CN102824824A - Amino wet combined desulfurization and denitration device and process - Google Patents
Amino wet combined desulfurization and denitration device and process Download PDFInfo
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- CN102824824A CN102824824A CN2012103340345A CN201210334034A CN102824824A CN 102824824 A CN102824824 A CN 102824824A CN 2012103340345 A CN2012103340345 A CN 2012103340345A CN 201210334034 A CN201210334034 A CN 201210334034A CN 102824824 A CN102824824 A CN 102824824A
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- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 34
- 230000023556 desulfurization Effects 0.000 title claims abstract description 29
- 230000008569 process Effects 0.000 title claims abstract description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 130
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 87
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 40
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 19
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003860 storage Methods 0.000 claims abstract description 12
- 239000000779 smoke Substances 0.000 claims abstract description 11
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims abstract description 10
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims description 117
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 67
- 239000003546 flue gas Substances 0.000 claims description 67
- 230000003009 desulfurizing effect Effects 0.000 claims description 42
- 229910021529 ammonia Inorganic materials 0.000 claims description 36
- 239000013078 crystal Substances 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 20
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 17
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 17
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 239000012530 fluid Substances 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 10
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000443 aerosol Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 210000002966 serum Anatomy 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000036651 mood Effects 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- SPEMQUPJTGQFIM-UHFFFAOYSA-N triazanium;hydrogen sulfite;sulfite Chemical compound [NH4+].[NH4+].[NH4+].OS([O-])=O.[O-]S([O-])=O SPEMQUPJTGQFIM-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Treating Waste Gases (AREA)
Abstract
The invention discloses amino wet combined desulfurization and denitration device and a process. The device comprises a desulfurization tower with an inlet flue, a liquid ammonia storage tank, an ozone generator, and a booster fan on the inlet flue; and a defogging layer, a spraying layer and a tower kettle are orderly arranged inside the desulfurization tower from top to bottom. The device also comprises an oxidization slot communicated with the tower kettle, and an oxidization fan connected to the oxidization slot; the liquid ammonia storage tank is communicated to the tower kettle through one path of pipeline, and is communicated to the bottom part of the oxidization slot through another pipeline; the ozone generator is communicated to an air inlet of the booster fan through the pipeline; ozone is sprayed into smoke from the air inlet of the booster fan; nitric oxide in the smoke is oxidized into nitrogen dioxide; the smoke oxidized by ozone is conveyed to the desulfurization tower; liquid ammonia is sprayed to desulfurize and denitrate; the smoke is discharged after being defogged and dried; and circulating liquid by which sulfur dioxide and nitrogen dioxide are absorbed is oxidized outside the tower, and the liquid ammonia is conveyed to the oxidization slot to adjust the pH (Potential Of Hydrogen) value in the oxidization slot during the oxidization process.
Description
Technical field
The present invention relates to the air pollution control technique field, be specifically related to wet method combined desulfuring and denitrifying apparatus of a kind of amino and technology, to removing and the by-product recovery utilization of sulfur dioxide in the fire coal boiler fume and nitrogen oxide.
Background technology
Ammonia-process desulfurization technique is to utilize liquefied ammonia, ammoniacal liquor or urea to remove the SO in the flue gas
2, generate high-quality ammonium sulfate (NH simultaneously
4)
2SO
4Ammonia-process desulfurization technique is particularly suitable for the burn tail gas SO of cheap high-sulfur combustor of large-scale thermal power machine group and chemical enterprise
2Remove, when using useless ammonia desulfurization, produce high-quality, highly purified ammonium sulfate, progressively become the mainstream technology of the recycling economy comprehensive utilization of mega project flue gas desulfurization.
Ammonia-process desulfurization technique has abundant raw material, and its maximum characteristics are SO
2But resource, can be with pollutant SO
2Recovery becomes high value-added product.Byproduct ammonium sulfate is a kind of nitrogenous fertilizer of function admirable, has good market prospects in China.
