Method of reduction of sulfur dioxide emissions during burning of coals

FIELD: treatment of coal for reduction of sulfur dioxide emissions during burning of coal.

SUBSTANCE: coal at high content of sulfur is placed in low-pressure medium for cracking of part of coal by extraction of atmospheric fluids entrapped in coal. Then cracked coal is brought in contact with aqueous composition of colloidal silicon oxide oversaturated with calcium carbonate and larger part of aqueous composition is brought out of contact with coal, after which coal is acted on by high pressure in carbon dioxide medium during period of time sufficient for penetration of calcium carbide into cracks in coal. Description is also given for coal cracked in vacuum which contains about 0.5 wt-% of sulfur and additionally contains calcium carbonate deposited in cracks in coal in the amount sufficient for obtaining Ca:S molar ratio equal to at least 0.5. Specification contains also description of obtaining energy in the course of burning coal at high content of sulfur at simultaneous reduction of sulfur dioxide in emissions. Specification contains also description of increase of calcium sulfate obtained in the course of burning coal at high content of sulfur and aqueous composition used for treatment of such coal. Specification contains also description of preparation of aqueous composition for treatment of coal at high content of sulfur in combustion products. Description is also given for device for treatment of coal at pressure.

EFFECT: considerable reduction of sulfur dioxide and other toxic gases formed during burning of coal.

25 cl, 8 dwg, 3 ex

 

The scope of the invention

The present invention relates generally to coal. More specifically, the present invention relates to the handling of coal in order to reduce the discharge of sulfur dioxide during the combustion of coal.

General prerequisites

Coal is one of the most common fuel sources in the world. Coal, as a rule, is extracted in the form of a material similar to graphite, with color from dark brown to black, which is formed from fossilized plant material. Coal typically contains amorphous carbon, combined with some organic and inorganic compounds. The quality and type of coal varies from high quality anthracite coal (i.e. coal with a high carbon content with small amounts of volatile impurities and burning with a clear flame) to bitumen (i.e. coal with a high percentage of volatile impurities having burning with a smoky flame and lignite (coal, softer than asphalt, and containing plant material is not completely converted to carbon, and having a combustion with a very smoky flame). Coal is burned in a coal-fired thermal power plants around the world to generate energy in the form of electricity. For many years it was known that certain impurities in the coal can have a significant impact on the types of emissions, about izvodimyh during the combustion of coal. Especially a lot of problems deliver such impurity as sulfur. Sulfur can be present in coal from very small quantities up to several weight percent (for example, up to 7 wt.%). Sulfur can be present in coal in various forms, such as organic sulfur, pyrite sulfur and sulfate sulfur. When coal containing sulfur, burning, generally in the atmosphere, the gases of combustion, releasing the sulfur dioxide (SO2). The presence of SO2in the atmosphere associated with the formation of acid rain, which occurs because of sulphuric or sulphurous acid, which are formed of SO2and water. Acid rain can harm the environment in many different ways, and in the United States of America Agency for environmental protection (EPA) has established standards for combustible coal, which limit emissions of SO2from coal thermal power plants.

Although in the United States, coal is mined in many areas of the country, most of the coal, which is easily extracted (and for this reason it is cheap), often contains high levels of sulfur, which leads to levels SO2in gases of combustion greater than that allowed by the EPA. Thus, coal-fired thermal power plants often have to buy coal of higher quality from the mines, which can be located at large distances from power plants, and carry significant Tr is sportie and other expenses. Over time we developed a significant number of technologies to reduce the number of SO2in gases of combustion resulting from combustion of coal with high sulfur content. This technology includes various kinds of processing coal before combustion, during combustion and after combustion. However, such processing typically do not achieve a satisfactory combination of efficiency while lowering emissions of SO2and affordability in the application.

This, again, was a prerequisite to the development of the present invention.

Brief description of the invention

One aspect of the present invention is a method for processing coal with high sulfur content, designed to reduce emissions of sulfur dioxide when coal is burned. The method includes:

(a) placement of coal in an environment with low pressure required for fracturing in parts of coal by extracting atmospheric fluids captured by the charcoal,

(b) bringing containing cracks of coal in contact with the aqueous composition of colloidal silica supersaturated calcium carbonate

(c) removal of much of the water composition from contact with the coal, and

(d) the influence of high pressure on coal, processed water composition in the atmosphere of carbon dioxide, over a period of time, all the full-time, in order calcium carbonate penetrated into cracks in the corner, formed in stage (a).

Another aspect of the present invention is a coal with high sulfur content, which contains at least about 0.5 wt.% sulphur, and in addition, contains calcium carbonate deposited within fractures in the coal, sufficient to ensure a molar ratio of Ca:S, is equal to at least 0.5, it is subjected to cracking in a vacuum.

Another aspect of the present invention is a method for producing energy by burning coal with high sulfur content, while reducing the content of sulfur dioxide in the emissions from this combustion, this method involves precipitation of calcium carbonate within the cracks of the coal is subjected to cracking in a vacuum, and the burning of the received coal with a high sulfur containing calcium carbonate at high temperatures.

Another aspect of the present invention is a method for increasing the amount of calcium sulfate resulting from the combustion of coal with high sulfur content, while reducing at the same time, emissions of sulfur dioxide from such burning, this method involves the combustion of coal with high sulfur content, subjected to cracking in a vacuum, with calcium carbonate, precipitated inside trese is in the corner, and removing the calcium sulfate resulting from such burning.

An additional aspect of the present invention is an aqueous composition for treatment of coal with high sulfur content to reduce the discharge of sulfur dioxide when treated coal is burned. The composition contains a supersaturated solution of calcium carbonate, combined with the alkaline aqueous composition of colloidal silicon dioxide.

Another additional aspect of the present invention is a method for obtaining aqueous composition suitable for the treatment of coal with high sulfur content, with the aim of lowering the sulphur dioxide in the products of combustion, when the treated coal is burned, this method involves the dissolution of calcium carbonate in alkaline aqueous compositions of colloidal silicon dioxide under conditions sufficient for the integration of calcium ions in the colloidal particles, obtained from oxide of silicon, with the aim of obtaining a supersaturated solution of calcium carbonate.

