CN106669413A - Denitration system and denitration method for smoke of particle material industrial boiler - Google Patents
Denitration system and denitration method for smoke of particle material industrial boiler Download PDFInfo
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- CN106669413A CN106669413A CN201611220490.1A CN201611220490A CN106669413A CN 106669413 A CN106669413 A CN 106669413A CN 201611220490 A CN201611220490 A CN 201611220490A CN 106669413 A CN106669413 A CN 106669413A
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- 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
- B01D53/8631—Processes characterised by a specific device
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- 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
- B01D53/90—Injecting reactants
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2063—Lanthanum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
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- B01D2255/20723—Vanadium
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- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20776—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
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- 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
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Abstract
The invention discloses a denitration system and a denitration method for smoke of a particle material industrial boiler. The denitration system comprises a particle material industrial boiler, a cyclone separation apparatus, a denitration apparatus, an air pre-heater, a desulphurization apparatus and a chimney, wherein a hearth side wall of the particle material industrial boiler is provided with a reducing agent nozzle, and the reducing agent nozzle is suitable for spraying a reducing agent into a hearth; the cyclone separation apparatus is connected with a smoke outlet of the particle material industrial boiler, and the cyclone separation apparatus is suitable for performing the dust collection treatment for the smoke; a denitration catalyst is arranged in the denitration apparatus, the denitration apparatus is connected with the cyclone separation apparatus, and the denitration apparatus is suitable for the denitration treatment for the smoke; the air pre-heater is connected with the denitration apparatus, and the air pre-heater is suitable for utilizing the smoke waste heat to pre-heat the oxygen-containing gas; the desulphurization apparatus is connected with the air pre-heater, and the desulphurization apparatus is suitable for removing sulfur oxides in the smoke; and the chimney is connected with the desulphurization apparatus. By utilizing the denitration system, the denitration reaction can be carried out without the dust removal, the operation is simple, and the denitration efficiency is high.
Description
Technical field
The invention belongs to denitrating flue gas field, specifically, the present invention relates to granule materials Industrial Boiler denitrating flue gas system
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 granule materials Industrial Boiler flue gas denitrification system and method for denitration, using the denitrating system and denitration
Method flue gas can carry out denitration reaction without the need for dedusting, simple to operate, and denitration efficiency is high.
According to an aspect of the present invention, the present invention proposes granule materials Industrial Boiler flue gas denitrification system, including：
Granule materials Industrial Boiler, is provided with reductant nozzle, institute on the burner hearth sidewall of the granule materials Industrial Boiler
State reductant nozzle to be suitable to spray into reducing agent into the burner hearth, make the reducing agent with granule materials Industrial Boiler flue gas in institute
State and mix in burner hearth and carry out pre- denitration process；
Cyclone separator, the cyclone separator is connected with the exhanst gas outlet of the granule materials Industrial Boiler, institute
State cyclone separator to be suitable to carry out dust removal process to flue gas；
There is denitrating catalyst, the denitrification apparatus and the cyclone separator in denitrification apparatus, the denitrification apparatus
It is connected, the denitrification apparatus are suitable to carry out denitration process to flue gas；
Air preheater, the air preheater is connected with the denitrification apparatus, and the air preheater is suitable to using fume afterheat to oxygen-containing
Gas is preheated；
Desulfurizer, the desulfurizer is connected with the air preheater, and the desulfurizer is suitable to remove the sulfur in flue gas
Oxide；And
Chimney, the chimney is connected with the desulfurizer.
Thus, using the granule materials Industrial Boiler flue gas denitrification system of above-described embodiment, reductant nozzle is arranged on
On burner hearth sidewall, and then flue gas is mixed with reducing agent in burner hearth carry out pre- denitration process, the cigarette after pre- denitration process
Gas carries out again reduction reaction in denitrification apparatus and carries out denitration process through dust removal process, and last Mist heat recovering is simultaneously carried 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.
In addition, granule materials Industrial Boiler flue gas denitrification system according to the above embodiment of the present invention can also have it is as follows
Additional technical characteristic：
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 denitrating catalyst is spherical, strip or honeycomb ceramics shape.
