CN102824814A - Wet-type redox desulfurizing and recycling method for smoke - Google Patents
Wet-type redox desulfurizing and recycling method for smoke Download PDFInfo
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- CN102824814A CN102824814A CN2012103356150A CN201210335615A CN102824814A CN 102824814 A CN102824814 A CN 102824814A CN 2012103356150 A CN2012103356150 A CN 2012103356150A CN 201210335615 A CN201210335615 A CN 201210335615A CN 102824814 A CN102824814 A CN 102824814A
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- desulfurization
- flue gas
- ferric
- sulfate
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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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
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Abstract
The invention relates to a wet-type redox desulfurizing and recycling method for smoke, which comprises the following steps: introducing the smoke containing SO2 into acidic trivalent ferric absorption solution, absorbing SO2 at the temperature of 0-100 DEG C to generate sulfate solution, thereby realizing the purpose of desulfurizing the smoke at last; after dissolving SO2 into water, oxidizing by trivalent ferric to generate ferrous sulfate aqueous solution; oxidizing the ferrous sulfate aqueous solution by introducing oxygen so as to convert divalent ferric into trivalent ferric to reuse for absorbing SO2 in the smoke; performing separation, purification and crystallization in time since the concentration of sulfate radical in the smoke desulfurizing absorption solution is obviously increased after circulations for many times, so as to obtain ferric sulfate or ferric chloride to recycle the resource.
Description
Technical field
The present invention relates to the purification method of flue gas, particularly a kind of fume wet-type reduction and desulfurization and resource utilization method.
Background technology
Containing the harmful components oxysulfide in the gas that the mineral matter fuel combustion generates, wherein mainly is the sulfur trioxide of sulfur dioxide and trace.Eliminate sulfur dioxide, the technical process that makes the emission gases purification is desulfurization.
Domestic and international application desulfur technology approach has three kinds: desulfurization and burning back desulfurization in desulfurization before the burning, the burning.To the effect that adopt physics, chemistry or the biological mode of desulfurization cleans the raw coal that boiler uses before the burning, and the sulphur in the coal is partly removed, and coal is purified; Desulfur technology is in coal combustion process, to carry out desulfurization to handle in the burning, promptly in coal, mixes and burns the solid sulphur of sulphur-fixing agent, Gu sulfur material is discharged with slag; Burning back desulfur technology is behind coal combustion, to carry out desulfurization to handle, and promptly tail flue gas is carried out desulfurization and handles, and flue reduces the SO in the flue gas
2Discharge capacity, i.e. flue gas desulfurization.
Flue gas desulfurization (FGD) is desulphurization plant carries out desulfurization to flue gas the method that installs additional at the flue place.Being the present desulfur technology of large-scale commercial applications application in the world, is control SO
2Effective way.
Flue gas desulfurization can be divided into two kinds of wet method and dry method (comprising semidry method).Wherein typical technology has the limestone/gypsum method, spray drying process, electronic beam method, ammonia process, magnesium method etc.
Dry desulfurizing process utilizes powdery or granular absorbents, removes the SO in the flue gas through effects such as absorption, catalytic reaction or high energy electron electrolysis
2Be reflected under the bone dry state that no liquid phase gets involved and carry out, reactant also be a powdered, does not exist to corrode and problem such as fouling.With respect to wet desulphurization technology, desulfurization by dry method have water consumption few, do not cause secondary pollution, sulphur to be convenient to advantages such as recoverys, but because gas-solid reaction speed is lower, cause that the sweetening process air speed is low, equipment is huge, the too late wet method of desulfurization degree.
The wet method limestone-gypsum flue gas desulfurizing is high and strong and become the flue gas desulfurization of using maximum technology, particularly large-scale burner to the adaptability of unit with its technology maturation, desulfuration efficiency.And the shortcoming of wet method FGD technology is that equipment is huge, and floor space is big, and investment and operating cost are high, and water consumption is big, and has secondary pollution.
Flue gas desulfurization will form environmental protection industry, must walk the road of recycling, exploitation non-secondary pollution, the desulfur technology that water consumption is few.
Summary of the invention
Technical problem to be solved by this invention provides a kind of fume wet-type reduction and desulfurization and resource utilization method.
