KR101687352B1

KR101687352B1 - Solid fuel for reducing malodor manufactured by mixing livestock excretions and absorbents and manufacturing method thereof

Info

Publication number: KR101687352B1
Application number: KR1020150097100A
Authority: KR
Inventors: 박상규; 최진호; 박효정
Original assignee: (주)비케이; 한국서부발전 주식회사
Priority date: 2015-07-08
Filing date: 2015-07-08
Publication date: 2016-12-16

Abstract

The present invention relates to a solid fuel prepared by mixing a manure compost and an absorbent with reduced malodor, and to a preparation method thereof. More particularly, a solid fuel is prepared by mixing a manure compost and an absorbent, and has reduced malodor by injecting ozone and drying with hot air in multiple stages. Thus, the solid fuel is used for a mixed fuel in a power plant, and is useful for heating facilities such as green house, and the like.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a malodor-reducing solid fuel produced by mixing an aldehyde component and an adsorbent,

The present invention relates to a malodor-reducing solid fuel produced by mixing a fossil fraction and an adsorbent, and a method for producing the same. More particularly, the present invention relates to a method for producing a solid fuel by mixing a fossil fraction and an adsorbent, The present invention relates to a solid fuel which is used not only for the fuel mixture of a power plant but also for the heating of a facility such as a vinyl house by reducing the generation of odor by reducing the generation of odor.

The water quality of major rivers in Korea has been seriously contaminated by the effluents from the livestock complex along with the wastewater from domestic sewage and industrial wastes, wastewater and so on.

Therefore, the government enacted various policies to improve river water quality, and considering that disposal of livestock wastewater is also an important issue, the law on the management and use of livestock manure in 2006 was enacted, , And has been striving to systematically manage livestock wastewater and to prevent pollution sources by strengthening the facilities for licensing and notification of livestock wastewater discharge facilities.

Therefore, it is possible to separate the manure excreted by the wastewater treatment method, and the liquid phase is introduced into the livestock manure treatment facility, discharged after treatment, or used as liquid fertilizer, and the excrement of the solid component stabilizes the organic matter to prevent hygienic problems And composting is being carried out.

In Korean Patent Registration No. 10-1175287 (Registered on Aug. 13, 2012, hereinafter referred to as "Prior Art 1"), the present invention provides a method for producing a carbonaceous coal using a shaft or sludge sludge. The above-mentioned prior art document 1 discloses a fossil fuel including at least one of fossil fuels or fossil fuels sludge; quicklime; A deodorant comprising at least one of purified water sludge and phosphoric acid or sulfuric acid and having a water content of 10 to 40%; And a coal having a calorific value of 3,000 to 8,000 kcal / kg. This prior art document 1 is disadvantageous in that the manufacturing cost is increased due to the use of expensive quicklime in order to remove the water content of 80% or more contained in the used planting material, and the heat of the planting material produced by the moisture of the planting material is not sufficiently high There are also disadvantages.

In the Korean Patent Registration No. 10-1343914 (Registered on Dec. 16, 2013, referred to as 'Prior Art Document 2'), a new high-calorific product using a new sludge or sludge sludge and a manufacturing method thereof have been proposed. The above-mentioned prior art document 2 discloses a honeycomb structure comprising: A deodorant comprising a dry matter having a moisture content of 10 to 40% by mixing at least one of phosphoric acid and sulfuric acid with purified water sludge; And coal having a calorific value of 3,000 to 8,000 kcal / kg. This prior art document 2 has an effect of reducing the water content of the shaft fraction or shaft fraction sludge to be used and thus making the production process shorter by mixing only one of the expensive quicklime or the deodorant to produce the shaft coal. However, since the shaft fraction is used, It is not suitable to be used as a fuel for heating an interior such as a heating in a house.

Therefore, it is necessary to study a manufacturing method capable of reducing the generation of odor.

Korean Registered Patent No. 10-1175287 (Registered on Aug. 13, 2012): Combustion using a shaft or sludge sludge and its manufacturing method Korean Registered Patent No. 10-1343914 (Registered on Dec. 16, 2013): High-calorific burnt sludge using new sludge or sludge sludge and its manufacturing method

Accordingly, the odor-reducing solid fuel of the present invention and the production method thereof,

The adsorbent coated with positively charged substance on the active mixture mixed with bottom ash and limestone is mixed with the pellets to form pellets and then dried, but ozone is supplied during the manufacturing process to make deodorization effect by ozone, The present invention provides a solid fuel in which deodorization is carried out by a multi-stage process such as providing high heat even in the process of deodorization by pyrolysis, thereby removing odor or odor generating components generated in the fuel production process, .

In order to attain the above object, the malodor-

5 to 15 parts by weight of an adsorbent coated with a positively charged substance is mixed with a mixture of BOTTOM ASH and limestone with respect to 100 parts by weight of an aqueous dispersion containing at least one of an aqueous dispersion of a starch and an aqueous dispersion of a starch sludge, .

50 to 200 parts by weight of coal having a calorific value of 3,000 to 8,000 kcal / kg can be further mixed with 100 parts by weight of the starch fraction.

