CN101480569A - Method and equipment for carrying desulphurization and denitrification processs for flue gas - Google Patents
Method and equipment for carrying desulphurization and denitrification processs for flue gas Download PDFInfo
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- CN101480569A CN101480569A CNA2008100006500A CN200810000650A CN101480569A CN 101480569 A CN101480569 A CN 101480569A CN A2008100006500 A CNA2008100006500 A CN A2008100006500A CN 200810000650 A CN200810000650 A CN 200810000650A CN 101480569 A CN101480569 A CN 101480569A
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- flue gas
- dilute acid
- acid soln
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Abstract
The invention discloses a process and equipment for carrying out desulphurization and denitrification treatment on flue gas of a coal burning boiler. The invention takes ferrite elements as a desulphurizing agent and utilizes iron ions formed by diluted acid generated by the flue gas to quickly absorb sulphur dioxide, and intermediate products of desulphurization reaction can play a role in denitrification, thereby the reasonable utilization of resources is realized. The invention has simple process method, small equipment investment and strong industry adaptability.
Description
Technical field
The present invention relates to a kind of technology of the flue gas of coal-burning boiler being carried out desulfurization and denitrogenation processing, particularly, the present invention relates to the ferro element that to be additive carry out the processing method of desulfurization, denitrogenation to flue gas, corresponding therewith, the invention still further relates to a kind of treatment facility of implementing this desulfurization, denitrogenation method.
Background technology
At present, along with the strictness day by day of environmental regulation and the generally raising of public's environmental consciousness, the smoke pollution of coal-burning boiler has become outstanding environmental issue, in view of leading position and the coal resources in China sulfur content common higher reality of present coal in China's energy system, in considerable time, the desulfurization of fire coal boiler fume, denitrogenation are great engineering problems.Common flue gas desulfurization, denitrification process and flow process have a variety of, and main have lime stone-gypsum method, Arbiso process, sulfurous acid ammonia process, an alkaline aluminum sulfate-SO
2Method, alkalescence aluminum sulfate-gypsum method, catalytic oxidation etc., the main desulfurizing agents such as lime stone, lime, alkali, ammonia that adopt, but the investment of above these technological processes is big, technological process is numerous and diverse, construction period is long, the desulfurizing agent price is high, the byproduct price is not high and difficult processing, and these shortcomings have had a strong impact on the process of industrialization of desulfurization, denitrification process.
In order to overcome these defectives, it is the sulfur method of catalyst that the engineering staff has developed with the ferro element, for example disclose the technology that desulfurization is carried out in a kind of catalytic action that utilizes divalence or ferric ion at patent document CN 1899668A, but this technology at applied environment be the oxidation phosphatization
Tail gas, concrete service condition and the desulfurization of coal-burning boiler are handled very big difference.Disclose among the patent document CN 1073613A and a kind of flue gas has been carried out the method and apparatus of desulfurization, in the method, absorbed SO in the flue gas by in weakly acidic environment, adding iron filings
2, the recovery product of this method is a ferrous sulfate, it is applicable to the flue gas of handling the sulphur coal burner, but the disclosed method of the document only can play the effect of desulfurization, can't reduce the concentration of nitrogen oxide in the flue gas.U.S. patent documents US 4222991A discloses a kind of SO that removes from flue gas
xMethod, the water-soluble absorbent that this method utilization contains formates absorbs the SO in the flue gas
x, and utilize the divalent iron salt of water-based to remove nitrogen oxide in the flue gas.Though this method can be finished the desulfurization of flue gas and denitrogenation processing, complex process, and need to use multiple additives and many treatment steps, be difficult to be applied in the industrial environment of middle and small scale.
Summary of the invention
Based on above-mentioned problem, the invention provides a kind of flue gas desulfurization, denitrification process and equipment.The present invention as desulfurizing agent, and carries out denitrogenation processing with the intermediate product of sulfur removal technology with ferro element.The present invention has overcome many defectives that above-mentioned prior art exists, and the process that is proposed is simple, and equipment investment is little, non-secondary pollution, and have the very strong adaptability of industry widely, will be very desirable flue gas desulfurization, denitrogenation new technology.