The last aspect of the present invention is a device for processing coal with high sulfur content using an aqueous composition under pressure, and the device includes:

the high pressure container suitable for holding charcoal,

the first input in order to enable water is the first song to enter the container and for coming in contact with charcoal,

the mechanism for removing water composition from the container,

the first input in order to allow carbon dioxide to enter the container at a pressure higher than atmospheric pressure,

the source of carbon dioxide high pressure connected to the first input, and

exit to remove coal from the container.

Other aspects of the present invention will be clear to the person skilled in the art upon review of the detailed description of the present invention.

Brief description of drawings

For further understanding of the nature, objectives and advantages of the present invention must be made by reference to the following detailed description, taken in conjunction with the following further drawings, in which similar positions indicate similar elements and where:

Figure 1 - picture of the proposed structure of colloidal particles of silicon oxide, in which ions of Ca+2are isolated, in accordance with one of the embodiments of the present invention.

Figure 2 - image of the double layer of water associated with typical colloidal particle of silicon oxide, formed in accordance with one of the embodiments of the present invention.

Figure 3 - view of the generator in accordance with one of the embodiments of the present invention.

4 is a view of the generator 3 in combination with three magnetic quadrup lname amplifying unit in accordance with one of the embodiments of the present invention.

5 is a top view in section of the generator figure 4 together with the magnetic fields and gradient magnetic fields in accordance with one of the embodiments of the present invention.

6 is an illustration of the method of sampling bituminous coal with high sulfur content of the trolleys during the pre-cooking and processing, in accordance with one of the embodiments of the present invention.

Fig.7 - type steam power installation, which handles, burns and converts the processed coal in thermal energy, emissions, water and ash (including gypsum), in accordance with one of the embodiments of the present invention.

Fig - type high-temperature furnace, where the treated coal is burned to produce heat, which can be used to generate electric energy, in accordance with one of the embodiments of the present invention.

Detailed description of the invention

Embodiments of the present invention determine an approach to reduce the SO2and other harmful gases of combustion through unique processing of coal before combustion. Coal can be processed with the aqueous composition of the colloidal oxide of silicon supersaturated with calcium carbonate, preferably associated with calcium oxide to significantly increase the amount of calcium (Ca) in the treated coal compared to untreated the first coal (for example, carbon is found in nature). More specifically, the coal may be applied vacuum to remove fluids from coal and fracturing in coal. Then, contains cracks coal can be brought into contact with the aqueous composition under pressure of carbon dioxide (CO2). This method, as it is believed, allows for penetration into cracks in the corner portion of the water composition, so that the calcium carbonate to crystallize in the cracks and cause additional fracturing in coal. When the treated coal is burned, sulfur is converted to CaSO4and Na2SO4and the coal is burned at high temperatures, through a chemical reaction between calcium carbonate, NaHCO3and sulfur dioxide - sulfuric acid and/or sulfurous acid. The advantage is that the combustion of coal followed by a low emissions of sulfur dioxide (SO2). In addition, there is evidence obtain lower emissions of nitrogen oxide (NOX), mercury (Hg), carbon monoxide (CO), carbon dioxide (CO2) and hydrocarbons (HC). At the same time improving the quality of emissions from combustion modified solid by-products of the combustion process with increasing quantities of useful solid products that can be collected. In particular, in the ash remains component (CaSO4), prigodin the th for use in cement production.

One of the embodiments of the present invention is a method for processing coal to reduce emissions of sulfur dioxide when coal is burned. In the first stage, the coal is placed in the environment with a reduced pressure sufficient to crack formation in part of the coal by extracting atmospheric fluids trapped in the corner. In the second stage, the coal is brought into contact with the aqueous composition of colloidal silica supersaturated with calcium carbonate. In the third stage, the water composition is removed from contact with the coal. At the fourth stage, the coal is subjected to high pressure in the atmosphere of carbon dioxide over a period of time sufficient for the calcium carbonate in order to get cracks in the coal obtained in the first stage.

The type of coal that can be processed using this method, is any coal, which has an undesirable level of sulfur, which will lead to unwanted or unauthorized levels SO2if it to burn without treatment. Thus, this coal can be a anthracite, bituminous coal or lignite, which has a sulfur content of about 0.2 wt.% to more than 7 wt.%. For some applications, the coal having a sulfur content of at least 0.5 wt.%, can be considered as coal with a high content of the career. The density of coal often depends on the type of coal and typically varies from about 1.2 g/cm3to 2.3 g/cm3(for example, the apparent density measured by using replacement fluid). The amount of coal that is processed at the stage of application of reduced pressure may be the size that comes from most of the mines, such as coal, having an irregular shape, with a maximum cross-sectional dimension of about 2 inches, and then to smaller around than 1/4 inch. The size that works for large mechanical furnaces, approximately 3/4 - 1 inch, while the size that works for small mechanical furnaces, is less about than 1/2 inch. Thus, this method can be used at the facility to handle near where the coal must be burned, or directly on the extraction site. If it is desirable, before the application of reduced pressure coal can be reduced in size, for example by crushing, fine crushing or fine dispersion of coal to a powder of particles having sizes less than about 5 cm, for example, less than 3 cm, sizes ranging from 50 μm to 300 μm, or from 50 μm to 100 μm, which are desirable for certain applications. This reduction in size of the coal may serve to increase surface area, which can p dergatsya the impact of reduced pressure and water composition, and may serve to reduce the amount of time required for the processing of coal. If desired, the coal, which has a reduced size, can be mixed with a liquid (e.g. water) with formation of a suspension. For certain applications it may be desirable conversion of coal into contact with the calcium oxide prior to application of reduced pressure, for example by mixing the coal with calcium oxide in powder form. The conversion of coal into contact with the calcium oxide may serve to further reduce the allocation of SO2.

