CN1546210A - Method for removing nitric oxide from waste gas - Google Patents
Method for removing nitric oxide from waste gas Download PDFInfo
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- CN1546210A CN1546210A CNA2003101106518A CN200310110651A CN1546210A CN 1546210 A CN1546210 A CN 1546210A CN A2003101106518 A CNA2003101106518 A CN A2003101106518A CN 200310110651 A CN200310110651 A CN 200310110651A CN 1546210 A CN1546210 A CN 1546210A
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Abstract
The invention refers to a method for eliminating nitrogen oxide from waste gas, which solves the problem of high investment and high cost by using current selective catalyst reducing method and selective non-catalyst reducing method. It uses the ferrous iron mist liquid as the denitriding liquid. The reducing matter is iron. The method uses ferrous chelator to react with the nitrogen oxide, generates nitrosyl complex, the nitrogen oxide in the waste gas enters the liquid phase, the iron and the nitrosyl complex react, reduces the nitrogen combined with the chelate iron into N2. The process is simple, the operation is convenient. The cost is low, and the efficiency is high.
Description
The technical field is as follows:
the invention relates to a method for removing nitric oxide in waste gas.
Background art:
the technology for removing nitric oxide in industrial waste gas mainly comprises the following steps: selective catalytic reductionand selective non-catalytic reduction. Both of these methods are relatively expensive to invest in and operate, and each has some disadvantages. Therefore, research and development of a new simple, cheap and applicable nitric oxide control technology is a popular topic in the field of air pollution control for over 20 years.
Since the 70 s of the 20 th century, the united states and japan made extensive studies on the simultaneous removal of SO2 and NOX from flue gas by liquid phase complexation. The results show that when the ferrous chelating agent is added into the wet desulphurization washing liquid for simultaneous desulphurization and denitrification, the operation cost is very high because the absorption liquid cannot be regenerated and recycled, so the method has not been industrialized.
The invention content is as follows:
the invention aims to provide a simple process. Easy operation, mild reaction conditions and low investment and operation cost. High denitrification efficiency and easy industrialization.
The purpose of the invention is realized by the following ways: a method for removing nitrogen monoxide in waste gas is characterized in that a denitrification washing liquid is a ferrous chelating agent solution, and a reducing agent is metallic iron.
1, the ferrous iron mixture can carry out complex reaction with nitric oxide to form a nitrosyl complex, so that the nitric oxide which is hardly dissolved in water in the waste gas enters a liquid phase.
2, the nitrogen removal can be realized by reacting with a ferrous nitrosyl complex to reduce the nitric oxide combined with the chelated iron to N2.
2. The chelating agent is regenerated while reducing nitrogen monoxide to N2, and part of Fe is removed in the denitrification process2+Is oxidized into Fe3This fraction of Fe3Meanwhile, the washing liquid can realize the circular denitrification by being reduced by iron. The metal iron used in the denitrification process can be scrap iron or iron powder. The iron consumed in the denitrification process is changed into a hydrated precipitate of ferric oxide, and the product has high purity and can be used for preparing pigments or other chemical products. The present invention can remove nitric oxide with high efficiency in any suitable absorption equipment.
The invention has the advantages that: 1. simple process, easy operation and mild reaction conditions. 2. The invention has low investment and operation cost, high deoxidation efficiency and easy industrialization, the deoxidation efficiency can reach more than 90 percent when the invention is used for treating the nitric oxide in the waste gas, and the investment cost is greatly lower than that of the prior selective catalytic reduction method and selective non-catalytic reduction method. 3. The invention can be combined with various existing waste gas desulfurization systems to realize the desulfurization and denitrification of waste gas. The denitrification washing liquid can be regenerated and recycled, the regeneration process is simple, the product formed in the regeneration process can be processed into chemical products, no harmful substance is generated, and no secondary pollution is caused.
The specific implementation mode is as follows: the invention contacts the ferrous chelator denitrogenation cleaning solution with a certain concentration with the waste gas containing nitric oxide in the absorption equipment added with iron powder or iron filings.
