CN101244360A - Catalytic oxidation technique for calcium sulfite - Google Patents
Catalytic oxidation technique for calcium sulfite Download PDFInfo
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- CN101244360A CN101244360A CNA2007100930443A CN200710093044A CN101244360A CN 101244360 A CN101244360 A CN 101244360A CN A2007100930443 A CNA2007100930443 A CN A2007100930443A CN 200710093044 A CN200710093044 A CN 200710093044A CN 101244360 A CN101244360 A CN 101244360A
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Abstract
The invention relates to a calcium sulfate catalytic oxidation process in limestone-gypsum wet flue gas desulfurization, which adopts the technical proposal that soluble ferrous salt and manganic salt or the mixture of the soluble ferrous salt and magnetic salt is used as catalyst and added in the slurry with absorbed SO2; the concentration of the soluble ferrous salt and manganic salt is 0.001 to 0.05mol/L; the pH value of the slurry with the added catalyst is 5 to 6. The calcium sulfate catalytic oxidation process has the advantages of greatly increasing the oxidation rate of the calcium sulfate, stabilizing the pH value of the system, facilitating the desulfurization operation with cheap and recyclable catalyst in the absorption tower, increasing the absorption rate of the SO2 due to the increased the oxidation rate of the calcium sulfate and reducing the scale possibility of the system.
Description
Technical field
The present invention relates to the oxidation technology of calcium sulfite in the flue gas desulfurization, particularly in the limestone-gypsum wet process of FGD, the catalytic oxidation technology of calcium sulfite.
Background technology
Along with economy development constantly rapidly, atmosphere is by SO
2The situation of severe contamination is day by day remarkable.Coal burning flue gas desulfurization (FGD) is uniquely now can reduce SO on a large scale
2The approach of discharging, in this technology, the limestone-gypsum wet process of FGD occupies leading position.In the limestone-gypsum wet fuel gas desulfurizing technology, the oxidation of calcium sulfite is an important chemical process, the height of its oxidation efficiency is directly connected to the quality of removal efficiency and the by-produced gypsum of SO2, and is therefore significant to the limestone-gypsum wet fuel gas desulfurizing technology by the oxidation efficiency of suitable approach raising calcium sulfite.Application number is the Chinese patent of 03147862.X, discloses " a kind of catalytic oxidation technology of desulfurization product of flue gas ", and the accessory substance of the solvable manganese salt pair of this process using flue gas desulfurization carries out catalytic oxidation, can significantly improve oxidation efficiency.But this technology only can be used for Ca (OH) 2/Mg (OH) 2 sulfur removal technologies, and is not suitable for limestone-gypsum technology.
Summary of the invention
The catalytic oxidation technology that the purpose of this invention is to provide calcium sulfite in a kind of limestone-gypsum wet process of FGD.Concrete technical scheme is as follows:
A kind of catalytic oxidation technology of calcium sulfite is characterized in that adding soluble ferrite, manganese salt or the two mixture as catalyst in the slurries after absorbing SO2; Described slurries are that CaCO3 absorbs the slurries that form behind the SO2, and the concentration of soluble ferrite, manganese salt is 0.001～0.05mol/L, and adding catalyst rear slurry pH value is 5～6.
Wherein said soluble ferrite, manganese salt are FeSO4, MnSO4.
The present invention is on the basis of routine techniques, in slurries, add solubility industry molysite, manganese salt or the two mixture as catalyst, concentration is 0.001～0.05mol/L, measuring slurry pH value behind the adding catalyst is 5～6, under this environment, can significantly improve the oxygenation efficiency of calcium sulfite, promote the absorptivity of SO2 in the flue gas.
In conjunction with Figure of description 1 as can be seen when adding the FeSO4 catalyst concentration when being 0.05mol/L, prolongation along with the time, the oxygenation efficiency of calcium sulfite is 91.2% when reaction proceeds to about 120 minutes, and when not adding catalyst, only be 63.4% in the oxygenation efficiency of same period calcium sulfite.As can be seen after adding catalyst, pH value fluctuates less, can remain in than stable state from pH value, oxidation rate and the time relation figure of accompanying drawing 2 catalytic oxidation processes, and oxidation rate also is in higher scope.
