CN103691288A - Manufacturing method for desulfurization and denitrification agent additive by limestone-gypsum method - Google Patents
Manufacturing method for desulfurization and denitrification agent additive by limestone-gypsum method Download PDFInfo
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- CN103691288A CN103691288A CN201410025932.1A CN201410025932A CN103691288A CN 103691288 A CN103691288 A CN 103691288A CN 201410025932 A CN201410025932 A CN 201410025932A CN 103691288 A CN103691288 A CN 103691288A
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Abstract
The invention discloses a manufacturing method for a desulfurization and denitrification agent additive by a limestone-gypsum method. The manufacturing method is characterized in that the additive consists of the components in percentage by weight: 40-60 percent of a catalytic promoter substance, 20-40 percent of organic acid and salt substances and 15-40 percent of a synergist substance. The additive adopted in the manufacturing method can improve the desulfurization efficiency of an absorption tower, adapt to high-sulfur coal and enable the SO2 outlet concentration to meet a standard; furthermore, a serous fluid circulating pump can be stopped to different extents, and the aim of saving the energy can be fulfilled; moreover, the additive is easily dissolved in water and can promote dissolving of limestone and reduce the using amount of the limestone; the pH value buffering capacity of limestone serous fluid is improved, and rapid reduction of the pH value of the limestone serous fluid in a continuous sulfur dioxide absorption process is relieved; generation of calcium sulfite soft dirt is inhibited, and a demister can be prevented from being blocked. The desulfurization and denitrification agent additive has the characteristics of simplicity and convenience in use, no production of air bubbles in the using process and no corrosion to equipment; compared with the conventional limestone, the desulfurization and denitrification agent additive has the advantages that the content of NO in smoke gas can be also reduced; under the same liquid-gas-ratio condition, the desulfurization efficiency is improved by 8-18 percent, and the denitrification efficiency is over 50 percent; desulfurization and denitrification effects and a smoke gas purification effect are achieved.
Description
Technical field
The invention belongs to smoke gas treatment and control technology field, concrete is exactly the manufacture method for limestone-gypsum method wet process of FGD denitration additive.
Background technology
Air Pollution Control becomes the theme of current era environmental improvement, atmosphere thing leading indicator titanium dioxide (SO
2) and oxynitrides (NO
x).Environmental Protection Department is combined the issue < < pollutant emission standard > > of thermal power plant and will, in enforcement on January 1st, 2012, clearly be stipulated: existing thermal power generation coal-burning boiler SO from 1 day January in 2014 with national quality supervision and inspection epidemic disease general bureau
2emission limit set is carried out 200mg/Nm
3, NO
xemission limit set is carried out, 100mg/Nm
3more stricter than existing GB13223-2003 regulation emission limit set, particularly for NO
xmoral discharge will be as executing index.
Limestone-gypsum Wet Flue Gas Desulfurization Process technique becomes most widely used in the world a kind of desulfur technology because its technical maturity, desulfuration efficiency are high, nearly 400,000,000 kilowatts of the thermal power generation unit of the domestic desulfurizer that put into operation at present, and wherein 80% unit adopts this desulfurization industry.Current coal-burning power plant in all parts of the country faces and purchases coal difficulty, and ature of coal is poor, the particularly high and large predicament of fluctuating of coal-fired sulphur content, and desulphurization system is usually in improper operating mode operation, and desulfuration efficiency is low.
Technical problem to be solved by this invention is to provide and a kind ofly can in Limestone-gypsum Wet Flue Gas Desulfurization Process industry, realizes desulphurization denitration simultaneously, and can improve the technical scheme of desulfuration efficiency.In order to solve the problems of the technologies described above.In the technical program, catalytic promoter can not direct and SO
2, NO
xreaction, is NO2 soluble in water to NO catalytic oxidation, and this is swift in response and carries out, and is conducive to moment alleviation desulphurization system entrance high concentration SO
2and higher concentration NO
x; Organic acid substance, the particularly acid of organic multicomponent antelope and organic multicomponent salt have promotion SO
2dissolve, cushion the effect of plasm PH value, promotion 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
- ) n and H
+reaction generates R (COOH) n and makes H
+be passed to liquid phase main body, H in liquid film
+concentration reduces and has promoted SO
2dissolving, alleviate pH value decrease speed: the SO dissolving in solid phase surface and liquid film simultaneously
3 -the H of dissociation
+reaction generates HCO
3 -, liquid phase main body, H+ and HCO
3 -reaction generates CO
2and H
2o, liquid phase main body HCO
3 -concentration reduce, thereby promoted the dissolving of calcium carbonate.