First, nitric oxide in the exhaust gas is complexed by the ferrous chelator into the liquid phase:
the NO bound to the chelate iron is then reduced by the ferrocene to N2 according to formula ② and the chelate iron is regenerated:
in the denitrification process by the above reaction, O in the exhaust gas2And NO bound to the chelated iron will partially react Fe via formulas ③ and ④2+Is oxidized into Fe3+And is of Fe3+The chelating agent can not generate complexation reaction with NO, and Fe in the absorption liquid can be maintained through the reaction ⑤2+So that the denitrification reaction can be continued:
the reactions ③ and ④ showed that the pH of the absorption solution gradually increased as the reaction proceeded, and the residual Fe in the system3And 2Fe2+The ions will constantly form hydrated precipitates of their oxides by the formula ⑥:
in order to maintain stable denitrification efficiency, the absorption liquid must be regenerated, which includes removal of Fe (OH) from the liquid phasen(H2O)mThe precipitate is treated with acid to adjust the pH.
Fe (OH) obtained during regenerationn(H2O)mThe precipitate has high purity, and can be used for preparing iron powder dye or other chemical products of iron.
Reactions ② through ⑥ are key steps in the denitrification process of the present invention and are a fundamental difference between the present invention and other chelators for removing NO from exhaust gas.
Example (b): firstly, preparing 5-45mM denitriding washing liquid by using an ammonia-carboxyl chelating agent and ferrous acid in an equimolar ratio, and adjusting the pH value to 1.0-10 by using alkali liquor; then, the absorption liquid is contacted with the waste gas containing NO in a denitrification device (if the used metallic iron is scrap iron, the absorption device is a packed tower, if the used metallic iron is iron powder, the absorption device can be a stirring reactor), and the denitrification process is carried out under the normal pressure or pressurization condition of 5-90 ℃; the absorption solution is regenerated by removing precipitate by precipitation, centrifugation or filtration, and adjusting pH by adding acid. Fe (OH) obtained during regenerationn(H2O)mThe precipitate can be used for preparing iron powder dye or other chemical products of iron. The method has simple process and high denitrification efficiency which can reach more than 90 percent, and the absorption liquid can be recycled through simple regeneration. Low investment in equipment, low running cost and no secondary pollution.
Claims (4)
1. A method for removing nitric oxide in waste gas is characterized in that: the denitrogenation washing liquid is ferrous chelator solution, and the reducing agent is metallic iron.
1) The ferrous iron mixture can perform a complexing reaction with the nitric oxide to form a nitrosyl complex, so that the nitric oxide which is hardly dissolved in water in the waste gas enters a liquid phase.
2) The metallic iron may react with the ferrocononitrile complex to reduce the nitric oxide bound to the chelated iron to N2, thereby effecting denitrification.
3) The iron regenerates the chelating agent while reducing the nitrogen monoxide to N2, and part of the Fe is removed in the denitrification process2+Is oxidized into Fe3+This fraction of Fe3+Meanwhile, the washing liquid can realize the circular denitrification by being reduced by iron.
2. The method for removing nitric oxide from exhaust gas according to claim 1, wherein: the metal iron used in the denitrification process can be scrap iron or iron powder.
3. The method for removing nitric oxide from exhaust gas according to claim 1, wherein: the iron consumed in the denitrification process is changed into a hydrated precipitate of ferric oxide, and the product has high purity and can be used for preparing pigments or other chemical products.
4. The method for removing nitric oxide from exhaust gas according to claim 1, wherein: the present invention can remove nitric oxide with high efficiency in any suitable absorption equipment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310110651 CN1240466C (en) | 2003-12-15 | 2003-12-15 | Method for removing nitric oxide from waste gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200310110651 CN1240466C (en) | 2003-12-15 | 2003-12-15 | Method for removing nitric oxide from waste gas |
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| CN1546210A true CN1546210A (en) | 2004-11-17 |
