RU2440179C2 - Method of reducing content of sulphur and/or mercury in flue gases (versions), sorbent composition, method of burning coal with reduced emission of harmful elements into environment (versions), coal ash obtained using said methods, and cement, pozzolan, concrete mixture and mortar thereof, concrete structure, method of producing cementing mixture, obtained based on or through said ash - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: components of a sorbent containing calcium, aluminium, silicon and halides are used when burning coal. Sorbents are added to the coal before ignition thereof and/or are added to the flame or gases coming from the flame, preferably at minimum temperatures, which enables complete formation of reflecting structures and enables to obtain various advantages of the described methods.

EFFECT: combined use of the compounds reduces emission of mercury and sulphur, reduces emission of elementary or oxidised mercury, increases efficiency of the coal combustion process due to slag removal, increases content of Hg, As, Pb and/or Cl in coal ash, reduces content of leached heavy metals in the ash, preferably lower than the detection limit, and also enables to obtain ash with good cementing properties.

71 cl, 2 tbl, 13 ex

Description

FIELD OF THE INVENTION

The invention is aimed at protecting the environment, in particular, at the creation of compositions and methods for reducing the mercury or sulfur content in flue gases emitted into the atmosphere when burning mercury-containing fuels such as coal. In particular, the invention is directed to the inclusion of various compositions containing halogens and other sorbents in plants operating on solid fuels during coal combustion.

State of the art

The world has significant coal reserves that can substantially satisfy the world's energy needs for the next two centuries. A significant part of the coal contains a large amount of sulfur; this coal requires additional processing to prevent the release of excess sulfur into the atmosphere during combustion. In the United States, low sulfur coals (in the form of low BTU coal) are mined in the Powder River basin of Wyoming and Montana, as well as in lignite deposits in the Northern and Central regions of North and South Dakota and Texas. But although these coals contain a small amount of sulfur, they contain a significant amount of elemental and oxidized mercury and / or heavy metals.

Unfortunately, when burning coal, mercury at least partially goes into volatile form. Thus, it does not remain in the ash, but passes into the composition of the flue gases. Unless special measures are taken, mercury from coal-fired fuel stations is released into the atmosphere. Currently, mercury is partially captured by treatment plants, such as wet-type treatment plants and SCR systems. However, most of the mercury is not captured and emitted through the exhaust pipes.

Atmospheric mercury emissions in the United States are approximately 50 tons per year. Coal fired plants such as thermal power plants account for a significant proportion of the emissions. It is well known that mercury poisons the environment and leads to diseases in humans and animals. To protect public health and the environment, the treatment industry continues to develop, test and implement systems to reduce the amount of mercury released into the atmosphere during plant operations. As for the combustion of carbon-containing substances, it would be desirable to develop a process that would capture mercury and other harmful compounds so that they would not enter the atmosphere during combustion.

In addition to wet-type treatment facilities and SCR control systems that partially remove mercury from the gases generated during coal combustion, other methods have been developed to control the content of this element. These include the use of activated carbon. The use of these systems is associated with high operating costs and capital costs. Moreover, the use of activated carbon based systems leads to carbon pollution of fly ash collected in exhaust air treatment systems such as dust collectors and electrostatic precipitators.

At the same time, it is expected that in the future there will only increase the need for cementing materials, such as Portland cement, used in infrastructure maintenance in developed countries and in the construction of roads, dams, bridges and other large structures in developing countries that are used to benefit them. residents.

When coal is burned, resulting in thermal energy, unburned matter and particles formed during combustion form ash with pozzolanic and / or cementing properties. Although the chemical composition of coal ash depends on the chemical composition of coal, usually ash contains a large amount of silicon and aluminum and a significantly lower amount of calcium.

The so-called fly ash generated during the combustion of crushed coal in a furnace or boiler is a powdery substance consisting of coal components that did not evaporate during combustion. Usually, the ash is carried away with the flue gas stream, it is usually collected from there by traditional devices, such as electrostatic precipitators, filtering devices, such as dust collectors, and / or mechanical devices, such as cyclones. When burning coal, a large amount of coal ash is formed, which must be disposed of. For example, under certain conditions, ash can be successfully used in the composition of cement as a partial replacement for Portland cement. Coal ash finds its application as a component in the production of fluid fillers, as well as stable basic and sub-basic mixtures. The amount of ash in these applications, especially when used to replace Portland cement, is limited by the severity of its cementing properties.

Even though reuse of the ash is preferable for economic reasons, its inclusion in cementitious mixtures is often unfavorable. In such cases, it must be buried or disposed of in another way as a waste product.

Methods and compositions that allow to obtain ash with highly cementing properties during the combustion of coal are extremely popular. They reduce the cost of processing waste from coal combustion, as well as the cost of cementing products for construction needs.

Disclosure of invention

The invention is directed to various sorbent compositions containing components that reduce the content of mercury and / or sulfur emitted into the atmosphere during such combustion. In accordance with various aspects, the use of sorbent compositions leads to the formation of fly ash during combustion, from which mercury and other heavy metals cannot enter the atmosphere in significant quantities (under acidic conditions).

In accordance with various aspects, the sorbent composition is added directly to the fuel before burning it; into the furnace or container during its burning; into flue gases at the exit of the combustion zone; various combinations are possible. Sorbent compositions include a source of calcium, aluminum and silicon, preferably in the form of alkaline powders. In accordance with various aspects, the use of sorbents containing calcium, silicon and aluminum in the form of alkaline powders reduces the amount of sulfur and / or mercury released into the atmosphere during coal combustion. In accordance with one aspect, alkaline powders reduce the amount of oxidized mercury, for example, in systems with a low flame temperature, for example, when the flame temperature is below 537.8 ° C.

According to a preferred aspect, the sorbent also includes a source of halogens, and / or a sorbent containing a source of halogens is added to the installation in which coal is burned separately. Among halogens, iodine and bromine are preferred. In accordance with various aspects, inorganic bromides are included in the composition of the sorbent. In accordance with various aspects, halogen-containing mercury sorption compositions, in particular bromine and / or iodine, are added to the fuel in powder or liquid form prior to ignition. Alternatively, halogen-containing (such as bromine or iodine) sorbent compositions are introduced into the fuel gases after the combustion chamber at a place where the temperature is higher than about 500 ° C (932 ° F), preferably higher than 1500 ° F (about 800 ° C), and / or into the furnace during combustion.

In accordance with preferred aspects, mercury emissions from coal combustion plants are reduced to such an extent that 90% or more of the mercury from the coal is captured before it enters the atmosphere. Most mercury is transferred from fly ash to a state in which it cannot enter the atmosphere; corrosion caused by sulfur dioxide is also reduced. In accordance with preferred aspects, a significant reduction in sulfur content is achieved.

The invention is directed to methods and compositions which, when applied to burning coal, make it possible to obtain ash with highly cementing properties. In accordance with various aspects, these properties allow the inclusion of ash in concrete, replacing up to 50% of Portland cement or more. In accordance with various aspects, the strength index of Portland cement based concrete containing up to 50% or more ash is greater than 75%, and preferably 100% or more. Thus, in accordance with some aspects, the ash of the present invention is used as the main cementitious material in Portland cement concrete, in stabilized substrates, in subbase mixtures, in flowable fillers (also called controlled low strength materials, or controlled low strength material or CLSM) and similar systems.

The fly ash generated during the combustion of coal with the indicated sorption components generally contains more calcium than is determined by the specifications for fly ash of class F or C, and the total content of silicon, aluminum and iron oxides, although significantly, is significantly lower than that indicated in the specifications for class F or C.

In accordance with various aspects, the invention is directed to a large number of cementitious products, such as Portland cement concrete, flowable filler, stabilized base and similar products, in which the conventionally used cement (Portland cement) is completely or partially replaced by the cementitious ash described in this application. In particular, in accordance with preferred aspects, a cement-based ash-based product of this application replaces 40% or more of the Portland cement commonly used in them.

In accordance with various aspects, the use of cementitious ash in building products to completely or partially replace Portland cement leads to a reduction in the carbon dioxide emission that occurs in the production of Portland cement. In addition to preventing the emission of carbon dioxide during the calcination of limestone used to produce Portland cement, and when burning fossil fuels to produce enough energy to produce Portland cement, the components of the sorbent can increase the efficiency of energy production during coal combustion, which further reduces greenhouse gas emissions from burning fossil fuels for energy.

Sorbents, their components and methods of use are described in the following patents and applications: U.S. Provisional Application No. 60 / 662,911, filed March 17, 2005; U.S. Provisional Application No. 60 / 742,154, filed December 2, 2005; U.S. Provisional Application No. 60 / 759,994, filed January 18, 2005; and U.S. Provisional Application No. 60 / 765,944, filed February 7, 2006, the contents of all these applications are included here by reference. Devices and methods for administering various compositions are described in these applications, as well as in U.S. Provisional Applications No. 60 / 759,943, filed January 18, 2006, and No. 60 / 760,424, filed January 19, 2006, their contents are also hereby incorporated by reference.

In accordance with various aspects, the invention is directed to compositions and methods for reducing the emission of mercury observed during the combustion of mercury-containing fuels such as coal. It is commercially significant to use the present invention to reduce emissions of sulfur and / or mercury from coal burning plants, which helps to protect the environment and bring the plant into operation in accordance with government requirements and commitments.

In accordance with various aspects, the invention prevents the release of mercury into the atmosphere from point sources such as coal-fired heating stations, leaving it in ash. Moreover, the methods prevent the release of mercury and other heavy metals into the environment, preventing their leakage (leaching) and from solid wastes, such as solid ash, formed during the combustion of mercury-containing coal. In both cases, mercury does not enter the water. Thus, preventing or reducing mercury emissions from plants such as coal-fired heating plants leads to many environmental benefits, including less air and water pollution, less hazardous waste, and therefore less soil pollution. For convenience, but not limited to, the benefits associated with the use of the present invention can be illustrated as preventing the contamination of air, water and soil with mercury and other heavy metals. The treatment of coal with various sorbent components is carried out before ignition, and / or they can be added to the flame and to the gases leaving the flame, preferably at a minimum temperature, to ensure the complete formation of reflective structures, which provide various advantages of the methods. Sorbent components include calcium, aluminum, silicon and halogens. In accordance with various aspects of the present invention, these components together:

- reduce emissions of mercury and sulfur;

- increase the efficiency of coal combustion, reducing the formation of scale on the tubes of the water heating station;

- increase the content of Hg, As, Pb and / or Cl in coal ash;

- reduce the content in the ash of heavy metals (such as Hg) in the composition of such compounds that are able to enter the environment, preferably, below the detection limit; as well as

- allow to obtain ash with highly cementing properties.

The term "calcium" means a compound or composition containing an appreciable amount of calcium. For example, many alkaline powders contain 20% calcium or more in terms of CaO. Examples are lime, limestone, calcium oxide, calcium hydroxide (slaked lime), Portland cement and other products obtained in industrial processes or accompanying them, as well as calcium aluminosilicates. The silicon or aluminum contents are expressed in SiO ₂ and Al ₂ O ₃ equivalents, although it is recognized that silicon and aluminum are often present in more complex chemical or molecular forms.

All percentages in this application are by weight unless otherwise stated. It should be noted that the chemical composition of the various compounds described herein is expressed in terms of simple oxides calculated on the basis of elemental analysis, usually carried out by X-ray fluorescence methods. Although various simple oxides may be present in the substance as more complex compounds (and are often present), oxide analysis is a useful method for expressing the concentrations of the compounds of interest in the respective compositions.

Although coal is generally referred to as fuel in the present application, it should be understood that the description of coal combustion is provided for illustration only and the invention is not limited to it. For example, another type of equipment for burning fuel with a potentially hazardous content of mercury and other heavy metals is waste cremation plants, such as domestic wastewater, hazardous wastewater from industrial plants, and sludge left in a sewage treatment plant. In addition, complex plants burn complex fuels that contain coal mixed with other fuels, such as natural or synthetic gas, as well as fuels from wastewater treatment.

A large number of effluents are burned at such plants, and often, for logistics reasons, these plants are built in densely populated areas. Domestic effluents may contain mercury from a wide variety of sources, such as used batteries and thermometers, as well as many consumer products containing measurable amounts of mercury. Hazardous industrial wastewater contains mercury from a wide variety of industrial or commercial sources. Precipitation remaining at the treatment plant may contain mercury from mercury-containing food and from other sources. Mercury gets into sewage and from natural sources. Waste incineration can produce gaseous mercury and mercury compounds that enter the air and settle on the ground in the vicinity of the plant, resulting in contamination of soil and groundwater, as well as degrading air quality. Thus, in accordance with various aspects of the present invention, wastewater containing mercury or other heavy metals is burned in the presence of various mercury sorbents added to the furnace, as described below. In accordance with preferred aspects, halogens, as well as preferably silicon and aluminum, are added in sufficient quantities to reduce mercury emissions into the atmosphere and put mercury in a state where it cannot enter the environment and remains in the ash.