summary of the invention
Technical problem to be solved by this invention provides a kind of can realize desulphurization denitration in Limestone-gypsum Wet Flue Gas Desulfurization Process technique simultaneously, and can improve the technical scheme of desulphurization denitration rate.In order to solve the problems of the technologies described above, technical scheme provided by the present invention is:
A kind of for wet desulfurization of flue gas by limestone-gypsum method denitration additive, the component of described additive and percentage by weight are: catalytic promoter 20-60] preferred, the component of described additive and percentage by weight are: catalytic promoter 30-55, organic acid and salts substances 20-60, builder material 15-35.
Preferably, described catalytic promoter class material comprises one or more of potassium permanganate, sodium chlorite, sodium chlorate, sodium chloride, magnesium sulfate, manganese sulfate, sodium nitrate, ammonium phosphate, diammonium hydrogen phosphate, cobalt oxide, cobalt nitrate, cobalt chloride, cobalt acetate, ferrous sulfate, ammonium carbonate, triethanolamine.
Preferably, described organic acid substance comprise adipic acid, adipic acid sodium, humic acid, sodium humate, citric acid, natrium citricum, sodium acetate, boric acid, borax, glutaric acid, succinic acid, ethanedioic acid, to one or more of antelope yl benzoic acid.
Preferably, described builder material sodium sulphate, alkali formula sodium sulphate, anhydrous sodium sulfite, akali sulphide, natrium citricum, copper chloride dihydrate, copper nitrate, copper carbonate, Kocide SD, cupric oxide, magnesium sulfate, sodium carbonate.
In the technical program, be to provide and a kind ofly can in Limestone-gypsum Wet Flue Gas Desulfurization Process industry, realize desulphurization denitration simultaneously, and can improve the technical scheme of desulfuration efficiency.In order to solve the problems of the technologies described above.In the technical program, catalytic promoter can not direct and SO
2, NO
xreaction, is NO2 soluble in water to NO catalytic oxidation, and this is swift in response and carries out, and is conducive to moment alleviation desulphurization system entrance high concentration SO
2and higher concentration NO
x; Organic acid and salts substances, the particularly acid of organic multicomponent antelope and organic multicomponent salt have promotion SO
2dissolve, cushion the effect of plasm PH value, promotion 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
- ) n and H
+reaction generates R (COOH) n and makes H
+be passed to liquid phase main body, H in liquid film
+concentration reduces and has promoted SO
2dissolving, alleviate pH value decrease speed: the SO dissolving in solid phase surface and liquid film simultaneously
3 -the H of dissociation
+reaction generates HCO
3 -, liquid phase main body, H+ and HCO
3 -reaction generates CO
2and H
2o, liquid phase main body HCO
3 -concentration reduce, thereby promoted the dissolving of calcium carbonate.Guarantee stable, the efficient operation of desulphurization system, improve desulfuration efficiency, below in conjunction with embodiment, the present invention is described in detail.
The specific embodiment
Embodiment 1
For a wet desulfurization of flue gas by limestone-gypsum method denitration additive, its component and percentage by weight are: sodium nitrate 20, cobalt chloride 5, cobalt oxide 1 magnesium sulfate 10 adipic acids 50, citric acid 7, copper chloride dihydrate 7 are uniformly mixed.
Desulphurization system inlet flue gas SO2 concentration 3000mg/Nm3; NOx concentration 840mg/Nm3; Liquid-gas ratio 9.9; Calcium sulfur ratio 1.05.It is 1000mg/l that additive adds concentration, and desulfuration efficiency improves 14%, and denitration efficiency is 68%.
Embodiment 2
For for a wet desulfurization of flue gas by limestone-gypsum method denitration additive, its component and percentage by weight are: potassium permanganate 40, cobalt oxide 1 adipic acid 30, cobalt nitrate 5, manganese sulfate 10, copper nitrate 10, humic acid 4 are uniformly mixed.
Desulphurization system inlet flue gas SO2 concentration 2500mg/Nm3; NOx concentration 880mg/Nm3; Liquid-gas ratio 9.8; Calcium sulfur ratio 1.05.It is 900mg/l that additive adds concentration, and desulfuration efficiency improves 15%, and denitration efficiency is 76%.
