CN109437448A - Pb-Zn deposits beneficiation wastewater treatment for reuse devices and methods therefor - Google Patents

Pb-Zn deposits beneficiation wastewater treatment for reuse devices and methods therefor Download PDF

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CN109437448A
CN109437448A CN201811411588.4A CN201811411588A CN109437448A CN 109437448 A CN109437448 A CN 109437448A CN 201811411588 A CN201811411588 A CN 201811411588A CN 109437448 A CN109437448 A CN 109437448A
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water
deposits
beneficiation wastewater
reuse
pump
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张博
戚可卓
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Jiangsu Zhuo Bo Environmental Protection Technology Co Ltd
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Jiangsu Zhuo Bo Environmental Protection 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • 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
    • C02F1/52—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
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • 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
    • C02F2101/30—Organic 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
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/14—Maintenance of water treatment installations
    • 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 present invention is Pb-Zn deposits beneficiation wastewater treatment for reuse devices and methods therefor, has the characteristics that high calcium, high pH, high suspended matter, high COD(COD mainly for Pb-Zn deposits beneficiation wastewater) and contain a large amount of beneficiation reagents and heavy metal ion；Using the calcium hydroxide reaction and precipitating in liquid CO 2 and waste water, while deliming, drop pH；And then organic pollutant is aoxidized using the strong oxidizer that cavitation and electrochemistry generate, degrade COD；Finally, being finally completed system deliming, removing heavy metals, drop COD, the target for dropping suspended matter by film filtering；Processing water outlet is transmitted back to Pb-Zn deposits mineral processing production process, reaches water-saving and emission-reducing, and guarantees the purpose that ore-sorting system operates normally.

Description

Pb-Zn deposits beneficiation wastewater treatment for reuse devices and methods therefor
Technical field
The present invention relates to Pb-Zn deposits beneficiation wastewater treatment for reuse devices and methods therefors, belong to the skill of Industrial Wastewater Treatment Art field.
Background technique
There are lead and zinc mineral resources abundant in China, plays a significant role in national economy, and lead zinc metal is widely applied In the industries such as metallurgy, mechanical, electrical, petrochemical industry, light industry, military project.A large amount of lime, carbon are added in usual Pb-Zn deposits ore dressing process The medicaments such as sour sodium, zinc sulfate, copper sulphate, xanthate class, black powder class, resulting Pb-Zn deposits beneficiation wastewater complicated component, have High pH, high Ca2+(calcium ion), high COD(COD), high suspended matter, the characteristics of containing heavy metal ion, if direct emission It will cause the serious pollution of soil and water source environment, and only simple process reuse, it not only will affect the index of Pb-Zn deposits ore dressing, it is long Phase operation due to a large amount of calcium sulfate scale can also Severe blockage process pipe, influence the production of Pb-Zn deposits ore dressing.
Traditional Pb-Zn deposits beneficiation wastewater treatment for reuse method at present are as follows: " sulfuric acid tune pH, alum coagulation, sodium carbonate deliming, The organic beneficiation reagent of powder electroless plating, precipitating effluent reuse "；And how golden a kind of lead zinc sulphur of patent 201610650335.7 is Belong to the quick processing system of ore dressing complexity waste water, main technique be " sodium carbonate remove hard precipitating, sulfuric acid tune pH, (heavy metal settling agent, Flocculant) coagulating sedimentation, the absorption of sulfuric acid souring activity charcoal, sodium hydroxide tune pH, two heavy, effluent reuses "；Due to largely to add Sulfuric acid and sodium carbonate is more expensive, can throw sodium carbonate less in actual motion, treatment effect is bad.Existing patent is such as 200410014572.1 method for cyclic utilizing mineral dressing waste water from sulphur ore of lead-zinc, main technique are " sulfuric acid and defoaming agent tune pH, (coagulation Agent, flocculant) coagulating sedimentation, activated carbon adsorption, effluent reuse "；And a kind of 201010244646.6 lead-zinc sulfide ore ore dressing Wastewater treatment and reuse method, main technique are " sulfuric acid tune pH, ferrous sulfate oxidation, polyacrylamide flocculation, precipitating, dioxy Change oxychloride, the absorption of active-carbon bed or porous ceramic grain catalysis oxidation "；It, which is equally existed, largely adds sulfuric acid drop pH, and active carbon is inhaled The bad problem of attached drop COD effect.
