CN103506001B - A kind of sulfur method containing low concentration sulphur dioxide flue gas - Google Patents
A kind of sulfur method containing low concentration sulphur dioxide flue gas Download PDFInfo
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- CN103506001B CN103506001B CN201310361569.6A CN201310361569A CN103506001B CN 103506001 B CN103506001 B CN 103506001B CN 201310361569 A CN201310361569 A CN 201310361569A CN 103506001 B CN103506001 B CN 103506001B
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- scrubbing tower
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Abstract
The present invention discloses a kind of sulfur method containing low concentration sulphur dioxide flue gas, wherein, comprise step: absorption slurries Second-rate zinc oxide powder being mixed with predetermined concentration, contact with containing low concentration sulphur dioxide flue gas is reverse in inverse spray feed pipe in dynamic wave scrubbing tower, utilize the reaction of zinc oxide and sulfur dioxide, be zinc sulfite by Sulphur Dioxide, then by electrolysis waste solution, zinc sulfite is decomposed into zinc sulfate, the sulfur dioxide produced after decomposing returns system for preparing sulfuric acid, for leaching after zinc sulfate filters.
Description
Technical field
The present invention relates to exhaust-gas treatment field, particularly relate to a kind of sulfur method containing low concentration sulphur dioxide flue gas.
Background technology
Based on the thermal power generation of alkene coal industry and with sulphide ore be raw material Non-ferrous Metallurgy industrial processes in, inevitably produce large volume low-concentration and the SO be worth without relieving haperacidity
2waste gas, this kind of SO
2waste gas is one of industrial waste gas causing atmosphere pollution the most serious at present, is also the industrial waste gas of more difficult effective improvement.
At present, the wet method industrial technologies such as domestic industry tail gas absorption many employings lime (stone)-gypsum, soda and ammonia absorption, the various problem of these method ubiquities: for limestone-gypsum method, its floor space is large, equipment investment is high, internal circulating load is large, power consumption is higher, the easy fouling of system, blocking, and byproduct market value is low; For Dual alkali, complex process, operation conditions is complicated, and byproduct is pollutant; For ammonia process, ammonia consumption is large, the transport of ammonia and store and all there is potential safety hazard, and operating cost is high; For liquid caustic soda method, operating cost is high; Produce large amount of sewage; Thermal desorption energy consumption is high, less economical.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of sulfur method containing low concentration sulphur dioxide flue gas, be intended to solve the various problems that in prior art, sulfur dioxide desulfurization method exists.
Technical scheme of the present invention is as follows:
Containing a sulfur method for low concentration sulphur dioxide flue gas, wherein, comprise step:
Second-rate zinc oxide powder is mixed with the absorption slurries of predetermined concentration, contact with containing low concentration sulphur dioxide flue gas is reverse in inverse spray feed pipe in dynamic wave scrubbing tower, utilize the reaction of zinc oxide and sulfur dioxide, be zinc sulfite by Sulphur Dioxide, then by electrolysis waste solution, zinc sulfite is decomposed into zinc sulfate, the sulfur dioxide produced after decomposing returns system for preparing sulfuric acid, for leaching after zinc sulfate filters.
The described sulfur method containing low concentration sulphur dioxide flue gas, wherein, in described absorption slurries, the mass percent of Second-rate zinc oxide powder is 20%.
The described sulfur method containing low concentration sulphur dioxide flue gas, wherein, described dynamic wave scrubbing tower is provided with two-stage: first order kinetics ripple scrubbing tower and second motive force ripple scrubbing tower, the inverse spray feed pipe top of first order kinetics ripple scrubbing tower is vertically entered into containing low concentration sulphur dioxide flue gas, the absorption slurries sprayed with one deck Dynawave nozzle of first order kinetics ripple scrubbing tower carry out reverse contact, form froth zone, froth zone cools rapidly and sulfur dioxide absorption, flue gas enters into the drop of demister except deentrainment subsequently, enter into second motive force ripple washing system again and carry out second time desulfurization.