Embodiment 3,
For a wet desulfurization of flue gas by limestone-gypsum method denitration additive, its component and percentage by weight are: sodium chlorite 40, cobalt oxide 1 ammonium phosphate 10, sodium acetate 10, sodium humate 10, natrium citricum 10, copper carbonate 10 cobalt oxides 9 are uniformly mixed.
Desulphurization system inlet flue gas SO2 concentration 3500mg/Nm3; NOx concentration 800mg/Nm3; Liquid-gas ratio 10.5; Calcium sulfur ratio 1.05.It is 1000mg/l that additive adds concentration, and desulfuration efficiency improves 12%, and denitration efficiency is 71%.
Embodiment 4,
For a wet desulfurization of flue gas by limestone-gypsum method denitration additive, its component and percentage by weight are: sodium chlorite 40, potassium permanganate 10, cobalt oxide 2 sodium acetates 30, sodium humate 10, copper carbonate 8 are uniformly mixed.
Desulphurization system inlet flue gas SO2 concentration 3000mg/Nm3; NOx concentration 880mg/Nm3; Liquid-gas ratio 10.0; Calcium sulfur ratio 1.05.It is 800mg/l that additive adds concentration, and desulfuration efficiency improves 10%, and denitration efficiency is 72%.
Embodiment 5
For a wet desulfurization of flue gas by limestone-gypsum method denitration additive, its component and percentage by weight are: ammonium phosphate 10, cobalt oxide 2 diammonium hydrogen phosphates 20, potassium permanganate 20 sodium humates 22, natrium citricum 8, copper carbonate 10 is uniformly mixed.
Desulphurization system inlet flue gas SO2 concentration 2800mg/Nm3; NOx concentration 900mg/Nm3; Liquid-gas ratio 10.1; Calcium
Embodiment 6
For a wet desulfurization of flue gas by limestone-gypsum method denitration additive, its component and percentage by weight are: potassium permanganate 40 ammonium phosphate 8.5, cobalt oxide 1.5 triethanolamines 12, sodium humate 20, copper carbonate 10, sodium carbonate 8 are uniformly mixed.
Desulphurization system inlet flue gas SO2 concentration 3500mg/Nm3; NOx concentration 840mg/Nm3; 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 75%.
Claims (8)
1. for a Limestone-gypsum Wet Flue Gas Desulfurization Process denitration additives production process, it is characterized in that the component of described additive and percentage by weight are: catalytic promoter class material 40-60 organic acid and salts substances 20-40, builder material 15-40.
2. a kind of for Limestone-gypsum Wet Flue Gas Desulfurization Process denitration additives production process according to described in claims 1, the component and the percentage by weight that it is characterized in that described additive are preferably: catalytic promoter 30-55, organic acid and salts substances 20-40, builder material 15-35.
3. according to claim 1 a kind of for Limestone-gypsum Wet Flue Gas Desulfurization Process denitration additives production process, it is characterized in that described catalytic promoter class material comprises one or more of potassium permanganate, sodium chlorite, sodium chlorate, magnesium sulfate, sodium chloride, manganese sulfate, sodium nitrate, ammonium phosphate, diammonium hydrogen phosphate, cobalt oxide, cobalt nitrate, cobalt chloride, cobalt acetate, ferrous sulfate, ammonium carbonate, triethanolamine.
4. according to claim 1 a kind of for Limestone-gypsum Wet Flue Gas Desulfurization Process denitration additives production process, it is characterized in that described organic acid and salts substances comprise adipic acid, adipic acid sodium, humic acid, sodium humate, citric acid, natrium citricum, sodium acetate, boric acid, borax, glutaric acid, succinic acid, ethanedioic acid, to one or more of antelope yl benzoic acid.
5. a kind of for Limestone-gypsum Wet Flue Gas Desulfurization Process denitration additive according to described in claim 1, is characterized in that described builder material sodium sulphate, alkali formula sodium sulphate, anhydrous sodium sulfite, akali sulphide, natrium citricum, copper chloride dihydrate, copper nitrate, copper carbonate, Kocide SD, cupric oxide, sodium carbonate.
6. a kind of for Limestone-gypsum Wet Flue Gas Desulfurization Process denitration additives production process according to described in claim 1, is characterized in that described catalytic promoter class material comprises one or more of potassium permanganate, sodium chlorite, sodium chlorate, sodium nitrate, magnesium sulfate, ammonium phosphate, diammonium hydrogen phosphate, cobalt oxide, cobalt nitrate, cobalt chloride, cobalt acetate, ferrous sulfate, ammonium carbonate, triethanolamine.