The ammonia recovering method technology all is converted into chemical fertilizer with the sulfur dioxide, the ammonia that reclaim, does not produce any waste water, waste liquid and waste residue, does not have secondary pollution, be one truly with the whole resources of pollutant, meet the desulfur technology that recycling economy requires.
Ammonia process of desulfurization accessory substance is worth high; The running of ammonia recovering method desulfurizer promptly is the production process of ammonium sulfate; 1 ton of liquefied ammonia of every absorption can remove 2 tons of sulfur dioxide; Produce 4 tons of ammonium sulfate, according to 2000 yuan/ton in conventional price liquefied ammonia, 700 yuan/ton in ammonium sulfate, then sulfur dioxide per ton has embodied about 400 yuan value in the flue gas.Therefore operating cost is little relatively, and sulfur content is higher in the coal, and operating cost is lower.Enterprise's cheap sulphur coal capable of using reduces fuel cost and desulfurization expense simultaneously significantly, kills two birds with one stone.
Ammonia-process desulfurization technique has stronger advantage aspect the pollutant comprehensive regulation and the resource, but owing to exists difficult problems such as the escaping of ammonia, oxidizing and crystallizing to hinder the development of ammonia-process desulfurization technique to a certain extent.Liquefied ammonia is volatile substances, in detach procedure, has certain the escaping of ammonia, and escape ammonia gets in the atmosphere can cause secondary pollution to environment; In the oxidizing process of ammonium sulfite, the NH of excessive concentrations
4 +Ion can have certain damping action to the oxidation of ammonium sulfite, cause system's oxidizing and crystallizing difficulty; Simultaneously, ammonia-process desulfurization technique is to the NO in the flue gas
XRemoval efficiency lower, to NO in the boiler smoke
XImprovement need set up a cover denitrification apparatus separately, if improve the denitration efficiency of ammonia-process desulfurization technique, realize that desulphurization denitration is another difficult problem that need solve of ammonia-process desulfurization technique simultaneously.
For example, application number is wet ammonia flue gas cleaning technology and the system thereof that 200710052129.7 Chinese invention patent discloses a kind of while desulphurization denitration.This technology makes the nitric oxide in the flue gas carry out oxidation reaction earlier and generates nitrogen dioxide; Sulfur in smoke and nitrogen dioxide are reacted with ammoniacal liquor respectively generate ammonium sulfite, ammonium nitrate and ammonium nilrite; Make wherein ammonium sulfite and ammonium nilrite generation oxidation reaction generate byproduct of ammonium sulfate and ammonium nitrate again; Simultaneously the flue gas behind the desulphurization denitration is carried out demist, finally obtain clean flue gas.Its system comprises pre-dedusting device, hydrogen peroxide solution or ozone injection apparatus and the desulphurization denitration tower that connects successively, and the desulphurization denitration tower bottom is connected with ammoniacal liquor device for supplying and air apparatus for feeding, and the middle part is provided with the ammonia spray layer of injection capable of circulation, and top is provided with demister.
The more difficult control of its pH value can not take into account the oxidizing and crystallizing efficient of the desulfuration efficiency and the ammonium sulfite of flue gas in this system; Simultaneously, the ammonia quantity delivered in this system in the desulfurizing tower is carried out based on sulfur dioxide in flue gas content, and sulfur in smoke content fluctuation range is bigger; Be difficult to control; Cause the pH value fluctuation range of whole slurries system bigger if fruit is controlled improper meeting, cause aerosol to produce in a large number, the desulfuration efficiency instability.
Summary of the invention
The invention provides a kind of amino wet method method combined desulfurization and denitrification process that can improve ammonia-process desulfurization technique denitration efficiency, reduction the escaping of ammonia, removal aerosol, improve sulfite oxidation speed and increase ammonia sulfate crystal particle.
The wet method combined desulfuring and denitrifying apparatus of a kind of amino; Comprise desulfurizing tower, liquid ammonia storage tank, the ozone generator of tape entry flue and be positioned at the booster fan on the gas approach; Be followed successively by demist layer, spraying layer and tower still in the said desulfurizing tower from top to bottom; Also comprise the oxidation trough that is communicated with said tower still and the oxidation fan that is connected to oxidation trough; Said liquid ammonia storage tank is communicated to said tower still through pipeline one tunnel, and another road is communicated to said oxidation trough bottom, and said ozone generator is through the air intake vent place of pipeline connection to said booster fan.
