CN110975590A - Coal-fired system and method for removing sulfur trioxide and mercury by using modified fly ash - Google Patents

Coal-fired system and method for removing sulfur trioxide and mercury by using modified fly ash Download PDF

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Publication number
CN110975590A
CN110975590A CN201911255817.2A CN201911255817A CN110975590A CN 110975590 A CN110975590 A CN 110975590A CN 201911255817 A CN201911255817 A CN 201911255817A CN 110975590 A CN110975590 A CN 110975590A
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China
Prior art keywords
fly ash
coal
mercury
ammonia
modified
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CN201911255817.2A
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Chinese (zh)
Inventor
张永生
王帅
王家伟
汪涛
潘伟平
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North China Electric Power University
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North China Electric Power University
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Priority to CN201911255817.2A priority Critical patent/CN110975590A/en
Publication of CN110975590A publication Critical patent/CN110975590A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81Solid phase processes
    • B01D53/83Solid phase processes with moving reactants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • B01D53/50Sulfur oxides
    • B01D53/508Sulfur oxides by treating the gases with solids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/64Heavy metals or compounds thereof, e.g. mercury
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/302Sulfur oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/60Heavy metals or heavy metal compounds
    • B01D2257/602Mercury or mercury compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases

Abstract

The application relates to the technical field of coal-fired power generation, in particular to a coal-fired system and method for removing sulfur trioxide and mercury by using modified fly ash. The coal-fired system sequentially comprises a boiler, a denitration device, an air preheater and a dust remover along the flowing direction of flue gas, wherein an injection pipeline is arranged between the denitration device and the air preheater; the spraying pipeline is connected with the dust remover, and the fly ash obtained from the dust remover is sprayed out from the spraying pipeline after being modified by the ammonia-containing halide. According to the coal-fired system provided by the invention, the fly ash obtained from the dust remover is modified by the ammonia halide and then is sprayed out from the spraying pipeline arranged between the denitration device and the air preheater, the fly ash modified by the ammonia halide can react with sulfur trioxide in the flue gas, and simultaneously, the halogen on the surface of the fly ash can also react with mercury in the flue gas to generate mercury halide, so that the coal-fired system can adsorb and remove the sulfur trioxide in the flue gas and can also adsorb and remove the mercury in the flue gas.

Description

Coal-fired system and method for removing sulfur trioxide and mercury by using modified fly ash
Technical Field
The application relates to the technical field of coal-fired power generation, in particular to a coal-fired system and method for removing sulfur trioxide and mercury by using modified fly ash.
Background
Sulfur trioxide (SO)3) The paint is corrosive, can corrode metal on the wall of the flue pipe, can form acid rain, and has influence on the environment around a power plant. After the denitration device is arranged in the coal-fired system, the catalyst in the denitration device can react with sulfur dioxide (SO)2) Carrying out catalytic oxidation to generate SO3To make SO in the flue gas3An increase in concentration of (c); part of ammonia (NH) gas will be generated in the denitration device4) Escape out of the flue gas and SO in the flue gas3Reaction to produce ammonium hydrogen sulfate (NH)4HSO4),NH4HSO4In the molten state in the temperature range of the air preheater, it is sticky, adheres to the surface of the air preheater, and adheres to fly ash in the flue, causing clogging of the air preheater. The existing desulfurization method mainly adopts limestone-gypsum wet desulfurization technology, and can effectively remove SO2But to SO3The removal efficiency is low.
Mercury (Hg) is a highly toxic substance and has serious effects on both the environment and the human body. The coal burning causes the mercury in the coal to be volatilized by heating and exist in the flue gas in the form of mercury vapor, China is a country with large coal reserves and a country with large consumption, and the coal burning causes the mercury discharge to be huge, thereby easily causing environmental pollution. The prior mercury removal method mainly uses active carbon as an adsorbent, but the price of the active carbon adsorbent is higher, and the sprayed active carbon adsorbent has certain influence on the secondary utilization of the system fly ash.
Therefore, there is a need for a new coal-fired system and method for removing sulfur trioxide and mercury from modified fly ash to solve the above problems.
Disclosure of Invention
The application provides a coal-fired system and method of utilizing modified flying ash desorption sulfur trioxide and mercury can adsorb the desorption to the sulfur trioxide in the flue gas, also can adsorb the desorption to the mercury in the flue gas, has reduced the control cost of pollutant, has improved the convenience that multiple pollutant discharge was controlled.
