KR20190125103A - Additive composition for solid fuel - Google Patents

Abstract

The present invention relates to an additive composition for solid fuels and, more specifically, to an additive composition for solid fuels capable of improving combustion efficiency of a fuel when added to a solid fuel comprising coal or coke, preventing slagging phenomena effectively, removing generated by-products such as a clinker or the like easily and reducing air pollution sources such as sulfur oxides, nitrogen oxides and fine dust effectively.

Description

Additive composition for solid fuels {ADDITIVE COMPOSITION FOR SOLID FUEL}

The present invention relates to an additive composition for a solid fuel, and more particularly, when added to a solid fuel containing coal, coke, or the like, it is possible to improve the combustion efficiency of the fuel and effectively prevent slagging phenomenon. The present invention relates to an additive composition for a solid fuel, which can easily remove by-products such as clinker, which can effectively reduce sulfur oxides, nitrogen oxides, fine dust, and the like as air pollutants.

In recent years, interest in the use of coal, which has been pushed back by conventional energy, has increased, and the use of coal-fired boilers and various heating furnaces has increased.

Coal collected from nature is classified as coal or Flaming Coal when the volatile content exceeds 11% according to the volatile content (Volatile), and is classified as anthracite when the volatile content is less than 10%.

Anthracite coal is mined in a state of fixed carbon content of more than 90%, caloric content of more than 8,000kcal and non-tacky powder. Bituminous coal, on the other hand, is usually mined in large chunks and is called coal or lump coal. Such bituminous coal has a relatively low fixed carbon content compared to anthracite coal, and may have a volatile content of more than about 20%, so that a large amount of soot may occur during combustion.

Such coal is widely used in smelting of iron in coal-fired power plants, steel mills, etc., pulverized coal and coke, and small household, agricultural, or industrial heating boilers.

Most coal is used for industrial purposes, but some private coal is used in the form of coal briquettes rather than in the form of pulverized coal. In particular, the most commonly used form of coal briquettes is briquettes, and a mixture of clay and water having high cohesiveness is mixed with powdered coal to form a variety of porous coals (eg, ball coal, 19 ball coal, 24 ball coal, etc.). It is often molded and used for heating.

However, compared with heavy oil, coal contains a small amount of volatiles and ash of fixed carbon and silicon oxide, aluminum oxide, titanium oxide, etc., resulting in low combustion efficiency and a large amount of ash in combustion. do.

More specifically, when the solid fuel such as coal is combusted, the above-described inorganic components contained in the coal may be converted into a coal circuit without burning, and discharged along the gas flow in a molten state in a region higher than the melting point. When the temperature is relatively low, it is attached to a boiler wall and a tube surface, and so on, and may form a clinker, which may cause many problems in operation, and may also cause a problem in that energy efficiency is also lowered.

In addition, due to the difficulty of complete combustion, some of the ash component is discharged in the form of flying ash, which not only promotes internal clinker formation, but also promotes internal clinker formation, especially in the case of a high ratio of sulfur oxide or nitrogen oxide in solid fuel Since harmful gases and fine dusts are generated a lot, environmental problems are increasing.

Therefore, during the combustion of solid fuel, slagging can be effectively prevented, and by-products such as clinker generated can be easily removed, and sulfur oxides, nitrogen oxides, and fine dusts, which are air pollutants, can be effectively reduced. There is a continuing need for research on methods.

The present invention, when added to a solid fuel containing coal, coke or the like, can improve the combustion efficiency of the fuel, effectively prevent the slagging phenomenon, and can easily remove the by-products such as clinker generated, while also being an air pollution source It is to provide an additive composition for solid fuel, which can effectively reduce phosphorus sulfur oxide, nitrogen oxide, fine dust and the like.

This specification,

Aluminum hydroxide nanoparticles;

Magnesium oxide nanoparticles;

Vanadium-titanium based composite oxide nanoparticles;

Graphene; And

An object of the present invention is to provide an additive composition for a solid fuel, including petroleum mineral oil.

The aluminum hydroxide nanoparticles may have a number average particle diameter of about 50 to about 150 nm, and a particle size distribution of about 10 to about 500 nm.

The additive composition for solid fuel may include about 10 to about 30 parts by weight of the aluminum hydroxide nanoparticles based on 100 parts by weight of the vanadium-titanium composite oxide nanoparticles.