The adsorbent may be prepared by mixing and calcining 5 to 20 parts by weight of limestone with respect to 100 parts by weight of bottom ash and coating the mixture with 0.01 to 5 parts by weight of positively charged substance with respect to 100 parts by weight of the calcined calcined material to have a size of 0.01 to 3 mm . In this case, the bottom ash may be a mixed bottom ash mixed with 50 to 80 wt% of bottom ash and 20 to 50 wt% of purified water sludge.

The adsorbent may further contain 0.001 to 0.2 parts by weight of metal or metal oxide relative to 100 parts by weight of bottom ash.

In addition, the present invention provides a method for producing a malodor-

Comprising: a first step of producing an aqueous dispersion having a water content of 30% or less, which is selected from at least one selected from the group consisting of an aqueous dispersion and an aqueous dispersion; A second step of preparing an activated carbon mixture by mixing and stirring the bottom ash and limestone, preparing a fired product by heating, and preparing an adsorbent having a positive charge material coated on the produced fired product; A first mixing step of mixing 5 to 15 parts by weight of an adsorbent with 100 parts by weight of the starting material of the first step by stirring; A fourth step of pelletizing the mixture by pellet molding; And a fifth step of moving the pellet in the fourth step to produce a solid fuel by hot-air drying at a moisture content of 10% or less.

A sixth step of receiving and pulverizing a part of the pellet type solid fuel obtained in the step 5; A seventh step in which the solid fuel pulverized in the sixth step is mixed with a mixture of the scrap of the third step and the adsorbent in a ratio of 1: 1 and supplied to the pellet molding machine of the fourth step; . &Lt; / RTI >

The adsorbent of the second step may include: 2a) mixing 5 to 20 parts by weight of limestone with respect to 100 parts by weight of bottom ash and stirring to produce an active mixture; A step 2b of heating the activated mixture in a baking furnace to produce a baked product; A second step c) of dissolving the positive charge material in a solvent to prepare a positive charge material dissolution solution; A second d step of mixing the positive charge material solution prepared in step 2c so that the positive charge material is coated in an amount of 0.01 to 0.5 part by weight with respect to 100 parts by weight of the sintered material prepared in step 2b; And a second stage in which the agitated material is stirred and then dried by an oven. In the step 2a, 0.001 to 0.2 part by weight of a metal or a metal oxide may be added to 100 parts by weight of the bottom ash.

In the third step, 50 to 200 parts by weight of coal having a calorific value of 3,000 to 8,000 kcal / kg may be further mixed with 100 parts by weight of the shredded material.

The odor-reducing solid fuel of the present invention and the method for producing the same,

The adsorption of fine particles or odor components by a potential difference reduces the generation of odor, and ozone deodorization by the supply of ozone during the production of pellets, It is possible to provide odor reduction type solid fuel that can be used as heating fuel of the enrichment industrial facility as well as the fuel of the power plant by minimizing the production process and the odor generation in the produced pellet type solid fuel by further pyrolysis by hot air drying .

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart illustrating a process for producing a solid fuel according to an embodiment of the present invention; FIG.
2A and 2B are schematic views showing a method of supplying hot air in a hot air dryer according to the present invention.
3 is a flow chart illustrating a process of manufacturing a solid fuel according to another embodiment of the present invention.
4 is a process diagram showing a solid fuel manufacturing process according to another embodiment of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments are only illustrative of the contents and scope of the technical idea of the present invention, and the technical scope of the present invention is not limited or changed. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the technical idea of the present invention based on these examples.

The malodor-reducing solid fuel according to the embodiment of the present invention comprises an adsorbent coated with a positive charge material and an impregnated powder made of at least one of an axial flow or an axial flow sludge.

The adsorbent is composed of a mixture of BOTTOM ASH and limestone coated with a positive charge material, and is composed of 5 to 15 parts by weight of an adsorbent mixed with 100 parts by weight of the shredded material.

Also, in order to increase the amount of heat, 50 to 200 parts by weight of coal having a calorific value of 3,000 to 8,000 kcal / kg may be mixed with 100 parts by weight of the plant material.

The adsorbent is prepared by mixing and calcining 5 to 20 parts by weight of limestone with respect to 100 parts by weight of bottom ash, and coating 0.01 to 5 parts by weight of positively charged substance with respect to 100 parts by weight of the calcined calcined material to have a size of 0.01 to 3 mm. The bottom ash is an ash produced in a thermal power plant. In the present invention, 40 to 60% of SiO ₂ , 15 to 20% of Al ₂ O ₃ , 10 to 20% of Fe ₂ O ₃ , %, Other TiO ₂ , MgO and Cl, etc., and it is crushed to a certain size or less to improve the mixing property.

The bottom ash may be a mixed bottom ash mixed with a certain amount of purified sludge, and the mixing ratio of the bottom ash with 50 to 80% by weight of bottom ash and 20 to 50% by weight of purified sludge may be used. Gt; can be < / RTI >

It is preferable to mix 5 to 20 parts by weight of limestone with respect to 100 parts by weight of the bottom ash. When the limestone is mixed with less than 5 parts by weight, surface area increase is insufficient. When the limestone is mixed with more than 20 parts by weight, It is important to maintain the proposed mixing ratio because performance degradation occurs.

