CN103657375A - Method and system for removing trace SO2 in tail gas by gas phase oxidation - Google Patents
Method and system for removing trace SO2 in tail gas by gas phase oxidation Download PDFInfo
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- CN103657375A CN103657375A CN201410006002.1A CN201410006002A CN103657375A CN 103657375 A CN103657375 A CN 103657375A CN 201410006002 A CN201410006002 A CN 201410006002A CN 103657375 A CN103657375 A CN 103657375A
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- tail gas
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Abstract
The invention discloses a method and a system for removing trace SO2 in tail gas by gas phase oxidation. The method comprises the following steps of spraying a gas phase oxidation medium into a pipe for conveying the tail gas, wherein the gas phase oxidation medium is mixed with the tail gas, is quickly subjected to oxidation-reduction reaction to be oxidized into SO2 and SO3, and is further hydrated into H2SO4 droplets; capturing and reclaiming the H2SO4 droplets at the output end of the pipe. According to the system, an oxidation medium output device is connected to an atomizing nozzle, the atomizing nozzle is arranged on the pipe, a capturing and collecting device is arranged at the output end of the pipe, the oxidation medium is oxidized into the SO2 and the SO3 and is further hydrated into the H2SO4 droplets, and the H2SO4 droplets are captured and reclaimed by the capturing and collecting device. The problem of tail gas exhaustion can be effectively solved, and the low-concentration harm gas contained in the tail gas exhausted from an industrial device is effectively processed and is reclaimed.
Description
Technical field
The present invention relates to SO
2the technical field reclaiming, relates in particular to a kind of gaseous oxidation and deviates from and reclaim trace SO in tail gas
2method and system.
Background technology
In the industrial production flow process of sulfuric acid,---being traditional dry process or novel wet method relieving haperacidity technology---all relates to SO
2be catalytically conveted to SO
3course of reaction.SO in this step reaction
2final conversion ratio directly have influence on SO in device exhaust discharge
2the height of gas concentration, however be limited to the reaction limit that thermodynamics determines, even if adopt the method for multistage catalytic bed and intersegmental heat exchange still can not realize the conversion of sulfur dioxide 100%, cause thus the SO that has trace in device exhaust discharge
2to meeting the environmental protection standard of increasingly stringent, challenge has been proposed.
Industrial circle is common removes trace SO in tail gas
2the method of gas is in spray column/absorption tower, to use NH
3h
2o, Ca (OH)
2, NaOH, NaHCO
3in the solution washing tail gas of one or more materials, absorb SO wherein
2generate corresponding sulphite or sulfate to reach the object of cleaning of off-gas.Obvious this method inevitably can produce new waste liquid, waste residue secondary pollution, and requires the tower for gas-liquid two-phase contact is installed, and has greatly increased the cost of vent gas treatment.
Process of the present invention can effectively address the above problem, can Quick Oxidation SO by spraying in exhaust pipe
2oxide, forced oxidation SO
2for SO
3, the SO producing
3further water and be H
2sO
4, then by capturing device, catch sulfuric acid aerosol, reclaim the dilute sulfuric acid product that obtains 40%--70%wt.Can treatment S O by the method
2concentration is low to moderate the tail gas of 100ppmV, and significantly saves the investment of purifier.
Therefore, the applicant is devoted to develop a kind of can effectively addressing the above problem, and efficiently processes the contained low concentration SO of commercial plant emission
2pernicious gas, and the gaseous oxidation of realize recycling is deviate from and reclaims trace SO in tail gas
2method and system.
Summary of the invention
In view of the deficiency that above-mentioned prior art exists, the present invention proposes a kind of can effectively addressing the above problem, and efficiently processes the contained low concentration SO of commercial plant emission
2pernicious gas, and the gaseous oxidation of realize recycling is deviate from and reclaims trace SO in tail gas
2method and system.
For achieving the above object, the invention provides a kind of gaseous oxidation and deviate from and reclaim trace SO in tail gas
2method, toward carrying in the pipeline of described tail gas, spray into gaseous oxidation medium, described gaseous oxidation medium mixes quick generation redox reaction with described tail gas, be oxidized SO
2for SO
3, and further hydration is H
2sO
4drop, finally the output at described pipeline carries out H
2sO
4the trapping of drop is reclaimed.
As a further improvement on the present invention, described H
2sO
4drop traps by high speed densification formula fiber demist and/or electric demister pattern.
As a further improvement on the present invention, described gaseous oxidation medium employing sprays in described pipeline with the mode that described exhaust gas flow direction is cross-flow or adverse current.