The magnesium oxide nanoparticles may have a number average particle diameter of about 150 to about 250 nm, and a particle size distribution of about 100 to about 500 nm.

The additive composition for solid fuel may include about 50 parts by weight to about 70 parts by weight of the magnesium oxide nanoparticles based on 100 parts by weight of the vanadium-titanium composite oxide nanoparticles.

The vanadium-titanium based composite oxide nanoparticles may include titanium dioxide (TiO ₂ ) nanoparticles on which vanadium oxide (V ₂ O ₅ ) nanoparticles are supported.

In this case, the vanadium-titanium-based composite oxide nanoparticles may have a number average particle diameter of about 400 to about 600 nm, and a particle size distribution of about 100 to about 1000 nm.

The graphene may include any one or more of graphene nanosheets and graphene nanoplatelets.

The additive composition for solid fuel may include 5 to 30 parts by weight of the graphene based on 100 parts by weight of the vanadium-titanium composite oxide nanoparticles.

The additive composition for a solid fuel may further include magnesium ferrite nanoparticles having a number average particle diameter of about 20 to about 100 nm.

At this time, the additive composition for solid fuel, the magnesium ferrite nanoparticles based on 100 parts by weight of the vanadium-titanium composite oxide nanoparticles It may include 5 to 30 parts by weight.

The additive composition for a solid fuel may further include aluminum-cobalt-based composite oxide nanoparticles having a number average particle diameter of about 10 nm to about 70 nm.

In this case, the additive composition for a solid fuel may include 10 to 50 parts by weight of the aluminum-cobalt-based composite oxide nanoparticles based on 100 parts by weight of the vanadium-titanium composite oxide nanoparticles.

The solid fuel additive composition may further include a nonionic surfactant.

In addition, the petroleum mineral oil may include a paraffinic oil modified by hydrotreated or dewaxed.

According to the additive composition for a solid fuel of the present invention, when added to a solid fuel containing coal, coke or the like, it is possible to improve the combustion efficiency of the fuel, effectively prevent the slagging phenomenon, and easily generate by-products such as clinker generated While being removable, it is possible to effectively reduce sulfur oxides, nitrogen oxides, and fine dust, which are air pollution sources.

FIG. 1 is a scanning electron microscope image of the bottom ash (Bottom-Ash) and slag (clinker) collected and observed after the combustion test according to Example 1. FIG.
FIG. 2 is a scanning electron microscope image obtained by collecting the bottom ash (Bottom-Ash) and slag (clinker) under the combustion test according to Comparative Example 1. FIG.

The present invention, aluminum hydroxide nanoparticles;

Magnesium oxide nanoparticles;

Vanadium-titanium based composite oxide nanoparticles;

Graphene; And

Provided is an additive composition for solid fuel, comprising petroleum mineral oil.

The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise", "comprise" or "have" are intended to indicate that there is a feature, number, step, component, or combination thereof, that is, one or more other features, It should be understood that it does not exclude in advance the possibility of the presence or addition of numbers, steps, components, or combinations thereof.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

In the present specification, the term "solid fuel" refers to a solid fuel generally used in a thermal power plant, a heating boiler, and the like, and is not limited to a specific type or form. For example, all kinds of coal and coke may be used. Comprehensive

In the present specification, the petroleum-based mineral oil means a mineral oil or mineral oil which is a by-product generated in the process of refining crude oil.

EMBODIMENT OF THE INVENTION Hereinafter, the additive composition for solid fuels of this invention is demonstrated in detail.

Solid fuel additive composition according to an aspect of the present invention,

Aluminum hydroxide nanoparticles;

Magnesium oxide nanoparticles;

Vanadium-titanium based composite oxide nanoparticles;

Graphene; And

Contains petroleum mineral oils.

Coal ash is generally known to include metal or nonmetal oxides such as silicon oxide, aluminum oxide, sodium oxide, iron oxide, potassium oxide, calcium oxide, magnesium oxide, titanium oxide, sulfur oxide and the like.

Of these, sulfur oxide is a basic material reactive with very high and present in the coal-times, high particular reactivity as the basicity is greater sodium oxide or potassium oxide, easy to sodium sulfate (Na ₂ SO ₄₎ or potassium sulfate (K ₂ SO ₄ ) and the like, these materials lower the melting point of the overall ash component, which is the main cause of the slagging phenomenon.

