CN102078762A - Nitrite wastewater denitrification process after wet denitration - Google Patents

Nitrite wastewater denitrification process after wet denitration Download PDF

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Publication number
CN102078762A
CN102078762A CN 201010603906 CN201010603906A CN102078762A CN 102078762 A CN102078762 A CN 102078762A CN 201010603906 CN201010603906 CN 201010603906 CN 201010603906 A CN201010603906 A CN 201010603906A CN 102078762 A CN102078762 A CN 102078762A
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China
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nitrite
waste water
denitration
wet
wastewater
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莫建松
鞠耀明
吴忠标
程常杰
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Zhejiang Tianlan Environmental Protection Technology Co Ltd
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Zhejiang Tianlan Environmental Protection Technology Co Ltd
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Abstract

The invention discloses a nitrite wastewater denitrification process after wet denitration. The process comprises the following steps of: (1) performing the wet denitration on smoke which is subjected to dust removal, wet desulfurization and nitrogen oxide oxidization, and repeatedly and circularly absorbing nitrogen oxide and nitrogen dioxide by using an absorbing liquid to form nitrite denitrated wastewater; and (2) introducing sulfite desulfurized wastewater formed by the wet desulfurization and the nitrite denitrated wastewater into a wastewater treatment tank, controlling the molar ratio of sulfite to nitrite to be between 1.0 and 2.0, adjusting the pH value to be between 3.0 and 6.0, controlling the reaction temperature to be between 30 and 70 DEG C, performing redox reaction to remove the nitrite from the wastewater and then discharging. In the process, the sulfite in the desulfurized wastewater is used as a reagent, and the nitrite is reduced into nitrogen through reaction under a mild condition, so that the nitrite in the denitrated wastewater is efficiently denitrified, and a technical route is provided for recycling the sulfite in the desulfurized wastewater and utilizing sulfate.

