CN102847418B - A kind of wet desulfurization of flue gas by limestone-gypsum method denitration additive - Google Patents
A kind of wet desulfurization of flue gas by limestone-gypsum method denitration additive Download PDFInfo
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- CN102847418B CN102847418B CN201110182031.XA CN201110182031A CN102847418B CN 102847418 B CN102847418 B CN 102847418B CN 201110182031 A CN201110182031 A CN 201110182031A CN 102847418 B CN102847418 B CN 102847418B
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- acid
- flue gas
- limestone
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The present invention discloses a kind of wet desulfurization of flue gas by limestone-gypsum method denitration additive, belongs to gas cleaning Treatment process.Additive of the present invention is mainly that three class materials are composite to be formed, and percentage by weight is: amine substance 40 ~ 60, organic acid substance 30 ~ 45, macromolecule organic carboxyl acid salt material 10 ~ 30.In this compound additive amine substance can directly and sour gas sulfur dioxide directly react generation ammonium sulfite, realize desulfurization; Amine substance can with NO
xreaction generates N
2, realize denitration.Organic acid and organic carboxyl acid salt material can promote the dissolving of lime stone, reduce the consumption of lime stone; Improve the pH value buffer capacity of lime stone slurry, slow down desulfurization slurry pH value in continuous sulfur dioxide absorption process and decline fast; Suppress the generation of the soft dirt of calcium sulfite, prevent demister from blocking.Compared with conventional limestone method, under identical liquid-gas ratio condition, improve desulfuration efficiency 5-10%, denitration efficiency reaches more than 50%.
Description
Technical field
The invention belongs to flue gases purification field, particularly relate to a kind of additive being applied to wet desulfurization of flue gas by limestone-gypsum method denitration.
Background technology
Air Pollution Control becomes the theme of current era environmental improvement, air thing leading indicator titanium dioxide (SO
2) and oxynitrides (NO
x).Environmental Protection Department is combined with State Administration for Quality Supervision and Inspection and Quarantine and is issued " fossil-fuel power plant atmospheric pollutant emission standard " and will implement on January 1st, 2012, clear stipulaties: from 1 day January in 2014, existing thermal power generation coal-burning boiler SO
2discharge restriction performs 200mg/Nm
3, NO
xdischarge restriction performs 100mg/Nm
3.Specify that emission limit is more strict, particularly for NO than existing GB13223-2003
xdischarge will as compulsory execution index.
At present, the method of domestic and international simultaneous SO_2 and NO removal mainly contains: 1) plasma method, it comprises electron beam and impulse electric corona two kinds, utilize that high energy electron makes the water in flue gas, oxygen equimolecular is activated, ionize or cracking, produce the strong oxidizing property active particles such as a large amount of electronics and free radical, make SO
2and NO
xoxidized, when injecting absorbent, realize desulphurization denitration.This complex process, adopts ammonia to make the volatile ammonia that causes of absorbent and loses and exhaust pollution; 2) catalysis method, utilizing desulfurizing and denitrifying process under catalyst action condition, this technique is in lab scale or pilot scale stage at present, the direct acting factor of catalysis method is the preparation of catalyst and regenerates more complicated, and cost is high, adopts ammonia to make the volatile ammonia that causes of absorbent simultaneously and lose and exhaust pollution; 3) wet chemical, the domestic soda solution that utilizes carries out comprehensive purifying process to industrial smoke, and the method can cause secondary wastewater to pollute and be difficult to process.
Limestone-gypsum Wet Flue Gas Desulfurization Process technique due to its technical maturity, desulfuration efficiency is high becomes a kind of desulfur technology most widely used in the world, nearly 400,000,000 kilowatts of the thermal power generation unit of the domestic desulfurizer that put into operation at present, wherein the unit of 80% adopts this sulfur removal technology.Current coal-burning power plant in all parts of the country faces and purchases that coal difficulty, ature of coal are poor, the particularly high and large predicament of fluctuating of coal-fired sulphur content, and desulphurization system is usually in damage and runs, and desulfuration efficiency is low.