Summary of the invention
Proposed by the present invention is a kind of Pb-Zn deposits beneficiation wastewater treatment for reuse devices and methods therefor, and purpose aims to solve the problem that lead The problems in zinc ore beneficiation wastewater processing, using adding LCO2(liquid CO 2) deliming, drop pH, electrochemistry and cavitation aoxidize COD and removing heavy metals, precipitating and film filtering completion system deliming, removing heavy metals, drop COD, the purpose for dropping suspended matter drop in organic matter, Effluent reuse is to Pb-Zn deposits ore dressing.Pb-Zn deposits beneficiation wastewater pH:10~12.5 before handling are discharged pH:6~9, before processing after processing Pb-Zn deposits beneficiation wastewater Ca2+: 100~700mg/L is discharged Ca after processing2+:≤40mg/L, removal rate reach 60~94.3%, place Pb-Zn deposits beneficiation wastewater COD:100~300mg/L before managing, be discharged COD after processing :≤60mg/L, removal rate reach 40~80%, Pb-Zn deposits beneficiation wastewater SS(suspended matter before handling): 100~1000mg/L is discharged SS after processing :≤10mg/L, removal rate reach 90~99%, meanwhile, the heavy metal being discharged after processing entirely reaches " lead, Zn Cr coating pollutant emission standard " (GB25466- 2010) limit value.
Technical solution of the invention: Pb-Zn deposits beneficiation wastewater treatment for reuse device, structure include reaction tank RT, sink Shallow lake pond ST, electrochemical appliance EC, digestion pool HT, membrane separation device MSD, cavitation reactor CR, Pb-Zn deposits beneficiation wastewater case WWT, Reuse water tank RCWT, coagulant and flocculation aid throwing device D1, feeding apparatus for powdered activated charcoal D2, liquid CO 2 add dress Set D3And raw water pump P1, suction water pump P2, reuse water pump P3, gas-liquid mixing pump P4, sludge reflux pump P5, sludge pump P6, backwash Water pump P7；Wherein Pb-Zn deposits beneficiation wastewater PbZnTWW accesses the water inlet of Pb-Zn deposits beneficiation wastewater case WWT, and Pb-Zn deposits ore dressing is useless The water outlet of water tank WWT passes through raw water pump P1Connect the water inlet of reaction tank RT, coagulant and flocculation aid throwing device D1Drug The feeding opening of mouth connection reaction tank RT, the inlet of the liquid outlet connection reaction tank RT of cavitation reactor CR, in reaction tank RT It is anti-that cavitation oxygenolysis organic pollutant, carbon dioxide deliming drop pH, coagulation and flocculation etc. are carried out for Pb-Zn deposits beneficiation wastewater It answers；The water inlet of the water outlet connection sedimentation basin ST of reaction tank RT falls the CaCO that reaction generates in sedimentation basin ST precipitating3(carbonic acid Calcium) and big wadding body object, deliming is completed, pH is reduced, reduces COD and suspended matter；The mud mouth of sedimentation basin ST is returned by sludge Stream pump P5The mud inlet for connecting reaction tank RT is reduced the dosage of coagulant and flocculation aid using returned sludge, and improves precipitating Effect；Meanwhile the mud mouth of sedimentation basin ST is passed through into sludge pump P6Excess sludge ES(is sent out to tailing thickening pond)；Sedimentation basin ST Inlet and outlet connection electrochemical appliance EC water inlet, utilize electrochemical appliance EC generate hydroxy radical (OH) and hypochlorous acid Root (OCl-) organic pollutant is further aoxidized, reduce COD；The water inlet of the water outlet connection digestion pool HT of electrochemical appliance EC Mouthful, feeding apparatus for powdered activated charcoal D2Medicine outlet connection digestion pool HT feeding opening, further reacted using digestion pool HT Extra oxidant, meanwhile, using Powdered Activated Carbon filtrating aid function, enhance the filter effect of membrane separation device MSD；Digestion pool HT Water outlet connection membrane separation device MSD water inlet, filtered using submerged ultrafiltration, further decrease the CaCO in water3、 COD, suspended matter and turbidity obtain the recycle-water of high-quality；The water outlet of membrane separation device MSD passes through suction water pump P2It connects back to Pass through backwash water pump P with the backwash water water outlet of the water inlet of water tank RCWT, reuse water tank RCWT7Connect membrane separation device MSD Backwash water water inlet, membrane separation device MSD backwash water water outlet connection reaction tank RT water return outlet, by membrane separation device The backwash draining of MSD is recycled；The water outlet of reuse water tank RCWT passes through reuse water pump P3Recycle-water RCW is sent out, is reached To by Pb-Zn deposits beneficiation wastewater treatment for reuse in the purpose of production.
