CN106669393A - Denitration system and denitration method for fuel gas of pulverized coal industrial boiler - Google Patents

Denitration system and denitration method for fuel gas of pulverized coal industrial boiler Download PDF

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Publication number
CN106669393A
CN106669393A CN201611221469.3A CN201611221469A CN106669393A CN 106669393 A CN106669393 A CN 106669393A CN 201611221469 A CN201611221469 A CN 201611221469A CN 106669393 A CN106669393 A CN 106669393A
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China
Prior art keywords
denitration
flue gas
industrial boiler
fine coal
heat storage
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CN201611221469.3A
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Chinese (zh)
Inventor
吴道洪
王志军
郭科宏
石为华
宋敏洁
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Beijing Shenwu Environmental and Energy Technology Co Ltd
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Beijing Shenwu Environmental and Energy Technology Co Ltd
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Priority to CN201611221469.3A priority Critical patent/CN106669393A/en
Publication of CN106669393A publication Critical patent/CN106669393A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
    • B01D45/12—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/006—Layout of treatment plant
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
    • F23J15/022—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow
    • F23J15/027—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow using cyclone separators
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
    • F23J15/04—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material using washing fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention discloses a denitration system and a denitration method for fuel gas of a pulverized coal industrial boiler. The denitration system comprises the pulverized coal industrial boiler, a cyclone separation device, a denitration heat accumulator, a desulfurization device and a chimney, wherein a reducing agent nozzle is formed in the side wall of a combustion chamber of the pulverized coal industrial boiler; the reducing agent nozzle is suitable for spraying a reducing agent into the combustion chamber, mixing the reducing agent and the flue gas of the pulverized coal industrial boiler in the combustion chamber and carrying out pre-denitration treatment; the cyclone separation device is connected with a flue gas outlet of the pulverized coal industrial boiler; the denitration heat accumulator is connected with the cyclone separation device; the denitration heat accumulator is suitable for recycling waste heat of the flue gas and carrying out denitration treatment of the flue gas; the desulfurization device is connected with the denitration heat accumulator; the chimney is connected with the desulfurization device. By utilizing the denitration system disclosed by the invention, the denitration treatment can be effectively carried out on the flue gas of the pulverized coal industrial boiler, and the denitration efficiency is remarkable.

Description

Fine coal Industrial Boiler flue gas denitrification system and method for denitration
Technical field
The invention belongs to denitrating flue gas field, specifically, the present invention relates to fine coal Industrial Boiler flue gas denitrification system and Method of denitration.
Background technology
With developing rapidly for China's economy, the Fossil fuel equal energy source such as natural gas, oil and coal obtains more extensive Using so that environmental problem is increasingly serious, therefore causes series of environmental problems, such as acid rain, depletion of the ozone layer, greenhouse effect Deng so that our living environment is further severe.Energy resource structure of the China based on coal determine China nitrogen oxides and Sulfur oxide emission is constantly in high situation, the discharge of a large amount of pollution gas so that environmental problem is increasingly tight It is high, the productive life of our people is not only had a strong impact on, and it is unfavorable for the sustainable development of China's economy.Therefore, environment is asked Topic has obtained national increasing concern.
The NO of mankind's activity dischargeXMore than 90% from fuel combustion process.It is various industrial furnaces, Civil energy-saving cooking stove, motor-driven During high temp. combustion of fuel in car and other internal combustion engines, the nitrogen substance oxidation in fuel generates NOX, participate in burning air or N in oxygen-enriched air2And O2Also NO can be generatedX.From the point of view of energy resource structure, in the primary energy of China and power generation energy resource composition, coal Occupy absolute leading position.And the coal of China more than 80% is directly burning, particularly for power station, Industrial Boiler And in civil boiler.Therefore, in considerably long period, the NO in flue gasXDischarge is to cause China air NOXOne master of pollution Factor is wanted, the NO of fixed source emission how is reducedXIt is an important topic of atmospheric environment improvement.
Denitrating flue gas belong to burning post-processing technology, and the smoke evacuation system of many developed countries all needs to install denitrating flue gas dress Put.Denitration method for flue gas is more, but obtains the only selective catalytic reduction of a large amount of commercial Applications at present and selectivity is non-urges Change reducing process, additive method is at present experimentation stage or pilot scale stage.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.For this purpose, the present invention One purpose is to propose fine coal Industrial Boiler flue gas denitrification system and method for denitration, using the denitrating system and method for denitration Using the denitration heat storage for having accumulation of heat and denitration function concurrently, surface is smooth, wear-resisting, and simple process is feasible, and flue gas is without the need for dedusting Denitration reaction can be carried out, simple to operate, denitration efficiency is high.
