CN106630027A - Method and system for treating high-chlorine desulfurization waste water by electrolytic method and performing flue gas mercury pollution control - Google Patents

Method and system for treating high-chlorine desulfurization waste water by electrolytic method and performing flue gas mercury pollution control Download PDF

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CN106630027A
CN106630027A CN201611255925.6A CN201611255925A CN106630027A CN 106630027 A CN106630027 A CN 106630027A CN 201611255925 A CN201611255925 A CN 201611255925A CN 106630027 A CN106630027 A CN 106630027A
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chlorine
electrolysis
hgcl
waste water
desulfurization wastewater
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刘松涛
梅玉倩
陈传敏
张智博
黄陈
曹强
周达海
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North China Electric Power University
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North China Electric Power University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/263—Drying gases or vapours by absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/28—Selection of materials for use as drying agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/108—Halogens or halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents

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Abstract

The invention discloses a method and a system for treating high-chlorine desulfurization waste water by an electrolytic method and performing flue gas mercury pollution control, and belongs to the technical field of waste water treatment. The method comprises the following steps: (1) pretreating the high-chlorine desulfurization waste water; (2) pumping the pretreated desulfurization waste water into an electrolysis device to perform electrolysis; (3) purifying chlorine generated by electrolysis and then introducing the purified chlorine into a chlorine liquefier to perform liquefied storage for future use; (4) carrying the stored chlorine by compressed air to be introduced into an SCR inlet flue of a coal-fired power plant boiler; and (5) refluxing the obtained desalted water into a wet scrubber. By the method, high-chlorine desulfurization waste water treatment and flue gas mercury pollution control are integrated, so the aim of treating the desulfurization waste water is fulfilled and the mercury in coal-fired flue gas is controlled.

Description

A kind of electrolysis process high chlorine desulfurization wastewater and be used for gas mercury method for governing pollution and System
Technical field
The invention belongs to technical field of waste water processing, and in particular to a kind of electrolysis processes high chlorine desulfurization wastewater and is used for cigarette Bicycle pump method for governing pollution and system.
Background technology
Coal-burning power plant's wet method fume desulfurizing system (WFGD) discharges a large amount of waste water, and the waste water is in faintly acid, containing a large amount of outstanding Float, gypsum particle, silica and hydroxide etc., and it is enriched plurality of heavy metal ion and chlorine, fluorine, sulfate ion Deng, wastewater treatment and recycle difficulty larger.In order to maintain desulphurization system safe and stable operation, ensure gypsum product quality and guarantor Card desulfuration efficiency, needs to control C1 in slurries-Concentration, it is general to require to be less than 20g/L, therefore a large amount of waste water of periodic exhaustion are needed, lead Desulphurization system water consumption is caused to increase.
At present, domestic and international power plant typically carries out following several processing modes to desulfurization wastewater：1) by neutralization, precipitation, The methods such as flocculation, clarification, oxidation are processed, and heel row is mixed to grey field with desulfuration byproduct gypsum after concentration；2) by electric cleaner Flue evaporation between air preheater；3) using discharge or reuse after the process of single Waste Water Treatment；4) electrodialysis Or reuse effluent part after reverse-osmosis treated；5) using technologies such as multiple-effect evaporation, Membrane Materials and molecular clocks；6) in addition with stream Change bed process, membrane separation process, ion-exchange and electric flocculation method etc..But these methods are the drawbacks of have certain, such as electrodialysis or Counter-infiltration cannot solve the problems such as desulfurization wastewater chloride ion content is too high, and the impurity such as organic matter is more, and film can be caused dirty stifled frequent. The technologies such as multiple-effect evaporation, Membrane Materials and molecular clock, removing chloride, but its evaporation process are removed to equipment by chloride saline crystallization The requirement of material is higher, and observable index is larger.