Ozone is fed gas approach, utilize ozone that the NO of indissoluble in the flue gas is oxidized to very easily by the NO of liquid-absorbent
2, the flue gas after oxidation gets in the desulfurizing tower and sprays desulphurization denitration; Circulation fluid behind the completion desulphurization denitration is sent into oxidation trough and is carried out oxidizing and crystallizing; The ammonia sulfate crystal mixed serum of accomplishing oxidation in the oxidation trough is further handled; Liquefied ammonia part in the liquid ammonia storage tank is supplied with and is given desulfurizing tower as desulfurizing agent, and another part is supplied with to the conditioning agent of oxidation trough as oxidation trough pH value.The desulphurization denitration of flue gas separates with the oxidizing and crystallizing of accomplishing the circulation fluid behind the desulphurization denitration and carries out.
Said ozone generator is communicated to the air intake vent place of booster fan; Be that the ozone inlet is booster fan air intake vent place; The booster fan air intake vent is a negative pressure; Can better prevent the ozone leakage, utilize the eddy current effect of booster fan impeller that flue gas is mixed with ozone fully simultaneously, realize complete oxidation NO NO in the flue gas
2, adopt the booster fan air intake vent to add ozone and saved the flue gas blender, reduced the resistance of system.
Defeated ammonia pipeline in the oxidation trough is arranged on the bottom; Adopt the bottom ammonification; In time the pH value of buffer oxide crystallizing layer (because treat that the slurries of oxidation are mainly ammonium sulfite and ammonium bisulfite, can discharge hydrogen ion, the pH value of slurries is sharply descended after bisulfite is oxidized; Make that oxide layer local pH value is low excessively, cause SO
2Escape and the reduction oxidation rate), guarantee that the lasting high speed of whole oxidizing process is carried out.
As preferably, be provided with porous plate in the said oxidation trough, porous plate is mainly used in the distribution bubble, makes to play stirring action simultaneously in the evenly whole oxidation trough volume of distribution inside of oxidation general mood bubble, accelerates the gas-liquid turbulent extent, improves oxidation rate.With orifice plate gas distribution mode, increase the contact of gas-liquid turbulent flow in the oxidation trough, improve the oxidation rate of ammonium sulfite, reduce the time of staying of ammonium sulfite in oxidation trough, reduce the volume of oxidation trough, saved system operation cost and cost of investment.
More preferably, said oxidation trough has the oxidation wind inlet that is communicated with oxidation fan, and said porous plate is positioned at 0.5～0.8m place, oxidation wind inlet top; The aperture of said porous plate is 3～5cm, and percent opening is 50～80%.
When the porous plate percent opening is 50-80%, when the aperture was 3-5cm, stirring action that plays and slurries oxidation effectiveness were best, and percent opening is meant that the gross area of porous plate perforate accounts for the ratio of the porous plate gross area.
Porous plate is two-layer with being divided in the oxidation trough, and lower floor is the oxidizing and crystallizing layer, and the crystal grain that ammonia sulfate crystal forms 0.5-3mm here is suspended in the slurries of bottom, and discharges from the oxidation trough bottom; The top is a clear layer, for ammonium sulfate, ammonium sulfite clear liquid, to the NO in the flue gas
XHave reduction, can further remove NO
X
Therefore; As preferably, said demist layer is made up of baffle flaggy and the sparge pipe that is positioned at baffle flaggy top, and the quantity of said demist layer is two-layer; Comprise bottom demist layer and top layer demist layer, the sparge pipe of said bottom demist layer is communicated with the top of said oxidation trough through pipeline.
The sparge pipe of the clear layer of porous plate top in the oxidation trough being delivered to bottom demist layer by corresponding conveying mechanism such as clear liquid flushing pump carries out degree of depth denitration to flue gas, removes the aerosol in the flue gas, prevents the escape ammonia in the flue gas.