According to an aspect of the present invention, the present invention proposes fine coal Industrial Boiler flue gas denitrification system, including：
Fine coal Industrial Boiler, is provided with reductant nozzle, the reducing agent on the burner hearth sidewall of the fine coal Industrial Boiler Nozzle is suitable to spray into reducing agent into the burner hearth, the reducing agent is mixed in the burner hearth with fine coal Industrial Boiler flue gas And carry out pre- denitration process；
Cyclone separator, the cyclone separator is connected with the exhanst gas outlet of the fine coal Industrial Boiler, the rotation Wind segregation apparatuss are suitable to carry out dust removal process to flue gas；
Denitration heat storage, the denitration heat storage is connected with the cyclone separator, and the denitration heat storage is suitable to back Receive fume afterheat and denitration process are carried out to flue gas；
Desulfurizer, the desulfurizer is connected with the denitration heat storage, and the desulfurizer is suitable to remove in flue gas Oxysulfide；And
Chimney, the chimney is connected with the desulfurizer.
Thus, using the fine coal Industrial Boiler flue gas denitrification system of above-described embodiment, reductant nozzle is arranged on into burner hearth On the wall of side, and then flue gas is mixed with reducing agent in burner hearth carry out pre- denitration process, the flue gas Jing after pre- denitration process Crossing dust removal process and carrying out reduction reaction again in denitration accumulation of heat body carries out denitration process and recovery waste heat, finally carries out at desulfurization Reason.The system carries out pre- denitration process, such that it is able to the nitrogen oxidation in partial removal flue gas using high temperature in burner hearth to flue gas Thing, mitigates the pressure of follow-up out of stock device, reduces the consumption of out of stock catalyst, reduces out-of-stock cost.
In addition, fine coal Industrial Boiler flue gas denitrification system according to the above embodiment of the present invention can also have following adding Technical characteristic：
In some embodiments of the invention, the denitration heat storage is spherical, strip, cylindrical shape or honeycomb ceramics shape.
In some embodiments of the invention, the through hole on the denitration heat storage is square, the square dimensions For (3-10mm) × (3-10mm), the wall thickness of the through hole is 0.5-2mm, and the specific surface area of the denitration heat storage is more than 500.
In some embodiments of the invention, the reductant nozzle is atomizer.
In some embodiments of the invention, the atomizer is ammonia atomization nozzle or carbamide atomizer.
In some embodiments of the invention, the denitration heat storage has fuel gas entrance and the outlet of hot fuel gas, institute State hot fuel gas outlet to be connected with the fuel inlet of the fine coal Industrial Boiler.
According to the second aspect of the invention, the invention allows for using the fine coal Industrial Boiler cigarette described in preceding embodiment The method that gas denitrating system processes fine coal Industrial Boiler flue gas, including：
Reducing agent is sprayed into into the burner hearth of fine coal Industrial Boiler by reductant nozzle, the reducing agent is made with fine coal industry Boiler smoke mixes and carries out pre- denitration process in the burner hearth；
The mixed flue gas discharged from fine coal Industrial Boiler are made to enter cyclone separator, to remove to mixed flue gas Dirt process；
Make through the dust removal process mixed flue gas enter denitration heat storage, so as to denitration heat storage carry out accumulation of heat and There are reduction reaction removing nitrogen oxides in the presence of catalyst；
Make the flue gas of removing nitrogen oxides carries out desulfurization process into desulfurizer, to be purified rear flue gas；
Flue gas after the purification is discharged by chimney.
Thus, using the fine coal Industrial Boiler denitration method for flue gas of above-described embodiment, reductant nozzle is arranged on into burner hearth On the wall of side, and then flue gas is mixed with reducing agent in burner hearth carry out pre- denitration process, the flue gas Jing after pre- denitration process Crossing dust removal process and carrying out reduction reaction again in denitration accumulation of heat body carries out denitration process and recovery waste heat, finally carries out at desulfurization Reason.The system carries out pre- denitration process, such that it is able to the nitrogen oxidation in partial removal flue gas using high temperature in burner hearth to flue gas Thing, mitigates the pressure of follow-up out of stock device, reduces the consumption of out of stock catalyst, reduces out-of-stock cost.
In addition, fine coal Industrial Boiler denitration method for flue gas according to the above embodiment of the present invention can also have following adding Technical characteristic：
In some embodiments of the invention, the method for denitration of above-described embodiment further includes, will be using denitration accumulation of heat Body is preheated to oxygen-containing gas, and is used for fine coal Industrial Boiler using the oxygen-containing gas after preheating as combustion adjuvant, after preheating The temperature of oxygen-containing gas is 250-450 degree Celsius.
In some embodiments of the invention, the temperature that the mixed flue gas occur reduction reaction is 300-500 degree Celsius.
In some embodiments of the invention, the denitration heat storage includes inorganic powder, denitrating catalyst and additive, Wherein, the load capacity of the inorganic powder is 50-100 mass %, and the load capacity of the denitrating catalyst is 5-40 mass %, institute The load capacity for stating additive is 1-10 mass %, and in the additive enamel is contained.
