CN101954239B - Method for removing sulphate and ammonia from smoke - Google Patents
Method for removing sulphate and ammonia from smoke Download PDFInfo
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- CN101954239B CN101954239B CN2010102917411A CN201010291741A CN101954239B CN 101954239 B CN101954239 B CN 101954239B CN 2010102917411 A CN2010102917411 A CN 2010102917411A CN 201010291741 A CN201010291741 A CN 201010291741A CN 101954239 B CN101954239 B CN 101954239B
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- flue gas
- cleaning solution
- ammonia
- gas
- absorption tower
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 provides a method for removing sulphate and ammonia from smoke, which comprises the following steps of: keeping the temperature of the smoke containing sulfur dioxide and the ammonia at 150 to 400 DEG C before the smoke enters an absorption tower; introducing the smoke into the absorption tower and cooling with cooling water; and washing the smoke with cleaning solution, wherein the pH value of the cleaning solution ranges from 4 to 9 and the temperature of the cleaning solution ranges from 40 to 90 DEG C. The method for removing the sulphate and ammonia from the smoke can effectively absorb the sulfur dioxide and the ammonia in the smoke at the same time.
Description
Technical field
The present invention relates to a kind of method of flue gas desulfurization deamination gas, specifically, relate to a kind of method that sulfur dioxide in the flue gas and ammonia are removed simultaneously.
Background technology
In most cases can contain a large amount of sulfur dioxide gas in the flue gas, the discharging of sulfur dioxide gas can affect air quality, the health of harmful to human.In addition, the sulfur dioxide that is discharged in the atmosphere can form acid rain, destroys the ecosystem.Processing method for sulfur dioxide in flue gas is more, can be divided into following four kinds of methods according to the kind of desulfurizing agent: with CaCO
3(lime stone) is the calcium method of desulfurizing agent, and the magnesium method take MgO as desulfurizing agent is with NH
3Be the ammonia process of desulfurizing agent and the organic alkaline process take organic base as desulfurizing agent.
In addition, contain sometimes ammonia in the flue gas.Ammonia can be for the manufacture of nitric acid, gunpowder and synthetic fibers, and in a large number for the manufacture of urea, ammonium fertilizer etc.Ammonia also has toxicity to human body.Therefore, enter atmosphere if will contain the flue gas of ammonia, then not only can affect environment, but also can cause the waste of resource.For the flue gas that contains ammonia, generally adopt acid or water to absorb ammonia in the flue gas, to remove the ammonia in the flue gas and to reclaim.
Yet, in some flue gas, can contain simultaneously sulfur dioxide gas and ammonia, for example, in the baking flue gas of vanadium oxide production wastewater evaporative crystallization thing, not only contain sulfur dioxide gas but also contain ammonia.For not only containing sulfur dioxide but also containing the flue gas of ammonia, utilize said method to be difficult to effectively remove sulfur dioxide and ammonia in the flue gas.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art, and a kind of method that sulfur dioxide in flue gas and ammonia are removed simultaneously is provided.
Method according to flue gas desulfurization deamination gas of the present invention may further comprise the steps: before the flue gas that contains sulfur dioxide and ammonia enters the absorption tower flue gas remained in 150 ℃～400 ℃ the temperature range; Flue gas is passed into the absorption tower and utilizes cooling water to cool off; Utilize cleaning solution that flue gas is washed, wherein, the pH value of cleaning solution is in 4～9 scope, and the temperature of cleaning solution is in 40 ℃～90 ℃ temperature range.
The method according to this invention, in the washing process of flue gas, the cleaning solution that uses at first is the aqueous solution of pH value in 4～9 scope of sulfuric acid and ammoniacal liquor formation.
The method according to this invention, the cooling water after the cooled flue gas mixes with cleaning solution.The cleaning solution that ammonium salt concentration does not reach emission request is used for the circulation cleaning flue gas.Ammonium salt concentration reaches the cleaning solution of emission request and recycles.Can utilize sulfuric acid and ammoniacal liquor to regulate the pH value of cleaning solution.Flue gas can remain on before entering the absorption tower in 200 ℃～300 ℃ the temperature range.
The present invention absorbs the sulfur dioxide in the flue gas and ammonia simultaneously by pH value and the temperature of regulating cleaning solution, and method is simple.
