CN105477995B - A kind of method of sulfur trioxide in removing coal-fired flue-gas - Google Patents
A kind of method of sulfur trioxide in removing coal-fired flue-gas Download PDFInfo
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- CN105477995B CN105477995B CN201610030666.0A CN201610030666A CN105477995B CN 105477995 B CN105477995 B CN 105477995B CN 201610030666 A CN201610030666 A CN 201610030666A CN 105477995 B CN105477995 B CN 105477995B
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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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/606—Carbonates
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Abstract
The invention proposes a kind of methods of sulfur trioxide in removing coal-fired flue-gas, according to the concentration of sulfur trioxide in selective catalytic reduction (SCR) denitration outlet flue gas, the good stripping liquid of ejection arrangement in flue gas into the exhaust gases passes between selective catalytic reduction (SCR) denitration outlet end and air preheater, the amount of injection of stripping liquid is 1-20 times of the molal quantity for the sulfur trioxide that the position needs to deviate from per unit volume flue gas.Gas liquid reaction occurs by the sulfur trioxide in stripping liquid and flue gas, the sulfur trioxide in flue gas is removed.Stripping liquid enters flue in a manner of spraying, and is atomized into droplet, forms minimum absorbent granules after evaporating in high-temperature flue gas.Particle is with respect to large specific surface area, and dispersibility is more preferable in flue, and contact sulfur trioxide is more abundant, it reacts more abundant, to considerably reduce the concentration of sulfur trioxide in flue gas, reduces the generation of ammonium hydrogen sulfate, avoid the corrosion of air preheater and the generation of clogging.
Description
Technical field
The invention belongs to atmosphere pollution Treatment process field, the side of sulfur trioxide in especially a kind of removing coal-fired flue-gas
Method.
Background technique
Sulfur-bearing coal combustion can generate a certain amount of sulfur dioxide and sulfur trioxide gas.Coal-burning power plant installs selective catalysis additional
After restoring (SCR) denitrification apparatus, denitrating catalyst not only converts nitrogen for nitric oxide, the nitrogen dioxide etc. in flue gas,
And sulfur dioxide can be promoted to sulphur trioxide conversion.Therefore in flue gas sulfur trioxide content, compared to not installing SCR denitration
When device, increase by about one time.
Sulfur trioxide can be reacted with the ammonia escaped in SCR reactor generates ammonium hydrogen sulfate (ABS).The fusing point of ammonium hydrogen sulfate is
147 DEG C, exist in liquid form in cold section of sulfureous in flue gas acid hydrogen ammonium of air preheater.The ammonium hydrogen sulfate of liquid is a kind of adhesion and corruption
The all very strong substance of corrosion, can be adhered to air preheater and Fan Equipment surface, it is extremely difficult to remove, cause air preheater to stain, corrosion.With
Ammonium hydrogen sulfate constantly adhere to fly ash granule, will cause the blocking of air preheater and trembling for blower, influence equipment normal operation.
The method of the sulfur trioxide of coal-fired flue-gas removing at present is mainly to be divided into dry absorbent using the method for injection absorbent
Gunite (DSI) and wet absorption agent gunite (WSI).
The Chinese patent of the patent No. 201510298152.9 proposes to spray calcium hydroxide or calcium oxide or oxidation into flue
Magnesium or magnesium hydroxide or sodium bicarbonate or concentrated crystal soda particle, dv=20~150 μm；In the patent No. 201410721263.1
The absorbent of state's patent injection is calcium hydroxide or magnesia or magnesium hydroxide or sodium bicarbonate or sodium carbonate particle, dv < 50 μm；
The Chinese patent of the patent No. 200680033934.9 then increases additive on the basis of spraying sodium absorbent, and sodium absorbent includes
Trona or sodium bicarbonate particle, dv < 40 μm.Additive be selected from magnesium carbonate or calcium carbonate or magnesium hydroxide or calcium hydroxide or its
Mixture, dv=20~25 μm.
The absorbent of above-mentioned patented method injection is alkaline dry powder, belongs to DSI technique.Commercially available powder particle size all compared with
Greatly, dv=100~250 μm, absorbent granules are relatively large in diameter, and are unfavorable for the reaction with sulfur trioxide in flue gas, therefore will be to powder
It is ground.Superfine powder grinding is divided into dry grinding and two kinds of wet grinding.Powder is ground to 8 μm by dry grinding most low energy
Left and right, but during the grinding process, powder temperature can rapidly rise because big energy imports, and after Particle pollution, grinding
It is also noted that Explosion-Proof；Wet grinding need to select abrasive media, dispersing agent and auxiliary agent etc. according to required partial size, and control temperature
Etc. factors, continuous powder milling time need a few houres even tens hours, grinding tens times are even up to a hundred time, therefore power plant usually wants
Automation continuous operation is realized using circulating operation mode, occupied area is larger and generates noise pollution.It is also wanted after wet-milling
Sieving, dehydration, drying and processing, obtain the minimum powder absorbent of dry partial size, just can be carried out injection, process is relatively complicated.