| CN1240466C CN1240466C (en) | 2006-02-08 |
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| CN 200310110651 Expired - Fee Related CN1240466C (en) | 2003-12-15 | 2003-12-15 | Method for removing nitric oxide from waste gas |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101711943B (en) * | 2009-09-15 | 2012-09-05 | 华东理工大学 | Method for controlling pollutant waste gas containing NO through low-temperature liquid phase catalytic reduction |
| CN102989302A (en) * | 2012-09-12 | 2013-03-27 | 河南绿典环保节能科技有限公司 | Smoke wet oxidation denitration method |
| CN103239981A (en) * | 2013-05-14 | 2013-08-14 | 成都信息工程学院 | Method for denitrating flue gas by ferrous-citrate-iron powder mixed-liquid wet process and by-producing ammonium nitrate |
| CN103908881A (en) * | 2014-04-08 | 2014-07-09 | 淮南市明月环保科技有限责任公司 | Electrolytic denitrification method |
| CN104084023A (en) * | 2014-07-17 | 2014-10-08 | 湖南平安环保有限责任公司 | Method for performing desulfurization and denitration on flue gas simultaneously |
| CN104084025A (en) * | 2014-07-17 | 2014-10-08 | 湖南平安环保有限责任公司 | Method for removing nitric oxides from boiler smoke |
| CN104190227A (en) * | 2014-07-30 | 2014-12-10 | 武汉悟拓科技有限公司 | Wet flue gas ammonia desulfurization-based synchronous denitration system |
| CN104474890A (en) * | 2014-12-05 | 2015-04-01 | 湘潭大学 | Method for denitrifying NO by directly decomposing NO catalytically by using supported metal oxide catalyst |
| CN110180390A (en) * | 2019-04-10 | 2019-08-30 | 武汉理工大学 | A kind of method of efficient Catalytic Reduction denitration complex liquid |
| CN112717694A (en) * | 2020-12-11 | 2021-04-30 | 攀钢集团攀枝花钢铁研究院有限公司 | Regeneration method of ineffective complexing denitration agent |
| CN114014281A (en) * | 2022-01-05 | 2022-02-08 | 浙江陶特容器科技股份有限公司 | Preparation method of high-purity nitric oxide and application of high-purity nitric oxide in semiconductor manufacturing process |
-
2003
- 2003-12-15 CN CN 200310110651 patent/CN1240466C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101711943B (en) * | 2009-09-15 | 2012-09-05 | 华东理工大学 | Method for controlling pollutant waste gas containing NO through low-temperature liquid phase catalytic reduction |
| CN102989302A (en) * | 2012-09-12 | 2013-03-27 | 河南绿典环保节能科技有限公司 | Smoke wet oxidation denitration method |
| CN103239981A (en) * | 2013-05-14 | 2013-08-14 | 成都信息工程学院 | Method for denitrating flue gas by ferrous-citrate-iron powder mixed-liquid wet process and by-producing ammonium nitrate |
| CN103908881B (en) * | 2014-04-08 | 2015-12-02 | 淮南市明月环保科技有限责任公司 | A kind of method of electrolysis denitration |
| CN103908881A (en) * | 2014-04-08 | 2014-07-09 | 淮南市明月环保科技有限责任公司 | Electrolytic denitrification method |
| CN104084023A (en) * | 2014-07-17 | 2014-10-08 | 湖南平安环保有限责任公司 | Method for performing desulfurization and denitration on flue gas simultaneously |
| CN104084025A (en) * | 2014-07-17 | 2014-10-08 | 湖南平安环保有限责任公司 | Method for removing nitric oxides from boiler smoke |
| CN104190227A (en) * | 2014-07-30 | 2014-12-10 | 武汉悟拓科技有限公司 | Wet flue gas ammonia desulfurization-based synchronous denitration system |
| CN104474890A (en) * | 2014-12-05 | 2015-04-01 | 湘潭大学 | Method for denitrifying NO by directly decomposing NO catalytically by using supported metal oxide catalyst |
| CN104474890B (en) * | 2014-12-05 | 2016-10-05 | 湘潭大学 | A kind of method of Engineering of Supported Metal Oxide Catalysts catalysis Direct Resolution NO denitration |
| CN110180390A (en) * | 2019-04-10 | 2019-08-30 | 武汉理工大学 | A kind of method of efficient Catalytic Reduction denitration complex liquid |
| CN110180390B (en) * | 2019-04-10 | 2020-11-17 | 武汉理工大学 | Method for regenerating denitration complex solution by efficient catalytic reduction |
| CN112717694A (en) * | 2020-12-11 | 2021-04-30 | 攀钢集团攀枝花钢铁研究院有限公司 | Regeneration method of ineffective complexing denitration agent |
| CN114014281A (en) * | 2022-01-05 | 2022-02-08 | 浙江陶特容器科技股份有限公司 | Preparation method of high-purity nitric oxide and application of high-purity nitric oxide in semiconductor manufacturing process |
| CN114014281B (en) * | 2022-01-05 | 2022-06-21 | 宿州伊维特新材料有限公司 | Preparation method of high-purity nitric oxide and application of high-purity nitric oxide in semiconductor manufacturing process |
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| Publication number | Publication date |
|---|---|
| CN1240466C (en) | 2006-02-08 |
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