Japanese laid-open patent publication No. 2016-125030 discloses a method for modifying a plant biofuel, which comprises micronizing a plant, immersing the plant in normal pressure water, dehydrating the plant immersed in normal pressure water, using the dehydrated plant as a fuel, and using the dehydrated solution as a fertilizer.

Japanese laid-open patent publication No. 11-240902 discloses a method for producing water-soluble hemicellulose, which is characterized by extracting water-soluble hemicellulose from a hemicellulose-containing raw material with an aqueous medium at a temperature of 80 to 140 ℃ and a pH of 2 to 7, concentrating the extract to 1.5 times or more, and removing insoluble substances.

Japanese patent No. 2688509 discloses a method for extracting and purifying hemicellulose, which comprises removing water-soluble substances from wheat residues by washing with water, treating the residues with 0.1-0.4 aqueous alkali solution to dissolve the major component of hemicellulose in the aqueous alkali solution, and purifying the solution with a membrane and an ion exchange resin.

Korean granted patent No. 10-0476239 discloses a method for producing water-soluble and insoluble hemicellulose from rice hulls. The manufacturing method mainly comprises the following steps. (1) Removing protein from rice hulls and washing the rice hulls; (2) extracting and filtering the rice hull with 0.5-1M sodium hydroxide solution; (3) adding phosphoric acid to the alkali extract obtained in the step (2) to lower the pH, and precipitating and recovering hemicellulose; (4) a decolorization step of washing the precipitate obtained in the step (3) with phosphoric acid or oxalyl followed by treatment with oxalate-potassium permanganate (oxalate-potassium permanganate); (5) a step of selectively separating water-soluble and insoluble hemicellulose from the decolorized hemicellulose obtained in the previous step by adjusting the pH of the solution, and recovering the water-soluble hemicellulose by adding phosphoric acid for precipitation or by adding calcium to convert the water-soluble hemicellulose into insoluble substances; (6) and a step of obtaining a fine powder from the water-soluble and insoluble hemicellulose obtained by the series of continuous steps by natural drying or spray drying, and then grinding the powder and passing the ground powder through a sieve having a predetermined size.

Korean patent laid-open publication No. 10-0413384 discloses a method for producing water-soluble dietary fibers. Mainly comprises the following procedures. (i) Removing starch and protein from corn bran; (ii) extracting corn bran from which starch and protein are removed with alkali liquor, and then filtering with filter cloth; (iii) (iii) treating the alkaline extract obtained in step (ii) with cellulase and cellobiase to carry out a reaction; (iv) (iv) treating the liquid enzyme reaction mixture obtained in the step (iii) with an adsorbent, and filtering the treated liquid enzyme reaction mixture through a membrane to obtain a filtrate; (v) and a step of purifying the filtrate.

Korean patent publication No. 10-1457470 discloses a paper making method for improving paper strength. The method comprises the following steps. a) A stage of extracting hemicelluloses from the biomass; b) a step of separating hemicellulose from the hemicellulose extract by precipitation; and c) feeding the separated hemicellulose into a paper making process stage.

Korean patent publication No. 10-0872358 discloses a dehydration method and apparatus using two-stage concentration dehydration. Mainly comprises the following steps. A first stage of throwing the waste water mixed with the sludge into the rotator through the inner space of the main shaft; a second stage of first concentration and separation in which the wastewater flowing from the first stage is separated into sludge and water by centrifugal force by a rotary shaft; a third stage of discharging the water separated from the second stage through the internal space of the rotary bearing, and discharging the sludge to the space between the rotor and the wedge-shaped silk screen by utilizing the concentration and rotation action; a fourth stage of compressing and dewatering the sludge discharged from the third stage by using a wedge-shaped wire mesh and a rotor; and a fifth stage of discharging the sludge cake obtained by compression dehydration in the fourth stage to a drain pipe through a slide valve and discharging the water discharged through the wedge-shaped wire mesh.

In the prior art, in order to remove lignin from biomass, a physicochemical treatment method is used to extract cellulose whose main component is glucose (glucose) and hemicellulose whose main component is xylose (xylose), but when chemicals such as acid or alkali are used, not only the cost of chemicals increases, but also a process for recovering the chemicals used is required, which results in a problem of complicated process. In order to utilize the separated components in the target raw materials, it is necessary to improve the purity and to separate the side reaction substances to the maximum extent. And the treatment at a high temperature of 100 ℃ or higher is required, which is disadvantageous in that energy costs are high.

Therefore, in order to promote the utilization and spread of new renewable energy and to ensure the supply stability of biomass fuel, it is urgently required to develop a technology related to a fuel production system for a boiler, which combines a dehydration and washing process, maintains the existing carbon source biomass components as much as possible under a low temperature condition for fundamentally eliminating process problems caused by ash, and selectively removes only ash-producing components within biomass, thereby efficiently extracting and separating fuel substances having a low ash content, and then uses the fuel substances.

Disclosure of Invention

Technical problem

The present invention has been made to solve the above problems, and an object of the present invention is to provide a fuel production system for a boiler, which removes ash-producing components in biomass under low temperature conditions in combination with a dehydration washing process, wherein ash-producing components that cause adverse effects such as scaling (fouling), slagging (slagging), high-temperature corrosion, and slag (clinker) on a reactor wall surface, a heat transfer surface such as a heat exchanger during operation of the boiler are physically and chemically removed from algal biomass of herbaceous and woody algae, the removed solid-phase components are used as solid fuel in single combustion or co-combustion, and a water treatment method using processes including acid treatment, alkali treatment, hot water treatment, membrane filtration, ion exchange, coagulation, adsorption, and centrifugal separation is applied to a liquid-phase component containing the ash-producing components.

Technical scheme

To this end, the present invention may provide a fuel production system for removing ash components in biomass in combination with a low temperature condition of a dehydration washing process, comprising: a reactor body 100 for treating the supplied raw material with a low-temperature catalyst so as to maximally separate an ash-producing component from the raw material; a pH adjusting tank 400 for supplying a low-temperature catalyst solution to the reactor body; a washing water storage tank 500 for supplying washing water to the reactor body; and a raw material injection device 700 for injecting raw materials into the reactor body.

In addition, the reactor body may include: a dehydration press 200 for pressing the reacted raw material; the transfer press 300 transfers the pressurized raw material.

In addition, a metal ion separating device 600 may be included, the metal ion separating device 600 separating metal ions in the dehydrated liquid discharged from the reactor body.

In addition, when the supplied low-temperature catalyst liquid and/or the washing water satisfy the predetermined reaction conditions with the raw material, the reactor body may perform an explosion stirring operation.