In order to increase the antibacterial activity, the adsorbent may further contain 0.001 to 0.2 parts by weight of metal or metal oxide per 100 parts by weight of bottom ash. The metal or metal oxide may be at least one selected from the group consisting of Y, Mo, Bi, Tel, Mn, Cob, (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au) and aluminum (Al). The metal or metal oxide is preferably used in an amount of 0.001 to 0.2 part by weight based on 100 parts by weight of bottom ash. When the amount is less than 0.001 part by weight, the antibacterial properties are insufficient. When the amount is less than 0.2 parts by weight, the effect of increasing the antibacterial activity is increased. However, since the metal or metal oxide forms a high price, Is preferably used.

In addition, the positive charge material may be coated with one or more selected from the group consisting of chitosan and quaternary ammonium. The chitosan and quaternary ammonium system may be used by dissolving in a solvent (water or acid). As a solvent for dissolving the chitosan, citric acid, acetic acid, Sulfuric acid, hydrochloric acid, and nitric acid. The acid solution may be diluted with water, and acetic acid is preferably used to prevent odor and environmental pollution.

The quaternary ammonium system may be selected from the group consisting of Choline, Carnitine, Benzalkonium chloride; Denatonium; Cetrimonium bromide; Diallyldimethyl ammonium chloride; 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHPTAC); 3-chloro-2-hydroxypropyltrimethylammonium chloride; Copolymers of acrylamide and quaternized dimethylammonium ethyl methacrylate (Copolymer of acrylamide and quaternized dimethylammonium methyl methacrylate); Poly (diallyldimethylammonium chloride); a diallyldimethylammonium chloride polymer; Copolymers of acrylamide and diallyldimethylammonium chloride (Copolymer of acrylamide and diallyldimethylammonium chloride); Quaternized hydroxyethylcellulose; Copolymers of vinylpyrrolidone and quaternized dimethylaminoethyl methacrylate (Copolymer of vinylpyrrolidone and quaternized dimethylaminoethyl methacrylate); Copolymers of vinylpyrrolidone and quaternized vinylimidazole (Copolymer of vinylpyrrolidone and quaternized vinylimidazole); Copolymers of acrylic acid and diallyldimethylammonium chloride (Copolymer of Acrylic Acid and Diallyldimethylammonium Chloride); Copolymers of vinylpyrrolidone and methacrylamidopropyltrimethylammonium (Copolymer of vinylpyrrolidone and methacrylamidopropyl trimethylammonium); Poly (acrylamide 2-methacryloxyethyltrimethyl ammonium chloride) (Poly (acrylamide 2-methacryloxyethylammonium chloride)); Acrylic acid, acrylamide and diallyldimethylammonium chloride (Terpolymer of Acrylic Acid, Acrylamide and Diallyldimethylammonium Chloride); Terpolymers of vinylcaprolactam, vinylpyrrolidone, and quaternized vinylimidazole; vinylcaprolactam, vinylpyrrolidone and quaternized vinylimidazole; And a trimer of acrylic acid, methacrylamidopropyltrimethylammonium, and methyl acrylate (Tetra Polymer of Acrylic Acid, Methacrylamidopropyl Trimethyl Ammonium Chloride, and Methyl Acrylate).

Next, a method of manufacturing a malodor-reducing solid fuel according to an embodiment of the present invention will be described with reference to FIG.

First, as a first step, an aqueous dispersion having a moisture content of 30% or less, which is composed of at least one selected from the shaft fraction or the shaft fractionation sludge, is prepared.

The starch sludge may be at least one selected from the group consisting of bovine syrup, pigeon sludge, manure sludge, manure sludge, manure sludge, manure sludge, manure sludge, , Anaerobic digestion residue sludge, and sludge generated from livestock wastewater treatment facilities, and the use of a shaft or sludge sludge having a water content of 30% or less is used.

The second step is to produce an activated mixture by mixing bottom ash and limestone with stirring, preparing a sintered material by heating, and then preparing an adsorbent coated with the positive charge material on the sintered material produced, and subdivided into steps 2a to 2e .

In step 2a, 5 to 20 parts by weight of limestone is mixed with 100 parts by weight of bottom ash and stirred to prepare an active mixture. At this time, the bottom ash and limestone may be crushed to be uniformly mixed, and 10 to 20 parts by weight of water may be further added to 100 parts by weight of the bottom ash and limestone mixture. The particle size of the bottom ash through the pulverization step is 0.1 to 1 mm and mixed. If the agitation time after the introduction of the water is short, mixing of the bottom ash and the limestone is not performed uniformly, and if the agitation time is exceeded, the uniform mixing is not promoted, so that the preferable agitation time is within 30 minutes to 3 hours.

