CN101585514A - Method for reclaiming sulfuric acid from liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product dilute acid solution by adopting film technology - Google Patents
Method for reclaiming sulfuric acid from liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product dilute acid solution by adopting film technology Download PDFInfo
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- CN101585514A CN101585514A CNA2009100942168A CN200910094216A CN101585514A CN 101585514 A CN101585514 A CN 101585514A CN A2009100942168 A CNA2009100942168 A CN A2009100942168A CN 200910094216 A CN200910094216 A CN 200910094216A CN 101585514 A CN101585514 A CN 101585514A
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- sulfuric acid
- flue gas
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- gas desulfurization
- catalytic oxidation
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Abstract
The invention relates to a method for reclaiming sulfuric acid from liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product dilute acid solution by adopting film technology, the method is characterized by comprising: firstly conveying the by-product dilute acid solution containing metallic ion as raw material to a preprocessing apparatus to filter; then conveying into a mixing slot for processing feed solution to mix; pressing into a nano filter membrane separated processing device by a pressure pump to perform nano filter membrane processing; obtaining the reclaimed sulfuric acid solution and reclaimed metallic ion solution simultaneously. According to the method of the invention, the apparatus is simple, the operation is convenient and is easy to control, the method is convenient for being popularized. The reclaimed sulfuric acid solution can be used as leaching solution used by wet-process metallurgy, the reclaimed metallic ion solution can be returned into the flue gas desulfurization purification apparatus to circulate for using. Accordingly, the technical method of the invention has great meanings for the rebuilding of the existing non-ferrous metallurgy enterprise flue gas desulfurization system and the reducing of the investment and the operating cost of the new enterprise SO2 flue gas purification system and the improving of the cleaning efficiency.
Description
Technical field:
The present invention relates to a kind of method with membrane technique reclaim(ed) sulfuric acid from liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product diluted acid.
Background technology:
Non-ferrous Metallurgy industry is SO
2One of discharging rich and influential family is though many non-ferrous metallurgical enterprise are being utilized the higher SO of concentration
2Flue gas during smelting is made sulfuric acid, but low concentration SO
2The Pollution abatement problem of flue gas is not still solved so far well.Particularly in the resourceful remote mountain areas of nonferrous metal ore, owing to reasons such as traffic, electric power, equipment scale and external conditionss, near the middle-size and small-size non-ferrous metals smelting works that build operation the mining area generally are difficult to utilize SO
2Flue gas during smelting is made sulfuric acid, its SO
2Flue gas just promptly effluxes through after the simple process usually.This not only can the heavily polluted area atmospheric environment, and has caused the waste of sulphur resource.Be provided with the hydrometallurgy production technique as coloured smelter for improving added value of product, then need to buy sulfuric acid and carry out hydrometallurgy production from the outside.This class enterprise buys the vitriolic trucking costs from the outside, generally be higher than the vitriolic sale price far away, sometimes up to several times, has caused heavy economical load to enterprise.If can work out the low concentration SO of effectively utilizing enterprise to efflux
2Flue gas is made the practical technique of the dilute sulfuric acid solution that is suitable for hydrometallurgy production, then is expected to reach the best effect of enterprise and environment " doulbe-sides' victory ".
Liquid phase catalytic oxidation-microbial method flue gas removes SO
2The advantage and the characteristic of the integrated liquid phase catalytic oxidation method of purification of technology and biological clarification, utilization small test biofilm packing Tower System adds metal ion catalyst in circulated sprinkling liquid, make SO in the waste gas
2Oxidized generation sulfuric acid also enters in the circulation fluid, thereby realizes flue gas desulfurization
[1-3]In cleansing operation, for keeping SO
2Purification efficiency need be discharged the diluted acid circulation fluid that a part contains metal ion.As the by product of flue gas desulfurization, sulfuric acid concentration wherein generally can reach 8～20%.If but the sulfuric acid liquid of these metal ion is not handled recovery, and will certainly cause secondary pollution, also be the waste of sulphur resource simultaneously.