The present invention provides a kind of fume wet-type reduction and desulfurization and resource utilization method, comprising: will contain SO
2Flue gas feed in the acid ferric iron solution, under 0-100 ℃ temperature conditions, absorb, absorbing sulfur dioxide generates sulfate liquor, then sulfate liquor is carried out oxidation processes, pending flue gas is reached realize recycling when cleaning.
Further, will contain SO
2Flue gas feed in the acid ferric iron solution; Under the temperature conditions of 1 atmospheric pressure, 0-100 ℃, absorb; Reaction 0-1.5h makes absorbing sulfur dioxide generate sulfate liquor; Then sulfate liquor is carried out oxidation processes, pending flue gas is reached realize recycling when cleaning.
Further, said acid ferric iron solution comprises iron chloride or ferric sulfate, and the concentration of ferric iron solution should be controlled at 1-3mol/L in its solution.
Further, hydrogen concentration is 0.6-1mol/L in the said acid ferric iron solution.
Further, aerating oxygen carries out oxidation processes in the sulfate liquor that after above-mentioned absorbing sulfur dioxide, generates, and makes that ferrous iron is converted into ferric iron in the sulfate liquor, and the circulation of gained ferric iron solution is used to absorb pending flue gas.
Further, with the high-concentration sulfuric acid salting liquid after the said recycled for multiple times separate, purifying, crystallization, obtain ferric sulfate or iron chloride, realize the recycling of flue gas desulfurization liquid.
The present invention provides a kind of fume wet-type reduction and desulfurization and resource utilization method, not only can realize the purpose of gas cleaning, but also can sulfur in smoke finally be reclaimed as the sulphur resource; Real realization energy-saving and emission-reduction; Recycling economy turns waste into wealth, and potential economic benefit is huge.
The specific embodiment
The present invention adopts the ferric iron acid solution to do the absorption liquid that contains sulfur dioxide flue gas; Ferric iron concentration is controlled at 1-3mol/L, and hydrogen ion concentration is 0.6-1mol/L in the acid medium, under 0-100 ℃ temperature conditions; Absorbing sulfur dioxide reaches the purpose of gas cleaning through post processing.Wherein ferric iron solution comprises iron chloride and/or ferric sulfate etc.; The kind of the acid in the acid medium comprises: hydrochloric acid and/or sulfuric acid.
Sulfur dioxide is soluble in water, is generated sulfate liquor by the oxidation of ferric iron institute afterwards.This solution oxygen oxidation makes ferrous iron be converted into ferric iron, does the absorption liquid of sulfur dioxide again, recycle.
After circulation repeatedly, the concentration of sulfate radical can obviously increase in the absorption liquid of flue gas desulfurization, can separate, purifying, crystallization in good time, makes ferric sulfate or iron chloride, realizes the resource of flue gas desulfurization liquid.
Embodiment 1
Getting hydrogen ion concentration is 1mol/L, and ferric iron concentration is the liquor ferri trichloridi 125mL of 2.0mol/L, in 30 ℃, and 1 the following feeding of atmospheric pressure sulfur dioxide, the feeding amount is 0.125mol, and the reaction time is 0-1.5h, and absorption liquid shoals.Testing result is: hydrogen ion concentration=1.56mol/L, Fe
2+=1.47mol/L, sulfate concentration are 0.81mol/L.
Feed excess of oxygen with generating in the solution after the above-mentioned absorbing sulfur dioxide, make the ferrous iron in the solution become ferric iron, the circulation of gained ferric iron solution is used for absorbing sulfur dioxide.
Repeat aforementioned operation, after three circulations, with gained high concentration sulphate solution concentration, separation, crystallization must contain the ferric sulfate product 63.5g of the crystallization water.Mother liquor after the crystallization is a sulfuric acid, and hydrochloric acid mixed solution adds the oxide or the hydroxide of iron, and the ferric iron solution that can make is done the absorption liquid of sulfur dioxide flue gas.
Embodiment 2
Getting hydrogen ion concentration is 0.64mol/L, and ferric iron concentration is the liquor ferri trichloridi 250mL of 1.0mol/L, in 30 ℃, and 1 the following feeding of atmospheric pressure sulfur dioxide, the feeding amount is 0.125mol, and the reaction time is 0-1.5h, and absorption liquid shoals.Testing result is: hydrogen ion concentration=1.07mol/L, Fe
2+=0.86mol/L, sulfate concentration are 0.45mol/L.