As a further improvement on the present invention, described gaseous oxidation medium is ozone or ultraviolet ray.
As a further improvement on the present invention, described gaseous oxidation medium is the trickle dropping liquid that potassium permanganate solution or hydrogen peroxide solution atomization form.
The present invention also proposes a kind of gaseous oxidation and deviates from and reclaim trace SO in tail gas
2system, comprising:
For delivery of the pipeline of described tail gas,
For exporting the oxide isolation output device of oxide isolation,
For described oxide isolation atomization is sprayed into the atomizer in described pipeline, and
Be used for carrying out H
2sO
4the capturing device that the trapping of drop is reclaimed.
Described oxide isolation output device is connected on described atomizer, described atomizer is arranged on described pipeline, described capturing device is arranged on the output of described pipeline, described oxide isolation output device is exported described oxide isolation and is sprayed in described pipeline to described atomizer atomization, oxide isolation after atomization mixes quick generation redox reaction with the tail gas in described pipeline, oxidation SO
2for SO
3, and further hydration is H
2sO
4drop, traps recovery by described capturing device.
As a further improvement on the present invention, the eddy current high speed nozzle that described atomizer is built-in vortex generator.
As a further improvement on the present invention, described capturing device consists of housing and the densification fibrage being arranged in described housing, on described housing, be provided with clean tail gas outlet, described densification fibrage is blocked between described pipeline output and described clean tail gas outlet, and tail gas sees through described densification fibrage and removes H wherein
2sO
4after drop, by described clean tail gas outlet, discharged.
As a further improvement on the present invention, the superfine fibre tow mechanical compaction that described densification fibrage is sulfuric acid corrosion resistant forms, containing H
2sO
4the air-flow of drop is during at a high speed by described densification fibrage, due to inertial collision and Brownian movement diffusion effect, described H
2sO
4drop will clash into described fibre bundle, after accumulation, along fibre bundle, flow downward and will collect output.
As a further improvement on the present invention, described atomizer spray into direction and described exhaust gas flow direction is cross-flow or counter-flow arrangement.
Gaseous oxidation of the present invention is deviate from and is reclaimed trace SO in tail gas
2method and system, there is following beneficial effect:
Gaseous oxidation of the present invention is deviate from and is reclaimed trace SO in tail gas
2method and system can effectively address the above problem, efficiently process the contained low concentration SO of commercial plant emission
2pernicious gas, and realize and recycling.Use the method and system of the present invention can treatment S O
2concentration is low to moderate the tail gas of 100ppmV, significantly saves the investment of purifier, and simple to operate, and oxidation is efficient.
Accompanying drawing explanation
Fig. 1 is that the gaseous oxidation of specific embodiment is deviate from and reclaims trace SO in tail gas
2the structural representation of system.
Fig. 2 is the atomizing nozzle structure schematic diagram of specific embodiment.
Fig. 3 is the densification fiber layer structure schematic diagram of specific embodiment.
Primary clustering symbol description in figure:
Pipeline 100, atomizer 200, vortex generator 210, capturing device 300, housing 310, densification fibrage 320.
The specific embodiment
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Embodiment mono-:
A kind of gaseous oxidation that the present embodiment proposes is deviate from and is reclaimed trace SO in tail gas
2method, toward carrying in the pipeline of described tail gas, spray into gaseous oxidation medium, described gaseous oxidation medium mixes quick generation redox reaction with described tail gas, be oxidized SO
2for SO
3, and further hydration is H
2sO
4drop, finally the output at described pipeline carries out H
2sO
4the trapping of drop is reclaimed.
Concrete, described H
2sO
4drop is that the mode by high speed densification formula fiber demist traps, described gaseous oxidation medium employing sprays in described pipeline with the mode that described exhaust gas flow direction is cross-flow or adverse current, and described gaseous oxidation medium is the trickle dropping liquid that potassium permanganate solution or hydrogen peroxide solution atomization form.
Trace SO in tail gas in the present embodiment
2mainly refer to containing SO
2concentration is the tail gas of the extremely low concentration of 300ppmV～12000ppmV, wherein in tail gas, also may comprise the NOx of extremely low concentration, H
2other gases such as S.
Certainly, in other specific embodiments, H
2sO
4the trapping of drop can also trap by other modes such as electric demists, and described gaseous oxidation medium can also adopt other oxide isolations such as ozone or ultraviolet ray, repeats no more herein.