In addition, the chlorine (Cl) component present in the coal can be converted to hydrochloric acid during coal combustion, which hydrochloric acid reacts with the iron component inside the combustion device, forming iron chloride on the surface of the combustion device, which is then contacted in the combustion process. The oxygen oxide can be converted into iron oxide to form an iron oxide film.

When the coal ash reaches the iron oxide film, salts such as sodium-iron-sulfate or potassium-iron-sulfate can be formed, and these materials exist as viscous liquids on the boiler tube surface because of their low melting point. As it flows down to the bottom of the boiler where it cannot reach the heat, it cools down gradually and becomes a solid, causing a problem of very large lumps of bottom ash.

According to an aspect of the present invention, an additive composition for a solid fuel includes, as one component, aluminum hydroxide nanoparticles.

The aluminum hydroxide nanoparticles may have a number average particle diameter of about 50 to about 150 nm, a particle size distribution of about 10 to 500 nm may be used, preferably about 10 to about 300 nm, or about 10 to about 200 nm. Can be used.

The aluminum hydroxide nanoparticles as described above are generally prepared by co-precipitation or sol gel method using aluminum isopropoxide (Al (OiPr) ₃ ), and at the time of reaction, The particle size can be controlled by adjusting the reaction conditions.

Such aluminum hydroxide nanoparticles can react with the above-described alkali metal complex salt and the like to produce a high melting point compound under high temperature conditions in which solid fuel is combusted, thereby effectively preventing slagging phenomenon and providing clinker at the furnace wall. It will be able to play a role in inducing them to drop out naturally. In addition, when the particles having an average particle diameter in the above range are used, the specific surface area per unit mass increases, so that the above-described effects can be further increased.

The aluminum hydroxide nanoparticles may be included in an amount of about 10 to about 30 parts by weight based on 100 parts by weight of the vanadium-titanium composite oxide nanoparticles.

If the content is too small, the reactivity with the above-described alkali metal complex salt may be lowered, and thus the effect of preventing clinker formation and reducing harmful gases may be significantly reduced. If the content is too high, economic problems may occur and dispersion of the composition may occur. Problems may occur in the properties, but rather increase the crystal precipitation and hardening, it may cause problems to promote the growth of clinker.

According to an aspect of the present invention, an additive composition for a solid fuel includes, as one component, magnesium oxide nanoparticles.

The magnesium oxide nanoparticles may have a number average particle diameter of about 150 nm to about 250 nm, and a particle diameter distribution of about 100 nm to about 500 nm, or about 100 nm to about 300 nm.

The magnesium oxide nanoparticles as described above may be prepared by a coprecipitation method or a sol gel method in which hydroxide ions are added to magnesium nitrate, and during the reaction, the particle size may be adjusted using a dispersing agent such as tetramethylammonium hydroxide. have.

Magnesium oxide nanoparticles are used for the purpose of preventing clinker formation and reducing harmful gases during solid fuel combustion. Specifically, the magnesium oxide nanoparticles may first react with the sulfur oxides as the temperature inside the combustion apparatus increases, thereby removing the sulfur oxides, thereby preventing the formation of the sulfate salt of the alkali metal described above, and thus, It is possible to suppress clinker production.

In particular, the magnesium sulfate produced by such a reaction has a higher melting point than the sulfate salt of the alkali metal described above, so that the slagging phenomenon can be prevented more effectively. It is softer than the case, and can be easily removed.

The magnesium oxide nanoparticles may be included in an amount of about 50 parts by weight to about 70 parts by weight based on 100 parts by weight of the vanadium-titanium composite oxide nanoparticles.

If the content is too small, the reactivity with sulfur oxides may be lowered, and the effect of preventing clinker formation and reducing harmful gases may be significantly reduced. If the content of magnesium oxide is too high, economic problems may occur, and the dispersibility of the composition may be reduced. A problem may occur, and a problem may occur in that the efficiency of the combustion reaction is significantly lowered due to the precipitation and hardening of the magnesium component.

In addition, the additive composition for a solid fuel according to an aspect of the present invention includes, as one component, vanadium-titanium composite oxide nanoparticles.