Description of drawings
Fig. 1 is the flue gas operation schematic diagram according to the method for flue gas desulfurization deamination gas of the present invention.
The specific embodiment
Describe the present invention in detail with embodiment below with reference to accompanying drawings.
Fig. 1 is the flue gas operation schematic diagram according to the method for flue gas desulfurization deamination gas of the present invention.With reference to Fig. 1, realize by following steps according to the method for desulfurization deamination gas of the present invention: at first, before the flue gas that contains sulfur dioxide and ammonia enters the absorption tower, flue gas remained in 150 ℃～400 ℃ the temperature range; The flue gas that then, will contain ammonia and sulfur dioxide passes into the absorption tower and utilizes cooling water that flue gas is cooled off; At last, utilize cleaning solution that flue gas is washed, the pH of cleaning solution is in 4～9 scope, and the temperature of cleaning solution is in 40 ℃～90 ℃ temperature range.Wherein, being washed sulfur dioxide that liquid absorbs and ammonia in the absorption tower reacts and generates ammonium bisulfite and/or ammonium sulfite.
In said method, in the washing process of flue gas, the cleaning solution that uses at first is the aqueous solution of pH in 4～9 scope of sulfuric acid and ammoniacal liquor formation.
In above-mentioned steps, flue gas utilizes cooling water to cool off after passing into the absorption tower, and the cooling water after the cooled flue gas mixes to be used for the washing flue gas with cleaning solution.The cleaning solution that ammonium salt concentration does not reach emission request is used for the circulation cleaning flue gas until the ammonium salt concentration of enrichment reaches the requirement of discharging.Ammonium salt concentration reaches the cleaning solution of emission request and recycles.The tail gas that obtains through carrying out washing treatment can discharge, but is not limited to this, for example, can recycle the tail gas that processing obtains.In actual mechanical process, should according to circumstances replenish new water to cleaning solution, so that washing process can carry out continuously.
Before the flue gas that contains sulfur dioxide and ammonia entered the absorption tower, if the temperature of flue gas is lower than 150 ℃, then the ammonia in the flue gas and sulfur dioxide will react before entering the absorption tower, form solid matter and make line clogging and cause corrosive pipeline.If the temperature of flue gas is higher than 400 ℃, then to the equipment such as pipeline and absorption tower require too highly, and make production cost too high.Therefore, before the flue gas that contains sulfur dioxide and ammonia enters the absorption tower flue gas remained in 150 ℃～400 ℃ the temperature range, here, the temperature range that flue gas enters before the absorption tower is preferably in 200 ℃～300 ℃ temperature range.
PH in 4～9 scopes and the cleaning solution of temperature in 40 ℃～90 ℃ scopes can effectively absorb sulfur dioxide and ammonia in the flue gas.If pH is less than 4, the ammonium sulfite that then generates in the washing process and ammonium bisulfite can decompose and discharge sulfur dioxide, and make the assimilation effect variation of sulfur dioxide in flue gas; If pH is greater than 9, the ammonium sulfite that then generates in the washing process and ammonium bisulfite can decompose and discharge ammonia, and make the assimilation effect variation of ammonia in flue gas gas.If the temperature of cleaning solution is higher than 90 ℃, the ammonium sulfite that then generates in the washing process and ammonium bisulfite can decompose and discharge sulfur dioxide and ammonia, make the deleterious of flue gas desulfurization deamination gas, and can make ammonia and sulfur dioxide in the tail gas exceed discharge standard; If the temperature of cleaning solution is lower than 40 ℃, then can absorb not exclusively because reaction rate makes ammonia and sulfur dioxide in the flue gas slowly.
As mentioned above, the cooling water after the cooled flue gas mixes to be used for the washing flue gas with cleaning solution, and this not only can effectively utilize cooling water, but also can effectively reclaim sulfur dioxide and the ammonia that absorbs in the cooling water, thereby avoids discharging the environmental pollution that causes.
