CN101530731A - Integrated equipment for desulfurization, denitrification and dedusting by coal ash and oxidant applying method under acidic condition - Google Patents
Integrated equipment for desulfurization, denitrification and dedusting by coal ash and oxidant applying method under acidic condition Download PDFInfo
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- CN101530731A CN101530731A CN200910119425A CN200910119425A CN101530731A CN 101530731 A CN101530731 A CN 101530731A CN 200910119425 A CN200910119425 A CN 200910119425A CN 200910119425 A CN200910119425 A CN 200910119425A CN 101530731 A CN101530731 A CN 101530731A
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- desulfurization
- coal ash
- denitrification
- dust collecting
- acid condition
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Abstract
The invention relates to integrated equipment for desulfurization, denitrification and dedusting by coal ash and oxidant applying method under acidic condition. In first-stage dedusting and desulfurization, flue gas and water react as follow: SO2+H2O=H2SO3=H<+>HSO3<->=2H<+>+SO3<-2> (1); (Na2O.K2O)+H2SO3=(Na.K)2SO3+H2O (2); (MgO.Ca2O)+H2SO3=(Mg.Ca)SO3+H2O (3); 4H<+>+2SO3<-2>+Fe2O3=FeSO4+FeSO3+2H2O (4); 4Fe<+2>+4H<+>+O2=4F<+3>+2H2O (5); NO+FeSO3=Fe(NO)SO3 (6); and 2Fe(NO)SO3+O2+H2SO4=Fe2(SO4)3+N2+H2O (7). In second-stage dedusting and desulfurization, a spray method is adopted to further increase desulfurization and dedusting efficiency and remove moisture in the flue gas. The present invention adopts novel iron ion desulfurization and denitrification process, utilizes iron ion to carry out desulfurization and denitrification, in actual operation, desulfurization reaches 95%, and denitrification reaches 60%. Compared with other desulfurization agent cost, expense is saved by 80%. Because iron ion is used as additive and can form flocculant by itself, water is not turbid and deposition is accelerated in operation process.
Description
Technical field
Patent of the present invention relates to a kind of method of utilizing coal ash and oxidant applying under acid condition, carries out the incorporate equipment of desulfur denitrate dust collecting.
Background technology
At present in industrial enterprise, particularly in the mine, factory floor etc. is local produces a large amount of dusty gases, the dust-removal and desulfurizing denitration problem of everyway when making great efforts to solve smoke evacuation, existing cleaner investment is expensive, floor space is big, desulfuration efficiency is low.This cleaner repeatedly utilizes the active principle in the flyash under acid condition, by the form of oxidant applying, carry out desulfurization, denitrogenation, dedusting where necessary.Reduce applying unit desulfurization expense, realized energy-saving and emission-reduction.
Summary of the invention
The purpose of patent of the present invention is to provide a kind of existing desulphurization denitration technical deficiency that overcomes, and a kind of denitrification efficiency height is provided, and the method for utilizing coal ash and oxidant applying under acid condition of comprehensive utilization of resources is carried out the incorporate equipment of desulfur denitrate dust collecting.To achieve these goals, patent of the present invention is achieved through the following technical solutions:
Elementary desulphurization denitration cleaning principle
The chemical principle of desulfurization removing nitric
1. desulfurization removing nitric
I by research alone mature in the world two kinds of sulfur methods are at present combined (both neutralisation and with iron ion as catalyst SO in the flue gas
2Make the method for sulfuric acid), be applied on the environment-friendly engineering of desulfurization removing nitric the existing practical experience that has obtained on coal-burning boiler.
Simultaneously I am according to nearly 10 years constantly discovering, only utilize coal ash simultaneously an amount of add ferro element, can reach good desulfurization off sulfide effect.
Be analyzed as follows according to already used Shanxi coal: cigarette ash component content (table 1)
| Title | SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | MgO | SO 3 | K 2O | TiO 2 | Other |
| Quantity | 47.68 | 30.85 | 10.43 | 2.91 | 1.4 | 1.91 | 1.62 | 1.64 | 1.61 |
| Percentage % | 49.22 | 32.19 | 9.68 | 2.7 | 1.16 | 1.46 | 1.29 | 1.18 | 1.12 |
Learn from above-mentioned flue gas analysis table: have nearly 48% metal oxide to have (aluminium oxide, iron oxide, calcium oxide, magnesia etc.).Wherein iron oxide content is up to 9.68%, and the sulfurous acid generation neutralization reaction in these metal oxides and the doctor solution generates corresponding sulfate, and iron oxide and sulfurous acid reaction generation Fe
2(SO
3)
3, Fe
2(SO
3)
3Meet water decomposition and generate iron hydroxide, it is not only the absorbent of sulfur dioxide, also is reducing agent.Simultaneously because the fe that adds, a large amount of abundant Fe (II) have been guaranteed to contain in the system, Fe (II) reacts with nitrogen oxide, when self is oxidized, nitrogen oxide is reduced to nitrogen, thereby reach denitration effect, according to above situation, for circulation dust-removal and desulfurizing denitrification integral provides prerequisite.