Description

Nitrite denitrogenation of waste water technology after a kind of wet method denitration
Technical field
The present invention relates to the Air Pollution Control field, specifically is the nitrite denitrogenation of waste water technology after a kind of wet method denitration.
Background knowledge
In recent years, along with attention to environment, the technology that removes (denitration technology) of nitrogen oxide becomes the focus of research, " oxidation-absorption " two step denitration technologies (wet method denitration technology) are subjected to researcher's more concern because of its high efficiency and economy, the end-product of absorption liquid is for containing nitrate and nitrite waste water, and the toxicity of nitrite is strong more a lot of than nitrate, nitrite is ingested and forms nitrosamine behind the human body, not only can produce strong " three cause " effect, can also reduce the blood oxygen carrying capacity, cause methemoglobinemia.
In fact, if control oxidizability well, the gained end-product overwhelming majority is a nitrite, publication number is that the Chinese invention patent application of CN101352644 discloses a kind of wet flue gas denitration technique that reclaims nitrite, comprise: adopt hydrogen peroxide or ozone as oxidant, oxidant evenly is ejected in the flue gas after pre-dedusting and desulfurization are handled carries out gas phase oxidation, make the oxidation of nitric oxide in the flue gas generate nitrogen dioxide; Then with alkali lye as absorbent, absorb the mixture of nitric oxide and nitrogen dioxide in the flue gas after peroxidating, generate nitrite; Absorbent behind concentrated absorption nitric oxide and the nitrogen dioxide, crystallisation by cooling obtains the nitrite crystal after the centrifugation.Therefore, the effective problem of handling of the nitrite waste water after the wet method denitration has to be solved.
In the relevant patent of nitrite method of wastewater treatment, most biological denitrificaion methods that adopt, be applicable to the nitrite waste water of low concentration, as: publication number is the Chinese patent of CN1263055, utilizes the bioanalysis denitrogenation to solve the pollution problem of drinking water nitrite preferably; Publication number is the Chinese patent of CN1990853, has introduced a kind of microorganism nitrite degradation agent and preparation method; Publication number is the Chinese patent of CN1800053, has set forth a kind of method of utilizing granule sludge to carry out nitrite denitrification.Generally, adopt chemical method can effectively handle high concentration nitrite waste water, but relevant patent is few in number, as: publication number is the Chinese patent of CN101157508, adopts the method for microwave aid in treatment to realize high concentration nitrite denitrogenation of waste water; Other has publication number is the Chinese patent of CN101481170, is that reagent has been realized in the aquaculture nitrite degradation in the water body with the sulfamic acid; (Ren Xianghong such as Ren Xianghong, Fan Bingan. sulphite is removed the nitrite [J] in the nitro oxidizer waste water. chemistry world, 2000,11:575-581) reported that a kind of is the nitrite waste water treatment process of reagent with the sodium sulfite, effect with efficient denitrification, but required pH value low excessively (pH≤2), this has wasted a large amount of acid reagents, is unfavorable for practical operation.
Summary of the invention
Effectively handle for nitrite waste water after realizing denitration, need further develop or improve some related-art process.The invention provides the nitrite denitrogenation of waste water technology after a kind of wet method denitration, at the nitrite waste water after the wet method denitration, utilize that sulphite is reagent in the desulfurization wastewater, under nearly condition of neutral pH, by the redox denitrification reaction, realized the denitrogenation of nitrite waste water high-efficiency.
Nitrite denitrogenation of waste water technology after a kind of wet method denitration is to the flue gas after process dedusting, wet desulphurization and the nitrogen oxide oxidation processes, handles by following processing step again:
1, wet method denitration
Wet method denitration absorbent is generally NaOH NaOH, sodium carbonate Na 2CO 3, potassium hydroxide KOH, potash K 2CO 3, calcium hydroxide Ca (OH) 2, calcium carbonate CaCO 3And dilute concentration ammoniacal liquor NH 3H 2The aqueous solution such as O, these absorption liquids can absorb nitric oxide and the nitrogen dioxide in the flue gas after peroxidating, generate corresponding nitrate and nitrite, if control oxidizability well, the overwhelming majority is nitrite (Chinese patent CN101352644) in the gained absorption liquid.Because nitrite solubility is all bigger, nitrite can be accumulated to quite high concentration (high concentration nitrite denitration waste water) in the absorption liquid.
2, denitrogenation of waste water
Because the wet desulphurization products therefrom is a sulphite, and calcium sulfite CaSO 3Solubility is very little, therefore in the above-mentioned denitration absorbent, removes calcium hydroxide Ca (OH) 2, calcium carbonate CaCO 3Outward, during as wet desulphurization absorbent, the corresponding sulphite of gained also can be accumulated to quite high concentration (high concentration sulphite desulfurization wastewater) in absorption liquid.
Nitrite waste water and sulphite waste water are introduced in the purification tank for liquid waste, controlled well the two concentration ratio, and regulate pH, redox reaction can take place remove nitrite in the waste water to faintly acid.Related electrode reaction and the standard electrode EMF of nitrite ion and sulfite ion and hydrogen ion generation denitrification reaction mainly comprises in the solution:
