CN104743727A - System and method for cooperatively removing mercury with desulfurization waste water - Google Patents
System and method for cooperatively removing mercury with desulfurization waste water Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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Abstract
The invention discloses a system and a method for cooperatively removing mercury with desulfurization waste water. The system comprises a sulfur removal tower, an impurity removal system, a concentration device, an electrolysis device and an alkaline liquor storage device. The method comprises the following steps: removing impurity ions of SO4<2->, magnesium ions, calcium ions and the like of the desulfurization waste water; deeply purifying and concentrating the desulfurization waste water with impurity ion removed; electrolyzing concentrated desulfurization waste water; introducing a chlorine gas produced by electrolysis into a flue of a desulfurization tower to oxide a mercury single substance, thereby removing the mercury in the smoke gas. According to the system and the method disclosed by the invention, the problem that the outlet water of a conventional desulfurization waste water treatment process is high in salt content is solved, efficient cooperative mercury removal can be realized, and Cl2 and NaOH solutions and a clean energy source H2 which are extensively applied can be obtained.
Description
Technical field
The invention belongs to technical field of waste water processing, be specifically related to the System and method for that a kind of desulfurization wastewater works in coordination with demercuration.
Background technology
China is coal production maximum in the world and country of consumption, the coal amount of China's production and consumption in 2013 accounts for 47.4% and 50.3% of world's total amount respectively, the ratio of coal in the primary energy structure of China is up to more than 70% for a long time, causes the SO that China discharges thus
2about 90% is had to come from fire coal.Coal fire discharged a large amount of SO
2cause significant damage to farm crop, forest, building and human health, China is every year because of SO
2the financial loss that causes of discharge reach hundreds billion of unit.
Limestone-gypsum method flue gas desulfurization technology (WFGD) because of its coal wide accommodation, the advantage such as desulfuration efficiency is high, sorbent utilization is high, technical maturity and serviceability are high, become application flue gas desulfurization technique the most widely in present stage world wide.In this technological process, chlorine element in chlorine element in flue gas, the chlorine element in process water and sweetening agent (Wingdale) constantly enters desulfurization slurry and enrichment gradually, the chlorion of slurries middle and high concentration has reduction desulfuration efficiency, acceleration equipment corrosion and affects numerous harm such as gypsum qualitt, therefore in this technique in operational process, in order to maintain system stability safe operation and keep higher desulfuration efficiency, a certain amount of waste water must be discharged.Main Anions in desulfurization wastewater is Cl
-and SO
4 2-, in usual desulfurization method of limestone-gypsum waste water, chlorine ion concentration can up to 20000mg/L, and the positively charged ion that in waste water, concentration is the highest is Ca
2+and Mg
2+.
Current thermal power plant adopts maximum method for treating desulfurized wastewaters to be traditional chemical precipitation method, and the method processes waste water through processes such as neutralization, sedimentation, flocculation and clarifications, and the waste water quality after process can reach higher standard.But the chlorion in desulfurization wastewater is not separated water body all the time in this process treatment process, therefore in the waste water after this art breading, chlorine ion concentration is still very high, cause the waste water after this method process cannot enter system recoveries to utilize, if and the chlorion in waste water does not add improvement directly enters rivers, the balance of nature of water body will be destroyed, make water quality deterioration, cause the destruction of fish production, aquaculture and Freshwater resources, also can polluted underground water and drinking water source time serious.In addition, in water, the too high meeting of chloride concentration has corrosive nature to water distribution system, as agricultural irrigation, then can make soil generation salinization, and hinder plant growth.To sum up, along with further strict to water pollution control of China, wet desulfurizing process is had to the problem that chlorion is removed in desulfurization wastewater.