More preferably, the nozzle on the sparge pipe of said demist layer is nozzle.
Bottom demist layer adopts nozzle, and the ammonium sulfite area of ejection is wide, great efforts, the escape ammonia in the flue gas and dust is had capture effect preferably, avoids exporting the aerosol phenomenon of flue gas; Top layer demist layer adopts nozzle, utilizes fresh water (FW) to wash, and prevents demister fouling obstruction.
The present invention also provides a kind of amino wet method combined process for desulfurization and denitration, comprising:
Air intake vent place by booster fan sprays in the flue gas with ozone; Nitrogen oxide in the flue gas is oxidized to nitrogen dioxide; Flue gas after ozone oxidation is sent in the desulfurizing tower, liquefied ammonia is sprayed into absorb sulfur in smoke and nitrogen dioxide in the desulfurizing tower, and flue gas is got rid of after the demist drying;
The circulation fluid that has absorbed behind sulfur dioxide and the nitrogen dioxide is introduced in the oxidation trough, in oxidation trough, is fed oxidation wind, circulation fluid is oxidized to the ammonia sulfate crystal slurries, after said ammonia sulfate crystal slurries are further handled the ammonium sulfate finished product; In oxidation trough, send into the pH value in the liquefied ammonia adjustment oxidation trough in the oxidizing process.
Ozone is sprayed in the flue gas by the air intake vent place of booster fan, and the booster fan air intake vent is a negative pressure, can better prevent the ozone leakage, utilizes the eddy current effect of booster fan impeller that flue gas is mixed with ozone fully simultaneously, realizes with NO complete oxidation in the flue gas being NO
2
Key reaction in the desulfurizing tower is SO
2And NO
2Generate ammonium bisulfite and ammonium nitrate solution with the ammonium sulfite solution reaction; The denitrification efficiency that guarantees desulfurizing tower must guarantee that slurries have certain density sulfite ion in the desulfurizing tower, need in desulfurizing tower, constantly supply with the reaction of liquefied ammonia and ammonium bisulfite and generate the ammonium sulfite solution with desulphurization denitration ability.
PH value in the said desulfurizing tower is 5.8～6.2, and the spraying layer liquid-gas ratio is 7-10L/m
3Desulfurizing tower entoplasm liquid system is mainly ammonium sulfite-bisulfite ammono-system, and during slurry pH value too high (＞7), the ammonium salt solution in the mixture system volatilizes ammonia; It is undesirable that the pH value is crossed when low desulfuration efficiency, when the slurries system pH at 5.8-6.2, liquid-gas ratio at 8-9L/m
3The time, to the SO in the flue gas
2And NO
2Have and be higher than 95% capture effect.
Ammonium bisulfite can generate ammonia sulfate crystal and sulfuric acid in oxidizing process simultaneously; Whole oxidizing process can constantly make the pH value of oxidation trough slurries continue to reduce; The final oxidation rate that influences bisulfite; Therefore, in oxidation trough, send into the pH value in the liquefied ammonia adjustment oxidation trough in the oxidizing process, the pH value that keeps oxidation trough is in the 5.6-6.0 scope.
Oxidation trough slurry reaction system at pH value of solution less than 5.6 o'clock (NH
4)
2SO
3Oxidation rate increase with the increase of pH; At pH greater than 6.0 o'clock, (NH
4)
2SO
3Oxidation rate reduce with the increase of pH.This mainly be because when pH value of solution less than 6.0 the time, have section H SO in the solution
3 -, at pH greater than 6.0 o'clock, a large amount of SO in the solution
3 2-, and HSO
3 -Oxidation rate be greater than SO
3 2-Oxidation rate.
Preferably, the mol ratio of nitrogen oxide is 1: 1 in the quantity delivered of said ozone and the flue gas.High concentration SO in the flue gas
2Can promote the oxygenation efficiency of NO rapidly, the high concentration SO in inlet flue gas
2Under the existence condition, the conversion ratio of NO surpasses 90%, is 1: 1 so set the ratio of NO amount in ozone supply amount and the flue gas.
