CN103143252B - Additive capable of simultaneous desulphurization and demercuration and preparation method thereof - Google Patents
Additive capable of simultaneous desulphurization and demercuration and preparation method thereof Download PDFInfo
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- CN103143252B CN103143252B CN201310056110.5A CN201310056110A CN103143252B CN 103143252 B CN103143252 B CN 103143252B CN 201310056110 A CN201310056110 A CN 201310056110A CN 103143252 B CN103143252 B CN 103143252B
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- demercuration
- adipic acid
- sodium benzoate
- desulfuration demercuration
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Abstract
The invention discloses an additive capable of simultaneous desulphurization and demercuration. The additive comprises sodium benzoate, ferric sulfate, adipic acid and ortho-phthalaldehyde. The invention further discloses a preparation method for the additive capable of simultaneous desulphurization and demercuration. The additive can realize simultaneous desulphurization and demercuration, has high desulphurization and demercuration efficiency and has the advantages of improvement of activity of limestone, capacity of preventing fouling and blocking of a WFGD system and reduction of system energy loss.
Description
Technical field
The present invention relates to a kind of desulfuration demercuration additive, be specifically related to a kind of desulfuration demercuration additive simultaneously.The invention still further relates to the preparation method of this additive.
Background technology
The flue gas pollutant of coal-burning power plant controls to be the major issue that environmental protection for electric power faces always, and at present, the application of the equipment such as flue gas desulfurization and denitrification and deduster can make flue gas substantially meet existing pollutant emission standard.Because Wet Flue Gas Desulfurization Technique has, desulfuration efficiency is high, applicability wide, and the coal-burning power plant of China more than 90% all adopts Gypsum Wet (WFGD) to carry out flue gas desulfurization.Mercury has serious physiological-toxicity, and " fossil-fuel power plant atmospheric pollutant emission standard " (GB 13223-2011) clear stipulaties of China's issue in 2011, the emission limit of mercury and mercuric compounds is 0.03mg/m
3.Along with the continuous attention to power station mercury pollution, the impact of FGD on mercury pollution emission performance also result in extensive concern, if while not affecting the normal desulfurization operation of WFGD, utilizing existing wet desulfurization system effectively can control the discharge of mercury, will be hopeful most future and have the pollutant catabolic gene method of good economic benefits.
Usually there is three kinds of forms and gaseous state Hg in the mercury in coal-fired flue-gas
0, divalent state Hg
2+with solid granulates attachment.Particle mercury is easily trapped by dust arrester and is removed, and gaseous mercury is high, water-soluble low due to volatility, is difficult to be removed by existing dust arrester, and oxidation state Hg
2+soluble in water, be easy to be removed by WFGD.Therefore, the height of WFGD system demercuration rate depends on Hg in flue gas
2+content, and actual motion test find, the Hg of power-plant flue gas 80% is with Hg
0form exist, although WFGD system is to Hg
2+have higher clearance, still allow of no optimist to the clearance of full mercury, therefore, for improving flue gas demercuration efficiency, current research concentrates on the Hg in flue gas
0be oxidized to Hg as far as possible
2+removed by wet desulphurization device again.
Desulfuration demercuration process for flue gas generally adopts solid absorbent, is respectively mercury removal agent and desulfurizing agent.Conventional demercuration adsorbent has active carbon, flying dust, calcium base class adsorbent etc.And the research of fume desulfurizing agent is comparatively ripe, main desulfurizing agent has calcium-based desulfurizing agent, sodium base desulfurizer, amido desulfurizing agent, Mg-base desulfurizing agent, metal oxide desulfurizer and citric acid desulfurizing agent and adsorption desulfurizing agent etc.Wet process of FGD generally adopts calcium-based desulfurizing agent as lime stone (CaCO
3).At present, in power-plant flue gas process, mercury removal agent and desulfurizing agent are all used alone, and the use of desulfurizing agent can reach higher desulfuration efficiency, and the application of especially current sulfur-removing additives more can effectively improve system limestone activity, improve the problem of scaling blocking, desulfurization degree up to more than 99%, but fails to significantly improve flue gas demercuration efficiency, and mercury removal agent is used alone and can effectively improves flue gas demercuration efficiency, but because the high operating cost that causes of the price of adsorbent own is high, cannot be applied.Therefore, current mercury removal agent and desulfurizing agent all can not solve the problem that WFGD scaling blocks and demercuration efficiency is not high well.
Summary of the invention
First object of the present invention is to provide a kind of desulfuration demercuration additive simultaneously, this additive both can simultaneously desulfuration demercuration, had higher desulfuration demercuration efficiency, also had raising limestone activity, prevent WFGD scaling and blocking, reduce the advantage of system capacity loss.
Second object of the present invention is to provide the preparation method of above-mentioned additive.