Summary of the invention
Technical problem to be solved by this invention is to provide one can realize desulphurization denitration in Limestone-gypsum Wet Flue Gas Desulfurization Process technique simultaneously, and can improve the technical scheme of desulfuration efficiency.In order to solve the problems of the technologies described above, technical scheme provided by the present invention is:
A kind of wet desulfurization of flue gas by limestone-gypsum method denitration additive, the component of described additive and percentage by weight are: amine substance 40 ~ 60, organic acid substance 30 ~ 45, macromolecule organic carboxyl acid salt material 10 ~ 30.
Preferably, the component of described additive and percentage by weight are: amine substance 45 ~ 55, organic acid substance 35 ~ 40, macromolecule organic carboxyl acid salt material 15 ~ 35.
Preferably, described amine substance comprises at least one in urea, ethylenediamine, ammonium phosphate, diammonium hydrogen phosphate, ammonium carbonate, ammonium hydrogen phosphate, triethanolamine.
Preferably, described organic acid substance comprises at least one in adipic acid, humic acid, citric acid, benzoic acid, glutaric acid, succinic acid, ethanedioic acid, P-hydroxybenzoic acid.
Preferably, described macromolecule organic carboxyl acid salt material comprises at least one in sodium humate, natrium citricum, adipic acid sodium, Sodium Benzoate.
Preferably, described amine substance comprises at least one in urea, ethylenediamine, ammonium phosphate, diammonium hydrogen phosphate, ammonium carbonate, ammonium hydrogen phosphate, triethanolamine, described organic acid substance comprises at least one in adipic acid, humic acid, citric acid, benzoic acid, glutaric acid, succinic acid, ethanedioic acid, P-hydroxybenzoic acid, and described macromolecule organic carboxyl acid salt material comprises at least one in sodium humate, natrium citricum, adipic acid sodium, Sodium Benzoate.
In the technical program, amine substance has two functions: 1) amine substance can directly and SO
2, NO
xreaction, generate ammonium sulfite, ammonium nilrite and ammonium nitrate, this is swift in response and carries out, and is conducive to instant relief desulphurization system entrance high concentration SO
2and higher concentration NO
x; 2) amine substance can react with NOx and generate N
2, reach the object of denitration; Organic acid substance, particularly organic polycarboxylic acid and organic multicomponent Barbiturates have promotion SO
2the effect of dissolving, cushioning slurry pH value, promoting dissolution of calcium carbonate.In gas phase surface and liquid film, the SO of dissolving
2react dissociation with water and go out H
+, liquid film and liquid phase main body border, R (COO
-)
nwith H
+reaction generates R (COOH)
n, make H
+be passed to liquid phase main body, H in liquid film
+concentration reduction facilitates SO
2dissolving, alleviate pH value decrease speed simultaneously; In solid phase surface and liquid film, the CO of dissolving
3 -with the H of dissociation
+reaction generates HCO
3 -, liquid phase main body, H
+with HCO
3 -reaction generates CO
2and H
2o, liquid phase main body HCO
3 -the reduction of concentration, thus the dissolving facilitating calcium carbonate.Three kinds of action functions can ensure that desulphurization system is stable, Effec-tive Function, improve desulfuration efficiency.Reaction equation principle is as follows:
Organic carboxyl acid ionization generates H
+
R(COOH)
n·←→R(COOH)
n-1(COO
-)+H
+←→R(COOH)
n-2(COO
-)
2+2H
+←→…
Flue gas SO
2dissolve hydration ionization and generate H
+
SO
2+H
2O→H
2SO
3
H
2SO
3→2H
++HSO
3
H
+again be combined with organic carboxylate and generate organic carboxyl acid
R(COO
-)
n·+nH
+←→R(COOH)
n·
The dissolving of calcium carbonate
CaCO
3(s)←→Ca
2++CO
3 2-
CO
3 2-+H
+←→HCO
3 -
HCO
3-+H
+←→CO
2(aq)+H
2O
Therefore, beneficial effect of the present invention has: 1) achieve desulphurization denitration simultaneously, and desulfuration efficiency can be improved more than 8% under identical liquid-gas ratio condition, denitration efficiency reaches more than 50%; 2) nonhazardous, have no side effect, soluble in water, stable chemical performance, can not secondary pollution be caused, corrosion-free to equipment.
