CN103463962B - Flue gas desulfurization synergistic agent - Google Patents
Flue gas desulfurization synergistic agent Download PDFInfo
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- CN103463962B CN103463962B CN201310423630.5A CN201310423630A CN103463962B CN 103463962 B CN103463962 B CN 103463962B CN 201310423630 A CN201310423630 A CN 201310423630A CN 103463962 B CN103463962 B CN 103463962B
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- flue gas
- gas desulfurization
- acid
- present
- synergist
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Abstract
The invention discloses a flue gas desulfurization synergistic agent which comprises the following substances based on mass percentage concentration: 90-91% nitrilotriacetic acid, 4-8% succinic acid and 2-6% hydroxyacetic acid. The flue gas desulfurization synergistic agent can improve the acidic ability in slurry, increase the dissolution rate limestone, accelerate the absorption of SO2, improve the desulfurization efficiency, is good in scale inhibition and scale removal effects, and enables a desulfurization system to run economically and stably.
Description
Technical field
The present invention relates to coal-fired field, particularly relate to a kind of flue gas desulfurization synergist.
Background technology
Power plant can give off a large amount of sulfur dioxide and cause severe contamination to environment in the process of coal combustion, and this pollution problem is the problem that state key is paid close attention to always.
Common solution has three kinds: one to be carry out capacity-increasing transformation to desulfurizer; Two is control coal-fired sulfur content; Three is use sulfur-removing additives.Desulphurization system capacity-increasing transformation not only cost is high, and the cycle is long, and is difficult to flexible adaptation coal and load variations; Control coal-fired sulfur content and then significantly increase fuel cost.Develop multiple sulfur-removing additives at present, be mainly divided into the large class of inorganic additive and organic additive two wherein for desulphurization system.Have magnesium sulfate, magnesia, magnesium hydroxide, sodium sulphate etc. in inorganic additive, organic additive is also called buffer additive, mostly is organic acid, as DBA ﹑ Ben Jia Suan ﹑ Ji bis-Suan ﹑ Jian Ben bis-Jia Suan ﹑ sodium formate etc.Although these known sulfur-removing additives have desulfurization, scale effect in desulphurization system, denitration effect is general, scale inhibition and descale effect poor, and cost is high.
Therefore, how to use most economical effective means, not only make desulphurization system economy, operation up to standard, and ensure device security, reliably operate, become those skilled in the art's urgent problem.
Summary of the invention
The object of this invention is to provide a kind of flue gas desulfurization synergist, flue gas desulfurization synergist of the present invention can improve the acid ability in slurries, improves the rate of dissolution of lime stone, and accelerates SO
2absorption, improve desulfuration efficiency, scale inhibition and features high scale-removing effect, make desulphurization system can economical, stably run.
The technical solution used in the present invention: a kind of flue gas desulfurization synergist, is made up of the material of following masses percent concentration:
Nitrilotriacetic acid 90 ~ 91%
Butanedioic acid 4 ~ 8%
Glycolic acid 2 ~ 6%.
Preferably, the constituent mass percent concentration of described flue gas desulfurization synergist is:
Nitrilotriacetic acid 90%
Butanedioic acid 4%
Glycolic acid 6%.
Preferably, the constituent mass percent concentration of described flue gas desulfurization synergist is:
Nitrilotriacetic acid 90%
Butanedioic acid 8%
Glycolic acid 2%.
Preferably, the constituent mass percent concentration of described flue gas desulfurization synergist is:
Nitrilotriacetic acid 90%
Butanedioic acid 5%
Glycolic acid 5%.
Preferably, the constituent mass percent concentration of described flue gas desulfurization synergist is:
Nitrilotriacetic acid 91%
Butanedioic acid 4%
Glycolic acid 5%.
Preferably, the constituent mass percent concentration of described flue gas desulfurization synergist is:
Nitrilotriacetic acid 91%
Butanedioic acid 6%
Glycolic acid 3%.