The composition of coal, in addition to carbon, also includes the following basic elements: silicon, aluminum, calcium and slightly smaller amounts of iron. In addition, usually there are trace amounts of heavy metals such as arsenic, antimony, lead, chromium, cadmium, nickel, vanadium, molybdenum, manganese, copper and barium. These elements are part of the ash formed during the combustion of coal. Coal also contains significant amounts of sulfur. During combustion, sulfur also burns, forming volatile sulfur oxides, which leave the heating station in gaseous form. It is advisable to remove sulfur oxides emitted into the atmosphere during the combustion of coal, or to reduce their content.

Coal also contains mercury. Although it is present in a small concentration, it easily evaporates during combustion and flies into the atmosphere. Even in the low concentrations resulting from coal burning, mercury emissions are undesirable, since the element is toxic and accumulates in the tissues of the body. Due to the harmful effects of mercury on health and the environment, mercury emissions have recently been regulated in the United States and around the world. Regardless of the legal regulation, it is extremely desirable to reduce the amount of mercury that enters the environment from coal-fired heating stations.

In a typical heating station, coal comes in trolleys and is discharged to a receiving conveyor, which delivers it to a grinding device. Ground coal is discharged onto a feed conveyor and transported to storage. In the bottom of the storage, usually, grate; The coal passing through them is delivered by conveyor belts to an open storage area, sometimes called a hopper. Coal is delivered to the furnace from the hopper or from the crusher. To get the coal into the furnace in a finely ground state, it is loaded with conveyors or other methods into grinding equipment, such as a grinder, and then into a spray gun. In the storage system, coal is atomized and transferred to a collector by a stream of air or gas, from where it is delivered to the warehouse, and from it enters the furnace as necessary. In a semi-direct system, coal from the atomizer enters the cyclone-type collector, and directly from the cyclone to the furnace.

In the process, coal enters the furnace and burns in the presence of oxygen. For high btu fuels, the typical flame temperature is approximately from 2700 ° F (about 1480 ° C) to 3000 ° F (about 1640 ° C) or even higher, for example from 3300 ° F (about 1815 ° C) to 3600 ° F (about 1982 ° C).

In accordance with various aspects of the present invention, the sorbent compositions of the invention are added to raw coal, to ground coal, to a receiving or feeding conveyor, to a coal storage area, to a collector, to a warehouse, to a cyclone-type collector, to a spray gun before or during spraying and / or when transferred from the atomizer to the combustion chamber. In accordance with various aspects, it is convenient to add sorbents during processes in which the mixing of coal occurs, for example when it is milled or sprayed. In accordance with various aspects, sorbents are added to coal in a spray bottle.

Alternatively or in addition to the above, the components of the sorbent are added to the installation in which coal is burned, introducing them into the furnace during its combustion. In accordance with a preferred aspect, they are introduced into the coal for kindling or in close proximity to it, for example, where the temperature is approximately 1093 ° C (2000 ° F), or 1260 ° C (2300 ° F), or 1482 ° C (2700 ° F). In accordance with the design of the burners and the furnace operating characteristics, it is effective to introduce the sorbent directly onto the fuel, into the primary combustion air, above the flame, together with or over sharp blast, etc. In addition, depending on the design and operation of the furnace, sorbents are thrown from one or more faces of the furnace or from one or more corners of the furnace. The introduction of compositions and components of sorbents is particularly effective if the temperature at the time of entry is high enough and / or if the aerodynamics of the burners and furnace provide an adequate mixture of powdered sorbents with fuel and / or combustion products. Alternatively or in addition to this, sorbents are added to the convection stream at the exit of the flame and furnace. In accordance with various aspects, in order to find the optimal place of introduction or use of sorbents, it is necessary to build a model of the furnace and select parameters (speed and place of introduction, distance from the flame, distance from the walls, spraying mode of the powder, etc.) leading to the best mixing sorbent, coal and combustion products to achieve the desired results.

In plants where coal is burned, hot gaseous products of combustion and air are carried away from the flame with a convection stream (away from fuel). The convection path of the furnace consists of a large number of zones characterized by the temperature of the gases and products of combustion in each of them. In general, the temperature of the combustion gases decreases with distance from the fuel. In a furnace in which coal burns, for example, at a temperature of approximately 2700-3600 ° F (about 1480-1650 ° C), fly ash and gaseous products of combustion move in a convection stream into areas of constantly decreasing temperatures. For example, immediately after the fuel there is a zone with a temperature below 1482 ° C (2700 ° F). A little further is the area with a temperature of about 815.6 ° C (1500 ° F). Between these two points is a zone with a temperature ranging from approximately 815.6 ° C (1500 ° F) to 1482 ° C (2700 ° F). Then a zone with a temperature lower than 815.6 ° C (1500 ° F), etc. is reached. Moving along the convection stream, gases and fly ash pass through areas of ever lower temperatures until they reach dust collectors or electrostatic precipitators, whose temperature is usually around 148.9 ° C (300 ° F) and after which the gases escape through the exhaust pipe.

Gaseous products of combustion contain carbon dioxide and various harmful gases containing sulfur and mercury. Convection, together with high-temperature gases, also transfers a large amount of ash. To remove the ash before the emission of gas into the atmosphere, special systems for removing small particles are installed. A variety of systems of this kind are installed on the convection stream, such as electrostatic precipitators and dust collectors. In addition, they also place chemical gas scrubbers. If desired, various other tools for monitoring gas components such as sulfur and mercury can be included in the system.

Thus, in accordance with various aspects, the present invention is directed to the introduction of sorbents:

- directly in the furnace during combustion (introduction in the "burning" mode);

- directly to fuel, such as coal, before combustion (pre-combustion mode);

- directly into the flow of gaseous products of combustion, preferably in a temperature zone of more than 500 ° C, preferably more than 800 ° C (post-combustion mode).

Joint introduction in combustion, pre-combustion and post-combustion modes

Sorbents are introduced into the coal burning unit in any of the pre-combustion, combustion and post-combustion modes, or in any combination thereof. In this case, it is said that coal and any other fuel burns "in the presence" of various sorbents, sorbent compositions or sorbent components.

In accordance with a preferred aspect, the introduction of sorbents in the exhaust gas stream is carried out at a temperature of from about 1500 ° F (815.6 ° C) to 2700 ° F (1482 ° C). In accordance with some aspects and depending on the design of the furnace and the location of convection flows, the distinction between “furnace”, “fuel” and “convection flows” can be quite arbitrary. In a certain place, the gases generated during combustion exit a well-defined furnace or combustion chamber and enter another area, which can be clearly defined as a chimney or convection path for gases at the outlet of the furnace. However, ovens are often quite large and allow sorbents to be added “to the oven” at a considerable distance from fuel or gas. For example, some stoves have a port for the entry of gases over a fire. Such a port and similar openings are specially designed to deliver additional oxygen to the area above the fuel, which allows for more complete combustion and / or control the emission of gases such as nitrogen oxides. These ports can be located 20 feet or higher above the fuel injection site. In accordance with various aspects, the components or compositions of the sorbents are injected directly into the fuel area together with the incoming coal, into the area directly above the coal, or beneath additional ports above the flame area or into a higher area of the combustion chamber, for example, directly or just below the bow of the furnace. Each such place is characterized by the temperature and state of the turbulent flow involved in mixing the sorbents with fuel and / or combustion products (for example, fly ash). In accordance with such aspects of the invention, when the sorbents enter the furnace or into the gas stream leaving it, the temperature at the inlet should preferably be above 815.6 ° C (1500 ° F), preferably above 1093 ° C ( 2000 ° F), even more preferably if above 1260 ° C (2300 ° F), and most preferably if above 1482 ° C (2700 ° F).

In accordance with various aspects, sorbents are added as coal is burned together with other fuels at co-generation stations. Such stations can operate on a wide variety of fuels. In addition to bituminous and non-bituminous coal, they can use fuels obtained from wastewater, including, but not limited to, domestic wastewater, sludge after sludge (sludge), wastewater from livestock farms and after processing plants (such as not limited to waste from woodworking plants, rice husks, sawdust, wood chips and / or agricultural waste), plastic debris, damaged tires, etc. If these fuels contain mercury or sulfur, then the use of the sorbents described in the present invention facilitates or reduces the emission of these elements, which would otherwise enter the atmosphere during combustion. Depending on the quality of the fuel, the flame temperature at such co-generation stations ranges from approximately 537.8-648.9 ° C (1000-1200 ° F) (for low-quality fuels or those that contain large amounts of biomass or other poorly burning components) up to 1482-1982 ° С (2700-3600 ° F) or higher (for fuel with a high BTU index). In accordance with various aspects, the sorbents of the present invention reduce mercury emissions from plants in which combustion occurs at a relatively low temperature. It is believed that sorbents are particularly effective in removing oxidized mercury from fuel gases, and oxidized mercury compounds are mainly formed during low-temperature combustion.

Thus, in accordance with various aspects, the addition of the sorbent compositions of the present invention to fuel at co-generation stations using a combination of coal and various other fuels can significantly reduce mercury and / or sulfur emissions. In accordance with various aspects described herein, sorbent compositions that reduce the release of mercury and / or sulfur during coal combustion also have a beneficial effect on the quality of the ash generated during fuel combustion; they give it cementing properties. As a result, such ash can be used commercially for partial or complete replacement of Portland cement in various cement and concrete products.

Burning coal with the sorbent compositions described herein leads to the formation of ash, characterized, in accordance with various aspects, with an increased content of heavy metals, compared with ash formed during the combustion of coal without sorbents. However, the content in such ashes of heavy metals capable of leakage from it into the environment is lower than in the case of ash formed without sorbents. Thus, the ash becomes safer to work with and can be used commercially, for example, as a cementitious material.

To obtain a product from ash, first of all, carbon-containing fuel is burned with the release of thermal energy. Unburned substances and combustion products in the form of particulates form ash, part of which remains on the bottom of the furnace, but most of it is collected in the form of fly ash in the chimney with precipitators or filters, for example dust collectors installed at a fuel burning plant. The composition of bottom ash or fly ash depends on the chemical composition of the coal and on the amount and composition of the components of the sorbent added to the furnace during combustion.

In accordance with various aspects, mercury emissions from fuel stations are monitored. Emissions are monitored by elemental mercury, oxidized mercury, or both. Elemental mercury represents mercury atoms in oxidation state 0, and oxidized mercury corresponds to oxidation state +1 or +2. Depending on the mercury content in the flue gas before being discharged from the station, the amount of sorbent compositions added before, during or after combustion can be increased, decreased or kept unchanged. In general, it is advisable to remove as much mercury as possible. In accordance with typical aspects, 90% of the mercury and more of the total mercury in the coal is removed. This number indicates the percentage of mercury removed from the flue gas, so that this mercury will not enter the atmosphere through the chimney. Typically, the removal of mercury from flue gases leads to an increase in the mercury content in the ash. To reduce the amount of sorbent added to coal during its combustion, so as to reduce the total amount of ash generated in the furnace, it is desirable, in accordance with various aspects of the invention, to measure mercury emissions. This will allow you to adjust the feed rate of the sorbent composition so as to achieve the desired reduction in mercury content without introducing an excessive amount of substance into the system.

In accordance with various aspects of the combustion process of coal or other fuels with sorbent components, mercury and other heavy metals included in coal, such as arsenic, antimony, lead and others, settle in a dust collector or electrostatic precipitator and become part of the total ash content of the heating station ; alternatively or in addition, mercury or other heavy metals are included in bottom ash. As a result, mercury and other heavy metals do not leave the incinerator. In general, mercury and other heavy ash metals are resistant to leaching under acidic conditions, even though their content in the ash is higher than in the ash obtained by burning coal without the sorbent components described here. The advantage is that heavy metals do not leach out of the ash more than is established by law; in fact, a decrease in the content of heavy metals in the ash occurs in the amount of several ppm (parts per million, parts per million), although the ash obtained by burning with sorbents contains significantly more of them. Due to the strengthening of the cementing nature of ash, it becomes suitable for sale and use, for example, as a cementing material in the manufacture of Portland cement, as well as concrete and ready-mixes.

In accordance with preferred aspects, the leaching (leakage) of heavy metals during combustion is periodically or continuously monitored and analyzed by these data. The most common method is the TCLP procedure developed by the US Environmental Protection Agency. Based on the results of the analysis, the amount of the sorbent, in particular, the components of the sorbent, containing Si (SiO ₂ or equivalents) and / or Al (Al ₂ O ₃ or equivalents) is regulated, thus providing the desired leaching level.