Preferably, said ammonia sulfate crystal slurries are after cyclonic separation, and underflow makes finished product ammonium sulfate after drying, and top stream is sent the desulfurizing tower inner top back to, and flue gas is carried out degree of depth denitration.In the stream of top is ammonium sulfate, ammonium sulfite clear liquid, to the NO in the flue gas
XHave reduction, can further remove NO
X, therefore, top stream is sent the desulfurizing tower top back to flue gas is carried out degree of depth denitration, and removes the escape ammonia in the flue gas.
More preferably, said top stream is 1-2L/m to the liquid-gas ratio that flue gas carries out degree of depth denitration
3
Beneficial effect of the present invention:
(1) the present invention separates the oxidation of the purification of flue gas and ammonium sulfite and ammonium bisulfite and carries out; Adopt the tower external oxidation; Control the pH value of two reaction systems respectively, increase substantially desulfuration efficiency and ammonia sulfate crystal quality, the ammonia sulfate crystal that crystallization is produced has bigger crystal particle diameter; Be more convenient for separating, thus the purity of raising ammonia sulfate crystal.
(2) ozone is sprayed in the flue gas by the air intake vent place of booster fan, can better prevent the ozone leakage, utilizes the eddy current effect of booster fan impeller that flue gas is mixed with ozone fully simultaneously, realizes the complete oxidation NO with NO in the flue gas
2, the utilization rate of raising ozone; Adopt the booster fan inlet to add ozone and saved the flue gas blender, reduced the resistance of system.
(3) liquefied ammonia of adjustment pH value is sent into by the oxidation trough bottom in the oxidation trough of tower external oxidation, and in time the pH value of buffer oxide crystallizing layer guarantees that the lasting high speed of whole oxidizing process is carried out.
(4) adopt orifice plate gas distribution mode in the oxidation trough, increase the contact of gas-liquid turbulent flow, improve the oxidation rate of ammonium sulfite, reduce between the stop of ammonium sulfite in oxidation trough, reduce the volume of oxidation trough, saved system operation cost and cost of investment.
(5) supernatant liquor in the oxidation trough or the top after cyclonic stream clear liquid carries out degree of depth denitration to flue gas, prevents the escaping of ammonia.
Description of drawings
Fig. 1 is a structural representation of the present invention.
The specific embodiment
As shown in Figure 1, the wet method combined desulfuring and denitrifying apparatus of a kind of amino comprises desulfurizing tower 3, liquid ammonia storage tank 1, ozone generator 19, oxidation trough 10 and cyclone separator 15.
Desulfurizing tower 3 adopts spray column; In the desulfurizing tower 3 by last be to spray the uptake zone between spraying layer 6 and the tower still from being followed successively by demist layer 7, spraying layer 6 and tower still down, the quantity of spraying layer 6 is provided with three layers; Three circulating pumps 4 of corresponding setting, every circulating pump 4 is communicated with tower still and corresponding spraying layer.
The quantity of demist layer 7 is provided with two-layer, and the one deck that is positioned at the below is a bottom demist layer, and the one deck that is positioned at the top is a top layer demist layer; Every layer of demist layer formed by the sparge pipe of hydraulic barrier layer and hydraulic barrier layer top; Fine mist under the hydraulic barrier layer retaining in the flue gas is carried out the demist drying to flue gas, and sparge pipe is to hydraulic barrier layer spray flushing liquor; Plurality of nozzles is set on the sparge pipe, and the nozzle of the nozzle of bottom demist layer and top layer demist layer all adopts nozzle.
The spray uptake zone of desulfurizing tower 3 is provided with smoke inlet, connects gas approach 5, and booster fan 18 is set on the gas approach 5, and ozone generator 19 is communicated with the air intake vent place of booster fan 18 through the ozone transfer pipeline.