The beneficial effect of the inventive method shows the following aspects:
1, the ability that has significant catalytic oxidation calcium sulfite.
2, pH value that can systems stabilisation is convenient to the desulfurization operation operation.
3, catalyst is cheap, and can recycle in the absorption tower, and cost is lower.
4, owing to improved the oxygenation efficiency of calcium sulfite, thereby the SO2 absorptivity is improved, reduced the possibility of system's fouling.
Description of drawings
Fig. 1 oxygenation efficiency and time relation figure
The pH value of Fig. 2 catalytic oxidation process, oxidation rate and time relation figure
Specific embodiment (totally 3 examples)
Adding concentration in the calcium sulfite slurries is the FeSO4 solution of 0.05mol/L, keep the pH value about 5～6, these slurries are carried out forced oxidation, the time dependent curve of its oxygenation efficiency as shown in Figure 1, as can be seen, when adding the FeSO4 catalyst concentration when being 0.05mol/L, calcium sulfite be oxidized to 91.2%, and not adding the oxidizing process of catalyst, its oxygenation efficiency only is 63.4%.In addition, it can also be seen that after adding catalyst, can keep the pH value to be in than stable state, oxidation rate also is in higher scope from accompanying drawing 2.
Adding concentration in the calcium sulfite slurries is the MnSO4 solution of 0.05mol/L, keep the pH value about 5～6, these slurries are carried out forced oxidation, make oxygenation efficiency and time relation figure equally as can be seen, after adding the MnSO4 catalyst, the oxygenation efficiency of calcium sulfite only is 63.4%.In addition, from pH value, oxidation rate and the time relation figure of catalytic oxidation process also as can be seen, after adding catalyst, can keep the pH value to be in than stable state, oxidation rate also is in higher scope.
Embodiment 3
Adding concentration in the calcium sulfite slurries is MnSO4 and the FeSO4 solution of 0.05mol/L, and both proportionate relationships are not done specific (special) requirements, keeps the pH value about 5～6 but add rear slurry.Make oxygenation efficiency and time relation figure equally as can be seen, after adding the MnSO4 catalyst, the oxygenation efficiency of calcium sulfite obviously increases, and can keep the pH value to be in than stable state, and oxidation rate also is in higher scope.
Claims (2)
1, a kind of catalytic oxidation technology of calcium sulfite is characterized in that adding soluble ferrite, manganese salt or the two mixture as catalyst in the slurries after absorbing SO2; Described slurries are that CaCO3 absorbs the slurries that form behind the SO2, and the concentration of soluble ferrite, manganese salt is 0.001～0.05mol/L, and adding catalyst rear slurry pH value is 5～6.
