CN103657375B - 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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- CN103657375B CN103657375B CN201410006002.1A CN201410006002A CN103657375B CN 103657375 B CN103657375 B CN 103657375B CN 201410006002 A CN201410006002 A CN 201410006002A CN 103657375 B CN103657375 B CN 103657375B
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- tail gas
- pipeline
- atomizer
- oxide isolation
- drop
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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 reclaimed, particularly relates to a kind of gaseous oxidation and deviates from and reclaim trace SO in tail gas
2method and system.
Background technology
---be traditional dry process or novel wet method relieving haperacidity technology---in the industrial process stream of sulfuric acid all to relate to SO
2be catalytically conveted to SO
3course of reaction.SO in this step reaction
2final conversion ratio directly have influence on device exhaust discharge in SO
2the height of gas concentration, but the reaction limit being limited to 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%, have the SO of trace in causing device exhaust to discharge thus
2challenge is proposed to the environmental protection standard meeting increasingly stringent.
Trace SO in the removing tail gas that industrial circle is common
2the method of gas uses NH in spray column/absorption tower
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 produces new waste liquid, waste residue secondary pollution, and requires to install the tower being used for gas-liquid two-phase contact, considerably increases the cost of vent gas treatment.
Process of the present invention can effectively solve the problem, can Quick Oxidation SO by spraying in exhaust pipe
2oxide, forced oxidation SO
2for SO
3, the SO produced
3further water and be H
2sO
4, then catch sulfuric acid aerosol by capturing device, reclaim the dilute sulfuric acid product obtaining 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 exploitation one and can effectively solves the problem, the low concentration SO contained by efficient process commercial plant emission
2pernicious gas, and the gaseous oxidation realizing 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 one and can effectively solve the problem, the low concentration SO contained by efficient process commercial plant emission
2pernicious gas, and the gaseous oxidation realizing 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 conveying described tail gas pipeline in spray into gaseous oxidation medium, described gaseous oxidation medium and described tail gas carry out mixing fast redox reaction occurring, be oxidized SO
2for SO
3, and hydration is H further
2sO
4drop, finally carries out H at the output of described pipeline
2sO
4the trapping of drop is reclaimed.
As a further improvement on the present invention, described H
2sO
4drop is trapped by high speed densification formula fiber demist and/or electric demister pattern.
As a further improvement on the present invention, the mode that described gaseous oxidation medium employing and described exhaust gas flow direction are cross-flow or adverse current sprays in described pipeline.
As a further improvement on the present invention, described gaseous oxidation medium is ozone or ultraviolet.
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 are formed.
The present invention also proposes a kind of gaseous oxidation and deviates from and reclaim trace SO in tail gas
2system, comprising:
For carrying the pipeline of described tail gas,
For exporting the oxide isolation output device of oxide isolation,
For described oxide isolation being atomized the atomizer sprayed in described pipeline, and
For carrying out H
2sO
4the capturing device of the trapping recovery of drop.
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 exports described oxide isolation and sprays in described pipeline to described atomizer atomization, oxide isolation after atomization and the tail gas in described pipeline carry out mixing fast redox reaction occurring, oxidation SO
2for SO
3, and hydration is H further
2sO
4drop, carries out trapping by described capturing device and reclaims.
As a further improvement on the present invention, described atomizer is the eddy current high speed nozzle of built in eddy current generator.
As a further improvement on the present invention, described capturing device is made up of housing and the densification fibrage be arranged in described housing, described housing is provided with clean offgas outlet, described densification fibrage is blocked between described pipeline output and described clean offgas outlet, and tail gas is through described densification fibrage removing H wherein
2sO
4after drop, discharged by described clean offgas outlet.
As a further improvement on the present invention, described densification fibrage is that the superfine fibre tow mechanical compaction of sulfuric acid corrosion resistant forms, containing H
2sO
4when the air-flow of drop is 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, flow downward collect output after accumulation along fibre bundle.
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 solve the problem, the low concentration SO contained by efficient process commercial plant emission
2pernicious gas, and realize recycling.Use 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.