At first the above stage, the coal is placed in a container that can be sealed and which can be installed low pressure. The application of reduced pressure will be sufficient for the removal of fluids, either gaseous or liquid trapped in the corner. As expected, this is the result of fracturing of the coal, i.e. the formation of cracks in the form of small cracks, defects or channels in the corner. Alternative or in conjunction with this, the application of reduced pressure can be used to remove fluids, either gaseous or liquid trapped in pre-existing fractures in the coal. Cracks or generated by application of reduced pressure, or pre-existing, as a rule, are elongated and may be of the trading with each other, or may defend from each other, situated essentially parallel to each other. Cracks must be present in appropriate quantities and the corresponding transverse dimensions to provide sufficient water compositions, supersaturated with calcium carbonate, the possibility of penetration into the cracks. For example, the application of reduced pressure can create numerous cracks in the coal, which have lateral dimensions in the range from 0.01 μm to 1 μm. As a rule, the application of reduced pressure is at ambient temperature, although, to facilitate the process, the coal may be heated. The pressure is reduced to a pressure less than the ambient pressure, for example, atmospheric pressure to about one-tenth of an atmosphere or less, depending on the capacity of your vacuum pump. Typically, the length of time during which the coal is subjected to a reduced pressure, typically less than an hour, for example less than about 15 minutes, however, for many applications, about 3-10 minutes is enough time.

After application to the coal of low pressure, it is brought into contact with the aqueous composition of colloidal silica supersaturated calcium carbonate, in a period of time sufficient for penetration of dissolved calcium carbonate in cracks. Considered the tsya, what this leads to a strong Association of calcium carbonate with charcoal and with the further fracturing of coal during the crystallization of calcium carbonate in cracks. To enhance fracturing in coal, it may be desirable that the aqueous composition contained the calcium oxide. Stage of bringing into contact takes place at ambient temperature, to simplify the process, although it can be used and higher temperatures. Typically, the amount of water composition will be from about 5 gallons to about 20 gallons, or more than one hundred pounds of coal. To save, usually used about 10 gallons per hundred pounds of coal. The aqueous composition may be sprayed or poured on the coal in the container, and coal can be shipped (e.g., fully immersed in the aqueous composition. If desired, the coal can be mixed or shake, for homogeneous mixing with the aqueous composition. Typically, only a few minutes, it will be necessary to add water composition to the coal at a temperature and ambient pressure. Additional details on the water composition will be discussed next.

After finding water composition in contact with coal within a reasonable amount of time, in the container in which is placed the coal, the mouth of avleat high blood pressure, with a gas, preferably carbon dioxide, in a period of time sufficient to discharge part of the water composition in the cracks of coal, in order to initiate crystallization of the dissolved calcium carbonate in cracks and for additional cracking in the corner. Preferably, the aqueous composition is removed from contact with the coal at the stage of application of high pressure. In particular, the remaining portion (for example, from 70% to 90%) water composition, which does not penetrate into the coal may be removed using various methods, for example by filtration of coal or simply by draining the remaining part of the aqueous composition from the container, through a mesh or sieve.

Generally, stage of application of high pressure will take place at ambient temperature and at a pressure that will not exceed 50 pounds per square inch (psi), preferably, greater than 100 psi. Although the pressure may exceed 300 psi, the evidence suggests that for most applications require no more than 300 psi. The application of high pressure, as a rule, takes place in a period of not more than one hour, usually about 20-45 minutes. After the application of high pressure, the coal can be burned or processed in another way, in accordance with any Oba is the principal method of extracting energy from coal. If desired, the coal can be reduced in size, after processing, for example, by crushing, fine crushing or fine dispersion of coal in the form of a powder particle. For some applications, the coal can be re-processed using the same method described above. In particular, all stages can be repeated two or more times, but usually not more than two cycles are necessary to obtain satisfactory results, with the aim of reducing emissions of SO2. Preferably, the filtrate is reused in the next cycle, this adds fresh water composition to provide the desired water relations and composition of the coal, as discussed earlier. It is believed that two cycles provide adequate supply in the coal of calcium carbonate, from the point of view of considerations of time and cost.

Processed in accordance with this method, the coal will contain calcium carbonate, associated with him, so that when the coal is burned at high temperatures, emissions of SO2lowered to the desired level. In particular, the treated coal may have a content of calcium carbonate, which the molar ratio of Ca to S detected in the treated coal, as a rule, is at least 0.5, and the value equal to at least 1 (e.g. the measures 1-4), is preferred. This is the content of calcium carbonate can reduce emissions of SO2at least about 5 percent, compared to the raw coal, for example, sometimes there is a reduction of less than 20 percent, and sometimes, from 60 percent to 100 percent. It is believed that the sulfur contained in the coal, interacts with calcium carbonate, obtaining calcium sulphate, thus reducing or eliminating the formation of SO2. Calcium sulfate, which is formed may be in the form CaSO4·2H2O (gypsum). It should be noted that the mass percentage of calcium carbonate found in the treated coal, as a rule, will vary, depending on the weight percent of sulfur in the raw coal, so as to achieve the desired molar ratio of Ca to s Also up to 50% sulfur in coal, which is burned, can remain in the ashes, and not released in the form of SO2. Accordingly, for some applications, the molar ratio of Ca to S less than 1 (for example, 0.5), may be adequate.