In addition, the range of recycling of wastes can be expanded by forming the bottom ash to be charged to produce the active mixture with pure bottom ash, or by replacing part of the bottom ash with purified water sludge. For example, instead of pure bottom ash, mixed bottom ash mixed with 50 to 80% by weight of bottom ash and 20 to 50% by weight of purified sludge may be mixed and mixed with 100 parts by weight of mixed bottom ash and 5 to 20 parts by weight of limestone have. However, the bottom ash has a higher content of SiO ₂ than the wastewater sludge, and is mixed with limestone in the future, resulting in a difference in strength of the granulated sintered product due to the difference in the production rate of calcium silicate during sintering. That is, in order to obtain the effect of increasing the strength of the granules than the purified sludge, at least the mixing amount of the purified sludge in the composition of the mixed bottom ash to be mixed in the production of the active mixture should be 50 wt% or less and 20 wt% However, in order to increase the efficiency of recycling water sludge, at least 20 wt% of water sludge should be mixed. Therefore, it is preferable to mix water sludge in the above range.

In the step 2a, 0.001 to 0.2 parts by weight of a metal or a metal oxide may be added to 100 parts by weight of the bottom ash. Said metal or metal oxide being selected from the group consisting of: (Y), molybdenum (Mo), Bi, Tele, Te, Mn, Cb, Rh, Ir, Ni, Pd ), Platinum (Pt), copper (Cu), silver (Ag), gold (Au) and aluminum (Al).

Next, in step 2b, the activated mixture is heated in a firing furnace to produce a fired product.

The calcination temperature is 400 to 600 ° C and the calcination time is 1 to 3 hours to heat the active mixture to produce a calcined product. The fired product is produced in the form of granules having a particle size of 0.01 to 3 mm by melting some of the components of the bottom ash constituting the active mixture by the firing and bonding with the adjacent components.

If the calcination temperature is lower than 400 ° C., the drying and calcination of the active mixture take a long time. If the calcination temperature is 600 ° C. or higher, the drying and calcination time can be shortened. However, And the particle size of the granules is excessively increased, so that it is preferable to add the above range.

In addition, in the calcination process, limestone (CaCO ₃ ) receives heat and changes into porous lime (CaO) while discharging carbon dioxide gas. In this process, the surface area is further increased. In addition, some quicklime is converted to calcium silicate (3CaO ₄ SiO ₂ , 2CaO ₄ SiO ₂ ) by combining the silicate component of bottom ash or the bottom ash with the silicate component of the purified water sludge, ) Is mixed, the crystallization is performed, and the strength is increased, so that the baked material can be granulated.

The fired product in this step means a powder or a granule having a particle diameter of 0.01 to 3 mm, but not limited thereto, and a powder or granule having a particle diameter of 0.01 mm or less may be included. However, since the handling is troublesome, It is preferable to use those having a grain size of 0.01 to 3 mm and having a grain size of 90% or more with respect to the total amount.

Step 2c is a step of dissolving the positive charge substance in a solvent to prepare a positive charge substance solution.

The positively chargeable substance is selected from the group consisting of chitosan or quaternary ammonium group and is dissolved in a solvent to prepare a positive charge substance dissolution liquid. The positive-electrode material solution may be coated with 0.01 to 5 parts by weight per 100 parts by weight of the sintered material, and water or acid may be used as the solvent.

The chitosan can be obtained by deacetylating chitin contained in the shrimp shell and shrimp shell in an amount of 60% or more, preferably 65 to 98%. The molecular weight of the chitosan is preferably in the range of 10,000 to 100,000. If the molecular weight is less than 10,000, the adhesive force is insufficient when coating the fired product, and the potential of the positive charge is lowered, so that the adhesion filtration rate of the fine dust or dust having a negative charge may be lowered. When the molecular weight exceeds 100,000, It is preferable to use the mixture in the above-mentioned range because the viscosity increases and the efficiency of the workability deteriorates.

As the solvent for dissolving the chitosan, citric acid, acetic acid which is an acid solution. Sulfuric acid, hydrochloric acid, and nitric acid. The acid solution may be diluted with water, and acetic acid is preferably used to prevent odor and environmental pollution.

Step 2d is a step of mixing the fired product of step 2b with the positive charge substance solution of step 2c and then stirring.

The stirring is performed such that the sintered material and the positive charge material solution are uniformly mixed so that the surface of the sintered product is uniformly coated with the positive charge material solution. The stirring is preferably carried out at a speed of 1000 to 3000 rpm for 30 minutes to 2 hours to uniformly mix. If the stirring is performed for less than 30 minutes, the mixture of the sintered material and the positive charge material solution is not uniformly mixed to lower the coating rate of the sintered material. If stirring is performed for 2 hours or more, the uniform coating is insufficient, desirable.

Step 2e is a step of injecting an agitated product of the sintered material and the positive charge material solution of step 2d into an oven and drying it to prepare an adsorbent coated with a positively charged substance on the sintered product.

The drying is carried out in a drying oven (dry oven). The drying oven is heated to a temperature in the range of 80 to 180 ° C and dried for 1 to 4 hours. Preferably, the drying time is shortened It is dried within a heating range of 100 to 180 ° C within 1 to 2 hours.

Next, the third step is a first mixing step in which 5 to 15 parts by weight of an adsorbent is mixed with 100 parts by weight of the starting material of the first step. When the adsorbent is mixed in an amount of not more than 5 parts by weight, the odor concentration generated due to low efficiency of adsorbing and removing the odor component generated from the shredded product is large and the odor concentration generated when the adsorbent is mixed with not less than 15 parts by weight However, since the degree of the effect is insufficient, it is preferable to mix and use in the above range.