In recent years, the someone studies and adopts membrane technique to handle the industrial acid-washed waste liquid that contains single or two metal ion species both at home and abroad, with sulfuric acid recycling wherein.But do not see as yet that at present multiple metal ion is (as Fe in the employing membrane technique while separating treatment sulphuric acid soln
2+, Mn
2+, Zn
2+, Al
3+) correlative study report.
Summary of the invention:
The present invention seeks to overcome above-mentioned the deficiencies in the prior art, on the basis of summing up successful experimental studies results, form, at in liquid phase catalytic oxidation-microbial method flue gas desulfurization technique as the diluted acid that contains multiple metal ion of by product, invention adopt membrane technique simultaneously separating treatment multiple metal ion wherein (as Fe
2+, Mn
2+, Zn
2+, Al
3+) and the new technology of reclaim(ed) sulfuric acid, concrete is adopts acidproof dialyzer that multiple metal ion in the liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product diluted acid is separated with sulfuric acid and the new technology of reclaim(ed) sulfuric acid, be a kind of employing film dialysis simultaneously in the separating treatment sulphuric acid soln multiple metal ion (as Fe
2+, Mn
2+, Zn
2+, Al
3+) and the new technique method of reclaim(ed) sulfuric acid.
The present invention adopts the method for membrane technique reclaim(ed) sulfuric acid from liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product diluted acid, it is characterized in that the by-product diluted acid (1) with metal ion is a raw material, be transported to earlier in the pretreatment unit (2) and filter, be transported to again to handle in the feed liquid tempering tank (3) and mix, after delivering to nanofiltration membrane treatment in the nanofiltration membrane separation treatment unit (5) with pressurization pump pressure (4), obtain reclaim(ed) sulfuric acid solution (6) and recovery metal ion solution (7) simultaneously.
Sulfuric acid concentration 4-10% scope in the by-product raw material diluted acid parting liquid, wherein contained each concentration of metal ions Fe
2+, Mn
2+, Zn
2+, Al
3+In the 0.13-1.7g/L scope.
In the nanofiltration membrane separation treatment unit (5), nanofiltration membrane is optionally filtered and is held back the metal ion component, allows H
+And SO
4 2-Negatively charged ion can effectively pass through nanofiltration membrane, thereby metal ion is separated with sulfuric acid.
Working pressure in the nanofiltration membrane separation treatment unit (5) is in the 15-20bar scope, and temperature is 0 ℃ of-45 ℃ of scope.
The filter membrane that described nanofiltration membrane separation treatment unit is installed is acidproof nanofiltration membrane.
Waste liquid is carried out pre-treatment, use the suspended substance in grid or the filter screen removal dilute sulfuric acid solution.
The sulphuric acid soln concentration that reclaim to obtain is in the 5-15% scope, wherein contained each concentration of metal ions Fe in the sulphuric acid soln of Hui Shouing
2+, Mn
2+, Zn
2+, Al
3+In the 10-100mg/L scope.
Metal ion and sulfuric acid in the membrane separation plant separating treatment liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product diluted acid that employing the present invention forms, under suitable Separation and Recovery operational condition, the sulfuric acid rate of recovery can reach about 70%-80%, to Fe
2+, Mn
2+, Zn
2+, Al
3+The separation rejection of four metal ion species all can reach about 93%-96%, good separation.
The technology of the present invention method required equipment is simple, and is easy to operate, and control easily is convenient to promote.The sulfuric acid that the technology of the present invention method reclaims can be used as the leaching liquid of hydrometallurgy, and the metal ion solution that reclaims then can return to circulate in the flue gas desulfurization refining plant and re-use.Therefore no matter the technology of the present invention method is to having the transformation of Non-ferrous Metallurgy enterprise flue gas desulphurization system now, still to the newly-built SO of enterprise
2Flue gas purification system investment and the reduction of running cost and the raising of purification efficiency all are significant.
Description of drawings
Below in conjunction with the accompanying drawing illustrated embodiment, structure is described further, but protection domain of the present invention is not limited thereto embodiment.