Have the characteristics that high calcium, high pH for Pb-Zn deposits beneficiation wastewater, deliming, the drop optimal method of pH are to utilize to add LCO2Ca (OH) in (liquid CO 2) and waste water2(calcium hydroxide) reaction, generates CaCO3(calcium carbonate) and H2O(water). It realizes while precipitating removes Ca2+(calcium ion) reduces pH, and reduces TDS(total dissolved solidss).And conventional calcium removal methods are to utilize Add Na2CO3(sodium carbonate) and Ca2+(calcium ion) it reacts, form CaCO3Precipitating, because sodium carbonate is more expensive, and 2 Na+(sodium Ion) 1 Ca of ratio2+(calcium ion) is heavier, so not only operating cost is high, but also increases the TDS and pH value of water, causes drop pH When, to add more sulfuric acid.Its main chemical reactions equation is as follows:
CO2 + Ca(OH)2 = CaCO3↓ + H2O ①
Na2CO3 + Ca(OH)2 = CaCO3↓ + 2NaOH ②
For more organic beneficiation reagent is contained in Pb-Zn deposits beneficiation wastewater, have the characteristics that high COD, has using cavitation oxidation Machine pollutant, degrade COD.Hydrodynamic cavitation refers to that water flow generates pressure drop quickly through restricted zone, so that local pressure is less than accordingly At a temperature of saturated vapour pressure, the moment for generating bubble crumbles and fall, and local high temperature and height are generated in minimum cavitation range Pressure, the hydrogen-oxygen bond fission in water form H(hydrogen-based), OH(hydroxy radical) etc. free radicals, to reach reduction organic contamination The purpose of object.
For in Pb-Zn deposits beneficiation wastewater contain more organic beneficiation reagent, such as butyl xanthate (CH3CH2CH2CH2OSSNa), aniline aerofloat ((C6H5NH)2PSSH) etc., have the characteristics that high COD, has using electrochemical oxidation Machine pollutant, come the COD that degrades.It is as follows with indirect oxidation that electrochemistry oxygen is divided into direct oxidation:
1) direct oxidation: OH(hydroxy radical in water) there is strong oxidizing property, it has no and selectively aoxidizes various organic pollutants.Directly The electrode reaction for connecing oxidation is as follows:
2H2O → 2·OH + 2H+ + 2e- ③
Organic matter+OH → CO2↑ + H2O ④
2) indirect oxidation: when containing the Cl of higher concentration in water-When (chloride ion), Cl-In anode ejected electron, Cl is formed2(chlorine Gas), ClO is further formed in the solution-(hypochlorite), ClO-Organic pollutant can be aoxidized, COD is reduced.It is reacted such as Under:
Anode: 4OH-→ 2H2O + O2↑ +4e- ⑤
2Cl-→ Cl2↑ + 2e- ⑥
In water: Cl2 + H2O → ClO- + H+ + Cl- ⑦
Organic matter+ClO-→ CO2↑ + H2O ⑧
For remaining tiny CaCO after oxidation, coagulation, precipitating in Pb-Zn deposits beneficiation wastewater3Particle, suspended matter and part are organic Without wadding body, system deliming, removing heavy metals, drop COD, the purpose for dropping suspended matter are finally completed using film filtering.Here, film filtering system System selects immersion hyperfiltration technique, and submerged ultrafiltration has the characteristics that stain resistance is strong, the water source for being suitble to influent quality poor. Ultrafiltration membrane selects submerged hollow fibre membrane module in bioreactor, is made of PVDF hollow-fibre membrane, has permanent hydrophilic, the pollution of film Weaken significantly, there is excellent long-term resistance tocrocking, guarantees that ultrafiltration membrane has stable strainability.
Pb-Zn deposits beneficiation wastewater treatment for reuse method, includes the following steps:
1) Pb-Zn deposits beneficiation wastewater after Pb-Zn deposits beneficiation wastewater case, raw water pump pressurization by sending；
2) Pb-Zn deposits beneficiation wastewater and coagulant and flocculation aid are carried out by coagulation and flocculation reaction by reaction tank, generates larger wadding Body；
3) liquid CO 2 dissolved through gas-liquid mixing pump is added to by reaction tank by cavitation reactor, carries out deliming, drop PH reaction；
4) it is precipitated by sedimentation basin, sends returned sludge back to reaction tank using sludge reflux pump, be discharged using sludge pump surplus Remaining sludge；
5) organic pollutants are aoxidized by electrochemical appliance；
6) organic pollutants, and the oxidant that stripping is extra are further aoxidized by digestion pool, by adding powder activity Charcoal increases absorption and filtrating aid function；
7) pass through membrane separation device and suction water pump final filtration, complete system deliming, removing heavy metals, drop COD, drop suspended matter Purpose；
8) Pb-Zn deposits mineral processing production process back to is sent processing water outlet by reuse water tank and reuse water pump, meanwhile, utilize backwash water It pumps and regular backwash is carried out to the ultrafiltration membrane of membrane separation device.