In some embodiments of the invention, the through hole on the denitrating catalyst 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 denitrating catalyst is more than 500.
In some embodiments of the invention, the combustion adjuvant entrance phase of the air preheater and the granule materials Industrial Boiler
Even, to be suitable to be passed through the oxygen-containing gas after preheating as combustion adjuvant in granule materials Industrial Boiler.
According to the second aspect of the invention, the invention allows for using the granule materials industry pot described in preceding embodiment
The method that kiln gas denitrating system processes granule materials Industrial Boiler flue gas, including：
Reducing agent is sprayed into into the burner hearth of granule materials Industrial Boiler by reductant nozzle, the reducing agent and granule is made
Material Industrial Boiler flue gas mixes and carries out pre- denitration process in the burner hearth；
The mixed flue gas discharged from granule materials Industrial Boiler are made to enter cyclone separator, to enter to mixed flue gas
Row dust removal process；
The mixed flue gas through the dust removal process are made to enter denitrification apparatus, to make to mix in the presence of denitrating catalyst
Close flue gas and reduction reaction removing nitrogen oxides occur；
The flue gas for making removing nitrogen oxides enters air preheater, to preheat oxygen-containing gas using fume afterheat；
Make to carry out desulfurization process into desulfurizer by the flue gas of the air preheater, to be purified rear flue gas；
Flue gas after the purification is discharged by chimney.
Thus, using the granule materials Industrial Boiler denitration method for flue gas of above-described embodiment, reductant nozzle is arranged on
On burner hearth sidewall, and then flue gas is mixed with reducing agent in burner hearth carry out pre- denitration process, the cigarette after pre- denitration process
Gas carries out again reduction reaction in denitrification apparatus and carries out denitration process through dust removal process, and last Mist heat recovering is simultaneously carried 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.
In addition, granule materials Industrial Boiler denitration method for flue gas according to the above embodiment of the present invention can also have it is as follows
Additional technical characteristic：
In some embodiments of the invention, the method for denitration of above-described embodiment further includes, will be using described empty pre-
The hot oxygen-containing gas that device preheating is obtained is used for granule materials Industrial Boiler as combustion adjuvant, and the temperature of the hot oxygen-containing gas is
200-400 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 denitrating catalyst is with TiO2-Al2O3Composite oxides are carrier, with work
Property charcoal be main active, with V2O5-WO3Composite oxides are Supplementary active ingredients, with transition metal iron, rare-earth elements of lanthanum
As auxiliary agent, using enamel as additive；
Wherein, based on the denitrating catalyst oeverall quality, the TiO2-Al2O3Composite oxide supported amount is 10~60
Quality %, the load capacity of the activated carbon is 10~50 mass %, the V2O5-WO3The load capacity of composite oxides is 5~20
Quality %, the transition metal iron load capacity is 0.1~10 mass %, the rare-earth elements of lanthanum load capacity is 0.1~10 matter
Amount %, the load capacity of the enamel is 1~10 mass %.
In some embodiments of the invention, the denitrating catalyst is prepared through the following steps：
(1) titanium source reagent and silicon source reagent are configured to into respectively titanium source aqueous solution and silicon source solution, and by the titanium source water
Solution and source of aluminium solution are co-precipitated, to prepare the precipitation mixture of titanium hydroxide and aluminium hydroxide；
(2) precipitation mixture is carried out into the first drying and the first roasting, to obtain TiO2-Al2O3Composite oxides
Support powder；
(3) by the TiO2-Al2O3Composite oxide carrier powder is carried out with active carbon powder, enamel powder and binding agent
Extrusion molding, sizing and drying, to obtain activated carbon/TiO2-Al2O3Composite catalyst；
(4) ammonium metatungstate, ammonium metavanadate are dissolved in oxalic acid, to obtain the first impregnation liquid；
(5) by the activated carbon/TiO2-Al2O3Composite catalyst carries out the first dipping in first impregnation liquid, complete
The second drying and the second roasting are carried out into after the dipping, to obtain V2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyzing
Agent；
(6) iron chloride, lanthanum chloride are configured to into mixed aqueous solution, to obtain the second impregnation liquid；And
(7) by the V2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyst carries out second in second impregnation liquid
Dipping, completes to carry out the 3rd drying and the 3rd roasting after second dipping, to obtain denitrating catalyst.