Fig. 1 is a membrane separation unit process flow diagram of the present invention.
Fig. 2 is a treatment unit structural principle synoptic diagram of the present invention.
Embodiment:
The present invention screens by experiment and determines that acidproof nano-filtration membrane equipment has good separating effect and work-ing life, and then set up metal ion and vitriolic novel method and device in the membrane separating liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product diluted acid, its device technique techniqueflow is seen Fig. 1.And investigated in handling experiment that factors such as sulfuric acid concentration, concentration of metal ions, working pressure have obtained suitable Separation and Recovery operational condition to the influence of sulfuric acid Separation and Recovery in the parting liquid.
Embodiment 1:
What the nanofiltration membrane of using was selected market sale for use reaches the acidproof nanofiltration membrane of S3B01-PBC8-2540 type that Sandamo Science and Technology (Xiamen) Co., Ltd. of group produces by Singapore three.Sulfuric acid concentration is 8% in liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product diluted acid, Fe
2+, Mn
2+, Zn
2+, Al
3+Concentration is respectively 1.01g/L, 0.65g/L, 1.13g/L, 0.81g/L (this group concentration is the best matched proportion density of metal ion catalyst in the liquid-phase catalytic oxidation-biological method flue gas desulfurization technology), it is 2: 1 that the separating metal ionic sees through nanofiltration membrane solution that produces and the solution ratio of failing through nanofiltration membrane, when working pressure is 18bar (1bar=0.1Mpa), adopt membrane separation technique of the present invention and device to handle, the sulfuric acid rate of recovery can reach about 80%, and four metal ion species rejection all can reach about 96%.
Embodiment 2:
What the nanofiltration membrane of using was selected market sale for use reaches the acidproof nanofiltration membrane of S3B01-PBC8-2540 type that Sandamo Science and Technology (Xiamen) Co., Ltd. of group produces by Singapore three.Sulfuric acid concentration is 10% in liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product diluted acid, Fe
2+, Mn
2+, Zn
2+, Al
3+Concentration is respectively 1.52g/L, 0.98g/L, 1.70g/L, 1.22g/L (best matched proportion density 1.5 times), separating metal ionic thin liquid is 2: 1 with the dope ratio, when working pressure is 20bar (1bar=0.1Mpa), adopt membrane separation technique of the present invention and device to handle, the sulfuric acid rate of recovery can reach about 80%, and four metal ion species rejection all can reach about 95%.
Embodiment 3:
What the nanofiltration membrane of using was selected market sale for use reaches the acidproof nanofiltration membrane of S3B01-PBC8-2540 type that Sandamo Science and Technology (Xiamen) Co., Ltd. of group produces by Singapore three.Sulfuric acid concentration is 4% in liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product diluted acid, Fe
2+, Mn
2+, Zn
2+, Al
3+Concentration is respectively 0.2g/L, 0.13g/L, 0.23g/L, 0.16g/L (best matched proportion density 0.2 times), separating metal ionic thin liquid is 2: 1 with the dope ratio, when working pressure is 15bar (1bar=0.1Mpa), adopt membrane separation technique of the present invention and device to handle, the sulfuric acid rate of recovery can reach about 70%, and four metal ion species rejection all can reach about 93%.
Claims (7)
1, a kind of method that adopts membrane technique reclaim(ed) sulfuric acid from liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product diluted acid, it is characterized in that the by-product diluted acid (1) with metal ion is a raw material, be transported to earlier in the pretreatment unit (2) and filter, be transported to again to handle in the feed liquid tempering tank (3) and mix, after delivering to nanofiltration membrane treatment in the nanofiltration membrane separation treatment unit (5) with pressurization pump pressure (4), obtain reclaim(ed) sulfuric acid solution (6) and recovery metal ion solution (7) simultaneously.
2, the method for employing membrane technique according to claim 1 reclaim(ed) sulfuric acid from liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product diluted acid, it is characterized in that sulfuric acid concentration 4-10% scope in the by-product raw material diluted acid parting liquid, wherein contained each concentration of metal ions Fe
2+, Mn
2+, Zn
2+, Al
3+In the 0.13-1.7g/L scope.