Preferably, the constituent mass percent concentration of described flue gas desulfurization synergist is:
Nitrilotriacetic acid 91%
Butanedioic acid 7%
Glycolic acid 2%.
The beneficial effect of flue gas desulfurization synergist of the present invention is as follows: nitrilotriacetic acid is a kind of ammonia carboxylic desulfurizing agent, and the invertibity mainly utilizing itself and sour gas to react, removes the hydrogen sulfide in coal-fired flue-gas, and it also has the character of scale inhibition, scale removal.Butanedioic acid is organic acid, as buffer cushioning liquid pH value, improves acid ability in slurries, and energy stable maintenance desulfurization slurry pH value, between 5.2-5.6, enhances SO
2absorption process, can not cause desulphurization plant sour corrosion.And butanedioic acid is due to its cushioning effect, the mass flux arriving limestone particle surface can be kept constant, SO
2the basicity required for absorption to CaCO
3or the dependence of calcium sulfite dissolution velocity reduces.
Meanwhile, activity coefficient has impact to desulfurized effect, as organic acid p
kawhen=4.5 ~ 5, desulfuration efficiency is the highest, and in this synergist, the p of butanedioic acid
k1=4.2, P
k2=5.62, except there is good cushioning effect to the pH value of lime stone slurry, improve the rate of dissolution of lime stone, reducing the residual volume of lime stone, and adding in slurries and SO
2ability, improve desulfuration efficiency.
The concentration of the solid matter (as chlorine, magnesium, sodium etc.) dissolved in desulfurization slurry affects the oxidation rate of calcium sulfite, these solid matters dissolved can have an impact to the concentration that other participates in the material of reaction, such as, the concentration of chlorine is higher, the concentration of the calcium dissolved in desulfurization slurry will be increased, thus reduce the solubility of calcium sulfite, glycolic acid is as a kind of hydroxy compounds, it is inhibited to the oxidation of calcium sulfite, the object suppressing oxidation is the fouling preventing gypsum in tower, promotes CaCO
3dissolving, improve CaSO
31/2 H
2the dewatering of O.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme of the present invention is explained in detail.
The Adding Way of flue gas desulfurization synergist of the present invention is: added by the entrance that adds of flue gas desulfurization synergist from lime stone slurry box top, addition is 0.1 ~ 0.2% of lime stone, make it to stir in lime stone slurry case, then through lime stone, pump at night is squeezed in desulfuration absorbing tower.The lime stone slurry dropped into after flue gas desulfurization synergist is atomized into tiny droplet and flue gas carries out mass transfer, SO
2absorbed by lime stone, purified gas is discharged from flue.Continuous mensuration imports and exports SO
2concentration, quantitative configuration lime stone slurry concentration and flow, can calculate the lower SO of certain metering thus
2clearance and limestone utilization.
Embodiment 1
Be nitrilotriacetic acid 90% by mass percent, the flue gas desulfurization synergist that is prepared from of butanedioic acid 4%, glycolic acid 6% Homogeneous phase mixing.
The present invention drops into before and after absorption tower, and the changes of contents of desulfuration efficiency and lime stone is as follows:
Table 1 adds the desulfuration efficiency result of the test before and after flue gas desulfurization synergist of the present invention
Desulfuration efficiency computing formula is η=(V1-V2)/V1, and as can be seen from Table 1, after adding synergist of the present invention, desulfuration efficiency significantly improves.
Table 2 adds the composition analysis result of lime stone before and after flue gas desulfurization synergist of the present invention
As can be seen from Table 2, after adding synergist of the present invention, the moisture of lime stone is substantially constant, CaCO
3content have dropped, CaSO
42 H
2the content of O raises to some extent.
Embodiment 2
Be nitrilotriacetic acid 90% by mass percent, the flue gas desulfurization synergist that is prepared from of butanedioic acid 8%, glycolic acid 2% Homogeneous phase mixing.