According to an aspect of the present invention, the application provides a kind of method that removes sulfur dioxide and nitrogen oxide from flue gas, and this method is an additive with the ferro element, and may further comprise the steps:
In dilute acid soln, obtaining ferric ion, and make the ratio of ferric ion number in dilute acid soln reach 2.5～3.3 grams per liters dissolved ferric iron;
Utilize spray technology that above-mentioned solution and the flue gas that contains sulfur dioxide are reacted;
As the complexed absorption agent, make reducing agent with ferrous ion that above-mentioned reaction is obtained (iron ions of two valencys), flue gas is carried out denitrogenation processing with sulphite; And utilize separating technology to remove molysite in the solution.
In the present invention, owing to made full use of ferrous ion (iron ions of two valencys) that the iron ion desulphurization reaction obtained as the complexed absorption agent, make reducing agent with sulphite, so can finish desulfurization, denitrogenation processing continuously with simple and effective way, and then simplified technological process, and eliminated the possibility of secondary pollution.Simultaneously, because the concentration limits of ferric ion is fixed in the preferable range that obtains through test of many times, so improved the usefulness of production technology.
According to a further aspect in the invention, in the step of dissolved ferric iron at dilute acid soln, oxygenation is to increase the oxygen concentration in the solution in solution.
By improving the oxygen concentration in the dilute acid soln, make reaction condition become the oxygen enrichment situation, thereby quickened the process of reaction, and strengthened the complexing of ferrous ion.
According to another aspect of the invention, the pH value of dilute acid soln is in 2～3 scope.
Through experimental verification,, can remove the SO in the flue gas to heavens if the pH value of flue gas washing solution is set in 2～3 the scope
2, the process of accelerated reaction, and can not cause adverse influence to production equipment.
According to a further aspect in the invention, described iron ion is that iron or di-iron trioxide generate in the diluted acid environment.
In accordance with a further aspect of the present invention, the application provides a kind of equipment of flue gas being carried out desulfurization, denitrogenation processing, this equipment comprises exhaust gases passes, spray column, liquid storage pool, material ditch and the circulatory system, the circulatory system makes dilute acid soln circulate between spray column and liquid storage pool, exhaust gases passes passes through from spray column, so that being carried out, handles flue gas, wherein:
Be provided with two in the described spray column and handle level, correspond respectively to desulfurization treatment process and denitrification treatment process.
According to a further aspect in the invention, described liquid storage pool is provided with the oxygenation pipeline, is used for filling oxygen to dilute acid soln.
In a word, technology utilization ferro element proposed by the invention acts in the desulfurization spray liquid, simultaneously, produces the formed iron ion fast Absorption of diluted acid sulfur dioxide certainly by flue gas, and the intermediate product of desulphurization reaction can play the effect of denitrogenation, thereby has realized the reasonable resources utilization.
From the detailed description of hereinafter doing, can more clearly understand above-mentioned content of the present invention and other feature and advantage with reference to accompanying drawing.
Description of drawings
Below with reference to accompanying drawings preferred implementation of the present invention is described in detail, in the accompanying drawings:
Accompanying drawing is the front view according to flue gas desulfurization of the present invention, denitrogenation processing equipment.
The specific embodiment
Referring to accompanying drawing, equipment of the present invention comprises exhaust gases passes 1, spray column 2, material ditch 3, the fresh water (FW) circulatory system 4 and liquid storage pool 5.For the said equipment, flue gas flows into from exhaust gases passes 1, and absorbs SO with recirculated water in the first order of spray column 2
2, make SO
2Become sulfurous acid, that is:
SO
2+H
2O→H
2SO
3
Iron is placed on forms molysite (ferrous sulfate and ferric sulfate) in the diluted acid, then, the liquid that contains sulfurous acid generates N with the NO reaction in the second level of spray column 2
2Gas and ferric sulfate, last, sediment, ferric sulfate and other metal oxides are deposited in the liquid storage pool 5, and are discharged from.
Wherein, the flow velocity of liquid is 3～4m/s in the spray column, the reaction time of spray column is 3～3.5 seconds, it is uniform that the air-flow of spray column distributes, be controlled as the pH value under the condition of 2～3 scopes at solution acidity, the corrosion resistance of spray column still can reach 10 years, and it is 0.5～1 that the water system of spray column reaches liquid-gas ratio, and the SR of spray column is lower than 800Pa.