Relatively electrode reaction equation (1)~(6) and corresponding electrode electromotive force can be found Electrode potential apparently higher than Etc. the oxidation-reduction electrode electromotive force.Obviously, oxidizing electrode And reducing electrode Redox reaction very easily takes place, and therefore, denitrification reaction mainly comprises as follows:
Consider in the acid solution simultaneously Decomposition reaction easily takes place in instability, and products therefrom will further cause a series of new reactions, mainly comprise as follows:
Therefore, by formula (9) reaction, the nitrite anions reduzate is actual to be nitrogen.The inferior sulfate radical reduzate is actual to be sulfate radical.To sum up, the overall budget chemical reaction of nitrite ion and sulfite ion and hydrogen ion generation denitrification reaction mainly comprises:
In above-mentioned steps, reaction temperature is controlled in the 30-70 ℃ of scope, is preferably 40-60 ℃; The mol ratio of inferior sulfate radical and nitrite anions is 1.0-2.0, is preferably between the 1.25-1.75; The pH value of slurries is 3.0-6.0, is preferably between the 4.0-5.5.
3, discharge of wastewater
Nitrite concentration is lower than the discharge standard value in guaranteeing waste water, can directly efflux or enter the circulatory pool recycling.
Sulphite is reagent in the technology utilization desulfurization wastewater of the present invention, under the condition of gentleness (faintly acid, low temperature), redox reaction takes place, and nitrite is reduced to nitrogen, has realized nitrite efficient denitrification in the denitration waste water.Simultaneously, because the end-product of sulfite oxidation is a sulfate, this will provide a technology path for the resource reclaim sulfuric acid salt utilization of sulphite in the waste water after the desulfurization.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
The specific embodiment
As shown in Figure 1, through the NO that contains after dedusting, desulfurization, the oxidation xFlue gas 1 enters absorption tower 2 and absorbs the back by chimney 8 dischargings.Absorbent 3 adds in the circulatory pool 4 that fills water and is mixed with absorption liquid, is conveyed into the absorption tower by circulating pump 5 and absorbs to enter again and finish one in the circulatory pool and take turns circulation; And so forth, constantly generate nitrite in the absorption liquid; Absorption liquid Central Asia nitrate concentration reaches waste water behind 0.5~5mol/L to be sent in the treatment pond 7 that fills desulfurization wastewater 6 denitrification reaction takes place, and after nitrite has been removed in guaranteeing waste water, can enters circulatory pool 4 recyclings or directly effluxes.
Embodiment 1: utilize the sodium sulfite desulfurization wastewater to handle natrium nitrosum denitration waste water
Flue gas after the oxidation enters the absorption tower, is absorbent with sodium carbonate, and concentration is 15%, and the waste water behind the denitration reaction (the natrium nitrosum denitration waste water of 0.5mol/L) is drained into the treatment pond from the absorption tower, according to the actual concentrations of nitrite anions, presses The NaOH that mol ratio 1.75 is introduced with concentration 10% is the desulfurization wastewater (sodium sulfite desulfurization wastewater) of absorbent, under 60 ℃ of reaction temperatures, regulate pH to 4.0, nitrite can be realized 100% nitric efficiency in the waste water, and the waste water after the processing returns the circulatory pool recycling.
Embodiment 2: utilize the sodium sulfite desulfurization wastewater to handle potassium nitrite denitration waste water
Flue gas after the oxidation enters the absorption tower, is absorbent with potash, and concentration is 20%, and the waste water behind the denitration reaction (the potassium nitrite denitration waste water of 1.25mol/L) is drained into the treatment pond from the absorption tower, according to the actual concentrations of nitrite anions, presses The NaOH that mol ratio 1.50 is introduced with concentration 10% is the desulfurization wastewater (sodium sulfite desulfurization wastewater) of absorbent, under 50 ℃ of reaction temperatures, regulates pH to 4.5, and nitrite can be realized 98% nitric efficiency in the waste water.Waste water after the processing returns the circulatory pool recycling.
Embodiment 3: utilize the potassium sulfite desulfurization wastewater to handle ammonium nilrite denitration waste water
Flue gas after the oxidation enters the absorption tower, is absorbent with ammoniacal liquor, and concentration is 10%, and the waste water behind the denitration reaction (the ammonium nilrite denitration waste water of 5.0mol/L) is drained into the treatment pond from the absorption tower, according to the actual concentrations of nitrite anions, presses The potash that mol ratio 1.50 is introduced with concentration 15% is the desulfurization wastewater (potassium sulfite desulfurization wastewater) of absorbent, under 40 ℃ of reaction temperatures, regulates pH to 5.0, and nitrite can be realized 93% nitric efficiency in the waste water.The nitrite concentration value is very low in the waste water after the processing, but qualified discharge.
Embodiment 4: utilize the ammonium sulfite desulfurization wastewater to handle calcium nitrite denitration waste water
Flue gas after the oxidation enters the absorption tower, is absorbent with calcium hydroxide, and concentration is 10%, and the waste water behind the denitration reaction (0.5mol/L calcium nitrite denitration waste water) is drained into the treatment pond from the absorption tower, according to the actual concentrations of nitrite anions, presses The ammoniacal liquor that mol ratio 1.25 is introduced with concentration 10% is the desulfurization wastewater (ammonium sulfite desulfurization wastewater) of absorbent, under 40 ℃ of reaction temperatures, regulates pH to 5.5, and nitrite can be realized 85% nitric efficiency in the waste water.The nitrite concentration value is very low in the waste water after the processing, but qualified discharge.