The eject position of above-mentioned patented method is in the flue before SCR denitration device input end, SCR denitration dress respectively
It sets in the flue between outlet end and air preheater and in the flue of the outlet end of denitrification apparatus.Dry method injection absorbent be
Strong basicity dry powder particle sprays in the flue before denitrification apparatus input end, will lead to the alkalosis of catalyst, influences to be catalyzed
Agent denitration efficiency；Enough residence times will be guaranteed by being ejected into the flue between denitration outlet end and air preheater,
Under the premise of spray-hole is rationally arranged, as far as possible far from upstream device.
In the absorbed dose and flue gas of the injection of above-mentioned patented method the stoichiometric ratio of sulfur trioxide be respectively (1.5~
15): 1 and (2~6): 1 etc..Absorbent dosage is larger, need to purchase a large amount of absorbent granules of deposit, and cost of investment is big, increases downstream
The burden of equipment fume treatment.
The Chinese patent of the patent No. 201310044506.8 discloses to be sprayed in a kind of flue excessive in the tail portion SCR bending
Removing of the trona slurries for sulfur trioxide in flue gas, mass concentration are 20%~30%, the trona of injection and three oxidations
The stoichiometric ratio of sulphur is 9:1 or so.This method belongs to WSI technique, although this method removal efficiency is very high (80%~90%),
But make absorbent using trona, dosage is big, increases using difficulty and cost.
WSI technique has the unexistent advantage of DSI technique, what the stripping liquid of atomization was formed after moisture high temperature evaporation
Little particle is small more than the particle that DSI technique is ground.When using same absorbent agent and equal the amount of injection, WSI technique forms small
Grain amount of monomer is more, and the dispersibility in flue is more preferable.And grain diameter is smaller, and opposite specific surface area is bigger, with three oxygen
The exposure level for changing sulphur is higher, so that reaction effect is more preferable, therefore seeking the high-efficient and small dosage WSI technique of one kind is to solve
Air preheater blocks the effective of etching problem caused by reacting generation ammonium hydrogen sulfate with the ammonia that SCR denitration reaction device is escaped because of sulfur trioxide
Method.
Summary of the invention
To solve the above-mentioned problems, the invention proposes it is a kind of removing coal-fired flue-gas in sulfur trioxide method, pass through to
Stripping liquid is sprayed in the flue gas in exhaust gases passes between denitration outlet end and air preheater to realize, is specifically included
Following steps:
Step 1 prepares stripping liquid, by one of or mixtures thereof sodium carbonate of powdery, sodium bicarbonate as master
Absorbent dissolves and is configured to dilution water the main absorbent solution of 10%-20% concentration, by the calcium carbonate of powdery, magnesium carbonate,
One of calcium hydroxide and magnesium hydroxide are a variety of as additive, are 1:(0.001-by the ratio between main absorbent and additive
0.2) additive is added prepared main absorbent solution, forms stripping liquid by ratio；
Step 2 passes through Benitration reactor exhaust pass and air preheater gas approach cigarette in dynamic monitoring exhaust gases passes
The concentration of sulfur trioxide in gas；
Step 3 goes out when the concentration value of measured sulfur trioxide reaches the target concentration value of setting to denitrification apparatus
Stripping liquid is sprayed in exhaust gases passes between mouth end and air preheater, the amount of injection is to need to take off in per unit volume flue gas
1-20 times of the molal quantity of sulfur trioxide out.
Further, when the main absorbent is the mixture of sodium carbonate and sodium bicarbonate, sodium carbonate and sodium bicarbonate
Ratio is 1:(0.01-0.1).
Further, the stripping liquid utilizes compressed air atomized spray, pressure 0.035-0.65MPa.
Further, when the additive is the mixture of calcium carbonate, magnesium carbonate, calcium hydroxide and magnesium hydroxide, carbonic acid
Calcium, magnesium carbonate, calcium hydroxide and magnesium hydroxide ratio be 1:(0.01-0.2): (0.3-0.6): (0.02-0.1).