The first aspect of the application provides a coal-fired system for removing sulfur trioxide and mercury by using modified fly ash, which sequentially comprises a boiler, a denitration device, an air preheater and a dust remover along the flow direction of flue gas, wherein an injection pipeline is arranged between the denitration device and the air preheater;
the spraying pipeline is connected with the dust remover, and the fly ash obtained from the dust remover is sprayed out from the spraying pipeline after being modified by ammonia halide.
Optionally, the ammonia-containing halide comprises ammonium chloride and/or ammonium bromide.
Optionally, the ratio of the ammonia-containing halide to fly ash taken from the precipitator is (0.001-0.3): 1.
optionally, a mill is provided between the injection duct and the precipitator for milling the fly ash obtained from the precipitator.
Optionally, an air inlet pipeline and an induced draft fan are arranged between the air preheater and the grinding mill;
air enters from the air inlet pipeline, is heated by the air preheater and then is driven by the draught fan to enter the grinding machine.
Optionally, an ash hopper and a material conveyor are arranged between the grinding mill and the dust remover, and the fly ash obtained from the dust remover is sent into the grinding mill through the ash hopper and the material conveyor in sequence.
Optionally, the spray conduit is in electrical communication with the precipitator.
The second aspect of the present application provides a method for removing sulfur trioxide and mercury by using modified fly ash, which adopts the above coal burning system, and comprises the following steps:
obtaining part of fly ash in a dust remover;
modifying the fly ash with an ammonia-containing halide;
and spraying the modified fly ash between the denitration device and the air preheater.
Optionally, the step of modifying the fly ash with an ammonia-containing halide further comprises:
the fly ash and the ammonia-containing halide are mixed and subjected to a grinding treatment.
Optionally, the injecting the modified fly ash between the denitration device and the air preheater further comprises:
and the air heated by the air preheater is used as carrier gas for conveying the modified fly ash.
After adopting above-mentioned technical scheme, beneficial effect is:
according to the coal-fired system provided by the invention, the fly ash obtained from the dust remover is modified by the ammonia halide and then is sprayed out from the spraying pipeline arranged between the denitration device and the air preheater, the fly ash modified by the ammonia halide can react with sulfur trioxide in flue gas, and simultaneously halogen on the surface of the fly ash can also react with mercury in the flue gas to generate mercury halide, so that the coal-fired system can adsorb and remove the sulfur trioxide in the flue gas and can also adsorb and remove the mercury in the flue gas, the control cost of pollutants is reduced, and the convenience of emission control of various pollutants is improved.
Drawings
FIG. 1 is a schematic diagram of a coal combustion system for removing sulfur trioxide and mercury using modified fly ash according to an embodiment of the present invention.
Reference numerals:
1-a boiler;
11-an injection conduit;
2-a dust remover;
21-an electric field;
22-ash bucket;
23-a material conveyor;
3-a denitration device;
4-an air preheater;
41-an air inlet pipeline;
42-a draught fan;
5-a grinder;
6-a desulfurizing tower;
7-chimney.
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, unless explicitly stated or limited otherwise, the terms "first", "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; the term "plurality" means two or more unless specified or indicated otherwise; the terms "connected," "fixed," and the like are to be construed broadly and may, for example, be fixedly connected, detachably connected, integrally connected, or electrically connected; may be directly connected or indirectly connected through an intermediate. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the description of the present invention, it should be understood that the terms "upper" and "lower" as used in the description of the embodiments of the present invention are used in the angle shown in the drawings, and should not be construed as limiting the embodiments of the present invention. In addition, in this context, it will also be understood that when an element is referred to as being "on" or "under" another element, it can be directly on "or" under "the other element or be indirectly on" or "under" the other element via an intermediate element.
Fig. 1 is a schematic diagram of a coal combustion system for removing sulfur trioxide and mercury by using modified fly ash according to an embodiment of the present invention. Coal fired system includes boiler 1, denitrification facility 3, air heater 4 and dust remover 2 along the flow direction of flue gas in proper order, wherein:
the boiler 1 is configured to provide a site for coal combustion and output flue gas resulting from the combustion; the dust remover 2 is communicated with the boiler 1, and the dust remover 2 is configured to collect fly ash in the flue gas; the denitration device 3 prevents excessive NO from being generated after the coal in the boiler 1 is burnedXThe environment is polluted; the air preheater 4 can preheat the air before entering the boiler 1 to a certain temperature through the internal radiating fins by the smoke in the tail flue of the boiler 1.
