CN102989273A - Compound absorbent capable of simultaneous desulfurization and denitrification as well as preparation and use methods thereof - Google Patents
Compound absorbent capable of simultaneous desulfurization and denitrification as well as preparation and use methods thereof Download PDFInfo
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- CN102989273A CN102989273A CN2012105756641A CN201210575664A CN102989273A CN 102989273 A CN102989273 A CN 102989273A CN 2012105756641 A CN2012105756641 A CN 2012105756641A CN 201210575664 A CN201210575664 A CN 201210575664A CN 102989273 A CN102989273 A CN 102989273A
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Abstract
The invention belongs to the technical field of flue gas cleaning and particularly relates to a compound absorbent capable of simultaneous desulfurization and denitrification as well as preparation and use methods thereof. The compound absorbent disclosed by the invention is formed by mixing sodium chlorite, sodium chlorate and sodium chloride in the molar ratio of (0-10):(0-10):1, wherein the pH (potential of Hydrogen) value of the compound absorbent solution is adjusted to 3-11 by using sodium hydroxide and hydrochloric acid and the flue gas absorption reaction at the flow rate of 0.05-0.5m/s is carried out at the temperature of 40-90 DEG C. The compound absorbent has the advantages that the sulfur dioxide removing efficiency is 100% and the nitrogen oxide removing efficiency is more than 60% and can be up to 91%; when being applied to the simultaneous desulfurization and denitrification of coal-fired flue gas, the compound absorbent disclosed by the invention has the characteristics of high removing efficiency, low investment and operating cost, simplicity in equipment, high utilization rate, easiness in product processing, convenience for popularization and the like; and the compound absorbent is suitable for large, medium and small boilers and other equipment generating sulfur dioxide and nitrogen oxide waste gases and has very good application prospect.
Description
Technical field
The invention belongs to the flue gases purification field, particularly a kind of compound absorbent and preparation and application thereof of while desulphurization denitration.
Background technology
In recent years, a large amount of burnings of fast development, the especially fossil fuel of China's industry and economy cause problem of environmental pollution to become increasingly conspicuous, wherein with SO
2The most typical with the harm of NOx.SO
2With NOx be the precursor of fine particle and acid rain, simultaneously a large amount of NOx photochemical reaction by series of complex in air forms and generates ozone.At present the aerial concentration of ozone is just presenting day by day serious trend, in some city of China even monitored the phenomenon of this pollutant severe overweight.SO
2, NOx and formation thereof secondary pollution not only damage ecological environment and affect health, also directly cause huge economic loss.Therefore, country is to SO
2, the pernicious gas such as NOx control, the management of polluting be increasing, and in succession put into effect more strict SO
2With the discharge standard of NOx, also strengthened the management of pollution charge.For these reasons, realize that flue gas desulfurization and denitrification becomes instant task, research and the application of its technology have been subject to extensive concern.
More to flue gas and desulfurizing and denitrifying technology report both at home and abroad, various countries have carried out out broad research at aspects such as removing mode and raising removal efficiency.At present, in flue gas desulfurization technique, wet desulphurization is mainstream technology, in wet desulphurization again take the calcium method as main.The advantage of calcium method desulfurization is that removal efficiency and sorbent utilization are high, but also has the easy fouling of equipment, obstruction, causes the problems such as system can't normally move.Denitration technology is then maximum with research and the application of selective catalytic oxidation method (SCR), but also exists investment and operating cost high, and catalyst is easily poisoned, reducing agent (NH
3) problem such as fugacity.The method is developed mainly for large-scale power station simultaneously, directly applies to Industrial Boiler and still has problems, is difficult to solve the denitration problem of a large amount of mediumand smallscale industrial boilers that exist of present China.Other oxidizing process denitrations of exploitation then ubiquity use oxidant expensive, even the gaseous oxidant of some employing is in the equipment problem such as potential safety hazard that exists in service.In addition, existing flue gas desulfurization and denitrification technology is the classification processing mode, and classification processes that not only floor space is large, system complex, and equipment investment and operation and maintenance cost height, can't promote the use of at the Built hydropower station of not reserving the desulphurization denitration position and the weak medium small boiler of ability to shoulder economically.Therefore, the desulphurization denitration technology becomes focus and the difficult point of research when exploiting economy, efficient, easy operating.
NaClO
2Be proved to be a kind of effective while desulphurization denitration reagent, but NaClO
2Price is more expensive, and no matter in acidity or alkaline environment, could obtain desirable denitration efficiency when its concentration is higher, and it is higher therefore to remove cost, is unfavorable for promoting the use of.
Summary of the invention
Not enough for prior art, efficient, economic, the safe compound while desulphurization denitration absorbent that will provide a kind of and existing desulphurization system operating condition to be complementary is provided.
