KR20070082069A - High Concentration Magnesium Fuel Additives in Fossil Fuel Combustors - Google Patents

Abstract

FIELD OF THE INVENTION The present invention relates generally to fuel additive compositions, and more particularly, to compositions comprising one or more overbase complexes of magnesium salts and organic acid complexing agents, which are introduced into a boiler firebox before or immediately after combustion in a fuel combustion device. A nanoparticle-sized fuel additive composition that synergizes and burns billions of magnesium oxide particles on the spot, adsorbing coal oxides, crude oil or heavy oil before combustion, thereby adsorbing sulfur oxides present in various forms from the outset. will be.

Description

HIGH CONCENTRATION NANOPARTICLE SIZE MAGNESIUM FUEL ADDITIVE FOR FOSSIL FUEL BURNING APPARATUS}

FIELD OF THE INVENTION The present invention relates generally to fuel additive compositions, and more particularly, to compositions comprising one or more overbase complexes of magnesium salts and organic acid complexing agents, which are introduced into a boiler firebox before or immediately after combustion in a fuel combustion device. A nanoparticle-sized fuel additive composition that synergizes and burns billions of magnesium oxide particles on the spot, adsorbing coal oxides, crude oil or heavy oil before combustion, thereby adsorbing sulfur oxides present in various forms from the outset. will be.

There is a growing interest in the safe use of coal, crude oil or residual heavy oil, but at the level of releasing components that are considered to be toxic to the environment. One element that has proven to be the most problematic is sulfur and its oxides.

Sulfur burns in the fire and primarily forms sulfur dioxide. Part of the sulfur dioxide reacts with the oxygen added for combustion to continue producing sulfur trioxide. When sufficient heat is removed from the combustion gas, the sulfur trioxide is condensed with water vapor to form sulfuric acid. This sulfuric acid corrodes ferrous metals and is also one of the main factors of acid rain.

To reduce the emissions of hazardous substances, many companies are obliged to purify flue gases before they are released to the outside. Depending on the nature of the pollutant, various techniques for purifying flue gas have been developed.

For example, the fly ash can be removed with an electrostatic precipitator (ESP), fabric filter (FF) or wet dust collector. Acid gases are mostly bonded to alkali compounds in a (semi) dry system with a spray dry absorber (SDA) or in a wet system using a dust collector.

Patents have been filed for the preparation of a fuel additive composition containing a small particle magnesium compound and magnesium. Hunt, U.S. Patent No. 3,150,089, discloses a stable dispersion in which inorganic compounds containing high base magnesium are supported on a nonvolatile carrier, wherein the inorganic compounds are present in the form of particles having a diameter of about 0.25 micron (250 nm) or less. Dispersions are described. The dispersion is an amount of at least a chemical equivalent required for the hydrolysis of the glycol ether solution of the oil-soluble magnesium alkoxide-carbonate complex, the oil-soluble dispersant, the liquid lubricating oil and the magnesium alkoxide-carbonate complex, prepared from a glycol ether having 8 or less carbon atoms. The water is mixed with (A) and the magnesium alkoxide-carbonate complex is hydrolyzed to form an oil-soluble magnesium-containing inorganic compound (B) and the nonvolatile carrier is removed (C).

U.S. Patent 4,056,479 to Redmore et al. Describes magnesium carboxylate-sulfonate complexes prepared by the method described in U.S. Patent 3,150,089, and 3,150,089 describes compositions made from carboxylic or sulfonic acids. In US Patent 4,056,479, the difference is disclosed in the complex prepared from the double complex of carboxylic acid and sulfonic acid.

In contrast to Patent No. 3,150,089 using liquid fatty acids at ambient temperatures below 15 ° C, US Pat. No. 4,056,479 may use high melting point carboxylic acids, such as stearic acid, which can be made from a combination of carboxylic acids and sulfonic acids.

US Patent 6,053,475 to McCormick et al. Discloses a method of mechanically milling a mixture of a metal compound precursor and a non-reactive diluent phase to produce ultra-fine powders that form uniformly dispersed nano-sized metal compound particles in the diluent phase. This is described. The method also includes a step of converting the nanosized metal compound particles into a metal oxide phase by heat treating the mixture of the nanosized metal compound particles uniformly dispersed in the diluent phase. The method further includes removing the diluent phase such that the nano-sized metal compound particles remain in the form of ultra fine powder (1-200 nm, specifically 10-100 nm).