The vanadium-titanium-based composite oxide nanoparticles are specifically, titanium dioxide (TiO ₂ ) nanoparticles on which vanadium oxide (V ₂ O ₅ ) nanoparticles are loaded (V ₂ O ₅ loaded TiO ₂ ; V ₂ O ₅ supported TiO ₂ ) It may be in the form of containing.

In this case, the vanadium oxide nanoparticles may be nanorods, nanowires, or amorphous nanoparticles, and the titanium dioxide may also be nanorods, nanowires, Nanobelt, nanopalte or amorphous nanoparticles, preferably porous particles.

The vanadium-titanium composite oxide nanoparticles may have a number average particle diameter of about 400 to about 600 nm, and a particle size distribution of about 100 to about 1000 nm.

Such vanadium-titanium-based composite oxide nanoparticles include vanadium compounds such as vanadium hydroxide (V (OH) ₃ ) and vanadium oxide (V ₂ O ₅ ) in the presence of porous alumina-silica, and titanium isopropoxide (Ti ( It may be prepared by a co-precipitation method or the like, which is co-precipitated with an alkoxide compound such as OiPr) ₄ ), and during the reaction, the particle size may be adjusted by using a dispersing agent such as tetramethylammonium hydroxide.

In addition, vanadium-titanium based composite oxide nanoparticles manufacturing method is, Journal of Photochemistry and Photobiology A: Chemistry, Volume 163, Issue 3, 21 May 2004, Pages 509-515; See Nano Letters, 2006, 6 (6), page 1297-1302.

The vanadium-titanium based composite oxide nanoparticles can act as a catalyst in a combustion reaction, and when used in an additive composition for a solid fuel, can greatly activate the combustion reaction and reduce nitrogen oxides.

In addition, the interaction between the solid fuel and each component included in the present additive composition, such as nanoparticles, may be enhanced to increase the effect of each component.

When the content of the vanadium-titanium based composite oxide nanoparticles is too small, the effect of reducing nitrogen oxides may be reduced, and when the content is too large, economic problems may occur, and problems may occur in the dispersibility of the composition. Due to crystal precipitation and hardening, a problem may occur that the efficiency of the combustion reaction is significantly reduced.

In addition, the additive composition for a solid fuel according to an aspect of the present invention includes, as one component, vanadium-based graphene.

Graphene is a material arranged in a shape having a hexagonal planar structure in which carbon atoms of graphite, which are three-dimensional structural carbon allotrope naturally existing in nature, are in the form of a two-dimensional sheet. Graphene's carbon atoms form sp2 bonds and form single-atomic planar sheets.

Graphene has a very good electrical conductivity and thermal conductivity, and has a high specific surface area, and when used in an additive composition for a solid fuel, greatly activates the combustion reaction, and is included in the present additive composition such as solid fuel and nanoparticles. It can play a role in enhancing the interaction of each component.

The graphene may be included in an amount of about 5 to about 30 parts by weight based on 100 parts by weight of the vanadium-titanium composite oxide nanoparticles.

In addition, the additive composition for a solid fuel according to an aspect of the present invention includes, as one component, petroleum mineral oil.

Petroleum-based mineral oils are liquid by-products produced during the refining of crude oil into petroleum, also called liquid paraffins.Paraffinic oils based on n-alkanes and cycloalkanes based on Naphthenic oil (Naphthenic oil), there is an aromatic oil (Aromatic oil) based on the aromatic hydrocarbon, petroleum mineral oil in the present invention is a concept including both the above-described oil and modified oil.

According to one embodiment of the present invention, the petroleum mineral oil is preferably paraffinic oil, and more preferably modified by hydrotreated and / or dewaxed. Can be.

Specifically, the paraffinic oils modified by hydrotreating and / or dewaxing are hydrotreated heavy paraffinic distillate (CAS No. 64742-54-7) or hydrotreated light. Hydrotreated light paraffinic distillate (CAS No. 64742-55-8), solvent-dewaxed heavy paraffinic distillate (CAS No. 64742-65-0), solvent-deal Waxed light paraffinic distillate (CAS No. 64742-56-9), Hydrotreated and dewaxed heavy paraffinic distillate; CAS No. 91995-39 -0), and hydrotreated and dewaxed light paraffinic distillate (Hydrotreated and dewaxed light paraffinic distillate; CAS No. 91995-40-3), but may be composed of one or more selected from the group consisting of This must It is not limited to this.