According to United Nations Environment Programme (UNEP) (UNEP) data presentation, mercury contaminants about 5000 tons is discharged every year in the whole world in air, wherein artificial mercury emission about 1930 tons, and fire coal is the important component part in artificial mercury emissions source, accounts for 45%.Power plant is as coal-fired rich and influential family, and its mercury emissions problem is day by day subject to people and pays close attention to.Mercury in coal-fired flue-gas mainly comprises three kinds of forms: Elemental Mercury (Hg
0), oxidation state mercury (Hg
2+) and particle mercury (Hg
p).Particle mercury (Hg
p) can be removed by the dust removal installation such as electrostatic precipitation and bag-type dust, oxidation state mercury (Hg
2+) can by flying dust adsorbing and removing in flue gas or by existing desulfurizer efficient removal.And Elemental Mercury (Hg
0) be difficult to remove owing to having stronger insoluble and stability.Therefore, in coal-fired plant flue gas, the removal efficiency of mercury greatly depends on the existing forms of mercury.
Based on above analysis, the present invention utilizes electrochemical principle, chlorion in desulfurization wastewater is translated into chlorine through electrolysis in ion-exchange membrane electrolyzer and is removed, before the chlorine part that electrolysis produces sends into thionizer, flue is the Elemental Mercury (Hg in flue gas
0) be oxidized to the oxidation state mercury (Hg being easy to be removed by wet desulfurization system
2+), both can solve the problem that traditional desulfuration waste water treatment process water outlet saltiness (especially chlorion) is high, the collaborative demercuration of existing wet desulphurization device can have been realized again.
Summary of the invention
The System and method for of the technical problem to be solved in the present invention for providing a kind of desulfurization wastewater to work in coordination with demercuration, solve existing desulfuration waste water treatment process effectively to remove chlorion in waste water and cause waste water saltiness high, thus the problem that cannot recycle or discharge, and can realize efficiently working in coordination with demercuration in existing wet desulphurization device.
In order to solve the problems of the technologies described above, the technical scheme that the present invention proposes is:
A kind of desulfurization wastewater works in coordination with the system of demercuration, comprise thionizer, Impurity removal system, concentrating unit, electrolyzer and alkali lye storing device, wherein, the outlet of thionizer and Impurity removal system connectivity, Impurity removal system is connected with concentrating unit, concentrating unit is connected with electrolyzer, and alkali lye storing device is connected with electrolyzer and Impurity removal system respectively, and electrolyzer is also communicated with the flue before described thionizer.
Preferably, described Impurity removal system comprises the settling pond, magnesium pond for recovering and the calcium pond for recovering that are connected successively.
Preferably, also exchange resin tower is connected with between described concentrating unit and electrolyzer.
Preferably, described electrolyzer is ion-exchange membrane electrolyzer.
Desulfurization wastewater works in coordination with a method for demercuration, comprises the following steps:
Desulfurization wastewater is through SO
4 2-remove, the process that the foreign ions such as magnesium ion removal and calcium ion removal are removed, desulfurization wastewater after foreign ion removal is concentrated after deep purifying, through concentrated desulfurization wastewater electrolysis, the chlorine that electrolysis produces passes into red precipitate simple substance in the flue of thionizer, and then by the mercury removing in flue gas in thionizer.
Preferably, at described SO
4 2-in removal process, in desulfurization wastewater, add BaCl
22H
2o, by SO
4 2-be converted into BaSO
4precipitation, SO
4 2-after removing, SO in desulfurization wastewater
4 2-concentration be 0.4-0.6g/L.By the suspended substance in waste water and newly-generated BaSO after clarification
4together remove.Its reaction mechanism is:
Ba
2++SO
4 2-→BaSO
4↓
Preferably, in described magnesium ion removal process, in desulfurization wastewater, add NaOH solution, the amount of the NaOH added exceedes theoretical amount 6-12mg/L, magnesium ion is converted into the Mg (OH) of indissoluble
2.Its reaction mechanism is:
Mg
2++2OH
-→Mg(OH)
2↓
Preferably, in calcium ion removal process, in desulfurization wastewater, Na is added
2cO
3solution, the NaCO added
3amount exceed theoretical amount 0.36-0.72g/L, by the Ca in waste water
2+be converted into the CaCO of indissoluble
3.Its reaction mechanism is:
Ca
2++CO
3 2-→CaCO
3↓
Preferably, the waste water after concentrated carries out electrolysis, and the part in the sodium hydroxide that electrolysis obtains is for the removal process of magnesium ion.Electrolytic reaction is:
2NaCl+2H
2O→H
2↑+Cl
2↑+2NaOH
Preferably, described concentration process is evaporation concentration, and institute's heat requirement is provided by the waste heat of flue gas in flue.