Further, the reactor main body performs primary dehydration in which the raw material and the dehydration liquid are separated by the dehydration press when a predetermined reaction completion condition is satisfied.

In addition, the raw material from which the dehydrating solution is separated may be subjected to aeration agitation washing.

In addition, secondary dehydration for separating the raw material and the washing liquid to be washed may be performed.

When the dehydrated liquid having passed through the metal ion separation device is equal to or less than a predetermined metal ion concentration, the dehydrated liquid is supplied to the pH adjustment tank.

Further, the washing liquid may be supplied to the metal ion separation device when the metal ion concentration of the washing liquid is equal to or higher than a predetermined concentration, and may be supplied to the washing water storage tank when the metal ion concentration of the washing liquid is lower than the predetermined concentration.

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

in addition, the metal ion separation apparatus may separate an ion component using an ion exchange resin and/or a membrane.

The dehydrated liquid can be supplied to an organic acid storage tank for producing an organic acid before being supplied to the pH adjustment tank.

In addition, the raw material may be transferred to the fuel processor 800 by the transfer press.

In addition, the dehydrated liquid containing the metal ions that have failed to pass through the metal ion separation device may be separated and supplied to the cation storage tank and the anion storage tank.

The water content of the raw material subjected to the secondary dehydration may be 15% or less.

Effects of the invention

According to the fuel production system for removing the ash-producing component in the biomass under the low-temperature condition, the ash-producing component and the like can be simply and effectively extracted and separated from the herbaceous or woody biomass under the low-temperature reaction condition of the catalyst such as acid or alkali, and thus the raw material for the biomass in the single-combustion and/or co-combustion boiler can be selectively obtained.

In addition, the present invention can contribute to simplification of the wastewater treatment process and cost saving by performing acid/alkali treatment under low temperature conditions, and can maximally prevent elution of carbon-based components such as cellulose, hemicellulose, and lignin.

In addition, by effectively removing ash-producing components such as alkali metals and alkaline earth metals, halogen elements, and the like contained in the biomass, problems of slag, scaling, and alkali metal corrosion that may occur during operation of a combustion system when applied to power plant fuels can be effectively reduced.

In addition, the liquid-phase component (sugar mostly including xylose) may be mixed with low-rank coal by a conventional coal blending process in which the liquid-phase component is impregnated and then carbonized, and thus, a conventional coal pulverization facility may be used in a conventional power plant, and a biomass pulverization device may not be additionally provided since only 3.5 wt% or less of biomass is charged and cofired.

In addition, since the molded fuel and the semi-carbonized fuel are produced by using the cellulose, hemicellulose and lignin of the biomass from which the ash-producing component has been removed, it is possible to fundamentally eliminate the problems of slag, scaling, high-temperature corrosion, and the like caused by the ash derived from the biomass after combustion and gasification in the fluidized bed, the micronization combustion furnace and the gasification furnace.

In addition, by applying the ion exchange resin and/or the membrane filtration process, the ash-producing component in the biomass liquid phase component is effectively separated, so that the treated water can be recycled.

Further, nitrogen components in the Fuel components are removed, thereby reducing Fuel-type nitrogen oxides (Fuel NOx) generated during combustion.

Drawings

Fig. 1 is a flowchart illustrating a boiler fuel production system for removing ash components in combination with a dehydration washing process according to an embodiment of the present invention.

Fig. 2 shows the composition change of the raw material before and after the boiler fuel production system for removing ash components in combination with the dehydration washing process according to an embodiment of the present invention.

Fig. 3 shows the change of mineral composition of the raw material before and after the boiler fuel production system for removing ash components in combination with the dehydration washing process according to an embodiment of the present invention.

FIG. 4 illustrates ash removal rate as a function of pH under alkaline treatment conditions for a boiler fuel production system for removing ash-producing components in conjunction with a dehydration washing process in accordance with an embodiment of the present invention.

FIG. 5 illustrates an ash removal rate as a function of temperature under alkaline treatment conditions of a boiler fuel production system for removing ash-producing components in conjunction with a dehydration washing process in accordance with an embodiment of the present invention.

FIG. 6 illustrates ash removal rate as a function of residence time under alkaline treatment conditions for a boiler fuel production system for removing ash-producing components in conjunction with a dehydration washing process in accordance with an embodiment of the present invention.

Fig. 7 illustrates an ash removal rate according to pH change under acid treatment conditions of a boiler fuel production system for removing ash components in combination with a dehydration washing process according to an embodiment of the present invention.

Fig. 8 illustrates an ash removal rate according to temperature change under acid treatment conditions of a boiler fuel production system for removing ash components in combination with a dehydration washing process according to an embodiment of the present invention.

Fig. 9 illustrates an ash removal rate of the boiler fuel production system for removing ash components in combination with a dehydration washing process according to an embodiment of the present invention as a function of a residence time under acid treatment conditions.

Fig. 10 shows SEM photographs of biomass before and after the boiler fuel production system with ash components removed in conjunction with the dehydration washing process according to an embodiment of the present invention.

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

Fig. 12 is a flowchart illustrating an operation of the boiler fuel production system for removing ash components in combination with a dehydration washing process in accordance with an embodiment of the present invention.

FIG. 13 is a pumping rate dependent solution residence time in a column for a boiler fuel production system incorporating a dehydration washing process to remove ash-producing components in accordance with an embodiment of the present invention.

FIG. 14 is a result of cation concentration depending on the time when the mixed bio-solution discharged from the dehydration unit flows out after passing through a cation exchange resin column in the boiler fuel production system for removing ash components in combination with the dehydration washing process according to an embodiment of the present invention.

FIG. 15 is a result of anion concentration depending on the time of flowing out of the mixed bio-solution discharged from the dehydration unit after passing through an anion exchange resin column in the boiler fuel production system for removing ash components in combination with the dehydration washing process according to an embodiment of the present invention.

Fig. 16 shows BTW of the low-temperature catalyst liquid charged per unit supply raw material in one embodiment of the present invention.

Fig. 17 is a flowchart illustrating a fuel production system for a boiler removing ash components according to an embodiment of the present invention.

Detailed Description

The terms or words used in the present specification and claims should not be construed as limited to conventional or dictionary meanings, but interpreted as meanings and concepts conforming to the technical idea of the present invention on the basis of the principle that the inventor can appropriately define the concept of the terms in order to describe his invention in the best way. Therefore, the embodiments described in the present specification are only preferred embodiments of the present invention and do not represent all the technical ideas of the present invention, and it should be understood that various equivalents and modifications capable of replacing them may exist at the time point of the present application.