US Pat. No. 4,163,728 to Cheng et al. Describes a process for preparing stable fluid magnesium containing dispersions from magnesium carboxylates with low carboxylate chemical equivalents. This method is essentially magnesium carboxyl in a nonvolatile process fluid containing a dispersant which can be heated to the decomposition temperature of the magnesium carboxylate and which can maintain the magnesium oxide formed by the decomposition in a stable suspension at a temperature above about 230 ° C. This involves the decomposition of the rate into magnesium oxide (MgO). This method comprises less than chemical equivalents of carboxylates based on Mg (OH) ₂ or its equivalent. The magnesium oxide particle size is preferably about 1 micron (1,000 nm) or less. This method requires acetic acid for this conversion.

US Patent 4,226,739 to Cheng et al. Describes a process for preparing stable fluid magnesium containing dispersions. This method essentially involves a process of pyrolyzing MgCO ₃ to MgO in a process fluid (high boiling hydrocarbon oil). The process fluid is stable and nonvolatile, and can be heated in the fluid state to the decomposition temperature of magnesium carbonate and contains a dispersant (magnesium naphthenate) which can maintain the magnesium oxide formed by the thermal decomposition in a stable suspension.

U.S. Patent 5,828,208 to Flanders et al. Describes an improved process for the conversion of vanadium containing feed streams in fluidized bed catalytic cracking equipment. According to this method, an effective amount of a composition comprising a magnesium or aluminum salt or a mixture thereof and at least one overbase complex of an organic acid complexing agent having a particle size of preferably 0.1 micron (100 nm) or less in a vanadium-containing feed stream in the form of a colloidal dispersion Input.

Many prior arts have produced magnesium oxide through gas phase reactions that require a lot of energy starting from very pure magnesium sources. These materials are difficult to manufacture and costly. In addition, the obtained compounds may also be difficult or impossible to put to practical use, and are also very expensive and have very little practical value for the desired use.

In order to solve the high cost and impurities, a large amount of magnesium oxide is obtained from other magnesium raw materials. These other raw materials have a relatively small surface area. Therefore, there is a problem in that a larger amount of magnesium oxide must be used to obtain the same effect.

 The present invention is to solve the above problems of the prior art, and relates to a nano-sized magnesium fuel additive composition of at least one overbase complex of magnesium salt and organic acid complexing agent. The additives in semisolid or colloidal dispersion are mixed with coal, crude oil or heavy oil before combustion in the fuel combustion device or immediately after combustion, before being put into the boiler fire, thereby burning sulfur oxides during or after their initial production. Billions of magnesium oxide particles adsorbing (sulfur dioxide and sulfur trioxide) generate synergistically on the spot. The magnesium oxide particles generated effectively remove sulfur trioxide from the exhausts of coal combusted products, crude oil burn products or residual heavy oil burn products.

In the present invention, "overbase" means a metal salt with a very high molar ratio of transition metal to stabilized carboxylic acid or sulfonic acid (eg 4: 1). The overbased preparation is suitably about 1/5 the level required for "simple" oxides (such as magnesium oxide) or "neutral" or "ordinary" metal salts with a base metal to acid ratio of 1: 1. Do. By "magnesium carboxylate" is meant a reaction product of magnesium metal salts and carboxylic acids. By "overbased complex" is meant an oxide or carbonate of magnesium and a magnesium salt of an organic acid "complexing agent".

The present invention is a composition comprising at least one overbase complex of magnesium salt (magnesium oxide) and an organic acid complexing agent, which is mixed with coal, crude oil or heavy oil prior to combustion in a fuel combustion device or immediately after combustion in a boiler firebox. By combustion, the invention relates to a nanoparticle-sized fuel additive composition which synergistically generates billions of magnesium oxide particles on site which adsorb sulfur oxides present in various forms from their initial production.

It is well known in the field of nanotechnology that the smaller the particle size, the larger the surface area. The advantages of small particle sizes can be seen in the table below.

diameter Total surface area of particles per liter per nm M ²

1000 1.91 x 10 ⁹ 6.0 x ^{10 3}

100 1.91 x ^{10 12} 6.0 x ^{10 4}

10 1.91 x 10 ¹⁵ 6.0 x 10 ⁵

1 1.91 x ^{10 18} 6.0 x ^{10 6}

As can be seen from the table, each time the diameter of the particle is 10 times smaller, the number of particles per liter increases by 1,000 times, and the surface area is increased by 10 times. The size of the particles is a very important property for effective bonding with sulfur oxides. Representative particle sizes of the present invention are much smaller than 200 nm (0.2 micron) and preferably have an average particle size of about 20.7 nm (0.0207 micron). This particle size becomes smaller as the compound passes through the flame during combustion, as described below.

