CN104084023A - Method for performing desulfurization and denitration on flue gas simultaneously - Google Patents
Method for performing desulfurization and denitration on flue gas simultaneously Download PDFInfo
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- CN104084023A CN104084023A CN201410341041.7A CN201410341041A CN104084023A CN 104084023 A CN104084023 A CN 104084023A CN 201410341041 A CN201410341041 A CN 201410341041A CN 104084023 A CN104084023 A CN 104084023A
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- flue gas
- denitration
- desulfurizing
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- denitrifying
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention discloses a method for performing desulfurization and denitration on flue gas simultaneously, belonging to the environment protection field. Nitrogen oxide-containing flue gas or exhaust gas enters a lower denitration section of an absorption tower, nitric oxides are complexed and absorbed by a ferrous chelate in a reactor and then are subjected to reduction reaction by metallic iron to obtain ammonia gas, flue gas together with NH3 generated in the denitration section enters a desulfuration section, NH3 and ammonium hydroxide supplemented in the desulfuration section are reacted with sulfur dioxide in the desulfuration section to obtain ammonium sulfite, then ammonium sulfite is oxidized to obtain ammonium sulfate to achieve desulfuration, and finally, the desulfurized flue gas or waste gas is directly exhausted to atmosphere after dehydration. According to the method, simultaneous desulfurization and denitration in one tower can be realized, the efficiency is high, the cost is low, the operation is simple, and the running is stable, the method is suitable for denitration of nitrogen oxide flue gas or waste gas mainly containing nitric oxide, and is particularly suitable for desulfurization and denitration of flue gas of medium-small boilers in China.
Description
Technical field
The present invention relates to a kind of method of gas cleaning, relate in particular to the method for flue gas exhuast gas desulfurization denitration, belong to field of environment protection.
Technical background
Nitrogen oxide (take NO as main) and sulfur dioxide are the atmosphere pollutions that is subject at present global extensive concern, have every year a large amount of nitrogen oxide and sulfur dioxide to enter atmosphere, cause serious environmental pollution and human body is had to very large harm.
At present, about the technique that removes sulfur dioxide in flue gas and nitrogen oxide comparative maturity, carry out already large-scale industrial application, but most technique is all only useful for one-component, nitrogen oxides in effluent and sulfur dioxide often exist simultaneously, if utilize these equipment that can only process Single Pollution thing to remove respectively nitrogen oxide and sulfur dioxide, have that floor space is large, high in cost of production problem.Therefore, further the technology of research and development while desulphurization denitration, significant for the control of atmosphere pollution.
The method that simultaneously removes sulfur dioxide and nitrogen oxide is mainly divided into dry method and the large class of wet method two.Dry process is at high temperature sulfur trioxide by Sulphur Dioxide as patent CN103263848A adopts oxidant, then with scrap iron and dilute acid recycle, obtains ferrous sulfate heptahydrate product, and nitric oxide or nitrogen dioxide are converted into nitrogen simultaneously.Patent CN102908883A produces a large amount of active materials with ultraviolet radiation flue gas, and the sulfur dioxide in flue gas and nitrogen oxide are oxidized and generate stable sulfuric acid and nitric acid, collects or passes into ammonia generate ammonium sulfate and ammonium nitrate with acid mist removal device.Sulfur dioxide, nitrogen oxide in ozone simultaneous oxidation flue gas for patent CN101337152A, oxidation product and water, in conjunction with generating mist droplet, are gathered into mix acid liquor after charged coalescence, then through chemical method separating-purifying, become sulfuric acid, nitric acid.Above processing method has higher denitrification efficiency, but agents useful for same and comparison in equipment are expensive, for the flue gas that discharge capacity is large, processes, and economy and engineering application are not strong.Wet-treating adopts different absorbents sulfur dioxide and nitrogen oxide to be removed to the method for processing as patent CN103301731A, CN102989273A, CN101352648A, CN102698599A, CN102698581A provide, the absorbent that these methods adopt is the compound absorbents such as sodium chlorite, sodium chlorate, with high costs and deal with improperly and easily cause secondary pollution.Patent CN103331095A is first nitrogen dioxide by the oxidation of nitric oxide in flue gas, and then sulfur dioxide and nitrogen oxide react with seawater base absorbent in hydrophobic hollow fiber film absorber, realize desulphurization denitration; CN203155066U adopts non-thermal discharge unit (the pin array corona discharge reactor that connects high voltage power distribution unit) to carry out pre-oxidation treatment to flue gas, then with alkali lye, sulfur dioxide and nitrogen oxide is absorbed; CN102500207A by flue gas oxidation, then