The main component of the desulfurization wastewater after the process of foreign ion removal process is NaCl, the NaCl solution of acquisition is sent in concentrating unit and carries out evaporation concentration, obtain saturated NaCl solution; NaCl solution after concentrated is after ion exchange resin deep purifying, send into ion-exchange membrane electrolyzer anolyte compartment and carry out electrolysis, the NaOH solution part that the outlet of electric tank cathode room obtains returns the recycle of calcium pond for recovering, another part reclaims as byproduct, the chlorine part that anode is separated out can be returned and be sprayed onto the anterior flue of thionizer, realizes Elemental Mercury (Hg in flue gas
0) oxidation, another part can be used as by-product recovery utilize, negative electrode separate out H
2can be used as clean recycling.
Chlorion in NaCl solution, owing to being subject to the restriction of cationic membrane, can not entering cathode compartment and on anode, be oxidized to chlorine gradually, the Na in solution
+move to cathode compartment through cationic exchange membrane under electrical forces effect, enter the Na of cathode compartment
+the OH produced with cathodic electrolytic water
-in conjunction with formation NaOH, on negative electrode, discharge hydrogen simultaneously.
Advantage of the present invention is:
1, in the present invention, ion-exchange membrane electrolyzer is set, the problem that the traditional chemical precipitator method effectively cannot remove desulfurization wastewater middle and high concentration chlorion can be solved.
2, the present invention can by the chlorion in waste water with Cl
2recycling treatment also can realize collaborative demercuration, can obtain widely used NaOH and clean energy H simultaneously
2, and the higher Mg of purity (OH) can be obtained in foreign ion removal process
2, CaCO
3in byproduct.
Accompanying drawing explanation
Fig. 1 is schema of the present invention;
Fig. 2 is structural representation of the present invention.
Wherein, 1, settling pond, 2, magnesium pond for recovering; 3, calcium pond for recovering, 4, concentrating unit, 5, exchange resin tower, 6, electrolyzer, 7, alkali lye storing device, 8, thionizer, 9, Impurity removal system.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
As depicted in figs. 1 and 2, a kind of desulfurization wastewater works in coordination with the system of demercuration, comprise thionizer 8, Impurity removal system 9, concentrating unit 4, electrolyzer 6 and alkali lye storing device 7, wherein, the outlet of thionizer 8 is communicated with Impurity removal system 9, and Impurity removal system 9 is connected with concentrating unit 4, and concentrating unit 4 is connected with electrolyzer 6, alkali lye storing device 7 is connected with electrolyzer 6 and Impurity removal system 9 respectively, and electrolyzer 6 is also communicated with the flue of described thionizer 8.
Wherein, Impurity removal system 9 comprises the settling pond 1, magnesium pond for recovering 2 and the calcium pond for recovering 3 that are connected successively.Exchange resin tower 5 is also connected with between concentrating unit 4 and electrolyzer 6.Described electrolyzer 6 is ion-exchange membrane electrolyzer.
The method that desulfurization wastewater of the present invention works in coordination with demercuration is as follows:
A 300MW fired power generating unit exhaust gas volumn is 112376Nm
3/ h, the wet desulphurization device waste water water yield is 5m
3/ h, waste water main component is: 17494.6mg/L Cl
-, 4328mg/L SO
4 2-, 3843mg/L Ca
2+with 3948mg/L Mg
2+.