Advantages of the present invention, present invention is generally directed to Pb-Zn deposits beneficiation wastewaters to have high calcium, high pH, high suspended matter, height COD and contain a large amount of beneficiation reagents and heavy metal ion the characteristics of；It is anti-using liquid CO 2 and the calcium hydroxide in waste water It should and precipitate, while deliming, drop pH；And then organic pollutant is aoxidized using the strong oxidizer that cavitation and electrochemistry generate, it drops Solve COD；Finally, being finally completed system deliming, removing heavy metals, drop COD, the target for dropping suspended matter by film filtering；Processing water outlet It is transmitted back to Pb-Zn deposits mineral processing production process, reaches water-saving and emission-reducing, and guarantees the purpose that ore-sorting system operates normally.
Detailed description of the invention
Attached drawing 1 is the general structure schematic diagram of Pb-Zn deposits beneficiation wastewater treatment for reuse device.
Attached drawing 2 is the water balance figure of Pb-Zn deposits beneficiation wastewater treatment for reuse devices and methods therefor embodiment；
Attached drawing 3 is reuse treatment process flow diagram.
PbZnTWW in attached drawing 1 indicates that Pb-Zn deposits beneficiation wastewater (tailing thickening pond overflow water), RCW indicate recycle-water, ES Indicate that excess sludge, WWT indicate that Pb-Zn deposits beneficiation wastewater case, RCWT indicate reuse water tank, D1Indicate that coagulant and flocculation aid are thrown Feeder apparatus, D2Indicate feeding apparatus for powdered activated charcoal, D3Indicate that liquid CO 2 throwing device, RT indicate that reaction tank, ST indicate Sedimentation basin, EC indicate that electrochemical appliance, HT indicate that digestion pool, MSD indicate that membrane separation device, CR indicate cavitation reactor, P1Table Show raw water pump, P2Indicate suction water pump, P3Indicate reuse water pump, P4Indicate gas-liquid mixing pump, P5Indicate sludge reflux pump, P6It indicates Sludge pump, P7Indicate backwash water pump.
Specific embodiment
Attached drawing 1 is compareed, Pb-Zn deposits beneficiation wastewater treatment for reuse device, structure includes reaction tank RT, sedimentation basin ST, electrification Learn device EC, digestion pool HT, membrane separation device MSD, cavitation reactor CR, Pb-Zn deposits beneficiation wastewater case WWT, reuse water tank RCWT, coagulant and flocculation aid throwing device D1, feeding apparatus for powdered activated charcoal D2, liquid CO 2 throwing device D3, and Raw water pump P1, suction water pump P2, reuse water pump P3, gas-liquid mixing pump P4, sludge reflux pump P5, sludge pump P6, backwash water pump P7；Its The water inlet of middle Pb-Zn deposits beneficiation wastewater PbZnTWW access Pb-Zn deposits beneficiation wastewater case WWT, Pb-Zn deposits beneficiation wastewater case WWT's Water outlet passes through raw water pump P1Connect the water inlet of reaction tank RT, coagulant and flocculation aid throwing device D1Medicine outlet connection it is anti- The feeding opening of pond RT is answered, the inlet of the liquid outlet connection reaction tank RT of cavitation reactor CR is directed to lead zinc in reaction tank RT Mine beneficiation wastewater carries out cavitation oxygenolysis organic pollutant, carbon dioxide deliming drop pH, coagulation and flocculation etc. and reacts；Reaction tank The water inlet of the water outlet connection sedimentation basin ST of RT falls the CaCO that reaction generates in sedimentation basin ST precipitating3It is (calcium carbonate) and big Wadding body object, complete deliming, reduce pH, reduce COD and suspended matter；The mud mouth of sedimentation basin ST passes through sludge reflux pump P5Connection The mud inlet of reaction tank RT is reduced the dosage of coagulant and flocculation aid using returned sludge, and improves sedimentation effect；Meanwhile The mud mouth of sedimentation basin ST is passed through into sludge pump P6Excess sludge ES(is sent out to tailing thickening pond)；The inlet and outlet of sedimentation basin ST connect The water inlet for meeting electrochemical appliance EC utilizes the electrochemical appliance EC hydroxy radical (OH) generated and hypochlorite (OCl-) into One step aoxidizes organic pollutant, reduces COD；The water inlet of the water outlet connection digestion pool HT of electrochemical appliance EC, powder activity Charcoal throwing device D2Medicine outlet connection digestion pool HT feeding opening, further reacted extra oxidation using digestion pool HT Agent, meanwhile, using Powdered Activated Carbon filtrating aid function, enhance the filter effect of membrane separation device MSD；The water outlet of digestion pool HT connects The water inlet for meeting membrane separation device MSD, is filtered using submerged ultrafiltration, further decreases the CaCO in water3, COD, suspended matter With turbidity, the recycle-water of high-quality is obtained；The water outlet of membrane separation device MSD passes through suction water pump P2Connect reuse water tank RCWT Water inlet, the backwash water water outlet of reuse water tank RCWT passes through backwash water pump P7Connect membrane separation device MSD backwash water into The mouth of a river, the water return outlet of the backwash water water outlet connection reaction tank RT of membrane separation device MSD, the backwash of membrane separation device MSD is arranged Water is recycled；The water outlet of reuse water tank RCWT passes through reuse water pump P3Recycle-water RCW is sent out, reaches and selects Pb-Zn deposits Mine wastewater treatment and renovation is in the purpose of production.