The following describes an embodiment of a method for preparing nano-sized magnesium carboxylate according to the present invention, but the present invention is not limited thereto.

Example 1 Semi-Solid Form

The three-necked flask was equipped with a stirrer, a thermometer and a condenser connected to an appropriate flush dust collector. 500 ml of water was placed in the flask, and 1110 g of nitric acid at 70% concentration was slowly added to the water. Next, 500 g of pure magnesium oxide was added very slowly to this nitric acid aqueous solution. If the magnesium oxide did not dissolve completely, further nitric acid was added until a clear solution. The mixture was heated while magnesium oxide was added to the mixture. After cooling, 850 g of stearic acid and 100 g of a paraffinic solvent or a naphthenic solvent were added with stirring. The contents of the flask were exposed to ultraviolet light with a wavelength of 75-280 mμ for at least 12 hours. This has an effect on the electronic structure and dynamics of the magnesium compound in preparation for the final reaction step. After the UV exposure process, the flask was equipped with a heating mantle. The solution in the flask was sufficiently heated to remove water, and all the produced nitrogen oxides were removed with the flush dust collector. Preferably, the solution was heated at 325 ° C. for at least 3 hours. While the warmth remained, the contents of the flask were poured into a suitable container and cooled. After cooling, about 1,400 g of a light colored semisolid magnesium compound (overbased complex of magnesium salt and organic acid complexing agent or magnesium carboxylate) was obtained. The semisolid magnesium material has a very small particle size and can be used as such or milled into small mills to produce smaller particles of the desired degree. These particles are easily broken up by force. The solvent can be appropriately selected depending on the intended use. The properties may vary depending on the application. In some cases, an aromatic solvent may be used, and in other cases, a paraffinic or naphthenic solvent may be used. If semi-solid materials are desired, it is important to minimize solvent use.

       Example 2-Colloidal Dispersion Forms

       After UV exposure and cooling, stearic acid and paraffinic or naphthenic solvents were used instead of 690 g of oleic acid and 200 g of aromatic solvent, which were added under stirring, in the same manner as in Example 1. In this example, after removing water and nitrogen oxide, about 1,400 g of a pale yellow liquid product (stable colloidal dispersion) was obtained. The product can be used in place of standard magnesium oxide (ionic solid MgO) in many applications without further processing.

      In the above embodiments, the particle size of the magnesium salt (magnesium oxide or magnesium carboxylate) component is in the range of about 10 nm to about 50 nm, preferably 17 nm to about 27 nm, more preferably 20 nm to about 22 nm, most preferably Preferably the average particle size is about 20.7 nm.

      In any of the above forms, the resulting fuel additive composition may be mixed with coal, crude oil or heavy oil in a fuel combustion apparatus such as a diesel engine before being put into a boiler firebox before or just after combustion.

      The magnesium salt is magnesium acetate dihydrate, magnesium caprylate, magnesium carbonate, magnesium hydroxide, magnesium citrate dihydrate, magnesium formate dihydrate, magnesium laurate, magnesium nitrate, magnesium oleate, magnesium oxide, And magnesium precursor material selected from the group consisting of magnesium oxylate, magnesium oxylate dihydrate, magnesium peroxide, magnesium stearate and magnesium hydroxy carbonate.

       One of the key features of the fuel additive composition of the present invention is that, upon combustion, the nanoparticle-sized magnesium composition generates billions of maximal reactive magnesium oxides in place, and the sulfur oxides on which the magnesium oxide particles are initially formed. (Sulfur dioxide and sulfur trioxide) are adsorbed during or after combustion, and the magnesium oxide particles generated are quite effective in removing sulfur trioxide from the emissions of coal combusted products, crude oil burn products or residual heavy oil burn products. Accordingly, the fuel additive composition of the present invention produces a very large number of particles that come into contact with, react with or adsorb various types of sulfur oxides (sulfur dioxide and sulfur trioxide) in the combustion exhaust stream. The more opportunities for chemical reactions or contacts, the more actual reactions or contacts occur. By supplying a very small number of particles, it is possible to obtain an economically and environmentally important level of interaction between magnesium oxide and sulfur trioxide.