In primary dust removing desulphurization denitration process, when flue gas impacts water, produce following reaction:
Iron oxide is dissolved by acidifying water, dissociate the iron ion that as oxidation catalyst, sulfurous acid is oxidized to sulfuric acid, again " neutralizing acid " aluminium oxide (amphoteric oxide) and other metal oxide that ability is the strongest also dissolved simultaneously, thereby under the situation of not adding other desulfurizing agent and denitrfying agent, can utilize the composition of flue gas self to carry out desulfurization.
SO
2With the reaction of metal oxide be neutralisation:
(MgO.CaO)+H
2SO
3＝(Mg、.Ca)SO
3+H
2O(2)
Also have in ash with kaolinite (Al
2O
32SiO
22H
2O) and the part analyte---the Al that the clay form exists
2O
3(amphoteric oxide) is only with regard to Al
2O
3Its weight percentage is all higher than other metal oxide component, with Fe
2O
3The same, also be amphoteric oxide, because of Al
2O
3Solubility product K
58=2 * 10
-33, promptly the pH value when circulation cleaning water is below 4.7, Al
3+Just begin molten being stored in the water, so also have only the circulation cleaning water ph value under lower situation, it could bring into play its antacid effect fully, and the sulfate that in the stronger water of acidity, crystallizes out, no matter its solubility size can not generate tiny, colloid shape precipitation, and be attached to equipment surface, cause equipment to stop up, and strainability might as well.But because the metal oxide amount is limited, desulfurization degree can only reach about 70% all the time, and denitration efficiency also has only about 30%.
For this reason, I have added a certain amount of fe in native system.
Utilize under the acid condition, by the Fe that acid wash water dissolved
2O
3Can produce following reaction:
4H
++2SO
3 2-+Fe
2O
3＝FeSO
4+FeSO
3+2H
2O (3)
Fe
2O
3H+ and with SO has promptly neutralized
3 2-Be oxidized to SO
4 2-, self be reduced into divalence Fe
2+, the sulfate radical that is produced is finally with the form stable existence (Al of sulfate
2(SO
4)
5Deng).
Ferrous ion is easy in acid water by remaining oxygen institute oxidation in the flue gas:
2Fe
2++1/2O
2+3H
2O＝2Fe(OH)
2 ++2H
+ (4)
H
++2Fe(OH)
2 ++HSO
3 -＝2Fe
2++SO
4 2-+3H
2O (5)
In this course, O
2Oxidation of Fe
2+Be Fe
3+, Fe
3+Complex ion Fe (OH) in the middle of forming-
2 +, and as the oxidant of subsequent reactions, thereby realized the conversion of S (IV) → S (VI).Simultaneously, in absorption liquid, also find to have red Fe (OH)
3Precipitation.At this moment, Fe (OH)
3Can be used as heterogeneous catalyst absorption O
2, make the O in the gas phase
2Become dissolving O
2Thereby, accelerate oxidation reaction.
From (1) formula as can be seen, quicken and increase SO
2Dissolving in washings (acidifying) is to improve desulfuration efficiency, and unique feasible way is exactly to remove the hydrogen ion (H that generates after the sulfurous acid hydrolysis
+) and sulfite ion (SO
3 2-) to break this balance.Therefore herein, exactly because Fe
3+Existence, just make hydrogen ion (H
+) and sulfite ion (SO
3 2-) can be removed rapidly, thereby guarantee SO
2Can manyly be dissolved in water more rapidly, remove by the time.The radius of iron ion is little simultaneously, and electropositive is strong, to the just in time asymmetric oxidation that produced of the electron distributions of another pollutant NO in the flue gas, has generated complex compound, its reaction equation:
NO+FeSO
3＝Fe(NO)SO
3 (6)
Generate nitroso sulfurous acid iron, under acid condition, easily oxidation produces following reaction:
2Fe(NO)SO
3+O
2+H
2SO
4＝Fe
2(SO
4)
3+N
2↑+H
2O (7)
Its effect makes harmful NO be reduced into N
2(nitrogen), thus reached the purpose of denitration.Because NO is in entering acid wash water the time, it compares O
2Easier in the SO in the water
3 2-Be oxidized to SO
4 2-Fe
2+Be oxidized to Fe
3+, than simple O
2Exist and have stronger desulphurizing ability.And learn that by practice the formation speed of NO is that the raising with furnace temperature increases, and furnace thermal efficiency increases, and NO also increases, and oxidability also strengthens.