Be provided with between liquid ammonia storage tank 1 and the desulfurizing tower 3 and supply ammonia pump 2, supply the inlet of ammonia pump 2 to be communicated with liquid ammonia storage tank 1, export a minute two-way, the one tunnel is communicated with the tower still of desulfurizing tower 3, and one the tunnel is communicated with the bottom of oxidation trough 10.
Be communicated with through circulation fluid excavationg pump 9 between oxidation trough 10 and the tower still; The inlet of circulation fluid excavationg pump 9 is communicated with the tower still; Outlet is communicated with oxidation trough 10, and the bottom of oxidation trough 10 is provided with oxidation airduct net, and oxidation wind inlet is set on oxidation trough 10 sidewalls; The air-supply pipeline of oxidation fan 14 is communicated with oxidation airduct net through this oxidation wind inlet; Through oxidation fan 14 delivery of oxygen wind transmission in oxidation trough 10, the bottom of oxidation trough 10 is communicated to cyclone separator 15 through crystal solution excavationg pump 13, and the top stream of cyclone separator 15 is back in the oxidation trough 10 through pipeline.
Porous plate 11 is set in the oxidation trough 10, and porous plate 11 is positioned at 0.5～0.8m place of oxidation wind inlet top, and the aperture of porous plate 11 is 3～5cm, and percent opening is 50～80%.Porous plate 11 is two-layer with being divided in the oxidation trough 10; Liquefied ammonia in the liquid ammonia storage tank 1, the circulation fluid in the tower still and the oxidation wind of oxidation fan 14 are all sent into porous plate 11 belows; The top of cyclonic device 15 stream is sent into the top of porous plate 11, is positioned on the oxidation trough 10 of porous plate 11 upper sections the sparge pipe that pipeline is connected to bottom demist layer is set.
Technological process of the present invention is following:
Boiler smoke is sent into desulfurizing tower through booster fan 18; The outlet of ozone generator 19 is positioned at booster fan 18 porch; Ozone evenly gets into the NO in the oxidation raw flue gas in the gas approach 5 under the effect of entrance negative pressure, and NO content is 1: 1 in the quantity delivered of ozone and the flue gas.High concentration SO in the raw flue gas
2Accelerated to a great extent that NO is converted into NO in the flue gas
2Speed; When flue gas moves to booster fan 18 inner chamber places, mixed flue gas has obtained abundant mixing under the eddy current effect that the rotation of impeller causes; This moment, NO obtained complete oxidation, and complete oxidation is also got in the desulfurizing towers 3 and moves upward through gas approach 5 by the raw flue gas of mixing.
Desulfurizing agent liquefied ammonia is stored in the liquid ammonia storage tank 1; Liquefied ammonia is delivered to desulfurizing tower 3 bottoms and oxidation trough 10 bottoms through supplying 2 fens two-way of ammonia pump; Circulating pump 4 is delivered to spraying layer 6 with circulation fluid in the desulfurizing tower 3 and is atomized into drop; Slurries drop through atomizing moves downward under the gravity effect, carries out sufficient absorption reaction with the flue gas that makes progress and generates ammonium sulfite, ammonium bisulfite, ammonium nilrite mixed serum and fall into the desulfurizing tower bottom.Through discharging chimneys from desulfurizing tower outlet 8 after 7 demist of the process of the flue gas behind desulphurization denitration demist layer.The pH value of flue gas and ammonium sulfite, ammonium bisulfite reaction system is 5.8-6.2 in the desulfurizing tower, and the spraying layer liquid-gas ratio is 7-10L/m
3
Circulation fluid after desulfurization, the denitration is delivered to oxidation trough 10 by circulation fluid excavationg pump 9; The bisulfite that the oxidation airduct net of the oxidized groove of oxidation air 10 bottoms of oxidation fan 14 outlets is scattered in the bubble oxidation slurries generates ammonia sulfate crystal deposition and sulfuric acid; The pH value of slurries descends in the oxidation trough 10; Regulate the liquefied ammonia flow that gets into oxidation trough 10, the pH value of control oxidation trough 10 is in the 5.6-6.0 scope.In oxide layer porous plate 11 is set, porous plate 11 percent openings are 50%-80%, and the aperture is 3cm-5cm, and porous plate 11 has aggravated the turbulent extent of oxidation bubble and slurries, improve the oxidation rate of ammonium bisulfite in the slurries.