Claims (5)

1. the nitrite denitrogenation of waste water technology after the wet method denitration comprises:
(1) wet method denitration
To carry out the wet method denitration through the flue gas after dedusting, wet desulphurization and the nitrogen oxide oxidation processes.The aqueous solution or dilute concentration ammoniacal liquor that described wet method denitration absorbent is sodium salt, sylvite, calcium salt, the oxidizability of nitrogen oxide in the control flue gas, absorbent circulates repeatedly in denitrating system and absorbs nitric oxide and nitrogen dioxide, make absorption liquid Central Asia nitrates accumulation, form nitrite denitration waste water;
(2) denitrogenation of waste water
Sulphite accumulation in the wet desulphurization absorption liquid, the sulphite desulfurization wastewater that forms, introduce in the purification tank for liquid waste with the nitrite waste water that step (1) forms, the mol ratio of control inferior sulfate radical and nitrite anions is 1.0-2.0, and adjusting pH to 3.0-6.0, reaction temperature is controlled at 30-70 ℃, and redox reaction takes place, and removes in the waste water and discharges behind the nitrite.
2. the nitrite denitrogenation of waste water technology after a kind of wet method denitration as claimed in claim 1 is characterized in that: absorption liquid Central Asia nitrates accumulation is 0.5~5mol/L to concentration in the described step (1).
3. the nitrite denitrogenation of waste water technology after a kind of wet method denitration as claimed in claim 1 is characterized in that: the mol ratio of inferior sulfate radical and nitrite anions is 1.25-1.75 in the described step (2).
4. the nitrite denitrogenation of waste water technology after a kind of wet method denitration as claimed in claim 1 is characterized in that: oxidizing reaction temperature is 40-60 ℃ in the described step (2).
5. the nitrite denitrogenation of waste water technology after a kind of wet method denitration as claimed in claim 1 is characterized in that: the pH value is adjusted to 4.0-5.5 in the described step (2).
CN 201010603906 2010-12-22 2010-12-22 Nitrite wastewater denitrification process after wet denitration Pending CN102078762A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102716648A (en) * 2012-05-16 2012-10-10 北京航空航天大学 Method for automatically controlling desulphurization and denitration by flue gas based on pH value and ORP value and apparatus thereof
CN104529012A (en) * 2015-01-05 2015-04-22 北京化工大学 Method for processing nitrite nitrogen in waste water
CN105457467A (en) * 2015-12-31 2016-04-06 安徽省绿巨人环境技术有限公司 Flue gas denitration device and method
CN105833695A (en) * 2016-05-03 2016-08-10 浙江天蓝环保技术股份有限公司 Device and technology for wet desulfurization and denitrification of flue gas of coal-fired boiler and treatment of wastewater
CN107737520A (en) * 2017-10-17 2018-02-27 上海交通大学 The method that coordinated desulfurization denitration is carried out to Flue Gas of Nonferrous Smelting using sodium alkali is circulated
CN109092017A (en) * 2018-09-19 2018-12-28 上海交通大学 A kind of method that flue gas oxidation and denitration controls nitrate generation in absorbing liquid
CN110505909A (en) * 2017-02-15 2019-11-26 通用电气技术有限公司 For improving the oxidation control of flue gas desulfurization performance

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102716648A (en) * 2012-05-16 2012-10-10 北京航空航天大学 Method for automatically controlling desulphurization and denitration by flue gas based on pH value and ORP value and apparatus thereof
CN104529012A (en) * 2015-01-05 2015-04-22 北京化工大学 Method for processing nitrite nitrogen in waste water
CN105457467A (en) * 2015-12-31 2016-04-06 安徽省绿巨人环境技术有限公司 Flue gas denitration device and method
CN105833695A (en) * 2016-05-03 2016-08-10 浙江天蓝环保技术股份有限公司 Device and technology for wet desulfurization and denitrification of flue gas of coal-fired boiler and treatment of wastewater
CN110505909A (en) * 2017-02-15 2019-11-26 通用电气技术有限公司 For improving the oxidation control of flue gas desulfurization performance
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CN107737520A (en) * 2017-10-17 2018-02-27 上海交通大学 The method that coordinated desulfurization denitration is carried out to Flue Gas of Nonferrous Smelting using sodium alkali is circulated
CN109092017A (en) * 2018-09-19 2018-12-28 上海交通大学 A kind of method that flue gas oxidation and denitration controls nitrate generation in absorbing liquid

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