Pb-Zn deposits beneficiation wastewater treatment for reuse method, includes the following steps:
1) Pb-Zn deposits beneficiation wastewater after Pb-Zn deposits beneficiation wastewater case, raw water pump pressurization by sending；
2) Pb-Zn deposits beneficiation wastewater and coagulant and flocculation aid are carried out by coagulation and flocculation reaction by reaction tank, generates larger wadding Body；
3) liquid CO 2 dissolved through gas-liquid mixing pump is added to by reaction tank by cavitation reactor, carries out deliming, drop PH reaction；
4) it is precipitated by sedimentation basin, sends returned sludge back to reaction tank using sludge reflux pump, be discharged using sludge pump surplus Remaining sludge；
5) organic pollutants are aoxidized by electrochemical appliance；
6) organic pollutants, and the oxidant that stripping is extra are further aoxidized by digestion pool, by adding powder activity Charcoal increases absorption and filtrating aid function；
7) pass through membrane separation device and suction water pump final filtration, complete system deliming, removing heavy metals, drop COD, drop suspended matter Purpose；
8) Pb-Zn deposits mineral processing production process back to is sent processing water outlet by reuse water tank and reuse water pump, meanwhile, utilize backwash water It pumps and regular backwash is carried out to the ultrafiltration membrane of membrane separation device.
The step 1) is by Pb-Zn deposits beneficiation wastewater case, and specifically Pb-Zn deposits beneficiation wastewater is in Pb-Zn deposits beneficiation wastewater The well-balanced adjustment of waste water quality, water is carried out in case, is then sent to reaction tank through raw water pump pressurization；
By reaction tank, the Pb-Zn deposits beneficiation wastewater elder generation dosing coagulant specifically in reaction tank is mixed the step 2) Solidifying reaction, then add flocculation aid and carry out flocculation reaction, it generates compared with big flocculating body, in favor of post precipitation；
The step 3) before liquid CO 2 is specifically added to gas-liquid mixing pump, utilizes gas by cavitation reactor The dissolution of liquid mixing pump, and Cavitation is carried out by cavitation reactor, it is then added to reaction tank, in Pb-Zn deposits beneficiation wastewater Calcium hydroxide sufficiently reacted, generate calcium carbonate, have the function that simultaneously deliming, drop pH, and correspondence calcium Concentration portion Reduce the TDS(total dissolved solidss of waste water) content, meanwhile, it is organic in the strong oxidizer oxidized waste water generated using Cavitation Pollutant reduces COD；
The step 4) is specifically sunk wadding body and calcium carbonate granule that reaction tank generates in sedimentation basin by sedimentation basin Form sediment, send returned sludge (generally the 5~10% of wastewater flow) back to reaction tank using sludge reflux pump, with save coagulant with Flocculant adds, while periodically or sludge concentration is when reaching 6~10%, utilizing sludge pump that excess sludge is discharged；
The step 5) passes through electrochemical appliance, the direct electrolytic oxidation specifically occurred at electrode using electrochemical appliance Effect, and the ClO generated using electrolysis-(hypochlorite) and OH(hydroxy radical) carry out indirect oxidation effect, into one Organic pollutant in step oxidation water, is decomposed into carbon dioxide and water for organic beneficiation reagent remaining in water, reduces COD；
The step 6) utilizes the oxidant that front unreacted is complete, further oxygen by digestion pool specifically in digestion pool Change organic pollutants, and the oxidant extra using blower stripping, increases suction-operated by adding Powdered Activated Carbon, and Filtrating aid function is played to subsequent film filtering；
The step 7) specifically combines suction water using the submerged ultrafiltration in membrane separation device by membrane separation device Pump carries out final filtration, completes system deliming, removing heavy metals, drop COD, the purpose for dropping suspended matter, effluent quality is controlled in pH: 6~9, Ca2+:≤40mg/L, COD :≤60mg/L, SS :≤10mg/L, heavy metal entirely reach " lead, Zn Cr coating pollutant emission Standard " (GB25466-2010) limit value；
The step 8) is specifically stored the water outlet handled well using reuse water tank, utilizes backwash water pump by reuse water tank Regular backwash is carried out to the ultrafiltration membrane of membrane separation device, to guarantee the long-term stable operation of membrane separation device；Utilize reuse water pump It sends processing water outlet back to Pb-Zn deposits mineral processing production process, reaches water-saving and emission-reducing, and guarantee what Pb-Zn deposits ore-sorting system operated normally Purpose.
