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WO2012064084A2 - Liquid-combustion catalyst composition including mixed metal-complex ionic compound - Google Patents

Liquid-combustion catalyst composition including mixed metal-complex ionic compound Download PDF

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Publication number
WO2012064084A2
WO2012064084A2 PCT/KR2011/008464 KR2011008464W WO2012064084A2 WO 2012064084 A2 WO2012064084 A2 WO 2012064084A2 KR 2011008464 W KR2011008464 W KR 2011008464W WO 2012064084 A2 WO2012064084 A2 WO 2012064084A2
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edta
compound
complex
combustion
catalyst composition
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WO2012064084A3 (en
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오미혜
류나현
류연석
류환우
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/27—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a liquid or molten state
    • C—CHEMISTRY; METALLURGY
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/00—Liquid carbonaceous fuels
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/12—Inorganic compounds
    • C10L1/1291—Silicon and boron containing compounds
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1802—Organic compounds containing oxygen natural products, e.g. waxes, extracts, fatty oils
    • C—CHEMISTRY; METALLURGY
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1826—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms poly-hydroxy
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C—CHEMISTRY; METALLURGY
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0204—Metals or alloys
    • C10L2200/0209—Group I metals: Li, Na, K, Rb, Cs, Fr, Cu, Ag, Au
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0204—Metals or alloys
    • C10L2200/0213—Group II metals: Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd, Hg
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0204—Metals or alloys
    • C10L2200/0218—Group III metals: Sc, Y, Al, Ga, In, Tl
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0204—Metals or alloys
    • C10L2200/0236—Group VII metals: Mn, To, Re

Definitions

  • the present invention relates to a liquid combustion catalyst composition comprising a complex metal complex ion compound, and more particularly, to the combustion of fuels such as hydrocarbons, fossils and biomass by adding ionic metal compounds during combustion in a combustion engine.
  • fuels such as hydrocarbons, fossils and biomass
  • ionic metal compounds during combustion in a combustion engine.
  • By suppressing the generation of sludge, clinker and fouling caused by the incombustible minerals it is possible to optimize the combustion of the combustion engine to increase the combustion rate per unit area and to increase the productivity of the combustion engine and its accessories.
  • It relates to a liquid combustion catalyst composition comprising.
  • combustion engines which typically use hydrocarbons and fossil fuels, especially boilers
  • the four main components of combustion are air (oxygen), fuel, heat and chimneys.
  • the fuel is composed of dehydrated organic matter and non-burnable inorganic matter (ash), but in order to increase the combustion efficiency by increasing the combustion speed for organic matter in order to improve thermal efficiency, a high temperature above the melting point of the inorganic matter (ash) is formed in the combustion engine.
  • the minerals (ash) melt and fuse to the combustion engine, hindering operation and at the same time dropping heat transfer, causing heat loss.
  • the pulverized coal blowing facility (PCI) has been developed and used as a fuel system for the combustion engine.
  • the pulverized coal blowing facility is used to hot-air the pulverized coal obtained by crushing coal of low quality in order to improve the output per unit volume of the combustion engine and to reduce the fuel cost. In addition, it is blown into the combustion engine to increase the combustion efficiency of the combustion engine.
  • the technology for increasing the efficiency of the combustion engine the technology to increase the combustion efficiency and thermal efficiency of the combustion engine by adding the combustion catalyst and the oxygen compound to the fuel used in the pulverized coal injection facility (Korea Patent Publication No. 10-2002 -0075758) has been developed, and in recent years, by applying an alkali metal catalyst that uses a mixture of alkali metal and oxygen as a combustion catalyst, the combustion reaction is accelerated and the melting point is lowered to induce stable operation of the combustion engine. And high productivity.
  • alkali metals promote combustion in a high temperature combustion state, but are difficult to manage at ordinary temperature without a special device.
  • Alkali oxides that provide oxygen are also unstable at room temperature and are difficult to exist in a liquid state.
  • the present invention is to solve the above problems, by adding a ionic composite metal catalyst during combustion in the combustion engine to accelerate the chemical thermal equilibrium required for the combustion of fuels such as hydrocarbons and fossils and biomass At the same time, by optimizing the amount of air containing oxygen, which is required by chemical equivalents, it improves thermal efficiency and efficiency of the combustion engine, thereby reducing the amount of fuel used as a heat source, and is generated by inorganic substances and soot that are not well burned during combustion in the combustion engine.
  • It provides a liquid combustion catalyst composition comprising a complex metal complex ion compound that can suppress the generation of sludge, clinker and fouling and sintering to optimize the combustion of the combustion engine to increase the combustion rate per unit area and improve the productivity of the combustion engine.
  • the liquid combustion catalyst composition is mixed with the fuel
  • the task is to solve the problem of widening the contact and specific surface area by fuel and ion unit and further activating the combustion catalyst functionality.
  • the present invention is capable of dissolving a complex metal chelate compound or a complex metal complex ion hydrate composed of at least one metal compound selected from Mg, Ca, Mn, Zn, and Al and at least one alkali metal compound selected from Li, K, and Na. It provides a liquid combustion catalyst composition (sometimes in a crystal state) containing a complex metal complex ion compound which is dissolved in a liquid and has a complex metal complex ion, and also has effects and thermal efficiency, such as promoting combustion and melting point control of the metal at a high temperature. Providing improvements and the like simultaneously is a solution to the problem.
  • the solution that can be dissolved is nitric acid or aqueous ammonia as the solution for the problem.
  • the soluble liquid further includes a surfactant selected from sorbitol, glycerin, EDTA, and ethanolamine to dissolve and disperse the metal compound.
  • a surfactant selected from sorbitol, glycerin, EDTA, and ethanolamine to dissolve and disperse the metal compound.
  • the composite metal complex ion hydrate is a conjugate base (NO 3 ⁇ ) to combine alkali metal (Li, K, Na) with alkaline metal (Mg, Ca), transition metal (Fe, Mn, Zn) and aluminum (Al). ) And the formation of complex ions through water molecules (H 2 O) or water molecules (H 2 O) serving as ligands is a solution to the problem.
  • the composite metal chelate compound is Li 2 [Ca edta] .4H 2 OK 2 , Li 2 [Mg edta] .4H 2 ONa 2 , K 2 [Ca edta] .4H 2 O, K 2 [Mg edta] .4H 2 O, Na 2 [Ca edta]. 4 H 2 O, Na 2 [Mg edta].
  • boron hydrates Na 2 B 4 O 7 .nH 2 0, B 2 O 3 .nH 2 O, B 2 O 4 .nH 2 0, NaBO 2 .nH 2 O, NaBO 3 .nH At least one boron compound selected from 2 O, Na 2 BO 4 .nH 2 O, H 3 BO 3 .nH 2 O; Mg 3 (PO 4 ) 2 .nH 2 O, MgHPO 4 .nH 2 O, AlPO 3 .nH 2 O, K 2 HPO 3 .nH 2 O, Zn 3 (PO 4 ) 2 .nH 2 O, MnHPO 3 .
  • liquid combustion catalyst composition comprising a complex metal complex ion compound or a complex metal complex ion hydrate according to the present invention, as a composition to be added to the fuel as the ionized metal and alkali metal to form an ionic state in the liquid phase in the liquid It is widely distributed in to promote the oxidation reaction and the combustion reaction, which induces the generation of high temperature, thereby obtaining the effect of improving the combustion efficiency and thermal efficiency.
  • a complex metal chelate compound or a complex metal complex ion hydrate composed of at least one metal compound selected from Mg, Ca, Mn, Zn, and Al and at least one alkali metal compound selected from Li, K, and Na is dissolved. It provides a liquid combustion catalyst composition containing a complex metal complex ion compound which is dissolved in a liquid as much as possible to form a complex metal complex ion, and at the same time provides the effects of promoting the combustion and the melting point of the metal at a high temperature and improving the thermal efficiency. It is characterized by the technical configuration.
  • the soluble liquid is characterized in that the technical configuration of nitric acid or ammonia water.
  • the soluble liquid is characterized by a technical configuration that further comprises a surfactant selected from sorbitol, glycerin, EDTA, ethanolamine so that the metal compound is dissolved and dispersed.
  • a surfactant selected from sorbitol, glycerin, EDTA, ethanolamine so that the metal compound is dissolved and dispersed.
  • the composite metal complex ion hydrate is a conjugate base (NO 3 ⁇ ) to combine alkali metal (Li, K, Na) with alkaline metal (Mg, Ca), transition metal (Fe, Mn, Zn) and aluminum (Al). ) And the formation of complex ions through the water molecule (H 2 O) or water molecule (H 2 O) as a ligand is a feature of the technical configuration.
  • the composite metal chelate compound is Li 2 [Ca edta] .4H 2 OK 2 , Li 2 [Mg edta] .4H 2 ONa 2 , K 2 [Ca edta] .4H 2 O, K 2 [Mg edta] .4H 2 O, Na 2 [Ca edta]. 4 H 2 O, Na 2 [Mg edta].
  • Li 2 [Mn edta], Li 2 [Zn edta], Li 2 [Al edta], K 2 [Mn edta ], K 2 [Zn edta], K 2 [Al edta], Na 2 [Mn edta], Na 2 [Zn edta], Na 2 [Al edta] is characterized by the technical configuration.
  • boron hydrates Na 2 B 4 O 7 .nH 2 0, B 2 O 3 .nH 2 O, B 2 O 4 .nH 2 0, NaBO 2 .nH 2 O, NaBO 3 .nH At least one boron compound selected from 2 O, Na 2 BO 4 .nH 2 O, H 3 BO 3 .nH 2 O; Mg 3 (PO 4 ) 2 .nH 2 O, MgHPO 4 .nH 2 O, AlPO 3 .nH 2 O, K 2 HPO 3 .nH 2 O, Zn 3 (PO 4 ) 2 .nH 2 O, MnHPO 3 .
  • liquid combustion catalyst composition including a complex metal complex ion compound according to the present invention will be described in detail.
  • embodiments of the present invention can be modified in many different forms, the scope of the invention is not to be construed as limited to the embodiments described below.
  • Embodiment of the present invention is provided to explain to those skilled in the art to understand the present invention.
  • the technical idea of the present invention is to promote the combustion reaction C + O 2 ⁇ CO 2 of carbon (C) in the organic material with an optimal amount of air (oxygen) through the composite metal ion to control the ignition point and to increase the combustion speed It is to reduce the heat loss caused by the amount of air to increase the combustion efficiency and to increase the effective heat transfer energy value due to the formed high temperature.
  • the present invention stabilizes the temperature in the combustion engine by preventing and fusion to the wall of the combustion engine by increasing and softening the Initial Deformed Temperature (IDT) of the inorganic material (ash) even when the inorganic material (ash) is exposed to high temperature. It is to increase the thermal efficiency of the engine.
  • IDT Initial Deformed Temperature
  • the liquid combustion catalyst composition comprising a composite metal complex ion compound of the present invention is at least one metal compound selected from Mg, Ca, Mn, Zn, Al and at least one alkali selected from Li, K, Na
  • a complex metal chelate compound or a complex metal complex ion hydrate composed of a metal compound is a liquid composition in which a complex metal complex ion is formed by dissolving in a soluble liquid.
  • the Mg, Ca, Mn, Zn, Al serves to increase the IDT (melting point) of the inorganic material (ash), is used for combustion by combining in the form of complex ion with alkali metal in the ionic state, maintained in a stable liquid form even at room temperature do.
  • liquids that dissolve Mg, Ca, Mn, Zn, Al can be dissolved in hydrochloric acid or sulfuric acid, but they are suitable for nitric acid or ammonia water because they release corrosion and air pollutants.
  • the alkali metal compound refers to six elements of rubidium (Rb), cesium (Cs), and francium (Fr), including potassium (K), sodium (Na), and lithium (Li), and reacts with water at room temperature to hydrogen.
  • the alkali metal is a silvery white soft metal which loses its luster soon, and has a low specific gravity, a melting point and a boiling point, and has a flame reaction, and is directly active with many nonmetallic elements.
  • it is a metal that is well combined with oxygen and reacts with hydrogen to form hydrides.
  • alkali metals have a characteristic of reacting with moisture (for example, carbon dioxide, etc.) in the air when left in the air as usual, and elements of other metals (nitrogen) contained in other metal elements or fuels under high temperature combustion conditions. Ionization is faster than carbon, sulfur, and the like, and promotes combustion with a catalyst that provides the transition state (thermal equilibrium) required for the oxidation of other materials.
  • alkali (Li, K, Na) metals promote the bond between oxygen and carbon.
  • the alkali metal compound is composed of at least one alkali metal compound selected from the group consisting of potassium, sodium, and lithium among six alkali metal elements.
  • the alkali metal compound may be one alkali metal compound selected from potassium, sodium, and lithium, or may be formed to be used by mixing two or more kinds.
  • the alkali metal compound is made such that the ionized alkali metal is present in a positive (+) state. That is, the alkali metal compound is ionized in the liquid state and is present in the liquid (water) in an ionic state such as K + , Na + , Li +, and thus widely distributed in minerals such as fuel and ash, thereby promoting combustion.
  • the alkali metal compound may be at least one alkali metal compound selected from the group consisting of a hydroxide compound, a carbonate compound, and an oxide compound.
  • the alkali metal compound is composed of a hydroxide-based compound, a carbonate-based compound, and an oxide-based compound, it is helpful to reduce the ignition point during combustion of the fuel and to improve thermal efficiency.
  • the hydroxide-based compound is composed of at least one selected from compounds consisting of potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH), the hydroxide-based compound is a hydroxide (OH) during combustion
  • KOH potassium hydroxide
  • NaOH sodium hydroxide
  • LiOH lithium hydroxide
  • the carbon conversion efficiency is increased to increase the combustion efficiency, and the melting point of the alumina oxide contained in the fuel is reduced to easily remove or suppress the formation of the fusion produced during combustion.
  • the compound of the carbonic acid series is potassium carbonate (K 2 CO 3 ), sodium carbonate (NaCO 3 ), lithium carbonate (LiCO 3 ), potassium hydrogen carbonate (KHCO 3 ), sodium hydrogen carbonate (NaHCO 3 ), lithium carbonate (LiHCO 3
  • K 2 CO 3 potassium carbonate
  • NaCO 3 sodium carbonate
  • LiCO 3 lithium carbonate
  • KHCO 3 potassium hydrogen carbonate
  • NaHCO 3 sodium hydrogen carbonate
  • LiHCO 3 lithium carbonate
  • LiHCO 3 lithium carbonate
  • One or more types are selected and comprised from the compound which consists of).
  • the carbonic acid-based compound When composed of the carbonic acid-based compound, it generates carbon dioxide (CO 2 ) during combustion.
  • CO 2 carbon dioxide
  • the carbon dioxide generated by the carbonate-based compound actively reacts with the carbon while contacting the surface of the fuel, which is a heat source, thereby improving combustion efficiency.
  • the compound of the oxide is potassium oxide (K 2 O), sodium oxide (Na 2 O), lithium oxide (Li 2 O), potassium peroxide (K 2 O 2 ), sodium peroxide (Na 2 O 2 ), lithium peroxide ( Li 2 O 2 ), potassium nitrate (KNO 3 ), sodium nitrate (NaNO 3 ), lithium nitrate (LiNO 3 ) is selected by at least one selected from the compound, and the compound of the oxide generates oxygen during combustion By promoting the reaction with the carbon to generate a high temperature to improve the combustion efficiency and thermal efficiency.
  • alkali (Li, K, Na) metals alone are unstable at normal room temperature and in water, making it difficult to maintain, store and use, and lower the melting point of ash by reacting with organic matter (ash) during combustion in combustion engines. Interfere with operation and reduce thermal efficiency.
  • Mg, Ca, Mn, Zn, Al are complex ion compounds combined with alkali metals (Li, K, Na), complex metal chelate compounds or complex metal complex ion hydrates, dissolved in nitric acid or ammonia water and handled and stable. Because of its excellent fuel contact and excellent fuel contact, when using these atomic and ionic metals as catalysts, the carbon (C) atoms in the fuel in the combustion state can be reduced even with a very small amount of heterogeneous catalytic state (about 0.01 to 0.1% of the fuel). It can act to achieve the effect of this invention.
  • the factors that promote combustion by using the complex metal chelate compound or complex metal complex ion hydrate are, firstly, calorie increase and high temperature formation due to the catalysis of alkali metals (Li, Na, K) and the reduction of unburnt. Second, the reduction of heat of intake and formation of high temperature due to the provision of radical oxygen (O), the decrease of air volume, and the fourth increase in calorie value according to the oxidation process (M + O ⁇ MO) of alkali metals and metals.
  • the particle surface of the solid fuel forms a high temperature and accelerates the combustion reaction to the adjacent particles in series and delivers the chain high temperature to each particle surface, thereby bringing a combustion promoting effect even with a small amount of complex metal complex ion.
  • At least one complex metal chelating compound selected from Mg, Ca, Mn, Zn, and Al, which forms a high melting point cargo in the form of an oxide after combustion may be, for example, Li 2 [Ca edta] .4H 2 OK 2 , Li 2 [Mg edta] .4H 2 ONa 2 , K 2 [Ca edta] .4H 2 O, K 2 [Mg edta] .4H 2 O, Na 2 [Ca edta] .4H 2 O, Na 2 [Mg edta] .4H 2 O, Li 2 [Mn edta], Li 2 [Zn edta], Li 2 [Al edta], K 2 [Mn edta], K 2 [Zn edta], K 2 [Al edta], Na 2 [ At least one selected from Mn edta], Na 2 [Zn e
  • EDTA Forma C 10 H 16 N 2 O 8 , Ethylenediaminetetraacetic acid
  • EDTA is a colorless crystalline powder which binds to the metal via four carboxylates and two amine groups. It has the characteristic of making stable water-soluble chelate with almost all metal ions such as Ca 2+ and Mg 2+ .
  • K 2 [Ca edta] .4H 2 O or the like is obtained as colorless rod-shaped crystals, but the aqueous solution is alkaline.
  • the complex metal chelate compound has excellent stability at room temperature and in a liquid state, and is convenient to use.
  • Alkali metal decomposed during combustion by adsorption on the surface of the fuel in an ionic state is a C + O 2 ⁇ CO 2 reaction of carbon (C).
  • C C + O 2 ⁇ CO 2 reaction of carbon
  • Mg, Ca, Mn, Zn, Al decomposed in the combustion process to prevent the ash adsorbed on the surface of the ash to melt and suppress Clinker, Fouling and Sintering.
  • the double metal complex ion hydrates are the alkali metal (Li, K, Na) and Mg, Ca, Mn, Zn, Conjugate Base in order to bond the Al (NO 3 -) and a ligand of water molecules (H 2 O) Form a complex ion through the medium.
  • K (NO 3 ) crystals and Mg (NO 3 ) 2 .6H 2 O combine to dissolve into complex metal complex hydrates of the form K (NO 3 ) .Mg (NO 3 ) 2 .13H 2 O And it forms a composite metal complex ion with excellent stability.
  • the alkali metal (Li, K, Na) and combines another and Mn (NO 3) forming a refractory metal oxide K 2 .9H combines 2 O (NO 3) .Mn ( NO 3) 2 .16H 2 O complex ion compound and Zn (NO 3) 2 .6H 2 0 and the combined K (NO 3) .Zn (NO 3) 2 in the case of ionic compounds of .15H 2 O are also excellent solubility and stability sheds brought the same effect.
  • all the complex metal complex ion hydrates other than the above three compounds had the same effect.
  • the complex metal complex ion hydrate that forms the coordination bond as described above is not easily decomposed, has excellent solubility and stability, is easy to store, transport and apply, and exhibits the same effect as the complex metal chelate even in a high temperature combustion state.
  • the complex metal complex ion compound decomposes during combustion to generate gases “N 2 ” and “O”, so that fuel particles of coal or heavy oil, which are fossil fuels, are finely divided to help the combustion by increasing the surface area necessary for combustion. Providing oxygen (O) necessary for exothermic reaction to increase the fraction of oxygen (O) to promote the reaction of "C + O 2 ⁇ CO 2 ".
  • the complex metal complex ion hydrate forms a hydrate-type crystal, which makes Clinker and Fouling a porous and hard material by the vapors (H 2 O and OH) generated from the hydrate during initial combustion. to further suppressed, so that welding on the body making a batch in this manner a porous, for example, K (NO 3) .Mg ( NO 3) 2 .9H the other compounds of the different hydrate forms in addition to complex ion compounds such as 2 O when added together there will be K (NO 3) .Mg (NO 3) 2 .9H 2 O man yi time for dropping the Clinker and Fouling and Sintering and sludge faster than the time it is used.
  • K (NO 3) .Mg (NO 3) 2 .9H 2 O man yi time for dropping the Clinker and Fouling and Sintering and sludge faster than the time it is used.
  • hydrate-type compounds include those with strong complex ions, such as Na 2 B 4 O 7 .nH 2 0, B 2 O 3 .nH 2 O, B 2 O 4 .nH 2 0, NaBO 2 at least one boron compound selected from .nH 2 O, NaBO 3 .nH 2 O, Na 2 BO 4 .nH 2 O, H 3 BO 3 .nH 2 O; Mg 3 (PO 4 ) 2 .nH 2 O, MgHPO 4 .nH 2 O, AlPO 3 .nH 2 O, K 2 HPO 3 .nH 2 O, Zn 3 (PO 4 ) 2 .nH 2 O, MnHPO 3 .
  • alkali metals Li, Na, K
  • K is converted to K 2 CO 3
  • Na is converted to Na 2 CO 3 when the catalytic function is completed during combustion. It also promotes the reduction of unburnt and the catalytic role of CO generated from incomplete combustion, thereby reducing CO by promoting "CO + O ⁇ CO 2 ".
  • decomposed Mg is MgO
  • Ca is CaO
  • Mn is MnO
  • Zn is ZnO
  • Al is Al 2 O 3 and is oxidized to high melting point oxide to adhere to the surface of the ash to cover the ash, and the melting point of the surface of the ash (IDT: By increasing the Initial Deformed Temperature, the inside of the ash is prevented from melting even if the melting point is low, helping alkali metals (Li, Na, K) to form at high temperatures in combustion engines and to improve combustion efficiency.
  • the ignition point is lower and the speed of reaching the effective heat transfer energy value is faster than that of the non-dissolved compound. It also reduces x and reduces the amount of air needed for initial combustion.
  • fuel for example, coal and coke, biomass, etc.
  • a liquid fuel for example, kerosene, diesel, coal tar, crude oil.
  • gaseous fuels for example, hydrocarbon-based fuels such as natural gas
  • the composition of the present invention is to maintain the pH so as to prevent precipitation and maintain solubility, but the pH should be managed to about 3 to 7 to prevent corrosion of metal materials such as iron, and excellent stability in a liquid state at room temperature It is convenient to use.
  • the composition of the alkali metal in the present composition is about 25% molar ratio is suitable, but can be adjusted in consideration of the slagging and fouling index, etc., depending on the ash content and composition of the coal.
  • a surfactant selected from sorbitol, glycerin, EDTA, and ethanolamine may be added, and the proportion thereof is a liquid combustion catalyst composition.
  • Surfactant: Water 1 ⁇ 25: 1 ⁇ 25: 25 ⁇ 80 It is mixed and used.
  • the composition prepared as described above is dried to the extent that crystals are present at 100 ° C. or lower, it becomes a transparent crystal with ionic bonds.
  • liquid combustion catalyst composition containing the complex metal complex ion compound in the present invention will be described in detail.
  • embodiments of the present invention can be modified in many different forms, the scope of the invention is not to be construed as limited to the embodiments described below.
  • Embodiment of the present invention is provided to explain to those skilled in the art to understand the present invention.
  • Sample 1 50 g of magnesium nitrate + 8 g of potassium nitrate
  • Sample 2 50 g of zinc nitrate + 8 g of potassium nitrate
  • sample 3 concentration of 70% nitric acid
  • Sample 1 After mixing 25g of nitric acid (concentration 65%) in 25g of water, 50g of zinc nitrate was mixed, and then dissolved and ionized at a ratio of 10g of potassium nitrate and 3g of borax to prepare a liquid combustion catalyst composition.
  • Sample 2 A mixture of 50 g of magnesium nitrate Mg (NO 3 ) 2 .6H 2 O was mixed with 100 g of water, and then 8 g of potassium nitrate K (NO 3 ) was dissolved and ionized to prepare a liquid combustion catalyst composition.
  • Boiler 200MWh supercritical perfusion type circulating fluidized bed boiler
  • Test type domestic 30%, Imported anthracite (Vietnam, Russia, North Korea) 75%
  • air pollutants NOx, SOx, and CO gas decreased 33.3 ppm 3.2 ppm and 6.6 ppm, respectively, and sample 2 decreased 43.3 ppm, 6.0 ppm, and 4.6 ppm, respectively. And 5.7 W% decreased compared to no addition.