Description of the drawings
Fig. 1 is the structural representation of granule materials Industrial Boiler flue gas denitrification system according to an embodiment of the invention.
Fig. 2 is the flow chart of granule materials 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 granule materials Industrial Boiler flue gas denitrification system, joins below
The granule materials Industrial Boiler flue gas denitrification system that Fig. 1 describes the embodiment of the present invention is examined, including：Granule materials Industrial Boiler 100,
Cyclone separator 200, denitrification apparatus 300, air preheater 400, desulfurizer 500 and chimney 600.
Wherein, reductant nozzle 110, the reducing agent spray are provided with the burner hearth sidewall of granule materials Industrial Boiler 100
Mouth 110 is suitable to spray into reducing agent into the burner hearth, makes the reducing agent with granule materials Industrial Boiler flue gas in the burner hearth
Interior mixing simultaneously carries out pre- denitration process；The exhanst gas outlet phase of cyclone separator 200 and the granule materials Industrial Boiler 100
Even, the cyclone separator 200 is suitable to carry out dust removal process to flue gas；There is denitrating catalyst in denitrification apparatus 300, it is described
Denitrification apparatus 300 are connected with the cyclone separator 200, and the denitrification apparatus are suitable to carry out denitration process to flue gas；It is empty pre-
Device 400 is connected with the denitrification apparatus 300, and the air preheater 400 is suitable to preheat oxygen-containing gas using fume afterheat；It is de-
Sulfur device 500 is connected with the air preheater 400, and the desulfurizer 500 is suitable to remove the oxysulfide in flue gas；And chimney
600 are connected with the desulfurizer 500.
Thus, using the granule materials Industrial Boiler flue gas denitrification system of above-described embodiment, reductant nozzle is arranged on
On burner hearth sidewall, and then flue gas is mixed with reducing agent in burner hearth carry out pre- denitration process, the cigarette after pre- denitration process
Gas carries out again reduction reaction in denitrification apparatus and carries out denitration process through dust removal process, and last Mist heat recovering is simultaneously carried 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 granule materials Industrial Boiler flue gas denitrification system of the specific embodiment of the invention is described below in detail.
Granule materials Industrial Boiler 100
Embodiments in accordance with the present invention, on the burner hearth sidewall of granule materials Industrial Boiler 100 reductant nozzle is provided with
110, reductant nozzle 110 is suitable to spray into reducing agent into burner hearth 120, makes reducing agent with granule materials Industrial Boiler flue gas in stove
Mix and carry out pre- denitration process in thorax.Thus, sprayed into into the burner hearth of granule materials Industrial Boiler also by reductant nozzle
Former agent, makes reducing agent mix and carry out pre- denitration process in burner hearth with granule materials Industrial Boiler flue gas.
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.Make reducing agent with granule materials Industrial Boiler flue gas in burner hearth
Mix and carry out pre- denitration process, so as to improve overall denitration efficiency.
Cyclone separator 200
The exhanst gas outlet 120 of embodiments in accordance with the present invention, cyclone separator 200 and granule materials Industrial Boiler 100
It is connected, cyclone separator 200 is suitable to carry out dust removal process to flue gas.Thus, make what is discharged from granule materials Industrial Boiler
Mixed flue gas enter cyclone separator, to carry out dust removal process to mixed flue gas.
Embodiments in accordance with the present invention, granule materials Industrial Boiler it is raw materials used can for anthracite, jet coal, bituminous coal,
One or more of brown coal etc., Task-size Controlling is between 50~500 μm.Therefore, burn in granule materials and produce the same of high-temperature flue gas
When can produce with substantial amounts of dust, and with flue gas discharge.By being carried out to flue gas using cyclone separator 200 in advance
Dust removal process, can further improve the denitration process efficiency of follow-up denitrification apparatus.
Denitrification apparatus 300
There is denitrating catalyst, denitrification apparatus 300 and cyclonic separation in embodiments in accordance with the present invention, denitrification apparatus 300
Device 200 is connected and is suitable to carry out denitration process to flue gas.Thus, the mixed flue gas through dust removal process are made to fill into denitration
Put, reduction reaction removing nitrogen oxides occur to make mixed flue gas in the presence of denitrating catalyst.