An injection pipeline 11 is arranged between the denitration device 3 and the air preheater 4, the injection pipeline 11 is connected with the dust remover 2, and the fly ash obtained from the dust remover 2 is modified by the ammonia-containing halide and then is sprayed out from the injection pipeline 11. According to the coal-fired system provided by the invention, the fly ash obtained from the dust remover 2 is modified by the ammonia-containing halide and then is sprayed out from the spraying pipeline 11 arranged between the denitration device 3 and the air preheater 4, the fly ash modified by the ammonia-containing halide can react with sulfur trioxide in flue gas, and simultaneously halogen on the surface of the fly ash can also react with mercury in the flue gas to generate mercury halide, so that the coal-fired system can adsorb and remove the sulfur trioxide in the flue gas and the mercury in the flue gas, the control cost of pollutants is reduced, and the convenience of emission control of various pollutants is improved.
The following explains the mechanism of reaction between the fly ash modified with the ammonia-containing halide and sulfur trioxide and mercury, respectively:
the sulfur trioxide reacts with ammonia-containing halide (such as ammonium bromide) on the surface of the fly ash to generate ammonium sulfate and ammonium bisulfate, and the resultant adheres to the surface of the fly ash and flows along with the flue gas, and is collected along with the fly ash when reaching the dust remover 2, so that the adsorption and removal of the sulfur trioxide in the flue gas can be realized. The reaction formula is as follows:
Hg2++2Br→HgBr2
it can be understood that the fly ash modified by the ammonia halide will release a part of ammonia gas in the flue gas due to heating, and it is originally: the ammonia in the flue gas can react with sulfur trioxide and generate ammonium sulfate and ammonium bisulfate, and ammonium bisulfate can be along with the flue gas arrives air heater, is in the molten state in air heater's temperature interval, can lead to the adhesion on air heater's metal wall to thereby can the adhesion flying ash cause air heater to block up. And the fly ash modified by the ammonia halide can cause the concentration of ammonia gas in the flue gas to rise through partial ammonia gas subjected to thermal decomposition, so that the generation of ammonium bisulfate can be inhibited, namely the generation of ammonium sulfate is promoted, and then the concentration of ammonium bisulfate is reduced, thereby greatly relieving the problem of air preheater blockage. The unreacted ammonia gas in the flue gas reaches the desulfurizing tower 6 along with the flue gas, and SO is neutralized in the desulfurizing tower 62、CO2The reaction generates ammonium bisulfite, ammonium sulfite, ammonium carbonate and the like, which are absorbed and removed without being discharged into the atmosphere along with the flue gas. The reaction formula is as follows:
NH3+SO3+H2O→NH4HSO4
2NH3+SO3+H2O→(NH4)2SO4
during the flowing process of the fly ash modified by the ammonia halide along with the flue gas in the flue, the halogen (such as bromine) on the surface of the fly ash reacts with mercury in the flue gas to generate mercury halide (such as mercury bromide), so that the mercury can be converted into Hg by using bromide ions0Oxidation to Hg2+Thereby further absorbing mercury in the flue gas by the fly ash. This is because: oxidized mercury (Hg)2+) A part of the fly ash particles is attached to fly ash particles and thus removed by the dust collector, and the water-soluble property thereof makes it possible to remove a part thereof in wet desulfurization; and elemental mercury (Hg)0) The most stable physical and chemical properties and the most difficult pollution by the existing atmosphereAnd (4) removing by using a dyeing control device.
In addition, the injection duct 11 is inserted into the boiler from the wall of the boiler 1, the injection duct 11 includes a plurality of nozzles arranged uniformly, and the injection range of the plurality of nozzles can be larger than the cross-sectional area of the furnace to improve the contact probability of the injected fly ash and the flue gas.
Alternatively, the ammonia-containing halide comprises ammonium chloride and/or ammonium bromide, preferably ammonium bromide, because ammonium bromide is more effective at removing sulfur trioxide and mercury than ammonium chloride. The ratio of the ammonia-containing halide to the fly ash taken from the dust separator 2 is (0.001-0.3): 1.
further, the coal burning system further comprises a grinder 5, the grinder 5 is disposed between the injection pipe 11 and the dust collector 2, and the grinder 5 is used for grinding the fly ash taken from the dust collector 2 and injecting the ground fly ash into the boiler 1 through the injection pipe 11. According to the coal-fired system provided by the first aspect of the invention, after the fly ash modified by the ammonia-containing halide is ground, the specific surface area of the fly ash is increased, so that the contact area and probability of sulfur trioxide and the ammonia-containing halide (such as ammonium bromide) on the surface of the fly ash are larger, and the ammonium sulfate and the ammonium bisulfate generated by the reaction are more easily adhered to the surface of the fly ash, thereby being beneficial to the adsorption and removal of sulfur trioxide; in addition, the fresh surface generated by grinding the fly ash has higher surface energy, and can further adsorb mercury in the flue gas, thereby reducing the content of sulfur trioxide and mercury in the flue gas.
