CN107253785A - A kind of Zero-discharge treating process of thermal power plant desulfurization wastewater - Google Patents

A kind of Zero-discharge treating process of thermal power plant desulfurization wastewater Download PDF

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Publication number
CN107253785A
CN107253785A CN201710706865.3A CN201710706865A CN107253785A CN 107253785 A CN107253785 A CN 107253785A CN 201710706865 A CN201710706865 A CN 201710706865A CN 107253785 A CN107253785 A CN 107253785A
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room feed
waste water
film device
feed liquids
electric drive
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Inventor
方毓淳
吴泽鹏
谈宾宾
李文扬
俞时智
朱元红
许莹莹
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Changxin Top Environment Technology Co Ltd
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Changxin Top Environment Technology Co Ltd
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • 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
    • C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
    • 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
    • C02F1/465—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electroflotation
    • 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
    • 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
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
    • 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
    • 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
    • C02F2101/101—Sulfur compounds
    • 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
    • C02F2101/14—Fluorine or fluorine-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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/02—Softening water by precipitation of the hardness

Abstract

The invention discloses a kind of Zero-discharge treating process of thermal power plant desulfurization wastewater, comprise the following steps：1) reaction tank reacts；2) electrolysis is handled；3) handled by High-rate sedimentation equipment integrating；4) handled by 1# electric drives film device, obtain being rich in SO4 2‑The light room feed liquids of 1# and rich in Cl‑The dense room feed liquids of 1#；5) by desulfurization island system to the processing of 1# light room feed liquids；6) the dense room feed liquids of 2# and the light room feed liquids of 2# are obtained to the processing of 1# dense room feed liquids by 2# electric drives film device；7) the light room feed liquids of 4# and the dense room feed liquids of 4# are obtained to the processing of 2# light room feed liquids by 4# electric drives film device；8) by 3# electric drives film device to the processing of 2# light room feed liquids.The present invention by the chemical reaction+electrochemical appliance+multivalence of High-rate sedimentation equipment integrating+one separate electric drive film+concentration electric drive film+bipolar dual-membrane process can in reuse desulfurization wastewater more than 90% moisture, while the Na in waste water can be utilized again2SO4And NaCl, production gypsum is without the bronsted lowry acids and bases bronsted lowry during procurement process.

Description

A kind of Zero-discharge treating process of thermal power plant desulfurization wastewater
Technical field
The present invention relates to thermal power plant desulfurization wastewater process field, more particularly, to a kind of thermal power plant desulfurization wastewater Zero-discharge treating process.
Background technology
At present, in the various desulfurization methods in thermal power plant, boiler smoke wet desulphurization occupies because its desulfuration efficiency is high Increasing ratio, but the shortcoming of the technique is waste water to be produced, and the pH value of waste water is 5~6, is suspended simultaneously containing substantial amounts of Thing (gypsum particle, SO2, Al and iron hydroxide), fluoride and As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Se, Sn, Zn etc. Heavy metal element, limestone scrubbing FGD handling process is used domestic power plant desulfurization more.In flue gas containing a small amount of from raw coal The F brought-And Cl-And various impurity, into desulfuration absorbing tower after be washed down and enter slurries, F-Join with the aluminium in slurries Cooperation produces screening effect with the dissolving to desulfurization absorbent lime stone, causes lime stone dissolubility to weaken, desulfuration efficiency reduction； Meanwhile, Cl-Excessive concentration has corrosiveness to absorption tower system and structure.Therefore, Limestone/Gypsum-based Wet Process Flue Gas Desulfuration It is generally necessary to a part of filtrate water (absorption tower slurries are produced after dehydration) be discharged as desulfurization wastewater, to reach control Cl-、F- Ion concentration and the purpose for maintaining absorption tower material balance.Because water quality is special, contaminative is strong, so desulfurization wastewater has to pass through Individually processing could be discharged, and very big pollution otherwise can be caused to environment.In addition, the comprehensive utilization ratio in order to improve water resource, Power plant typically can by reverse osmosis concentrated water, all kinds of drainings such as circulatory system sewer as wet method fume desulfurizing system technique water Source.Desulfurization wastewater turns into the worst waste water of coal-burning power plant's system end water quality.Therefore, advanced treating is carried out to desulfurization wastewater, Realize the new challenge that desulfurization wastewater " zero-emission " has turned into coal-burning power plant's planning and designing, environmentally friendly upgrading work faces.