The stirring may be carried out at a speed of 1500 rpm for 0.5 to 2 hours, but the present invention is not limited to this, and may be carried out in a mixing tank, followed by proceeding to the next step or by stirring with a stirring screw.

In addition, by supplying ozone to the inside of the mixing process, it is possible to decompose and remove the odor components of the debris, thereby reducing odor generation. For example, the ozone gas may be used alone or in combination with a carrier gas for discharging noxious gases including odors generated during a mixing process or a transfer process for forming pellets, thereby causing decomposition and removal of odor components while discharging odor and noxious gas .

In the fourth step, the mixture is pelletized by pelletizing the mixture. In this step, the size of the pellet generated according to the size of the nozzle head can be adjusted. In addition, since the pelletization is performed before the moisture drying process, the agglomeration force between the materials is increased, so that breakage of the pellets formed by pressurization can be minimized. At this time, the molding may be performed in various forms of solid fuel such as a briquettes,

The fifth step is a step of hot-air drying at a moisture content of 10% or less while moving the pellet in the fourth step. In this step, the pellets are extruded by extruding the water-containing shredded material, and the pellets are dried by supplying hot air with high heat while transferring the pellets through a hot air drier.

At this time, the supplied hot air is supplied to either the inflow side or the discharge side of the hot air dryer and discharged to the other side, thereby heating the hot air dryer to dry the pellets passing through the hot air dryer, So that the entire hot air dryer is formed at a predetermined temperature or more, so that the drying can be continuously performed.

For example, as shown in FIG. 2A, the hot dry gas is supplied to the pellet discharge side to be discharged through the pellet inflow side to dry the pellet, or the gas heated and dried at a predetermined interval is supplied at a predetermined interval as shown in FIG. And drying can be carried out by discharging gas having a high water content through the inlet side. However, as the drying efficiency increases with temperature from 100 ° C to 180 ° C, the drying efficiency increases. Therefore, it is important to maintain the temperature of the entire hot-air dryer within the temperature range of 100 to 180 ° C in order to maximize the drying efficiency while reducing the energy consumption. Therefore, the hot air of 150 ° C or more, preferably 150 to 180 ° C, So that the low temperature zone does not fall below 100 ° C in the entire section, thereby maintaining the hot air temperature at 100-180 ° C.

In this regard, in the fifth step of the hot air drying of the present invention by applying the method of FIG. 2B, the nozzles for spraying the hot air dried at a predetermined interval at regular intervals are formed, .

In this way, the hot air drying can decompose the odor discharged from the pellet or the odor component on the surface of the pellet, thereby minimizing the discharge of the odor component, thereby reducing the capacity of the filter used for treating the odor component.

In addition, the odor component contained in the shaft fraction is deodorized with the primary adsorbent, deodorized with the secondary ozone, and pyrolyzed and removed by the tertiary hot air to reduce the odor emitted from the final solid fuel, In addition, it can be used as a heating fuel for farming and fishing facilities.

3, the method for manufacturing a malodor-reducing solid fuel according to the present invention includes a sixth step of receiving and pulverizing a part of dried solid fuel, and a seventh step of charging and mixing the pulverized product into a third step .

In the sixth step, the pellet type solid fuel dried through the fifth step is partially received and pulverized. That is, the solid fuel having been subjected to the fifth step is shaped like a pellet in order to improve the transportability, so that the solid fuel is pulverized so as to be mixed as uniformly as possible with the mixture of the third step. The pellet type solid fuel in this step is ground to a diameter of 1 mm or less, preferably 0.1 to 1 mm, so as to be uniformly mixed with the mixture of the three stages.

The seventh step is a second mixing step in which the solid fuel pulverized in the sixth step is mixed with the first mixture, which is a mixture of the condensate of the third step and the adsorbent, at a ratio of 1: 1. The mixing ratio of the first mixture and the solid fuel pulverizer is not fixed at 1: 1, and may be mixed at a ratio of 50 to 150 parts by weight with respect to 100 parts by weight of the first mixture.

Since the solid fuel pulverized product is dried, the moisture content of the second mixture in which the solid fuel pulverized product is mixed can be lowered as the mixing ratio of the first fuel component with the higher water content is higher. At this time, if the solid fuel pulverized material is mixed in an amount of less than 50 parts by weight with respect to 100 parts by weight of the first mixture, the degree of shortening the drying time by lowering the moisture content is low. If the amount is more than 150 parts by weight, The degree of aggregation due to extrusion is low and is easily broken. Therefore, it is preferable to mix them in the above range.

The mixing of the second mixture is carried out for 0.5 to 2 hours so that sufficient mixing is achieved.

A fourth step in which the first mixture obtained by mixing the starting material and the adsorbent and the second mixture obtained by mixing the solid fuel pulverized material at a ratio of 1: 0.5 to 1.5 is put into a pellet molding machine to perform molding, The fifth step can be re-run to produce a solid fuel.

The manufacturing method of the present invention will be briefly described with reference to the manufacturing apparatus of Fig.

