CN107998856A - A kind of flue gas pollutant joint removal methods based on activity solid absorbent - Google Patents
A kind of flue gas pollutant joint removal methods based on activity solid absorbent Download PDFInfo
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- B01D53/46—Removing components of defined structure
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Abstract
The present invention provides a kind of flue gas pollutant joint removal methods based on activity solid absorbent, comprises the following steps:Oxidant is uniformly blended into boiler tail flue gas so that the NO in flue gas is oxidized to higher nitrogen oxides, and nonvalent mercury is oxidized to high-valence state mercuride, the flue gas after being aoxidized;Flue gas after the oxidation is come into full contact with solid particle, while removes the oxysulfide in flue gas, higher nitrogen oxides, high-valence state mercuride, obtains the ash-laden gas after pollutant removing;The ash-laden gas is obtained into clean flue gas after dedusting, the solid particle of deduster bottom collection is sent into storage bin, fraction solids particle is activated and humidification after, Returning reactor continues to participate in reaction, and redundance is from the discharge of storage bin bottom to maintain material balance.This method uses half dry type absorption process, i.e. calcium-base absorbing agent sprays into reactor with the solid particulate form that is humidified, and water consumption is few, and final product is solid-state, and without handling waste water, technique is simple, can be widely used in industrial smoke processing procedure.
Description
Technical field
The present invention relates to environmental technology field, and in particular to a kind of smoke pollution Internet of Things based on activity solid absorbent
Removal methods are closed, suitable for coal-burned industrial boiler, Industrial Stoves.
Background technology
Environmental protection standard is increasingly stringent at present, but middle-size and small-size Industrial Boiler, Industrial Stoves often have that capacity is small, pollutant
The features such as concentration is high, place is small, pollutant control difficulty is big, causes to administer difficult with transformation.Relative to large-sized station boiler
Low emission, intensive, densification, integrated dedusting, desulphurization and denitration cooperation-removal technology are the development of Industrial Boiler low emission
Direction.
The patent of publication number CN104474857A discloses NO and SO2 in the preposition oxidative absorption coal-fired flue-gas of bioactive molecule
Method and apparatus, the wet method soda liquor absorption technique used using the strong oxidizing property of bioactive molecule ozone, downstream, although desulfurization takes off
Nitre efficiency is higher, but water consumption is big and process for treating waste liquor is complex.
Publication number CN105056749A patents disclose side that is a kind of while removing nitrogen oxides in effluent and oxysulfide
Method, catalysed oxidn of the patent using calcium-based desulfurizing agent to NO, but actual industrial test finds this catalysis oxidation efficiency
Not high, so as to cause denitration rate relatively low, the removal efficiency that NOx is also mentioned in this patent is only more than 65%.Additionally, due to use
The humidification mode of water spray in recirculating fluidized bed tower, easily causes the blocking of reactor inner nozzle, and local material overly moist causes material to glue wall
The problems such as.
Publication number CN200610102077.5 patents disclose a kind of removing sulfur, nitrate and mercury simultaneously from boiler flue gas method and
Device, sprays into oxygen-enriched highly active absorbent simultaneous SO_2 and NO removal demercuration, but removal of nitrogen oxide in circulating fluid bed reactor
It is less efficient, and (digestion) technique is prepared using wet absorption agent, process is relatively complicated.
The content of the invention
To solve the deficiencies in the prior art, the object of the present invention is to provide one kind to be based on activity solid absorbent
Flue gas pollutant joint removal methods, preposition oxidation is carried out to flue gas using the ozone of high oxidation activity, utilizes high activity powder
Coal ash is as absorbent, and absorptivity is high and cost reduction, the method be suitable for the relatively small coal-burned industrial boiler of scale and
Kiln.
The scale of the coal-burned industrial boiler and kiln steams t/h grades of following capacity scales for 200.
Flue gas pollutant joint removal methods provided by the present invention based on activity solid absorbent, including following steps
Suddenly:
1) oxidant being uniformly blended into boiler tail flue gas so that the NO in flue gas is oxidized to higher nitrogen oxides, and zero
Valency mercury oxidation is into high-valence state mercuride, the flue gas after being aoxidized;
2) flue gas after oxidation and solid particle absorbent are come into full contact with the reactor, while removes the sulphur in flue gas
Oxide, higher nitrogen oxides, high-valence state mercuride etc., obtain the ash-laden gas after pollutant removing;
3) ash-laden gas is obtained to clean flue gas after dedusting, the solid particle of deduster bottom collection is sent into storage bin,
Fraction solids particle is activated and humidification after, return to the reactor and continue to participate in reaction, redundance is from storage bin bottom row
Go out to maintain material balance.