In some embodiments of the invention, the denitration heat storage is prepared through the following steps：
(1) inorganic powder, ceramic powders, enamel, binding agent, plasticising wetting agent, lubricant and water are mixed, are mediated And roasting, to obtain honeycomb heat accumulation body；
(2) TiO is prepared by coprecipitation2-Al2O3Composite oxides, and by the TiO2-Al2O3Combined oxidation Thing is mixed with activated carbon, obtains denitration catalyst carrier solution；
(3) obtain the denitration containing tungsten, vanadium, ferrum, lanthanum and urge using ammonium metatungstate, ammonium metavanadate, iron chloride, lanthanum chloride preparation Agent active component solution；
(4) honeycomb heat accumulation body is carried out in denitration catalyst carrier solution the first impregnation process, drying and roasting；
(5) honeycomb heat accumulation body after step (4) process is carried out into the in the denitrating catalyst active component solution Two dippings, dry and roasting, to obtain the denitration heat storage.
Description of the drawings
Fig. 1 is the structural representation of fine coal Industrial Boiler flue gas denitrification system according to an embodiment of the invention.
Fig. 2 is the flow chart of fine coal Industrial Boiler denitration method for flue gas according to an embodiment of the invention.
Specific embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from start to finish Same or similar label represents same or similar element or the element with same or like function.Below with reference to attached The embodiment of figure description is exemplary, it is intended to for explaining the present invention, and be not considered as limiting the invention.
According to an aspect of the present invention, the present invention proposes fine coal Industrial Boiler flue gas denitrification system, below with reference to Fig. 1 The fine coal Industrial Boiler flue gas denitrification system of the description embodiment of the present invention, including：Fine coal Industrial Boiler 100, cyclone separator 200th, denitration heat storage 300, desulfurizer 400 and chimney 500.
Wherein, reductant nozzle 110 is provided with the burner hearth sidewall of fine coal Industrial Boiler 100, reductant nozzle 110 is suitable to Reducing agent is sprayed into into burner hearth 120, makes reducing agent mix and carry out pre- denitration process in burner hearth with fine coal Industrial Boiler flue gas； Cyclone separator 200 is connected with the exhanst gas outlet 120 of fine coal Industrial Boiler 100, and cyclone separator 200 is suitable to enter flue gas Row dust removal process；Denitration heat storage 300 is connected with cyclone separator 200, the body of denitration accumulation of heat 300 be suitable to Mist heat recovering and Denitration process are carried out to flue gas；Desulfurizer 400 is connected with denitration heat storage 300, and desulfurizer 400 is suitable to remove in flue gas Oxysulfide；And chimney 500 is connected with desulfurizer 400.
Thus, using the fine coal Industrial Boiler flue gas denitrification system of above-described embodiment, reductant nozzle is arranged on into burner hearth On the wall of side, and then flue gas is mixed with reducing agent in burner hearth carry out pre- denitration process, the flue gas Jing after pre- denitration process Crossing dust removal process and carrying out reduction reaction again in denitration accumulation of heat body carries out denitration process and recovery waste heat, finally carries out at desulfurization Reason.The system carries out pre- denitration process, such that it is able to the nitrogen oxidation in partial removal flue gas using high temperature in burner hearth to flue gas Thing, mitigates the pressure of follow-up out of stock device, reduces the consumption of out of stock catalyst, reduces out-of-stock cost.
The fine coal Industrial Boiler flue gas denitrification system of the specific embodiment of the invention is described below in detail.
Fine coal Industrial Boiler 100
Embodiments in accordance with the present invention, are provided with reductant nozzle 110 on the burner hearth sidewall of fine coal Industrial Boiler 100, also Former agent nozzle 110 is suitable to spray into reducing agent into burner hearth 120, reducing agent is mixed simultaneously in burner hearth with fine coal Industrial Boiler flue gas Carry out pre- denitration process.Thus, reducing agent is sprayed into into the burner hearth of fine coal Industrial Boiler by reductant nozzle, make reducing agent with Fine coal Industrial Boiler flue gas mixes and carries out pre- denitration process in burner hearth.
Embodiments in accordance with the present invention, reductant nozzle is arranged on burner hearth, and reducing agent can Quick-gasifying or decomposition after spraying Into gaseous ammonia, and mix with high-temperature flue gas rapidly, and the nitrogen oxides and reducing agent in the presence of high temperature in burner hearth, in flue gas Generation reduction reaction, by the part removal of nitrogen oxide in flue gas, can mitigate the out of stock pressure of follow-up out of stock device, reduce out of stock The consumption of catalyst, reduces operating cost.
According to a particular embodiment of the invention, reductant nozzle is atomizer.Thus effervescent atomization technology is adopted, is used High pressure air or oxygen-enriched air make the moment atomization that reducing agent sprays be little droplet as atomizing medium, and droplet granule can Less than 40 μm are reached, can be good at mixing homogeneously with flue gas.
According to a particular embodiment of the invention, atomizer can be ammonia atomization nozzle or carbamide atomizer.By This sprays into ammonia or carbamide into burner hearth 120 as reducing agent.Reducing agent is set to mix in burner hearth with fine coal Industrial Boiler flue gas And pre- denitration process are carried out, so as to improve overall denitration efficiency.