        The resulting small particles are highly reactive and very well dispersed throughout the combustion gas. Since the particles are produced during the actual combustion of coal, crude oil or heavy oil containing the additives, there is a greater chance that new magnesium oxide particles come into contact with new sulfur trioxide molecules. More collision reactions are possible with the same activity for several minutes in a conventional boiler firebox on the exhaust purification site side, compared to contacting sulfur trioxide for a few seconds before reaching the electrostatic precipitator (ESP) or fabric filter (FF). The resulting more particles are more effectively captured by ESP or FF.

        In the method for preparing nanoparticle sized magnesium carboxylates, purified or crude magnesium compounds dissolved in inorganic or organic acids can be used initially. The magnesium salt is magnesium acetate dihydrate, magnesium caprate, magnesium carbonate, magnesium hydroxide, magnesium citrate dihydrate, magnesium formate dihydrate, magnesium laurate, magnesium nitrate, magnesium oleate, magnesium oxide, It can be formed from a magnesium precursor material selected from the group consisting of magnesium oxylate, magnesium oxylate dihydrate, magnesium peroxide, magnesium stearate and magnesium hydroxy carbonate.

A stable dispersion of magnesium carboxylate can be obtained by the ultraviolet irradiation process, particle size separation technique and / or pyrolysis process after removal of water and impurities. Since the complex of the present invention is an organic soluble component, all inorganic impurities can be easily removed by filtration before packaging of the product.

       By changing the formulation composition ratio, it is possible to obtain a liquid or semisolid product. This gives you the flexibility to deliver products similar to those required for any customer or industry. The flexibility of this composition ratio is obtained by changing the ratio of the carboxylic acid blend and the transition metal (magnesium). By changing the proportions it is possible to produce products with a wide variety of properties. Likewise, by changing the composition ratio of the components of the carboxylic acid blend, materials with very different properties can be obtained.

       For example, when a solid carboxylic acid, for example stearic acid, is used, an oily semisolid product can be obtained. Likewise, when using a liquid blend of carboxylic acid, for example oleic acid, a liquid product is obtained. Therefore, the flexibility of the composition of the final active agent is further increased, which is a unique characteristic only in the carboxylates.

According to the present invention, natural carboxylic acids or acid mixtures, or carboxylic acids or acid mixtures derived from natural products or synthetic acids such as aliphatic fatty acids or tolactic acids can be used, and the synthetic acids include alkoxy and phenoxy fatty acids, ere And neoacids such as thioether monocarboxylic acid, isopentanoic acid, 2-ethylhexophosphoric acid, isooctanoic acid, isononanophosphoric acid or neodecanoic acid. The carboxylic acid or acid mixture is contacted with a metal powder or a reaction raw material of a desired metal in the form of a suitable oxide, hydroxide, carbonate or other simple salt, and after the appropriate reaction is completed, the unwanted by-products are suitably removed to obtain the desired product. .

       Since the formulations are essentially organic compositions, they can be mixed with various solvents such as aromatic or paraffinic, depending on the characteristics desired by the user. Therefore, the user can select a wider range as needed.

       As described above, according to the fuel additive composition of the present invention, the mixture is combusted with coal, crude oil or heavy oil before combustion in a fuel combustion device or immediately after combustion, before being introduced into a boiler fire chamber. Synergistically generating billions of magnesium oxide particles that adsorb sulfur oxides on the spot. Upon combustion, the nanoparticle-sized magnesium composition generates billions of maximal reactive magnesium oxides in situ, adsorbing sulfur oxides (sulfur dioxide and sulfur trioxide) on which the magnesium oxide particles are initially formed during or after combustion. The generated magnesium oxide particles can effectively remove sulfur trioxide from emissions of coal combusted products, crude oil burn products or residual heavy oil burn products.