A kind of compound absorbent of while desulphurization denitration, it is comprised of sodium chlorite, sodium chlorate and sodium chloride mixed solution, and wherein the mol ratio of sodium chlorite, sodium chlorate and sodium chloride is (0 ~ 10): (0 ~ 10): 1, the pH value of mixed solution is 3 ~ 11.
The preparation method of the compound absorbent of a kind of while desulphurization denitration, its concrete scheme is as follows:
Take by weighing in molar ratio respectively sodium chlorite, sodium chlorate and sodium chloride, in preparation feedback device or slurries preparation vessel with deionized water dissolving and mix, and with NaOH or hydrochloric acid the pH value is adjusted to 3 ~ 11, obtain the compound absorbent of a kind of while desulphurization denitration.
The amount of substance concentration of sodium chlorite, sodium chlorate and sodium chloride is followed successively by 0 mol/L ~ 0.5 mol/L, 0 mol/L ~ 0.5 mol/L and 0 mol/L ~ 0.05 mol/L in the described compound absorbent
The using method of the compound absorbent of a kind of while desulphurization denitration, its concrete scheme is as follows:
The compound absorbent of freshly prepd while desulphurization denitration is packed in the bubbling reactor, the temperature that keeps compound absorbent is 40 ℃～90 ℃, passing into flow velocity is the pending flue gas of 0.05 m/s ~ 0.5 m/s, utilizes flue gas analyzer to measure sulfur dioxide and the nitrous oxides concentration that enters the bubbling reactor front and back.
Sodium chlorite in the compound absorbent of the present invention and sodium chlorate are strong oxidizer, can with flue gas in sulfur dioxide (SO
2) reaction generation sodium sulphate (NaSO
4), with nitrogen oxide (NOx) the reaction generation sodium nitrate (NaNO in the flue gas
3), thereby remove sulfur dioxide in flue gas and nitrogen oxide.Under certain pH value and temperature conditions, sodium chlorite and sodium chlorate generate the stronger chlorine dioxide (ClO of oxidisability by disproportionated reaction simultaneously
2) and chlorine (Cl
2), thereby the oxidability of absorbent solution is greatly improved.In addition, sodium chlorate and sulfur dioxide reaction can produce chlorine dioxide, but chlorine dioxide Quick Oxidation nitric oxide generates nitrate anion (NO
3 -), this characteristic is particularly advantageous in simultaneously the carrying out of desulfurization and denitrification reaction.The key reaction process is as follows:
Proof procedure is: get a certain amount of compound absorbent and be mixed with and add behind the solution in the bubbling reactor, enter sulfur dioxide in flue gas before and after the reactor and the concentration of nitrogen oxide with the flue gas analyzer monitoring, by calculating denitrification efficiency.The laboratory room small-sized experimental result shows, behind the adding absorbent, can obtain desirable denitrification efficiency, and desulfuration efficiency reaches 100%, and denitration efficiency is up to 91%.
Beneficial effect of the present invention is:
The present invention utilizes strong oxidizer and reaction intermediate thereof significantly to accelerate the oxidation rate of sulfur dioxide and nitrogen oxide, thereby has obviously improved removal efficiency, and removing product is sulfate radical, nitrate anion and chlorion, is easy to process, and does not have the secondary pollution problem.Compare with prior art, the present invention has the following advantages:
(1) raw sorbent of the present invention is solid, is easy to transportation and storage, and preparation process is simple.
(2) while desulfurization off sulfide effect of the present invention is remarkable, and desulfuration efficiency reaches 100%, and denitration efficiency can reach more than 60%, is up to 91%.
(3) the present invention can realize desulphurization denitration simultaneously in a reactor.The present invention need not to transform the desulfurization body construction, and only by changing or adding absorbent and just can realize the simultaneously purpose of desulphurization denitration, denitration is transformed when therefore being particularly useful for existing desulphurization system.
(4) absorbent activity of the present invention is low, and consumption is little, and it is low therefore to remove expense, and almost the non-secondary pollution problem produces.
Description of drawings
Fig. 1 is the denitrification efficiency temporal evolution curve of the compound absorbent of various embodiments of the present invention.
The specific embodiment
The invention provides a kind of compound absorbent and preparation and application thereof of while desulphurization denitration, the present invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment 1
Take by weighing respectively sodium chlorite 4.525 g, sodium chlorate 5.325 g and sodium chloride 1.463 g, be dissolved in the 1 L deionized water, with NaOH and salt acid for adjusting pH value to 5, fully dissolving is made compound while desulphurization denitration absorbent solution after mixing.In the compound absorbent of present embodiment gained, the concentration of the amount of substance of sodium chlorite and sodium chlorate is 0.05 mol/L, and the concentration of the amount of substance of sodium chloride is 0.025 mol/L, and the mol ratio of sodium chlorite, sodium chlorate and sodium chloride is 2:2:1 at this moment.