The fuel used in the present invention means any one or more of peat, lignite, subbituminous coal, bituminous coal, anthracite and the like, which are coal used as a boiler fuel, and is considered as low-rank coal in this field.

Additionally, the feedstock may be biomass. The biomass feedstock may use woody species and herbaceous species. The wood can be wood block, wood chip, log, branch, cut wood chip, fallen leaf, wood board, sawdust, lignin, xylose, lignocellulose, coconut tree, Palm Kernel Shell (PKS), coconut fiber, Empty Fruit Bunch (EFB), Fresh Fruit Bunch (FFB), coconut leaf, coconut powder, etc. Examples of herbs that can be used include corn stalks, straw, sorghum stalks, sugar cane stalks, grain (rice, sorghum, coffee, etc.) husks, beet leaves, bagasse, millet, artichoke, molasses, flax, hemp, kenaf, cotton stalks, tobacco stalks, starchy corn, potato, cassava, wheat, barley, rye, other starch-based processing residues, avocado, jatropha and their processing residues.

Algae (algae) can be used as the biomass raw material. As the algae, Green algae (Green algae), blue algae (Cyanobacteria), diatoms (Diatom), red algae, chlorella (chlorella), Spirulina (Spirulina), Dunaliella (Dunaliella), laver (Porphyridium), Phaeodactylum (Phaeodactylum), and the like can be used.

Hereinafter, a fuel production system for a boiler to remove ash components in combination with a dehydration washing process according to the present invention will be described in detail with reference to the accompanying drawings.

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

A fuel production system for removing ash-producing components in biomass in conjunction with low temperature conditions of a dehydration washing process may include: a reactor body 100 for treating the supplied raw material with a low-temperature catalyst so as to maximally separate an ash-producing component from the raw material; a pH adjusting tank 400 for supplying a low-temperature catalyst solution to the reactor body; a washing water storage tank 500 for supplying washing water to the reactor body; and a raw material injection device 700 for injecting raw materials into the reactor body.

The reactor body may include a reactor insulation 101. The heat insulating material is not limited to the material as long as the heat insulating material has a heat insulating effect.

The heat insulation material can be any one or more than two of glass wool, rubber foam, polyethylene foam, Perlite (Perlite) and urethane.

May preferably be 0.05[ g/cm ]³]、0.035[W/m·k]The rubber foam insulation material (Hiplex). More preferably 0.05[ g/cm ]³]、0.035[W/m·k]A mass specific absorption rate of 3% or less, 5 to 10 ng/m²·s·Pa]The rubber foam insulation material (Hiplex).

If the condition is exceeded, the heat preservation effect cannot be obtained.

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

The catalyst may be supplied through the temperature-increasing catalyst liquid inflow portion 110.

The washing water may be supplied through the washing water inflow part 120. The washing water may be supplied in admixture with the catalyst.

The reactor body may include a reaction temperature raiser 130 to adjust the temperature. The shape of the reaction temperature raiser is obviously not limited as long as the reaction temperature raiser can control the temperature of the reactor body. The reaction temperature increasing reactor may have a temperature increasing rate of 1 to 5 deg.c/min.

If the above condition is exceeded, the temperature increase effect may not be obtained.

In addition, the degassing operation for maintaining the internal pressure condition of the reactor body may be performed through the degassing part 140.

A high pressure gas generator 150 may be included to maintain the pressure conditions of the reactor body.

A high pressure gas first injection part for supplying the high pressure gas generated by the high pressure gas generator to the dehydration press may be formed, and a high pressure gas second injection part may be formed on the reactor body.

The high pressure gas condition may be 1 to 5m³Min, 1 to 10kg/cm². If the pressure exceeds the above range, a sufficient pressure condition cannot be obtained.

The high-pressure gas supplied from the high-pressure gas second injection portion also has an explosion effect. The high-pressure gas may be any one or more of air, oxygen, nitrogen and helium.

The fuel can be discharged through a solid fuel discharge port for discharging the fuel after the metal ion removing reaction, the dehydration washing process.

The pH adjusting tank is a device for supplying a catalyst to the reactor body. The pH adjustment tank may include a processing water supply part 210 for supplying water that may be mixed with the catalyst. A catalyst storage tank 430 for supplying a catalyst to the pH adjustment tank may be formed, and the catalyst may be supplied to the pH adjustment tank. The catalyst supply part 420 may be formed. An organic acid storage tank 440 for producing an organic acid from the dehydrated liquid and/or washing water of the raw material may be additionally formed. The organic acid may be generated by reacting any one or more of cellulose, hemicellulose and lignin separated from the raw material with a catalyst. The pH adjustment tank is formed with a stirrer 401 for the mixing property of the internal catalyst. When the capacity of the pH adjusting tank is 100L, the stirrer may be operated at 100 to 500rpm, preferably 350 rpm. The pH adjusting tank may include a temperature increasing unit 403 for adjusting the temperature. The shape of the temperature raiser is obviously not limited as long as the temperature raiser can adjust the temperature of the reactor body. The reaction temperature increasing reactor may have a temperature increasing rate of 1 to 5 deg.c/min.

If the above condition is exceeded, the temperature increase effect may not be obtained.

The pH adjustment tank may include a thermal insulation material 402. The heat insulating material is not limited to the material as long as the heat insulating material has a heat insulating effect.

The heat insulation material can be any one or more than two of glass wool, rubber foam, polyethylene foam, Perlite (Perlite) and urethane.

May preferably be 0.05[ g/cm ]³]、0.035[W/m·k]The rubber foam insulation material (Hiplex). More preferably 0.05[ g/cm ]³]、0.035[W/m·k]A mass specific absorption rate of 3% or less, 5 to 10 ng/m²·s·Pa]The rubber foam insulation material (Hiplex).

If the condition is exceeded, the heat-retaining effect may not be obtained.

The pH adjusting tank may be additionally provided with a processing water supply part 410 for supplying water.

A temperature-increasing catalyst liquid discharge portion 460 for supplying the catalyst to the reactor body may be formed.

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

A washing water supply part 510 for supplying water to the washing water storage tank may be formed. A secondary dehydration supply part 520 for supplying the washing water discharged from the reactor body through washing to the washing water storage tank may be formed. A washing water drain part 530 may be formed, the washing water drain part 530 for supplying the washing water generated from the washing water storage tank to the reactor body. A washing water discharge part 540 for discharging the remaining washing water of the washing water storage tank may be formed.

A water level meter capable of confirming a liquid level may be additionally formed at the reactor body, the pH adjusting tank, and the washing water storage tank.

The raw material injection apparatus may include: a pulverization unit for making the biomass into a raw material of a prescribed size; a hopper for storing the raw material; a raw material feeder for quantitatively supplying the raw material stored in the hopper to a rear end.