The present invention drops into before and after absorption tower, and the changes of contents of desulfuration efficiency and lime stone is as follows:
Table 3 adds the desulfuration efficiency result of the test before and after flue gas desulfurization synergist of the present invention
Desulfuration efficiency computing formula is η=(V1-V2)/V1, and as can be seen from Table 3, after adding synergist of the present invention, desulfuration efficiency significantly improves.
Table 4 adds the composition analysis result of lime stone before and after flue gas desulfurization synergist of the present invention
As can be seen from Table 4, after adding synergist of the present invention, the moisture of lime stone is substantially constant, CaCO
3content have dropped, CaSO
42 H
2the content of O raises to some extent.
Embodiment 3
Be nitrilotriacetic acid 90% by mass percent, the flue gas desulfurization synergist that is prepared from of butanedioic acid 5%, glycolic acid 5% Homogeneous phase mixing.
The present invention drops into before and after absorption tower, and the changes of contents of desulfuration efficiency and lime stone is as follows:
Table 5 adds the desulfuration efficiency result of the test before and after flue gas desulfurization synergist of the present invention
Desulfuration efficiency computing formula is η=(V1-V2)/V1, and as can be seen from Table 5, after adding synergist of the present invention, desulfuration efficiency significantly improves.
Table 6 adds the composition analysis result of lime stone before and after flue gas desulfurization synergist of the present invention
As can be seen from Table 6, after adding synergist of the present invention, the moisture of lime stone is substantially constant, CaCO
3content have dropped, CaSO
42 H
2the content of O raises to some extent.
Embodiment 4
Be nitrilotriacetic acid 91% by mass percent, the flue gas desulfurization synergist that is prepared from of butanedioic acid 4%, glycolic acid 5% Homogeneous phase mixing.
The present invention drops into before and after absorption tower, and the changes of contents of desulfuration efficiency and lime stone is as follows:
Table 7 adds the desulfuration efficiency result of the test before and after flue gas desulfurization synergist of the present invention
Desulfuration efficiency computing formula is η=(V1-V2)/V1, and as can be seen from Table 7, after adding synergist of the present invention, desulfuration efficiency significantly improves.
Table 8 adds the composition analysis result of lime stone before and after flue gas desulfurization synergist of the present invention
As can be seen from Table 8, after adding synergist of the present invention, the moisture of lime stone is substantially constant, CaCO
3content have dropped, CaSO
42 H
2the content of O raises to some extent.
Embodiment 5
Be nitrilotriacetic acid 91% by mass percent, the flue gas desulfurization synergist that is prepared from of butanedioic acid 6%, glycolic acid 3% Homogeneous phase mixing.
The present invention drops into before and after absorption tower, and the changes of contents of desulfuration efficiency and lime stone is as follows:
Table 9 adds the desulfuration efficiency result of the test before and after flue gas desulfurization synergist of the present invention
Desulfuration efficiency computing formula is η=(V1-V2)/V1, and as can be seen from Table 9, after adding synergist of the present invention, desulfuration efficiency significantly improves.
Table 10 adds the composition analysis result of lime stone before and after flue gas desulfurization synergist of the present invention
As can be seen from Table 10, after adding synergist of the present invention, the moisture of lime stone is substantially constant, CaCO
3content have dropped, CaSO
42 H
2the content of O raises to some extent.
Embodiment 6
Be nitrilotriacetic acid 91% by mass percent, the flue gas desulfurization synergist that is prepared from of butanedioic acid 7%, glycolic acid 2% Homogeneous phase mixing.
Table 11 adds the desulfuration efficiency result of the test before and after flue gas desulfurization synergist of the present invention
Desulfuration efficiency computing formula is η=(V1-V2)/V1, and as can be seen from Table 11, after adding synergist of the present invention, desulfuration efficiency significantly improves.
Table 12 adds the composition analysis result of lime stone before and after flue gas desulfurization synergist of the present invention
As can be seen from Table 12, after adding synergist of the present invention, the moisture of lime stone is substantially constant, CaCO
3content have dropped, CaSO
42 H
2the content of O raises to some extent.