In accordance with one aspect, the method aims to reduce the amount of mercury released into the atmosphere during coal combustion. The method includes applying to the coal combustion plant sorbent compositions containing halogen compounds. Halogen compounds are preferably bromine compounds; in accordance with a preferred aspect, the sorbent does not contain alkali metal compounds, which avoids corrosion of the boiler pipes and other components of the furnace. Coal is burned in a furnace to produce ash and combustion gases. The latter contain mercury, sulfur and other components. In order to achieve the desired reduction in the mercury content in the combustion gases and thereby limit their emission into the atmosphere, it is preferable to monitor the mercury content in these gases, for example, by measuring this content by analytical methods. In accordance with preferred aspects, the amount of sorbent composition introduced is controlled (i.e., increased, decreased, or sometimes left unchanged), depending on the mercury content in the flue gas. In accordance with a preferred aspect, the sorbent is introduced into the installation, mixing it with coal before ignition, and then the coal containing the sorbent is delivered to the furnace as fuel.

In accordance with another aspect, sorbent components are introduced into the coal combustion unit, including halogen compounds (preferably bromine or iodine, most preferably bromine) and at least one aluminosilicate. The components are administered individually or as an integral composition; they are added before ignition of the mixture, in the furnace during combustion, or in flue gases at the outlet of the furnace at a suitable temperature. In accordance with a preferred aspect, the components are mixed with coal before ignition, and then the sorbent-containing coal is delivered to the furnace as fuel. As before, it is preferable to monitor the mercury content in the flue gas and change the feed rate of the sorbent depending on the data on the mercury content. Halogen compounds reduce mercury emissions, and aluminosilicates make mercury in the ash non-leachable. In accordance with a related aspect, a method of reducing the leaching of mercury and / or other heavy metals in the ash generated by the combustion of coal or other fuels in a heating system or in an incinerator, includes introducing silicon or aluminum containing sorbents therein during combustion, measuring the leaching of mercury and other heavy metals from the resulting ash and controlling the amount of added silicon or aluminum depending on the data obtained. If leaching is stronger than necessary, then the feed rate of the sorbents can be increased to lower the leach rate to the desired values. In accordance with a preferred aspect, the sorbent also contains halogen compounds (e.g. bromine) that enhance the capture of mercury and its conversion to ash.

In accordance with one aspect, the invention is directed to a method for reducing the amount of oxidized mercury in flue gases generated by burning mercury-containing carbon-containing fuels such as coal, and thereby producing ashes with cementitious properties. The method includes burning fuel in the presence of an alkaline powder sorbent, where the alkaline powder sorbent contains calcium, silicon and aluminum. Alkaline powder is added to coal before ignition, introduced into the furnace during combustion, added to the flue gases at the outlet of the furnace (preferably at a temperature of 815.6 ° C (1500 ° F) or higher); any combinations are possible. The powders are alkaline, when mixed with water, the pH of the mixture should be above 7, preferably above 8, even more preferably above 9. Preferably, the sorbent contains from 0.01 to about 5% alkali by weight, for example, it can be alkali based on Na ₂ O and K ₂ O. In accordance with various aspects, the sorbent also contains iron and magnesium. In accordance with various aspects, the content of alumina in the sorbent is higher than in Portland cement, preferably above 5% or above 7%.

When burning fuel, the mercury content (oxidized, elemental, or both) is measured in flue gases at the outlet of the furnace. The measured level is compared with a predetermined value, and if it exceeds a predetermined value, the amount of powdered sorbent added to the combusted fuel is increased. Alternatively, if the measured level is less than a predetermined one, the feed rate of the sorbent can be reduced or left unchanged.

In accordance with another aspect, the powder composition is an alkaline sorbent composition containing an alkaline calcium component together with a large amount of silica and alumina. In accordance with a non-limiting aspect of the invention, the powder composition contains from 2 to 50% aluminosilicate and from 50 to 98% by weight of an alkaline powder containing calcium. According to a preferred aspect, the alkaline powder contains one or more components of lime, calcium oxide, Portland cement, calcined cement, calcined lime and beet lime, and the aluminosilicate is one or more components of calcium montmorillonite, sodium montmorillonite and kaolin. The powder composition is added to coal in an amount of about 0.1 to 10% by weight of the amount of coal introduced into the furnace together with it, or of the amount of coal consumed during continuous combustion. In accordance with a preferred aspect, this rate is from 1 to 8% by weight, from 2 to 8% by weight, from 4 to 8% by weight, from 4 to 6% by weight, or about 6% by weight. In accordance with preferred aspects, the powder composition is introduced into the fuel site or into the furnace during combustion and / or mixed with coal at ambient temperature prior to ignition. Preferably, the temperature at the injection site of the composition is at least 537.8 ° C (1000 ° F) or higher. For some low-quality fuels, this requires introduction into or near the fuel area.

In accordance with another aspect, the invention is directed to new sorbent compositions containing from 50 to 98% by weight of at least one component of Portland cement, calcined cement, calcined lime and beet lime, as well as from 2 to 50% by weight of aluminosilicate . In accordance with various aspects, the compositions also contain bromide compounds, for example bromide, such as calcium bromide.

The use of sorbents for coal combustion described above allows one to reduce emissions of harmful sulfur or mercury compounds and, at the same time, to obtain ash acceptable from the point of view of environmental safety (i.e., leaching of heavy metals is lower than the level required by law and lower than for ash obtained with burning coal without sorbent additives) and having cementing properties, so that such ash is a complete or partial (more than 40%, preferably more than 50%) replacement of Portland cement in cementitious mixtures and in processes of their application.

In accordance with another aspect, the method aims to control the combustion of fuels containing mercury and possibly sulfur, so as to reduce the amount of harmful components that enter the combustion gases and then into the environment. In accordance with a preferred aspect, the method includes introducing the sorbent into the fuel and burning the fuel with the sorbent to form gases and fly ash. The sorbent contains bromine, calcium, silica and alumina.

In accordance with another preferred aspect, a method of reducing the content of mercury and / or sulfur released into the environment by burning coal in heating stations includes introducing bromine, calcium, silica and alumina components into a coal burning plant and burning coal in the presence of components sorbent to produce combustion gases and fly ash. In this case, the amount of mercury in the combustion gases is measured and the amount of bromine-containing components added to the unit is controlled, depending on the required mercury content in the combustion gases.

In accordance with various aspects, the four components (calcium, silica, aluminum oxides and bromine) are added together or separately to the coal before ignition, to the furnace and / or to the combustion gases at a suitable temperature, as described in this application. Preferably, the bromine is present in an amount that effectively intercepts and transfers to ash at least 90% of the mercury of coal, and silica and alumina in an amount that allows the efficient production of fly ash with leaching of less than 0.2 ppm (200 ppb) no ratio to mercury, preferably less than 100 ppb Hg, less than 50 ppb, and most preferably less than 2 ppb with respect to mercury. A ppb level of 2 corresponds to the current lower limit of mercury leach detection for the TCLP test.

In accordance with a specific aspect, a double sorption system is used when calcium, silica and aluminum oxides are added as a powder sorbent, and bromine or other halogens as a part of a liquid sorbent. Liquid and powder sorbents are introduced into the coal burning unit, applying them to coal before ignition, into the furnace and into the furnace gases (at a suitable temperature, as described in this application), or in any combination. In accordance with a preferred aspect, the liquid sorbent is applied to coal before it is ignited, and the powdered sorbent is either applied to coal before it is ignited, or to the furnace during combustion. The contents of the liquid and powder sorbent, as well as preferred compositions are described in this application.

In accordance with preferred aspects, the method is directed to producing coal ash and / or fly ash containing mercury in a concentration corresponding to at least 90% of the mercury originally contained in the coal before burning it. In accordance with some aspects, the mercury content is higher than in known fly ash, due to the fact that most of the mercury is in the ash and not released into the atmosphere. Obtained during the process described fly ash contains up to 200 ppm of mercury or higher; in accordance with some aspects, the mercury content in fly ash exceeds 250 ppm. Since, as a rule, the ash volume increases with the use of sorbents (in accordance with typical aspects, the ash volume is usually doubled), the increased measured mercury content in the ash means a significant capture of mercury, which would otherwise enter the atmosphere. In general, the content of mercury and other heavy metals, such as lead, chromium, arsenic, and cadmium, in the resulting fly ash is much higher than in the ash formed during the combustion of coal without additional sorbents or their components.

In accordance with various aspects, the ash generated by burning coal in the presence of sorbent components contains calcium, silica, alumina and, preferably, halogens such as bromine. Components in one or more sorbent compositions are introduced into a coal combustion plant. In accordance with one non-limiting example, the sorbent containing calcium, silica and aluminum oxides is an alkaline powder composition comprising approximately 2-15% Al ₂ O ₃ by weight, 30-75% CaO by weight, 5-20% SiO ₂ by weight, 1-10% Fe ₂ O ₃ and 0.1-5% of the total alkali, such as sodium or potassium oxide. In accordance with a preferred aspect, the sorbents contain approximately 2-10% Al ₂ O ₃ , 40-70% CaO and about 5-15% SiO ₂ in addition to alkalis. In accordance with a preferred aspect, the sorbent powder composition described herein comprises one or more alkaline powders containing calcium and, in smaller amounts, one or more aluminosilicate materials. If required, a halogen-containing component is added to the alkaline powder, or it is administered separately as part of a liquid or powder composition. The inclusion of sorbents in a coal combustion plant leads to such an advantage as a decrease in the content of sulfur, mercury and other heavy metals.

In accordance with another aspect, the method of the present invention allows to obtain coal ash containing mercury in a concentration corresponding to the capture of at least 90% of the mercury that was originally part of the coal before burning the mixture. The process for producing coal ash involves burning coal in the presence of added calcium, silica and aluminum oxides, and preferably in the presence of halogens such as bromine. In accordance with a preferred aspect, ash is obtained by burning coal in the presence of sorbents or components of the sorbent described in this application. Preferably, the mercury in the ash is in an un-leachable state, so that the concentration of mercury in its extracts is less than 0.2 ppm when tested using the Toxicity Characteristic Leaching Procedure (TCLP), test Method 1311, described in Test Methods for Evaluating Solid Waste, Physical / Chemical Methods ", EPA Publication SW - 846 - Third Edition, incorporated by reference 40 CFR §260.11. Typically, fly ash generated after burning coal with the sorbents described here contains less leachable mercury than fly ash obtained from burning coal without sorbents, even though the total mercury content of ash obtained from coal with sorbents is 2 times or more content in ash obtained from coal without sorbents. By way of example, a typical ash after coal combustion of PRB contains approximately 100-125 ppm of mercury; in accordance with various aspects, the ash formed after burning PRB coal, with about 6% of the sorbents described herein by weight, contains about 200-250 ppm mercury or more.

In accordance with another aspect, the invention is directed to a hydraulic cementitious product containing Portland cement and from about 0.1% to 99% by weight (of the total weight of the cementitious product) of coal ash or fly ash described above.

In accordance with another aspect, the invention is directed to a pozzolanic product containing pozzolan and from about 0.1% to 99% by weight (of the total weight of the pozzolanic product) of coal ash or fly ash described above.

The invention is also directed to a cementitious mixture containing a hydraulic cementitious product.

The invention is also directed to finished concrete containing aggregate and hydraulic cementitious product.

In accordance with another aspect, the cementitious mixture comprises coal ash described herein as the only cementitious product; in these aspects, ash completely replaces traditional cements such as Portland cement. Cementing mixtures contain cement and possibly aggregates, fillers and / or other impurities. Cementing mixtures are usually mixed with water and used as concrete, mortar, mortar, flowing filler, stabilized base and other compositions.

The implementation of the invention

Thus, the methods are aimed at burning coal with sorbents to produce coal ash and energy to generate heat or electricity. The ash is then reduced and used as part of cementitious mixtures, including cements, lime mortars and grouts.

Used in various aspects of the present invention and the above-described sorbent compositions and their constituent components contain calcium, silica and / or aluminum oxides, preferably in the form of alkaline powders. In accordance with various aspects, the compositions also contain iron oxide, as well as basic powders based on sodium oxide (Na ₂ O) and potassium (K ₂ O). According to a non-limiting example, the powder sorbent contains approximately 2-10% Al ₂ O ₃ by weight, 40-70% CaO, 5-15% SiO ₂ , 2-9% Fe ₂ O ₃ and 0.1-5 % alkalis, such as sodium or potassium oxide. Components containing calcium, silica and aluminum oxides, as well as other elements, if any, are combined into a single composition or added individually or in any possible combination to a fuel combustion unit. In accordance with preferred aspects, the use of sorbents reduces the amount of sulfur and / or mercury released into the atmosphere. In accordance with various aspects, the use of sorbent compositions removes mercury, especially oxidized mercury.