Although the present invention has been described with the above embodiments, the present invention is not limited to these embodiments, and although not described herein, various modifications are possible within the scope of the present invention. It will be self-evident to those who have

Claims (19)

In nanoparticle-sized magnesium fuel additive compositions which are mixed with fossil fuels before they are combusted in a fuel combustor or immediately after combustion are put into a boiler firebox: One or more overbased complexes of magnesium salts and organic acid complexing agents; Nanoparticle-sized magnesium fuel additive composition which, upon combustion in the fuel combustor, synergistically generates billions of magnesium oxide particles on the spot which adsorb sulfur oxides present in various forms from their initial production. .        The nanoparticle-sized magnesium fuel additive composition of claim 1, wherein the concentration of the magnesium salt component in the composition is about 20% to about 55%.        The nanoparticle sized magnesium fuel additive composition of claim 1, wherein the composition is semisolid.        The nanoparticle sized magnesium fuel additive composition of claim 1, wherein the composition is a stable colloidal dispersion.        The nanoparticle sized magnesium fuel additive composition of claim 1, wherein the magnesium salt component has a particle size of about 10 nm to about 50 nm.        6. The nano fuel sized magnesium fuel additive composition of claim 5, wherein the magnesium salt component has a particle size of about 17 nm to about 27 nm.        7. The nanoparticle-sized magnesium fuel additive composition of claim 6, wherein the magnesium salt component has a particle size of about 20 nm to about 22 nm.        8. The nano fuel sized magnesium fuel additive composition according to claim 7, wherein the magnesium salt component has an average particle size of about 20.7 nm.        The nanoparticle sized magnesium fuel additive composition according to claim 1, wherein the magnesium salt is an oxide or carbonate of magnesium.        The nanoparticle sized magnesium fuel additive composition according to claim 1, wherein the organic acid complexing agent is carboxylic acid, sulfonate, phenate or phosphoric acid.        The nanoparticle-sized magnesium fuel additive composition according to claim 1, wherein the overbase complex comprises a complex of magnesium salt and magnesium salt of an organic acid complexing agent.        The method of claim 1, wherein the overbased complex is:        An overbased complex of magnesium oxide and magnesium salt of an organic acid complexing agent;        Overbase Complexes of Magnesium Salts of Magnesium Carbonate and Organic Acid Complexing Agent Nanoparticle size magnesium fuel additive composition comprising a.        The method of claim 1, wherein the overbased complex is:        An overbased complex of magnesium oxide and magnesium salt of a fatty acid complexing agent;        Overbase Complex of Magnesium Salt of Magnesium Carbonate and Fatty Acid Complexing Agent Nanoparticle size magnesium fuel additive composition comprising a.        The method of claim 1, wherein the magnesium salt is magnesium acetate dihydrate, magnesium caprylate, magnesium carbonate, magnesium hydroxide, magnesium citrate dihydrate, magnesium formate dihydrate, magnesium laurate, magnesium nitrate, magnesium allol Nanoparticle sized magnesium fuel additive composition, characterized in that it is formed from a magnesium precursor material selected from the group consisting of latex, magnesium oxide, magnesium oxylate, magnesium oxylate dihydrate, magnesium peroxide, magnesium stearate and magnesium hydroxy carbonate.        The nanoparticle-sized magnesium fuel additive composition according to claim 1, wherein ultraviolet rays are irradiated to the overbase complex of the magnesium salt and the organic acid complexing agent.        In a method for preparing a nanoparticle-sized magnesium fuel additive composition mixed with fossil fuels:         Adding magnesium oxide while heating in a high concentration of nitric acid solution;         Cooling the magnesium oxide / water / acid mixture solution;        To the magnesium oxide / water / acid solution, a mixture of an acid selected from stearic acid and oleic acid and a solvent selected from paraffinic, naphthenic and aromatic solvents is added with continuous stirring;         Irradiating the magnesium oxide / water / acid / solvent mixture with ultraviolet rays;        Boiling the magnesium oxide / water / acid / solvent mixture sufficiently to remove all moisture and nitrogen oxides, thereby producing overbased complexes or magnesium carboxylates of magnesium salts and organic acid complexing agents having nanoscale magnesium salt components. A method for producing a nanoparticle-sized magnesium fuel additive composition.        17. The method of claim 16, further comprising reducing the particle size of the nano-sized magnesium salt component within the range of about 20 nm to about 22 nm.        17. The method of claim 16, wherein the magnesium oxide / water / acid / solvent mixture is exposed to ultraviolet light having a wavelength of 50 to 300 mμ for at least 12 hours.        In a method of removing sulfur oxides in a boiler firebox during or immediately after combustion in a fossil fuel combustor:         Mixing the nano-sized magnesium fuel additive composition comprising at least one overbased complex of magnesium salt with an organic acid complexing agent with fossil fuel prior to combusting in a fuel combustor or into a combustion direct boiler firebox;         Wherein the additive composition synergistically generates billions of magnesium oxide particles on the spot upon combustion in the fuel combustor, adsorbing sulfur oxides present in various forms from their initial production. .