With the attention to environmental protection, coal-fired flue-gas mercury pollution problem has caused the extensive concern in worldwide. China《Fossil-fuel power plant atmospheric pollutant emission standard》Regulation power plants mercury and mercuric compounds in (GB 13223-2011) Emission limit is 0.03mg/m3.The existence form of Mercury In Coal Combustion Flue Gas mainly has 3 kinds：Oxidation state (Hg2+), particle mercury (Hgp) With elemental mercury (Hg0)。Hg2+It is soluble in water, with the absorbable flue gas of existing wet desulphurization device 80%～90% Hg2+； HgpOn flying dust of the absorption in flue gas, can be removed by cleaner；Hg0With higher vapour pressure and water is insoluble in, is removed Dirt equipment and wet type desulfurizing equipment are difficult its Direct Acquisition.How effectively the Hg in flue gas0It is converted into Hg2+And HgP, profit Removed with existing cleaner and wet desulphurization device, become the break-through point of demercuration technological development.Research discovery, oxidizing atmosphere Under, chlorinity is higher in coal-fired flue-gas, Hg in flue gas0It is converted into Hg2+Ratio it is higher, i.e., chlorine element can promote flue gas in flue gas The oxidation of middle mercury, is conducive to using the mercury in existing pollution control device cooperation-removal flue gas.
The content of the invention
Drawbacks described above of the present invention for prior art, there is provided a kind of electrolysis processes high chlorine desulfurization wastewater and is used for cigarette Bicycle pump method for governing pollution and system, it is characterised in that the method and system are comprised the following steps：
(1) high chlorine desulfurization wastewater is pre-processed；
(2) pretreated high chlorine desulfurization wastewater is pumped into the anode room of electrolysis unit, while being 0.5mol/ by concentration The sodium hydroxide solution of L is pumped into the negative electrode room of electrolysis unit, backward electrolysis unit in be passed through direct current and control electric current is 3A；In electrolytic process, by near the minus plate that bubbling reactor is passed through air in negative electrode room, increasing molten near minus plate Solution oxygen content, concurrently gives birth to reduction reaction and generates water；There is oxidation reaction at the positive plate of anode chamber and produce chlorine, in anode room Obtain desalted water；
(3) HCl and moisture during the chlorine for producing passes sequentially through saturated aqueous common salt and anhydrous calcium chloride to remove chlorine, Chlorine after purification is passed through chlorine liquefier, and to carry out liquefied storage standby；
(4) chlorine of storage in step (3) is entered by the SCR system that compressed air carrying imports to coal-fired power station boiler Mouth flue, aoxidizes to the elemental mercury in flue gas, and chlorine element is reacted with the homogeneous oxidizing of mercury in flue gas：
Hg+Cl+M=HgCl+M；
Hg+HOCl=HgCl+OH；
HgCl+Cl2=HgCl2+Cl；
HgCl+HCl=HgCl2+H；
Wherein, Hg is to generate HgCl by HOCl and Cl oxidations first, and HgCl is then in Cl2It is oxidized with the presence of HCl Into HgCl2, i.e. the main oxidation path of mercury is Hg → HgCl → HgCl2；
(5) desalted water that step (2) is obtained is back in wet scrubber as recirculation water.
Pretreatment described in step (1) is " pH regulation+mixed flocculations+clarification precipitation " pretreatment, comprises the following steps that：
A () pumps into high chlorine desulfurization wastewater in neutralization case, add the NaOH solution of 0.5mol/L, adjusts pH value to 8-9；
B the waste water after () neutralization is entered in blending bin, and add tri-thiol three and chant in a loud voice sodium salt, and dosage is 7.5mg/L；
C () mixed waste water is entered in flocculation tanks, and add sulfuric acid chlorine iron and polyacrylamide, and dosage is respectively 25mg/L, 2.5mg/L, are flocculated；
D the waste water outflow after () flocculation enters cantboard clarifier, supernatant is pumped into and is electrolysed in the anode room of electrolytic cell Process.
Electrolysis unit described in step (2) is the dual chamber electrolytic cell with cation-exchange membrane, wherein, anode chamber is provided with anode Plate, positive plate is ruthenium system coated titanium electrode；Cathode chamber is provided with minus plate, and minus plate is ODC micropore oxygen catalysis electrodes；The anode The spacing of plate and minus plate is adjustable.
Electrolysis unit described in step (2) by the way of multipair positive plate is in parallel with multipair minus plate, to improve process Efficiency.