In above method step 1), the preferred O of oxidant3, O30.1s is no less than with the time of contact of flue gas, specifically may be used
For 0.5s, O3Molar ratio with the NO in flue gas is 0.8-1.2, and reaction temperature window is 90-200 DEG C.
In above method step 2), the solid particle absorbent be Reactor inlet flue gas in carry fresh coal fly ash and
The recycle stock of the fully active component containing unreacted after activated humidification, the active component are the alkalescence such as CaO, MgO, NaO
Compound, wherein (unified when being related to the dosage of active component below to be converted by CaO), CaO content > 10%- based on CaO
20%.
Carry fresh coal fly ash in the Reactor inlet flue gas, in terms of CaO, with Reactor inlet sulfide in flue gas and
The molar ratio nCaO of nitrogen oxides:(S+0.5N) it is 1-2.5.The detection method recommendation sucrose of flyash base active component-
EDTA titrations.
The solid-gas ratio of the solid particle absorbent and flue gas is controlled in 300-1500g/m3。
The solid particle absorbent and residence time ≮ 1s of the flue gas in reactor.
In step 2), the solid particle is contacted with the flue gas after oxidation under certain temperature and relative humidity, the phase
It is 10-95% to humidity, the temperature of the temperature and nearly adiabatic saturation temperature is away from control at 5-25 DEG C.
Temperature and relative humidity required in reactor are adjusted by process water humidification solid particle or segmentation humidification mode.
The segmentation humidification mode is that part humidification water is sprayed into reactor posterior segment, and control sprays into the humidification in reactor
Water ratio is less than 20%, and (ratio that two sections of humidification waters account for total water spray is less than 20%, and total Water is two sections of humidification+circulating ash
Be humidified water).
Further, when being humidified using segmentation, what is sprayed into reactor is oxidizing agent solution, oxidant NaClO, Ca
(ClO)2、KMnO4/H2O2In one kind, in solution the mass concentration of oxidant for 20-95% (addition of oxidizing agent solution than
Less than 20%).
In step 3), activation process is carried out to solid particle by spraying into appropriate process water or steam.Soak time is not small
In 5 minutes.
Such as activated using process water, according to the addition of the process for controlling content water of active component in solid particle, nCaO:
H2O=1-2 (molar ratio), technique coolant-temperature gage are 70-100 DEG C.
Steam activation is such as used, according to the intake of the content control steam of active component in solid particle, nCaO:H2O
=1-2 (molar ratio), vapor (steam) temperature are 110 DEG C -300 DEG C.
Further, to ensure enough soak times, intermittent activator can be used.
Further, to further improve the activity of absorbent, when carrying out activation process to solid particle, part Ca is added
(OH)2Or CaO, relative to the quality of activating solid particle, addition mass ratio < 10%.
In step 3), the solid particle after activated processing further adds water to be humidified, and fibre selection is passed in and out according to reactor
Water is added, the water content 2-8% of solid particle after humidification.
The utilization rate improved to absorbent is circulated by solid particle material.The endless form can be outer circulation or outer
Circulation+interior circulation.
The outer circulation refers to the material that flue gas is collected after deduster dedusting after the reactor, passes through conveying device
Quantitatively send back to as needed in reactor.
It is described it is interior circulation refer to set Loop Seal in reactor outlet, fraction solids material Returning reactor middle and upper part is again
Participate in reaction.
To obtain that there is the flyash of high-selenium corn activity, it is proposed that boiler oil use high calcium coal (when sulfur content in coal amount for
During 0.5-1%, CaO content > 10%-20% in ash content);Require, can be mixed in coal a certain amount of as fuel is less than for calcium content
CaCO3、Ca(OH)2Or CaO.Or outsourcing high-active flyash is as absorbent.
The above method further includes, and the clean flue gas after the pollutant removing is discharged into air by chimney by air-introduced machine.
Due to taking above technical scheme, it has the following advantages the present invention:
Oxidation and denitration and recirculating fluidized bed desulfurization are coupled by the present invention, have high-specific surface area and height afterwards using activated
The flyash of activity is absorbed as absorbent, realizes desulphurization and denitration, demercuration and dust removal integrated.Due to NO2Presence to sulphur oxygen
The removing of compound has facilitation, and this method is higher than the desulfuration efficiency of regular circulation fluid bed.In addition ozone oxidation converts
Rate height (more than 90%) and long lifespan, it is not high to temperature requirement, it is particularly suitable for handling boiler tail low-temperature flue gas, flue is arranged
It is of less demanding.The desulfurization of this method and denitration efficiency are respectively 90%, more than 80%, dirty in conventional industrial boiler or kiln gas
Contaminate in the range of thing concentration of emission, the discharge of sulfur dioxide and nitrogen oxides can meet or exceed national requirements for environmental protection, and transport
Row and equipment cost are low.