Embodiment bis-:
Fig. 1 is that the gaseous oxidation of specific embodiment is deviate from and reclaims trace SO in tail gas
2the structural representation of system.As shown in Figure 1, the present embodiment also proposes a kind of gaseous oxidation and deviates from and reclaim trace SO in tail gas
2system, comprising:
For delivery of the pipeline 100 of described tail gas,
For exporting the oxide isolation output device (not shown) of oxide isolation,
For described oxide isolation atomization is sprayed into the atomizer 200 in pipeline 100, and
Be used for carrying out H
2sO
4the capturing device 300 that the trapping of drop is reclaimed;
Described oxide isolation output device is connected on atomizer 200, atomizer 200 is arranged on pipeline 100, capturing device 300 is arranged on the output of pipeline 100, described oxide isolation output device is exported described oxide isolation and is sprayed in described pipeline to atomizer 200 atomizations, oxide isolation after atomization mixes quick generation redox reaction with the tail gas in pipeline 100, oxidation SO
2for SO
3, and further hydration is H
2sO
4drop, traps recovery by capturing device 300.
Concrete, as shown in Figure 2, the atomizer 200 of the present embodiment is the eddy current high speed nozzle of built-in vortex generator 210.As shown in Figure 1, the capturing device 300 of the present embodiment consists of housing 310 and the densification fibrage 320 being arranged in housing 310, on housing 310, be provided with clean tail gas outlet (not shown), densification fibrage 320 is blocked between pipeline 100 outputs and described clean tail gas outlet, and tail gas sees through densification fibrage 320 and removes H wherein
2sO
4after drop, by described clean tail gas outlet, discharged.As shown in Figure 1, spray into direction and the described exhaust gas flow direction of atomizer 200 are faulting and spread and put.As shown in Figure 3, densification fibrage 320 is for the superfine fibre tow mechanical compaction of sulfuric acid corrosion resistant forms, containing H
2sO
4the air-flow of drop is during at a high speed by densification fibrage 320, due to inertial collision and Brownian movement diffusion effect, described H
2sO
4drop will clash into described fibre bundle, after accumulation, along fibre bundle, flow downward and will collect output.Concrete, a plurality of clean tail gas outlets can be offered in the upper surface of housing 310 simultaneously, in each clean tail gas outlet, extend internally and enclose the densification fibrage that forms a tubular, and tail gas is filtered.
Exemplary, trace SO in the gaseous oxidation of the present embodiment is deviate from and reclaimed tail gas
2system on, the gaseous oxidation that utilizes embodiment mono-to describe is deviate from and is reclaimed trace SO in tail gas
2method carry out vent gas treatment, find that the nebulization efficiency (particle diameter of drop distributes) of oxide isolation affects reaction efficiency, mixed effect affects reaction efficiency, relation is as follows:
In other specific embodiments, atomizer can also be the nozzle of other types, because oxide isolation particle diameter should be as far as possible little, contribute to improve the specific area of drop, improve the efficiency of gas-liquid contact, and then raising effecting reaction ratio, and reduce the requirement of the time of staying, can be according to the oxide isolation difference adopting and vent gas treatment need to select different atomizers, as adopt the oxide isolation of gas phase and liquid phase, gaseous oxidation medium can directly spray in pipeline as ozone and ultraviolet ray, liquid phase oxidation medium as potassium permanganate solution and hydrogen peroxide solution can be by spraying into again in pipeline after atomizer atomization, spraying into direction can be also that cross-flow or the countercurrent direction that is other angles sprays into, gaseous oxidation medium is mixed by force with tail gas, the capturing device of selecting also can be selected the fiber capturing device of electrostatic precipitator or other types as required, repeats no more herein.
Embodiment tri-:
Trace SO in the gaseous oxidation of embodiment bis-is deviate from and reclaimed tail gas
2system on, the gaseous oxidation that utilizes embodiment mono-to describe is deviate from and is reclaimed trace SO in tail gas
2method to carry out the concrete applicable cases of vent gas treatment as follows:
For pipeline 100 diameters of exporting pending tail gas, be 250mm, it is 20% hydrogen peroxide solution that oxide isolation is selected mass concentration, as shown in Figure 1, by atomizer 200 atomizations, sprays in pipeline 100, and SO circulates in pipeline 100
2concentration is the air-flow of 700-900ppmV, and temperature is 85 ℃.Atomizer 200 is placed in the top of pipeline, and the drop average grain diameter of the hydrogen peroxide solution after atomizer 200 atomizations is 150 μ m, and is dispersed in SO
2in air-flow, the rear chemical reaction by is below by SO
2be converted into H
2sO
4:
H
2O
2+SO
2==H
2SO
4
The straying quatity of hydrogen peroxide solution is: F
h2O2=1.3 * (F
sO2* C
sO2).Hydrogen peroxide (H
2o
2) the effecting reaction ratio of solution is 63%, SO in tail gas
2be reduced to 48-55ppmV, the H that reaction produces
2sO
4drop, capturing device 300 trappings through pipeline 100 outputs, collect the sulfuric acid that obtains 52%wt.