The condensate 10 prepared in the first step and the adsorbent 20 prepared in the second step are introduced into the mixing chamber 30 and mixed while being stirred to produce the first mixture (the third step).

The first mixture is poured into a molding machine 40, extruded through a nozzle head at the end of the molding machine, and molded into pellets (fourth step).

The molded pellets are dried at a moisture content of 10% or less (fifth step) while passing through a hot air dryer (50) to produce solid fuel.

(Step 6), and the solid fuel pulverized product is mixed with the first mixture at a ratio of 1: 0.5 to 1.5, or preferably 1: 1, to the first mixture The mixture is supplied to the mixing tank 30 to produce a second mixture by stirring, and the second mixture is passed through the molding machine 40 and the hot air dryer 50 to produce a solid fuel.

Here, the mixing tank 30 may be connected to the ozone generator 70 to supply ozone generated by the ozone generator to decompose and remove odor components.

Therefore, the manufacturing method according to the present invention can decompose and remove odorous components in three stages by pyrolysis by the primary adsorbent, the secondary ozone, and the tertiary hot air drying, thereby minimizing the generation of odor from the produced solid fuel, As a fuel or fuel additive.

&Lt; Example 1 - Production of solid fuel of the present invention &

1) Preparation of adsorbent

1 kg of limestone was mixed with 10 kg of crushed bottom ash supplied from Taean Thermal Power Plant and stirred for 1 hour to prepare an active mixture.

The prepared activated mixture was put into a sintering furnace and fired at a temperature of 500 ° C for 1 hour to produce a sintered product

1 kg of deacetylated chitosan (molecular weight: 50,000) was mixed with a mixed solvent of 1 L of acetic acid and 9 L of distilled water and stirred to prepare a positively charged substance solution.

10 kg of the produced fired product was weighed, and 2 L of the positive charge material solution was added thereto. Finally, 0.2 kg of the positive charge material was mixed with 10 kg of the fired product and stirred for 1 hour for coating.

The stirred mixture was put into an oven and dried at 120 DEG C for 1 hour to be completely dried to prepare an adsorbent.

2) Production of solid fuel

100 kg of a poultice having a moisture content of 30% or less was prepared, 10 kg of the prepared adsorbent was mixed and stirred for 30 minutes to prepare a first mixture, and ozone was supplied during the production.

The first mixture was pelletized by pelletizing machine.

The prepared pellets were dried in a hot-air dryer maintained at a temperature ranging from 70 to 80 ° C for 1 hour to prepare solid fuel.

&Lt; Example 2 >

The ozone was not supplied in the first mixture manufacturing process, and the remaining solid fuel was produced in the same manner as in Example 1. [

&Lt; Example 3 >

Solid fuels were prepared in the same manner as in Example 1, except for using fodder instead of fodder.

<Example 4>

In the preparation of the first mixture, 100 kg of coal having a calorific value of 5,000-5,500 kcal / kg was also mixed, and the remaining solid fuel was prepared in the same manner as in Example 1.

&Lt; Example 5 >

A solid fuel was produced in the same manner as in Example 1 except that a part of the solid fuel dried in the hot air drier was received and pulverized to produce a solid fuel pulverized product.

The solid fuel pulverized material was mixed with the same amount (110 kg) as the first mixture (100 kg of pork and 10 kg of adsorbent) to prepare a second mixture, and the second mixture was pelletized by pellet molding machine.

&Lt; Example 6 >

The ozone was not supplied in the first mixture production process, and the remaining solid fuel was produced in the same manner as in Example 5.

&Lt; Example 7 >

Solid fuels were prepared in the same manner as in Example 5, except for using fodder instead of fodder.

&Lt; Example 8 >

In the preparation of the first mixture, 100 kg of coal having a calorific value of 5,000 kcal / kg was also mixed, and the rest of the solid fuel was prepared in the same manner as in Example 5.

&Lt; Comparative Example 1 &

A solid fuel was prepared using the same adsorbent as in Example 1 except that a positive charge material was not coated in the preparation of the adsorbent.

&Lt; Comparative Example 2 &

A solid fuel was prepared using the same adsorbent as in Example 5 except that a positive charge material was not coated in the preparation of the adsorbent.

Examples 1 to 8 and Comparative Examples 1 and 2 are summarized in Table 1 below.

The calorific value was measured with the sample shown in Table 1 below. The amount of heat generated when completely burning, expressed in kcal as a result of combustion of unit weight (kg), expressed in kcal / kg.

As a result of measurement, calorific values of Examples 4 and 8 in which coal was added showed a calorific value in a range of 4550 to 4650 kcal / kg.

Also, in Example 1, Example 2, Example 5, Example 6, Comparative Example 1, and Comparative Example 2 in which pigs were used without adding coal, calorific values appeared in the range of 2050 to 2100 kcal / kg.

In addition, in Examples 3 and 7 in which cow powder was used without adding coal, calorific values were shown in a range of 2650 to 2700 kcal / kg.

It was found that whether or not the adsorbent is coated with a positive charge material and whether or not the ozone deodorization process is performed does not affect the calorific value.