removes the flue gas after being oxidized with ammoniacal liquor in reaction of low temperature plasma device; CN102247750A is provided with ozone generator in bottom, absorption tower, and in absorption liquid, has added catalyst, utilizes ozone and catalyst by the sulfur dioxide in flue gas and nitrogen oxide efficient oxidation, and then water or alkaline matter absorb processing; CN101745306A, in twin shaft impact reactor, utilizes urea/ammoniacal liquor mixed solution to carry out absorbing and removing to sulfur dioxide and nitrogen oxide; The treatment facility complex structure that above method adopts, has increased the cost of operation and maintenance, economical not.Patent CN103230734A adopts the absorption technique of associating FGD technique (limestone/gypsum sulfur removal technology) and metal complex solution to remove sulfur dioxide and nitrogen oxide, subtractive process is by active carbon (AC) catalysis and electrochemistry booster action, and end product is sulfate and N
2.Its complex process, equipment are various, and accessory substance gypsum, containing various heavy, pollutes large.Patent CN102989272A adopts bioanalysis, utilize synchronized desulfuring denitrogenation flora to remove sulfur dioxide and the nitrogen oxide of wash-out tower wash-out, the domestication of the method microorganism and longer to the processing time of pollutant, change in concentration reply for pollutant in waste gas is slow, the excessive death that even can cause microorganism of change in concentration.Patent CN103301749A adopts the particulate of transition metal oxide or containing the particulate of the mixture of transition metal oxide, the sulfur dioxide in flue gas and nitric oxide Catalytic Oxygen is changed into sulfur trioxide and nitrogen dioxide, then water absorbs processing.The problem that the method exists metal oxide easily to be poisoned.
To sum up, desulfurization denitration method when having developed at present, respectively has merits and demerits, but is all unsuitable for commercial Application generally.Therefore, develop and be a kind ofly applicable to commercial Application to be particularly applicable to the method for integrated while desulphurization denitration of China significant.
Summary of the invention
The object of the invention is for shortcomings and deficiencies of the prior art, a kind of method of flue gas and desulfurizing and denitrifying is provided.
Technical scheme provided by the invention is:
A method for flue gas and desulfurizing and denitrifying, comprises the steps:
Cigarette (giving up) gas enters the bottom denitration section on absorption tower, carries out denitration reaction with the ferrous chelating agent of denitration circulation fluid from denitration circulating tank, makes NO enter liquid phase, with the form of ferrous nitrosyl complex, exists; Metallic iron can react with ferrous nitrosyl complex, the ferrous chelating agent produce NH of regenerating
3, the activity of recovery denitrfying agent; Process has consumed iron powder or iron filings, and output iron hydroxide or the disposal of resources of ferrous hydroxide precipitation, can be used for producing iron oxide red pigment etc.
Denitration reaction is:
2Fe
2+EDTA(NO)+Fe+8H
+→2Fe
2+EDTA+Fe(OH)
2+2NH
3
4Fe
2+EDTA+O
2+4H
+→4Fe
3+EDTA+2H
2O
2Fe
2+EDTA+Fe+2OH
-→2Fe
2+EDTA+Fe(OH)
2
2Fe(OH)
2+2H
++O
2→2Fe(OH)
3
2Fe(OH)
3+Fe→3Fe(OH)
2
The NH that denitrification process produces
3with flue gas, enter desulfurization section, together with the desulfurizing agent adding, sulfur dioxide removal is obtained to ammonium sulfite or ammonium bisulfite, final oxidation obtains ammonium sulfate product, ammonium sulfite has good absorbability to sulfur dioxide, and ammonium sulfite or ammonium bisulfite are finally oxidized to ammonium sulfate as fertilizer selling.
Desulphurization reaction is:
SO
2+NH
3+H
2O→NH
4HSO
3
SO
2+2NH
3+H
2O→(NH
4)
2SO
3
SO
2+(NH
4)
2SO
3+H
2O→2NH
4HSO
3
NH
3+NH
4HSO
3→(NH
4)
2SO
3
2(NH
4)
2SO
3+O
2→2(NH
4)
2SO
4
The method of above-mentioned flue gas and desulfurizing and denitrifying, the temperature of described denitration reaction is 10～60 ℃, pH value is 6.0～8.0.
The method of above-mentioned flue gas and desulfurizing and denitrifying, described absorption tower is sieve-plate tower, rotating stream tray scrubber, spray column or bubble tower.
The method of above-mentioned flue gas and desulfurizing and denitrifying, the temperature of described desulphurization reaction is 10～60 ℃, pH value is 5～7.
The method of above-mentioned flue gas and desulfurizing and denitrifying, described desulfurizing agent is ammoniacal liquor, the mass fraction of described ammoniacal liquor is 5～20%.
Beneficial effect of the present invention is:
(1) the present invention, under the condition without catalyst, has realized and in a system, has removed sulfur dioxide (S0 in cigarette (giving up) gas simultaneously
2) and nitrogen oxide (NO
x), with low cost, simple to operate, stable;
(2) the present invention first carries out denitration processing by absorption process to flue gas, then with metallic iron, denitration liquid is reduced, and not only realizes recycling of denitration liquid, and the NH of reduction process generation
3can be used for desulfurization, both made denitration liquid be fully used, cost-saving, reduced again the process of subsequent treatment.