To improve the removal effect of solid absorbent, the method for the present invention has carried out process optimization, has such as been separately provided activator,
Improve the absorption activity of solid particle absorbent;Top sets two level humidification spout in the reactor, and returning charge structure is set in exit
Part makes fraction solids particulate matter reflux to reactor middle and upper part, the assimilation effect of enhanced reactor second half section;Additionally by solid-state
Matter Transfer, improves the concentration of solid active thing in reactor, and Ca/ (S+0.5N) orders of magnitude increase dozens or even hundreds of
The strong absorption probability to SO2 and high-valence state NOx, while improve the utilization rate of absorbent.
To obtain temperature and relative humidity required in reactor, this method is humidified using solid particle or solid particle increases
(ratio of control the latter's humidification water, less than 20%), humidification water forms one layer of water to segmentation humidification in particle surface in wet+reactor
Film, while absorbent high activity is ensured, turn avoid material caused by humidification possibility in mortar gunite method or reactor and glues wall, spray
The negative effect such as mouth or slurries conveying injection apparatus blocking.
This method uses half dry type absorption process, and water consumption is few, and final product is solid-state, and without handling waste water, technique is simple.
It can be widely used in industrial smoke processing procedure.
Brief description of the drawings
Fig. 1 is present invention process flow diagram.
Embodiment
As shown in Figure 1, the technological principle of this method is:
Strong oxidizer is uniformly blended into the flue gas of 90-200 DEG C of temperature of boiler tail, in a short time, oxidant is by cigarette
NO, nonvalent mercury in gas, which are oxidized into, to be more easy to by the higher nitrogen oxides and high-valence state mercuride of alkaline absorbent removing.
Afterwards in reactor, the solid particle after activation humidification comes into full contact with flue gas, the moisture of solid particles surface
Evaporation is so that smoke temperature quickly drops to suitable temperature, in the presence of the water that is humidified, in absorbent neutral and alkali component and flue gas
SO2、SO3, higher nitrogen oxides and other acid gas react and removed, while adsorb high-valence state mercuride.
Being humidified, water is most important to the absorbing reaction in reactor, and reaction process terminates with the disappearance of liquid water.By
Form water membrane on solid material surface in humidification water, disengagement area is big, into reactor after exhausted big portion in solid material
Divide moisture just to be evaporate into reactor front half section in flue gas, to extend the evaporation time of moisture in solid material, use
Segmentation humidification, i.e., back segment sprays into part humidification water in the reactor.To avoid local overly moist from causing material to glue wall, control sprays into anti-
Humidification water ratio in device is answered to be less than 20%.
Loop Seal is set in reactor exit so that fraction solids material Returning reactor middle and upper part participates in instead again
Should.
Ash-laden gas obtains clean flue gas after dedusting, and the solid particle of deduster bottom collection is sent into storage bin, part
Solid particle enters activator through conveying device, it is carried out at activation by spraying into a certain amount of technique atomized water or steam
Reason.Key reaction principle is that the basic anhydride component in solid particle absorbs the high hydrogen-oxygen of activity with water or steam reaction generation
Compound, increases additionally, due to the volumetric capacity of product, changes the microcellular structure of flyash so that the specific surface area of solid particle
Increase.Such as soak time long enough, hydroxide continues that " volcanic ash " reaction generation occurs with the silicoaluminate in flyash
The alumino-silicate of specific surface area and active higher.
Material after activation, which enters in humidification mixer, sprays into a certain amount of technique atomized water humidification, subsequent quilt containing wet stock
Reaction is continued to participate in negative pressure sucting reaction device, unnecessary material is sent into grey storehouse to maintain material balance in storage bin.
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.
Experimental method used in following embodiments is conventional method unless otherwise specified;Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
Example 1
In 120 DEG C of boiler back end ductwork section of temperature, high-concentrated ozone is sprayed into, is uniformly mixed with flue gas, O3/ N molar ratios
0.6, residence time 0.5s;NO and nonvalent mercury in flue gas are oxidized to high-valence state nitrogen oxides and mercuride.
(ash-laden gas obtains clean flue gas to particle containing wet solid after activation after dedusting, and deduster bottom collection is consolidated
Body particle is sent into storage bin, and fraction solids particle enters activator through conveying device, by spraying into a certain amount of technique atomized water
Or steam carries out activation process to it.Material after activation, which enters in humidification mixer, sprays into a certain amount of technique atomized water increasing
It is wet) enter reactor, flue-gas temperature is rapidly decreased to 70 DEG C, and come into full contact with the flue gas after oxidation, with SO therein2、SO3、
Higher nitrogen oxides, which react, generates sulphite, nitrite, sulfate, nitrate etc., while produces suction to mercuride
Attached effect.Flue gas containing high concentrate dust is handled by deduster, and clean flue gas is discharged into air, the solid of deduster bottom collection
Back into carrying out subsequent cycle in reactor after the activated humidifications of the particle overwhelming majority.SO2Removal efficiency is 90%, NO removal efficiencies
80%.