The ammonium sulfate at oxidation trough 10 tops, ammonium sulfite, ammonium nitrate solution are delivered to the shower of bottom demist layer by the clear liquid flushing pump, and the flue gas after desulfurization, the denitration is carried out deep desulfuration, denitration, deamination; The crystal mixed liquor of bottom is delivered to cyclone 15 through crystal solution excavationg pump 13 and is carried out cyclonic separation.Cyclone 15 underflows get into crystallizing and drying system 16 and make finished product ammonium sulfate, ammonium nitrate, and top stream clear liquid returns and carries out precipitate and separate in the oxidation trough 10.Fresh water (FW) 17 is delivered to the sparge pipe of top layer demist layer through pressurizeing, and demist layer 7 is washed, and prevents fouling.
Embodiment 1
Certain steam power plant, 3 130t/h boilers adopt this desulfurization, denitrating technique, and the desulfurizing tower liquid-gas ratio is 8L/m
3, desulfurizing tower pH value is controlled at 5.9-6.0, and oxidation trough pH value is controlled at 5.6-6.0, and the ozone supply amount is 1: 1, and porous plate is positioned at oxidation airduct top 0.6m; Inlet SO
2Concentration is 6324mg/m
3, NO concentration is 273mg/m
3, flue-gas temperature is 142 ℃, outlet SO
2Concentration is 38mg/m
3, NO concentration is 13mg/m
3, ammonium sulfate purity is 96.9%, the ammonia sulfate crystal particle size range is 1mm-3mm.
Embodiment 2
Certain power plant for self-supply, 1 335WM unit adopts this desulfurization, denitrating technique, and the desulfurizing tower liquid-gas ratio is 8, and desulfurizing tower pH value is controlled at 5.9-6.2, and oxidation trough pH value is controlled at 5.8-6.0, and the ozone supply amount is 1: 1, and porous plate is positioned at oxidation airduct top 0.5m; Inlet SO
2Concentration is 5428mg/m
3, NO concentration is 413mg/m
3, flue-gas temperature is 139 ℃, outlet SO
2Concentration is 27mg/m3, and NO concentration is 17mg/m
3, ammonium sulfate purity is 97.3%, the ammonia sulfate crystal particle size range is 1mm-3mm.
Embodiment 3
Certain power plant, 5 75t/h boilers adopt this desulfurization, denitrating technique, and the desulfurizing tower liquid-gas ratio is 7, and desulfurizing tower pH value is controlled at 5.9-6.1, and oxidation trough pH value is controlled at 5.6-5.8, and the ozone supply amount is 1: 1, and porous plate is positioned at oxidation airduct top 0.7m; Inlet SO
2Concentration is 3861mg/m
3, NO concentration is 477mg/m
3, flue-gas temperature is 137 ℃, outlet SO
2Concentration is 18mg/m3, and NO concentration is 21mg/m
3, ammonium sulfate purity is 96.1%, the ammonia sulfate crystal particle size range is 1mm-3mm.
Claims (10)
1. wet method combined desulfuring and denitrifying apparatus of amino; Comprise desulfurizing tower (3), liquid ammonia storage tank (1), the ozone generator (19) of tape entry flue (5) and be positioned at the booster fan (18) on the gas approach (5); Be followed successively by demist layer, spraying layer and tower still in the said desulfurizing tower (3) from top to bottom; It is characterized in that also comprise the oxidation trough (10) that is communicated with said tower still and the oxidation fan (14) that is connected to oxidation trough (10), said liquid ammonia storage tank (1) is communicated to said tower still through pipeline one tunnel; Another road is communicated to said oxidation trough (10) bottom, and said ozone generator (19) is through the air intake vent place of pipeline connection to said booster fan (18).
2. the wet method combined desulfuring and denitrifying apparatus of amino according to claim 1 is characterized in that, is provided with porous plate (11) in the said oxidation trough (10).