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Abstract

The present invention relates to a liquid-combustion catalyst composition including a mixed metal-complex ionic compound, and more particularly, to a liquid-combustion catalyst composition including a mixed metal-complex ionic compound that is added to a combustion process of a combustion engine to quickly reach a chemical-thermal equilibrium state required for burning (for example, a hydrocarbon fuel, a fossil fuel, or a biomass fuel) and to optimize an amount of air including a required chemical equivalent of oxygen according to the chemical thermal equilibrium state, thereby improving thermal efficiency and the efficiency of the combustion engine. Accordingly, the used amount of the fuel as a heat source can be decreased, and the occurrence of sludge, clinker, fouling, and sintering due to incomplete combustion of an inorganic material within the combustion engine is prevented, so as to optimize the combustion process of the combustion engine and thus increase the combustion rate per unit area and improving productivity of the combustion engine. According to the present invention, a mixed-metal chelate compound or a mixed metal-complex ionic hydrate, which includes: one or more metal compounds selected from Mg, Ca, Mn, Zn, and Al; and one or more alkali metal compounds selected from Li, K, and Na, is dissolved in a solvent to generate mixed-metal complex ions.

Description

복합 금속착이온화합물을 포함하는 액상 연소촉매 조성물Liquid Combustion Catalyst Composition Containing Complex Metal Complex Ion Compound

본 발명은 복합 금속착이온화합물을 포함하는 액상 연소촉매 조성물에 관한 것으로서, 더욱 상세하게는 연소기관에서 연소시 이온성을 가진 금속화합물을 첨가함으로써 탄화수소와 화석 및 바이오매스와 같은 연료의 연소에 필요한 화학적인 열적 평형상태를 빠르게 함과 동시에, 이에 따르는 화학당량적으로 필요한 산소를 포함하는 공기량을 최적화시킴으로써 열효율 및 연소기관의 효율을 증진하여 열원인 연료의 사용량을 절감하며, 연소기관 내부에서 연소중에 잘 연소되지 않는 무기물에 의해서 발생하는 Sludge, Clinker와 Fouling의 발생을 억제하여 연소기관의 연소를 최적화시켜 단위면적당 연소율을 높이고 연소기관 및 부속기기의의 생산성을 증진시킬 수 있는 복합 금속착이온화합물을 포함하는 액상 연소촉매 조성물에 관한 것이다.The present invention relates to a liquid combustion catalyst composition comprising a complex metal complex ion compound, and more particularly, to the combustion of fuels such as hydrocarbons, fossils and biomass by adding ionic metal compounds during combustion in a combustion engine. By speeding up chemical thermal equilibrium and optimizing the amount of air containing oxygen, which is required by chemical equivalence, it improves thermal efficiency and efficiency of the combustion engine, reducing the amount of fuel used as a heat source, and during combustion in the combustion engine. By suppressing the generation of sludge, clinker and fouling caused by the incombustible minerals, it is possible to optimize the combustion of the combustion engine to increase the combustion rate per unit area and to increase the productivity of the combustion engine and its accessories. It relates to a liquid combustion catalyst composition comprising.

일반적으로 탄화수소 및 화석연료를 사용하는 연소기관 특히 보일러의 경우 연소의 4대 요소는 조건은 공기(산소), 연료, 열 그리고 굴뚝이다. 그 중 연료는 탈수 있는 유기물과 타지 않는 무기물(회분)로 이루어져 있으나 열효율을 높이기 위해 유기물에 대한 연소속도를 높여 연소효율을 증진시키는 경우, 연소기관 내에서 무기물(회분)의 융점 이상의 고온이 형성되어 무기물(회분)이 녹아 연소기관에 융착하여 운전을 방해함과 동시에 열전달을 떨어뜨려 열손실을 야기한다. In combustion engines, which typically use hydrocarbons and fossil fuels, especially boilers, the four main components of combustion are air (oxygen), fuel, heat and chimneys. Among them, the fuel is composed of dehydrated organic matter and non-burnable inorganic matter (ash), but in order to increase the combustion efficiency by increasing the combustion speed for organic matter in order to improve thermal efficiency, a high temperature above the melting point of the inorganic matter (ash) is formed in the combustion engine. The minerals (ash) melt and fuse to the combustion engine, hindering operation and at the same time dropping heat transfer, causing heat loss.