It will be appreciated that the mill 5 may be any type of mill, such as a horizontal mill, a vertical mill, an air mill, etc., as long as it is ensured that the particle size of the fly ash can be milled to be small, so that the specific surface area of the fly ash is increased, and the fly ash can simultaneously react with and adsorb the sulfur trioxide and mercury in the flue gas, thereby reducing the content of sulfur trioxide and mercury.
In the working process of the grinding machine 5, the grinding time is a factor influencing the fly ash removal effect, and the best fly ash removal effect cannot be achieved by too short grinding time or too long grinding time. Preferably, the grinding time may be 10min to 30min, so that not only is not too much electric energy wasted (since the grinder 5 is driven by electric energy), but also a superior fly ash removal effect is ensured. The grinding time is the time when the fly ash is in the grinder 5 in operation, so that each batch of fly ash can be sent to the grinder 5 for grinding, or each batch of fly ash can be continuously sent to the grinder 5 for grinding, and in the latter operation mode, the time difference between the fly ash entering the grinder 5 and the fly ash leaving the grinder 5 is ensured to be 10min-30 min.
Further, an air inlet pipeline 41 and an induced draft fan 42 are arranged between the air preheater 4 and the grinding mill 5, air enters from the air inlet pipeline 41, and is heated by the air preheater 4 and then enters the grinding mill 5 through the induced draft fan 42. In the embodiment, the high-temperature air is used as a carrier to convey the ground fly ash, so that the ground fly ash has a certain temperature (usually 50-80 ℃) when entering a hearth, the temperature difference of the fly ash and coal can be reduced, and the uniform mixing of the fly ash and the coal and the heat energy loss of combustion are further ensured.
Further, an ash hopper 22 and a material conveyor 23 are provided between the grinding mill 5 and the dust collector 2, and the fly ash taken from the dust collector 2 is fed into the grinding mill 5 through the ash hopper 22 and the material conveyor 23 in this order. Alternatively, the material conveyor 23 includes a screw feeder and a variable frequency feeder, so that the fly ash in the ash hopper 22 is continuously fed into the grinding mill 5 conveniently and quickly.
Further, the obtained fly ash is fly ash in an electric field 21 of the dust collector 2. Generally, the dust collector 2 has four electric fields, the fly ash in the flue gas gradually becomes smaller in particle size along the directions of the electric fields 21 to four, and the fly ash with larger particle size is best ground, i.e. is most easily damaged to generate a fresh surface.
Further, the boiler system further comprises an electric control device, and the electric control device can be electrically connected with the induced draft fan 42, the material conveyor 23 and the grinding mill 5 so as to realize the automation and continuous operation of the whole boiler system. The boiler system also comprises a desulfurizing tower 6 and a chimney 7, so that flue gas generated by combustion is discharged after being desulfurized.
The second aspect of the present invention also provides a method for removing sulfur trioxide and mercury by using modified fly ash, which adopts the above coal burning system and comprises the following steps:
s1, obtaining part of fly ash in the dust collector 2;
specifically, the bottom of the dust collector 2 is connected with an ash hopper 22 and a material conveyor 23, and the fly ash obtained from the dust collector 2 is conveyed through the ash hopper 22 and the material conveyor 23 in sequence. Alternatively, the material conveyor 23 includes a screw feeder and a variable frequency feeder, so that the fly ash in the hopper 22 is continuously conveyed conveniently and quickly.
Further, the obtained fly ash is fly ash in an electric field 21 of the dust collector 2. Generally, the dust collector 2 has four electric fields, the fly ash in the flue gas gradually becomes smaller in particle size along the directions of the electric fields 21 to four, and the fly ash with larger particle size is best ground, i.e. is most easily damaged to generate a fresh surface.