In addition, the compositions reduce the content of sulfur released during combustion, due to their calcium compounds.

An advantage is that the sorbent compositions contain sufficiently high levels of silica and alumina. It is believed that the presence of alumina and / or silica leads to several advantages when using the sorbent. For example, it is believed that the presence of alumina and / or silica and / or the balance of silicon / aluminum and calcium, iron and other ingredients provides slight acidic leaching of mercury and / or other heavy metals, observed in the ash obtained by burning coal or other fuels containing mercury in the presence of sorbents.

In accordance with various aspects and observational data, it is believed that the use of sorbent compositions during the combustion of coal or other fuels leads to the formation of reflective linings on the walls of the furnace and in the pipes of the boiler. It is also believed that such a lining reflects heat in the furnace and raises the temperature of the boiler. In accordance with various aspects, it is also noted that the use of a sorbent reduces the formation of carbon deposits or slagging on boiler pipes. Thus, the use of the sorbent leads to greater purity of the furnaces and, more importantly, improves the heat transfer between the burning coal and water in the boiler pipes. As a result, in accordance with various aspects, the use of sorbents leads to a higher temperature of the water in the boiler pipes while burning the same amount of fuel. Alternatively, it is noted that the use of a sorbent can reduce the feed rate of, for example, coal, providing the same output or water temperature of the boiler at the outlet. To illustrate, the introduction of a 6% sorbent leads to the combustion of the coal / sorbent composition, during which the same energy is released as during the combustion of the composition of the same weight, consisting entirely of coal. In accordance with these aspects, it is seen that the use of a sorbent, which is usually then captured as part of fly ash and recycled, actually increases the efficiency of coal combustion with less fuel consumption. The advantage of this process is that fly ash, the volume of which, as a rule, increases with the use of the sorbent, is recycled and can be used for the manufacture of Portland cement and similar compositions, since it has improved cementing properties and low leachability of heavy metals.

As already mentioned, calcium, silica and / or alumina containing components are preferably used in the form of alkaline powders. Without limiting themselves to theoretical concepts, the inventors believe that the alkaline nature of the components of the sorbent, at least partially determines the required properties described here. For example, it is believed that the alkaline nature of the powders leads to a decrease in the formation of sulfur pits. It is believed that after neutralization in the presence of sorbents, a geopolymer ash is formed - it interacts with silicates and alumina from the sorbent with the formation of a ceramic-like matrix constituting a stabilized ash. Stabilized ash is characterized by extremely low leaching of mercury and other heavy metals. In accordance with some aspects, leaching of mercury is below detection limits.

Sources of calcium for the sorbent compositions of the present invention include, but are not limited to, calcium powders such as calcium carbonate, lime, dolomite, calcium oxide, calcium hydroxide, calcium phosphate and other calcium salts. The main share of calcium salts is made up of industrial products such as lime, limestone, slaked lime. All of them are suitable components of the sorbent compositions of the present invention.

Other sources of calcium include a variety of industrial products. Such products are commercially available, some of which are waste products or by-products of other industrial processes. In accordance with preferred aspects, the products also contribute silica, aluminosilicates, or both to the compositions of the invention. Non-limiting examples of industrial products containing silica and / or aluminum oxides (other than calcium) are Portland cement, kiln-burned cement and lime, beet lime, various types of scale (such as steel, stainless steel and blast furnace scale), dome stop filter, as well as dust from the top of the furnace.

These and possibly other materials are mixed to form alkaline powders or calcium containing mixtures of alkaline powders; these mixtures preferably also contain silica and aluminum oxides. Other alkaline powders containing calcium, silica, and aluminum oxides include pozzolanic materials, wood ash, ash after burning rice husks, fly ash class C and class F. In accordance with various aspects, these and similar materials are suitable components of the sorbent compositions, especially if the finished the composition contains them in the form of components in an amount of about 2-15% by weight of Al ₂ O ₃ , 30-75% by weight of CaO, 5-20% by weight of SiO ₂ , 1-10% Fe ₂ O ₃ and, approximately , 0.1-5% by weight of total alkali. Mixtures of materials are also used. Non-limiting examples include mixtures of Portland cement and lime, as well as mixtures containing calcined cement, such as cement dust and calcareous dust, calcined in a kiln.

Beetroot (sugar beet lime) lime is a solid waste formed in the production of sugar from sugar beets. It contains a large amount of calcium, as well as various impurities precipitated during the isolation of sugar using lime from their sugar beets. This commercial product is usually sold to landscape workers, farmers, and other categories of buyers as a soil supplement.

Burnt cement dust (burnt cement, cement kiln dust (CKD)) is usually understood to mean a by-product formed in a cement kiln or similar devices in the manufacture of Portland cement.

In general, CKD contains a combination of various particles generated at various locations in the furnace, in pre-treatment devices and / or in storage systems, including, for example, clinker dust, especially fully calcined dust, as well as “raw material” dust ( hydrogenated and dehydrated). The composition of CKD depends on the starting materials and fuels used, the conditions of production and processing, as well as the location of the collection points of CKD in the cement production process. CKD may include dust or particles collected from furnace effluent streams, clinker cooler effluent, precalcification effluent, air pollution control devices, and the like.

Although the composition of CKD depends on the type of furnace, usually CKD is characterized by at least some cementing and / or pozzolanic properties due to the presence of clinker dust and calcined substances. Typically, CKD compositions include silicon-containing materials such as silicates, including tricalcium silicate, dicalcium silicate; aluminum-containing materials such as aluminates, including tricalcium aluminate; and iron-containing materials such as ferrites, including tetracalcium aluminoferrite. In general, CKDs contain calcium oxide (CaO). Examples of CKD compositions include from about 10 to 60% calcium oxide, possibly from 25 to 50%, or even from 30 to 45% by weight. In accordance with some aspects, CKDs contain free lime (available for hydration water reaction) at a concentration of from about 1 to 10%, possibly from 1 to 5%, or, in some aspects, from 3 to 5%. Moreover, in accordance with some aspects, CKDs include, but are not limited to, alkali metal, alkaline earth metal, and sulfur compounds.

Other examples of alkaline powders containing calcium and, preferably, also containing silica and aluminum oxides, include various products associated and concomitant with the production of cement (in addition to the Portland cement and CKD described above). One example of such a product is a mixture of various types of cement. Such cement mixtures typically contain a mixture of Portland cement and / or clinker with scale (s) and / or pozzolan (pozzolan) (e.g. fly ash, silicate smoke, burnt shale). Pozzolans are usually silicate substances, which in themselves do not have cementing properties, but acquire the properties of hydraulic cement when interacting with free lime (free CaO) and water. Other sources are stone cement and / or hydraulic lime, including mixtures of Portland cement and / or its clinker with lime or limestone. You can also specify aluminum cement, which is a hydraulic cement prepared by roasting a mixture of limestone and bauxite (a natural heterogeneous material consisting of one or more minerals of aluminum hydroxides, as well as various mixtures of silica, iron oxides, titanium, aluminosilicates and other impurities present in small or trace amounts). Another example is pozzolanic cement, which is a mixture of cements containing a significant amount of pozzolan. Typically, pozzolanic cement contains calcium oxide but does not contain Portland cement. Common examples of commonly used pozzolans include natural pozzolans (such as volcanic ash or tuff, some diatoms, calcined clay and shales), as well as synthetic pozzolans (such as silicate smoke and fly ash).

Calcined lime dust (calcined lime, lime kiln dust (LKD)) is a product associated with lime production. LKD is dust or particles collected in a lime kiln or similar equipment. Lime produced in industry can be divided into high calcium and dolomite lime, the composition of LKD depends on the processes that form it. Lime is often obtained by calcining by heating calcites, such as calcium carbonate (CaCO ₃ ), to produce free (quicklime) lime CaO and carbon dioxide (CO ₂ ). High calcium limes contain a lot of calcium oxide and, as a rule, some impurities, including aluminum and iron compounds. High calcium lime is typically obtained from high purity calcium carbonate (purity approximately 95% or higher). A typical content of calcium oxide in LKD obtained from high calcium lime is not less than 75% by weight, possibly not less than 85% by weight and sometimes not less than 90% by weight. In some lime industries, dolomite (CaCO ₃ · MgCO ₃ ) is decomposed by heating, first producing oxides of calcium (CaO) and magnesium (MgO). This is called dolomite lime. If LKD is obtained by treating dolomite lime, then the content of calcium oxide may be at least 45% by weight, possibly at least 50% by weight, and sometimes at least 55% by weight. Although the composition of LKD depends on the type of lime being processed, it usually contains a large amount of quicklime. Typical amounts of quicklime in LKD are approximately 10 to 50%, possibly 20 to 40%, depending on the relative concentration of calcium oxide present in the resulting lime.

Dross, usually a product associated with the production and processing of metals. The term “scale” encompasses a large number of such concomitant compounds. Usually, there are many non-metallic products that accompany the production and processing of iron and / or steel. In general, scale is a mixture of various metal oxides, although it also contains sulfides and metal atoms in elemental form.

Examples of various kinds of scale that are useful for certain aspects of the present invention are glandular scales, such as those obtained in blast furnaces (also called dome furnaces), including, for example, air-cooled domain scale (ACBFS), expanded or foamy scale from a granular domain dross from a different type of domain (GBFS) and the like. Steel scales are obtained in the main oxygen furnaces for steel production or in furnaces operating on the principle of an electric arc. It is known that many types of scale have cementing and / or pozzolanic properties, however, the severity of these properties depends on their relative composition and the process of their production, which should be understood by an experienced specialist. Examples of scale include calcium-containing compounds, silicon-containing compounds, aluminum-containing compounds, magnesium-containing compounds, iron-containing compounds, manganese-containing compounds and / or sulfur-containing compounds. In accordance with some aspects, the scale also contains about 25 to 60% calcium oxide, possibly 30 to 50%, or even 30 to 45% by weight. An example of a suitable scale, generally having cementitious properties, is ground granulated blast furnace slag (GGBFS).

As mentioned, other suitable examples are blast furnace dust (from a dome) collected by air control devices installed in blast furnaces, such as dome filters. Another suitable by-product is ash after burning paper. A competent specialist understands that there are many related products obtained in production processes that are an acceptable source of calcium for alkaline powders of the sorbent compositions of the invention. Many of these well-known related products also contain silica or aluminum oxides. Some of them, such as calcined lime, contain a lot of CaO and relatively little silica and aluminum oxides. Combinations of these and other related products are also suitable for use as alkaline powders of certain aspects of the present invention.

In accordance with various aspects, the desired level of silica and / or alumina is superior to that obtained by the addition of materials such as Portland cement, calcined cement or lime, and beet lime. To provide a preferred level of silicon or aluminum, it is possible to add substances such as aluminosilicates, for example, without limitation, clays (for example, montmorillonite, kaolinite and the like). In accordance with various aspects, the additional aluminosilicates comprise at least 2%, and preferably at least 5% by weight of the total number of sorbent components introduced into the coal combustion plant. In general, from a technical point of view, there is no upper limit, if only an adequate amount of calcium is added. However, in terms of cost, it is usually desirable to limit the amount of expensive aluminosilicates. Thus, the components of the sorbent preferably contain from about 2 to 50%, preferably from 2 to 20% and, most preferably, from 2 to 10% aluminosilicates by weight (the above clays are examples of aluminosilicates). A non-limiting example of a sorbent is a product containing approximately 93% of a mixture of CKD and LKD by weight (e.g., a 50:50 mixture) and about 7% aluminosilicate clay.

In accordance with various aspects, alkaline powder sorbent compositions comprise one or more calcium-containing powders, such as Portland cement, calcined cement or lime, various scale, beet lime, and aluminosilicate clay, for example, but not limited to, montmorillonite or kaolinite. The sorbent composition preferably contains SiO ₂ and Al ₂ O ₃ forming a reflective mixture with calcium sulfate, which is formed during the combustion of sulfur-containing types of coal in the presence of a CaO sorbent component with calcium sulfate capture by a control system for the content of particles in furnace gases; or forming a reflective mixture with mercury and other heavy metals, such that the latter do not leach out of the ash under acidic conditions. In accordance with preferred aspects, the calcium-containing sorbent powder contains, by weight, at least 2% silica and 2% alumina, preferably at least 5% silica and 5% alumina. Preferably, the content of aluminum oxides is higher than in Portland cement, that is, higher than about 5% by weight, preferably higher than 6% by weight, based on Al ₂ O ₃ .