Another variant of implementation of the present invention stems from the method described previously. This option represents the containing cracks coal with calcium carbonate, precipitated inside the cracks of coal. Cracks or created by application of reduced pressure, or earlier, the AK rule, are oblong and can be connected to each other or can be separated from each other, usually in a parallel manner, and can have lateral dimensions in the range from 0.01 μm to 1 μm. Coal can be obtained using the method discussed above, and contains calcium carbonate, precipitated inside the cracks of coal, so that the molar ratio of Ca to S, as a rule, is at least 0.5 in. In addition, coal can contain inside cracks from about 0.15% of the mass of up to 2.5 percent of the mass of silicon oxide. In addition, the coal may contain calcium oxide, precipitated inside the cracks, and the calcium oxide will contribute to the achievement of the desired molar ratio of Ca to s As discussed earlier, the type of coal that can be processed using the present method, is any coal, which has an undesirable level of sulfur, which will lead to undesirable or unacceptable levels of SO2incineration without treatment, and may have a sulfur content of about 0.2 wt.% to more than 7 wt.%. The amount of coal that is processed may be from about 2 inches and to a smaller, approximately than 1/4 inch, or it can be reduced, for example, by grinding, fine grinding or fine dispersion of coal in the powder of particles having a size smaller when is Erno, than 5 cm, for example, less than 3 cm, however, for certain applications, are desirable sizes ranging from 50 μm to 100 μm.

Another embodiment of the present invention is a method of obtaining energy by burning coal, while reducing the content of sulfur dioxide in the emissions from this combustion, this method involves precipitation of calcium carbonate within the cracks in the coal and combustion of the resulting coal containing calcium carbonate at high temperature, generating energy. In particular, the calcium carbonate may be deposited within the fractures in the coal, in accordance with the method discussed above, using water compositions of colloidal silica supersaturated calcium carbonate, coal, containing calcium carbonate, contains calcium carbonate, precipitated inside the cracks of coal. Coal, containing calcium carbonate, can be burned in accordance with a variety of technologies, including a variety of conventional technologies, generating energy. For example, coal, containing calcium carbonate, can be burned in accordance with the method of combustion in a fixed bed (for example, in the method using a mechanical furnace with the lower fuel supply, the method using a mechanical furnace with a moving grate or in the method using a mechanical furnace with razbrasivat the LEM), with the method of burning suspensions (for example, the method of burning finely dispersed fuel or injection of particles), the method of combustion in the fluidized bed (for example, combustion in a circulating fluidized bed or combustion in the fluidized bed under pressure), magnetohydrodynamic power generation and so on. Concrete technology and equipment selected for burning coal, containing calcium carbonate, may affect one or more of the following characteristics associated with the stage of combustion: (1) at the temperature occurring during combustion (e.g., from about 1800°F approximately 4000°F); (2) whether coal, containing calcium carbonate, in the wet form, after deposition of calcium carbonate, or first dried; (3) the size of the used coal containing calcium carbonate; and (4) the amount of energy that can be obtained. For example, coal, containing calcium carbonate, can have a particle size of less roughly than 1 inch, and is combusted in a mechanical kiln, at a temperature of from about 2400°F approximately 2600°F. as another example, coal, containing calcium carbonate, can be crushed to a powder with particle sizes less than about 300 microns, and burned at a temperature of from about 3200°F approximately 3700°F (for example, primers the 3500° F) by blowing it into the furnace, mixing it with a source of oxygen and igniting the mixture in accordance with the suspension firing.

Another variant of implementation of the present invention is a method for increasing the amount of calcium sulfate resulting from the combustion of coal with high sulfur content, while at the same time reducing the emission of sulfur dioxide from such burning. This method involves burning coal with calcium carbonate, precipitated inside the cracks in the coal and removing the calcium sulfate resulting from such burning. Calcium carbonate may be precipitated inside the cracks, in accordance with the method discussed above, using water compositions of colloidal silica supersaturated calcium carbonate and coal can be burned in accordance with a variety of technologies, as discussed earlier. Depending on the technologies used for coal combustion, can be obtained from one or more of a variety of combustion products, such as ash, blast furnace ash, blast furnace slag, and the volatile material gas desulphurization. Such combustion products may find use in many applications, such as cement, concrete, ceramics, fillers for plastics, composites with metal matrix and carbon sinks. E.g. the measures ashes from coal combustion in accordance with the present embodiment can be used in the manufacture of cement. In particular, the sulfur contained in the coal, interacts with calcium carbonate, precipitated inside the cracks, obtaining calcium sulphate. As previously discussed, calcium sulfate, which is obtained, as a rule, is in the form of gypsum (CaSO4·2H2O)which remains in the ashes. This ash can be used as is, or one or more separation methods known in this field can be used to extract CaSO4·2H2O for use as a component of cement (such as Portland cement).

Another variant of implementation of the present invention is an aqueous composition suitable for the treatment of coal with high sulfur content, with the aim of reducing emissions of sulfur dioxide, when the treated coal is burned. The aqueous composition contains a supersaturated solution of calcium carbonate combined with the aqueous composition of colloidal silica, and optionally associated with calcium oxide. In particular, the aqueous composition may contain from about 2 wt./vol.% up to 40 wt./vol.% sodium silicate, or silicon dioxide, from about 15 wt./vol.% up to 40 wt./vol.% calcium carbonate, and from about 1.5 wt./vol.% to 4.0 wt./vol.% of calcium oxide. As it is used here, 1 the EU./vol.% substance refers to the concentration of a substance in the composition, equivalent to 1 mg of substance per 100 ml of composition.

Another variant of implementation of the present invention is a method for obtaining aqueous composition suitable for the treatment of coal with high sulfur content, with the aim of reducing emissions of sulfur dioxide, when the treated coal is burned, this method involves the dissolution of calcium carbonate in strongly alkaline aqueous compositions of colloidal silicon dioxide, under conditions sufficient to activate the calcium ions in the colloidal particles, obtained from oxide of silicon with the formation of charged colloidal particles. For ease of discussion, these two implementation will be discussed together.

Silicon oxide is also known as silicon dioxide (SiO2), and she is about sixty percent of the earth's crust, either in the free form (e.g., sand), or in combination with other oxides, in the form of silicates. About silica unknown to cause any toxic effects when consumed by humans in small quantities (as SiO2or as silicate), and it is regularly found in drinking water, in most public water systems across the United States. Alkaline composition suitable for use in this embodiment of the invention, prepared from the alkaline aqueous compositions call IGNOU oxide of silicon, which may be referred to as dispersion or colloidal suspension.