In above-mentioned treatment facility, following desulfurization, denitrogenation flow process have been realized.
At first, with dissolved ferric iron in pickle and obtain ferric ion, wherein the concentration of ferric ion in dilute acid soln reaches 2.5～3.3 grams per liters, be preferably 3 grams per liters, the acidity of solution is controlled as the pH value in 2～3 scope, simultaneously, in order to improve reaction efficiency, oxygenation is to increase oxyty in solution.
Then, above-mentioned solution is reacted by spray column and the flue gas that contains sulfur dioxide
Under excess oxygen:
2FeSO
4+SO
2+O
2＝Fe
2(SO
4)
3 (1)
Under non-excess oxygen:
Fe
2(SO
4)
3+SO
2+H
2O＝2FeSO
4+2H
2SO
4 (2)
Therefore, the iron of trivalent has played the effect of carrier.
Actual course of reaction is comparatively complicated, is roughly following process:
(1) makes catalyst with iron ion, SO
2The H that water-soluble back generates
2SO
3Be reoxidised into H
2SO
4, because SO
2Water-soluble process is a kind of reversible reaction, formula as follows:
Because SO
2The process that is dissolved in water is a kind of reversible reaction, in this process at first with SO
3 2-Remove, it is oxidized to stable SO
4 2-, can reduce the H in the circulation fluid
+Concentration.Occurred like this allowing H
+There is Cmax, to promote SO
2Solubility.Use ferrous ion Fe
2-Do the complexed absorption agent, just the nitric oxide complexed absorption in the flue gas in water, use the sulphite reducing agent, form nitrogen because nitric oxide NO has electric asymmetry, therefore attracted to form complex compound by iron ion, following reaction equation is so just arranged:
FeSO
3+NO＝Fe(NO)SO
3 (6)
2Fe(NO)SO
3+1/2?O
2+H
2SO
4＝Fe
2(SO
4)
3+N
2↑+H
2O (7)
Make SO like this
3 2Can be oxidized to SO rapidly
4 2Thereby, promote SO
2In circulation fluid, dissolve rapidly, quickened desulfurization and denitrification process.This process is that aerobic is participated in.
(2) Fe
3+Play catalytic action with complex form, impel SO
2Generate sulfuric acid with the dissolved oxygen reaction.Formula as follows:
(9)
By formula (11) and (12) as can be known, Fe
3' play catalytic action with complex form, impel SO
2Generate sulfuric acid with the dissolved oxygen reaction.The sulfuric acid that generates also has part and iron ion reaction to generate molysite.In follow-up process, adopt isolation technics that it is separated from solution.
Be to make catalyst in a word, sulfur dioxide is made sulfuric acid with the formed iron ion of ferro element that adds; Do the complexed absorption agent with ferrous ion, make reducing agent, be reduced into nitrogen after nitric oxide is absorbed in water with sulphite.
Although above the specific embodiment of the present invention is described, but this only is exemplary, those skilled in the art can figure out: in claims institute restricted portion, multiple other embodiment can also be arranged, and all based on the embodiment of design philosophy of the present invention all within the scope of the invention.
Claims (6)
1, a kind of method that from flue gas, removes sulfur dioxide and nitrogen oxide, this method is an additive with the ferro element, may further comprise the steps:
In dilute acid soln, obtaining ferric ion, and make the ratio of ferric ion number in dilute acid soln reach 2.5～3.3 grams per liters dissolved ferric iron;
Utilize spray technology that above-mentioned solution and the flue gas that contains sulfur dioxide are reacted;
As the complexed absorption agent, make reducing agent with ferrous ion that above-mentioned reaction was generated, flue gas is carried out denitrogenation processing with sulphite; And utilize separating technology to remove molysite in the solution.
2, method according to claim 1 is characterized in that: in the step of dissolved ferric iron at dilute acid soln, oxygenation is to increase the oxygen concentration in the solution in solution.
3, according to claim 1 or described method, it is characterized in that: the pH value of dilute acid soln is in 2～3 scope.