The initial concentration of sulfur dioxide and nitrogen oxide (nitric oxide accounts for 95%, and nitrogen dioxide accounts for 5%) is respectively 2000 mg/m
3With 500 mg/m
3Above-mentioned compound absorbent solution is packed in the bubbling reactor, keep 60 ℃ of absorbent solution constant temperature, pass into the flue gas that flow velocity is 0.05 m/s, measure sulfur dioxide and the nitrous oxides concentration that enters the reactor front and back with flue gas analyzer, recording desulfuration efficiency is 100%, and denitration efficiency is up to more than 90%.
Embodiment 2
Take by weighing respectively sodium chlorite 4.525 g, sodium chlorate 2.663 g and sodium chloride 1.463 g, be dissolved in the 1 L deionized water, with NaOH and salt acid for adjusting pH value to 8, fully dissolving is made compound while desulphurization denitration absorbent solution after mixing.In the compound absorbent of present embodiment gained, the concentration of the amount of substance of sodium chlorite is 0.05 mol/L, and the concentration of the amount of substance of sodium chloride and sodium chlorate is 0.025 mol/L, and the molar ratio of sodium chlorite, sodium chlorate and sodium chloride is 2:1:1 at this moment.
The initial concentration of sulfur dioxide and nitrogen oxide (nitric oxide accounts for 95%, and nitrogen dioxide accounts for 5%) is respectively 2000 mg/m
3With 500 mg/m
3Above-mentioned compound absorbent solution is packed in the bubbling reactor, keep 90 ℃ of absorbent solution constant temperature, pass into the flue gas that flow velocity is 0.5 m/s, measure sulfur dioxide and the nitrous oxides concentration that enters the reactor front and back with flue gas analyzer, recording desulfuration efficiency is 100%, and denitration efficiency is up to more than 61%.
Embodiment 3
Take by weighing respectively sodium chlorite 0.453 g, sodium chlorate 0.533 g and sodium chloride 1.463 g, be dissolved in the 1 L deionized water, with NaOH and salt acid for adjusting pH value to 3, fully dissolving is made compound while desulphurization denitration absorbent solution after mixing.In the compound absorbent of present embodiment gained, the concentration of the amount of substance of sodium chlorite and sodium chlorate is 0.005 mol/L, and the concentration of the amount of substance of sodium chloride is 0.025 mol/L, and the molar ratio of sodium chlorite, sodium chlorate and sodium chloride is 1:1:5 at this moment.
The initial concentration of sulfur dioxide and nitrogen oxide (nitric oxide accounts for 95%, and nitrogen dioxide accounts for 5%) is respectively 2000 mg/m
3With 500 mg/m
3Above-mentioned compound absorbent solution is packed in the bubbling reactor, keep 40 ℃ of absorbent solution constant temperature, pass into the flue gas that flow velocity is 0.3 m/s, measure sulfur dioxide and the nitrous oxides concentration that enters the reactor front and back with flue gas analyzer, recording desulfuration efficiency is 100%, and denitration efficiency is up to more than 85%.
Embodiment 4
Take by weighing respectively sodium chlorite 0.226 g, sodium chlorate 0.266 g and sodium chloride 0.146 g, be dissolved in the 1 L deionized water, with NaOH and salt acid for adjusting pH value to 4, fully dissolving is made compound while desulphurization denitration absorbent solution after mixing.In the compound absorbent of present embodiment gained, the concentration of the amount of substance of sodium chlorite, sodium chlorate and sodium chloride is 0.0025 mol/L, and the molar ratio of sodium chlorite, sodium chlorate and sodium chloride is 1:1:1 at this moment.
The initial concentration of sulfur dioxide and nitrogen oxide (nitric oxide accounts for 95%, and nitrogen dioxide accounts for 5%) is respectively 2000 mg/m
3With 500 mg/m
3Above-mentioned compound absorbent solution is packed in the bubbling reactor, keep 50 ℃ of absorbent solution constant temperature, pass into the flue gas that flow velocity is 0.2 m/s, measure sulfur dioxide and the nitrous oxides concentration that enters the reactor front and back with flue gas analyzer, recording desulfuration efficiency is 100%, and denitration efficiency is up to more than 75%.
Embodiment 5
Take by weighing respectively sodium chlorite 0.226g, sodium chlorate 0.533g and sodium chloride 0.146g, be dissolved in the 1L deionized water, with NaOH and salt acid for adjusting pH value to 6, fully dissolving is made compound while desulphurization denitration absorbent solution after mixing.In the compound absorbent of present embodiment gained, the concentration of the amount of substance of sodium chlorite and sodium chloride is 0.0025 mol/L, and the concentration of the amount of substance of sodium chlorate is 0.005 mol/L, and the molar ratio of sodium chlorite, sodium chlorate and sodium chloride is 1:2:1 at this moment.