The aqueous composition is prepared by dissolving particles of silicon oxide in the strongly alkaline water, which is prepared by dissolving in water a strong base to obtain an aqueous solution which is alkaline (i.e. pH greater than 10, preferably at least 12, and more preferably at least 13,5). As a rule, a strong Foundation will be a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide, preferably the latter. The molar amount equal to at least 3 will be used for the preparation of the alkaline solution in such a quantity that will be used to maintain pH at the desired level. Because the solubility (its ability to form stable colloidal composition) of silicon oxide increases with increasing temperature, it is preferable that the alkaline solution was heated to a temperature exceeding the ambient temperature to the boiling point of the solution, and including it. Though can be used in temperatures exceeding the boiling point, it is generally not preferred because of the need in the high pressure container. Upon the dissolution of the silica in water is made alkaline with OSU sodium hydroxide, it is believed that formed the sodium silicate solution. The composition will vary depending on the different relationships between sodium and silicon oxide, for example density. The greater the ratio of Na2O to SiO2the more alkalinity and adhesion of mortar. Alternatively, the same result can be achieved by dissolving solid sodium silicate in water. Numerous aqueous colloidal composition of sodium silicate are available commercially, from about 20 to about 50 wt./vol.%. A well-known solution known as "egg preservative, which can be cooked using this method, and, according to the calculations, contains about 40 weight./vol.% Na2Si3O7(widely available dry form of sodium silicate). Standard commercially available sodium silicate contains 27 wt./vol.% sodium silicate.

Not wanting to be limited to any particular theory, it is assumed that the chemistry of dissolution can be approximately described by the following equations.

After preparation of the alkaline composition of the colloidal silica, to this mixture a carbonate of alkaline earth metal, preferably calcium carbonate, preferably in the form of finely ground powder. It is believed that the addition of calcium carbonate contributes to the formation of the camera is through the colloidal composition, calcium ions (Ca+2)included in the colloidal structure. In addition, it is also preferable to add the calcium oxide, which is later converted inside the cracks of coal in CaCO3at high pressure atmospheric CO2in the way discussed earlier. Adding a source of ions of Ca+2by calcium carbonate and calcium oxide) may cause polymerization of Si(OH)4that can be depicted as follows:

It is believed that this leads to the formation of colloidal particles, in which ions of Ca+2are isolated, for example, as shown in figure 1. Note that figure 1 is used, the base must be a potassium hydroxide, which provides the ions K+. Colloid formed in accordance with the present embodiments, as is, is more strongly related and more extensive than the well-known colloidal systems. In addition, it is believed that figure 2 is a view of a typical double layer of water associated with typical colloidal particle of silicon oxide, formed in accordance with the present method. As shown in figure 2, the colloidal particle of silicon oxide has a negative total charge and is surrounded by charged ions in the surrounding water. In the stern layer, nearest the eat to the solid surface of colloidal particles of silicon oxide, ions are charged for the most part positively and may include ions of Ca+2that are attracted to the negatively charged colloidal particle of silicon oxide. It should be noted that one or more ions of Ca+2can be enclosed in the internal space of the colloidal particles of silicon oxide.

During the preparation of aqueous compositions of the present invention, it is preferably treated to increase the electrostatic charge on the colloidal particles of silicon oxide. This is done using a generator, shown in figure 3 and 4. Additional details can be found in the application for U.S. patent No. 09/749243, Holcomb, registered on December 26, 2000, and published as U.S. patent 2001/0027219 4 October 2001, and in U.S. patent No. 5537363, Holcomb, issued July 16, 1996, the details of which are included here as a reference, in their entirety. Dimensions and volumes in these publications and are presented here for illustration only and are not limiting. The function generator includes a pump 1, which selects the aqueous composition 5, which is placed in the container 3, and sends the aqueous composition 5 through the passage 2, and then, through the pump 1. Pump 1 generates a speed which depends on the size of the pump and pipes. It can range from about 1 gallon in mine is (gallon/min) to about 100 Gal/min (for example, approximately 4 gallons per minute to about 10 Gal/min, in smaller systems) and a pressure of about 10 psi. The water composition 5, at the above pressure and velocity, flows through the passage 6 and flows into the passage 7, which is surrounded by at least one concentric passageway (for example, a passage 13). As shown in figure 2, the water composition 5 flows through the passage 7 and leaves it through the holes 8, entering the passage 13 (for example, pipe 1 inch). Then the water composition 5 flows in the opposite direction through the passage 13, and leaves it through the holes 9, and again changes the direction opposite to that flowing through the passage 14 (e.g., pipe 1.5 inches). The water composition 5 leaves the passage 14 through the holes 10, flows into the passage 15, enters the chamber 11, flows through the passage 12, and is returned back into the container 3 through the passage 4.

The countercurrent flow through the device at a sufficient rate and for a sufficient amount of time, will generate a preferred composition in accordance with the embodiments of the present invention, due to the effect of counter-current charging. This counter-current effect, as it is believed, generates a magnetic field gradients, which, in turn, creates an electrostatic charge on the colloidal particles of silicon oxide, moving against Atochem process in concentric passages of the generator. This electrostatic charge is believed to be associated with colloidal particles of silicon oxide are larger in size, which are more stable and can, in turn, provide an opportunity for the inclusion in the aqueous composition is more of calcium carbonate, for example, by isolation of large quantities of ions of Ca+2. Preferably, use one or more magnetic amplifier nodes, to enhance this effect, a counter-current charging, by generating multiple magnetic fields directed in opposite directions. Figure 4 illustrates the functioning and location of the magnetic amplifier nodes, which can be used together with the generator, is shown in figure 3. If you add a magnetic amplifier nodes figure 4 (nodes A, B and C), it is observed that the electrostatic charge is created on the colloidal particles of silicon oxide much faster. Although figure 4 shows three magnetic amplifier node, you can see that it can be used more or fewer nodes, depending on the particular application. Generally, it is desirable that the two adjacent magnetic amplifying host (for example, nodes A and B) were at a sufficient distance from each other, to reduce interaction between the magnetic the mi fields, generated by the corresponding nodes.