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

Preferably, the fruit juice is one or more of Miscanthus sinensis, Empty Fruit Bunch (EFB), kenaf, cornstalk, rice hull and bamboo.

The predetermined size may be 500mm or less.

Preferably 10 μm to 300mm or less.

More preferably 20mm to 50mm or less.

If the size is out of the range, the pulverization cost may be excessively high or the efficiency of removing the ash-producing component may be lowered.

The comminution apparatus may be crushing (crushing) and/or grinding (grinding). The crushing apparatus may utilize any one or more physical properties of compression, impact, friction, shearing, and bending, and the method is not limited as long as the object of reducing the size and increasing the surface area by cutting or the like can be achieved.

The crushing apparatus may be any one of a Jaw crusher (Jaw cruser), a gyratory crusher (gyrotryshredder), a Roll crusher (Roll cruser), a Roll crusher (Edge runner), a hammer crusher (Hammercrusher), a Ball mill (Ball mill), a Jet mill (Jet mill), and a Disk crusher (Disk cruser).

The raw material feeder is not particularly limited as long as it is a device that can quantitatively supply the raw material to the rear end. Preferably a screw feeder or a hopper.

The ash-producing component is an inorganic component contained in biomass used for a combustion reaction, and is physically and chemically attached to a reactor wall surface at the rear end of the reaction, a heat exchanger, and a surface of a rear-end exhaust gas treatment device, and causes scaling, slagging, corrosion, slag formation, and the like.

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

The ash-producing component is preferably sodium, potassium or chlorine.

The temperature of the injection water for the hot water treatment of the prescribed temperature may be 30 ℃ to 500 ℃. Preferably 120 ℃ to 300 ℃, more preferably 30 ℃ to 99 ℃. The temperature of the low-temperature catalyst liquid for the hot water treatment of the prescribed temperature may be 40 ℃ to 60 ℃.

If the temperature condition is exceeded, the ash-producing components in the raw materials cannot be sufficiently separated. The temperature conditions may vary depending on the starting materials.

The residence time of the feed stock in the reactor body may be from 10 minutes to 10 hours, preferably from 20 minutes to 2 hours, more preferably from 30 minutes to 1 hour. If the retention time is exceeded, the ash-producing components in the raw material cannot be sufficiently separated

The residence time may vary from feedstock to feedstock.

In the fuel treatment apparatus, the fuel is carbonized or semi-carbonized by treatment with hot water of a prescribed temperature.

The amount of heat generated per unit fuel may increase while the fuel is carbonized or semi-carbonized.

The carbonized or semi-carbonized fuel may have a calorific value of 3,500kcal/kg to 4,500kcal/kg on the basis of a lower calorific value.

If the temperature and time conditions are exceeded, the removal efficiency may be reduced or the process cost may be increased.

Fig. 16 shows BTW of the low-temperature catalyst solution required to be charged per unit supply of the raw material in one embodiment of the present invention.

The amount of the low-temperature catalyst liquid to be charged per unit supply of the raw material varies depending on the type of Biomass, and is defined as a Biomass to Water ratio (BTW, biological to Water, kg/kg). Preferably, for each biomass, the purple mango 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; cornstalks 0.05 to 0.2, preferably 0.11 to 0.13, more preferably 0.125; elephant grass 0.05 to 0.2, preferably 0.14 to 0.18, more preferably 0.1667; an EFB of 0.1 to 0.4, preferably 0.15 to 0.25, more preferably 0.2; a PKS of from 0.3 to 0.9, preferably from 0.45 to 0.75, more preferably 0.6667; cashew nut shell 0.3 to 0.9, preferably 0.45 to 0.75, more preferably 0.5; coffee shell 0.2 to 0.6, preferably 0.35 to 0.45, more preferably 0.4; wood particles of 0.05 to 0.2, preferably 0.14 to 0.18, more preferably 0.1667; pine tree 0.1 to 0.4, preferably 0.15 to 0.25, more preferably 0.2; the forest by-product is 0.1 to 0.4, preferably 0.15 to 0.25, more preferably 0.2. Most preferably within a range of ± 10% permissible for each biomass.

If the BTW ratio is exceeded, the ash content separation efficiency is reduced.

Water, an acidic solution, and an alkaline solution for adjusting the separation efficiency may be injected at the front end or the rear end of the reactor body.

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

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

The co-firing conditions may be 1 to 50 wt%, preferably 3 to 40 wt%, more preferably 5 to 30 wt% of the existing fossil fuel.

The liquid-phase component discharged from the reactor body may include the ash-producing component.

The liquid phase component may be an aqueous solution containing a small amount of organic compounds and ash-producing components. The main constituent of the organic compound may be carbon, hydrogen, nitrogen, oxygen, sulfur. Preferably, the liquid phase component may comprise hemicellulose, organic acids, furfural, 5-hydroxymethylfurfural (5-HMF)), and inorganic substances.

The solid phase component discharged from the reactor body may comprise a combustible component from which the ash-producing component is separated.

The combustible component may be an organic compound. The combustible component may be carbon, hydrogen, nitrogen, oxygen, or sulfur as a main constituent. The combustible components are characterized in that the carbon ratio increases and the hydrogen, nitrogen, oxygen, sulfur components decrease per unit mass of the feedstock.

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

The pH is more preferably 2.5 to 4 or less.

The optimum pH condition of the liquid phase component is 3.

The pH of the liquid phase component is technically characterized by a decrease in pH due to the organic acid in the feedstock. The organic acid may be acetic acid (acetic acid), formic acid (formic acid), levulinic acid (levulinic acid), 5-hydroxymethylfurfural (5-HMF), Furfural (furfurfuel), propionic acid (propanoic acid), 4-hydroxybutyric acid (4-hydroxy-butanoic acid), 2-butyric acid (2-butanoic acid), or the like. The organic acid may be in the form of one or a mixture of more than one. Preferably, the organic acid concentration used to maintain a pH of 3.11 may be 10 wt% formic acid (formic acid), 43.81 wt% acetic acid (acetic acid), 4.58 wt% levulinic acid (levulinic acid), 0.91 wt% 5-HMF, 40.04 wt% furfural (furfurfuel). More preferably, the concentration of the organic acid may be in a form of being mixed with water in order to maintain pH 3.11.

In addition, in order to improve the reactivity of the ash component separation unit, acetic acid (C) may be further added₂H₄O₂) Formic acid (HCOOH), propionic acid (CH)₃CH₂COOH), 4-hydroxybutyric acid, 2-butyric acid, sulfuric acid (H)₂SO₄) Hydrochloric acid (HCl), nitric acid (HNO)₃) Phosphoric acid (H)₃PO₄) Peroxyacetic acid (C)₂H₄O₃) Acetic acid (CH)₃COOH), oxalic acid (C)₂H₂O₄) Any one or more of these acids.