A kind of electrolysis processes high chlorine desulfurization wastewater and for the system of flue gas mercuric pollution treatment, it is characterised in that this is System includes coal-fired power station boiler, SCR system, cleaner, air-introduced machine, wet scrubber, chimney, neutralization case, blending bin, flocculation Case, cantboard clarifier, electrolysis unit, bubbling reactor, air compressor machine, compressed air gas source, chlorine liquefier；Wherein, it is described wet Formula washer is connected by pipeline with neutralization case, is neutralized case and is sequentially connected with blending bin, flocculation tanks, flocculation tanks and cantboard clarifier It is connected, the overflow of cantboard clarifier is pumped into the anode room of electrolysis unit；The air of air compressor machine is passed through electricity by bubbling reactor Near minus plate in solution device negative electrode room；The anode chamber of electrolysis unit is connected with wet scrubber, and the desalted water after electrolysis is made It is back in wet scrubber for recirculation water, as wet scrubbing water is used；Produce at the positive plate of electrolytic process middle-jiao yang, function of the spleen and stomach pole room Chlorine purification after be passed through chlorine liquefier, carried by compressed air from compressed air gas source and import to coal fired power plant pot The gas approach of the SCR system of stove.
The principle of the present invention is as follows：
After being powered to electrolytic cell, by the oxidation reaction of the chlorion in solution, mol-chloric is formed, existed as a kind of gas The positive plate effusion of electrolytic cell, the process of oxidation reaction is as follows：
2Cl-(aq)-2e-=Cl2(g) E0=1.36V
There is reduction reaction in negative electrode, process is as follows：
O2(g)+4H+(aq)+4e-=2H2O E0=1.23V
The chlorine that anode electrolysis are produced is passed through the SCR flue entrances of coal-burning boiler after reclaiming, to the elemental mercury in flue gas Aoxidized, chlorine element is reacted with the homogeneous oxidizing of mercury in flue gas：
Hg+Cl+M=HgCl+M；
Hg+HOCl=HgCl+OH；
HgCl+Cl2=HgCl2+Cl；
HgCl+HCl=HgCl2+H；
Wherein, Hg is to generate HgCl by HOCl and Cl oxidations first, and HgCl is then in Cl2It is oxidized with the presence of HCl Into HgCl2, i.e. the main oxidation path of mercury is Hg → HgCl → HgCl2。
The Advantageous Effects of the present invention：
1st, the wet scrubber used during this method fume treatment can use the less material of corrosion resistance, can subtract Few electric power factory equipment spending；
2nd, this method adopts oxygen-consuming cathodes technology, negative electrode not to produce hydrogen, reduces the discharge potential of negative electrode, and power consumption is reduced Substantially, there is significant economic benefit；
3rd, the chlorine reuse that anode electrolysis are produced is sprayed onto the present invention SCR system gas approach of power plant, the presence of chlorine Effect of the SCR catalyst to mercury oxidation can be strengthened, promote the oxidation of Elemental Mercury, remove the oxygen in flue gas in wet flue gas then Change state mercury；
4th, The method reduces the discharge of desulfurization wastewater, and the recycling of desulfurization wastewater is realized；
5th, this method can realize marketing one's own products for power plant, reduce production cost, and promote using existing pollutant catabolic gene Device realizes the control to mercury emissions, environmentally friendly and economical；
6th, its electrolysis system principle is simple, will can transform on the original basis, and improvement cost is low.
Description of the drawings
Fig. 1 is that the electrolysis of the present invention processes high chlorine desulfurization wastewater and for gas mercury pollution abatement system schematic diagram.
Specific embodiment
The invention provides a kind of electrolysis processes high chlorine desulfurization wastewater and for gas mercury method for governing pollution and system, With reference to the accompanying drawings and examples the present invention is further described, and the content of embodiment is not as to protection scope of the present invention Limit.
As shown in figure 1, a kind of electrolysis processes high chlorine desulfurization wastewater and includes for gas mercury pollution abatement system：It is coal-fired Station boiler 1, SCR system 2, cleaner 3, air-introduced machine 4, wet scrubber 5, chimney 6, neutralization case 7, blending bin 8, flocculation tanks 9th, cantboard clarifier 10, electrolysis unit 13, bubbling reactor 12, air compressor machine 11, compressed air gas source 14, chlorine liquefier 15.