It is proposed by the present invention it is a kind of removing coal-fired flue-gas in sulfur trioxide method, stripping liquid in a manner of spraying into
Enter flue, be atomized into droplet, forms minimum absorbent granules after evaporating in high-temperature flue gas.Particle is with respect to specific surface area
Greatly, amount of monomer is more, and dispersibility is more preferable in flue, and contact sulfur trioxide is more abundant, reacts more abundant, to be greatly lowered
The concentration of sulfur trioxide, reduces the generation of ammonium hydrogen sulfate, avoids and lead to the problem of sour corrosion in flue gas, and three in flue gas
Sulfur oxide is removed, and is reduced and is reacted with escape ammonia, avoids the corrosion of air preheater and the generation of clogging, reduce electricity
The operation of factory's flue gas system and processing cost.
Specific embodiment
The method of sulfur trioxide carries out in detail in removing coal-fired flue-gas a kind of to the present invention With reference to embodiment
Illustrate, examples are only for illustrating the present invention and not for limiting the scope of the present invention for this, and those skilled in the art are to the present invention
The modifications of various equivalent forms fall within the application range as defined in the appended claims.
The method of sulfur trioxide in a kind of removing coal-fired flue-gas of the present invention, by denitration outlet end and air preheat
Stripping liquid is sprayed in the flue gas in exhaust gases passes between device to realize, suitable for equipping the coal-burning power plant of SCR denitration device,
Handle the boiler smoke that sulfur-bearing coal combustion generates.
Embodiment 1
Select the mixture of powdered sodium carbonate and sodium bicarbonate as the mixing of main absorbent, powder lime carbonate and magnesium carbonate
For object as additive, the ratio of sodium carbonate and sodium bicarbonate is 1:0.03, and the ratio of calcium carbonate and magnesium carbonate is 1:0.12.
Firstly, preparing stripping liquid, the mixture of the sodium carbonate of powdery and sodium bicarbonate is dissolved and being matched with dilution water
The main absorbent solution of 10% concentration is made, additive is added the ratio for being 1:0.001 in the ratio between main absorbent and additive
Prepared main absorbent solution forms stripping liquid；It is successively arranged selective catalysis from up to down on power plant's discharge flue
Reduction method (SCR) denitrification apparatus and air preheater monitor in exhaust gases passes through Benitration reactor outlet and air preheat
The concentration of sulfur trioxide is 56.5mg/Nm in flue gas between device entrance3When, using compressed air by stripping liquid into
Then row atomization, pressure 0.035MPa are sprayed into the exhaust gases passes between denitration outlet end and air preheater
Stripping liquid after atomization, the amount of injection 60mg/Nm3, gas-liquid is occurred by the sulfur trioxide in stripping liquid and flue gas
Reaction removes the sulfur trioxide in flue gas, and the flue gas by purification is discharged by air preheater.The results show takes off
Except the concentration of sulfur trioxide is less than 8mg/Nm in flue gas after sulfur trioxide3, 86% or more desulfuration efficiency.
Embodiment 2
Select powdered sodium carbonate as main absorbent, powder lime carbonate as additive.
Firstly, preparing stripping liquid, the main suction of 15% concentration is configured to by the sodium carbonate dissolution of powdery and with dilution water
Agent solution is received, it is molten prepared main absorbent to be added in additive by the ratio for being 1:0.05 in the ratio between main absorbent and additive
Liquid forms stripping liquid；Selective catalytic reduction (SCR) denitrification apparatus is successively arranged on power plant's discharge flue from up to down
And air preheater, it monitors in exhaust gases passes through the flue gas between Benitration reactor outlet and air preheater entrance
The concentration of middle sulfur trioxide is 56.5mg/Nm3When, stripping liquid is atomized using compressed air, pressure is
0.05MPa, the then liquid absorbent into the exhaust gases passes between denitration outlet end and air preheater after jet atomization
Agent, the amount of injection 167mg/Nm3, gas liquid reaction is occurred by the sulfur trioxide in stripping liquid and flue gas, it will be in flue gas
Sulfur trioxide removing, the flue gas by purification are discharged by air preheater.The results show removes flue gas after sulfur trioxide
The concentration of middle sulfur trioxide is less than 5mg/Nm3, 90% or more desulfuration efficiency.
Embodiment 3
Select powder sodium bicarbonate as main absorbent, the mixture of powder lime carbonate, magnesium carbonate and magnesium hydroxide, which is used as, to be added
Add agent, the ratio of calcium carbonate, magnesium carbonate and magnesium hydroxide is 1:0.02:0.02.