(3) denitrification efficiency of the present invention is high, all reach more than 90%, and product easily processes, and the flue gas after processing can directly enter atmosphere, has effectively avoided flue gas to cause secondary pollution.
(4) present device investment operating cost is low, has reduced largely the cost that flue gas is processed, and being applicable to containing nitric oxide is main nitrogen oxide cigarette (giving up) qi exhaustion nitre, is particularly suitable for China's medium and small boiler denitrating flue gas desulfurization.
Accompanying drawing explanation
Fig. 1 is process chart of the present invention.
Fig. 2 is the structural representation of flue gas and desulfurizing and denitrifying device of the present invention:
The 1st, former flue gas/exhaust gas import, the 2nd, denitration section, the 3rd, desulfurization section, the 4th, dehydrator, the 5th, clean flue gas/exhaust gas outlet, the 6th, denitration circulating tank, the 7th, denitration liquid preparation tank, the 8th, desulphurization circulating tank, the 9th, ammoniacal liquor holding vessel.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further details, but the present invention is not limited to this.
As depicted in figs. 1 and 2, flue gas or waste gas enter denitration unit by former flue gas/exhaust gas import 1, the ferrous chelating agent Fe in denitration circulating tank 6
2+eDTA solution and metallic iron are respectively as denitrfying agent and reducing agent, and the denitration reaction that completes flue gas and ferrous chelating agent in denitration section 2 removes NO, form ferrous nitrosyl complex, then metallic iron and complex compound generation reduction reaction, the Fe that oxidation is obtained
3+eDTA is reduced into Fe
2+eDTA maintains the activity of denitration liquid, generates NH simultaneously
3, NH
3with flue gas, enter desulfurization section 3, NH
3jointly realize desulfurization with the desulfurizing agent ammoniacal liquor in ammoniacal liquor holding vessel 9, flue gas is through entering atmosphere by dehydrator 4 from clean flue gas/exhaust gas outlet 5 after desulphurization denitration.
The pH value of this denitration reaction operation is controlled at 6～8, and temperature is 10～60 ℃.Denitrification process has consumed iron powder or iron filings, has eliminated NO, and output ammonia is for desulfurization, and the iron hydroxide of output or ferrous hydroxide are for the production of iron oxide red pigment etc.
After flue gas or exhaust gas denitration, enter desulfurization stage, this stage, pH was controlled at 5～7, and 10～60 ℃ of temperature are utilized the NH that the ammoniacal liquor prepared in desulfurization pond and denitration stage produce
3sulfur dioxide in flue gas or waste gas is removed, product contains ammonium bisulfite, ammonium sulfite and ammonium sulfate, ammonium sulfite has good absorbability to sulfur dioxide, and ammonium sulfite or ammonium bisulfite are finally oxidized to ammonium sulfate as fertilizer selling.
Embodiment 1
At Φ
in=40mm, in the reactor of L=400mm, adds the Fe of 15mmol/L
2+eDTA chelating liquid 200mL and iron powder 0.8g, pH=8.0, temperature is controlled at 20 ℃, passes into 0.6m
3/ h simulated exhaust (1000 * 10
-6sO
2, 200 * 10
-6nO, all the other are air).Flue gas after denitration passes into Φ
inin the sieve-plate tower of the built-in 4 layers of sieve plate of=100mm, in tank used for storing ammonia, ammonia mass fraction is 13.5%, pH=5.2.Through desulphurization denitration, process, the removal efficiency of NOx is 94.2%, SO
2removal efficiency be 90.3%.
Embodiment 2
At Φ
in=40mm, in the reactor of L=400mm, adds the Fe of 15mmol/L
2+eDTA chelating liquid 200mL and iron powder 0.8g, pH=8.0, temperature is controlled at 30 ℃, passes into 0.6m
3/ h simulated exhaust (1000 * 10
-6sO
2, 200 * 10
-6nO, all the other are air).Flue gas after denitration passes into Φ
inin the sieve-plate tower of the built-in 4 layers of sieve plate of=100mm, in ammonia process of desulfurization circulating tank, ammonia mass fraction is 18.5%, pH=5.6.Through desulphurization denitration, process, the removal efficiency of NOx is 96.5%, SO
2removal efficiency be 91.1%.