Embodiment
It is 2000 ton/days that certain mining company's lead and zinc, which produces processing capacity, and long term is expanded to 3000 ton/days, and production technology is " lead diffeential floatation-select lead spoil reclaming zinc-zinc coarse concentrate regrinding after selected " technique, because of ore properties and complex process, ore dressing A large amount of all kinds of beneficiation reagents need to be consumed when processing, the mine tailing wastewater water quality for causing ore dressing to generate is complicated, and direct reuse is to ore dressing Index Influence is larger, reuse after need to being handled.In the production of the operations such as the flotation of lead and zinc, concentration, filtering, flushing discharge In waste water, solid suspension content is high, so that the appearance of beneficiation wastewater is poor, while also to some extent containing choosing in waste water Mine medicament, heavy metal ion etc., such as black powder, xanthate, sulfide, As3+、Pb2+、Cu2+、Zn2+And other metal ions, thus shape At the high calcium containing plurality of heavy metal ion and floating agent, high pH, high suspended matter, high COD beneficiation wastewater.If direct emission The beneficiation wastewater is unfavorable for environmental protection, can also endanger animal and the health of people；If beneficiation wastewater is directly returned without processing With longtime running can block production pipeline, moreover, because the influence of remaining beneficiation reagent and heavy metal ion, will lead to sorting Index is deteriorated and influences concentrate product quality.For this purpose, a Pb-Zn deposits beneficiation wastewater treatment for reuse system has been built, by Pb-Zn deposits It after beneficiation wastewater carries out advanced treating, is back to use among Pb-Zn deposits beneficiating process, preferably solves whose pollution and ore dressing is produced The influence problem of quality.
Project major design data are as follows:
1) water-in and water-out water quality and water are designed
It designs Pb-Zn deposits beneficiation wastewater and handles water: 7500T/D(313T/H).
The lead and zinc has added the organic compounds such as a large amount of xanthate, diethyldithiocarbamate, black powder in Pb-Zn deposits ore-dressing technique And the beneficiation reagents such as lime, sodium carbonate, sulfide, furthermore plurality of heavy metal copper ion is also added in Pb-Zn deposits ore dressing process.This A little beneficiation reagents are added in Pb-Zn deposits ore-dressing technique with solution state, and in Pb-Zn deposits ore-dressing technique ore grinding generate subparticle and Colloidal solid can also be such that suspended matter in Pb-Zn deposits beneficiation wastewater increases.Thereby result in pH, COD in Pb-Zn deposits beneficiation wastewaterCr(chromium Forensic chemistry oxygen demand), suspended matter, total copper, the indexs such as sulfide be more than " lead, Zn Cr coating pollutant emission standard " (GB25466- 2010) discharge standard as defined in, meanwhile, Ca2+Also higher.It therefore, need to be by pH, COD in beneficiation wastewaterCr, suspended matter, total copper, After the processing such as sulfide is up to standard, meanwhile, reduce Ca2+Content after, just allow discharge or reuse.
It is as follows to design water-in and water-out water quality indicator:
Note: Ca in table2+Not in the limit value of the standard of " lead, Zn Cr coating pollutant emission standard " (GB25466-2010).
2) technical flow design
Reuse after the softened clarification of Pb-Zn deposits beneficiation wastewater, electrolysis, hyperfiltration treatment.Consider to have added in Pb-Zn deposits ore dressing process big Lime, copper sulphate and the organic medicament of amount, Pb-Zn deposits beneficiation wastewater have high pH, high rigidity, high CODCr, high suspended matter Feature will reduce pH, Ca simultaneously2+、CODCr, suspended matter, to be back to Pb-Zn deposits mineral processing production.It, can be with according to the water quality characteristics Using adding liquid CO2, with the Ca (OH) in waste water2Reaction generates CaCO3And H2O, directly reduction pH and hardness, reduce simultaneously Part TDS in waste water, and by adding flocculant PFS(bodied ferric sulfate), flocculation aid PAM(polyacrylamide), assist lead The precipitating of pH, hardness, suspended matter in zinc ore beneficiation wastewater carry out precipitating and sludge condensation by highly effective reaction sedimentation basin, into And pass through electrolysis unit, cavitation, digestion pool, membrane separation device filtering, initial stage CODCrDust active carbon (PAC) is added when high, further Reduce CODCr；So that pH 7~8, the Ca of recycle-water2+≤ 40mg/L, suspended matter≤1mg/L, CODCr≤60mg/L.Meet discharge With the requirement of reuse standard.
Reuse treatment process flow diagram is as shown in Figure 3.