Ammonium salt in the cleaning solution mainly is ammonium sulfite and ammonium bisulfite, method for subsequent processing for such ammonium salt mainly contains two kinds, a kind of for utilizing air that ammonium salt is oxidized into ammonium sulfate, another kind of is to add acid to make it generate corresponding salt in the cleaning solution of discharging, for example, adding sulfuric acid in the cleaning solution of discharging makes it generate ammonium sulfate or ammonium hydrogen sulfate.In the washing process of flue gas, the discharge standard of cleaning solution is then decided according to the follow-up processing method of cleaning solution, for example, when utilizing the air oxidation ammonium salt to process cleaning solution, the NH in cleaning solution
4 +When being no more than 1.5mol/L, concentration can discharge cleaning solution.
In above-mentioned steps, do not consider and bring new ion into cleaning solution, utilize sulfuric acid and ammoniacal liquor to regulate the pH value of cleaning solution.
Embodiment 1
200 ℃ flue gases (composition sees Table 1) are passed into the absorption tower, utilize cooling water to cool off, the pH value of then utilizing 70 ℃ is that 6.5 cleaning solution washs.Wherein, the cooling water that cooled off flue gas mixes to come the circulation cleaning flue gas with cleaning solution.At last, utilize the Vario Plus flue gas analyzer of MRU company to analyze SO in the tail gas
2, utilize the NH in the PortaSens II detector analysis tail gas
3Wherein, SO in the tail gas
2Volume ratio be 110ppm, NH
3Volume ratio be 150ppm.
Table 1
Embodiment 2
The baking flue gas (composition sees Table 2) of 300 ℃ of vanadium oxide production wastewater evaporation and concentration post crystallization things is passed into the absorption tower, utilize cooling water to carry out spraying cooling, the pH value of then utilizing 60 ℃ is that 6 cleaning solution washs.Wherein, the cooling water that cooled off flue gas mixes to come the circulation cleaning flue gas with cleaning solution.At last, utilize the Vario Plus flue gas analyzer of MRU company to analyze SO in the tail gas
2, utilize the NH in the PortaSens II detector analysis tail gas
3Wherein, SO in the tail gas
2Volume ratio be 40ppm, NH
3Volume ratio be 90ppm.
Table 2
Embodiment 3
The baking flue gas (composition sees Table 3) of 400 ℃ of vanadium oxide production wastewater evaporation and concentration post crystallization things is passed into the absorption tower, utilize cooling water to carry out spraying cooling, the pH value of then utilizing 40 ℃ is that 4 cleaning solution washs.Wherein, the cooling water that cooled off flue gas mixes to come the circulation cleaning flue gas with cleaning solution.At last, utilize the Vario Plus flue gas analyzer of MRU company to analyze SO in the tail gas
2, utilize the NH in the PortaSens II detector analysis tail gas
3Wherein, SO in the tail gas
2Volume ratio be 420ppm, NH
3Volume ratio be 120ppm.
Table 3
Embodiment 4
The baking flue gas (composition sees Table 4) of 150 ℃ of vanadium oxide production wastewater evaporation and concentration post crystallization things is passed into the absorption tower, utilize cooling water to carry out spraying cooling, the pH value of then utilizing 90 ℃ is that 9 cleaning solution washs.Wherein, the cooling water that cooled off flue gas mixes to come the circulation cleaning flue gas with cleaning solution.At last, utilize the Vario Plus flue gas analyzer of MRU company to analyze SO in the tail gas
2, utilize the NH in the PortaSens II detector analysis tail gas
3Wherein, SO in the tail gas
2Volume ratio be 350ppm, NH
3Volume ratio be 850ppm.
Table 4
To finding out in the description of the embodiment of the invention, the method for flue gas desulfurization deamination gas of the present invention can be removed the sulfur dioxide in the flue gas and ammonia simultaneously effectively, and method is simple by top.
Claims (7)
1. the method for a flue gas desulfurization deamination gas said method comprising the steps of:
Before the flue gas that contains sulfur dioxide and ammonia enters the absorption tower, flue gas remained in 150 ℃～400 ℃ the temperature range, before entering the absorption tower, react and form solid matter to prevent sulfur dioxide in the flue gas and ammonia;
Flue gas is passed into the absorption tower and utilizes cooling water to cool off;
Utilize cleaning solution that flue gas is washed, wherein, the pH value of cleaning solution is in 4～9 scope, and the temperature of cleaning solution is in 40 ℃～90 ℃ scope.