The amount of the acid solution added may be 10% by weight or more of the total amount of hot water added.

The pH value depending on the addition of the acid solution is preferably 4 or less.

The pH value may be more preferably 2.5 to 4 or less.

The low pH aqueous solution from which the organic compounds are separated from the liquid phase component can be recycled to the reactor body.

In order to remove the organic compound from the liquid phase component, any one or more of centrifugal separation, coagulation, adsorption, filtration membrane, and ion exchange resin may be used.

The solid phase component of the raw material discharged after the reaction from the reactor body may be an organic compound. The combustible component may be a constituent component mainly containing carbon, hydrogen, nitrogen, oxygen, and sulfur. The combustible component is characterized in that the ratio of carbon in the raw material per unit mass of carbon, hydrogen, nitrogen, oxygen and sulfur is increased, and the content of hydrogen, nitrogen, oxygen and sulfur is decreased.

The dehydrated liquid and/or washing water discharged from the reactor main body by dehydration and/or washing may be an aqueous solution containing a small amount of organic compounds and inorganic substances. The organic compound may be a constituent mainly containing carbon, hydrogen, nitrogen, oxygen, and sulfur. The organic compound is preferably lignin. The inorganic material preferably contains at least one of Al, Si, P, Ca, Ti, Mn and Fe.

The fuel processing apparatus may further comprise a shaped fuel unit for producing a shaped fuel from the solid phase component.

A membrane filter unit may be further provided to separate ionic components from the liquid phase component.

The membrane filter can be any one or more than two of a micro filter, an ultra-filter, a nano filter and a reverse osmosis membrane. Water, an acidic solution, and an alkaline solution for adjusting pH concentration may be injected at the front end or the rear end of the membrane filter unit. At the front end or the rear end of the membrane filter unit, the solid component in the liquid component can be separated by at least one of water evaporation, centrifugal separation, precipitation, coagulation, and adsorption. The hemicellulose in the liquid phase component is separated by refining and can be used as a substitute of dietary fiber.

The reactor body may be dehydrated and/or washed.

The biomass in the boiler may be ash producing component-depleted fuel produced from a fuel production system for single-firing and/or co-firing.

The biomass is herbaceous or woody biomass based on lignocellulose, and is not limited as long as it is a biomass. Also, first or third generation biomass can be used, as will be apparent. Cellulose is a polysaccharide having a stable structure in which glucose is linked by β -1,4 bonds, as a main component of lignocellulose. And is composed of another main component of 5-carbon sugar xylose polymer, and also composed of polymers of 5-carbon sugar arabinose (arabinose), 6-carbon sugar mannose (mannose), galactose (galactose), glucose (glucose), rhamnose (rhamnose), and the like.

Also, glucan (glucan) is a general term for polysaccharides constituting glucose, and has various kinds according to the form of D-glucose (glucose) binding, and is classified into α -glucan and β -glucan according to the arrangement of carbon atoms. Alpha-glucans may include amylose (alpha-1, 4 binding), amylopectin (alpha-1, 4 and alpha-1, 6 binding), glycogen (alpha-1, 4 and alpha-1, 6 binding), bacterial glucan (alpha-1, 6 binding), and the like. Typical examples of the β -glucan include cellulose (. beta. -1, 4-linked), laminarin of brown algae (. beta. -1, 3-linked), lichenin of lichen (β -1, 3-linked and. beta. -1, 4-linked), and the like.

The liquid phase component containing xylan (xylan) may contain xylan (xylan), glucuronoxylan (glucuronoxylan), arabinoxylan (arabinoxylan), glucomannan (glucomanan), xyloglucan (xyloglucan), and the like. The described components are not limited to the liquid phase components containing xylan, and various components are separated depending on the biomass components to be charged.

The saccharide is not limited to the above-described components, and various saccharides can be produced according to the kind of the second generation biomass. Therefore, the sugar is divided into two-carbon sugar, three-carbon sugar, four-carbon sugar, five-carbon sugar and six-carbon sugar according to the number of carbon elements. The disaccharide is glycolaldehyde (Glycoaldehyde), the trisaccharide is Glyceraldehyde (Glycoaldehyde), Dihydroxyacetone (Dihydroxyacetone), the tetrasaccharide is erythrose (erythrose), erythrulose (erythrose), the pentasaccharide is ribose (ribose), arabinose (arabinosine), xylose (xylose), ribulose (ribulose), xylulose (xylulose), and the hexasaccharide is glucose (glucose), fructose (fructose), galactose (galactose), and mannose (mannose).

The disaccharide combining two monosaccharides may be lactose, maltose, sucrose, trehalose (trehalose), melibiose (melibiose), cellobiose (cellobiose).

The saccharides having 2 to 10 molecules of sugar may be selected from raffinose, melezitose and maltotriose, and the saccharides may be selected from tetrasaccharide, stachyose, schrodose, and oligosaccharides including galactooligosaccharide, isomaltooligosaccharide and fructooligosaccharide.

The polysaccharide may be pentosan (pentasaccharide) bonded with pentose, and may be simple polysaccharide such as xylan (xylosan) and arabinosan (araban).

Examples of hexose condensed with hexose include starch and starch (starch), and examples of the glucose polymer include amylose (amylose), dextrin (dextrin), glycogen (glycogen), cellulose (cellulose), fructan (fructan), galactan (galactan), and mannan (mannan).

Examples of the complex polysaccharides include agar (agar), alginic acid (alginic acid), carrageenan (carrageenan), chitin (chitin), hemicellulose (hemicellulose), and pectin (pectin).

As the acid participating in the reaction, sulfuric acid (H) may be mentioned₂SO₄) Hydrochloric acid (HCl), nitric acid (HNO)₃) Phosphoric acid (H)₃PO₄) Peroxyacetic acid (C)₂H₄O₃) Acetic acid (CH)₃COOH), oxalic acid (C)₂H₂O₄) And the like. The acid is not limited to the above-mentioned acids, and any acid that can decompose hemicellulose and cellulose may be used. As the alkali to be involved in the reaction, there may be mentioned sodium hydroxide, potassium hydroxide, urea and the like. The base is not limited to the above-mentioned ones, and any base can be used as long as it can improve the reaction characteristics.