In settling pond 1, add BaCl
22H
2o (55.05kg/h), by the SO in waste water
4 2-be converted into BaSO
4precipitation, BaSO
4precipitation and the suspended substance in waste water are together crossed and are filtered; Magnesium pond for recovering 2 sent into by the clear liquid that settling pond 1 exports, and adds the NaOH solution (0.076m that concentration is 32% (wt) in clear liquid
3/ h), make the Mg in waste water
2+form indissoluble thing Mg (OH)
2, the higher Mg of purity (OH) can be obtained after filtration
2(47.35kg/h); Isolate Mg (OH)
2clear liquid after precipitation imports calcium pond for recovering 3, and adds Na wherein
2cO
3(50.92kg/h) Ca in waste water, is made
2+form the CaCO of indissoluble
3, the higher CaCO of purity can be obtained after filtration
3(48.04kg/h); Isolate CaCO
3after the NaCl dilute solution (5.07m of clear liquid main component to be concentration be 28.45g/L
3/ h), dilute NaCl solution (210g/L, the 1.35m of this NaCl solution and ion-exchange membrane electrolyzer anode compartment outlet
3/ h) mixing after together deliver to concentrating unit 4, in concentrating unit 4, NaCl solution is constantly concentrated into saturated, saturated NaCl solution (317g/L, 1.35m
3/ h) in exchange resin tower 5, carry out deep purifying after, import the anolyte compartment of ion-exchange membrane electrolyzer, in ion-exchange membrane electrolyzer, electrolytic reaction occur.At ion-exchange membrane electrolyzer positive plate, Cl
-constantly be oxidized to Cl
2(87.47kg/h), a part of Cl
2(17kg/h) before delivering to thionizer, the elemental mercury oxidation in flue gas is the oxidation state mercury being easy to remove by flue, and another part reclaims as Industrial products; Anode compartment outlet dilute NaCl solution (210g/L, 1.35m
3/ h) derive ion-exchange membrane electrolyzer after with rough purification after waste water together send into concentrating unit 4 and concentrate Posterior circle and utilize; Enter the Na of cathode compartment
+the OH produced with cathodic electrolytic water
-continuous combination forms NaOH (32%wt, 0.23m
3/ h), the NaOH solution of cathode chamber outlet imports alkali lye storing device 7, a part of NaOH solution (0.076m
3/ h) deliver to the recycle of magnesium pond for recovering, another part NaOH solution (0.154m
3/ h)) as by-product recovery; Negative electrode discharges H
2(2.47kg/h) recycle as clean energy.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but the restriction not to invention protection domain; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still in protection scope of the present invention.
Claims (10)
1. a desulfurization wastewater works in coordination with the system of demercuration, it is characterized in that: comprise thionizer, Impurity removal system, concentrating unit, electrolyzer and alkali lye storing device, wherein, the outlet of thionizer is connected with Impurity removal system, Impurity removal system is connected with concentrating unit, concentrating unit is connected with electrolyzer, and alkali lye storing device is connected with electrolyzer and Impurity removal system respectively, and electrolyzer is also communicated with the flue of described thionizer.
2. desulfurization wastewater according to claim 1 works in coordination with the system of demercuration, it is characterized in that: described Impurity removal system comprises the settling pond, magnesium pond for recovering and the calcium pond for recovering that are connected successively.
3. desulfurization wastewater according to claim 1 works in coordination with the system of demercuration, it is characterized in that: be also connected with exchange resin tower between described concentrating unit and electrolyzer.
4. desulfurization wastewater according to claim 1 works in coordination with the system of demercuration, it is characterized in that: described electrolyzer is ion-exchange membrane electrolyzer.