연소기관에 사용되는 연료시스템으로는 미분탄 취입설비(PCI)가 개발되어 사용되고 있는데, 이러한 미분탄 취입설비는 연소기관의 단위 용적당 생산량의 향상 및 연료비 저감을 위해서 저질인 석탄의 파쇄로 얻어진 미분탄을 열풍과 함께 연소기관 내부에 취입하여 연소기관의 연소효율을 높인다.The pulverized coal blowing facility (PCI) has been developed and used as a fuel system for the combustion engine. The pulverized coal blowing facility is used to hot-air the pulverized coal obtained by crushing coal of low quality in order to improve the output per unit volume of the combustion engine and to reduce the fuel cost. In addition, it is blown into the combustion engine to increase the combustion efficiency of the combustion engine.

그러나, 미분탄 취입설비는 열원인 화석연료(석탄 등)의 사용으로 연소시 연소기관에 회분(ash)이 녹아 생성되는 융착물로 인해 연소기관의 열효율 및 생산성이 저하되기 때문에 정상적인 연소기관의 운전에 어려움이 있었다.However, pulverized coal injection equipment is used for the operation of normal combustion engine because the thermal efficiency and productivity of combustion engine are lowered due to fusion produced by melting ash in ash in combustion engine by using fossil fuel (coal, etc.) as a heat source. There was a difficulty.

따라서, 연소기관 내에 연소효율성을 높이는데 있어서 물리적인 방법보다는 화학적인 방법이 바람직하고, 최근에는 화학적인 방법으로서 첨가제를 이용한 화학적인 반응을 통하여 연소기관의 효율성을 높이도록 하는 첨가제 조성물이 대두되고 있다.Therefore, in order to increase the combustion efficiency in a combustion engine, a chemical method is preferable rather than a physical method, and recently, an additive composition for increasing the efficiency of a combustion engine through chemical reaction using an additive as a chemical method has emerged. .

이와 관련하여, 연소기관의 효율을 높이기 위한 것으로서, 미분탄 취입설비에서 사용하는 연료에 연소촉진촉매 및 산소화합물을 첨가하여 사용하므로 연소기관의 연소효율 및 열효율을 높이는 기술(대한민국공개특허 제10-2002-0075758호)이 개발되었고, 최근에는 연소촉진촉매로 알칼리금속과 산소를 가진 화합물을 혼합사용하는 알칼리금속촉매를 적용하여 사용함에 따라 연소반응의 촉진 및 융점이 저하되어 연소기관의 안정적인 운전을 유도하고, 높은 생산성을 발휘하게 되었다.In this regard, the technology for increasing the efficiency of the combustion engine, the technology to increase the combustion efficiency and thermal efficiency of the combustion engine by adding the combustion catalyst and the oxygen compound to the fuel used in the pulverized coal injection facility (Korea Patent Publication No. 10-2002 -0075758) has been developed, and in recent years, by applying an alkali metal catalyst that uses a mixture of alkali metal and oxygen as a combustion catalyst, the combustion reaction is accelerated and the melting point is lowered to induce stable operation of the combustion engine. And high productivity.

그러나, 종래의 첨가제로서 알칼리금속은 고온인 연소상태에서는 연소를 촉진하나 평상시 상온에서는 특별한 장치 없이 관리하기가 어려우며, 산소를 제공하는 알칼리산화물도 상온에서 불안정하여 액체상태로 존재하기가 어려워 고체상태 및 이온이 아닌 상태로 사용하여 제대로 된 연소효율을 발휘하기가 어려운 문제점이 있었다. 이에, 안정성이 뛰어나면서도 이온성이 강한 액체상태의 첨가제 조성물이 절실히 요구되고 있는 실정이다.However, as a conventional additive, alkali metals promote combustion in a high temperature combustion state, but are difficult to manage at ordinary temperature without a special device.Alkali oxides that provide oxygen are also unstable at room temperature and are difficult to exist in a liquid state. There was a problem that it is difficult to exert a proper combustion efficiency by using the non-ion state. Accordingly, there is an urgent need for a liquid additive composition having excellent stability and strong ionicity.

본 발명은 상기와 같은 문제점을 해결하기 위한 것으로서, 연소기관에서 연소시 이온성을 가진 복합금속촉매를 첨가함으로써 탄화수소와 화석 및 바이오매스와 같은 연료의 연소에 필요한 화학적인 열적 평형상태를 빠르게 함과 동시에 이에 따르는 화학당량적으로 필요한 산소를 포함하는 공기량을 최적화시킴으로써 열효율 및 연소기관의 효율을 증진하여 열원인 연료의 사용량을 절감하며, 연소기관 내부에서 연소중에 잘 연소되지 않는 무기물 및 Soot 등에 의해서 발생하는 Sludge, Clinker와 Fouling 그리고 Sintering의 발생을 억제하여 연소기관의 연소를 최적화시켜 단위면적당 연소율을 높이고 연소기관의 생산성을 증진시킬 수 있는 복합 금속착이온화합물을 포함하는 액상 연소촉매 조성물을 제공하고 상기 액상 연소촉매 조성물이 연료와 혼합되어 연료와 이온단위로 접촉, 비표면적을 넓히고 연소촉매적 기능성을 더욱 활성화시키는 것을 해결하려는 과제로 한다.The present invention is to solve the above problems, by adding a ionic composite metal catalyst during combustion in the combustion engine to accelerate the chemical thermal equilibrium required for the combustion of fuels such as hydrocarbons and fossils and biomass At the same time, by optimizing the amount of air containing oxygen, which is required by chemical equivalents, it improves thermal efficiency and efficiency of the combustion engine, thereby reducing the amount of fuel used as a heat source, and is generated by inorganic substances and soot that are not well burned during combustion in the combustion engine. It provides a liquid combustion catalyst composition comprising a complex metal complex ion compound that can suppress the generation of sludge, clinker and fouling and sintering to optimize the combustion of the combustion engine to increase the combustion rate per unit area and improve the productivity of the combustion engine. The liquid combustion catalyst composition is mixed with the fuel The task is to solve the problem of widening the contact and specific surface area by fuel and ion unit and further activating the combustion catalyst functionality.

본 발명은 Mg, Ca, Mn, Zn, Al으로부터 선택되는 1종 이상의 금속화합물과 Li, K, Na으로부터 선택되는 1종 이상의 알칼리금속화합물로 구성된 복합금속킬레이트화합물 또는 복합금속착이온 수화물이 용해 가능한 액체에 용해되어 복합금속착이온이 형성된 복합금속착이온화합물을 포함하는 액상 연소촉매 조성물(Crystal 상태로 존재하기도 함)을 제공하고 더불어 고온에서의 금속의 연소촉진성 및 융점조절 등의 효과 및 열효율 개선 등을 동시적으로 제공하는 것을 과제의 해결수단으로 한다.The present invention is capable of dissolving a complex metal chelate compound or a complex metal complex ion hydrate composed of at least one metal compound selected from Mg, Ca, Mn, Zn, and Al and at least one alkali metal compound selected from Li, K, and Na. It provides a liquid combustion catalyst composition (sometimes in a crystal state) containing a complex metal complex ion compound which is dissolved in a liquid and has a complex metal complex ion, and also has effects and thermal efficiency, such as promoting combustion and melting point control of the metal at a high temperature. Providing improvements and the like simultaneously is a solution to the problem.

또한, 상기 용해 가능한 액체는 질산 또는 암모니아수인 것을 과제의 해결 수단으로 한다.In addition, the solution that can be dissolved is nitric acid or aqueous ammonia as the solution for the problem.

또한, 상기 용해 가능한 액체는 금속화합물이 용해 및 분산되도록 솔비톨, 글리세린, EDTA, 에탄올아민으로부터 선택되는 계면활성제를 더 포함하는 것을 과제의 해결 수단으로 한다.The soluble liquid further includes a surfactant selected from sorbitol, glycerin, EDTA, and ethanolamine to dissolve and disperse the metal compound.

상기 복합금속착이온 수화물은 알카리 금속(Li,K,Na)과 알카리토금속(Mg, Ca), 전이금속(Fe, Mn, Zn) 그리고 알루미늄(Al)을 결합하기 위해서 Conjugate Base인 (NO3 -)와 리간드인 물분자 (H2O) 또는 물분자(H2O)를 매개로 하여 착이온을 형성하는 것을 과제의 해결 수단으로 한다.The composite metal complex ion hydrate is a conjugate base (NO 3 − ) to combine alkali metal (Li, K, Na) with alkaline metal (Mg, Ca), transition metal (Fe, Mn, Zn) and aluminum (Al). ) And the formation of complex ions through water molecules (H 2 O) or water molecules (H 2 O) serving as ligands is a solution to the problem.

상기 복합금속킬레이트화합물은 Li2[Ca edta].4H2OK2, Li2[Mg edta].4H2ONa2, K2[Ca edta].4H2O, K2[Mg edta].4H2O, Na2[Ca edta].4H2O, Na2[Mg edta].4H2O, Li2[Mn edta], Li2[Zn edta], Li2[Al edta], K2[Mn edta], K2[Zn edta], K2[Al edta], Na2[Mn edta], Na2[Zn edta], Na2[Al edta]에서 선택되는 1종 이상인 것을 과제의 해결 수단으로 한다.The composite metal chelate compound is Li 2 [Ca edta] .4H 2 OK 2 , Li 2 [Mg edta] .4H 2 ONa 2 , K 2 [Ca edta] .4H 2 O, K 2 [Mg edta] .4H 2 O, Na 2 [Ca edta]. 4 H 2 O, Na 2 [Mg edta]. 4 H 2 O, Li 2 [Mn edta], Li 2 [Zn edta], Li 2 [Al edta], K 2 [Mn edta ], K 2 [Zn edta], K 2 [Al edta], Na 2 [Mn edta], Na 2 [Zn edta], Na 2 [Al edta] It is one or more types chosen from the solution of a subject.

상기 복합금속착이온 수화물은 K(NO3).Mg(NO3)2.13H2O, K(NO3).Mn(NO3)2.16H2O, K(NO3).Zn(NO3)2.15H2O, Na(NO3).Mg(NO3)2.13H2O, Na(NO3).Mn(NO3)2.16H2O, Na(NO3).Zn(NO3)2.15H2O, Li(NO3).Mg(NO3)2.13H2O, Li(NO3).Mn(NO3)2.16H2O, Li(NO3).Zn(NO3)2.15H2O, K(NO3).Al(NO3)3.9H2O Na(NO3).Al(NO3)3.9H2O, Li(NO3).Al(NO3)3.9H2O 에서 선택되는 1종 이상인 것을 과제의 해결 수단으로 한다.The composite metal complex ion hydrate K (NO 3) .Mg (NO 3) 2 .13H 2 O, K (NO 3) .Mn (NO 3) 2 .16H 2 O, K (NO 3) .Zn (NO 3 ) 2 .15H 2 O, Na (NO 3 ) .Mg (NO 3 ) 2 .13H 2 O, Na (NO 3 ) .Mn (NO 3 ) 2 .16H 2 O, Na (NO 3 ) .Zn ( NO 3 ) 2 .15H 2 O, Li (NO 3 ) .Mg (NO 3 ) 2 .13H 2 O, Li (NO 3 ) .Mn (NO 3 ) 2 .16H 2 O, Li (NO 3 ) .Zn (NO 3 ) 2 .15H 2 O, K (NO 3 ) .Al (NO 3 ) 3 .9H 2 O Na (NO 3 ) .Al (NO 3 ) 3 .9H 2 O, Li (NO 3 ) .Al (NO 3) is not less than one element selected from 3 .9H 2 O as a solving means of the problem.

또한, 상기 이외의 것들로 붕소수화물인 Na2B4O7.nH20, B2O3.nH2O, B2O4.nH20, NaBO2.nH2O, NaBO3.nH2O, Na2BO4.nH2O, H3BO3.nH2O 으로부터 선택되는 1종 이상의 붕소화합물; Mg3(PO4)2.nH2O, MgHPO4.nH2O, AlPO3.nH2O, K2HPO3.nH2O, Zn3(PO4)2.nH2O, MnHPO3.nH2O, Na3PO3.nH2O, Al(NO3)3.nH2O 으로부터 선택되는 1종 이상의 인산화합물; Mg(OH)2.nH2O, MgCO3.nH2O 으로부터 선택되는 1종 이상의 마그네슘화합물; Mn(OH)2.nH2O, MnCO3.nH2O, KMnO4.nH2O, Mn(NO3)2.nH2O으로부터 선택되는 1종 이상의 망간화합물; FeO.nH2O, Fe2O3.nH2O, Fe3O4.nH2O, [Fe edta].nH2O 으로부터 선택되는 1종 이상의 철화합물; NaSiO2.nH2O, KSiO2.nH2O, LiSiO2.nH2O 으로부터 선택되는 1종 이상의 규소화합물;을 각각 또는 1종 이상을 질산, 암모니아, EDTA, 글리세린, 솔비톨 또는 에탄올아민에 녹여 상기 액상 연소촉매 조성물에 더 첨가하여 이온성 복합착염의 형성 및 이온성을 높이고, 연소촉진, 크링커 및 파울링의 제거 효율을 더 높이는 것을 과제의 해결 수단으로 한다.In addition, other than those above, boron hydrates Na 2 B 4 O 7 .nH 2 0, B 2 O 3 .nH 2 O, B 2 O 4 .nH 2 0, NaBO 2 .nH 2 O, NaBO 3 .nH At least one boron compound selected from 2 O, Na 2 BO 4 .nH 2 O, H 3 BO 3 .nH 2 O; Mg 3 (PO 4 ) 2 .nH 2 O, MgHPO 4 .nH 2 O, AlPO 3 .nH 2 O, K 2 HPO 3 .nH 2 O, Zn 3 (PO 4 ) 2 .nH 2 O, MnHPO 3 . at least one phosphoric acid compound selected from nH 2 O, Na 3 PO 3 .nH 2 O, Al (NO 3 ) 3 .nH 2 O; Mg (OH) 2 .nH 2 O , MgCO 3 .nH least one magnesium compound selected from 2 O; At least one manganese compound selected from Mn (OH) 2 .nH 2 O, MnCO 3 .nH 2 O, KMnO 4 .nH 2 O, Mn (NO 3 ) 2 .nH 2 O; At least one iron compound selected from FeO.nH 2 O, Fe 2 O 3 .nH 2 O, Fe 3 O 4 .nH 2 O, and [Fe edta] .nH 2 O; At least one silicon compound selected from NaSiO 2 .nH 2 O, KSiO 2 .nH 2 O, and LiSiO 2 .nH 2 O; each or at least one of them is dissolved in nitric acid, ammonia, EDTA, glycerin, sorbitol, or ethanolamine In addition to the liquid combustion catalyst composition to increase the formation and ionicity of the ionic complex complex salt, and to further increase the efficiency of the combustion promotion, clinker and fouling to solve the problem.