Example 2
Other steps are identical with example 1, and difference is to change solid particle humidification into two sections of humidification (containing after activation
Wet solid particle enters reactor, and flue-gas temperature is first quickly down to 80 DEG C, and portion's suitable position sprays into a small amount of work in the reactor
Skill atomized water carries out two level humidification, and smoke temperature is further reduced to 70 DEG C), SO2Removal efficiency is 92%, NO removal efficiencies 82%.
Example 3
It is molten to change a small amount of process water sprayed into the middle part of reactor into NaClO that concentration is 80% with example 2 for other steps
Liquid.Not only play the role of humidification, but also can continue to further improve absorptivity in oxidation reactor to aoxidize complete NO and Hg.
SO2Removal efficiency is 92%, NO removal efficiencies 85%.
Claims (9)
1. a kind of flue gas pollutant joint removal methods based on activity solid absorbent, comprise the following steps:
1) oxidant is uniformly blended into boiler tail flue gas so that the NO in flue gas is oxidized to higher nitrogen oxides, nonvalent mercury
High-valence state mercuride is oxidized to, the flue gas after being aoxidized;
2) flue gas after the oxidation and solid particle absorbent are come into full contact with the reactor, while removes the sulphur in flue gas
Oxide, higher nitrogen oxides, high-valence state mercuride, obtain the ash-laden gas after pollutant removing;
3) ash-laden gas being obtained into clean flue gas after dedusting, the solid particle of deduster bottom collection is sent into storage bin,
Fraction solids particle is activated and humidification after, return to the reactor and continue to participate in reaction, redundance is from storage bin bottom row
Go out to maintain material balance.
2. according to the method described in claim 1, it is characterized in that:In step 1), the oxidant is O3, O3In stopping for flue gas
The time is stayed to be no less than 0.1s, O3Molar ratio with the NO in flue gas is 0.8-1.2, and reaction temperature window is 90-200 DEG C.
3. method according to claim 1 or 2, it is characterised in that:In step 2), the solid particle absorbent is reaction
The recycle stock of the fully active component containing unreacted after fresh coal fly ash and activated humidification is carried in device import flue gas;
The solid-gas ratio of the solid particle absorbent and flue gas is controlled in 300-1500g/m3;
The solid particle absorbent is not less than 1s with residence time of the flue gas in reactor.
4. method according to any one of claim 1-3, it is characterised in that:In step 2), the solid particle and oxygen
Flue gas after change contacts under certain temperature and relative humidity, and the relative humidity is 10-95%, and the temperature and nearly thermal insulation are full
With temperature temperature away from control at 5-25 DEG C.
5. according to the method described in claim 4, it is characterized in that:Pass through process water humidification solid particle or segmentation humidification mode
Temperature and relative humidity needed for adjusting;
The segmentation humidification mode is that part humidification water is sprayed into reactor posterior segment, and control sprays into the humidification water ratio in reactor
Example is less than the 20% of total water spray;
Or
Oxidizing agent solution is sprayed into reactor, wherein, oxidant NaClO, Ca (ClO)2、KMnO4/H2O2In one kind, solution
The mass concentration of middle oxidant is 20-95%.
6. according to the method any one of claim 1-5, it is characterised in that:In step 3), by spraying into appropriate technique
Water or steam carry out activation process to solid particle;
Activated using process water, according to the addition of the process for controlling content water of active component in solid particle, CaO and H2O's rubs
Your ratio is 1-2, and technique coolant-temperature gage is 70-100 DEG C;
Using steam activation, according to the intake of the content control steam of active component in solid particle, CaO and H2The molar ratio of O
For 1-2, vapor (steam) temperature is 110 DEG C -300 DEG C.
7. according to the method any one of claim 1-6, it is characterised in that:In step 3), carried out to solid particle
During activation process, Ca (OH) is added2Or CaO, relative to the quality of activated fixed particle, addition mass ratio < 10%.
8. according to the method any one of claim 1-8, it is characterised in that:In step 3), consolidating after activated processing
Body particle further adds water to be humidified, the water content 2-8% of solid particle after humidification.
9. according to the method any one of claim 1-8, it is characterised in that:The method further includes, by the pollution
Clean flue gas after thing removing is discharged into air by air-introduced machine by chimney.
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CN115121216A (en) * | 2022-08-24 | 2022-09-30 | 大唐环境产业集团股份有限公司 | Water humidifying dechlorinating agent and preparation method and application thereof |
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