Nowadays domestic heat power plant boiler flue gas desulfurization waste-water " zero-emission " treatment technology mainly has riverhead power plant desulfurization The permanent beneficial power plant desulfurization wastewater processing system of waste water zero emission system, three water, Huaneng Group Changxing power plant desulfurization wastewater processing system and State's electricity Hanchuan Power Plant desulfurization wastewater " zero-emission " system.Wherein, riverhead power plant desulfurization wastewater " zero-emission " system uses four Evaporation and crystallization system is imitated, is put into operation so far up to 7 years on December 18th, 2009, is domestic initiation, system maturation is reliable, produces water Reuse water standard is reached, generation sludge is brick-making raw material, and crystal salt is used in printing and dyeing mill, according to calculating, ton water process steam consumption Measure 300kg, power consumption 30kWh；The permanent beneficial power plant desulfurization wastewater processing system of three water was put into operation in 2012 so far up to 4 years, stable, Effluent quality reaches circulating cooling water quality requirement, because pretreatment simplifies, and produces crystal salt for carnallite, as fixed-end forces, According to calculating, ton water process steam consumption quantity 89.21kg, power consumption 26.63kWh；Huaneng Group Changxing power plant desulfurization wastewater processing system is used Positive infiltration technology, on April 5th, 2015, debugging terminated, and crystal salt main component is NaCl and Na2SO4, purity is more than 95%, mesh Preceding to study the system of transforming, NaCl purity to be improved provides condition for comprehensive utilization, according to calculating, ton water process steam consumption Measure 90kg, power consumption 8.3kWh；State's electricity Hanchuan Power Plant desulfurization wastewater " zero-emission " system use " TMF softenings+NF points of salt+ SWRO+DTRO+MVR " process routes, are currently under the debugging stage.Above-mentioned 4 desulfuration waste water treatment process routes have each Pros and Cons, but all there are the following problems：1) pre-treatment medicaments softening dosing cost is high, according to calculating, ton water softening medicament Cost is in 20-30 members/m3Left and right；2) the crystallization purity salt after evaporating relatively is difficult to ensure card, and solid waste (danger can only be used as when purity is low It is useless) processing, increase ton water process expense；3) evaporative crystallization processing cost is high, and steam consumption quantity and power consumption are high, processing cost height etc.. In order to overcome the defect of above-mentioned various commercial Application process route physical presence, the present invention is special to propose that has a softening medicament Cost is low, without evaporative crystallization the advantages of desulfurization wastewater " zero-emission " process route.
The content of the invention
In view of the above-mentioned problems, the invention provides a kind of Zero-discharge treating process of thermal power plant desulfurization wastewater, effectively The problem of solving to point out in background technology.
Technical scheme is as follows：
A kind of Zero-discharge treating process of thermal power plant desulfurization wastewater, comprises the following steps：
1), waste water is sent into reaction tank, and adds Ca (OH)2Reacted, remove the F contained in waste water-, part SO4 2-And Mg2+；
2), by step 1) treated waste water carries out electrolysis processing, further removes Mg2+, reduction waste water in NaCl and CODCr concentration, the micro-bubble that electrolysis is produced can play air flotation effect, the removal effect for suspension of increasing water quality；
3), by step 2) treated waste water feeding High-rate sedimentation equipment integrating, by adding NaOH, blast in air CO2, remove the Mg in waste water2+And Ca2+, make the total hardness of waste water in below 20mg/L, High-rate sedimentation equipment integrating water outlet passes through Add HCl regulations pH to 7.0-9.0；
4), by step 3) treated waste water feeding 1# electric drive film devices, made by the processing of 1# electric drive film devices Obtain the Cl in waste water-And SO4 2-Separation, obtains being rich in SO4 2-The light room feed liquids of 1# and rich in Cl-The dense room feed liquids of 1#；
5), by step 4) the light room feed liquid feeding desulfurization island system of obtained 1#, by with the Ca in desulfurization island slurries2+Reaction Form CaSO4And remove SO4 2-, obtain desulfurization wastewater；
6), by step 4) the dense room feed liquid feeding 2# electric drives film device of obtained 1# carries out concentration, obtains the dense rooms of 2# Feed liquid and the light room feed liquids of 2#；
7), by step 6) the light room feed liquid feeding 4# electric drives film device of obtained 2# carries out purified treatment, obtains the light rooms of 4# Feed liquid and the dense room feed liquids of 4#, the light room feed liquids of 4# are fresh water, and the dense room feed liquids of 4# are the salt solution of 1.5~2.0% concentration, the dense room feed liquids of 4# Be back to step 6) in 2# electric drive film devices water inlet end；
8), by step 6) the light room feed liquid feeding 3# electric drives film device of obtained 2# carries out electrolysis processing, salt room after electrolysis Brine strength reach step 6) in 2# electric drive film device water inlet ends concentration after be back to 2# electric drive film device water inlet ends, Alkali room feed liquid is back to step 3) in be used for the reaction zone dosing of High-rate sedimentation equipment integrating, sour room feed liquid is back to step 3) in The pH of High-rate sedimentation equipment integrating water outlet pulls back to 7.0-9.0.