본 발명에 따른 복합 금속착이온화합물 또는 복합금속착이온 수화물을 포함하는 액상 연소촉매 조성물에 의하면, 연료에 첨가되는 조성물로서 이온화된 금속 및 알칼리금속이 이온상태를 이루며 액체 속에 액상으로 존재함에 따라 연료에 넓게 분포되어 산화반응 및 연소반응을 촉진시키고, 이는 고온의 발생을 유도하므로 연소효율 및 열효율을 증진시킬 수 있는 효과를 얻는다.According to the liquid combustion catalyst composition comprising a complex metal complex ion compound or a complex metal complex ion hydrate according to the present invention, as a composition to be added to the fuel as the ionized metal and alkali metal to form an ionic state in the liquid phase in the liquid It is widely distributed in to promote the oxidation reaction and the combustion reaction, which induces the generation of high temperature, thereby obtaining the effect of improving the combustion efficiency and thermal efficiency.

또한, 연료를 적게 사용하여도 높은 연소효율 및 열효율이 발휘됨으로써, 전반적인 연료의 사용량을 절감하여 원료비용을 최소화하고, 연료의 양을 줄이면서 연소기관 내에 융착물(크링커, 파울링, 신터링 등)이 생성되는 것을 억제함에 따라 연소기관의 온도를 안정화시키고 연소기관의 생산성 및 효율을 극대화할 수 있는 효과가 있다.In addition, high combustion efficiency and thermal efficiency are exhibited even when less fuel is used, thereby reducing overall fuel consumption, minimizing raw material costs, and reducing the amount of fuel while fusion (clinker, fouling, sintering, etc.) in the combustion engine. By suppressing the generation of), it is possible to stabilize the temperature of the combustion engine and maximize the productivity and efficiency of the combustion engine.

본 발명은 Mg, Ca, Mn, Zn, Al으로 부터 선택되는 1종 이상의 금속화합물과 Li, K, Na으로부터 선택되는 1종 이상의 알칼리금속화합물로 구성된 복합금속킬레이트화합물 또는 복합금속착이온 수화물이 용해 가능한 액체에 용해되어 복합금속착이온이 형성된 복합금속착이온화합물을 포함하는 액상 연소촉매 조성물을 제공하고 더불어 고온에서의 금속의 연소촉진성 및 융점조절 등의 효과 및 열효율 개선 등을 동시적으로 제공하는 것을 기술구성의 특징으로 한다.In the present invention, a complex metal chelate compound or a complex metal complex ion hydrate composed of at least one metal compound selected from Mg, Ca, Mn, Zn, and Al and at least one alkali metal compound selected from Li, K, and Na is dissolved. It provides a liquid combustion catalyst composition containing a complex metal complex ion compound which is dissolved in a liquid as much as possible to form a complex metal complex ion, and at the same time provides the effects of promoting the combustion and the melting point of the metal at a high temperature and improving the thermal efficiency. It is characterized by the technical configuration.

또한, 상기 용해 가능한 액체는 질산 또는 암모니아수인 것을 기술구성의 특징으로 한다.In addition, the soluble liquid is characterized in that the technical configuration of nitric acid or ammonia water.

또한, 상기 용해 가능한 액체는 금속화합물이 용해 및 분산되도록 솔비톨, 글리세린, EDTA, 에탄올아민으로부터 선택되는 계면활성제를 더 포함하는 것을 기술구성의 특징으로 한다.In addition, the soluble liquid is characterized by a technical configuration that further comprises a surfactant selected from sorbitol, glycerin, EDTA, ethanolamine so that the metal compound is dissolved and dispersed.

상기 복합금속착이온 수화물은 알카리 금속(Li,K,Na)과 알카리토금속(Mg, Ca), 전이금속(Fe, Mn, Zn) 그리고 알루미늄(Al)을 결합하기 위해서 Conjugate Base인 (NO3 -)와 리간드인 물분자 (H2O) 또는 물분자(H2O)를 매개로 하여 착이온을 형성하는 것을 기술구성의 특징으로 한다.The composite metal complex ion hydrate is a conjugate base (NO 3 − ) to combine alkali metal (Li, K, Na) with alkaline metal (Mg, Ca), transition metal (Fe, Mn, Zn) and aluminum (Al). ) And the formation of complex ions through the water molecule (H 2 O) or water molecule (H 2 O) as a ligand is a feature of the technical configuration.

상기 복합금속킬레이트화합물은 Li2[Ca edta].4H2OK2, Li2[Mg edta].4H2ONa2, K2[Ca edta].4H2O, K2[Mg edta].4H2O, Na2[Ca edta].4H2O, Na2[Mg edta].4H2O, Li2[Mn edta], Li2[Zn edta], Li2[Al edta], K2[Mn edta], K2[Zn edta], K2[Al edta], Na2[Mn edta], Na2[Zn edta], Na2[Al edta]에서 선택되는 1종 이상인 것을 기술구성의 특징으로 한다.The composite metal chelate compound is Li 2 [Ca edta] .4H 2 OK 2 , Li 2 [Mg edta] .4H 2 ONa 2 , K 2 [Ca edta] .4H 2 O, K 2 [Mg edta] .4H 2 O, Na 2 [Ca edta]. 4 H 2 O, Na 2 [Mg edta]. 4 H 2 O, Li 2 [Mn edta], Li 2 [Zn edta], Li 2 [Al edta], K 2 [Mn edta ], K 2 [Zn edta], K 2 [Al edta], Na 2 [Mn edta], Na 2 [Zn edta], Na 2 [Al edta] is characterized by the technical configuration.

상기 복합금속착이온 수화물은 K(NO3).Mg(NO3)2.13H2O, K(NO3).Mn(NO3)2.16H2O, K(NO3).Zn(NO3)2.15H2O, Na(NO3).Mg(NO3)2.13H2O, Na(NO3).Mn(NO3)2.16H2O, Na(NO3).Zn(NO3)2.15H2O, Li(NO3).Mg(NO3)2.13H2O, Li(NO3).Mn(NO3)2.16H2O, Li(NO3).Zn(NO3)2.15H2O, K(NO3).Al(NO3)3.9H2O Na(NO3).Al(NO3)3.9H2O, Li(NO3).Al(NO3)3.9H2O 에서 선택되는 1종 이상인 것을 기술구성의 특징으로 한다.The composite metal complex ion hydrate K (NO 3) .Mg (NO 3) 2 .13H 2 O, K (NO 3) .Mn (NO 3) 2 .16H 2 O, K (NO 3) .Zn (NO 3 ) 2 .15H 2 O, Na (NO 3 ) .Mg (NO 3 ) 2 .13H 2 O, Na (NO 3 ) .Mn (NO 3 ) 2 .16H 2 O, Na (NO 3 ) .Zn ( NO 3 ) 2 .15H 2 O, Li (NO 3 ) .Mg (NO 3 ) 2 .13H 2 O, Li (NO 3 ) .Mn (NO 3 ) 2 .16H 2 O, Li (NO 3 ) .Zn (NO 3 ) 2 .15H 2 O, K (NO 3 ) .Al (NO 3 ) 3 .9H 2 O Na (NO 3 ) .Al (NO 3 ) 3 .9H 2 O, Li (NO 3 ) .Al (NO 3 ) Features at least one member selected from 3 .9H 2 O as a feature of the technical configuration.

또한, 상기 이외의 것들로 붕소수화물인 Na2B4O7.nH20, B2O3.nH2O, B2O4.nH20, NaBO2.nH2O, NaBO3.nH2O, Na2BO4.nH2O, H3BO3.nH2O 으로부터 선택되는 1종 이상의 붕소화합물; Mg3(PO4)2.nH2O, MgHPO4.nH2O, AlPO3.nH2O, K2HPO3.nH2O, Zn3(PO4)2.nH2O, MnHPO3.nH2O, Na3PO3.nH2O, Al(NO3)3.nH2O 으로부터 선택되는 1종 이상의 인산화합물; Mg(OH)2.nH2O, MgCO3.nH2O 으로부터 선택되는 1종 이상의 마그네슘화합물; Mn(OH)2.nH2O, MnCO3.nH2O, KMnO4.nH2O, Mn(NO3)2.nH2O으로부터 선택되는 1종 이상의 망간화합물; FeO.nH2O, Fe2O3.nH2O, Fe3O4.nH2O, [Fe edta].nH2O 으로부터 선택되는 1종 이상의 철화합물; NaSiO2.nH2O, KSiO2.nH2O, LiSiO2.nH2O 으로부터 선택되는 1종 이상의 규소화합물;을 각각 또는 1종 이상을 질산, 암모니아, EDTA, 글리세린, 솔비톨 또는 에탄올아민에 녹여 상기 액상 연소촉매 조성물에 더 첨가하여 이온성 복합착염의 형성 및 이온성을 높이고, 연소촉진, 크링커 및 파울링의 제거 효율을 더 높이는 것을 기술구성의 특징으로 한다.In addition, other than those above, boron hydrates Na 2 B 4 O 7 .nH 2 0, B 2 O 3 .nH 2 O, B 2 O 4 .nH 2 0, NaBO 2 .nH 2 O, NaBO 3 .nH At least one boron compound selected from 2 O, Na 2 BO 4 .nH 2 O, H 3 BO 3 .nH 2 O; Mg 3 (PO 4 ) 2 .nH 2 O, MgHPO 4 .nH 2 O, AlPO 3 .nH 2 O, K 2 HPO 3 .nH 2 O, Zn 3 (PO 4 ) 2 .nH 2 O, MnHPO 3 . at least one phosphoric acid compound selected from nH 2 O, Na 3 PO 3 .nH 2 O, Al (NO 3 ) 3 .nH 2 O; Mg (OH) 2 .nH 2 O , MgCO 3 .nH least one magnesium compound selected from 2 O; At least one manganese compound selected from Mn (OH) 2 .nH 2 O, MnCO 3 .nH 2 O, KMnO 4 .nH 2 O, Mn (NO 3 ) 2 .nH 2 O; At least one iron compound selected from FeO.nH 2 O, Fe 2 O 3 .nH 2 O, Fe 3 O 4 .nH 2 O, and [Fe edta] .nH 2 O; At least one silicon compound selected from NaSiO 2 .nH 2 O, KSiO 2 .nH 2 O, and LiSiO 2 .nH 2 O; each or at least one of them is dissolved in nitric acid, ammonia, EDTA, glycerin, sorbitol, or ethanolamine In addition to the liquid combustion catalyst composition to increase the formation and ionicity of the ionic complex complex salt, and further increase the efficiency of the removal of the combustion promotion, clinker and fouling is characterized in the technical configuration.

이하에서는 본 발명에 따른 복합 금속착이온화합물을 포함하는 액상 연소촉매 조성물에 대해 상세히 설명한다. 그러나, 본 발명의 실시예는 여러 가지 다양한 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예로 한정되는 것으로 해석되지 않는다. 본 발명의 실시예는 해당 기술분야에서 보통의 지식을 가진 자가 본 발명을 이해할 수 있도록 설명하기 위해서 제공되는 것이다.Hereinafter, a liquid combustion catalyst composition including a complex metal complex ion compound according to the present invention will be described in detail. However, embodiments of the present invention can be modified in many different forms, the scope of the invention is not to be construed as limited to the embodiments described below. Embodiment of the present invention is provided to explain to those skilled in the art to understand the present invention.

먼저, 본 발명의 기술적 사상은 복합금속이온을 통해 최적의 적은 공기(산소)량으로 유기물 중에서 탄소(C)의 연소반응 C + O2 → CO2을 촉진시켜 착화점을 조절하고 연소속도를 높여 고온을 형성시켜 공기량에 의한 열손실을 줄이고 연소효율을 높이며 형성된 고온에 의한 유효한 열전달에너지 값을 증진시키는 것이다. First, the technical idea of the present invention is to promote the combustion reaction C + O 2 → CO 2 of carbon (C) in the organic material with an optimal amount of air (oxygen) through the composite metal ion to control the ignition point and to increase the combustion speed It is to reduce the heat loss caused by the amount of air to increase the combustion efficiency and to increase the effective heat transfer energy value due to the formed high temperature.

또한, 본 발명은 연료 중의 무기물(회분)이 고온에 노출되더라도 무기물(회분)의 IDT(Initial Deformed Temperature)을 높이고 Soft하게 하여 연소기관의 벽에 융착하는 것을 방지하여 연소기관 내의 온도를 안정화시켜 연소기관의 열효율을 증진시키는 것이다.In addition, the present invention stabilizes the temperature in the combustion engine by preventing and fusion to the wall of the combustion engine by increasing and softening the Initial Deformed Temperature (IDT) of the inorganic material (ash) even when the inorganic material (ash) is exposed to high temperature. It is to increase the thermal efficiency of the engine.

이를 위하여, 본 발명의 복합금속착이온화합물을 포함하는 액상 연소촉매 조성물은 Mg, Ca, Mn, Zn, Al으로 부터 선택되는 1종 이상의 금속화합물과 Li, K, Na으로부터 선택되는 1종 이상의 알칼리금속화합물로 구성된 복합금속킬레이트화합물 또는 복합금속착이온 수화물이 용해 가능한 액체에 용해되어 복합금속착이온이 형성된 액상 조성물이다.To this end, the liquid combustion catalyst composition comprising a composite metal complex ion compound of the present invention is at least one metal compound selected from Mg, Ca, Mn, Zn, Al and at least one alkali selected from Li, K, Na A complex metal chelate compound or a complex metal complex ion hydrate composed of a metal compound is a liquid composition in which a complex metal complex ion is formed by dissolving in a soluble liquid.

상기 Mg, Ca, Mn, Zn, Al은 무기물(회분)의 IDT(회융점)을 높이는 역할을 하며, 이온 상태의 알칼리금속과 착이온 형태로 결합하여 연소에 사용되고, 상온에서도 안정한 액상형태로 유지된다.The Mg, Ca, Mn, Zn, Al serves to increase the IDT (melting point) of the inorganic material (ash), is used for combustion by combining in the form of complex ion with alkali metal in the ionic state, maintained in a stable liquid form even at room temperature do.