Detailed description of the invention
In order to clearer elaboration technology contents of the present invention; be described in detail at this in conjunction with the embodiments; obviously; arranging huge embodiment is preferred section Example, and other embodiments that those skilled in the art draw apparently according to disclosed technical data still belong to protection scope of the present invention.
Wet process of FGD denitration additive embodiment of the present invention is carried out in the supporting desulfurization by lime gypsum method system of certain 300MW station boiler.This desulphurization system design entry flue gas SO
2concentration 1584mg/Nm
3; Liquid-gas ratio 9.81; Calcium sulfur ratio≤1.025; Exiting flue gas SO
2concentration≤71.21, desulfuration efficiency>=95%.
Embodiment 1
A kind of additive for desulfurization denitrification agent, its component and percentage by weight are: urea 8, ethylenediamine 10, ammonium phosphate 5, diammonium hydrogen phosphate 10, ammonium carbonate 15, ammonium hydrogen phosphate 10, triethanolamine 2, adipic acid 5, humic acid 5, citric acid 3, benzoic acid 2, glutaric acid 5, succinic acid 2, ethanedioic acid 5, P-hydroxybenzoic acid 3, sodium humate 1, natrium citricum 4, adipic acid sodium 3, Sodium Benzoate 2.
Desulphurization system inlet flue gas SO
2concentration 2100mg/Nm
3; NOx concentration 850mg/Nm
3; Liquid-gas ratio 10.1; Calcium sulfur ratio 1.1.It is 850mg/L that additive adds concentration, and desulfuration efficiency improves 11%, and denitration efficiency is 68%.
Embodiment 2
A kind of additive for desulfurization denitrification agent, its component and percentage by weight are: urea 18, ethylenediamine 12, ammonium phosphate 6, diammonium hydrogen phosphate 2, ammonium carbonate 15, ammonium hydrogen phosphate 5, adipic acid 3, humic acid 2, citric acid 7, benzoic acid 9, glutaric acid 4, succinic acid 5, sodium humate 4, natrium citricum 3, adipic acid sodium 5.
Desulphurization system inlet flue gas SO
2concentration 2200mg/Nm
3; NOx concentration 840mg/Nm
3; Liquid-gas ratio 9.9; Calcium sulfur ratio 1.05.It is 900mg/L that additive adds concentration, and desulfuration efficiency improves 14%, and denitration efficiency is 60%.
Embodiment 3
A kind of additive for desulfurization denitrification agent, its component and percentage by weight are: ethylenediamine 6, ammonium phosphate 10, diammonium hydrogen phosphate 15, ammonium carbonate 18, ammonium hydrogen phosphate 7, humic acid 3, benzoic acid 10, glutaric acid 11, succinic acid 4, ethanedioic acid 5, natrium citricum 5, adipic acid sodium 6.
Desulphurization system inlet flue gas SO
2concentration 2000mg/Nm
3; NOx concentration 850mg/Nm
3; Liquid-gas ratio 9.8; Calcium sulfur ratio 1.03.It is 800mg/L that additive adds concentration, and desulfuration efficiency improves 15%, and denitration efficiency is 65%.
Embodiment 4
For an additive for desulfurization denitrification agent, its component and percentage by weight are: urea 11, ammonium phosphate 15, ammonium carbonate 5, ammonium hydrogen phosphate 10, triethanolamine 10, citric acid 34.5, sodium humate 10, Sodium Benzoate 4.5.