Preferably, the step 1) in reaction tank be used for the Ca (OH) that adds2With the F in waste water-、SO4 2-、Mg2+Reaction Formed and mechanical stirring equipment and high efficient aeration equipment are provided with insoluble substance, reaction tank, for improving waste water in reaction tank Reaction efficiency.
Preferably, the step 2) in waste water is electrolysed using electrochemical appliance, described electrochemical appliance bag Electrode, rectifier, pond body equipment and cable are included, described electrode is the steel of iron content.
Preferably, described electrochemical appliance is in the process of running with the rise of rectifier current output, electrode is not Disconnected dissolving forms Fe2+, flocculation crane span structure effect is played in waste water, the NaOH that negative electrode is produced can further remove the Mg in waste water2 +, the H of generation2There is air flotation effect in waste water, the clearance of suspension in waste water, the Cl that anode is produced can be improved2It can aoxidize useless COD in reducing substances and most of organic matter in water, reduction waste waterCr, improve the stability of aftertreatment systems.
Preferably, the step 3) in High-rate sedimentation equipment integrating be provided with adding of agent area, reaction zone and settling zone, Described adding of agent area adds entrance provided with NaOH, the outlet conduit of the High-rate sedimentation equipment integrating provided with HCl add into Mouthful.
Preferably, the step 4) in 1# electric drives film device for a multivalent ion separate electric drive film device, institute State step 6) in 2# electric drives film device be using homogeneous ion-exchange membrane concentration electric drive film device, the step 8) in 3# electric drives film device be bipolar membrane device, the step 7) in 4# electric drives film device to use homogeneous ion-exchange membrane Concentration electric drive film device.
Preferably, described 1# electric drives film device carries out a point salt treatment to the water outlet of High-rate sedimentation equipment integrating, obtain With the dense room feed liquids of 1# rich in NaCl and rich in Na2SO4The light room feed liquids of 1#, the light room feed liquids of described 1# deliver to desulfurization island system, With the Ca in the loop slurry of desulfurization island system2+Reaction forms CaSO4And remove SO4 2-。
Preferably, after described 3# electric drive film devices electrolysis processing, the sour room feed liquid of formation is 2.5mol/L concentration HCl solution, alkali room feed liquid be 3.2mol/L concentration NaOH solution.