Cyclone separator 200
Embodiments in accordance with the present invention, cyclone separator 200 is connected with the exhanst gas outlet 120 of fine coal Industrial Boiler 100, Cyclone separator 200 is suitable to carry out dust removal process to flue gas.Thus, enter the mixed flue gas discharged from fine coal Industrial Boiler Enter cyclone separator, to carry out dust removal process to mixed flue gas.
Embodiments in accordance with the present invention, it can be anthracite, jet coal, bituminous coal, brown coal that fine coal Industrial Boiler is raw materials used Deng one or more, Task-size Controlling is between 50~500 μm.Therefore, can be adjoint while pulverized coal friring produces high-temperature flue gas There is substantial amounts of dust to produce, and as flue gas is discharged.By being carried out at dedusting to flue gas using cyclone separator 200 in advance Reason, can further improve the denitration process efficiency of follow-up denitrification apparatus.
Denitration heat storage 300
Embodiments in accordance with the present invention, denitration heat storage 300 be connected with cyclone separator 200 and be suitable to recovered flue gas more than Heat and denitration process are carried out to flue gas.Thus, the mixed flue gas through dust removal process are made to enter denitration heat storage, so as in denitration Make mixed flue gas that reduction reaction removing nitrogen oxides occur in accumulation of heat body in the presence of catalyst.
Embodiments in accordance with the present invention, denitration heat storage is spherical, strip, cylindrical shape or honeycomb ceramics shape.
Embodiments in accordance with the present invention, the through hole on denitration heat storage is square, and the square dimensions are (3- 10mm) × (3-10mm), the wall thickness of the through hole is 0.5-2mm, and the specific surface area of the denitration heat storage is more than 500.
Embodiments in accordance with the present invention, denitration heat storage includes inorganic powder, denitrating catalyst and additive, wherein, institute The load capacity for stating inorganic powder is 50-100 mass %, and the load capacity of the denitrating catalyst is 5-40 mass %, the addition The load capacity of agent is 1-10 mass %, and in the additive enamel is contained.
According to a particular embodiment of the invention, the high-temperature flue gas that burning is produced and the reductant nozzle spray being arranged on burner hearth The reducing agent hybrid concurrency for going out is survived after former reactive moieties removing nitrogen oxides, from fine coal industrial boiler furnace out, Jing convection current After tube bank, flue-gas temperature enters denitration heat storage Jing after cyclone separator rough dusting after being reduced to 300-600 DEG C.In denitration In the presence of denitrating catalyst in accumulation of heat body, there is reduction reaction in the nitrogen oxides in flue gas with ammonia, remove nitrogen oxides, Removal efficiency is up to more than 98%, while flue gas carries out accumulation of heat in denitration accumulation of heat body.Cigarette after denitration enters flue gas desulfurization system System, after removing the sulfide in flue gas, is externally discharged by chimney.According to a particular embodiment of the invention, flue gas stores in denitration The hot temperature that reduction reaction occurs in vivo is 300-500 degree Celsius.It is possible thereby to further improve catalytic denitration reaction, nitrogen is improved Oxide removal rate.
Desulfurizer 400 and chimney 500
Embodiments in accordance with the present invention, desulfurizer 400 is connected with denitration heat storage 300, and desulfurizer 500 is suitable to remove Oxysulfide in flue gas；And chimney 500 is connected with desulfurizer 400.Thus, enter the flue gas after dust removal process Desulfurizer carries out desulfurization process, to be purified rear flue gas, flue gas after purification is discharged by chimney.
According to the second aspect of the invention, the present invention proposes fine coal Industrial Boiler denitration method for flue gas, and the method is utilized The fine coal Industrial Boiler flue gas denitrification system of preceding embodiment is carried out.
Included according to the fine coal Industrial Boiler denitration method for flue gas of the specific embodiment of the invention：By reductant nozzle to powder Reducing agent is sprayed in the burner hearth of coal Industrial Boiler, the reducing agent is mixed simultaneously in the burner hearth with fine coal Industrial Boiler flue gas Carry out pre- denitration process；The mixed flue gas discharged from fine coal Industrial Boiler are made to enter cyclone separator, so as to mixing cigarette Gas carries out dust removal process；The mixed flue gas through the dust removal process are made to enter denitration heat storage, to enter in denitration heat storage Row accumulation of heat and in the presence of catalyst occur reduction reaction removing nitrogen oxides；The flue gas for making removing nitrogen oxides enters desulfurization Device carries out desulfurization process, to be purified rear flue gas；Flue gas after the purification is discharged by chimney.