Firstly, preparing stripping liquid, the master of 20% concentration is configured to by the sodium bicarbonate dissolution of powdery and with dilution water
Absorbent solution, the ratio for being 1:0.2 in the ratio between main absorbent and additive, it is molten to be added prepared main absorbent for additive
Liquid forms stripping liquid；Selective catalytic reduction (SCR) denitrification apparatus is successively arranged on power plant's discharge flue from up to down
And air preheater, it monitors in exhaust gases passes through the flue gas between Benitration reactor outlet and air preheater entrance
The concentration of middle sulfur trioxide is 56.5mg/Nm3When, stripping liquid is atomized using compressed air, pressure is
0.65MPa, the then liquid absorbent into the exhaust gases passes between denitration outlet end and air preheater after jet atomization
Agent, the amount of injection 1130mg/Nm3, gas liquid reaction is occurred by the sulfur trioxide in stripping liquid and flue gas, it will be in flue gas
Sulfur trioxide removing, the flue gas by purification are discharged by air preheater.The results show removes flue gas after sulfur trioxide
The concentration of middle sulfur trioxide is less than 3mg/Nm3, 95% or more desulfuration efficiency.
The advantage of the invention is that injection is the stripping liquid being atomized, the minimum particle that high temperature evaporation is formed.?
The opposite large specific surface area of grain, amount of monomer is more, and dispersibility is more preferable in flue, and contact sulfur trioxide is more abundant, thus reacts more
Sufficiently, removal efficiency is higher.The moment moisture that absorbent sprays into will not be generated the sodium bisulfate of liquid, be avoided by high temperature evaporation
Lead to the problem of sour corrosion.The carbonate cooperation additive of sodium base makees absorbent, and dosage is according to practical sulfur trioxide in flue gas
Changes of contents and adjust.Sulfur trioxide in flue gas is removed, and is reduced and is reacted with escape ammonia, avoids the corrosion of air preheater
And blockage problem, reduce the operation of power-plant flue gas system and processing cost.
It is described the prefered embodiments of the present invention in detail above in conjunction with specific embodiment, still, the present invention is simultaneously unlimited
Detail in above embodiment, within the scope of the technical concept of the present invention, can to technical solution of the present invention into
The a variety of simple variants of row, these simple variants all belong to the scope of protection of the present invention.
Claims (2)
1. a kind of method of sulfur trioxide in removing coal-fired flue-gas, by between denitration outlet end and air preheater
Stripping liquid is sprayed in flue gas in exhaust gases passes to realize, specifically includes the following steps:
Step 1 prepares stripping liquid, using the sodium carbonate of powdery, sodium bicarbonate mixture as main absorbent, sodium carbonate with
The ratio of sodium bicarbonate is 1:(0.01-0.1), the main absorbent solution of 10%-20% concentration is dissolved and is configured to dilution water,
By one of the calcium carbonate of powdery, magnesium carbonate, calcium hydroxide and magnesium hydroxide or it is a variety of be used as additive, by main absorbent and
The ratio between additive is the ratio of 1:(0.001-0.2), and prepared main absorbent solution is added in additive, forms liquid and inhales
Receive agent；
Step 2, by Benitration reactor exhaust pass and air preheater gas approach flue gas in dynamic monitoring exhaust gases passes
The concentration of sulfur trioxide；
Step 3, when the concentration value of measured sulfur trioxide reaches the target concentration value of setting, to denitration outlet end
Stripping liquid is sprayed in exhaust gases passes between air preheater, the amount of injection is to need to deviate from per unit volume flue gas
1-20 times of the molal quantity of sulfur trioxide, injection pressure are 0.035-0.65MPa.
2. the method for sulfur trioxide in removing coal-fired flue-gas according to claim 1, which is characterized in that the additive is
Calcium carbonate, magnesium carbonate, calcium hydroxide and magnesium hydroxide mixture when, calcium carbonate, magnesium carbonate, calcium hydroxide and magnesium hydroxide
Ratio is 1:(0.01-0.2): (0.3-0.6): (0.02-0.1).
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| CN106492603B (en) * | 2016-11-21 | 2019-03-01 | 西安交通大学 | It is a kind of for removing the device of sulfur trioxide before air preheater |
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| CN110075683A (en) * | 2019-04-16 | 2019-08-02 | 中国能源建设集团广东省电力设计研究院有限公司 | SO in a kind of removing boiler smoke3Method and system |
| CN112495151A (en) * | 2020-10-30 | 2021-03-16 | 张家港市艾尔环保工程有限公司 | Method for eliminating blue smoke plume of chimney of coal-fired boiler |
| CN113731113B (en) * | 2021-09-15 | 2022-05-17 | 北京工大环能科技有限公司 | System for reducing blockage of ammonium bisulfate of air preheater of coal-fired power plant |
| CN117049718B (en) * | 2023-06-28 | 2024-04-09 | 北京清新环境技术股份有限公司 | Method for removing chloride ions from desulfurization slurry |
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