The petroleum mineral oil may serve to lower the ignition temperature of the fuel in the combustion reaction of the solid fuel, may help the initial ignition, improve the calorific value of the solid fuel, stabilize the combustion reaction, combustion of the solid fuel The efficiency can be improved. It can also maintain the form of sludge redispersed into fine particles and act as a lubricant for internal combustion engines.

The petroleum mineral oil may be included in an amount of about 1 wt% to about 15 wt% based on the total composition, and more preferably about 5 wt% to about 10 wt%.

If the content of the petroleum mineral oil is too small, there may be a problem that does not improve the combustion efficiency, if the content of the petroleum mineral oil is too large, the dispersibility is lowered by the layer separation phenomenon of the additive, This may cause incomplete combustion and increase the amount of harmful gases.

According to an embodiment of the present invention, the additive composition for solid fuel may further include magnesium ferrite nanoparticles having a number average particle diameter of about 20 to about 100 nm.

Magnesium ferrite nanoparticles are obtained by producing magnesium ferrite (MgFe ₂ O ₄ ) by coprecipitation method using a salt such as iron chloride (FeCl ₃ ) and MgCl ₂ (magnesium chloride), and calcining at about 130 to about 500 ° C. Can lose.

Magnesium ferrite nanoparticles, due to their unique ferromagnetic properties, can enhance the activity and interaction of other additives, and can also affect the injected solid fuel to improve combustion efficiency.

The magnesium ferrite nanoparticles may be included in an amount of about 5 to about 30 parts by weight based on 100 parts by weight of the vanadium-titanium based composite oxide nanoparticles.

According to another embodiment of the present invention, the additive composition for a solid fuel may further include aluminum-cobalt-based composite oxide nanoparticles having a number average particle diameter of about 10 nm to about 70 nm.

The aluminum cobalt-based composite oxide nanoparticles may be, for example, a compound represented by a composition formula of Al ₂ CoO ₄ or Al ₂ Co ₂ O ₅ , cobalt oxide (Co ₂ O ₃ ), aluminum nitrate (Al (NO ₃ ) ₂ ), after the sol-gel method using citric acid and ethanol (C ₂ H ₅ OH), separately added alumina (Al ₂ O ₃ ) after a high temperature firing process of about 700 to about 800 ℃ Can be prepared.

Aluminum-cobalt-based composite oxide nanoparticles can also enhance the activity and interaction of other additives due to their unique ferromagnetic properties, and can also affect the injected solid fuel to improve combustion efficiency.

The aluminum-cobalt-based composite nanoparticles may be included in an amount of about 10 to about 50 parts by weight based on 100 parts by weight of the vanadium-titanium-based composite oxide nanoparticles.

The above-mentioned nanoparticles may all use commercial products, such as US Research Nanomaterials, AMERICAN ELEMENTS, Nanostructured & Amorphous Material, and Creative Diagnostics.

According to another example of the invention, the solid fuel additive composition may further comprise a nonionic surfactant. Nonionic surfactants can increase the dispersibility of each component in the form of nanoparticles, thereby helping to achieve uniform mixing, and in particular, increase the miscibility with petroleum-based mineral oils, and adverse effects such as foaming during dispersion. Can be minimized.

Specifically, the above-mentioned nonionic surfactant can use commercial items, such as TWEEN 80 (polysorbate 80, the product made by Sigma-Aldrich), for example.

The additive composition for a solid fuel according to another embodiment of the present invention may further include porous inorganic particles.

Such porous inorganic particles have pores having an average diameter of about 1 to about 20 nm, preferably about 1 to about 10 nm, on the particle surface, and have an average particle diameter of about 50 to about 2000 nm, preferably about 100. It is desirable to have a feature that is from about 1500 nm or about 500 to about 1500 nm. Such materials may include, for example, silica, alumina, zirconia, mixtures thereof, and the like, and commercially available porous zeolites and the like may also be used.

In the porous inorganic particles, the porous material may adsorb sulfur oxides and nitrogen oxides by utilizing internal pores in a combustion reaction of a solid fuel, thereby reducing emissions of harmful gases.

The porous inorganic particles may be included in about 1 to about 5% by weight based on the total composition.