The flue gas that coal-fired power station boiler 1 is produced carries out denitration process into SCR system 2, afterwards, into cleaner 3 Dust removal process is carried out, after dedusting, carrying out washing treatment is carried out into wet scrubber 5 in the presence of air-introduced machine 4, after carrying out washing treatment Flue gas discharged by chimney 6.Wherein, the desulfurization wastewater discharged in wet scrubber 5 sequentially enters neutralization case 7, the and of blending bin 8 Flocculation tanks 9 are pre-processed, and after pretreatment, are clarified by cantboard clarifier 10, and the water after clarification is pumped to electrolysis dress Put in 13 anode room, and sodium hydroxide solution is pumped into the negative electrode room of electrolysis unit 13, meanwhile, by bubbling reactor 12 by near the minus plate that the air of air compressor machine 11 is passed through in the negative electrode room, to increase the dissolving near the minus plate Oxygen content, concurrently gives birth to reduction reaction and generates water, and the desalted water after electrolysis is back in wet scrubber 5 as recirculation water, is used as Wet scrubbing uses water；Desulfurization wastewater be electrolysed when at the positive plate of anode chamber produce chlorine pass sequentially through saturated aqueous common salt and Anhydrous calcium chloride to remove chlorine in HCl and moisture, afterwards, the chlorine after purification is passed through into chlorine liquefier 15 carries out liquid Change is stored for future use, and the chlorine stored in chlorine liquefier 15 is carried by the compressed air from compressed air gas source 14 and imported to The gas approach of the SCR system 2 of coal-fired power station boiler 1, promotes the mercury that elemental mercury oxidation in flue gas is oxidation state so that oxidation state Mercury remove in wet desulfurization system, realize the removing to mercury in flue gas.
The high chlorine desulfurization wastewater of electrolysis process and the method for being used for flue gas mercuric pollution treatment, specifically include following steps：
First, high chlorine desulfurization wastewater is pre-processed, the pretreatment is " pH regulation+mixed flocculations+clarification precipitation " Pretreatment, comprises the following steps that：
(1) desulfurization wastewater is pumped into neutralization case 7,0.5mol/L is added to the desulfurization wastewater in the neutralization case 7 NaOH solution, adjust pH value to 8-9；
(2) desulfurization wastewater after neutralizing is entered in blending bin 8, and is thrown in the desulfurization wastewater in the blending bin 8 Plus tri-thiol three chants in a loud voice sodium salt, dosage is 7.5mg/L, to remove desulfurization wastewater in Cr3+、Hg2+、Cd2+Etc. heavy metal ion；
(3) desulfurization wastewater for making removal part heavy metal ion is entered in flocculation tanks 9, and is added in the flocculation tanks 9 Sulfuric acid chlorine iron (trade name PFS) and polyacrylamide (trade name PAM), dosage is respectively PFS 25mg/L, PAM 2.5mg/ L, PFS and PAM's uses cooperatively, the tiny flocculate of inorganic salts, heavy metal complex and the suspension that can make to have crystallized precipitation Accumulation becomes larger particles, the flocculating setting after waste water enters clarifier.
(4) the desulfurization wastewater overflow after flocculating is clarified into cantboard clarifier 10, wherein, supernatant pumps into dual chamber electricity Electrolysis process is carried out in the anode room of solution device 13.
Additionally, in the present invention the neutralization case 7, blending bin 8 and flocculation tanks 9 can be using neutralization, mixing, flocculations three Case.
Secondly, pretreated high chlorine desulfurization wastewater is pumped into the anode room of electrolysis unit 13, while being by concentration The sodium hydroxide solution of 0.5mol/L is pumped into the negative electrode room of the electrolysis unit 13；Wherein desulfurization wastewater and NaOH are molten Liquid fills respectively the anode chamber and the cathode chamber, afterwards, direct current and control electric current is passed through in the electrolysis unit 13 For 3A, desalted water is obtained in the anode room of the electrolysis unit 13 by electrolysis.
In electrolytic process, the moon that will be passed through from the air of air compressor machine 11 in the negative electrode room by bubbling reactor 12 Near pole plate, to increase the dissolved oxygen content near the minus plate, concurrently give birth to reduction reaction and generate water.
The electrolysis unit is the dual chamber electrolytic cell with cation-exchange membrane, and anode chamber is provided with positive plate, and positive plate is ruthenium It is coated titanium electrode；Cathode chamber is provided with minus plate, and minus plate is ODC micropore oxygen catalysis electrodes, the positive plate and minus plate Spacing is adjustable.By the way of multipair positive plate is in parallel with multipair minus plate, to improve treatment effeciency.
Then, the chlorine produced at the positive plate of anode chamber when desulfurization wastewater is electrolysed passes sequentially through saturated aqueous common salt and nothing Water calcium chloride to remove chlorine in HCl and moisture, the chlorine after purification is passed through into chlorine liquefier 15 carries out liquefied storage It is standby.