The ionic liquid involved in the reaction is imidazole (imidazole) compound, and may be 1-ethyl acrylate-3-methylimidazolium chloride (1-ethyl acrylate-3-methylimidazolium chloride), 1-butyl-3-methylimidazolium chloride (1-butyl-3-methylimidazolium chloride), 1-butyl-3-methylimidazolium tetrafluoroborate (1-butyl-3-methylimidazolium tetrafluoroborate), 1-butyl-3-methylimidazolium hexafluorophosphate (1-butyl-3-methylimidazolium hexafluorophosphate), 1-butyl-3-methylimidazolium trifluoromethanesulfonate (1-butyl-3-methylimidazolium trifluoromethanesulfonate), 1-ethyl-3-methylimidazolium trifluoroacetate (1-butyl-3-methylimidazolium trifluoroacetate), 1-benzyl-3-methylimidazolium chloride (1-benzyl-3-methylimidazolium chloride), 1,3-dimethylimidazolium methyl sulfate (1,3-dimethylimidazolium methyl sulfate), 1-butyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium acetate, etc., and there may be ethylmethylimidazolium chloride ([ EMIM ] Cl), ethylmethylimidazolium bromide ([ EMIM ] Br), ethylmethylimidazolium iodide ([ EMIM ] I), 1-ethyl-3-methylimidazolium, 1-ethylimidazolium nitrate, 1-ethylimidazolium bromide, 1-ethyl-3-methylimidazolium chloride, 1-ethylimidazolium chloride, 1,2, 3-trimethylimidazolmethylmethylsulfate, 1-methylimidazolium chloride, 1-butyl-3-methylimidazole, 1-butyl-3-methylimidazolium tetrachloroaluminate, 1-ethyl-3-methylimidazolium hydrogen sulfate, 1-butyl-3-methylimidazolium hydrogen sulfate, methylimidazolium chloride, 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, Tris-2 (hydroxyethyl) ammonium methylsulfate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium methanesulfonate, tri-n-butylammonium methylsulfate, 1-butyl-3-methylimidazolium chloride, methyl imidazolium chloride, ethyl-3-methyl, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium 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-hexyl-3-methylimidazolium chloride, methyl imidazolium chloride, ethyl, 1-hexyl-3-methylimidazole nitrate, 1-hexyl-3-methylimidazole acetate and 1-hexyl-3-methylimidazolium tetrafluoroborate.

The amount of one or more of the enzyme, the acid, the alkali, and the ionic liquid to be charged into the reactor main body may be not charged depending on the reaction conditions.

In addition, the solid phase component can participate in high-temperature and high-pressure reaction through the reactor body to generate compounds such as furfural (furfuel).

The pressure condition of the reactor body may be 1 to 150atm, preferably 1 to 100atm, and more preferably 1 to 50 atm. The reactor body can vary the pressure conditions depending on the feedstock.

If the pressure conditions are exceeded, the metal ions in the feedstock may not be separated.

The fuel without ash can be used in fluidized bed boiler, grate furnace, micronization boiler and gasification furnace, and can fundamentally eliminate the blocking phenomena of slag, scale formation and the like caused by inorganic matters containing metal elements in the fuel in combustion and gasification and the corrosion phenomenon caused by alkali metals.

In addition, a metal ion separating means 600 may be included, and the metal ion separating means 600 is used to separate metal ion components in the low-temperature alkaline solution and/or the acidic dehydration solution discharged from the reactor body.

In addition, the low temperature conditions in the reactor body may be below 100 ℃ in order to eliminate latent heat of vaporization losses. The low temperature conditions may be 40 to 80 ℃ in order to eliminate latent heat of vaporization losses. The low temperature condition may be 60 ℃.

In addition, the acid solution supplied to the reactor body may employ an organic acid generated by a separate biomass soaking process.

The metal ion separation apparatus is not particularly limited as long as it can separate an ion component by an ion exchange resin, an ion exchange membrane and/or a membrane and remove ions in a separation/dehydration solution. For example, the ion exchange resin may be one that selectively separates Ba²⁺、Pb²⁺、Sr²⁺、Ca²⁺、Ni²⁺、Cd²⁺、Cu²⁺、Zn²⁺、Tl⁺、Ag⁺、Cs⁺、Rb⁺、K⁺、NH⁴⁺、Na⁺、Li⁺One or more than two kinds of cation exchange resin.

And, the ion exchange resin may be a selective separation of Citrate (Citrate), SO₄ ^2-Oxalate (Oxalate), I^-、NO₃ ^-、CrO₄ ^2-、Br-、SCN^-、Cl^-Formate (Formate), Acetate (Acetate), F^-、OH^-One or two or more kinds of anion exchange resins.

Here, the anion exchange resin and the cation exchange resin preferably use a strongly acidic cation exchange resin or a strongly basic anion exchange resin so as to be able to be used in a wide pH range.

The metal ion separation apparatus may include a first cation exchange module 601, a first anion exchange module 602, a second cation exchange module 603, a second anion exchange module 604. The ion exchange module may be provided with a plurality of cation and anion exchange modules in parallel. The ion exchange module may operate in part or in whole. A pump for supplying the dehydrating liquid to the ion exchange module may be formed.

The dehydrated liquid passed through the cation and anion exchange resins of the ion exchange module may be supplied to a pH adjustment tank. The ionic liquid separated by the cation and anion exchange resins 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, and the dehydration storage tank 610 may be capable of storing the dehydrated liquid discharged from the reactor body before being supplied to the metal ion separation unit.

The membrane may be one or two or more of a nanofiltration membrane and a reverse osmosis membrane capable of separating cationic and/or anionic substances contained in the dehydrated liquid.

(experiment for separating Metal ion)

To carry out the experiment for separating metal ions from the dehydrated liquid, a column (5 cm in diameter, 24cm in length, 471cm in volume)³) Glass wool was packed at the lower end to prevent leakage of the resin, and after a predetermined amount of the objective ion exchange resin (cation exchange resin 402g, anion exchange resin 346g) was packed at the upper part, glass wool was packed at the upper part.

The concentration of each ion was measured by transferring the model solution to the separation column at a speed of 50rpm, 30rpm, or 10rpm by a pump, sampling the solution flowing out through the separation column, taking a predetermined amount of the sampled sample solution after a predetermined time has elapsed, and analyzing the sample solution.

The residence time of the solution in the separation column depending on the draw rate is shown in fig. 13. The metal ion concentration of the dehydrated liquid discharged from the metal ion separation device was analyzed by ICP.