When the content of the porous inorganic particles described above is too small, the effect of reducing harmful gas emissions may be insignificant, and when the content of the porous inorganic particles is too large, it becomes difficult to secure homogeneity and dispersibility in the composition.

According to another embodiment of the present invention, the additive composition for a solid fuel of the present invention may further include an ammonium salt of an organic acid having 5 to 10 carbon atoms.

Examples of the amine compound used as the ammonium salt include, for example, monoethanolamine, diethanolamine, triethanolamine, 1-aminoisopropanol, 1-imidazolidine ethanol, hydroxyethylpiperazine, and the like. Although it may be mentioned, the present invention is not limited thereto.

Specific examples of the organic acid include acetic acid, propanoic acid, butanoic acid, citric acid and the like.

Ammonium salts of these organic acids can generate generator oxygen in the combustion reaction of solid fuels, leading to the complete combustion of unburned carbon that may be present in Bottom Ash and Flying Ash, Combustion of unburned carbon contained in the clinker may cause the clinker to fall off.

In addition, it is preferable to use such an organic acid ammonium salt in about 1 to 10 weight% with respect to the whole composition.

In addition to the above-described components, the additive composition for solid fuel of the present invention may further include various additives generally used in the technical field to which the present invention belongs, such as a surfactant, a combustion promoting catalyst, a stabilizer, a dispersant, The content can be appropriately increased or decreased within the object to be achieved by the present invention.

The additive composition for solid fuel of the present invention has a NOx reduction rate of about 40% or more and a SOx reduction rate of about 50% or more when it is added to a solid fuel such as coal or coke, and is a type of hazardous gas generated during solid fuel combustion. The amount can be drastically reduced, the occurrence of clinker can be significantly reduced, and the combustion efficiency can be dramatically increased.

Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific examples of the invention. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined.

<Example>

Preparation of additive composition for solid fuel

Example 1:

1 kg of aluminum hydroxide nanoparticles with an average particle diameter of about 100 nm

3kg of magnesium oxide nanoparticles with an average particle diameter of about 200 nm

5 kg of vanadium-titanium composite oxide nanoparticles with an average particle diameter of about 500 nm

1 kg of magnesium ferrite nanoparticles with an average particle diameter of about 50 nm,

2kg of aluminum-cobalt-based composite oxide nanoparticles,

1 kg of TWEEN 80 as a nonionic surfactant;

2 kg of an aqueous slurry solution containing 1 kg of graphene;

1 kg of heavy paraffinic distillate hydrotreated with petroleum mineral oil;

1 kg of porous zeolite;

1 kg tetramethylammonium; And remaining water were added to prepare a 20 kg composition.

Comparative Example 1:

An additive composition was prepared using magnesium oxide, which is widely used as an additive for solid fuels.

10 kg of an aqueous slurry solution containing 5 kg of magnesium oxide;

5 kg of SPAN 60 (Sigma-Aldrich) as a cationic surfactant;

5 kg of a mixture of citric acid and monoethanol amine (1: 1 equivalent); And remaining water were added to prepare 100 kg of the composition.

Combustion reaction

A test furnace with a combustion capacity of 20 kg / h and a feed cell device capable of adjusting the time fuel fraction was prepared. The width of the main body of the furnace is 0.87m, the internal height is 1.50m, and a stainless steel internal structure is installed to compensate for the short height.Inside, a castable refractory is installed for insulation and peeled off and re-coated for each experiment. Used.

Coal was processed into an average particle size of 75 μm pulverized coal using a first and second fine powder manufacturing apparatus, and then water was removed using a dryer. In the case of using the additive, the additive was mixed with coal in a weight ratio of 1: 1000 and introduced into a combustion furnace. The coal mixed with raw coal and the additive was dried at 50 ° C. for 72 h to reduce the influence of moisture, thereby increasing the intrinsic moisture content. It was prepared to be 2wt% or less.

The prepared fuel was stored in a feed cell differential feeder.

In consideration of the calorific value, the fuel supply amount is set to 15kg / h, preheated using a preheated gas burner (LPG, capacity 210,000kcal / kg), and adjusted to an initial temperature (about 800 ° C to about 1000 ° C) suitable for experimental conditions, and then 100h The combustion test was run continuously.

After performing the combustion test, NOx, Sox reduction rate and clinker state, coal reduction rate was calculated as a weight percent value based on the coal burned, the results are summarized in Table 1 below.