Present invention also offers a kind of zero-discharge treatment system of thermal power plant desulfurization wastewater, including：
Reaction tank, by toward adding Ca (OH) in reaction tank2, remove the F contained in waste water-, part SO4 2-And Mg2+；
Electrochemical appliance, Mg is further removed by electrochemical appliance to the water electrolysis processing that goes out of reaction tank2+, reduce waste water In NaCl and CODCrConcentration, the micro-bubble of generation can play air flotation effect, the removal effect for suspension of increasing water quality；
High-rate sedimentation equipment integrating, electrochemical appliance water outlet enters High-rate sedimentation equipment integrating, High-rate sedimentation equipment integrating By adding NaOH, the CO in air is blasted2, remove the Mg in waste water2+And Ca2+, make the total hardness of waste water in below 20mg/L, The water outlet of High-rate sedimentation equipment integrating adjusts pH to 7.0-9.0 by adding HCl；
1# electric drive film devices, High-rate sedimentation equipment integrating water outlet enters 1# electric drive film devices, passes through 1# electric drive films The processing of device causes the Cl in waste water-And SO4 2-Separation, obtains being rich in SO4 2-The light room feed liquids of 1# and rich in Cl-The dense rooms of 1# Feed liquid；
Desulfurization island system, the light room feed liquids of 1# that 1# electric drive film devices are obtained are back to desulfurization island system, by with desulfurization Ca in the slurries of island2+Reaction forms CaSO4And remove SO4 2-, obtain desulfurization wastewater；
2# electric drive film devices, the dense room feed liquids of 1# that 1# electric drive film devices are obtained enter 2# electric drives film and carried out at concentration Reason, obtains the dense room feed liquids of 2# and the light room feed liquids of 2#；
4# electric drive film devices, the light room feed liquids of 2# for being obtained to 2# electric drive film devices carry out purified treatment, obtain The light room feed liquids of 4# and the dense room feed liquids of 4#, the light room feed liquids of 4# are fresh water, and the dense room feed liquids of 4# are the salt solution of 1.5~2.0% concentration, and 4# is dense The dense room feed liquids of 1# that the water inlet end that room feed liquid is recycled to 2# electric drive film devices is obtained with 1# electric drive film devices are mixed；
3# electric drive film devices, for carrying out electrolysis processing to the dense room feed liquids of 2#, the brine strength of salt room reaches after electrolysis 2# electric drive film device water inlet ends are back to after the concentration of 2# electric drive film device water inlet ends, alkali room feed liquid is used for High-rate sedimentation one The reaction zone dosing of body equipment, the pH that sour room feed liquid is used for High-rate sedimentation equipment integrating water outlet pulls back to 7.0-9.0.
Preferably, described reaction tank is used for the Ca (OH) added2With the F in waste water-、SO4 2-、Mg2+Reaction is formed not Mechanical stirring equipment and high efficient aeration equipment are provided with soluble substance, reaction tank, the reaction for improving waste water in reaction tank is imitated Rate.
Preferably, described electrochemical appliance includes electrode, rectifier, pond body equipment and cable, described electrode is For the steel of iron content.
Preferably, described electrochemical appliance is in the process of running with the rise of rectifier current output, electrode is not Disconnected dissolving forms Fe2+, flocculation crane span structure effect is played in waste water, the NaOH that negative electrode is produced can further remove the Mg in waste water2 +, the H of generation2There is air flotation effect in waste water, the clearance of suspension in waste water, the Cl that anode is produced can be improved2It can aoxidize useless COD in reducing substances and most of organic matter in water, reduction waste waterCr, improve the stability of aftertreatment systems.
Preferably, the High-rate sedimentation equipment integrating is provided with adding of agent area, reaction zone and settling zone, described medicament Add area and add entrance provided with NaOH, the outlet conduit of the High-rate sedimentation equipment integrating adds entrance provided with HCl.
Electric drive film device, described 2# electricity are separated preferably, described 1# electric drives film device is a multivalent ion It is the concentration electric drive film device using homogeneous ion-exchange membrane to drive film device, and described 3# electric drives film device is Bipolar Membrane Device, described 4# electric drives film device is the concentration electric drive film device using homogeneous ion-exchange membrane.
Preferably, described 1# electric drives film device carries out a point salt treatment to the water outlet of High-rate sedimentation equipment integrating, obtain With the dense room feed liquids of 1# rich in NaCl and rich in Na2SO4The light room feed liquids of 1#, the light room feed liquids of described 1# are back to desulfurization island system System, with the Ca in the loop slurry of desulfurization island system2+Reaction forms CaSO4And remove SO4 2-。
Preferably, after described 3# electric drive film devices electrolysis processing, the sour room feed liquid of formation is 2.5mol/L concentration HCl solution, alkali room feed liquid be 3.2mol/L concentration NaOH solution.
Electrochemical appliance is the sewage treatment equipment for being provided with the electrode containing Fe, mainly including rectifier, electrode, pond body and electricity Cable etc., by the DC electric field of rectifier, there is redox reaction in electrode, and negative electrode constantly produces NaOH and H2, anode is continuous Produce Cl2, the Mg in waste water can typically be reduced by the electrolysis of electrochemical appliance2+, the inorganic ions such as heavy metal, and can lead to Cross the Cl produced2The content of organics in waste water is reduced, and is electrolysed the H produced2It can play again in air supporting effect, reduction waste water Suspension content.