Simultaneously, there is data to show, Fe
3+To SO
2Oxidation have a quick oxidation reaction stage, this stage SO
2The same Fe of oxidation rate
3+Concentration be directly proportional.The change of absorption liquid pH is to Fe
3+Catalytic oxidation speed considerable influence is arranged.At pH〉during certain value, Fe is with Fe (OH), and form exists, Fe
3+Concentration begins to reduce, and the main matter of a catalytic action is Fe
3+Therefore, the pH value increases, and reaction rate promptly reduces.During pH＜certain value, reduce Fe with the pH value
3+Concentration increases, but this moment SO
2Solubility reduces, and whole catalytic oxidation system is controlled by the air film resistance, and reaction rate reduces, therefore, and Fe
3+Catalytic oxidation speed in whole pH value scope with pH maximum during in the definite value scope.
That on the contrary, denitration is played a decisive role is Fe
2+, and Fe
2+Need be lower in the pH value and situation that Fe is excessive under can stable existence, and bring into play its effect, therefore need control system pH value, guarantee that it reaches the optimum efficiency of desulphurization denitration.Confirm in actual applications, pH when certain is interval, its desulfurization off sulfide effect the best.
Simultaneously, except ferro element, other alkaline matters in the coal ash also play a big part to desulfurization.Analysis by following alkaline matter dissolution rate and pH value relation table can learn that pH is when certain is interval, and the dissolution rate of other alkaline matters also is maximum.
Beneficial effect
Dust-removal and desulfurizing adopts the new technology of iron ion desulphurization denitration, utilizes iron ion to carry out desulphurization denitration, and in actual motion, desulfurization has reached 95%, and denitration has reached 60%.Compare with other desulfurizing agent costs, reduce expenses 80%.Owing to utilize iron ion as additive, self-forming is held agent with fixed attention, and water quality is not muddy in the middle of operation, quickens precipitation.
Description of drawings
Fig. 1 is the side view of patent of the present invention;
Fig. 2 is the plane of patent of the present invention;
Fig. 3 is the principle sketch of patent of the present invention.
Patent of the present invention is as depicted in figs. 1 and 2 advanced air-introduced machine flue, 9-PH view, 10-running water, 11-magnetic valve, 12-mixer, 13-pond, 14-water pump, 15-iron nitre, 16-PH by the import of 1-deduster, 2-S type passage, 3-mucking machine, 4-deduster, 5-flue, 6-desulfurizing tower, 7-shower, 8-and is reconciled water pipe, 17-and impact pigment coal ash, 18-desulphurization denitration water, 19-deduster and form.
The specific embodiment
Dusty gas enters through air admission hole, the gas shock water surface, and big grit falls into the water, contain less grit gas and pass through 2-S type passage, evoke a large amount of sprays, air water is fully contacted with the speed of 18-25 meter per second, fine grit is sneaked in the water, and dusty gas is purified; In dedusting, sulfurous gas contacts with atomized water, produces acid water, reacts with the alkaline matter in the coal ash and the ferro element of adding, finishes sweetening process; Because the fe that adds has guaranteed to contain in the system a large amount of abundant Fe (II), Fe (II) reacts with nitrogen oxide simultaneously, when self is oxidized, nitrogen oxide is reduced to nitrogen, thereby reaches denitration effect, finished primary dust removing desulphurization denitration process to this.The gas that purifies fully not, behind the 6-desulfurizing tower, reverse once more spray reaches the effect of dust-removal and desulfurizing denitration once more, and purified gas enters atmosphere after dewatering by the dehydrator that is located at cat head.
Claims (8)
1, utilize the method for coal ash and oxidant applying under acid condition, carry out the incorporate equipment of desulfur denitrate dust collecting, it is characterized in that: this equipment is finished by secondary, and one-level is a deduster, and secondary is that desulfurizing tower is formed.
2, the method for utilizing coal ash and oxidant applying under acid condition according to claim 1, carry out the incorporate equipment of desulfur denitrate dust collecting and it is characterized in that: deduster adopts flyash, water, dust-removal and desulfurizing denitration.
3, the method for utilizing coal ash and oxidant applying under acid condition according to claim 1, carry out the incorporate equipment of desulfur denitrate dust collecting and it is characterized in that: desulphurization denitration adopts iron ion water.
4, the method for utilizing coal ash and oxidant applying under acid condition according to claim 1 is carried out the incorporate equipment of desulfur denitrate dust collecting and be it is characterized in that: the desulphurization denitration pond.