Thus, using the fine coal Industrial Boiler denitration method for flue gas of above-described embodiment, reductant nozzle is arranged on into burner hearth On the wall of side, and then flue gas is mixed with reducing agent in burner hearth carry out pre- denitration process, the flue gas Jing after pre- denitration process Crossing dust removal process and carrying out reduction reaction again in denitration accumulation of heat body carries out denitration process simultaneously Mist heat recovering, finally carries out Desulfurization process.The system carries out pre- denitration process, such that it is able to the nitrogen in partial removal flue gas using high temperature in burner hearth to flue gas Oxide, mitigates the pressure of follow-up out of stock device, reduces the consumption of out of stock catalyst, reduces out-of-stock cost.
The fine coal Industrial Boiler denitration method for flue gas of the specific embodiment of the invention is described in detail below with reference to Fig. 2.
S100：Pre- denitration process in burner hearth
Embodiments in accordance with the present invention, reducing agent is sprayed into by reductant nozzle into the burner hearth of fine coal Industrial Boiler, is made Reducing agent mixes and carries out pre- denitration process with fine coal Industrial Boiler flue gas in burner hearth.
Embodiments in accordance with the present invention, reductant nozzle is arranged on burner hearth, and reducing agent can Quick-gasifying or decomposition after spraying Into gaseous ammonia, and mix with high-temperature flue gas rapidly, and the nitrogen oxides and reducing agent in the presence of high temperature in burner hearth, in flue gas Generation reduction reaction, by the part removal of nitrogen oxide in flue gas, can mitigate the out of stock pressure of follow-up out of stock device, reduce out of stock The consumption of catalyst, reduces operating cost.
According to a particular embodiment of the invention, reductant nozzle is atomizer.Thus effervescent atomization technology is adopted, is used High pressure air or oxygen-enriched air make the moment atomization that reducing agent sprays be little droplet as atomizing medium, and droplet granule can Less than 40 μm are reached, can be good at mixing homogeneously with flue gas.
According to a particular embodiment of the invention, atomizer can be ammonia atomization nozzle or carbamide atomizer.By This sprays into ammonia or carbamide into burner hearth 120 as reducing agent.Reducing agent is set to mix in burner hearth with fine coal Industrial Boiler flue gas And pre- denitration process are carried out, so as to improve overall denitration efficiency.
S200：Dust removal process
Embodiments in accordance with the present invention, make the mixed flue gas discharged from fine coal Industrial Boiler enter cyclone separator, To carry out dust removal process to mixed flue gas.
Embodiments in accordance with the present invention, it can be anthracite, jet coal, bituminous coal, brown coal that fine coal Industrial Boiler is raw materials used Deng one or more, Task-size Controlling is between 50~500 μm.Therefore, can be adjoint while pulverized coal friring produces high-temperature flue gas There is substantial amounts of dust to produce, and as flue gas is discharged.Dust removal process is carried out to flue gas using cyclone separator by advance, can Further to improve the denitration process efficiency of follow-up denitrification apparatus.
S300：Reduction reaction removes nitrogen oxides
Embodiments in accordance with the present invention, make through the dust removal process mixed flue gas enter denitration heat storage, so as to Denitration heat storage carries out accumulation of heat and reduction reaction removing nitrogen oxides occurs in the presence of catalyst.
Embodiments in accordance with the present invention, denitration heat storage is spherical, strip, cylindrical shape or honeycomb ceramics shape.
Embodiments in accordance with the present invention, the through hole on denitration heat storage is square, and the square dimensions are (3- 10mm) × (3-10mm), the wall thickness of the through hole is 0.5-2mm, and the specific surface area of the denitration heat storage is more than 500.
Embodiments in accordance with the present invention, denitration heat storage includes inorganic powder, denitrating catalyst and additive, wherein, institute The load capacity for stating inorganic powder is 50-100 mass %, and the load capacity of the denitrating catalyst is 5-40 mass %, the addition The load capacity of agent is 1-10 mass %, and in the additive enamel is contained.Denitration heat storage is carried on catalyst on heat storage, It is allowed to have the function of accumulation of heat and denitration concurrently, is acted on by the accumulation of heat of denitration heat storage, be arranged as needed, denitration can be made Catalyst stabilization in accumulation of heat body carries out denitration reaction in the range of optimal temperature, and denitration efficiency is high.
According to a particular embodiment of the invention, the high-temperature flue gas that burning is produced and the reductant nozzle spray being arranged on burner hearth The reducing agent hybrid concurrency for going out is survived after former reactive moieties removing nitrogen oxides, from pulverized coal boiler burner hearth out, Jing convection banks Afterwards, Jing after cyclone separator rough dusting into denitration heat storage after flue-gas temperature is reduced to 300-600 DEG C.In denitration accumulation of heat Have in vivo in the presence of denitrating catalyst, the nitrogen oxides in flue gas occur reduction reaction with ammonia, remove nitrogen oxides, take off Except efficiency is up to more than 98%, while flue gas carries out accumulation of heat in denitration accumulation of heat body.Cigarette after denitration enters flue gas desulphurization system, After sulfide in removing flue gas, externally discharged by chimney.According to a particular embodiment of the invention, flue gas is in denitration heat storage The interior temperature that reduction reaction occurs is 300-500 degree Celsius.It is possible thereby to further improve catalytic denitration reaction, nitrogen oxidation is improved Thing removal efficiency.