S2, modifying the fly ash by using ammonia-containing halide;
the fly ash modified by the ammonia halide can react with sulfur trioxide in the flue gas, and simultaneously, the halogen on the surface of the fly ash can also react with mercury in the flue gas to generate mercury halide, so that the coal-fired system can adsorb and remove the sulfur trioxide in the flue gas and can also adsorb and remove the mercury in the flue gas, the control cost of pollutants is reduced, and the convenience of emission control of various pollutants is improved. The detailed adsorption removal mechanism is described above.
S21, mixing the fly ash and the ammonia-containing halide, and grinding;
after the fly ash modified by the ammonia-containing halide is ground (particularly by a grinding machine 5), the specific surface area of the fly ash is increased, so that the contact area and probability of sulfur trioxide and the ammonia-containing halide (such as ammonium bromide) on the surface of the fly ash are larger, and the ammonium sulfate and the ammonium bisulfate generated by the reaction are more easily adhered to the surface of the fly ash, thereby being beneficial to the adsorption and removal of the sulfur trioxide; in addition, the fresh surface generated by grinding the fly ash has higher surface energy, and can further adsorb mercury in the flue gas, thereby reducing the content of sulfur trioxide and mercury in the flue gas.
S3, spraying the modified fly ash between the denitration device 3 and the air preheater 4;
the fly ash obtained from the dust collector 2 is modified by the ammonia halide and then is ejected from the ejection pipe 11. The injection duct 11 is inserted into the boiler from the wall of the boiler 1, the injection duct 11 comprises a plurality of nozzles arranged uniformly, and the injection range of the plurality of nozzles can be larger than the cross-sectional area of the furnace to improve the contact probability of the injected fly ash and the flue gas.
S31, using the air heated by the air preheater 4 as the carrier gas for conveying the modified fly ash;
the fly ash after grinding is conveyed by adopting high-temperature air as a carrier, so that the ground fly ash has a certain temperature (usually 50-80 ℃) when entering a hearth, the temperature difference of the fly ash and coal can be reduced, and the uniform mixing of the fly ash and the coal and the heat energy loss of combustion are further ensured.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A coal-fired system for removing sulfur trioxide and mercury by using modified fly ash is characterized by sequentially comprising a boiler (1), a denitration device (3), an air preheater (4) and a dust remover (2) along the flow direction of flue gas, wherein a jet pipeline (11) is arranged between the denitration device (3) and the air preheater (4);
the spraying pipeline (11) is connected with the dust remover (2), and the fly ash obtained from the dust remover (2) is sprayed out from the spraying pipeline (11) after being modified by ammonia-containing halide.
2. The coal burning system of claim 1, wherein the ammonia-containing halide comprises ammonium chloride and/or ammonium bromide.
3. The coal burning system according to claim 1, wherein the ratio of the ammonia-containing halide to the fly ash taken from the dust separator (2) is (0.001-0.3): 1.
4. the coal burning system according to claim 1, wherein a grinding mill (5) is provided between the injection duct (11) and the dust separator (2), the grinding mill (5) being adapted to grind fly ash taken from the dust separator (2).
5. The coal burning system according to claim 4, wherein an air inlet pipe (41) and an induced draft fan (42) are arranged between the air preheater (4) and the grinding mill (5);
air enters from the air inlet pipeline (41), is heated by the air preheater (4), and is driven by the induced draft fan (42) to enter the grinding machine (5).
6. The coal burning system according to claim 4, wherein an ash hopper (22) and a material conveyor (23) are provided between the mill (5) and the dust collector (2), and fly ash taken from the dust collector (2) is fed into the mill (5) through the ash hopper (22) and the material conveyor (23) in this order.
7. The coal burning system according to any one of claims 1 to 6, wherein the injection pipe (11) is connected to an electric field (21) of the dust separator (2).
8. A process for the removal of sulfur trioxide and mercury from modified fly ash, characterized in that a coal combustion system according to any one of claims 1 to 7 is used and comprises the following steps:
obtaining part of fly ash in the dust remover (2);
modifying the fly ash with an ammonia-containing halide;
and spraying the modified fly ash between the denitration device (3) and the air preheater (4).
9. The method of claim 8, wherein said step of modifying said fly ash with an ammoniacal halide further comprises:
the fly ash and the ammonia-containing halide are mixed and subjected to a grinding treatment.
10. The method of claim 8, wherein the step of injecting the modified fly ash between the denitrator (3) and the air preheater (4) further comprises:
and the air heated by the air preheater (4) is used as a carrier gas for conveying the modified fly ash.
CN201911255817.2A 2019-12-10 2019-12-10 Coal-fired system and method for removing sulfur trioxide and mercury by using modified fly ash Pending CN110975590A (en)

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