3) water balance
Referring to the water balance figure of 2 Pb-Zn deposits beneficiation wastewater treatment for reuse devices and methods therefor embodiment of attached drawing.
4) system main design parameters
● civil engineering:
Note: (1) equipment in effluent treatment plant being arranged include: reaction tank, flocculation basin, sedimentation basin, electrolysis unit, digestion pool, Membrane separation device, hyperfiltration reverse-rinsing water tank, ultrafiltration discharge casing；
(2) equipment of automatically controlled setting middle between dosing mainly has: control cabinet, power distribution cabinet, DCS system, coagulant, flocculation aid, powder Last activated charcoal adding apparatus, ultrafiltration chemicals dosing plant and ultrafiltration chemically-cleaning device etc..
● capital equipment:

Claims (10)

1. Pb-Zn deposits beneficiation wastewater treatment for reuse device, it is characterized in that include reaction tank, sedimentation basin, electrochemical appliance, digestion pool, Membrane separation device, cavitation reactor, Pb-Zn deposits beneficiation wastewater case, reuse water tank, coagulant and flocculation aid throwing device, powder are living Property charcoal throwing device, liquid CO 2 throwing device and raw water pump, suction water pump, reuse water pump, gas-liquid mixing pump, dirt Mud reflux pump, sludge pump, backwash water pump；Wherein the water inlet of Pb-Zn deposits beneficiation wastewater case is used to access Pb-Zn deposits beneficiation wastewater, The water outlet of Pb-Zn deposits beneficiation wastewater case connects the water inlet of reaction tank, coagulant and flocculation aid throwing device by raw water pump Medicine outlet connects the feeding opening of reaction tank, and the inlet of the liquid outlet connection reaction tank of cavitation reactor is directed in reaction tank Pb-Zn deposits beneficiation wastewater carries out cavitation oxygenolysis organic pollutant, carbon dioxide deliming drop, coagulation and flocculation reaction；Reaction tank Water outlet connection sedimentation basin water inlet, sedimentation basin precipitating fall reaction generate CaCO3And big wadding body object, it completes to remove Calcium reduces pH, reduces COD and suspended matter；The mud mouth of sedimentation basin connects the mud inlet of reaction tank by sludge reflux pump, utilizes Returned sludge reduces the dosage of coagulant and flocculation aid, and improves sedimentation effect；Meanwhile the mud mouth of sedimentation basin is passed through into row Dredge pump sends out excess sludge to tailing thickening pond；The water inlet of the inlet and outlet connection electrochemical appliance of sedimentation basin, utilizes electrochemistry The hydroxy radical OH and hypochlorite OCl that device generates-Organic pollutant is further aoxidized, COD is reduced；Electrochemical appliance Water outlet connects the water inlet of digestion pool, the feeding opening of the medicine outlet connection digestion pool of feeding apparatus for powdered activated charcoal, using disappearing Xie Chi has further reacted extra oxidant, meanwhile, using Powdered Activated Carbon filtrating aid function, enhance the filtering of membrane separation device Effect；The water inlet of the water outlet connection membrane separation device of digestion pool, is filtered using submerged ultrafiltration, is further decreased in water CaCO3, COD, suspended matter and turbidity, obtain the recycle-water of high-quality；The water outlet of membrane separation device is connected by suction water pump Take back the water inlet with water tank, the backwash water water outlet of reuse water tank by the backwash water of backwash water pump connection membrane separation device into The mouth of a river, the water return outlet of the backwash water water outlet connection reaction tank of membrane separation device, the backwash of membrane separation device is drained back Receipts processing；The water outlet of reuse water tank pumps out recycle-water by recycle-water, reach by Pb-Zn deposits beneficiation wastewater treatment for reuse in The purpose of production.
2. using the Pb-Zn deposits beneficiation wastewater treatment for reuse of Pb-Zn deposits beneficiation wastewater treatment for reuse device as described in claim 1 Method, it is characterized in that including the following steps:
1) Pb-Zn deposits beneficiation wastewater after Pb-Zn deposits beneficiation wastewater case, raw water pump pressurization by sending；
2) Pb-Zn deposits beneficiation wastewater and coagulant and flocculation aid are carried out by coagulation and flocculation reaction by reaction tank, generates wadding body；
3) liquid CO 2 dissolved through gas-liquid mixing pump is added to by reaction tank by cavitation reactor, carries out deliming, drop PH reaction；
4) it is precipitated by sedimentation basin, sends returned sludge back to reaction tank using sludge reflux pump, be discharged using sludge pump surplus Remaining sludge；
5) organic pollutants are aoxidized by electrochemical appliance；
6) organic pollutants, and the oxidant that stripping is extra are further aoxidized by digestion pool, by adding powder activity Charcoal increases absorption and filtrating aid function；
7) pass through membrane separation device and suction water pump final filtration, complete system deliming, removing heavy metals, drop COD, drop suspended matter Purpose；
8) Pb-Zn deposits mineral processing production process back to is sent processing water outlet by reuse water tank and reuse water pump, meanwhile, utilize backwash water It pumps and regular backwash is carried out to the ultrafiltration membrane of membrane separation device.