K depending on the time of flowing-out of the mixed biological solution discharged from the dehydration unit after passing through the cation exchange resin separation column⁺、Na⁺、Mg²⁺The change in the cation concentration is shown in FIG. 14. Which shows K depending on the time of flowing-out of the mixed biological solution discharged from the dehydration unit after passing through the cation exchange resin separation column⁺、Na⁺、Mg²⁺The concentration of the cation changes. K⁺The initial concentration of the ion was 457.092ppm, after 3 minutes the concentration dropped sharply to 6.474ppm, after 9 minutes it was shown to be 6.833ppm and then decreased gradually, at 55 minutes it was shown to be a value of 5.809 ppm. Mg (magnesium)²⁺The initial concentration of the ion was 57.114ppm, after 3 minutes the concentration dropped sharply to 1.636ppm, after 9 minutes it was shown to be 0.454ppm, followed by a gradual decrease, at 55 minutes it was shown to be a value of 0.079 ppm. Na (Na)⁺The initial concentration of the ions was 32.687ppm, increasing sharply to 180.224ppm after 3 minutes, showing 139.157ppm after 9 minutes, then decreasing gradually, showing a value of 75.739ppm at 22 minutes, and then showing an almost constant value. Can confirm K⁺、Mg²⁺Most of the ions were removed after passing through the cation exchange resin separation column for 3 minutes.

The separation results of anions over time, taking into account the residence time of the solution in the separation column depending on the draw rate, are shown in fig. 15. The metal ion concentration of the dehydrated liquid discharged from the metal ion separation device was analyzed by ICP.

Cl^-The initial concentration of the ions was 1051.60ppm, after 3 minutes the concentration dropped sharply to 183.18ppm, after 9 minutes it appeared as 169.07ppm and then decreased gradually, after 22 minutes it was147.85ppm, indicating an almost constant value, Cl was confirmed^-Most of the ions were removed after 22 minutes of passing through the anion exchange resin separation column.

On the other hand, the ion water discharged from the metal ion separation device may contain various particulate matters containing ash-producing components, which reduce the ion exchange capacity of the cation exchange resin or the anion exchange resin and close the gaps between the ion exchange resins. In addition, when cations or anions are removed by using a nanofiltration membrane or a reverse osmosis membrane, the permeability is drastically reduced by the particulate matter, and therefore, it is preferable to provide an appropriate pretreatment unit.

For example, the pretreatment unit may be introduced into a coagulation and/or precipitation process, or may be supplied to an ion exchange resin, a nano-filtration membrane or a reverse osmosis membrane after removing particulate matter using a large-pore ultrafiltration membrane or a fine filtration membrane.

In addition, the dehydrated liquid from which the ionic component is separated by the metal ion separation means may be recycled to the reactor main body.

The biomass may have a particle size of 10 μm to 1000 mm. Preferably 10 μm to 100mm, more preferably 10 μm to 10 mm. If such conditions are exceeded, this may result in a reduction in the efficiency of the separation of the metal ions in the feedstock.

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

It will be apparent that the wastewater treatment unit may include ion exchange resins, separation membranes, coagulation, adsorption, and the like. The ionic substances removed and separated from the wastewater treatment unit may be landfilled or incinerated by a commission treatment, and may further include a discharge unit for discharging the treated water from which the substances are removed to a water system (river, etc.). The discharge unit may be a pump.

(catalytic reaction example)

The biomass base sample was dried in an oven at 105 ℃ to remove moisture. Water is added to a portion of the sample (e.g., EFB) after drying to maintain a viscosity below 5000 cP. The conditions are such that in the case of EFB, the weight ratio of EFB to water is 1 to 3. To the aqueous solution was added 1 wt% NaOH. The treatment solution was charged to the reactor and maintained at a temperature of 60 ℃ for 10 minutes. The stirrer was stirred at 10 to 1000 rpm. The reaction was carried out at the temperature of 2 ℃ per minute from the 60 ℃ for 40 minutes.

After the reaction, solid-liquid separation was performed using a 1um filter. The recovered solid was dried in an oven at 105 ℃. The sample recovered from the oven and the aqueous acetic acid solution were stirred at a ratio of 1 wt% to 3 wt% (the ratio of the treatment solution and acetic acid was 1: 1).

The treatment solution was charged into the reactor and then held at 60 ℃ for 10 minutes. By the process, in the reactor, Na ions contained in the treatment liquid are removed with acetic acid.

And (3) performing solid-liquid separation on the treated liquid after the reaction by using a 1um filter. The residue was washed with distilled water.

After final drying in an oven at 105 ℃, the biomass from which the ash-producing components, i.e., the metal components, within the biomass have been removed is discharged.

The separated metal can be applied to secondary batteries, fuel cells and super capacitors.

Preferably, an Energy Storage System (ESS) using the separated metal ions may be provided, which is connected to a fuel production System for removing ash components in biomass in combination with a low temperature condition of a dehydration washing process.

The energy storage system may be any one or more of a secondary battery, a fuel cell, a super capacitor, and a Flow battery (Flow battery).

It may be preferable to use a power generation device using a potential difference of the ionic solution.

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

Fig. 2 shows the change in the composition of the raw material before and after the boiler fuel production system from which the ash components are removed according to the embodiment of the present invention.

Considered as fuelThe biomass includes herbs, lignins, algae, etc., and fig. 2 shows the fuel property analysis results using viola awn, corn stalk, etc., which are herbaceous biomass, and pine, which is ligneous biomass. The biomass without ash-producing components prepared by the process shows a removal efficiency of 77-97% on a dry basis, and obtains an average heating value increasing effect of about 10%. And, additionally, the fuel itself as fuel NO_xProduct and SO_xThe values of N and S of the resulting material decreased by about 80%. The calorific value of biomass fuel lower than that of coal or the influence caused by ash can be improved by the present pretreatment process.

Fig. 3 shows the change in mineral composition of the raw material before and after the boiler fuel production system from which the ash component is removed according to the embodiment of the present invention.

FIG. 3 shows the fuel ash characteristics with the ash producing component removed. K with a melting point of 349 deg.C (shown as minimum)₂The removal efficiency of O reaches more than 95 percent, and the melting point is Na with the temperature of 1132 DEG C₂The removal efficiency of O reaches more than 95 percent. By removing the ash-producing components in this way, it is possible to prevent in advance the formation of slag, scale, slag, and other inducing substances on the boiler tubes and wall surfaces, and to maintain a stable boiler operation rate (the operation rate of a typical biomass single-fired boiler is less than 70%).

FIG. 4 illustrates ash removal rate as a function of pH under alkaline treatment conditions for a boiler fuel production system for removing ash-producing components in accordance with an embodiment of the present invention.