Embodiments in accordance with the present invention, denitrating catalyst is spherical, strip, cylindrical shape or honeycomb ceramics shape.
Embodiments in accordance with the present invention, the through hole on denitrating catalyst is square, square dimensions be (3-10mm) ×
(3-10mm), the wall thickness of through hole is 0.5-2mm, and the specific surface area of denitrating catalyst is more than 500.
The denitrating catalyst is with TiO2-Al2O3Composite oxides are carrier, with activated carbon as main active, with
V2O5-WO3Composite oxides are Supplementary active ingredients, using transition metal iron, rare-earth elements of lanthanum as auxiliary agent, using enamel as adding
Plus agent；
Wherein, based on the denitrating catalyst oeverall quality, the TiO2-Al2O3Composite oxide supported amount is 10~60
Quality %, the load capacity of the activated carbon is 10~50 mass %, the V2O5-WO3The load capacity of composite oxides is 5~20
Quality %, the transition metal iron load capacity is 0.1~10 mass %, the rare-earth elements of lanthanum load capacity is 0.1~10 matter
Amount %, the load capacity of the enamel is 1~10 mass %.
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 granule materials boiler furnace out, Jing convection current
After tube bank, flue-gas temperature enters denitrification apparatus Jing after cyclone separator rough dusting after being reduced to 300-600 DEG C.In denitration dress
Have in putting 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%.The abundant recovery waste heat of flue gas Jing air preheaters after denitration, subsequently into flue gas desulphurization system, removing
After sulfide in flue gas, externally discharged by chimney.According to a particular embodiment of the invention, flue gas occurs in denitrification apparatus
The temperature of reduction reaction is 300-600 degree Celsius.It is possible thereby to further improve catalytic denitration reaction, removal of nitrogen oxide is improved
Rate.
Air preheater 400
Embodiments in accordance with the present invention, air preheater 400 is connected with denitrification apparatus 300, and air preheater 400 is suitable to utilize more than flue gas
Heat is preheated to oxygen-containing gas.Thus, the flue gas for making removing nitrogen oxides enters air preheater, to be preheated using fume afterheat
Oxygen-containing gas.
Embodiments in accordance with the present invention, air preheater is connected with the combustion adjuvant entrance of granule materials Industrial Boiler, to be suitable to
It is passed through the oxygen-containing gas after preheating as combustion adjuvant in granule materials Industrial Boiler.It is possible thereby to will be preheated using air preheater
The hot oxygen-containing gas for arriving is used for granule materials Industrial Boiler as combustion adjuvant, and the temperature of hot oxygen-containing gas is 200-400 degree Celsius.
Desulfurizer 500 and chimney 600
Embodiments in accordance with the present invention, desulfurizer 500 is connected with air preheater 400, and desulfurizer 500 is suitable to remove flue gas
In oxysulfide；And chimney 600 is connected with desulfurizer 500.Thus, the flue gas after dust removal process is made to enter desulfurization
Device 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 granule materials Industrial Boiler denitration method for flue gas, the method
Carried out using the granule materials Industrial Boiler flue gas denitrification system of preceding embodiment.
Included according to the granule materials Industrial Boiler denitration method for flue gas of the specific embodiment of the invention：By reductant nozzle
Reducing agent is sprayed into into the burner hearth of granule materials Industrial Boiler, makes the reducing agent with granule materials Industrial Boiler flue gas described
Mix and carry out pre- denitration process in burner hearth；The mixed flue gas discharged from granule materials Industrial Boiler are made to fill into cyclonic separation
Put, to carry out dust removal process to mixed flue gas；Make the mixed flue gas through the dust removal process enter denitrification apparatus, so as to
Make mixed flue gas that reduction reaction removing nitrogen oxides occur in the presence of denitrating catalyst；The flue gas for making removing nitrogen oxides is entered
Air preheater, to preheat oxygen-containing gas using fume afterheat；Make to be taken off into desulfurizer by the flue gas of the air preheater
Sulphuring treatment, to be purified rear flue gas；Flue gas after the purification is discharged by chimney.