5. desulfurization wastewater works in coordination with a method for demercuration, comprises the following steps: desulfurization wastewater is through SO
4 2-remove, the process that the foreign ions such as magnesium ion removal and calcium ion removal are removed, desulfurization wastewater after foreign ion removal is concentrated after deep purifying, through concentrated desulfurization wastewater electrolysis, the chlorine that electrolysis produces passes in the flue of thionizer the mercury simple substance be oxidized in flue gas, and then by the mercury removing in flue gas.
6. desulfurization wastewater according to claim 5 works in coordination with the method for demercuration, it is characterized in that: at described SO
4 2-in removal process, in desulfurization wastewater, add BaCl
22H
2o, by SO
4 2-be converted into precipitate B aSO
4, through SO
4 2-after removal, SO in desulfurization wastewater
4 2-concentration be 0.4-0.6g/L.
7. desulfurization wastewater according to claim 5 works in coordination with the method for demercuration, it is characterized in that: in described magnesium ion removal process, in desulfurization wastewater, add NaOH solution, the amount of the NaOH added exceedes theoretical amount 6-12mg/L, magnesium ion is converted into the Mg (OH) of indissoluble
2.
8. desulfurization wastewater according to claim 5 works in coordination with the method for demercuration, it is characterized in that: in calcium ion removal process, in desulfurization wastewater, add Na
2cO
3solution, the NaCO added
3amount exceed theoretical amount 0.36-0.72g/L, by the Ca in waste water
2+be converted into the CaCO of indissoluble
3.
9. desulfurization wastewater according to claim 1 works in coordination with the method for demercuration, it is characterized in that: the waste water after concentrated carries out electrolysis, and the part in the sodium hydroxide that electrolysis obtains removes process for magnesium ion.
10. desulfurization wastewater according to claim 1 works in coordination with the method for demercuration, it is characterized in that: described concentration process is evaporation concentration, and institute's heat requirement is provided by flue gas in flue.
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| CN105540958A (en) * | 2016-01-26 | 2016-05-04 | 河北省电力勘测设计研究院 | Zero-discharge treatment process of power plant wastewater |
| CN106039980A (en) * | 2016-08-04 | 2016-10-26 | 山东奥特高科环保科技有限公司 | High temperature flue gas mercury removal device and technology |
| CN106517605A (en) * | 2016-11-25 | 2017-03-22 | 武汉尚源新能环境有限公司 | Zero-discharge process and equipment for desulfurization wastewater |
| CN106630027A (en) * | 2016-12-30 | 2017-05-10 | 华北电力大学（保定） | Method and system for treating high-chlorine desulfurization waste water by electrolytic method and performing flue gas mercury pollution control |
| CN107098527A (en) * | 2017-03-29 | 2017-08-29 | 扬州祥发资源综合利用有限公司 | A kind of method of desulfurization wastewater recycling |
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| CN109095484A (en) * | 2018-10-30 | 2018-12-28 | 华北电力大学（保定） | A method of utilizing desulfurization wastewater preparing magnesium hydroxide |
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| CN111170518A (en) * | 2018-11-12 | 2020-05-19 | 国家能源投资集团有限责任公司 | Treatment process and treatment system for desulfurization wastewater |
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| CN111170517A (en) * | 2018-11-12 | 2020-05-19 | 国家能源投资集团有限责任公司 | Treatment process and treatment system for desulfurization wastewater |
| CN111170519A (en) * | 2018-11-12 | 2020-05-19 | 国家能源投资集团有限责任公司 | Treatment process and treatment system for desulfurization wastewater |
| CN112337290A (en) * | 2020-10-12 | 2021-02-09 | 广东原之生农业科技有限公司 | Water electrolysis disinfection system for livestock and poultry breeding |
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| CN109095484A (en) * | 2018-10-30 | 2018-12-28 | 华北电力大学（保定） | A method of utilizing desulfurization wastewater preparing magnesium hydroxide |
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| CN111170518A (en) * | 2018-11-12 | 2020-05-19 | 国家能源投资集团有限责任公司 | Treatment process and treatment system for desulfurization wastewater |
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