Embodiment tetra-:
Trace SO in the gaseous oxidation of embodiment bis-is deviate from and reclaimed tail gas
2system on, the gaseous oxidation that utilizes embodiment mono-to describe is deviate from and is reclaimed trace SO in tail gas
2method to carry out the concrete applicable cases of vent gas treatment as follows:
For exporting the pipe diameter of pending tail gas, be 250mm, the hydrogen peroxide solution that the mass concentration that oxide isolation is selected is 35%, as shown in Figure 1, sprays in pipeline 100 by atomizer 200 atomizations, and SO circulates in pipeline 100
2concentration is the air-flow of 1000-2000ppmV, and temperature is 85 ℃.Atomizer 200 is placed in the top of pipeline 100, and the drop average grain diameter of the hydrogen peroxide solution after atomizer 200 atomizations is 150 μ m, and is dispersed in SO
2in air-flow, the rear chemical reaction by is below by SO
2be converted into H
2sO
4:
H
2O
2+SO
2==H
2SO
4
The straying quatity of hydrogen peroxide solution is: F
h2O2=1.45 * (F
sO2* C
sO2).Hydrogen peroxide (H
2o
2) the effecting reaction ratio of solution is 67%, the time of staying is greater than 5 seconds, SO in tail gas
2be reduced to 70-76ppmV, the H that reaction produces
2sO
4drop, capturing device 300 trappings through pipeline 100 outputs, collect the sulfuric acid that obtains 62%wt.
Embodiment five:
Trace SO in the gaseous oxidation of embodiment bis-is deviate from and reclaimed tail gas
2system on, the gaseous oxidation that utilizes embodiment mono-to describe is deviate from and is reclaimed trace SO in tail gas
2method to carry out the concrete applicable cases of vent gas treatment as follows:
For exporting pipeline 100 diameters of pending tail gas, be 400mm, the hydrogen peroxide solution that the mass concentration that oxide isolation is selected is 20%, as shown in Figure 1, sprays in pipeline 100 by atomizer 200 atomizations, and SO circulates in pipeline 100
2concentration is the air-flow of 1000-2000ppmV, and temperature is 85 ℃.Atomizer 200 is placed in the top of pipeline 100, and the drop average grain diameter of the hydrogen peroxide solution after atomizer 200 atomizations is 200 μ m, and is dispersed in SO
2in air-flow, the rear chemical reaction by is below by SO
2be converted into H
2sO
4:
H
2O
2+SO
2==H
2SO
4
The straying quatity of hydrogen peroxide solution is: F
h2O2=1.8 * (F
sO2* C
sO2).Hydrogen peroxide (H
2o
2) the effecting reaction ratio of solution is 47%, the time of staying is greater than 5 seconds, SO in tail gas
2be reduced to 100-120ppmV, the H that reaction produces
2sO
4drop, capturing device 300 trappings through pipeline 100 outputs, collect the sulfuric acid that obtains 60%wt.
Embodiment six:
Trace SO in the gaseous oxidation of embodiment bis-is deviate from and reclaimed tail gas
2system on, the gaseous oxidation that utilizes embodiment mono-to describe is deviate from and is reclaimed trace SO in tail gas
2method to carry out the concrete applicable cases of vent gas treatment as follows:
For exporting pipeline 100 diameters of pending tail gas, be 400mm, the hydrogen peroxide solution that the mass concentration that oxide isolation is selected is 35%, as shown in Figure 1, sprays in pipeline 100 by atomizer 200 atomizations, and SO circulates in pipeline 100
2concentration is the air-flow of 2000-3000ppmV, and temperature is 85 ℃.Atomizer 200 is placed in the top of pipeline 100, and the drop average grain diameter of the hydrogen peroxide solution after atomizer 200 atomizations is 300 μ m, and is dispersed in SO
2in air-flow, the rear chemical reaction by is below by SO
2be converted into H
2sO
4:
H
2O
2+SO
2==H
2SO
4
The straying quatity of hydrogen peroxide solution is: F
h2O2=2.1 * (F
sO2* C
sO2).Hydrogen peroxide (H
2o
2) the effecting reaction ratio of solution is 43%, the time of staying is greater than 7 seconds, SO in tail gas
2be reduced to 175-220ppmV, the H that reaction produces
2sO
4drop, capturing device 300 trappings through pipeline 100 outputs, collect the sulfuric acid that obtains 63.5%wt.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a gaseous oxidation is deviate from and is reclaimed trace SO in tail gas
2method, it is characterized in that: toward carrying in the pipeline of described tail gas, spray into gaseous oxidation medium, described gaseous oxidation medium mixes quick generation redox reaction with described tail gas, be oxidized SO
2for SO
3, and further hydration is H
2sO
4drop, finally the output at described pipeline carries out H
2sO
4the trapping of drop is reclaimed.