Thus, using the granule materials Industrial Boiler denitration method for flue gas of above-described embodiment, reductant nozzle is arranged on
On burner hearth sidewall, and then flue gas is mixed with reducing agent in burner hearth carry out pre- denitration process, the cigarette after pre- denitration process
Gas carries out again reduction reaction in denitrification apparatus and carries out denitration process through dust removal process, and last Mist heat recovering is simultaneously carried 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 granule materials 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, by reductant nozzle reduction is sprayed into into the burner hearth of granule materials Industrial Boiler
Agent, makes reducing agent mix and carry out pre- denitration process in burner hearth with granule materials Industrial Boiler flue gas.
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.Make reducing agent with granule materials Industrial Boiler flue gas in burner hearth
Mix and carry out pre- denitration process, 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 granule materials Industrial Boiler fill into cyclonic separation
Put, to carry out dust removal process to mixed flue gas.
Embodiments in accordance with the present invention, granule materials Industrial Boiler it is raw materials used can for anthracite, jet coal, bituminous coal,
One or more of brown coal etc., Task-size Controlling is between 50~500 μm.Therefore, burn in granule materials and produce the same of high-temperature flue gas
When can produce with substantial amounts of dust, and with flue gas discharge.By being removed to flue gas using cyclone separator in advance
Dirt process, can further improve the denitration process efficiency of follow-up denitrification apparatus.
S300：Reduction reaction removes nitrogen oxides
Embodiments in accordance with the present invention, make the mixed flue gas through the dust removal process enter denitrification apparatus, so as to de-
Make mixed flue gas that reduction reaction removing nitrogen oxides occur in the presence of denox catalyst.
Embodiments in accordance with the present invention, denitrating catalyst is spherical, strip, cylindrical shape or honeycomb ceramics shape.
Embodiments in accordance with the present invention, the through hole on denitrating catalyst is square, square dimensions be (3-10mm) ×
(3-10mm), the wall thickness of through hole is 0.5-2mm, and the specific surface area of denitrating catalyst is more than 500.
Embodiments in accordance with the present invention, denitrating catalyst is with TiO2-Al2O3Composite oxides are carrier, based on activated carbon
Active component is wanted, with V2O5-WO3Composite oxides are Supplementary active ingredients, using transition metal iron, rare-earth elements of lanthanum as auxiliary agent,
Using enamel as additive；
Wherein, based on denitrating catalyst oeverall quality, TiO2-Al2O3Composite oxide supported amount is 10~60 mass %,
The load capacity of activated carbon be 10~50 mass %, V2O5-WO3The load capacity of composite oxides be 5~20 mass %, transition metal
Ferrum load capacity is 0.1~10 mass %, rare-earth elements of lanthanum load capacity is 0.1~10 mass %, and the load capacity of enamel is 1~10 matter
Amount %.
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 granule materials boiler furnace out, Jing convection current
After tube bank, flue-gas temperature enters denitrification apparatus Jing after cyclone separator rough dusting after being reduced to 300-600 DEG C.In denitration dress
Have in putting 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%.The abundant recovery waste heat of flue gas Jing air preheaters after denitration, subsequently into flue gas desulphurization system, removing
After sulfide in flue gas, externally discharged by chimney.According to a particular embodiment of the invention, flue gas occurs in denitrification apparatus
The temperature of reduction reaction is 300-500 degree Celsius.It is possible thereby to further improve catalytic denitration reaction, removal of nitrogen oxide is improved
Rate.