Then, the chlorine stored in the chlorine liquefier 15 is taken by the compressed air from compressed air gas source 14 Band imports to the SCR2 gas approach of coal-fired power station boiler, promotes the mercury that elemental mercury oxidation in flue gas is oxidation state so that oxidation The mercury of state is removed in wet desulfurization system, realizes the improvement to mercury in flue gas.
Finally, it is back to the desalted water of acquisition as recirculation water in wet scrubber 5, the use water as wet scrubbing, Because the water that the wet scrubber 5 is used is the water after dechlorination, therefore, the washer can be less using corrosion resistance Material, can reduce electric power factory equipment spending.
Pretreated high chlorine desulfurization wastewater is pumped into the present invention anode chamber of the dual chamber electrolytic cell with amberplex, cloudy Pole room pumps into sodium hydroxide solution to improve solution conductivity, and to electrolytic cell direct current is passed through, and chlorion is in positive plate in waste water Nearby betatopic is oxidized to chlorine and escapes and carry out Recovery Purifying, and air is passed through by bubbling reactor near minus plate, increases Plus dissolved oxygen content near minus plate, concurrently give birth to reduction reaction and generate water.The chlorine of collection is carried by compressed air and imports combustion The SCR flue entrances of coal burning boiler, promote the Hg in flue gas0Aoxidized so as to remove in wet desulphurization equipment.
The above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not to the present invention Embodiment restriction.For those of ordinary skill in the field, can also make on the basis of the above description The change or variation of other multi-forms.Here all of embodiment cannot be exhaustive.Every skill for belonging to the present invention Obvious change that art scheme is extended out changes row still in protection scope of the present invention.

Claims (5)

1. a kind of electrolysis processes high chlorine desulfurization wastewater and is used for gas mercury method for governing pollution, it is characterised in that including following Step：
(1) high chlorine desulfurization wastewater is pre-processed；
(2) pretreated high chlorine desulfurization wastewater is pumped into the anode room of electrolysis unit, while by concentration for 0.5mol/L's Sodium hydroxide solution is pumped into the negative electrode room of electrolysis unit, direct current is passed through in electrolysis unit and control electric current is 3A；Electrolysis During, contained by near the minus plate that bubbling reactor is passed through air in negative electrode room, increasing the dissolved oxygen near minus plate Amount, concurrently gives birth to reduction reaction and generates water；There is oxidation reaction at the positive plate of anode chamber and produce chlorine, anode is taken off in room Salt solution；
(3) HCl and moisture during the chlorine for producing passes sequentially through saturated aqueous common salt and anhydrous calcium chloride to remove chlorine, purification Chlorine afterwards is passed through chlorine liquefier, and to carry out liquefied storage standby；
(4) chlorine of storage in step (3) is carried the SCR system entrance cigarette for importing to coal-fired power station boiler by compressed air Road, aoxidizes to the elemental mercury in flue gas, and chlorine element occurs homogeneous oxidizing reaction with the mercury in flue gas：
Hg+Cl+M=HgCl+M；
Hg+HOCl=HgCl+OH；
HgCl+Cl2=HgCl2+Cl；
HgCl+HCl=HgCl2+H；
Wherein, Hg is to generate HgCl by HOCl and Cl oxidations first, and HgCl is then in Cl2It is oxidized to in the presence of HCl HgCl2, i.e. the main oxidation path of mercury is Hg → HgCl → HgCl2；
(5) desalted water that step (2) is obtained is back in wet scrubber as recirculation water.
2. a kind of electrolysis according to claim 1 processes high chlorine desulfurization wastewater and is used for gas mercury method for governing pollution, Characterized in that, the pretreatment described in step (1) is pH regulation+mixed flocculations+clarification precipitation, comprise the following steps that：
A () pumps into high chlorine desulfurization wastewater in neutralization case, add the NaOH solution of 0.5mol/L, adjusts pH value to 8-9；
B the waste water after () neutralization is entered in blending bin, and add tri-thiol three and chant in a loud voice sodium salt, and dosage is 7.5mg/L；
C () mixed waste water is entered in flocculation tanks, and add sulfuric acid chlorine iron and polyacrylamide, and dosage is respectively 25mg/ L, 2.5mg/L, are flocculated；
D the waste water outflow after () flocculation enters cantboard clarifier, supernatant is pumped into and carry out in the anode room of electrolytic cell electrolysis process.