Electric drive membrane technology refers in the case where electric field force is acted on ion by the membrane separating process of selective ion exchange membrane, its Core is anion and cation exchange membrane, i.e., only allow cation to pass through using cation-exchange membrane, anion-exchange membrane is only permitted Perhaps the characteristic that anion passes through carries out the technology of Selective Separation to effects of ion, under electric field force effect, the moon in solution Directional migration occurs for cation, and another part water body is moved to from a part of water body, so as to reach solution separation, purification and concentrate Purpose, the appearance of Bipolar Membrane makes electrodialytic purposes be expanded, and Bipolar Membrane is by anion-exchange membrane and cation exchange What film was composited, be commonly referred to as intermediate catalyst layer two layers of centre, its principle is：It is molten when adding voltage in Bipolar Membrane both sides Directional migration can occur for the ion in liquid, and at the same time hydrone can enter intermediate catalyst layer through anion and cation exchange membrane, Occur electrolytically generated hydrogen ion and hydroxide ion under the effect of both sides active group, charge carrier is served as with this, consumption Water permeates further through the water in surrounding medium and supplemented to film intermediate layer, compared with conventional electrodialysis, in Bipolar Membrane effect Lower water decomposition speed is enhanced more than 5 thousands of times, therefore energy consumption is substantially reduced, and electrodialytic application also extends significantly.It is double Pole EDBM falls within electrodialysis application, be by the way that Bipolar Membrane is combined with amberplex, constitute it is different every Room (sour room, alkali room and feed liquid room), makes it have the advantage of uniqueness in soda acid preparation field, under certain voltage effect, negative and positive Ion can be respectively by anion and cation exchange membrane, and the hydrogen ion and hydroxide ion produced with Bipolar Membrane combines the corresponding acid of generation And alkali.
Beneficial effects of the present invention are as follows：
1) electric drive film+concentration electricity, is separated by chemical reaction+electrochemical appliance+multivalence of High-rate sedimentation equipment integrating+one Drive membrane+bipolar dual-membrane process can in reuse desulfurization wastewater more than 90% moisture, while again can be in recycling waste water Na2SO4And NaCl, produce gypsum and without the bronsted lowry acids and bases bronsted lowry during procurement process；
2) Ca (OH) can be reduced by, handling desulfurization wastewater by group technology2Chemical feeding quantity and CaSO4Yield, further subtract Few processing cost, improves the stability of electrochemical appliance operation；
3) CaSO, can be improved by electrochemical appliance4Settling rate, and the COD in waste water can be removedCr, improve system The stability of operation；
4) strong brine, is handled by bipolar membrane device and had not both needed the evaporative crystallization processing system of high energy consumption, and can be improved Resource utilization in waste water；
5) the solid waste disposal expense produced by evaporative crystallization processing method, can be removed by the present invention, to a certain degree On reduce the zero discharge treatment cost of desulfurization wastewater；
6), the present invention has economic benefit and social benefit concurrently, with research and extension value.
Brief description of the drawings
Fig. 1 is flowage structure schematic diagram of the invention.
Embodiment
The present invention is described in further detail below by specific embodiment and with reference to accompanying drawing.