Embodiments in accordance with the present invention, denitration heat storage is prepared through the following steps：
(1) inorganic powder, ceramic powders, enamel, binding agent, plasticising wetting agent, lubricant and water are mixed, are mediated And roasting, to obtain honeycomb heat accumulation body；
(2) TiO is prepared by coprecipitation2-Al2O3Composite oxides, and by the TiO2-Al2O3Combined oxidation Thing is mixed with activated carbon, obtains denitration catalyst carrier solution；
(3) obtain the denitration containing tungsten, vanadium, ferrum, lanthanum and urge using ammonium metatungstate, ammonium metavanadate, iron chloride, lanthanum chloride preparation Agent active component solution；
(4) honeycomb heat accumulation body is carried out in denitration catalyst carrier solution the first impregnation process, drying and roasting；
(5) honeycomb heat accumulation body after step (4) process is carried out into the in the denitrating catalyst active component solution Two dippings, dry and roasting, to obtain the denitration heat storage.
According to a particular embodiment of the invention, the preparation method of denitration heat storage is specifically included：
(1) refining of heat storage idiosome
By appropriate inorganic powder, ceramic powders, binding agent, plasticising wetting agent, mix lubricant, and add appropriate going Ionized water carries out kneading refining, obtains pug standby.
Clod is carried out it is old, old ambient temperature be 15~25 DEG C, the old time be 24h~48h, Jing vacuum refinings, Vacuum is extruded into the green honeycomb of required specification.
Again green honeycomb is re-fed in drying machine sizing, is dried, fire under the conditions of 1200 DEG C~1400 DEG C into Product.
(2)TiO2-Al2O3The preparation of composite oxides
A certain amount of titanyl sulfate and aluminum chloride are taken, in being dissolved separately in appropriate deionized water, is stirred, made respectively Titanium source and silicon source solution are obtained, the ratio of both concentration is 1：(0.01~2).By titanium source solution, silicon source solution, ammonia by cocurrent Mode, is instilled in the reactor equipped with a small amount of deionized water by certain flow rate, is provided with agitating device in the reactor, it is ensured that solution Mix homogeneously, reaction are abundant.Titanium source solution is identical with silicon source solution instillation speed, the instillation speed of ammonia is controlled, by reactant liquor PH value control between 9~11, co-precipitation obtains the precipitation mixture of titanium hydroxide and aluminium hydroxide.
Activated carbon is mixed with precipitation mixture obtained above, and adds deionized water to adjust the pH value of mixture, will PH value is controlled 9 or so.
(3) configuration of mixed liquor
A certain amount of ammonium metatungstate, ammonium metavanadate reagent are dissolved in appropriate oxalic acid, the addition of oxalic acid, control is adjusted Between 5~7, the mol ratio of vanadium tungsten is 1 to solution pH value processed in solution：(0.1~5).
By a certain amount of iron chloride (FeCl3), lanthanum chloride (LaCl3) it is dissolved in appropriate deionized water, obtain iron chloride With the mixed solution of lanthanum chloride.The solution is mixed with solution obtained above, the mixed solution of tungstenic, vanadium, ferrum, lanthanum is obtained.
(4) main active component load
Acid-wash activation process is carried out after the honeycomb wares deionized water obtained in step (1) is cleaned, cleaning is drained The precipitation mixture obtained in step (2), 35~60 DEG C of dipping temperature, after 8~15h of dip time, by honeycomb ceramics are impregnated in afterwards Take out and blow off the remnants in its hole, after being then dried 8~15h under the conditions of 85~115 DEG C, under the conditions of 350~750 DEG C Weigh after 5~8h of roasting.It is repeated several times, until weight is not further added by.
(5) Supplementary active compounds and auxiliary agent are loaded
In the solid immersion mixed solution that therewith isopyknic step (3) obtains that step (4) is obtained, dipping temperature 15 ~30 DEG C, after 8~15h of dip time, after being dried 8~15h under the conditions of 85~115 DEG C, the roasting 5 under the conditions of 350~600 DEG C Final product is obtained after~8h.
In the denitration scheme of the present invention, a large amount of dust, Jing whirlwind are contained from fine coal Industrial Boiler high-temperature flue gas out Dust arrester is removed after most of dust, and into denitration heat storage denitration reaction and accumulation of heat are carried out.The denitration that the present invention is adopted stores Through hole on hot body is square, and the square dimensions are (3-10mm) × (3-10mm), and the wall thickness of the through hole is 0.5- 2mm, the specific surface area of the denitration heat storage is more than 500.Due to from fine coal Industrial Boiler high-temperature flue gas out containing big Amount dust, although eliminate most of dust through cyclone dust collector, but also contain a certain amount of dust in flue gas, therefore, The aperture that the denitration accumulation of heat honeycomb ceramics selected herein is used can not be too little.But the present invention uses the denitration storage for being added with enamel Hot body, its surface is smooth, wear-resisting, with good anti-clogging, just can be reached well from the denitration heat storage of above-mentioned size Denitration effect.