Embodiment 3
At Φ
in=40mm, in the reactor of L=400mm, adds the Fe of 15mmol/L
2+eDTA chelating liquid 200mL and iron powder 0.8g, pH=6.0, temperature is controlled at 10 ℃, passes into 0.6m
3/ h simulated exhaust (1000 * 10
-6sO
2, 200 * 10
-6nO, all the other are air).Flue gas after denitration passes in bubble tower, and in ammonia process of desulfurization circulating tank, ammonia mass fraction is 20%, pH=7.0.Through desulphurization denitration, process, the removal efficiency of NOx is 93.6%, SO
2removal efficiency be 96.4%.
Embodiment 4
At Φ
in=40mm, in the reactor of L=400mm, adds the Fe of 15mmol/L
2+eDTA chelating liquid 200mL and iron powder 0.8g, pH=7.0, temperature is controlled at 50 ℃, passes into 0.6m
3/ h simulated exhaust (1000 * 10
-6sO
2, 200 * 10
-6nO, all the other are air).Flue gas after denitration passes in spray column, and in ammonia process of desulfurization circulating tank, ammonia mass fraction is 5%, pH=5.0.Through desulphurization denitration, process, the removal efficiency of NOx is 95.1%, SO
2removal efficiency be 90.8%.
Embodiment 5
At Φ
in=40mm, in the reactor of L=400mm, adds the Fe of 15mmol/L
2+eDTA chelating liquid 200mL and iron powder 0.8g, pH=7.0, temperature is controlled at 60 ℃, passes into 0.6m
3/ h simulated exhaust (1000 * 10
-6sO
2, 200 * 10
-6nO, all the other are air).Flue gas after denitration passes in rotating stream tray scrubber, and in ammonia process of desulfurization circulating tank, ammonia mass fraction is 16%, pH=6.0.Through desulphurization denitration, process, the removal efficiency of NOx is 90.8%, SO
2removal efficiency be 92.6%.
Embodiment 6
At Φ
in=40mm, in the reactor of L=400mm, adds the Fe of 15mmol/L
2+eDTA chelating liquid 200mL and iron powder 0.8g, pH=6.8, temperature is controlled at 45 ℃, passes into 0.6m
3/ h simulated exhaust (1000 * 10
-6sO
2, 200 * 10
-6nO, all the other are air).Flue gas after denitration passes into Φ
inin the sieve-plate tower of the built-in 4 layers of sieve plate of=100mm, in ammonia process of desulfurization circulating tank, ammonia mass fraction is 9.5%, pH=5.8.Through desulphurization denitration, process, the removal efficiency of NOx is 94.6%, SO
2removal efficiency be 92.6%.
Claims (6)
1. a method for flue gas and desulfurizing and denitrifying, comprises the steps:
(1) flue gas enters the denitration section of bottom, absorption tower, carries out denitration reaction with the ferrous chelating agent of denitrfying agent from denitration circulating tank, makes nitrogen oxide in flue gas enter liquid phase with the form of ferrous nitrosyl complex;
(2) metallic iron and ferrous nitrosyl complex react, the ferrous chelating agent produce NH of regenerating
3, simultaneously by by the Fe of dioxygen oxidation in flue gas
3+be reduced to Fe
2+, the activity of maintenance denitrfying agent;
(3) NH that denitrification process produces
3, with flue gas, enter desulfurization section, carry out desulphurization reaction together with the desulfurizing agent adding, by sulfur dioxide removal;
(4) flue gas after desulphurization reaction discharges after entering dehydrator.
2. the method for flue gas and desulfurizing and denitrifying according to claim 1, described metallic iron is iron powder or iron filings.
3. the method for flue gas and desulfurizing and denitrifying according to claim 1, the temperature of described denitration reaction is 10～60 ℃, pH value is 6～8.
4. the method for flue gas and desulfurizing and denitrifying according to claim 1, described absorption tower is sieve-plate tower, rotating stream tray scrubber, spray column or bubble tower.
5. the method for flue gas and desulfurizing and denitrifying according to claim 1, the temperature of described desulphurization reaction is 10～60 ℃, pH value is 5～7.
6. the method for flue gas and desulfurizing and denitrifying according to claim 1, described desulfurizing agent is ammoniacal liquor, the mass fraction of described ammoniacal liquor is 5～20%.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110327761A (en) * | 2019-06-28 | 2019-10-15 | 苏州仕净环保科技股份有限公司 | The technique of NOx in a kind of removing flue gas |
| CN112408421A (en) * | 2020-04-03 | 2021-02-26 | 中冶长天国际工程有限责任公司 | Method for preparing high-purity ammonium sulfite by using ammonia desulfurization wastewater |
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| CN112408421A (en) * | 2020-04-03 | 2021-02-26 | 中冶长天国际工程有限责任公司 | Method for preparing high-purity ammonium sulfite by using ammonia desulfurization wastewater |
| CN112408421B (en) * | 2020-04-03 | 2022-04-08 | 中冶长天国际工程有限责任公司 | Method for preparing high-purity ammonium sulfite by using ammonia desulfurization wastewater |
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Application publication date: 20141008 |