The described sulfur method containing low concentration sulphur dioxide flue gas, wherein, be also provided with two layers of Dynawave nozzle in described first order kinetics ripple scrubbing tower, one deck Dynawave nozzle and two layers of Dynawave nozzle are provided with circulating pump,
The described sulfur method containing low concentration sulphur dioxide flue gas, wherein, the h 2 so 4 concentration of electrolysis waste solution is 12%.
The described sulfur method containing low concentration sulphur dioxide flue gas, wherein, the zinc sulfate generated after decomposing enters into zinc sulfate storage tank, arranges the stirring system for stirring at zinc sulfate storage tank.
The described sulfur method containing low concentration sulphur dioxide flue gas, wherein, be decomposed into by zinc sulfite in the reaction of zinc sulfate, reaction temperature is 25 degree, and the reaction time is 40 ~ 80min.
The described sulfur method containing low concentration sulphur dioxide flue gas, wherein, zinc sulfite is decomposed in the reaction of zinc sulfate, and the mol ratio of zinc sulfite and sulfuric acid is 1: 1 ~ 2.
Beneficial effect: the absorption slurries that the present invention modulates using intermediate product Second-rate zinc oxide powder are as absorbent, efficient absorption low-concentration sulfur dioxide oxygen, and leach after the zinc sulfite of generation being converted into zinc sulfate filtration, the invention solves the system jams problem that zinc oxide desulfurization technique exists, full technique produces without waste residue, realize pollution treatment and do not produce dirt, there is the feature of contamination-reducing synergistic, cleaner production.
Detailed description of the invention
The invention provides a kind of sulfur method containing low concentration sulphur dioxide flue gas, for making object of the present invention, technical scheme and effect clearly, clearly, the present invention is described in more detail below.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
A kind of sulfur method containing low concentration sulphur dioxide flue gas provided by the invention, it comprises step:
Second-rate zinc oxide powder is mixed with the absorption slurries of predetermined concentration, contact with containing low concentration sulphur dioxide flue gas is reverse in inverse spray feed pipe in dynamic wave scrubbing tower, utilize the reaction of zinc oxide and sulfur dioxide, be zinc sulfite by Sulphur Dioxide, then by electrolysis waste solution, zinc sulfite is decomposed into zinc sulfate, the sulfur dioxide produced after decomposing returns system for preparing sulfuric acid, for leaching after zinc sulfate filters.
Process route of the present invention is: zinc oxide absorption+sulfurous acid zincic acid decomposes, flue gas washs through second motive force ripple washing system, selective oxidation zinc is as absorbent sulfur dioxide absorption, absorb the zinc sulfite slurries generated and carry out acid decomposition after filtering, filtrate major part retrieval system after filtration is used for supplementing fresh water (FW), unnecessary partial discharge.And the sulfur dioxide negative pressure that sulfurous acid zincic acid produces after decomposing returns acid making system, decomposed solution solution of zinc sulfate returns main shop for leaching.
Process runs well of the present invention, reliable, safety.Adopt own zinc oxide as absorbent, greatly reduce operating cost, equipment investment is low, and while the treatment of wastes with processes of wastes against one another, for enterprise creates certain economic benefit, and the concentration of outer waste air is lower than domestic row's standard.
Absorbent of the present invention is Second-rate zinc oxide powder, and compared with oxide powder and zinc, the zinc oxide relative concentration of Second-rate zinc oxide powder is lower, and its main component is in table one.
Second-rate zinc oxide powder and the tail desorption system that be transported in the present invention filling by powder tank car, be delivered to zinc oxide feed bin by air compressing to store, and be delivered to slurrying in groove with slurry by conveyer of weighing, zinc oxide bin bottom is provided with mechanical arch breaking apparatus, in blanking process, continuous stirring prevents zinc oxide from luming can not blanking.The mass percent absorbing slurries is generally 20%, and the absorption slurries prepared are pumped into slurries storage tank by slurries elevator pump, in slurries storage tank, be provided with agitating device, prevent material from precipitating, and other impurity of slurries tank bottom are regularly discharged by bottom valve.
Flue gas in the present invention is Rotary Kiln high-temperature flue gas, and this flue gas is containing low-concentration sulfur dioxide.Flue gas tolerance is 55000Nm
3/ h, sulfur dioxide in flue gas mass fraction is 0.38%.