S400：Fume afterheat is utilized
Embodiments in accordance with the present invention, make the mixed flue gas through dust removal process enter denitration heat storage, and flue gas is being entered The recovery of fume afterheat is realized while row denitration process.
Embodiments in accordance with the present invention, above-mentioned method of denitration further includes, will be using denitration heat storage to oxygen-containing gas Preheated, and be used for fine coal Industrial Boiler, the temperature of the oxygen-containing gas after preheating using the oxygen-containing gas after preheating as combustion adjuvant Spend for 250-450 degree Celsius.Thus the high-temperature flue gas waste heat for making full use of burning to produce, energy-efficient, energy utilization rate is high.
S500：Desulfurization process
Embodiments in accordance with the present invention, make the flue gas of removing nitrogen oxides carries out desulfurization process into desulfurizer, so as to It is purified rear flue gas；Flue gas is discharged by chimney after purifying.
Embodiments in accordance with the present invention, the fine coal Industrial Boiler flue gas denitrification system of the above embodiment of the present invention and denitration side Method at least has one of following advantages：
(1) using the denitration heat storage containing enamel, catalyst surface is smooth, wear-resisting, and denitrating technique is simple and feasible, operation letter Single, denitration efficiency is high.
(2) flue gas that burning is produced temperature Jing after convection bank is reduced to 300-500 DEG C, is taken off into denitration heat storage After nitre process, then abundant recovery waste heat is externally discharged Jing after desulfurization by chimney, reduces exhaust gas temperature, reduces smoke evacuation Loss, reduces nitrogen oxide emission, energy-efficient, environmental protection.
(3) burning is participated in after air/oxygen-enriched air is heated to 150~300 DEG C by denitration heat storage, combustion is made full use of The high-temperature flue gas waste heat for producing is burnt, energy-efficient, energy utilization rate is high.
(4) reductant nozzle is arranged on into burner hearth, under high temperature action of the reducing agent in burner hearth, the high temperature produced with burning There is reduction reaction in the nitrogen oxides in flue gas, can mitigate follow-up out of stock device with the nitrogen oxides in partial removal flue gas Pressure, reduces the consumption of out of stock catalyst, reduces out-of-stock cost.
Embodiment
Less than 100 μm of jet coal will be crushed to spray in boiler furnace by nozzle, with by aerator burner hearth is sent into Burnt after interior air mixing, temperature is up to more than 1050 DEG C in burner hearth.It is arranged at the atomization reductant nozzle spray of burner hearth Go out carbamide droplet, in the presence of high temperature in burner hearth, carbamide fast decoupled goes out ammonia, the nitrogen in the high-temperature flue gas that ammonia is produced with burning There is reduction reaction, the configured convection tube in burner hearth smoke outlet of high-temperature flue gas of partial removal nitrogen oxides in oxide Beam, flue-gas temperature enters denitration accumulation of heat integral system Jing after cyclone dust collector rough dusting after being reduced to 250-350 DEG C.Temperature Degree is reduced to less than 200 DEG C of flue gas and denitrating system is entered Jing after cyclone dust collector rough dusting.In the work of out of stock catalyst With under, there is reduction reaction in the nitrogen oxides in flue gas, further remove nitrogen oxides with ammonia, and removal efficiency is up to 98%. Simultaneously the heat of flue gas passes to combustion air by denitration heat storage.Subsequently into flue gas desulphurization system, the sulfur in flue gas is removed After compound, externally discharged by chimney.
The air for sending into burner hearth above by aerator sends into burner hearth after denitration heat storage is preheated to 250-450 DEG C Burnt after mixing with fine coal, efficiency of combustion can be effectively improved, saved raw material dosage, cut operating costs.
The concrete proportioning of the denitration heat storage is as follows：On the basis of heat storage total quality, the mass loading of inorganic powder Measure as 60%, the mass loading amount of denitrating catalyst is 25%, the mass loading amount of additive (including enamel) is 15%.Its In, the active component activated carbon of denitrating catalyst accounts for 20%, V of catalyst weight2O5-WO3The 18% of catalyst weight is accounted for, is added Plus agent enamel accounts for the 55% of weight of additive.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show The description of example " or " some examples " etc. means to combine specific features, structure, material or spy that the embodiment or example are described Point is contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be arbitrary Combine in an appropriate manner in individual or multiple embodiments or example.Additionally, in the case of not conflicting, the technology of this area Personnel can be combined the feature of the different embodiments or example described in this specification and different embodiments or example And combination.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned Embodiment is changed, changes, replacing and modification.