3, the method for employing membrane technique according to claim 1 and 2 reclaim(ed) sulfuric acid from liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product diluted acid, it is characterized in that in the nanofiltration membrane separation treatment unit (5), nanofiltration membrane is optionally filtered and is held back the metal ion component, allows H
+And SO
4 2-Negatively charged ion can effectively pass through nanofiltration membrane, thereby metal ion is separated with sulfuric acid.
4, the method for employing membrane technique according to claim 1 reclaim(ed) sulfuric acid from liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product diluted acid, it is characterized in that working pressure in the nanofiltration membrane separation treatment unit (5) in the 15-20bar scope, temperature is 0 ℃ of-45 ℃ of scope.
5, the method for employing membrane technique according to claim 1 and 2 reclaim(ed) sulfuric acid from liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product diluted acid is characterized in that the filter membrane that described nanofiltration membrane separation treatment unit is installed is acidproof nanofiltration membrane.
6, the method for employing membrane technique according to claim 1 reclaim(ed) sulfuric acid from liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product diluted acid is characterized in that waste liquid is carried out pre-treatment, uses the suspended substance in grid or the filter screen removal dilute sulfuric acid solution.
7, the method for employing membrane technique according to claim 1 reclaim(ed) sulfuric acid from liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product diluted acid, the sulphuric acid soln concentration that it is characterized in that reclaiming acquisition is in the 5-15% scope, wherein contained each concentration of metal ions Fe in the sulphuric acid soln of Hui Shouing
2+, Mn
2+, Zn
2+, Al
3+In the 10-100mg/L scope.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100942168A CN101585514A (en) | 2009-03-13 | 2009-03-13 | Method for reclaiming sulfuric acid from liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product dilute acid solution by adopting film technology |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100942168A CN101585514A (en) | 2009-03-13 | 2009-03-13 | Method for reclaiming sulfuric acid from liquid-phase catalytic oxidation-biological method flue gas desulfurization by-product dilute acid solution by adopting film technology |
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|---|---|
| CN101585514A true CN101585514A (en) | 2009-11-25 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857315A (en) * | 2010-06-22 | 2010-10-13 | 赵胜利 | Noble metal waste liquor recovering and regenerating process by film integration-dialysis separation and concentration |
| CN103172036A (en) * | 2013-03-27 | 2013-06-26 | 刘立文 | Method for decoloring sulfuric acid by using nanomaterial filter screen |
| WO2016074190A1 (en) * | 2014-11-13 | 2016-05-19 | Dow Global Technologies Llc | Treatment of flue gas desulfurization wastewater |
| CN108502850A (en) * | 2018-04-02 | 2018-09-07 | 杨大鹏 | A kind of gas washing in SA production clarifying smoke system |
| CN115924860A (en) * | 2023-02-07 | 2023-04-07 | 无锡中天固废处置有限公司 | Method for recycling sulfuric acid containing organic pollutants |
-
2009
- 2009-03-13 CN CNA2009100942168A patent/CN101585514A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857315A (en) * | 2010-06-22 | 2010-10-13 | 赵胜利 | Noble metal waste liquor recovering and regenerating process by film integration-dialysis separation and concentration |
| CN103172036A (en) * | 2013-03-27 | 2013-06-26 | 刘立文 | Method for decoloring sulfuric acid by using nanomaterial filter screen |
| WO2016074190A1 (en) * | 2014-11-13 | 2016-05-19 | Dow Global Technologies Llc | Treatment of flue gas desulfurization wastewater |
| CN108502850A (en) * | 2018-04-02 | 2018-09-07 | 杨大鹏 | A kind of gas washing in SA production clarifying smoke system |
| CN115924860A (en) * | 2023-02-07 | 2023-04-07 | 无锡中天固废处置有限公司 | Method for recycling sulfuric acid containing organic pollutants |
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Open date: 20091125 |