Fig. 4 is a graph showing the ash extraction rate and the recovery rate of the combustible substance ALB in the alkaline region. The fuel for removing ash-producing components in biomass to be developed according to the present invention is characterized in that combustible materials as solid materials are maintained to the maximum and only ash-producing components are removed. It is found that the efficiency of removing the ash content is lowered in the region of pH 13.4 or more, and the ALB yield is also lowered. Therefore, the extraction of ash should be performed in a pH range of 13.3 to 13.4 as a limiting condition.

FIG. 5 illustrates an ash removal rate as a function of temperature under alkaline treatment conditions for a boiler fuel production system for removing ash-producing components according to an embodiment of the present invention.

Fig. 5 is based on the previous experimental results of fig. 4, taking into account the effect of temperature at pH 13.4. It is known that the ash extraction rate substantially increases with an increase in temperature, and the maximum value can be seen in the 80 c region. However, since the yield of the combustible material ALB is low, the temperature range of 55 to 65 ℃ is suitable for achieving a good extraction rate of ash and a good recovery rate of combustible material.

FIG. 6 shows ash removal rate as a function of residence time under alkaline treatment conditions for a boiler fuel production system for removing ash-producing components in accordance with an embodiment of the present invention.

FIG. 6 is a graph in which the influence depending on the residence time is considered in the temperature region of pH 13.4 and 60 ℃. The ash extraction was greatest at a residence time of 10 minutes, maintaining similar performance over time. Since the recovery rate gradually decreases with the passage of time, a residence time of 10 minutes or more in the alkaline region can be said to be a meaningless condition.

Fig. 7 illustrates an ash removal rate according to pH change under acid treatment conditions of the boiler fuel production system for removing ash components according to an embodiment of the present invention.

Fig. 7 is a graph showing the ash extraction rate and the recovery rate of the combustible substance ALB in the acidic region. The fuel for removing ash-producing components from biomass to be developed in the present invention is characterized in that only ash-producing components are removed while maintaining combustible materials as solid materials to the maximum. The ash-producing component removal efficiency increased with an increase in pH to 1.7, but showed a tendency to decrease again when it reached 1.8 or more. Therefore, the extraction of ash is performed in a pH range of 1.7 to 1.8 as a limiting condition.

Fig. 8 illustrates an ash removal rate according to a temperature change under acid treatment conditions of the boiler fuel production system for removing ash components according to an embodiment of the present invention.

Fig. 8 is based on the previous experimental results of fig. 7, taking into account the effect of temperature under the pH 17.6 condition. It is known that the ash extraction rate increases with increasing temperature, but the ash extraction rate decreases under the temperature condition of 60 ℃ or higher. Therefore, the optimum temperature is in the range of 50 to 60 ℃.

Fig. 9 illustrates an ash removal rate of the boiler fuel production system for removing ash components according to an embodiment of the present invention as a function of a retention time under acid treatment conditions.

Fig. 9 considers the effect on the residence time in the region of pH 17.6 at a temperature of 60 ℃. It is seen that ash extraction is shown to be greatest at 10 minutes residence time, maintaining similar performance over time. Since the recovery rate gradually decreases with the passage of time, a residence time of 10 minutes or more in the acidic region can be said to be a meaningless condition.

Fig. 10 shows SEM photographs of biomass before and after the boiler fuel production system from which an ash component is removed according to an embodiment of the present invention.

Fig. 10 compares the surface structure change of an untreated raw sample (viola awn) and a viola awn sample from which an ash-producing component has been removed, using SEM. It can be seen that the surface of the original sample contains a large amount of mineral components in the form of irregular impurities, while the surface shape in a clean state can be seen in the sample from which the ash-producing components have been removed. The present process can be considered as the most suitable process in terms of not causing structural change of the sample itself and selectively removing only the mineral component.

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

Fig. 11 shows that only about 20 wt% of carbon remains when biomass is treated by pretreatment in a conventional bioethanol process, and that about 80 wt% or more of carbon remains when the biomass is treated with an acid and/or an alkali according to an embodiment of the present invention.

FIG. 12 is a flow diagram of the operation of a fuel production system that incorporates the low temperature conditions of a dehydration wash process to remove ash-producing components within biomass.

The operation steps of the reactor body are as follows in sequence: 1) from the lower part of the reactor body, a dehydration transfer device is used with a volume of 80-160 kg/cm²To the reactor body; 2) supplying a raw material as biomass to the reactor body through the raw material injection device; 3) by the saidA pH adjusting tank for supplying a low-temperature catalytic liquid, wherein the mass ratio of the low-temperature catalytic liquid/biomass can be 1 to 10; 4) through the high-pressure gas generator, air is supplied to the reactor body for aeration and stirring, and the air pressure can be 3-5 kg/cm²The air flow is 0.1-1 m³Min; 5) filtering the biomass for a predetermined time after a predetermined reaction time by a high pressure gas generator, wherein the air pressure is 3-5 kg/cm²The air flow is 0.5-2 m³Min; 6) the press machine of the dehydration and pressurization device can be 80-160 kg/cm²Then, in order to perform dehydration, while introducing high-pressure air through a high-pressure gas generator, the water is pressurized by a press machine to perform dehydration; 7) the pressurizing press moves to the upper part, and the dehydration is finished; 8) washing water may be supplied from the washing water storage tank to the reactor body to wash the biomass; 9) repeating the steps 4) to 7); 10) after the dewatering and transferring device moves downward, the biomass raw material is discharged and then transferred to the fuel processing device 800 by the fuel transferring device 810.

Reference numerals

1: ash removal reactor

100: reactor body

101: reactor thermal insulation material

110: temperature-raising catalyst inflow part

120: washing water inflow part

130: reaction temperature rising device

140: exhaust part

150: high-pressure gas generator

151: high-pressure gas first injection part

152: second injection part of high-pressure gas

160: solid fuel discharge part

200: dewatering and pressurizing device

210: dewatering press

300: dewatering transfer device

310: transfer press

320: second dewatering discharge part

330: a first dewatering discharge part

340: metal ion sensor

400: PH adjusting tank

401: stirrer

402: heat insulation material

403: temperature rising device

410: supply part of treated water

420: catalyst supply unit

430: catalyst storage tank

440: organic acid storage tank

450: primary dehydration supply part

460: temperature-raising catalyst liquid discharge unit

470: PH adjusting tank drainage part

500: washing water storage tank

510: washing water supply part

520: secondary dewatering supply part

530: washing water discharge part

540: water discharge part of washing water

600: metal ion separation device

601: a first cation exchange module

602: a first anion exchange module

601: second cation exchange module

602: a 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 processing device

810: fuel transfer device

900: energy storage system

1000: crushing unit

2000: hopper

2100: raw material feeder

3000: first separation unit

4000: second separation unit

5000: wastewater treatment unit