The upper part of figure 5 illustrates a top view in cross section of concentric passages depicted in figure 4. As can be seen in figure 5, the magnetic amplifier node (e.g. node a) contains a number of magnets (e.g., electromagnets). It depicts four magnet located in a plane and forming a vertex of the quadrangular shape (e.g. a rectangle or a square)in this plane. Poles of adjacent magnets have opposite orientation, as indicated by means of signs "+" and "-"shown in figure 5. As shown in the lower part of figure 5, this system of four magnets creates multiple magnetic field gradients along the z-axis (i.e. the component of the magnetic field along the axis coming out of the plane, depicted in the upper part of figure 5). Here is the measurement for the magnetic field along the z axis, along the line A-A', which is about one inch above the plane of the magnets. There may also be a magnetic field gradients along the x-axis and y-axis (i.e. the component of the magnetic field along lines A-A' and B-B'). These multiple gradients are responsible for a significant electrostatic charge, which can be formed on the colloidal particle of silicon oxide, when the generator continuously processes the aqueous composition. By treating the water to the position with the help of the generator, depicted in figure 4, it is possible to produce colloidal particles of silicon oxide having a size in the range from about 1 micron to about 200 microns, typically in the range of from about 1 micron to about 150 microns, or from about 1 μm to about 110 μm. Colloidal particles of silicon oxide can have Zeta potentials in the range from about -5 millivolts (mV), approximately, to more than -75 mV, and typically in the range from about -30 mV to about -50 and to -60 mV. As understood by the person skilled in the art, the Zeta potential is the electrostatic charge, demonstrating a colloidal particle and a Zeta potential of greater magnitude, as a rule, corresponds to a more stable colloid system (e.g., the repulsion between particles).

Another embodiment of the present invention is a device for processing coal with high sulfur content using an aqueous composition under pressure. The device includes a container, where a high pressure, suitable for holding coal, the first input to allow the flow of water composition in the container and its contact with the coal, the mechanism for removing water composition from the container, the first input to allow the flow of carbon dioxide into the container under pressure higher than atmospheric pressure, and is the source of carbon dioxide high pressure, connected with the first inlet, and an outlet for removal of coal from the container.

This embodiment of the present invention can be seen in the discussion of the sequence of operations shown in Fig.6. The coal is fed into a steam installation using trolleys 102 and poured on the coal tray 103 under the tower 100 control. Alternatively, coal can be processed in the coal yard, instead of the generator set. Then the coal is fed onto the tape 104 of the conveyor and transported to the coal crusher 108 and 109, through the passage 105. The rock is of poor quality and waste are transported to the dumps 111 and 112 of the breed, through the passages 106 and 107. Coal comes out of the crusher, after crushing to a particle size of 1-2 mm in diameter. The coal falls onto a conveyor 110, which resets it to the passage 114, and then into the passages 113 and 114a. The passage 114a moves the coal to the tray 115, which resets the coal through the gate high pressure in tank 16 high pressure. The gate of the high-pressure closed under the tray 115 and the outlet passage 18 with the tank 16 high pressure. When coal is introduced into the tank 16 through the tray 115, the screw 17 pushes the coal to the far side of the tank 16 when the tank 16 is tilted about 45°. The tank 16 is sealed, and the vacuum (from about 26 inches to 30 inches of water column) is applied for 20 minutes using a vacuum pump to which chose 23, and the tank 16 is lowered back to the neutral position. The water composition of the present invention, which can be synthesized in the structure 27, is pumped into the tank 24 for storing, through the passage 35, and then is pumped through the passage 34 through the passage 21 and is pumped into the tank 16 when the valve is open to vacuum. Aqueous composition containing colloidal particles of silicon oxide, ionized calcium carbonate, calcium oxide and water, and injected into the evacuated pores of the coal. After equilibration of the system, the remaining portion of the aqueous composition is removed, and the valves open, to allow for the occurrence of CO2from the tank 26 through the passage 36, through the controller 23, and then through the passage 21. The pressure of about 100-300 psi is maintained for at most one hour (e.g., 5-40 minutes), and released. The pressure of CO2increases the load of bicarbonate ions in the pores of the coal. The increasing availability of bicarbonate ions causes the crystallization of CaCO3in the pores of the coal, thereby causing cracks in it and making a greater number of pores of larger size available for the penetration of calcium carbonate and calcium oxide. At this point, the operation is preferably repeated one or two times in order to maximize the inclusion of calcium carbonate contained in the oxide of silicon in the coal. After processing the weave the resulting charcoal is then taken out through the passage 18, with the help of the screw 17, the tape 30, which transfers the processed coal in the Bunker inventory for the current boot" 31.

The processed coal is fed from the Hopper stock for the current boot" on the tape 32, the conveyor 33. The treated coal can be burned as fuel coal, mechanical furnace, at temperatures from about 2400°F approximately 2600°F, or can be finely chopped and burned in the furnace with the charge at temperatures of about 3200°F - 3700°F. As can be seen in Fig.7, the treated coal is transferred to a furnace where it is burned. Burning coal heats water, with the formation of steam, which drives turbines. The turbine, in turn, actuate the generators of electrical energy, which direct the energy along the transmission lines. Alternatively, as shown in Fig, the treated coal is delivered to the coal bunkers 210, on the conveyor 201 which communicates with the conveyor 33 figure 6. Coal is measured according to needs, by weights of 209, shredder 207, to obtain a powdered coal. This powdered coal is sent through line 205 to a mixture of carbon powder and air into the furnace 204, through a nozzle 203 for fuel injection. This powdered coal is blown into the furnace 204, where it is ignited in an intense, swirling flame that is burning about 3500° F. During combustion, calcium carbonate, calcium oxide, water and sulfur dioxide react in the presence of intense heat, with the formation of large quantities of gypsum (CaSO4·2H2O) and lime, which remains in the ash. The increase in the content of gypsum increases the value of ashes upon receipt of the cement, and it is removed for this purpose from the hopper 206 ash. Therefore, coal with high sulfur content can be burned with greatly reduced emissions, and improved quality of combustion products. It is believed that the resulting ash also has a higher quality of silicates, especially in the form of microspheres. These microsphere silicates have high insulating properties, which are useful, for example, insulating paints.