In accordance with various aspects, the components of the sorbents of the alkaline powder sorbent composition, possibly together with the added compound or halogen compounds (such as bromine) intercept chloride, as well as mercury, lead, arsenic and other heavy metals, holding them in the ash make them non-leachable in acidic conditions and increase the cementing properties of the resulting ash. As a result, the emission of harmful elements decreases, decreases or ceases, and valuable cementitious material is formed as a concomitant of the combustion product.

Suitable aluminosilicates include a large number of inorganic substances and minerals. For example, a large number of minerals, natural and synthetic substances contain silicon and aluminum in an oxidizing environment, as well as, possibly, other cations, such as, but not limited to, Na, K, Be, Mg, Ca, Zr, V, Zn, Fe , Mn, and / or other anions, such as hydroxide, sulfate, chloride, carbonate, and possibly hydration water. Such natural and synthetic substances are referred to herein as aluminosilicates; for example, you can, without limitation, call the above clay.

In aluminosilicates, silicon usually forms tetrahedra, and aluminum forms tetrahedra, octahedra, or a combination thereof. Chains or networks of aluminosilicates in such substances are formed by the socialization of 1, 2 or 3 oxygen atoms between the tetrahedra or octahedra of silicon and aluminum. For such minerals, there are many names, for example silica, alumina, aluminosilicates, geopolymers, silicates and aluminates. In any case, compounds containing aluminum and / or silicon emit silicon and aluminum oxides upon exposure to high combustion temperatures in the presence of oxygen.

In accordance with one aspect, aluminosilicates include SiO ₂ · Al ₂ O ₃ polymorphs. For example, a silyminate contains a silicon octahedron and aluminum uniformly distributed between tetrahedral and octahedral structures. Kyanite is based on the structures of a silicon tetrahedron and an aluminum octahedron. Another polymorph of SiO ₂ · Al ₂ O ₃ is andalysite.

In accordance with other aspects, chain aluminosilicates contribute to the composition of the invention, they supply there silicon (in the form of silicon oxides) and / or aluminum (in the form of aluminum oxides). Chain silicates include, but are not limited to, pyroxene and pyroxenoid silicates consisting of endless chains of SiO ₄ tetrahedra linked by common oxygen atoms.

Other suitable aluminosilicates include laminates, such as, without limitation, mica, clay, chrysolites (such as asbestos), talc, soapstone, pyrophyllite and kaolinite. Such substances are characterized by the presence of layered structures in which the octahedra and tetrahedra of silicon and aluminum are interconnected via two common oxygen atoms. Laminated aluminosilicates include clays such as chlorite, glauconite, illite, polygorxite, pyrophyllite, saukonite, vermiculite, kaolinite, calcium and sodium montmorillonite and bentonite. You can also specify mica and talc.

Suitable aluminosilicates include synthetic and natural zeolites, such as, but not limited to, analcime, sodalite, habazite, natrolite, phillipsite and mordenite. Other zeolites include hjulandite, brosterite, epistilbit, steelbit, lagavaralite, laumontite, ferrierite, Paulingite, and clionptiolite. Zeolites are minerals or synthetic substances characterized by the presence of an aluminosilicate tetrahedral structure, large cations that can undergo ion exchange (such as Na, K, Ca, Ba and Sr), and weakly retained water molecules.

In accordance with other aspects, framework, or 3D, silicates, aluminates and aluminosilicates are used. Frame aluminosilicates are characterized by the presence of a structure in which SiO ₄ , AlO ₄ tetrahedra and / or AlO ₆ octahedra are connected in three directions. Non-limiting examples of framework silicates containing silicon and aluminum include feldspars such as albite, anorthite, andesine, bitovnit, labradorite, microcline, sanidin and orthoclas.

In accordance with one aspect, the sorbent powder compositions contain a large amount of calcium, preferably more than 20% by weight, calculated as calcium oxide, and also have a higher silica and alumina content than commercial products such as Portland cement. In accordance with preferred aspects, the sorbent composition contains more than 5% alumina by weight, preferably more than 6%, even more preferably more than 7% and, most preferably, more than 8%. Coal or other fuels are treated with sorbent compositions in such quantities as to effectively control the amount of sulfur and / or mercury released into the atmosphere during combustion. In accordance with various aspects, the total content of the components of the sorbent ranges from 0.1 to 20% by weight relative to the weight of the processed coal or relative to the coal consumed during combustion, the sorbent being a powder sorbent containing calcium, silica and alumina. If the components of the sorbent are combined into one composition, then the content of the component corresponds to the content of the sorbent. Thus, it is possible to create a single sorbent composition and measure it when determining additives in a coal combustion plant. In general, it is desirable to use a minimum amount of sorbent so as not to overload the installation with an excessive amount of ash, however, so that this amount is sufficient for the desired effect on the emission of mercury and / or sulfur. Thus, in accordance with preferred aspects, the sorbent content ranges from about 1 to 10% by weight, preferably from 1-2% by weight to about 10% by weight. For many types of coal, 6% powder sorbent by weight is sufficient.

Powder sorbents containing calcium, silica and alumina, as described in this application, in the General case, effectively reduce the amount of sulfur in the gases formed during the combustion of coal. To reduce sulfur emissions, it is preferable to add at least 1: 1 calcium relative to the number of moles of sulfur in the combustible fuel (such as coal) in the composition. If it is desirable to avoid the formation of excess ash, then the amount of calcium can be limited by a molar ratio, for example, 3: 1 again relative to the amount of sulfur in the coal.

In accordance with some aspects, the amount of mercury in the discharge decreases, decreases, or mercury is eliminated altogether when using such sorbents even without the introduction of additional halogen. It is believed that sorbents effectively remove oxidized mercury in plants where the flame temperature is not higher than 537.8 ° C (1000 ° F). However, in many aspects, including when the flame temperature is well above 537.8 ° C (1000 ° F), it is preferable to treat the coal with sorbent compositions containing halogen compounds. The inclusion of halogen compounds in an alkaline powder sorbent reduces the amount of unoxidized mercury in the exhaust gases.

Sorbent compositions with halogen compounds contain one or more inorganic halogen compounds. Halogens include chlorine, bromine and iodine. Preferred halogens are bromine and iodine. Halogen compounds are sources of halogens, especially bromine and iodine. In the case of bromine, halogen sources include various inorganic bromine salts, including bromides, bromates and hypobromites. In accordance with various aspects, organic bromine compounds are less preferred due to their cost or availability. However, the scope of the invention includes organic sources of bromine containing a sufficiently large amount of this element. Non-limiting examples of organic bromine compounds include methylene bromide, ethyl bromide, bromoform and carbon tetrabromide. Non-limiting inorganic sources of iodine include hypoiodites, iodates, and iodides, with iodides being preferred. Organic iodine compounds may also be used.

If an inorganic compound is used as a halogen source, it is preferably a bromine or iodine salt of an alkaline earth element. Examples of alkaline earth elements include beryllium, magnesium and calcium. Among the halogen compounds, alkaline earth metal bromides and iodides, such as calcium, are particularly preferred. Compounds of bromine and iodine and alkali metals, such as bromides and iodides of alkali metals, effectively reduce mercury emissions. However, in accordance with some aspects, they are less preferred because they can cause corrosion of the boiler tubes and other steel surfaces, and also contribute to the destruction of the tubes and / or refractory bricks. In accordance with some aspects, in order to prevent destruction of the furnace, it is desirable to avoid potassium halogen compounds.

In accordance with various aspects, it has been found that the use of alkaline earth metal salts, such as calcium, avoids the problems associated with the use of sodium and / or potassium. Thus, in accordance with various aspects, the sorbents added to the coal combustion plant do not actually contain bromine or iodine and alkali metal compounds, or, more specifically, do not actually contain sodium or potassium-containing bromine or iodine compounds.

In accordance with various aspects, halogen-containing sorbent compositions are liquid or solid compositions. In accordance with various aspects, halogen-containing compositions are mixed with coal before ignition, added to the furnace during combustion, and / or introduced into the gas stream at the outlet of the furnace. If the halogen composition is in solid form, it may also contain calcium, silica and alumina described herein as a powder sorbent. Alternatively, the solid halogen composition is mixed with coal and / or otherwise introduced into the combustion unit separately from the sorbent composition containing calcium, silica and alumina. If halogen compounds are administered in liquid form, they are usually administered separately from other parts of the composition.

In accordance with various aspects, a liquid mercury sorbent is a solution containing from 5 to 60% by weight of a soluble salt of bromine or iodine. Non-limiting examples of preferred bromine or iodine salts include bromide and calcium iodide. In accordance with various aspects, liquid sorbents contain 5-60% calcium bromide and / or calcium iodide by weight. In accordance with various aspects, when adding the composition to coal before ignition, it is preferable to introduce mercury sorbents containing as high a concentration of bromine or iodine as possible to increase efficiency. In accordance with a non-limiting aspect, the liquid sorbent contains at least 50% by weight of the halogen compound (e.g., calcium bromide or calcium iodide).

In accordance with various aspects, halogen compounds containing sorbent compositions further comprise nitrate, nitrite compounds or a combination of nitrate and nitrite compounds. Preferred compounds of nitrates and nitrites include compounds of magnesium and calcium, in particular calcium.

To further illustrate, one aspect of the present invention includes introducing a liquid mercury sorbent directly into raw or ground coal before burning it. For example, a mercury sorbent can be added to coal on a fuel feed tape. The amount of liquid mercury sorbent ranges from 0.01 to 5%. In accordance with various aspects, the amount of sorbent is less than 5%, less than 4%, less than 3%, or less than 2%, where all percentages are expressed relative to the amount of coal processed or burned. You can add more sorbent, but it is wasted, since a larger amount does not provide additional benefits. A preferred sorbent content is from about 0.025 to 2.5% by weight relative to the content of raw coal. If a solid salt of bromine or iodine is added in the same way as in the case of a liquid sorbent, then, of course, it requires less, taking into account the proportion of the sorbent in the liquid system. As an illustrative aspect, bromine or iodine compounds are administered in a low concentration, for example, from 0.01 to 1% by weight of the fuel. In the case of using a 50% solution, in order to achieve the same content of the introduced components, it is necessary to add already 0.02% -2% of the sorbent. For example, in accordance with a preferred aspect, the coal is treated with a liquid sorbent in an amount of 0.02-1%, preferably 0.02-0.5%, based on the assumption that the concentration of calcium bromide is 50% by weight of the sorbent. According to a typical aspect, approximately 1%, 0.5% or 0.25% of a liquid sorbent containing 50% calcium bromide is mixed with coal before ignition, the percentage is determined based on the weight of the coal. In accordance with a preferred aspect, a small concentration of sorbent (for example, 0.01-0.1%) is added first and then gradually increased to achieve the desired (low) level of mercury emission based on monitoring data. The treatment scheme for halogen compounds remains the same if these compounds are administered alone or as part of a multicomponent composition, where the other components are calcium, silica, aluminum and iron oxides, etc.

In the process of use, the liquid sorbent is sprayed, sprayed or otherwise applied to coal or introduced into the combustion plant. In accordance with various aspects, additives are added to coal or other fuel at ambient temperature before the fuel / sorbent composition is delivered to the furnace. For example, the sorbent is mixed with powdered charcoal before entering the latter into the furnace. Alternatively or in addition, the liquid sorbent is introduced into the furnace during combustion and / or into the flue gases at the outlet of the furnace. The introduction of halogen-containing sorbing mercury compositions is often accompanied by a drop in the content of mercury in flue gases occurring within one or several minutes; in accordance with various aspects, this reduction in mercury occurs regardless of the reduction caused by the use of alkaline powder sorbents based on calcium, silica and alumina.

In accordance with another aspect, the halogen-containing component (for illustration, it may be a solution of calcium bromide) is introduced directly into the furnace during combustion. In accordance with another aspect, the invention is directed to the introduction of a solution of calcium bromide, for example, described above, in the gas stream at the outlet of the furnace in an area characterized by a temperature of from 1482 ° C (2700 ° F) to 815.6 ° C (1500 ° F), preferably from 1204 ° C (2200 ° F) to 815.6 ° C (1500 ° F). In accordance with various aspects, bromine compounds (eg, calcium bromide) are introduced into the furnace during combustion, as well as in pre- and post-combustion in any proportions.