또한, Mg, Ca, Mn, Zn, Al을 용해시키는 액체는 염산이나 황산에도 용해가 가능하나 이들은 부식 및 대기오염물질을 배출시킴으로 바람직하기는 질산 또는 암모니아수가 적합하다.In addition, liquids that dissolve Mg, Ca, Mn, Zn, Al can be dissolved in hydrochloric acid or sulfuric acid, but they are suitable for nitric acid or ammonia water because they release corrosion and air pollutants.

상기 알칼리금속화합물은 칼륨(K), 나트륨(Na), 리튬(Li)을 비롯하여 루비듐(Rb), 세슘(Cs), 프랑슘(Fr)의 6원소를 총칭하는 것이고, 상온에서는 물과 반응하여 수소를 발생시키며 강한 염기인 수산화물을 생성하게 된다. 좀 더 구체적으로 설명하면, 알칼리금속은 은백색의 무른 금속으로 공기 중에서는 곧 광택을 잃어버리며, 비중과 녹는점 및 끓는점 등이 낮은 것을 특징으로 하고, 불꽃반응을 나타내면서 많은 비금속원소들과 활발하게 직접 작용하는데, 특히 산소 등과 잘 화합하며 수소와 반응하여 수소화물을 만드는 특징이 있는 금속이다.The alkali metal compound refers to six elements of rubidium (Rb), cesium (Cs), and francium (Fr), including potassium (K), sodium (Na), and lithium (Li), and reacts with water at room temperature to hydrogen. To generate a strong base of hydroxide. More specifically, the alkali metal is a silvery white soft metal which loses its luster soon, and has a low specific gravity, a melting point and a boiling point, and has a flame reaction, and is directly active with many nonmetallic elements. In particular, it is a metal that is well combined with oxygen and reacts with hydrogen to form hydrides.

또한, 알칼리금속은 평소 공기 중에 그대로 방치할 경우, 공기 중에서 습기(예를 들면, 이산화탄소 등)와 반응하는 특성이 있고, 고온의 연소상태에서 다른 금속원소나 연료 중에 포함된 다른 물질의 원소(질소, 탄소, 황 등)에 비해 이온화가 빠르게 진행되면서 다른 물질의 산화에 필요한 전이 상태(열적평형상태)을 제공하는 촉매제로 연소를 촉진한다. 특히 탄소의 연소반응 C + O2 → CO2에 있어 알카리(Li,K,Na)금속은 산소와 탄소의 결합을 촉진한다. In addition, alkali metals have a characteristic of reacting with moisture (for example, carbon dioxide, etc.) in the air when left in the air as usual, and elements of other metals (nitrogen) contained in other metal elements or fuels under high temperature combustion conditions. Ionization is faster than carbon, sulfur, and the like, and promotes combustion with a catalyst that provides the transition state (thermal equilibrium) required for the oxidation of other materials. In particular, in the combustion reaction of carbon C + O 2 → CO 2 , alkali (Li, K, Na) metals promote the bond between oxygen and carbon.

상기 알칼리금속화합물은 알칼리금속 6원소 중에서 칼륨, 나트륨, 리튬으로 이루어지는 군에서 선택된 1종 이상의 알칼리금속화합물로 이루어진다.The alkali metal compound is composed of at least one alkali metal compound selected from the group consisting of potassium, sodium, and lithium among six alkali metal elements.

상기 알칼리금속화합물은 칼륨, 나트륨, 리튬 중에서 선택된 1종의 알칼리금속화합물을 사용하는 것도 가능하고, 2종 이상을 혼합하여 사용하도록 형성하는 것도 가능하다.The alkali metal compound may be one alkali metal compound selected from potassium, sodium, and lithium, or may be formed to be used by mixing two or more kinds.

상기 알칼리금속화합물의 금속화합물을 2종 이상으로 혼합했을 때, 이온성 및 촉매성에 의한 연소촉진이 상승작용하여 연소촉진기능을 더욱 증진시키는 효과가 있으므로 상기 알칼리금속화합물의 금속화합물을 2종 이상으로 혼합하여 사용하는 것이 바람직하다.When two or more kinds of metal compounds of the alkali metal compound are mixed, there is an effect of synergistically promoting combustion by ionic and catalytic properties and further enhancing the combustion promoting function. It is preferable to mix and use.

상기 알칼리금속화합물의 금속화합물을 2종 이상으로 혼합하는 경우에 상기 금속화합물의 알칼리금속인 칼륨, 나트륨, 리튬 중에서 2종 이상을 선택하여 혼합사용하는 것도 가능하고, 상기 금속화합물의 알칼리금속(칼륨, 나트륨, 리튬) 1종 이상과 그외의 알칼리금속인 루비듐, 세슘, 프랑슘 중에서 1종 이상을 선택하여 혼합 사용하는 것도 가능하다.When mixing two or more kinds of the metal compounds of the alkali metal compound, it is also possible to select and use two or more kinds among the alkali metals of the alkali metal of the metal compound and mix them. , Sodium, lithium) and at least one selected from among rubidium, cesium and francium, which are other alkali metals, may be mixed and used.

상기 알칼리금속화합물은 이온화된 알칼리금속이 양(+)이온 상태로 존재하도록 이루어진다. 즉, 상기 알칼리금속화합물은 액체상태에서 이온화되어 K+, Na+, Li+와 같은 이온상태로 액체(물) 속에 존재함에 따라 연료 및 회분 등의 광물질에 넓게 분포되므로 연소를 촉진한다.The alkali metal compound is made such that the ionized alkali metal is present in a positive (+) state. That is, the alkali metal compound is ionized in the liquid state and is present in the liquid (water) in an ionic state such as K + , Na + , Li +, and thus widely distributed in minerals such as fuel and ash, thereby promoting combustion.

또한, 상기 알칼리금속화합물은 수산화물계열의 화합물, 탄산계열의 화합물, 산화물계열의 화합물로 이루어지는 군에서 선택된 1종 이상의 알칼리금속화합물을 사용할 수도 있다.In addition, the alkali metal compound may be at least one alkali metal compound selected from the group consisting of a hydroxide compound, a carbonate compound, and an oxide compound.

상기 알칼리금속화합물이 수산화물계열의 화합물이나 탄산계열의 화합물 및 산화물계열의 화합물로 구성하게 되면, 연료의 연소시 착화점의 저하 및 열효율의 개선에 도움이 된다.When the alkali metal compound is composed of a hydroxide-based compound, a carbonate-based compound, and an oxide-based compound, it is helpful to reduce the ignition point during combustion of the fuel and to improve thermal efficiency.

상기 수산화물계열의 화합물은 수산화칼륨(KOH), 수산화나트륨(NaOH), 수산화리튬(LiOH)으로 이루어지는 화합물에서 1종 이상을 선택하여 구성하게 되며, 상기 수산화물계열의 화합물은 연소시 수산화물(OH)이 분해되면서 탄소전환효율을 증가시켜 연소효율을 높이고, 연료에 함유된 알루미나산화물의 녹는점을 낮춰 연소시 생성되는 융착물을 쉽게 제거하거나 생성을 억제하여 준다.The hydroxide-based compound is composed of at least one selected from compounds consisting of potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH), the hydroxide-based compound is a hydroxide (OH) during combustion As it decomposes, the carbon conversion efficiency is increased to increase the combustion efficiency, and the melting point of the alumina oxide contained in the fuel is reduced to easily remove or suppress the formation of the fusion produced during combustion.

상기 탄산계열의 화합물은 탄산칼륨(K2CO3), 탄산나트륨(NaCO3), 탄산리튬(LiCO3), 탄산수소칼륨(KHCO3), 탄산수소나트륨(NaHCO3), 탄산수소리튬(LiHCO3)으로 이루어지는 화합물 중에서 1종 이상을 선택하여 구성하게 된다. The compound of the carbonic acid series is potassium carbonate (K 2 CO 3 ), sodium carbonate (NaCO 3 ), lithium carbonate (LiCO 3 ), potassium hydrogen carbonate (KHCO 3 ), sodium hydrogen carbonate (NaHCO 3 ), lithium carbonate (LiHCO 3 One or more types are selected and comprised from the compound which consists of).

상기 탄산계열의 화합물로 구성하게 되면, 연소시 이산화탄소(CO2)를 발생시킨다. 좀 더 구체적으로 설명하면, 상기 탄산계열의 화합물에 의해 발생하는 이산화탄소는 열원인 연료의 표면에 접촉하면서 탄소와 활발하게 반응하여 연소효율을 증진시킨다.When composed of the carbonic acid-based compound, it generates carbon dioxide (CO 2 ) during combustion. In more detail, the carbon dioxide generated by the carbonate-based compound actively reacts with the carbon while contacting the surface of the fuel, which is a heat source, thereby improving combustion efficiency.

상기 산화물의 화합물은 산화칼륨(K2O), 산화나트륨(Na2O), 산화리튬(Li2O), 과산화칼륨(K2O2), 과산화나트륨(Na2O2), 과산화리튬(Li2O2), 질산칼륨(KNO3), 질산나트륨(NaNO3), 질산리튬(LiNO3)으로 이루어지는 화합물에서 1종 이상을 선택하여 구성하게 되고, 상기 산화물의 화합물은 연소시 산소를 발생시켜 탄소와의 반응을 촉진하므로 고온을 발생시켜 연소효율과 열효율을 증진시키게 된다.The compound of the oxide is potassium oxide (K 2 O), sodium oxide (Na 2 O), lithium oxide (Li 2 O), potassium peroxide (K 2 O 2 ), sodium peroxide (Na 2 O 2 ), lithium peroxide ( Li 2 O 2 ), potassium nitrate (KNO 3 ), sodium nitrate (NaNO 3 ), lithium nitrate (LiNO 3 ) is selected by at least one selected from the compound, and the compound of the oxide generates oxygen during combustion By promoting the reaction with the carbon to generate a high temperature to improve the combustion efficiency and thermal efficiency.

그러나, 알카리(Li,K,Na)금속 그 자체만으로는 일반 상온 및 물속에서 불안정하여 유지, 보관, 이용이 곤란하고 더불어 연소기관 내에서 연소 중에 유기물(회분)과 반응하여 회분의 융점을 저하시킴으로서 오히려 운전을 방해하고 열효율을 저하시킨다. However, alkali (Li, K, Na) metals alone are unstable at normal room temperature and in water, making it difficult to maintain, store and use, and lower the melting point of ash by reacting with organic matter (ash) during combustion in combustion engines. Interfere with operation and reduce thermal efficiency.

따라서, Mg, Ca, Mn, Zn, Al은 알카리 금속(Li,K,Na)과 결합한 착이온화합물로서 복합금속킬레이트화합물 또는 복합금속착이온 수화물의 형태로서, 질산 또는 암모니아수에 용해되어 취급 및 안정성이 뛰어나고 연료접촉성도 뛰어나므로 이러한 원자단위 및 이온 상태의 금속을 촉매로 이용할 경우, 아주 적은 불균일 촉매상태의 양(연료대비 0.01~0.1% 정도)으로도 연소 상태의 연료 중의 탄소(C)원자와 작용하여 본 발명의 효과를 달성할 수가 있다. Therefore, Mg, Ca, Mn, Zn, Al are complex ion compounds combined with alkali metals (Li, K, Na), complex metal chelate compounds or complex metal complex ion hydrates, dissolved in nitric acid or ammonia water and handled and stable. Because of its excellent fuel contact and excellent fuel contact, when using these atomic and ionic metals as catalysts, the carbon (C) atoms in the fuel in the combustion state can be reduced even with a very small amount of heterogeneous catalytic state (about 0.01 to 0.1% of the fuel). It can act to achieve the effect of this invention.

이와 같이, 복합금속킬레이트화합물 또는 복합금속착이온 수화물을 사용함으로써 연소를 촉진시키는 인자는 첫째, 알카리금속(Li,Na,K)의 촉매작용과 그에 따른 미연분의 감소에 따른 열량증가 및 고온형성, 둘째 라디칼산소(O)의 제공, 셋째 공기량 저감에 따른 흡입열의 감소 및 고온형성, 넷째 알카리 금속 및 금속의 산화과정(M+O→MO)에 따른 열량 증가, 다섯째, 연소증진 반응에 연소된 고체 연료의 입자표면은 고온을 형성하며 옆에 있는 입자에 연쇄적으로 연소반응을 촉진시키고 각각의 입자표면에 연쇄적 고온을 전달함으로 적은 양의 복합금속착이온으로도 연소촉진효과를 가져온다. As such, the factors that promote combustion by using the complex metal chelate compound or complex metal complex ion hydrate are, firstly, calorie increase and high temperature formation due to the catalysis of alkali metals (Li, Na, K) and the reduction of unburnt. Second, the reduction of heat of intake and formation of high temperature due to the provision of radical oxygen (O), the decrease of air volume, and the fourth increase in calorie value according to the oxidation process (M + O → MO) of alkali metals and metals. The particle surface of the solid fuel forms a high temperature and accelerates the combustion reaction to the adjacent particles in series and delivers the chain high temperature to each particle surface, thereby bringing a combustion promoting effect even with a small amount of complex metal complex ion.

본 발명에서 연소후 산화물 형태의 고융점 화물을 형성하는 Mg, Ca, Mn, Zn, Al으로부터 선택되는 1종 이상의 복합금속킬레이트화합물은 예를들어 Li2[Ca edta].4H2OK2, Li2[Mg edta].4H2ONa2, K2[Ca edta].4H2O, K2[Mg edta].4H2O, Na2[Ca edta].4H2O, Na2[Mg edta].4H2O, Li2[Mn edta], Li2[Zn edta], Li2[Al edta], K2[Mn edta], K2[Zn edta], K2[Al edta], Na2[Mn edta], Na2[Zn edta], Na2[Al edta]에서 선택되는 1종 이상을 사용한다.In the present invention, at least one complex metal chelating compound selected from Mg, Ca, Mn, Zn, and Al, which forms a high melting point cargo in the form of an oxide after combustion, may be, for example, Li 2 [Ca edta] .4H 2 OK 2 , Li 2 [Mg edta] .4H 2 ONa 2 , K 2 [Ca edta] .4H 2 O, K 2 [Mg edta] .4H 2 O, Na 2 [Ca edta] .4H 2 O, Na 2 [Mg edta] .4H 2 O, Li 2 [Mn edta], Li 2 [Zn edta], Li 2 [Al edta], K 2 [Mn edta], K 2 [Zn edta], K 2 [Al edta], Na 2 [ At least one selected from Mn edta], Na 2 [Zn edta], and Na 2 [Al edta].