The following examples describe specific aspects of the present invention, for illustration and the invention is intended for professionals in this field. The examples should not be construed as limiting the present invention, as examples only give a specific technique that is useful for understanding and implementing the present invention.

Example I

This example describes a method for the preparation of aqueous compositions of the present invention, which is used to process coal before combustion. Five gallons of water is of good quality is placed in the container. Water circulates through the electret generator (see application for U.S. patent No. 09/749243 above), at a rate of 4.5 to 5 Gal/min and a pressure of 20 ft/inch2within one hour, and released. 5 liters of sodium silicate is placed in the generator, when he continues, at a rate of 4.5 to 5 Gal/min This silicate is at a concentration of 27 wt./vol.% 4.0 molar NaOH. After all the sodium silicate will be in the system, the generator continues to operate for one hour. Slowly add to the mixture 615 grams of calcium carbonate, in the form of a suspension, for more than 20 minutes. The generator runs for an additional hour under the same conditions. At this point, the pH is greater than 10.0. The solution continues to flow through the generator at a speed ranging from 4.5 to 5 Gal/min, when slowly add 500 grams of calcium oxide (CaO). The solution continues to flow through the generator for another one hour. At this point, the material is a grey and slightly muddy, very dense colloid.

Example II

This example describes a representative aqueous composition of the present invention, together with a method for its preparation. The reference to "generator" refers to the device described in application for U.S. patent No. 09/749243, Holcomb, registered on December 26, 2000, and published as U.S. patent US 2001/0027219 4 October 2001. G is nerator has a capacity of 150 gallons and a flow rate of about 90-100 gallons per minute (Gal/min). The final composition shows the concentration of sodium silicate to about 40,000 ppm or 4 weight./vol.%.

42 gallon water (pH 8,13) is added to the generator and provide circulation through the generator for 20 minutes. In the generator, add 8 gallons of sodium silicate (concentration of 27 wt./vol.%) and provide circulation within 45 minutes. This gives, in General, 50 gallons of sodium silicate solution, having a pH 12,20.

of 14.6 pounds of pellets of NaOH (sodium hydroxide) dissolved in 5 gallons of solution from the generator and the resulting solution is added back into the generator. In the generator add 2.5 gallons of water and provide circulation within 90 minutes, to obtain the composition having a pH of at 13.84.

Twenty gallons of solution is pumped from the tank of the generator in the container and dissolve in it for 51.3 per pound of calcium carbonate. The resulting solution was added slowly back to the generator, within a 20-minute period. Composition circulates within 20 minutes and shows pH 13,88. Again 20 gallons of solution removed from the generator and dissolve additional 51.3 per pound of calcium carbonate. The resulting composition measure in the generator within a 20-minute period (pH 13,91). Additional circulation for 20 minutes gives a composition with a pH 13,92.

Ten gallons of the resulting solution is extracted from the generator and add to a container of 5.5 pounds of calcium oxide, h what about the results in suspension, which is added back to the generator, within a 10-minute period of time. The resulting composition is circulated for 30 minutes (pH 13,98).

Twenty gallons of circulating composition is added in a barrel for mixing and slowly add 1.0 kg of ammonium chloride, with stirring. This song add back into the generator, within a 10-minute period, and maintain a circulation in the generator within 30 minutes (pH 13,93).

55 gallons of the resulting composition is placed in an appropriate container or containers for future use, for processing of coal, in the way discussed here. The consistency of the resulting composition is more viscous than water and similar in appearance to the viscosity of a thick milk shake.

Example III

This example gives details of the implementation of the method according to the present invention in the processing of coal.

Crushed coal is screened to a size suitable for small mechanical furnace (less approximately than 1/2 inch), and 100 pounds are weighed and placed in a barrel 50 gallons, a barrel cover and rotate around a horizontal axis for 10 minutes, stirring coal. The coal is removed portions 8 pounds, random, and placed alternately in two containers: (a) control, 50 pounds, and (b) for processing by 50 pounds.

Five pounds of calcium oxide) is t with a 50-fontovi sample (b) coal and put it in a tray for the sample from the high-pressure chamber, and the tray is placed in the high pressure chamber. Keeping the pressure door is closed and sealed for hermetic sealing. Pump vacuum (29 inches - 30 inches of water column) and support it within these limits within 45 minutes.

4-gallon sample of the composition prepared in example II, is drawn into the tray for the sample under vacuum, and the system provide the ability to balance, within 10 minutes. Vacuum treated by slow income CO2in the camera.

The excess liquid is removed from the coal, and the camera re-seal. The air is removed by vacuum, and apply pressure with the help of CO2up to 300 psi (within 100 psi to 300 psi). The hold pressure for 30 minutes, and the gas release. These stages are repeated for two additional cycles.

After the process is complete, the excess liquid is removed and the coal is stored, transported or combusted. When the coal is burned, sulphur dioxide, as can be seen, reduced by about 95%-100%. In conjunction with this reduction, there is also a reduction of about 40%-60%, emissions of NOX40%-80%, emissions of carbon monoxide, 40%-60%, hydrocarbon emissions, and 12%-16%, of carbon dioxide emissions. Though not fully understanding the reasons for this reduction, we can assume that the silica may play a role the IDA catalyst, contributing to a more complete combustion of the gases and the formation of solid products.

Each of the patent applications, patents, publications, and other published documents considered or mentioned in the present description, are included here by reference, in their entirety, to the same extent as if each individual patent, patent, publication, and another published document was specifically and individually indicated to be included as a reference.