4, method according to claim 1 is characterized in that: described iron ion is that iron or di-iron trioxide generate in the diluted acid environment.
5, a kind of equipment of flue gas being carried out desulfurization, denitrogenation processing, this equipment comprises exhaust gases passes, spray column, liquid storage pool, material ditch and the circulatory system, the circulatory system makes dilute acid soln circulate between spray column and liquid storage pool, exhaust gases passes passes from spray column, handle so that flue gas is carried out, it is characterized in that:
Be provided with two in the described spray column and handle level, correspond respectively to desulfurization treatment process and denitrification treatment process.
6, equipment according to claim 5 is characterized in that: liquid storage pool is provided with the oxygenation facility, is used for filling oxygen to dilute acid soln.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100006500A CN101480569A (en) | 2008-01-11 | 2008-01-11 | Method and equipment for carrying desulphurization and denitrification processs for flue gas |
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|---|---|---|---|
| CNA2008100006500A CN101480569A (en) | 2008-01-11 | 2008-01-11 | Method and equipment for carrying desulphurization and denitrification processs for flue gas |
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|---|---|
| CN101480569A true CN101480569A (en) | 2009-07-15 |
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| CNA2008100006500A Pending CN101480569A (en) | 2008-01-11 | 2008-01-11 | Method and equipment for carrying desulphurization and denitrification processs for flue gas |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989301A (en) * | 2012-09-12 | 2013-03-27 | 河南绿典环保节能科技有限公司 | Flue gas wet reduction integrated desulfurization, denitrification, harmless treatment and resource utilization method |
| CN102989303A (en) * | 2012-09-12 | 2013-03-27 | 河南绿典环保节能科技有限公司 | Smoke wet-type oxidation integral desulfuration denitration and energy using method |
| CN103007718A (en) * | 2012-09-12 | 2013-04-03 | 河南绿典环保节能科技有限公司 | Wet redox, desulfuration and resource utilization method for flue gas |
| CN105214466A (en) * | 2015-10-29 | 2016-01-06 | 北京市环境保护科学研究院 | A kind of wet method coordinated desulfurization denitrating technique utilizing composite absorption liquid |
| CN105964127A (en) * | 2016-07-06 | 2016-09-28 | 扬州大学 | SO2 absorbing and converting technological method |
-
2008
- 2008-01-11 CN CNA2008100006500A patent/CN101480569A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989301A (en) * | 2012-09-12 | 2013-03-27 | 河南绿典环保节能科技有限公司 | Flue gas wet reduction integrated desulfurization, denitrification, harmless treatment and resource utilization method |
| CN102989303A (en) * | 2012-09-12 | 2013-03-27 | 河南绿典环保节能科技有限公司 | Smoke wet-type oxidation integral desulfuration denitration and energy using method |
| CN103007718A (en) * | 2012-09-12 | 2013-04-03 | 河南绿典环保节能科技有限公司 | Wet redox, desulfuration and resource utilization method for flue gas |
| 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 |
| CN102989301B (en) * | 2012-09-12 | 2014-05-28 | 河南绿典环保节能科技有限公司 | Flue gas wet reduction integrated desulfurization, denitrification, harmless treatment and resource utilization method |
| CN102989303B (en) * | 2012-09-12 | 2014-10-08 | 河南绿典环保节能科技有限公司 | Smoke wet-type oxidation integral desulfuration denitration and energy using method |
| 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 |
| CN103007718B (en) * | 2012-09-12 | 2015-03-18 | 河南绿典环保节能科技有限公司 | Wet redox, desulfuration and resource utilization method for flue gas |
| CN105214466A (en) * | 2015-10-29 | 2016-01-06 | 北京市环境保护科学研究院 | A kind of wet method coordinated desulfurization denitrating technique utilizing composite absorption liquid |
| CN105214466B (en) * | 2015-10-29 | 2018-05-18 | 北京市环境保护科学研究院 | A kind of wet method coordinated desulfurization denitrating technique using composite absorption liquid |
| CN105964127A (en) * | 2016-07-06 | 2016-09-28 | 扬州大学 | SO2 absorbing and converting technological method |
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Open date: 20090715 |