3. a kind of electrolysis according to claim 1 processes high chlorine desulfurization wastewater and is used for gas mercury method for governing pollution, Characterized in that, electrolysis unit described in step (2) is the dual chamber electrolytic cell with cation-exchange membrane, wherein, anode chamber is provided with Positive plate, positive plate is ruthenium system coated titanium electrode；Cathode chamber is provided with minus plate, and minus plate is ODC micropore oxygen catalysis electrodes；It is described The spacing of positive plate and minus plate is adjustable.
4. a kind of electrolysis according to claim 1 processes high chlorine desulfurization wastewater and is used for gas mercury method for governing pollution, Characterized in that, electrolysis unit described in step (2) is by the way of multipair positive plate is in parallel with multipair minus plate, to improve place Reason efficiency.
5. a kind of electrolysis processes high chlorine desulfurization wastewater and for the system of flue gas mercuric pollution treatment, it is characterised in that the system Including coal-fired power station boiler, SCR system, cleaner, air-introduced machine, wet scrubber, chimney, neutralization case, blending bin, flocculation Case, cantboard clarifier, electrolysis unit, bubbling reactor, air compressor machine, compressed air gas source, chlorine liquefier；Wherein, it is described wet Formula washer is connected by pipeline with neutralization case, is neutralized case and is sequentially connected with blending bin, flocculation tanks, flocculation tanks and cantboard clarifier It is connected, the overflow of cantboard clarifier is pumped into the anode room of electrolysis unit；The air of air compressor machine is passed through electricity by bubbling reactor Near minus plate in solution device negative electrode room；The anode chamber of electrolysis unit is connected with wet scrubber, and the desalted water after electrolysis is made It is back in wet scrubber for recirculation water, as wet scrubbing water is used；Produce at the positive plate of electrolytic process middle-jiao yang, function of the spleen and stomach pole room Chlorine purification after be passed through chlorine liquefier, carried by compressed air from compressed air gas source and import to coal fired power plant pot The gas approach of the SCR system of stove.
CN201611255925.6A 2016-12-30 2016-12-30 Method and system for treating high-chlorine desulfurization waste water by electrolytic method and performing flue gas mercury pollution control Pending CN106630027A (en)

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CN108946670A (en) * 2017-05-23 2018-12-07 北京中睿水研环保科技有限公司 Desulfurization wastewater is electrolysed removing chloride sodium hypochlorite equipment
CN108946670B (en) * 2017-05-23 2023-08-01 北京中睿水研环保科技有限公司 Equipment for preparing sodium hypochlorite by electrolysis and chloride ion removal of desulfurization wastewater
CN107596868A (en) * 2017-10-27 2018-01-19 四川省洪雅青衣江元明粉有限公司 A kind of Chlorine Scrubber
CN108314149A (en) * 2018-03-01 2018-07-24 南京工程学院 Desulfurization wastewater is electrolysed and its method of product denitrification integral
CN108314149B (en) * 2018-03-01 2021-03-02 南京工程学院 Method for integrating desulfurization wastewater electrolysis and product denitration
CN108371879A (en) * 2018-03-14 2018-08-07 武汉大学 It is a kind of to be electrolysed the system and method for handling high chlorine desulfurization wastewater and coupling denitration demercuration
CN108744960A (en) * 2018-06-14 2018-11-06 华北电力大学（保定） A kind of flue gas and desulfurizing and denitrifying demercuration and recycling unit and method
CN110872651A (en) * 2018-09-04 2020-03-10 中国科学院过程工程研究所 Method for removing chloride ions in chlorine-containing sulfuric acid solution by adopting fluidized bed electrode
CN109293062A (en) * 2018-10-30 2019-02-01 华北电力大学（保定） A kind of flue gas method recycles the device of calcium and magnesium in desulfurization wastewater
CN111135692A (en) * 2018-11-05 2020-05-12 新疆硅基新材料创新中心有限公司 Method and system for recycling waste slurry obtained by power plant boiler flue gas desulfurization and denitrating power plant boiler flue gas
CN112387050A (en) * 2020-11-13 2021-02-23 攀枝花钢企欣宇化工有限公司 Magnesium electrolysis chlorine gas purification process

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