Although the present invention is described with reference to its specific embodiments, a person skilled in the art should understand that can be done various modifications and equivalents can be used as a replacement, without deviating from the true spirit and scope of the present invention as defined by the claims. In addition to this can be done many modifications to adapt a particular situation, material, composition of material, method, stage or stages of the method, the objectives, spirit and scope of the present invention. All such modifications, as expected, are within the scope of the claims appended to this description. In particular, although the methods described herein are described with reference to a particular stage, carried out in a particular order, it will be clear that these stages can be combined is ENES, divided or arranged in a different order, with the receipt of equivalent ways, without deviating from the concepts of the present invention. Accordingly, if only here is not specifically stated otherwise, the order and grouping of stages is not a limitation of the present invention.

1. The method of processing coal with high sulfur content to reduce emissions of sulfur dioxide by burning coal, which

(a) put the coal in the environment of reduced pressure sufficient to crack formation in part of the coal by extracting atmospheric fluids trapped in coal

(b) lead containing cracks coal in contact with the aqueous composition of colloidal silica supersaturated calcium carbonate

(c) remove most of the water composition from contact with the coal and

(d) effect of high pressure on the coal treated by an aqueous composition, in an environment of carbon dioxide over a period of time sufficient for penetration of calcium carbonate in cracks in the coal obtained in stage (a).

2. The method according to claim 1, in which before fracturing in coal coal is crushed to a size corresponding to a maximum cross-sectional size less than about 5 cm

3. The method according to claim 1, in which the environment carbon dioxide has a pressure equal to at least 50 psi.

4. SPO is about according to claim 1, in which the coal is brought into contact with the aqueous composition by sprinkling coal water composition or by immersing the coal in the aqueous composition to form a suspension.

5. The method according to claim 1, wherein the aqueous composition further comprises an oxide of calcium.

6. The method according to claim 5, in which the aqueous composition has a pH of at least 13.5 and contains from about 2 to 40 weight./vol.% sodium silicate, from about 15 to 40 weight./vol.% calcium carbonate and from about 1.5 to 4.0 wt./vol.% of calcium oxide.

7. The method according to claim 1, in which the coal obtained from treatments in the stages (a), (b) and (C), contains calcium carbonate, precipitated inside it, enough to get a quantity sufficient to obtain a molar ratio of Ca:S at least 0.5 in.

8. The method according to claim 1, in which stage (a), (b), (C)and (d) is repeated twice.

9. The method according to claim 1, in which the coal is mixed with calcium oxide before cracking it.

10. Coal with high sulfur content, which is coal, rasterscan in vacuum, contains at least about 0.5 wt.% sulfur and optionally contains calcium carbonate deposited within fractures in the coal, in a quantity sufficient to obtain a molar ratio of Ca:S at least 0.5 in.

11. Coal with high sulfur content of claim 10, in which the sulfur content is from about 0.5 and about to 7.0 ve is.% sulfur, the calcium carbonate deposited within fractures in the coal, is sufficient to ensure a molar ratio of Ca:S approximately 1-4.

12. Coal with high sulfur content of claim 10, in which the coal further comprises a silicon oxide, is present at a level of at least 0.15 wt.%.

13. The method of obtaining energy from the combustion of coal with high sulfur content with simultaneous reduction of sulphur dioxide emissions from the combustion, in which the precipitated calcium carbonate inside the cracks in the corner, castresana in vacuum, and burn received coal with a high sulfur containing calcium carbonate at high temperatures.

14. The method according to item 13, which burn powdered coal at a temperature of from about 3200 to about 3700°F by blowing it into the furnace, mixing it with a source of oxygen and igniting the mixture.

15. The way to increase the amount of calcium sulfate resulting from the combustion of coal with high sulfur content, while reducing emissions of sulfur dioxide from such combustion, which burn coal with high sulfur content, rastreskivanii in vacuum, containing calcium carbonate, precipitated inside the cracks in the coal and extract the calcium sulfate resulting from such burning.

16. The method according to item 15, in which the coal contains, less is th least about 0.5 wt.% sulfur and optionally contains calcium carbonate deposited within fractures in the coal, sufficient to ensure a molar ratio of Ca:S at least 0.5 in.

17. The method according to item 15, in which the coal has a particle size less than 1 inch, and is combusted in a mechanical kiln at a temperature of from about 2400 to about 2600°F.

18. The method according to clause 15, which burn powdered coal at a temperature of from about 3200 to about 3700°F, by blowing it into the furnace, mixing it with a source of oxygen and igniting the mixture.

19. Aqueous composition for the treatment of coal with high sulfur content to reduce emissions of sulfur dioxide during the combustion of processed coal, which contains a supersaturated solution of calcium carbonate combined with the aqueous composition is colloidal silicon dioxide.

20. The aqueous composition according to claim 19, which has a pH of at least 12 and selectively further comprises an oxide of calcium.

21. The aqueous composition according to claim 19, which contains colloidal particles having a Zeta potential of -40 to -75 mV.

22. The aqueous composition according to claim 19, which contains from about 2 to 40 weight./vol.% sodium silicate, from about 15 to 40 weight./vol.% calcium carbonate and from about 1.5 to 4.0 wt./vol.% of calcium oxide.

23. Method of preparation of aqueous compositions for the treatment of coal with a high content of the minimum level to reduce the content of sulfur dioxide in the products of combustion of the treated coal, in which is dissolved the calcium carbonate in alkaline aqueous compositions of colloidal silicon dioxide under conditions sufficient to activate the calcium ions in the colloidal particles, obtained from oxide of silicon, for forming a supersaturated solution of calcium carbonate.

24. The method according to item 23, in which the resulting composition is passed, at least one magnetic field gradient.

25. A device for processing coal with high sulfur content using an aqueous composition under pressure, which contains

the high pressure container for storing coal,

the first input to ensure that the water composition in the container for contact with the coal,

the mechanism for removing water composition from the container,

the first input to ensure that carbon dioxide in the container under pressure higher than atmospheric pressure,

the source of carbon dioxide high pressure, is connected to the first input, and

the output for the removal of coal from the container.



 

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