Embodiments in accordance with the present invention, denitrating catalyst is prepared through the following steps：
(1) titanium source reagent and silicon source reagent are configured to into respectively titanium source aqueous solution and silicon source solution, and by titanium source aqueous solution
It is co-precipitated with silicon source solution, to prepare the precipitation mixture of titanium hydroxide and aluminium hydroxide；
(2) precipitation mixture is carried out into the first drying and the first roasting, to obtain TiO2-Al2O3Composite oxide carrier
Powder；
(3) by TiO2-Al2O3Composite oxide carrier powder is extruded with active carbon powder, enamel powder and binding agent
Molding, sizing and drying, to obtain activated carbon/TiO2-Al2O3Composite catalyst；
(4) ammonium metatungstate, ammonium metavanadate are dissolved in oxalic acid, to obtain the first impregnation liquid；
(5) by activated carbon/TiO2-Al2O3Composite catalyst carries out the first dipping in the first impregnation liquid, after completing dipping
The second drying and the second roasting are carried out, to obtain V2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyst；
(6) iron chloride, lanthanum chloride are configured to into mixed aqueous solution, to obtain the second impregnation liquid；And
(7) by V2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyst carries out the second dipping in the second impregnation liquid, complete
The 3rd drying and the 3rd roasting are carried out into after the second dipping, to obtain denitrating catalyst.
Embodiments in accordance with the present invention, the preparation method of denitrating catalyst is specifically included：
(1) preparation of carrier
A certain amount of titanium source reagent of sulfuric acid oxygen titanium and silicon source reagent aluminum chloride are taken, appropriate deionized water is dissolved separately in
In, stir, titanium source and silicon source solution are obtained respectively, the ratio of both concentration is 1：(0.01~2).By titanium source solution, silicon source
Solution, ammonia are instilled in the reactor equipped with a small amount of deionized water by way of cocurrent by certain flow rate, are set in the reactor
There is agitating device, it is ensured that solution mix homogeneously, reaction are abundant.Titanium source solution is identical with silicon source solution instillation speed, controls ammonia
Instillation speed, the pH value of reactant liquor is controlled between 9~11, co-precipitation obtains titanium hydroxide and mixes with the precipitation of aluminium hydroxide
Compound.By the precipitate sucking filtration, washing, it is repeated several times, until pH value is to 7 or so.Then 8 are dried under the conditions of 85~115 DEG C
After~15h, 5~8h of roasting, obtains TiO under the conditions of 350~600 DEG C2-Al2O3Composite oxide carrier.
(2) active component load
Active component active carbon powder, enamel powder are mixed homogeneously with the support powder that above-mentioned steps are obtained, addition adds
Plus after agent enamel, binding agent glycerol stir, suppressed or extrusion molding, can be spherical, strip or honeycomb ceramics shape etc..
Then this part shaped under the conditions of 95~115 DEG C, be dried, obtained activated carbon/TiO2-Al2O3Composite catalyst.
Then a certain amount of ammonium metatungstate, ammonium metavanadate reagent are dissolved in appropriate oxalic acid, previous step is obtained
Activated carbon/TiO2-Al2O3Composite catalyst is dipped in isopyknic solution, and the mol ratio of vanadium tungsten is 1 wherein in the solution：
(0.1~5).Dipping temperature is room temperature, 5~8h of dip time, and 8~15h is dried under the conditions of 85~115 DEG C after the completion of dipping
Afterwards, 5~8h of roasting under the conditions of 350~600 DEG C.
(3) auxiliary agent load
By a certain amount of iron chloride (FeCl3·6H2O), lanthanum chloride (LaCl3·7H2O) it is dissolved in appropriate deionized water
In, and catalyst precursor obtained above being dipped in isopyknic solution, dipping temperature is room temperature, dip time 5~
8h, after being dried 8~15h under the conditions of 85~115 DEG C after the completion of dipping, 5~8h of roasting, is made pottery under the conditions of 350~600 DEG C
Porcelain is the denitrating catalyst finished product of additive.
S400：Fume afterheat is utilized
Embodiments in accordance with the present invention, the flue gas for making removing nitrogen oxides enters air preheater, so as to pre- using fume afterheat
Hot oxygen-containing gas.
Embodiments in accordance with the present invention, above-mentioned method of denitration further includes, the heat obtained using air preheater preheating is contained
Carrier of oxygen is used for granule materials Industrial Boiler as combustion adjuvant, and the temperature of hot oxygen-containing gas is 200-400 degree Celsius.Thus it is abundant
The high-temperature flue gas waste heat produced using burning, energy-efficient, energy utilization rate is high.
S500：Desulfurization process
Embodiments in accordance with the present invention, make the flue gas after dust removal process carry out desulfurization process into desulfurizer, with
Just it is purified rear flue gas；Flue gas is discharged by chimney after purifying.