Detailed description of the invention
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Embodiment one:
A kind of gaseous oxidation that the present embodiment proposes is deviate from and reclaims trace SO in tail gas
2method, toward conveying described tail gas pipeline in spray into gaseous oxidation medium, described gaseous oxidation medium and described tail gas carry out mixing fast redox reaction occurring, be oxidized SO
2for SO
3, and hydration is H further
2sO
4drop, finally carries out H at the output of described pipeline
2sO
4the trapping of drop is reclaimed.
Concrete, described H
2sO
4drop is undertaken trapping by the mode of high speed densification formula fiber demist, the mode that described gaseous oxidation medium employing and described exhaust gas flow direction are cross-flow or adverse current sprays in described pipeline, and described gaseous oxidation medium is the trickle dropping liquid that potassium permanganate solution or hydrogen peroxide solution atomization are formed.
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 also may comprise the NOx of extremely low concentration in tail gas, H
2other gases such as S.
Of course, in other specific embodiments, H
2sO
4the trapping of drop can also be trapped by other modes such as electric demists, and described gaseous oxidation medium can also adopt other oxide isolations such as ozone or ultraviolet, repeats no more herein.
Embodiment two:
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 carrying the pipeline 100 of described tail gas,
For exporting the oxide isolation output device (not shown) of oxide isolation,
For described oxide isolation being atomized the atomizer 200 sprayed in pipeline 100, and
For carrying out H
2sO
4the capturing device 300 of the trapping recovery of drop;
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 exports described oxide isolation and sprays in described pipeline after atomizer 200 is atomized, oxide isolation after atomization and the tail gas in pipeline 100 carry out mixing fast redox reaction occurring, oxidation SO
2for SO
3, and hydration is H further
2sO
4drop, carries out trapping by capturing device 300 and reclaims.
Concrete, as shown in Figure 2, the atomizer 200 of the present embodiment is the eddy current high speed nozzle of built in eddy current generator 210.As shown in Figure 1, the capturing device 300 of the present embodiment is made up of housing 310 and the densification fibrage 320 be arranged in housing 310, housing 310 is provided with clean offgas outlet (not shown), densification fibrage 320 is blocked between pipeline 100 output and described clean offgas outlet, and tail gas removes H wherein through densification fibrage 320
2sO
4after drop, discharged by described clean offgas outlet.As shown in Figure 1, spray into direction and the described exhaust gas flow direction of atomizer 200 are that faulting is spread and put.As shown in Figure 3, densification fibrage 320 is that the superfine fibre tow mechanical compaction of sulfuric acid corrosion resistant forms, containing H
2sO
4when the air-flow of drop is 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, flow downward collect output after accumulation along fibre bundle.Concrete, multiple clean offgas outlet can be offered in the upper surface of housing 310 simultaneously, and extending internally at each clean offgas outlet encloses the densification fibrage of formation one tubular, filters tail gas.
Exemplary, deviate from the gaseous oxidation of the present embodiment and reclaim trace SO in tail gas
2system on, the gaseous oxidation utilizing embodiment one to describe is deviate from and is reclaimed trace SO in tail gas
2method carry out vent gas treatment, find that the nebulization efficiency (domain size distribution of drop) of oxide isolation affects reaction efficiency, mixed effect affects reaction efficiency, and 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 the specific area improving drop, improve the efficiency of gas-liquid contact, and then improve effecting reaction ratio, and reduce the requirement of the time of staying, can according to the oxide isolation adopted different and vent gas treatment need select different atomizers, as adopted the oxide isolation of gas phase and liquid phase, gaseous oxidation medium such as ozone and ultraviolet can directly spray in pipeline, liquid phase oxidation medium is if potassium permanganate solution and hydrogen peroxide solution are by spraying in pipeline after atomizer atomization again, spraying into direction also can be in the cross-flow of other angles or countercurrent direction sprays into, gaseous oxidation medium is mixed by force with tail gas, the capturing device selected also can select the fiber capturing device of electrostatic precipitator or other types as required, repeats no more herein.