In accordance with one aspect, various components of the sorbent are mixed with coal prior to ignition. Preferably, the coal is pulverized, and optionally pulverized or pulverized by conventional methods. In accordance with a non-limiting example, coal is atomized so that 75% of the particles by weight can pass through a sieve with an opening 200 (the diameter of the opening 200 in the filter is 75 μm). In accordance with various aspects, the components of the sorbent are mixed with coal in solid form or in a combination of solid and liquid formulations. In general, solid sorbent compositions are used in the form of powders. If the sorbent is introduced in the form of a liquid (for example, in the form of a solution of one or more bromine salts in water), then, in accordance with one aspect, the coal remains crude until it enters the furnace. In accordance with various aspects, the sorbent composition is fed onto the coal continuously by spraying or mixing them with coal while the latter is on a conveyor, screw extruder or other feeding device. In addition or alternatively, the sorbent composition can be mixed with coal separately in the furnace for burning it or at the place of its production. In accordance with a preferred aspect, the sorbent composition is mixed with coal in the form of a liquid or powder when it enters the combustion chamber. For example, in accordance with a preferred commercial aspect, the sorbent is introduced into the atomizer, which grinds the coal before it is fed into the furnace. If required, the rate of administration of the sorbent composition is varied to achieve the desired mercury emission level. In accordance with one aspect, the mercury content of the combustion gases is monitored, and the sorbent feed rate is increased or decreased to maintain the desired emission level.

In accordance with various aspects, the mercury and / or sulfur content entering the atmosphere from a fuel station is monitored using conventional analytical equipment using industry standard detection methods. In accordance with one aspect, monitoring is carried out periodically, automatically or manually. In accordance with a non-limiting example, monitoring is carried out once an hour, this complies with the requirements of the law. For example, the Ontario hydro method (Ontario Hydro method) is used. In accordance with this well-known method, gases are collected at a predetermined time, for example, once per hour. Mercury settles from the collected gases, after which the elemental or oxidized mercury content is quantified by a suitable method, for example, atomic absorption. Depending on technical or commercial feasibility, monitoring can be carried out more often or less often than once per hour. Commercial systems for continuous monitoring of mercury content allow you to measure this parameter at any given frequency, for example, every 3-7 minutes. In accordance with various aspects, based on the mercury content monitoring data, the sorbent feed rate of this element can be changed. Depending on the results of monitoring, the feed rate of the sorbent is changed - increased or decreased - and can be left unchanged. For example, if, according to monitoring data, the mercury content is higher than required, then the sorbent feed rate is increased until the mercury content drops to the required level. If the mercury content remains at the required level, the feed rate of the sorbent can be left unchanged. Alternatively, the feed rate of the sorbent can be reduced until, according to monitoring data, it appears that it needs to be increased in order to prevent large emissions. In this way, it is possible to reduce mercury emissions and to avoid excessive consumption of the sorbent (and a corresponding increase in the amount of ash).

Monitoring of mercury in convection flows is carried out in suitable places. In accordance with various aspects, the release of mercury into the atmosphere is recorded on the clean side of the particulate control system. Mercury monitoring can also be carried out in the upward convection flow of the particle control system. According to experiments, in the absence of mercury sorbents, 20 to 30% of this element remains in the ash. In accordance with preferred aspects, the administration of mercury sorbents described herein increases this number to 90% or more. Emission of mercury to the atmosphere is correspondingly reduced.

In accordance with various aspects, the components of the sorbent or composition of the present invention are introduced more or less evenly, mixing with coal before ignition, adding to the furnace during combustion or into convection flows in the temperature range from 815.6 ° C (1500 ° F) to 1482 ° C (2700 ° F). In accordance with various aspects, automatic feedback is established between mercury monitoring devices and sorbent feed devices. This provides continuous monitoring of mercury content and regulation of the sorbent feed rate to control the process.

In accordance with preferred aspects, the mercury and sulfur contents are monitored by industry standard methods, such as those published by the American Society for Testing and Materials (ASTM), or by international standard methods published by the International Standards Organization Standards Organization (ISO)). The instrument containing the analytical instrument is preferably installed in the convection path after the injection site of the mercury and sulfur sorbents. In accordance with a preferred aspect, the mercury monitor is placed on the clean side of the particle control system. Alternatively or in addition, flue gases are analyzed at suitable locations on the convection path without the need for a monitoring tool or instrument. In accordance with various aspects, the measured mercury or sulfur content can provide feedback to pumps, coils, nebulizers, and other devices that activate or control the feed rate of the sorbent composition to the coal combustion plant. Alternatively or in addition, the human operator can also change the sorbent feed rate based on the determined sulfur and / or mercury content.

In accordance with various aspects, the ash obtained by burning coal with the sorbents described herein has cementitious properties in the sense that after mixing with water it solidifies and becomes solid. Due to the calcium present in it, ash has a tendency to self-trace. Alone or mixed with Portland cement, it can be used as hydraulic cement, suitable for inclusion in cementitious mixtures, such as mortar or concrete. The concrete mixture of the present invention can be used for the manufacture of concrete structures by hydrating it.

The cementing nature of the ash obtained by the method described above can be demonstrated, for example, by the strength index of the ash or, more precisely, containing the ash of the cementitious mixture. As described in ASTM C311-05, the strength index is measured by comparing the curing behavior of concrete made from 100% Portland cement and test concrete, in which 20% of Portland cement is replaced with an equal amount of tested cement. In a standard test, strength is compared after 7 and 28 days. A test is considered “passed” if the strength of the test concrete is at least 75% of the strength of Portland cement concrete. In accordance with various aspects, the ash of the present invention exhibits a strength of 100% to 150% in accordance with the ASTM test, which means very convincing "passing the test." Similar results are observed when performing tests on mixtures with other ratios of the amount of Portland cement to ash, and not only 80:20. In accordance with various aspects, a strength index of 100 to 150% is observed when using mixtures of a composition of 85:15 to 50:50, where the first digit corresponds to the proportion of Portland cement, and the second to the proportion of ash prepared in accordance with the present invention. In accordance with specific aspects, the strength of a single cement test cementitious mixture (i.e., ash represents 100% of the cement mixture) is more than 50% of the strength of a Portland cement mixture, preferably more than 75%, more preferably more than 100%, for example 100- 150% These results demonstrate the extremely strong cementitious nature of the ash obtained by burning coal or other fuels in the presence of the sorbent compositions described herein.

Since the ash obtained by burning coal according to the methods of the present invention contains mercury in a form that cannot be leached, this ash can be sold commercially. Non-limiting examples of the use of fly ash or bottom ash generated as waste include the production of cement such as Portland cement. In accordance with various aspects, cement contains from 0.1 to 99% by weight of coal ash generated by combustion of the compositions of the present invention. In accordance with one aspect, the fact that the mercury and other heavy metals included in the coal ash of the present invention does not leach out makes it suitable for all industrial applications that conventional coal ash finds.

Coal ash according to the present invention, especially ash collected by a particle control system (dust collectors, electrostatic precipitators, etc.), is used in Portland cement concrete (PCC) as a partial or complete replacement for Portland cement. In accordance with various aspects, ash is used as a mineral additive or as a component of mixed cement. As an additive, ash can be used to completely or partially replace Portland cement, and it can be added directly to the finished concrete mix in a concrete mixer. Alternatively or in addition, ash is added to the cement clinker or mixed with Portland cement to form mixed cements.

Classes of fly ash F and C are described, for example, in US Standard ASTM C 618. ASTM can be used as a specification for fly ash, which is used to partially replace Portland cement. It should be noted that coal ash obtained by the methods described here contains more calcium and less silica and aluminum oxides than described in ASTM C 618 for Class F and C ash. Typical values of these parameters for fly ash are more than 50% by weight CaO and less than 25% SiO ₂ / Al ₂ O ₃ / Fe ₂ O ₃ . In accordance with various aspects, the ash of the present invention contains from 51 to 80% CaO by weight and from 2 to 25% of the total content of silica, alumina and iron oxide. According to the experiments, the fly ash corresponding to the present invention has highly cementing properties, which makes it possible to replace or reduce the amount of Portland cement in such cementitious materials by 50% or more. In accordance with various aspects, coal ash obtained by burning coal with the sorbents described here is characterized by sufficiently pronounced cementing properties, which allows it to be used for a complete (100%) replacement of Portland cement in such compositions.

To further illustrate the invention, it should be noted that the American Concrete Institute (ACI) recommended replacing Class F ashes with 15 to 25% Portland cement, and Class C ashes with 25 to 35%. It was found that the cementing properties of coal ash obtained by the methods described here allow replacing it with up to 50% of Portland cement, and 28 days after hardening, the strength will be the same as in the case of concrete, 100% of Portland cement. This means that although, in accordance with various aspects of the invention, the ash does not correspond to the chemical composition of class C or F (according to ASTM C 618), it can nevertheless be used to formulate high-strength concrete.

The coal ash prepared in accordance with the present invention can be used as a component in the production of fluid fillers, which are also called controlled low strength material (CLSM). CLSM is used as a self-leveling, self-compacting filler that can be used in place of compressed earth or other fillers. The ash described herein, in accordance with various aspects, can 100% replace Portland cement in such CLSM materials. Such compositions are prepared from water, cement and aggregate, providing the required flow and tensile strength. For example, the tensile strength of a fluid filler should not exceed 1035 kPa (150 psi) if it is necessary to ensure that the substance can be removed after it has solidified. If the resulting mixture has a higher tensile strength, then a hammer may be required to remove it. However, if it is necessary to formulate a flowable filler for use in conditions where it will have a heavy load, it is possible to design mixtures with a large compressive strength.

Obtained as described here coal ash can also be used as a component of stabilized bases and subbasic mixtures. Since the 1950s, various combinations of base lime / fly ash / aggregate have been used to prepare stabilized base mixes. For example, a stabilized base can be used as a stabilized road base. To illustrate, instead of using the ash of real compositions, roads with a gravel base can be restored (recycled). The road surface is crushed and poured again to its original place. Ash, for example, obtained by the methods described here, is sprayed on top of the crushed road material and mixed with it. After compaction, the road surface is laid on top. The ash of the present invention is useful in such applications because it does not contain heavy metals leached at the concentrations described in existing law. Moreover, the ash obtained by the methods of the present invention contains less leachable mercury and other heavy metals (such as arsenic and lead) than coal ash obtained by burning fuel without the sorbents described herein.

Thus, the present invention is directed to various methods, eliminating the need to bury (bury) coal ash or fly ash generated by burning coal with a high mercury content. Instead of an expensive burial procedure, ash can be sold or otherwise used as source material.

In accordance with a preferred aspect, the use of a sorbent makes it possible to obtain a cementitious ash capable of completely or partially replacing Portland cement in a variety of applications. Due to the possibility of reuse of the cementitious product, it is possible to at least reduce the production of Portland cement, saving the energy required for its production and avoiding the significant carbon dioxide emissions occurring during the production of cement. The reduction in carbon dioxide emissions is also due to the reduced need for lime or calcium carbonate for desulfurizing scrubbers. Thus, the invention is directed, in accordance with its various aspects, to methods for saving energy and reducing greenhouse gas emissions, such as carbon dioxide. Additional details of the various lines of implementation of these aspects are described below.

Portland cement is made in a raw or dry kiln. Although the wet and dry processes are different, in both cases there is a gradual heating of the starting material. Cement production feedstocks include sources of calcium, silica, iron, and alumina, and are typically lime and various other materials, such as clay, sand, and / or shale. At the first stage, preheating is performed when moisture is evaporated from the starting materials, hydration water is removed, and their temperature is raised to approximately 815.6 ° C (1500 ° F). The second stage is calcination, usually occurring in the temperature range from 815.6 ° C (1500 ° F) to 1093 ° C (2000 ° F), while limestone releases carbon dioxide (CO ₂ ) and turns into quicklime. After this, the starting materials are heated to a maximum temperature of approximately 1371-1649 ° C (2500-3000 ° F) in the combustion zone, where they melt and sinter to a large extent, forming inorganic compounds such as tricalcium silicate, dicalcium silicate, tricalcium aluminate and tetracalcium aluminoferrite. A typical analysis of Portland cement shows that it contains approximately 65-70% CaO, 20% SiO ₂ , 5% Al ₂ O ₃ , 4% Fe ₂ O ₃ and slightly smaller amounts of other compounds, such as oxides of magnesium, sulfur, potassium , sodium and the like. The molten "raw material" is cooled to solidify to form small lumps of an intermediate product called clinker, which is then removed from the furnace. The clinker is ground and mixed with other additives (such as a curing retarder, gypsum) to produce Portland cement. The latter can then be mixed with aggregate and water to form concrete.

Cement production is an energy-intensive process in which a combination of starting materials is chemically modified by strong heating to give a compound with binding properties. Cement production is the largest industrial source of carbon dioxide, not related to energy production. This gas is released when limestone is heated, accounting for approximately 80% of the total amount of starting materials. During the production of cement under the influence of high temperature, limestone turns into quicklime with the release of carbon dioxide into the atmosphere. In this case, one molecule of calcium carbonate decomposes with the formation of one molecule of gaseous carbon dioxide and one molecule of calcium oxide.