2, the catalytic oxidation technology of calcium sulfite as claimed in claim 1, wherein said soluble ferrite, manganese salt are respectively FeSO4, MnSO4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100930443A CN101244360A (en) | 2007-11-26 | 2007-11-26 | Catalytic oxidation technique for calcium sulfite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100930443A CN101244360A (en) | 2007-11-26 | 2007-11-26 | Catalytic oxidation technique for calcium sulfite |
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| CN101244360A true CN101244360A (en) | 2008-08-20 |
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| CNA2007100930443A Pending CN101244360A (en) | 2007-11-26 | 2007-11-26 | Catalytic oxidation technique for calcium sulfite |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000491A (en) * | 2010-11-18 | 2011-04-06 | 华北电力大学（保定） | Combined synergist for wet flue gas desulfurization process and use method thereof |
| CN102172469A (en) * | 2011-03-09 | 2011-09-07 | 浙江大学 | Composite flue gas purification additive for wet flue gas desulfurization system |
| CN102380301A (en) * | 2011-08-15 | 2012-03-21 | 西安热工研究院有限公司 | Limestone-plaster wet method flue gas desulfurization composite synergistic agent |
| CN102464459A (en) * | 2010-11-12 | 2012-05-23 | 中国建筑材料科学研究总院 | Fast oxidizing agent for calcium sulfite in desulfurization gypsum and application of fast oxidizing agent |
| CN101734875B (en) * | 2009-12-28 | 2012-10-31 | 华北电力大学（保定） | Method for catalytic oxidation of calcium sulfite in desulphurization ash by dry method and semi-dry method |
| CN103803828A (en) * | 2013-12-25 | 2014-05-21 | 武汉武新新型建材有限公司 | Modified desulfurization ash for cement and concrete and preparation method thereof |
| CN110960968A (en) * | 2019-12-04 | 2020-04-07 | 济南裕兴化工有限责任公司 | New process for oxidation treatment of sodium-method pregnant solution in tail gas desulfurization of titanium sulfate |
| CN112442702A (en) * | 2020-12-04 | 2021-03-05 | 鞍钢集团矿业有限公司 | Electrochemical catalytic oxidation method for calcium sulfite in desulfurized fly ash |
| CN114788987A (en) * | 2021-05-26 | 2022-07-26 | 上海未来企业股份有限公司 | Synergist with high desulfurization efficiency and obvious energy-saving effect and preparation method thereof |
| CN115650694A (en) * | 2022-12-07 | 2023-01-31 | 广东保碧亿固新材料研究院有限公司 | Dry powder self-leveling terrace mortar produced by completely using solid wastes |
-
2007
- 2007-11-26 CN CNA2007100930443A patent/CN101244360A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734875B (en) * | 2009-12-28 | 2012-10-31 | 华北电力大学（保定） | Method for catalytic oxidation of calcium sulfite in desulphurization ash by dry method and semi-dry method |
| CN102464459A (en) * | 2010-11-12 | 2012-05-23 | 中国建筑材料科学研究总院 | Fast oxidizing agent for calcium sulfite in desulfurization gypsum and application of fast oxidizing agent |
| CN102464459B (en) * | 2010-11-12 | 2015-06-10 | 中国建筑材料科学研究总院 | Fast oxidizing agent for calcium sulfite in desulfurization gypsum and application of fast oxidizing agent |
| CN102000491A (en) * | 2010-11-18 | 2011-04-06 | 华北电力大学（保定） | Combined synergist for wet flue gas desulfurization process and use method thereof |
| CN102172469A (en) * | 2011-03-09 | 2011-09-07 | 浙江大学 | Composite flue gas purification additive for wet flue gas desulfurization system |
| CN102380301A (en) * | 2011-08-15 | 2012-03-21 | 西安热工研究院有限公司 | Limestone-plaster wet method flue gas desulfurization composite synergistic agent |
| CN103803828A (en) * | 2013-12-25 | 2014-05-21 | 武汉武新新型建材有限公司 | Modified desulfurization ash for cement and concrete and preparation method thereof |
| CN110960968A (en) * | 2019-12-04 | 2020-04-07 | 济南裕兴化工有限责任公司 | New process for oxidation treatment of sodium-method pregnant solution in tail gas desulfurization of titanium sulfate |
| CN112442702A (en) * | 2020-12-04 | 2021-03-05 | 鞍钢集团矿业有限公司 | Electrochemical catalytic oxidation method for calcium sulfite in desulfurized fly ash |
| CN114788987A (en) * | 2021-05-26 | 2022-07-26 | 上海未来企业股份有限公司 | Synergist with high desulfurization efficiency and obvious energy-saving effect and preparation method thereof |
| CN114788987B (en) * | 2021-05-26 | 2023-11-10 | 上海未来企业股份有限公司 | Synergist with high desulfurization efficiency and obvious energy-saving effect and preparation method thereof |
| CN115650694A (en) * | 2022-12-07 | 2023-01-31 | 广东保碧亿固新材料研究院有限公司 | Dry powder self-leveling terrace mortar produced by completely using solid wastes |
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Open date: 20080820 |