5, the method for utilizing coal ash and oxidant applying under acid condition according to claim 1, carry out the incorporate equipment of desulfur denitrate dust collecting and it is characterized in that: alkaline matter is adopted in reduction, and is provided with agitator.
6, the method for utilizing coal ash and oxidant applying under acid condition according to claim 1 is carried out the incorporate equipment of desulfur denitrate dust collecting and be it is characterized in that: utilizes PH instrument control water ph value.
7, the method for utilizing coal ash and oxidant applying under acid condition according to claim 1 is carried out the incorporate equipment of desulfur denitrate dust collecting and be it is characterized in that: is provided with iron nitre dissolving tank.
8, the method for utilizing coal ash and oxidant applying under acid condition according to claim 1, carry out the incorporate equipment of desulfur denitrate dust collecting and it is characterized in that: PH reconciles water pipe.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910119425A CN101530731A (en) | 2009-03-13 | 2009-03-13 | Integrated equipment for desulfurization, denitrification and dedusting by coal ash and oxidant applying method under acidic condition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910119425A CN101530731A (en) | 2009-03-13 | 2009-03-13 | Integrated equipment for desulfurization, denitrification and dedusting by coal ash and oxidant applying method under acidic condition |
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| CN101530731A true CN101530731A (en) | 2009-09-16 |
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|---|---|---|---|
| CN200910119425A Pending CN101530731A (en) | 2009-03-13 | 2009-03-13 | Integrated equipment for desulfurization, denitrification and dedusting by coal ash and oxidant applying method under acidic condition |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101780374A (en) * | 2010-04-01 | 2010-07-21 | 史汉祥 | Synchronized dust removal and desulfuration for smoke of coal-fired boiler and comprehensive utilization of flyash of coal-fired boiler |
| CN102423616A (en) * | 2011-08-30 | 2012-04-25 | 湖南麓南脱硫脱硝科技有限公司 | Flue gas purification device for middle and small coal-fired boiler |
| CN103028313A (en) * | 2012-09-12 | 2013-04-10 | 河南绿典环保节能科技有限公司 | Integrated desulfuration and denitration method for wet oxidation of flue gas |
| CN103239981A (en) * | 2013-05-14 | 2013-08-14 | 成都信息工程学院 | Method for denitrating flue gas by ferrous-citrate-iron powder mixed-liquid wet process and by-producing ammonium nitrate |
| CN106984100A (en) * | 2017-05-27 | 2017-07-28 | 赵萍 | The special dedusting of LD type wet desulphurizations removes water unit |
| CN108283879A (en) * | 2018-04-19 | 2018-07-17 | 丹东蓝天环保锅炉制造有限公司 | Boiler double back journey desulfuring and denitrifying apparatus |
-
2009
- 2009-03-13 CN CN200910119425A patent/CN101530731A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101780374A (en) * | 2010-04-01 | 2010-07-21 | 史汉祥 | Synchronized dust removal and desulfuration for smoke of coal-fired boiler and comprehensive utilization of flyash of coal-fired boiler |
| CN101780374B (en) * | 2010-04-01 | 2013-03-27 | 史汉祥 | Synchronized dust removal and desulfuration for smoke of coal-fired boiler and comprehensive utilization of flyash of coal-fired boiler |
| CN102423616A (en) * | 2011-08-30 | 2012-04-25 | 湖南麓南脱硫脱硝科技有限公司 | Flue gas purification device for middle and small coal-fired boiler |
| CN103028313A (en) * | 2012-09-12 | 2013-04-10 | 河南绿典环保节能科技有限公司 | Integrated desulfuration and denitration method for wet oxidation of flue gas |
| CN103028313B (en) * | 2012-09-12 | 2015-01-21 | 河南绿典环保节能科技有限公司 | Integrated desulfuration and denitration method for wet oxidation of flue gas |
| CN103239981A (en) * | 2013-05-14 | 2013-08-14 | 成都信息工程学院 | Method for denitrating flue gas by ferrous-citrate-iron powder mixed-liquid wet process and by-producing ammonium nitrate |
| CN106984100A (en) * | 2017-05-27 | 2017-07-28 | 赵萍 | The special dedusting of LD type wet desulphurizations removes water unit |
| CN108283879A (en) * | 2018-04-19 | 2018-07-17 | 丹东蓝天环保锅炉制造有限公司 | Boiler double back journey desulfuring and denitrifying apparatus |
| CN108283879B (en) * | 2018-04-19 | 2023-09-01 | 丹东蓝天环保锅炉制造有限公司 | Double-return desulfurization and denitrification device for boiler |
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Open date: 20090916 |