Embodiments in accordance with the present invention, the granule materials Industrial Boiler flue gas denitrification system of the above embodiment of the present invention and de-
Nitre method at least has one of following advantages：
(1) using the denitrating catalyst 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 300-600 DEG C, and into denitrating system denitration is carried out
After process, then abundant recovery waste heat is externally discharged Jing after desulfurization by chimney, reduces exhaust gas temperature, is reduced smoke evacuation and is damaged
Lose, reduce nitrogen oxide emission, energy-efficient, environmental protection.
(3) burning is participated in after air/oxygen-enriched air is heated to 200~400 DEG C by air preheater, makes full use of burning to produce
Raw high-temperature flue gas waste heat, 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
The anthracite for being crushed to below 6mm is entered in boiler furnace by charging gear, with by aerator burner hearth is sent into
Burnt after interior air mixing, temperature is up to 1250 DEG C in burner hearth.The atomization reductant nozzle for being arranged at burner hearth sprays urine
Plain droplet, in the presence of high temperature in burner hearth, carbamide fast decoupled goes out ammonia, the nitrogen oxidation in the high-temperature flue gas that ammonia is produced with burning
There is reduction reaction, the configured convection bank in burner hearth smoke outlet of high-temperature flue gas of partial removal nitrogen oxides, temperature in thing
Degree is reduced to less than 350 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%.
The abundant recovery waste heat of flue gas Jing air preheaters after denitration, subsequently into flue gas desulphurization system, after removing the sulfide in flue gas, leads to
Cross chimney externally to discharge.
The air for sending into burner hearth above by aerator sends into burner hearth and raw material after air preheater is preheated to 200-400 DEG C
Burnt after coal mixing, efficiency of combustion can be effectively improved, saved raw material dosage, cut operating costs.
The concrete proportioning of the denitrating catalyst is as follows：On the basis of catalyst total quality, wherein TiO2-Al2O3Composite oxygen
The mass loading amount of compound carrier is 48%, and the mass loading amount of activated carbon is 27%, V2O5-WO3Composite oxides active component
Mass loading amount be 15%, auxiliary agent ferrum, the mass loading amount of lanthanum auxiliary agent are respectively 1%, 4%, and the quality of additive enamel is born
Carrying capacity is 5%.
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 granule materials Industrial Boiler flue gas denitrification system, it is characterised in that include：
Granule materials Industrial Boiler, is provided with reductant nozzle on the burner hearth sidewall of the granule materials Industrial Boiler, described to go back
Former agent nozzle is suitable to spray into reducing agent into the burner hearth, makes the reducing agent with granule materials Industrial Boiler flue gas in the stove
Mix and carry out pre- denitration process in thorax；
Cyclone separator, the cyclone separator is connected with the exhanst gas outlet of the granule materials Industrial Boiler, the rotation
Wind segregation apparatuss are suitable to carry out dust removal process to flue gas；
There is denitrating catalyst, the denitrification apparatus are connected with the cyclone separator in denitrification apparatus, the denitrification apparatus,
The denitrification apparatus are suitable to carry out denitration process to flue gas；
Air preheater, the air preheater is connected with the denitrification apparatus, and the air preheater is suitable to using fume afterheat to oxygen-containing gas
Preheated；
Desulfurizer, the desulfurizer is connected with the air preheater, and the desulfurizer is suitable to remove the sulfur oxidation in flue gas
Thing；And
Chimney, the chimney is connected with the desulfurizer.
2. granule materials Industrial Boiler flue gas denitrification system according to claim 1, it is characterised in that the reducing agent spray
Mouth is atomizer,
Optionally, the atomizer is ammonia atomization nozzle or carbamide atomizer.
3. granule materials Industrial Boiler flue gas denitrification system according to claim 1, it is characterised in that the denitration catalyst
Agent is spherical, strip or honeycomb ceramics shape.
4. granule materials Industrial Boiler flue gas denitrification system according to claim 3, it is characterised in that the denitration catalyst
Through hole in agent 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 denitrating catalyst is more than 500.