3rd object of the present invention is the application of above-mentioned additive.
The object of the invention is to be achieved through the following technical solutions: a kind of desulfuration demercuration additive simultaneously, is made up of Sodium Benzoate, ferric sulfate, adipic acid and OPA.
As an embodiment of the invention, the described each weight percentages of components of desulfuration demercuration additive is:
Sodium Benzoate 35%-50%, ferric sulfate 20%-25%, adipic acid 22%-35%, OPA 8%-15%.
In the present invention, Sodium Benzoate, as cosolvent, can accelerate the dissolving of lime stone in wet desulfurization system, prevents fouling and clogging in WFGD system; Adipic acid is organic acid, can promote the mass transfer between wet desulfurization system air film and liquid film thus fast reaction speed; Ferric sulfate is conducive to Hg as oxidant
0to Hg
2+conversion; OPA, as organic aldehyde material, is conducive to and Hg
2+form chelate, suppress Hg
2+reduction.Four kinds of components play respective effect, complement each other again, reach and improve desulfuration demercuration efficiency, and improve limestone activity, prevent WFGD scaling and blocking, reduce system capacity loss.
Second object of the present invention is achieved through the following technical solutions: the preparation method of desulfuration demercuration additive while of a kind of, by Sodium Benzoate, ferric sulfate, adipic acid and OPA by proportioning mixing, add water and be uniformly mixed, heating water bath is also constantly stirred to each components dissolved, obtained composite solution, then dry 12 ~ 24h at 100 ~ 105 DEG C of temperature, is cooled to room temperature, obtained desulfuration demercuration additive.
The application of the above-mentioned desulfuration demercuration additive of the present invention in the desulfurization of coal-fired plant flue gas demercuration.
The Adding Way of desulfuration demercuration additive of the present invention is: can add in the optional position in serum recycle loop, proposes different schemes according to power plant's time ruuning situation.If add in serum producing system, then its using method is, according to the requirement of WFGD system desulphurization plant, desulfurizing agent (lime stone) and water mix and blend are made lime stone slurry, then in lime stone slurry, add desulfuration demercuration additive of the present invention, its addition is 3.5 ‰ of lime stone weight, then stir and desulfuration demercuration additive and lime stone slurry are fully mixed contact, mixing time is 24-36 hour, whipping temp is 50-60 DEG C, after mixing completely, slurries is delivered to flue gas desulfurization device.When setting up the background concentration of desulfuration demercuration additive in the slurries of desulphurization system absorption tower, can use agitator that desulfuration demercuration additive stirring and dissolving is evenly directly squeezed into absorption tower by ground pump afterwards.
compared with prior art, the present invention has following beneficial effect:
1. desulfuration demercuration additive of the present invention can significantly improve the desulfuration demercuration efficiency of wet desulfurizing process, and it can effectively by the Hg in flue gas
0be oxidized to Hg
2+, thus mercury is converted into stable low toxicity compounds, be dissolved in the slurries of absorption tower, form insoluble matter with sulphion etc. to precipitate, through Separation of Solid and Liquid, mercury is thoroughly removed, solve the secondary pollution problem that it is potential, reduce the pollution to environment, there is good economic and social benefit.Meanwhile, with the addition of chelating agent in sulfur and mercury removing agent and effectively can suppress Hg
2+reduction release, thus strengthen the demercuration ability of wet desulfurization system.
2. the present invention not only has catalytic reaction effect, also improves limestone activity, prevents the fouling of WFGD system equipment and blocking, effectively improves the utilization rate of wet desulfurization system desulfurizing agent, and reduces system capacity loss, to coal-fired flue-gas SO
2with the improvement of Hg, there is good effect.
3. desulfuration demercuration additive of the present invention can utilize the existing wet desulfurization system removal of mercury, reaches good pollutant catabolic gene effect, have a extensive future by lower operation cost of investment.
Detailed description of the invention
embodiment 1
By Sodium Benzoate, ferric sulfate, adipic acid and OPA according to the mixing of constant weight proportioning, wherein, Sodium Benzoate 40wt%, ferric sulfate 20wt%, adipic acid 30wt%, OPA 10wt%.Add water and be uniformly mixed, heating water bath at 60 DEG C also constantly stirs, and each component is fully dissolved, obtained composite solution, and 105 DEG C of dry 24h, are cooled to room temperature, obtained desulfuration demercuration additive.
embodiment 2
By Sodium Benzoate, ferric sulfate, adipic acid and OPA according to the mixing of constant weight proportioning, wherein, Sodium Benzoate 35wt%, ferric sulfate 22wt%, adipic acid 32wt%, OPA 11wt%.Add water and be uniformly mixed, heating water bath at 60 DEG C also constantly stirs, and each component is fully dissolved, obtained composite solution, and 105 DEG C of dry 12h, are cooled to room temperature, obtained desulfuration demercuration additive.