Flue gas vertically enters into first order kinetics ripple scrubbing tower inverse spray feed pipe top through supercharging extension set, reverse contact is carried out with the absorption slurries sprayed without one deck Dynawave nozzle blocked by heavy caliber perforate, absorption slurries spray afterwards from Dynawave nozzle and smoke contacts forms froth zone, and the froth zone of this high turbulent flow contacts high mass transfer by drop with gas and produces.Froth zone makes drop constantly cool and upgrade, rapid cooled flue gas and sulfur dioxide absorption.Two layers of Dynawave nozzle are provided with: one deck Dynawave nozzle and two layers of Dynawave nozzle in first order kinetics ripple scrubbing tower, every layer of Dynawave nozzle is all supporting circulating pump, enter at the bottom of tower by the absorption slurries after two layers of Dynawave nozzle contact, the flue gas absorbed enters demister, this demister is double-deck deflection plate demister, and the drop except deentrainment enters into second motive force ripple scrubbing tower.
Removal rate of sulfur dioxide in flue gas after first order kinetics ripple scrubbing tower is about 90%, flue gas passes through the washing of one deck Dynawave nozzle again at second motive force ripple scrubbing tower, flue gas after washing is again by the drop of demister except deentrainment, reach the requirement of exhanst gas outlet exhaust, directly enter chimney and carry out high altitude discharge.
The key reaction of absorption process is:
ZnO+SO
2+5/2H
2O==2ZnSO
3·5/2H
2O
ZnO+2SO
2+H
2O==Zn(HSO
3)
2
ZnSO
3+SO
2+H
2O==Zn(HSO
3)
2
In the present invention, filtrate water as a supplement after adopting zinc sulfite to filter, in order to maintain the emission request of suitable discharge opeing concentration and guarantee tail gas, oxidative system is provided with in second motive force ripple scrubbing tower, and adopt oxidation fan to blast air and agitator constantly stirs, accelerated oxidation process, makes to absorb the ZnSO in the absorption slurries of sulfur dioxide
3be oxidized to ZnSO
4.
Oxidation reaction process is: 2ZnSO
3+ O
2=2ZnSO
4
The moisture that water loss in first order kinetics ripple scrubbing tower and second motive force ripple scrubbing tower carries when mainly the water taken away of saturated tail gas and zinc sulfate are arranged outward, the loss of water can filter with add zinc sulfite after filtrate to maintain the liquid level of second motive force ripple scrubbing tower.When second motive force ripple scrubbing tower liquid level is lower than setting liquid level, filtrate the supplementing after being filtered by zinc sulfite enters into second motive force ripple scrubbing tower.The moisturizing of first order kinetics ripple scrubbing tower is undertaken by the circulating pump of second motive force ripple scrubbing tower, when first order kinetics ripple scrubbing tower liquid level is lower than setting liquid level, entered supplementary for the absorption slurries in second motive force ripple scrubbing tower in first order kinetics ripple scrubbing tower by the circulating pump of second motive force ripple scrubbing tower.
The ZnSO generated after absorbing
3water insoluble, the ZnSO that first order kinetics ripple scrubbing tower is discharged
3slurries enter into zinc sulfite storage tank, and be then promoted to plate and frame filter press by zinc sulfite pump and carry out press filtration, the filtrate flow after filtration, in filtrate tank, is returned for supplementing water by filtrate pump.
ZnSO after filtration
3solid enters into sour decomposition reaction groove by filter press discharge bin, and add the waste liquid after electrolysis (160.1g/l amounts to sulfuric acid concentration about 12%) carry out acid decompose, acid decompose produce sulfur dioxide be back to acid system by negative pressure system, decompose after generate ZnSO
4solution enters into zinc sulfate storage tank, in zinc sulfate storage tank, be provided with agitating device, and the insoluble matter deposition after preventing acid from decomposing, is then returned for Treatment for Reuse by zinc sulfate pump.
Acid decomposition reaction principle: ZnSO
3+ H
2sO
4=ZnSO
4+ SO
2+ H
2o
Acid decomposition reaction condition is easily carried out, reaction speed is fast, and by negative pressure, sulfur dioxide is removed from solution of zinc sulfate, greatly reduce the content of sulfur dioxide in solution of zinc sulfate, to decrease in subsequent operation process because of the secondary pollution that sulfur dioxide residue causes, decrease the corrosion to peripheral equipment.