Claims (10)

1. a kind of fine coal Industrial Boiler flue gas denitrification system, it is characterised in that include：
Fine coal Industrial Boiler, is provided with reductant nozzle, the reductant nozzle on the burner hearth sidewall of the fine coal Industrial Boiler It is suitable to spray into reducing agent into the burner hearth, the reducing agent is mixed in the burner hearth with fine coal Industrial Boiler flue gas and go forward side by side The pre- denitration process of row；
Cyclone separator, the cyclone separator is connected with the exhanst gas outlet of the fine coal Industrial Boiler, the whirlwind point It is suitable to carry out dust removal process to flue gas from device；
Denitration heat storage, the denitration heat storage is connected with the cyclone separator, and the denitration heat storage is suitable to reclaim cigarette Gas waste heat and denitration process are carried out to flue gas；
Desulfurizer, the desulfurizer is connected with the denitration heat storage, and the desulfurizer is suitable to remove the sulfur in flue gas Oxide；And
Chimney, the chimney is connected with the desulfurizer.
2. fine coal Industrial Boiler flue gas denitrification system according to claim 1, it is characterised in that the denitration heat storage is Spherical, strip, cylindrical shape or honeycomb ceramics shape.
3. fine coal Industrial Boiler flue gas denitrification system according to claim 2, it is characterised in that on the denitration heat storage Through hole it is square, the square dimensions are (3-10mm) × (3-10mm), and the wall thickness of the through hole is 0.5-2mm, institute The specific surface area for stating denitration heat storage is more than 500.
4. fine coal Industrial Boiler flue gas denitrification system according to claim 1, it is characterised in that the reductant nozzle is Atomizer,
Optionally, the atomizer is ammonia atomization nozzle or carbamide atomizer.
5. fine coal Industrial Boiler flue gas denitrification system according to claim 1, it is characterised in that the denitration heat storage tool There are fuel gas entrance and the outlet of hot fuel gas, the hot fuel gas outlet is connected with the fuel inlet of the fine coal Industrial Boiler.
6. the method that the fine coal Industrial Boiler flue gas denitrification system described in a kind of any one of utilization claim 1-5 processes flue gas, Including：
Reducing agent is sprayed into into the burner hearth of fine coal Industrial Boiler by reductant nozzle, the reducing agent and fine coal Industrial Boiler is made Flue gas mixes and carries out pre- denitration process in the burner hearth；
The mixed flue gas discharged from fine coal Industrial Boiler are made to enter cyclone separator, to carry out at dedusting to mixed flue gas Reason；
The mixed flue gas through the dust removal process are made to enter denitration heat storage, to carry out accumulation of heat in denitration heat storage and to urge There are reduction reaction removing nitrogen oxides in the presence of agent；
Make the flue gas of removing nitrogen oxides carries out desulfurization process into desulfurizer, to be purified rear flue gas；
Flue gas after the purification is discharged by chimney.
7. method according to claim 6, it is characterised in that further include, will be using denitration heat storage to oxygenous Body is preheated, and is used for fine coal Industrial Boiler using the oxygen-containing gas after preheating as combustion adjuvant, the oxygen-containing gas after preheating Temperature is 250-450 degree Celsius.
8. method according to claim 6, it is characterised in that it is 300- that the mixed flue gas occur the temperature of reduction reaction 500 degrees Celsius.
9. method according to claim 6, it is characterised in that the denitration heat storage includes inorganic powder, denitration catalyst Agent and additive, wherein, the load capacity of the inorganic powder is 50-100 mass %, and the load capacity of the denitrating catalyst is 5- 40 mass %, the load capacity of the additive is 1-10 mass %, and in the additive enamel is contained.
10. method according to claim 9, it is characterised in that the denitration heat storage is prepared through the following steps：
(1) inorganic powder, ceramic powders, enamel, binding agent, plasticising wetting agent, lubricant and water are mixed, mediated and is roasted Burn, to obtain honeycomb heat accumulation body；
(2) TiO is prepared by coprecipitation2-Al2O3Composite oxides, and by the TiO2-Al2O3Composite oxides with Activated carbon is mixed, and obtains denitration catalyst carrier solution；
(3) using ammonium metatungstate, ammonium metavanadate, iron chloride, lanthanum chloride prepare obtain containing tungsten, vanadium, ferrum, lanthanum denitrating catalyst Active component solution；
(4) honeycomb heat accumulation body is carried out in denitration catalyst carrier solution the first impregnation process, drying and roasting；
(5) honeycomb heat accumulation body after step (4) process is carried out into the second leaching in the denitrating catalyst active component solution Stain, drying and roasting, to obtain the denitration heat storage.
CN201611221469.3A 2016-12-26 2016-12-26 Denitration system and denitration method for fuel gas of pulverized coal industrial boiler Pending CN106669393A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109012107A (en) * 2018-09-10 2018-12-18 索通发展股份有限公司 A kind of prebaked anode for aluminium electrolysis purifying fume from calcining furnace system

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109012107A (en) * 2018-09-10 2018-12-18 索通发展股份有限公司 A kind of prebaked anode for aluminium electrolysis purifying fume from calcining furnace system
CN109012107B (en) * 2018-09-10 2020-12-11 索通发展股份有限公司 Flue gas purification system of pre-baked anode roasting furnace for aluminum electrolysis

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