Embodiment 1
A kind of Zero-discharge treating process of thermal power plant desulfurization wastewater, comprises the following steps：
1), waste water is sent into reaction tank, and adds Ca (OH)2Reacted, Ca (OH)2With the F in waste water-、SO4 2-、 Mg2+Reaction forms insoluble substance, removes the F contained in waste water-, part SO4 2-And Mg2+, reaction tank is interior to be set provided with mechanical agitation Standby and high efficient aeration equipment, the reaction efficiency for improving waste water in reaction tank；
2), by step 1) treated waste water feeding electrochemical appliance is electrolysed, and further removes Mg2+, reduce waste water In NaCl and CODCr concentration, described electrochemical appliance includes electrode, rectifier, pond body equipment and cable, described electrode For the steel for iron content, electrochemical appliance is in the process of running with the rise of rectifier current output, and electrode constantly dissolves shape Into Fe2+, flocculation crane span structure effect is played in waste water, the NaOH that negative electrode is produced can further remove the Mg in waste water2+, the H of generation2 There is air flotation effect in waste water, the clearance of suspension in waste water, the Cl that anode is produced can be improved2Reduction in energy oxidized waste water Property material and most of organic matter, the COD in reduction waste waterCr, improve the stability of aftertreatment systems；
3), by step 2) treated waste water feeding High-rate sedimentation equipment integrating, by adding NaOH, blast in air CO2, remove the Mg in waste water2+And Ca2+, make the total hardness of waste water in below 20mg/L, High-rate sedimentation equipment integrating water outlet passes through HCl regulation pH to 7.0-9.0 are added, High-rate sedimentation equipment integrating is provided with adding of agent area, reaction zone and settling zone, described medicine Agent adds area and adds entrance provided with NaOH, and the outlet conduit of the High-rate sedimentation equipment integrating adds entrance provided with HCl；
4), by step 3) treated waste water feeding 1# electric drive film devices, 1# electric drives film device is to High-rate sedimentation one The water outlet of body equipment carries out a point salt treatment, obtains with the dense room feed liquids of 1# rich in NaCl and rich in Na2SO4The light room feed liquids of 1#, it is described The light room feed liquids of 1# deliver to desulfurization island system, with the Ca in the loop slurry of desulfurization island system2+Reaction forms CaSO4And remove SO4 2, 1# electric drives film device is that a multivalent ion separates electric drive film device；
5), by step 4) the light room feed liquid feeding desulfurization island system of obtained 1#, by with the Ca in desulfurization island slurries2+Reaction Form CaSO4And remove SO4 2-, obtain desulfurization wastewater；
6), by step 4) the dense room feed liquid feeding 2# electric drives film device of obtained 1# carries out concentration, obtains the dense rooms of 2# Feed liquid and the light room feed liquids of 2#, 2# electric drives film device are the concentration electric drive film device using homogeneous ion-exchange membrane；
7), by step 6) the light room feed liquid feeding 4# electric drives film device of obtained 2# carries out purified treatment, obtains the light rooms of 4# Feed liquid and the dense room feed liquids of 4#, the light room feed liquids of 4# are fresh water, and the dense room feed liquids of 4# are the salt solution of 1.5~2.0% concentration, the dense room feed liquids of 4# Be back to step 6) in 2# electric drive film devices water inlet end, 4# electric drives film device be using homogeneous ion-exchange membrane concentration Electric drive film device；
8), by step 6) the light room feed liquid feeding 3# electric drives film device of obtained 2# carries out electrolysis processing, 3# electric drive films After device electrolysis processing, the sour room feed liquid of formation is the HCl solution of 2.5mol/L concentration, and alkali room feed liquid is 3.2mol/L concentration The brine strength of salt room reaches step 6 after NaOH solution, electrolysis) in 2# electric drive film device water inlet ends concentration after be back to 2# Electric drive film device water inlet end, alkali room feed liquid is back to step 3) in be used for High-rate sedimentation equipment integrating reaction zone dosing, acid Room feed liquid is back to step 3) in the pH of High-rate sedimentation equipment integrating water outlet pull back to 7.0-9.0,3# electric drive film devices are double Pole film device.
Embodiment 2
As shown in figure 1, a kind of zero-discharge treatment system of thermal power plant desulfurization wastewater, including：