5. granule materials Industrial Boiler flue gas denitrification system according to claim 1, it is characterised in that the air preheater with
The combustion adjuvant entrance of the granule materials Industrial Boiler is connected, to be suitable to be passed through the oxygen-containing gas after preheating as combustion adjuvant
In granule materials Industrial Boiler.
6. the granule materials Industrial Boiler flue gas denitrification system described in a kind of any one of utilization claim 1-5 processes granule materials
The method of Industrial Boiler flue gas, including：
Reducing agent is sprayed into into the burner hearth of granule materials Industrial Boiler by reductant nozzle, the reducing agent and granule materials are made
Industrial Boiler flue gas mixes and carries out pre- denitration process in the burner hearth；
The mixed flue gas discharged from granule materials Industrial Boiler are made to enter cyclone separator, to remove to mixed flue gas
Dirt process；
The mixed flue gas through the dust removal process are made to enter denitrification apparatus, to make mixing cigarette in the presence of denitrating catalyst
There are reduction reaction removing nitrogen oxides in gas；
The flue gas for making removing nitrogen oxides enters air preheater, to preheat oxygen-containing gas using fume afterheat；
Make to carry out desulfurization process into desulfurizer by the flue gas of the air preheater, 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：
The hot oxygen-containing gas obtained by the use of air preheater preheating is used for into granule materials Industrial Boiler, the heat as combustion adjuvant
The temperature of oxygen-containing gas is 200-400 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 denitrating catalyst is with TiO2-Al2O3Composite oxides
For carrier, with activated carbon as main active, with V2O5-WO3Composite oxides are Supplementary active ingredients, with transition metal iron,
Rare-earth elements of lanthanum as auxiliary agent, using enamel as additive；
Wherein, based on the denitrating catalyst oeverall quality, the TiO2-Al2O3Composite oxide supported amount is 10~60 matter
Amount %, the load capacity of the activated carbon is 10~50 mass %, the V2O5-WO3The load capacity of composite oxides is 5~20 matter
Amount %, the transition metal iron load capacity is 0.1~10 mass %, the rare-earth elements of lanthanum load capacity is 0.1~10 mass %,
The load capacity of the enamel is 1~10 mass %.
10. method according to claim 9, it is characterised in that the denitrating catalyst is prepared through the following steps：
(1) titanium source reagent and silicon source reagent are configured to into respectively titanium source aqueous solution and silicon source solution, and by the titanium source aqueous solution
It is co-precipitated with source of aluminium solution, to prepare the precipitation mixture of titanium hydroxide and aluminium hydroxide；
(2) precipitation mixture is carried out into the first drying and the first roasting, to obtain TiO2-Al2O3Composite oxide carrier
Powder；
(3) by the TiO2-Al2O3Composite oxide carrier powder is extruded with active carbon powder, enamel powder and binding agent
Molding, sizing and drying, to obtain activated carbon/TiO2-Al2O3Composite catalyst；
(4) ammonium metatungstate, ammonium metavanadate are dissolved in oxalic acid, to obtain the first impregnation liquid；
(5) by the activated carbon/TiO2-Al2O3Composite catalyst carries out the first dipping in first impregnation liquid, completes institute
State and carry out the second drying and the second roasting after dipping, to obtain V2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyst；
(6) iron chloride, lanthanum chloride are configured to into mixed aqueous solution, to obtain the second impregnation liquid；And
(7) by the V2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyst carries out the second leaching in second impregnation liquid
Stain, completes to carry out the 3rd drying and the 3rd roasting after second dipping, to obtain denitrating catalyst.
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| CN113828148A (en) * | 2020-06-23 | 2021-12-24 | 中冶长天国际工程有限责任公司 | Flue gas treatment system and flue gas treatment method for efficiently utilizing carbon monoxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113828148A (en) * | 2020-06-23 | 2021-12-24 | 中冶长天国际工程有限责任公司 | Flue gas treatment system and flue gas treatment method for efficiently utilizing carbon monoxide |
| CN113828148B (en) * | 2020-06-23 | 2023-06-27 | 中冶长天国际工程有限责任公司 | Flue gas treatment system and flue gas treatment method for efficiently utilizing carbon monoxide |
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