Approximately 100% of the calcium oxide produced by calcining calcium carbonate is spent on cement production. Thus, the amount of calcium oxide in cement clinker is a good characteristic of the amount of carbon dioxide obtained during its production. For example, to estimate carbon dioxide emissions from cement production, an emission factor is obtained by multiplying the proportion of lime in the cement clinker by a constant that reflects the mass of carbon released per unit of lime. To illustrate, assuming that the average lime content is 64.6% (based on the recommendations of the International Panel for Climate Control), an emission factor of 0.138 tons of carbon per ton of clinker is obtained. Additional carbon dioxide will be released when an additional portion of lime is added. For example, this is the case when producing stone cement, which is more plastic and is usually used in the manufacture of mortar.

The emission of carbon dioxide in the production of cement is due to the combustion of fuel to obtain the required energy and the decomposition of calcium carbonate in the production of clinker. The level of carbon dioxide emissions may depend on the source of fuel for energy. For example, cleaner fuel, such as natural gas, results in lower carbon dioxide emissions than fuels such as coal. In accordance with various aspects, the invention described above can be used in the manufacture of cement. However, the use of the present invention in the production of cement reduces the emission of carbon dioxide.

In accordance with various aspects, the invention described above can be used in the manufacture of cement to obtain “credits for carbon dioxide emissions” by reducing emissions of dioxide in cement production. In accordance with preferred aspects, a point source of air emissions, such as a cement plant or heating station, will be brought into compliance with the Kyoto Protocol.

Although the present invention is not limited by theoretical considerations, it is believed that the sorbent compositions described above are an additional source of silica and alumina during coal combustion. Coal burning in the presence of additional silica and alumina forms a geopolymer matrix known in cold ceramics. Although coal naturally contains a small amount of silica and alumina, it is believed that usually this amount is not enough to form a geopolymer matrix during combustion. Moreover, natural silica and alumina in coal are not always balanced by natural calcium and therefore do not provide optimal capture of sulfur and / or mercury and / or production of ash with cementing properties during combustion.

In accordance with various aspects, the invention is directed to methods for improving the resistance to leaching of heavy metals from coal, such as mercury. The method includes introducing into the coal an additional amount of silica and alumina so that a geopolymer is formed during combustion. Preferably, silica and alumina are added together with a sufficient amount of alkaline powders to avoid the formation of sulfur shells. Alkaline powders neutralize silica and alumina to form a geopolymer ash and react with silica and / or alumina to form a ceramic-like matrix called stabilized ash. When burning with coal, silica and alumina can also form a composition with a reflective surface, including compounds of mercury, lead, arsenic, cadmium, antimony, cobalt, copper, manganese, zinc and / or other heavy metals. The resulting coal ash or fly ash contains heavy metals that are resistant to leaching under standard conditions. As already mentioned, the resistance of coal ash to leaching leads to commercial advantages, since such a product can no longer be considered a dangerous substance.

Examples

In Examples 1-6, coals with different BTU values, as well as different sulfur and mercury contents, were burned in CTF furnaces at the University of North Dakota's Environmental Research Center (EERC) at the University of North Dakota ) The percentage of mercury was calculated based on the total amount of the element in the coal before burning. The percentage of sulfur removal is a decrease in the percentage of sulfur relative to the baseline, where the baseline was determined by measuring sulfur emissions from combustion without sorbent.

Example 1

This example illustrates the ability of a solution of calcium bromide in water to adsorb mercury when burning sub-bituminous coal mined in a Powder River basin. After firing, the moisture content of coal was 2.408%, the ash content was 4.83%, the sulfur content was 0.29%, the calorific value was 8.999 BTU, and the mercury content was 0.122 μg / g. When burning without sorbent, the concentration of mercury in the exhaust gases was 13.9 μg / m ³ . The coal was crushed to a state where 70% of this coal passed through a sieve (filter) with a mesh size of 200, and mixed with the sorbent in the following proportions: 6% powder sorbent and 0.5% liquid sorbent in terms of the mass of coal. The powder contained 40-45% Portland cement, 40-45% calcium oxide, and the rest was sodium or calcium montmorillonite. The liquid is a 50% (w / w) aqueous solution of calcium bromide.

Sorbents were mixed directly with fuel for 3 minutes and then left to burn. The treated charcoal was placed in an oven. As a result of burning by the dust-collecting chamber, 90% of mercury (of the total amount) and 80% of sulfur (according to the data at the outlet of the chamber) were removed.

Example 2

This example illustrates the application of powdered and liquid sorbents to three types of bituminous coals with different mercury contents. All coals were prepared as described in example 1, the sorbent content was the same as described in example 1.

Parameter Coal % mercury removal % sulfur removal % humidity; 8.48 Coal 97.97 40,0 % sulfur; 2.28 Pittsburgh mercury; 16.2 mcg / m ³ Seam-bailey BTU value 13,324 % humidity; 10.46 Freeman 97.9 36.0 % sulfur; 4.24 Crown III mercury; 8.53 mcg / m ³ BTU value 11,824 % humidity; 1,0 Kentucky 90.1 52.0 % sulfur; 1.25 Blend mercury; 5.26 mcg / m ³ BTU value 12,937

Example 3

This example illustrates the addition of mercury sorbents after incineration. Pittsburgh Seam-Bailey coal was crushed to a state where 70% of this coal passed through a 200 mesh filter. No sorbent was added to the fuel before burning. A liquid sorbent containing a 50% aqueous solution of calcium bromide was introduced through a pipe into a stream of gaseous products of combustion in a furnace in the temperature zone 1204-815.6 ° C (2200-1500 ° F). A liquid sorbent was introduced at a rate of approximately 1.5% by weight of coal.

Type of coal The composition of the sorbent % reduction S Hg reduction Coal Pittsburgh 50% CaBr ₂ 28.13 96.0 Seam-bailey 50% H ₂ O

Example 4

This example illustrates the addition of liquid and powder sorbent after combustion. No sorbent was added directly to the fuel. Both used fuels of the brands Freeman Crown III and Pittsburgh Seam-Bailey were bituminous. In both cases, the coal was crushed before burning to a state where 70% of this coal passed through a filter with a mesh size of 200. Powdered and liquid sorbents were used as described in Example 1. The proportions in which the liquid and powder were added (calculation was based on weight coal burned), as well as the level of reduction of mercury and sulfur are presented in the table.

Type of coal Liquid sorbent injection rate Powder sorbent injection rate S decrease Hg reduction Coal Freeman 1,0 4.0 36.27 97.89 Crown III Pittsburgh 1,5 6.10 33.90 96.00 Seam-bailey

Example 5

Pittsburgh Seam-Bailey coal was prepared as described in Example 1. The powder sorbent of Example 1 was added to coal before ignition in an amount of 9.5% by weight. The liquid sorbent from Example 1 (50% aqueous solution of calcium bromide) was introduced after combustion into the temperature zone of 815.6-1204 ° C (1500-2200 ° F) at a rate of 0.77% of the rate of combustion of coal. The level of decrease in sulfur content was 56.89%, the level of decrease in mercury content was 93.67%.

Example 6

Coal Kentucky Blend was prepared as described in Example 1. The powder sorbent of Example 1 was added to coal before ignition at the rate of 6% by weight. The liquid sorbent from Example 1 (50% aqueous solution of calcium bromide) was introduced after combustion in the temperature zone of 815.6-1204 ° C (1500-2200 ° F) at a rate of 2.63% of the rate of combustion of coal. The level of decrease in sulfur content was 54.91%; The level of decrease in mercury content was 93.0%.

In Examples 7-10, coals with different BTU values, sulfur and mercury content were burned in various boilers of thermal power plants. The percentage reduction in mercury was calculated based on the total amount of the element in the coal before burning. Sulfur removal percentage is the percentage reduction relative to the baseline, where the baseline was determined by measuring sulfur emissions from combustion without sorbent.

Example 7

Fuel containing bituminous and sub bituminous coal, petroleum coke, wood chips and used car tires was burned in a furnace with a mechanical feed system so as to produce 60 MW of electricity. The draft in the boiler furnace was regulated. Basic emission of mercury from fuel without the addition of a sorbent showed that mercury is mainly in oxidized form. After establishing the baseline, the composition of the powdered sorbent was added to the furnace at a rate of 5.5-6% by weight about two feet above the grate through the furnace tubes for the regeneration / reintroduction of fly ash. After the establishment of the quasistationary state, mercury retention was 96%. A powder sorbent composition was composed of 93% by weight 50:50 mixture of powder of calcined cement and calcined lime and 7% by weight of calcium montmorillonite. Providing a constant speed of adding the composition of the powdered sorbent, a liquid sorbent containing 50% by weight aqueous solution of calcium bromide was added to the fuel prior to combustion, based on a 0.5% plumb of spent fuel. With the addition of a liquid sorbent, mercury retention increased to 99.5%.

Example 8

The PRB coal (crushed to 75% of the passage through a 200 sieve) was burned in a tangential boiler with an adjustable draft, so as to produce 160 mW of electricity. After establishing the base emission value of S and Hg during coal combustion without adding a sorbent, the powder sorbent composition described in Example 7 was added to the furnace to a content of 5.5-6%. Sorbent was introduced through a pipe protruding 4 feet from the inside of the furnace and located 20 feet above the flame. The flue gas temperature at the injection point was approximately 1316-1427 ° C (2400-2600 ° F) and was measured using a temperature sensor. Sulfur retention increased to 65% above baseline. Retention of mercury, calculated on the basis of the total amount of mercury in the coal grade PRB, amounted to 3%. Then, while continuing to add the powdered sorbent, another 50% aqueous solution of calcium bromide was added to the coal dust. The input was carried out in crushed coal in the coal supply system by dropping at a rate of 0.5% relative to the rate of consumption of coal. Mercury retention increased to 90%.

Example 9

The PRB coal, crushed before passing through a 200 mesh sieve, was burned in an adjustable draft tangential furnace to produce approximately 164 MW of electricity. After establishing the base value of sulfur and mercury emissions during coal combustion without adding a sorbent (mercury in the exhaust flue gases was present mainly in elemental form), the composition of the powdered sorbent described in Example 7 was added at the rate of 5.5-6.0% by weight of fuel in the furnace immediately below the neck of the furnace, 20 feet above the flame. The temperature at the injection point was approximately 1649 ° C (3000 ° F) to 1816 ° C (3300 ° F). The addition was carried out through a series of 3 face-offs along one side of the furnace. Each serving contained approximately the same amount of powder and penetrated the oven approximately 3 feet from its inner wall. Sulfur retention increased to 50% above baseline. Mercury retention was approximately 1-3% above the baseline. Continuing to add the composition of the powdered sorbent to the furnace, a 50% aqueous solution of calcium bromide was introduced directly into the fuel. The input was carried out directly into the fuel in its supply system at a rate of approximately 0.2% by weight relative to the rate of consumption of coal. Mercury retention increased to 90%.

Example 10

The same procedure was followed as in Example 9, except that a powdered sorbent was added immediately before being fed into the furnace, and not directly into the furnace. The same sulfur and mercury reduction values are obtained as in Example 9.

Example 11

PRB brand coal was burned in a tangential boiler with artificial ventilation, so as to produce electricity in the quantity necessary for consumers. The crushed coal (75% passage through a 200 sieve) was placed in a boiler. Before the introduction of the crushed coal into the furnace, a powdery sorbent was added to it at a rate of 6% by weight of the rate of burning of coal. The powder sorbent contained 93% by weight of a mixture of 50/50 calcined powder cement and calcined lime powder and 7% by weight calcium montmorillonite. At the same time, coal was added by dropping a 50% aqueous solution of calcium bromide at a rate of 0.1 to 2% by weight of the rate of consumption of coal during combustion. Samples of fly ash were collected before the addition of sorbents (baseline) and after the addition of powdered and liquid sorbents. The content of chlorine and heavy metals was determined by the standard method. The results are presented in table 1.

Table 1 The composition of fly ash with and without the use of sorbents Element Test - after adding the sorbent (ppm, except chlorine) Baseline - before adding sorbent (ppm, except chlorine) As 59.3 26.5 Wa 1.3 1.4 Cd 2,3 1,1 Co 44.8 38.5 Cr 52.0 34.3 Cu 61.0 48.8 Mn 445.7 395.5 Mo 26.0 31.5 Ni 208.5 325.5 Pb 45.8 31.3 Sb 23.0 7.3 V 473.0 874.5 Zn 3954.0 974.7 Mercury 0.246 0.128 Chlorine 0.940% 0.56%

The table shows that the use of sorbents increases the level of some heavy metals contained in fly ash. For example, arsenic, cadmium, chromium, lead, mercury and chlorine in test ash samples are found in larger quantities compared to the baseline. Presumably, this is due to increased capture of elements by fly ash. It is not clear what is associated with increased levels of zinc in test samples of ash. Perhaps this is due to the high level of slag removal from the boiler pipes when using the sorbents of the present invention. It can be assumed that elevated levels of zinc can be associated with the removal of substances from boiler pipes when burning coal with sorbents.