3. the wet method combined desulfuring and denitrifying apparatus of amino according to claim 2 is characterized in that, said oxidation trough (10) has the oxidation wind inlet that is communicated with oxidation fan (14), and said porous plate (11) is positioned at 0.5～0.8m place, oxidation wind inlet top.
4. the wet method combined desulfuring and denitrifying apparatus of amino according to claim 3 is characterized in that the aperture of said porous plate (11) is 3～5cm, and percent opening is 50～80%.
5. the wet method combined desulfuring and denitrifying apparatus of amino according to claim 4; It is characterized in that; Said demist layer is made up of baffle flaggy and the sparge pipe that is positioned at baffle flaggy top; The quantity of said demist layer is two-layer, comprises bottom demist layer and top layer demist layer, and the sparge pipe of said bottom demist layer is communicated with the top of said oxidation trough (10) through pipeline.
6. the wet method combined desulfuring and denitrifying apparatus of amino according to claim 5 is characterized in that the nozzle on the sparge pipe of said demist layer is nozzle.
7. an amino wet method combined process for desulfurization and denitration is characterized in that, comprising:
Air intake vent place by booster fan sprays in the flue gas with ozone; Nitrogen oxide in the flue gas is oxidized to nitrogen dioxide; Flue gas after ozone oxidation is sent in the desulfurizing tower, liquefied ammonia is sprayed into absorb sulfur in smoke and nitrogen dioxide in the desulfurizing tower, and flue gas is got rid of after the demist drying;
The circulation fluid that has absorbed in the desulfurizing tower behind sulfur dioxide and the nitrogen dioxide is introduced in the oxidation trough, in oxidation trough, fed oxidation wind, circulation fluid is oxidized to the ammonia sulfate crystal slurries; In oxidation trough, send into the pH value in the liquefied ammonia adjustment oxidation trough in the oxidizing process.
8. amino wet method combined process for desulfurization and denitration according to claim 7 is characterized in that, the pH value in the said desulfurizing tower is 5.8～6.2, and the pH value in the said oxidation trough is 5.6-6.0.
9. amino wet method combined process for desulfurization and denitration according to claim 7 is characterized in that, the mol ratio of nitrogen oxide is 1: 1 in the quantity delivered of said ozone and the flue gas.
10. amino wet method combined process for desulfurization and denitration according to claim 7 is characterized in that, said ammonia sulfate crystal slurries are after cyclonic separation, and underflow makes finished product ammonium sulfate after drying, and top stream is sent the desulfurizing tower inner top back to, and flue gas is carried out degree of depth denitration.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105169923A (en) * | 2015-07-21 | 2015-12-23 | 大唐华银电力股份有限公司金竹山火力发电分公司 | Improved limestone/lime-gypsum wet flue gas desulphurization technology |
| CN106076089A (en) * | 2016-08-16 | 2016-11-09 | 攀枝花市九鼎智远知识产权运营有限公司 | A kind of desulphurization denitration vent gas treatment tower |
| CN106823753A (en) * | 2017-03-30 | 2017-06-13 | 贵州诺威施生物工程有限公司 | Desulfurizing tower and desulfurization recovery system |
| CN108499335A (en) * | 2018-06-08 | 2018-09-07 | 大唐环境产业集团股份有限公司 | A kind of string tower desulphurization system for rinsing demister using recycling filtrate water |
| CN112675690A (en) * | 2020-12-11 | 2021-04-20 | 杭州蕴泽环境科技有限公司 | Low-water-consumption wet desulphurization system and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108499335A (en) * | 2018-06-08 | 2018-09-07 | 大唐环境产业集团股份有限公司 | A kind of string tower desulphurization system for rinsing demister using recycling filtrate water |
| CN112675690A (en) * | 2020-12-11 | 2021-04-20 | 杭州蕴泽环境科技有限公司 | Low-water-consumption wet desulphurization system and method |
| CN121155331A (en) * | 2025-11-20 | 2025-12-19 | 山东明晟环保科技有限公司 | Ammonia desulfurization system and desulfurization method |
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