Experimental Example 2 - Ammonia Emission Experiment [

The ammonia release rate of the sample of Table 1 over time was experimented.

1) 1 kg of the sample of Table 1 was put into a 5 L sized Tedlar bag and sealed.

The internal gas of Tedlarbach was measured by the provisions of KS I 2218 and the temperature was maintained at 23 ± 4 ° C and the humidity was maintained at 50 ± 10% during the test.

The concentration of the internal gas was measured at the initial (0 day), 5, 10, 20, and 30 days, and is shown in Table 2 below

As shown in Table 2 above, the adsorbents were mixed in both the examples and the comparative examples, and the ammonia concentration was low as a whole.

In Examples 2 and 6 in which ozone deodorization was not performed, the ammonia concentration was measured to be somewhat higher.

Further, the ammonia concentration in Examples 5 to 8, in which the step of crushing and remixing the produced solid fuel was further performed, was lower than that in Examples 1 to 4. As a result of repeated hot air drying and deodorization of ozone, Of the total population.

In addition, the ammonia concentration was lowest in Examples 4 and 8 in which coal was mixed, and it was considered that odorous components were adsorbed and removed by the coal to be mixed, and ammonia was less generated due to relatively low mixing amount of the fodder.

In addition, since ammonia emission was lower than that of Comparative Examples 1 and 2 using the adsorbent in which the positive charge material was not coated under the same conditions of Example 1 and Example 5 using the adsorbent coated with the positive charge material, .

Claims

5 to 15 parts by weight of an adsorbent coated with a positively charged substance is mixed with a mixture of BOTTOM ASH and limestone with respect to 100 parts by weight of an aqueous dispersion containing at least one of water,
The adsorbent is formed by mixing and calcining 5 to 20 parts by weight of limestone with respect to 100 parts by weight of bottom ash, coating 0.01 to 5 parts by weight of positively charged substance with respect to 100 parts by weight of the calcined calcined material to have a size of 0.01 to 3 mm,
Wherein the positive charge material is selected from the group consisting of chitosan and quaternary ammonium based coatings,
The quaternary ammonium system
Choline, Carnitine, Benzalkonium chloride; Denatonium; Cetrimonium bromide; Diallyldimethyl ammonium chloride; 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHPTAC); 3-chloro-2-hydroxypropyltrimethylammonium chloride; Copolymers of acrylamide and quaternized dimethylammonium ethyl methacrylate (Copolymer of acrylamide and quaternized dimethylammonium methyl methacrylate); Poly (diallyldimethylammonium chloride); a diallyldimethylammonium chloride polymer; Copolymers of acrylamide and diallyldimethylammonium chloride (Copolymer of acrylamide and diallyldimethylammonium chloride); Quaternized hydroxyethylcellulose; Copolymers of vinylpyrrolidone and quaternized dimethylaminoethyl methacrylate (Copolymer of vinylpyrrolidone and quaternized dimethylaminoethyl methacrylate); Copolymers of vinylpyrrolidone and quaternized vinylimidazole (Copolymer of vinylpyrrolidone and quaternized vinylimidazole); Copolymers of acrylic acid and diallyldimethylammonium chloride (Copolymer of Acrylic Acid and Diallyldimethylammonium Chloride); Copolymers of vinylpyrrolidone and methacrylamidopropyltrimethylammonium (Copolymer of vinylpyrrolidone and methacrylamidopropyl trimethylammonium); Poly (acrylamide 2-methacryloxyethyltrimethyl ammonium chloride) (Poly (acrylamide 2-methacryloxyethylammonium chloride)); Acrylic acid, acrylamide and diallyldimethylammonium chloride (Terpolymer of Acrylic Acid, Acrylamide and Diallyldimethylammonium Chloride); Terpolymers of vinylcaprolactam, vinylpyrrolidone, and quaternized vinylimidazole; vinylcaprolactam, vinylpyrrolidone and quaternized vinylimidazole; And a trimer of acrylic acid, methacrylamidopropyltrimethylammonium and methyl acrylate (Methacrylamidopropyl Trimethyl Ammonium Chloride, and Methyl Acrylate).

The method according to claim 1,
With respect to 100 parts by weight of the starch fraction,
50 to 200 parts by weight of coal having a calorific value of 3,000 to 8,000 kcal / kg is further mixed.

delete

The method according to claim 1,
Wherein the bottom ash is a mixed bottom ash obtained by mixing 50 to 80% by weight of bottom ash with 20 to 50% by weight of purified water sludge, and 5 to 20 parts by weight of limestone is mixed with 100 parts by weight of mixed bottom ash, Reduced solid fuel.