Reaction tank, by toward adding Ca (OH) in reaction tank2, with the F in waste water-、SO4 2-、Mg2+Reaction forms insoluble Material, so as to remove the F contained in waste water-, part SO4 2-And Mg2+, reaction tank is interior to be provided with mechanical stirring equipment and high efficient aeration Equipment, the reaction efficiency for improving waste water in reaction tank；
Electrochemical appliance, electrochemical appliance includes electrode, rectifier, pond body equipment and cable, and electrode is the steel of iron content Material, Mg is further removed by electrochemical appliance to the water electrolysis processing that goes out of reaction tank2+, reduce the NaCl and COD in waste waterCr Concentration, the micro-bubble of generation can play air flotation effect, the removal effect for suspension of increasing water quality, and electrochemical appliance is in running In with the rise of rectifier current output, electrode constantly dissolving forms Fe2+, flocculation crane span structure effect, negative electrode are played in waste water The NaOH of generation can further remove the Mg in waste water2+, the H of generation2There is air flotation effect in waste water, can improve in waste water and suspend The clearance of thing, the Cl that anode is produced2In reducing substances and most of organic matter in energy oxidized waste water, reduction waste water CODCr, improve the stability of aftertreatment systems；
High-rate sedimentation equipment integrating, electrochemical appliance water outlet enters High-rate sedimentation equipment integrating, High-rate sedimentation equipment integrating Provided with adding of agent area, reaction zone and settling zone, described adding of agent area adds entrance, the High-rate sedimentation one provided with NaOH The outlet conduit of body equipment adds entrance provided with HCl, and High-rate sedimentation equipment integrating blasts the CO in air by adding NaOH2, Remove the Mg in waste water2+And Ca2+, make the total hardness of waste water in below 20mg/L, High-rate sedimentation equipment integrating water outlet is by adding HCl adjusts pH to 7.0-9.0；
1# electric drive film devices, High-rate sedimentation equipment integrating water outlet enters 1# electric drive film devices, 1# electric drive film devices A point salt treatment is carried out to the water outlet of High-rate sedimentation equipment integrating, obtained with the dense room feed liquids of 1# rich in NaCl and rich in Na2SO41# Light room feed liquid, the light room feed liquids of 1# are back to desulfurization island system, with the Ca in the loop slurry of desulfurization island system2+Reaction is formed CaSO4And remove SO4 2-, 1# electric drives film device is that a multivalent ion separates electric drive film device；
Desulfurization island system, the light room feed liquids of 1# that 1# electric drive film devices are obtained are back to desulfurization island system, by with desulfurization Ca in the slurries of island2+Reaction forms CaSO4And remove SO4 2-, obtain desulfurization wastewater；
2# electric drive film devices, the dense room feed liquids of 1# that 1# electric drive film devices are obtained enter 2# electric drives film and carried out at concentration Reason, obtains the dense room feed liquids of 2# and the light room feed liquids of 2#, and 2# electric drives film device is the concentration electric drive using homogeneous ion-exchange membrane Film device；
4# electric drive film devices, the light room feed liquids of 2# for being obtained to 2# electric drive film devices carry out purified treatment, obtain The light room feed liquids of 4# and the dense room feed liquids of 4#, the light room feed liquids of 4# are fresh water, and the dense room feed liquids of 4# are the salt solution of 1.5~2.0% concentration, and 4# is dense The dense room feed liquids of 1# that the water inlet end that room feed liquid is recycled to 2# electric drive film devices is obtained with 1# electric drive film devices are mixed, and 4# electricity drives Dynamic film device is the concentration electric drive film device using homogeneous ion-exchange membrane；
3# electric drive film devices, for carrying out electrolysis processing to the dense room feed liquids of 2#, after 3# electric drive film devices electrolysis processing, The sour room feed liquid of formation is the HCl solution of 2.5mol/L concentration, and alkali room feed liquid is the NaOH solution of 3.2mol/L concentration, after electrolysis The brine strength of salt room, which reaches, is back to 2# electric drive film device water inlet ends, alkali room after the concentration of 2# electric drive film device water inlet ends Feed liquid is used for the reaction zone dosing of High-rate sedimentation equipment integrating, and the pH that sour room feed liquid is used for High-rate sedimentation equipment integrating water outlet is adjusted back To 7.0-9.0,3# electric drives film device is bipolar membrane device.