embodiment 3
By Sodium Benzoate, ferric sulfate, adipic acid and OPA according to the mixing of constant weight proportioning, wherein, Sodium Benzoate 42wt%, ferric sulfate 22wt%, adipic acid 28wt%, OPA 8wt%.Add water and be uniformly mixed, heating water bath at 60 DEG C also constantly stirs, and each component is fully dissolved, obtained composite solution, and 105 DEG C of dry 20h, are cooled to room temperature, obtained desulfuration demercuration additive.
embodiment 4
By Sodium Benzoate, ferric sulfate, adipic acid and OPA according to the mixing of constant weight proportioning, wherein Sodium Benzoate 44wt%, ferric sulfate 20wt%, adipic acid 26wt%, OPA 10wt%.Add water and be uniformly mixed, heating water bath at 60 DEG C also constantly stirs, and each component is fully dissolved, obtained composite solution, and 105 DEG C of dry 18h, are cooled to room temperature, obtained desulfuration demercuration additive.
embodiment 5
By Sodium Benzoate, ferric sulfate, adipic acid and OPA according to the mixing of constant weight proportioning, wherein, Sodium Benzoate 46wt%, ferric sulfate 22wt%, adipic acid 24wt%, OPA 8wt%.Add water and be uniformly mixed, heating water bath at 60 DEG C also constantly stirs, and each component is fully dissolved, obtained composite solution, and 105 DEG C of dry 23h, are cooled to room temperature, obtained desulfuration demercuration additive.
embodiment 6
By Sodium Benzoate, ferric sulfate, adipic acid and OPA according to the mixing of constant weight proportioning, wherein, Sodium Benzoate 42wt%, ferric sulfate 24wt%, adipic acid 25wt%, OPA 9wt%.Add water and be uniformly mixed, heating water bath at 60 DEG C also constantly stirs, and each component is fully dissolved, obtained composite solution, and 105 DEG C of dry 15h, are cooled to room temperature, obtained desulfuration demercuration additive.
experimental example:
Add in lime stone slurry with the desulfuration demercuration additive that embodiment 1 to 6 is obtained, addition is 3.5 ‰ of lime stone weight, and lime stone slurry density is 1100kg/m
3~ 1200kg/m
3, pH is 5.5 ~ 5.8, and desulfuration demercuration additive adds rear mix and blend 24 ~ 36 hours, and whipping temp is 50 ~ 60 DEG C, after mixing completely, slurries is delivered to desulfuration absorbing tower.The simulated flue gas constituent passed in absorption tower is O
2be 3%, CO
2be 12%, Hg
0for 0.3mg/m
3, SO
2for 2000ppm, HCl are 5ppm, all the other are N
2, temperature is 60 DEG C, control gas flow be under 1L/min desulfuration demercuration additive to mercury and sulfur dioxide (SO
2) removal efficiency.The results are shown in Table 1.
The present invention can summarize with other the concrete form without prejudice to spirit of the present invention or principal character.Above-mentioned embodiment of the present invention all can only be thought explanation of the present invention instead of restriction, therefore every above embodiment is done according to substantial technological of the present invention any trickle amendment, equivalent variations and modification, all belong in the scope of technical solution of the present invention.
Claims (4)
1. desulfuration demercuration additive while, it is characterized in that, be made up of Sodium Benzoate, ferric sulfate, adipic acid and OPA, the percentage by weight of each component is:
Sodium Benzoate 35%-50%, ferric sulfate 20%-25%, adipic acid 22%-35%, OPA 8%-15%.
2. one kind according to claim 1 while desulfuration demercuration additive preparation method, it is characterized in that, by Sodium Benzoate, ferric sulfate, adipic acid and OPA by proportioning mixing, add water and be uniformly mixed, heating water bath is also constantly stirred to each components dissolved, obtained composite solution, then dry 12 ~ 24h at 100 ~ 105 DEG C of temperature, be cooled to room temperature, obtained desulfuration demercuration additive.
3. the application of desulfuration demercuration additive in the desulfurization of coal-fired plant flue gas demercuration while according to claim 1.
4. application according to claim 3, is characterized in that, the addition of described desulfuration demercuration additive is 3.5 ‰ of lime stone weight.
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| CN103341310B (en) * | 2013-07-03 | 2015-07-08 | 上海交通大学 | Method for recycling gas-state zero-valence mercury and sulfur dioxide from non-ferrous metal metallurgy smoke gas |
| CN106000275A (en) * | 2016-06-20 | 2016-10-12 | 广东电网有限责任公司电力科学研究院 | Adsorbent and preparation method and application thereof |
| CN112058071A (en) * | 2020-07-24 | 2020-12-11 | 中国恩菲工程技术有限公司 | Demercuration slurry and preparation method thereof |
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