According to claim 1 organic acid and salts substances comprise adipic acid, adipic acid sodium, humic acid, sodium humate, citric acid, natrium citricum, sodium acetate, boric acid, borax, glutaric acid, succinic acid, ethanedioic acid, to one or more of antelope yl benzoic acid.
According to claim 1 builder material sodium sulphate, alkali formula sodium sulphate, anhydrous sodium sulfite, akali sulphide, natrium citricum, copper chloride dihydrate, copper nitrate, copper carbonate, Kocide SD, cupric oxide, magnesium sulfate, sodium carbonate one or more.
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CN105536489A (en) * | 2015-12-09 | 2016-05-04 | 安徽中泰创展环境科技有限公司 | Slurry for flue gas desulfurization |
CN105925332A (en) * | 2016-07-01 | 2016-09-07 | 西北师范大学 | High-efficiency sulfur-fixation coal briquette composite adhesive |
CN106268293A (en) * | 2015-05-14 | 2017-01-04 | 王立群 | A kind of wet desulphurization denitration synergist for coal-burning boiler |
CN106582246A (en) * | 2016-12-26 | 2017-04-26 | 合肥天翔环境工程有限公司 | Carbide slag wet-method flue gas simultaneous desulfurization and denitrification process |
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 |
CN107648998A (en) * | 2017-11-13 | 2018-02-02 | 盐城工学院 | A kind of oxidized form compound additive for Wet Fgd By Limestone and preparation method thereof |
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CN112520823A (en) * | 2020-11-10 | 2021-03-19 | 河北国华定州发电有限责任公司 | Method for adding composite gypsum crystallization accelerator for improving crystallization quality of desulfurization slurry |
CN114195272A (en) * | 2021-12-23 | 2022-03-18 | 华北电力科学研究院有限责任公司 | Desulfurization wastewater treatment method |
CN114832610A (en) * | 2022-04-02 | 2022-08-02 | 徐州宏阳新材料科技股份有限公司 | Deep desulfurization method for shaft furnace flue gas |
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CN106268293A (en) * | 2015-05-14 | 2017-01-04 | 王立群 | A kind of wet desulphurization denitration synergist for coal-burning boiler |
CN105536489A (en) * | 2015-12-09 | 2016-05-04 | 安徽中泰创展环境科技有限公司 | Slurry for flue gas desulfurization |
CN105925332B (en) * | 2016-07-01 | 2018-11-02 | 西北师范大学 | A kind of efficiency of sulfur retention composite adhesive for briquette |
CN105925332A (en) * | 2016-07-01 | 2016-09-07 | 西北师范大学 | High-efficiency sulfur-fixation coal briquette composite adhesive |
CN106582246A (en) * | 2016-12-26 | 2017-04-26 | 合肥天翔环境工程有限公司 | Carbide slag wet-method flue gas simultaneous desulfurization and denitrification process |
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 |
CN107648998A (en) * | 2017-11-13 | 2018-02-02 | 盐城工学院 | A kind of oxidized form compound additive for Wet Fgd By Limestone and preparation method thereof |
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 |
CN107876090A (en) * | 2017-11-28 | 2018-04-06 | 张家界鸿燕新材料科技发展有限公司 | A kind 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 |
CN112520823A (en) * | 2020-11-10 | 2021-03-19 | 河北国华定州发电有限责任公司 | Method for adding composite gypsum crystallization accelerator for improving crystallization quality of desulfurization slurry |
CN112520823B (en) * | 2020-11-10 | 2022-10-11 | 河北国华定州发电有限责任公司 | Method for adding composite gypsum crystallization accelerator for improving crystallization quality of desulfurization slurry |
CN114195272A (en) * | 2021-12-23 | 2022-03-18 | 华北电力科学研究院有限责任公司 | Desulfurization wastewater treatment method |
CN114195272B (en) * | 2021-12-23 | 2024-02-27 | 华北电力科学研究院有限责任公司 | Desulfurization wastewater treatment method |
CN114832610A (en) * | 2022-04-02 | 2022-08-02 | 徐州宏阳新材料科技股份有限公司 | Deep desulfurization method for shaft furnace flue gas |
CN115197761A (en) * | 2022-06-28 | 2022-10-18 | 福建坤净生环保科技有限公司 | Multifunctional drying-free powder binder for sludge granulation and heat-increasing combustion |
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