3. Pb-Zn deposits beneficiation wastewater treatment for reuse method according to claim 2, it is characterized in that the step 1) passes through Pb-Zn deposits beneficiation wastewater case, specifically Pb-Zn deposits beneficiation wastewater carry out in Pb-Zn deposits beneficiation wastewater case waste water quality, water Then well-balanced adjustment is sent to reaction tank through raw water pump pressurization.
4. Pb-Zn deposits beneficiation wastewater treatment for reuse method according to claim 2, it is characterized in that the step 2) passes through Reaction tank, Pb-Zn deposits beneficiation wastewater elder generation's dosing coagulant specifically in reaction tank carries out coagulating, then adds flocculation aid Flocculation reaction is carried out, wadding body is generated, in favor of post precipitation.
5. Pb-Zn deposits beneficiation wastewater treatment for reuse method according to claim 2, it is characterized in that the step 3) passes through Cavitation reactor before liquid CO 2 is specifically added to gas-liquid mixing pump, is dissolved using gas-liquid mixing pump, and passes through sky Change reactor and carry out Cavitation, be then added to reaction tank, is carried out with the calcium hydroxide in Pb-Zn deposits beneficiation wastewater sufficiently anti- It answers, generates calcium carbonate, have the function that deliming simultaneously, drop pH, and the TDS(of the Concentration portion reduction waste water of corresponding calcium always dissolves Solid) content, meanwhile, the organic pollutant in strong oxidizer oxidized waste water generated using Cavitation reduces COD.
6. Pb-Zn deposits beneficiation wastewater treatment for reuse method according to claim 2, it is characterized in that the step 4) passes through Sedimentation basin specifically precipitates wadding body and calcium carbonate granule that reaction tank generates in sedimentation basin, will using sludge reflux pump Returned sludge sends reaction tank back to, to save adding for coagulant and flocculant, while periodically or when sludge concentration reaches 6~10%, Excess sludge is discharged using sludge pump.
7. Pb-Zn deposits beneficiation wastewater treatment for reuse method according to claim 2, it is characterized in that the step 5) passes through Electrochemical appliance is specifically acted on using the direct electrolytic oxidation that electrochemical appliance occurs at electrode, and is produced using electrolysis Raw ClO-The indirect oxidation effect that hypochlorite and OH hydroxy radical carry out, further aoxidizes the organic pollutant in water, Organic beneficiation reagent remaining in water is decomposed into carbon dioxide and water, reduces COD.
8. Pb-Zn deposits beneficiation wastewater treatment for reuse method according to claim 2, it is characterized in that the step 6) passes through Digestion pool further aoxidizes organic pollutants, and benefit using the oxidant that front unreacted is complete specifically in digestion pool With the extra oxidant of blower stripping, increase suction-operated by adding Powdered Activated Carbon, and drainage is played to subsequent film filtering Effect.
9. Pb-Zn deposits beneficiation wastewater treatment for reuse method according to claim 2, it is characterized in that the step 7) passes through Membrane separation device specifically combines suction water pump to carry out final filtration, completes using the submerged ultrafiltration in membrane separation device System deliming, removing heavy metals, drop COD, the purpose for dropping suspended matter, effluent quality is controlled in pH6~9, Ca2+≤40mg/L、COD ≤ 60mg/L, SS≤10mg/L, heavy metal entirely reach the limit value of GB25466-2010.
10. Pb-Zn deposits beneficiation wastewater treatment for reuse method according to claim 2, it is characterized in that the step 8) passes through Reuse water tank specifically stores the water outlet handled well, using backwash water pump to the ultrafiltration membrane of membrane separation device using reuse water tank Regular backwash is carried out, to guarantee the long-term stable operation of membrane separation device；Processing water outlet is sent back to Pb-Zn deposits using reuse water pump Mineral processing production process reaches water-saving and emission-reducing, and guarantees the purpose that Pb-Zn deposits ore-sorting system operates normally.
CN201811411588.4A 2018-11-24 2018-11-24 Pb-Zn deposits beneficiation wastewater treatment for reuse devices and methods therefor Pending CN109437448A (en)

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CN110510848A (en) * 2019-08-19 2019-11-29 东莞市逸轩环保科技有限公司 Biochemical sludge decrement treatment system
CN111547879A (en) * 2020-04-30 2020-08-18 云南驰宏锌锗股份有限公司 Hardness reduction treatment method for lead-zinc smelting industrial wastewater subjected to standard treatment

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