특히, EDTA(화학식 C10H16N2O8, 에틸렌다이아민테트라아세트산)는 4개의 카복실산염과 2개의 아민기를 매개로 하여 금속과 결합하는 무색의 결정성 가루이다. Ca2+, Mg2+ 등 거의 모든 금속이온과 안정한 수용성 킬레이트를 만드는 특징을 갖고 있다. 예를 들면, 무색의 막대 모양 결정으로서 K2[Ca edta].4H2O 등이 얻어지는데, 그 수용액은 알칼리성이다.In particular, EDTA (Formula C 10 H 16 N 2 O 8 , Ethylenediaminetetraacetic acid) is a colorless crystalline powder which binds to the metal via four carboxylates and two amine groups. It has the characteristic of making stable water-soluble chelate with almost all metal ions such as Ca 2+ and Mg 2+ . For example, K 2 [Ca edta] .4H 2 O or the like is obtained as colorless rod-shaped crystals, but the aqueous solution is alkaline.

상기 복합금속킬레이트화합물은 상온 및 액체 상태에서 안정성이 뛰어나 이용하기가 편리하고, 이온상태로 연료의 표면에 흡착하여 연소과정에서 분해된 알카리 금속은 탄소(C)의 C + O2 → CO2 반응 및 연소반응을 촉진하고, 연소과정에서 분해된 Mg, Ca, Mn, Zn, Al는 회분의 표면에 흡착된 회분이 용융하는 것을 방지하고 Clinker, Fouling 및 Sintering를 억제한다.The complex metal chelate compound has excellent stability at room temperature and in a liquid state, and is convenient to use. Alkali metal decomposed during combustion by adsorption on the surface of the fuel in an ionic state is a C + O 2 → CO 2 reaction of carbon (C). And accelerate the combustion reaction, Mg, Ca, Mn, Zn, Al decomposed in the combustion process to prevent the ash adsorbed on the surface of the ash to melt and suppress Clinker, Fouling and Sintering.

한편, 상기 복합금속착이온 수화물은 알카리금속(Li,K,Na)과 Mg, Ca, Mn, Zn, Al을 결합하기 위해서 Conjugate Base인 (NO3 -)와 리간드인 물분자 (H2O)를 매개로 하여 착이온을 형성한다. 예를들면 K(NO3)결정체와 Mg(NO3)2.6H2O이 결합하여 K(NO3).Mg(NO3)2.13H2O 형태의 복합금속착이온 수화물로 용해되면 용해성 및 안정성이 뛰어난 복합금속착이온을 형성한다. On the other hand, the double metal complex ion hydrates are the alkali metal (Li, K, Na) and Mg, Ca, Mn, Zn, Conjugate Base in order to bond the Al (NO 3 -) and a ligand of water molecules (H 2 O) Form a complex ion through the medium. For example, K (NO 3 ) crystals and Mg (NO 3 ) 2 .6H 2 O combine to dissolve into complex metal complex hydrates of the form K (NO 3 ) .Mg (NO 3 ) 2 .13H 2 O And it forms a composite metal complex ion with excellent stability.

또한 알카리 금속(Li,K,Na)과 결합한 또 다른 고융점 금속산화물을 형성하는 Mn(NO3)2.9H2O를 결합한 K(NO3).Mn(NO3)2.16H2O의 착이온화합물과 Zn(NO3)2.6H20와 결합한 K(NO3).Zn(NO3)2.15H2O의 이온성 화합물의 경우도 용해성 및 안정성이 뛰어 나고 같은 효과를 가져왔으며, 상기 3개 화합물 외의 모든 복합금속착이온수화물들도 마찬가지의 효과를 가져왔다.In addition, the alkali metal (Li, K, Na) and combines another and Mn (NO 3) forming a refractory metal oxide K 2 .9H combines 2 O (NO 3) .Mn ( NO 3) 2 .16H 2 O complex ion compound and Zn (NO 3) 2 .6H 2 0 and the combined K (NO 3) .Zn (NO 3) 2 in the case of ionic compounds of .15H 2 O are also excellent solubility and stability sheds brought the same effect In addition, all the complex metal complex ion hydrates other than the above three compounds had the same effect.

결국 상기와 같은 배위 결합을 형성하는 복합금속착이온 수화물은 쉽게 분해되지 않고 용해성과 안정성이 뛰어나며 보관 및 운반과 적용이 쉬우며 고온의 연소상태에도 복합금속킬레이트와 같은 효과를 나타낸다.As a result, the complex metal complex ion hydrate that forms the coordination bond as described above is not easily decomposed, has excellent solubility and stability, is easy to store, transport and apply, and exhibits the same effect as the complex metal chelate even in a high temperature combustion state.

이와 같은 복합 금속착이온화합물은 연소중에 분해되어 기체 "N2" 및 "O" 을 발생시킴으로써 화석연료인 Coal 또는 Heavy Oil의 연료입자를 잘게 쪼개어 연소에 필요한 표면적을 넓혀 연소를 도와줌은 물론이고 발열반응에 필요한 산소(O)를 제공하여 산소(O)의 분율을 높여 "C+O2→CO2"의 반응을 촉진시킨다. The complex metal complex ion compound decomposes during combustion to generate gases “N 2 ” and “O”, so that fuel particles of coal or heavy oil, which are fossil fuels, are finely divided to help the combustion by increasing the surface area necessary for combustion. Providing oxygen (O) necessary for exothermic reaction to increase the fraction of oxygen (O) to promote the reaction of "C + O 2 → CO 2 ".

뿐만 아니라, 복합금속착이온 수화물은 수화물형태의 결정체를 이루고 있는 바, 초기 연소시 수화물에서 발생하는 증기(H2O 및 OH)에 의해 Clinker 및 Fouling을 다공성이면서도 단단한 물질로 만들어 연소기관의 벽 및 몸체에 융착하는 것을 더욱 억제하므로 이와 같이 회분을 다공성으로 만들기 위해서는, 예를들어, K(NO3).Mg(NO3)2.9H2O과 같은 착이온 화합물 외에 기타 다른 수화물 형태의 화합물을 함께 첨가하는 경우에는 K(NO3).Mg(NO3)2.9H2O만 사용할 때보다도 Clinker 및 Fouling과 Sintering 그리고 슬러지를 탈락시키는 시간이 빨라지게 된다.In addition, the complex metal complex ion hydrate forms a hydrate-type crystal, which makes Clinker and Fouling a porous and hard material by the vapors (H 2 O and OH) generated from the hydrate during initial combustion. to further suppressed, so that welding on the body making a batch in this manner a porous, for example, K (NO 3) .Mg ( NO 3) 2 .9H the other compounds of the different hydrate forms in addition to complex ion compounds such as 2 O when added together there will be K (NO 3) .Mg (NO 3) 2 .9H 2 O man yi time for dropping the Clinker and Fouling and Sintering and sludge faster than the time it is used.

기타 다른 수화물 형태의 화합물로는 착이온성이 강한 것들로서, 붕소수화물인 Na2B4O7.nH20, B2O3.nH2O, B2O4.nH20, NaBO2.nH2O, NaBO3.nH2O, Na2BO4.nH2O, H3BO3.nH2O 으로부터 선택되는 1종 이상의 붕소화합물; Mg3(PO4)2.nH2O, MgHPO4.nH2O, AlPO3.nH2O, K2HPO3.nH2O, Zn3(PO4)2.nH2O, MnHPO3.nH2O, Na3PO3.nH2O, Al(NO3)3.nH2O 으로부터 선택되는 1종 이상의 인산화합물; Mg(OH)2.nH2O, MgCO3.nH2O 으로부터 선택되는 1종 이상의 마그네슘화합물; Mn(OH)2.nH2O, MnCO3.nH2O, KMnO4.nH2O, Mn(NO3)2.nH2O으로부터 선택되는 1종 이상의 망간화합물; FeO.nH2O, Fe2O3.nH2O, Fe3O4.nH2O, [Fe edta].nH2O 으로부터 선택되는 1종 이상의 철화합물; NaSiO2.nH2O, KSiO2.nH2O, LiSiO2.nH2O 으로부터 선택되는 1종 이상의 규소화합물;을 사용할 수 있으며, 상기 화합물 각각 또는 1종 이상을 질산, 암모니아, EDTA, 글리세린, 솔비톨 또는 에탄올아민에 녹여 상기 액상 연소촉매 조성물에 더 첨가함으로써, Conjugate Base인 (NO3 -)와 리간드인 물분자(H2O)에 의한 복합착염의 형성 및 이온성을 높이고, 연소촉진, 크링커 및 파울링의 제거 효율을 더 높일 수 있다.(상기에서 n은 물분자의 몰수를 나타내며, 바람직하게 상기 n은 1~20의 값을 가질 수 있다.)Other hydrate-type compounds include those with strong complex ions, such as Na 2 B 4 O 7 .nH 2 0, B 2 O 3 .nH 2 O, B 2 O 4 .nH 2 0, NaBO 2 at least one boron compound selected from .nH 2 O, NaBO 3 .nH 2 O, Na 2 BO 4 .nH 2 O, H 3 BO 3 .nH 2 O; Mg 3 (PO 4 ) 2 .nH 2 O, MgHPO 4 .nH 2 O, AlPO 3 .nH 2 O, K 2 HPO 3 .nH 2 O, Zn 3 (PO 4 ) 2 .nH 2 O, MnHPO 3 . at least one phosphoric acid compound selected from nH 2 O, Na 3 PO 3 .nH 2 O, Al (NO 3 ) 3 .nH 2 O; Mg (OH) 2 .nH 2 O , MgCO 3 .nH least one magnesium compound selected from 2 O; At least one manganese compound selected from Mn (OH) 2 .nH 2 O, MnCO 3 .nH 2 O, KMnO 4 .nH 2 O, Mn (NO 3 ) 2 .nH 2 O; At least one iron compound selected from FeO.nH 2 O, Fe 2 O 3 .nH 2 O, Fe 3 O 4 .nH 2 O, and [Fe edta] .nH 2 O; At least one silicon compound selected from NaSiO 2 .nH 2 O, KSiO 2 .nH 2 O, and LiSiO 2 .nH 2 O; each or one or more of the compounds may be selected from nitric acid, ammonia, EDTA, glycerin, By dissolving in sorbitol or ethanolamine and further adding to the liquid combustion catalyst composition, the formation of complex complex salts by the conjugate base (NO 3 − ) and the ligand water molecule (H 2 O) and the ionicity are enhanced, and the combustion promotion and clinker And the removal efficiency of fouling may be further increased. (Wherein n represents the number of moles of the water molecule, and preferably n may have a value of 1 to 20).

또한, 알카리금속(Li,Na,K)은 연소중에 촉매기능이 끝나면 Li는 Li2CO3로 K는 K2CO3, Na는 Na2CO3로 전환되어 연소중에 형성된 Char에 부착되어 표면연소를 촉진함으로써 미연분을 줄이고 불완전연소에서 발생한 CO에 촉매적 역할을 하여 "CO+O →CO2"의 촉진으로 CO를 줄이는 역할도 한다.In addition, alkali metals (Li, Na, K) are converted to Li 2 CO 3 , K is converted to K 2 CO 3 , and Na is converted to Na 2 CO 3 when the catalytic function is completed during combustion. It also promotes the reduction of unburnt and the catalytic role of CO generated from incomplete combustion, thereby reducing CO by promoting "CO + O → CO 2 ".

또한, 분해된 Mg는 MgO, Ca는 CaO, Mn은 MnO, Zn은 ZnO, Al은 Al2O3로 고융점 산화물로 산화되어 회분의 표면에 부착하여 회분을 감싸고 회분의 겉면의 융점(IDT: Initial Deformed Temperature)을 높여 회분의 내부가 비록 융점이 낮은 물질일지라도 용융되는 것을 방지하여 알카리금속(Li,Na,K)이 연소기관에서 고온 형성 및 연소효율 증진하도록 도움을 준다. In addition, decomposed Mg is MgO, Ca is CaO, Mn is MnO, Zn is ZnO, Al is Al 2 O 3 and is oxidized to high melting point oxide to adhere to the surface of the ash to cover the ash, and the melting point of the surface of the ash (IDT: By increasing the Initial Deformed Temperature, the inside of the ash is prevented from melting even if the melting point is low, helping alkali metals (Li, Na, K) to form at high temperatures in combustion engines and to improve combustion efficiency.

또한, 이들 착이온화합물을 용해시켜 액상으로 사용하는 경우에는 용해시키지 않고 사용한 경우보다도 더욱 착화점이 낮아지고 열전달 유효에너지 값의 도달 속도가 빨라져 미연분이 더욱 줄고 열효율이 증진되며, 대기오염`물질인 SOx도 줄이고 초기연소에 필요한 공기량을 줄일 수 있다.In addition, in the case of dissolving these complex ionic compounds in a liquid phase, the ignition point is lower and the speed of reaching the effective heat transfer energy value is faster than that of the non-dissolved compound. It also reduces x and reduces the amount of air needed for initial combustion.

본 발명의 조성물이 첨가되는 연료의 종류를 특별히 한정하거나 제한하는 것은 아니고 고체연료(예를 들면, 석탄 및 코크스, 바이오매스 등), 액체연료(예를 들면, 등유, 경유, 콜타르, 크루드오일, 액화석유 등), 기체연료(예를 들면, 천연가스 등의 탄화수소계열 연료) 등의 연소에 적용되는 모든 연료를 포함하여 적용할 수 있다.It does not specifically limit or limit the kind of fuel to which the composition of the present invention is added, but it is a solid fuel (for example, coal and coke, biomass, etc.), a liquid fuel (for example, kerosene, diesel, coal tar, crude oil). , Liquefied petroleum, etc.) and gaseous fuels (for example, hydrocarbon-based fuels such as natural gas) can be used including all fuels applied to the combustion.

본 발명의 조성물은 침전을 방지하고 용해성을 유지하기 위한 pH는 1~8정도이나 철과 같은 금속재질의 부식을 방지하기 위해 pH를 3~7정도로 관리하여야 하며, 상온에서 액체 상태로 안정성이 뛰어나 이용하기가 편리하다. 본 조성물에서 알칼리 금속의 구성은 몰비 기준 25% 정도가 적당하나 석탄의 회분량 및 성분에 따라 슬래깅 및 파울링 지수 등을 고려하여 조절이 가능하다. The composition of the present invention is to maintain the pH so as to prevent precipitation and maintain solubility, but the pH should be managed to about 3 to 7 to prevent corrosion of metal materials such as iron, and excellent stability in a liquid state at room temperature It is convenient to use. The composition of the alkali metal in the present composition is about 25% molar ratio is suitable, but can be adjusted in consideration of the slagging and fouling index, etc., depending on the ash content and composition of the coal.