The optimum process condition parameter of above-mentioned sour decomposition reaction is: reaction temperature 25 DEG C, and the reaction time is 40 ~ 80min, and reaction and negative pressure is 2000Pa, ZnSO
3and H
2sO
4mol ratio be 1: 1 ~ 2.Wherein, preferably the reaction time is 60min, ZnSO
3and H
2sO
4mol ratio be 1: 1.2.
In sum, the absorption slurries that the present invention modulates using intermediate product Second-rate zinc oxide powder are as absorbent, efficient absorption low-concentration sulfur dioxide oxygen, and leach after the zinc sulfite of generation being converted into zinc sulfate filtration, the invention solves the system jams problem that zinc oxide desulfurization technique exists, full technique produces without waste residue, realizes pollution treatment and does not produce dirt, has the feature of contamination-reducing synergistic, cleaner production.
Should be understood that, application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (1)
1., containing a sulfur method for low concentration sulphur dioxide flue gas, it is characterized in that, comprise step:
Second-rate zinc oxide powder is mixed with the absorption slurries of predetermined concentration, contact with containing low concentration sulphur dioxide flue gas is reverse in inverse spray feed pipe in dynamic wave scrubbing tower, utilize the reaction of zinc oxide and sulfur dioxide, be zinc sulfite by Sulphur Dioxide, then by electrolysis waste solution, zinc sulfite is decomposed into zinc sulfate, the sulfur dioxide produced after decomposing returns system for preparing sulfuric acid, for leaching after zinc sulfate filters;
Be decomposed into by zinc sulfite in the reaction of zinc sulfate, reaction temperature is 25 degree, and the reaction time is 60min; The mol ratio of zinc sulfite and sulfuric acid is 1:1 ~ 2;
By mass percentage, the elemental composition of described Second-rate zinc oxide powder comprises: Zn is 56.8%, Fe be 7.2%, Cu be 0.5%, Cd is 0.38%, and the S existed with sulfate radical form, for 1.5%, is that 0.8%, Pb is for 8.5%, SiO with the S that elemental sulfur form exists
2be 2.5%, Ca be 0.4%, Mg be 0.2%, F be 0.036%, Cl be 0.11%;
In described absorption slurries, the mass percent of Second-rate zinc oxide powder is 20%;
Described dynamic wave scrubbing tower is provided with two-stage: first order kinetics ripple scrubbing tower and second motive force ripple scrubbing tower, the inverse spray feed pipe top of first order kinetics ripple scrubbing tower is vertically entered into containing low concentration sulphur dioxide flue gas, the absorption slurries sprayed with one deck Dynawave nozzle of first order kinetics ripple scrubbing tower carry out reverse contact, form froth zone, froth zone cools rapidly and sulfur dioxide absorption, flue gas enters into demister except the drop of deentrainment subsequently, then enters into second motive force ripple washing system and carry out second time desulfurization;
Described demister is double-deck deflection plate demister, the washing of the flue gas after first order kinetics ripple scrubbing tower again by one deck Dynawave nozzle in second motive force ripple scrubbing tower, and the flue gas after washing is again by the drop of demister except deentrainment;
Also be provided with two layers of Dynawave nozzle in described first order kinetics ripple scrubbing tower, one deck Dynawave nozzle and two layers of Dynawave nozzle are provided with circulating pump;
Filtrate water as a supplement after adopting zinc sulfite to filter;
The h 2 so 4 concentration of electrolysis waste solution is 12%;
The zinc sulfate generated after decomposing enters into zinc sulfate storage tank, arranges the stirring system for stirring at zinc sulfate storage tank;
Acid is decomposed the sulfur dioxide produced and is back to acid system by negative pressure system.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107998864A (en) * | 2017-12-21 | 2018-05-08 | 双盾环境科技有限公司 | A kind of zinc oxide desulfurization forces oxidation technology |
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| CN104437053A (en) * | 2014-11-24 | 2015-03-25 | 江西瑞林稀贵金属科技有限公司 | Flue gas treatment method and system |
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