Example 12

The following ash samples were tested according to the TCLP procedure developed by the U.S. Environmental Protection Agency (EPA) to determine the threshold acid leach of key elements. The results are presented in table 2.

table 2 TCLP test results for fly ash Element EPA Threshold Limit (ppm) Baseline - before adding the sorbent (ppm) Test - together with the addition of sorbent (ppm) Arsenic 5,0 <0.04 <0.04 Barium 100.0 0.814 0.313 Cadmium 1,0 <0.04 <0.04 Chromium 5,0 0,030 <0.007 Lead 5,0 0.513 0,096 Mercury 0.20 0,095 0,078 Selenium 1,0 <0.07 <0.07 Silver 5,0 3,835 3,291

Table 2 shows that although the absolute amount of elements such as arsenic, lead, and mercury in the ash is higher, the amount of leached arsenic, lead, and mercury in the test samples of ash is lower compared to the baseline.

Example 13

Coal PRB (75% passing through a 200 sieve) was burned in a balanced traction tangential furnace to produce 160 MW of energy. Coal was burned as long as needed to get 8 trolleys of fly ash. Powdered sorbent was added to the unit at a rate of 4-6% by weight throughout the entire period of the experiment. In the first third of the period, the sorbent was added only to the furnace exactly below the furnace dome through the nozzle in the furnace wall. In the next third of the period, half of the sorbent was added to the furnace and half to the crushed coal before ignition. In the last third, 100% powdered sorbent was added to coal before ignition. Throughout the experiment, a liquid sorbent (50% aqueous solution of calcium bromide) was added to the crushed coal at the pre-combustion stage at a rate of 0.15% by weight relative to the rate of coal burned. A pooled sample showing the composition of 8 ash trolleys was collected and its leach was determined using the US EPA TCLP method. The barium leach was 26 ppm, well below the legal level of 100 ppm. The TCLP values for As, Cd, Cr, Pb, Hg, Se, and Ag were below the sensitivity limit of the test used. In particular, the leaching of mercury was <0.0020 ppm, which is less than 2 ppb.

Claims (71)

1. A method of reducing the mercury content in flue gases obtained by burning coal in solid fuel plants, characterized by the use of sorbent components in said plants, which include a halogen compound and at least one aluminosilicate mineral, by burning coal to produce ash and combustion gases, by measuring the mercury content in the gaseous products of combustion and by adjusting the amount of the halogen compound used based on the obtained mercury value. 2. The method according to claim 1, in which the use of the components of the sorbent is carried out before the supply of coal to the installation and its combustion. 3. The method according to claim 1, in which the composition of the sorbent include bromide. 4. The method according to claim 1, in which the composition of the sorbent include calcium bromide. 5. The method according to claim 1, in which the aluminosilicate mineral is a layered structure comprising at least one mineral selected from the following group: clay, kaolinite, sodium montmorillonite, calcium montmorillonite, vermiculite, mica, talc, chrysolite and pyrophyllitis. 6. The method according to claim 1, in which the aluminosilicate mineral is at least one layered structure selected from the following group: kaolinite, calcium montmorillonite and sodium montmorillonite. 7. A method of reducing the content of oxidized mercury in flue gases generated by burning mercury-containing types of carbon fuel in plants, characterized by introducing an alkaline powder sorbent into carbon fuel before burning or directly into the plant during combustion, burning fuel in the presence of said alkaline powder sorbent, measuring the content mercury in flue gases, by comparing the measured mercury level with a predetermined level and at a measured value greater than a predetermined level by increasing the amount of added powder sorbent relative to the amount of fuel, while calcium, silica and alumina are included in the composition of the powder sorbent. 8. The method according to claim 7, in which the composition of the powder sorbent further include iron and magnesium. 9. The method according to claim 7, in which the content of alumina in the sorbent is higher than the content of alumina in Portland cement. 10. The method according to claim 7, in which the content of alumina in the powder sorbent is taken greater than 7% by weight. 11. The method according to claim 7, in which the powdered sorbent is introduced into the installation in the process of burning fuel. 12. The method according to claim 7, in which the fuel contains coal and at least one component selected from the following group: biomass, production waste and damaged tires. 13. The method according to claim 7, in which the composition of the powdered sorbent further includes aluminosilicate and at least one component selected from the following group: Portland cement, calcium oxide, lime, limestone, beet lime, calcined cement and calcined lime. 14. The method according to item 13, in which the composition of the powdered sorbent include at least two substances. 15. A method of reducing the content of sulfur or sulfur and mercury in flue gases obtained by burning coal in solid fuel plants, characterized by introducing a powder composition into coal before burning it and / or during burning in the following ratio of components, wt.%:
alkaline powder containing calcium 50 ÷ 98 aluminosilicate 2 ÷ 50 16. The method according to clause 15, in which the combustion of coal is carried out at a temperature of about 537.8 ° C. 17. The method according to clause 15, in which the content of aluminosilicate in the powder composition is 2 ÷ 20 wt.%. 18. The method according to clause 15, in which the content of aluminosilicate in the powder composition is 2 ÷ 10 wt.%. 19. The method according to clause 15, in which the composition of the alkaline powder includes at least one substance selected from the following group: Portland cement, calcined cement, calcined lime and beet lime. 20. The method according to clause 15, in which the composition of the alkaline powder includes calcined cement and calcined lime. 21. The method according to clause 15, which uses aluminosilicate containing at least one substance selected from the following group: calcium montmorillonite, sodium montmorillonite and kaolin. 22. The method according to clause 15, in which the powder composition is administered in a ratio of 0.1 ÷ 10 wt.% In relation to the weight of combustible coal. 23. The method according to clause 15, in which the powder composition is introduced into the furnace. 24. The method according to item 23, in which the temperature at the point of introduction of the powder composition exceeds 1093 ° C. 25. The composition of the sorbent to reduce the content of mercury and sulfur in the combustion gases, containing alkaline powder and aluminosilicate in the following ratio of components, wt.%:
alkaline powder containing calcium 50 ÷ 98 aluminosilicate 2 ÷ 50,
wherein the alkaline powder contains at least one of the following components selected from the group consisting of: Portland cement, calcined cement, calcined lime and beet lime. 26. The composition according A.25, which further comprises a bromine compound. 27. The composition according A.25, in which the alkaline powder includes additionally calcined cement and calcined lime. 28. The composition according A.25, in which the content of aluminosilicate is 2-20 wt.%. 29. The composition according to p. 28, in which the aluminosilicate is at least one substance selected from the group comprising calcium montmorillonite, sodium montmorillonite and kaolinite. 30. A method of burning coal with a reduced amount of mercury emissions into the atmosphere, characterized by introducing into the coal a liquid sorbent composition containing a bromine compound, feeding coal with a sorbent into a coal burning furnace, introducing a powder composition containing calcium, silica and alumina into a furnace burning and burning coal together with a liquid and powder composition in a furnace for burning coal to produce ash and combustion gases. 31. The method according to claim 30, wherein the amount of mercury leached from the ash is additionally measured, and depending on the results of said measurement, the composition of the sorbent composition introduced into the coal is controlled by the amount of silica and alumina introduced. 32. The method according to clause 30, in which the liquid composition of the sorbent includes bromide. 33. The method according to p, in which the liquid sorbent composition essentially does not contain alkali metal compounds. 34. The method according to clause 30, in which the composition of the powder composition includes aluminosilicate. 35. The method according to clause 30, in which the composition of the powder composition includes at least one component selected from the group comprising Portland cement, calcined cement and calcined lime. 36. The method according to clause 30, in which the composition of the sorbent include calcined cement, calcined lime and aluminosilicate. 37. The method according to clause 30, in which the introduction of the powder composition is carried out at a temperature of about 1093 ° C. 38. The method according to clause 30, in which the introduction of the powder composition is carried out at a temperature of about 1260 ° C. 39. The method according to clause 30, in which the introduction of the powder composition is carried out at a temperature of about 1482 ° C. 40. A method of burning mercury-containing coal in a solid fuel-fired plant consisting of a furnace and a convection path for flue gases at the furnace exit, characterized by introducing into the installation a liquid composition containing a bromine compound, adding a powder composition including calcium to the installation during combustion at least 2 wt.% silica and at least 2 wt.% alumina, and burning coal to form flue gases and fly ash with a reduced sulfur and mercury content. 41. The method according to p, in which the liquid composition is introduced into coal before burning it. 42. The method according to p, in which the powder composition is added to coal before burning it. 43. The method of claim 40, wherein the liquid composition comprises calcium bromide. 44. The method according to p, in which the powder composition includes aluminosilicate and additionally at least one component selected from the group comprising Portland cement, calcined cement, beet lime and calcined lime. 45. The method according to p, in which the powder composition is added as a sorbent in a percentage of 1 ÷ 10 wt.% Relative to the weight of the coal burned. 46. The method according to p, in which the bromine compound is introduced in a percentage ratio of 0.5 ÷ 1 wt.% Relative to the weight of the coal burned. 47. A method of burning coal with a reduced amount of harmful elements released into the environment, characterized by adding to the coal a sorbent composition comprising calcium, silica, alumina and a halogen compound selected from the group consisting of bromine and iodine, and burning coal to produce ash and gases combustion with reduced sulfur and mercury. 48. The method according to clause 47, which further determines the mercury content in the combustion gases and adjusts the amount of bromine compounds added to coal based on mercury content data. 49. The method according to clause 47, in which the bromine compound is added to coal in an amount sufficient to reduce mercury emissions into the environment by 90% or more compared with the emission observed during the combustion of coal without bromine-containing additives. 50. The method according to clause 47, in which the composition of the sorbent includes calcium bromide. 51. The method according to clause 47, in which a liquid composition comprising a bromine compound is added to coal. 52. The method of claim 51, wherein the liquid composition comprises calcium bromide. 53. A method of reducing the mercury content in flue gases generated during the combustion of coal in a furnace of a solid fuel-fired plant, characterized by introducing sorbent components into the plant, including halogen, calcium, silica and alumina, and burning coal to form ash and combustion gases . 54. The method according to item 53, which further determines the mercury content in the combustion gases and regulates the amount of halogen compounds introduced into the installation, based on the mercury content. 55. The method according to item 53, in which the halogen compound is a bromine compound. 56. The method according to item 53, in which at least one component of the sorbent is introduced into coal before burning it. 57. The method according to item 53, in which at least one component of the sorbent is injected directly into the furnace. 58. The method according to item 53, in which at least one component of the sorbent is introduced into the convection stream of the installation at the outlet of the furnace. 59. The method according to item 53, which introduces a liquid sorbent containing bromine, and a powder sorbent containing calcium, silica and alumina. 60. The method according to p, in which the powder sorbent includes at least one component selected from the group comprising Portland cement, calcined cement, calcined lime and aluminosilicate clay. 61. The method according to p, in which a powder sorbent is introduced in a ratio of 1 ÷ 10 wt.% Relative to the weight of the coal burned. 62. Coal ash obtained by the method according to any one of paragraphs.30, 40, 47 and 53. 63. Cement in which approximately 0.1–99% by weight of coal ash is added to Portland cement according to claim 62 relative to the total weight of the cement. 64. Pozzolan, which added about 0.1 ÷ 99 wt.% Coal ash according to item 62 relative to the total weight of pozzolan. 65. Concrete mixture, ready for use, including aggregate and cement, which contains coal ash according to paragraph 62. 66. The composition of concrete, mortar, mortar, fluid filler and stabilizing base, containing water and concrete mixture according to item 65. 67. Concrete structure obtained by hydration of a concrete mixture according to item 65. 68. A method of obtaining a cementitious mixture, characterized by burning coal in the presence of 1 ÷ 10 wt.% Added sorbent with a content of approximately 30 ÷ 75 wt.% CaO, 2 ÷ 15 wt.% Alumina, 5 ÷ 20 wt.% Silica, 1 ÷ 10 wt.% Fe ₂ O ₃ and 0.1 ÷ 5 wt.% Alkali selected from the group comprising Na ₂ O and K ₂ O, obtaining ash from coal combustion, subsequent collection of ash and preparation of the cementitious mixture containing ash. 69. The method according to p, in which the combustion of coal is carried out additionally in the presence of a bromine compound. 70. The method according to p, in which the added sorbent includes aluminosilicate. 71. The method according to p, in which the added sorbent includes calcined cement.