Desulphurization system inlet flue gas SO
2concentration 2200mg/Nm
3; NOx concentration 780mg/Nm
3; Liquid-gas ratio 10.0; Calcium sulfur ratio 1.05.It is 1000mg/L that additive adds concentration, and desulfuration efficiency improves 16%, and denitration efficiency is 61%.
Embodiment 5
For an additive for desulfurization denitrification agent, its component and percentage by weight are: ethylenediamine 19, ammonium phosphate 10, diammonium hydrogen phosphate 10, ammonium carbonate 10, glutaric acid 5, sodium humate 6, adipic acid sodium 10.
Desulphurization system inlet flue gas SO
2concentration 2500mg/Nm
3; NOx concentration 800mg/Nm
3; Liquid-gas ratio 10.0; Calcium sulfur ratio 1.05.It is 1200mg/L that additive adds concentration, and desulfuration efficiency improves 15%, and denitration efficiency is 70%.
Embodiment 6
For an additive for desulfurization denitrification agent, its component and percentage by weight are: ammonium phosphate 10, diammonium hydrogen phosphate 20, ammonium carbonate 10, ammonium hydrogen phosphate 10, humic acid 22, citric acid 10, natrium citricum 8, Sodium Benzoate 10.
Desulphurization system inlet flue gas SO
2concentration 2100mg/Nm
3; NOx concentration 850mg/Nm
3; Liquid-gas ratio 10.1; Calcium sulfur ratio 1.1.It is 800mg/L that additive adds concentration, and desulfuration efficiency improves 10%, and denitration efficiency is 60%.
Embodiment 7
For an additive for desulfurization denitrification agent, its component and percentage by weight are: ammonium phosphate 8, diammonium hydrogen phosphate 5, ammonium carbonate 7, ammonium hydrogen phosphate 8, triethanolamine 12, humic acid 19, benzoic acid 15, glutaric acid 4, sodium humate 12, adipic acid sodium 10.
Desulphurization system inlet flue gas SO
2concentration 2200mg/Nm
3; NOx concentration 840mg/Nm
3; Liquid-gas ratio 9.9; Calcium sulfur ratio 1.05.It is 800mg/L that additive adds concentration, and desulfuration efficiency improves 14%, and denitration efficiency is 55%.
Embodiment 8
For an additive for desulfurization denitrification agent, its component and percentage by weight are: urea 25, diammonium hydrogen phosphate 20, glutaric acid 10, succinic acid 15, ethanedioic acid 5, P-hydroxybenzoic acid 10, sodium humate 5, natrium citricum 5, adipic acid sodium 2, Sodium Benzoate 3.
Desulphurization system inlet flue gas SO
2concentration 2000mg/Nm
3; NOx concentration 850mg/Nm
3; Liquid-gas ratio 9.8; Calcium sulfur ratio 1.03.It is 900mg/L that additive adds concentration, and desulfuration efficiency improves 15%, and denitration efficiency is 65%.
Embodiment 9
For an additive for desulfurization denitrification agent, its component and percentage by weight are: ammonium phosphate 20, triethanolamine 20, humic acid 15, citric acid 10, benzoic acid 10, adipic acid sodium 15, Sodium Benzoate 10.
Desulphurization system inlet flue gas SO
2concentration 2200mg/Nm
3; NOx concentration 780mg/Nm
3; Liquid-gas ratio 10.0; Calcium sulfur ratio 1.05.It is 700mg/L that additive adds concentration, and desulfuration efficiency improves 16%, and denitration efficiency is 61%.
Embodiment 10
For an additive for desulfurization denitrification agent, its component and percentage by weight are: ammonium carbonate 40, citric acid 10, benzoic acid 5, second 2 15, natrium citricum 30.
Desulphurization system inlet flue gas SO
2concentration 2500mg/Nm
3; NOx concentration 800mg/Nm
3; Liquid-gas ratio 10.0; Calcium sulfur ratio 1.05.It is 1200mg/L that additive adds concentration, and desulfuration efficiency improves 15%, and denitration efficiency is 65%.