본 발명의 액상 연소촉매조성물은 이온상태의 원자 및 분자단위로 용해 및 분산되어 있도록 하기 위해서 솔비톨, 글리세린로, EDTA, 에탄올아민으로부터 선택되는 계면활성제를 첨가할 수도 있으며, 그 비율은 액상 연소촉매조성물 : 계면활성제 : 물 = 1~25 : 1~25 : 25~80의 비율로 혼합하여 사용한다.In order to dissolve and disperse the liquid combustion catalyst composition of the present invention in an atomic and molecular unit in an ionic state, a surfactant selected from sorbitol, glycerin, EDTA, and ethanolamine may be added, and the proportion thereof is a liquid combustion catalyst composition. : Surfactant: Water = 1 ~ 25: 1 ~ 25: 25 ~ 80 It is mixed and used.

본 발명의 액상 연소촉매조성물의 사용비율은 액상 연소촉매조성물 : 물 : 연료 = 1~5 : 1~10 : 1000이 적절하나 반드시 상기 비율만을 요구하는 것이 아니며 필요에 따라 조절할 수 있다. 즉 효율을 높이고자 하면 조성물의 사용비율을 높이면 된다. 상기에서와 같이 제조한 조성물은 100℃이하에서 결정체가 존재할 정도로 건조시키면 이온결합을 한 투명한 결정체가 되며 이를 사용해도 이온상태를 유지함으로 같은 효과를 가져 온다. The use ratio of the liquid combustion catalyst composition of the present invention is suitable for the liquid combustion catalyst composition: water: fuel = 1-5: 1-10: 1000, but it does not necessarily require the above ratio and can be adjusted as necessary. In other words, if you want to increase the efficiency, you can increase the use ratio of the composition. When the composition prepared as described above is dried to the extent that crystals are present at 100 ° C. or lower, it becomes a transparent crystal with ionic bonds.

이하에서는 본 발명에 상기 복합 금속착이온화합물을 포함하는 액상 연소촉매 조성물의 실시에 대해 상세히 설명한다. 그러나, 본 발명의 실시예는 여러 가지 다양한 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예로 한정되는 것으로 해석되지 않는다. 본 발명의 실시예는 해당 기술분야에서 보통의 지식을 가진 자가 본 발명을 이해할 수 있도록 설명하기 위해서 제공되는 것이다.Hereinafter, the implementation of the liquid combustion catalyst composition containing the complex metal complex ion compound in the present invention will be described in detail. However, embodiments of the present invention can be modified in many different forms, the scope of the invention is not to be construed as limited to the embodiments described below. Embodiment of the present invention is provided to explain to those skilled in the art to understand the present invention.

다음 실시예를 통해 본 발명에 따른 액상 연소촉매조성물을 첨가하기 전과 첨가한 후의 연소상태를 각각 실험하여 측정하였다.Through the following examples, the combustion state before and after the addition of the liquid combustion catalyst composition according to the present invention was measured and measured, respectively.

실시예 1 : 융점실험Example 1 Melting Point Test

물 100g에 질산(농도 65%)를 27g 혼합한 다음에 샘플을 다음과 같이 각각 샘플1(질산마그네슘50g+질산칼륨8g), 샘플2(질산아연50g+질산칼륨8g), 샘플3(농도 70% 질산50g+산화마그네슘8g+붕사3g), 샘플4[질산마그네슘50g+산화붕사(B2O3)8g], 샘플5(질산철4g+질산마그네슘50g), 샘플6(질산알루미늄40g+탄산칼륨3g), 샘플7(인산마그네슘50g+인산칼륨3g), 샘플8(인산알루미늄50g+질산칼륨3g), 샘플9(인산망간50g+붕산4g), 샘플10(인산아연50g+붕산10g), 샘플11(인산철10g+인산알루미늄50g+인산아연 수화물 Zn3(PO4)2.4H2O 15g), 샘플12(질산칼륨수화물 K(NO3).Mg(NO3)2.13H2O 30g+질산알루미늄 50g+붕사 수화물7g)을 이온화시켜 액상 연소 첨가제를 만들었다.After mixing 27 g of nitric acid (concentration 65%) in 100 g of water, the samples were prepared as follows: Sample 1 (50 g of magnesium nitrate + 8 g of potassium nitrate), Sample 2 (50 g of zinc nitrate + 8 g of potassium nitrate), and sample 3 (concentration of 70% nitric acid). 50 g + magnesium oxide 8 g + borax 3 g), sample 4 [magnesium nitrate 50 g + borax oxide (B 2 O 3 ) 8 g], sample 5 (iron nitrate 4 g + magnesium nitrate 50 g), sample 6 (aluminum nitrate 40 g + potassium carbonate 3 g), sample 7 ( 50 g of magnesium phosphate + 3 g of potassium phosphate, sample 8 (50 g of aluminum phosphate + 3 g of potassium nitrate), sample 9 (50 g of manganese phosphate + 4 g of boric acid), sample 10 (50 g of zinc phosphate + 10 g of borate), sample 11 (10 g of iron phosphate + 50 g of aluminum phosphate) Liquid phase combustion by ionizing hydrate Zn 3 (PO 4 ) 2 .4H 2 O 15g), sample 12 (potassium nitrate hydrate K (NO 3 ) .Mg (NO 3 ) 2 .13H 2 O 30g + aluminum nitrate 50g + borax hydrate 7g) An additive was made.

그 다음, 각각의 샘플을 중국에서 수입한 대동을 원산지로 하는 석탄(내수분 7W%, 고정탄소분 45W%, 휘발분 13W%, 회분 24W% 및 유황1W%)을 구하여 수분을 제거하고 석탄 : 물 : 액상 연소촉매조성물 = 1000 : 5 : 5의 비율로 혼합하고, ASTM D 1857 방법에 의해서 회융점(IDT)를 테스트 하고, 테스트하고 남은 시료로 100℃에서 1시간동안 건조시킨후, KSM0602에 의거 고체비중 측정법 중 비중병에 의한 방법으로 겉보기 비중을 테스트한 결과, 하기 표 1 및 표 2에 나타내었다.Then, each sample was taken from China and imported coal from Daedong (water content of 7W%, fixed carbon content 45W%, volatile matter 13W%, ash 24W% and sulfur 1W%) to remove moisture and remove coal: water: Liquid Combustion Catalyst Composition = 1000: 5: 5, mixed at the ratio of the melting point (IDT) by the ASTM D 1857 method, tested and dried at 100 ℃ for 1 hour, the solid according to KSM0602 As a result of testing the apparent specific gravity by the method of specific gravity in the specific gravity measurement method, it is shown in Table 1 and Table 2.

표 1 <회융점(IDT)> 무첨가 샘플 1 샘플 2 샘플 3 샘플 4 샘플 5 샘플 6 IDT(℃) 1333.5 1347.3 1343.6 1343.9 1345.2 1347.7 1347.1 차이 13.8 10.1 10.4 11.7 14.2 13.6 비중(g/cm2) 2.7 1.5 1.6 1.7 1.5 1.6 1.6 차이 -1.2 -1.1 -1 -1.2 -1.1 -1.1 Table 1 <Melting point (IDT)> No addition Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 IDT (℃) 1333.5 1347.3 1343.6 1343.9 1345.2 1347.7 1347.1 Difference 13.8 10.1 10.4 11.7 14.2 13.6 Specific gravity (g / cm 2 ) 2.7 1.5 1.6 1.7 1.5 1.6 1.6 Difference -1.2 -1.1 -One -1.2 -1.1 -1.1

표 2 <회융점(IDT)> 샘플 7 샘플 8 샘플 9 샘플 10 평균 샘플 11 샘플 12 평균 비중차이 1346.8 1345.1 1345.8 1344.6 1345.7 1344.7 1345.7 1345.2 13.3 11.6 12.3 11.1 12.21 11.2 12.2 11.7 1.5 1.7 1.5 1.6 1.58 1.2 1.2 1.2 -1.2 -1 -1.2 -1.1 -1.12 -1.5 -1.5 -1.5 0.38 TABLE 2 <Melting point (IDT)> Sample 7 Sample 8 Sample 9 Sample 10 Average Sample 11 Sample 12 Average Specific gravity difference 1346.8 1345.1 1345.8 1344.6 1345.7 1344.7 1345.7 1345.2 13.3 11.6 12.3 11.1 12.21 11.2 12.2 11.7 1.5 1.7 1.5 1.6 1.58 1.2 1.2 1.2 -1.2 -One -1.2 -1.1 -1.12 -1.5 -1.5 -1.5 0.38

상기 표 1 및 표 2에 나타낸 바와 같이, 본 발명의 액상 연소촉매조성물을 사용하여 연료에 첨가한 경우인 샘플 모두는 첨가하지 않은 경우인 무첨가에 비해 무기물 융해시작 온도인 회융점(IDT)이 10~14℃로 높아져 무기물(회분)이 녹는 것을 방지하여 연소기관에 융착되지 않는 효과가 있음을 알 수 있다. 단, IDT의 값은 회분의 성분에 따라 달라질 수 있음.As shown in Table 1 and Table 2, all samples in the case of adding to the fuel using the liquid combustion catalyst composition of the present invention has a melting point (IDT) of 10 which is an inorganic melting start temperature compared to no addition. It can be seen that there is an effect of preventing the melting of the inorganic material (ash) by increasing to ˜14 ° C. so that the combustion engine is not fused. However, the value of IDT may vary depending on the components of the ash.

실시예 2 : 열효율(발전효율), 노 내 온도, 크링커 파울링 및 배기가스 실험Example 2 thermal efficiency (power generation efficiency), furnace temperature, clinker fouling and exhaust gas experiment

샘플 1 : 물 100g에 질산(농도 65%) 25g 혼합한 후에 질산아연 50g을 섞은 다음에 질산칼륨 10g과 붕사 3g의 비율로 용해 및 이온화시켜 액상 연소촉매조성물을 제조하였다.Sample 1: After mixing 25g of nitric acid (concentration 65%) in 25g of water, 50g of zinc nitrate was mixed, and then dissolved and ionized at a ratio of 10g of potassium nitrate and 3g of borax to prepare a liquid combustion catalyst composition.

샘플 2 : 물 100g에 질산마그네슘 Mg(NO3)2.6H2O 50g을 섞은 다음에 질산칼륨 K(NO3)8g을 용해시킨 후 이온화시켜 액상 연소촉매조성물을 제조하였다.Sample 2: A mixture of 50 g of magnesium nitrate Mg (NO 3 ) 2 .6H 2 O was mixed with 100 g of water, and then 8 g of potassium nitrate K (NO 3 ) was dissolved and ionized to prepare a liquid combustion catalyst composition.

상기 복합금속착이온화합물을 포함하는 액상 연소촉매 조성물을 연료:물:조성물 = 1000kg:1kg:2kg 비율로 혼합한 후, 다음 시험조건 및 측정방법에 따라 열효율 개선효과를 계산하여 하기 표 3에 나타내었다.After mixing the liquid combustion catalyst composition containing the composite metal complex ion compound in a fuel: water: composition = 1000kg: 1kg: 2kg ratio, the thermal efficiency improvement effect is calculated according to the following test conditions and measurement methods, and is shown in Table 3 below. It was.

1. 시험조건1. Test condition

1) 주입방식 : 액상 연소촉매 조성물을 이송중인 석탄(CV-06) 위에 분사1) Injection method: Spraying liquid combustion catalyst composition on transporting coal (CV-06)

2) 보일러 : 200MWh급 초임계 관류형 순환유동층 보일러2) Boiler: 200MWh supercritical perfusion type circulating fluidized bed boiler

3) 시험탄종: 국내 탄 30%, 수입무연탄(베트남, 러시아, 북한산) 75%3) Test type: Domestic 30%, Imported anthracite (Vietnam, Russia, North Korea) 75%

2. 측정방법2. Measuring method

1) ASME Code에 의거 효율(%) = (출열 / 입열) X 1001) Efficiency (%) = (heating / heat input) X 100 according to ASME Code

즉, [발전량(MWh)]/ 석탄사용량(kg/h) x [열량(Kcal/kg)/860,000] x100    That is, [power generation (MWh)] / coal consumption (kg / h) x [calorie (Kcal / kg) / 860,000] x100

2) 시험기간 : 1차(Sample 1): 3.16 ~ 3.26 (11일간)2) Test Period: Sample 1: 3.16 ~ 3.26 (11 days)

2차(Sample 2): 4. 5 ~ 4.15 (11일간)                     Sample 2: 4. 5 to 4.15 (11 days)

표 3 <열효율, 노 내 온도, 및 배기가스 및 미연분 분석> 구분 샘플 1 샘플 2 첨가전 첨가후 차이 첨가전 첨가후 차이 발전량(MW/hr) 199.0 199.5 0.5 199.0 199.7 0.7 사용된 석탄량(Ton/hr) 107.1 104.1 -3.1 107.1 103.8 -3.3 사용된 공기량(NM3/sec) 181.1 179.2 -1.9 181.1 179.6 -1.4 Cyclone Outlet 가스 온도(℃) 957.5 942.2 -15.3 957.5 947.3 -10.2 Seal Spot 가스 온도(℃) 531.4 501.3 -30.1 531.4 512.1 -19.4 SOx(ppm) 88.4 55.1 -33.3 88.4 45.1 -43.3 NOx(ppm) 34.1 30.9 -3.2 34.1 28.2 -6.0 Dust(mg/m3) 3.4 3.5 0 3.4 3.1 -0.3 CO(ppm) 87.9 81.4 -6.6 87.9 83.3 -4.6 ECO Outlet O2(%) 2.4 2.3 -0.1 2.4 2.3 -0.1 미연분(in Fly Ash) wt% 12.5 7.2 -5.4 12.5 6.8 -5.7 TABLE 3 Thermal Efficiency, Furnace Temperature, and Emissions and Flue Gas Analysis division Sample 1 Sample 2 Before addition After addition Difference Before addition After addition Difference Generating amount (MW / hr) 199.0 199.5 0.5 199.0 199.7 0.7 Coal Used (Ton / hr) 107.1 104.1 -3.1 107.1 103.8 -3.3 Air volume used (NM3 / sec) 181.1 179.2 -1.9 181.1 179.6 -1.4 Cyclone Outlet Gas Temperature (℃) 957.5 942.2 -15.3 957.5 947.3 -10.2 Seal Spot Gas Temperature (℃) 531.4 501.3 -30.1 531.4 512.1 -19.4 SOx (ppm) 88.4 55.1 -33.3 88.4 45.1 -43.3 NOx (ppm) 34.1 30.9 -3.2 34.1 28.2 -6.0 Dust (mg / m 3 ) 3.4 3.5 0 3.4 3.1 -0.3 CO (ppm) 87.9 81.4 -6.6 87.9 83.3 -4.6 ECO Outlet O 2 (%) 2.4 2.3 -0.1 2.4 2.3 -0.1 In Fly Ash wt% 12.5 7.2 -5.4 12.5 6.8 -5.7

상기 표 3에 나타낸 바와 같이, 본 발명의 샘플 1 및 2가 무첨가에 비해 발전량이 각각 0.5 MW/hr 및 0.7 MW/h 증가하였고, 사용된 석탄은 시간당 각각 3.1톤과 3.3톤이 감소하였으며, 공기량도 무첨가에 비해 각각 초당 1.9Nm3 및 1.4 Nm3씩 감소하였고, Cyclone Outlet 온도가 15.3℃와 10.2℃ 감소하여 노내 온도가 안정됨을 알 수 있다.As shown in Table 3, compared to the sample 1 and 2 of the present invention, the amount of electricity generated increased by 0.5 MW / hr and 0.7 MW / h, respectively, and the amount of coal used decreased by 3.1 tons and 3.3 tons per hour, respectively. Compared with no additives, 1.9Nm 3 and 1.4 Nm 3 per second, respectively, were reduced, and the temperature in the furnace was stabilized by decreasing the Cyclone Outlet temperature by 15.3 ° C and 10.2 ° C.