Generate in the solution behind the receipts sulfur dioxide and feed excess of oxygen, make the ferrous iron in the solution become ferric iron, the circulation of gained ferric iron solution is used for absorbing sulfur dioxide.
Repeat aforementioned operation, after three circulations, with gained high concentration sulphate solution concentration, separation, crystallization must contain the ferric sulfate product 59.2g of the crystallization water.Mother liquor after the crystallization is a sulfuric acid, and hydrochloric acid mixed solution adds the oxide or the hydroxide of iron, and the ferric iron solution that can make is done the absorption liquid of sulfur dioxide flue gas.
The present invention has following beneficial effect:
1, changes existing treatment process, when realizing sulfur dioxide removal, reduced cost of investment and unit scale; Reduced operating cost; Be a important breakthrough, really realized social benefit, the organic unity of economic benefit and environmental benefit flue gas desulfurization technique.
2, open the once technical revolution of desulfurization industry, had good future in engineering applications.Technological precedence belongs to domestic initiation, and will fill up international blank.Its Transformation Application will have far-reaching social value.
3, to be used for the iron of sweetening process be absorption liquid to this technology, can regenerate, and can realize recycle, thereby reduce the operating cost of system.Sulfur in smoke finally reclaims as the sulphur resource, really realizes energy-saving and emission-reduction, and recycling economy turns waste into wealth, and potential economic benefit is huge.
4, in the processing procedure and recycling process of this technology operation, non-secondary pollution is realized the innoxious of flue gas and cleans discharging that environmental benefit is obvious.
5, compare with existing desulfur technology, have equipment and simplify, take up an area of and lack, reduced investment, operating cost is low, and desulfuration efficiency is stable, and operation is simple and reliable, the characteristics of convenient management.
It should be noted last that; The above specific embodiment is only unrestricted in order to technical scheme of the present invention to be described; Although with reference to instance the present invention is specified, those of ordinary skill in the art should be appreciated that and can make amendment or be equal to replacement technical scheme of the present invention; And not breaking away from the spirit and the scope of technical scheme of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (6)
1. fume wet-type reduction and desulfurization and resource utilization method is characterized in that, comprising:
To contain SO
2Flue gas feed in the acid ferric iron solution, under 0-100 ℃ temperature conditions, absorb, absorbing sulfur dioxide generates sulfate liquor, then sulfate liquor is carried out oxidation processes, pending flue gas is reached realize recycling when cleaning.
2. according to said fume wet-type reduction and desulfurization of claim 1 and resource utilization method, it is characterized in that:
To contain SO
2Flue gas feed in the acid ferric iron solution; Under the temperature conditions of 1 atmospheric pressure, 0-100 ℃, absorb; Reaction 0-1.5h makes absorbing sulfur dioxide generate sulfate liquor; Then sulfate liquor is carried out oxidation processes, pending flue gas is reached realize recycling when cleaning.
3. according to claim 1 or 2 said fume wet-type reduction and desulfurization and resource utilization method, it is characterized in that said acid ferric iron solution comprises:
Iron chloride or ferric sulfate, the concentration of ferric iron solution should be controlled at 1-3mol/L in its solution.
4. according to claim 1 or 2 said fume wet-type reduction and desulfurization and resource utilization method, it is characterized in that:
Hydrogen concentration is 0.6-1mol/L in the said acid ferric iron solution.
5. according to claim 1 or 2 said fume wet-type reduction and desulfurization and resource utilization method, it is characterized in that:
Aerating oxygen carries out oxidation processes in the sulfate liquor that after above-mentioned absorbing sulfur dioxide, generates, and makes that ferrous iron is converted into ferric iron in the sulfate liquor, and the circulation of gained ferric iron solution is used to absorb pending flue gas.