Embodiment three:
Deviate from the gaseous oxidation of embodiment two and reclaim trace SO in tail gas
2system on, the gaseous oxidation utilizing embodiment one to describe is deviate from and is reclaimed trace SO in tail gas
2method to carry out the embody rule situation of vent gas treatment as follows:
Be 250mm for exporting pipeline 100 diameter of pending tail gas, oxide isolation select mass concentration be 20% hydrogen peroxide solution, as shown in Figure 1, spray in pipeline 100 by atomizer 200 atomization, circulate in pipeline 100 SO
2concentration is the air-flow of 700-900ppmV, and temperature is 85 DEG C.Atomizer 200 is placed in the top of pipeline, and the mean droplet size of the hydrogen peroxide solution after atomizer 200 is atomized is 150 μm, and is dispersed in SO
2in air-flow, rear by chemical reaction 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, react the H produced
2sO
4drop, the capturing device 300 through pipeline 100 output traps, and collects the sulfuric acid obtaining 52%wt.
Embodiment four:
Deviate from the gaseous oxidation of embodiment two and reclaim trace SO in tail gas
2system on, the gaseous oxidation utilizing embodiment one to describe is deviate from and is reclaimed trace SO in tail gas
2method to carry out the embody rule situation of vent gas treatment as follows:
Be 250mm for exporting the pipe diameter of pending tail gas, the mass concentration that oxide isolation is selected is the hydrogen peroxide solution of 35%, and as shown in Figure 1, spray in pipeline 100 by atomizer 200 atomization, circulate in pipeline 100 SO
2concentration is the air-flow of 1000-2000ppmV, and temperature is 85 DEG C.Atomizer 200 is placed in the top of pipeline 100, and the mean droplet size of the hydrogen peroxide solution after atomizer 200 is atomized is 150 μm, and is dispersed in SO
2in air-flow, rear by chemical reaction 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, react the H produced
2sO
4drop, the capturing device 300 through pipeline 100 output traps, and collects the sulfuric acid obtaining 62%wt.
Embodiment five:
Deviate from the gaseous oxidation of embodiment two and reclaim trace SO in tail gas
2system on, the gaseous oxidation utilizing embodiment one to describe is deviate from and is reclaimed trace SO in tail gas
2method to carry out the embody rule situation of vent gas treatment as follows:
Be 400mm for exporting pipeline 100 diameter of pending tail gas, the mass concentration that oxide isolation is selected is the hydrogen peroxide solution of 20%, and as shown in Figure 1, spray in pipeline 100 by atomizer 200 atomization, circulate in pipeline 100 SO
2concentration is the air-flow of 1000-2000ppmV, and temperature is 85 DEG C.Atomizer 200 is placed in the top of pipeline 100, and the mean droplet size of the hydrogen peroxide solution after atomizer 200 is atomized is 200 μm, and is dispersed in SO
2in air-flow, rear by chemical reaction 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, react the H produced
2sO
4drop, the capturing device 300 through pipeline 100 output traps, and collects the sulfuric acid obtaining 60%wt.
Embodiment six:
Deviate from the gaseous oxidation of embodiment two and reclaim trace SO in tail gas
2system on, the gaseous oxidation utilizing embodiment one to describe is deviate from and is reclaimed trace SO in tail gas
2method to carry out the embody rule situation of vent gas treatment as follows:
Be 400mm for exporting pipeline 100 diameter of pending tail gas, the mass concentration that oxide isolation is selected is the hydrogen peroxide solution of 35%, and as shown in Figure 1, spray in pipeline 100 by atomizer 200 atomization, circulate in pipeline 100 SO
2concentration is the air-flow of 2000-3000ppmV, and temperature is 85 DEG C.Atomizer 200 is placed in the top of pipeline 100, and the mean droplet size of the hydrogen peroxide solution after atomizer 200 is atomized is 300 μm, and is dispersed in SO
2in air-flow, rear by chemical reaction 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, react the H produced
2sO
4drop, the capturing device 300 through pipeline 100 output traps, and collects the sulfuric acid obtaining 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 (4)
1. a gaseous oxidation is deviate from and reclaims trace SO in tail gas
2system, it is characterized in that: comprising:
For carrying the pipeline of described tail gas,
For exporting the oxide isolation output device of oxide isolation,
For described oxide isolation being atomized the atomizer sprayed in described pipeline, and
For carrying out H
2sO
4the capturing device of the trapping recovery of drop;
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 exports described oxide isolation and sprays in described pipeline to described atomizer atomization, oxide isolation after atomization and the tail gas in described pipeline carry out mixing fast redox reaction occurring, oxidation SO
2for SO
3, and hydration is H further
2sO
4drop, carries out trapping by described capturing device and reclaims;
Described capturing device is made up of housing and the densification fibrage be arranged in described housing, described housing is provided with clean offgas outlet, described densification fibrage is blocked between described pipeline output and described clean offgas outlet, described densification fibrage is extended internally to enclose by offgas outlet clean described in each and forms a tubular, and tail gas is through described densification fibrage removing H wherein
2sO
4after drop, discharged by described clean offgas outlet.