2. the method for flue gas desulfurization deamination gas as claimed in claim 1 is characterized in that, in the washing process of flue gas, the cleaning solution that uses at first is pH value aqueous solution in 4～9 scope of sulfuric acid and ammoniacal liquor formation.
3. the method for flue gas desulfurization deamination gas as claimed in claim 1 is characterized in that, the cooling water after the cooled flue gas mixes with cleaning solution.
4. the method for flue gas desulfurization deamination gas as claimed in claim 1 is characterized in that, the cleaning solution that ammonium salt concentration does not reach emission request is used for the circulation cleaning flue gas.
5. the method for flue gas desulfurization deamination gas as claimed in claim 1 is characterized in that, ammonium salt concentration reaches the cleaning solution of emission request and recycles.
6. the method for flue gas desulfurization deamination gas as claimed in claim 1 is characterized in that, utilizes sulfuric acid and ammoniacal liquor to regulate the pH value of cleaning solution.
7. the method for flue gas desulfurization deamination gas as claimed in claim 1 is characterized in that, flue gas remained on before entering the absorption tower in 200 ℃～300 ℃ the temperature range.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102917411A CN101954239B (en) | 2010-09-26 | 2010-09-26 | Method for removing sulphate and ammonia from smoke |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102917411A CN101954239B (en) | 2010-09-26 | 2010-09-26 | Method for removing sulphate and ammonia from smoke |
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| Publication Number | Publication Date |
|---|---|
| CN101954239A CN101954239A (en) | 2011-01-26 |
| CN101954239B true CN101954239B (en) | 2013-01-23 |
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| CN2010102917411A Expired - Fee Related CN101954239B (en) | 2010-09-26 | 2010-09-26 | Method for removing sulphate and ammonia from smoke |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105403057B (en) * | 2014-09-10 | 2017-11-03 | 中国石油化工股份有限公司 | A kind of processing method of molecular sieve baking tail gases |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1368898A (en) * | 1999-08-12 | 2002-09-11 | 株式会社荏原制作所 | Method and apparatus for treating exhaust gas |
| DE10119991A1 (en) * | 2001-04-23 | 2002-10-24 | Stephan Pieper | Purification of biogas containing hydrogen sulfide and ammonia, removes hydrogen sulfide at least partially by absorption into alkaline wash solution |
| TW200510055A (en) * | 2003-09-05 | 2005-03-16 | Ind Tech Res Inst | Method and apparatus for treating waste gas containing acids and/or bases |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2571500A (en) * | 1999-02-16 | 2000-09-04 | Ebara Corporation | Gas cooling device, gas treatment device, and boiler equipment |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1368898A (en) * | 1999-08-12 | 2002-09-11 | 株式会社荏原制作所 | Method and apparatus for treating exhaust gas |
| DE10119991A1 (en) * | 2001-04-23 | 2002-10-24 | Stephan Pieper | Purification of biogas containing hydrogen sulfide and ammonia, removes hydrogen sulfide at least partially by absorption into alkaline wash solution |
| TW200510055A (en) * | 2003-09-05 | 2005-03-16 | Ind Tech Res Inst | Method and apparatus for treating waste gas containing acids and/or bases |
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| CB02 | Change of applicant information |
Address after: Panzhihua City, Sichuan province 617067 Xiangyang Village East Applicant after: Pangang Group Steel Vanadium & Titanium Co., Ltd. Co-applicant after: Pangang Group Panzhihua Iron & Steel Research Institute Co., Ltd. Co-applicant after: Pan'gang Group Engineering Technology Co., Ltd. Co-applicant after: Pangang Group Panzhihua Steel Vanadium Co., Ltd. Address before: Panzhihua City, Sichuan province 617067 Xiangyang Village East Applicant before: Pangang Group Steel Vanadium & Titanium Co., Ltd. Co-applicant before: Pangang Group Panzhihua Iron & Steel Research Institute Co., Ltd. Co-applicant before: Pangang Group Metallugical Engineering Technology Co., Ltd. Co-applicant before: Pangang Group Panzhihua Steel Vanadium Co., Ltd. |
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| C14 | Grant of patent or utility model | ||
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Granted publication date: 20130123 Termination date: 20170926 |
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| CF01 | Termination of patent right due to non-payment of annual fee |