또한, 대기 오염물질인 NOx, SOx 및 CO가스는 각각 샘플 1은 33.3ppm 3.2ppm, 6.6ppm 감소하고 샘플 2는 각각 43.3 ppm, 6.0ppm, 4.6ppm 감소함은 물론 Fly Ash의 미연분도 5.4W%와 5.7 W%가 무첨가에 비해 감소하였다. In addition, air pollutants NOx, SOx, and CO gas decreased 33.3 ppm 3.2 ppm and 6.6 ppm, respectively, and sample 2 decreased 43.3 ppm, 6.0 ppm, and 4.6 ppm, respectively. And 5.7 W% decreased compared to no addition.

또한, 크링커, 파울링 및 신터링의 제거 효과는 크링커, 파울링 및 신터링의 생성에 따라 Ash VV Position의 지수가 증가하므로 이를 분석하여 하기 표 4에 나타내었다.In addition, the removal effect of the clinker, fouling and sintering is shown in Table 4 by analyzing this since the index of Ash VV Position increases with the creation of the clinker, fouling and sintering.

표 4 <Ash VV Position> 구분 무첨가 첨가 Ash VVP 3/1 3/2 3/3 3/13 3/14 3/15 3/16 3/17 3/22 3/23 3/24 3/25 1EM O1C 19.5 24.3 39.4 32.0 36.4 39.2 40.4 43.7 47.4 44.9 47.4 41.1 1EM O1B 19.3 20.7 23.3 33.0 32.9 34.2 33.7 34.6 37.6 36.8 37.2 37.5 1EM O1C 26.8 29.7 33.3 43.2 40.0 44.8 46.3 50.1 52.7 52.0 49.6 47.5 평균 21.9 24.9 32.0 36.0 36.4 39.4 40.2 42.8 45.9 44.6 44.7 42.0 평균증가폭 17.5 1.8 Table 4 Ash VV Position division No addition adding Ash VVP 3/1 3/2 3/3 3/13 3/14 3/15 3/16 3/17 3/22 3/23 3/24 3/25 1EM O1C 19.5 24.3 39.4 32.0 36.4 39.2 40.4 43.7 47.4 44.9 47.4 41.1 1EM O1B 19.3 20.7 23.3 33.0 32.9 34.2 33.7 34.6 37.6 36.8 37.2 37.5 1EM O1C 26.8 29.7 33.3 43.2 40.0 44.8 46.3 50.1 52.7 52.0 49.6 47.5 Average 21.9 24.9 32.0 36.0 36.4 39.4 40.2 42.8 45.9 44.6 44.7 42.0 Average increase 17.5 1.8

상기 표 4에서 나타난 바와 같이, 3개의 Ash VV Position(값이 커지면 크링커 및 파울링 증가 의미)의 값을 평균 계산한 값에서 무첨가 및 첨가 기간 동안의 시작일과 종료일의 값을 비교해 보면 무첨가 기간에는 파울링 및 크링커의 발생으로 3/1일에서 3/15일 사이에 17.5%(39.4(종료일)-21.9(시작일))의 증가폭을 보이나, 첨가 실험기간 동안에는 단지 1.8%(= 42.0(종료일) - 40.2(시작일)) 증가하여 파울링 및 크링커의 형성이 급격히 감소하여 이로부터 본 발명의 액상 연소촉매 조성물 첨가 후 크링커 및 파울링 부착이 억제됨을 알 수 있다.As shown in Table 4 above, when the values of the three Ash VV Positions (meaning the increase of the clinker and fouling increase as the value increases) are compared with the values of the start date and the end date during the no addition and addition periods, Ring and clinker development increased by 17.5% (39.4 (end date)-21.9 (start date)) between 3/1 and 3/15, but only 1.8% (= 42.0 (end date)-40.2 during the addition experiment). (Starting date)) It can be seen that the formation of fouling and clinker is drastically reduced, thereby suppressing clinker and fouling adhesion after the addition of the liquid combustion catalyst composition of the present invention.

Claims (8)

Mg, Ca, Mn, Zn Al으로 부터 선택되는 1종 이상의 금속화합물과 Li, K, Na으로부터 선택되는 1종 이상의 알칼리금속화합물로 구성된 복합 금속킬레이트화합물 또는 복합금속착이온 수화물이 용해 가능한 액체에 용해되어 복합금속착이온이 형성되는 것을 특징으로 하는 복합금속착이온화합물을 포함하는 액상연소촉매 조성물Soluble in a soluble liquid with a complex metal chelate compound or a complex metal complex ion hydrate composed of at least one metal compound selected from Mg, Ca, Mn and Zn Al and at least one alkali metal compound selected from Li, K and Na Liquid combustion catalyst composition comprising a complex metal complex ion compound characterized in that the complex metal complex ion is formed 제1항에 있어서,The method of claim 1, 상기 용해가능한 액체는 질산 또는 암모니아수인 것을 특징으로 하는 복합금속착이온화합물을 포함하는 액상 연소촉매 조성물The soluble liquid is a liquid combustion catalyst composition comprising a complex metal complex ion compound, characterized in that the nitric acid or ammonia water 제1항에 있어서,The method of claim 1, 상기 복합금속킬레이트화합물은 Li2[Ca edta].4H2OK2, Li2[Mg edta].4H2ONa2, K2[Ca edta].4H2O, K2[Mg edta].4H2O, Na2[Ca edta].4H2O, Na2[Mg edta].4H2O, Li2[Mn edta], Li2[Zn edta], Li2[Al edta], K2[Mn edta], K2[Zn edta], K2[Al edta], Na2[Mn edta], Na2[Zn edta], Na2[Al edta]에서 선택되는 1종 이상인 것을 특징으로 하는 복합금속착이온화합물을 포함하는 액상 연소촉매 조성물The composite metal chelate compound is Li 2 [Ca edta] .4H 2 OK 2 , Li 2 [Mg edta] .4H 2 ONa 2 , K 2 [Ca edta] .4H 2 O, K 2 [Mg edta] .4H 2 O, Na 2 [Ca edta]. 4 H 2 O, Na 2 [Mg edta]. 4 H 2 O, Li 2 [Mn edta], Li 2 [Zn edta], Li 2 [Al edta], K 2 [Mn edta ], K 2 [Zn edta], K 2 [Al edta], Na 2 [Mn edta], Na 2 [Zn edta], Na 2 [Al edta] Liquid Combustion Catalyst Composition Containing Compound 제1항에 있어서,The method of claim 1, 상기 복합금속착이온 수화물은 알카리 금속(Li,K,Na)과 Mg, Ca, Mn, Zn 또는Al과 결합하기 위해서 Conjugate Base인 (NO3 -)와 리간드인 물분자(H2O) 또는 물분자(H2O)를 매개로 하여 착이온을 형성하는 것을 특징으로 하는 복합금속착이온화합물을 포함하는 액상 연소촉매 조성물The composite metal complex ion hydrate is conjugated with alkali metal (Li, K, Na) and Mg, Ca, Mn, Zn or Al (NO 3 − ) and a water molecule (H 2 O) or ligand as a ligand. Liquid combustion catalyst composition comprising a complex metal complex ion compound, characterized in that to form a complex ion through the molecule (H 2 O) 제4항에 있어서,The method of claim 4, wherein 상기 복합금속착이온 수화물은 K(NO3).Mg(NO3)2.13H2O, K(NO3).Mn(NO3)2.16H2O, K(NO3).Zn(NO3)2.15H2O, Na(NO3).Mg(NO3)2.13H2O, Na(NO3).Mn(NO3)2.16H2O, Na(NO3).Zn(NO3)2.15H2O, Li(NO3).Mg(NO3)2.13H2O, Li(NO3).Mn(NO3)2.16H2O, Li(NO3).Zn(NO3)2.15H2O, K(NO3).Al(NO3)3.9H2O Na(NO3).Al(NO3)3.9H2O, Li(NO3).Al(NO3)3.9H2O 에서 선택되는 1종 이상인 것을 특징으로 하는 복합금속착이온화합물을 포함하는 액상 연소촉매 조성물The composite metal complex ion hydrate K (NO 3) .Mg (NO 3) 2 .13H 2 O, K (NO 3) .Mn (NO 3) 2 .16H 2 O, K (NO 3) .Zn (NO 3 ) 2 .15H 2 O, Na (NO 3 ) .Mg (NO 3 ) 2 .13H 2 O, Na (NO 3 ) .Mn (NO 3 ) 2 .16H 2 O, Na (NO 3 ) .Zn ( NO 3 ) 2 .15H 2 O, Li (NO 3 ) .Mg (NO 3 ) 2 .13H 2 O, Li (NO 3 ) .Mn (NO 3 ) 2 .16H 2 O, Li (NO 3 ) .Zn (NO 3 ) 2 .15H 2 O, K (NO 3 ) .Al (NO 3 ) 3 .9H 2 O Na (NO 3 ) .Al (NO 3 ) 3 .9H 2 O, Li (NO 3 ) .Al (NO 3) 3 .9H liquid combustion catalyst composition comprising a complex metal complex ion compound, characterized in that at least one species selected from 2 O 제1항 내지 제5항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 5, 상기 복합금속착이온화합물을 포함하는 액상연소촉매 조성물은 붕소수화물인Na2B4O7.nH20, B2O3.nH2O, B2O4.nH20, NaBO2.nH2O, NaBO3.nH2O, Na2BO4.nH2O, H3BO3.nH2O 으로부터 선택되는 1종 이상의 붕소화합물; Mg3(PO4)2.nH2O, MgHPO4.nH2O, AlPO3.nH2O, K2HPO3.nH2O, Zn3(PO4)2.nH2O, MnHPO3.nH2O, Na3PO3.nH2O, Al(NO3)3.nH2O 으로부터 선택되는 1종 이상의 인산화합물; Mg(OH)2.nH2O, MgCO3.nH2O 으로부터 선택되는 1종 이상의 마그네슘화합물; Mn(OH)2.nH2O, MnCO3.nH2O, KMnO4.nH2O, Mn(NO3)2.nH2O으로부터 선택되는 1종 이상의 망간화합물; FeO.nH2O, Fe2O3.nH2O, Fe3O4.nH2O, [Fe edta].nH2O 으로부터 선택되는 1종 이상의 철화합물; NaSiO2.nH2O, KSiO2.nH2O, LiSiO2.nH2O 으로부터 선택되는 1종 이상의 규소화합물;을 각각 또는 1종 이상이 더 첨가되어 이온성 복합착염의 형성 및 이온성을 높이고, 연소촉진, 크링커 및 파울링의 제거 효율을 더 높이는 것을 특징으로 하는 복합금속착이온화합물을 포함하는 액상 연소촉매 조성물The liquid combustion catalyst composition comprising the complex metal complex ion compound is boron hydrate Na 2 B 4 O 7 .nH 2 0, B 2 O 3 .nH 2 O, B 2 O 4 .nH 2 0, NaBO 2 .nH At least one boron compound selected from 2 O, NaBO 3 .nH 2 O, Na 2 BO 4 .nH 2 O, H 3 BO 3 .nH 2 O; Mg 3 (PO 4 ) 2 .nH 2 O, MgHPO 4 .nH 2 O, AlPO 3 .nH 2 O, K 2 HPO 3 .nH 2 O, Zn 3 (PO 4 ) 2 .nH 2 O, MnHPO 3 . at least one phosphoric acid compound selected from nH 2 O, Na 3 PO 3 .nH 2 O, Al (NO 3 ) 3 .nH 2 O; Mg (OH) 2 .nH 2 O , MgCO 3 .nH least one magnesium compound selected from 2 O; At least one manganese compound selected from Mn (OH) 2 .nH 2 O, MnCO 3 .nH 2 O, KMnO 4 .nH 2 O, Mn (NO 3 ) 2 .nH 2 O; At least one iron compound selected from FeO.nH 2 O, Fe 2 O 3 .nH 2 O, Fe 3 O 4 .nH 2 O, and [Fe edta] .nH 2 O; At least one silicon compound selected from NaSiO 2 .nH 2 O, KSiO 2 .nH 2 O, and LiSiO 2 .nH 2 O; or at least one more is added to increase the formation and ionicity of the ionic complex salt. , Liquid combustion catalyst composition comprising a complex metal complex ion compound, characterized in that further enhance the efficiency of combustion, clinker and fouling 제6항에 있어서,The method of claim 6, 상기 복합금속착이온화합물을 포함하는 액상연소촉매 조성물은 100℃이하에서 결정체가 존재할 정도로 건조시켜 이온결합을 한 투명한 수화물 결정체로 사용하는 것을 특징으로 하는 복합금속착이온화합물을 포함하는 액상 연소촉매 조성물The liquid combustion catalyst composition comprising the composite metal complex ionic compound is dried to the extent that crystals are present at 100 ° C. or lower, and used as a transparent hydrate crystal that is ion-bonded. 제6항에 있어서,The method of claim 6, 상기 용해가능한 액체는 복합금속착이온화합물이 용해 및 분산되도록 솔비톨, 글리세린, EDTA, 에탄올아민으로부터 선택되는 계면활성제를 더 포함하는 것을 특징으로 하는 복합금속착이온화합물을 포함하는 액상 연소촉매 조성물The soluble liquid is a liquid combustion catalyst composition comprising a complex metal complex ionic compound further comprises a surfactant selected from sorbitol, glycerin, EDTA, ethanolamine so that the complex metal complex ionic compound is dissolved and dispersed
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