Claims (8)

1. a kind of Zero-discharge treating process of thermal power plant desulfurization wastewater, it is characterised in that comprise the following steps：
1), waste water is sent into reaction tank, and adds Ca (OH)2Reacted, remove the F contained in waste water-, part SO4 2-With Mg2+；
2), by step 1) treated waste water carries out electrolysis processing, further removes Mg2+, reduce the NaCl and CODCr in waste water Concentration, the micro-bubble that electrolysis is produced can play air flotation effect, the removal effect for suspension of increasing water quality；
3), by step 2) treated waste water feeding High-rate sedimentation equipment integrating, by adding NaOH, blast the CO in air2, Remove the Mg in waste water2+And Ca2+, make the total hardness of waste water in below 20mg/L, High-rate sedimentation equipment integrating water outlet is by adding HCl adjusts pH to 7.0-9.0；
4), by step 3) treated waste water feeding 1# electric drive film devices, to give up by the processing of 1# electric drive film devices Cl in water-And SO4 2-Separation, obtains being rich in SO4 2-The light room feed liquids of 1# and rich in Cl-The dense room feed liquids of 1#；
5), by step 4) the light room feed liquid feeding desulfurization island system of obtained 1#, by with the Ca in desulfurization island slurries2+Reaction is formed CaSO4And remove SO4 2-, obtain desulfurization wastewater；
6), by step 4) the dense room feed liquid feeding 2# electric drives film device of obtained 1# carries out concentration, obtains the dense room feed liquids of 2# With the light room feed liquids of 2#；
7), by step 6) the light room feed liquid feeding 4# electric drives film device of obtained 2# carries out purified treatment, obtains the light room feed liquids of 4# With the dense room feed liquids of 4#, the light room feed liquids of 4# are fresh water, and the dense room feed liquids of 4# are the salt solution of 1.5~2.0% concentration, and the dense room feed liquids of 4# are returned To step 6) in 2# electric drive film devices water inlet end；
8), by step 6) the light room feed liquid feeding 3# electric drives film device of obtained 2# carries out electrolysis processing, the salt of salt room after electrolysis Water concentration reaches step 6) in 2# electric drive film device water inlet ends concentration after be back to 2# electric drive film device water inlet ends, alkali room Feed liquid is back to step 3) in be used for the reaction zone dosing of High-rate sedimentation equipment integrating, sour room feed liquid is back to step 3) in efficiently The pH of precipitation equipment integrating water outlet pulls back to 7.0-9.0.
2. a kind of Zero-discharge treating process of thermal power plant desulfurization wastewater according to claim 1, it is characterised in that institute State step 1) in reaction tank be used for the Ca (OH) that adds2With the F in waste water-、SO4 2-、Mg2+Reaction forms insoluble substance, reacts Mechanical stirring equipment and high efficient aeration equipment, the reaction efficiency for improving waste water in reaction tank are provided with pond.
3. a kind of Zero-discharge treating process of thermal power plant desulfurization wastewater according to claim 1 or 2, its feature exists In the step 2) in waste water is electrolysed using electrochemical appliance, described electrochemical appliance including electrode, rectifier, Pond body equipment and cable, described electrode are the steel of iron content.
4. a kind of Zero-discharge treating process of thermal power plant desulfurization wastewater according to claim 3, it is characterised in that institute The electrochemical appliance stated is in the process of running with the rise of rectifier current output, and electrode constantly dissolving forms Fe2+, in waste water In play flocculation crane span structure effect, negative electrode produce NaOH can further remove the Mg in waste water2+, the H of generation2There is gas in waste water Floating effect, can improve the clearance of suspension in waste water, the Cl that anode is produced2Reducing substances and big portion in energy oxidized waste water The COD divided in organic matter, reduction waste waterCr, improve the stability of aftertreatment systems.
5. a kind of Zero-discharge treating process of thermal power plant desulfurization wastewater according to claim 4, it is characterised in that institute State step 3) in High-rate sedimentation equipment integrating be provided with adding of agent area, reaction zone and settling zone, described adding of agent area is set There is NaOH to add entrance, the outlet conduit of the High-rate sedimentation equipment integrating adds entrance provided with HCl.
6. a kind of Zero-discharge treating process of thermal power plant desulfurization wastewater according to claim 5, it is characterised in that institute State step 4) in 1# electric drives film device for a multivalent ion separate electric drive film device, the step 6) in 2# electric drives Film device be using homogeneous ion-exchange membrane concentration electric drive film device, the step 8) in 3# electric drive film devices be double Pole film device, the step 7) in 4# electric drives film device be using homogeneous ion-exchange membrane concentration electric drive film device.
7. a kind of Zero-discharge treating process of thermal power plant desulfurization wastewater according to claim 6, it is characterised in that institute The 1# electric drives film device stated carries out point salt treatment to the water outlet of High-rate sedimentation equipment integrating, obtains with the dense room material of 1# rich in NaCl Liquid and rich in Na2SO4The light room feed liquids of 1#, the light room feed liquids of described 1# deliver to desulfurization island system, the recycle slurry with desulfurization island system Ca in liquid2+Reaction forms CaSO4And remove SO4 2-。
8. a kind of Zero-discharge treating process of thermal power plant desulfurization wastewater according to claim 7, it is characterised in that institute After the 3# electric drive film devices electrolysis processing stated, the sour room feed liquid of formation is the HCl solution of 2.5mol/L concentration, and alkali room feed liquid is The NaOH solution of 3.2mol/L concentration.
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