To sum up the interpretation of result of table 1 ~ 12 can draw, flue gas desulfurization synergist desulfurized effect of the present invention is obvious, and the moisture of lime stone is substantially constant, CaCO
3content decline to some extent, CaSO
42H
2the content of O raises to some extent, mainly due to the composition in sulfur-removing additives, facilitates CaCO
3dissolving, enhance H+ by the transmission of gas phase to solid phase simultaneously, accelerate SO
2chemical absorbing, decrease the CaCO discharged completely and with gypsum because unreacted
3amount, therefore improve desulfurizing agent CaCO
3utilization rate, improve the purity of gypsum simultaneously.
Claims (7)
1. a flue gas desulfurization synergist, is characterized in that: be made up of the material of following masses percent concentration:
Nitrilotriacetic acid 90 ~ 91%
Butanedioic acid 4 ~ 8%
Glycolic acid 2 ~ 6%.
2. flue gas desulfurization synergist according to claim 1, is characterized in that: the mass percent concentration of described component is:
Nitrilotriacetic acid 90%
Butanedioic acid 4%
Glycolic acid 6%.
3. flue gas desulfurization synergist according to claim 1, is characterized in that: the mass percent concentration of described component is:
Nitrilotriacetic acid 90%
Butanedioic acid 8%
Glycolic acid 2%.
4. flue gas desulfurization synergist according to claim 1, is characterized in that: the mass percent concentration of described component is:
Nitrilotriacetic acid 90%
Butanedioic acid 5%
Glycolic acid 5%.
5. flue gas desulfurization synergist according to claim 1, is characterized in that: the mass percent concentration of described component is:
Nitrilotriacetic acid 91%
Butanedioic acid 4%
Glycolic acid 5%.
6. flue gas desulfurization synergist according to claim 1, is characterized in that: the mass percent concentration of described component is:
Nitrilotriacetic acid 91%
Butanedioic acid 6%
Glycolic acid 3%.
7. flue gas desulfurization synergist according to claim 1, is characterized in that: the mass percent concentration of described component is:
Nitrilotriacetic acid 91%
Butanedioic acid 7%
Glycolic acid 2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310423630.5A CN103463962B (en) | 2013-09-17 | 2013-09-17 | Flue gas desulfurization synergistic agent |
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|---|---|---|---|
| CN201310423630.5A CN103463962B (en) | 2013-09-17 | 2013-09-17 | Flue gas desulfurization synergistic agent |
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| CN103463962A CN103463962A (en) | 2013-12-25 |
| CN103463962B true CN103463962B (en) | 2015-07-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112156641A (en) * | 2020-09-23 | 2021-01-01 | 浙江浙能技术研究院有限公司 | Calcium-based wet desulphurization synergist |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5096478A (en) * | 1973-12-27 | 1975-07-31 | ||
| JPS57177331A (en) * | 1981-04-23 | 1982-11-01 | Tokyo Gas Co Ltd | Removal of hydrogen sulfide |
| SE502925C2 (en) * | 1994-06-23 | 1996-02-19 | Abb Flaekt Ind Ab | Methods and apparatus for removing sulfur dioxide from a gas |
| US20130039829A1 (en) * | 2011-08-09 | 2013-02-14 | Cansolv Technologies Inc. | Acid gas recovery utilizing organic acid salted diamine |
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Effective date of registration: 20170330 Address after: 95 No. 409100 Chongqing City Shizhu Tujia Autonomous County Nanbin town captaincy Avenue Patentee after: Chongqing high environmental technology development Co., Ltd. Address before: Huadu Huadu District 510000 Guangdong Avenue Huashan section of city of Guangzhou province No. 3 Jiang Department of logistics building second Patentee before: Guangzhou Gaocheng Environmental Protection Limited Company |
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Granted publication date: 20150722 Termination date: 20190917 |