Coal reduction rate
(weight%) Clinker status NOx reduction rate
(weight%) SOx reduction rate
(weight%) Example 1 15.3 Clinker can be removed by soft nitridation / hand 42 50 Comparative Example 1 3.2 Some softening /
Clinker cannot be removed by hand 4 7

Referring to Table 1, in the embodiment of the present invention, under the same combustion conditions, the weight reduction rate of coal is 15.3, it can be confirmed that about 5 times as large as compared to Comparative Example 1, that is, under the same combustion conditions By the additive composition for solid fuels, it can be inferred and confirmed that a combustion reaction occurred with high efficiency.

In addition, although the coal reduction rate was increased five times, it can be seen that the harmful substances such as NOx, SOx is rather reduced.

FIG. 1 is a scanning electron microscope image of the bottom ash (Bottom-Ash) and slag (clinker) collected and observed after the combustion test according to Example 1. FIG.

FIG. 2 is a scanning electron microscope image obtained by collecting the bottom ash (Bottom-Ash) and slag (clinker) under the combustion test according to Comparative Example 1. FIG.

Looking at the shape of the ash and clinker particles with reference to FIGS. 1 and 2, the ash and clinker collected in the comparative example has a large, hard and not easily broken form and can be confirmed that the crystallization is good, compared to the embodiment Ash and clinker collected in the low crystallinity, it can be seen that it has a fragile form.

Claims (15)

Aluminum hydroxide nanoparticles;
Magnesium oxide nanoparticles;
Vanadium-titanium based composite oxide nanoparticles;
Graphene; And
An additive composition for solid fuel, comprising petroleum mineral oil.
The method of claim 1,
The said aluminum hydroxide nanoparticle has a number average particle diameter of 50-150 nm, and particle size distribution is 10-500 nm, The additive composition for solid fuels.
The method of claim 1,
An additive composition for a solid fuel comprising 10 to 30 parts by weight of the aluminum hydroxide nanoparticles, based on 100 parts by weight of the vanadium-titanium composite oxide nanoparticles.
The method of claim 1,
The magnesium oxide nanoparticles have a number average particle diameter of 150 to 250 nm and a particle diameter distribution of 100 to 500 nm.
The method of claim 1,
An additive composition for solid fuel, comprising 50 to 70 parts by weight of the magnesium oxide nanoparticles, based on 100 parts by weight of the vanadium-titanium composite oxide nanoparticles.
The method of claim 1,
The vanadium-titanium-based composite oxide nanoparticles, titanium dioxide (TiO ₂ ) nanoparticles on which vanadium oxide (V ₂ O ₅ ) nanoparticles are supported, solid additive composition for fuel.
The method of claim 1,
The vanadium-titanium composite oxide nanoparticles have a number average particle size of 400 to 600 nm, particle size distribution of 100 to 1000 nm, solid fuel additive composition.
The method of claim 1,
The graphene, any one or more of graphene nanosheets and graphene nanoplatelets, solid fuel additive composition.
The method of claim 1,
To about 100 parts by weight of the vanadium-titanium-based composite oxide nanoparticles, comprising 5 to 30 parts by weight of the graphene, solid fuel additive composition.
The method of claim 1,
Further comprising a magnesium ferrite nanoparticles, the number average particle diameter of 20 to 100nm, solid fuel additive composition.
The method of claim 10,
An additive composition for a solid fuel comprising 5 to 30 parts by weight of the magnesium ferrite nanoparticles based on 100 parts by weight of the vanadium-titanium composite oxide nanoparticles.
The method of claim 1,
The additive composition for a solid fuel further comprising aluminum-cobalt-based composite oxide nanoparticles having a number average particle diameter of 10 to 70 nm.
The method of claim 12,
An additive composition for a solid fuel comprising 10 to 50 parts by weight of the aluminum-cobalt-based composite oxide nanoparticles based on 100 parts by weight of the vanadium-titanium composite oxide nanoparticles.
The method of claim 1,
Further comprising a nonionic surfactant, solid fuel additive composition.
The method of claim 1,
The petroleum mineral oil, a paraffinic oil (Paraffinic oil) modified by the hydrotreated or dewaxed (Dewaxed), additive composition for solid fuel.

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