2. gaseous oxidation as claimed in claim 1 is deviate from and reclaims trace SO in tail gas
2system, it is characterized in that: described atomizer is the eddy current high speed nozzle of built in eddy current generator.
3. gaseous oxidation as claimed in claim 1 is deviate from and reclaims trace SO in tail gas
2system, it is characterized in that: described densification fibrage is that the superfine fibre tow mechanical compaction of sulfuric acid corrosion resistant forms, containing H
2sO
4when the air-flow of drop is 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, flow downward collect output after accumulation along fibre bundle.
4. the gaseous oxidation as described in any one of claim 1-3 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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|---|---|---|---|
| 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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| CN103657375A CN103657375A (en) | 2014-03-26 |
| CN103657375B true CN103657375B (en) | 2015-07-08 |
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| CN105457464B (en) * | 2015-11-23 | 2018-06-22 | 中南大学 | A kind of technique of sintering flue gas desulfurization denitration |
| CN105289236B (en) * | 2015-11-23 | 2017-11-07 | 中南大学 | A kind of technique based on hydrogen peroxide and the intensified-sintered flue gas synchronized desulfuring and denitrifyings of potassium permanganate oxidation NO |
| 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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| US5388766A (en) * | 1993-09-22 | 1995-02-14 | The Procter & Gamble Company | High pressure atomization systems for high viscosity products |
| CA2511311C (en) * | 2002-12-21 | 2011-09-20 | Haldor Topsoe A/S | Process for removal of so2 from off-gases by reaction with h2o2 |
| CN1190238C (en) * | 2003-02-18 | 2005-02-23 | 上海城市排水设备制造安装工程有限公司 | Method of treating smelly gases by use of ultraviolet radiation at high end and its equipments |
| DE102005041794A1 (en) * | 2005-09-02 | 2007-03-08 | Basf Ag | Method and apparatus for removing sulfur dioxide from a dry gas stream |
| CN101385943A (en) * | 2008-10-17 | 2009-03-18 | 中电投远达环保工程有限公司 | Deprivation technique based on semi-dry process |
| CN101785961B (en) * | 2010-02-09 | 2012-06-27 | 浙江工业大学 | Spiral photo-reactor used for waste gas treatment and waste gas treatment process |
| CN102755820A (en) * | 2012-08-09 | 2012-10-31 | 大恩(天津)环境技术研发有限公司 | Synchronous deep purification technology for various pollutants in industrial flue gas |
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Owner name: KEYON ENVIRONMENT ENGINEERING (SHANGHAI) CO., LTD. Free format text: FORMER OWNER: SHANGHAI KEYONTECHS CO., LTD. Effective date: 20150819 |
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Effective date of registration: 20150819 Address after: 201203, No. 518, Shangcheng Road, 18, Shanghai, Pudong New Area Patentee after: KEYANG ENVIRONMENTAL ENGINEERING (SHANGHAI) CO., LTD. Patentee after: Huang Rui Address before: 201203, No. 518, Shangcheng Road, 18, Shanghai, Pudong New Area Patentee before: SHANGHAI KEYONTECHS CO., LTD. Patentee before: Huang Rui |