2. gaseous oxidation as claimed in claim 1 is deviate from and is reclaimed trace SO in tail gas
2method, it is characterized in that: described H
2sO
4drop traps by high speed densification formula fiber demist and/or electric demister pattern.
3. gaseous oxidation as claimed in claim 1 is deviate from and is reclaimed trace SO in tail gas
2method, it is characterized in that: described gaseous oxidation medium adopts the mode that is cross-flow or adverse current with described exhaust gas flow direction to spray in described pipeline.
4. the gaseous oxidation as described in claim 1 or 3 is deviate from and is reclaimed trace SO in tail gas
2method, it is characterized in that: described gaseous oxidation medium is ozone or ultraviolet ray.
5. the gaseous oxidation as described in claim 1 or 3 is deviate from and is reclaimed trace SO in tail gas
2method, it is characterized in that: described gaseous oxidation medium is the trickle dropping liquid that potassium permanganate solution or hydrogen peroxide solution atomization form.
6. a gaseous oxidation is deviate from and is reclaimed trace SO in tail gas
2system, it is characterized in that: comprising:
For delivery of the pipeline of described tail gas,
For exporting the oxide isolation output device of oxide isolation,
For described oxide isolation atomization is sprayed into the atomizer in described pipeline, and
Be used for carrying out H
2sO
4the capturing device that the trapping of drop is reclaimed;
Described oxide isolation output device is connected on described atomizer, described atomizer is arranged on described pipeline, described capturing device is arranged on the output of described pipeline, described oxide isolation output device is exported described oxide isolation and is sprayed in described pipeline to described atomizer atomization, oxide isolation after atomization mixes quick generation redox reaction with the tail gas in described pipeline, oxidation SO
2for SO
3, and further hydration is H
2sO
4drop, traps recovery by described capturing device.
7. gaseous oxidation as claimed in claim 6 is deviate from and is reclaimed trace SO in tail gas
2system, it is characterized in that: the eddy current high speed nozzle that described atomizer is built-in vortex generator.
8. gaseous oxidation as claimed in claim 6 is deviate from and is reclaimed trace SO in tail gas
2system, it is characterized in that: described capturing device consists of housing and the densification fibrage being arranged in described housing, on described housing, be provided with clean tail gas outlet, described densification fibrage is blocked between described pipeline output and described clean tail gas outlet, and tail gas sees through described densification fibrage and removes H wherein
2sO
4after drop, by described clean tail gas outlet, discharged.
9. gaseous oxidation as claimed in claim 8 is deviate from and is reclaimed trace SO in tail gas
2system, it is characterized in that: the superfine fibre tow mechanical compaction that described densification fibrage is sulfuric acid corrosion resistant forms, containing H
2sO
4the air-flow of drop is during at a high speed by described densification fibrage, due to inertial collision and Brownian movement diffusion effect, described H
2sO
4drop will clash into described fibre bundle, after accumulation, along fibre bundle, flow downward and will collect output.
10. the gaseous oxidation as described in claim 6-9 any one is deviate from and is reclaimed trace SO in tail gas
2system, it is characterized in that: described atomizer spray into direction and described exhaust gas flow direction is cross-flow or counter-flow arrangement.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410006002.1A CN103657375B (en) | 2014-01-07 | 2014-01-07 | Method and system for removing trace SO2 in tail gas by gas phase oxidation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410006002.1A CN103657375B (en) | 2014-01-07 | 2014-01-07 | Method and system for removing trace SO2 in tail gas by gas phase oxidation |
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| CN105457464A (en) * | 2015-11-23 | 2016-04-06 | 中南大学 | Sintering flue gas desulfurization and denitrification technology |
| CN109516442A (en) * | 2018-12-26 | 2019-03-26 | 科洋环境工程（上海）有限公司 | Convert sulfur-containing smoke gas to the process system and process of sulfuric acid |
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| Publication number | Publication date |
|---|---|
| CN103657375B (en) | 2015-07-08 |
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