The method according to claim 1,
Wherein the adsorbent is further comprised of 0.001 to 0.2 parts by weight of a metal or a metal oxide mixed with 100 parts by weight of bottom ash,
The metal or metal oxide
(Y), molybdenum (Mo), Bi, Tele, Te, Mn, Cb, Rh, Ir, Ni, Pd ), At least one of platinum (Pt), copper (Cu), silver (Ag), gold (Au) and aluminum (Al).

delete

Comprising: a first step of producing an aqueous dispersion having a water content of 30% or less, which is selected from at least one selected from the group consisting of an aqueous dispersion and an aqueous dispersion;
A second step of preparing an activated carbon mixture by mixing and stirring the bottom ash and limestone, preparing a fired product by heating, and preparing an adsorbent having a positive charge material coated on the produced fired product;
A first mixing step of mixing 5 to 15 parts by weight of an adsorbent with 100 parts by weight of the starting material of the first step by stirring;
A fourth step of pelletizing the mixture by pellet molding;
A fifth step of producing a solid fuel by moving the pellets in the fourth step with hot air to a moisture content of 10% or less;
A sixth step of receiving and pulverizing a part of the pellet-shaped solid fuel obtained in the fifth step;
A seventh step in which the solid fuel pulverized in the sixth step is mixed with a mixture of the scrap of the third step and the adsorbent in a ratio of 1: 1 and supplied to the pellet molding machine of the fourth step; Wherein the solid fuel is a solid fuel.

delete

8. The method of claim 7,
The adsorbent preparation in the second stage
A step 2a of mixing and stirring 5 to 20 parts by weight of limestone with respect to 100 parts by weight of bottom ash to prepare an active mixture;
A step 2b of heating the activated mixture in a baking furnace to produce a baked product;
A second step c) of dissolving the positive charge material in a solvent to prepare a positive charge material dissolution solution;
A second d step of mixing the positive charge material solution prepared in step 2c so that the positive charge material is coated in an amount of 0.01 to 0.5 part by weight with respect to 100 parts by weight of the sintered material prepared in step 2b; And
And a step (2e) of adding an agitated mixture to an agitating furnace and drying it.

10. The method of claim 9,
In the step 2a,
0.001 to 0.2 part by weight of a metal or a metal oxide with respect to 100 parts by weight of bottom ash,
Said metal or metal oxide being selected from the group consisting of: (Y), molybdenum (Mo), Bi, Tele, Te, Mn, Cb, Rh, Ir, Ni, Pd ), At least one of platinum (Pt), copper (Cu), silver (Ag), gold (Au) and aluminum (Al).

10. The method of claim 9,
The solvent of step 2c is a water or an acid solution,
The acid solution is citric acid, acetic acid. Sulfuric acid, hydrochloric acid, and nitric acid,
The positive charge material may be selected from the group consisting of chitosan and quaternary ammonium, and the quaternary ammonium is selected from the group consisting of choline, carnitine, benzalkonium chloride; Denatonium; Cetrimonium bromide; Diallyldimethyl ammonium chloride; 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHPTAC); 3-chloro-2-hydroxypropyltrimethylammonium chloride; Copolymers of acrylamide and quaternized dimethylammonium ethyl methacrylate (Copolymer of acrylamide and quaternized dimethylammonium methyl methacrylate); Poly (diallyldimethylammonium chloride); a diallyldimethylammonium chloride polymer; Copolymers of acrylamide and diallyldimethylammonium chloride (Copolymer of acrylamide and diallyldimethylammonium chloride); Quaternized hydroxyethylcellulose; Copolymers of vinylpyrrolidone and quaternized dimethylaminoethyl methacrylate (Copolymer of vinylpyrrolidone and quaternized dimethylaminoethyl methacrylate); Copolymers of vinylpyrrolidone and quaternized vinylimidazole (Copolymer of vinylpyrrolidone and quaternized vinylimidazole); Copolymers of acrylic acid and diallyldimethylammonium chloride (Copolymer of Acrylic Acid and Diallyldimethylammonium Chloride); Copolymers of vinylpyrrolidone and methacrylamidopropyltrimethylammonium (Copolymer of vinylpyrrolidone and methacrylamidopropyl trimethylammonium); Poly (acrylamide 2-methacryloxyethyltrimethyl ammonium chloride) (Poly (acrylamide 2-methacryloxyethylammonium chloride)); Acrylic acid, acrylamide and diallyldimethylammonium chloride (Terpolymer of Acrylic Acid, Acrylamide and Diallyldimethylammonium Chloride); Terpolymers of vinylcaprolactam, vinylpyrrolidone, and quaternized vinylimidazole; vinylcaprolactam, vinylpyrrolidone and quaternized vinylimidazole; And methacrylamidopropyltrimethylammonium and methyl acrylate. The method for producing a malodor-reducing solid fuel according to claim 1, wherein the polymer is selected from the group consisting of acrylic acid, methacrylamidopropyltrimethylammonium and methyl acrylate.

8. The method of claim 7,
Wherein the third step further comprises mixing 50 to 200 parts by weight of coal having a calorific value of 3,000 to 8,000 kcal / kg with respect to 100 parts by weight of the shredded material.

8. The method of claim 7,
The ozone supply step may be included in any one or both of the third step and the fourth step to supply the ozone in the mixing step or the pellet forming step of the adsorbent and the ozone supplying step to provide a deodorizing effect by ozone Wherein said solid fuel is a solid fuel.

8. The method of claim 7,
The fifth step is to spray hot air at a temperature of 150 to 180 ° C to the pellets passing through the hot air dryer to maintain a drying temperature of 100 to 180 ° C in the hot air drying section .