Claims (6)
1. a wet desulfurization of flue gas by limestone-gypsum method denitration additive, is characterized in that the component of described additive and percentage by weight are: amine substance 40 ~ 60, organic acid substance 30 ~ 45, macromolecule organic carboxyl acid salt material 10 ~ 30.
2. a kind of wet desulfurization of flue gas by limestone-gypsum method denitration additive according to claims 1, it is characterized in that component and the percentage by weight of described additive are: amine substance 45 ~ 55, organic acid substance 35 ~ 40, macromolecule organic carboxyl acid salt material 15 ~ 30, above weight percentages of components amounts to 100%.
3. a kind of wet desulfurization of flue gas by limestone-gypsum method denitration additive according to claim 1 and 2, is characterized in that described amine substance comprises at least one in urea, ethylenediamine, ammonium phosphate, diammonium hydrogen phosphate, ammonium carbonate, ammonium hydrogen phosphate, triethanolamine.
4. a kind of wet desulfurization of flue gas by limestone-gypsum method denitration additive according to claim 1 and 2, is characterized in that described organic acid substance comprises at least one in adipic acid, humic acid, citric acid, benzoic acid, glutaric acid, succinic acid, ethanedioic acid, P-hydroxybenzoic acid.
5. a kind of wet desulfurization of flue gas by limestone-gypsum method denitration additive according to claim 1 and 2, is characterized in that described macromolecule organic carboxyl acid salt material comprises at least one in sodium humate, natrium citricum, adipic acid sodium, Sodium Benzoate.
6. a kind of wet desulfurization of flue gas by limestone-gypsum method denitration additive according to claim 1 and 2, it is characterized in that described amine substance comprises at least one in urea, ethylenediamine, ammonium phosphate, diammonium hydrogen phosphate, ammonium carbonate, ammonium hydrogen phosphate, triethanolamine, described organic acid substance comprises at least one in adipic acid, humic acid, citric acid, benzoic acid, glutaric acid, succinic acid, ethanedioic acid, P-hydroxybenzoic acid, and described macromolecule organic carboxyl acid salt material comprises at least one in sodium humate, natrium citricum, adipic acid sodium, Sodium Benzoate.
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| CN102847418B true CN102847418B (en) | 2016-03-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143252B (en) * | 2013-02-22 | 2015-06-10 | 广东电网公司电力科学研究院 | Additive capable of simultaneous desulphurization and demercuration and preparation method thereof |
| CN103272472B (en) * | 2013-06-18 | 2015-06-17 | 上海电力学院 | Flue gas desulfurization synergist for wet desulfurization system, and preparation method and application thereof |
| CN103691288A (en) * | 2014-01-21 | 2014-04-02 | 高同柱 | Manufacturing method for desulfurization and denitrification agent additive by limestone-gypsum method |
| CN106031844B (en) * | 2015-03-20 | 2020-01-07 | 江西永丰博源实业有限公司 | Desulfurization and denitrification agent |
| CN104998537A (en) * | 2015-07-28 | 2015-10-28 | 珲春承奕环保节能产品有限公司 | Efficient and environmentally-friendly desulfuration additive |
| CN107812537A (en) * | 2017-11-28 | 2018-03-20 | 张家界鸿燕新材料科技发展有限公司 | A kind of preparation method of denitrating catalyst |
| CN107876090B (en) * | 2017-11-28 | 2020-09-15 | 张家界鸿燕新材料科技发展有限公司 | Denitration catalyst |
| CN112246080A (en) * | 2020-09-14 | 2021-01-22 | 佛山市粤罡环保设备有限公司 | Organic amine denitration agent and preparation method thereof |
| CN112371038A (en) * | 2020-10-29 | 2021-02-19 | 南京霖厚环保科技有限公司 | Wet flue gas desulfurization and denitrification method |
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