The initial concentration of sulfur dioxide and nitrogen oxide (nitric oxide accounts for 95%, and nitrogen dioxide accounts for 5%) is respectively 2000 mg/m
3With 500 mg/m
3Above-mentioned compound absorbent solution is packed in the bubbling reactor, keep 70 ℃ of absorbent solution constant temperature, pass into the flue gas that flow velocity is 0.08 m/s, measure sulfur dioxide and the nitrous oxides concentration that enters the reactor front and back with flue gas analyzer, recording desulfuration efficiency is 100%, and denitration efficiency is up to more than the .65%.
The experimental result of above-described embodiment as shown in Figure 1.
Claims (4)
1. compound absorbent of desulphurization denitration simultaneously, it is characterized in that: described compound absorbent is comprised of sodium chlorite, sodium chlorate and sodium chloride mixed solution, wherein the mol ratio of sodium chlorite, sodium chlorate and sodium chloride is (0 ~ 10): (0 ~ 10): 1, and the pH value of mixed solution is 3 ~ 11.
2. the preparation method of the compound absorbent of a kind of while desulphurization denitration as claimed in claim 1 is characterized in that concrete scheme is as follows:
Take by weighing in molar ratio respectively sodium chlorite, sodium chlorate and sodium chloride, in preparation feedback device or slurries preparation vessel with deionized water dissolving and mix, and with NaOH and hydrochloric acid the pH value is adjusted to 3 ~ 11, obtain the compound absorbent of a kind of while desulphurization denitration.
3. the preparation method of the compound absorbent of a kind of while desulphurization denitration according to claim 2, it is characterized in that: the amount of substance concentration of sodium chlorite, sodium chlorate and sodium chloride is followed successively by 0 mol/L ~ 0.5 mol/L, 0 mol/L ~ 0.5 mol/L and 0 mol/L ~ 0.05 mol/L in the described compound absorbent.
4. the using method of the compound absorbent of a kind of while desulphurization denitration as claimed in claim 1 is characterized in that concrete scheme is as follows:
The compound absorbent of freshly prepd while desulphurization denitration is packed in the bubbling reactor, the temperature that keeps compound absorbent is 40 ℃～90 ℃, then passing into flow velocity is the pending flue gas of 0.05 m/s ~ 0.5 m/s, utilizes flue gas analyzer to measure sulfur dioxide and the nitrous oxides concentration that enters the bubbling reactor front and back.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107497273A (en) * | 2017-09-25 | 2017-12-22 | 济南大学 | A kind of preparation method and application of environment protection, low cost smoke denitrifier |
| CN107648995A (en) * | 2017-11-06 | 2018-02-02 | 济南大学 | A kind of environment protection, low cost flue gas desulfurization and denitrification agent and its preparation method and application |
| CN111135692A (en) * | 2018-11-05 | 2020-05-12 | 新疆硅基新材料创新中心有限公司 | Method and system for recycling waste slurry obtained by power plant boiler flue gas desulfurization and denitrating power plant boiler flue gas |
| WO2021134925A1 (en) * | 2019-12-30 | 2021-07-08 | 童裳慧 | Semi-dry flue gas desulfurization and denitrification method |
| CN113121133A (en) * | 2019-12-31 | 2021-07-16 | 可徕卡（上海）环境科技有限公司 | Integrated process for preparing cementing material by flue gas desulfurization and denitrification in synergy |
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| CN1883768A (en) * | 2006-05-29 | 2006-12-27 | 浙江大学 | Wet method combined process for desulfurization and denitration for chlorine-containing strong oxidizer absorption liquid |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107497273A (en) * | 2017-09-25 | 2017-12-22 | 济南大学 | A kind of preparation method and application of environment protection, low cost smoke denitrifier |
| CN107648995A (en) * | 2017-11-06 | 2018-02-02 | 济南大学 | A kind of environment protection, low cost flue gas desulfurization and denitrification agent and its preparation method and application |
| CN111135692A (en) * | 2018-11-05 | 2020-05-12 | 新疆硅基新材料创新中心有限公司 | Method and system for recycling waste slurry obtained by power plant boiler flue gas desulfurization and denitrating power plant boiler flue gas |
| WO2021134925A1 (en) * | 2019-12-30 | 2021-07-08 | 童裳慧 | Semi-dry flue gas desulfurization and denitrification method |
| CN113121133A (en) * | 2019-12-31 | 2021-07-16 | 可徕卡（上海）环境科技有限公司 | Integrated process for preparing cementing material by flue gas desulfurization and denitrification in synergy |
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Application publication date: 20130327 |