6. according to said fume wet-type reduction and desulfurization of claim 5 and resource utilization method, it is characterized in that:
With the high-concentration sulfuric acid salting liquid after the said recycled for multiple times separate, purifying, crystallization, obtain ferric sulfate or iron chloride, realize the recycling of flue gas desulfurization liquid.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103356150A CN102824814A (en) | 2012-09-12 | 2012-09-12 | Wet-type redox desulfurizing and recycling method for smoke |
| CN201210580849.1A CN103007718B (en) | 2012-09-12 | 2012-12-27 | Wet redox, desulfuration and resource utilization method for flue gas |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103356150A CN102824814A (en) | 2012-09-12 | 2012-09-12 | Wet-type redox desulfurizing and recycling method for smoke |
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| CN102824814A true CN102824814A (en) | 2012-12-19 |
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| CN2012103356150A Withdrawn CN102824814A (en) | 2012-09-12 | 2012-09-12 | Wet-type redox desulfurizing and recycling method for smoke |
| CN201210580849.1A Expired - Fee Related CN103007718B (en) | 2012-09-12 | 2012-12-27 | Wet redox, desulfuration and resource utilization method for flue gas |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126567A (en) * | 2014-10-11 | 2015-12-09 | 黄立维 | Method and device for removing nitric oxide and sulfur oxide from gas flow |
| CN105964127A (en) * | 2016-07-06 | 2016-09-28 | 扬州大学 | SO2 absorbing and converting technological method |
| CN109276995A (en) * | 2018-11-21 | 2019-01-29 | 安徽工业大学 | A kind of sintering flue gas and kiln gas iron catalytic desulfurization device and method |
| CN109569234A (en) * | 2018-11-09 | 2019-04-05 | 河北东华冀衡化工有限公司 | A method of removing monoxone sulfur dioxide in tail gas |
| CN110090548A (en) * | 2019-04-11 | 2019-08-06 | 昆明理工大学 | A kind of method that copper ashes tailing cooperates with the wet desulphurization of zinc abstraction dedusting ash and recycles zinc sulfate |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106039964B (en) * | 2016-07-06 | 2018-12-11 | 扬州大学 | A kind of method of desulfurization co-producing hydrogen and sulfuric acid |
| CN106824996B (en) * | 2017-02-16 | 2020-02-07 | 广东工业大学 | Method for degrading biomass waste through photo-thermal coupling |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL168321C (en) * | 1971-03-29 | Chiyoda Chem Eng Construct Co | ||
| US4070441A (en) * | 1975-01-31 | 1978-01-24 | American Electronic Laboratories, Inc. | Method of removing sulfur dioxide from flue gases |
| CN100506353C (en) * | 2007-09-13 | 2009-07-01 | 大连理工大学 | Techniques of flue gas desulpurizing through catalytic oxidation method and by-product polymerizing iron sulfate through catalytic method |
| CN101480569A (en) * | 2008-01-11 | 2009-07-15 | 李成岳 | Method and equipment for carrying desulphurization and denitrification processs for flue gas |
-
2012
- 2012-09-12 CN CN2012103356150A patent/CN102824814A/en not_active Withdrawn
- 2012-12-27 CN CN201210580849.1A patent/CN103007718B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126567A (en) * | 2014-10-11 | 2015-12-09 | 黄立维 | Method and device for removing nitric oxide and sulfur oxide from gas flow |
| CN105126567B (en) * | 2014-10-11 | 2019-08-20 | 黄立维 | A kind of method and device thereof for removing denitrification and oxysulfide from air-flow |
| CN105964127A (en) * | 2016-07-06 | 2016-09-28 | 扬州大学 | SO2 absorbing and converting technological method |
| CN109569234A (en) * | 2018-11-09 | 2019-04-05 | 河北东华冀衡化工有限公司 | A method of removing monoxone sulfur dioxide in tail gas |
| CN109276995A (en) * | 2018-11-21 | 2019-01-29 | 安徽工业大学 | A kind of sintering flue gas and kiln gas iron catalytic desulfurization device and method |
| CN110090548A (en) * | 2019-04-11 | 2019-08-06 | 昆明理工大学 | A kind of method that copper ashes tailing cooperates with the wet desulphurization of zinc abstraction dedusting ash and recycles zinc sulfate |
| CN110090548B (en) * | 2019-04-11 | 2021-11-30 | 昆明理工大学 | Method for wet desulphurization and zinc sulfate recovery of copper slag tailings and zinc smelting fly ash |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103007718B (en) | 2015-03-18 |
| CN103007718A (en) | 2013-04-03 |
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Application publication date: 20121219 |